US3502474A - Process for producing photographic light-sensitive elements - Google Patents

Process for producing photographic light-sensitive elements Download PDF

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Publication number
US3502474A
US3502474A US568414A US3502474DA US3502474A US 3502474 A US3502474 A US 3502474A US 568414 A US568414 A US 568414A US 3502474D A US3502474D A US 3502474DA US 3502474 A US3502474 A US 3502474A
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dye
layer
organic solvent
solution
solvent
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US568414A
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Momotoshi Tsuda
Teruo Kobayashi
Keisuke Shiba
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes

Definitions

  • Y and Z are unsubstituted or substituted carbon ring-forming groups or substituted or unsubstituted heterocyclic ring-forming groups.
  • M is hydrogen or HNRRR (where R, -R" and R are hydrogen, lower alkyl or lower hydroxyalkyl) and n is 0, 1 or 2, the oxonol dye solvent can be represented by the formula:
  • R is an alkyl group of less than 14 carbon atoms or NCO(CHz)mm where R, and R are lower alkyl and m is a positive integer of less than and R and R are alkyl.
  • the present invention relates to photography and more particularly to a process for the production of a photographic light-sensitive element having an anti-irradiation effect, an anti-halation effect, and a filter effect.
  • a photographic light-sensitive element is usually provided with an anti-irradiation layer, an anti-halation' layer and a filter layer for improving the photographic properties and they are colored layers for absorbing harmful reffected light, scattered light and diffused light among the colored lights applied on the light-sensitive element.
  • the coloring materials used for the above-mentioned purposes are required to have spectral absorption chaacteristics suited for the purpose, to povide high optical densities in coating thicknesses which are as thin as possible, and further to be decolored completely into a colorless state or dissolved out of the layers during the photographic processing steps.
  • An object of this invention is to provide a process for the production of a photographic light-sensitive element ice having a layer having an anti-irradiation effect, an antihalation effect and a filter effect without being accompanied by the above-mentioned difficulties.
  • Another object of the present invention is to provide a layer having dispersed therein a colored material for a photographic light-sensitive element, said colored material giving no bad influences on the photographic properties of an adjacent emulsion layer contacted with the layer, having an anti-diffusion property, having the spectral absorption characteristics suited to the purposes of giving the above-mentioned effects, having high optical density in an effective absorption wave length, and being completely de-colored or dissolved out by the developing step.
  • R2 Rr-CON Ra (B) wherein R represents an alkyl group having less than 14 carbon atoms or No0(oH2)ml m where R and R2 represent a lower alkyl group and m is a positive integer less than 10, and R and R represent a lower alkyl group.
  • the resulting solution is dispersed in a solution containing gelatin, which is then added in an emulsion or a gelatin solution to provide a coating solution and the coating solution is applied to a support to provide a colored layer having an anti-irradiation effect, an anti-halation effect and a filter effect.
  • the dyes shown in the general Formula A may be incorporated in the layer alone or as a mixture thereof.
  • the suitable groups Y and Z in the above-mentioned general Formula A are rings having active methylene groups, such as a pyrazolone ring, iso-oxazolone ring, thiobarbituric acid ring, barbituric acid ring, 3-oxythionaphthene ring, 1,3-indandione ring and rhodanine ring.
  • oxonol acid dye having a sulfon group or a carboxyl group, which is a water-soluble group is unsuitable in the present invention.
  • the symmetric or antisymmetric oxonol dye having a methyl group at the 3-position of the pyrazolone ring as shown in UK. Patent 506,385 and US. Patent 2,621,125 are slightly dissolved in water although they have no water-soluble group and hence such a dye will diffuse into adjacent emulsion layers and have a bad influence on the photographic properties.
  • the organic emulsion represented by general Formula B in accordance with this invention the dye becomes diffusion resistant and has almost no bad influence on the photographic properties.
  • the symmetric or antisymmetric oxonol dye wherein the 3-position of the pyrazclone ring has been substituted with a carboxyalkyl group (ether type) or oxyalkyl group (ether type) are more profitable in the following respect than the above than the above-mentioned symmetric or anti-symmetric dye in which the 3-position of the pyrazolone ring has been substituted with a methyl group as described in UK. Patent 506,385 and U.S. Patent 2,621,125.
  • the oxonol dye of the former type has a higher solubility in the organic solvent represented by the general Formula B to be used in the invention than the latter type known dyes, and the absorption maximum of the former oxonol dye is shifted to about 10 to 35 millimicron longer wave length side of the ester type and about 10 to 20 millimicron shorter wave length side in the ether side, by which it can be easily adopted for the desired spectral absortpion characteristics.
  • the organic solvent having the general Formula B used in the invention has a very good solubility to the dyes shown by general Formula A as compared with conventionally known weak, Water-soluble, organic solvents. It also has an extremely high molar extinction coefficient t the desired optical absorption wave length. Since the organic solvent used in this invention has such properties, the amount of the organic solvent incorporated in photographic elements may be small and a sufficient optical density can be obtained even by a thin film, the dye itself is completely protected from the silver halide particles, and the photographic properties of the photographic element are not injured.
  • the organic solvent having general Formula B used in the present invention has a very strong polarity as well as a proper solubility to water, the use of the solvent makes easy the addition reaction of sulfite ions and the like to the dye having general Formula A. Therefore, this is valuable in the case of de-coloring and dissolving off the dye in the photographic developing process.
  • the dyes shown by general Formula A used in this invention are illustrated as follows although the dyes are magenta color (colored layer by the invention) cyan c0101
  • the organic solvents shown by general Formula B used in this invention are illustrated as follows but the solvents should not be limited to these examples by any means:
  • the dyes used in this invention may be generally prepared as follows. That is, the symmetric dyes corresponding to the general formula wherein n is 0.1 or 2, may be obtained, as shown in UK. Patent 506,385 and UK. Patent 646,125, by subjecting to a condensation reaction 2 mols of a compound having an active methylene group in the ring with 1 mol of formamidine, malondialdehydedianil, or glutacondialdehydedianil in an alcohol in the presence of a condensing agent, such as triethylamine, diethanolamine, ammonia or pyridine.
  • a condensing agent such as triethylamine, diethanolamine, ammonia or pyridine.
  • anti-symmetric dyes used in this invention may be prepared as follows, as shown in US. Patent 2,631,125 and UK. Patent 624,462 (pentamethine oxonol dye) and US. Patent 2,611,696 and UK. Patent 663,- 042 (mono-methine oxonol dye and polymethine oxonol dye). That is, 1 mol of the compound having the formula:
  • the condensation reaction may be conducted in a nonpolar solvent such as ligroin or in an alcoholic solvent in the presence of pyridine or triethanolamine. Thereafter, by reacting 1 mol of the intermediate product with 1 mol of the compound having the following formula:
  • the intermediate product was obtained by the reaction of N-ethyl-rhodanine and with equimoles of dialdehyde-dianilide hydrochloride in absolute alcohol with reflux in the presence of triethylamine.
  • purple crystals having a melting point (decomposition) of 199 C. were obtained.
  • Analytical value found (percent): C, 60.56; H, 5.29; and N, 8.74. Calculated (percent): C, 60.76; H, 5.06; and N, 8.86.
  • Dye II was obtained.
  • the melting point of the dye was 193 C.
  • the absorption maximum of a methanol solution of 5 p.p.m. of the dye was 658 nm.
  • the extinction coefficient was 0.98.
  • Dye II or Dye II was added in 50g. of a 10% gelatin solution.
  • a solution of sodium alkylbenzene sulfonate was added to the solution, the mixture was emulsified by means of a high-speed rotary mixer to provide the emulsified dispersion of Dye II or Dye II;
  • the light-sensitive element was edge exposed to red light, developed as usual in a color developing solution mainly consisting of N,N-diethyl-p-aminianiline sulfate, and then subjected to fixing, bleaching and fixing to provide a cyan image.
  • the sharpness of the cyan image was clearly improved as compared with that of a lightsensitive element having no anti-halation layer of this invention, and further, the cyan color of Dye II or Dye II after development was completely de-colored.
  • a mixture of 100 g. of a 7% gelatin solution and 20 g. of the emulsified dispersion of Dye VI and Dye IX was applied to a film support and dried to give a film having an anti-halation layer. Further, on the thus formed anti-halation layer was coated a mixture of 100 g. of a red-sensitive silver iodo-bromide emulsion containing a cyan coupler and g. of the emulsified dispersion of Dye VIII followed by drying to provide a red-sensitive emulsion layer.
  • the emulsion layer was coated a 2% gelatin solution containing a hardening agent followed by drying to provide an intermediate layer.
  • a green-sensitive silver iodobromide emulsion followed by dry to provide a light-sensitive element.
  • the thus obtained light-sensitive element was exposed to red light by using a contact chart for measuring rectangular wave response and then was subjected to processing as in Example 1 to provide a cyan image.
  • the sharpness of the resulting cyan image was higher than that of a light-sensitive element wherein the emulsion of Dye VIII had not been incorporated in the red-sensitive emulsion, and moreover it was observed that the lightsensitive element of this invention had an irradiation pre venting effect. Further, Dyes VI, IX, and VIH had been completely dissolved out.
  • Example 2 instead of the intermediate layer of Example 2 there was employed a magenta-colored intermediate layer that had been formed by applying a mixture of 100 g. of a 2% gelatin and g. of the emulsified dispersion of Dye V.
  • the resulting light-sensitive layer was exposed to green light and processed as in Example 1 to provide a magenta image. It was confirmed that the sharpness of the magenta image had been increased by the anti-halation effect of the magenta-colored intermediate layer.
  • the filter effect of the colored intermediate layer the unnecessary green-sensitivity of the red-sensitive emulsion layer was reduced and the color separation between the magenta image and cyan image was improved. Moreover, the stain and recoloring of Dye V after photographic processing were not observed.
  • Example 3 The same results as in Example 3 were obtained by employing the thus prepared emulsified dispersion of Dye I or Dye 1' instead of the emulsified dispersion of Dye V in Example 3.
  • EXAMPLE 5 Between a panchromatic emulsion layer for black and white photography and a film support was formed the following anti-halation layer. That is, 0.3 g. of Dye X, 0.2 g. of Dye VII, 0.1 g. of Dye IV and 0.2 g. of Dye III were dissolved into 10 ml. of organic solvent (a) and the solution was treated as in Example 1 to provide an emulsified dispersion of the dyes. Then, 20 g. of the thus obtained emulsified dispersion was added into g.
  • a process for producing a photographic lightsensitive element comprising applying a film support an emulsion containing a solvent solution of at least one water-insoluble oxonol dye, said oxonol dye being represented by the general formula:
  • R and R each represent a lower alkyl group and sisting of an alkyl group having less than 14 carbon atoms.
  • R and R each represent a lower alkyl group and m is a positive integer less than 10, and R and R each is an alkyl group.
  • a photographic light-sensitive element comprising a film support and a layer formed on said support said layer being produced by drying an emulsion containing the solvent solution of at least one water-insoluble oxonol dye, said oxonol dye being represented by the general formula:
  • Y and Z each represents a member selected from the group consisting of unsubstituted and substituted carbon ring-forming groups and unsubstituted and substituted heterocyclic ring-forming groups
  • M represents a member selected from the group consisting of a hydrogen atom and HNR'RR"' (where R, R", and R each represents a member selected from the group consisting of a hydrogen atom, a lower alkyl group, and a lower hydroxylalkyl group)
  • n is 0, 1, or 2, dissolved in an organic solvent selected from the group consisting of those represented by the following general formula:
  • R is a member selected from the group con- 11 12 sisting of an alkyl group having less than 14 carbon References Cited atoms and UNITED STATES PATENTS 3,220,843 10/1965 Louick 9684 2)m 2,892,712 6/1959 Plambeck 9684 5 2,621,125 12/1952 Van Dormael 9684 where R and R each represents a lower alkyl group and m is 'a positive integer less than 10, and R and R RONALD SMITH Primary Exammer each is an alkyl group.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
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US568414A 1965-07-28 1966-07-28 Process for producing photographic light-sensitive elements Expired - Lifetime US3502474A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647460A (en) * 1969-05-30 1972-03-07 Agfa Gevaert Nv Method of producing photographic images by rapid processing
US3778273A (en) * 1971-06-30 1973-12-11 Agfa Gevaert Ag Photographic material
US3932188A (en) * 1974-02-25 1976-01-13 Mitsubishi Paper Mills, Ltd. Silver halide photographic lightsensitive material
US3933798A (en) * 1974-08-27 1976-01-20 Polaroid Corporation Novel bis-pyrazolone oxonol dyes
US4092168A (en) * 1976-01-16 1978-05-30 Agfa-Gevaert, N.V. Light-absorbing dyes for silver halide material
US4994356A (en) * 1990-04-04 1991-02-19 Eastman Kodak Company Solid particle dispersions of filter dyes for photographic elements
EP0459456A1 (en) * 1990-06-01 1991-12-04 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0460616A1 (en) * 1990-06-04 1991-12-11 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5238798A (en) * 1990-06-01 1993-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic material containing dispersed dye
US6670475B2 (en) * 1996-09-30 2003-12-30 Fuji Photo Film Co., Ltd. Information recording medium

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2621125A (en) * 1946-11-22 1952-12-09 Gevaert Photo Prod Nv Light-sensitive photographic element having a light-absorbing layer
US2892712A (en) * 1954-04-23 1959-06-30 Du Pont Process for preparing relief images
US3220843A (en) * 1961-01-13 1965-11-30 Eastman Kodak Co Sound recording motion picture film with anti-halation layer thereon

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2621125A (en) * 1946-11-22 1952-12-09 Gevaert Photo Prod Nv Light-sensitive photographic element having a light-absorbing layer
US2892712A (en) * 1954-04-23 1959-06-30 Du Pont Process for preparing relief images
US3220843A (en) * 1961-01-13 1965-11-30 Eastman Kodak Co Sound recording motion picture film with anti-halation layer thereon

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647460A (en) * 1969-05-30 1972-03-07 Agfa Gevaert Nv Method of producing photographic images by rapid processing
US3778273A (en) * 1971-06-30 1973-12-11 Agfa Gevaert Ag Photographic material
US3932188A (en) * 1974-02-25 1976-01-13 Mitsubishi Paper Mills, Ltd. Silver halide photographic lightsensitive material
US3933798A (en) * 1974-08-27 1976-01-20 Polaroid Corporation Novel bis-pyrazolone oxonol dyes
US4092168A (en) * 1976-01-16 1978-05-30 Agfa-Gevaert, N.V. Light-absorbing dyes for silver halide material
US4994356A (en) * 1990-04-04 1991-02-19 Eastman Kodak Company Solid particle dispersions of filter dyes for photographic elements
EP0459456A1 (en) * 1990-06-01 1991-12-04 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5238798A (en) * 1990-06-01 1993-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic material containing dispersed dye
EP0460616A1 (en) * 1990-06-04 1991-12-11 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5238799A (en) * 1990-06-04 1993-08-24 Fuji Photo Film Co., Ltd. Silver halide photographic material
US6670475B2 (en) * 1996-09-30 2003-12-30 Fuji Photo Film Co., Ltd. Information recording medium
US20040115560A1 (en) * 1996-09-30 2004-06-17 Fuji Photo Film Co., Ltd. Information recording medium
US6849316B2 (en) 1996-09-30 2005-02-01 Fuji Photo Film Co., Ltd. Information recording medium

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