GB1574294A - Photographic light-sensitive material with surface layer containing silica - Google Patents

Description

(54) PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL WITH SURFACE LAYER CONTAINING SILICA (71) We FUJI PHOTO FILM CO., LTD., a Japanese Company, of No. 210, Naka@@@@ @@@@@@ @@@@@@@@ @@@ @@@@@@@@ @@ ERRATA SPECIFICATION No. 1,574,294 Page 2, line 9, for as (first occurrence) read of Page 7, line 9, for butter read buffer Page 15, line 8, for s triazine read s-triazine Page 16, lines 5 and 16, for mposition read composition Page 17, line 27, for 2.3 g/100 g read 2.8 g/100 g Page 17, line 31, after gelatin Start nezv para- graph insert Samples (21) to (23) were subjected to a development processing for a color paper as described below and then adhesion testing and cracking test ing of each of the samples were carried out.

Page 17, lines 39 to 41, delete whole lines Page 19, line 33, after Claim delete 1, insert 1 or 2, THE PATENT OFFICE 10th November, 1980 mu the omder or the pnotographic material snouid be fiexible in order to prevent a dimensional change due to variations in temperature or humidity, to prevent the photographic material from cracking. In order to render the binder flexible, a method wherein various kinds of polymer latexes are incorporated into the binder is also well known to those skilled in the art. Such a method is described, for example, in Japanese Patent Publication Nos. 4272/64,17702/64 and 13482/68 and U. S. Patents 2, 376,005,2,763,625,2,772,166,2,852,386,2,853,457 and 3, 397,988.

However, a binder containing such a polymer latex has the disadvantages that it is much more adhesive than a binder which does not contain such a polymer latex.

(54) PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL WITH SURFACE LAYER CONTAINING SILICA (71) We FUJI PHOTO FILM CO., LTD., a Japanese Company, of No. 210, Nakanuma, Minami Ashigara-Shi, Kanagawa, Japan, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement :- The present invention relates to a photographic light-sensitive material with improved physical properties and to a method for improving the physical proper ties of a layer of a photographic light-sensitive material and particularly to a method for preventing cracking and dimensional change and for preventing adhesion.

A conventionally used silver halide photographic material has a surface layer containing a hydrophilic colloid such as gelatin as a binder. Therefore, the adhesiveness or tackiness of the surface of such a photographic material increases in an atmosphere of high humidity, especially under high temperature and high humidity conditions, to result in adhesion easily to another material with which the photographic material comes into contact. Various disadvantages often occur due to this adhesion phenomenon which takes place between different parts of a photographic material or between a photographic material and another material when they are allowed to stand in contact with each other during manufacture of the photographic material, while taking a photograph, during processing the photographic material, on projecting the photographic material or while storing the photographic material.

In order to solve such a problem, the method of using a so-called matt layer is well known to those skilled in the art, wherein a powder having an average particle size of 2 to 5 microns, for example, a powder of an inorganic compound such as silica (silicon dioxide), magnesium oxide, titanium dioxide, calcium carbonate, etc., or a powder of an organic compound such as polymethylmethacrylate, cellulose acetate propionate, etc., is incorporated in the surface layer to cause the coarse ness of the surface to increase and to result in a decrease in the adhesiveness of the surface. However, when such a method using a matt layer is carried out to the extent of obtaining sufficient anti-adhesive properties, some undesirable side effects also occur in that the transparency of the image formed is reduced, the granularity of the image formed is degraded, the photographic material tends to be scratched because of the decrease in the slipping ability of the surface, and the like.

Accordingly, a method for improving the anti-adhesive properties of the photographic material unaccompanied by such additional disadvantageous effects has been desired.

Also the binder of the photographic material should be flexible in order to prevent a dimensional change due to variations in temperature or humidity, to prevent the photographic material from cracking. In order to render the binder flexible, a method wherein various kinds of polymer latexes are incorporated into the binder is also well known to those skilled in the art. Such a method is described, for example, in Japanese Patent Publication Nos. 4272/64, 17702/64 and 13482/68 and U. S. Patents 2, 376, 005, 2, 763, 625, 2, 772, 166, 2, 852, 386, 2, 853, 457 and 3, 397, 988.

However, a binder containing such a polymer latex has the disadvantages that it is much more adhesive than a binder which does not contain such a polymer latex, An object of the present invention is to provide a method for improving the anti-adhesive properties of a photographic material where not only are dimensional stability and the flexibility not impared but also the transparency and the granular ity of the image produced therefrom are not degraded.

Another object of the present invention is to provide a photographic material having improved anti-adhesive properties.

According to the present invention a photographic light-sensitive material comprises a support and an outermost light-insensitive layer consisting essentially as (l) gelatin as a binder (2) colloidal silica of average particle size 7 to 120 milli microns and (3) a polymer which has been coated from a composition containing a polymer latex of average particle size 7 to 120 millimicrons.

The colloidal silica which can be used in the present invention has an average particle size of 7 mu to about 120 mu and contains silicon dioxide as a major component, e. g., in an amount of about 98% by weight or more based on the total solid content weight. The colloidal silica may also contain alumina or sodium aluminate as a minor component, e. g., in an amount of about 2% by weight or less based on the solid content weight. Further, the colloidal silica may contain, as a stabilizer, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia or an organic base such as tetramethylammonium ion, etc. A suitable amount of stabilizer which can be used in this invention is about 0.05 to about 2.0% by weight based on the weight of the silicon dioxide.

Colloidal silica has been described in detail in, for example, Surface and Colloid Science, Volume 6, pages 3-100, edited by Egon Matijevic, John Wiley & Sons (1973).

Examples of colloidal silica which can be used include those commercially available under the trade names: Ludox AM, Ludox AS, Ludox LS, Ludox TM and Ludox HS, produced by E. I. Du Pont de Nemours & Co. (U. S. A.), those commer cially available under the trade names: Snowtex 20, Snowtex C, Snowtex N and Snowtex O, produced by Nissan Chemicals Ind. Ltd., Tokyo, Japan, those commer cially. available under the trade names: Syton C-30 and Syton 200, produced by Monsanto Co. (U. S. A.) and those commercially available under the trade names: Nalcoag 1030, Nalcoag 1060 and Nalcoag ID-21-64, produced by Nalco Chem.

Co. (U. S. A.)."Ludox","Syton"and"Snowtex"are registered Trade Marks.

A preferred amount of the colloidal silica used in the present invention is 0.05 to 1. 0, particularly, 0.2 to 0.5 part by weight, per part by weight of the dry Relatin used as the binder in the outermost layer.

The polymer latex which can be used in the present invention is an aqueous dispersion of a water-insoluble polymer, which has been coated from a composi tion containing a latex of the polymer, having an average particle size of 30 m, to 80 m, u. The aforesaid average particle sizes are arithmetical averages, by the maximum number of particles. A preferred amount of the polymer latex used for forming a layer to make a material of the present invention is 0.01 to 1. 0, particularly 0. 1 to 0.5, part by weight per part by weight of the dry gelatin used as the binder in the outermost layer.

Preferred examples of polymer latexes which can be used in the present invention include polymers having an average molecular weight above 100, 000 and, particularly, 300,000 to 500,000, and which contain an alkyl ester, a hydroxyalkyl ester or a glycidyl ester of acrylic acid or methacrylic acid as a monomer unit.

Specific examples of these polymers are illustrated by the following formulae: Polymer (1)

Polymer (2)

Polymer (3)

Polymer (4)

Polymer ()

m : n = 5 :-5 (molar ratio) Polymer (6)

m : n = 1: 9 (polar ratio) The term"outermost light-insensitive layer"according to the present invention specifically includes a protective layer (e. g., an emulsion protective layer of a formed photographic light-sensitive material) and a back layer. A preferred thickness for the protective layer is about 0.1 to about 3 u and, particularly, I to 2, u.

A preferred thickness for the back layer is about I to about 10y and, particularly, 3 to 6, u.

The application of colloidal silica and an acrylic acid polymer in a subbing layer is described in U. S. Patent 3,161,519. However, the technique described in U. S. Patent 3, 161,519 does not suggest the present invention as described below.

The object of the technique in U. S. Patent 3,161, 519 is to improve the adhesion of a layer to a paper support and/or a photographic emulsion by incor porating colloidal silica and the acrylic acid polymer into the layer. On the other hand, the present invention is based on the discovery that a layer containing colloidal silica, a polymer latex and gelatin is hardly adhesive to another similar layer or to other gelatin-containing layers and the objects of the present invention are completely different from those of U. S. Patent 3,161,519.

According to the present invention, as ilustrated in Example 3 hereinafter, a sufficient image can be obtained by development processing in a limited period of time. On the contrary, it is difficult to satisfy the above-described requirement for a layer of colloidal silica and the acrylic acid polymer as disclosed m U. S. Patent 3,161, 519, since the permeability of the layer to a developer solution, a fixing solution of water, etc., is poor in comparison with a layer containing colloidal silica, the polymer latex and gelatin according to the present invention. That is, the permeability of the layer to an aqueous solution is improved by the addition of the gelatin to the layer.

While the disclosure in U. S. Patent 3, 161, 519 is to obtain an opaque layer based on the disclosure therein wherein the terms"white surface"and"opaqueness"are used, in the present invention, the transparency of the layer is improved.

Further, in U. S. Patent 3,161, 519, the preferred ratio of colloidal silica to total binder is 95 to 99.6 weight %, while the preferred ratio of colloidal silica to total binder in the present invention is about 50 weight % or less. In general, when colloidal silica is added to a mixture of gelatin and a hydrophilic polymer used as a binder and the amount of colloidal silica exceeds 50 weight %, the viscosity of the solution mixture increases too much or the particles tend to aggregate resulting in coating difficulties and in a degradation of the transparency of the image produced therefrom. Therefore, the technique of U. S. Patent 3,161,519 does not contemplate the use of gelatin together with colloidal silica and a polymer to achieve antiadhesive properties and improved transparency.

The amount of the gelatin which is employed in the outermost layer is about 0.1 to about 7 g/m2, preferably 0.3 to 4 g/m2. A suitable amount of additional hydrophilic colloid which can be present in the outermost layer is 0 to about 30% by weight based on the dry weight of the gelatin. The reason for the use of gelatin in the present invention is not only to improve the permeability of an aqueous solution but also to facilitate simultaneous coating of such a layer together with the coating of other layers. The gelatin which can be used can be lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin.

Suitable examples of supports for the photographic light-sensitive material of the present invention include a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, laminates of these films, a thin glass plate, paper, etc. Further, papers coated or laminated with baryta or an a-olefin polymer, in particular, a polymer of an a-olefin having 2 to lQ carbon atoms, such as polyethylene, polypropylene, an ethytene-butene copotymer, etc., synthetic resin films whose surfaces have been roughened to improve adhesion to other polymer materials and to increase printability, e. g., as described in Japanese Patent Publication No. 19068/72, and like supports can be used. Transparent or opaque supports can be selected depending upon the end use of the light-sensitive material. Also, with transparent supports, not only colorless, transparent supports but transparent supports colored by adding dyes or pigments thereto can be used as well. Heretofore, X-ray films have used such supports, e. g., as described in J. SMPTE, Vol. 67, p. 296 (1958), etc.

Suitable opaque supports include intrinsically opaque supports such as paper, and, in addition, supports prepared by adding dyes or pigments such as titanium oxide to a transparent film, a synthetic resin film surface-treated according to the method described in Japanese Patent Publication No. 19068/72, papers or synthetic resin Films to which carbon black, a dye or the like has been added to render them completely light-shielding and the like. Where the adhesion between the support and the photographic emulsion layer is insufficient, a subbing layer can be provided to an adhesive layer which is adhesive to both the support and the photographic emulsion layer. Also, in order to further improve adhesion, the surface of the support may be subjected to a preliminary processing such as a corona discharge, irradiation with ultraviolet light, flame treatment, etc.

In the photographic light-sensitive material of the present invention, the photographic layers other than the outermost light-insensitive layer described hereinbefore can contain various binders, as desired. For example, hydrophilic colloid binders such as proteins (e. g., gelatin, colloidal albumin, casin, etc.), cellulose compounds (e. g., carboxymethyl cellulose, hydroxyethyl cellulose, etc.), saccharide derivatives (e. g., agar-agar, sodium alginate, starch derivatives, etc.), synthetic hydrophilic colloids (e. g., polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyacrylic acid copolymers, polyacrylamide, the derivatives thereof or the partially hydrolyzed products thereof, etc.) can be used. If desired or necessary, a mixture of two or more of these colloids can be used.

Of these, the hydrophilic colloid most used is gelatin. Suitable examples of gelatin which can be used include lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. The gelatin can be replaced in these layers, partly or completely, by a synthetic high molecular weight material as exemplified above, by a gelatin derivative (prepared by processing and modifying gelatin with an agent having a group capable of reacting with the functional groups contained in the gelatin molecule (i. e., the amino groups, imino groups, hydroxy groups or carboxy groups)), or by a graft polymer prepared by grafting a molecular chain of another high molecular weight material onto the gelatin molecule.

Suitable agents for preparing the above-described gelatin derivatives are described in U. S. Patent 2,956,884, Polymer Letters, 5, 595 (1967), Phot. Sci. Eng., 9, 148 (1965), J. Polymer Sci., 9, 3199 (1971), and the like. Homopolymers or copolymers of vinyl monomers, such as acrylic acid, methacrylic acid, the ester, the amide, or the nitrile derivatives thereof, styrene, etc., can be used. However, hydrophilic vinyl polymers which are compatible to some extent with gelatin, such as homopolymers or copolymers of acrylic acid, acrylamide, methacrylamide, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, etc., are particularly preferred.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by mixing a solution of a water-soluble silver salt (e. g., silver nitrate, etc.) with a solution of a water-soluble halide (e. g., potassium bromide, etc.) in the presence of a solution of a water-soluble high molecular weight polymer such as gelatin.

The silver halide emulsion layers and other hydrophilic colloidal layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardeners (individually or in combination), if desired or necessary.

Examples of suitable hardeners which can be used are described in C. E. K.

Mees & T. H. James, The Theory of the Photographic Process, 3rd Ed., Macmillan & Co., New York (1966), U. S. Patents 3,316,095,3,232,764,3,288,775,2,732,303, 3, 635,718,3,232,763,2,732, 316,2,5g6,168,3,103,437,3,017,280,2,983,611,2,725,294, 2,725,295,3,100,704,3,091,537,3,321,313,3,543,292,3,125,449, British Patents 994,869,1,167,027, etc. Typical examples of hardeners include aldehyde compounds such as mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dimethylol urea, trimethylol melamine, glyoxal, monomethyl glyoxal, 2,3-dihydroxy-1,4-dioxane, 2,3-di hydroxy-5-methyl-1, 4-dioxane, succinaldehyde, 2,5-dimethoxytetrahydrofuran, glutaraldehyde, or like aldehyde compounds; active vinyl compounds such as divinylsulfone, methylenebismaleimide, 5-acetyl-1, 3-diacryloyl-hexahydro-striazine, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-trivinylsulfonyl-hexahydro-striazine, bis- (vinylsulfonylethyl) ether, 1, 3-bis (vinylsulfonyl)-2-propanol, 1, 3 bis (vinylsulfonylacetamido) propane, etc.; active halogen compounds such as 2,4dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6-methoxy-s-triazine, 2,4 dichloro-6- (4-sulfoanilino)-s-triazine sodium salt, 2,4-dichloro-6- (2-sulfoethylamino)-s-triazine, N, N'-bis (2-chloroethylcarbamyl) piperadine, etc. ; epoxy compounds such as bis (2, 3-epoxypropyl) methylpropyl-ammonium p-toluene- sulfonate, 1, 4-bis (2,3'-epoxypropyloxy) butane, 1, 3,5-triglyc idyl isocyanurate, 1, 3 diglycidyl-5- (y-acetoxy-/3-hydroxypropyl) isocyanurate, etc.; ethyleneimine compounds such as 2,4,6-triethyleneimino-s-triazine, 1, 6-hexamethylene-N, N'-bisethyleneurea, bis-, 8-ethyleneiminoethyl thioether, etc.; methanesulfonic acid ester compounds such as 1, 2-di (methanesulfonoxy) ethane, 1, 4-di (methanesulfonoxy)butane, 1, 5-di (methanesulfonoxy) pentane, etc. ; carbodiimide compounds such as dicyclohexylcarbodiimide, 1-cyclohexyl-3- (3-trimethylaminopropyl) carbodiimide p-toluenesulfonate I-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydro chloride etc.; isoxazole compounds such as 2, 5-dimethylisoxazole perchlorate, 2 ethyl-5-phenylsioxazole-3'-sulfonate, 5,5'-(p-phenylene) bisisoxazole, etc.; inorganic compounds such as chromium alum, chromium acetate, etc.

Surface active agents individually or in combination may be added to the photographic material layers of the present invention. The surface active agents are generally used as a coating aid but, in some cases, they are used for other purposes, e. g., for the improvement of emulsion dispersion, sensitization and other photographic properties, to provide a desired adjustment in the triboelectric charging propensity of the surface, etc.

Suitable surface active agents which can be used are natural surface active agents such as saponin ; nonionic surface active agents such as those of the alkylene oxide series, glycerin series, glycidol series, etc.; cationic surface active agents such as higher alkylamines, quaternary ammonium salts, heterocyclic compounds (e. g., pyridine, etc.), phosphonium compounds, sulfonium compounds, etc. ; anionic surface active agents having an acidic group such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfuric acid ester group, a phosphoric acid ester group, etc.; amphoteric surface active agents such as aminoacids, aminosulfonic acids, sulfuric or phosphoric acid esters of aminoalcohols, etc.

Some examples of suitable surface active agents are described in patents such as U. S. Patents 2, 271, 623, 2, 240,472,2,288,226,2,739,891,3,068,10i, 3, 518, 484, 3,201,253,3,210, 191,3,294,540,3,415, 649, 3, 441, 413, 3, 442,654,3,475, 174, 3,545,947,3,666,478,3,507,660, British Patent 1, 198, 450 and references such as Ryohei Oda, Synthesis and Application of Surface Active Agents, Maki Shoten, Tokyo (1964), A. M. Schwartz et al., Surface Active Agents, Interscience Publications Inc., (1958), J. P. Sisley et al., Encyclopedia of Surface Active Agents, Vol. 2, Chemical Publishing Co. (1964), and the like.

Also, in the present invention, a lubricating agent such as a silicone as described in U. S. Patent 3, 079, 837,3,080,317,3,545,970,3,294,537, etc., or a modified silicone as represented by the following general formula :

wherein I represents an integer of 0 to 100, m, represents an integer of 0 to 100, I + m, + n, is an integer of 15 to 1, 000, p represents an integer of I to 100, R represents an alkyl group having I to 18 carbon atoms or an aralkyl group (e. g., a benzyl group, an alkyl substituted aralkyl group, etc.), and R, represents a hydrogen atom or an alkyl group having I to 18 carbon atoms; can be incorporated in a photographic material layer (s).

The photographic light-sensitive material of the present invention can contain a brightening agent such as a stilbene, triazine, oxazole and coumarin compound; and an ultraviolet light absorbing agent such as benzotriazole or a thiazolidine compound in an auxiliary layer thereof.

The present invention is applicable to various kinds of photographic materials containing hydrophilic colloid layers. For example, it can be typically applied to photographic materials in which silver halide is used as a light-sensitive component, such as lithographic light-sensitive materials, light-sensitive materials for X-ray use, conventional negative type light-sensitive materials, conventional reversal type light-sensitive materials, conventional positive type light-sensitive materials or direct positive type light-sensitive materials, etc.

There are no limitations on the method of exposing the light-sensitive materials of the present invention to light or on the method of development thereof. For example, descriptions of suitable exposure and development methods which can be used are disclosed in Japanese Patent Applications 24783/76, 31539/76 and 38559/76 and in Product Licensing Index, Vol. 92, 9232 (Dec. 1971).

More specifically, the light-sensitive materials of the present invention can be exposed to obtain photographic images in a conventional manner. Light from various known light sources, such as natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a cathode ray tube display flying spot and so on can be employed as a light source. Exposure times commonly used when photographic pictures are taken with a camera ranging from 1/1, 000 sec. to I sec. and exposure times shorter than 1/1, 000 sec., for example, I/104 to 1/106 second exposure using a xenon flash lamp or a cathode ray tube display, and an exposure time longer than I sec. can be used for the photographic materials of the present invention. A color filter which selectively absorbs lights of certain wavelengths can be optionally employed for controlling the spectral distribution of the light source used. Moreover, the photographic light-sensitive materials of the present invention may be exposed to laser rays, or rays emitted from various kinds of fluorescent materials which are excited by irradiation of electron beams, X-rays, y-rays, a-rays or the like.

The photographic materials of this invention can be processed using known methods. In this case, known processing solutions can be used. The processing temperature is usually from about 18 C to about 50 C but may be lower than about 18 C or higher than about 50 C, if necessary.

This invention is useful for image formation using a development process (black-and-white photographic process) for forming silver images. Further, the invention can also be applied to a color photographic process using a development process in which dye images are formed. The developers used for black-and-white photographic processing can contain known developing agents. For example, aminophenols (such as N-methyl-p-aminophenol), 3-pyrazolidones (such as L : phenyl-3-pyrazolidone), I-phenyt-3-pyrazolines, dihydroxybenzenes (such as hydroquinone) and ascorbic acid, etc., or combinations thereof can be used as a developing agent.

Moreover, the developers usually contain a known antioxidant, an alkali agent, a pH butter, an anti-fogging agent or the like and, if desired, a dissolving aid, a color toning agent, a development accelerator, a surface active agent, an anti foaming agent, a water softener, a hardener, a tackifier, etc., may be present.

So-called"lith-type"development processing can be applied to the photo graphic materials of this invention. In"lith-type"development processing, di hydroxybenzenes are usually used as a developing agent and the development process is carried out infectiously with a low concentration of sulfite ion for photo graphic reproduction of line images and half-tone dot images."Lith-type"develop ment processing is described in detail in L. F. A. Mason, Photographic Processing Chemistry, pages 163 to 165, The Focal Press (1966).

Fixing solutions having a composition generally employed in the art can be used in the present invention. Not only thiosulfates and thiocyanates but also organic sulfur compounds known as fixing agents can be used as fixing agents in the present invention. The fixing solutions may contain a water-soluble aluminum salt as a hardener, if desired.

The present inventionisittustratedbe!ow in greater detail by reference to examples thereof. However, the present invention is not to be construed as being limited to these specific examples. Unless otherwise indicated, all parts, percents, ratios and the like are by ~ Example 1, On a surface of a polyethylene terephthalate film (thickness: 100, u) having a subbing layer, a silver halide emulsion layer having the following Composition (1) was coated at a dry thickness of 0.6p and at a coated silver amount of 5 0 g/m2 and a protective layer having the following Composition (2) was coated simultaneously on the silver halide emulsion layer. Then, on the opposite surface of the poly ethylene terephthalate film to the surface on which the silver halide emulsion was coated a gelatin back layer having the following Composition (3) was coated at a dry thickness of 5. Op to prepare Samples (I) to (4).

Composition (1) : Composition of Silver Halide Emulsion Layer Gelatin g/m Silver Chloroiodobromide (Cl : 80 mol %, Br: 19.5 mol %, I : 0.5 mol %) Chloroauric Acid 0.1 mg/m, Polyethyl Acrylate Latex (same as that 1. 5 g/m2 described in Example 3 of U. S. Patent 3,525,620) PolyoxyethyleneCompound:

Sensitizing Dye: 3-Allyl-5-[2-(1-ethyl)-4-methyl-2- 6 mg/m2 tetrazolin-5-ylidene-ethylidenel-rhodanine Antifogging Agent 4-Hydroxy-6-methyl-1, 3,3a, 7- 30 mg/m2 tetrazaindene Gelatin Hardening Agent: 2-Hydroxy-4,6-dichloro-s-triazine 60 mg/m2 Sodium Salt Viscosity Increasing Agent: Potassium Polystyrene Sulfonate 100 mg/m' Surface Active Agent: Sodium p-Dodecylbenzenesulfonate 40 mg/m' Composition (2): Composition of Protective Layer Gelatin 1 g,'m 2 Matting Agent: Polymethyl methacrylate having an 0. 05 g/m' average particle size of 3.0 to 4.0 tL Surface Active Agent 30 mg/m2 (same compound as described in Composition (1)) Gelatin Hardening Agent 10 mg./m2 (same compound as described in Composition (1)) Viscosity Increasing Agent 10 mg/m2 (same compound as described in Composition (1)) Composition (3): Composition of Back Layer Gelatin, matting agent, surface active agent, gelatin hardening agent and viscosity increasing agent were the same as those described in Composition (2) for the protective layer. The matting agent was not employed in Samples (3) and (4).

Dye: Mixture of Dyes (I), (11) and (III) 0.3 g/m'in a 1 : 1 : I weight ratio

Colloidal Silica : Snowtex-O, the pH of which was adjusted to 9.5 with potassium hydroxide.

The colloidal silica was not present in Sample (1).

Polyethyl Acrylate Latex (same as that used in Composition (1) for the silver halide emulsion layer). The latex was not present in Sample (4).

TABLE 1 Composition of Back Layer Component Sample (1) Sample (2) Sample (3) Sample (4) (control) Gelatin 5 g/m'5 g/m, 5 g/m'5 g/m' Matting Agent 0.8 g/100 g 0. 3 g/100 g None None of gelatin of gelatin Polymer Latex 50 g/100 g 50 g/100 g 50 g/lOOg None of gelatin of gelatin of gelatin Colloidal None 50 g/100 g 50 g/100 g 50 g/100 g Silica of gelatin of gelatin of gelatin Surface Active 40 mg/m'40 mg/cn'40 mg/ms-40 mg/mz Agent Dye 0.3 g/m'0. 3 g/m'0. 3 g/m'0. 3 g/m' Gelatin Hardening 60 mg/m2 60 mg/m 60 mg/m 60 mgXm Agent Viscosity Increasing 100 mg/m'100 mg/m'100 mg/m'100 mg/m' Agent Samples (I) to (4) were tested in the following manner.

(a) Evaluation of Antiadhesive Property : Each sample was cut in a size of 4 cm x 4 cm to make two sheets which form one set. After conditioning at 35 C and 75% RH (relative humidity) for 24 hours, a back layer of the sample was brought into contact with a protective layer in the same set, to which a load of 1 kg was applied and the assembly was allowed to stand at 35 C and 75% RH for 24 hours. Then, the load was removed and the back layer and the protective layer were separated and the area of adhesion (the area on the protective layer colored by dyes transferred from the back layer) was measured.

Evaluation of the antiadhesive property was carried out using following grades : A-Area of adhesion was 0-25% B-Area of adhesion was 26-50% C-Area of adhesion was 51-75% D-Area of adhesion was 76% or more, or it was impossible to separate because of firm adhesion.

(bJ Evaluation of Transparency : An unexposed sample was developed at 27 C for I minute and 45 seconds with Fuji Lithdeveloper LD-322 (manufactured by Fuji Photo Film Co., Ltd.) using an FG-24 Pakoroll automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.), fixed, washed with water and dried. The transparency of the sample was measured. The measurement of transparency (haze value) was carried out using an ANA-147 type haze meter (manufactured by Tokyo Koden Co., Ltd.). The smaller haze value means a better transparency.

(c) Dimensional Stability : The elongation (x: positive number) of a sample having a length of 20 cm at 25 C and 50% RH when the sample was conditioned at 25 C and 65% RH and the contraction (y: positive number) of the sample when the conditions were changed from 25 C and 50% RH to 25 C and 30% RH were measured. Then, the dimensional change, i. e., x + y was calculated. A smaller value of x + y means a better dimensional stability.

The results of evaluation of the antiadhesive property, the transparency and the dimensional stability are shown in Table 2 below.

TABLE 2 Sample (1) Sample (2) Sample (3) Sample (4) (control) Antiadhesive Property D A B A Eiaze Value (To) 15 5.0 2. 1 0.9 Dimensional Changer) 80 80 80 174 It is apparent from the results in Table 2 that both the antiadhesive property and the transparency are improved while the dimensional stability is maintained at the same level in Samples (2) and (3) in which gelatin, colloidal silica. and a polymer are present in the back layer in comparison with the control Sample (1).

Example 2.

On one surface of a polyethylene terephthalate film (thickness: lOO du) having a subbing layer thereon, a silver halide emulsion layer the same as described in Example 1 and a protective layer having the following Composition (4) were coated in the same layer structure as described in Example 1. Then, a gelatin back layer having the following Composition (5) was coated on the opposite surface of the polyethylene terephthalate film to that on which the silver halide emulsion was coated at thedrythicknessof5.0 u to prepareSamples(11) to (14).

Composition (4): Composition of Protective Layer The gelatin, matting agent, surface active agent, gelatin hardening agent and viscosity increasing agent were the same as those described in the protective layer of Example 1.

Colloidal Silica: Snowtex N Polymer Latex: Latex Polymer (6) described hereinbefore (average molecular weight: 500, 000, average particle size: 70 m, u) TABLE 3 Composition of Protective Layer Component Sample (11) Sample (12) Sample (13) Sample (14) (control) Gelatin 1 g/m2 1 g/m2 1 g/m2 1 g/m2 Matting Agent 1 g,'100 g 1 g/100 g 0.5 g/100 g 0.5 g/100 g of gelatin of gelatin of gelatin of gelatin Polymer Latex None 2.0 g/100 g 2.0 g/100 g 2.0 g/100 g of gelatin of gelatin of gelatin Colloidal None 2.5 g/100 g 2.5 g/100 g 2.5 g/100 g Silica of gelatin of gelatin of gelatin Surface Active 30 mg/m'30 mg/m 30 mg/m 30 mg/m Agent Gelatin Hardening 10 mg/m2 100 mg/m2 10 mg/m2 10 mg/m2 Agent Viscosity Increasing 10 mgYm 10 mg/m2 10 mg/m2 10 mg/m2 Agent Composition (5): Composition of Back Layer The gelatin, matting agent, surface active agent, dye, gelatin hardening agent and viscosity increasing agent were the same as those described in the back layer of Example 1.

Colloidal Silica : Snowtex N Polymer Latex: Latex of Polymer (1) described hereinbefore (average molecular weight: 300,000, average particle size: 50 m ) TABLE 4 Composition of Back Layer Component Sample (11) Sample (12) Sample (13) Sample (14) (contre)) Gelatin 4g/m'4g/m'4g/m'4g/m' Matting Agent 0. 8 g/100 g 0.3 g/100 g 0. 8 g/100 g 0.3 g/100 g of gelatin of gelatin of gelatin of gelatin Polymer 50 g/100 g 50 g/100 g 50 g/100 g 50 g/100 g Latex of gelatin of gelatin of gelatin of gelatin Colloidal None 50 g/100 g None 50 g/100 g Silica of gelatin of gelatin Surface Active 40 mg/m 40 mg/m2 40 mg/m2 40 rim2 Agent Gelatin Hardening 60 mg/m 60 mg/m 60 mg/m 60 mg/m Agent Viscosity Increasing 100 mg/m'100 mg/m'100 mg/m'100 mg/m, Agent Dye 0.3 mg/m'0. 3 mg/m'0. 3 mg/m'0. 3 mg/m' The antiadhesive property, the transparency and the dimensional stability of each sample were evaluated in the same manner as described in Example 1.

The results of examination of the antiadhesive property, the transparency and the dimensional stability are set forth in Table 5 below.

TABLE 5 Sample (11) Sample (12) Sample (13) Sample (14) (control) Antiadhesive D A A A Property Haze Value (%) 15 4. 8 7.0 3.1 Dimensional 80 80 78 80 Change (Z) It is apparent from the results in Table 5 above that both the antiadhesive property and the transparency are improved while the dimensional stability is maintained at the same level in the samples in which gelatin, colloidal silica and a polymer latex are present in the protective layer and/or the back layer in comparison with the control sample.

Example 3.

On one surface of a polyethylene laminated paper, a blue-sensitive silver halide emulsion layer, an intermediate layer, a green-sensitive silver halide emulsion layer, an ultraviolet light absorbing layer, a red-sensitive silver halide emulsion layer and a protective layer each having the following Composition (6) were coated in this order to prepare Samples (21) to (23).

Composition (6) Composition (6-1) : Composition of Protective Layer Gelatin 1.5 g/m' Surface Active Agent: Sodium salt of 2-sulfonatosuccinic acid 1.4 g/100 g bis (2-ethylhexyl) ester of gelatin Gelatin Hardening Agent: 2-Hydroxy-4,6-dichloro-s triazine sodium salt 1.5 g/100 g of gelatin Polyethyl Acrylate Latex (same as described in Example 1) Colloidal Silica : Ludox LS TABLE 6 Composition of Protective Layer Component Sample (21) Sample (22) Sample (23) Gelatin 1. 5 g/m'1. 5 g/m'1. 5 g/m' Surface Active 1.4 g/100 g 1.4 g/100 g 1.4 g/100 g Agent of binder of binder of binder Gelatin Hardening 1.5 g/100 g 1.5 g/100 g 1.5 g/100 g Agent of binder of binder of binder Polymer Latex None None 1. 4 g/100 g of binder Colloidal Silica None 30 g/100 g 30 g/100 g of binder of binder Composition (6-2) : Composition of Red-Sensitive Silver Halide Emulsion Layer Gelatin : 1.5 g/m'+ Cellulose sulfate having an 0.15 g/m' average molecular weight of 100,000 Silver Halide : AgBr : 50 mot % + AgCI : 50 mol % 0. 5 g/m' Couplet'.

2- [a- (2, 4-Di-tert-amylphenoxy)- 100 g/100 g of butyramido]-4, 6-dichloro-5-methylphenol silver halide Sensitizing Dye: Anhydro 3,3'-di-8-sulfobutyl- 0.3 g/100 of 5,5', 6, 6'-tetramethyl silver halide thiacarbocyanine hydroxide Antifogging Agent : 4-Hydroxy-6-methyl-1, 3,3a, 7- 0. 9 g/100 g of tetrazaindene silver halide Gelatin Hardening Agent : bis (Vinylsulfonyl ethyl) ether 3.5 g/100 g of gelatin Surface Active Agent: Sodium dodecylbenzenesu (fonate 1 g ! 100 g of gelatin mposition (6-3) : Composition of Ultraviolet Light Absorbing Layer Gelatin: 1 g/m'+ Cellulose sulfate having an 0.1 g/m average molecular weight of 100,000 Ultraviolet Light Absorbing Agent: Tinuvin 1 g/m' Gelatin Hardening Agent: 2-Hydroxy-4,6-dichloro-s-triazine 1.5 g/100 g sodium salt of gelatin Surface Active Agent: Sodium dodecylbenzenesulfonate 1 g/100 g of gelatin mposition (6-4) : Composition of Green-Sensitive Silver Halide Emulsion Layer Gelatin : 1.5 g/m'+ Cellulose sulfate having 0.15 g/m2 an average molecular weight of 100,000 Silver Halide : AgBr: 50 mol % + AgCI : 50 mol % 0.7 g/m' Coupler : 1-(2,4,6-Trichlorophenyl)-3-(2- 57 g/100 g of chloro-5-tetradecanamido) anilino- silver halide 2-pyrazolin-5-one Sensitizing Dye: Anhydro 3,3'-di-3-sulfopropyl- 0.3 g/100 g of 5,5'-dipheny 1-9-ethyl carbocyanine silver halide hydroxide sodium salt AntifoggingAgent: 4-Hydroxy-6-methyl-1,3,3a,7- 0. 6 g/100 g of tetrazaindene silver halide Gelatin Hardening Agent: bi s (Vinyl sulfonyl ethyl) ether 3 g/100 g of gelatin Surface Active Agent: Sodium dodecylbenzenesulfonate 0.8 g/100 g of gelatin Composition (6-5) : Composition of Intermediate Layer Gelatin: 1.5 g/m'+ Cellulose sulfate having an 0.15 g/m' average molecular weight of 100,000 Gelatin Hardening : 2-Hydroxy-4, 6-dichloro-s-triazine 1.5 g/100 g sodium salt of gelatin Surface Active Agent: Sodium dodecylbenzenesulfonate 0.6 g/100 g of gelatin Composition (6-6) : Composition of Blue-Sensitive Silver Halide Emulsion Layer Gelatin : 1.5 g/m'+ Cellulose sulfate having an 0. 15 g/m2 average molecular weight of 100,000 Silver Halide : AgBr: 80 mol % + AgCI : 20mol % 0.7 g/m' Coupler : a-Pivaloyl-a- (2, 4-dioxo-5, 5-0.7 g/100 of dimethyloxazolidin-3-yl)-2-chloro-silver halide 5- [a- (2, 4-di-tert-amylphenoxy)- butyramido] acetanilide AntifoggingAgent: 4-Hydroxy-6-methyl-1, 3,3a, 7- 0. 4 g/100 g of tetrazaindene silver halide Gelatin Hardening Agent: bis (Vinylsulfonylethyl) ether 2.3 g/100 g of gelatin Surface Active Agent : Sodium dodecylbenzenesulfonate 0.3 g/100 g of gelatin Development Processing Temperature Time Color Development 31 C 3 min 30 sec Stop-Fixing"30 sec Bleach-Fixing"1 min 30 sec Water Washing"1 1 min Stabilizing"1 min Rinse"1 1 min Samples (21) to (23) were subjected to. a development processing for a color paper as described below and then adhesion testing and cracking testing of each of the samples were carried out.

The processing solutions used had the toltowmg compositions.

Composition of Color Developer Solution Benzyl Alcohol 15 ml Sodium Sulfite 5 g Potassium Bromide 0.5 g Hydroxylamine Sulfate 2 g Sodium Carbonate 30 g Sodium Nitrilotriacetate 2 g 4-Amino-3-methyl-N-ethyl-N- -(methane-5 g sulfonamido)ethylaniline Water to make 1,000 ml Composition of Stop-Fixing Solution Sodium Thiosulfate 30 g Sodium Sulfite 2 g Sodium Acetate 25 g Tartaric Acid 4.3 g Sodium Carbonate (monohydrate) 1.9 g Water to make 1,000 ml Composition of Bleach-Fixing Solution Ammonium Thiosulfate (70% aq. soin.) 150 ml Iron-ethylenediaminetetraacetate 36.6 g Disodium Ethylenediaminetetraacetate 3.4 g Sodium Sulfite 2 g Sodium Carbonate (monohydrate) 5.5 g Water to make 1,000 ml Compositionof Stabilizing Solution Sodium Benzoate 0.5 g Citric Acid (monohydrate) 6.7 g Diethanolamine 2.2 g Water to make 1,000 ml ! A) Adhesion Testing Each of the samples thus-processed and dried was cut into a size of 4 cm x 8 cm to make two sheets which form one set. After conditioning at-35 C, 90 RH for 24 hours, a protective layer of one sheet was brought into contact with a protective layer of another sheet of the same set. A load of I kg was applied to the assembly and the assembly was allowed to stand at 35 C, 90"o RH for 24 hours. Then the load was removed and the protective layers were separated and the area adhered (area in which the gloss of surface changed) was measured.

Evaluation of the antiadhesive property was carried out according to the following grades: A-Area of adhesion was 0-40% B-Area of adhesion was 41-80% C-Area of adhesion was 81 % or more, or the adhesion was too strong with a part of the emulsion layer or the support peeling off.

(B Cracking Testing Each of the samples thus-processed was dried 30 seconds by exposure to air at 90 C. All of the samples curled toward their protective layer sides. The curled sample was pressed flat and the occurrence of cracking was observed. The results of adhesion testing and cracking testing are set forth in Table 7 below.

TABLE 7 Sample (21) Sample (22) Sample (23) (control) Antiadhesive Property C A A Cracking None Occurred None It is apparent from the results in Table 7 above that the sample containing gelatin, colloidal silica and a polymer latex in the protective layer had improved antiadhesive property and cracking did not occur.

Claims (9)

WHAT WE CLAIM IS :-

1. A photographic light-sensitive material comprising a support and having thereon an outermost light-insensitive layer consisting essentially of (1) gelatin as a binder, (2) colloidal silica of average particle size of 7 to 120 millimicrons and (3) a polymer which has been coated from a composition containing a polymer latex of average particle size 30 to 80 millimicrons.

2. A photographic material as claimed in Claim 1, wherein the colloidal silica is present in an amount of 0.05 to 1.0 part by weight per part by weight on a dry basis of gelatin present in said layer.

3. A photographic material as claimed in Claim 1, wherein the polymer latex was present in an amount (not including the water in the latex) of 0.01 to 1. 0 part by weight per part by weight on a dry basis of the gelatin present in said layer.

4. A photographic material as claimed in Claims 1,2 or 3, wherein said outermost layer is a protective layer.

5. A photographic material as claimed in Claim 4, wherein the protective layer has a thickness of 0.1 to 3 millimicrons.

6. A photographic material as claimed in Claim 1,2 or 3, wherein said outermost layer is a back layer.

7. A photographic material as claimed in Claim 6, wherein the back layer has a thickness of 1 to 10 microns.

8. A photographic material as claimed in any preceding Claim, which includes at least one layer of silver halide photographic emulsion.

9. A photographic light-sensitive material as claimed in Claim 1, substantially as hereinbefore described with reference to any of the Examples.