US3743531A - Photographic product - Google Patents

Abstract

PHOTOGRAPHIC ELEMENTS COMPRISES A SUPPORT HAVING THEREON, A LAYER CONTAINING BARIUM SULFATE, POLYVINYL ALCOHOL AND AN OPTICAL BRIGHTENER SUCH AS A STILBRENE, ANTHRACENE, TERPHENY; TETRAPHENYLBUTADIENE OR QUINOXALINE. PARTICULARLY USEFUL BRIGHTENERS ARE STILBENE BRIGHTENERS. THE SUPPORT CAN BE COMPRISED OF PAPER OR PAPER HAVING THE BARYTA LAYER OVERCOATED WITH POLYOLEFIN COATING SUCH AS POLYETHYLENE. THESE ELEMENTS CAN BE USED AS SUPPORTS FOR RECEIVING LAYERS FOR USE IN THE CHEMICAL TRANSFER SYSTEM AND ALSO AS A SUPPORT FOR SILVER HALIDE EMULSION OR SIMILAR LIGHT SENSITIVE COATINGS.

Description

United States Patent O PHOTOGRAPHIC PRODUCT Gerald Louis Ducharrne, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, NY. No Drawing. Filed July 19, 1971, Ser. No. 164,050

Int. Cl. B41111 1/18; C23C; D21k I U.S. Cl. 117-76 P 16 Claims ABSTRACT OF THE DISCLOSURE Photographic elements comprise a support having thereon, a layer containing barium sulfate, polyvinyl alcohol and an optical brightener such as a stilbene, anthracene, terphenyl, tetraphenylbutadiene or quinoxaline. Particularly useful brighteners are stilbene brighteners. The support can be comprised of paper or paper having the baryta layer overcoated with polyolefin coating such as polyethylene. These elements can be used as supports for receiving layers for use in the chemical transfer system and also as a support for silver halide emulsions or similar light sensitive coatings.

FIELD OF INVENTION This invention relates to novel photographic elements. More particularly, this invention relates to photographic supports having a stable brightened barium sulfate layer thereon in order to provide improved supports for photographic prints and to a coating composition comprising a stable brightening agent.

BACKGROUND OF THE INVENTION The highlight areas of photographic color prints and other products, such as, fibrous or plastic articles are often made to look whiter by incorporating optical brightening agents. These brightening agents fluoresce under radiation with ultraviolet light, emitting visible light, usually bluish in hue thus enhancing the whiteness of the object. Such products also frequently contain ultraviolet sensitive ingredients such as dyes, organic polymers, etc., which require protection from irradiation in the ultraviolet re- HO-CHr- C H gion, especially from 360-400 mu. Brighteners are inherently ultraviolet absorbers and depend on this characteristic for the energy required to fluoresce in the visible region of the spectrum. Most of the known brightening agents are decomposed by prolonged exposure to ultraviolet radiation, and thus lose their ability to fluoresce and serve as brightening agents. Brighteners containing substituted vinylene groups, e.g., stilbenes, styrenes and vinylenes are well known and are efiicient brighteners which absorb and fluoresce in desirable regions of the spectrum. Other known brighteners include those that contain at least one heterocyclic five-membered or sixmembered ring, for example, an oxazole, a thiazole, an imidazole, a triazole, a pyrazole, a furan, a thiophene, or a coumarin ring.

Photographic paper conventionally has a layer thereon containing barium sulfate known as baryta or blanc fixed in a colloid binder such as gelatin. The paper can have a layer of gelatin or similar colloid coated over the baryta layer containing a silver precipitating agent such as noble metal nuclei for use in a diffusion transfer process. The

Patented July 3, 1973 brightener can be incorporated in the baryta layer under the layer containing the image.

It has been particularly desirable to incorporate a water soluble brightener in the baryta layer since this provides a relatively easy method of providing a coating and avoids the problem of dispersing a water insoluble material in a hydrophilic colloid containing a barium sulfate pigment. A coating of this type is described in U.S. Pat. 3,269,840, issued to Pattyn et al. Aug. 30, 1966, in which a baryta layer is provided which employs gelatin as the essential binding agent and has incorporated in the coating a watersoluble brightener and a water-soluble vinylpolymer, in order to avoid the problem of rinsing or bleeding of the brightening agents out of the layers to which they are added. However, the problem of stability of the brightener in the baryta layer remains. Therefore, it has been desirable to provide a baryta layer containing a water soluble brightening agent which would be more stable and which would also be essentially free from leaching or bleeding from the layer.

One object of this invention is to provide a coating comprising baryta, an optical brightener and polyvinyl alcohol which when coated on a support has improved fading resistance to light, humidity and temperature. Another object of this invention is to provide a baryta layer which can be overcoated with a relatively clear polymeric layer which can be used to provide an improved photographic print. A further object is to provide a brightened photographic print. A still further object is to provide a stable brightened photographic print produced by a diffusion transfer process.

SUMMARY OF THE INVENTION It has now been found that the above objects are attained by preparing a coating composition by dispersing the baryta and brightener in polyvinyl alcohol as a binder substantially free from a protein such as gelatin. In a preferred embodiment, a paper base is employed which has coated thereon a baryta formulation containing poly vinyl alcohol and a brightener having the following chemical structure:

SAQNa SOaNa In still another preferred embodiment, the baryta layer is overcoated with a layer of polyethylene and the resulting element used as a receiving sheet in a diffusion transfer process. A product having a brightened baryta layer of this invention with a polyethylene overcoat can also be used as a photographic support by coating thereon a lightsensitive coating such as a silver halide emulsion.

A receiving element as described above is used advantageously to provide a photographic print having an image in a receiving layer on a support by the photographic silver salt diffusion transfer process or color diffusion transfer process.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Any suitable support may be used on which to place the baryta layer containing polyvinyl alcohol and brightener. However, paper is our preferred support although it-will be understood that supports including polymeric materials such as polyesters, cellulose esters, and the like, glass, metal, etc., may all be used.

Suitable paper supports include any of the conventional paper supports including those prepared from cotton, linen, and wood (sulfate and sulfite pulped). Such supports are typically about 5-60 pounds per 1,000 square foot. A particularly desirable paper base is that having a high alpha cellulose content. Advantageously the paper base can have wet strength imparted by the incorporation of wet strength resin. If the coating to be applied is not adversely effected by formaldehyde, the wet strength resin can be for example melamine formaldehyde or urea formaldehyde resin. However, where a coating such as a photographic emulsion adversely effected by formaldehyde is used, it is desirable to incorporate a non-aldehydic wet strength resin in the paper, for example, a cationic thermosetting polyamide-epichlorohydrin resin as described in U.S. Pat. 2,926,154, available commercially under the name Kymene.

The polyvinyl alcohol is substantially completely deacetlylated polyvinyl acetate containing at least about 98% polyvinyl alcohol.

In addition to the barium sulfate dispersed in the polyvinyl alcohol coating, there may also be present a blue pigment or dye or a mixture of blue pigment and magenta pigment, which further improves the quality of the photographic prints obtained. The amount of tint or colored pigment when used is kept minor ordinarily being no more than 1% by weight based on the coating composition, preferably a fraction of 1%. The pigments used should be non-wandering and compatible with a silver halide photographic emulsion so as not to effect the sensitivity of the emulsion and should not wander from the baryta layer either to the emulsion layer or to the support. Also these pigments should be light stable and if an extrusion polymeric coating is used, the brightened layer should exhibit light and heat stability.

Some pigments which are examples of pigments of this type which are useful in barium sulfate-polyvinyl alcohol coatings in accordance with the invention are:

BLUE PIGMENTS Ultra-Marine Blue EBEX Shepard Cobalt Blue #3 Manufacturer: Shepard Co.

Composition: Stoichiometric mixture of cobalt oxide and aluminum hydrate.

Description: Pigment Blue 28.

Cobalt Aluminated Blue V-3285 Manufacturer: Ferro Colors Corp.

Composition: Mixture of cobalt oxide and aluminum oxide.

Fastusol Blue Dye LFFRL Manufacturer: General Aniline and Film El. Direct Blue #108 Color Index 51320 MAGENTA PIGMENTS Raspberry V-6260 or Raspberry V-8295 Manufacturer: Fero Colors Corp. Composition: Mixture of cobalt oxide and phosphorus oxide.

Hostaperm Pink E-13-7000 Manufacturer: American-Hocchst Co. Composition: Quinacridone Type Red. Description: Pigment Red-122.

In a typical coating composition the blue dye or pigment can comprise from about 0.001 to about 0.010%, by weight, of the baryta coating composition and the magenta pigment can comprise from about 0.1 to about 1.0%, by weight, of the baryta coating composition.

The barium sulfate may be naturally occuring or syn thetic. Synthetic barium sulfate, sometimes known as blanc fixe, is typically prepared by the action of barium chloride on aluminum sulfate. The average particle size is generally below about 1.5 microns and preferably between about 0.25 and 1.0 micron.

Barium sulfate may be coated in an amount of about 2.5 to about 6.0 grams per square foot and polyvinyl alcohol about 5 to 20% by weight of the baryta layer.

The term optical brightening agent as used herein is intended to include those colorless or substantially colorless organic compounds which absorb ultraviolet light from sunlight or fluorescent light and emit the absorbed energy as visible blue or blue-green light. Thus, such compounds contain fluorescent chromophores in contradistinction to dyes, which contain colored chromophores. Water soluble indicates a solubility of at least 1 part in 10 parts of water at 20 C.

Suitable optical brightening agents include, for example, those brighteners selected from the following general classes of organic compounds: triazine-stilbenes, coumarins, anthracenes, terphenyls, tetraphenylbutadienes, quinoxalines, and the like. Triazine stilbene compounds which are conventional for use as fluorescent agents and as optical brightening agents, are described in U.S. Pat. 2,933,390 and have the following general formula:

wherein R R R and R each represent a hydrogen atom, hydroxyl, aryloxy (e.g., phenoxy, o toloxy, p-sulfophenoxy, etc.), alkoxy (e.g., methoxy, ethoxy, etc.) a halogen atom (e.g., chlorine, bromine, etc.), a heterocyclic radical (e.g., morpholinyl, piperidyl, etc.), an alkylthio group (e.g., methylthio, ethylthio, etc.), an arylthio group (e.g., phenylthio, tolylthio, etc.), a heterocyclylthio group (e.g., benzothiazylthio, etc.), an amino group, an alkylamino group (e.g., methylamino, ethylamino, propylamino, dimethylamino, diethylamino, d0- decylamino, cyclohexylamino, fi-hydroxyethylamino, difi-hydroxyethylamino, 3-sulfoethylamino, etc.), an arylamino group (e.g., anilino, o-, 111-, and p-sulfoanilino, o-, m-, and p-chloroanilino, 0-, 111-, and p-carboxyanilino, hydroxyanilino, sulfonaphthylamino, o-, m-, and p-aminoanilino, p-acetamidoanilino, etc.), etc., and R and R each represent a hydrogen atom or a water-solubilizing group, such as sulfo, carboxyl, etc. .(as well as alkali metal or amine salts of such groups).

Examples of these compounds include 4,4'-bis[4-(3'- sulfoanilino)-6-amino-s-triazin 2 ylamino] stilbene- 2,2'-disulfonic acid; 4,4 bis [4,6 di(;3 hydroxyethylamino)-s-triazin-2-ylamino]-stilbene-2,2' disulfonic acid, and the like.

Compounds of the above type are also described in one or more of the following patents: U.S. 2,171,427; 2,473,- 475; 2,595,030; 2,660,578; British Pats. 595,065; 623,849; 624,051; 624,052; 678,291; 681,642; 705,406. Additionally, compounds suitable for use in the reception element of the present invention are commercially available under such trade names as Tinopa [SP, WR, SFG, .BV277, 2B, GS, NG], Leucophor B. Calcofluor White MR, Blamefor SC, Hitamine [BSP, N, 801., 6T6], and the like.

Suitable coumarin optical brightening agents are, for

example, the 3-phenyl-7-ureidocouma-rins described in British Pat. 786,234 and which have the general formula:

104:, R1-CO--NH \0/ 0 wherein R represents NH or an organic primary or secondary amine, such as, for example, methylamino, diethylamino, etc., and R represents a phenyl group, such as, for example, phenylthio, anilino, etc. or a halogen.

Examples of these compounds include: N -[3-p-methyl phenyl-coumarinyl-(7)]-urea; N-propyl-N -[3-phenylcoumarinyl (7)]urea; N-3-sulphoethyl-N -3-phenyl coumarinyl-(7)-urea and the like. These compounds are commercially available under such trade names as Tinopal SFG (Geigy), etc.

Similarly, anthracenes, terphenyls, tetraphenylbutadienes and quinoxalines are conventional optical brightening agents and are well known in the art. Preferably the brightener is water soluble.

The concentration of the optical brightening agent may be varied over a wide range. Suitable concentrations include those in the range of between about 0.25 and about 10 milligrams of the optical brightening agent per square foot of reception element surface area, preferably between about 1.0 and about 5.0 milligrams per square foot. Higher concentrations of the brightening agent may be employed, but it is both unnecessary and impractical to do so.

The brightening compositions of this invention are advantageously used in image-receiving elements that are used to receive diffusion transfer images during the diffusion transfer process. In these processes, a light-sensitive diffusion transfer element containing a light-image exposed silver halide emulsion is processed with the exposed emulsion layer in contact with the silver precipitating layer of an image-receiving element in the presence of a silver halide developing agent, such as hydroquinone, 1- phenyl 3 pyrazolidone, p-methylaminophenol, etc., a silver halide solvent or complexing agent, such as an alkali metal thiosulfate, ammonium thiosulfate, an alkali metal thiocyanate, ammonium thiocyanate, etc. In a particularly useful process, a thickening agent, such as carboxymethylcellulose, carboxyethylcellulose, etc. is used.

During development, undeveloped silver halide forms a complex with the complexing agent which diffuses in an imagewise manner to the silver-precipitating layer on the image-receiving element where a silver image is precipitated from the silver halide complex. In an integral element, a silver halide emulsion coated over a silver precipitating layer is removed such as by washing, to disclose the transferred image.

In a color diffusion transfer process, an image-exposed light-sensitive silver halide color diffusion transfer element is contacted with the receiving layer of an imagereceiving element in the presence of a developer solution which causes the release of a diifusible dye image that transfers to the mordanted receiving layer. The desired dye image remains in the receiving layer when the receiving element is separated from the developed diffusion transfer element. The diffusible dye image is formed from an incorporated non-diffusible coupler that couples with an imagewise pattern of oxidized primary aromatic amine color developing agent, produced by development of lightexposed silver halide. In another system, the dye image is formed from incorporated dye developing agents, such as hydroquinone derivatives that contain a chromophore as a substituent; the hydroquinone form of these compounds forms in the alkaline developer solution a ditfusible dye while the dye developer that is oxidized to the quinone form (when it develops light-exposed silver halide to silver) is insoluble and does not diffuse to the image-receiving layer.

The image-receiving elements of this invention usually comprise a support as described previously that has been coated in succession with (1) a baryta layer containing the brightening composition, and (2) an image-receiving layer for a silver image comprising a silver precipitating agent or an image-receiving layer for a dye image comprising any suitable hydrophilic colloids containing a basic mordant for mordanting acid solubilized diifusible dyes.

Usually it is advantageous to have a hydrophobic resin layer between the baryta layer and the image-receiving layer. Hydrophobic resins that are advantageously used include poly(ethylene terephthalate), polyethylene, polypropylene, poly(3-methylbutene-1), poly(octene-l), poly- (decene-l), polyamides, polyacetate, polycarbonates, cellulose triacetate, cellulose acetate butyrate, ethyl cellulose, etc.; preferably the hydrophobic resin layer is treated with corona discharge techniques just prior to coating the first hydrophilic colloid layer over the resin as described in U.S. patents such as 3,220,842, 2,864,755, 2,864,756, etc.

Any suitable silver precipitant is advantageously used in the receiving layer. As examples of suitable silver precipitating agents and of image-receiving elements containing such silver precipitating agents, reference may be made to U.S. Pat. Nos. 2,698,237, 2,698,238 and 2,698,245, issued to Edwin H. Land on Dec. 28, 1954; {U.S. Pat. No. 2,774,667, issued to Edwin H. Land and Meroe M. Morse on Dec. 18, 1956, U.S. Pat. No. 2,823,122, issued to Edwin H. Land on Feb. 11, 1958, U.S. Pat. No. 3,396,018, issued to Beavers et al., Aug. 6, 1968 and also U.S. Pat. 3,369,901, issued to Fogg et al., Feb. 20, 1968. The noble metals, silver, gold, platinium, palladium, etc. in the collodidal form are particularly useful.

Noble metal nuclei are particularly active and useful when formed by reducing a noble metal salt using a borohydride or hypophosphite in the presence of a colloid. The metal nuclei are prepared in the presence of a colloid such as gelatin and coated on the receiving element. The coating composition generally contains not only nuclei, but also reaction products which are obtained from reducing the metal salt.

The amount of colloid used in preparing the above active noble metal nuclei can be varied depending upon the particular colloid, reducing agent, ratio of proportions, etc. Typically, about 0.5% to about 20%, by Weight, based on the total reaction mixture of colloid is used, preferably from about 1% to about 10%.

In a particularly useful embodiment, 30 to ,ug./ft. of the active noble metal nuclei in 80 mg. of colloid (solids basis) is coated persquare foot of support. The colloid binder is advantageously coated in a range of about 5 to about 50 mg./ft. Suitable concentrations on the receiving sheets of active noble metal nuclei as disclosed above can be about 1 to about 200 pg./ft. Other silver precipitants can be coated in a concentration of up to 5 mg./ft.

Any mordants that have a charge opposite to the charge of the dye being transferred are used to advantage in the image-receiving elements of my invention for dye transfer images. Since most of the useful photo-graphic imagetransfer dyes have acidic solubilizing groups, basic or cationic mordants are generally used. Typical mordants are organic quarternary pohsphonium salts, organic ternary sulfonium salts and organic quarternary ammonium salts. Suitable mordants include polymers of amino guanidine derivatives of vinyl methyl ketone described in Minsk, U.S. Pat. 2,882,156. Other suitable mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate, poly 4-vinyl-pyridine, thorium salt and similar compounds described in Sprague et al., U.S. Pat. 2,484,- 430.

A particularly useful class of mordanting compositions is disclosed in Bush, U.S. Pat. 3,271,147. Basic or cationic, nonpolymeric mordant compounds of Bush include quaternary ammonium and phosphonium, and ternary sulfonic composition in which there is linked to the N, P or S 7 8 onium atom at least one hydrophobic ballast group, such overcoated with a substantially clear layer of polyethylene as long-chain alkyl or substituted alkyl groups. The onium and used as support for a photographic silver chloride atom can be part of an open-chain or of a heterocyclic emulsion. After processing to obtain a silver image on ring and there can be more than one onium ring in the the support, the samples are exposed as in Example 1 molecule. When referring to the nonpolymeric nature of to 1800 foot candle intensity, of light at 85% RH and the mordant compounds of such mordanting compositions, 110 F., with the same resistance to fading for the polyit is understood that the cationic or the basic mordant vinyl alcohol sample as compared to a distinct fading of does not have regularly occurring units containing the brightener fluorescence in the sample using gelatin. cationic group beyond the dimer structures. However, the EXAMPLE 3 ballast group attached to the quaternary or ternary atom 10 of the cation group can contain repeating groups such as Paper Samples are P p as described in Example tetl-aethoxy, n/ h l In addition, pigmented polyethylene is coated on the back In both the black and white and color diffusion trans- Side Of the P p and C1631" l y y Over the brightfer processes it is useful to have a polymeric acid layer ehed 'y y Over the hflghtehed hafyta layer and located under the image receiving layer as described in the p y y surface, after electron bombardment, i

Rogers et a1. U.S. Pat. No. 3,353,956 issued Nov. 21, Coated layer of Cellulose acetate Containing p y 1967 to act as an alkali scavenging layer. Additional ma- (slyfene/maleic y and 0V6! this layer a gelatin t i l hi h may b d i d d a copolymer of li layer containing silver precipitating nuclei. In another emacid and a monomer containing an active methylene funchodiment for use in 60101 difihsioh transfer, a gelatin tion that serves as a site for cross-linking with convenmofdalltfid receiving layer is used instead Of a Silver P tional hardening agents such as aldehydes or vinyl sul- Cipitating y When the receiving Sheets described are foneg Typical polymers are disclosed in Smith US, Pat, used in black and white and in color diffusion transfer 3,488,708 issued Jan. 6, 1970. Particularly useful copoly- Systems respectively, y are found to Pmyide P mers are copoly (acrylic acid/Z-acetoacetoxyethyl methgraphic Prints having good chafacteristics- Th6 gelatin acrylate) containing 90 wt. percent or 95 wt. percent dispersion of the brightener is found to fade as compared acrylic acid and copoly (acrylic acid/N-cyananoacetylto h P y y alcohol Sample Which s table t0 fading N-methacryloylhydrazine) containing 90 wt. percent or Under the Conditions described in Example 95 wt. percent acrylic acid.

The following examples are included for further under- EXAMPLE standing f the invention; A br1ghtened baryta layer containmg polyvinyl alcohol on paper is used as a support and coated in succession EXAMPLE 1 (over the brightening layer) with (1) an ordinary blue- A paper ba e i oated at a coverage f 55 2 sensitive gelatin silver chlorobromide emulsion and a (dry) with the following composition: dispersion of a yellow dye-forming coupler of the type described in McCrossen et al. U.S. Pat. 2,875,057 (2) a gelatin interlayer, (3) a gelatin layer containing an ordi- Dry weight, gms.

04 nary green-sensitized gelatin silver chlorobromide emul- Fastusol Blue Dye l 'f V8295 Plgment sion, a dispersion of a magenta dye-forming coupler, such f F 80000 as, one of the couplers described in Loria, et al. U.S. Pat. Dlspefsmg agent 250 40 2,600,788, (4) a gelatin layer, (5) a gelatin layer con- Polyymyl 11901101 106-00 taining an ordinary red-sensitized gelatin silver chloro- UVItQX CF 1200 bromide emulsion, a dispersion of a cyan dye-forming coug g y g g 3-28 pler such as is described in Fierke =U.S. Pat. 2,801,171, Colloidal Silica d 5-40 and (6) a gelatln protectlve layer.

The photographic element is exposed in an intensity scale sensitomer and then color processed as described in Example 1, columns 5 and 6 of Van Campen U.S. Pat.

Total 942.86

*Uvitex CF.

Samples of the coated base are exposed to full spectrum 2,956,879 using 12 minutes development in the color lighting at 1800- foot candle intensity, under conditions developer. The processed color print has brightened highof 85% RH and 110 F. After six days exposure there is lights that even after prolonged exposure to the light, very little evidence of fluorescent fading or color change. retain their brightness to a much higher degree than con- Similar systems using gelatin instead of polyvinyl alcohol trol color prints made by the same way except that the ma binder show a distinct loss of fluorescence and color brightening agent is dispersed in gelatin. vvihlelgaetxposed to the same conditions of light, humid EXAMPLE 5 EXAMPLE 2 The brighteners listed below are coated in clear layers of polyvinyl alcohol and gelatin at concentrations of 1.0% Baryta coated paper samples are prepared as described of the dry polyvinyl alcohol or gelatin, The layers are in Examplel Both the sample employing polyvinyl alcocoated at a coverage of approximately 10 gm./m. on a hol as a binder and the sample employing gelatin are clear polyethylene coated support.

2 days fluorescence Manu- 1,800 it. e Brightener faoturet Binder Fresh 110 F. 85 RE 6 days 1 Tinopal 4BM... Geigy {gglA Excigent lxceleentun llgxcgellent. 2 Tinopal RBS do "pag I- Tinopal AMS -do 4 Tinopal TASQ. .do.... 5 Uvitex CF CIBA (}Z1 NOTE.-NG indicates unsatisfactory stability, it. cd., foot candles.

All of the above brighteners found to be unsatisfactory silver bromoiodide, silver chlorobromoiodide or mixtures in gelatin are improved when used in polyvinyl alcohol. 5 thereof. The emulsions may be coarse or fine grain and Uvitex CF used in baryta formulations comparing gelacan be prepared by any of the well-known procedures, tin versus polyvinyl alcohol binders for the baryta layer e.g., single jet emulsions, double jet emulsions, such as shows that it has significantly better stability to light, Lippmann emulsions, ammoniacal emulsions, thiocyanate heat, and humidity in the polyvinyl alcohol baryta than or thioether ripened emulsions such as those described in in the gelatin baryta. 2 Nietz et al. U.S. Pat. 2,222,264; Illingsworth U.S. Pat. (1) Tinopal 4BM: 3,320,069; and McBride U.S. Pat. 3,271,157. Surface confirm-o CHNCH=CHNHC o-nNofln, l l I Q y SOaNa SOsNa I It N-CHa OHa HZOHZOH GH CHQOH (2) Tinopal RBS: Sodium 4-(2H-naphtho[1,2-d]tri- 30 image emulsions may be used or internal image emulsions azol-2yl)-2-stilbenesulfonate: such as those described in Davey et al. U.S. Pat. 2,592,-

250; Porter et al. U.S. Pat. 3,206,313; Berriman U.S. Pat. OH CH 3,367,778 and Bacon et a1. U.S. Pat. 3,447,927. If del sired, mixtures of surface and internal image emulsions 0 a 35 may be used as described in Luckey et a1. U.S. Pat. 2,996,-

382. The emulsions may be regular grain emulsions such as the type described in Klein and Moisar, J. Phot. Sci., vol. 12, No. 5, Sept./ Oct. 1964, pp. 242-251.

The emulsions may be sensitized with chemical sensi- (3) Ti l AMS; 40 tizers, such as with reducing agents; sulfur, selenium or N N CGH5NHC/ \GHNCH=CH NHC \CHNCQH5 i 1', g i l \C% QaNE S OsNa \c% I I 1% 11 0 on, 1120 om HZC JHg Hg CH: W Tinopal TASQ $3 5251? 25 133521331 23? 535 $$e N N HrCtNHC CHNCH=CHNHC C-HNOuH i1 1 1 l t i: ii I SO3Na S03Na C C 1 1N055 I-iNmHls described in Sheppard et al. U.S. Pat. 1,623,499; Waller (5) Uvitex CF: et a1. U.S. Pat. 2,399,083; McVeigh U.S. Pat. 3,297,447;

and Dunn U.S. Pat. 3,297,446.

SO3N8 SOaNa N HO-CHz-Og CH CH OH H0CH -C, cHrom-oH Further addenda and variations in the compositions of The emulsion can be protected against the production the invention are discussed hereinafter. of fog and can be stabilized against loss of sensitivity dur- The silver halide emulsions used in accordance with ing keeping. Suitable antifoggants and stabilizers each this invention can comprise silver chloride, silver bromide, '75 used alone or in combination include thiazolium salts 1 1 described in Brooker et al. U.S. Pat. 2,131,038 and Allen et al. U.S. Pat. 2,694,716; the azaindenes described in Piper U.S. Pat. 2,886,437 and Heimbach et al. U.S. Pat. 2,444,605; the mercury salts as described in Allen et al. U.S. Pat. 2,728,663; the urazoles described in Anderson et al. U.S. Pat. 3,287,135; the sulfocatechols described in Kennard et al. U.S. Pat. 3,236,652; the oximes described in Carroll et al. British Pat. 623,448; nitron; nitroindazoles; the mercaptotetrazoles described in Kendall et al. U.S. Pat. 2,403,927; Kenuard et al. U.S. Pat. 3,266,897 and Luckey et al. U.S. Pat. 3,397,987; the polyvalent metal salts described in Jones U.S. Pat. 2,839,405; the palladium, platinum and gold salts described in Trivelli et al. U.S. Pat. 2,566,263 and Yutzy et al. U.S. Pat. 2,597,915.

The photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides, e.g., dialdehyde starch, oxyguargum and the like.

The photographic emulsions and elements can contain various colloids alone or in combination as vehicles, binding agents and various layers. Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds like poly (vinylpyrrolidone) acrylamide polymers and the like.

The described photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain alone or in combination With hydrophilic, water permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials. Suitable synthetic polymers include those described for example, in Nottorf U.S. Pat. 3,142,568, issued July 28, 1964; White U.S. Pat. 3,193,386, issued July 6, 1965; Houck et al. U.S. Pat. 3,062,674, issued Nov. 6, 1962; Houck et al. U.S. Pat. 3,220,844, issued Nov. 30, 1965; Ream et al. U.S. Pat. 3,287,289, issued Nov. 22, 1966; and Dykstra U.S. Pat. 3,411,911, issued Nov. 19, 1968; particularly efifective are those water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those which have cross-linking ,sites which facilitate hardening or curing and those having recurring sulfobetaine units as described in Dykstra Canadian Pat. 774,054.

The photographic elements used with this invention may contain antistatic or conducting layers; such layers may comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk U.S. Pat. 2,861,056 and Sterman et al. U.S. Pat. 3,206,312 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. 3,428,451.

The photographic layers and other layers of a photographic element employed as described herein can be coated on a Wide variety of supports. Typical supports include cellulose nitrate film, cellulose ester film, poly- (vinyl acetal) film, polystyrene film, poly(ethyene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like. Typically, a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.

The photographic layers employed in the practice of this invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,765 and Duane U.S. Pat. 3,121,060; and silicone resins such as those described in Du Pont British Pat. 955,061.

The photographic layers employed in the practice of this invention may contain surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. 1,022,878.

The photographic elements employed in the practice of this invention may contain matting agents such as starch, titanium, dioxide, zinc oxide, silica, polymeric beads including :beads of the type described in Jelley et al. U.S.

Pat. 2,992,101 and Lynn U.S. Pat. 2,701,245.

The photographic elements used in this invention may contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents. {Water soluble brightening agents may be used such as those described in Albers et al. German Pat. 972,067 and McFall et al. U.S. Pat. 2,933,390 or dispersions of brighteners may be used such as those described in Jansen German Pat. 1,150,274, Oetiker et al. U.S. Pat. 3,406,070 and Heidke French Pat. 1,530,244.

Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light sensitive silver halide emulsion of the multilayer photographic elements which are developed in accordance with our invention. For instance, additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of a dispersion as described in Owens et al. British Pat. 1,154,781. For optimum results, the dye may either be added to the emulsion as a final step or at some earlier stage.

Scnsitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. U.S. Pat. 2,526,- 632, issued Oct. 24, 1950; Sprague U.S. Pat. 2,503,776, issued Apr. 11, 1950; Brooker et al. U.S. Pat. 2,493,748; and Tabor et al. U.S. Pat. 3,384,486. Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g., enamine hemicyanines), oxonols and hemioxonols.

The various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawdey U.S. Pat. 3,253,921; Gaspar U.S. Pat. 2,274,782; Silberstein et al. U.S. Pat. 2,527,583 and Van Campen U.S. Pat. 2,956,879. If desired, the dyes can be mordanted, for example, as described in Jones et al. U.S. Pat. 3,282,699.

The photographic layers used in the practice of this invention may be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin U.S. Pat. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell U.S. Pat. 2,761,791 and Wynn British Pat. 837,095. This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat. 968,453 and LuValle et al. U.S. Pat. 3,219,451.

This invention may be used with elements designed for colloid transfer processes such as described in Yutzy et al. U.S. Pat. 2,716,059; silver salt difiusion transfer processes such as described in Rott U.S. Pat. 2,352,014, Land U.S. Pat. 2,543,181, Yackel et al. U.S. Pat. 3,020,155,

14 and Land U.S. Pat. 2,861,885; color image transfer proc- 8. An element of claim 1 having over the said polyesses such as described in Rogers U.S. Pats. 3,087,817; olefin layer, a receiving layer comprising a silver precip- 3,185,567; and 2,983,606; Weyerts et al. U.S. Pat. 3,253,- itating agent. 915, Whitmore et al. U.S. Pat. 3,227,550; Barr et al. U.S. 9. Anrelement of claim 1 having over said layer a light Pat. 3,227,551; Whitmore U.S. Pat. 3,227,552; and Land sensitive silver halide emulsion. U.S. Pats. 3,415,644; 3,415,645; 3,415,646; and imbibi- 10. An element of claim 1 having over said polyolefin tion transfer processes as described in Minsk U.S. Pat. layer a light sensitive silver halide emulsion. 2,882,156. 11. An element of claim 1 in which the optical bright- This invention may be used with elements designed for ener is a compound of the formula:

color photography, for example, elements containing N N color-forming couplers such as those described in Frohlich R's-f W-NH NH j-R4 et a1. U.S. Pat. 2,376,679, Jelley et al. US. Pat. 2,322,027, I 1i Fierke et a1. U.S. Pat. 2,801,171, Godowsky U.S. Pat. N 2,698,794, Barr et al. U.S. Pat. 3,227,554 and Graham et R4 R5 al. U.S. Pat. 3,046,129; or elements to be developed in ii: R; solutions containing color-forming couplers such as those wherein R2 R3, R6 and R7 each represent a member select.

described in Mannes et a1. U.S. Pat. 2,252,718, Carroll ed f the group consisting f a hydrogen atom, a et a1. U.S. Pat. 2,592,243 and Schwan et al. U.S. Pat. droxyl group, an aryloxy group, an alkoxy group, a h l 2,950,970; and false-sensitized color materials such as gen atom a heterocyclic radical, an alkylthio group, an those desc 1 Hanson f 2,763,549; arylthio group, and an amino group, and R and R each The invention has bee descrlbed m detall with P represent a member selected from the group consisting ticular reference to preferred embodiments thereof, but it f a h d atom, a lf group d a b l group, will be understood that variations and modifications can 12 A l t of 1 i 1 i hi h i b i ht h be effected within the spirit and scope of the invention. the formula:

I claim: 13. An element of claim 1 in which said brightener has 1. An element comprising a support which has thereon the for l a substantially protein-free layer containing barium sulfate, polyvinyl alcohol and an optical brightner, having over said layer a layer of polyolefin. /N

2. An element of claim 1 in which the support is paper. 3. An element of claim 1 in which the polyolefin is polyethylene. OaNa 4. An element according to claim 1 in which said layer contains a blue pigment. I

5. An element of claim 1 which contains in said layer about 3-15 by weight of said layer, of barium sulfate and about 0.02-0.50% by weight of said layer of optical Sodium 4- (2H-naphtho [1,2-d] trlazol-2-yl) -2-stilbenesulfonate brightener.

6. An element of claim 1 in which said brightener is 14. An element of claim 1 in which said brightener has water-soluble. the formula:

N CaH NH(|'|) (IJHN CH=CH-NHC% o N N A 1 1 y OaNa OaNa i N 1120 OH, H C oH,

H H H H 7. An element of claim 1, having over the said layer 7 15. An element of claim 1 in which said brightener has a receiving layer containing a silver precipitating agent. the formula:

/N\ /N mo mrh oHN-or1=oH--NH-o C-HNCeH N N A N ILI \C/ OaNa SOSNa \Q/ lkN CaHs IiINCuH;

15 16 16. An element of claim 1 in which said brightener has the formula:

H E Q Q E H N N N" /I I AOaNa OaNa /N\ HO-CHz-CH1 \CHT-CHPOBI H0CH3-OH1 CH3-CH10H References Cited UNITED STATES PATENTS 3,592,645 7/1971 Weyerts et a1. 9682 3,269,840 8/1966 Koerber et al. 96-82 3,512,984 5/1970 Amano et a1 9682 NORMAN G. TORCHIN, Primary Examiner J. L. GOODROW, Assistant Examiner US. Cl. X.R. 9676