Classifications

• • 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
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
• • 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

• the present invention relates to a photographic colour negative or a colour intermediate film element comprising light-absorbing antihalation layers.
• Colour negative films are light-sensitive recording elements having a flexible transparent support and light-sensitive layers composed in such a way that by normal exposure to light in a camera and subsequent chemical processing a negative colour image is obtained.
• Colour intermediate films are light-sensitive recording elements also having a flexible transparent support and light-sensitive layers composed in such a way that by exposure to light through an original colour negative and subsequent chemical processing a duplicate positive of said original colour negative is obtained and that by exposure to light of another colour intermediate film through said duplicate positive and subsequent chemical processing a duplicate of said original colour negative is obtained.
• Both types of colour films basically consist of a transparent film support carrying in the given order at least one red-sensitized silver halide emulsion layer, at least one green-sensitized silver halide emulsion layer, at least one blue-sensitive silver halide emulsion layer, and a gelatin antistress layer.
• a transparent film support carrying in the given order at least one red-sensitized silver halide emulsion layer, at least one green-sensitized silver halide emulsion layer, at least one blue-sensitive silver halide emulsion layer, and a gelatin antistress layer.
• intermediate layers of a hydrophilic colloid, mostly gelatin are provided for better colour separation.
• the intermediate layer beneath the blue-sensitive layer(s) currently is a yellow filter layer that absorbs the blue light not absorbed by the blue-sensitive layer(s) and transmits the red and green light to which the lower layers are sensitive.
• a gelatin intermediate layer is often used, which helps to prevent interactions between the sensitive layers during coating operations and helps to prevent colour contaminations by oxidized developer wandering from one layer into another during the development reaction.
• the side of the transparent film support opposite to that carrying the emulsion layers is coated with a carbon black antihalation back layer.
• a carbon black antihalation back layer indeed provides excellent halation protection and consequently yields high image sharpness.
• carbon black has the disadvantage of getting loose easily from the antihalation back layer, thus creating dust that smears the photographic elements and exerts a disturbing influence during the imagewise exposure thereof.
• the removal of the carbon black antihalation back layer, which is to take place before the colour development can be started, is rather cumbersome.
• antihalation dyes in these elements in the same way as it is done in other types of photographic elements, in which one or several antihalation dyes having light absorption spectra depending on the spectral sensitivity of the light-sensitive layers are employed. It is for instance known to use in a panchromatic graphic arts material a combination of antihalation dyes, which absorb in the entire visible spectral range.
• blue dyes have not been used hitherto in an antihalation undercoat of commercial films is that the light-absorbing dye or mixture of light-absorbing dyes that provides the desired absorption spectrum does not fully comply with the requirement of being non-diffusing towards other colloid layers. It is indeed experienced unfortunately that the blue dye or mixture of blue dyes that provide(s) the desired absorption spectrum, often is (are) not entirely fast to diffusion and as a consequence migrate(s) at least partially to the adjacent red-sensitized emulsion layer and may sensitize this emulsion layer to an unwanted part of the spectrum so that its sensitivity to red light is reduced.
• This object can be accomplished according to the present invention by providing a photographic colour negative or colour intermediate film element comprising a transparent film support and coated thereon in succession, a blue antihalation layer, at least one red-sensitized silver halide emulsion layer comprising at least one cyan-forming coupler, an intermediate layer, at least one green-sensitized silver halide emulsion layer comprising at least one magenta-forming coupler, a yellow filter layer, at least one blue-sensitive silver halide emulsion layer comprising at least one yellow-forming coupler, and an antistress layer, characterized in that said blue antihalation layer comprises at least one blue non-diffusing pentamethine oxonol-type barbituric acid derivative dye in dispersed state in a hydrophilic colloid, said dye absorbing red light and being removable and/or decolourizable in a processing bath.
• said blue antihalation layer comprises at least one dispersed blue non-diffusing pentamethine oxonol-type barbituric acid derivative dye corresponding to the general formula I : in which: each of R1 and R2, which may be the same or different, represents: hydrogen, a C1-C4 alkyl group e.g. n-butyl, a substituted C1-C4 alkyl group, a C1-C4 alkoxy group, an aryl group e.g.
• phenyl or a substituted aryl group such as phenyl substituted with at least one substituent chosen from the group consisting of a halogen atom, hydroxy, alkyl , alkoxy, carboxy, carbamoyl , sulphamoyl, alkoxycarbonyl, aryloxycarbonyl, alkoxysulphonyl, aryloxysulphonyl, and heterocyclylsulphonyl, e.g.
• each of R3 and R4 which may be the same or different, represents: one of the groups represented by R1 and R2, or a cycloalkyl group e.g. cyclohexyl.
• the blue pentamethine oxonol-type barbituric acid derivative dyes absorb light of the spectral range between about 585 nm and about 605 nm, which as such is inappropriate for use as antihalation dye(s) in the blue antihalation layer.
• the absorption maximum of these dyes is found to be shifted bathochromically by at least 100 nm, which makes them highly suited for use as antihalation dye(s) in the blue antihalation layer. In dispersed state, they show a broad and fairly uniform absorption spectrum.
• the image sharpness obtained with photographic colour negative and colour intermediate film elements of the present invention comprising a blue antihalation layer between the support and the red-sensitized emulsion layer(s), said blue antihalation layer being a hydrophilic colloid layer incorporating at least one blue non-diffusing pentamethine oxonol-type barbituric acid derivative dye in dispersed state, equals the sharpness obtained with comparable known film elements comprising a carbon black antihalation back layer instead.
• the pentamethine oxonol-type barbituric acid derivative dyes meet the demands made on light-absorbing dyes for photographic silver halide elements. They are readily compatible with photographic binders such as e.g. gelatin and they can easily be incorporated into the photographic element. Moreover, they possess a high absorptive power. Below a pH-value of 7 they do not migrate in hydrophilic colloid layers and do not dissolve in water, whereas they dissolve readily in water above pH 7. Although during processing they decolour very quickly, even in rapid processing, they are very stable in coating compositions. Furthermore, they are discharged quickly, completely, and irreversibly in an alkaline processing solution, e.g. a developing solution, without forming coloured degradation products, so that there is no residual colour in the material after the processing, nor in the processing liquid.
• an alkaline processing solution e.g. a developing solution
• Table 1 shows a non-restrictive list of representative examples of blue pentamethine oxonol-type barbituric acid derivatives corresponding to general formula I, which can be used according to the present invention.
• the symbols used in Table 1 refer to general formula I.
• the blue dye B-01 can be prepared as described in Preparation 1 hereinafter.
• a volume of 5 l of dimethylformamide is brought in a 20 l open flanged vessel provided with a mechanical stirrer, a thermometer, a dropping funnel, and a cooling tub.
• An amount of 949 g (4 mol) of barbituric acid is added with stirring thereto at room temperature.
• an amount of 569 g (2 mol) of glutaconaldehyde dianilide hydrochloride is added also at room temperature.
• a volume of 1680 ml of triethylamine is added dropwise at 20 - 30°C with cooling on a mixture of ice and water. The mixture is stirred for 15 min.
• pentamethine oxonol-type barbituric acid derivative dyes for use in accordance with the present invention can be prepared analogously.
• Dye B-01 was found to be particularly suited for use as blue antihalation dye according to the present invention in its ammonium salt form.
• the absorption characteristics of the pentamethine oxonol-type barbituric acid derivative dyes of Table 1 are listed in the following Table 2.
• the values of absorption maximum given in Table 2 were measured in solution. In dissolved state these dyes absorb between about 585 and about 605 nm. In dispersed state in gelatin the absorption maximum was found to have shifted bathochromically by at least 100 nm. TABLE 2 Dye no.
• the yellow filter layer between the green-sensitized emulsion layer(s) and the blue-sensitive emulsion layer(s) is a hydrophilic colloid layer, usually a gelatin layer, comprising at least one dispersed yellow non-diffusing dye that absorbs blue light, is removable and/or decolourizable in a processing bath, and is chosen from the group consisting of :
• the yellow merostyryl dyes corresponding to the above general formula II and the yellow monomethine oxonol dyes corresponding to the above general formula III are preferably used in dispersed state in a hydrophilic colloid, since in such state they also show a broad rather uniform absorption spectrum and are thus capable of absorbing any blue light not absorbed by the blue-sensitive emulsion layer(s).
• the yellow merostyryl dyes of general formula II and monomethine oxonol dyes of general formula III also meet the demands made on light-absorbing dyes for photographic silver halide elements, which demands have been described already above for the blue pentamethine oxonol -type barbituric acid derivative dyes of general formula I.
• Table 3 shows a non-restrictive list of representative examples of merostyryl dyes, which can be used according to an above-mentioned preferred embodiment of the present invention.
• the symbols refer to general formula II.
• TABLE 3 Yellow merostyryl dyes Dye N° R5 R6 R7 Position of -OH YM-01 p-carboxyphenyl methyl m-methoxy para YM-02 p-carboxyphenyl methyl m-methoxy ortho YM-03 p-carboxyphenyl methyl hydrogen para YM-04 p-carboxyphenyl methyl hydrogen ortho YM-05 p-carboxyphenyl ethoxycarbonyl hydrogen para YM-06 phenyl carboxy hydrogen para YM-07 trifluoroethyl carbamoyl hydrogen para YM-08 phenyl carbomoyl hydrogen para
• the merostyryl dyes can be prepared as described in US-A 4,311,787.
• the absorption characteristics of the merostyryl dyes of Table 3 are listed in the following Table 4.
• the absorption maxima measured in a non-polar solvent vary between about 380 and 440 nm, whereas in a mixture of a non-polar solvent and a base (e.g. triethylamine) or in a polar solvent (e.g. dimethylformamide) an absorption maximum shifted bathochromically by up to 100 nm is obtained.
• a non-polar solvent e.g. methanol
• a base e.g. triethylamine
• a polar solvent e.g. dimethylformamide
• the dye 1-(p-carboxyphenyl)-3-methyl-4-(p-hydroxybenzylidene)-2-pyrazolin-5-one (YM-03) listed in Table 3 is used as merostyryl dye in dispersed state in the yellow filter layer, preferably a gelatin-containing filter layer, between the at least one green-sensitized emulsion layer and the at least one blue-sensitive emulsion layer.
• Table 5 shows a non-restrictive list of representative examples of yellow monomethine oxonol dyes corresponding to general formula III, which can be used according to an above-mentioned preferred embodiment of the present invention.
• the symbols refer to general formula III.
• the yellow monomethine oxonol dyes corresponding to general formula III can be prepared according to methods known in the art; reference can be made in this respect to US-A 4,092,168, 4,266,014, and 4,288,534.
• the dye B-01 listed in Table 1 is used in its ammonium salt form as pentamethine oxonol-type barbituric acid derivative dye in dispersed state in the gelatin-containing intermediate layer between the support and the at least one red-sensitized emulsion layer and the dye YM-03 listed in Table 3 is used as merostyryl dye in dispersed state in the yellow gelatin-containing filter layer between the at least one green-sensitized emulsion layer and the at least one blue-sensitive emulsion layer.
• the blue pentamethine oxonol-type barbituric acid derivative dyes used in accordance with the present invention as well as the yellow merostyryl dyes according to general formula II and/or the monomethine oxonol dyes according to general formula III can be incorporated into hydrophilic colloid compositions according to any of the dispersion techniques known for incorporating water-insoluble colour couplers in hydrophilic colloid media.
• a dispersion of the blue pentamethine oxonol-type barbituric acid derivative dyes in an aqueous hydrophilic colloid composition by finely grinding the dyes in a mill e.g. a ball mill, a sand mill, or a colloid mill in the presence of one or more dispersing agents; the hydrophilic colloid e.g. gelatin is added after or before the milling process.
• the dispersion obtained can then be mixed with other ingredients to form a coating composition for the blue antihalation layer of the photographic colour negative or colour intermediate film element of the present invention.
• the dispersion obtained can also be mixed with other ingredients to form the coating composition for the yellow filter layer of the photographic colour negative or colour intermediate film element of the present invention.
• hydrophilic colloid binder of the layers containing the dyes according to the present invention is usually gelatin.
• Other hydrophilic colloids such as casein, polyvinyl alcohol, poly-N-vinyl pyrrolidone, sodium alginate, sodium carboxymethylcellulose, etc. can also be used either or not in combination with gelatin.
• the transparent film support of the photographic colour negative or colour intermediate film element of the present invention is a film of cellulose triacetate, a polyalkylene terephthalate e.g. polyethylene terephthalate, or polycarbonate.
• the side of the transparent film support of the photographic colour negative or colour intermediate film element, opposite to that carrying the emulsion layers is provided with an antistatic layer comprising an electroconductive polymer e.g. as described in US-A 4,089,997, preferably an antistatic layer comprising polystyrene sulphonic acid sodium salt.
• This antistatic layer may comprise polymer beads as described in EP-A 0,080,225, these beads protruding from the antistatic layer surface and consequently acting as spacing agents to reduce contact with adjacent surfaces.
• the thickness of the blue antihalation layer is not critical, though generally a thickness of 0.5 to 3 ⁇ m is used.
• the thickness and the amount of the dyes present therein are preferably chosen in such a way that the resulting antihalation layer has an optical density of about 0.5 to about 1.5 as measured in its own absorption range.
• the amount of the blue pentamethine oxonol-type barbituric acid derivative dye in the blue antihalation layer may vary from 750 mg to 10 mg per m2, preferably from 250 to 25 mg per m2.
• the thickness of the yellow filter layer and the amount of the yellow dyes present therein are not critical either and they generally are chosen in the ranges described above for the blue antihalation layer.
• a dispersion was made of the blue dye B-01 (in its ammonium salt form) in 2% aqueous gelatin by milling in a swinging mill with a concentration of 250 mg of dye per 100 g of dispersion.
• a coating composition was made by adding gelatin and water, the resulting composition containing 5.4 g of the blue dye.
• the composition was coated on a subbed cellulose triacetate support in such a way that 2.5 g of gelatin and 270 mg of the dye were present per m2.
• the blue gelatin layer obtained was covered with a non-spectrally-sensitized silver chlorobromide emulsion layer comprising an amount of silver halide equivalent to 1.04 g of silver nitrate per m2.
• the dye in the blue gelatin layer showed an excellent fastness to diffusion. No desensitization of the emulsion layer could be measured. Neither did the spectral sensitivity of the emulsion layer change, because the dye had not migrated at all into the emulsion layer and as a consequence could not have exerted any sensitizing effect on it.
• Samples of colour negative film elements A to C were made. Each sample had a transparent film support, a subbing layer, a red-sensitized silver halide emulsion layer comprising a cyan-forming coupler, an intermediate gelatin layer, a green-sensitized silver halide emulsion layer comprising a magenta-forming coupler, a yellow filter layer, a blue-sensitive silver halide emulsion layer comprising a yellow-forming coupler, and an antistress layer. All samples were identical except for the position and composition of the antihalation layer(s), as explained hereinafter.
• Element A additionally carried a carbon black antihalation layer on the rear side of the support, the carbon black layer having a thickness of 1 ⁇ m and comprising 250 mg of carbon black per m2.
• Element B had no carbon black antihalation back layer, but instead had a blue antihalation layer between the support and the red-sensitized silver halide emulsion layer, the blue antihalation layer having a thickness of 1 ⁇ m and comprising 50 mg of the blue dye B-01 (in its ammonium salt form) and 0.7 g of gelatin per m2.
• Element C had no carbon black antihalation back layer, but instead had an identical blue antihalation layer as in Element B and in addition thereto comprised a yellow filter layer between the green-sensitized emulsion layer and the blue-sensitive emulsion layer, which filter layer comprised the yellow dye YM-03 in an amount of 200 mg per m2, the amount of gelatin being 1 g per m2.
• Element Speed MTF value (%) Red-sensitive layer 2 5 10 30 60 100 lines/mm A exposed to red 100 114 111 93 57 24 17 B exposed to red 103 112 108 91 55 23 16 C exposed to red 105 110 105 85 50 20 15 Blue-sensitive layer 2 5 10 30 60 100 lines/mm A exposed to blue 100 110 108 102 84 52 40 B exposed to blue 100 114 112 106 88 55 44 C exposed to blue 102 112 110 102 81 48 36
• the image sharpness obtained in the blue-sensitive emulsion layer of the film element C equals the image sharpness obtained in the blue-sensitive emulsion layer of a comparable film element comprising a carbon black antihalation back layer.

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Citations (5)

• 1992
  • 1992-08-03 EP EP92202390A patent/EP0582000A1/de not_active Withdrawn
• 1993
  • 1993-07-12 JP JP19541293A patent/JPH0682966A/ja active Pending

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