US3887597A - Process for producing an organic silver carboxylate - Google Patents

Process for producing an organic silver carboxylate Download PDF

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US3887597A
US3887597A US356560A US35656073A US3887597A US 3887597 A US3887597 A US 3887597A US 356560 A US356560 A US 356560A US 35656073 A US35656073 A US 35656073A US 3887597 A US3887597 A US 3887597A
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carboxylic acid
silver
acid
solution
mercuric
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Kinji Ohkubo
Takao Masuda
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP4386772A external-priority patent/JPS491511A/ja
Priority claimed from JP4845372A external-priority patent/JPS4911814A/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49809—Organic silver compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part

Definitions

  • the present invention relates to a process of produc ing a silver salt of an organic carboxylic acid (in the present specification the terms silver salt of organic carboxylic acid, and organic silver carboxylate refer to the reaction product of the process of the present invention between silver and the organic carboxylic acid.
  • the former is generally used.
  • More particularly it relates to a process for producing a silver salt of an organic carboxylic acid having a fine grain size which is suitable for use in a thermally developable lightsensitive element.
  • the present invention is directed to a process for producing silver salt of an organic carboxylic acid which comprises mixing an aqueous silver nitrate solution or an aqueous silver complex solution with a solution of an organic carboxylic acid in a solvent which is sparingly miscible with water, in which the organic carboxylic acid is soluble and the silver salt of an organic carboxylic acid and silver nitrate are hardly soluble to react, whereby the reaction of the organic carboxylic acid and silver ions is conducted in the presence of a mercury or lead compound(s).
  • the thermally developable light-sensitive material is substantially composed of a silver salt of an organic carboxylic acid, e.g., silver behenate, silver halide obtained by reacting a halide with the silver salt or silver halide separately prepared and a reducing agent. After the thermally developable light-sensitive material is exposed imagewise and heated, a silver image is obtained by the reaction of the silver salt of an organic carboxylic acid with the reducing agent which is caused by the action of the exposed silver halide upon heating.
  • an organic carboxylic acid e.g., silver behenate
  • silver halide obtained by reacting a halide with the silver salt or silver halide separately prepared and a reducing agent.
  • the light-sensitive material is usually merely heated after imagewise exposure to develop it, and other operations are omitted. That is, operations for silver halide photographic light-sensitive materials are not conducted such operations involving treating after development with a fixing solution containing a compound capable of forming a silver halide complex, e.g., sodium thiosulfate, to convert the undeveloped silver halide to a watersoluble silver complex which is washed with water to remove the silver complex and then fixed.
  • a compound capable of forming a silver halide complex e.g., sodium thiosulfate
  • the silver salt of an organic carboxylic acid which is employed in a thermally developable light-sensitive material is not eliminated after development, unlike silver halide employed in a silver halide photographic light-sensitive material. Accordingly, a transparent photographic film cannot be formed when a silver salt of an organic carboxylic acid used in a thermally developable light-sensitive material is coated on a transparent film support. There are, of course, no difficulties in coating on opaque paper.
  • thermally developable elements are different from silver halide photographic lightsensitive materials in which fixing is conducted after development where the coated layer which is opaque before development is developed, fixed and washed with water to remove silver halide, so that the lightsensitive material thus treated becomes transparent, even if silver halide having a coarse grain size is used in a silver halide photographic light-sensitive material.
  • a silver salt of an organic carboxylic acid having a fine grain size must be employed as the silver salt of an organic carboxylic acid used in the case that a transparent light-sensitive material coated layer is desired using a silver salt of an organic carboxylic acid in a thermally developable light-sensitive material.
  • Silver salts of an organic carboxylic acid have been prepared, e.g., by adding an aqueous silver nitrate solution to an aqueous solution of an organic carboxylate such as the sodium salt of an organic carboxylic acid, which is described, for instance, in the Examples of Japanese Pat. Publication No. 13354/66 and Japanese Pat. Publication No. 4924/68. According to this process, however, coarse spindle-like crystals in which the long side thereof is over several microns is obtained. Coating of such coarse silver salt of an organic carboxylic acid grains on, e.g., a transparent film support, gives an opaque coated layer. Further, insufficient image density is obtained since it is difficult to develop.
  • a process which comprises incorporating a solution of a silver salt of an organic carboxylic acid in a water-immiscible solvent into an aqueous solution of an alkalisoluble silver complex to obtain silver salt of an organic carboxylic acid having fine grain size, which is described in US. Pat. No. 3,458,544.
  • the silver salt of an organic carboxylic acid in accordance with the above process is in the form of fine spindles having about a llL long side diameter so that .
  • a thermally developable light-sensitive material obtained from the silver salt of an organic carboxylic acid gives an image having a clear, high density after exposure and thermal development, while the coated layer is still somewhat opaque when coated on a transparent film support, and thus a transparent thermally developable photographic film can not be obtained.
  • the present invention is directed to a process of producing a silver salt of an organic carboxylic acid which comprises mixing an aqueous silver nitrate solution or an aqueous silver complex solution with a solution of an organic carboxylic acid in a solvent in which the organic carboxylic acid is soluble, both the silver salt of an organic carboxylic acid and silver nitrate are almost insoluble and with which water is sparingly miscible, to react the organic carboyxlic acid with silver ions, the reaction being conducted in the presence of a mercury compound or a lead compound.
  • a silver salt of an organic carboxylic acid having a grain size of less than 1p. in diameter which is almost spherical can be obtained by the reaction of the organic carboxylic acid with silver ions in the preparation of the silver salt of an organic carboxylic acid having a fine grain size as described above when the reaction is conducted in the presence of a lead compound or a mercury compound.
  • a surface active agent may be present when reacting the organic carboxylic acid and the silver ion.
  • One object of the present invention thus lies in easily producing a silver salt of an organic carboxylic acid of fine grain size by which images having high resolving power can be obtained and which can be used to formed a thermally developable light-sensitive element having a transparent coated layer.
  • Another object of this invention is to provide a process of easily producing fine-grained silver salts of organic carboxylic acids capable of preparing thermally developable photosensitive materials which give images having high density and excellent resolving power with a reduced amount of coated silver and which can have transparent coated layers.
  • a further object is to provide thermally developable photosensitive materials prepared by using such fine grained organic silver carboxylates which give an image having less thermal fog, high image density and good contrast.
  • thermal fog in this specification means the fog or black density formed when unexposed areas of the photosensitive material are heated.
  • the formation of thermal fog is reduced in the thermally developable photosensitive material prepared by using the finegrained organic silver carboxylates because, we believe, organic silver carboxylates produced by the process of this invention partially contain the lead compound or mercury compound. We are unsure if this is a reaction product or a mixture, but believe it is probably a mixture.
  • a further substantial benefit of the lead compound embodiment of the invention is that the process results in lowered toxicity as compared to the mercury compound embodiment, not only to workers but to the environment if such compounds are accidentally discharged, e.g., to fish, shellfish or humans if ingested.
  • the silver complex salts are not particularly limited, though most preferred are the alkali soluble silver complexes having a dissociation constant higher than the silver salt of the organic carboxylic acid, e.g., a silver ammonium complex, a silver amine complex (e.g., the silver complexes of methyl amine or ethyl amine) and the like.
  • the lead and mercury compounds must be completely soluble in water or organic solvents and must yield lead or mercury ions in solution.
  • Preferred materials are the inorganic lead or mercury compounds or lead or mercury compounds of organic acids.
  • organic mercury compounds such as mercuric phenyl acetate, methyl mercuric chloride, ethyl mercuric chloride, phenyl mercury p-toluene sulfanilide, benzyl mercury-p-toluene sulfanilide, mercuric chloranilate, 2-acetamido-1,3,4-thiadiazolyl-(5)-mercuric chloride, phenyl mercury dinaphthylmethane disulfonate, etc.
  • lead compounds suitably used in this invention there are illustrated lead nitrate, lead acetate, lead carbonate, lead sulfate, lead phosphate, and lead halide but the use of lead nitrate is most preferable.
  • organic lead compounds such as lead benzoate, lead citrate and lead lactate can also be used in this invention.
  • aqueous solution of silver nitrate It is preferred to dissolve or disperse these mercury compounds and/or lead compounds in an aqueous solution of silver nitrate.
  • a solution containing the mercury compound(s) and/or lead compound(s) may be incorporated into a solution of the organic carboxylic acid.
  • the silver salts thereof which are relatively stable to light are preferred silver salts of organic carboxylic acids (considered comparatively stable to light when upon long exposure to light it does not blacken, whereas a silver halide would blacken under the same conditions).
  • organic carboxylic acids having more than 10 carbon atoms are preferred, which are exemplified by capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, etc.
  • Other organic carboxylic acids can, of course, be used. Mixtures of such acids can, of also, be used.
  • Solvents which dissolve the organic carboxylic acid and hardly dissolve both the silver salt of an organic carboxylic acid and silver nitrate or silver complex and are further sparingly miscible with water i.e., solvents for the organic carboxylic acids, include phosphoric acid esters, phthalic acid esters or carboxylic acid esters of alcohols or phenols which are liquid at normal temperature, or glycerin esters of higher fatty acids. There can also be used aromatic hydrocarbons.
  • solvents are tricresyl phosphate, tributyl phosphate, monooctylidibutyl phosphate, diethyl phthalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, amyl acetate, isoamyl acetate, isobutyl acetate, isopropyl acetate, ethyl acetate, 2-ethylbutyl acetate, butyl acetate, propyl acetate, dioctyl sebacate, dibutyl sebacate, diethyl sebacate, diethyl succinate, ethyl formate, propyl formate, butyl formate, amyl formate, ethyl valerate, diethyl tartarate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamy
  • Preferred solvents which hardly dissolve the recited compounds are those which dissolve 1 percent by weight or less, most preferably 0.1 percent by weight or less, of the salt and of the silver nitrate or complex, which are 35 percent by weight or less, most preferably by weight or less, soluble in water and most preferably in which the acids are completely soluble.
  • a solution of 3.4g of behenic acid in 100 ml. of xylene is maintained at 60C. and 100 ml. of an aqueous diluted nitric acid solution (pH 2.0 at 25C.) containing 0.1 g. of mercuric nitrate is added thereto.
  • 100 ml. of an aqueous ammonium silver nitrate complex solution containing 1.7, g. of silver nitrate which has been cooled at 0C. is added over 1 minute to react behenic acid with silver ion. Almost spherical crystals of silver behenate can thus be obtained, which have about a 0.2;]. diameter.
  • spindle-like crystals of silver behenate are obtained which have about a 0.7 about In long side and about a 0.05 about 0.1a short side.
  • spindle shape denotes a shape simular to a sausage link
  • the fine crystals of the silver salt of an organic carboxylic acid thus obtained can be isolated by separating the solvent layer containing the Silver salt of an organic carboxylic acid from the aqueous layer, e.g., by decantation, to remove the aqueous layer and then repeating washing with water until watersoluble silver nitrate, mercuric nitrate and/or lead nitrate and nitric acid are eliminated.
  • the solvent layer of organic carboxylic acids in which fine crystals of the silver salt of an organic carboxylic acid are present is washed using a solvent for undesired materials such as the organic carboxylic acid and reaction solvent, e.g., methanol as a solvent for the unreacted behenic acid and xylene.
  • a solvent for undesired materials such as the organic carboxylic acid and reaction solvent, e.g., methanol as a solvent for the unreacted behenic acid and xylene.
  • methanol a solvent for the unreacted behenic acid and xylene.
  • centrifugal separation is suitable.
  • the fine crystals of the silver salt of an organic carboxylic acid thus obtained which have been thoroughly washed are dispersed in, e.g, a solution of polyvinyl butyral, e.g., using a ball mill, to prepare a thermally developable lightsensitive material.
  • surface active agents may be incorporated therein to improve the dispersion.
  • the organic carboxylic acid silver salt produced by the process of the present invention is, of course, used in a thermally developable light-sensitive element, as has been heretofore described.
  • the organic carboxylic acid silver salts produced in accordance with the present invention offer superior results as compared to the prior art when used in any thermally developable system as heretofore described. However, especially preferred results are obtained when the organic carboxylic acid silver salt produced in accordance with the present invention is used in elements as described below.
  • a thermally developable light-sensitive material obtained using the fine crystals of the silver salt of an organic carboxylic acid thus obtained comprises the following components on a support: (1) the fine crystals of the silver salt of an organic carboxylic acid obtained in accordance with the present invention, (2) a silver halide, preferably one which is in situ prepared by the reaction of the silver salt of an organic carboxylic acid with an inorganic or organic halide, (3) a compound as a reducing agent which can provide silver images by reducing the silver salt of an organic carboxylic acid upon heating in the presence of exposed silver halide and (4) a binder.
  • the preferred inorganic halides are those represented by the formula MXn, where M is H, NI-If, or a metal, X is Cl, Br, or I, and n is the valence of M, e.g., hydrogen bromide, hydrogen iodine, ammonium bromide, ammonium iodide, ammonium chloride, or where M is a metal such as strontium, cadmium, zinc, tin, chromium, sodium, barium, iron, cesium, lanthanum, copper, calcium, nickel, magnesium, potassium, aluminum, antimony, gold, cobalt, mercury, lead, beryllium, lithuim, manganese, gallium, indium, rhodium, ruthenium, palladium, iridium, platinum, thallium, bismuth, etc., which can be used alone or in mixture.
  • organic halogen compounds such as chlorotriphenylmethyl, bromotriphenylmethyl, 2- bromo-Z-methyl propane, 2-bromo-butyrate, 2-bromoethanol, di chlorobenzophenone, iodoform, bromoform, and 4-bromocarbonate can be used.
  • the silver halides per se used include silver chloride, silver bromide, silver bromoiodide, silver chloroiodide, silver chlorobromide and silver iodide.
  • highly preferred are the silver halides formed by reaction of the inorganic or organic halide with the silver salt of the organic carboxylic acid.
  • the emulsions which contain the light-sensitive silver halide can be made by any method which is widely known in the photographic field, for example, emulsions formed by the single jet method, double jet method, a Lipmann emulsion, by the ammonia method, and can use thiocyanate or thioester ripened emulsions and the emulsions which are described in U.S. Pat, Nos. 2,222,264, 3,320,069 and 3,271,157.
  • the silver halide which used in this invention is generally used in a chemically sensitized silver halide emulsion, e.g., sensitized by reducing agents such as sulfur or selenium compounds, with gold or platinum sensitizers or with palladium compounds, or combinations thereof.
  • reducing agents such as sulfur or selenium compounds
  • gold or platinum sensitizers or with palladium compounds or combinations thereof.
  • Preferred sensitization methods are shown in US. Pat. Nos. 2,623,499; 2,399,083; 3,297,447; and 3,297,446.
  • the amount of component (2) added is preferably about 0.001 0.5 mol per 1 mol of the silver salt of organic carboxylic acid. If the amount of component (2) is too much less than this extent, sensitization is bad, and if too much greater this becomes the cause of blacking of non-image portions and also lowers the contrast of image portions.
  • reaction of the inorganic or organic halide and the silver salt of an organic carboxylic acid generally proceeds quite easily, and in practice the stoichometric amount of halide is mixed with the silver salt of an organic carboxylic acid system (polymer dispersion) and well agitated for a short period of time, e.g., on the order of seconds.
  • the preferred reducing agents are substituted phenols, substituted or non substituted bisphenols, substituted or nonsubstituted naphthols, di-or poly-hydroxy benzenes, dior polyhydroxynaphthalenes, hydroquinone mono-ether, reducing sugar, 5-hydroxy-2-hydroxymethyl-e-pyrone, pyrazoline-S-one, 4- isopropyltropolone, where typical substituents are alkyl (C C alkoxy (C, C phenyl, halogen, amino, alkyl substituted amino, (C1 C8 benzyl, hydroxyalkyl, acetyl, nitro, etc.
  • Reducing agents used in this invention must form silver images when heated under the catalysis of exposed silver halide to reduce the organic carboxylic acid silver salt.
  • useful reducing agents are hydroquinone, methylhydroquinone, chlorohydroquinone, bromohydroquinone, phenylhydroquinone, hydroquinone mono-sulfonic acid, toctylhydroquinone, t-butylhydroquinone, 2,5-dimethylhydroquinone, 2,6- dimethylhydroquinone, methoxyhydroquinone, ethoxyhydroquinone, pmethoxyphenol, p-ethoxyphenol, hydroquinone monobenzyl ether, catechol, 1,2,3-trihydroxybenzene, 1,3- dihydroxybenzene, p-amino phenol, o-aminophenol, N-methyl-p-aminophenol, 2-methoxy-4-aminophenol, 2,4-diaminophenol, 2-B-hydroxyethyl-4-aminophenol, p-t-butylphenol, p-t-aminophenol
  • Combinations of more than two kinds of these reducing agents can be used at one time.
  • Suitable reducing agents are decided by the combination with the organic carboxylic acid silver salt.
  • higher fatty acid silver salts such as behenic acid silver are hard to reduce, so strong reducing agents, such as 4,4'-methylene bis-(3-methyl-5-t-butylphenol), one of the bis phenols is preferred.
  • aromatic acid silver salts such as behenic acid silver
  • strong reducing agents such as 4,4'-methylene bis-(3-methyl-5-t-butylphenol)
  • an organic carboxylic acid silver salt which is easily reduced like silver laurate, substituted phenols like pphenyl phenol are preferred.
  • the amount of the reducing agent used in this invention varies depending upon the organic carboxylic silver salt and the reducing agent it is difficult to set an all encompassing range, but generally 0.1 0.5 moles thereof per mole of organic carboxylic acid silver salt is preferred.
  • Components (1), (2) and (3) above are dispersed in a binder and coated on a support. Altermatively, one can coat on the support as separate components.
  • the binder can be a cellulose derivative, synthetic olymer, etc. Specific examples are gelatin, phthalated gelatin, polyacrylic acids, polyvinyl butyrate, cellulose acetatepropionate, polymethyl methacrylate, polyvinyl pyr rolidone, polystyrene, ethyl cellulose, po y inyl c lo e, chlorinated rubbers, polyisobutylene, butadienestyrene copolymers, vinyl chloride-vinyl acetate copolymers, copolymers of vinyl acetate and vinyl chloride and malonic acid, polyvinyl alcohol, polyacetic vinyl material, benzyl cellulose, cellulose acetate cellulose propionate, cellulose acetate phthalate and the like.
  • the amOunt of the binder is preferably 4/ 1- 1/4 (weight ratio) to the organic carboxylic acid silver salt.
  • component l or (3) is a relatively high molecular weight material which functions as a binder, a separate binder can be omitted.
  • Typical supports are, cellulose nitrate films, organic cellulose ester films, polyvinyl acetal films, polystyrene films, polyethylene terepthalate films, polycarbonate films, glass, paper and metals.
  • the light sensitive layers(s) will generally be 1p. p. thick, preferably 3p. 10p. thick.
  • the exposed elements are simply developed by heating at 100C 180C, preferably 120 160C, for 1 sec. 60 sec. preferably 2 sec. sec. Exposure is usually a contact printing or stretch printing at ambient conditions.
  • the thermally developable light-sensitive layer can further contain an agent for blackening the image such as mercapto compounds, azolethiones or phthalaziones; organic carboxylic acids as a development accelerating agent; compounds which afford basicity upon heating, e.g., amine oxalates or water containing inorganic hydroxides which lose water upon heating; photolytic reducing agents e.g., when using an ascorbic acid ester, a compound which accelerates photolysis thereof, exemplified by benzil; and spectral sensitizers which sensitize to long wavelength light, e.g., merocyanine dyes having a thiohydantoin or a rhodamine nucleus.
  • an agent for blackening the image such as mercapto compounds, azolethiones or phthalaziones; organic carboxylic acids as a development accelerating agent; compounds which afford basicity upon heating, e.g., amine oxalates or water
  • the fine grained silver salt of an organic carboxylic acid of the present invention is especially advantageous for providing remarkably good images without the use of compounds which afford basicity upon heating or development accelerating agents such as aliphatic carboxylic acids, etc., that is by using a thermally developable light-sensitive element comprising a support having thereon a silver salt of an organic carboxylic acid of fine grain size, a light-sensitive silver halide, a reducing agent and a binder.
  • a color toning agent a compound capable of affording basicity upon heating and a development accelerating agent in the case that images of higher quality are required.
  • the absolute amount of silver salt of an organic carboxylic acid present is that necessary to provide a discernable image upon exposure and development.
  • a minimum of about l/lOOO mol m of support will be advisable, with no better results being provided by using more than about l/lO mol m as compared to about l/10 mol m
  • coating well be at 1/300 l/50 mol m
  • the use of the silver salt of an or- 10 ganic carboxylic acid, having a fine grain size gives images of higher density as compared to the use of a conventional silver salt of an organic carboxylic acid having a coarse grain size, and it is sufficient to use the fine grained silver salt of an organic carboxylic acid in a smaller amount to obtain the an image of the same density so that a decrease in cost can be attained.
  • preparation operations can be improved since it becomes easy to disperse the silver salt of an organic carboxylic acid in a polymer binder due to the fine grain size thereof. Further, it is unnecessary to add a compound which affords basicity upon heating or an acid so that improved storage capability of the product before treatment is obtained.
  • the thermally developable light-sensitive material which is prepared using the silver salt of an organic carboxylic acid according to the present invention gives images of high density and high resolving power in which the coated layer becomes transparent.
  • the mercury compounds have strong toxicity, and thus the lead compound embodiment increases the ease of working, which results in lowering the danger to workers and the danger of environmental pollution upon reactant or reaction product accidental disposal.
  • the mercury compounds should be prevented from being mixed with other photosensitive materials since mercury compounds have a strong desensitizing action thereon and this point is improved in the lead embodiment process of this invention.
  • organocarboxylic acid/solvent 10/1-1/1000 preferably 2/1- l/lOO (weight) organocarboxylic acid/silver 4/ l-l/4, preferably 2/1-1/2 nitrate or complex salt (molar) organocarboxylic acid/lead 2/1-1000/1, preferably l0/1 and/or mercury compound 1 (molar.)
  • the process temperature is 30C +80C, more preferably C +60C.
  • the pressure is typically 1 atmosphere, and while this is not limitative there is little merit to operation at subor super atmospheric pressure.
  • the process time is merely that needed to complete the reaction, usually 1 sec 1 hour, preferably 30 sec 30 minutes is used, with the intermediate times being more common.
  • the silver salt of an organic carboxylic acid of the present invention is spherical or substantially spherical as opposed to the spindle or semi-tube shaped silver salt of an organic carboxylic acid of the prior art. While variable with process conditions, following the guidelines of this specification one can obtain a silver salt of an organic carboxylic acids of suprior effect of a diameter of 0.01 1 u, with best results in element use being obtained when the silver salt of an organic carboxylic acid has a diameter of 0.1 0.5,u.
  • EXAMPLE 1 Two solutions were made by dissolving 3.4 g of behenic acid in 100 ml. of tricresyl phosphate at 60C. The solutions were maintained at 60C (Solutions A). A solution was prepared by dissolving 0.1 g. of mercuric nitrate in 100 ml. of an aqueous diluted nitric acid solution which was adjusted with nitric acid to pH 2.0 at 25C (Solution 8,).
  • the reaction liquid was separated into an aqueous layer and a tricresyl phosphate layer. After the removal of the aqueous layer, 400 ml. of fresh water was added for washing and the operation was repeated three times. Thereafter, 400 ml. of methanol was added to the tricresyl phosphate layer for washing. The resulting fine crystals of silver behenate were separated by centrifugal separation. Thus, 4.0 g of silver behenate was obtained, which was in the form of spherical grains having about a 01; diameter; from the A/B, system and the A/B system.
  • Example 2 The procedures of Example 1 were repeated except that the same amount of toluene was used in place of tricresyl phosphate.
  • the amount of silver behenate obtained for the A/B and A/B system was 4.1 g., which were spherical grains having a grain size of about 0.3;). in diameter.
  • Example 3 The procedure of Example I was followed except that the same amount of mercuric acetate was employed instead of mercuric nitrate and the same amount of lead carbonate was employed instead of lead nitrate. Silver behenate was obtained in an amount of 4.0 g., which had spherical grains having a grain size of about 0.5;1. in diameter for the mercury run and about 0.2,u. for the lead run.
  • EXAMPLE 4 Using silver behenate as obtained in Example 2 from the A/B and A/B runs and silver behenate obtained as in Example 2 but without the addition of mercuric nitrate or lead nitrate (spindle like grains having a long diameter of about In and a short diameter of about 005p.) respectively, light-sensitive compositions for thermal development having the following formulation were prepared and each of them was coated in a dry thickness of 8 J.(same in all Examples) on a transparent polyethylene terephthalate film support to give a lightsensitive element for thermal development.
  • mercuric nitrate or lead nitrate spindle like grains having a long diameter of about In and a short diameter of about 005p.
  • the light-sensitive element thus prepared was exposed (10 lux-same in all Examples) to a tungsten lamp through a transparent negative original having gradation and heated at C. for 30 seconds for the mercuric nitrate embodiment and for 20 seconds for the lead nitrate embodiment, to obtain positive images having gradation.
  • the density of the images, resolving power and transparency of the coated layer are shown in the table below.
  • the ratio of maximum density and resolving power increased, the coated layer became transparent, and hence a desirable transparent light-sensitive element for thermal development was obtained.
  • the ratio of maximum density is meant the ratio of the maximum densities of the images given by both methods, i.e., the maximum densities of the image obtained using the silver salt prepared by the use of the mercury compound (or the lead compound) to the maximum density of the image obtained using the silver salt prepared without using the mercury or lead compound the density of the latter being denoted by 1.0.
  • the weight of silver behenate coated per unit area was substantially identical in all cases.
  • the transmittance is denoted by the value measured at 500 mu using a spectrophotometer. No difference in results whether ball milled for l or 4 hours or exposed 20 or 30 seconds.
  • EXAMPLE 5 o C C S
  • 100 ml. of butyl acetate was dissolved g. of lauy ric acid at 60C. and the solution was then cooled to N c c s 10C.
  • a solution was prepared by dissolving 0.25 g. of l 2 ml. mercuric nitrate in 100 ml of an aqueous diluted nitric N acid solution which was adjusted with nitric acid to pH H 2.0 (C.), and the both solutions were. mixed to- 25 M m I H l l t 2 5 gether.
  • the solution mixture was maintained at 10C. 5 fi s Z gfgg lj ffi fi con dmmg 1 m1.
  • EXAMPLE 6 Using silver laurate as obtained in Example 5 and silver laurate obtained as in Example 5 but without the addition of mercuric nitrate (spindle-like grains having a long side diameter of about 1p. and a short side diameter of about 0.05 a), respectively, light-sensitive compositions for thermal development having the following formulation were prepared and each of them was coated on a transparent polyethylene terephthalate film support to give a light-sensitive element for thermal development.
  • mercuric nitrate spindle-like grains having a long side diameter of about 1p. and a short side diameter of about 0.05 a
  • the light-sensitive element thus prepared was exposed to a tungsten lamp through a transparent negative original having gradation and heated at 120C. for 20 seconds to obtain positive images having gradation.
  • the density of the images, resolving power and transparency of the coated layer are shown in the table below.
  • the ratio of maximum density and resolving power increased, the coated layer became transparent, and hence a desirable transparent light-sensitive element for thermal development was obtained.
  • the ratio of maximum density is meant the ratio of maximum densities of the image obtained by both methods, i.e., the maximum density of the image obtained using the silver salt prepared by the use of the mercury compound to the maximum density of the image obtained using the silver salt Polymer dispersion the Silver 5,11 45 ml, prepared without using the mercury compound, the Methanol 5011mm containing 5 wt% of density of the latter being denoted as 1.0. Needless to ammonium bromide 1 ml.
  • Chloroform solution containing 0.2wt% of y t e welg t 51 aurate coate per umt :benzoxazolylidene rhodanin sensitizing wassubstantially identical in both cases.
  • Amount of Silver coated 1.0 g. Ag/m 1.0 g. Ag/m The transmittance is denoted by the value measured at 500 mu using a spectrophotomcr.
  • EXAMPLE 7 EXAMPLE 11 When the same procedure as in Example 1 was followed but using the same amount of lead carbonate in place of lead nitrate, 4.0 g of silver behenate was obtained as almost spherical grains having a diameter of about 0.2 micron.
  • EXAMPLE 8 The same procedure as in Example 1 was followed but using the same amount of lead lactate in place of lead nitrate, whereby 4.1 g of silver behenate as almost spherical grains having a diameter of about 0.5 micron was obtained.
  • EXAMPLE 10 l 1 g of lauric acid was dissolved in 100 ml of butyl acetate at 60C and then the solution was cooled to 10C. Then, a solution prepared by dissolving 0.5 g of lead nitrate in 100 ml of diluted aqueous nitric acid solution (pH 2.0 at 25C) was mixed with the solution prepared above by means of a stirrer.
  • an aqueous solution prepared by adding aqueous ammonia to a solution of 8.5 g of silver nitrate in about 40 ml of water to form a silver-ammonia complex and then adding water to the complex salt solution was added to the mixed solution prepared above with stirring, whereby precipitates containing silver laurate were obtained.
  • the reaction product was allowed to stand for minutes at room temperature, the product separated into an aqueous phase and a butyl acetate phase.
  • the aqueous phase was first removed and the butyl acetate phase was washed by adding 400 ml of water. After repeating the washing operation three times, the butyl acetate solution phase was washed with 400 ml of methanol. By recovering the fine crystalsof silver laurate formed by a centrifugal separator, 14 g of fine granular silver laurate was obtained. The silver laurate thus obtained was of almost spherical form, having a diameter of about 0.1 micron.
  • thermally developable photosensitive compositions having the following compositions were prepared using the silver laurate produced in Example 10 in one and using silver laurate of a spindle grain shape having a long side of about 1 micron and a short side of about 0.05 micron prepared by the same procedure as in Example 10 without using lead nitrate in the other. Each composition was coated on a transparent polyethylene terephthalate film to give a thermally developable photosensitive material.
  • the above described polymer dispersion of the silver salt was prepared by adding 5 g of the silver salt to a 40 ml isopropyl alcohol solution containing 4 g of polyvinyl butyral and stirring the mixture by means of a ball mill for 1 hour to disperse the silver salt.
  • EXAMPLE l2 2. The process of claim 1 where said reaction is con- The effect of lead nitrate was measured according to ducted at the following ratios:
  • an aqueous solution prepared by adding aqueous ammonia to 40 ml of an aqueous solution containing 0.85 g of silver nitrate to form a silverammonium complex salt, adding water to the complex salt solution, and adjusting the temperature of the solution to 25C, was added with stirring to the abovementioned solution mixture, whereby precipitates containing silver behenate were formed.
  • the reaction product was allowed to stand for 20 minutes at room temperature, it separated into a aqueous phase and a benzene phase. The aqueous phase was first removed and the benzene solution phase was washed with 400 ml of water followed by decantation.
  • the benzene solution phase was washed with 400 ml of methanol by means of a centrifugal separator and the fine crystals of silver behenate thus formed were recovered, whereby 2.0 g of silver behenate of a spherical form having a diameter of about 0.5 micron was obtained.
  • silver behenate was also prepared in an identical manner but for using 500 ml' of diluted aqueous nitric acid solution (pH 2.0 at 60C) without lead nitrate in place of the diluted aqueous nitric acid solution containing lead nitrate in the above process. Only coarse, spindle shaped crystals of silver behenate having a long side of 2 microns and short side of 0.1 micron were obtained.
  • a process of producing silver salt ofa long chain aliphatic carboxylic acid which comprises mixing an aqueous silver nitrate solution or an aqueous silver complex solution with a solution of a carboxylic acid in a solvent in which said carboxylic acid is soluble, both said silver salt of the carboxylic acid and silver nitrate are almost insoluble and with which water is sparingly miscible, to react said carboxylic acid with silver ions, the improvement which comprises conducting said reaction of the carboxylic acid with silver ions in the presence of a mercury compound and/or lead compound.
  • the solvent is less than 35% soluble in water
  • said long chain aliphatic carboxylic acid is selected from the group consisting of capric acid, laurie acid, myristic acid, palmitic acid, stearic acid and behenic acid.
  • said solvent is selected from the group consisting of a phosphoric acid ester, a phthalic acid ester or a earboxylic acid ester of an alcohol or a phenol, liquid at room temperature, and a glycerin ester of a higher fatty acid.
  • said solvent is selected from the group consisting of tricresyl phosphate, tributyl phosphate, monooctyl dibutyl phosphate, diethyl phthalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, amyl acetate, isoamyl acetate, isobutyl acetate, isopropyl acetate, ethyl acetate, Z-ethyl butyl acetate, butyl acetate, propyl acetate, dioctyl sebacate, dibutyl sebacate, diethyl sebacate, diethyl succinate, ethyl formate, propyl formate, butyl formate.
  • amyl formate ethyl valerate, diethyl tartarate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, castor oil, benzene, toluene and xylene.
  • carboxylic acid is selected from the group consisting of behenic acid and lauric acid.
  • cron in diameter and is substantially spherical.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113496A (en) * 1975-12-16 1978-09-12 Asahi Kasei Kogyo Kabushiki Kaisha Dry image forming material
US4152162A (en) * 1976-09-16 1979-05-01 Fuji Photo Film Co., Ltd. Thermally developable light-sensitive materials
US4723024A (en) * 1986-06-20 1988-02-02 Mooney Chemicals, Inc. Preparation of silver carboxylates
US5466570A (en) * 1995-02-21 1995-11-14 Eastman Kodak Company Sonic micro reaction zones in silver halide emulsion precipitation process
US5843632A (en) * 1997-06-27 1998-12-01 Eastman Kodak Company Photothermographic composition of enhanced photosensitivity and a process for its preparation
US5858637A (en) * 1997-06-27 1999-01-12 Eastman Kodak Company Process of preparing a photothermographic composition of enhanced photosensitivity
WO2001059519A2 (en) * 2000-02-10 2001-08-16 Eastman Kodak Company Silver carboxylate nanoparticle compositions with phosphoric acid ester surface modifiers
US6365336B1 (en) 2000-10-31 2002-04-02 Eastman Kodak Company Aqueous photothermographic imaging elements comprising aqueous silver halide emulsions precipitated in the presence of cationic starch peptizing agent
US6391537B2 (en) 2000-02-10 2002-05-21 Eastman Kodak Company Polyacrylamide surface modifiers for silver carboxylate nanoparticles

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS573051B2 (da) * 1974-02-26 1982-01-20
JPS6014010B2 (ja) * 1978-09-14 1985-04-11 旭化成株式会社 有機銀塩の製造法
US5891616A (en) * 1995-07-18 1999-04-06 Agfa-Gevaert Process for producing a suspension of particles containing an organic silver salt for use in the production of thermographic and photothermographic materials
EP0848286B1 (en) * 1996-12-10 2005-04-06 Agfa-Gevaert Thermographic recording material with improved image tone and/or stability upon thermal development
EP0962812A1 (en) * 1998-06-03 1999-12-08 Fuji Photo Film Co., Ltd. Aqueous dispersion of fatty acid silver salt particles, method for redispersing fatty acid silver salt particles, photothermographic light-sensitive material, and method for producing the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2395307A (en) * 1943-10-06 1946-02-19 Du Pont Preparation of organic salts
US3255223A (en) * 1962-10-29 1966-06-07 Yardney International Corp Method of preparing stable silvercontaining compositions
US3255222A (en) * 1961-10-23 1966-06-07 Yardney International Corp Silver salt complexes of fatty acids and method of making same
US3764328A (en) * 1972-01-03 1973-10-09 Minnesota Mining & Mfg Photothermic silver halide element containing an organic mercuric soap and a color forming coupler
US3773512A (en) * 1970-11-19 1973-11-20 Agfa Gevaert Nv Photothermic material containing a light-insensitive silver salt and an indane-1,3-dione reducing agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2395307A (en) * 1943-10-06 1946-02-19 Du Pont Preparation of organic salts
US3255222A (en) * 1961-10-23 1966-06-07 Yardney International Corp Silver salt complexes of fatty acids and method of making same
US3255223A (en) * 1962-10-29 1966-06-07 Yardney International Corp Method of preparing stable silvercontaining compositions
US3773512A (en) * 1970-11-19 1973-11-20 Agfa Gevaert Nv Photothermic material containing a light-insensitive silver salt and an indane-1,3-dione reducing agent
US3764328A (en) * 1972-01-03 1973-10-09 Minnesota Mining & Mfg Photothermic silver halide element containing an organic mercuric soap and a color forming coupler

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113496A (en) * 1975-12-16 1978-09-12 Asahi Kasei Kogyo Kabushiki Kaisha Dry image forming material
US4152162A (en) * 1976-09-16 1979-05-01 Fuji Photo Film Co., Ltd. Thermally developable light-sensitive materials
US4723024A (en) * 1986-06-20 1988-02-02 Mooney Chemicals, Inc. Preparation of silver carboxylates
US5466570A (en) * 1995-02-21 1995-11-14 Eastman Kodak Company Sonic micro reaction zones in silver halide emulsion precipitation process
US5843632A (en) * 1997-06-27 1998-12-01 Eastman Kodak Company Photothermographic composition of enhanced photosensitivity and a process for its preparation
US5858637A (en) * 1997-06-27 1999-01-12 Eastman Kodak Company Process of preparing a photothermographic composition of enhanced photosensitivity
WO2001059519A2 (en) * 2000-02-10 2001-08-16 Eastman Kodak Company Silver carboxylate nanoparticle compositions with phosphoric acid ester surface modifiers
WO2001059519A3 (en) * 2000-02-10 2002-03-14 Eastman Kodak Co Silver carboxylate nanoparticle compositions with phosphoric acid ester surface modifiers
US6387611B2 (en) 2000-02-10 2002-05-14 Eastman Kodak Company Phosphoric acid ester surface modifiers for silver carboxylate nanoparticles
US6391537B2 (en) 2000-02-10 2002-05-21 Eastman Kodak Company Polyacrylamide surface modifiers for silver carboxylate nanoparticles
US6365336B1 (en) 2000-10-31 2002-04-02 Eastman Kodak Company Aqueous photothermographic imaging elements comprising aqueous silver halide emulsions precipitated in the presence of cationic starch peptizing agent

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GB1378734A (en) 1974-12-27
DE2322096A1 (de) 1973-11-22
FR2183143B1 (da) 1976-05-28
FR2183143A1 (da) 1973-12-14

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