US3310402A - Photographic colour material - Google Patents

Photographic colour material Download PDF

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Publication number
US3310402A
US3310402A US278453A US27845363A US3310402A US 3310402 A US3310402 A US 3310402A US 278453 A US278453 A US 278453A US 27845363 A US27845363 A US 27845363A US 3310402 A US3310402 A US 3310402A
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Prior art keywords
colour
photographic
image
light
cyan
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US278453A
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English (en)
Inventor
Jaeken Jan
Hugo Vital Van Goethem
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Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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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
    • G03C7/32—Colour coupling substances
    • G03C7/34—Couplers containing phenols
    • G03C7/344—Naphtholic couplers

Definitions

  • the cyan dye which should absorb red light and transmit green and blue light usually absorbs a major proportion of red light as well as a small amount of green and blue light.
  • the magenta dye which should absorb green light and transmit blue and red light usually absorbs aconsiderable amount of blue light and a small amount of red light.
  • the yellow dye which should absorb blue light 0 and transmit green and red light is usually satisfactory.
  • a process is described'for the manufacture of a colourcorrected image in the photographic material comprising a silver halide emulsion layer and a colour coupler (more particularly a colour coupler of the naphthol type) which is reactive with the oxidation product of an aromatic amino developing agent to form by colour-development a primary dye image (more particularly a cyan dye image) which absorbs a major proportion of light in one region of the visible spectrum (more particularly the red light) and undesirably absorbs a minor proportion of light in at least one other region of the.
  • a primary dye image more particularly a cyan dye image
  • anobject of the present invention to provide a new integral masking method for forming a colour corrected photographic colour image used for printing.
  • an image-wise exposed photographic element comprising at least one silver halide emulsion layer and a colour coupler, which on development by reaction with the oxidation product of an aromatic primary amino developing agent forms a primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, with an oxidizing solution in the presence of a 3-amino-guanidine compound of the following general formula:
  • R represents a hydrogen atom, an alkyl radical, a substituted alkyl radical, an aralkyl radical, a substituted aralkyl radical, and aryl radical, a substituted aryl radical, a heterocyclic radical, or a substituted heterocyclic radical, and
  • R represents a hydrogen atom or an acyl radical, e.g. an
  • a method of forming a colour corrected cyan dye image has been found by forming an integral orange to red mask image in a photographic colour material having in a red-sensitized silver halide emulsion' layer, or in a water-permeable non light-sensitive colloid layer adjacent thereto, a colour coupler for cyan of the phenol type, preferably of the naphthol type, comprising image-wise exposing, colour developing with an aromatic primary amino developing agent, and before or after fixing treating said colour material in a sufficiently strong oxidizing solution eg a photographic bleaching bath comprising potassium ferricyanide, in the presence of a 3-amino-guanidine compound as described above, which couples oxidatively with the residual colour coupler for cyan, thus forming a mask image of opposite gradation to the primary dye image compensating the unwanted side-absorptions of the cyan dye image in the blue and at least partly in the green.
  • a colour coupler for cyan of the phenol type preferably of the naphthol
  • the oxidatively coupling compounds are preferably used in combination with colour couplers for cyan with the following general formula:
  • X represents an oxygen atom, a sulphur atom, a
  • Y represents a hydrogen atom or a halogen atom
  • D represents a diffusion inhibiting group eg an aliphatic hydrocarbon radical with 5 to carbon atoms, preferably with 14, 16 or 18 carbon atoms, and
  • M represents a hydrogen atom, an alkali metal atom or an ammonium group.
  • colour couplers for cyan can be prepared eg a by the condensation of 1-hydroxy-2-naphthoic acid or its derivatives with the suitable aromatic amides according to the process described in the German patent specification 1,121,061.
  • Suitable mask-forming compounds which may be used in the process according to the invention are those the formulae of which are given in Table I.
  • the compounds with the Formulae 1 to 6 are not fast to diffusion.
  • the mask-forming compounds which are not fast to diffusion can be applied in one of the processing baths e.g. the developing bath or the bleaching bath.
  • they are incorporated int-o the photographic emulsion layer as bicarbonate thus being more or less fast to diffusion.
  • Mask-forming compounds corresponding to the above general formula can also comprise a diffusion fast making group such as a long aliphatic carbon chain. Examples of compounds which are fast to diffusion and which preferably are incorporated in the emulsion layer are given in Table II.
  • the mask-forming compounds used, in the process according to the present invention are photographically inert and do not cause fog.
  • a solution of benzoyl isothiocyanate is prepared from 8.5- g. of ammonium thiocyanate and 11.5 cm. of benzoyl chloride in 50 cm. of acetone as described in preparation 3. At the boiling temperature a solution of 16.7 g. of p-cetyloxyaniline in 50 cm. of acetone isdropwise added. After pouring out into water the obtained precipitate of N-(p-cetyloxyphenyl)-N-benzoyl thiourea is sucked off and refluxed for 15 min. in a solution of 8 g. of sodium hydroxide in 70 cm. of water. The saponified product precipitates immediately. The reaction mixture is neutralized and the p-cetyl-oxyphenyl thiourea is sucked off. After recrystallizing' from benzene the product melts at 129 C.
  • thiouronium iodide 1.6 g. of the obtained thiouronium iodide are allowed to react at room temperature in cm. of pyridine, for 3 days with 0.5 cm. of hydrazine hydrate. When pouring out intoice the formed l-(p-cetyloxy phenyl)-3-aminoguanidine precipitates. After sucking off and recrystallizing from acetonitrile the aminoguanidine melts at 90 C.
  • a solution of benzoyl isothiocyanate is prepared from 18.8 g. of ammonium thi'ocyanate and 26.6 cos. of benzoyl chloride in 200 ccs. of acetone as described in preparation 3'. At boiling temperature a solution of 84.6 g. of p-cetylsulphonyl aniline in. 800 ccs. of acetone is added gradually. The reaction is completed by refluxing for still 1 hour. After cooling the reaction mixture and pouring it into water, the formed precipitate of N-(p-cetylsulphonyl. phenyl)-N'-benzoyl thiourea is sucked off. This product is shortly boiled with a solution. of 45 g.
  • the colour couplers and mask compounds are preferably incorporated into a photographic silver halide emulsion prepared by means. of the colloids usually employed therefor, such as for instance gelatin, polyvinyl alcohol, collodion or other natural or synthetic colloids.
  • the silver halide emulsion is preferably coated on a transparent support consisting of glass, nitrocellulose, cellulose esters such as cellulose triacetate, polyester, polystyrene or another natural or synthetic resin, and forms part of a photographic material with one or more emulsion layers.
  • a multilayer photographic colour material is usually composed of the following layers which are coated onto a support; a red-sensitive emulsion layer having a colour coupler for cyan, a green-sensitive emulsion layer having a colour coupler for magenta and a blue-sensitive emulsion layer having a colour coupler for yellow.
  • a yellow filter composed in most of the cases of a gelatin layer containing dispersed colloidal silver, located between the blue-sensitive emulsion layer and the emulsion layer sensitized to green.
  • the colour couplers are not only possible to incorporate the colour couplers into the lightsensitive silver halide emulsion layer itself but they can also be incorporated into an adjacent non-light-sensitive colloid layer or into a non-light-sensitive layer which is separated from the light-sensitive emulsion layer by a water-permeable colloid layer.
  • the back side of the transparent support is usually coated with an antihalation layer.
  • the mask-forming compound used in this invention is preferably incorporated into the red-sensitive silver halide emulsion layer containing a colour coupler for'cyanof the naphthol type.
  • the mask-forming compounds according to the invention can also be used in combination with one.
  • the mask-forming compounds described inthe German patent specification 1,119,666 wherein is described how magenta coloured mask images, which mainly compensate the undesirbale side-absorption in the green part of the spectrum of a cyan dye image, are obtained by oxidative coupling of a 4-aminopyrazolinone-3 compound corresponding to the following general formula: 1
  • R represents a lower alkyl group
  • R represents a lower alkyl group, an aryl group of the benzene series, or a substituted aryl group of the henzene series, and
  • R represents a diffusion fast making aliphatic radical comprising a linear chain of at least 5 and at most 20 carbon atoms
  • a light-sensitive multilayer colour material as described above, comprising in the red-sensitive silver halide emulsion layer a colour coupler for cyan of the naphthol type as well as an oxidatively coupling mask-forming compound used in this invention, is exposed to a colour original.
  • This exposed material is developed in a usual colour-developing bath whereby in the exposed areas of the light-sensitive emulsion layers the silver halide is reduced to silver by means of an aromatic primary amino developing agent the oxidation product of which in its turn couples with the colour coupler which is present in the emulsion layers.
  • a cyan colour image which mainly absorbs the red light but also undesirably absorbs a little blue and green light is hereby obtained in the red-sensitive emulsion layer.
  • the maskforming compound in the red-sensitive layer remains; unaffected during colour-development.
  • the colour-developed material is then before or after fixing brought in an oxidative photographic bleaching bath wherein the metallie silver dissolves and the mask-forming compound oxidatively couples with the colour coupler for cyan which is still available in the unexposed areas of the red-sensitive emulsion layer.
  • an orange to red dye mask image is formed, whereby the difference in absorption in the blue and green between the exposed and unexposed parts, which arises by the side-absorption in the blue and the green of the cyan dye image, is compensated.
  • the oxidative coupling of the mask-forming compounds used in the present invention does not take place by the oxidative power of the exposed silver halide nor by the oxidative power of the oxidized colour developing agents.
  • the oxidative coupling whereby the mask image is formed proceeds with an alkaline oxidizing solution the oxidation power of which is preferably of the same strength as the oxidative power of the normally used photographic bleaching baths.
  • aromatic primary amino-compounds can be used as developers for such material: mono-, diand triaminoaryl compounds, more especially N,N-dialkyl-p-phenylenediamines, such as N,N-die thyl-p-phen-- ylenediamine and N,N-diethyl-Z-methyl-p-phenylene diamine, and derivatives thereof such as N,N-dialkyl-N'- sulphomethylor carboxymethyl-p-phenylenediamine.
  • monoamino-developers should be cited: aminophenols and aminocresols or their halogen derivatives and also the aminonaphthols.
  • the bleaching bath generally contains potassium bromide, borax, boric acid, magnesium sulphate and especially potassium ferricyanide. These elements are dissolved in precisely determined amounts of water so that a solution with a determined pH value above 7 is obtained.
  • EXAMPLE 1 To 500 cm. of a red-sensitized bromoiodide emulsion (2% of iodide) containing mol of silver halide, are added g. of the colour coupler: sodium salt of N-(2'- n-hexadecyl sulphonyl-5'-sulpho)-phenyl 1 hydroxy-Z- naphthoic acid amide dissolved in 7 cm. of 2 N sodium hydroxide and 193 cm? of distilled water. To this emulsion is further added 5 g. of the mask-forming compound 1-hexadecyl-3-aminoguanidine dissolved in 12.5 cm? of N sodium hydroxide and 37.5 cm.
  • the colour coupler sodium salt of N-(2'- n-hexadecyl sulphonyl-5'-sulpho)-phenyl 1 hydroxy-Z- naphthoic acid amide dissolved in 7 cm. of 2 N sodium hydroxide and
  • ethylene glycol monomethyl ether After acidifying with 32.5 cm. of N acetic acid to pH 5.7 and after adding the usual ingredients such as hardeners and wetting agents, distilled water is added to the emulsion up to 1000 cm. This emulsion is coated on a suitable support and dried. After exposure through a grey-wedge with a constant 0.15 the material is developed for 9 min. at C. in
  • This material is rinsed for 30 minutes at 18 to 20 C. and fixed for 5 minutes at 20 C. in a fixing bath of the following composition:
  • this emulsion forms part of a multilayer photographic material consisting of the following superposed layers in the indicated sequence: an anti-halation layer, a transparent cellulose triacetate support, a subbing layer, the layer of the above-mentioned red-sensitized emulsion with colour coupler for cyan, a gelatin interlayer, a green-sensitized emulsion layer with colour coupler for magenta, a yellow filter layer, a bluesensitive emulsion layer with colour coupler for yellow and at last a gelatin overcoat as antistress layer.
  • Example 1 After exposure through a grey wedge with a constant 0.15 the photographic material is developed and further treated as in Example 1.
  • a magenta and orange colored mask image is formed with a graduation opposed to that of the cyan image, and which compensates the undesired side-absorptions of the cyan dye image in the blue as well as in the green.
  • a method of forming a colour corrected photographic colour image in a photographic element comprising at least one silver halide emulsion layer and a naphthol colour coupler, for cyan which on development by reaction with the oxidation product of an aromatic primary amino developing agent forms a primary cyan dye image, which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other reigon of the visible spectrum, which method comprises treating said photographic element, after image-wise exposure and colour development, with an oxidizing solution in the presthe following general formula:
  • R is a member selected from the group consisting of hydrogen, an alkyl radical, an aralkyl radical, an aryl radical and a heterocyclic radical, and R is a member selected from the group consisting of hydrogen and an acyl radical, said method comprising treating said photographic element, after image-wise exposure and colour development, with an oxidizing solution, whereby the colour coupler remaining undeveloped after said colour development reacts with said mask-forming compound to form a secondary dye image absorbing light in at least one such other region of the spectrum and having a gradation opposite to that of the primary dye image but transmitting substantially all of that light absorbed in major proportion by said primary dye image.
  • X is a member selected from the-group consisting of oxygen, sulfur,
  • Y is a member selected from the group consisting of hydrogen and halogen
  • D is a group making the colour coupler molecule fast to diffusion, comprising an aliphatic hydrocarbon radical with 5 to carbon atoms, and
  • M is a member selected from the group consisting of hydrogen, an alkali metal atomand an ammonium group.
  • oxidizing solution is an alkaline photographic bleaching bath comprising potassium hexacyanoferrate (III).
  • red sensitized silver halide emulsion layer of the photographic element also contains a 4-amino-pyrazolinone-3 compound corresponding to the following general formula:
  • R is a lower alkyl group
  • R is a member selected from the group consisting of a lower alkyl group, an aryl group of the benzene series, and a substituted aryl group of the benzene series, and
  • R is a radical rendering said compound fast to diffu sion, comprising an aliphatic, linear, hydrocarbon radical of at least 5 and at most 20 carbon atoms.
  • Photographic multilayer colour material having superposed silver halide emulsion layers sensitive to different regions of the visible spectrum, at least one of said layers containing a naphthol colour coupler for cyan which is reactive with the oxidation product of an aromatic amino developing agent to form by colour development a primary cyan dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, and a mask-forming compound corresponding to the following general formula:
  • R is a member selected from the group consisting of hydrogen, an alkyl radical, an aralkyl radical, an aryl radical, and a heterocyclic radical, and
  • R is a member selected from the group consisting of hydrogen, and an acyl radical.
  • Photographic multilayer colour material according to claim 8, wherein said silver halide emulsion layer containing a colour coupler for cyan of the naphthol type is sensitive to red light.
  • Photographic multilayer colour material having superposed silver halide emulsion layers sensitive to different regions of the visible spectrum as in claim 9, wherein the napththol colour coupler for cyan-contained in said redsensitive emulsion layer has the formula:
  • X is a member selected from the group consisting of oxygen, sulfur,
  • R is a member selected from the group consisting of hydrogen, an alkyl radical, an aralkyl radical, an aryl radical and a heterocyclic radical, and
  • R is a member selected from the group consisting of hydrogen and an acyl group.
  • Photographic multilayer colour material as in claim 9 wherein' said red-sensitive emulsion layer also contains a mask-forming compound of the formula:
  • R is a group making the mask-forming compound fast to diffusion and comprising an aliphatic, linear hydrocarbon chain of at least 5 and at most carbon atoms.
  • Photographic multilayer colour material having superposed silver halide emulsion layers sensitive to different regions of the visible spectrum, wherein the red-sensitive emulsion layer contains the sodium salt of N-(2'-n-hexadecyl sulfonyl-S-sulfophenyl)-1-hydroxy-2-naphthoic acid amide and 1 (p-n-hexadecyloxyphenyl)-3-aminoguanidine.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US278453A 1962-05-04 1963-05-06 Photographic colour material Expired - Lifetime US3310402A (en)

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GB17249/62A GB995798A (en) 1962-05-04 1962-05-04 Photographic colour material and improved method for producing corrected colour images

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US (1) US3310402A (en, 2012)
AT (1) AT246567B (en, 2012)
BE (1) BE631903A (en, 2012)
CH (1) CH440969A (en, 2012)
DE (1) DE1161138B (en, 2012)
GB (1) GB995798A (en, 2012)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2704710A (en) * 1950-04-18 1955-03-22 Gen Aniline & Film Corp Precipitation of azo dyes in silver halide emulsions by means of guanidine and biguanide compounds containing long alkyl chains
US3013879A (en) * 1956-12-31 1961-12-19 Gevaert Photo Prod Nv Production of color photographic images
US3141771A (en) * 1961-02-01 1964-07-21 Eastman Kodak Co Aldehyde scavengers for photographic silver halide developers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2704710A (en) * 1950-04-18 1955-03-22 Gen Aniline & Film Corp Precipitation of azo dyes in silver halide emulsions by means of guanidine and biguanide compounds containing long alkyl chains
US3013879A (en) * 1956-12-31 1961-12-19 Gevaert Photo Prod Nv Production of color photographic images
US3141771A (en) * 1961-02-01 1964-07-21 Eastman Kodak Co Aldehyde scavengers for photographic silver halide developers

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DE1161138B (de) 1964-01-09
CH440969A (de) 1967-07-31
GB995798A (en) 1965-06-23
AT246567B (de) 1966-04-25
BE631903A (en, 2012)

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