US3096197A - Marking method - Google Patents
Marking method Download PDFInfo
- Publication number
- US3096197A US3096197A US3791A US379160A US3096197A US 3096197 A US3096197 A US 3096197A US 3791 A US3791 A US 3791A US 379160 A US379160 A US 379160A US 3096197 A US3096197 A US 3096197A
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- US
- United States
- Prior art keywords
- marking
- photograph
- article
- stencil
- reactive
- 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
- 238000000034 method Methods 0.000 title claims description 19
- 239000000203 mixture Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 5
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- 239000008273 gelatin Substances 0.000 description 5
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- 229910052742 iron Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- -1 amine compounds Chemical class 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 210000004209 hair Anatomy 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WZUVPPKBWHMQCE-UHFFFAOYSA-N Haematoxylin Chemical compound C12=CC(O)=C(O)C=C2CC2(O)C1C1=CC=C(O)C(O)=C1OC2 WZUVPPKBWHMQCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- LRDSAYMGIIOCKF-UHFFFAOYSA-N 1,4-dihydroxycyclohexa-2,4-diene-1-carbaldehyde Chemical compound OC1=CCC(O)(C=O)C=C1 LRDSAYMGIIOCKF-UHFFFAOYSA-N 0.000 description 1
- WDJPBIRJSVMEKJ-UHFFFAOYSA-N 1-anilino-3-phenyliminourea;1,3-dianilinourea Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1.C=1C=CC=CC=1N=NC(=O)NNC1=CC=CC=C1 WDJPBIRJSVMEKJ-UHFFFAOYSA-N 0.000 description 1
- IXWOUPGDGMCKGT-UHFFFAOYSA-N 2,3-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1O IXWOUPGDGMCKGT-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical group OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- 101100025412 Arabidopsis thaliana XI-A gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001072332 Monia Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960001506 brilliant green Drugs 0.000 description 1
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- XEYBHCRIKKKOSS-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide Chemical compound [Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N XEYBHCRIKKKOSS-UHFFFAOYSA-N 0.000 description 1
- OAEGRYMCJYIXQT-UHFFFAOYSA-N dithiooxamide Chemical compound NC(=S)C(N)=S OAEGRYMCJYIXQT-UHFFFAOYSA-N 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940083618 sodium nitroprusside Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- NZFNXWQNBYZDAQ-UHFFFAOYSA-N thioridazine hydrochloride Chemical compound Cl.C12=CC(SC)=CC=C2SC2=CC=CC=C2N1CCC1CCCCN1C NZFNXWQNBYZDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 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
- G03C11/00—Auxiliary processes in photography
- G03C11/02—Marking or applying text
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S101/00—Printing
- Y10S101/29—Printing involving a color-forming phenomenon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/152—Making camera copy, e.g. mechanical negative
Definitions
- This invention relates to methods for marking photoraphs, and more particularly relates to methods for acurately stenciling and imprinting reference marks, numerals or descriptive information on photographs, paintngs or similar graphic articles without destruction of he surface of the article. Marking may be accomlished by applying a coating of reactive material on the vr'ticle and producing a mark by reacting the coating with suitable material.
- preiminary markings are made on photographs by coating he surface of a photograph with a transparent film of naterial and then producing a mark on the photograph )y exposing the coating material through a stencil to a eactive vapor to produce markings which are visible in iltra violet light.
- the stencil may be corrected when necessary Jefore the photograph is permanently marked with a marking material which is normally visible.
- Permanent IIIible markings may be made by stenciling or printing he article with ink in conventional manner or by applyng a fusible marking material to the article. Marking :an also be accomplished by applying an additional coatng to the photograph and forming an image by contactng the coating composition with certain metals or metal ialt compositions.
- FIGURE 1 is a cutaway of a perspective view of a de vice for marking photographs
- FIGURE 2 is an elevation of the device of FIGURE 1;
- FIGURE 3 is a perspective view of another embodiment of a device for marking photographs.
- stencil is configured as an enclosure with perforations 11 therein and is preferably constructed of a transparent material such as glass, synthetic resin or cellulosic material, but may also be comprised of metal or other opaque material.
- Perforations 11 are provided in stencil '10 to enable vapor to contact a reactive coating on photograph :12 to produce markings thereon.
- a marking may be made with a composition which is visible only in fluorescent light. Permanent visible markings may be subsequently imprinted on the photograph after alignment of the marks made with fluorescent material has been found to be satisfactory.
- FIGURE 3 is shown a wire printing device which may be heated by resistance to electric current flow therethrough produced by connection to electric leads 14 and 14' and be contacted to a material coated on photograph 12.
- the sur face of the photograph may be first coated with a film of reactive composition and a stencil be placed thereover before the photograph is exposed to a reactive vapor or liquid through the stencil.
- the product which is obtained from the reaction between the coating composition and the vapor iluoresces visible in ultra violet light, but is invisible in ordinary light.
- the photograph may then be stenciled with visible ink, or may be again coated and printed with a reaction product of the coating material.
- Example I An aerial photograph was prepared for marking by being dipped in a 2% solution of 2,4-dihydroxybenzaldehyde in water. The photograph was dried and a trans parent stencil was laid on the face of the photograph and visual alignment of photograph and stencil was made. Exposure of the stencil to vapors of hydrazine and acetic acid produced markings of 5 milsiZ mils line width from a stencil perforation 3 mils in width. After exposure for one minute, the markings on the photograph fiuoresced brilliant green when exposed to the rays of an ultra violet lamp, but were otherwise invisible.
- Example I An X-ray photograph was coated with a film of gelatin containing dissolved acidified salicyclic aldehyde. The coating was dried and a stencil was placed upon photograph before the assembly was exposed to hydrazine vapor. A reaction took place between the aldehyde and the hydrazine yielding an aldazine reaction product which fiuoresced brilliant yellow during exposure to an ultra violet lamp.
- Example III Example IV Markings visible in ordinary light were printed on photographs subsequent to marking by the method of Examples I-JI-I by using complex ions formed by reaction of cobalt, chromium, nickel, iron, magnesium, aluminum or manganese with amine compounds or ammonia.
- Example V Gelatin was admixed with sodium nitroprusside solution to provide a solution for visible marking of photographs. A photograph was dipped therein and dried. The photograph was exposed through a stencil to acetone vapors and a colored trace was formed. The marking was water sensitive and could be removed by washing.
- Example VI Acidic hematoxylin solution was coated on a photograph as in Example IV. A purple trace was developed upon exposing the coating to ammonia fumes through a stencil.
- Example VII A photograph was immersed in a solution of cupric sulfate and was dried. A stencil was laid on the photograph and the assembly was exposed to hydrogen chloride gas. Bleaching of the photographic silver occurred to yield visible light colored stenciled indicia.
- Example VIII The procedure of Example VII was repeated using solutions of Na CrO and Cu(NO with amines of molecular weights of less than 100 as additives. Bleaching occurred as in Example VII.
- Example IX Two parts of CuSO was dissolved in 4 parts of water and 1 part of ethylene glycol. Dimethyl formamide and tetra hydroxyethyl ethylene amine were added to insure that spontaneous bleaching would not occur. A wetting agent was added. Upon exposure to fumes of 10% hydrochloric acid bleaching took place.
- Example X Two parts of CuSO 10 parts water, 3 parts ethylene glycol, and 0.05 part of a wetting agent were mixed and several photographs were immersed in the mixture and dried. Immersion in the mixture for five minutes yielded a distinct trace with A second exposure times to hydrogen chloride. Fine lines were obtained with slits as narrow as 0.5 mil at shutter speeds of second.
- Example XI A solution of 1,S-diphenylcarbohydrazide and cellulose acetate was dissolved in nitroethane and deposited upon the face of an aerial photograph. The solvent was allowed to evaporate and the photograph was marked by bringing Nichrome cross hairs heated to between 300 400 F. into contact with the coating. A purple trace image of the cross hairs appeared on the photograph. It is believed that ion transfer from the cross hairs to the coating occurred and imparted to the coating composition a characteristic color.
- Example XII l,4-dihydrox ybenzaldehyde was dissolved in water in 1% concentration and a photograph was immersed in the solution and dried. An iron wire having a slight oxide coating was heated by electric current therein while the wire was pressed against the coated photograph. A brown colored image of the wire appeared on the photograph.
- Example XIII The procedure of Example -I was repeated using a 1% solution of gallic acid in place of dihydroxybenzaldehyde. A similar mark was obtained.
- Example XIV 1% solutions of the following reagents in ethanol were deposited on photographs: rhodamine; 2-nitrosalicyclic acid; dithioxamide; S-diphenylcarbazone; 6-mercaptoben- Zoic acid.
- rhodamine 2-nitrosalicyclic acid
- dithioxamide dithioxamide
- S-diphenylcarbazone 6-mercaptoben- Zoic acid.
- Each of the photographs was contacted with a heated wire. Nichrome wire and iron wire which had not been freshly cleaned produced the most satisfactory marks. It was found that moist photographs could be marked more distinctly than thoroughly dried photographs with all wires. It is believed that all metals that will form a fine crystalline oxide can be used for operable marking.
- compositions that can be used for marking photographs are those which are actinically insensitive and which can be chemically reacted to provide a durable, tack free adherent mark on the surface of a photograph.
- a process for marking an article of graphic art comprising (a) a preliminary treatment for applying a fluorescent marking visible only in ultraviolet light to an article of graphic art, said preliminary treatment including (1) coating said article of graphic art with a reactive first composition,
- a secondary treatment for applying a permanent marking to said article of graphic art marked with said preliminary fluorescent marking including (1) coating said article of graphic art with a third reactive composition
- said first reactive composition is a hydroxy aromatic derivative selected from the group consisting of salicylaldehyde, 2,4-dihydroxybenzaldehyde, and gallic acid; and said vaporous second composition is hydrazine.
- a process for marking an article of the graphic art as claimed in claim 1 said article of graphic art having a developed silver emulsion on one surface wherein said third reactive composition brought in contact with said emulsion is an inorganic salt selected from the group consisting of Na CrO C1r(NO Cu said third reactive composition containing an additive amine to retard spontaneous bleaching by said fourth reactive substance, and said fourth reactive substance being hydrogen chloride gas.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Printing Methods (AREA)
Description
y 2, 1963 R. w. BUETOW YETAL 3,096,197
MARKING METHOD Filed Jan. 21, 1960 2 Sheets-Sheet 1 FIG. I
l I D R \J INVENTOR RALPH W. BUETOW ROBERT P. COX
BY ym/ ATTORNEY July 2, 1963 R. w. BUETOW ETAL 3,096,197
MARKING METHOD 2 Sheets-Sheet 2 Filed Jan. 21, 1960 INVENTOR RALPH W. BUETOW ROBERT P. COX
ATTORNEY United States Patent 3,096,197 Patented July 2, 1963 3,096,197 MARKING METHOD lalph W. Buetow and Robert P. Cox, Madison, Wis, as-
siguors, by mesne assignments, to the United States of America as represented by the Secretary of the Army Filed Jan. 21, 1960, Ser. No. 3,791 6 Claims. (Cl. 117-335) This invention relates to methods for marking photoraphs, and more particularly relates to methods for acurately stenciling and imprinting reference marks, numerals or descriptive information on photographs, paintngs or similar graphic articles without destruction of he surface of the article. Marking may be accomlished by applying a coating of reactive material on the vr'ticle and producing a mark by reacting the coating with suitable material.
When stenciling reference data on art work or photographs it is often desirable to obtain alignment of markngs upon the work without first making facsimile copies assure the proper alignment of the mark on the work. fhe application of this invention tothe marking of moaics of aerial photographs is of particular utility.
In accordance with the process of this invention, preiminary markings are made on photographs by coating he surface of a photograph with a transparent film of naterial and then producing a mark on the photograph )y exposing the coating material through a stencil to a eactive vapor to produce markings which are visible in iltra violet light. After the markings are viewed in ultra iolet light the stencil may be corrected when necessary Jefore the photograph is permanently marked with a marking material which is normally visible. Permanent zisible markings may be made by stenciling or printing he article with ink in conventional manner or by applyng a fusible marking material to the article. Marking :an also be accomplished by applying an additional coatng to the photograph and forming an image by contactng the coating composition with certain metals or metal ialt compositions.
It is an object of this invention to provide a method of narking articles with fluorescent marking materials.
It is another object of this invention to provide a method of permanently marking photographs without scratching the photographic emulsion.
It is another object of this invention to provide a means of marking photographs with the reaction product of a coating material and a metal or metal salt.
Other objects will become apparent from the drawings and from the following detailed description in which it is intended to illustrate the applicability of the invention without thereby limiting its scope to less than that of all equivalents which will be apparent to one skilled in the art. In the drawings like reference numerals refer to like parts and:
FIGURE 1 is a cutaway of a perspective view of a de vice for marking photographs;
FIGURE 2 is an elevation of the device of FIGURE 1;
FIGURE 3 is a perspective view of another embodiment of a device for marking photographs.
In FIGURES l and 2 stencil is configured as an enclosure with perforations 11 therein and is preferably constructed of a transparent material such as glass, synthetic resin or cellulosic material, but may also be comprised of metal or other opaque material. Perforations 11 are provided in stencil '10 to enable vapor to contact a reactive coating on photograph :12 to produce markings thereon. To insure that perforations '11 precisely corrolate with points to be marked upon photograph 12 a marking may be made with a composition which is visible only in fluorescent light. Permanent visible markings may be subsequently imprinted on the photograph after alignment of the marks made with fluorescent material has been found to be satisfactory.
In FIGURE 3 is shown a wire printing device which may be heated by resistance to electric current flow therethrough produced by connection to electric leads 14 and 14' and be contacted to a material coated on photograph 12.
In the preferred embodiment of this invention the sur face of the photograph may be first coated with a film of reactive composition and a stencil be placed thereover before the photograph is exposed to a reactive vapor or liquid through the stencil. The product which is obtained from the reaction between the coating composition and the vapor iluoresces visible in ultra violet light, but is invisible in ordinary light. The photograph may then be stenciled with visible ink, or may be again coated and printed with a reaction product of the coating material.
Example I An aerial photograph was prepared for marking by being dipped in a 2% solution of 2,4-dihydroxybenzaldehyde in water. The photograph was dried and a trans parent stencil was laid on the face of the photograph and visual alignment of photograph and stencil was made. Exposure of the stencil to vapors of hydrazine and acetic acid produced markings of 5 milsiZ mils line width from a stencil perforation 3 mils in width. After exposure for one minute, the markings on the photograph fiuoresced brilliant green when exposed to the rays of an ultra violet lamp, but were otherwise invisible.
Example I] An X-ray photograph was coated with a film of gelatin containing dissolved acidified salicyclic aldehyde. The coating was dried and a stencil was placed upon photograph before the assembly was exposed to hydrazine vapor. A reaction took place between the aldehyde and the hydrazine yielding an aldazine reaction product which fiuoresced brilliant yellow during exposure to an ultra violet lamp.
Example III Example IV Markings visible in ordinary light were printed on photographs subsequent to marking by the method of Examples I-JI-I by using complex ions formed by reaction of cobalt, chromium, nickel, iron, magnesium, aluminum or manganese with amine compounds or ammonia. A
3,0 3 photograph coated with a gelatin film was dipped into an aqueous solution of a salt, e.g. chloride, of one of the enumerated metals. Metal ions which diffused into the gelatin coating from the solution formed colored traces on the photograph after exposure of the photograph to vapors of either ammonia or amine compounds through a template masking the photograph.
Example V Gelatin was admixed with sodium nitroprusside solution to provide a solution for visible marking of photographs. A photograph was dipped therein and dried. The photograph was exposed through a stencil to acetone vapors and a colored trace was formed. The marking was water sensitive and could be removed by washing.
Example VI Acidic hematoxylin solution was coated on a photograph as in Example IV. A purple trace was developed upon exposing the coating to ammonia fumes through a stencil.
Example VII A photograph was immersed in a solution of cupric sulfate and was dried. A stencil was laid on the photograph and the assembly was exposed to hydrogen chloride gas. Bleaching of the photographic silver occurred to yield visible light colored stenciled indicia.
Example VIII The procedure of Example VII was repeated using solutions of Na CrO and Cu(NO with amines of molecular weights of less than 100 as additives. Bleaching occurred as in Example VII.
Example IX Two parts of CuSO was dissolved in 4 parts of water and 1 part of ethylene glycol. Dimethyl formamide and tetra hydroxyethyl ethylene amine were added to insure that spontaneous bleaching would not occur. A wetting agent was added. Upon exposure to fumes of 10% hydrochloric acid bleaching took place.
Example X Two parts of CuSO 10 parts water, 3 parts ethylene glycol, and 0.05 part of a wetting agent were mixed and several photographs were immersed in the mixture and dried. Immersion in the mixture for five minutes yielded a distinct trace with A second exposure times to hydrogen chloride. Fine lines were obtained with slits as narrow as 0.5 mil at shutter speeds of second.
Example XI A solution of 1,S-diphenylcarbohydrazide and cellulose acetate was dissolved in nitroethane and deposited upon the face of an aerial photograph. The solvent was allowed to evaporate and the photograph was marked by bringing Nichrome cross hairs heated to between 300 400 F. into contact with the coating. A purple trace image of the cross hairs appeared on the photograph. It is believed that ion transfer from the cross hairs to the coating occurred and imparted to the coating composition a characteristic color.
Example XII l,4-dihydrox ybenzaldehyde was dissolved in water in 1% concentration and a photograph was immersed in the solution and dried. An iron wire having a slight oxide coating was heated by electric current therein while the wire was pressed against the coated photograph. A brown colored image of the wire appeared on the photograph.
Example XIII The procedure of Example -I was repeated using a 1% solution of gallic acid in place of dihydroxybenzaldehyde. A similar mark was obtained.
Example XIV 1% solutions of the following reagents in ethanol were deposited on photographs: rhodamine; 2-nitrosalicyclic acid; dithioxamide; S-diphenylcarbazone; 6-mercaptoben- Zoic acid. Each of the photographs was contacted with a heated wire. Nichrome wire and iron wire which had not been freshly cleaned produced the most satisfactory marks. It was found that moist photographs could be marked more distinctly than thoroughly dried photographs with all wires. It is believed that all metals that will form a fine crystalline oxide can be used for operable marking.
Generally, compositions that can be used for marking photographs are those which are actinically insensitive and which can be chemically reacted to provide a durable, tack free adherent mark on the surface of a photograph.
While certain modifications and embodiments of the invention have been described, it is of course to be understood that there are a great number of variations which will suggest themselves to anyone familiar with the subject matter thereof and it is to be distinctly understood that this invention should not be limited except by such limitations as are clearly imposed in the appended claims.
We claim:
1. A process for marking an article of graphic art comprising (a) a preliminary treatment for applying a fluorescent marking visible only in ultraviolet light to an article of graphic art, said preliminary treatment including (1) coating said article of graphic art with a reactive first composition,
(2) applying a stencil to said article of graphic art,
(3) reacting the areas exposed by said stencil with a vaporous second composition, the reaction product of said first and second compositions being visible only in ultraviolet light;
(b) a secondary treatment for applying a permanent marking to said article of graphic art marked with said preliminary fluorescent marking including (1) coating said article of graphic art with a third reactive composition,
(2) aligning said stencil to said fluorescent marking, and
(3) applying a fourth reactive substance in the exposed areas of said stencil, the reaction product of said third reactive composition and said fourth reactive substance giving a permanent marking visible in actinic light.
2. A process for marking an article of graphic art as claimed in claim 1 wherein said first reactive composition is a hydroxy aromatic derivative selected from the group consisting of salicylaldehyde, 2,4-dihydroxybenzaldehyde, and gallic acid; and said vaporous second composition is hydrazine.
3. A process for marking an article of the graphic art as claimed in claim 1 wherein said first reactive composition is gelatin and said second vaporous composition is elected from the group consisting of furfural, glutaraldehyde a-cetyl and acetone.
4. A process for marking an article of the graphic art as claimed in claim 1 said article of graphic art having a developed silver emulsion on one surface wherein said third reactive composition brought in contact with said emulsion is an inorganic salt selected from the group consisting of Na CrO C1r(NO Cu said third reactive composition containing an additive amine to retard spontaneous bleaching by said fourth reactive substance, and said fourth reactive substance being hydrogen chloride gas.
5. A process for marking an article of the graphic art as claimed in claim- 1 wherein said first reactive composition is gelatin and said third reactive substance is the References Cited in the file of this patent chloride salt of a metal selected from the group consisting UNITED STATES PATENTS of cobalt, chromium, nickel, iron, magnesium and aluminum, and said fourth reactive substance is the vapor of 80943 Glieenfield 1868 a compound selected from the group consisting of am- 5 115,005 Wlnccx May 15, 1871 monia and amine compounds. 243,342 Ford June 1881 6. A process for marking articles of the graphic art as 2,073,381 Sen 1937 claimed in claim 1 wherein said third reactive composi- 2464128 Gearhart, 1949 tion is 1,4-dihydroxybenzaldehyde dissolved in H O at ggz g g fi et a1 "1 12;; is a strength of 1% and said fourth reactive substance 1s a 10 2,701,215 Kroeck u Feb. 1955 heated iron wire having an oxide coating.
Claims (1)
1. A PROCESS FOR MARKING AN ARTICLE OF GRAPHIC ART COMPRISING (A) A PRELIMINARY TREATMENT FOR APPLYING A FLUORESCENT MARKING VISIBLE ONLY IN ULTRAVIOLET LIGHT TO AN ARTICLE OF GRAPHIC ART, SAID PRELIMINARY TREATMENT INCLUDING (1) COATING SAID ARTICLE OF GRAPHIC ART WITH A REACTIVE FIRST COMPOSITION, (2) APPLYING A STENCIL TO SAID ARTICLE OF GRAPHIC ART, (3) REACTING THE AREAS EXPOSED BY SAID STENCIL WITH A VAPOROUS SECOND COMPOSITION, THE REACTION PRODUCT OF SAID FIRST AND SECOND COMPOSITIONS BEING VISIBLE ONLY IN ULTRAVIOLET LIGHT; (B) A SECONDARY TREATMENT FOR APPLYING A PERMANENT MARKING TO SAID ARTICLE OF GRAPHIC ART MARKED WITH SAID PRELIMINARY FLUORESCENT MARKING INCLUDING (1) COATING SAID ARTICLE OF GRAPHIC ART WITH A THIRD REACTIVE COMPOSITION, (2) ALIGNING SAID STENCIL TO SAID FLUORESCENT MARKING, AND (3) APPLYING A FOURTH REACTIVE SUBSTANCE IN THE EXPOSED AREAS OF SAID STENCIL, THE REACTION PRODUCT OF SAID THIRD REACTIVE COMPOSITION AND SAID FOURTH REACTIVE SUBSTANCE GIVING A PERMANENT MARKING VISIBLE IN A ACTINIC LIGHT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3791A US3096197A (en) | 1960-01-21 | 1960-01-21 | Marking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3791A US3096197A (en) | 1960-01-21 | 1960-01-21 | Marking method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3096197A true US3096197A (en) | 1963-07-02 |
Family
ID=21707619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US3791A Expired - Lifetime US3096197A (en) | 1960-01-21 | 1960-01-21 | Marking method |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3096197A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3659049A (en) * | 1969-11-17 | 1972-04-25 | Hughes Aircraft Co | Apparatus for synchronizing an opaque video tape with a video display |
| US3772099A (en) * | 1971-05-17 | 1973-11-13 | Westinghouse Electric Corp | Phosphor combination and method, particularly adapted for use with explosives, for providing a distinctive information label |
| USRE29334E (en) * | 1971-05-17 | 1977-08-02 | Westinghouse Electric Corporation | Phosphor combination and method, particularly adapted for use with explosives, for providing a distinctive information label |
| US4129076A (en) * | 1977-12-07 | 1978-12-12 | Gardner Robert F | Color-keyed fabric for screen printing |
| US4708057A (en) * | 1986-04-23 | 1987-11-24 | T. Parker Distributing Company, Inc. | Platen assembly for screen printing |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US80943A (en) * | 1868-08-11 | Henry greenfield | ||
| US115005A (en) * | 1871-05-16 | Improvement in paper for bank-notes, bonds | ||
| US243342A (en) * | 1881-06-21 | Alfred ford | ||
| US2073381A (en) * | 1935-04-24 | 1937-03-09 | Nat Marking Mach Co | Laundry identification |
| US2464128A (en) * | 1947-07-23 | 1949-03-08 | Eastman Kodak Co | Cellulose organic acid ester compositions containing 2, 2'-dihydroxy benzalazine |
| US2538784A (en) * | 1946-04-12 | 1951-01-23 | Morris S Kantrowitz | Process for identifying normally invisible markings and composition therefor |
| US2597306A (en) * | 1949-10-05 | 1952-05-20 | Little Inc A | Printing process wherein an alkaline substance passing through stencil openings effects coupling of an azo dye in situ |
| US2701215A (en) * | 1953-05-29 | 1955-02-01 | Corning Glass Works | Method of coloring glass and resulting article |
-
1960
- 1960-01-21 US US3791A patent/US3096197A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US80943A (en) * | 1868-08-11 | Henry greenfield | ||
| US115005A (en) * | 1871-05-16 | Improvement in paper for bank-notes, bonds | ||
| US243342A (en) * | 1881-06-21 | Alfred ford | ||
| US2073381A (en) * | 1935-04-24 | 1937-03-09 | Nat Marking Mach Co | Laundry identification |
| US2538784A (en) * | 1946-04-12 | 1951-01-23 | Morris S Kantrowitz | Process for identifying normally invisible markings and composition therefor |
| US2464128A (en) * | 1947-07-23 | 1949-03-08 | Eastman Kodak Co | Cellulose organic acid ester compositions containing 2, 2'-dihydroxy benzalazine |
| US2597306A (en) * | 1949-10-05 | 1952-05-20 | Little Inc A | Printing process wherein an alkaline substance passing through stencil openings effects coupling of an azo dye in situ |
| US2701215A (en) * | 1953-05-29 | 1955-02-01 | Corning Glass Works | Method of coloring glass and resulting article |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3659049A (en) * | 1969-11-17 | 1972-04-25 | Hughes Aircraft Co | Apparatus for synchronizing an opaque video tape with a video display |
| US3772099A (en) * | 1971-05-17 | 1973-11-13 | Westinghouse Electric Corp | Phosphor combination and method, particularly adapted for use with explosives, for providing a distinctive information label |
| USRE29334E (en) * | 1971-05-17 | 1977-08-02 | Westinghouse Electric Corporation | Phosphor combination and method, particularly adapted for use with explosives, for providing a distinctive information label |
| US4129076A (en) * | 1977-12-07 | 1978-12-12 | Gardner Robert F | Color-keyed fabric for screen printing |
| US4708057A (en) * | 1986-04-23 | 1987-11-24 | T. Parker Distributing Company, Inc. | Platen assembly for screen printing |
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