US3765897A - Process of incorporating additives into photographic emulsions - Google Patents

Process of incorporating additives into photographic emulsions Download PDF

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Publication number
US3765897A
US3765897A US00187554A US3765897DA US3765897A US 3765897 A US3765897 A US 3765897A US 00187554 A US00187554 A US 00187554A US 3765897D A US3765897D A US 3765897DA US 3765897 A US3765897 A US 3765897A
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US
United States
Prior art keywords
combination
emulsified
gelatin
photographic
emulsion
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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.)
Expired - Lifetime
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US00187554A
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English (en)
Inventor
F Nittel
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • 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
    • G03C7/3885—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific solvent
    • 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
    • G03C1/38—Dispersants; Agents facilitating spreading

Definitions

  • the present invention relates to a process for incorporating substances in materials which are used to form photographic layers and auxiliary layers.
  • emulsifiable compounds such as color couplers, UV absorbers, white toners and similar additives may be incorporated in gelatin solutions by using so-called oil forming agents.
  • color couplers used in the production of photographic products are incorporated in emulsions by dissolving the color coupler in an organic liquid of relatively high boiling point which is insoluble in water, and emulsifying or dispersing the solution in the emulsions.
  • hydrophilic developers e.g., N-butyl-N-w-sulphobutyl-pphenylenediamine
  • hydrophilic developers e.g., N-butyl-N-w-sulphobutyl-pphenylenediamine
  • This causes loss in sensitivity, flattening of the gradation and a reduced image density.
  • residues of hydrophobic developer may be retained in the droplets and cause fogging when the photographic material is treated in oxidizing bleaching baths.
  • l-lydrophilic substances such as color couplers which carry a carboxyl group are incorporated in gelatin in the form of their sodium salts. Since the gelatine solutions are subsequently adjusted to a pH of 6.2 to 6.5, these compounds are generally present in microcrystalline distribution. The protective colloidal action of gelatin is in many cases insufficient, so that recrystallization occurs influencing sensitivity, gradation and color brilliance in an uncontrollable manner.
  • hydrophilic substances such as color couplers which carry SO H groups are generally more compatible with gelatin than the above mentioned compounds, recrystallization still occurs in manycases during digestion of the gelatine, especially in the case of compounds that have an enolate form which promotes solubility in an alkaline medium.
  • the action of the S Na group in preventing recrystallization is no longer sufficient. This again leads to a loss in sensitivity, reduction in the color brilliance and loss in gradation.
  • the use of lithium salts and increased amounts of wetting agents has been found to also bring no significant improvements.
  • hydrophilic substances of the above mentioned types have the property of increasing the viscosity of the casting solution,- in some cases to such an extent that such solutions can no longer be worked up.
  • the compounds according to the invention are prepared by reacting suitable phenols or'cyclohexyl alco- .hols with long chained substituted succinic acid anhydride in a known manner, preferably in the presence of acid or' basic catalysts, such as sulfuric acid or pyridine.
  • acid or' basic catalysts such as sulfuric acid or pyridine.
  • the succinic acid anyhdride ring is opened with formation of an ester bond and a carboxyl group.
  • Products in which the long chained radical is in the d-pOSltlOl'l to the carboxyl group and those in which it is in the fi-position to the carboxyl group are formed side by side.
  • only one of these forms is represented in the general formula and in the examples, but the invention is not thus limited to hi .99, 9L1-, m r
  • Substances which are capable of being emulsified e.g., color couplers, UV absorbents, white toners, stabilizers or developers, are dissolved in an organic solvent which is immiscible with water, together with the compounds which are to be used according to the invention and the resulting solution is emulsified in the casting solution for the photographic layer by means of an if
  • the compounds form soaps in alkaline pH ranges, in
  • the compounds described here are not washed out in an alkaline medium. They, therefore, prevent precipitation of the dyewhich is formed in the coupling reaction, and the occurrence of uneven colour surfaces. The crystallization of color couplers, which may otherwise already occur during the process of digestion, is also prevented. Furthermore, in contrast to the known hydrophobic oil-forming agents, the compounds used according to the invention cause neither flattening of the gradation nor a reduction in the image.
  • the compounds according to the invention have the following advantages over the compounds described in patent application Ser. No. 814,808.
  • the compounds described here are generally used in the proportion of 0.1 to parts by weight for each part by weight of the substance which is to be incorporated, the proportion being preferably within the range of 0.3 to 1 part by weight.
  • the higher concentrations of up to 10 parts by weight are useful for those cases' in which only small quantities of additive, e.g., a stabilizer, should be introduced into the casting solution.
  • additive e.g., a stabilizer
  • particularly suitable organic solvents which are not miscible with water are chlorinated short chained aliphatic compounds, e.g., methylene chloride, as well as ethyl acetate and diethyl carbonate.
  • the binder used for the photographic layers is preferably gelatin although this may be partly replaced by other film-forming natural or synthetic polymers, e.g., alginic acid and its derivatives such as its salts, esters or amides, earboxymethyl cellulose, alkyl cellulose, starch and its derivatives, polyvinyl alcohol, copolymers containing vinyl alcohol and vinyl acetate units, polyvinyl pyrrolidone and the like, anionic polyurethanes and other latices, e.g., copolymers of acrylic acid esters, acrylonitrile or acrylamide.
  • alginic acid and its derivatives such as its salts, esters or amides
  • earboxymethyl cellulose alkyl cellulose
  • starch and its derivatives polyvinyl alcohol, copolymers containing vinyl alcohol and vinyl acetate units
  • anionic polyurethanes and other latices e.g., copolymers of acrylic acid esters, acrylonit
  • the photographic layers may contain all the known 5 additives such as anti-fog agents, stabilizers, hardeners, plasticizers and wetting agents. Furthermore, they may be both chemically and spectrally sensitized.
  • the light-sensitive emulsions may be chemically sensitized by carrying out the ripening process in the pres- 10 ence of small quantities of compounds which contain sulfur, for example allyl isothiocyanate, allyl thiourea or sodium thiosulfate, or they may be sensitized by means of the compounds described in Belgian Pat. specifications Nos. 493,464 and 568,687, the iminoaminomethane sulfinic acid compounds described in Belgian Pat. specification No. 547,323, or small quantities of noble metal compounds such as compounds of gold, platinum, palladium, iridium, ru-
  • the emulsions may also be sensitized with polyalkylene oxide derivatives, elg., polyethylene oxide having a molecular weight of between 1,000 and 20,000, condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have a molecular weight of at least 700, and preferably more than 1,000.
  • the resulting mixture is used within a colour photographic multilayered material in the usual manner as a red-sensitive layer which contains. cyan-forming coupier.
  • Example 1 The mixture is worked up as in Example l.
  • the green-sensitive layer with regard to gradation and density shows the properties described. in Example 1.
  • EXAMPLE 4 3 8 of fel wesllw figi s N rHu and 10 g of Compound 25 are dissolved in ethyl acetate and emulsified in 1 kg of a 10 percent gelatin solution. The emulsion is cast as a UV protective layer over a color photographic material.
  • the protective layer prepared by the process accord- ,ing to the invention is clear, whereas a layer which has awareness! .wiflzww npqsss 2229315 9951 1;-
  • EXAMPLE 5 30 g of the UV absorbent used for Example 4 and 15 g of Compound 8 are dissolved in ethyl acetate and emulsified in 1 kg of a 10 percent gelatin solution. The emulsion is cast as a UV protective layer over a color photographic material. The result is similar to that obtained in Example 4.
  • the oil former has l esmuiaa RCHCOOH R- H-COwO-R' wherein one R is hydrogen and the other is a saturated or unsaturated straight chained or branched aliphatic radical having six to 18 carbon atoms, and R a cycloalkyl group, an aryl group or a heterocyclic aromatic group.
  • the material to be emulsified is soluble in aqueous alkali, and is dissolved in an aqueous alkaline solution along with the oil former and the resulting solution emulsified into the gelatin emulsion.
  • R is hydrogen and the other a saturated or unsaturated straight chained or branched aliphatic radical having six to 18 carbon atoms, and .w R a cycloalkyl group, an aryl group or a heterocyclic aromatic group. 7. The combination of claim 6 in which R is substit led with another radical of the formula:
  • R-CH-COOH 9 The combination of claim 6 in which the photographic additive is a UV absorber.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
US00187554A 1970-10-09 1971-10-07 Process of incorporating additives into photographic emulsions Expired - Lifetime US3765897A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702049689 DE2049689A1 (de) 1970-10-09 1970-10-09 Einlagerungsverfahren

Publications (1)

Publication Number Publication Date
US3765897A true US3765897A (en) 1973-10-16

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US00187554A Expired - Lifetime US3765897A (en) 1970-10-09 1971-10-07 Process of incorporating additives into photographic emulsions

Country Status (6)

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US (1) US3765897A (cs)
JP (1) JPS53131028A (cs)
BE (1) BE773584R (cs)
DE (1) DE2049689A1 (cs)
FR (1) FR2113006A6 (cs)
GB (1) GB1370151A (cs)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929485A (en) * 1973-07-26 1975-12-30 Fuji Photo Film Co Ltd Dispersion of silver halide developing agent with surface active polymers of maleic acid half esters
US4161408A (en) * 1977-06-06 1979-07-17 Minnesota Mining And Manufacturing Company Method for the preparation of a photothermographic system
US4330617A (en) * 1980-02-05 1982-05-18 Mitsubishi Paper Mills, Ltd. Photographic elements containing novel developing agent precursors
US4368259A (en) * 1980-01-22 1983-01-11 Agfa-Gevaert Aktiengesellschaft Color photographic recording material containing an emulsified, hydrophilic color-forming compound
US4446216A (en) * 1981-12-10 1984-05-01 Smith Norman A Photographic material
US4464464A (en) * 1981-07-30 1984-08-07 Agfa-Gevaert Aktiengesellschaft Color photographic recording material
US4810625A (en) * 1986-04-25 1989-03-07 Agfa-Gevaert Aktiengesellschaft Photographic material with pyrazolone coupler and oil former
US4933270A (en) * 1988-09-26 1990-06-12 Eastman Kodak Company Process for the precipitation of stable colloidal dispersions of base degradable components of photographic systems in the absence of polymeric steric stabilizers
US5089380A (en) * 1989-10-02 1992-02-18 Eastman Kodak Company Methods of preparation of precipitated coupler dispersions with increased photographic activity
EP0696758A1 (de) 1994-08-10 1996-02-14 Agfa-Gevaert AG Lichtempfindliches fotografisches Aufzeichnungsmaterial mit lichtabsorbierendem Farbstoff
US5580705A (en) * 1991-12-27 1996-12-03 Konica Corporation Method of bleaching silver halide color photographic light-sensitive materials using particular ferric chelates
US5624467A (en) * 1991-12-20 1997-04-29 Eastman Kodak Company Microprecipitation process for dispersing photographic filter dyes
US5674668A (en) * 1995-09-06 1997-10-07 Agfa-Gevaert Photographic recording material
WO2012014955A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
WO2012014954A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
EP2455431A1 (en) 2003-10-23 2012-05-23 Fujifilm Corporation Ink and ink set for inkjet recording
EP2712894A1 (en) 2012-09-26 2014-04-02 Fujifilm Corporation Azo compound, aqueous solution, ink composition, ink for inkjet recording, inkjet recording method, ink cartridge for inkjet recording, and inkjet recorded material

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07119996B2 (ja) * 1987-03-27 1995-12-20 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689271A (en) * 1968-04-11 1972-09-05 Agfa Gevaert Ag Incorporation process for materials used to form photographic layers

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689271A (en) * 1968-04-11 1972-09-05 Agfa Gevaert Ag Incorporation process for materials used to form photographic layers

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929485A (en) * 1973-07-26 1975-12-30 Fuji Photo Film Co Ltd Dispersion of silver halide developing agent with surface active polymers of maleic acid half esters
US4161408A (en) * 1977-06-06 1979-07-17 Minnesota Mining And Manufacturing Company Method for the preparation of a photothermographic system
US4368259A (en) * 1980-01-22 1983-01-11 Agfa-Gevaert Aktiengesellschaft Color photographic recording material containing an emulsified, hydrophilic color-forming compound
US4330617A (en) * 1980-02-05 1982-05-18 Mitsubishi Paper Mills, Ltd. Photographic elements containing novel developing agent precursors
US4464464A (en) * 1981-07-30 1984-08-07 Agfa-Gevaert Aktiengesellschaft Color photographic recording material
US4446216A (en) * 1981-12-10 1984-05-01 Smith Norman A Photographic material
US4810625A (en) * 1986-04-25 1989-03-07 Agfa-Gevaert Aktiengesellschaft Photographic material with pyrazolone coupler and oil former
US4933270A (en) * 1988-09-26 1990-06-12 Eastman Kodak Company Process for the precipitation of stable colloidal dispersions of base degradable components of photographic systems in the absence of polymeric steric stabilizers
US5089380A (en) * 1989-10-02 1992-02-18 Eastman Kodak Company Methods of preparation of precipitated coupler dispersions with increased photographic activity
US5624467A (en) * 1991-12-20 1997-04-29 Eastman Kodak Company Microprecipitation process for dispersing photographic filter dyes
US5580705A (en) * 1991-12-27 1996-12-03 Konica Corporation Method of bleaching silver halide color photographic light-sensitive materials using particular ferric chelates
EP0696758A1 (de) 1994-08-10 1996-02-14 Agfa-Gevaert AG Lichtempfindliches fotografisches Aufzeichnungsmaterial mit lichtabsorbierendem Farbstoff
US5674668A (en) * 1995-09-06 1997-10-07 Agfa-Gevaert Photographic recording material
EP2455431A1 (en) 2003-10-23 2012-05-23 Fujifilm Corporation Ink and ink set for inkjet recording
WO2012014955A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
WO2012014954A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
EP2712894A1 (en) 2012-09-26 2014-04-02 Fujifilm Corporation Azo compound, aqueous solution, ink composition, ink for inkjet recording, inkjet recording method, ink cartridge for inkjet recording, and inkjet recorded material

Also Published As

Publication number Publication date
DE2049689A1 (de) 1972-07-20
BE773584R (nl) 1972-04-07
JPS53131028A (en) 1978-11-15
FR2113006A6 (cs) 1972-06-23
GB1370151A (en) 1974-10-09
JPS5424290B2 (cs) 1979-08-20

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