Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/333—Radicals substituted by oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
• • 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
• • 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
  • G03C1/835—Macromolecular substances therefor, e.g. mordants

Definitions

• the dye contains at least one carboxyl group, each of R, and R stands for hydrogen, an alkyl group, allyl group, cycloalkyl group or aryl group and Z rep resents the atoms necessary to close a pyrrole ring.
• the dyes contain no sulpho group they can be used in water-insoluble alkali-soluble polymeric antihalation coatings for photographic silver halide elements. They are fully compatible with the polymeric binder of the antihalation coating and leave no stain upon processing.
• the present invention relates to photographic silver halide film material having on the back of the film support an antihalation coating comprising a waterinsoluble, alkali-soluble polymeric binder.
• the antihalation layer (which may be coated on the back of the film support) comprises dyes so chosen that they absorb the light penetrating through the emulsion layer(s).
• the binders used for the antihalation layers applied to the side of the film support opposite to that of the emulsion layer(s) are usually hydrophilic colloids, more particularly gelatin.
• hydrophilic colloids more particularly gelatin.
• water-insoluble, alkali-soluble polymeric binders so that the layers are completely removed in an alkaline processing bath more particularly the alkaline developing solution.
• the latter binders are preferred over gela- .tin for example where the gelatin layers, which are not removed upon processing, are too soft and give rise to handling problems as in microfilm material or where adhesion of polymeric layers to the hydrophobic film support, e.g., polyethylene terephthalate support is superior over the adhesion of gelatin layers.
• Light-absorbing dyes should meet severe demands in order to be useful in photographic film material. They should not affect the inherent sensitivity or spectral sensitivity of light-sensitive emulsions with which they may come into contact. They should have good absorption characteristics and should not give rise to fogging. Further they should be readily rendered ineffective, i.e., decolourized or destroyed and removed, in at least one of the photographic processing liquids.
• dyes have been employed successfully in antihalation layers comprising gelatin as binder, most of them are unsuitable for use in antihalation layers comprising a water-insoluble, alkali-soluble polymeric binder.
• some dyes are not readily or not completely discoloured in the alkaline developing solution so that, even though the polymeric layer is removed in the alkaline solution, the residual dye stains the photographic material and the developing bath.
• Other dyes are insoluble in the organic solvent, general a lower alcohol, from which the water-insoluble, alkali soluble polymeric antihalation coating is applied or they are not compatible with the polymeric binder so that they precipitate or give rise to crystallization in the coating.
• novel lightabsorbing dyes are provided corresponding to the following general formula:
• each of R, and R represents hydrogen, alkyl including substituted alkyl (e.g., aralkyl, hydroxyalkyl, carboxyalkyl, alkoxycarbonylalkyl), allyl, cycloalkyl, substituted cycloalkyl or aryl including substituted aryl (e.g., hydroxyphenyl, carboxyphenyl, alkoxycarbonylphenyl), and Z represents the atoms necessary to close a pyrrole ring or a substituted pyrrole ring e.g.
• the dyestuff molecule containing at least one carboxyl group e.g. in a substituent of the barbituric acid nucleus and/or in a substituent of the pyrrole-nucleus.
• the dyestuffs corresponding to the above general formula, provided they do not comprise a sulpho group in acid or salt form lend themselves perfectly for use in antihalation coatings comprising as binder a waterinsoluble, alkali-soluble polymer. They are highly compatible with the water-insoluble, alkali-soluble polymeric binders and do not give rise to crystallization therein. They can be easily dissolved in the organic solvent medium, e.g., a lower alcohol such as ethanol, used to dissolve and coat the polymeric material. They are discoloured in alkaline developing solutions without leaving an objectionable residual stain.
• a lower alcohol such as ethanol
• the present invention therefore also provides a coating of a water-insoluble, alkali-soluble polymeric binder comprising a dyestuff corresponding to the above general formula which comprises in its molecule at least one carboxyl group. It also provides a lightsensitive photographic element having a support and at least one light-sensitive silver halide emulsion layer, the said support carrying at the side opposite to that carrying the emulsion layer(s) an antihalation layer of a water-insoluble, alkali-soluble polymeric binder comprising a dyestuff, corresponding to the above general formula that contains in its molecule at least one carboxyl group and is free from sulpho group in acid or salt form.
• HCC 0H 0 NCHzCH-CH3 CH2 OH I (I I )a a 1130-4: (J-CH3 0:0 0:0
• HCC CH O N-CHzCOOCzHs l N N 1130-0
• CI:CH; o t
• novel light-absorbing dyes corresponding to the above general formula can be prepared by reaction of the appropriately substituted barbituric acid with a 3-pyrrolecarboxaldehyde.
• the 3-pyrrole carboxaldehydes can be prepared from the corresponding pyrroles according to the Vilsmeier and Haack reaction (Ber. 60, 119, 1927) using dimethylformamide as formylating agent.
• the required barbituric acids can be prepared without difficulty as known in the art by reaction of the appropriate urea with malonic acid in the presence of acetic anhydride.
• the urea can be obtained by reaction in an inert solvent such as benzene and chloroform, of an organic isocyanate or an inorganic cyanate, e.g., potassium cyanate with a primary amine.
• an inert solvent such as benzene and chloroform
• an organic isocyanate or an inorganic cyanate e.g., potassium cyanate with a primary amine.
• Preparations of some appropriately substituted bartiburic acids can be found in the U.l(. Pat. Nos. 1,241,692 and 1,265,485 both filed May 21, 1968 by Gevaert-Agfa NV.
• the following preparation illustrates how the dyes of the present invention can be prepared.
• polymeric binders for the antihalation layers of the present invention are water-insoluble but should be alkali-soluble so that they readily dissolve in alkaline photographic developer baths. These polymers may belong to different classes of polymers.
• Suitable alkali-soluble polymers are, e.g.,
• copolymers include for example:
• the above polymers in their acid form are insoluble in water but dissolve readily in an alkaline photographic developer so that the antihalation composition is eliminated from the photographic film support and a clear photographic film remains.
• the thickness of the antihalation layer is not critical, though generally thicknesses of 0.5 to 3 micron are used.
• the thickness of the layer and the amount of dye are preferably regulated so that the resulting layer has an optical density of about 0.5 to 3.
• one or more dyes according to the present invention can be used simultaneously or they can be used together with other suitable light-absorbing dyes e.g. those described in the two British Pat. applications Nos. 29385/72 and 29387/72 both filed June 22, 1972 by Agfa-Gevaert N.V. filed as Applications for Patents of Addition to British Pat. Nos. 1,265,485 and 1,241,692 both filed May 21, 1968 by Gevaert-Agfa Nl.V. respectively.
• the coating composition for the antihalation layer may further comprise one or more surface-active agents as coating aids as well as matting agents, e.g., finely divided silicon dioxide, finely dispersed polymethylmethacrylate particles and finely dispersed particles of the reaction product according to UK. Pat. No. 981,198 filed Jan. 1, 1962 by Gevaert Photo- Producten N.V. of starch with urea and formaldehyde.
• surface-active agents as coating aids as well as matting agents, e.g., finely divided silicon dioxide, finely dispersed polymethylmethacrylate particles and finely dispersed particles of the reaction product according to UK. Pat. No. 981,198 filed Jan. 1, 1962 by Gevaert Photo- Producten N.V. of starch with urea and formaldehyde.
• the antihalation coating composition may be applied to the film support by spray, brush, roller, doctor blade, air brush, or wiping techniques.
• film supports are films of cellulose triacetate, polyalkylene terephthalate, or polycarbonates.
• the polyester film support may be provided with a subbing layer, comprising a copolymer of at least one of the chlorine-containing monomers vinylidene chloride and vinyl chloride.
• This subbing layer has been described in the British Pat. No. 1,234,755 filed Sept. 28, 1967 by GevaertAgfa N.V.
• the polyester film support surface may also be treated with a solution of a swelling agent for the polyester as described e.g. in Belgian Pat. No. 754,145 filed July 30, 1970 by Gevaert-Agfa NV.
• an intermediate layer which is formed from a mixture of l to 3 parts by weight of a cellulose ester, e.g., cellulose diacetate and 3 to 1 part by weight of at least one alkali-soluble polymer as referred to above. More details about such intermediate layers can be found in Belgian Pat. No. 773,588 filed Oct. 20, 1970 by Agfa-Gevaert NV.
• EXAMPLE 1 A biaxially oriented polyethylene terephthalate film of 100 micron thickness was provided with a subbing layer of a copolymer of vinylidene chloride, vinyl chloride, n-butyl acrylate and itaconic acid as described in example 3 of British Pat. No. 1,234,755 as mentioned hereinbefore.
• the subbing layer was overcoated pro rata of 1 liter per 50 sq.m with the following antihalation composition:
• dyestuff 2 6 g co(styrene/acrylic acid) (70:30% by weight) 30 g ethanol 450 ml n-butanol 50 ml acetone 500 ml
• the dye of the antihalation layer is not extractable with waterbut discolours completely in a conventional photographic developing solution without staining the solution.
• EXAMPLE 2 A cellulose triacetate film of 140 micron thickness comprising 15 by weight of triphenyl phosphate was coated at a ratio of 1 liter per 45 sq.m with the following coating composition:
• a light-sensitive photographic element comprising a support and at least one light-sensitive silver halide emulsion layer wherein the side of the support, opposite to that carrying the said silver halide emulsion layer(s) is provided with an antihalation layer of a water-insoluble, alkali-soluble polymeric binder and a dye corresponding to the formula:
• the dyestuff molecule contains at least one carboxyl group and is free from sulpho group in acid or salt form, and wherein each of R, and R stands for hydrogen, and alkyl group, an allyl group, a cycloalkyl group or an aryl group, and
• Z represents the atoms necessary to close a pyrrole nucleus.
• a photographic element according to claim I wherein a subbing layer is provided between the support and the antihalation layer.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Plural Heterocyclic Compounds (AREA)

Applications Claiming Priority (1)

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Cited By (4)

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Citations (2)

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• 1972
  • 1972-06-22 GB GB2938872A patent/GB1426179A/en not_active Expired
• 1973
  • 1973-05-29 US US00364326A patent/US3853563A/en not_active Expired - Lifetime
  • 1973-05-29 BE BE1005100A patent/BE800160A/xx unknown
  • 1973-05-30 FR FR7320276*A patent/FR2189468B1/fr not_active Expired
  • 1973-05-31 CA CA172,804A patent/CA1013350A/en not_active Expired
  • 1973-06-01 DE DE2327964A patent/DE2327964A1/de active Pending
  • 1973-06-05 JP JP48063293A patent/JPS4964420A/ja active Pending

Patent Citations (2)

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