US3833380A - Novel photographic elements - Google Patents

Novel photographic elements Download PDF

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US3833380A
US3833380A US00292365A US29236572A US3833380A US 3833380 A US3833380 A US 3833380A US 00292365 A US00292365 A US 00292365A US 29236572 A US29236572 A US 29236572A US 3833380 A US3833380 A US 3833380A
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spectrum
photographic element
range
titanium dioxide
percent
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English (en)
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I Crawford
F Hartman
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to JP41005904A priority Critical patent/JPS4927046B1/ja
Priority to DE19661547674 priority patent/DE1547674A1/de
Priority to GB15326/66A priority patent/GB1134197A/en
Priority to GB15325/66A priority patent/GB1134196A/en
Priority to FR57028A priority patent/FR1475329A/fr
Priority to BE679409D priority patent/BE679409A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US00292365A priority patent/US3833380A/en
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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
    • 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
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • 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
    • Y10S430/132—Anti-ultraviolet fading

Definitions

  • ABSTRACT pound and has, on its emulsion side surface, an average reflectance of no more than about 25 percent over wavelengths'in the ultraviolet region of the spectrum in the range of about 360 to about 400 mp,
  • This invention relates to novel photographic elements. More particularly, this invention relates to color photographic papers which yield dye images resistant to ultraviolet radiation.
  • Color photographs particularly where the dye images are formed in sensitive silver halide emulsion layers by color development, are susceptible to fading and discoloration by the action of ultraviolet radiation to which the photographs are subjected during viewing. Furthermore, residual couplers contained in the emulsion layers after formation of the picture images in certain processes are attacked by ultraviolet radiation and form a yellow stain (background stain) which is undesirable in the finished photograph.
  • Another object of this invention is to provide color photographic papers which can be processed to produce dye images having a high resistance to ultraviolet radiation.
  • Another object of this invention is to provide a method for preparing color photographic papers which can be processed to produce dye images having a high resistance to ultraviolet radiation.
  • Another object of this invention is to provide color photographic papers which can be processed to produce color photographs which have a low propensity to stain in the non-image areas.
  • Still another object of this invention is to provide color photographic papers which can be processed to produce dye images having high resistance to ultraviolet radiation, improved sharpness and which can be processed to produce glossy prints without drying in face-to-face contact with a smooth surface.
  • a paper support containing a non-fluorescing ultraviolet radiation absorbing compound and having reflectance characteristics on its emulsion side surface as described herein significantly improves resistance to fading and yellow stain and, in certain cases, sharpness of multicolor photographic layers coated over the support. Furthermore, the use of an additional ultraviolet absorbing layer or layers over one or more of the colorforming photographic layers results in a still further improvement in quality.
  • the incorporation of an ultraviolet absorbing compound into a photographic emulsion layer can lead to contamination and desensitization.
  • oilsoluble ultraviolet radiation absorbers when incorporated into a photographic emulsion layer or an interlayer, they tend to create opalescence in a wet processed print which makes it difficult to judge color quality until the print is dry. If water soluble ultraviolet radiation absorbers are employed the viscosity of the melts are increased to a point where severe coating problems are encountered. Incorporating the ultraviolet radiation absorber into the support where it is firmly held overcomes such problems.
  • a significant feature of this invention is that when titanium dioxide is employed asthe non-fluorescing ultraviolet absorbing compound, only certain physical forms are satisfactory, as shown in Example 3 which follows. Furthermore, fillers such as barium sulfate, which are often employed to whiten photographic paper, do not impart the requiredReflectance to the paper support. Therefore, such materials, in the absence of a suitable ultraviolet radiation absorber, cannot be employed in practicing this invention, as shown in Example 1, which follows.
  • the paper support employed in the practice of this invention must exhibit an average Reflectance, on its emulsion side surface, of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 rnu,
  • the paper support In combination with the aforementioned average reflectance, the paper support generally has a profile in which the Reflectance, on its emulsion side surface, is no more than about 10 percent, preferably not more than about 8 Reflectance is that fraction of light which is reflected from the surface of the opaque paper support at the defined wavelength of the spectrum, and can be determined using any method suitable for this purpose.
  • a standard recording spectrophotometer can be employed to measure Reflectance at different wavelengths over the range of about 360 to about 400 mp.
  • a Hardy General Electric Recording Spectrophotometer (Stovepipe Model) is employed in which an integrating sphere is used to measure diffuse reflectance according to the C.I.E. recommended standards geometry 8/D.
  • Typical reflectance curves are shown in VanCampen US. Pat. No. 2,956,879 issued Oct. 18, 1960.
  • the reflectance at the wavelengths over this range must be less than 25 percent if the support is to be used in the practice of this invention.
  • This average Reflectance is exhibited by the surface or surfaces of the paper support over which photographic emulsion layers containing an incorporated coupler are coated. Such surfaces arereferred to herein as the emulsion side surface of the paper support.
  • the ultraviolet absorbing compounds in the support absorb radiation in the ultraviolet region of the spectrum and do not emit absorbed radiation in the visible region of the spectrum, i.e., they are non-fluorescent. Any ultraviolet radiation absorbing compound which will impart the required reflectance to the support can be used in the practice of this invention.
  • the ultraviolet radiation absorbing compound can be inorganic, as exemplified by metal oxides such as zinc oxide and titanium dioxide, preferably titanium dioxide of the rutile crystal structure.
  • metal oxides such as zinc oxide and titanium dioxide, preferably titanium dioxide of the rutile crystal structure.
  • rutile titanium dioxide used to provide desired reflectance values measured with an optical microscope preferably has an average particle size of about 0.5 to about microns.
  • the average particle size can be varied widely and values for average particle size measured on an electron microscope typically appear to have an average particle size of 0. 19 to 0.4 micron indicating that possibly agglomerates of smaller particles are measured on an optical microscope.
  • R, R and R can each represent a hydrogen atom, a halogen atom, such as chlorine, bromine, iodine, etc., a nitro group, an alkyl group having from 1 to 18 carbon atoms such as methyl, ethyl, propyl, isopropyl, aminopropyl, butyl, sec-butyl, chlorobutyl, amyl, isoamyl, hexyl, octyl, nonyl, stearamidobutyl, decyl, dodecyl, pentadecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, phenylethyl, phenylpropyl, etc., an alkoxy group having from one to 18 carbon atoms, such as methoxy, propoxy, chlorobutoxy, decoxy, nonoxy, diamylphenoxyethoxy, pen
  • Suitable compounds of this type include, for example, 2 -(2 -hydroxy-5-noctylphenyl)benzotriazole, 2-(2 -hyd roxy-3 ,5 -di tert-amylphenyl)benzotriazole, 2-(2-hydroxy-3-tert- 2-(2 -hydr0xy-3 -n-butyl-5"-tert-amyl phenfflbenzotriazole, chl0ro-2(2 -hydr0xy-3 -tert-butyl-5 -cyclohexylphenyl)benzotriazole, 5-methyl-2 (2 '-hydroxy- 3 -tert-amyl-5 '-phenoxyphenyl)benzotri azole, and the like.
  • R represents a hydrogen atom, an alkyl group (e.g., methyl, ethyl, ,B-hydroxyethyl, B-sulfoethyl, B-diethoxyethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, cetyl, etc.), a cycloalkyl group (e.g., cyqlopentyl, cyclohexyl, etc.
  • an alkyl group e.g., methyl, ethyl, ,B-hydroxyethyl, B-sulfoethyl, B-diethoxyethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, heptyl, octyl, nony
  • an aryl group e.g.,phenyl, o-, mand p-tolyl, o-, mand p-ethylphenyl, p-i'sopropylphenyl, pamylphenyl, o-, mand p-methoxyphenyl, o-, mand p-ethoxyphenyl, ,B-hydroxyethylphenyl, o-, mand pchlorophenyl, o-, mand p-hydroxyphenyl, o-, mand p-sulfophenyl (and alkali metal salts thereof, e.g., sodium, potassium etc.), 4-methoxy-3-sulfophenyl (and alkali metal salts thereof, e.g., sodium, potassium, etc.).
  • Typical compounds of this type include, for example, 5-benzylidene-3-ethyl-2- phenylimino-4-thiazolidone, 5-p-methylbenzal-3- phenyl-Z-phenylimino-4-thiazolidone, 5-mnitrobenzal-3-phenyl-2-phenylimino-4-thiazolidone, 5-benzal-3-methyl-2,4-thiazolidinedione, 5 -benzal-3- n-cetyl-2phenylimino-4-thiazolidone and 3-p-(B- hydroxyethyl)phenyl-2-p-(,B-hydroxyethyl)phenyl-S- (4-methoxy-3-sulfobenzal)-4-thiazolidone.
  • the ultraviolet radiation absorbing compounds can be incorporated into the paper support using any procedure which is suitable for this purpose.
  • the paper forming the support can be impregnated with the ultraviolet absorbing compound during its manufacture.
  • a colloidal binder such as gelatin, a cellulose ester such as cellulose acetate, a synthetic resin such as polyvinyl acetal, hydrolyzed polyvinyl acetate, polyolefins, or the like.
  • inorganic ultraviolet absorbing radiation com-' pounds such as titanium dioxide
  • polyolefins such as polyethylene, polypropylene, propylene-butene copolymers, and the like
  • the ultraviolet absorbing compounds such as titanium dioxide are dispersed in polyolefin, preferably polyethylene, in a concentration of about 3 to about percent, preferably about 6 to about 13 percent, by weight.
  • the dispersion can then be coated at a concentration of about 1 to about 11, preferably about 3 to about 8 grams/ft of paper substrate.
  • the term support when employed herein, includes a support of paper stock impregnated with the ultraviolet absorbing compound as well as paper in which the ultraviolet radiation absorber is impregnated in a coating, e.g., a polyolefin coating forming a part of the support. It other words, the support is the foundation upon which at least one light sensitive photographic layer containing a dye-forming or color coupler is superimposed.
  • a photographic element of this invention can also be provided with an ultraviolet filter layer over at least one color layer which is subject to the harmful effects of ultraviolet radiation.
  • an ultraviolet filter layer can be placed between the blue and green sensitive layers.
  • concentration of ultraviolet absorbing compound employed in the paper support according to this invention can be varied depending upon the effect desired and the use to which the photographic element is to be put. However, it is generally desirable to employ a concentration of ultraviolet absorbing compound that is at least 50 milligrams, and generally up to about 3 grams per square foot of support to obtain the required average reflectance.
  • the coupler containing emulsions employed in the practice of this invention will ordinarily comprise the emulsion layers of multilayer color films which emulsion layers are customarily differentially sensitized to the primary regions of the visible spectrum and contain coupler compounds producing dye images colored complementary to the sensitivity of the emulsion layers.
  • emulsions sensitized to the red, green and blue regions of the spectrum are superimposed on the support described herein and contain cyan, magenta and yellow color-forming coupler compounds, respectivelyiA yellow filter layer
  • Suitable silver halides include, for example, silver chloride, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide, silver bromoiodide and the like.
  • Emulsions which form a latent image mostly inside the silver halide grains can be employed in the practice of this invention.
  • packet emulsions i.e., emulsions in which a silver halide and a color forming coupler are incorporated in a discrete packet within an emulsion layer with other discrete packets of silver halide containing other color forming couplers, can be employed.
  • the dispersing agent for the photographic silver halide can be gelatin or other hydrophilic material such as colloidal albumin, cellulose derivatives, synthetic resins, such as polyvinyl compounds, acrylamide polymers and the like.
  • the photographic silver halide emulsions employedin this invention are spectrally sensitized or unsensitized.
  • the usual spectral sensitizing dyes used include, for example, the cyanines, merocyanines, complex- (trinuclear)cyanines, complex(trinuclear)merocyanines, styryls, hemicyanines and the like.
  • These dyes can contain the conventional basic nuclei such as triazole, benzotriazole, naphthotriazole, benzoxazole, naphthoxazole, benzoselenazole, benzimidazole, quinoline, etc., or in the case of merocyanine dyes such nuclei as rhodanine, 2-thiohydantoin, oxazoledione, pyrazolone, etc.
  • Such dyes for example, are described in Brooker U.S. Pat. No. 2,185,182 issued Jan. 2, 1940, Brooker U.S. Pat. No. 2,241,237 issued May 6, 1941, Carroll U.S. Pat. No. 2,635,961 issued Apr. 21, 1953, Carroll U.S.
  • the coupler compounds used in the emulsion layers which are coated over the paper support described herein can be any of the well known compounds which combine with the oxidation products of primary aromatic amino silver halide color developing agents to form dyes.
  • Suitable coupler compounds include, for example, the phenolic compounds vof U.S. Pat. Nos. 2,266,452, 2,363,598, 2,589,004, 2,474,293, 2,521,908, and 2,423,730; the pyrazolone compounds of U.S. Pat. Nos. 1,969,479, 2,369,489, 2,600,788, 2,618,641, and 2,51 1,231 and the open chain reactive methylene compounds of U.S. Pat. Nos.
  • the emulsions can contain color coupler forming compounds as described in U.S. Pat. Nos. 2,706,684, 2,455,169, 2,694,703, 2,455,170 and 2,453,661.
  • the couplers can be dispersed in the emulsion layers by means of an oily coupler solvent according to the methods of U.S. Pat. Nos. 2,304,940 and 2,322,027.
  • the couplers contain solubilizing groups such as 1-1 groups which render the compounds soluble in alkali solution
  • the oily coupler solvent can be dispensed with and the coupler can be added to the emulsion from aqueous solution as the alkali metal salt.
  • FIG. 1 is a diagrammatical cross-sectional view of a multicolor element according to the invention.
  • FIG. 1 there is shown a cross-sectional view of a photographic color element of the type which can be advantageously employed in the practice of this invention.
  • the element comprises a support 1 of paper stock containing titanium dioxide dispersed in polyethylene.
  • the element contains a blue sensitive silver halide emulsion layer 2, coated on top of the support.
  • the blue sensitive emulsion can contain a coupler or color forming compound which reacts with the oxidation product of the color developer to produce a yellow image.
  • Coated on top of the blue sensitive layer is a green sensitive silver halide emulsion layer 3 which can contain a coupler or color forming compound capable of coupling with the oxidation product of the color developer to produce a magenta'image.
  • the element shown has an outermost red sensitive silver halide emulsion layer 4 which is coated on top of the green sensitive layer.
  • the red sensitive layer can contain a coupler or color forming compound capable of coupling with the oxidation product of the color developer to produce a cyan image.
  • the support illustrated, if desired, can also contain additional layers (not shown) such as gelatin layers, subbing layers, antihalation layers, and the like.
  • Curve B is interpreted in a similar way by adding 50 and 73 together and dividing by 2 to give a value of 6 percent.
  • Curve C is not a straight line due to the curve in the toe portion of the curve, segments of the curve are treated as separate straight line portions and the values read at increments of about 10 millimicrons. Therefore, the value at 360 is about 5; 370 about 5; 380 about 390 about 35; and 400 about 65. The sum of these values is about 115 which, when divided by 5, gives an average percent reflectance of 23 percent which is less than the specified 25 percent.
  • Curve D which approximates a straight line over the section between 360 and 400 millimicrons provides an average reflectance value by adding about 1 1 and about 63 which, when divided by 2, equals about 37 percent as given in Example 3 for average reflectance of the support at 360-400 millimicrons.
  • the coupler containing silver halide emulsions employed in this invention can also contain such addenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see Baldsiefen U.S. Pat. No. 2,540,085 dated Feb. 6, 1951, Damshroder U.S. Pat. No. 2,597,856 dated May 27, 1952 and Yutzy and Leermakers U.S. Pat. No. 2,597,915 dated May 27,
  • a second support is prepared by coating the above baryta coated paper fiber sheet with titanium dioxide of rutile crystal structure dispersed in gelatin at a coverage of about 300 mg of titanium dioxide and 300 mg of gelatin/ft?
  • the surface of the support has an average reflectance of about 17 percent between 360 and 400 mu.
  • the Magenta Dye Loss and Yellow Dye Loss are measured in the green and blue regions of the spectrum, respectively, using a conventional spectrophotometer or a densitometer through an Example 2
  • the inorganic non-fluorescent ultraviolet radiation absorbing compounds such as the metal oxides, particularly titanium dioxide, are preferred in the practice of this invention. However, the organic non-fluorescent ultraviolet radiation absorbing compounds can be employed.
  • a series of paper supports prepared as described in Example 1 except that organic ultraviolet absorbers are incorporated in the support over the baryta surface, are coated with a series of layers to produce a multilayer photographic element as described in Example 1.
  • One support has an aryl imino thiazolidone of the type described in Sawdey U.S. Pat. No. 2,739,888, dispersed in gelatin, incorporated in the surface of the support and the other support has an aryl benzotriazole of the type described in German Pat. No. 1,166,623 and Belgian Pat. No. 623,419 dispersed in gelatin, incorporated in the surface at a coverage of about 150 mg of the ultraviolet absorber and 300 mg of gelatin/ft?
  • Example 4 Average reflectance Crystal structure of the support (Predominately) at 360-400 my Background stain Rutile 16% 1% Anatase 37% 5%
  • Example 4 nium dioxide/ft?
  • the paper supports having the polyethylene surfaces are electron bombarded as described in British Pat. No. 971,058.
  • Each of these supports is coated with a-series of emulsion layers to provide a multicolor photographic element as described in Example 1.
  • the multicolor photographic elements are exposed and processed as described in Example 1 to produce color dye images. When the processed strips containing the dye images are exposed four days to a Xenon arc the following results are obtained:
  • Polyethylene 26% Increases 58% Polyethylene- 21% Decreases 16% titanium dioxide in Example 3, has the sharpest images.
  • a further increase in sharpness is obtained by including absorbing dyes in the emulsion layers of the photographic element. These dyes absorb in the same region of the spectrum to which the emulsion is sensitive. Suitable absorbing dyes are described in U.S. Pat. Nos. 2,956,879, 2,629,658 and 2,947,628. If desired, a polyethylene layer can be coated on each surface of the paper fiber sheet.
  • the multilayer element coated on the paper supports with the polyethylene surfaces give glossy prints when dried on a hot drum with the back of the paper in contact with the drum surface or when dried by air impingement upon the emulsion side of the element.
  • the processed element on the baryta support of Example 1 does not produce glossy prints when dried in this manner.
  • Example 5 The combination of an ultraviolet filter layer with the particular type of paper support described herein gives a completely unexpected improvement in fading characteristics.
  • two multilayer color coatings are made of the polyethylene-titanium dioxide surface support described in Example 4.
  • the support is coated Ultraviolet absorbing Magenta dye loss interlayer Absent 25% Present 22%
  • Example 6 The concentration of the ultraviolet absorber in the surface of the support is subject to wide variation. However, there must be sufficient ultraviolet absorber present to provide a support having an average reflectance of less than about 25 percent between 360 and 400 m,u.
  • multilayer color coatings are made as described in Example 1 on a series of paper supports having different concentrations of titanium dioxide on the surface. In each case the supports have an average reflectance less than 25 percent between 360 and 400 mu.
  • a further improvement in image dye fading and resistance to background stain is obtained by incorporating in one or more of the emulsion layers a hydroxysubstituted aromatic antistain agent such as an antistain agent described in Loria et al U.S. Pat. No. 2,728,659, Thirtle et al U.S. Pat. 'No. 2,701,197, 2,360,290, 2,991,177 and 2,735,765, e.g., alkyl substituted hydroquinones and alkyl substituted phenols.
  • a hydroxysubstituted aromatic antistain agent such as an antistain agent described in Loria et al U.S. Pat. No. 2,728,659, Thirtle et al U.S. Pat. 'No. 2,701,197, 2,360,290, 2,991,177 and 2,735,765, e.g., alkyl substituted hydroquinones and alkyl substituted phenols.
  • Example 7 Titanium dioxide is preferably employed in the practice of this invention.
  • a paper support having a zinc oxide-polyethylene surface is prepared by coating zinc oxide dispersed in polyethylene on a paper fiber sheet at a coverage of about 0.80 g of polyethylene and 0.33 g of zinc oxide/ft".
  • a second support having a titanium dioxide-polyethylene surface is prepared by coating titanium dioxide dispersed in polyethylene on a paper fiber sheet at a coverage of about 0.70 g of polyethylene and 0.125 g of titanium dioxide/ft Multilayer color coatings are made, using these supports, as described in Example 1.
  • These elements are exposed and processed through a reversal color process of the type described in Example 2 of U.S. Pat. No. 2,944,900. When the processed strips containing the dye images are exposed for 10 days to daylight in a north window, the following results are obtained:
  • a unique photographic element comprising multilayer incorporated coupler emulsions superimposed upon a paper support which element exhibits improved resistance of fading and yellow stain as well as increase in the sharpness of the photographic image.
  • the support employed in practicing this invention can contain the non-fluorescent ultraviolet absorbing compounds described herein as the sole ultraviolet absorber or it can contain additional ultraviolet absorbers, fluorescent or non-fluorescent, so long as the additional addenda do not deleteriously affect the Reflectance characteristics of the support.
  • Suitable additives of this type include, for example, filler type substances such as barium sulfate, silicon dioxide, or other whiteners generally employed in photographic paper supports.
  • a photographic element comprising a silver halide emulsion layer which is sensitive to a visible region of the spectrum and contains an incorporated color forming coupler, said layer being coated upon a surface on a paper support, said surface comprising a polyolefin impregnated with an ultraviolet radiation absorbing compound which does not emit any substantial amount of absorbed radiation in the visible region of the spectrum, said polyolefin surface having an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 millimicrons and at least about 60 percent, at a wavelength in the visible region of the spectrum in the range of about 420 to about 500 mu.
  • a photographic element comprising a silver halide emulsion layer which is sensitive to a visible region of the spectrum and contains an incorporated color forming coupler, said layer being coated upon a surface on a paper support, said surface comprising polyethylene impregnated with an ultraviolet radiation absorbing compound which does not emit any substantial amount of absorbed radiation in the visible region of the spectrum, said polyethylene surface having an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 millimicrons and at least about 60 percent, at a wavelength in the visible region of the spectrum in the range of about 420 to about 500 mu.
  • a photographic element comprising a silver halide emulsion layer which is sensitive to a visible region of the spectrum and contains an incorporated color forming coupler, said layer being coated upon a surface on a paper support, said surface comprising polyethylene impregnated with titanium dioxide, said polyethylene surface having an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 millimicrons and at least about 60 percent, at a wavelength in the visible region of the spectrum in the range of about 420 to about 500 mu.
  • a photographic element of claim 5 in which said titanium dioxide is employed in a concentration of from 50 milligrams to about 3 grams per square foot.
  • a photographic element of claim 1 in which the ultraviolet radiation absorbing compound is a benzotriazole.
  • a photographic element of claim 1 in which the ultraviolet radiation absorbing compound is a thiazolidone.
  • a photographic element comprising:
  • said surface comprising a polyolefin impregnated with titanium dioxide
  • said polyolefin surface having an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 millimicrons and at least about percent, at a wavelength in the visible region of the spectrum in the range of about 420 to about 500 mu.
  • a photographic element comprising a developed and fixed photographic emulsion layer containing a developed dye image subject to fading by the action of ultraviolet radiation, said layer being coated upon a surface on a paper support, said surface comprising a polyolefin impregnated with an ultraviolet radiation absorbing compound, which does not emit any substantial amount of absorbed radiation in the visible region of the spectrum, said polyolefin surface having an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 millimicrons and at least about 60 percent, at a wavelength in the visible region of the spectrum in the range of about 420 to about 500 mu.
  • a photographic element comprising a developed and fixed photographic emulsion layer containing a developed dye image subject to fading by the action of ultraviolet radiation, said layer being coated upon a surface on a paper support, said surface comprising a polyolefin impregnated with titanium dioxide, said polyolefin surface having an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 millimicrons and at least about 60 percent, at a wavelength in the visible region of the spectrum in the range of about 420 to about 500 1..
  • a photographic element comprising a developed and fixed photographic emulsion layer containing a developed dye image subject to fading by the action of ultraviolet radiation, said layer being coated upon a surface on a paper support, said surface comprising polyethylene impregnated with titanium dioxide, said polyethylene surface having an average reflectance of no more than about 25 percent over wavelengths in the ultraviolet region of the spectrum in the range of about 360 to about 400 millimicrons and at least about 60 percent, at a wavelength in the visible region of the spectrum in the range of about 420 to about 500 u.
  • a photographic element comprising a developed and fixed photographic emulsion layer containing a developed dye image subject to fading by the action of ultraviolet radiation, said layer being coated upon a surface on a paper support, said surface comprising polyethylene impregnated with 50 milligrams to about 3 grams per square foot of titanium dioxide predominately rutile form, said polyethylene surface having an average reflectance of no more than about 25 percent the visible region of the spectrum in the range of about over wavelengths in the ultraviolet region of the spec- 420 to about 500 11..

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US00292365A 1965-04-12 1972-09-26 Novel photographic elements Expired - Lifetime US3833380A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP41005904A JPS4927046B1 (da) 1965-04-12 1966-02-03
DE19661547674 DE1547674A1 (de) 1965-04-12 1966-03-14 Photographisches Material
GB15326/66A GB1134197A (en) 1965-04-12 1966-04-06 Colour photographic materials
GB15325/66A GB1134196A (en) 1965-04-12 1966-04-06 Colour photographic materials
FR57028A FR1475329A (fr) 1965-04-12 1966-04-08 Nouveau produit photographique donnant des images en couleurs stables à l'ultraviolet
BE679409D BE679409A (da) 1965-04-12 1966-04-12
US00292365A US3833380A (en) 1965-04-12 1972-09-26 Novel photographic elements

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US44737365A 1965-04-12 1965-04-12
US00292365A US3833380A (en) 1965-04-12 1972-09-26 Novel photographic elements

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US3833380A true US3833380A (en) 1974-09-03

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980478A (en) * 1974-07-05 1976-09-14 Eastman Kodak Company Method of making an ultraviolet light image recording using a visible-light reflective intermediate element
DE3043864A1 (de) * 1980-11-21 1982-07-08 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Weisser fotografischer papiertraeger und verfahren zu seiner herstellung
US4518686A (en) * 1982-06-05 1985-05-21 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds
DE3636790C1 (de) * 1986-10-29 1988-06-01 Schoeller F Jun Gmbh Co Kg Wasserfester fotografischer Papiertraeger
US4894321A (en) * 1986-07-17 1990-01-16 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
US5262286A (en) * 1992-07-31 1993-11-16 Eastman Kodak Company Reduction of yellow stain in photographic prints
US5667950A (en) * 1995-11-14 1997-09-16 Eastman Kodak Company High-contrast photographic elements protected against halation
US5780214A (en) * 1996-05-17 1998-07-14 Agfa-Gevaert Ag Color photographic silver halide material with TiO2 and U.V. absorber
USRE37693E1 (en) * 1982-06-05 2002-05-07 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds
US6391532B1 (en) 2000-04-07 2002-05-21 Eastman Kodak Company Photographic paper containing calcium carbonate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5143777B2 (da) * 1973-03-06 1976-11-24

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US2647835A (en) * 1948-09-29 1953-08-04 Du Pont Light-sensitive photographic element and process of coating
US2698235A (en) * 1950-03-16 1954-12-28 Du Pont Photographic elements

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US2647835A (en) * 1948-09-29 1953-08-04 Du Pont Light-sensitive photographic element and process of coating
US2698235A (en) * 1950-03-16 1954-12-28 Du Pont Photographic elements

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British Titan Products Co., Technical Bulletin No. 2, York, England, 12 18 59, pages 2, 3 and 15. *
British Titan Products Co., Titanium Pigments, The Manfuacture And Uses, 12 18 59, York, England, pages 11, 17, 28 & 29. *
Mellor, J. W., D. Sc., Comprehensive Treatise on Inorganic and Theoretical Chemistry, Longmans, Green & Co., N. N.Y., 1927, Vol. VII, pages 30 38. *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3980478A (en) * 1974-07-05 1976-09-14 Eastman Kodak Company Method of making an ultraviolet light image recording using a visible-light reflective intermediate element
DE3043864A1 (de) * 1980-11-21 1982-07-08 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Weisser fotografischer papiertraeger und verfahren zu seiner herstellung
US4396671A (en) * 1980-11-21 1983-08-02 Felix Schoeller, Jr., Gmbh & Co., K.G. White photographic paper support and method of producing same
US4518686A (en) * 1982-06-05 1985-05-21 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds
USRE37693E1 (en) * 1982-06-05 2002-05-07 Konishiroku Photo Industry Co., Ltd. Color photographic light-sensitive material containing UV filter compounds
US4894321A (en) * 1986-07-17 1990-01-16 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
DE3636790C1 (de) * 1986-10-29 1988-06-01 Schoeller F Jun Gmbh Co Kg Wasserfester fotografischer Papiertraeger
US5262286A (en) * 1992-07-31 1993-11-16 Eastman Kodak Company Reduction of yellow stain in photographic prints
US5667950A (en) * 1995-11-14 1997-09-16 Eastman Kodak Company High-contrast photographic elements protected against halation
US5780214A (en) * 1996-05-17 1998-07-14 Agfa-Gevaert Ag Color photographic silver halide material with TiO2 and U.V. absorber
US6391532B1 (en) 2000-04-07 2002-05-21 Eastman Kodak Company Photographic paper containing calcium carbonate

Also Published As

Publication number Publication date
GB1134197A (en) 1968-11-20
BE679409A (da) 1966-09-16
JPS4927046B1 (da) 1974-07-15
DE1547674A1 (de) 1969-12-04
GB1134196A (en) 1968-11-20

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