US3326687A - Photographic colloid transfer system - Google Patents
Photographic colloid transfer system Download PDFInfo
- Publication number
- US3326687A US3326687A US410275A US41027564A US3326687A US 3326687 A US3326687 A US 3326687A US 410275 A US410275 A US 410275A US 41027564 A US41027564 A US 41027564A US 3326687 A US3326687 A US 3326687A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- silver halide
- colloid
- bis
- ethylene
- 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
- 239000000084 colloidal system Substances 0.000 title claims description 23
- 238000012546 transfer Methods 0.000 title description 13
- 239000000839 emulsion Substances 0.000 claims description 51
- -1 SILVER HALIDE Chemical class 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 12
- MGFJDEHFNMWYBD-OWOJBTEDSA-N 4-[(e)-2-pyridin-4-ylethenyl]pyridine Chemical compound C=1C=NC=CC=1/C=C/C1=CC=NC=C1 MGFJDEHFNMWYBD-OWOJBTEDSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 13
- 108010010803 Gelatin Proteins 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 12
- 235000019322 gelatine Nutrition 0.000 description 12
- 235000011852 gelatine desserts Nutrition 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229940090898 Desensitizer Drugs 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 125000004964 sulfoalkyl group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- XAKBSHICSHRJCL-UHFFFAOYSA-N [CH2]C(=O)C1=CC=CC=C1 Chemical group [CH2]C(=O)C1=CC=CC=C1 XAKBSHICSHRJCL-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000586 desensitisation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QDNPCYCBQFHNJC-UHFFFAOYSA-N 1,1'-biphenyl-3,4-diol Chemical compound C1=C(O)C(O)=CC=C1C1=CC=CC=C1 QDNPCYCBQFHNJC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 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
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
-
- 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
-
- 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
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/315—Tanning development
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/06—Silver salts
Definitions
- the silver halide emulsion used for office copying purposes is handled in roomlight so that there is a need for adding a substance to the emulsion which acts to reduce the emulsion speed to a level which will permit roomlight handling in light, such as fluorescent light, rich in blue light.
- roomlight handling in light such as fluorescent light, rich in blue light.
- Methylene blue has been proposed for this purpose.
- methylene blue has not been entirely satisfactory since it interferes with certain spectral sensitizess causing a loss in sensitized speed which is reflected in rerequiring increased exposure.
- the incorporated developer causes the emulsion containig methylene blue to'become resensitized both to the printing light and to roomlight.
- there is a limited desensitization possible with methylene blue since the desensitization approaches a maximum asymptotically as the concentration is increased.
- One object of this invention is to provide an unhardened silver halide emulsion containing a desensitizer which permits roomlight handling of the emulsion without seriously reducing its sensitivity to the printing light.
- a further object is to provide a l,2-bis(4-pyridyl)ethylene desensitized colloid transfer silver halide emulsion which has improved desensitization with respect to that obtained from methylene blue and reduced interference with the tanning action of the tanning developer.
- a useful method of incorporatnig a derivative which is not water soluble is to dissolve it in a small amount of a water-miscible solvent such as, for example, acetone, methanol, ethanol, etc.
- 0.5 to 3 grams of the quaternarized derivative of 1,2-bis(4-pyridyl)ethylene per mole of silver halide are added to a spectrally sensitized, substantially unhardened colloid silver halide emulsion containing a tanning silver halide developer.
- our preferred emulsion is a silver chloride emulsion
- other silver halide emulsions can be used, including silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide and silver chlorobromoiodide. Mixtures of these may also be used.
- the tanning developers which may be used are those disclosed in the above US. patents describing colloid transfer emulsions.
- non-tanning ilver halide developers may be incorporated in the emulsions as described in the above patents or used in the developing solution to improve the density of the transferred image.
- colloid transfer emulsions of this invention may also be used to prepare lithographic plates, and the emulsions of this invention may be exposed either by the reflex method or through appropriate optical systems. de-
- the concentration of the tanning developing agent in the emulsion is dependent in part upon the result desired but can be of the order of 350 grams of tanning developing agent per kilogram ofsilver nitrate converted to silver halide, used in making the emulsion, to obtain good density of about 250 grams per kilogram of silver nitrate to obtain adequate density and an emulsion having optimum keeping properties.
- the photographic emulsion layer used in this process can be a dispersion of silverihalide grains in a colloid vehicle such as gelatin or, in a resin such as polyvinyl alcohol, polyacrylamide, etc., capable of being differentially tanned.
- the emulsion layer be not harder than would be the case with gelatin containing 0.25 ounce of formaldehyde solution (40 percent diluted 1:3 with water); or 0.7 gram of dry formaldehyde per pound when freshly coated; or 0.1 ounce of the solution per pound for a sample aged 3 to 6 months.
- a substantially unhardened gelatino-silver halide emulsion containing 1 mole of silver chloride, 300 grams of gelatin and 5700 grams of water is gelled, noodled and washed for one-half hour with water, then melted at 40 C., and the following addition made:
- a green sensitizing merocyanine dye To samples of this emulsion is added a green sensitizing merocyanine dye and to each sample to be tested, a desensitizer in an amount as shown in the table below.
- the emulsion is coated at 190 mg. of silver per square foot on a paper support and dried.
- results shown in the table below were obtained by testing with light, which simulated blue light, and also with white light in which the light to which the emulsion is inherently sensitive had been removed.
- the test using the Wratten No. 4 filter indicate the response of the emulsion to white light which has the light to which the emulsion is inherently sensitive, removed therefrom.
- the test using the Wratten No. 35 and 38A filters shows the response to white light in which all wavelengths of the spectrum have been removed except for the blue light.
- Each set of samples are grouped under a control containing methylene blue, indicating the data obtained at the same time as the given control. In order to obtain sensitometric data, the exposed test strips were processed using D-72 developer for one minute.
- the coatings in each instance were exposed on a Verifax Regent Copier to incandescent light for 20 seconds, immersed for 60 seconds in an activator solution having the following composition:
- Verifax receiving paper held at a temperature of 81 F. and rolled in contact with Verifax receiving paper.
- Desensitizer B is an oxoniurn salt of the following structure:
- the emulsion of this invention can be coated on various supports such as paper, glass, and the like.
- the unhardened emulsion can be coated on a porous base material and after developing in an alkaline activator it can be washed with hot water to provide a stencil master.
- the particular fabric useful for this embodiment depends, of course, on the ultimate result desired. However, tea bag stock may be used as well as silk screen stock, and the like, customarily used for the silk screens process.
- the emulsion can be exposed, developed and contacted against a receiving support to remove the unhardened areas of the emulsion. After this step, a subsequent Washing step may be used, if needed, to remove the additional unhardened emulsion which remains in the interstices of the fabric.
- a substantially unhardened hydrophilic colloid silver halide emulsion containing a colloid tanning silver halide Blue Speed (Wratten Spectral Sensitization Nos. 35-1-38 Filters) (Wratten No. 4 Filter) Room-light Teler- Printing Speed Coating No. Desensitizer (gJAg. mole) M100 Control) (R61. to Control) Rel. Speed Fog Rel. Speed Fog Methylene Blue (0.03) 100.0 0.43 23 .0 0 Control. A 17 .2 0.20 3 .2 0.19 Very much lower. Methylene Blue (0.03)... 100 .0 0.20 145 .0 0.25 Control Control.
- This desensitizer interferes with the tanning action of the developer on the gelatin in the exposed, nonimage areas and thus results in poor transfers.
- Desensitizers (I) 1,2-bis(l-phenacyl-4-pyridiniurn bromide)ethylene 6 (II) l,2-bis(1-methyl-4-pyridiniurn p-toluenesulfonate) ethylene (III) 1,2-bis(4-pyridyl-1-sulfopropyl)ethylene Methylene Blue, also called 3,7-bis(dimethyamino)- phenazathioniurn chloride, is a sulfonium salt of the following structure:
- R represents a group selected from the class consisting of phenacyl, alkyl and substituted alkyl in which the alkyl moiety has from 1-10 carbon atoms,
- X represent an anion except when -R is a sulfoalkyl derivative and the negative charge siassumed by the sulfonalkyl group itself,
- a process of preparing a substantially unhardened colloid silver halide emulsion for roomlight handling comprising dissolving in a water-miscible solvent a desensitizing compound which is a quaternarized derivative of a 1,2-bis(4-pyridyl)ethylene and adding a desensitizing amount to the substantially unhardened colloid silver halide emulsion.
- R represents a group selected from the class consisting of phenacyl, alkyl and substituted alkyl in which the alkyl moiety has from 1-10 carbon atoms,
- X represents an anion except when R is a sulfoalkyl derivative and the negatve charge is assumed by the sulfoalkyl group itself.
- R represents a group selected from the class consisting of phenacyl, alkyl and substituted alkyl in which the alkyl moiety has from -l-10 carbon atoms,
- X represents an anion except when R is a sulfoalkyl derivative and the negative charge is assumed by the sulfoalkyl group itself,
- the desensitizing compound is added in an amount of 0.5 to 3 grams per mole of silver halide.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Pyridine Compounds (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent Ofifice 3,326,687 Patented June 20, 1967 This invention relates to colloid transfer photographic materials, more particularly to light sensitive materials which are suitable for roomlight handling.
In the photographic colloid transfer system, as described in Yutzy et al. US. Patents 2,596,756 and 2,716,- 059, an unhardened silver halide photographic emulsion containing a tanning developer is exposed to an image and after sufiicient development, the developing silver halide emulsion is pressed against a surface to transfer a stratum of unexposed, untanned gelatin to the receiving surface. In this way, a positive image is obtained of the exposed image.
In one embodiment of colloid transfer, the silver halide emulsion used for office copying purposes is handled in roomlight so that there is a need for adding a substance to the emulsion which acts to reduce the emulsion speed to a level which will permit roomlight handling in light, such as fluorescent light, rich in blue light. However, it is necessary to preserve the sensitivity of the emulsion t incandescent lamps, sufficiently to permit exposure on the office copying apparatus.
Methylene blue has been proposed for this purpose. However, methylene blue has not been entirely satisfactory since it interferes with certain spectral sensitizess causing a loss in sensitized speed which is reflected in rerequiring increased exposure. In some instances, the incorporated developer causes the emulsion containig methylene blue to'become resensitized both to the printing light and to roomlight. Moreover, there is a limited desensitization possible with methylene blue, since the desensitization approaches a maximum asymptotically as the concentration is increased.
It has been desirable to find an additive for the unhardened colloid transfer type emulsions which contain tanning type silver halide developers, whichwould overcome the disadvantages of methylene blue. However, such an additive needs to be stable to provide for good keeping. It needs to be inert to the incorporated developers in the emulsion and to be compatible with both methylene blue and the silver halide emulsions. In addition, the additive should not interfere with the tanning action of the developer on the colloid such as gelatin in the exposed non-image areas so that poor transfers result.
I have found that certain quaternarized derivatives of 1,2-bis (4-pyridyl)ethylene can be used to overcome some of the deficiencies of methylene blue in the colloid transfer emulsions.
One object of this invention is to provide an unhardened silver halide emulsion containing a desensitizer which permits roomlight handling of the emulsion without seriously reducing its sensitivity to the printing light. A further object is to provide a l,2-bis(4-pyridyl)ethylene desensitized colloid transfer silver halide emulsion which has improved desensitization with respect to that obtained from methylene blue and reduced interference with the tanning action of the tanning developer.
The above objects are attained by incorporating into an unhardened silver halide emulsion at least one quaternarized derivative of 1,2-bis (4-pyridyl)ethylene. derivative may have the following structure:
CH=CH The e To
where A useful method of incorporatnig a derivative which is not water soluble is to dissolve it in a small amount of a water-miscible solvent such as, for example, acetone, methanol, ethanol, etc.
In our preferred embodiment 0.5 to 3 grams of the quaternarized derivative of 1,2-bis(4-pyridyl)ethylene per mole of silver halide are added to a spectrally sensitized, substantially unhardened colloid silver halide emulsion containing a tanning silver halide developer.
Although our preferred emulsion is a silver chloride emulsion, other silver halide emulsions can be used, including silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide and silver chlorobromoiodide. Mixtures of these may also be used.
The tanning developers which may be used are those disclosed in the above US. patents describing colloid transfer emulsions. In addition, non-tanning ilver halide developers may be incorporated in the emulsions as described in the above patents or used in the developing solution to improve the density of the transferred image.
The colloid transfer emulsions of this invention may also be used to prepare lithographic plates, and the emulsions of this invention may be exposed either by the reflex method or through appropriate optical systems. de-
, pending upon the speed of the emulsionused, the desired result, etc.
The concentration of the tanning developing agent in the emulsion is dependent in part upon the result desired but can be of the order of 350 grams of tanning developing agent per kilogram ofsilver nitrate converted to silver halide, used in making the emulsion, to obtain good density of about 250 grams per kilogram of silver nitrate to obtain adequate density and an emulsion having optimum keeping properties. a
The photographic emulsion layer used in this process can be a dispersion of silverihalide grains in a colloid vehicle such as gelatin or, in a resin such as polyvinyl alcohol, polyacrylamide, etc., capable of being differentially tanned.
It is necessary for the successful operation of the invention that the emulsion layer be not harder than would be the case with gelatin containing 0.25 ounce of formaldehyde solution (40 percent diluted 1:3 with water); or 0.7 gram of dry formaldehyde per pound when freshly coated; or 0.1 ounce of the solution per pound for a sample aged 3 to 6 months. By substantially unhardened as used herein, and in the appended claims, it is to be understood that this means a hardness of the order obtained with gelaamass? tin treated with formaldehyde under the conditions above.
The following examples are intended to illustrate my invention but not to limit it in any way.
A substantially unhardened gelatino-silver halide emulsion containing 1 mole of silver chloride, 300 grams of gelatin and 5700 grams of water is gelled, noodled and washed for one-half hour with water, then melted at 40 C., and the following addition made:
650 grams of 8 percent aqueous saponin 600 grams of a dispersion of 4-phenylcatechol prepared by dissolving 50 grams of 4-phenylcatechol in 70 grams of dibutyl phthalate at 80 C. and pouring it into a vigorously stirred solution of 50 grams of gelatin in 50 grams of 8 percent aqueous saponin solution and 500 ccs. of water at 40 C.
To samples of this emulsion is added a green sensitizing merocyanine dye and to each sample to be tested, a desensitizer in an amount as shown in the table below. The emulsion is coated at 190 mg. of silver per square foot on a paper support and dried.
The results shown in the table below were obtained by testing with light, which simulated blue light, and also with white light in which the light to which the emulsion is inherently sensitive had been removed. The test using the Wratten No. 4 filter indicate the response of the emulsion to white light which has the light to which the emulsion is inherently sensitive, removed therefrom. The test using the Wratten No. 35 and 38A filters shows the response to white light in which all wavelengths of the spectrum have been removed except for the blue light. Each set of samples are grouped under a control containing methylene blue, indicating the data obtained at the same time as the given control. In order to obtain sensitometric data, the exposed test strips were processed using D-72 developer for one minute.
To obtain transfer performance data, the coatings in each instance were exposed on a Verifax Regent Copier to incandescent light for 20 seconds, immersed for 60 seconds in an activator solution having the following composition:
Grams Na CO -H O Urea 50 Water to 1 liter.
held at a temperature of 81 F. and rolled in contact with Verifax receiving paper.
l Desensitizer A has the following structure:
E 01- 5 ll Desensitizer B is an oxoniurn salt of the following structure:
/@C CHCH=CH- N oHa)z-(B1M)- ea 0.119
The emulsion of this invention can be coated on various supports such as paper, glass, and the like. In a useful embodiment, the unhardened emulsion can be coated on a porous base material and after developing in an alkaline activator it can be washed with hot water to provide a stencil master. The particular fabric useful for this embodiment depends, of course, on the ultimate result desired. However, tea bag stock may be used as well as silk screen stock, and the like, customarily used for the silk screens process. If desired, the emulsion can be exposed, developed and contacted against a receiving support to remove the unhardened areas of the emulsion. After this step, a subsequent Washing step may be used, if needed, to remove the additional unhardened emulsion which remains in the interstices of the fabric.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
I claim:
1. A substantially unhardened hydrophilic colloid silver halide emulsion containing a colloid tanning silver halide Blue Speed (Wratten Spectral Sensitization Nos. 35-1-38 Filters) (Wratten No. 4 Filter) Room-light Teler- Printing Speed Coating No. Desensitizer (gJAg. mole) M100 Control) (R61. to Control) Rel. Speed Fog Rel. Speed Fog Methylene Blue (0.03) 100.0 0.43 23 .0 0 Control. A 17 .2 0.20 3 .2 0.19 Very much lower. Methylene Blue (0.03)... 100 .0 0.20 145 .0 0.25 Control Control.
.0)* 120 .0 0 .14 209 .0 0.17 Lower Slightly higher. Methylene Blue (0 03). 100.0 0.10 126 .0 0.12 Control Control. Compound I (0 O3) 162.0 0.10 589 .0 0.10 Equal 4 times higher. Methylene Blue (0 03) 100 .0 0 .05 105 .0 0 .04 Control Control. Compound 11 (0.04).-. 148 .0 0.03 229 .0 0.02 Much Higher. Equal. Compound III (0.05) 289 .0 0.03 741.0 0 .04 Lower 20 times higher.
This desensitizer interferes with the tanning action of the developer on the gelatin in the exposed, nonimage areas and thus results in poor transfers.
Desensitizers (I) 1,2-bis(l-phenacyl-4-pyridiniurn bromide)ethylene 6 (II) l,2-bis(1-methyl-4-pyridiniurn p-toluenesulfonate) ethylene (III) 1,2-bis(4-pyridyl-1-sulfopropyl)ethylene Methylene Blue, also called 3,7-bis(dimethyamino)- phenazathioniurn chloride, is a sulfonium salt of the following structure:
developing agent and a desensitizing amount of a de sensitizing compound which is a quaternarized derivative of a 1,2-bis(4-pyridyl)ethylene.
2. An emulsion of claim 1 in which the l,2-bis(4-pyridyl)ethylene has the general formula:
-C1=CH e f T e; x R R X where R represents a group selected from the class consisting of phenacyl, alkyl and substituted alkyl in which the alkyl moiety has from 110 carbon atoms, X represents an anion except where R is a sulfoalkyl derivative and the negative charge is assumed by the sulfoalkyl group itself. 3. An emulsion of claim 1 in which the colloid is gelatin. 7
4. An emulsion of claim 1 in which the colloid is gelatin and the 1,2-bis (4-pyridyl)ethylene has the general formula:
CH=CH CH=CH \N X it where R represents a group selected from the class consisting of phenacyl, alkyl and substituted alkyl in which the alkyl moiety has from 1-10 carbon atoms,
X represent an anion except when -R is a sulfoalkyl derivative and the negative charge siassumed by the sulfonalkyl group itself,
and in which the proportion of desensitizing compound is from 0.5 to 3 grams per mole of silver halide.
7. An emulsion of claim 1 in which the colloid is gelatin and the proportion of desensitizing compound is from 0.5 to 3 grams per mole of silver halide.
8. An emulsion of claim 1 in which the desensitizing compound is 1,2-bis(1-phenacyl-4-pyridinium bromide) ethylene.
9. An emulsion of claim 1 in which the desensitizing compound is 1,2-bis(1-metl1yl-4-pyridinium p-toluenesulfonate)ethylene.
10. An emulsion of claim 1 in which the desensitizing compound is 1,2-bis (4-pyridyl-1-sulfopropyl)ethylene.
11. A process of preparing a substantially unhardened colloid silver halide emulsion for roomlight handling comprising dissolving in a water-miscible solvent a desensitizing compound which is a quaternarized derivative of a 1,2-bis(4-pyridyl)ethylene and adding a desensitizing amount to the substantially unhardened colloid silver halide emulsion.
12. A process of claim 11 in which the colloid is gelatin.
13. A process of claim 11 in which the desensitizing compound has the general formula:
Gonzo].
r \N R where R represents a group selected from the class consisting of phenacyl, alkyl and substituted alkyl in which the alkyl moiety has from 1-10 carbon atoms,
X represents an anion except when R is a sulfoalkyl derivative and the negatve charge is assumed by the sulfoalkyl group itself.
14. A process of claim 11 in which the colloid is gelatin and the desensitizing compound has the general formula:
fe X it R X where R represents a group selected from the class consisting of phenacyl, alkyl and substituted alkyl in which the alkyl moiety has from -l-10 carbon atoms,
X represents an anion except when R is a sulfoalkyl derivative and the negative charge is assumed by the sulfoalkyl group itself,
and the desensitizing compound is added in an amount of 0.5 to 3 grams per mole of silver halide.
References Cited UNITED STATES PATENTS 2,596,756 5/1952 Yutzy et a1. 9628 3,035,917 5/1962 Fry 96101 3,124,458 3/1964 Fry 96-101 NORMAN G. TORCHIN, Primary Examiner.
V. P. CANNEY, Assistant Examiner.
Claims (2)
1. A SUBSTANTIALLY UNHARDENED HYDROPHILIC COLLOID SILVER HALIDE EMULSION CONTAINING A COLLOID TANNING SILVER HALIDE DEVELOPING AGENT AND A DESENSITIZING AMOUNT OF A DESENSITIZING COMPOUND WHICH IS A QUATERNARIZED DERIVATIVE OF A 1,2-BIS(4-PYRIDYL)ETHYLENE.
2. AN EMULSION OF CLAIM 1 IN WHICH THE 1,2-BIS(4-PYRIDYL)ETHYLENE HAS THE GENERAL FORMULA:
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US410275A US3326687A (en) | 1964-11-10 | 1964-11-10 | Photographic colloid transfer system |
| FR37034A FR1454125A (en) | 1964-11-10 | 1965-11-03 | Process for preparing photographic emulsions for colloid transfer and emulsions obtained |
| BE671773A BE671773A (en) | 1964-11-10 | 1965-11-03 | |
| DE19651472867 DE1472867A1 (en) | 1964-11-10 | 1965-11-05 | Use of quaternary 1,2-bis (4-pyridyl) ethylenes in photographic emulsions |
| GB47582/65A GB1127134A (en) | 1964-11-10 | 1965-11-09 | Photographic silver halide emulsions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US410275A US3326687A (en) | 1964-11-10 | 1964-11-10 | Photographic colloid transfer system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3326687A true US3326687A (en) | 1967-06-20 |
Family
ID=23624013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US410275A Expired - Lifetime US3326687A (en) | 1964-11-10 | 1964-11-10 | Photographic colloid transfer system |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3326687A (en) |
| BE (1) | BE671773A (en) |
| DE (1) | DE1472867A1 (en) |
| FR (1) | FR1454125A (en) |
| GB (1) | GB1127134A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539291A (en) * | 1982-12-24 | 1985-09-03 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photographic materials |
| US4666827A (en) * | 1984-07-16 | 1987-05-19 | Mitsubishi Paper Mills, Ltd. | Silver halide photographic emulsion |
| US4892812A (en) * | 1983-02-04 | 1990-01-09 | Mitsubishi Paper Mills, Ltd. | Silver halide photosensitive materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596756A (en) * | 1947-11-04 | 1952-05-13 | Eastman Kodak Co | Photomechanical copy method |
| US3035917A (en) * | 1958-11-12 | 1962-05-22 | Ilford Ltd | Direct positive emulsions |
| US3124458A (en) * | 1961-03-10 | 1964-03-10 | Direct positive photographic materials |
-
1964
- 1964-11-10 US US410275A patent/US3326687A/en not_active Expired - Lifetime
-
1965
- 1965-11-03 FR FR37034A patent/FR1454125A/en not_active Expired
- 1965-11-03 BE BE671773A patent/BE671773A/xx unknown
- 1965-11-05 DE DE19651472867 patent/DE1472867A1/en active Pending
- 1965-11-09 GB GB47582/65A patent/GB1127134A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2596756A (en) * | 1947-11-04 | 1952-05-13 | Eastman Kodak Co | Photomechanical copy method |
| US3035917A (en) * | 1958-11-12 | 1962-05-22 | Ilford Ltd | Direct positive emulsions |
| US3124458A (en) * | 1961-03-10 | 1964-03-10 | Direct positive photographic materials |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539291A (en) * | 1982-12-24 | 1985-09-03 | Fuji Photo Film Co., Ltd. | Direct positive silver halide photographic materials |
| US4892812A (en) * | 1983-02-04 | 1990-01-09 | Mitsubishi Paper Mills, Ltd. | Silver halide photosensitive materials |
| US4666827A (en) * | 1984-07-16 | 1987-05-19 | Mitsubishi Paper Mills, Ltd. | Silver halide photographic emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1454125A (en) | 1966-07-22 |
| GB1127134A (en) | 1968-09-11 |
| DE1472867A1 (en) | 1969-01-23 |
| BE671773A (en) | 1966-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3761266A (en) | Silver halide emulsions predominantly chloride containing silver halide grains with surfaces chemically sensitized and interiors free fromchemical sensitization and the use thereof in reversal processes | |
| US4336321A (en) | Silver halide photographic materials | |
| US3150977A (en) | Light-sensitive photographic materials | |
| US3650749A (en) | Photographic development | |
| US3765901A (en) | Spectral sensitization of light-sensitive silver halide emulsions | |
| US3632340A (en) | Cored direct positive silver halide emulsion developed with polyhydroxybenzene | |
| US3326687A (en) | Photographic colloid transfer system | |
| US3446619A (en) | Radiation sensitive silver-dye complexes | |
| US3404980A (en) | Silver images in light-sensitive print-forming layers | |
| US3260605A (en) | Method for preparing light-sensitive silver halide emulsions suitable for print-out recording materials | |
| US3689270A (en) | Light-sensitive compositions comprising a silver salt of a tetraazaindene | |
| US3615510A (en) | Silver halide complexing agents | |
| US3615517A (en) | Direct-positive silver halide emulsion containing halogen conductor and electron acceptor developed with polyhydroxy benzene | |
| US3340063A (en) | Photographic colloid transfer system | |
| JPS5832370B2 (en) | squirrel beetle | |
| US3260604A (en) | Photographic colloid transfer system | |
| US3586505A (en) | Sensitizing silver halide emulsion layers | |
| US3615443A (en) | Presensitized planographic printing plate | |
| CA1063855A (en) | Photosensitive composition containing cadmium iodide and cuprous iodide in a binder | |
| US3796577A (en) | Direct positive process involving uniform exposure of an imagewise exposed internally sensitive silver halide emulsion to high intensity radiation | |
| US3250618A (en) | Thermal resensitization of desensitized silver halide photographic emulsions | |
| USRE28668E (en) | Silver halide emulsions containing alkyl selenols and thiols as antifoggants | |
| US2369449A (en) | Print-out emulsions | |
| US3249440A (en) | Radiation-sensitive elements and their preparation | |
| US3745013A (en) | Method for making hardened gelatin images |