US3904420A - Information receiving element containing a yellow dye and an optical brightener - Google Patents
Information receiving element containing a yellow dye and an optical brightener Download PDFInfo
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- US3904420A US3904420A US395792A US39579273A US3904420A US 3904420 A US3904420 A US 3904420A US 395792 A US395792 A US 395792A US 39579273 A US39579273 A US 39579273A US 3904420 A US3904420 A US 3904420A
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- element according
- radiation
- yellow dye
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- 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
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- 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
- G03C1/7954—Polyesters
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- 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
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- 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
- Y10S430/134—Brightener containing
Definitions
- ILLS. 1C 96/82; 96/44; 96/45; 96/87 R; 96/75; 96/84 R; 96/84 UV; 96/1 R; 117/335; ll7/3S.6; 283/6.l7; 283/60 11111. 131. G03C l/92; G03C l/94; GO3C 1/52 1 111811111 1:111 Searchong 96/84 R, 84 UV, 8 N, 87 R, 96/44, 45, 75; 117/333, 35.6; 283/6, 17, 6O
- This invention relates generally to information receiving elements and more particularly to a photographic film element suitable for receiving microimages, such as microfilm.
- microfilm has been used as a medium for publishing books, reports, catalogs, and other useful information having a market value to interested readers.
- Microtilm is ideally suited to the publication field because it is a form of information receiving element by means of which a large amount of information can be condensed within a small storage area.
- One of the prac tical difficulties that a producer or distributor of microfilms of copyrighted material faces is the possibility of copying, or duplication of the material, by persons without permission of the copyright owner. Such unauthorized duplication often is carried out by means of an inexpensive copying method, i.e., by the diazo process.
- microimages are reproduced by the diazo process by the use of radiation from a mercury lamp or a thorium doped mercury lamp to project a microimage from a microfilm onto diazo film or paper.
- the radiation reaching the film or paper consists primarily of radiation of wavelengths 313.15, 366.3, 404.6, 420, and 435.8 nm (nanometers).
- Diazo film and paper normally are sensitive to radiation in a wavelength range from 300 to 460 nm.
- the information receiving element is a photographic film.
- the invention will be exemplified herein by means of such a film.
- photographic film includes an element having in combination a radiation sensitive layer, a suppport material in the form ofa film, and various other layers which comprise a photographic element.
- the element of the present invention comprises a support and one or more layers carried by the support.
- one of the layers comprises a radiation sensitive composition suitable for recording microimages therein.
- the element contains, in addition, an optical brightener and yellow dye incorporated in the support and/or in at least one of the layers coated on the support.
- the element of this invention is an element comprising a support that transmits visible radiation and a radiation sensitive layer, said element being characterized in that it contains both an optical brightener and a yellow dye which, together, absorb radiation in the range of about 300 to about 460 nm.
- the element of the invention is an element adapted to substantially impede duplication of the image therefrom by the use of actinic radiation in the region between 300 nm and 460 nm, said element comprising a support having incorporated therein an optical brightener and a yellow dye which together absorb actinic radiation in the range of about 300 to about 460 nm, and an image-bearing layer carried by said support.
- the dye and brightener are incorporated preferably in a layer or layers other than a radiation sensitive layer, since the dye and brightener can adversely affect sensitometric properties of the radiation sensitive composition.
- the combination of the yellow dye and optical brightener does not prevent the exposure of the radiation sensitive layer, i.e., the radiation sensitivity of the layer is not restricted to that part of the specturm in which said com bination of dye and brightener absorbs light radiation.
- the optical brightener has the function of suppressing transmission of radiation by absorbing between 300 and 400 nm in wavelength.
- the yellow dye has as one of its functions a similar function, namely, to absorb radiation in the region between 400 and 460 nm and to suppress its transmission.
- the yellow dye has the further function of absorbing the fluorescent radiation accompanying light ab sorption by the optical brightener.
- a preferred range of absorption of the combination of yellow dye and optical brightener lies between 300 and about 435 nm.
- optical brightener and yellow dye in the element, or photographic film prevents the copying ofimages contained in an information receiving ele ment made from photographic film, such as a microfiche, by means of the diazo copying method, or by any other copying method using as its principal light source radiation between 300 and 460 nm. (e.g. a mercury lamp).
- the present invention is intended especially for use in film from which microimages are projectable or readable by transmission of light radiation.
- the expression projectable or readable is used herein to refer to any film for producing images when light radiation is directed therethrough and is intended to include elements with image patterns consisting of silver, dyes, minute bubbles, and other image forming materials in a light transmissive medium.
- the film comprises a silver halide emulsion coated on a yellow, transparent linear polyester support. The emulsion is developable by conventional methods.
- any of the support materials which will transmit at least some visible radiation can be used in the practice of this invention.
- Such support materials are typically polymeric and include, for example, cellulose nitrate film, cellulose acetate film, poly (vinyl acetal) film, polystyrene film, polycarbonate film and related films or resinous materials.
- Linear polyester is a preferred support material, since linear polyester materials have excellent dimensional stability.
- These polyester materials are generally linear polyesters of at least one glycol having 2 to carbon atoms and at least one dibasic acid comprising at least 50 mole percent of an acid having two carboxyl radicals attached to a carbocyclic nucleus having from 4 to 6 carbon atoms per ring.
- the ester generally has a number average molecular weight of from about 10,000 to about 100,000, an inherent viscosity in a mixture of 60% phenol and 40% chlorobenzene of at least about 0.3 to about 1.3 deciliters per gram and melts at from about l75to about 350C. Viscosity is determined at 25C. with solutions of 0.25 g of the polyester per 100 milliliters of phenol: chlorobenzene.
- polyester materials are poly (ethylene terephthalate), poly 1,4-cyclohexylenedimethylene terephthalate), poly(ethyleneisophthalate), poly(ethylene naphthalenedicarboxylate), and mixtures of at least two of these.
- linear polyester also includes copolyesters based on these polyesters, such copolyesters being obtained by replacing a portion of the terephthalic acid by another acid or by a hydroxycarboxylic acid, and/or by replacing a portion of the glycol with a different glycol.
- the microimages are reproduced on diazo film or paper by exposing the film or paper to actinic light projected through the microimage carrying element.
- an optical brightener and a yellow dye are incorporated into the support or together in at least one of the layers other than the radiation sensitive layer of the information receivng element, or separately in at least two such layers. The location in the element of a layer containing dye and/or brightener is not important.
- the brightener and dye both are incorporated in a polyester support.
- any optical brightener that (a) is compatible with the polyester, (b) does not adversely affect the sensitometric properties of the radiation-sensitive layer, and (c) is stable at the temperatures encountered in forming the polyester support and in processing the photographic element can be used.
- the optical brightener is a fluorescent 4,4bis(benzoxazol-Z-yl) stilbene compound of the following formula I:
- R is a bivalent 4,4'-stilbene radical of the formula and A and A are each an o-phenylene radical of the formula III.
- the substituents R of the bivalent 4,4-stilbene radical and each of the phenylene radicals can be the same or different monovalent substituents.
- Typical substituents R which are suitable include a hydrogen atom, a halogen atom, and alkyl, aryl, substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy, amino, and substituted amino radicals.
- the substituents R are all hydrogen atoms.
- Other substituents are defined in U.S. Pat. No. 3,322,680 which is incorporated herein by reference.
- the substituents Y which are suitable include a hydrogen atom, and alkyl, aryl and cyano radicals. In the preferred embodiment the substituents Y are hydrogen atoms. Reference may be had to the above patent for further definition of Y substituents.
- optical brighteners that may be used in this invention are those indicated below:
- R represents a 5 or 6 membered nitrogen-containing heterocyclic ring having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring to which X is attached.
- the heterocyclic ring may contain substituents or it may form part of a fused ring system which may also contain substituents such as the radical COOR wherein R represents hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, or hydroxyalkoxyalkyl.
- R and X may be substituted by at least one radical COOR as hereinbefore defined.
- a dye suitable for incorporation in the polyester supports mentioned above is 2-(2-quinolyl)-l,3- indandione. In its pure form, this dye is a skin sensitizer, but polyester film containing the dye is not. This dye has the following structure:
- yellow dyes which may also be 55 used are the following:
- the optical brightener When used with a polyester support, the optical brightener is added to the polyester at a concentration of about 300 to 4000ppm, and the yellow dye is added in amounts of from about 300 to about 8000ppm. These quantities would be suitable in polyester used for casting a film support having a final thickness of about 0.004. inches. Of course, the quantities could be adjusted for polyester used for casting film support whose thickness is other than 0.004. inches.
- concentration of dye and optical brightener should be inversely proportional to the thickness.
- a polyester support is prepared in a conventional manner by mixing an optical brightener and a yellow dye with polyester powder or pellets and the mixture is then melted at a temperature of about 250 to 300C. The melt is then extruded into sheet form which is then biaxially stretched in conven tional manner to form film useful as a support for a photographic element.
- the dye may also be mixed with a small portion of the polyester and then heated to about l60-l90C for about 2 hours as taught in copending US. Pat. applicationof Barkey et al., Ser. No. 285,397, filed Aug. 31, 1972, incorporated herein by reference. The concentrate so prepared can then be mixed with the remainder of the polyester and the optical brightener as above.
- the photographic element can be of conventional structure, and it can be exposed in conventional man ner to form a projectable or readable mieroimage infor mation bearing element. If an unauthorized person attempts to duplicate the information onto diazo film or which compound is 4,4-bis[benzoxazole-Z-yl]stilbene.
- EXAMPLE II To poly(ethylene terephthalate) as in Example I were added 2000ppm of the preferred optical brightener and ZOOOppm of 2,2'bis[4-2,2 dicyanovinyl) N-ethyl- 3toluidino]diethyl adipate. The mixture was melted and extruded to form a support 4 mils thick. This support had a filter factor of about 275.
- an optical brightener and a yellow dye are incorporated into a polyester support
- the optical brightener and the yellow dye are incorporated in one or several other layers of the information receiving elements of the invention; e.g., such layers can be 'interlayers between the support and the radiation sensitive layer, or they may be outer layers or overcoats on the side opposite the radiation sensitive layer, or on the radiation sensitive layer itself.
- the combina tion of the optical brightener and the yellow dye may be incorporated in one and the same layer or the optical brightener may be located in one layer and the dye in another while still obtaining the advantages and benefits of the invention.
- An information receiving film element for providing a processed, substantially non-fluorescent, optically brightened, substantially transparent information bearing, polymeric film element from which the information processed thereon is substantially nonreproducible when said information bearing film element is placed over a diazo film or print paper and is subjected to exposure to radiation having a wavelength in the range of between about 300 and 460 nanometers, said information receiving film element comprising:
- a transparent polymeric film support that transmits visible radiation, and which can absorb radiation having a wavelength in the range between about 300 and 460 nanometers, said support having incorporated therein a. an optical brightening amount of at least one optical brightener compound capable of absorbing radiation in said wavelength range, and
- At least one radiation sensitive layer which, when exposed to informaion-providing radiation and processed to develop the information received forms an information bearing transparency, said optical brightener and said yellow dye both being present in said support in a total amount at least sufficient to absorb radiation having said wavelength but insufficient to prevent passage of visible light through the element while said yellow dye also absorbs the fluorescence of said optical brightener 4,4'-bis- 15 g. 2-(4,6-dimethoxy-2s triazinyl)pyrene;
- each R which can be the same or different is selected from the group consisting of hydrogen atoms, halogen atoms, alkyl, aryl, substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy, amino, and substituted amino radicals and each Y which can be the same or different is selected from the group consisting of hydrogen atoms, alkyl, aryl, and cyano radicals.
- each R and each Y are hydrogen atoms.
- R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached.
- said support is a linear polyester support wherein the polyester is poly(ethylene terephthalate), poly( l,4-cyclohexylenedimethylene terephthalate), poly(ethylene isophthalate), poly( ethylene naphthalenedicarboxylate), or a mixture of at least two of said polyesters.
- a transparent polymeric fllm support that transmits visible radiation, and which can absorb radiation having a wavelength in the range between about 300 and 460 nanometers, said support having incorporated therein a. an optical brightening amount of at least one optical brightener compound capable of absorbing radiation in said wavelength range, and b. a fluorescence and radiation absorbing amount of at least one yellow dye capable of absorbing radiation in said Wavelenth range, and ii.
- optical brightener and said yellow dye both being present in said support in a total amount at least sufficient to absorb radiation having said wavelength but insufficient to prevent passage of visible light through the element while said yellow dye also absorbs the fluorescence of said optical brightener both before and after processing of the element to its information bearing film element form, said optical brightener being a fluorescent compound selected from a. at least one fluorescent 4,4-bis- (benzoxazol- 2-yl) stilbene compound; b. 4,4'-bis(4,6-diphenyl-s-triaxin-Z-yl)-stilbene; c. 2,5,bis[5-(a, -dimethylbenzyl)benzoxaol- 2-yl]-thioph ene;
- R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached.
- R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached;
- biS[4(22 dicyanoviny1) N ethyl 3 15 yellow dye is 2-(2-quinolyl)-l,3-indandione.
- toluidinoldiethyl sulfone 14 An element according to claim 11 wherein said d 2,2, biS[4(2,2ldicyanOvinyl N ethy1 yellow dye is 2,2'bis[4(2,2 dicyanovinyl)-N-ethyl-3- anilino]diethyl isophthalate; toluldmOl l adlpate- ⁇ 4 (2,2 dicyanoviny1) N ethy1 1 5.
- a light pro ectable, substantially nonfluorescent, 3 toluidino ethyl] terephthalamide; optically brightened substantially transparent informa- 2,2, biS[4(2z dicyanovinyl) N ethy] 3 tion bearing microfilm element according to claim 9.
- a microfilm element according to claim 15 toluidino]diethyl succinate
- each R which can be the same or different is i selected from the group consisting of hydrogen atoms, g n atoms, y ryl, and cyano radicalshalogen atoms, alkyl, aryl, substituted aryl, hydroxy, 17.
- a microfilm element according to claim 16 alkoxy, aryloxy, acyl, acyloxy, amino, and substituted wherein each R and Y are hydrogen atoms.
- a microfilm element according b claim 16 different is selected from the group consisting of hydrowherein said yellow dye is selected from the group congen atoms, alkyl, aryl, and cyano radicals. sisting of:
- said yellow dye is selected from the group consisting of: O O O H H H ⁇ l i C 0 P II 2 1 H f C ⁇ c RZ C R or i ⁇ c 55 0 H H II C C ⁇ or R2- C CR wherein R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached.
- a microfilm element according to claim 17 wherein said yellow dye is 2(2-quinolyl)-l,3- indandione.
- a microfilm element according to claim 17 wherein said yellow dye is 2,2'bis[4(2,2 dicyanovinyl)- N-ethyl-B-toluidino]diethyl adipate.
- An information bearing film element according to claim 9 wherein said support is a polyester, cellulose nitrate, cellulose acetate, poly(vinyl acetal), polystyrene or polycarbonate film support.
Abstract
An element comprising a support that transmits visible radiation, a radiation sensitive layer, and containing both an optical brightener and a yellow dye which, together, absorb radiation in the range from about 300 to about 460 nm. The element is useful for providing a microfilm from which an image cannot be duplicated by the diazo process.
Description
11111 States Patent Hunter Sept. 9, 11975 INFORMATION RECEIVING ELEMENT 3,406,070 10/1968 Detiker et al 96/82 CUNTMNING A DYE AND AN 3,460,961 8/1969 Young et a]. 96/84 UV 3,499,762 3/1970 Cressman et al. 96/82 OP'MCAL BRIGHTENER 3,503,779 3/1970 Young ct a1. 96/84 uv [75] Inventor: C. Shelburn Hunter, Rochester, 3,506,470 1970 Young et 4 UV 3,525,618 8/1970 Keller et al. 96/75 3,622,582 11/1971 Schefczik 8/55 [73] Assigneec Eastman K dak C mp ny, 3,626,008 12/1971 Biland et a]. 96 84 uv Rochester, NY. 3,630,738 12 1971 Dear et a1. 96 84 uv 3,666,591 5/1972 Reed 96 75 [221 Flled? 1973 3,679,415 7/1972 McNally 96 49 NO 3,694,211 9/1972 S310 61. 31. 96/84 UV 3,705,807 12/1972 Busatto 96 84 R Related US. Application Data Continuation-impart of Ser. No, 285,398, Aug. 31, 1972, abandoned.
ILLS. 1C1. 96/82; 96/44; 96/45; 96/87 R; 96/75; 96/84 R; 96/84 UV; 96/1 R; 117/335; ll7/3S.6; 283/6.l7; 283/60 11111. 131. G03C l/92; G03C l/94; GO3C 1/52 1 111811111 1:111 Search..... 96/84 R, 84 UV, 8 N, 87 R, 96/44, 45, 75; 117/333, 35.6; 283/6, 17, 6O
[56] References Cited UNITED STATES PATENTS 2,304,838 12/1942 Marx 96/45 2,373,489 4/1945 Marx... 96/45 3,322,680 5/1967 Hedberg ct a] 1. 117/335 T Primary ExaminerRoland E. Martin, Jr. Assistant Examiner.l. P. Brammer Attorney, Agent, or Firm E. W. Milan 5 7 ABSTRACT 26 Claims, N0 Drawings INFORMATION RECEIVING ELEMENT CONTAINING A YELLOW DYE AND AN OPTICAL BRIGHTENER This application is a continuation-in-part of US. Pat. application Ser. No. 285,398, filed Aug. 31, 1972, now abandoned.
FIELD OF THE INVENTION This invention relates generally to information receiving elements and more particularly to a photographic film element suitable for receiving microimages, such as microfilm.
BACKGROUND OF THE INVENTION In recent years, microfilm has been used as a medium for publishing books, reports, catalogs, and other useful information having a market value to interested readers. Microtilm is ideally suited to the publication field because it is a form of information receiving element by means of which a large amount of information can be condensed within a small storage area. One of the prac tical difficulties that a producer or distributor of microfilms of copyrighted material faces is the possibility of copying, or duplication of the material, by persons without permission of the copyright owner. Such unauthorized duplication often is carried out by means of an inexpensive copying method, i.e., by the diazo process. The possibility that such copying will occur often results in reluctance on the part of copyright owners to make disclosures to the public. As a result of the subject matter of this invention, these copyright owners are now provided with means by which they will be better able to control dissemination of their copyrighted material and should be more inclined to copyright more information for divulgation to the general public. Accordingly, it is an object of the present invention to provide microfilm form of information receiving ele ment from which an image cannot be duplicated readily by the diazo process.
Customarily, microimages are reproduced by the diazo process by the use of radiation from a mercury lamp or a thorium doped mercury lamp to project a microimage from a microfilm onto diazo film or paper. The radiation reaching the film or paper consists primarily of radiation of wavelengths 313.15, 366.3, 404.6, 420, and 435.8 nm (nanometers). Diazo film and paper normally are sensitive to radiation in a wavelength range from 300 to 460 nm.
It is an object of this invention to provide an information receiving element which is useful for recording thereon a microimage, and thereby make possible storage of information in microsize form, and which also renders substantially impossible duplication of the recorded microimage from the element onto diazo paper or film. This object is accomplished by incorporation in the element of materials which together absorb radiation to which the diazo system is sensitive. Preferably, the information receiving element is a photographic film. The invention will be exemplified herein by means of such a film. As used generally, the term photographic film includes an element having in combination a radiation sensitive layer, a suppport material in the form ofa film, and various other layers which comprise a photographic element.
The element of the present invention comprises a support and one or more layers carried by the support. Generally, one of the layers comprises a radiation sensitive composition suitable for recording microimages therein. The element contains, in addition, an optical brightener and yellow dye incorporated in the support and/or in at least one of the layers coated on the support. Broadly, the element of this invention is an element comprising a support that transmits visible radiation and a radiation sensitive layer, said element being characterized in that it contains both an optical brightener and a yellow dye which, together, absorb radiation in the range of about 300 to about 460 nm. Particularly, the element of the invention is an element adapted to substantially impede duplication of the image therefrom by the use of actinic radiation in the region between 300 nm and 460 nm, said element comprising a support having incorporated therein an optical brightener and a yellow dye which together absorb actinic radiation in the range of about 300 to about 460 nm, and an image-bearing layer carried by said support.
In practicing the invention, the dye and brightener are incorporated preferably in a layer or layers other than a radiation sensitive layer, since the dye and brightener can adversely affect sensitometric properties of the radiation sensitive composition. Within the context of the invention it is the intention that the combination of the yellow dye and optical brightener does not prevent the exposure of the radiation sensitive layer, i.e., the radiation sensitivity of the layer is not restricted to that part of the specturm in which said com bination of dye and brightener absorbs light radiation.
From US. Pat. Nos. 3,322,680 and 3,260,715, as well as from Japanese Patent 1 1242/68, it is known to incorporate fluorescent organic compounds as whiteners and brightening agents into a variety of synthetic polymers. However, the incorporation is carried out for the sole purpose of improving the whiteness and brightness of industrial products and fabrics using such synthetic resins. This prior art is not concerned with the problem solved by the present invention, namely, effectivesuppression of transmission of radiation in the region between 300 and 460 nm. The present invention solves this problem by the combined use of an otpical brightener and a yellow dye in the support and/or in at least one of the layers coated on the support of an element, as discussed above.
In this combined use, the optical brightener has the function of suppressing transmission of radiation by absorbing between 300 and 400 nm in wavelength. The yellow dye has as one of its functions a similar function, namely, to absorb radiation in the region between 400 and 460 nm and to suppress its transmission. In addition, the yellow dye has the further function of absorbing the fluorescent radiation accompanying light ab sorption by the optical brightener. A preferred range of absorption of the combination of yellow dye and optical brightener lies between 300 and about 435 nm. The combined effect of optical brightener and yellow dye in the element, or photographic film, prevents the copying ofimages contained in an information receiving ele ment made from photographic film, such as a microfiche, by means of the diazo copying method, or by any other copying method using as its principal light source radiation between 300 and 460 nm. (e.g. a mercury lamp).
The present invention is intended especially for use in film from which microimages are projectable or readable by transmission of light radiation. The expression projectable or readable is used herein to refer to any film for producing images when light radiation is directed therethrough and is intended to include elements with image patterns consisting of silver, dyes, minute bubbles, and other image forming materials in a light transmissive medium. In a preferred embodiment the film comprises a silver halide emulsion coated on a yellow, transparent linear polyester support. The emulsion is developable by conventional methods.
Any of the support materials which will transmit at least some visible radiation can be used in the practice of this invention. Such support materials are typically polymeric and include, for example, cellulose nitrate film, cellulose acetate film, poly (vinyl acetal) film, polystyrene film, polycarbonate film and related films or resinous materials. Linear polyester is a preferred support material, since linear polyester materials have excellent dimensional stability. These polyester materials are generally linear polyesters of at least one glycol having 2 to carbon atoms and at least one dibasic acid comprising at least 50 mole percent of an acid having two carboxyl radicals attached to a carbocyclic nucleus having from 4 to 6 carbon atoms per ring. The ester generally has a number average molecular weight of from about 10,000 to about 100,000, an inherent viscosity in a mixture of 60% phenol and 40% chlorobenzene of at least about 0.3 to about 1.3 deciliters per gram and melts at from about l75to about 350C. Viscosity is determined at 25C. with solutions of 0.25 g of the polyester per 100 milliliters of phenol: chlorobenzene.
In this regard, particularly preferred polyester materials are poly (ethylene terephthalate), poly 1,4-cyclohexylenedimethylene terephthalate), poly(ethyleneisophthalate), poly(ethylene naphthalenedicarboxylate), and mixtures of at least two of these. The term linear polyester also includes copolyesters based on these polyesters, such copolyesters being obtained by replacing a portion of the terephthalic acid by another acid or by a hydroxycarboxylic acid, and/or by replacing a portion of the glycol with a different glycol.
In conventional microfilm reproduction methods, the microimages are reproduced on diazo film or paper by exposing the film or paper to actinic light projected through the microimage carrying element. According to the present invention, in order to prevent such copying, an optical brightener and a yellow dye are incorporated into the support or together in at least one of the layers other than the radiation sensitive layer of the information receivng element, or separately in at least two such layers. The location in the element of a layer containing dye and/or brightener is not important.
In a preferred embodiment, the brightener and dye both are incorporated in a polyester support.
In such a preferred embodiment, any optical brightener that (a) is compatible with the polyester, (b) does not adversely affect the sensitometric properties of the radiation-sensitive layer, and (c) is stable at the temperatures encountered in forming the polyester support and in processing the photographic element can be used.
I 3 N N Q1 CJLS1 In a preferred embodiment, the optical brightener is a fluorescent 4,4bis(benzoxazol-Z-yl) stilbene compound of the following formula I:
wherein R is a bivalent 4,4'-stilbene radical of the formula and A and A are each an o-phenylene radical of the formula III.
The substituents R of the bivalent 4,4-stilbene radical and each of the phenylene radicals can be the same or different monovalent substituents. Typical substituents R which are suitable include a hydrogen atom, a halogen atom, and alkyl, aryl, substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy, amino, and substituted amino radicals. In the preferred embodiment the substituents R are all hydrogen atoms. Other substituents are defined in U.S. Pat. No. 3,322,680 which is incorporated herein by reference.
The substituents Y which are suitable include a hydrogen atom, and alkyl, aryl and cyano radicals. In the preferred embodiment the substituents Y are hydrogen atoms. Reference may be had to the above patent for further definition of Y substituents.
Among other optical brighteners that may be used in this invention are those indicated below:
4,4-Bis(4,6-diphenyl-s-triaxin-2-yl )-stilbene l C CH R represents a 5 or 6 membered nitrogen-containing heterocyclic ring having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring to which X is attached. The heterocyclic ring may contain substituents or it may form part of a fused ring system which may also contain substituents such as the radical COOR wherein R represents hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, or hydroxyalkoxyalkyl. One of R and X may be substituted by at least one radical COOR as hereinbefore defined.
A dye suitable for incorporation in the polyester supports mentioned above is 2-(2-quinolyl)-l,3- indandione. In its pure form, this dye is a skin sensitizer, but polyester film containing the dye is not. This dye has the following structure:
This yellow dye and other yellow dyes which may be used according to' this invention are disclosed in and l l (i=c NC prepared by the methods disclosed in US. Pat. Nos 3,417,048 and 3,622,582 incorporated herein by reference. Among the other yellow dyes which may also be 55 used are the following:
1,5 Bis( 1 ,2,4-triazol5-ylthio )anthraquinone 2,2'-Bis[4( 2,2-dicyanovinyl )-N-ethyl-3- toluidino ldiethyl Sulfone II I 2,2-Bis[4(2,2-dicyanovinyl)-N-ethyl anilino]diethyl Isophthalate H 0 l ll 0 @l NHCZH,
N,N'-Bis[2- {4 2,2 dicyan'ovinyl)-N-ethyl-3- toluidino}ethyl]terephthalamide A I 2,2-Bis[4(2,2 dicyanovinyl)-N-ethyl-3- toluidino]diethyl Succinate toluidino]diethyl Adipate O H H N l C C/ N \c Ii 0.
2,6-Bis( 2-quinolyl )-shydrindacene l ,3 ,5 ,7-tetrone T Ii 2-( 2-Quinolyl)- 1 ,S-indandione-S,6-dicarboxylic anhydride 2(3-Hydroxyquinol-2-yl)-1,3-indandione 10 paper, he or she is prevented from obtaining a diazo copy in the normal way because the actinic light used to expose diazo emulsions is absorbed by the film of this invention and its transmission is suppressed.
When used with a polyester support, the optical brightener is added to the polyester at a concentration of about 300 to 4000ppm, and the yellow dye is added in amounts of from about 300 to about 8000ppm. These quantities would be suitable in polyester used for casting a film support having a final thickness of about 0.004. inches. Of course, the quantities could be adjusted for polyester used for casting film support whose thickness is other than 0.004. inches. The concentration of dye and optical brightener should be inversely proportional to the thickness.
The following examples further illustrate the invention.
EXAMPLE I To poly( ethylene terephthalate) resin having a number average molecular weight of about 20,000 and an inherent viscosity of about 0.62 were added 2000ppm optical brightener of the formula:
In one embodiment, a polyester support is prepared in a conventional manner by mixing an optical brightener and a yellow dye with polyester powder or pellets and the mixture is then melted at a temperature of about 250 to 300C. The melt is then extruded into sheet form which is then biaxially stretched in conven tional manner to form film useful as a support for a photographic element. The dye may also be mixed with a small portion of the polyester and then heated to about l60-l90C for about 2 hours as taught in copending US. Pat. applicationof Barkey et al., Ser. No. 285,397, filed Aug. 31, 1972, incorporated herein by reference. The concentrate so prepared can then be mixed with the remainder of the polyester and the optical brightener as above.
The photographic element can be of conventional structure, and it can be exposed in conventional man ner to form a projectable or readable mieroimage infor mation bearing element. If an unauthorized person attempts to duplicate the information onto diazo film or which compound is 4,4-bis[benzoxazole-Z-yl]stilbene.
, Also added were l750ppm yellow dye of the formula:
when the master is on the special (yellow) film base, compared to the amount of light that is needed to get a usable copy when the master is on regular (water white) film base.
EXAMPLE II To poly(ethylene terephthalate) as in Example I were added 2000ppm of the preferred optical brightener and ZOOOppm of 2,2'bis[4-2,2 dicyanovinyl) N-ethyl- 3toluidino]diethyl adipate. The mixture was melted and extruded to form a support 4 mils thick. This support had a filter factor of about 275.
Although in a preferred embodiment of the present invention, an optical brightener and a yellow dye are incorporated into a polyester support, it is also advantageous to prepare information receiving elements of this invention in which the optical brightener and the yellow dye are incorporated in one or several other layers of the information receiving elements of the invention; e.g., such layers can be 'interlayers between the support and the radiation sensitive layer, or they may be outer layers or overcoats on the side opposite the radiation sensitive layer, or on the radiation sensitive layer itself. It should be emphasized that the combina tion of the optical brightener and the yellow dye may be incorporated in one and the same layer or the optical brightener may be located in one layer and the dye in another while still obtaining the advantages and benefits of the invention.
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.
Whatis claimed is: 1. An information receiving film element for providing a processed, substantially non-fluorescent, optically brightened, substantially transparent information bearing, polymeric film element from which the information processed thereon is substantially nonreproducible when said information bearing film element is placed over a diazo film or print paper and is subjected to exposure to radiation having a wavelength in the range of between about 300 and 460 nanometers, said information receiving film element comprising:
i. a transparent polymeric film support that transmits visible radiation, and which can absorb radiation having a wavelength in the range between about 300 and 460 nanometers, said support having incorporated therein a. an optical brightening amount of at least one optical brightener compound capable of absorbing radiation in said wavelength range, and
b. a fluorescence and radiation absorbing amount of at least one yellow dye capable of absorbing radiation in said wavelength range, and
ii. at least one radiation sensitive layer, which, when exposed to informaion-providing radiation and processed to develop the information received forms an information bearing transparency, said optical brightener and said yellow dye both being present in said support in a total amount at least sufficient to absorb radiation having said wavelength but insufficient to prevent passage of visible light through the element while said yellow dye also absorbs the fluorescence of said optical brightener 4,4'-bis- 15 g. 2-(4,6-dimethoxy-2s triazinyl)pyrene;
h. phenyl-4-( 2H-naphtho[ 1,2-d ]triazol-2-yl 2-stilbene sulfonate; i. 4-(2-benzoxazolyl)-4-stilbene carboxylic acid; j. l,4-bis(Z-benzoxazolyl)naphthalene; k. 1,4-bis( 5-methoxycarbonyl-Z-benzoxazolyl) naphthalene; l. methyl-4'(Z-benzoxazolyl) 4-stilbene carboxylate; and said yellow dye being selected from a. at least one dyestuff of the following formulas:
O H t C I H l R 0 2 i/ O r H 1 l 40 C or illc c R 2-(2-quinolyl )-l ,3-indandione-5 ,6-
dicarboxylic anhydride; and j. 2-( 3-hydroxyquinol-2-yl )-l ,3-indandione. 2. An element according to claim 1 characterized in that said suport is a polyester, cellulose nitrate, cellulose acetate, poly(vinyl acetal), polystyrene, or polycarbonate support.
3. An element according to claim 1 wherein said stilbene compound is of the formula:
wherein each R which can be the same or different is selected from the group consisting of hydrogen atoms, halogen atoms, alkyl, aryl, substituted aryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy, amino, and substituted amino radicals and each Y which can be the same or different is selected from the group consisting of hydrogen atoms, alkyl, aryl, and cyano radicals.
4. An element according to claim 3 wherein each R and each Y are hydrogen atoms.
5. An element according to claim 3 wherein said yellow dye is selected from the group consisting of:
wherein R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached.
6. An element according to claim 4 wherein said yellow dye is 2-(2-quinolyl)-l,3-indandione.
7. An element according to claim 4 wherein said yellow dye is 2,2'bis[4(2,2 dicyanovinyl)'N-ethyl-3 toluidino]diethyl adipate.
8. An information receiving film element according to claim 1 wherein said support is a linear polyester support wherein the polyester is poly(ethylene terephthalate), poly( l,4-cyclohexylenedimethylene terephthalate), poly(ethylene isophthalate), poly( ethylene naphthalenedicarboxylate), or a mixture of at least two of said polyesters.
9. A substantially non-fluorescent, optically brightened, substantially transparent information bearing polymeric film element from which the information carried thereon is substantially non-reproducible when said element is placed over a diazo film or print paper and is subjected to exposure to radiation having a wavelength in the range between about 300 and 460 nanometers, said element comprising:
i. a transparent polymeric fllm support that transmits visible radiation, and which can absorb radiation having a wavelength in the range between about 300 and 460 nanometers, said support having incorporated therein a. an optical brightening amount of at least one optical brightener compound capable of absorbing radiation in said wavelength range, and b. a fluorescence and radiation absorbing amount of at least one yellow dye capable of absorbing radiation in said Wavelenth range, and ii. at least one information bearing layer, which when exposed to information-reproducing radiation transmits visible radiation and absorbs radiation in said Wavelength range, said optical brightener and said yellow dye both being present in said support in a total amount at least sufficient to absorb radiation having said wavelength but insufficient to prevent passage of visible light through the element while said yellow dye also absorbs the fluorescence of said optical brightener both before and after processing of the element to its information bearing film element form, said optical brightener being a fluorescent compound selected from a. at least one fluorescent 4,4-bis- (benzoxazol- 2-yl) stilbene compound; b. 4,4'-bis(4,6-diphenyl-s-triaxin-Z-yl)-stilbene; c. 2,5,bis[5-(a, -dimethylbenzyl)benzoxaol- 2-yl]-thioph ene;
7-( 2H-naphtho[ l,2-d]triazol-2-yl )-3-phenyl- 2-chromanone; e. 6-acetamido-2-buty1 phenalenel ,3-(2H)-dione; f. 6( 4-methyl-5-phenyl-v-triazol-2-yl )-3- phenyl-2-chromanone; g. 2-(4,6-dimethoxy-2-s-triazinyl)pyrene; h. phenyl-4-( 2H-naphtho[ l,2-d]triazol-2-yl 2stilbene sulfonate; i. 4'-(2-benzoxazolyl)-4-stilbene carboxylic acid; j. l,4-bis(Z-benzoxazolyl)naphthalene; k. l,4-bis( 5-methoxycarbonyl-2-benzoxazolyl) naphthalene; l. methyl-4-(Z-benzoxazolyl)-4-stilbene carboxylate; and said yellow dye being selected from a. at least one dyestuff of the following formuals:
O H I H i T l l T or I 2 /C C c wherein R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached.
13. An element according to claim 11 wherein said wherein R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached;
b. l,5-bis( l ,2,4-triazol-5-ylthio)anthraquinone;
22, biS[4(22 dicyanoviny1) N ethyl 3 15 yellow dye is 2-(2-quinolyl)-l,3-indandione.
toluidinoldiethyl sulfone 14. An element according to claim 11 wherein said d 2,2, biS[4(2,2ldicyanOvinyl N ethy1 yellow dye is 2,2'bis[4(2,2 dicyanovinyl)-N-ethyl-3- anilino]diethyl isophthalate; toluldmOl l adlpate- {4 (2,2 dicyanoviny1) N ethy1 1 5. A light pro ectable, substantially nonfluorescent, 3 toluidino ethyl] terephthalamide; optically brightened substantially transparent informa- 2,2, biS[4(2z dicyanovinyl) N ethy] 3 tion bearing microfilm element according to claim 9.
16. A microfilm element according to claim 15 toluidino]diethyl succinate;
wherein said stilbene compound s of the formula:
g'. 2,2'-bis[4(2,2-dicyanovinyl)-N-ethyl-3- l l R R Y Y R R N 1 R N\C i R1 C =C R1 0 l l l R:L toluidino]diethyl adipate; R1 R R R R q y y wherein each R which can be the same or different is tetrone; selected from the group consisting of hydrogen atoms, 'q a halogen atoms, alkyl, aryl, substituted aryl, hydroxy, dlcarboxyllc anljlydrlde; and alkoxy, aryloxy, acyl, acyloxy, amino, and substituted J- y q -y amino radicals and each Y which can be the same or An element according to clalm 9 Where"! Sald different is selected from the group consisting of hydrostilbene compound is of the formula:
1 e l 1 1 i 1 l R R R R T T R R l 1 N R c c 0 1 R Q 1 1 1 1 R R R wherein each R which can be the same or different is i selected from the group consisting of hydrogen atoms, g n atoms, y ryl, and cyano radicalshalogen atoms, alkyl, aryl, substituted aryl, hydroxy, 17. A microfilm element according to claim 16 alkoxy, aryloxy, acyl, acyloxy, amino, and substituted wherein each R and Y are hydrogen atoms.
amino radicals and each Y which can be the same or 18. A microfilm element according b claim 16 different is selected from the group consisting of hydrowherein said yellow dye is selected from the group congen atoms, alkyl, aryl, and cyano radicals. sisting of:
11. An element according to claim 10 wherein each R and Y are hydrogen atoms.
12. An element according to claim 10 wherein said yellow dye is selected from the group consisting of: O O O H H \l i C 0 P II 2 1 H f C \c RZ C R or i \c 55 0 H H II C C\ or R2- C CR wherein R is selected from the group consisting of 5 or 6 membered nitrogen-containing heterocyclic rings having a heterocyclic nitrogen atom attached through a double bond to a carbon atom of the ring through which R is attached.
20. A microfilm element according to claim 17 wherein said yellow dye is 2(2-quinolyl)-l,3- indandione.
21. A microfilm element according to claim 17 wherein said yellow dye is 2,2'bis[4(2,2 dicyanovinyl)- N-ethyl-B-toluidino]diethyl adipate.
22. A microfilm element according to claim 15 in which said support is a polymeric support.
23. A microfilm element according to claim 22 in which said polymeric support is a polyester, cellulose nitrate, cellulose acetate, poly(vinyl acetal), polystyrene, or polycarbonate support.
24. An information bearing film element according to claim 9 wherein said support is a linear polyester support wherein the polyester is poly(ethylene terephthalate), poly-( l,4-cyclohexylenedimethylene terephthalate), poly(ethylene isophthalate), poly(ethylene naphthalenedicarboxylate), or a mixture of at least two of said polyesters.
25. An information bearing film element according to claim 9 wherein said support is a polyester, cellulose nitrate, cellulose acetate, poly(vinyl acetal), polystyrene or polycarbonate film support.
26. A microfilm element according to claim 24.
* l l k UNITED STATES PATENT AND TRADEMARK OFFICE EERTIFICATE 0F CRRECTION PATENT NO. 1 3,90 r,h20 DATED September 9, 1975 V W I C Shelburn Hunter It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
C01. l t, line il should read:
- 0. 2,5-bisL-0i, -dimethylbenzyl) benzoxazol-2yl 7- thiophene;
Signed and Scaled this A ttes t:
RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner oj'Parenls and Trademarks UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,9o r iZO DATED September 9, 1975 INV ENT R( 1 C Shelburn Hunter it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown beiow:
Col. l t line il should read:
- c 2,5-bis[5 di,oC dimethylbenzyl) benzoXazol-2yl 7- thiophene;
Signed and Scaled this third Day of February 1976 [SEAL] Attest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ufParents and Trademarks
Claims (26)
1. AN INFORMATION RECEIVING FILM ELEMENT FOR PROVIDING A PROCESSED, SUBSTANTIALLY NON-FLUORESCENT, OPTICALLY BRIGHTENED, SUBSTANTIALLY TRANSPARENT INFORMATION BEARING, POLYMERIC FILM ELEMENT FROM WHICH THE INFORMATION PROCESSED THEREON IS SUBSTANTIALLY NON-REPRODUCIBLE WHEN SAID INFORMATION BEARING FILM ELEMENT IS PLACED OVER A DIAZO FILM OR PRINT PAPER AND IS SUBJECTED TO EXPOSURE TO RADIATION HAVING A WAVELENGTH IN THE RANGE OF BETWEEN ABOUT 300 AND 460 NANOMETERS, SAID INFORMATION RECEIVING FILM ELEMENT COMPRISING: I. A TRANSPARENT POLYMERIC FILM SUPPORT THAT TRANSMITS VISIBLE RADIATION, AND WHICH CAN ABSORB RADIATION HAVING A WAVELENGTH IN THE RANGE BETWEEN ABOUT 300 AND 460 NANOMETERS, SAID SUPPORT HAVING INCORPORATED THEREIN A. AN OPTICAL BRIGHTENING AMOUNT OF AT LEAST ONE OPTICAL BRIGHTENER COMPOUND CAPABLE OF ABSORBING RADIATION IN SAID WAVELENGTH RANGE, AND B. A FLUORESCENCE AND RADIATION ABSORBING AMOUNT OF AT LEAST ONE YELLOW DYE CAPABLE OF ABSORBING RADIATION IN SAID WAVELENGTH RANGE, AND II. AT LEAST ONE RADIATION SENSITIVE LAYER, WHICH, WHEN EXPOSED TO INFORMATION-PROVIDING RADIATION AND PROCESSED TO DEVELOP THE INFORMATION RECEIVED FORMS AN INFORMATION BEARING TRANSPARENCY, SAID OPTICAL BRIGHTENER AND SAID YELLOW DYE BOTH BEING PRESENT IN SAID SUPPORT IN A TOTAL AMOUNT AT LEAST SUFFICIENT TO ABSORB RADIATION HAVING SAID WAVELENGTH BUT SUFFICIENT TO PREVENT PASSAGE OF VISIBLE LIGHT THROUGH THE ELEMENT WHILE SAID YELLOW DYE ALSO ABSORBS THE FLUORESCENCE OF SAID OPTICAL BRIGHTENER BOTH BEFORE AND AFTER PROCESSING OF THE ELEMENT TO ITS INFORMATION BEARING FILM ELEMENT FORM, SAID OPTICAL BRIGHTENER BEING A FLUORESCENT COMPOUND SELECTED FROM A. AT LEAST ONE FLUORESCENT 4,4''-BIS-(BENZOXAZOL-2-YL) STILBENE COMPOUND, B. 4,4''-BIS(4,6-DIPHENYL-S-TRIAZIN-2-YL)-STILBENE, C. 2,5, BIS(5-(A,A-DIMETHYLBENZYL)BENZOXAZOL-2-YL)-THIOPHEN, D. 7-(2H-NAPHTHO(1,2-D)TRIAZOL-2-YL)-3-PHENYL-2CHROMANONE, E. 6-ACETAMIDO-2-BUTYL PHENALENE-1,3-(2H)-DIONE, F. 6-(4-METHYL-5-PHENYL-V-TRIAZOL-2-YL)-3-PHENYL-2CHROMANONE, G. 2-(4,6-DIMETOXY-2-S-TRIAZINYL)PYRENE, H. PHENYL-4-(2H-NAPHTHO(1,2-D)TRIAZOL-2-YL)-2-STILBENE SULFONATE, I. 4''-(2-BENZOXAZOLYL)-4-STILBENE CARBOXYLIC ACID, J. 1,4-BIS(2-BENZOXAZOLYL)NAPHTHALENE, K. 1,4-BIS(5-METHOXYCARBONYL-2-BENZOXAZOLYL) NAPHTHALENE, L. METHYL-4''(2-BENZOXAZOLYL)-4-STILBENE CARBOXYLATE, AND SAID YELLOW DYE BEING SELECTED FROM A . AT LEAST ONE DYESTUFF OF THE FOLLOWING FORMULAS:
2. An element according to claim 1 characterized in that said suport is a polyester, cellulose nitrate, cellulose acetate, poly(vinyl acetal), polystyrene, or polycarbonate support.
3. An element according to claim 1 wherein said stilbene compound is of the formula:
4. An element according to claim 3 wherein each R1 and each Y are hydrogen atoms.
5. An element according to claim 3 wherein said yellow dye is selected from the group consisting of:
6. An element according to claim 4 wherein said yellow dye is 2-(2-quinolyl)-1,3-indandione.
7. An element according to claim 4 wherein said yellow dye is 2, 2''bis(4(2,2 dicyanovinyl)-N-ethyl-3-toluidino) diethyl adipate.
8. An information receiving film element according to claim 1 wherein said support is a linear polyester support wherein the polyester is poly(ethylene terephthalate), poly(1,4-cyclohexylenedimethylene terephthalate), poly(ethylene isophthalate), poly(ethylene naphthalenedicarboxylate), or a mixture of at least two of said polyesters.
9. A substantially non-fluorescent, optically brightened, substantially transparent information bearing polymeric film element from which the information carried thereon is substantially non-reproducible when said element is placed over a diazo film or print paper and is subjected to exposure to radiation having a wavelength in the range between about 300 and 460 nanometers, said element comprising: i. a transparent polymeric film support that transmits visible radiation, and which can absorb radiation having a wavelength in the range between about 300 and 460 nanometers, said support having incorporated therein a. an optical brightening amount of at least one optical brightener compound capable of absorbing radiation in said wavelength range, and b. a fluorescence and radiation absorbing amount of at least one yellow dye capable of absorbing radiation in said wavelenth range, and ii. at least one information bearing layer, which when exposed to information-reproducing radiation transmits visible radiation and absorbs radiation in said wavelength range, said optical brightener and said yellow dye both being present in said support in a total amount at least sufficient to absorb radiation having said wavelength but insufficient to prevent passage of visible light through the element while said yellow dye also absorbs the fluorescence of said optical brightener both before and after processing of the element to its information bearing film element form, said optical brightener being a fluorescent compound selected from a. at least one fluorescent 4,4''-bis- (benzoxazol-2-yl) stilbene compound; b. 4,4''-bis(4,6-diphenyl-s-triaxin-2-yl)-stilbene; c. 2,5,bis(5-(60-dimethylbenzyl)benzoxaol-2-yl)-thiophene; d. 7-(2H-naphtho( 1,2-d) triazol-2-yl)-3-phenyl-2-chromanone; e. 6-acetamido-2-butyl phenalene-1,3-(2H)-dione; f. 6-(4-methyl-5-phenyl-v-triazol-2-yl)-3-phenyl-2-chromanone; g. 2-(4,6-dimethoxy-2-s-triazinyl)pyrene; h. phenyl-4-(2H-naphtho( 1,2-d) triazol-2-yl)-2-stilbene sulfonate; i. 4''-(2-benzoxazolyl)-4-stilbene carboxylic acid; j. 1,4-bis(2-benzoxazolyl)naphthalene; k. 1,4-bis(5-methoxycarbonyl-2-benzoxazolyl) naphthalene; l. methyl-4''-(2-benzoxazolyl)-4-stilbene carboxylate; and said yellow dye being selected from a. at least one dyestuff of the following formuals:
10. An element according to claim 9 wherein said stilbene compound is of the formula:
11. An element according to claim 10 wherein each R1 and Y are hydrogen atoms.
12. An element according to claim 10 wherein said yellow dye is selected from the group consisting of:
13. An element according to claim 11 wherein said yellow dye is 2-(2-quinolyl)-1,3-indandione.
14. An element according to claim 11 wherein said yellow dye is 2,2''bis( 4(2,2 dicyanovinyl)-N-ethyl-3-toluidino) diethyl adipate.
15. A light projectable, substantially nonfluorescent, optically brightened substantially transparent information bearing microfilm element according to claim 9.
16. A microfilm element according to claim 15 wherein said stilbene compound is of the formula:
17. A microfilm element according to claim 16 wherein each R1 and Y are hydrogen atoms.
18. A microfilm element according to claim 16 wherein said yellow dye is selected from the group consisting of:
19. A microfilm element according to claim 17 wherein said yellow dye is selected from the group consisting of:
20. A microfilm element according to claim 17 wherein said yellow dye is 2-(2-quinolyl)-1,3-indandione.
21. A microfilm element according to claim 17 wherein said yellow dye is 2,2''bis(4(2,2 dicyanovinyl)-N-ethyl-3-toluidino) diethyl adipate.
22. A microfilm element according to claim 15 in which said support is a polymeric support.
23. A microfilm element according to claim 22 in which said polymeric support is a polyester, cellulose nitrate, cellulose acetate, poly(vinyl acetal), polystyrene, or polycarbonate support.
24. An information bearing film element according to claim 9 wherein said support is a linear polyester support wherein the polyester is poly(ethylene terephthalate), poly-(1,4-cyclohexylenedimethylene terephthalate), poly(ethylene isophthalate), poly(ethylene naphthalenedicarboxylate), or a mixture of at least two of said polyesters.
25. An information bearing film element according to claim 9 wherein said support is a polyester, cellulose nitrate, cellulose acetate, poly(vinyl acetal), polystyrene or polycarbonate film support.
26. A microfilm element according to claim 24.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA179,945A CA1005676A (en) | 1972-08-31 | 1973-08-29 | Information receiving element |
US395792A US3904420A (en) | 1972-08-31 | 1973-09-10 | Information receiving element containing a yellow dye and an optical brightener |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US28539872A | 1972-08-31 | 1972-08-31 | |
US395792A US3904420A (en) | 1972-08-31 | 1973-09-10 | Information receiving element containing a yellow dye and an optical brightener |
Publications (1)
Publication Number | Publication Date |
---|---|
US3904420A true US3904420A (en) | 1975-09-09 |
Family
ID=26963176
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US395792A Expired - Lifetime US3904420A (en) | 1972-08-31 | 1973-09-10 | Information receiving element containing a yellow dye and an optical brightener |
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US4147552A (en) * | 1976-05-21 | 1979-04-03 | Eastman Kodak Company | Light-sensitive compositions with 3-substituted coumarin compounds as spectral sensitizers |
US4152156A (en) * | 1974-10-15 | 1979-05-01 | Xidex Corporation | Duplication-proof photographic film |
US4455039A (en) * | 1979-10-16 | 1984-06-19 | Coulter Systems Corporation | Encoded security document |
US6521399B1 (en) * | 1998-06-09 | 2003-02-18 | Eastman Kodak Company | Imaging member with biaxially oriented sheets containing optical brighteners |
CN105899975A (en) * | 2013-12-23 | 2016-08-24 | 埃西勒国际通用光学公司 | Transparent optical article having a reduced yellowness appearance |
US10203524B2 (en) | 2013-12-23 | 2019-02-12 | Essilor International (Compagnie Generale D'optique) | Transparent optical article having a colorless appearance |
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US3666591A (en) * | 1968-10-03 | 1972-05-30 | Scm Corp | Method of bonding a resinous film to a substrate using high energy radiation |
US3679415A (en) * | 1969-07-18 | 1972-07-25 | Eastman Kodak Co | Diazotype photographic elements having extended exposure latitude with specific u-v absorber |
US3694211A (en) * | 1970-04-17 | 1972-09-26 | Konishiroku Photo Ind | Organic materials containing uv-absorbers |
US3705807A (en) * | 1970-04-24 | 1972-12-12 | Minnesota Mining & Mfg | Photosensitive material for radiography |
-
1973
- 1973-08-29 CA CA179,945A patent/CA1005676A/en not_active Expired
- 1973-09-10 US US395792A patent/US3904420A/en not_active Expired - Lifetime
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US2373489A (en) * | 1941-10-18 | 1945-04-10 | Halftone photoengraving process | |
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US3406070A (en) * | 1964-03-04 | 1968-10-15 | Ciba Ltd | Process for the manufacture of optically brightened photographic material |
US3525618A (en) * | 1964-12-04 | 1970-08-25 | Geigy Ag J R | Diazotype film materials |
US3460961A (en) * | 1965-04-21 | 1969-08-12 | Monsanto Co | Process of coating a substrate with a polymeric ultraviolet light barrier coating and the coated substrate |
US3503779A (en) * | 1965-07-08 | 1970-03-31 | Monsanto Co | Substrates coated with polymeric ultraviolet light barrier coatings |
US3506470A (en) * | 1965-07-08 | 1970-04-14 | Monsanto Co | Photoprints coated with polymeric ultraviolet light barrier coatings |
US3499762A (en) * | 1966-11-03 | 1970-03-10 | Eastman Kodak Co | Photographic elements comprising novel u.v.-absorbing optical brightening agents |
US3626008A (en) * | 1967-03-20 | 1971-12-07 | Ciba Ltd | Novel phenyl and naphthalene substituted oxalic acid diamides useful as protection agents against ultraviolet irradiation |
US3622582A (en) * | 1967-05-23 | 1971-11-23 | Basf Ag | Disperse quinophthalone dyes containing a carboxylic ester group |
US3666591A (en) * | 1968-10-03 | 1972-05-30 | Scm Corp | Method of bonding a resinous film to a substrate using high energy radiation |
US3630738A (en) * | 1969-05-23 | 1971-12-28 | Eastman Kodak Co | Brightening agents |
US3679415A (en) * | 1969-07-18 | 1972-07-25 | Eastman Kodak Co | Diazotype photographic elements having extended exposure latitude with specific u-v absorber |
US3694211A (en) * | 1970-04-17 | 1972-09-26 | Konishiroku Photo Ind | Organic materials containing uv-absorbers |
US3705807A (en) * | 1970-04-24 | 1972-12-12 | Minnesota Mining & Mfg | Photosensitive material for radiography |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4152156A (en) * | 1974-10-15 | 1979-05-01 | Xidex Corporation | Duplication-proof photographic film |
US4080208A (en) * | 1975-01-13 | 1978-03-21 | Addressograph Multigraph Corporation | Photosensitive diazomicrofilm adapted to be readable but nonreproducible upon processing |
US4147552A (en) * | 1976-05-21 | 1979-04-03 | Eastman Kodak Company | Light-sensitive compositions with 3-substituted coumarin compounds as spectral sensitizers |
US4455039A (en) * | 1979-10-16 | 1984-06-19 | Coulter Systems Corporation | Encoded security document |
US6521399B1 (en) * | 1998-06-09 | 2003-02-18 | Eastman Kodak Company | Imaging member with biaxially oriented sheets containing optical brighteners |
CN105899975A (en) * | 2013-12-23 | 2016-08-24 | 埃西勒国际通用光学公司 | Transparent optical article having a reduced yellowness appearance |
US10114234B2 (en) | 2013-12-23 | 2018-10-30 | Essilor International (Compagnie Generale D'optique | Transparent optical article having a reduced yellowness appearance |
US10203524B2 (en) | 2013-12-23 | 2019-02-12 | Essilor International (Compagnie Generale D'optique) | Transparent optical article having a colorless appearance |
CN105899975B (en) * | 2013-12-23 | 2019-10-25 | 依视路国际公司 | The transparent optical article of yellowing appearance with reduction |
CN109651889A (en) * | 2018-12-21 | 2019-04-19 | 天津环球磁卡股份有限公司 | A kind of temperature becomes Antiforge fluorescent ink and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CA1005676A (en) | 1977-02-22 |
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