US3854952A

US3854952A - Photosensitive silver halide composition

Info

Publication number: US3854952A
Application number: US00398719A
Authority: US
Inventors: J Kenney
Original assignee: Western Electric Co Inc
Current assignee: AT&T Corp
Priority date: 1973-09-19
Filing date: 1973-09-19
Publication date: 1974-12-17
Anticipated expiration: 1991-12-17

Abstract

A photosensitive silver halide composition is disclosed. The composition comprises a silver halide deposited or sorbed on colloidal particles of a hydrous oxide of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Si, Ge, Sn, Th and mixtures thereof.

Description

Elite States ate t [191 Kenney Dec. 17, 1974 1 PI-IOTOSENSITIVE SILVER HALIDE COMPOSITION [75} Inventor:

I73] Assigncc: Western Electric Company,

' Incorporated, New York, N.Y.

22 Filed: Sept. 19, 1973 [21 Appl. No.: 398,719

John Thomas Kenney, Trenton, NJ.

[52] US. Cl 96/94 BF, 96/108, 96/109,

. 252/213 R [51] Int. Cl G036 1/02 [58] Field of Search 96/94 BF, 95, 108, 109,

[56] References Cited UNITED STATES PATENTS 1,995,444 3/1935 Berry et a1. 96/95 2,839,405 6/1958 Jones 96/107 2,950,972 8/1960 Mueller et a1. 96/108 3,556,797 1/1971 Pattijw et a1 96/109 3,657,003 4/1972 Kenney 117/120 3,767,590 10/1973 Kenney 252 313 R Primary Examiner-Norman G. Torchin Assistant Examiner-Alfonso T. Suro Pico Attorney, Agent, or Firm-J. Rosenstock [57] ABSTRACT 12 Claims, N0 Drawings PHOTOSENSITIVE SILVER HALIDE COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photosensitive silver halide composition and a method of forming the composition and more particularly, to a composition comprising a silver halide deposited on suitable colloidal particles of a hydrous oxide.

2. 1 Description of the Prior Art Silver halide films for photography are made from silver halide dispersed in gelatin. The resultant gelatin films are dimensionally unstable due to both thermal expansion and water absorption. Where the silver halide is to be applied to a hydrophobic surface, the use of gelatin films thereof have not proved satisfactory due to the poor wettability attained. A gelatin-free silver halide film which is dimensionally stable, which is resistant to decomposition for relatively long periods of time and which is capable of wetting hydrophobic surfaces is desired and is an object of the subject invention.

SUMMARY OF THE INVENTION This invention relates to a photosensitive silver halide composition and a method of forming the composition and more particularly, to a composition comprising a silver halide deposited on suitable colloidal particles of a hydrous oxide.

The photosensitive silver halide composition is a wetting silver halide composition in that it is capable of l) rendering a non-wettable surface wettable and (2) tenaciously adhering to the non-w'ettable or hydrophobic surface. The composition comprises a silver halide deposited or sorbed on colloidal particles of a hydrous oxide of at least one element selected from the group comprising Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Cu, Zn, Cd, Hg, Al, In, Si, Ge, Sn, Th. The method of forming such a composition includes combining a suitable silver salt, e.g., AgNO with a suitable stable aqueous wetting colloidal solution, formed by a controlled hydrolysis and nucleation reaction, comprising a halide ion and insoluble hydrous oxide particles of a selected element in its most stable oxidation state which does not oxidize in water in the presence of oxygen or reduce silver ions (Be Mg, Ti, Zr, V, V, Cr, MO+6, w-t-fi w u F -HS n +2 +2 +2 va +3 +1 "n+1 n n s -l-i and Th). The particles have a size within the range of A to 10,000A and the hydrolysis reaction includes at least l dissolution of a salt of the selected element in an aqueous medium and (2) maintenance of thepH of the aqueous medium at a point where no flocculate results.

DETAILED DESCRIPTION The present invention is described primarily in terms of a wetting photosensitive silver halide composition and a method of forming such a composition. However, it will be understood that such description is exemplary only and is for purposes of exposition and not for purposes of limitation. It will be readily appreciated that the inventive concept described is equally applicable to wetting compositions comprising a photosensitive halide of an element other than silver, e.g., Hg.

A suitable silver salt is selected. A suitable silver salt is one which is water soluble and which is compatible with a suitable colloidal wetting solution, comprising a halide ion and an insoluble hydrous oxide of a selected element, with which the silver salt is destined to be combined. By compatible is meant that the silver salt is not reduced to metallic silver by the colloidal solution and the colloidal state of the solution is not destroyed by the addition of the silver salt thereto. The silver salt, e.g., AgNO is dissolved in water to form an aqueous solution typically in concentration of about 0.1-1.0 weight percent of AgNO It is to be noted, however, that the concentration of the aqueous AgNO solution is not critical and the invention is not to be restricted thereby.

A suitable aqueous colloidal wetting solution comprising a halide ion and insoluble colloidal particles of a hydrous oxide is selected. A suitable colloidal wetting solution is a stable colloidal wetting solution formed by a controlled hydrolysis and nucleation reaction in an aqueous medium wherein (l) colloidal particles of the colloidal solution have a size within the range of 10A to 10,000A, (2) colloidal particles of the colloidal solution comprise an insoluble hydrous oxide of one or more elements selected from the group comprising Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, nd Th, (3) no species is present, atomic or ionic, including any species of the above enumerated element, which is capable of reducing the silver salt, destined to be added thereto or combined therewith, to metallic silver, and (4) a halid ion is present. It is to be emphasized that the hydrous oxide is of an element in its most stable oxidation state which does not oxidize in water in the presence of oxygen or reduce silver ions to metallic silver. Typical of such elemental oxidation states are Be, Mg, Ti, Zr, V, V+4 3 w m n w s-2 +2 and/or hydroxides:

1. True Hydrous Oxides-Those oxides which include an indefinite amount of H 0 in other than stochiometric fashion. That is, a salt of a selected element hydrous H O.

2. True Hydroxides Those compounds of a salt which contain actual OH-groups. That is, a salt of a selected element only sufficient stochiometric H O to form a hydroxide.

3. Hydrous Hydroxides True hydroxides which also contain hydrOu'sI-I O in indefinite amounts. That is, a salt of a selected element stochiometric H O necessary to form a hydroxide hydrous H 0.

4. Hydrous hydrates A salt of a, selected element some of the stochiometric H O necessary to form a hydroxide hydrous H O.

A more detailed explanation of the term hydrous oxide" is contained in both Inorganic Colloid Chemistry by H. B. Weiser, Vol. 11, The Hydrous Oxides and I-Iyroxides," Chapter I, John Wiley and Sons, Inc., New York (1935); and Inorganic Chemistry, An Advanced to water carried by the compound in other than stochiometric fashion. Specifically, such water is probably 'not carried in chemical fashion but is rather surface sorbed, occluded or held as a part of the unit crystal.

The hydrolysis reaction includes dissolving a salt of the selected element in the aqueous medium and maintaining the pH of the aqueous medium at a point where no flocculate results.

Suitable colloidal solutions include some of the colloidal wetting solutions revealed in U.S. Pat. No. 3,657,003, filed Feb. 2, 1970, assigned to the assignee hereof and incorporated by reference herein. More specifically, the following solutions disclosed in U.S. Pat. No. 3,657,003 are some suitable colloidal wetting solutions for purposes of this invention:

1. The colorless (light, milky white) colloidal wetting solution of Example l-A which is obtained by (a) dissolving xweight percent of beryllium chloride [BeCl in 100 ml. of deionized water and (b) raising the initial pH of 3.0 to a value of 5.6-5.8 by adding dilute NH OH (H O dilution of 1/20) thereto; 1

2. The colorless (light, milky white) wetting solution of Example l-B which is obtained by (a) dissolving 1 weight percent of beryllium chloride [BeCl in 100 ml. of deionized water and (b) raising the inital pH with NaOH to about 5;

3. The colorless (light, milky white) wetting solution of Example l-C which is obtained by (a) adding V4 to weight percent of beryllium chloride [BeCl 4 to to 100 ml. of deionized water and (b) heating the resultant solution for about 1 hour at 70C;

4. The colorless (light, milky white) wetting solution of Example ll-A which is obtained by (a) dissolving 1 weight percent of magnesium chloride [MgCl or MgCl .6H O] in 100 ml. of deionized water and (b) raising the initial pH with univalent alkali to about 8;

5. The yellowwetting solution of Example llI-C which is obtained by (a) adding particulated titanium metal (Ti) to a hot or boiling (about 80C) concentrated univalent acid, such as HCl, until 0.2-3 weight percent of the titanium is dissolved, (b) allowing the solution to cool to room temperature, (c) adding sufficient H 0 to quantitatively render all the dissolved titanium (Ti to Ti and (d) raising the pH with a univalent alkali, such as NaOH,- to the range of about 1.2-2.0; 1

6. The blue wetting solution of Example Ill-D which is obtained by (a) adding particulated anhydrous titanium trichloride lTiCl to a concentrated univalent acid diluted with deionized water 1 weight percent of the titanium trichloride is dissolved and (b) raising the initial pH to about 10 with a univalent alkali, such as NaOH, to form TiO 7. The murky, pale yellow wetting solution of example lll-E which is'obtained by (a) adding one gram of fused titanium metal [Ti] to 70 ml. of concentrated HCl, (b) boiling the resultant solution until it assumes a pale blue color. (c) heating the solution without boiling until most or all of the titanium metal has been dissolved and reacted to obtain a blue-purple solution having a very low pH. ((1) raising the pH to about 0.5 with lN-NaOH to obtain a pale lavender solution, (e)

adding dilute 50% H 0 to the solution to render it colorless (adding l-2 drops in excess), and (f) raising the pH to about 1.0-1.2 with lN-NaOH;

8. The wetting solution of Example III-F which is obtained by adding 0.1-5 weight percent of solid particulated (about 100A) titanium dioxide [TiO to water;

9. The wetting solution of Example lll-G which is obtained by (a) adding 0.5-5 weight percent of titanium tetrachloride [TiCl to concentrated HCl and (b) slowly raising the initial pH of the resultant solution by the addition thereto of H 0 or a dilute base-such as NaOH or NH OH to a pH of 0.5-5;

10. The colorless (light, milky white) wetting solution of Example IV which is obtained by (a) dissolving 1 Weight percent zirconyl chloride [ZrOCl2.l-l O] in 100 ml. of deionized'water, (b) when the initial pH of the resultant solution is less than 1, heating the solution or adding thereto NaOH until the pH is about 1.4-2, or alternatively, if the pH is greater than 1 the pH is lowered to lor' less with a univalent acid, such as HCl, and (c) either heating or adding NaOH until the pH is about l .42;

11. The red-brown wetting solution of Example V-A which is obtained by (a) dissolving 1 weight percent of vanadium oxychloride [VOCl] in 100ml. of hot or boiling concentrated univalent acid such as HNO (b) raising the pH of the resultant solution to about 1.5-2 with a univalent alkali solution and (c) heating the solution and adding a small amount of H 0 thereto;

12. The red-brown colloidal wetting solution of Example V-B which is obtained by (a) dissolving 1 weight percent-of sodium vanadate [NaVO potassium vanadate [KVO or ammonium meta-vanadate [NH VO in 100 ml. of deionized water and (b) lowering the initial alkaline pH of the solution to a value of about 5-6 with HCl;

13. The brown-red colloidal wetting solution of Example V-C which is obtained by (a) adding 1/2 weight percent of vanadium tetrachloride [VCl to concentrated HCl and (b) slowly raising thepH to about 1, e.g., by diluting with H O;

14. The wetting solution of Example VI which is obtained'by (a) dissolving l/2 weight percent of green chromic chloride [CrCl .6H O], but probably more properly [Cr(H O) Cl ]Cl.2H O or [Cr(H O) Cl).6- H O] in 100 ml. of deionized water and (b) raising the initial pH of the resultant solution to about 5 with a univalent alkali;

15. The slightly yellow wetting solution of Example V" which is obtained by (a) dissolving 1 weight percent of sodium molybdate [Na MoO.,.2H O or Na.,(- 6Mo O- ).4H O] in 100 ml. of deionized water and (b) lowering the initial pH with a HCl to just below 7;

16. The faint yellow wetting solution of Example Vlll which is obtained by (a) dissolving l-5 weight percent of sodium tungstate dihydrate [Na WO .2H O] in 100 ml. of deionized water and (b) lowering the pH with a HCl to below 1;

17. The muddy brown wetting solution of Example lX-B which is obtained by (a) dissolving 1 weight percent of manganese trichloride [MnCl in sufficient 18. The tan wetting solution of Example X-A which is obtained by dissolving 1 weight percent of ferric chloride [FeCl .6H O] in 100 ml. of deionized water, the dissolution being added by gradually heating to about 50-80C and stirring to obtain a wetting solution at a pH of 1.7-1.9;

19. The wetting solution of Example X-B which is obtained by (a) dissolving 0.5-5 weight percent of ferric chloride [FeCl .6l-l O] in 100 ml. of deionized water, (b) adusting the final pH of the resultant solution to about 1.5-2.0 with either HCl (at low ferric chloride concentrations) or NaOH (at high ferric chloride concentrations) and (c) heating the solution to 70C within 20 minutes;

20. The wetting solution of Example X-C which is obtained by (a) dispersing 1.5 weight percent of ferric chloride [FeCl .6H O] in 100 ml. of deionized water to a final pH of about 1.7-1.9 and (b) allowing the resultant solution to stand in ambient for 1-2 weeks;

21. The wetting solution of Example X-D which is obtained in the same manner as Examples X-B and X-C, described above [(19) and (20)], except that ferric bromide [FeBr or FeBr .6l-l O] is employed;

22. The wetting solution of Example X-E which is obtained by dissolving 0.5-5 weight percent of ferric chloride [FeCl .6l-l O] in 100 ml. of deionized water which was first heated to 70C;

23..The wetting solution of Example X-F which is obtained by (a) adding l weight percent of ferric oxide [Fe O which was particulated and powdered to a particulate size of about 150A in 100 ml. of deionized water, (b) ultrasonically agitating the mixture to aid in the dissolution of the ferric oxide and (c) lowering the pH of the resultant solution from 3-3.5 to 1.0 with HCl;

24. The wetting solution of Example X-G which is obtained by (a) adding 1 weight percent of ferric oxide [Fe O which was particulated and powdered to a particulate size of about 150A in 100 ml. of deionized water, (b) ultrasonically agitating the mixture toaid in the dissolution of the ferric oxide [Fe O and (c) lowering the pH of the resultant solution from 3-35 to 1.0 with HCl;

25. The wetting solution of Example X-H which is obtained by (a) heating 100 ml. of deionized water to 80C and (b) adding 1-2 weight percent offerric chloride [FeCl .6H O] to the deionized water with stirring until dissolution occurs;

26. The blue wetting solution of Example Xl-A which is obtained by (a) dissolving 1 weight percent of cobaltous chloride [CoCl .6H O] in 100 ml. of deionized water and (b) raising the pH from 4.9-5.1 to about 7.0-7.2 with lN-NaOH;

27. The wetting solution of Example Xl-B which is obtained by (a) adding 1 weight percent of cobaltous chloride [CoCl .6H O] to 100 ml. of deionized water, (b) adding sufficient NaOH to the resultant solution to effect the onset of a Tyndal cone and (c) heating the solution to about 60-70C for 2 days while adusting the pH, as necessary, with NaOH to about 4',

28. The wetting solution of Example Xl-C which is obtained by (a) adding 1 weight percent of cobaltous chloride [CoCl .6H O] to 100 ml. of deionized water, (b) heating the resultant solution to about 60-70C with constant stirring, (0) raising the pH to about 2 with NaOH, (d) heating the solution again and raising the pH again to about 2 and (e) continuing the above procedure until the onset of a Tyndal cone or for about 6 hours (the resultant wetting solution has a life of about one hour);

29. The green wetting solution of Example XII-A which is obtained by (a) dissolving one weight percent of nickel chloride [NiCl .6H O] in 100 ml. of deionized water, (b) adding sufficient NaOH to effect the onset of a Tyndal cone and (c) heating the solution at about 6070C for 2 days keeping the pH adjusted to about 4 with NaOH;

30. The pale green wetting solution of Example Xll-B which is obtained by (a) dissolving 1 weight percent of nickel chloride [N iCl .6H O] in deionized water and (b) raising the pH of the resultant solution to about 6-6 .5 with Na0H;

31. The blue wetting solution of Example XV which is obtained by (a) dissolving 1 weight percent of cupric chloride [CuCl in 100 ml. of deionized water and (b) heating the resultant solution to about C while continually adjusting the pH to about 6 with Na0H;

32. The wetting solution of Example XVIII which is obtained by (a) dissolving 1 weight percent of zinc chloride [ZnCl in ml. of deionized water, (b) adding a sufficient amount of a univalent alkali, such as NaOH, to effect a slight precipitate at a pH of about 4, (c) heating the resultant solution at 60-80C until the precipitate dissolves, (d) adding dilute univalent alkali, such as NaOH, until the onset of a Tyndal cone, and tinally, (e) the heating and acid addition steps are repeated until a colloidal solution results;

33. The wetting solution of Example XIX which is obtained by (a) dissolving 1 weight percent of cadmium chloride [CDCL L /zH O] in 100 ml. of deionized water and (b) slowly raising the pH of the resultant solution (over several hours time) to about 8-9 with a very dilute univalent alkali, such as NaOH,

during which time the solution is slightly (about 34. The yellow wettin g amioh' of Example XX which is obtained by (a) dissolving 1 weight percent of mercuric chloride (corrosive sublimate) [HgCl in 100 ml. of deionized water and (b) slowly adding a dilute univalent alkali, such as Na0H, to raise the pH to about 5;

35. The wetting solution of Example XXI-A which is obtained byv (a) adding 1 weight percent of finely powdered aluminum chloride [AlCl to 100ml. of deionized water, (b) raising the pH to about 5.2 with a univalent alkali such as NaOH and (c) heating the resultant solution for about 2 hours at about 60-80C;

36. The wetting solution of Example XXI-B which is obtained by (a) heating 100 m1. of deionized water to about 60C. (b) adding 1 weight percent of aluminum chloride [AlCl .H O] thereto and (0) while the solution is still hot raising the pH from 2.5 to about 5.0- 5.2 with a univalent alkali, such as lN-NaOH;

37. The wetting solution of Example XXII-A which is obtained by (a) dissolving 1 weight percent of indium trichloride [lnCl in 100 ml. of deionized water and (b) raising the pH of the resultant solution to about 3 with NaOH;

38. The whitish wetting solution of Example XXII-B which is obtained by (a) dissolving )2 weight percent of indium monochloride [lnCl] in 100 m1. of deionized water and (b) raising the pH to about 3.9 with dilute (factor of 20 with H 0) Nl-l llH;

39. The yellow wetting solution of Example XXlll which is obtained by (a) adding 0.1 weight percent of thallium monochloride [TlCl] to 100 ml. of deionized water, (b) raising the pH of the resultant solution to about 7.58 with NaOH and adding a few ml. of dilute potassium ferricyanide [K Fe(CN) to the solution with stirring; I

40. The wetting solution of Example XXIV which is obtained by (a) adding 0. lweight percent of silicon tetrachloride or tetrachlorosilane [SiCl to concentrated HCl and (b) stirring the resultant solution;

41. The colloidal wetting solution of Example XXV which is obtained by (a) adding 1-2 weight percent of germanium tetrachloride [GeCl to concentrated HCl and (b) diluting the resultant solution with H 0 to raise the pH to about 0.5;

42. The wetting solution of ExampleXXVl-A which is obtained by (a) dissolving l-3 weight percent of stannic chloride [SnCl .5H O] in 100 ml. of deionized water and (b) permitting the resultant solution to stand at room temperature for l-3 days or at an elevated temperature (about 60C) for about 1 hour until a flocculate forms. The supernatant portion is a wetting solution;

43. The wetting solution of Example XXVl-B which is obtained by (a) dissolving kweight percent of stannic chloride [SnCl .5H O] in .100 ml, of deionized water and (b) permitting the solution of stand for about 1 month until the pH thereof is about 0.8 l.8 and a flocculate forms at the bottom thereof. The supernatant portion of this solution is the wetting solution;

44. The colorless wetting solution of Example XXVI- C which is obtained by adding sufficient HCl to the bottom layer (containing the flocculate) of the solution of Example XXVI-B, described above, to lower the pH to about 0.8-].8;

45. The colorless wetting solution of Example XXVI- D which is obtained by heating to 90C for about 30 minutes the bottom layer (containing the flocculate) of the solution of Example XXVI-B, described above;

46. The wetting solution of Example XXVI-E which is obtained by (a) dissolving 1 weight percent of sodium hydroxo stannate [Na Sn0 .3H 0 or Na Sn(0H) in 100 ml. of deionized water and (b) lowering the pH of the resultant solution to about 7.5-8.5 by the slow addition of HCl;

47. The colorless (milky white) wetting solution of Example XXVlll which is obtained by (a) dissolving l weight percent of bismuth trichloride [BiCl in 100 ml. of dilute (pH about 0.2) HCl and (b) raising the I pH of the resultant solution to about 3-4 with NaOH;

suitable colloidal solution with which it is destined to be combined. Following the pH adjustment, if required, the aqueous AgNO solution is added to a selected suitable colloidal solution comprising a halide ion and insoluble colloidal hydrous oxide particles of a particular element. Upon the addition of the aqueous AgNO solution, a reaction occurs between the Agfions and the halide ion, e.g., Cl, Br, 1, contained in the colloidal solution whereby a silver halide, e.g., AgCl, AgBr, Agl, forms and is precipitated or deposited or sorbed on the individual colloidal hydrous oxide particles.

It is to be noted and stressed at this point that both the silver halide formed and the solution containing the silver halide are wetting, i.e., they both are capable of rendering a hydrophobic surface hydrophilic and also the silver halide composition formed is capable of adhering very well to the hydrophobic surface. In this regard, a film of the silver halide deposited on a hydrophobic surface, e.g., polytetrafluoroethylene, cannot be removed by the application of a cellophane adhesive tape peel test thereto. It is also to be noted and stressed at this point that usually upon the addition of an electrolyte to a colloidal solution flocculation of the colloid occurs destroying the colloidal solution and the properties associated therewith, e.g., wetting ability. Surprisingly, such has been found not to occur with the addition of the silver salt, e.g., AgN0 to the abovedescribed colloidal wetting solutions. The resultant solution retains both its colloidal state and its wetting ability (along with the formed silver halide).

Where the resultant silver halide composition is intended for photographic applications, a suitable support base, e.g., a cellulose support, a paper support, etc., is selected. Suitable support bases and the properties thereof depend upon the purpose of the photographic application. Such support bases are well known in the art to those skilled therein and will not be elaborated herein. The selected support base (hydrophilic or hydrophobic) is immersed in the resultant colloidal solution, comprising colloidal hydrous oxide particles having a silver halide deposit thereon, for a period of time sufficient to uniformly wet the surfaces thereof with the solution and deposit a uniform film of silver halide coated colloidal particles thereon. For most support bases an immersion of about one minute at 25C is sufficient. In the case of a Teflon (polytetrafluoroethylene) support base, which is very hydrophobic and upon which a silver halide gelatin film cannot adequately adhere, an immersion of about 10 minutes is required.

It is to be noted that the amount of deposited film can be controlled by the length of time the surface or support base is immersed in the resultant wetting silver halide colloidal solution. The deposit can also be built up by removing the support base from the colloidal solution, rinsing, drying, heating at 60 to C for l-5 minutes and then repeating the sequence of steps starting with the immersion.

The support base is removed from the wetting silver halide containing colloidal solution, is rinsed in flowing deionized water and is then air dried. A surface coated with a wetting silver halide film is then selectively exposed to a source of suitable photographic light radiation to obtain a latent image comprising silver metal [Ag] nuclei on those areas of the surface exposed. It is to be noted that the silver halide film coated surface is exposed to the light radiation for a period of time sufficient to form the latent image. Such a period of time is readily ascertained experimentally by one skilled in the art for a particular light source. It is to be noted, however, that the time of exposure is interdependent upon the intensity of the light source, i.e., upon the amount of energy transmitted by the source to the surface. This interdependency is well known in the art or is easily ascertained by one skilled therein. A typical exposure may range from 1 to 10 millijoules/cm at a wavelength ranging from 2000 to 3600A. It is to be pointed out that the wavelength dependence can be altered employing standard techniques well known in the art, e.g., by the use of various dyes.

The latent image is then developed using conventional silver halide photographic developers, including development of the silver halide by exposure to suitable radiation, which are well known to those skilled in the art and which will not be elaborated herein. Alternatively, the latent image can be physically developed by immersion in an electroless metal plating solution wherein the silver nuclei catalyze the reduction of electroless metal ions of electroless metal to obtain an electroless metal pattern corresponding to the latent image.

EXAMPLE I A. A 1.0 weight percent aqueous AgNO solution was prepared. The pH of the solution was adjusted with HNO to a value of about 5. The resultant AgNO solution was then added, in a concentration of 005 Weight percent of the total solution, to a stable colloidal solution comprising (1) colloidal particles of a hydrous oxide of beryllium and (2) chloride ions, to form silver chloride which was deposited on or covered each of the individual colloidal beryllium hydrous oxide particles. The colloidal solution was prepared in the following manner. One weight percent of beryllium chloride [BeCl was added to and dissolved in 100 ml. of deionized water. The initial pH was raised with NaOH until it was about 5 whereat a Tyndal cone was observed.

A hydrophobic polyethylene terephthalate film, commercially obtained, was immersed in the resultant wetting silver chloride deposited colloidal solution for about 2 seconds at 25C. The film was removed and rinsed in flowing deionized water for one minute whereafter it was air dried. This procedure was then repeated but with a hydrophobic polyimide film, commerically obtained. This procedure was repeated again but with a hydrophobic polytetrafiuorethylene film which was immersed in the resultant solution for 20 minutes. i

A surface of each of the dried films (polyethylene terephthalate, polyimide and polytetrafluoroethylene), having a photosensitive layer comprising silver chloride deposited or coated colloidal beryllium hydrous oxide particles, was then selectively exposed to a source of ultraviolet radiation (l millijoules/cm intensity, A 2537A). The light-exposed surface was then immersed in an electroless copper plating solution, commercially obtained. to obtain a 0.01 mil thick electroless copper deposit on the areas of each surface exposed to the light.

B. The procedure of Example l-A was repeated except that 0.5 weight percent (of the total weight of the resultant mixture) of AgNO was added to the colloid solution.

A physical development comprising a 0.01 mil thick electroless copper pattern on each of the three respective film surfaces was obtained.

C. The procedure of Example I-A was repeated except that the beryllium hydrous oxide colloid particle containing solution was prepared in the following manner. One weight percent of beryllium chloride [BeCl' was dissolved in 100 ml. of deionized water. The initial pH of the solution was raised with NaOH until it was about 5 whereat a Tyndal cone was observed. A colorless (e.g., light, milky white) wetting solution was obtained. The pH of the aqueous AgNO solution was adjusted to about 5 and was combined with the colloidal solution in a concentration of 0.05 weight percent Ag- N0 A physical development comprising a 0.01 mil thick electroless copper pattern on each of the three respective film surfaces was obtained.

D. The procedure of Example l-A was repeated except that the beryllium hydrous oxide colloid particle containing solution was prepared in the following manner. About 1/4 weight percent of beryllium chloride [BeCl was added to deionized water. The resultant solution was heated for about l hour at 70"C resulting in a colorless (light, milky white) colloid wetting solution. The aqueous AgNO solution was adjusted to a pH of 5.0 prior to the addition thereof to the colloidal solution.

EXAMPLE II The procedure of Example I-A was repeated except that a colloid solution comprising. colloidal hydrous o'xide particles of magnesium was employed. The colloidal solution was prepared in the following manner. One weight percent of magnesium chloride [MgCl or MgCl .2H O] was dissolved in ml. of deionized water. The initial pH of the solution was then raised with a univalent alkali, i.e. NaOH to about 8. A colorless (light, milky white) wetting solution was produced. The aqueous AgNO solution was added to the colloidal solution.

EXAMPLE 111 A. The procedure of Example l-A was repeated except that a 1 weight percent aqueous AgNO solution was prepared and added to a colloidal solution comprising colloidal hydrous oxide particles of chromium. The AgNO was present in the resultant solution in a concentration of 0.5 weight percent. The colloidal solution was prepared in the following manner. One-half weight percent of a green chromic chloride [CrCl .6l-1 O] was dissolved in 100 ml. of deionized water. The initial pH was raised to about 5 with NaOH to obtain a green wetting solution. Prior to combining the aqueous solutions, the pH of the AgNO solution was adjusted to about 5 with HNO A physical development evidenced by a 0.01 mil thick electroless copper pattern on each of the three respective film surfaces was obtained.

B. The procedure of Example Ill-A was repeated except that the AgNO added to the colloidal solution was present in an amount of 0.01 weight percent. The results obtained were the same as in Example II-A above.

EXAMPLE IV The procedure of Example l-A was repeated except that a 0.1 weight percent aqueous AgNO solution was prepared. The aqueous AgNO solution was combined with a stable aqueous colloidal solution comprising colloidal hydrous oxide particles of cobalt, The AgNO being present in a concentration of 0.01 weight percent. The colloidal solution was prepared in the following manner. One weight percent of cobaltous chloride [CoCl .6H O] was added to 100 ml. of deionized water 5 to form a rose colored solution having a' pH of about 4.9-5.1. The pH was then raised with NH OH to about 7.5-7.8 to obtain a blue wetting solution.

A physical development evidenced by a 0.01 mil thick electroless copper pattern on each of the. three respective film surfaces was obtained.

EXAMPLE V The procedure of Example l-A was repeated except that the 0.1 weight percent aqueous AgNO solution was combined with a stable colloidal solution comprising colloidal hydrous oxide particles of copper, the

AgNO being present therein in a concentration of 0.05 weight percent. The colloidal solution was prepared in the following manner. One weight percent of cupric chloride [CuCl was dissolved in 100 ml. of deionized water. The pH of the solution was raised by the slow addition of a 10% solution of NH OH to a pH of 7.2-7.5. This was a wetting solution.

A physical development evidenced by a 0.01 mil thick electroless copper pattern on each of the three respective film surfaces was obtained.

EXAMPLE VI A. The procedure of Example l-A was repeated except that a 0.1 weight percent aqueous AgNO solution was prepared. The resultant AgNo solution was then combined with a colloidal aqueous solution comprising insoluble hydrous oxide particles of zinc, the AgNO being present in the resultant mixture in a concentration of 0.05 weight percent. The colloidal hydrous zinc oxide solution was prepared in the following manner. One weight percent of zinc chloride -[ZnCl was dissolved in 100 ml. of deionized water. A sufficient amount of NH OH was then added to the resultant solution to obtain a pH of about 7.0-7.5 to yield a colloidal wetting solution.

B. The procedure of Example Vl-A was repeated except that the AgNO was added to the colloidal solution in a concentration of 0.05 weight percent. The results obtained were the same as in Example Vl-A.

EXAMPLE Vll A. The procedure of Example l-A was repeated except that a 0.01 weight percent aqueous AgNO solution was prepared whose pH was adjusted to about 5.2 by the addition of HNO thereto. The resultant AgNO solution was then combined with a colloidal aqueous solution comprising insoluble hydrous oxide particles of aluminum. The AgNO was present in the resultant mixture in a concentration of 0.5 weight percent. The colloidal solution was prepared in the following manner. One weight percent of finely powered aluminum chloride [AlCl was added to 100 ml. of deionized water. The pH of the resultant solution was raised with NaOH to about 5.2. This solution was heated for about 2 hours at about 6080C to yield a colorless (milky white wetting solution.

A physical development evidenced by a 0.01 mil thick electroless copper pattern on each of the three respecitve film surfaces was obtained.

B. The procedure of Example VII-A was repeated except that the AgNO was added to the colloidal solution in a concentration of 0.05 weight percent. The results obtained were the same as in Example Vll-A.

EXAMPLE \llllv The procedure of Example l-A was repeated except that a 0.1 weight percent aqueous AgNO solution was prepared whose pH was adjusted to about 3 by the addition of HNO thereto. The resultant AgNO solution was then combined with a colloidal aqueous solution comprising insoluble hydrous oxide particles of indium, the AgNO being present in the resultant mixture in a concentration of 0.05 weight percent. The colloidal solution was prepared in the following manner. One weight percent of indium trichloride [lnCl was dissolved in ml. of deionized water. The pH of this solution was raised to about 3 with NaOH yielding a colorless (milky white) wetting solution.

A physical development evidenced by a 0.0l mil thick electroless copper pattern on each of the three respective film surfaces was obtained.

EXAMPLE IX A. The procedure of Example I-A was repeated except that a 0.01 weight percent aqueous AgNO solution was prepared whose pH was adjusted to about 1.0 by the addition of HNO thereto. The resultant AgNO solution was then combined with a colloidal aqueous solution comprising insoluble hydrous oxide particles of tin, the AgNO being present in the resultant mixture in a concentration of 0.05 weight percent. The colloidal solution was prepared in the following manner. One weight precent of stannic chloride [SnCl.,.5H O] was dissolved in 100 ml. of deionized water. The solution was allowed to stand at a temperature of about 60C for 1 hour until a flocculate formed.

B. The procedure of Example lX-A was repeated except that the colloidal solution was prepared in the following manner. One-half weight precent of stannic chloride [SnCl.,.5H O] was dissolved in 100 ml. of deionized water. The resultant solution was allowed to stand for approximately 1 month until the pH thereof was about 0.8-1.8 and a flocculate formed at the bottom thereof. The supernatant portion is a wetting solution. The pH of the AgNO was adjusted to about 0.8-1.8 by the addition of HNO thereto and was then combined with the supernatant portion.

A physical development evidenced by a 0.01 mil thick electroless copper pattern on each of the three respective film was obtained.

C. The procedure of Example lX-A was repeated except that the colloidal wetting solution was prepared in the following manner. The bottom layer containing the flocculate, described in Example lX-B, above, had added thereto sufficient HCl to lower the pH to about 0.8 -1 .8 to yield a colorless (milky white) wetting solution. The results achieved were the same as in Example lX-B, above.

D. The procedure of Example lX-B was repeated except that the colloidal wetting solution was prepared in the following manner. The bottom layer containing the flocculate of the solution of Example IX-B, described above, was heated to 3090C for about 30 minutes to yield a colorless (milky white) wetting solution. The results obtained were the same as in Example lX-B, above. 1

E. The procedure of Example lX-A was repeated except that the colloidal wetting solution was obtained in the following manner. To concentrated HCl was added 2 weight percent of stannic chloride [SnCl .5H O]. The initial pH of this solution was raised to within the range of 0.5-0.8 with NaOH to yield a colloidal wetting solution. The pH of the aqueous AgNO solution was similary adjusted to 0.5-0.8 by the addition thereto of HNO prior to the combining with the colloidal solution.

F. The procedure of Example lX-A was repeated except that the colloidal wetting solution was prepared in the following manner. To concentrated HBr was added l-2 weight percent of stannic bromide [SnBr The pH of the resultant solution was then raised to within the range of 1.0-1.1 with NaOH. The pH of the aqueous AgNO solution was then lowered to 1.0-1.1 by the addition of HNO thereto prior to combining with the col loidal solution. Upon the combining of the AgNO solution with the colloidal wetting solution a silver bromide, deposit on the colloidal tin hydrous oxide partcles was obtained which was photosensitive.

EXAMPLE 'X A. The procedure of Example l-A was repeated except that a 0.1 weight percent aqueous AgNO solution was prepared whose pH was adjusted to about 1.7-1 .9 by the addition of HNO thereto. The resultant AgNO solution was then combined with a colloidal aqueous solution comprising insoluble hydrous oxide particles of iron, the AgNO being present in the resultant mixture in a concentration of 0.05 weight percent. The colloidal solution was prepared in the following manner. One weight percent of ferric chloride [FeCl .6H O] was dissolved in 100 ml. of deionized water. This solution was aided by gradually heating to about 60-80C and stirring. At a pH of about 1.7-1 .9 a tan wetting solution was produced.

A physical development evidenced by a 0.01-mil thick electroless copper pattern on each of the three respective film surfaces was obtained.

B. The procedure of Example X-A was repeated except that the colloidal wetting solution was prepared in the followingmanner. One-half weight percent of ferric chloride [FeCl .6H O] was dissolved in 100 ml. of deionized water. The final pH of this solution was ad justed to about 1.5-2.0 with HCl. The solution was then heated to 70C within 20 minutes yielding a coffeepumpkin color wetting solution.

C. The procedure of Example X-A was repeated except that the colloidal wetting solution was prepared in the following manner. One-half weight percent of ferric 14} chloride [FeCl .6H O] was dispersed in 100 ml. of deionized water of a final pH of about 1.7-1 .9. The solution was allowed to stand in ambient for l-2 weeks thereby yielding a coffee-pumpkin color wetting solution. Prior to the combining of the AgNO with the resultant wetting solution the aqueous AgNO solution was adjusted to a pH of l.7-l'.9 by the addition of HNO thereto.

D. The procedure of Example X-A was repeated except that the colloidal wetting solution was prepared in the following manner. 100 ml. of deionized water was first heated to C. 1.5-5 weight percent of ferric chloride was added thereto and dissolved therein. The final pH of this wetting solution was 1.5-2.0. The pH of the aqueous AgNO; solution was adjusted to 1.5-2.0 by the addition of HNO thereto prior to combining the AgNO with the colloidal solution.

E. The procedure of Example X-A was repeated except that the colloidal wetting solution was prepared in the following manner. 100 ml. of deionized water was heated to C. l-2 weight percent of ferric chloride was added and the solution was stirred until the ferric chloride dissolved. Upon cooling to 25C a vermouth colored wetting solution was obtained. The pH of the aqueous AgNO solution was adjusted to 1.3 by the addition of HNO thereto and then combined with the resultant wetting solution.

F. The procedure of Example X-A was repeated except that 0.5 weight percent of sodium bromide (NaBr) was added to the colloidal wetting solution prior to the combination of AgNO therewith. A mixed silver halide salt was obtained, namely, silver bromide and silver chloride, which were deposited on the hydrous oxide colloidal particles to form a photosensitive composition.

G. The procedure of Example X-F was repeated except that 0.5 weight percent of sodium iodide (Nal) was added. A mixed silver chloride, silver iodide deposit was obtained to yield a photosensitive composition.

H. The procedure of Example X-A was repeated except that the colloidal wetting solution was prepared as follows. One weight percent of ferric bromide [FeBr .6H O] was dissolved in ml. of deionized water. The solution was heated to about 60C forabout 16 hours resulting in a colloidal wetting solution having a pH of about 1.8. The aqueous AgNO solution was adjusted to a pH of 1.8 by the addition of HNO thereto and was then combined with the colloidal solution. Silver bromide was deposited or precipitated on the colloidal iron hydrous oxide particles to form a photosensitive composition.

1. The procedure of Example X-H was repeated except that 2.0 weight percent of ferrous iodide [Fel .4- H O] was employed. The pH of the resultant colloidal wetting solution was 2.5. The pH of the aqueous AgNO solution was adjusted to about 2.5 by the addition of HNO thereto and was then added to the colloidal wetting solution. Silver iodide was deposited or precipitated on the colloidal iron hydrous oxide particles to form a photosensitive composition.

It is to be understood that the above-described embodiments are simply illustrative of the principles of the invention. Various other modifications and changes may be made by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof.

What is claimed is:

1. A photosensitive silver halide composition comprising a silver halide deposited on colloidal particles of a hydrous oxide of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, in, T1, Si, Ge, Sn, Bi, Th, and mixtures thereof.

2. The composition as defined in claim 1 wherein said silver halide comprises silver chloride.

3. A photosensitive silver halide composition comprising silver halide precipitated in the presence of a stable aqueous colloidal wetting solution, formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, ln, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof, said particles having a size within the range of A to l0,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected element in an aqueous medium and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results.

4. The composition as defined in claim 3 wherein said silver halide comprises silver chloride.

5. A method of forming a wetting photosensitive silver halide composition which comprises combining a suitable silver salt with a stable aqueous colloidal wetting solution, formed by a hydrolysis and nucleation reaction, comprising (a) a halide ion and (b) insoluble hydrous oxide particles of an element selected from the group consisting of Be,Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, A], In, Tl, Si, Ge, Sn, Bi,

further comprises treating the exposed film with a Th, and mixtures thereof, said particles having a sizewithin the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected element in an aqueous medium and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results.

6. The method as defined in claim 5 wherein said suitable silver salt comprises AgNO and said halide ion comprises a chloride ion.

7. A method of rendering a surface photosensitive which comprises: I

a. combining a water-soluble silver species with a stable aqueous colloidal wetting solution, formed by a hydrolysis and nucleation reaction, comprising a halide species and insoluble hydrous oxide particles of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, A], In, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof, to precipitate a silver halide and to coat said hydrous oxide particles with said precipitated silver halide; and

b. contacting the surface with said coated particles to deposit a photosensitive film thereof thereon.

8 The method as defined in claim 7 wherein said silver species comprises AgNO and said halide species comprises chloride ions.

9. In the method of making a photographic image comprising exposing to a light image a photosensitive film comprising silver halide to form a latent image therein, the improvement wherein the photosensitive film which comprises a silver halide deposited on insoluble collidal particles of a hy-' drous oxide of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof. 1( The method as defined in claim 9 wherein said silver halide comprises silver chloride.

11. The method as defined in claim 9 which suitable developer to develop a visible image therein.

12. The method as defined in claim 9 which further comprises depositing said silver halide deposited colloidal particles on a support medium to form the photosensitive film thereon.

L SSS-PT UNITED STATES PATENT OFFICE CERTIFICATE OF CQRRECTIQN p 3, 5 ,95 Damd December 17, 197A lnventor(s) J- 1" Ken-ney It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the specification, Column 1, line ll, "2. 1 Description" should read 2. Description-. Column 2, line 27, "hd Th" should read --ahd Th-, line 31, "halid" should read -halide-; line 65, "Vol. ll," should read -Vol. II,-. Column 3, line 1, "nd Sons should read -and Sons; lin 33, M to to" should read --to--; line 55, "water 1" should read water until l-; line 59, "example" should read -EXample. Column A, line 13, "0.5-5" should read -O.5l.5-5 line 65, "0.6-8" shouldread --o.6-o.8--. Column 6, line 32, "CDCL .l/2H2O" should read -CdCl2.l/2H2O- line 53, "60C." should read -60C,--. Column 7, line 2i, "1/2 weight" should read --l/2-2 weight--; line 26, "of stand" shoid read --to stande-.

Column 9, line 1%, "ions of" should read --ions to--. Column ll, line 1, "cobalt, The" should read --cobalt, the, line 33, AgNog" should read --AgNO line 37, '0.05" should read -O.5-5 line 5M, "0.01" should read -O.l-; line 62, "powered" should read --powdered--. Column 12, line #6, "precent" should read --percent-; line 57, "film was" should read --film surfaces was-. Column 1M, line 2, "water of" should read water to--.

In the claims, Column 16, claim 9, line 31, "wherein" should read -wherein:-.

Signed and Eaealcd this twenty-sixth Day Of August 1975 [SEAL] A ttes r.-

RUTl-l C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Patents and Trademarks Q L-566-PT UNITED STATES PATENT OFFICE L. J IFICATE OF CORRECTION Patent 3,85%,952 Dated December 17, 1974 Inventor-(s) Kenney h is certified that error appears in the above-idenrified parent and that said Letters Parent are hereby corrected as shown below:

In the specification, Column 1, line ll, 2 1 Description" should read 2. Description. Column 2,

' line 27, "nd Th should read and Th"; line 31, halid" should read halide-, line 65, "vol. ll, should read Vol. II,--. Column 3, line l, "nd Sons should read and Sons"; line 33, to to" should read -to--; line 55, "water 1" should read Water until l-, line 59, "example" should read -EXample. Column L, line 13,

9 "0.5-5" should read "0.5-1.5"; line 65, 0.6-8 should read --o.6-o.8--. Column 6, line 32, CDCL .l/2H O" should read -CdCl2.l/2H O--- lin 53, "60C." should read --60C,--. Column 7, line 2i, "1/2 Weight should read -l/22 weight"; line 26, "of stand" should read to 6 stand\--.

Column 9, line l t, "ions of" should read ions to. Column ll, line 1, "cobalt, The" should read cobalt, the, line 33, AgNog" should read --Agl\TO --5 line 37, 0.05 should read --o.5--, lihs 5A, "0.01" should read O.l-; line 62, "powered" should read powdered-- Column 12, line #6, "precent" should read -percent-; line 57, film was" should read film surfaces was--. Column l t, line 2, water of" should read water to.

In the claims, column 16, claim 9, line 31, wherein should read Wherein:

Signed and Sealed this twenty-sixth Day Of August1975 Q [SEAL] Arrest:

RUTH C. MASON c. MARSHALL DANN Commissioner of Patentr and Trademarks Alresting Officer

Claims

1. A PHOTOSENSITIVE SILVER HALIDE COMPOSITION COMPRISING A SILVER HALIDE DEPOSITED ON COLLOIDAL PARTICLES OF A HYDROUS OXIDE OF AN ELEMENT SELECTED FROM THE GROUP CONSISTING OF BE, MG, TI, ZR, V, CR, MO, W, MN, FE, CO, NI, CU, ZN, CD, HG, AL, IN, TL, SI, GE, SN, BI, TH, AND MIXTURES THEREOF.

3. A photosensitive silver halide composition comprising silver halide precipitated in the presence of a stable aqueous colloidal wetting solution, formed by a hydrolysis and nucleation reaction, comprising insoluble hydrous oxide particles of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof, said particles having a size within the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected element in an aqueous medium and (2) maintenance of the pH of said aqueous medium at a point where no flocculate rEsults.

5. A method of forming a wetting photosensitive silver halide composition which comprises combining a suitable silver salt with a stable aqueous colloidal wetting solution, formed by a hydrolysis and nucleation reaction, comprising (a) a halide ion and (b) insoluble hydrous oxide particles of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof, said particles having a size within the range of 10A to 10,000A and said hydrolysis reaction including at least (1) dissolution of a salt of said selected element in an aqueous medium and (2) maintenance of the pH of said aqueous medium at a point where no flocculate results.

6. The method as defined in claim 5 wherein said suitable silver salt comprises AgNO3 and said halide ion comprises a chloride ion.

7. A method of rendering a surface photosensitive which comprises: a. combining a water-soluble silver species with a stable aqueous colloidal wetting solution, formed by a hydrolysis and nucleation reaction, comprising a halide species and insoluble hydrous oxide particles of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof, to precipitate a silver halide and to coat said hydrous oxide particles with said precipitated silver halide; and b. contacting the surface with said coated particles to deposit a photosensitive film thereof thereon.

8. The method as defined in claim 7 wherein said silver species comprises AgNO3 and said halide species comprises chloride ions.

9. In the method of making a photographic image comprising exposing to a light image a photosensitive film comprising silver halide to form a latent image therein, the improvement wherein the photosensitive film which comprises a silver halide deposited on insoluble collidal particles of a hydrous oxide of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Bi, Th, and mixtures thereof.

10. The method as defined in claim 9 wherein said silver halide comprises silver chloride.

11. The method as defined in claim 9 which further comprises treating the exposed composition with a suitable developer to develop a visible image therein.