US3554755A - Photographic emulsions containing chemical adjuvants dispersed in crystalloidal solvents - Google Patents

Photographic emulsions containing chemical adjuvants dispersed in crystalloidal solvents Download PDF

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Publication number
US3554755A
US3554755A US681921A US3554755DA US3554755A US 3554755 A US3554755 A US 3554755A US 681921 A US681921 A US 681921A US 3554755D A US3554755D A US 3554755DA US 3554755 A US3554755 A US 3554755A
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crystalloidal
photographic
solvents
radical
emulsion
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US681921A
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Giancarlo Rinauro
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Ferrania SpA
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Ferrania SpA
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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 novel classes of organic crystalloidal solvents, particularly suitable for use for introducing chemical adjuvants in photosensitive and even non-photosensitive layers of a silver halide photographic element, according to the dispersion method.
  • the adjuvants which most frequently are incorporated by this method in said materials are those compounds known as color formers or couplers that are introduced into the silver halide emulsions utilized in the preparation of photographic materials for color photography. It is known that in such photographic materials the colored images form by reaction of the color formers with the oxidation products of the color developer.
  • a photographic material of this type usually comprises three layers superimposed one on another, each of which is sensitized to one of the three regions in which the visible spectrum is conventionally divided, namely yellow, magenta and cyan. Each layer contains at least a color former which, owing to the action of the oxidized developer, produces an image colored in one of those three colors.
  • the chemical adjuvants to be added to the photosensitive emulsions and especially the couplers remain essentially immobile in the layer in which they are placed.
  • the first effectual solution was to increase the molecular weight of the adjuvant that one desires to make non-diffusing, usually by the introduction of long saturated aliphatic chains (generally having 12-18 carbon atoms). This causes a decrease in the water solubility of the adjuvant.
  • the problem was solved by introducing into the coupler molecule acidic functions capable of forming a salt, whereby the compound is made soluble in alkaline aqueous solutions, and then dissolving it in the hydrophilic colloid of the photographic emulsion.
  • Another method widely used is the so-called dispersion Patented Jan. 12, 1971 method.
  • couplers or other adjuvants having a predominantly lyophilic nature.
  • Said couplers are then dissolved in a non-water miscible or only slightly miscible crystalloidal organic liquid having a high boiling point, a good solvent power and a good permeability to the developing agents.
  • the solution of the coupler in said crystalloidal solvent is emulsified by means of a homogenizer with water with or without a.
  • the dispersion obtained, formed by extremely small droplets of crystalloidal solvent containing the color former uniformly distributed in the water phase may then be introduced into the photographic emulsion with no ditficulty.
  • crystalloidal solvents of the present invention are esters prepared from the condensation of linear or branched alkanolamines with fatty acids, the ester products having the general formula:
  • R represents a linear or branched chain alkyl radical having from 1 to 18 carbon atoms; n is an integer up to 6, X and Y individually represent a hydrogen atom or an alkyl radical (preferably C to C R' represents hydrogen, alkyl or the monovalent radical:
  • R, X, Y and n have the same meaning as above; and R" represents a hydrogen atom, or acyl having from 1 to 18 carbon atoms, either linear or branched chain.
  • These compounds are for the most liquid at room temperature, and those which are not liquid form liquid systems with the couplers at room temperature. They have a rather high boiling point (higher than 347.0" F. C.), at atmospheric pressure), and therefore during the drying subsequent to the coating of the photographic emulsion they do not evaporate. Moreover, they have a good light and heat stability as well as a good permeability to the oxidized products of the color developer.
  • These solvents have also a solvent power higher than that of the crystalloidal solvents heretofore known, such as for example dibutyl phthalate, tricresyl phosphate, dibutyl lauramide, and like (see for example Italian Pat. No. 432,- 885), which permits a desirable reduction in the amount of crystalloidal solvent (e.g. from 30 to 50%) as compared to those solvents presently used.
  • One of the major disadvantages of the dispersed coupler system is derived from the presence in the photographic element of the crystalloidal solvent, which tends to adversely aifect the sensitization, increase the turbidity, and impair the adhesion of the layers. Since this invention permits the amount of said solvent to be noticeably reduced, it is obvious that such disadvantages are considerably minimized, if not completely eliminated.
  • a further advantage associated with the lesser amount of solvent required is the reduced thickness of the layers, with resulting improvement of image definition. Moreover, it has been found that in the photographic materials containing solvents according to the present invention no formation of yellow fog in storage is observed.
  • Table I Illustrative compounds suitable for use as crystalloidal solvents according to the present invention are listed in Table I.
  • Table I In the third column of the table the relative values of the solvent power of each material (expressed as milliliters of solvent required to bring into solution at a temperature of 158.0 F. (70 C.) are given) the standard for comparison being one gram of a conventional coupler having the formula
  • Table I also reports the solvent power of three known crystalloidal solvents, identified as (a), (b), and (c).
  • reaction mixture was allowed to cool down to room temperature and 300 ml. of diethyl ether were added. It was then washed three times in a separatory funnel with m1. of 10% HCl, thereafter three times with 100 ml. of water, then three times with 100 ml. of 5% Na CO and finally again with water until neutral.
  • the ether solution was dried with 10 g. of dry Na SO for 24 hours, then was filtered on a folded filter to remove the sodium sulfate and finally was evaporated on a Water bath. The residue was distilled under reduced. pressure. The portion of overheads boiling below 212.0 F. (100 C.) was discarded then the distillation was continued while further reducing the pressure. 50 g. of compound 13 having a B.P. of 392.0393.8 F. (200- 201 C.)/1 mm. Hg, were recovered. Yield: 62%.
  • the dispersions are prepared according to known techniques in a homogenizer, colloid mill or other similar apparatus, with or without the addition of emulsifiers. Sometimes it may be expedient to prepare the dispersion by adding a low boiling auxiliary solvent such as ethyl acetate, butyl acetate and like, into water or into a water solution of a naturally occurring or synthetic, waterpermeable, hydrophilic colloid, such as gelatin, polyvinyl alcohol, agar-agar, etc. In many cases it can be advantageous to use mixtures of two or more solvents in order to obtain dispersions having the desired photographic properties. For example, together with one of the crystalloidal solvents of the present invention, another solvent which is capable of changing the refractive index or other physical properties of the dispersion may be used.
  • a low boiling auxiliary solvent such as ethyl acetate, butyl acetate and like
  • the coupler-solvent mixture is liquid at ambient or room temperature.
  • the mixture forms, by dispersion in water or in a hydrophilic colloid, extremely small droplets which contain the coupler enclosed therein.
  • These dispersions are quite stable, and they are permeable to the photographic processing baths.
  • the photographic emulsions in which said dispersions of couplers or other chemical adjuvants can be introduced are the usual gelatinsilver halide emulsions, however, as stated hereinabove, the protective colloid can be wholly or partly replaced by other natural or synthetic hydrophilic colloids, such as polyvinyl alcohol, agar-agar, and like.
  • EXAMPLE 1 1 gram of the coupler was dissolved in 2 ml. of the compound No. 7 (see Table I), by heating at 212.0 F. (100 C.). The hot solution was poured into 20 ml. of a 4% gelatin solution containing 2 ml. of 10% sodium tetradecyl sulfate. The mixture was emulsified in a homogenizer, then introduced into a silver halide emulsion. This emulsion was then coated onto a suitable support and dried. The material thus prepared was exposed and then subjected to the usual color development bleaching and fixing processing steps. A magenta image having a good definition and no fogging was thus obtained.
  • EXAMPLE 2 1 gram of the coupler was dissolved in 2 ml. of the compound No. 5 of Table I by heating at 2l2.0 F. (100 C.). The hot solution was poured into 20 ml. of 4% gelatin containing 2 ml. of sodium tetradecyl sulfate. The mixture was emulsified in a homogenizer and was introduced into the silver halide emulsion. After coating the emulsion containing the dispersion onto a support, drying, exposure, color development and subsequent bleaching and fixing a magentacolored image was obtained.
  • EXAMPLE 3 1 gram of the coupler was dissolved by heating at 158.0F. (70 C.) in 0.5 ml. of the compound No. 8 of Table I in 4 ml. of ethyl acetate. The solution was poured into ml. of 4% gelatin containing 2 ml. of 10% sodium tetradecyl sulfate. The mixture was emulsified in a homogenizer and was introduced into the silver halide emulsion. After coating the emulsion containing the dispersion onto a support, drying, exposure, color development and subsequent bleaching and fixing, a magenta-colored image was obtained.
  • EXAMPLE 4 1 gram of the coupler 8 EXAMPLE 5 I gram of the ultraviolet obsorber 2-phenylamino-3- tetradecyl-5-benzal-4-thiazolidone of the formula was dissolved in 0.2 ml. of compound No. 10 in Table I by heating at l22.0 F. C.) with 2 ml. of ethyl acetate. The solution was poured into 20 ml. of 4% gelatin containing 2 ml. of 10% sodium tetradecyl sulfate. The mixture was emulsified in a homogenizer and was ready to be introduced into a silver halide emulsion or into another photographic emulsion layer.
  • EXAMPLE 6 I gram of the ultraviolet absorber (i)C H was dissolved in .02 ml. of compound No. 10 of Table I by heating at 122.0 F. (50 C.) with 2 ml. of ethyl acetate. The solution was poured into 20 ml. of 4% gelatin containing 2 ml. of 10% sodium tetradecyl sulfate. The mixture was emulsified in a homogenizer and was ready to be introduced into a silver halide emulsion or into another photographic layer.
  • a photographic emulsion including a water-permeable hydrophilic colloid and having uniformly distributed therein a dispersion of a crystalloidal solvent containing at least one chemical adjuvant, said solvent being characterized by the formula 0 RI! ll R O (C 'I)n CIIN l I X Y R wherein R is an alkyl radical having l-18 carbon atoms, 11 is an integer of from 1 to 6, X and Y individually represent a hydrogen atom or a C -C alkyl group, R" is a hydrogen atom or an alkyl carbonyl group, having 1-18 carbon atoms, and R is a hydrogen atom, an alkyl group, or the monovalent radical wherein R, X, Y and n are as defined above.
  • a photographic element having at least one layer comprising a photographic emulsion of claim 1.
  • references Cited 591,688 2/1960 can a a 96-94 UNITED STATES PATENTS 1,425,126 3/1967' France 96-94 12/1939 Jennings at 96100X WILLIAM D. MARTIN, Primary Examiner 33: 2:3 5 M. R. P. PARRONE, JR., Assistant Examiner FOREIGN PATENTS US. Cl. X.R. 10/1962 Great Britain 96-94 9 .400, 114 7, 115; 2 0 404 8/1965 Great Britain 96-94 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated foundedx 12, 1971 Giancarlo Rinauro Patent No.

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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)
US681921A 1966-11-17 1967-11-09 Photographic emulsions containing chemical adjuvants dispersed in crystalloidal solvents Expired - Lifetime US3554755A (en)

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IT4292366 1966-11-17

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BE (1) BE706622A (it)
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DE (1) DE1643516A1 (it)
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GB (1) GB1213307A (it)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779765A (en) * 1972-08-31 1973-12-18 Eastman Kodak Co Silver halide emulsions containing coupler solvents
US4075022A (en) * 1975-04-03 1978-02-21 Wignsberghe Leo Augus Aqueous dispersions of photographic ingredients
US4290964A (en) * 1979-03-12 1981-09-22 Ciba-Geigy Corporation Undescanoic acids and esters thereof
US4353979A (en) * 1979-07-25 1982-10-12 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4840881A (en) * 1977-02-10 1989-06-20 Konishiroku Photo Industry Co., Ltd. Process for the production of light-sensitive silver halide photographic material
US5426019A (en) * 1993-12-30 1995-06-20 Eastman Kodak Company Color photographic element
US5451497A (en) * 1993-12-30 1995-09-19 Eastman Kodak Company Photographic dispersion having improved stability
US6045985A (en) * 1997-12-02 2000-04-04 Tulalip Consultoria Comercial Sociedade Unipessoal S.A. Light-sensitive silver halide photographic elements containing yellow filter dyes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779765A (en) * 1972-08-31 1973-12-18 Eastman Kodak Co Silver halide emulsions containing coupler solvents
US4075022A (en) * 1975-04-03 1978-02-21 Wignsberghe Leo Augus Aqueous dispersions of photographic ingredients
US4840881A (en) * 1977-02-10 1989-06-20 Konishiroku Photo Industry Co., Ltd. Process for the production of light-sensitive silver halide photographic material
US4290964A (en) * 1979-03-12 1981-09-22 Ciba-Geigy Corporation Undescanoic acids and esters thereof
US4353979A (en) * 1979-07-25 1982-10-12 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US5426019A (en) * 1993-12-30 1995-06-20 Eastman Kodak Company Color photographic element
US5451497A (en) * 1993-12-30 1995-09-19 Eastman Kodak Company Photographic dispersion having improved stability
US6045985A (en) * 1997-12-02 2000-04-04 Tulalip Consultoria Comercial Sociedade Unipessoal S.A. Light-sensitive silver halide photographic elements containing yellow filter dyes

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Publication number Publication date
GB1213307A (en) 1970-11-25
CH491411A (it) 1970-05-31
FR1558950A (it) 1969-03-07
DE1643516A1 (de) 1971-07-01
BE706622A (it) 1968-04-01

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