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Photographic element containing acrylic latex polymers

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US3632342A
US3632342A US3632342DA US3632342A US 3632342 A US3632342 A US 3632342A US 3632342D A US3632342D A US 3632342DA US 3632342 A US3632342 A US 3632342A
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silver
layer
photographic
acrylic
halide
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Eugene Dennis Salesin
Robert Calvin Harvey
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Eastman Kodak Co
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Eastman Kodak Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/46Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/81Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/151Matting or other surface reflectivity altering material

Abstract

Multilayer photographic elements with improved sensitometric properties are disclosed. In one aspect, this invention relates to a multilayer photographic element comprising a support, 1) at least one layer containing a light-sensitive silver halide emulsion and a synthetic polymeric acrylic latex material and 2) at least one additional layer positioned outward from said support with respect to any light-sensitive silver halide layer comprising a synthetic polymeric acrylic latex, wherein said additional layer comprises a silver halide and a hydrophilic colloid material which is substantially free of synthetic polymeric acrylic latex micelles.

Description

United States Patent 3,022,169 2/1962 Heckelmann et a1. 96/1 14 3,369,901 2/1968 Fogg et a1. 96/114 3,488,708 1ll970 Smith 96/84 3,450,536 6/1969 Wyckoff 96/68 Primary ExaminerNormun G. Torchin Amt/stun! Iixumt'm'r-Jldward (T. Kimlin Almrneys -W. H. J. Kline, B. I). Wicsc and A. P. Rosenberg ABSTRACT: Multilayer photographic elements with improved sensitometric properties are disclosed. In one aspect, this invention relates to a multilayer photographic element comprising a support, 1 at least one layer containing a lightsensitive silver halide emulsion and a synthetic polymeric acrylic latex material and 2) at least one additional layer positioned outward from said support with respect to any lightsensitive silver halide layer comprising a synthetic polymeric acrylic latex, wherein said additional layer comprises a silver halide and a hydrophilic colloid material which is substantially free of synthetic polymeric acrylic latex micelles.

PHOTOGRAPIIIC ELEMENT CONTAINING ACRYLIC LATEX POLYMERS This invention relates to a method for improving image pro perties of multilayer photographic elements. In a specific aspect, this invention relates to a method for improving image properties of multilayer photographic elements comprising high-contrast silver halide emulsions,

It is known that synthetic latex polymers used with gelatin as binder vehicles for silver halide emulsions impart certain photographic properties such as dimensional stability, flexibility, etc. It is also known that certain substances such as matting agents can be incorporated in outer layers of photographic elements to affect surface characteristics of the element. However, photographic elements containing synthetic latex polymers or matting agents often demonstrate pinholing or areas where no silver is present in maximum density regions after processing. Moreover, surface gloss of the element is often too high where synthetic polymeric latexes are used in various layers of the element.

An improved photographic element is desirable which incorporates the advantages obtained with the synthetic polymeric latex materials and the matting agents without the often observed inherent disadvantageous side effects such as pinholing and high surface gloss.

We have now found a way to improve the photographic properties of multilayer photographic elements which generally comprises incorporating outward from a support with respect to a light-sensitive silver halide emulsion layer a solutionpenetrable layer comprising a silver halide emulsion layer a solution and a binder vehicle consisting essentially of proteinaceous compounds and the like.

The practice of our invention results in a photographic element having decreased surface gloss, elimination of pinholes, increased maximum density and the like. Pinholes are unsensitized points of very low density in the high-density region of a photographic image.

In one embodiment, said photographic element comprises a support, (1) at least one layer comprising a light-sensitive silver halide emulsion and a synthetic polymeric latex material and (2) at least one additional layer positioned outward from said support with respect to any light-sensitive silver halide layer comprising a synthetic polymeric latex wherein said additional layer comprises a silver halide and a hydrophilic co]- loid material which is substantially free of synthetic polymeric latex micelles.

In one preferred embodiment, the nonlatex-containing layer contains a high silver halide to vehicle ratio, by weight.

In another embodiment, said synthetic polymeric latex is an acrylic interpolymer comprising units having water-solubilizing groups thereon.

In a preferred embodiment, said light-sensitive layer comprises a high-contrast silver halide emulsion.

In another embodiment, this invention results in multilayer photographic element comprising a support, a light-sensitive silver halide layer, a gelatin interlayer and an over-coat layer comprising a water-permeable resinous material and a matting agent.

l-lydrophilic colloid materials which can be used in the practice of the invention include those water-permeable binder vehicles which are substantially free of polymeric latex micelles. These micelles are colloidal particles which are suspended in a colloidal dispersion by low concentrations of soluble groups (e.g., carboxylic, hydroxyl, etc.) in the polymer and said micelles can be observed as discrete particles in photomicrographs of the binder vehicle. Hydrophilic colloids suitable as binder vehicles include proteinaceous compounds such as, for example, gelatin, colloidal albumin and other hydrophilic colloids such as, for example, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc., though gelatin materials are preferred. The high-molecular weight binder vehicles which are generally considered soluble in aqueous solutions and do not form small discrete particles when mixed with an aqueous gelatin emulsion, as can be determined upon observation of a photomicrograph, can be considered hydrophilic colloids for purposes of this invention.

The synthetic polymeric latex materials referred to herein are generally polymeric materials which are relatively insoluble in water compared to water-soluble polymers, but have sufficient water solubility to form colloidal suspensions of small polymeric micelles, Typical latex polymeric materials can be made by rapid copolymerization with vigorous agitation in a liquid carrier, such as the common bonfire polymerization, of at least one monomer which would form a hydrophobic homopolymer and at least one monomer which would form a hydrophilic homopolymer. In certain preferred embodiments, from about 1 to about 30 percent, by weight, of units of monomer containing the water-solubilizing group is present in the copolymer product. Copolymers prepared by this method and analogous methods provide discrete micelles of the copolymer which have low viscosities in aqueous suspensions. Typical useful copolymers include interpolymers of acrylic esters and sulfoesters as disclosed in Dykstra, U.S. Pat. No. 3,411,911 issued Nov. 19, 1968, interpolymers of acrylic esters and sulfobetains as described in Dykstra and Whiteley, U.S. Pat. No. 3,41 1,912 issued Nov. 19, 1968, interpolymers of alkyl acrylates and acrylic acids as disclosed in Ream and Fowler, U.S. Pat. No. 3,287,289 issued Nov. 22, 1966, interpolymers of vinyl acetate, alkyl acrylates and acrylic acids as disclosed in Corey, U.S. Pat. No. 3,296,169, and interpolymers as disclosed in Smith, U.S. Ser. NO. 525,272 filed Dec. 20, 1965, now U.S. Pat. No. 3,459,790 issued Aug. 5, I969. Polymeric latex materials can also be made by rapid polymerization with vigorous agitation of hydrophobic polymers when polymerized in the presence of high concentrations of surfactants which contain water-solubilizing groups. The surfactants are apparently entrained in the micelle and the solubilizing group of the surfactant provides sufficient compatibility with aqueous liquids to provide a dispersion very much like a soap. Generally good latex materials are also disclosed in Nottorf, U.S. Pat. No. 3,142,568 is sued July 28, 1964; White, U.S. Pat. No. 3,193,386 issued July 6, 1965; Houck et al., U.S. Pat. No. 3,062,674 issued Nov. 6, 1962; and Houck et al., U.S. Pat. No. 3,220,844 issued Nov. 30, 1965.

The synthetic polymeric latex materials are generally polymerized in manner to produce micelles of about 1.0 micron average diameter or smaller to be highly useful in photographic emulsions and preferably the discrete micelles are less than 0.3 micron in average diameter. Generally, the micelles can be observed by photomicrographs when incorporated in gelatino emulsions; however, it is understood that some coalescing can occur when the emulsions are coated and dried.

In one embodiment, the latex polymers which can be used according to this invention are acrylic interpolymers, i.e., those interpolymers prepared from polymerizable acrylic monomers containing the characteristic acrylic group Such polymers are conveniently prepared by the interpolymerization of an acrylic monomer with at least one dissimilar monomer which can be another acrylic monomer or some other different polymerizable ethylenically unsaturated monomer. It is, of course, understood that the acrylic interpolymers employed in the practice of this invention are compatible with gelatin and have a Tg of less than 20 C. (Tg can be calculated by differential thermal analysis as disclosed in Techniques and Methods of Polymer Evaluation, Vol. 1, Marcel Dekker, Inc., N.Y., 1966) In one embodiment, preferred interpolymers which can be used in this invention comprise units of an alkyl acrylate such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylates (e.g., n-butyl or t-butyl acrylates), amyl acrylates, hexyl acrylates and the like. Acrylic interpolymers containing units of acrylic acid or a sulfoester acrylate are especially useful in the process. Typical polymers of this type are copoly(butyl acrylate-acrylic acid), copoly(methyl acrylate-acrylic acid), copoly(ethyl acrylate-acrylic acid), copoly(butyl acrylate-sulfopropyl acrylate) and the like. In a preferred embodiment, the copolymer comprises up to about 30 percent, by weight, of acrylic acid or the sulfoester acrylate; especially good results being obtained with latex alkyl acrylate copolymers having up to about 20 percent, by weight, of the acrylic acid or the sulfoester acrylate. High ratios of solubilizing groups, such as the acrylic acid groups or the sulfoester groups produce a more soluble solution-type polymer with respect to water carrier solvents and therefore preferably concentrations of about to about 25 percent by weight are utilized to provide the better latex polymers, depending on the molecular weight of the monomer unit. Mixtures of the more soluble solution-type polymers and the latex polymers can also be used within the scope of this invention to achieve the desired emulsion characteristics. The acrylic interpolymer generally comprises at least percent and to about 99 percent, by weight, of the binder vehicle for the emulsion. In the preferred embodiments, the binder vehicle comprises from about to about 75 percent of the acrylic interpolymer and from about 75 percent to about 25 percent, by weight, gelatin of the total binder. Generally the emulsion comprises less than 100 grams of gelatin per mole of silver halide in the emulsion to permit fast drying times of the developed emulsion. Preferably the emulsion comprises less than 75 grams of gelatin per mole of silver halide.

In another preferred embodiment of this invention, the above-mentioned copolymers contain units of a third monomer. Exceptionally good results are obtained in the process of this invention when the synthetic polymers comprise units of (l alkyl acrylates, (2) acrylic acid or sulfoester acrylates and (3) an acrylic monomer unit having active methylene groups in side chains such as in malonic ester groups, acetoacetic ester groups, cyanoacetic ester groups or l,3-diketone groups such as disclosed in Smith, U.S, Ser. No. 625,593 filed Mar. 24, 1967, now U.S. Pat. No. 3,488,708 issued .Ian. 6, 1970. Typical polymers of this class include copoly(ethyl acrylate-acrylic acid-Z-acetoacetoxy-ethyl methacrylate), copoly(butyl acrylate-sodium acryloxy propane sulfonate-Z-acetoacetoxyethyl methacrylate), copoly( methyl acrylate-sodium acryloyloxypropane sulfonate-2-acetoacetoxyethyl methacrylate), copoly(butyl acrylate-acrylic acid-Z-cyanoacetoxyethyl methacrylate) and the like and mixtures thereof. The copolymers of (1) alkyl acrylates and (2) acrylic acid or the sulfoester can also contain units of (3) sulfobetaines, N-methacryloyl-N'-glycylhydrazine hydrachlorides, 2-[Z-methacryloyloxy-ethyl]isothiouroniurn methane sulfonate and the like. Typical copolymers having sulfobetaine units include copoly(butyl acrylate-acrylic acid- 4,4,9-trimeth yl-8-oxo-7-oxa-4-azonia-9-decenel -sulfonate) and the like.

Certain embodiments of this invention relate to a photographic element comprising a support, (1) a light-sensitive layer containing a latex polymer, (2) an additional layer (or interlayer) coated over said light-sensitive layer wherein said additional layer is substantially free of synthetic latex micelles and (3) an overcoat containing a matting agent. The combination structure provides improved image properties as compounds compared with a similar arrangement which does not contain the interlayer between the latex-containing layer and the matting agent-containing layer. Typical good matting agents which are useful in this embodiment include ground glass, silica, polymethacrylate beads such as disclosed in U.S. Pat. No. 2,322,037 and the like. The overlayer can generally contain any resinous binder material, but is preferably waterpermeable to allow penetration of processing solutions, and in certain embodiments it is one of the hydrophilic colloids previously mentioned and is preferably a proteinaceous composition.

The emulsions used in this invention can contain, for example, silver bromide, silver chlorobromide, silver chlorobromoiodide and the like. In one embodiment of this invention, the light-sensitive silver halide emulsions highly useful in multilayer lithographic elements are those in which the halide is predominantly chloride, i.e., at least 50 mole percent chloride. Silver halide emulsions in which the halide concentration is at least mole percent chloride and photographic contrast is high are preferred.

The additional layer (or interlayer) of the invention which comprises a hydrophilic colloid and a silver halide, but which is free of synthetic polymeric latexes, can contain light-sensitive silver halides as disclosed hereinabove, or said layer can contain a silver halide which is substantially insensitive to light. This additional layer preferably contains a high silver halide to hinder vehicle ratio. Generally a ratio of at least I part of silver halide for every 5 parts, by weight, of binder vehicle and preferably ratios of at least 1:3 are utilized in this layer to achieve low-gloss characteristics. a

The light-sensitive layer in the multilayer photographic element of this invention can contain a high-contrast emulsion which is sensitized using any of the well-known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium and/or gold compounds. The emulsions can be sensitized with salts or noble metals of Group VIII of the Periodic Table which have an atomic weight greater than 100, The emulsions can also contain addenda which increase speed and/or contrast such as quaternary ammonium salts, polyethylene glycols, thioether sensitizers or combinations thereof.

The light-sensitive silver halide emulsion of the multilayer photographic elements of the invention can conveniently be orthosensitized or pansensitized with spectral sensitizing dyes. For instance, these emulsions can be spectrally sensitized by treating with a solution of a sensitizing dye in an organic solvent. Sensitizing dyes useful in sensitizing such emulsions are described, for example, in U.S. Pats. Nos. 2,526,632 of Brooker and White issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, i950. Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls and hemicyanines.

The various layers of the multilayer photographic elements of the invention can also contain conventional addenda such as gelatin plasticizers, coating aids, antifoggants such as the azaindines and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), m'aleic dialdehyde, aziridines, dioxane derivatives and oxypolysaccharides.

The silver halide emulsion of the high-contrast photographic elements of the invention can be coated on a wide variety of supports. Hydrophilic colloid layers can be coated on one or both sides of the support, if desired. Typical sup ports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) film, and related films or resinous materials, as well as glass, paper, metal and the like. Supports such as paper, which are coated with a-olefin polymers, particularly polymers of aolefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethyl copolymers and the like, can also be employed.

This invention is further illustrated by the following examples.

EXAMPLE I Sample 1 An orthochromatically sensitized silver chlorobromoiodide gelatin emulsion containing mole percent chloride, 9-mole percent bromide and l-mole percent iodide is coated on a poly(ethylene-terephthalate) polyester support at 456 mg.

silver/foot and 270 mg. gelatin/foot? In addition to the gelatin binder vehicle, the emulsion also contains the synthetic latex, copoly(methyl acrylate-sulfopropyl acrylate-Z- acetoacetoxyethyl methacrylate) (90:5:5 by weight) having an average micelle size of 0.2 micron, at 200 mg./ft., a coating aid and a hardening agent.

A gelatin layer is coated over the emulsion layer at a rate of 85 mg. gelatin/foot? Polymethacrylate beads having an average diameter of 3 microns are dispersed at a rate of 14 mg./ft. in the gelatin layer.

An antihalation gelatin layer is coated at a rate of 500 mg. gelatin/foot on the side of said support opposite the emulsion side. The antihalation layer also contains the vinyl polymer given above and coated at a rate of 180 mg./ft. polymethacrylate beads coated at 52 mg./ft. a coating aid and a hardening agent.

Sample 2 A multilayer photographic element is prepared as described in sample 1 with the following exceptions. A gelatin interlayer coated at the rate of 85 mg. gelatin/foot is coated between the light-sensitive emulsion layer and the gelatin overcoat layer. The gelatin interlayer contains suitable coating aids and hardening agents. The top or overcoat layer is reduced from 85 mg. gelatin/foot to 42 mg. gelatin/foot? Sample 3 A multilayer photographic element is prepared as described in sample 2 with the exception that a silver chlorobromoiodide emulsion (90:9: 1) is incorporated in the gelatin chlorobromoiodide The interlayer is then coated at a rate of l 1.2 mg. silver/foott and 77 mg. gelatin/foot? Sample 4 A photographic element is prepared as described in sample 3 with the exception that the coverage of the interlayer is changed to 22.4 mg. silver/foot and 74 mg. gelatin/foot.

Sample 5 A photographic element is prepared as described in sample 3 with the exception that the coverage of the interlayer is changed to 33.6 mg. silver/foot and 62 mg. gelatin/foot.

The above samples are exposed to a step wedge through a magenta contact screen to a tungsten light source, developed in Kodak Developer D-85 given below, fixed, washed and dried.

Kodak Developer D-85 Sodium sulfite 30.0 grams Paraformaldehyde 7.5 grams Sodium bisullite 2.2 grams Boric acid 7.5 grams Hydroquinone 22.5 grams Potassium bromide 1.6 grams Water to make 1 liter pH 10.1

Sensitometric properties of Samples 1 through 5 are set forth in Table 1 below:

The gloss values reported above are readings taken in the maximum density (Dmax) area of the exposure. A number of lower value indicates less gloss.

Results indicate that lower gloss and higher maximum density are observed in photographic elements comprising the interlayer of our invention.

EXAMPLE 2 Sample 6 A multilayer photographic element is prepared as described in sample 1 with the exception that the emulsion layer contains an orthochromatically sensitized fine grain silver chlorobromide emulsion (:20) and is coated at 512 mg. silver/foot and 151 mg. gelatin/foot". The vinyl polymer used in sample 1 is coated at 320 mg./ft.

Sample 7 A multilayer photographic element is prepared as described in sample 1 except that an interlayer comprising an orthochromatically sensitized fine grain silver chlorobromide emulsion (80:20) is coated at mg. silver/foot and mg. gelatin/foot between the light-sensitive silver halide layer and the overcoat layer. Silver coverage in the light-sensitive silver halide layer is reduced to 412 mg. silver/foot The above samples are exposed and processed as described in example 1.

Sensitometric results similar to those given in Table l are set forth below.

Similar improvements in gloss are obtained when latex polymers copoly(ethylacrylate-acrylic acid) (90:10) and copoly(ethyl acrylate-sulfopropyl acrylate) (87:13) are incorporated into the light-sensitive layerv Although the invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, variations and modifications can be effected within the spirit and scope of the invention.

We claim:

1. A multilayer photographic element comprising a support, (1) at least one layer containing a light-sensitive silver halide emulsion and a synthetic polymeric acrylic latex material and (2) at least one additional layer positioned outward from said support with respect to any light-sensitive silver halide layer comprising a synthetic polymeric acrylic latex, wherein said additional layer comprises a silver halide and a hydrophilic colloid material which is substantially free of synthetic polymeric latex micelles.

2. A multilayer photographic element according to claim 1 wherein said synthetic polymeric acrylic latex is an acrylic interpolymer comprising water-solubilizing groups thereon.

3. A multilayer photographic element according to claim 1 wherein said silver halide emulsion in said light-sensitive layer is a high-contrast emulsion.

4. A multilayer photographic element according to claim 1 wherein the silver halide in said additional layer is substantially less sensitive to light than the silver halide in the said light-sensitive layer.

5. A multilayer photographic element according to claim 1 wherein said hydrophilic colloid is gelatin.

6. A multilayer photographic element according to claim 1 wherein the hydrophilic colloid in said additional layer consists essentially of a proteinaceous compound.

7. A multilayer photographic element according to claim 1 wherein said synthetic polymeric acrylic latex material is in the form of micelles having an average size of less than i micron.

8 A multilayer photographic element according to claim 1 wherein said synthetic polymeric acrylic latex is copoly(methyl acrylate-sulfopropyl acrylate-Z-acetoacetoxyethyl methacrylate 9. A multilayer photographic element according to claim 1 wherein said additional layer contains a ratio of silver halide to hydrophobic colloid of at least 1:4 by weight.

10. A multilayer photographic element comprising a support, (1) at least one layer containing a lighbsensitive silver halide emulsion and a synthetic polymeric acrylic latex material, (2) at least one interlayer positioned outward from said support with respect to any light-sensitive silver halide layer comprising a synthetic polymeric acrylic latex, wherein said interlayer comprises a silver halide and a hydrophilic colloid material which is substantially free of synthetic polymeric latex micelles, and (3) an overcoat layer positioned outward from said support with respect to said interlayer, wherein said overcoat comprises a water-permeable resinous material and a matting agent.

11. A multilayer photographic element according to claim wherein the silver halide in said interlayer is substantially less sensitive to light than the silver halide in the said light-sensitive layer,

12. A multilayer photographic element according to claim 10 wherein said synthetic polymeric acrylic latex is an acrylic interpolymer comprising water-solubilizing groups thereon.

13. A multilayer photographic element according to claim 10 wherein said silver halide emulsion in said light-sensitive layer is a high-contrast emulsion.

14. A multilayer photographic element according to claim 10 wherein the hydrophilic colloid in said additional layer is a proteinaceous compound.

15. A multilayer photographic element according to claim 10 wherein said hydrophilic colloid is gelatin.

16. A multilayer photographic element according to claim 10 wherein said synthetic polymeric acrylic latex material is in the form of micelles having an average size of less than l micron.

17. A multilayer photographic element according to claim 10 wherein said synthetic polymeric acrylic latex is copoly(methyl acrylate-sulfopropyl acrylate-Z-acetoacetoxyethyl methacrylate 18. A multilayer photographic element according to claim 10 wherein said additional layer contains a ratio of silver halide to hydrophilic colloid of at least l :4 by weight.

UNHED STATES PATENT OFFHCE ERTEHATE @P QQRREUHQN Patent No. 3,632,342 {Dated January 4, 1972 Inventor) Eugene D. Salesin and Robert C. Harvey It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 30, "silver halide emulsion layer a solution and a binder" should read a silver halide and a binder;

Column 4, line 64, "ethyl copolymers" should read --ethylene-butene copolymers-.

Signed and sealed this 10th day oi October 1972.

(SEAL) Attest:

EDWARD M.,l'*LE'lCHER,JRo ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents

Claims (17)

  1. 2. A multilayer photographic element according to claim 1 wherein said synthetic polymeric acrylic latex is an acrylic interpolymer comprising water-solubilizing groups thereon.
  2. 3. A multilayer photographic element according to claim 1 wherein said silver halide emulsion in said light-sensitive layer is a high-contrast emulsion.
  3. 4. A multilayer photographic element according to claim 1 wherein the silver halide in said additional layer is substantially less sensitive to light than the silver halide in the said light-sensitive layer.
  4. 5. A multilayer photographic element according to claim 1 wherein said hydrophilic colloid is gelatin.
  5. 6. A multilayer photographic element according to claim 1 wherein the hydrophilic colloid in said additional layer consists essentially of a proteinaceous compound.
  6. 7. A multilayer photographic element according to claim 1 wherein said synthetic polymeric acrylic latex material is in the form of micelles having an average size of less than 1 micron.
  7. 8. A multilayer photographic element according to claim 1 wherein said synthetic polymeric acrylic latex is copoly(methyl acrylate-sulfopropyl acrylate-2-acetoacetoxyethyl methacrylate).
  8. 9. A multilayer photographic element according to claim 1 wherein said additional layer contains a ratio of silver halide to hydrophobic colloid of at least 1:4 by weight.
  9. 10. A multilayer photographic element comprising a support, (1) at least one layer containing a light-sensitive silver halide emulsion and a synthetic polymeric acrylic latex material, (2) at least one interlayer positioned outward from said support with respect to any light-sensitive silver halide layer comprising a synthetic polymeric acrylic latex, wherein said interlayer comprises a silver halide and a hydrophilic colloid material which is substantially free of synthetic polymeric latex micelles, and (3) an overcoat layer positioned outward from said support with respect to said interlayer, wherein said overcoat comprises a water-permeable resinous material and a matting agent.
  10. 11. A multilayer photographic element according to claim 10 wherein the silver halide in said interlayer is substantially less sensitive to light than the silver halide in the said light-sensitive layer.
  11. 12. A multilayer photographic element according to claim 10 wherein said synthetic polymeric acrylic latex is an acrylic interpolymer comprising water-solubilizing groups thereon.
  12. 13. A multilayer photographic element according to claim 10 wherein said silver halide emulsion in said light-sensitive layer is a high-contrast emulsion.
  13. 14. A multilayer photographic element according to claim 10 wherein the hydrophilic colloid in said additional layer is a proteinaceous compound.
  14. 15. A multilayer photographic element according to claim 10 wherein said hydrophilic colloid is gelatin.
  15. 16. A multilayer photographic element according to claim 10 wherein said synthetic polymeric acrylic latex material is in the form of micelles having an average size of less than 1 micron.
  16. 17. A multilayer photographic element according to claim 10 wherein said synthetic polymeric acrylic latex is copoly(methyl acrylate-sulfopropyl acrylate-2-acetoacetoxyethyl methacrylate).
  17. 18. A multilayer photographic element according to claim 10 wherein said additional layer contains a ratio of silver halide to hydrophilic colloid of at least 1:4 by weight.
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Cited By (15)

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US3888676A (en) * 1973-08-27 1975-06-10 Du Pont Silver halide films with wide exposure latitude and low gradient
US4131471A (en) * 1975-12-08 1978-12-26 Polaroid Corporation Synthetic polymeric silver halide peptizer
WO1979001020A1 (en) * 1978-05-02 1979-11-29 Polaroid Corp Photosensitive elements
US4221858A (en) * 1976-06-18 1980-09-09 Fuji Photo Film Co., Ltd. Process for preparing a planographic printing plate
US4233393A (en) * 1976-06-18 1980-11-11 Fuji Photo Film Co., Ltd. Silver halidephotosensitive material
US4396706A (en) * 1980-07-01 1983-08-02 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material and image forming method
US4495273A (en) * 1980-09-17 1985-01-22 Minnesota Mining And Manufacturing Company Color photographic elements with improved mechanical properties
US4504575A (en) * 1983-10-31 1985-03-12 E. I. Du Pont De Nemours And Company Heat-developable film containing silver sulfonate physical developer
US4510238A (en) * 1982-03-11 1985-04-09 Ciba Geigy Ag Photographic material and a process for its manufacture
US4529689A (en) * 1983-10-31 1985-07-16 E. I. Du Pont De Nemours And Company Silver sulfinate photothermographic films
US4605753A (en) * 1983-10-31 1986-08-12 E. I. Du Pont De Nemours And Company Silver sulfinate physical developer for heat-developable photographic films
EP0287809A2 (en) * 1987-03-25 1988-10-26 Du Pont De Nemours (Deutschland) Gmbh Process for the production of matted photographic registration materials
US4980273A (en) * 1987-01-10 1990-12-25 E. I. Dupont De Nemours And Company Matted photographic imaging materials
US5057407A (en) * 1987-05-21 1991-10-15 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5770353A (en) * 1996-06-28 1998-06-23 Eastman Kodak Company Photographic element having improved ferrotyping resistance and surface appearance

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JPS579052B2 (en) * 1977-03-18 1982-02-19
DE3852089T2 (en) * 1987-11-16 1995-06-01 Konishiroku Photo Ind A photographic light-sensitive material and method for its production.

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US3022169A (en) * 1958-03-05 1962-02-20 Agfa Ag Matting of photographic layers
US3369901A (en) * 1964-01-16 1968-02-20 Eastman Kodak Co Coating method for wash-off solvent transfer
US3450536A (en) * 1961-03-24 1969-06-17 Eg & G Inc Silver halide photographic film having increased exposure-response characteristics
US3488708A (en) * 1965-12-20 1970-01-06 Eastman Kodak Co Photographic materials containing novel polymers

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US2956884A (en) * 1957-03-26 1960-10-18 Eastman Kodak Co Compositions of polyacrylates with gelatin and other proteins
US3022169A (en) * 1958-03-05 1962-02-20 Agfa Ag Matting of photographic layers
US3450536A (en) * 1961-03-24 1969-06-17 Eg & G Inc Silver halide photographic film having increased exposure-response characteristics
US3369901A (en) * 1964-01-16 1968-02-20 Eastman Kodak Co Coating method for wash-off solvent transfer
US3488708A (en) * 1965-12-20 1970-01-06 Eastman Kodak Co Photographic materials containing novel polymers

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3888676A (en) * 1973-08-27 1975-06-10 Du Pont Silver halide films with wide exposure latitude and low gradient
US4131471A (en) * 1975-12-08 1978-12-26 Polaroid Corporation Synthetic polymeric silver halide peptizer
US4221858A (en) * 1976-06-18 1980-09-09 Fuji Photo Film Co., Ltd. Process for preparing a planographic printing plate
US4233393A (en) * 1976-06-18 1980-11-11 Fuji Photo Film Co., Ltd. Silver halidephotosensitive material
WO1979001020A1 (en) * 1978-05-02 1979-11-29 Polaroid Corp Photosensitive elements
US4396706A (en) * 1980-07-01 1983-08-02 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material and image forming method
US4495273A (en) * 1980-09-17 1985-01-22 Minnesota Mining And Manufacturing Company Color photographic elements with improved mechanical properties
US4510238A (en) * 1982-03-11 1985-04-09 Ciba Geigy Ag Photographic material and a process for its manufacture
US4504575A (en) * 1983-10-31 1985-03-12 E. I. Du Pont De Nemours And Company Heat-developable film containing silver sulfonate physical developer
US4529689A (en) * 1983-10-31 1985-07-16 E. I. Du Pont De Nemours And Company Silver sulfinate photothermographic films
US4605753A (en) * 1983-10-31 1986-08-12 E. I. Du Pont De Nemours And Company Silver sulfinate physical developer for heat-developable photographic films
US4980273A (en) * 1987-01-10 1990-12-25 E. I. Dupont De Nemours And Company Matted photographic imaging materials
EP0287809A2 (en) * 1987-03-25 1988-10-26 Du Pont De Nemours (Deutschland) Gmbh Process for the production of matted photographic registration materials
EP0287809A3 (en) * 1987-03-25 1990-07-04 Du Pont De Nemours (Deutschland) Gmbh Process for the production of matted photographic registration materials
US5057407A (en) * 1987-05-21 1991-10-15 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5770353A (en) * 1996-06-28 1998-06-23 Eastman Kodak Company Photographic element having improved ferrotyping resistance and surface appearance

Also Published As

Publication number Publication date Type
BE746803A1 (en) grant
FR2037526A5 (en) 1970-12-31 application
GB1285247A (en) 1972-08-16 application
DE2003993A1 (en) 1970-09-10 application
BE746803A (en) 1970-08-17 grant
CA925748A1 (en) grant
DE2003993B2 (en) 1977-12-01 application
CA925748A (en) 1973-05-08 grant
DE2003993C3 (en) 1978-08-03 grant

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