EP0502531A1 - Verfahren zur Herstellung einer hydrophoben Verbindung zum photographischen Gebrauch - Google Patents

Verfahren zur Herstellung einer hydrophoben Verbindung zum photographischen Gebrauch Download PDF

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Publication number
EP0502531A1
EP0502531A1 EP92103789A EP92103789A EP0502531A1 EP 0502531 A1 EP0502531 A1 EP 0502531A1 EP 92103789 A EP92103789 A EP 92103789A EP 92103789 A EP92103789 A EP 92103789A EP 0502531 A1 EP0502531 A1 EP 0502531A1
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EP
European Patent Office
Prior art keywords
water
solution
organic solvent
hydrophobic substance
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP92103789A
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English (en)
French (fr)
Inventor
Hideaki c/o KONICA CORPORATION Kimura
Yoko c/o KONICA CORPORATION Yaginuma
Sanae c/o KONICA CORPORATION Oyama
Kazuyoshi C/O Konica Corporation Ichikawa
Shinichi c/o KONICA CORPORATION Suzuki
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Konica Minolta Inc
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Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP3318015A external-priority patent/JPH0519394A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0502531A1 publication Critical patent/EP0502531A1/de
Withdrawn legal-status Critical Current

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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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/51—Methods thereof
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor

Definitions

  • the present invention relates to a method for preparing a hydrophobic substance for use in photography, and more particularly relates to a method for preparing a hydrophobic substance characterized in that: all kinds of hydrophobic substance can be precipitated when oil-in-water type dispersion is formed only by water-insoluble low boiling point organic solvent substantially without using high boiling point organic solvent; and a hydrophobic substance of a predetermined particle size can be easily obtained.
  • a dispersion of a predetermined particle size is obtained in such a manner that: after a hydrophobic substance such as a color-image forming compound (a coupler), compound for use in diffusion transfer material, anti-color fogging agent, anti-color fading agent, anti-color mixing agent, UV absorbent and whitening agent, has been dissolved in a high boiling point organic solvent such as alkylphthalate, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides and fatty acid esters, the solution is dispersed in water. In this case, it is very important to control the particle size of the dispersed substance. Especially when a coupler is used to finally prepare a photosensitive material, the particle size has influence on photographic characteristics.
  • a hydrophobic substance such as a color-image forming compound (a coupler)
  • a coupler compound for use in diffusion transfer material
  • anti-color fogging agent anti-color fogging agent
  • anti-color fading agent anti-color mixing agent
  • the high boiling point organic solvent remains in a coating film, so that the thickness of the film is increased. Accordingly, sharpness is deteriorated, and further color bleeding is caused by the high boiling point organic solvent.
  • the methods disclosed by British Patent No. 1,193,349 and European Patent Application Open to Public Inspection No. 374, 837 are disadvantageous in that: the methods can be applied only to coupler in which the solubility is changed by pH. Furthermore, the methods can not be applied to the coupler having an ester group capable of being hydrolyzed upon the change of pH value. Precipitation caused by the change of pH can be quickly stabilized by a binder or surface active agent, so that a fine particle size can be obtained. However, it is difficult to control the particle size.
  • British Patent 1,099,414 is disadvantageous in that: oil-in-water type dispersion comes into contact with a solvent over a long period of time; and accordingly, the oil-in-water type dispersdoid coagulates, so that coarse particles are generated.
  • the first object of the present invention is to solve the aforementioned problem by forming a oil-in-water type dispersion without substantially using a high boiling point organic solvent.
  • the second object of the present invention is to provide a method for preparing a hydrophobic substance for photographic use by which fine particles of a hydrophobic substance can be obtained, irrespective of the kind of the hydrophobic substance, whereby the particle size can be easily controlled.
  • the aforementioned problems can be solved by adopting a method for dispersing a hydrophobic substance for photographic use in water characterized in that: the first solution in which the aforementioned hydrophobic substance is substantially dissolved only in a water-insoluble low boiling point organic solvent, and the second solution in which only a surfactant, or both a surfactant and a binder are dissolved in water, are dispersed in each other so as to form a oil-in-water type of dispersion; and when the dispersion is stirred under reduced pressure, the aforementioned water insoluble low boiling point organic solvent contained in the aforementioned oil-in-water type dispersion, is removed so as to form finally dispersed precipitates of a hydrophobic substance.
  • a high speed stirring type of dispersing apparatus may be utilized so that the dispersion is stirred under the condition that the dispersing circumferential speed is not less than 10 m/sec.
  • the coating thickness can be prevented from becoming thick, sharpness can be improved, and the occurrence of bleeding of color can be prevented without using a high boiling point organic solvent.
  • fine particles of a hydrophobic substance can be obtained and the particle size can be easily controlled irrespective of the kinds of hydrophobic substances.
  • Fig. 1 showing a manufacturing apparatus in which a coupler is utilized as a hydrophobic substance.
  • the first solution is obtained by dissolving a hydrophobic coupler in a water insoluble low boiling point organic solvent.
  • the second solution is obtained by dissolving both a surface active agent and a binder in water.
  • the obtained first and second solution are emulsionized and dispersed in a dispersion tank 3 provided with a high speed stirring type dispersing apparatus 3A so that an oil-in-water type of dispersion is made.
  • the dissolution tank 3 is evacuated by a vacuum pump 4, and at the same time the high speed stirring type dispersing apparatus 3A is operated so that the water insoluble low boiling point organic solvent is evaporated.
  • the solvent vapor is condensed by cooling with a refrigerant 6 in a heat exchanger 5 so that the water insoluble low boiling point organic solvent is removed in the form of liquid, which is recovered into a recovery tank 7, and at the same time a coupler is precipitated from the recovered liquid in the dissolution tank 3. Then, a stabilized solid-liquid dispersion in which a solid is dispersed in a liquid medium, can be obtained by the action of a surfactant and a binder.
  • the first dissolution tank 1 and the second dissolution tank 2 may be provided with a heating jacket 8 and a heater in order to facilitate dissolution, dispersion, and stabilization so that the temperature of the solution can be controlled.
  • a dissolver type, oar type, propeller type, and homo-mixer type of high speed stirring dispersing apparatus can be adopted. It is preferable to maintain the temperature in the dispersion tank 3 at 15 - 60°C.
  • the first and the second solution may not be put into the dispersion tank 3 separately, but may be mixed with each other and put into the tank 3.
  • the operation of the high speed stirring type of dispersing apparatus is started.
  • the dispersing operation can be performed while the first and the second solution are being supplied during the operation of the high speed stirring type of dispersing apparatus 3A.
  • the operation conducted during dispersion has great influence on the dispersing property.
  • the particle size of the dispersion mainly depends on the rotation speed of the dispersing apparatus, the stirring time, and the amount of the activator.
  • the dispersing circumferential speed is preferably not less than 10 m/sec and not more than 100 m/sec.
  • Fig. 2 shows an example in which the solution temperature is maintained at 45°C during the process of standing.
  • the stirring time relates to the particle size to be obtained. However, it is preferable to maintain the stirring time in 3 - 60 minutes.
  • the pressure is gently reduced to 100 Torr, and preferably the evacuating operation may be conducted according to the method disclosed in the Japanese Patent Application open to Public Inspection No. 102303/1990.
  • the temperature of the solution in the case of removal of the water impermeable low boiling point organic solvent is preferably 40 - 80°C, and more preferably 50 - 70°C.
  • the removal of the water-insoluble low boiling point organic solvent is preferably conducted until its content becomes not more than 1 wt%.
  • the amount of the surface active agnet to be added relates to the kinds of binder and coupler of the water-insoluble low boiling point organic solvent.
  • the amount of the surface active agent is preferably in the range from the critical micelle concentration to 50 times of the critical micelle concentration.
  • the liquid particle size can be controlled to be 0.01 - 3 ⁇ m in the present invention.
  • the circumferential dispersing speed in the process of dispersion and the stirring circumferential speed in the process of removal of the water-insoluble low boiling point organic solvent may be different from each other.
  • a solution in which only the surface active agent is dissolved in water may be utilized as the second solution without using the hydrophilic binder.
  • the content may be 3 - 30 wt% in the solution put in the dispersing tank 3.
  • the boiling point of the water-insoluble low boiling point organic solvent is not more than 100°C, and more preferably not more than 85°C.
  • the specific examples are ethyl acetate, methyl acetate, m-hexane, m-pentane, benzene, cyclohexane, cyclopentane, chloroform, and dichloromethane.
  • the objective hydrophobic substance is substantially dissolved only in the water-insoluble low boiling point organic solvent.
  • a high boiling point organic solvent is not contained at all.
  • a high boiling point organic solvent such as dimethyl form-amide (DMF)
  • DMF dimethyl form-amide
  • a coupler which is a hydrophobic substance applied the various photographic materials of the present invention is a color image forming compound which forms a dye upon reaction with an oxidized product of color developing agent, for example aromatic amine (the first class amine).
  • a non-diffusible coupler having a hydrophobic group referred to as a ballast group is preferably used, and either 4 equivalent or 2 equivalent coupler may be used.
  • the aforementioned coupler includes a colored coupler provided with color correction effect, and a DIR coupler which releases a developing inhibitor while developing is conducted.
  • a widely known closed ketomethylene coupler can be utilized as a yellow coupler. Benzoyl acetoamide compounds and pivaloyl acetoamide compounds are advantageously used.
  • Pyrazolone compounds, indazolone compounds, and cyanoacetyl compounds can be used as a magenta coupler, wherein pyrazolone compounds are advantageous.
  • Phenol compounds and naphthol compounds can be used as a cyan coloring coupler.
  • a coupler disclosed in the official gazette of Japanese Patent Application Open to Public Inspection No. 42121/1977 can be used as a colored coupler.
  • a coupler disclosed in the Japanese Patent Application Open to Public Inspection No. 69624/1977 can be used as a DIR coupler. Except for the aforementioned DIR coupler, a compound which releases a developing inhibitor during a developing process may be contained in the photographic material, and for example, a compound disclosed in the official gazette of Japanese Patent Application Open to Public Inspection No. 9116/1978 can be used.
  • non-ionic surface active agents are used for the present invention: a saponin (steroid) derivative; an alkyleneoxide derivative (for example, polyethylene glycol, condensation of polyethylene glycol/polypropylene glycol, polyethylene glycol alkyl or alkylaryl ether, polyethylene glycol ester, polyethylene glycol sorbitan ester, polyalkylene glycol alkylamine or amide, and polyethylene oxide additive product of silicon); a glycidol derivative (for example, alkenyl succinic acid polyglyceride, and alkylphenol polyglyceride); fatty acid ester of polyhydric alcohol; alkyl ester of sugar; and urethane or ether.
  • an alkyleneoxide derivative for example, polyethylene glycol, condensation of polyethylene glycol/polypropylene glycol, polyethylene glycol alkyl or alkylaryl ether, polyethylene glycol ester, polyethylene glycol sorbitan ester, polyalkylene glycol alkylamine or
  • anion surface active agents containing the following acidic groups such as a carboxyl group, a sulfo group, a sulfate ester group, and a phosphoric ester group are used for the present invention: saponin of triterpenoide, alkylcarboxylic acid slat, alkylsulfonic acid salt, alkylbenzene sulfonic acid salt, alkylnaphthalene sulfonic acid salt, alkylsulfate ester, alkyl phosphoric ester, N-acyl-N-alkyltaurine, sulfosuccinic acid ester, sulfoalkylpolyoxyethylene alkylphenyl ether, and polyoxy ethylene alkyl phosphoric ester.
  • amphoteric surface active agents are used for the present invention: amino acid; aminoalkyl sulfonic acid; aminoalkyl sulphuric acid or phosphoric ester; alkylbetaine; amineimide; and amineoxide.
  • cationic surface active agents can be used for the present invention: heterocyclic quarternary ammonium salt such as alkylamine salt, aromatic or aliphatic quarternary ammonium salt, pyridinium, and idazolium; and aliphatic or heterocyclic phosphonium or sulfonium salt.
  • heterocyclic quarternary ammonium salt such as alkylamine salt, aromatic or aliphatic quarternary ammonium salt, pyridinium, and idazolium
  • aliphatic or heterocyclic phosphonium or sulfonium salt aliphatic or heterocyclic phosphonium or sulfonium salt.
  • an anionic surface active agent such as dodecyl benzene sulfonic acid, dodecyl sodium sulfate, and "Aerosol A102" (made by Cyananid Co.) is preferably used.
  • Protein such as gelatin, a gelatin derivative, a graft polymer of gelatin and other high polymers, albumin, and casein is used for the aforementioned water soluble binder.
  • a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate ester, and a sugar derivative such as sodium alginate and a starch derivative are also used for the aforementioned water soluble binder.
  • Synthetic hydrophilic high molecular substance such as polyvinyl alcohol, polyvinyl alcohol acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylic amide, polyvinyl imidazol, and polyvinyl pyrazole, or synthetic hydrophilic high molecular substance of a copolymer of the compounds described above, are used for the aforementioned water soluble binder.
  • gelatin for the binder.
  • DDR coupler DDR coupler
  • DDR compound diffusible dye releasing reducer
  • hydroquinone derivative aminophenol derivative, gallic acid derivative and ascorbic acid derivative are used as the aforementioned anti-stain agent.
  • a hydroxybenzene derivative, dihydroxynaphthalene derivative, aminonaphthol derivative, sufonicamide phenol derivative, and sulfonic amide naphthol derivative are used for the aforementioned anti-fading agent.
  • a benzotritriazole compound substituted by an aryl group, 4-thiazolidone compound, benzophenone compound, cinnamic acid ester compound, butadiene compound, and benzoxazole compound can be used for the aforementioned ultraviolet ray absorbent.
  • an ultraviolet ray absorbing coupler and ultraviolet ray absorbing polymer may be used.
  • a compound of stilbenzene, triazine, oxazole or cumalin is used for the aforementioned whitening agent.
  • Coupler (1) 5 kg Ethyl acetate 10 l DMF 300 ml
  • the first and the second solution were mixed, and dispersed by a dispersing apparatus provided with a disperser having a diameter of 10 cm, at a circumferential dispersing speed of 20 m/sec for 10 and 20 minutes, and at a circumferential dispersing speed of 30 m/sec for 10 minutes. Then, the solution was evacuated and stirred until the residual concentration of ethylacetate became not more than 0.3 wt% so as to remove ethylacetate, and subsequently, the solution was diluted with water to make 100 l.
  • the particle size could be controlled by the circumferential dispersing speed and stirring time.
  • the particle size could not be controlled, and the coloring density was only 103%.
  • composition of the second solution was as follows, wherein the dissolving conditions were the same. Water 50 l Surface active agent (3) 2 l (Concentration 33%)
  • Example 2 A dispersing operation was conducted in the same manner as that of Example 1 to remove ethylacetate.
  • the particle size of dispersion and coloring density are shown in Table 2. It was ensured that the particle size could be controlled in the case of coupler (2).
  • TABLE 2 20 m/sec 20 min 50 m/sec 20 min Blank Particle size 254 nm 105 nm 200 nm Dmax 115% 104% 100% MTF 0.68 0.70 0.57
  • the coated sample was exposed to white light through a step wedge for sensitometory, and processed under the following conditions.
  • the amount of replenishment is expressed by the unit of ml/m2 of photosensitive material.
  • Water is added to make 1 l, and pH is adjusted to 10.06 using potassium hydroxide or 20% sulphuric acid.
  • Water is added to make 1 l, and pH is adjusted to 4.4 using aqueous ammonia solution or glacial acetic acid.
  • Water is added to make 1l, and pH is adjusted to 4.0 using aqueous ammonia solution or glacial acetic acid.
  • Water is added to make 1l, and pH is adjusted to 6.2 using aqueous ammonia solution or glacial acetic acid.
  • Water is added to make 1 l, and pH is adjusted to 8.5 using aqueous ammonia solution or 50% sulphuric acid.
  • a hydrophobic substance of fine particles can be obtained irrespective of the kind of the substance, as well as the deterioration of sharpness and dye bleeding caused when a high boiling point organic solvent remains in a coated film can be prevented.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Colloid Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP92103789A 1991-03-06 1992-03-05 Verfahren zur Herstellung einer hydrophoben Verbindung zum photographischen Gebrauch Withdrawn EP0502531A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP40058/91 1991-03-06
JP4005891 1991-03-06
JP318015/91 1991-12-02
JP3318015A JPH0519394A (ja) 1991-03-06 1991-12-02 写真用疎水性物質の製造方法

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EP0502531A1 true EP0502531A1 (de) 1992-09-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2301444A (en) * 1995-03-23 1996-12-04 Eastman Kodak Co Photographic elements comprising cyan coupler dispersions
US5679507A (en) * 1994-09-01 1997-10-21 Konica Corporation Method for chemically sensitizing silver halide photographic emulsion
US5726003A (en) * 1996-08-15 1998-03-10 Eastman Kodak Company Cyan coupler dispersion with increased activity

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2101616A5 (de) * 1970-08-13 1972-03-31 Agfa Gevaert Nv
JPS53112731A (en) * 1977-03-14 1978-10-02 Fuji Photo Film Co Ltd Method and apparatus for production of photographic materials
GB2106885A (en) * 1981-09-22 1983-04-20 Fuji Photo Film Co Ltd Process for preparing aqueous dispersion of carbon black

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2101616A5 (de) * 1970-08-13 1972-03-31 Agfa Gevaert Nv
JPS53112731A (en) * 1977-03-14 1978-10-02 Fuji Photo Film Co Ltd Method and apparatus for production of photographic materials
GB2106885A (en) * 1981-09-22 1983-04-20 Fuji Photo Film Co Ltd Process for preparing aqueous dispersion of carbon black

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5679507A (en) * 1994-09-01 1997-10-21 Konica Corporation Method for chemically sensitizing silver halide photographic emulsion
GB2301444A (en) * 1995-03-23 1996-12-04 Eastman Kodak Co Photographic elements comprising cyan coupler dispersions
GB2301444B (en) * 1995-03-23 1999-02-24 Eastman Kodak Co Photographic elements comprising cyan coupler dispersions with improved stability and increased activity
US5726003A (en) * 1996-08-15 1998-03-10 Eastman Kodak Company Cyan coupler dispersion with increased activity

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