EP0895119A1 - Verfahren zur Dispersion eines Spektralsensibilisators und hierdurch erhaltene Dispersion - Google Patents

Verfahren zur Dispersion eines Spektralsensibilisators und hierdurch erhaltene Dispersion Download PDF

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Publication number
EP0895119A1
EP0895119A1 EP98114460A EP98114460A EP0895119A1 EP 0895119 A1 EP0895119 A1 EP 0895119A1 EP 98114460 A EP98114460 A EP 98114460A EP 98114460 A EP98114460 A EP 98114460A EP 0895119 A1 EP0895119 A1 EP 0895119A1
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EP
European Patent Office
Prior art keywords
spectral sensitizer
dispersion
water
weight
page
Prior art date
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Granted
Application number
EP98114460A
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English (en)
French (fr)
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EP0895119B1 (de
Inventor
Taisei Nishimi
Keiji Mihayashi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0895119A1 publication Critical patent/EP0895119A1/de
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Publication of EP0895119B1 publication Critical patent/EP0895119B1/de
Anticipated expiration legal-status Critical
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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
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes

Definitions

  • the present invention relates to a method of obtaining an aqueous dispersion of a spectral sensitizer used for silver halide photographic materials and to a dispersion obtained by the method.
  • a spectral sensitizing technique that is, the method of sufficiently sensitizing the light-sensitive materials up to the visible region is very important and, in particular, the sensitizing method is an indispensable technique for color photographic materials. Accordingly, about the addition method of a spectral sensitizer necessary for spectrally sensitizing silver halide emulsions, various methods have been developed.
  • JP-B-49-46416 a method of adding a spectral sensitize to a silver halide emulsion after dissolving it in an organic solvent having a water miscibility is disclosed, for example, in JP-B-49-46416 (the term "JP-B" as used herein means an "examined published Japanese patent application”.
  • JP-B a method of dissolving a spectral sensitizer in an organic solvent and after adding the solution to a silver halide emulsion, removing the organic solvent by heating is disclosed, for example, in JP-B-44-22948.
  • a technique of completely dissolving a certain kind of spectral sensitizer in water under an acidic condition and then adding the solution to a silver halide emulsion is disclosed, for example, in JP-B-44-23389 and JP-B-50-80826.
  • the method is limited to the applicable spectral sensitizers and also there is a problem in the chemical stability of these spectral sensitizers used in these methods.
  • a technique of dissolving a spectral sensitizer in water containing a water-soluble organic compound and then adding the solution to a silver halide emulsion is disclosed, for example, in JP-B-57-22094 and JP-B-2-135437.
  • it is required to use a water-soluble organic compound in an amount almost same as that of the spectral sensitizer, which gives a possibility of causing an inferior adsorption of the spectral sensitizer to a silver halide emulsion.
  • JP-B-53-16624 discloses a technique of melting a spectral sensitizer in an organic compound and then adding the melt to a silver halide emulsion.
  • JP-B-53-102732 and JP-B-53-102733 a technique of forming photographically inactive water-soluble fine solids and a spectral sensitizer into tablets or granules and adding the tablets or the granules to a silver halide emulsion is disclosed.
  • these methods because after dispersing the spectral sensitizer in a liquid, the spectral sensitizer is taken out as a solid state, a complicated process is required.
  • a method of dispersing a spectral sensitizer in water containing gelatin only as the fine solids is disclosed, for example, in JP-B-61-45217 and WO 93/23792. These methods are very excellent as a dispersion method of a spectral sensitizer because the methods do not use unnecessary additives such as an organic solvent and a dispersing agent and also the operation of the method is simple.
  • JP-A-4-125031 and JP-A-5-297496 the term "JP-A” as used herein means an "unexamined published Japanese patent application”
  • JP-A-4-125031 and JP-A-5-297496 the term "JP-A” as used herein means an "unexamined published Japanese patent application”
  • an object of the present invention is to provide a method of obtaining a highly concentrated dispersion of a spectral sensitizer solving the above-described problems.
  • a dispersion method of a spectral sensitizer which comprising after dissolving an inorganic salt in an amount of at least 0.5% by weight in water which does not substantially contain a surface active agent, an organic solvent, and a silver halide emulsion, adding to the solution a spectral sensitizer in an amount of at least 0.5% by weight and dispersing the spectral sensitizer as the fine solids thereof.
  • a dispersion method of a spectral sensitizer of the 1st aspect wherein the spectral sensitizer is added to the dissolved solution in an amount of from 2% by weight to 30% by weight.
  • a dispersion method of a spectral sensitizer of the 1st aspect wherein the pH in the case of dissolving the inorganic salt in an amount of at least 0.5% by weight in water which does not substantially contain a surface active agent, an organic solvent, and a silver halide emulsion is in the range of from 4 to 10.
  • a dispersion method of a spectral sensitizer of the 3rd aspect wherein the dissolved solution obtained by dissolving the inorganic salt in an amount of at least 0.5% by weight in water which does not substantially contain a surface active agent, an organic solvent and a silver halide emulsion has a pH of 6 to 8.
  • an 8th aspect of the present invention there is provided a dispersion method of a spectral sensitizer of the aspect 7, wherein the concentration of the water-soluble polymer in water is at least 0.5% by weight.
  • a spectral sensitizer forms a fibrous associated material in an aqueous dispersion of the spectral sensitizer having a high viscosity and the fibrous associated material forms a three-dimensional network structure.
  • the fibrous associated material is caused by that the spectral sensitizer once dissolved in water is fibrously recrystallized in water. That is, it is considered that the existent state of the spectral sensitizer molecule in water is shown by the following equilibrium; crystal ⁇ monomer ⁇ fibrous associated material
  • the present inventor has considered that it is not effective to increase the solubility of a spectral sensitizer in a solvent, which is hitherto been believed to be effective, and it is effective to lower the solubility of the spectral sensitizer to restrain the increase of the viscosity of the dispersion. That is, the inventor set up a hypothesis that the prevention of a spectral sensitizer from dissolving as a monomer in water restrains the formation of the fibrous associated material, that is, is effective for restraining the increase of the viscosity of the dispersion.
  • the inorganic salt in the present invention is a salt of an acid without containing carbon, such as hydrochloric acid, sulfuric acid, nitric acid, etc., and an alkali metal, an alkaline earth metal, or ammonium and practically includes lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium chloride, rubidium bromide, cesium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, magnesium iodide, calcium iodide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, ammonium sulfate, lithium nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, calcium n
  • preferable salts are sodium nitrate, sodium sulfate, ammonium nitrate, and ammonium sulfate each containing no halogen atom which is worried about making an interaction with a silver halide emulsion, and sodium nitrate and sodium sulfate are more preferred.
  • the inorganic salts may be used singly or as a combination of them.
  • the concentration of the inorganic salt in water is at least 5% by weight, preferably from 1% by weight to 50% by weight, and more preferably from 2% by weight to 30% by weight.
  • the above-described inorganic salt that the pH of water at dissolving the above-described inorganic salt is in the range of from 4 to 10, preferably in the range of from 5 to 9, and more preferably from 6 to 8 is used.
  • the spectral sensitizer in the present invention means a compound which causes a photoinductive electron transfer to a silver halide emulsion when the compound adsorbs on the silver halide emulsion and does not include organic dyestuffs not having the above function (photoinductive electron transfer).
  • the spectral sensitizer used in the present invention includes methine dyes such as cyanine dyes, merocyanine dyes, hemicyanine dyes, rhodacyanine dyes, oxonol dyes, hemioxonol dyes, etc., and styryl dyes.
  • cyanine dyes are particularly preferred. More preferably, an anionic cyanine dye having one or two hydrophilic group (for example, a sulfo group, a sulfoalkyl group, and a carboxyl group) is effective.
  • the concentration of the spectral sensitizer in water is at least 0.5% by weight, preferably in the range of from 1 to 30% by weight, and more preferably in the range of from 2 to 20% by weight.
  • the weight ratio of the inorganic salt and the spectral sensitizer has a large meaning to the viscosity of the dispersion. To restrain the viscosity of dispersion of the spectral sensitizer, it is effective to disperse the spectral sensitizer in water having dissolved therein the inorganic salt in an amount of preferably at least 1/2, and more preferably at least an equivalent amount to the addition amount of the spectral sensitizer.
  • various dispersing means can be effectively used.
  • a high-speed stirring means a ball mill, a sand mill, an attritor, a ultrasonic dispersing means, etc., can be used.
  • the temperature in the case of dispersing the spectral sensitizer in water is in the range of from 0°C to 100°C, preferably in the range of from 20°C to 80°C, and more preferably from 50°C to 80°C.
  • the dispersion of the spectral sensitizer obtained by the present invention is mixed with a water-soluble polymer for having a precipitation preventing property and can be stored for long period of time at a temperature of 30°C or lower or can be refrigerated.
  • the water-soluble polymer used in the present invention is a linear high-molecular compound having a molecular weight of at least 1,000 and can be dissolved in water at room temperature in an amount of 0.5% by weight and practically includes gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, a cellulose sulfuric acid ester, chondroitin sulfuric acid, sodium alginate, chitin, chitosan, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, sodium polyacrylate, polyvinyl pyrroidone, etc., and the copolymers of them.
  • the water-soluble polymers may be used singly or as a combination of the plural water-soluble polymers.
  • the water-soluble polymer may be added to a silver halide emulsion as the aqueous solution thereof or as solids thereof. Also, in the case of adding the water-soluble polymer, if necessary, a known antiseptic maya be used.
  • the concentration of the water-soluble polymer used in the present invention is preferably at least 0.5% by weight, more preferably from 1% by weight to 50% by weight, and far more preferably from 2% by weight to 10% by weight.
  • the high-concentration dispersion of a spectral sensitizer which has never been obtained by conventional methods, can be prepared without increasing the viscosity thereof.
  • the mixed composition is prepared using the water-soluble polymer
  • the dispersion of the spectral sensitizer prepared can be stably stored for a long period of time by simply cooling the composition without carrying out drying, etc.
  • various additives according to the purposes may be added. Also, for the photographic light-sensitive materials prepared by such silver halide emulsions. various additives can be used.
  • Sample Nos. 1 to 5 are samples of comparative example and Sample Nos. 6 to 13 are samples of this invention.
  • the concentration of the spectral sensitizer 1 when the concentration of the spectral sensitizer 1 was 1% by weight or lower, the dispersion had a fluidity but when the concentration was 2% by weight or higher, the viscosity increased with the progress of the dispersion and the dispersion could not be carried out. Also, when the concentration of the spectral sensitizer 1 was 10% by weight, at the time of adding the spectral sensitizer 1 to water, the system was gelled and thus the dispersion became impossible.
  • Sample No. 4 having increased viscosity was lyophilized, and after vapor-depositing platinum thereto, observation by SEM (scanning type electron microscope) was carried out. As the result, a three-dimensional structure of intertwined fibrous associated material was observed as shown in Fig. 1.
  • Sample Nos. 14 to 17 are comparative samples and Sample Nos. 18 to 23 are samples of this invention.
  • each of the spectral sensitizers 2 to 5 was added to 90 g of water.
  • 10 g of each of spectral sensitizers 2 to 7 was added and dispersed under the condition of 60°C, using a dissolver blade at 2,000 r.p.m. over a period of about one hour.
  • This example shows the influence of the ratio of the addition amount of a spectral sensitizer and the addition amount of an inorganic salt in the dispersion method of the present invention to the viscosity of the dispersion (see Table 3).
  • the present invention is very effective for restraining the increase of the viscosity of the dispersion to disperse a spectral sensitizer in water containing an inorganic salt in an amount of almost same as the amount of the spectral sensitizer.
  • Sample No. 29 was same as Sample No. 11 described above. That is, after dissolving 10 g of sodium nitrate in 80 g of ion-exchanged water, 10 g of the spectral sensitizer was added and dispersed under the condition of 60°C using a dissolver blade at 2,000 r.p.m. over a period of about one hour.
  • Sample No. 30 was prepared by adding 50 g of an aqueous solution of 12% by weight gelatin to 50 g of the dispersion obtained by the manner as preparing Sample No. 29.
  • Sample Nos. 31 and 32 were prepared by light-shielding Sample Nos. 29 and 30 respectively and stored in a refrigerator of 10°C for 4 weeks.
  • Sample Nos. 29 and 31 were diluted to 20,000 times with water/methanol (volume ratio 1/1)
  • Sample Nos. 30 and 32 were diluted to 10,000 times with water/methanol (volume ratio 1/1)
  • the ultraviolet and visible absorption spectra were measured about these diluted samples, and the absorption of each solution obtained from each dispersion showed the same spectrum. It was also confirmed that at mixing with gelatin and during storing in the cold dark place, the chemical decomposition of the spectral sensitizer in each dispersion did not occur.
  • the high-concentrate dispersion of a spectral sensitizer which has never been obtained by conventional methods, can be prepared without increasing the viscosity thereof.
  • the mixed composition was prepared using a water-soluble polymer by the dispersion method of the present invention, the dispersion of the spectral sensitizer prepared can be stably stored for long period of time as 1 month or longer by simply cooling it without need of drying, etc.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Colloid Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP98114460A 1997-07-31 1998-07-30 Verfahren zur Dispersion eines Spektralsensibilisators und hierdurch erhaltene Dispersion Expired - Lifetime EP0895119B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP219005/97 1997-07-31
JP21900597 1997-07-31
JP9219005A JPH1152507A (ja) 1997-07-31 1997-07-31 分光増感剤の分散方法及びこれにより得られた分散物

Publications (2)

Publication Number Publication Date
EP0895119A1 true EP0895119A1 (de) 1999-02-03
EP0895119B1 EP0895119B1 (de) 2003-06-25

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EP (1) EP0895119B1 (de)
JP (1) JPH1152507A (de)
AT (1) ATE243856T1 (de)
DE (1) DE69815765T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0915376A1 (de) * 1997-11-06 1999-05-12 Fuji Photo Film Co., Ltd. Emulgierte Dispersion von einer photographischen, hydrophobischen Verbindung und ein photographisches, lichtempfindliches Silberhalogenidmaterial

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60143154D1 (de) 2001-04-17 2010-11-11 Fujifilm Corp Photographisches Silberhalogenidmaterial enthaltend einen Methinfarbstoff
US7241564B2 (en) 2004-08-02 2007-07-10 Fujifilm Corporation Silver halide holographic sensitive material and system for taking holographic images by using the same
EP1691237A3 (de) 2005-02-15 2006-10-18 Fuji Photo Film Co., Ltd. Holographisches Aufzeichnungsmaterial und holographisches Aufzeichnungsverfahren

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006025A (en) * 1975-06-06 1977-02-01 Polaroid Corporation Process for dispersing sensitizing dyes
US4683193A (en) * 1984-03-21 1987-07-28 Fuji Photo Film Co., Ltd. Process for producing silver halide photographic emulsion

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006025A (en) * 1975-06-06 1977-02-01 Polaroid Corporation Process for dispersing sensitizing dyes
US4683193A (en) * 1984-03-21 1987-07-28 Fuji Photo Film Co., Ltd. Process for producing silver halide photographic emulsion

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0915376A1 (de) * 1997-11-06 1999-05-12 Fuji Photo Film Co., Ltd. Emulgierte Dispersion von einer photographischen, hydrophobischen Verbindung und ein photographisches, lichtempfindliches Silberhalogenidmaterial
US6309812B1 (en) 1997-11-06 2001-10-30 Fuji Photo Film Co., Ltd. Emulsified dispersion of photographic hydrophobic compound and silver halide photographic light-sensitive material

Also Published As

Publication number Publication date
ATE243856T1 (de) 2003-07-15
DE69815765T2 (de) 2004-05-19
JPH1152507A (ja) 1999-02-26
DE69815765D1 (de) 2003-07-31
EP0895119B1 (de) 2003-06-25

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