US3833380A

US3833380A - Novel photographic elements

Info

Publication number: US3833380A
Application number: US00292365A
Authority: US
Inventors: I Crawford; F Hartman
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1965-04-12
Filing date: 1972-09-26
Publication date: 1974-09-03
Anticipated expiration: 1991-09-03
Also published as: GB1134196A; JPS4927046B1; BE679409A; GB1134197A; DE1547674A1

Abstract

Color photographic elements having improved resistance to ultraviolet radiation, improved sharpness and low propensity to stain in the non-image areas comprise a paper support having coated thereon a silver halide emulsion layer which is sensitive to a visible region of the spectrum, which contains an incorporated color forming coupler. The paper support contains a non-fluorescing ultraviolet radiation absorbing compound 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 m Mu .

Description

United States Patent [191 Crawford et al.

[451 Sept. 3, 1974 NOVEL PHOTOGRAPHIC ELEMENTS [75] Inventors: Irvin H. Crawford; Francis M.

Hartman, both of Rochester, NY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: Sept. 26, 1972 [21] App]. No.: 292,365

Related US. Application Data [63] Continuation-in-part of Ser. No. 447,373, April 12,

1965, abandoned.

[52] US. Cl. 96/74, 96/84 R, 96/84 UV, 96/85, 96/87 R [51] Int. Cl G03c 1/84, G030 1/76 [58] Field of Search 117/333; 96/84 R, 84 UV, 96/85, 74

[56] References Cited UNITED STATES PATENTS 2,647,835 8/1953 Weaver 96/84 R 2,698,235 12/1954 Swindells 96/87 OTHER PUBLICATIONS British Titan Products Co., Titanium Pigments, The Manfuacture And Uses, 12-18-59, York, England,

PERCENT REF LE CTANCE N (u 0 Q WAVELENGTH IN MILLIMICRONS pages 11, 17, 28 & 29.

British Titan Products Co., Technical Bulletin No. 2, York, England, 12-1859,

pages

2, 3 and 15.

Mellor, J. W., D. Sc., Comprehensive Treatise on Inorganic and Theoretical Chemistry, Longmans, Green & Co., N. N.Y., 1927, Vol. VII, pages 30-38.

Primary Examiner-Ronald H. Smith Assistant Examiner-Alfonso T. Suro Pico Attorney, Agent, or FirmMr. Henry E. Byers [5 7] 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,

18 Claims, 2 Drawing Figures FOR CYAN IMAGE SENSITIVE EMULSION FOR MAGENTA IMAGE SENSITIVE EMULSION COUPLER FOR YELLOW IMAGE BLUE-SENSITIVE EMULSION TITANIUM DIOXIDE POLYETHYLENE PAPER Pmmsnsrr 31914 PERCENT REFLECTANCE. U]

/COUPL ER FOR CYAN IMAGE RED-SENSITIVE EMULSION COUPLER FOR MAGENTA IMAGE GREEN- SENSITIVE EMULSION r I :COUPLER FOR YELLOW IMAGE,

BLUE-SENSITIVE EMULSION TITANIUM DIOXIDE K POLYETHYLENE PAPER WAVELENGTH IN MILLIMICRONS IRVIN H- CRAWFORD FRANCIS M HARTMAN INVENTORS ATTORNEYS NOVEL PHOTOGRAPHIC ELEMENTS This application is a continuation-in-part of U.S. Pat. Application Ser. No. 447,373 filed Apr. 12, 1965 now abandoned.

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.

The action of ultraviolet radiation on finished color photographs is particularly noticeable in positive prints on paper supports, since this type of print is frequently viewed in daylight. It is also desirable for color prints on paper supports to have sharp images and in many cases to have glossy surfaces. These glossy surfaces are usually achieved by drying the processed print in faceto-face contact with the surface of a hot drum which requires the emulsion surface to be highly hardened to prevent sticking or melting of the emulsion which would result in surface mottle. It is difficult, however, to highly harden photographic elements containing dye-forming couplers since hardeners tend to react with the couplers. It is evident, therefore, that a photographic element in which the aforementioned undesirable characteristics are improved or eliminated would enhance the state of the art.

Accordingly, it is an object of this invention to provide a novel photographic element.

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.

In accordance with this invention it has'been found that 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.

It is well known that ultraviolet radiation absorbing layers can be placed over dye images to screen out ultraviolet radiation to reduce dye fading. 'However, it could not have been predicted that a support, as described herein; could improve the resistance to fading of multicolor layers coated thereon since the ultraviolet absorber in the support is under, rather than over, the photographic color layer or layers. Furthermore, it would have been expected that such a support would add no significant improvement to the dye stability of an incorporated coupler containing emulsion layer lying between it and an ultraviolet filter layer. However, as shown in Example 5 which follows, there is a significant improvement achieved by using an ultraviolet filter layer in combination with the support having the reflectance characteristics described herein.

The incorporation of the ultraviolet radiation absorbing compounds into the support, as in this invention, rather than into a photographic emulsion layer or layers between photographic emulsions, offers several significant advantages. For example, the incorporation of an ultraviolet absorbing compound into a photographic emulsion layer can lead to contamination and desensitization. Furthermore, when oilsoluble ultraviolet radiation absorbers are 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,

preferably about 380 to about 400 mu. 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. For example, a standard recording spectrophotometer can be employed to measure Reflectance at different wavelengths over the range of about 360 to about 400 mp. Typically 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.

When averaged, 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. Various average particle size ranges may be used provided the desired reflectance values are obtained. For instance, 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. However, 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.

Good results are also obtained in practicing this invention with organic non-fluorescing ultraviolet absorbing bensotriazoles of the type disclosed in Belgian Pat. No. 623,419 and German Pat. No.. 1,166,623. These pounds. have th rmula:

wherein 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, pentadecoxy, octadecoxy, carhomcthoxy, carbobutoxy, carbohexoxy, carbododecoxy, carbopentadecoxy, etc., an aryl group, such as phenyl, 4-methylphenyl, 4-ethoxyphenyl, 2- hexoxyphenyl, 3-hexoxyphenyl, etc., an aryloxy group, such as phenoxy, 4-methylphenoxy, 2-propylphenoxy, 3-amylphenoxy, etc., such that at least one of the groups, R, R and R shall contain at least five carbon atoms, and the total numberof carbon atoms represented in R R is at least 8. 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.

Another class of organic ultraviolet radiation absorbing thiazolidones which can be used with advantage in this invention are disclosed in US. Pat. No. 2,739,888 which issued Mar. 27, 1956. These compounds have the formula:

wherein 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 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. 2,4-dicarboxymethylphenyl (and alkali metal salts thereof, e.g., sodium, 'potassium, etc.), o-, mand pcarboxyphenyl (and alkali metal salts thereof, e.g., sodium, potassium, etc.), 3-(3sulfobenzamido)phenyl (and alkali metal salts thereof, e.g., sodium, potassium, etc.), o-carbobutoxyphenyl, diamylphenoxyacetoxyphenyl, etc., or an aralkyl group (e.g., benzyl, ,B-phenylethyl, a-phenylethyl, etc.), R represents an aryl group (e.g., those aryl groups defined above wherein R is an aryl group), and Q represents a divalent, non-metallic atom (e.g., oxygen, sulfur, etc.) or imino radical (e.g., imino, phenylimino, o-, m-. and pchlorophenylimino, benzylimino, B-phenylethylimino, a-phenylethylimino, o-, mand p-tolylimino, o-, mand p-ethylphenylimino, p-amylphenylimino, o-, mand pethoxyphenylimino, 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. For example, the paper forming the support can be impregnated with the ultraviolet absorbing compound during its manufacture. However, it is generally more desirable to dissolve or disperse the ultraviolet absorbing compound in a solvent medium together with 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, and coat the resulting mixture on the emulsion side of the paper. This results in a paper support containing a vehicle, e.g., polyethylene impregnated with the ultraviolet absorber. Particularly advantageous results are obtained with inorganic ultraviolet absorbing radiation com-' pounds such as titanium dioxide where polyolefins such as polyethylene, polypropylene, propylene-butene copolymers, and the like, are used as binding agents for the ultraviolet radiation absorber. In this case, 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. It should be understood that 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.

In addition to the ultraviolet radiation absorbing compound contained in the support, 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. For example, in a multilayer material comprising three differentially sensitized layers, the red sensitive layer being adjacent to the support, the green sensitive layer being superimposed on the red sensitive layer and the blue sensitive layer being outermost with respect to the other light sensitive layers; the ultraviolet filter layer can be placed between the blue and green sensitive layers. The 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. In a typical color film, 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 such as 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. Furthermore, 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. Pat. No. 2,652,330 issued Sept. 15, 1953, Heseltine and Brooker U.S. Pat. No. 2,666,761 issued Jan. 19, l954-and Carroll and Jones U.S. Pat. No. 2,704,715 issued Mar. 22, 1955.

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. 2,298,443, 2,652,329, 2,407,210 and 2,271,238. Likewise, 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. However, if as may be the case, 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.

This invention can be further illustrated by reference to the accompanying drawings in which:

FIG. 1 is a diagrammatical cross-sectional view of a multicolor element according to the invention;

FIG. 2 is a set of reflectance curves for four supports containing two different physical forms of titanium dioxide, barium sulfate or zinc oxide.

in 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.

FIG. 2 gives the reflectance curves for four paper supports containing (A) titanium dioxide predominately of the rutile crystal structure, as shown in Examples l and 3, (B) barium sulfate, as shown in Example 1, (C) zinc oxide, as shown in Example 7 and (D) titanium dioxide, predominately of the anatase crystal structure, as shown in Example 3.

In Curve A, the percent reflectance value of about 7 at the 360 line and about 38 at the 400 line can be added together and divided by 2 to give a value of about 23 percent.

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.

Since 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,

1952), various palladium compounds such as palladium chloride (Baldsiefen et al U.S. Pat. No. 2,540,086 dated Feb. 6, 1951), potassium chloropalladate (Stauffer and Smith US. Pat. No. 2,598,079 dated May 5 27, 1952) etc., or mixtures of such sensitizers, antifoggants, such as ammonium chloroplatinate (Trivelli and Smith U.S. Pat. No. 2,566,245 dated Aug. 28, 1951), ammonium chloroplatinite (Trivelli and Smith U.S. Pat. No. 2,566,263 dated Aug. 28, 1951), benzotriazole, nitrobenzimidazole, S-nitroindazole, benzidine, mercaptans, etc. (see Mees The Theory of the Photographic Process, MacMillian Pub. 1942, page 460) or mixtures thereof, hardeners such as aldehyde hardeners, aziridine-hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxystarch or oxy plant gums and other types of hardeners for gelatin and hydrophilic colloids. Dispersing agents for color couplers, such as those set forth in Jelley and Vittum U.S. Pat. No. 2,322,027 dated June 15, 1943 and Marines and Godowsky U.S. Pat. No. 2,304,940 dated Dec. 15, 1942 can also beemployed in the above described emulsions. v

The following examples are included for a further understanding of the invention.

Example 1 As already indicated, a paper support containing a non-fluorescent ultraviolet absorbing compound and having the required reflectance provides a multicolor photographic element exhibiting improved resistance to image dye fading. Furthermore, compounds such as barium sulfate which have been used as fillers to whiten photographic paper do not impart the required reflectance to the support. To illustrate, a paper support is prepared by coating a paper fiber sheet with a baryta layer (barium sulfate, average particle size about 2 microns in diameter, dispersed in gelatin and coated at a coverage of about 3 g. of barium sulfate/ft? The baryta surface of the support has an average Reflectance of 40 about 63 percent between 360 and 400 mm. 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.

Eachof the above supports is coated with a series of photographic layers to produce a multicolor photographic element comprising thesupport having coated thereon in the following order:

1. a blue sensitive gelatino silver chlorobromide emulsion containing an open chain coupler for the yellow image, such as' one of the yellow couplers described in McCrossen et a] U.S. Pat. No. 2,875,057, e.g., 4-benzoylacetamido-3-methoxy- (2,4'-di-tert-amylphenoxy )-acetanilide;

2. a gelatin interlayer;

3. a green sensitive gelatino silver chlorobromide emulsion containing a pyrazolone coupler for the magenta image, such as one of the pyrazolone couplers described in Loria et al U.S. Pat. No. 2,600,788, e.g., l-(2,5-dichlorophenyl)3[3"- (2,4"'-di-tert-amyl-phenoxyacetamido)benzamido]-5-pyrazolone;

4. a gelatin interlayer;

5. a red sensitive gelatino silver chlorobromide emulsion containing a phenolic coupler for the cyan image, such as one of the phenolic couplers described four days to a Xenon arc, the following results are obin Fierke US. Pat. No 2,801,171, e.g., rai d;

Average rcllccluncc Back- Paper Support of the Support Magenta Ycllow ground Containing at 360-400 mp. Dye Loss Dye Loss Stain Baryta 63% 36% 17% Aryl imino thia- 6% 26% 12% 2% zolidone Aryl benzotriazole 6% 28% 1 1% 2% 6-{ {a-{4-[a-(2 ,4-di-tert-amylph enoxy)-butyr- Example .3

amido]phenoxy}-acetamido}}2,4-dichloro-3- methylphenol;

6. a gelatin protective overcoat.

The multicolor photographic elements are exposed and processed as described in Example 1 of US. Pat.-

No. 2,956,879 to produce color dye images. When the processed strips containing the dye images are exposed to ultraviolet radiation, e.g., four days to a Xenon arc, the following results are obtained:

Paper Support Magenta Yellow Background Containing Dye Loss Dye Loss Stain Baryta 36.7% 17% 5% Titanium dioxide 28.6% 13% 1% The Magenta Dye Loss and Yellow Dye Loss, as reported herein, 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. Thus, 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? These supports have the Reflectance characteristics indicated in the following table. The multicolor photographic elements are exposed and processed as described in Example 1 of US. Pat. No. 2,956,879 to produce color images. When the processed strips containing the dye images are exposed for As previously pointed out, not all physical forms of titanium dioxide can be employed in the practice of this invention to give optimum results. To illustrate, two paper supports prepared as described in Example 1 with titanium dioxide having different crystal structures. Titanium dioxide containing about 100 percent by weight rutile on one support and containing about 85 percent by weight anatase in the coating on the other support are coated with a series of layers to produce a multilayer photo graphic element. When these elements are exposed, processed and tested as described in Example 1, the following characteristics are observed:

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:

Average reflectance Paper support Magenta Background of the support containing dye loss stain at 360-400 mp.

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.

In addition, 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.

Similar improvements are obtained when paper supports having an average reflectance of less than about 25 percent between 360 and 400 mu are coated with single layer mixed packet multicolor elements of the type described in U.S. Pat. Nos. 2,168,182, 2,698,765, 2,698,766 and 2,965,484.

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. To illustrate, 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. To illustrate, 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. When these multicolor elements are exposed, processed and tested as described in Example 1, the following results are obtained:

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.

Example 7 Titanium dioxide is preferably employed in the practice of this invention. However, other inorganic nonfluorescent compounds can be employed. Thus, 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:

Average reflectance The photographic coating on the titanium dioxide surface exhibits sharper images than the coating on the zinc oxide surface.

Thus, by the practice of this invention there is provided 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.

Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected without departing from the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. 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.

2. 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.

3. A photographic element of claim 1 in which said silver halide emulsion has coated thereon an ultraviolet radiation absorbing compound.

4. A photographic element of claim 1 in which said silver halide emulsion layer contains a hydroxysubstituted aromatic antistain agent.

5. 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.

6. A photographic element of claim in which said titanium dioxide is predominately rutile titanium dioxide.

7. 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.

8. A photographic element of claim 1 in which the ultraviolet radiation absorbing compound is a benzotriazole.

9. A photographic element of claim 1 in which the ultraviolet radiation absorbing compound is a thiazolidone.

10. A photographic element of claim 1 in which said coupler is an incorporated pyrazolone magenta coupler and said visible region of the spectrum is the green region.

11. A photographic element comprising:

a. a silver halide emulsion layer having a blue sensitive layer containing an incorporated yellow forming coupler,

b. a silver halide emulsion layer containing a red sensitive layer containing an incorporated cyan forming coupler, and

c. a green sensitive layer containing a magenta forming coupler,

d. said layers being coated upon a surface on a paper support,

e. said surface comprising a polyolefin impregnated with titanium dioxide,

f. 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.

12. A photographic element of claim 11 in which said titanium dioxide is predominately rutile titanium dioxide.

13. A photographic element of claim 11 in which said polyolefin is polyethylene.

14. 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.

15. 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..

16. 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.

17. A photographic element of claim 16 in which said titanium dioxide is predominately rutile titantium dioxide.

18. 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..

trum in the range of about 360 to about 400 millimicrons and at least about 60 percent, at a wavelength in UNITED STATES PATENT AND TRADEMARK OFFTICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,833,380 i b DATED September 3, 197

INVENTOR( Irvin H. Crawford and Francis M. Hartman It is certified that error appears in the aboveiden tified patent and that said Letters Patent are hereby corrected as shown below:

Column l, line 1 r, "triazole, chloro- 2(2'hydroxy-3'- tert-butyl-5'-cyclo-" should read triazole, 5-chloroi 2-(2'hydroxy-3'-tertbutyl5' -cyclo I Column 6, line 2, "low" should read --yellow--.

Column 12, line A l, "of fading should read ---to fading-5 line LL14, after "as well as" insert -an--.

Column 1h, line M5, "500 1" should read ---5oo milp line 57, "500 1" should read ---5OO mp1---.

Column 16, line 2, "500 )1" should read --5OO rrr,u. g

Signed and Scaled this twenty-first Day of October 1975 [SEAL] Attest:

RUTH c. MASON c. MARSHALL DANN Arresting Officer Commissioner nj'Parents and Trademarks

Claims

2. 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 m Mu .
3. A photographic element of claim 1 in which said silver halide emulsion has coated thereon an ultraviolet radiation absorbing compound.
4. A photographic element of claim 1 in which said silver halide emulsion layer contains a hydroxy-substituted aromatic antistain agent.
5. 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 m Mu .
6. A photographic element of claim 5 in which said titanium dioxide is predominately rutile titanium dioxide.
7. 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.
8. A photographic element of claim 1 in which the ultraviolet radiation absorbing compound is a benzotriazole.
9. A photographic element of claim 1 in which the ultraviolet radiation absorbing compound is a thiazolidone.
10. A photographic element of claim 1 in which said coupler is an incorporated pyrazolone magenta coupler and said visible region of the spectrum is the green region.
11. A photographic element comprising: a. a silver halide emulsion layer having a blue sensitive layer containing an incorporated yellow forming coupler, b. a silver halide emulsion layer containing a red sensitive layer containing an incorporated cyan forming coupler, and c. a green sensitive layer containing a magenta forming coupler, d. said layers being coated upon a surface on a paper support, e. said surface comprising a polyolefin impregnated with titanium dioxide, f. 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 m Mu .
12. A photographic element of claim 11 in which said titanium dioxide is predominately rutile titanium dioxide.
13. A photographic element of claim 11 in which said polyolefin is polyethylene.
14. 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 m Mu .
15. 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 Mu .
16. 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 Mu .
17. A photographic element of claim 16 in which said titanium dioxide is predominately rutile titantium dioxide.
18. 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 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 .