US3699114A - Process for producing silver salt of benzotriazole - Google Patents

Process for producing silver salt of benzotriazole Download PDF

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Publication number
US3699114A
US3699114A US56521A US3699114DA US3699114A US 3699114 A US3699114 A US 3699114A US 56521 A US56521 A US 56521A US 3699114D A US3699114D A US 3699114DA US 3699114 A US3699114 A US 3699114A
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United States
Prior art keywords
solvent
benzotriazole
silver salt
silver
silver nitrate
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Expired - Lifetime
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US56521A
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English (en)
Inventor
Kinji Ohkubo
Junpei Noguchi
Takao Masuda
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages

Definitions

  • the silver salt of benzotriazole having a particle size of less than 5 microns in length is prepared by a specific combination of solvents used for the reaction of silver nitrate and benzotriazole in solution.
  • Silver nitrate is dissolved in solvent A which is miscible with nitric acid which might be formed by the above reaction.
  • Solvent ;A may, for example, be water, dimethylformamide or dimethylsulfoxide.
  • Benzotriazole is dissolved in solvent B which is a solvent for benzotriazole, but which does not substantially or completely dissolve the silver salt of benzotriazole.
  • solvent B may, .for example, be tricresyl phosphate, dimethoxy ethyl phthalate, di-n-butyl phthalate, diethyl sebacate, monooctyl-dibutyl phosphate, tributyl phosphate or castor oil.
  • solvent A is dimethyl formarnide or dimethyl sulfaox'ide
  • solvent B may, for example, be cottonseed oil
  • the present invention relates to a process for producing the silver salt of benzotriazole and more particularly, is concerned with a process for producing the silver salts of benzotriazole having a small particle size which are suitable for use in heat developable light sensitive materials.
  • a heat-developable light-sensitive material in which a silver salt of benzotriazole, an inorganic halogen compound capable of forming a silver halide by reaction with the silver salt of benzotriazole, a material capable of forming a basic substance by. heating and reducing agent are incorported in a layer provided on a support.
  • the silver salt of benzotriazole is prepared, in general, by mixing a solution of silver nitrate in water and a solution of benzotriazole in methanol and reacting silver nitrate and benzotriazole.
  • aprocess for producing a silver salt of benzotriazole having a small particle size which comprises mixing a solution of silver nitrate dissolved in a first solvent A, in which silver nitrate is soluble and nitric acid is miscible but in which the silver salt of benzotriazole is insoluble, with .a solution of benzotriazole dissolved in a second solvent 'B, in which benzotriazole is soluble but in which the silver salt of benzotriazole and silver nitrate are insoluble, said solvent A being miscible with solvent B in an amount of from 1 to 30% by weight of the total weight of solutions A and B, and reacting said silver nitrate and said benzotriazole to form the silver salt of benzotriazole.
  • soluble and related language is meant that more than 0.5 g.," preferably more than 5 g. of the solute is dissolved in g. of a solvent, and by insoluble and solvent.
  • a small particle-size is meant a.
  • particle size of less than 5 1. in length, more preferably less than 1, in length.
  • the main feature of the present invention lies in the selection of a suitable combina- BRIEF DESCRIPTION OF THE DRAWING
  • the single figure of the drawing represents the mutual solubility curves of solvents A and B and washing liquid C on trigonometric coordinates.
  • Solvent A of the invention dissolves silver nitrate, and is miscible with nitric acid formed by the reaction of silver nitrate ancl benzotriazole, but little or no silver salt of benzotriazole is dissolved therein.
  • Illustrative of such solvents are water, dialkylformamides such as dimethylformamide and diethylformamide, and dialkylsulfoxide such as dimethylsulfoxide, diethylsulfoxide anddi-nor -iso-propylsulfoxide. Although it is most preferred that solvent A does not dissolve benzotriazole, some dissolving does not render the process inoperable,
  • Such a solvent may be used as occasion demands.
  • Solvent B is capable of dissolving benzotriazole, but little or none of the silver salt of benzotriazole and silver nitrate.
  • solvent A and solvent B must mutually have the relationship that the solubility of solvent A in solvent B is 1-30% by weight based upon the total weight of mixed solvents A and B. Examining practical solvents satisfying this relation, it is found that, in many cases, solvent A hardly dissolves solvent B. When the solubility of solvent A in solvent B is large, as in the foregoing combination of methanol and water, coarse crystals of silver salt of benzotriazole are formed, while when it is too small, for example, as in the combination of oil and water, and toluene and water, the silver salt of benzotriazole is not formed in a satisfactory yield. Therefore, suitable materials used as solvent B are phosphates, phthalates and. esters of dibasic acids as well as glycerine esters such as castor oil, cotton oil, linseed oil and tsubaki oil.
  • solvent B trialkyl phosphates such as triethyl phosphate, tributyl phosphate and octyl-di-butyl phosphate; triaryloxy phosphates such as tricresyl phosphate; and diesters of phthalic acid such as dimethyl phthalate, diethyl phthalate, dipropyl' phthalate, dibutyl phthalate, di-iso-butyl phthalate, dioctyl phthalate, di-Z-ethylhexyl phthalate, and dimethoxyethyl phthalate; diesters of sebacic acid such as dimethyl sebacate, dibutyl sebacate, and dioctyl sebacate; and castor oil when water, dimethyl formamide, and dimethyl sulfoxide are used as solvent A.
  • More desirable results can be obtained by adding a surfactant to the reaction system of the invention such that the reaction. between benzotriazole and silver nitrate can be homogeneously carried out, thereby causing an average particle size of the reaction product within the limited range.
  • any surfactant As a surfactant 1or surfactant mixture, any surfactant,
  • anionic or nonionic surfactants can be used.
  • the purpose of sucha surfactant is to enable a homogeneous reaction system to be formed.
  • Some specific surfactants that can be protonated'and used in the process of the invention include compounds of the following formula: AS O B, Where A can be an alkyl substituted aryl group preferably with l-4- carbon atoms in the-alkyl group, an alkoxy group, an alkyl amide-substituted alkylene group preferably with .1-4 carbon atoms, and an alkyl substituted carboxyalkyl group.
  • B is a cation, preferably K or Na.
  • Such a surfactant may be added to the solution of silver nitrate or may be added to the solution of benzotriazole as an aqueous or alcoholic solution, onma'y be added upon mixing with the silver nitrate. solution simultaneously.
  • the amount thereof to be added is 0.01 g. to 20 g. preferably 0.1 g. to 10 g., per 100 g. of the silver nitrate used.
  • washing liquid C used for taking and washing the silver salt of benzotriazole formed after the reaction of silver nitrate and benzotriazole.
  • This washing liquid .C is a solvent, preferably a volatile liquid miscible with solvent A or solvent B in any arbitrary ratio which is capable of forming a uniform ternary phase system containing more than 10% of solvents A and B respectively, and which is capable of dissolving little or none of the silver salt of benzotriazole (as, heretofore defined).
  • Illustrative of such washing liquids are methanol, ethanol and acetone.
  • Mark (9, shown near apex C, is the composition of the three component homogeneous 'phase described above. With reference to the properties to be endowed to washing liquid C, the curves must be lower than-this point.
  • the nitric acid formed by .the reaction of silver nitrate and benzotriazole is mainly present in the phase enriched with solvent A.
  • the phase enriched-with solvent A is removed by .de-
  • spindle-shaped crystals of a silver salt of benzotriazole having a length of-0.13 microns are produced. These crystal particles are generally present as a solid phase dispersed in a solvent B-rich phase which has been separated from a solvent A-rich phase, while nitric acid formed by the reaction of silver nitrate and benzotriazole is mainly present in the solvent A-rich phase.
  • Fine crystals of the silver salt of benzotriazole are recovered from this system by removing the solvent A- rich phase by decantation or the like, washing repeatedly the remaining solvent B-rich phase containing a silver salt of benzotriazole with the solvent A or other liquid and then with a washing liquid C having a mutual solubility with, the solvents A and B as mentioned hereinbefore.
  • the further remaining silver salt of benzotriazole is dried to vaporize the washing liquid C to obtain a silver salt-of benzotriazole of high purity.
  • fine crystal particles can be obtained by suitably selecting solvents for the silver nitrate and benzotriazole having a suitable mutual solubility. with each other.
  • the mixing conditions of a solution of silver nitrate and a solution of benzotriazole are not limited to the foregoing embodiment, but the solution concentrations, solution temperatures, mixing speed and stirring condition may be optionally varied according to any desired particle diameter.
  • Set forth below are several specific examples of this invention, illustrating the best methods of preparing the fine crystals of the silver salt of benzotriazole. I
  • Light-sensitive compositions having the following com ponents were applied to photographic papers "to make a heat-developable light-sensitive material using particles of a silver salt of benzotriazole prepared by the known meth- 0d using a solvent system of water and methanol and as obtained in Examples 1 and 2. Ethanol was used as the solvent.”
  • the maximum density ratio described hereinbefore means the ratio of the maximum density of the images obtained by the methods according to the present invention to that in the case of the conventional method.
  • EXAMPLE 3 The procedure described in Example 1 was repeated except that di-n-butyl phthalate was used as the solvent of benzotriazole," dimethylformamidewas used as the solvent of silver nitrate and acetone was used as the washing liquid. 17 g. of silver salt of benzotriazole was obtained having an average particle size of 1.0 micron.
  • benzotriazole was 0.1 micron. In this case, the effect of p the surfactant was recognized on the particle size.
  • EXAMPLE 7 The similar procedure described in Example 1 was repeated except that dibutyl phthalate was used in place of tricresyl phosphate and polyoxyethylene sorbitol'rnonolaurate as a surfactant wasused in place of CmHg and the average particle size of the resulting silver salt of benzotriazole was 1.5; in length.
  • EXAMPLE 8 The procedure as stated in Example 1 was repeated except that the following surfactant was used in place of C H OSO Na.
  • the average particle size of the thus pre pared silver salt of benzotriazole was 0.05 11. in length.
  • EXAMPLE 10 The procedure as stated in Example 1 was repeated except that dimethyl formamide was used in place of water as a solvent of silver nitrate with the use of 0.5 g./100 cc. of water surfactant The average particle size of the thus prepared silver salt of benzotriazole was 0.5g in length.
  • a process for producing a silver salt of benzotriazole in the form of finely divided particles which comprises mixing a solution of silver nitrate dissolved in a solvent A, in which silver nitrate and nitric acid are soluble but in which the silver salt of benzotriazole is insoluble, with a solution benzotriazole dissolved in a solvent 'B, 'in which benzotriazole is soluble but in which the silver salt of benzotriazole and silber nitrate are insoluble, said solvent A being miscible with solvent B in an amount of from 1 to 30% by weight of the totalweight of the solutions A and B, to react said silver nitrate with said benzotriazole to form the silver salt of benzotriazole.
  • reac- 'vent B is selected from the group consisting of a phosphate, diester of phthalic acid, a diester. of sebacic acid, castor oil, cottonseed oil, linseed oil and tsubaki oil.
  • nitric acid is formed as a by-product of said reaction, said nitric acid being present primarily in said solvent A.
  • said phosphate is a trialkyl phosphate selected from the group consisting of triethyl phosphate, tributyl phosphate and octyl-dibutyl phosphate.
  • di- "ester of phthalic acid is selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutylphthalate, di-iso-butyl phthalate, dioctyl phthalate, di-2-ethyl hexyl phthalate and dimethoxyethyl phthalate.
  • diesterof sebacic acid is selected from the group consisting of diethyl sebacate, dibutyl se'bacate and dioctyl sebacate.
  • the process as claimed in claim 2 wherein the amount of said surfactant is 0.1 to 10 g. per g. of silver nitrate used.
  • said surfactant is selected from thegroup consisting of those represented by the general formula A-SO B, where A is from the group consisting of an alkyl substituted aryl group, an alkoxy group, an alkyl amide-substituted alkylene group and an alkyl substituted carboxyalkyl group, and B is selected from the group consisting of Na or K.
US56521A 1966-04-12 1970-07-20 Process for producing silver salt of benzotriazole Expired - Lifetime US3699114A (en)

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BE (1) BE696925A (xx)
CH (1) CH483654A (xx)
DE (1) DE1670845C3 (xx)
FR (1) FR1603330A (xx)
GB (1) GB1173426A (xx)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4065312A (en) * 1974-04-19 1977-12-27 Agfa-Gevaert, A.G. Process for the production of photographic vesicular images in photographic silver halide material
US4076539A (en) * 1973-07-23 1978-02-28 Fuji Photo Film Co., Ltd. Process for preparing silver halide dispersions
US4123274A (en) * 1977-03-16 1978-10-31 Eastman Kodak Company Heat developable imaging materials and process
US4255395A (en) * 1979-08-30 1981-03-10 King Industries, Inc. Solvent-extraction process for recovery and separation of metal values
US4260674A (en) * 1974-04-19 1981-04-07 Agfa-Gevaert Aktiengesellschaft Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency
WO2001059519A2 (en) * 2000-02-10 2001-08-16 Eastman Kodak Company Silver carboxylate nanoparticle compositions with phosphoric acid ester surface modifiers
US20050167640A1 (en) * 2004-02-03 2005-08-04 Dowa Mining Co., Ltd. Silver powder and method for producing same
WO2005106581A1 (en) * 2004-04-16 2005-11-10 Eastman Kodak Company Thermally developable materials containing organic silver salts
CN106115739A (zh) * 2016-06-29 2016-11-16 晋城市鸿生化工有限公司 一种黄血盐钠的生产方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820617A (en) * 1986-04-28 1989-04-11 Oriental Photo Industrial Co., Ltd. Heat-developable photosensitive material
DE4331162A1 (de) * 1993-09-14 1995-03-16 Bayer Ag Verfahren zur Herstellung von Cyaninfarbstoffen
EP0751006B1 (en) 1995-06-27 2000-01-19 Agfa-Gevaert N.V. New method for the formation of a heat mode image

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076539A (en) * 1973-07-23 1978-02-28 Fuji Photo Film Co., Ltd. Process for preparing silver halide dispersions
US4065312A (en) * 1974-04-19 1977-12-27 Agfa-Gevaert, A.G. Process for the production of photographic vesicular images in photographic silver halide material
US4260674A (en) * 1974-04-19 1981-04-07 Agfa-Gevaert Aktiengesellschaft Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency
US4123274A (en) * 1977-03-16 1978-10-31 Eastman Kodak Company Heat developable imaging materials and process
US4128557A (en) * 1977-03-16 1978-12-05 Eastman Kodak Company Silver salts of 1,2,4-mercaptotriazole derivatives
US4255395A (en) * 1979-08-30 1981-03-10 King Industries, Inc. Solvent-extraction process for recovery and separation of metal values
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
US20050167640A1 (en) * 2004-02-03 2005-08-04 Dowa Mining Co., Ltd. Silver powder and method for producing same
US7641817B2 (en) * 2004-02-03 2010-01-05 Dowa Mining Co., Ltd. Silver powder and method for producing same
WO2005106581A1 (en) * 2004-04-16 2005-11-10 Eastman Kodak Company Thermally developable materials containing organic silver salts
CN106115739A (zh) * 2016-06-29 2016-11-16 晋城市鸿生化工有限公司 一种黄血盐钠的生产方法

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Publication number Publication date
FR1603330A (xx) 1971-04-05
GB1173426A (en) 1969-12-10
DE1670845B2 (de) 1974-04-25
DE1670845C3 (de) 1975-01-02
CH483654A (de) 1969-12-31
DE1670845A1 (de) 1972-02-24
BE696925A (xx) 1967-09-18

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