EP0782045B1 - Silver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser - Google Patents
Silver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser Download PDFInfo
- Publication number
- EP0782045B1 EP0782045B1 EP19960120156 EP96120156A EP0782045B1 EP 0782045 B1 EP0782045 B1 EP 0782045B1 EP 19960120156 EP19960120156 EP 19960120156 EP 96120156 A EP96120156 A EP 96120156A EP 0782045 B1 EP0782045 B1 EP 0782045B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- compounds
- silver halide
- film element
- light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
-
- 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
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
-
- 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
- G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
- G03C1/93—Macromolecular substances therefor
-
- 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
- G03C11/00—Auxiliary processes in photography
- G03C11/02—Marking or applying text
-
- 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
- G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
-
- 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
- G03C2200/00—Details
- G03C2200/23—Filter dye
-
- 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
- G03C2200/00—Details
- G03C2200/35—Intermediate layer
-
- 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
Definitions
- the present invention relates to silver halide colour photographic film elements having a thermoplastic support that are capable of being marked by means of a laser.
- Well-known transparent film supports used for silver halide photographic projection film elements or photographic film sheets to be examined as for e.g. colour print film applications can be e.g. cellulose triacetate, a polyester like a polyalkylene terephthalate or naphthalate e.g. polyethylene terephthalate or polyethylene napthalate, or polycarbonate.
- marking of such elements, before or after exposure to heat or radiation can be performed by means of mechanical or chemical methods, by heat or radiation, wherein said technique of radiation may be performed by means of a laser beam, travelling over the zone of film that should be marked.
- Marks added to a photographic film element may be e.g. graphic elements, characters, bar codes or text.
- the quality of the result depends on the nature of the emulsion(s) and on the background density of the images on which the subtitles are to be etched.
- Working parameters in particular the power of the laser beam radiation applied to the film and the displacement speed of the laser beam, are determining the sharpness of the subtitles to a large extent.
- the power, the exposure time and the wavelength are selected so as to destroy the photographic image forming emulsion elements completely at points where the laser beam strikes the film. Due to the nonuniform release of gelatinous residues, gelatin present as a main protective hydrophilic colloid in the coated photographic layers, or to the damage of the support and as a result thereof leaving dark spots and coloured spots, an unquiet and unpleasant enlarged view is projected on the screen in the cinema.
- EP-A 0 201 391 A method and apparatus for subtitling colour multilayer motion pictures or photographic plates by means of continuous or broken lines with a laser have been described in EP-A 0 201 391. Another method and apparatus makes use of a mask to produce subtitles and has been described in EP-A 0 282 611. Further EP-A 0 464 270 describes the application of a protective layer over at least portions of a film or tape, whereupon characters should be written by means of a laser beam.
- Said method essentially comprises the steps of travelling the laser beam over the film at a speed of displacement V lying in the range from about 1 to about 200 cm/s with a power of the laser P lying in the range of about 100 mW to about 20 W, in order to have a ratio V/P lying in the range from 10 to 30, followed by a washing step in order to remove particles that have been heated and disclocated from the zones of the film that have previously been marked by the low power laser beam.
- the method is well adapted to subtitle motion picture films on a support constituted by a cellulose derivative such as cellulose triacetate, but is equally applicable to film supports based on a thermoplastic polymer material, such as polyester.
- a transparant polyester support such as e.g. polyethylene terephthalate
- lowering of the power of the laser results in grayish or slightly yellow coloured zones.
- a silver halide colour photographic film element wherein said element is a colour photographic motion picture projection film element comprising a transparent thermoplastic film support having a subbing layer unit and coated thereon in succession, a blue-sensitive silver halide emulsion layer comprising a yellow-forming coupler, an intermediate layer, a red-sensitised silver halide emulsion layer comprising a cyan-forming coupler, an intermediate layer, a green-sensitised silver halide emulsion layer comprising a magenta-forming coupler, and an antistress layer characterised in that
- Thermoplastic polyesters are substantially composed of linear saturated polyester.
- Preferred are homopolymers or copolymers having one recurring unit or at least two different recurring units such as polyalkylene terephthalate or polyalkylene naphthalate.
- Typical examples are butylene terephthalate, ethylene terephthalate, butylene naphthalene dicarboxylate and ethylene naphthalene dicarboxylate, or mixtures of these.
- Examples of the homopolymers are polybutylene terephthalate, polyethylene terephthalate, polybutylene napthalene dicarboxylate, polyethylene napthalene dicarboxylate and mixtures thereof.
- the transparent polyester film support with a primer coating or a subbing layer before the application of further silver halide photographic emulsion layers.
- An interesting primer coating for application between e.g. a polyethylene terephthalate support and the said hydrophilic layers has been described e.g. in US-A 4,132,552.
- Said primer coating, also called “subbing layer” is substantially composed of at least one hydrophobic layer directly contacting the transparant film support and at least one hydrophilic layer coated thereupon.
- the said subbing layer comprising at least one hydrophobic polymer together with the adjacent hydrophilic layer coated thereupon forms the "subbing layer unit" as set forth in the statement of this invention.
- Preferred hydrophobic polymers used as subbing layers are styrene-butadiene copolymers, vinylidene chloride copolymers, water-soluble polyesters and polyacrylic esters. From these hydrophobic polymers styrene-butadiene copolymers and vinylidene chloride copolymers are the most preferred. However it has been established that, according to this invention, styrene-butadiene copolymers are the most preferred in order to find a solution for the problem of getting laser marked zones on the film showing the fewest optical failures.
- the hydrophilic layer coated adjacent to the subbing layer may be in the form of an aqueous dispersion e.g. a latex, optionally containing a cross-linking agent, a swelling agent, a matting agent or an antistatic agent.
- a cross-linking agent examples include triazine compounds as described e.g.
- hydrophilic colloids such as dextran, polyacrylamide, polyvinylalcohol and polyvinyl pyrrolidone may be used, but particularly preferred is gelatin, optionally in combination with at least one of the other hydrophilic colloids cited.
- hydrophilic layers are gelatinous layers.
- the gelatin used therein can be lime-treated or acid-treated gelatin. The preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
- the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot.
- Gelatine derivatives may be useful. Said derivatives have e.g. been described in US-Patents 4,978,607; 5,378,598; 5,395,748 and 5,439,791 and in EP-A's 0 628 860 and 0 666 498.
- a matting agent present in the "subbing layer unit” use can be made of fine particles of organic compounds such as polymethyl methacrylate homopolymer, copolymer of methyl methacrylate with acrylic acid, starch and/or fine particles of inorganic compounds such as colloidal silica, synthetic clay and titanium dioxide.
- organic compounds such as polymethyl methacrylate homopolymer, copolymer of methyl methacrylate with acrylic acid, starch and/or fine particles of inorganic compounds such as colloidal silica, synthetic clay and titanium dioxide.
- an antistatic agent present in the "subbing layer unit” use can be made of metal oxides, as described, e.g., in US-A's 4,394,441 and 5,439,785; of conductive polymers, as described e.g. in US-A's 3,437,484 and 4,898,808; of fluoro-substuted compounds as described e.g. in US-A's 4,407,937 and 4,366,238 or a combination thereof.
- At least said "subbing layer unit” defined above comprises a chemical compound having reducing properties and a light-stabilising agent, also called light-stabiliser, absorbing ultraviolet radiation. Both types of compounds are mentioned as they compensate for or neutralise both an oxidation reaction which takes place as a pure thermal process at a locally elevated temperature or with the assistance of (laser) light respectively. In a preferred embodiment both types of compounds are coated in the hydrophilic layer of the "subbing layer unit", coated adjacent to the hydrophobic subbing layer which is in direct adhesive contact with the support.
- the film element according to the present invention thus preferably comprises said light-stabiliser and said chemical compound having reducing properties in the said hydrophilic colloid layer: the other hydrophilic layers may simultaneously contain one or more light-stabiliser(s) (which may e.g. also be present in the blue-sensitive layer) and one or more chemical compound(s) having reducing properties (which is preferably not present in light-sensitive emulsion layers comprising silver halide crystals, as fog and instability may form a problem) or may contain one of more light-stabilizer or one or more chemical compound(s) having reducing properties.
- the other hydrophilic layers may simultaneously contain one or more light-stabiliser(s) (which may e.g. also be present in the blue-sensitive layer) and one or more chemical compound(s) having reducing properties (which is preferably not present in light-sensitive emulsion layers comprising silver halide crystals, as fog and instability may form a problem) or may contain one of more light-stabilizer or one or more chemical compound(s) having reducing properties
- Reducing properties of the corresponding chemical compound having reducing properties are derived from the sum of its polarographically determined anodic and cathodic potentials which should be positive.
- anti-oxidants To retard the thermal oxidation addition of anti-oxidants is the most commonly used method of stabilisation.
- Especially preventive oxidants also called secondary antioxidants, that are responsible for the destruction of e.g. oxygen radicals, hydroxyl-radicals and peroxy radicals generated rapidly in the presence of a sufficient amount of oxygen at high temperatures, are particularly preferred.
- antioxidants should not decompose during different thermal attacks of a polymer. Nevertheless at temperatures of up to 300°C and more parts of the oxidants are consumed as a consequence of its protective function. Moreover it is important to match the required amounts of antioxidants thereupon.
- antioxidants are alkylphenols, hydroxyphenylpropionates, hydroxybenzyl compounds, alkylidene bisphenols, secondary aromatic amines, thiobisphenols, aminophenols, thioethers, phosphites and phosphonites, sterically hindered amines, etc.. Said products are sold under well-known trade names as e.g. AGE RITE and VANOW, both from R.T.
- a further type of useful compounds which may additionally be added in order to reach the objects of this invention is a so-called "flame retarding" agent.
- the layer unit adjacent to the thermoplastic support comprises one or more flame retarding agents
- its action is based on the formation of a "microshield" upon the support in order to separate the combustible materials from oxygen, necessary for the combustion process, which process is accelerated by heat, generated e.g. by laser marking.
- Typical useful compounds to reach that goal are phosphorous compounds.
- the range of effectively working products containing phosphor is extremely versatile and extends over several oxidation states: phosphines; phosphine oxides, phosphonium compounds, phosphonates, elemental red phosphor, phosphites and phosphates.
- Phosphorous compounds containing halogen, particularly bromine have an increased effectiveness as a flame retardant.
- chlorinated flame retardants are cycloaliphatic chlorinated flame retardants like "dechlorane plus” and “HET-acid” and its anhydride. Aromatic chlorinated compounds are not useful due to their limited flame retardancy.
- Light-stabilising agents and more particularly those absorbing ultraviolet radiation for linear or thermoplastic polyesters like polyethylene or polybutylene terephthalate, show an absorption spectrum, which going from larger to smaller wavelengths begins at 360 nm, significantly increases below 320 nm and becomes most pronounced below 300 nm.
- Suitable light-stabilising agents absorbing ultraviolet radiation are selected from the group of organic compounds consisting of 2-hydroxybenzophenones and 2-hydroxophenyl benzotriazoles, sterically hindered amines (nitroxyl radicals as effectively absorbing agent) and organic nickel compounds (like n-butylamine-nickel-2,2'-thio-bis-(4-t-octylphenolate)).
- benzotriazole type UV absorbers are generally chosen because they inhibit low initial color and good color stability. Recently the effectiveness of sterically hindered amines has been taken in consideration as opening new horizons.
- HOSTAVIN from HOECHST, Frankfurt, Germany
- IRGASTAB CHIMASSORB and TINUVIN from Ciba Geigy, Basel, Switzerland
- UVINIL and SICOSTAB from BASF, Ludwigshafen, Germany
- UC-CHEK AM from Ferro Corp., Cleveland, USA
- UV-ABSORBER BAYER from Bayer AG, Leverkusen, Germany
- SANDUVOR from Sandoz AG, Basel, Switzerland
- GOODRITE UV from BF Goodrich, Cleveland, USA
- CYASORB UV from American Cyanamid Co., Wayne, USA
- EASTMAN INHIBITOR from Eastman Chemical Products Inc., Kingsport, USA
- RYLEX from Du Pont de Nemours, WILMINGTON, USA
- SALOL from Dow Chemical Co., Midland, USA; etc., without however being limited thereto.
- Especially preferred concentrations of light stabilisers are in the range from 0.05 to 2 % by weight with respect to the layer or material to be protected.
- UV-absorbers known from patent literature are e.g. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71 and US-A 3,503,330, cinnamic ester compounds as described in US-A 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, butadiene compounds having a pyrrolidine nucleus as has been disclosed in RD No. 18032 (April 1979), p. 139-140; benzoxazole compounds as described in US-P 3,700,455 and polymeric stilbene-triazine compounds as in US-P 3,615,547.
- At least said subbing layer unit comprises a chemical compound having reducing properties and/or a light-stabilising chemical compound absorbing ultraviolet radiation.
- gelatin is the most preferred colloid.
- colour photographic motion picture projection film elements as multilayer colour print film elements intended for making colour release prints are subtitled after colour processing.
- Said elements basically consist of a transparent polyester film support carrying in the given order a blue-sensitive silver halide emulsion layer, a red-sensitised silver halide emulsion layer, and a green-sensitised silver halide emulsion layer. Between the emulsion layers intermediate layers of a hydrophilic colloid, mostly gelatin, are provided for better colour separation.
- 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 has excellent antistatic properties.
- a colour photographic motion picture projection film element comprising a transparent film support and coated thereon in succession, a blue-sensitive silver halide emulsion layer comprising a yellow-forming coupler, an intermediate layer, a red-sensitised silver halide emulsion layer comprising a cyan-forming coupler, an intermediate layer, a green-sensitised silver halide emulsion layer comprising a magenta-forming coupler, and an antistress layer, characterised in that between said support and said blue-sensitive silver halide emulsion layer a yellow antihalation undercoat is provided, which comprises at least one yellow non-diffusing dye that absorbs blue light and is removable and/or decolourisable in a processing bath and that between said blue-sensitive silver halide emulsion layer and said red-sensitised silver
- Suitable amounts of both the ultraviolet light-absorbing compound and the reducing agent are comprised between 25 and 250 mg/m 2 and more preferably between 50 and 150 mg/m 2 .
- the said yellow antihalation undercoat contains said at least one reducing agent and at least one light-stabiliser, preferably in amounts as set forth hereinbefore.
- Dispersions of said reducing agent and of said light-stabiliser in this hydrophilic yellow antihalation layer are preferably prepared in the presence of oil-formers as e.g. tricresyl-phosphate, dibutylphthalate, diethyllaurate, myristol, di-pentylphenol and the like.
- oil-formers as e.g. tricresyl-phosphate, dibutylphthalate, diethyllaurate, myristol, di-pentylphenol and the like.
- the type and the amounts of oil-former used in the dispersion and coated therefrom in the "subbing layer unit" preferably in the hydrophilic uppermost layer thereof, are decisive for the adhesion characteristics of "subbing layer unit" and support.
- bromine-containing agents are much better flame-retardant or flame-resistant agents than chloride-containing agents.
- the use of silver halide emulsions rich in chloride leads to a much larger extent to a laser marking optical failure than the use of silver bromide or silver bromoiodide emulsions, used preferably in e.g. colour negative films, microfilms, X-ray films and the like.
- Materials in which silver halide emulsions rich in chloride are used as e.g. colour print films, films for graphic applications and for diffusion transfer are expected to be more sensitive to the phenomenon of flame-sensitivity, which causes problems when laser engraving methods are applied to mark such films before processing.
- the power of the laser is one of the factors determining the quality of the marks, obtained by laser engraving techniques.
- Suitable lasers to be used, depending on the application are gas-, dye- or semiconductor lasers emitting light in the wavelength ranges from ultraviolet to infrared as well as a plasma light source. Said light sources are known as suitable light sources for recording but in order to get subtitling action a "green-blue" YAG-laser having a well-defined power and subtitling velocity, as e.g. described in US-A 5,367,348 is preferred.
- Another laser used in the Examples hereinafter is an Ar-laser, emitting green-blue (488 nm) or, preferably, green (515 nm) light.
- Other lasers having a typical emission in the longer (red) wavelength region are He-Ne and Kr-lasers.
- Samples of colour photographic motion picture projection film elements A, B, C ....to K were made. Each sample had a transparent film support, a subbing layer, a blue-sensitive silver halide emulsion layer comprising a yellow-forming coupler, an intermediate gelatin layer, a red-sensitised silver halide emulsion layer comprising a cyan-forming coupler, an intermediate gelatin layer, a green-sensitised silver halide emulsion layer comprising a magenta-forming coupler, and an antistress layer as has also been described in EP-Specification 0 252 550. All samples were identical except for the composition of the combination of reducing agent and light-stabiliser, as summarised in Table 1.
- Element A had a yellow antihalation undercoat between the support and the blue-sensitive emulsion layer, the yellow antihalation undercoat having a thickness of 1 ⁇ m and comprising 290 mg of a yellow dye and 0.6 g of gelatin per m2.
- Elements B, C .. to K had an identical yellow antihalation undercoat as in Element A and in addition thereto the corresponding ultraviolet (UV) absorber compound in an amount of 100 mg per m 2 and as a reducing agent in an amount of 100 mg per m 2 , both UV-absorber and reducing agent as summarised in Table 1.
- UV absorber compound in an amount of 100 mg per m 2
- reducing agent in an amount of 100 mg per m 2
- the print film was subtitled by means of a laser having a power of 6 W, 5 W and 4 W.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Another method and apparatus makes use of a mask to produce subtitles and has been described in EP-A 0 282 611. Further EP-A 0 464 270 describes the application of a protective layer over at least portions of a film or tape, whereupon characters should be written by means of a laser beam.
- a phosphite like compound (I.1)
- an aminophenol like compound (I.2)
- an alkylphenol like compound (I.3)
- a di-ester of di-t-butylphenol like compound (I.4)
- a 2,5-dialkylester substituted hydroquinone like compound (I.5)
- (a) compounds with two benzene rings such as e.g. decabromodiphenyl ether, hexabromodiphenoxy ethane etc.;
- (b) tetrabromophthalic anhydride and derivatives like e.g. tetrabromophthalate diols and polyethers or ethylene bis(tetrabromophthalimide);
- (c) tetrabromobisphenol A (TBBA) and derivatives like e.g. TBBA-based epoxy resin, TBBA-carbonate oligomer, TBBA-bis(allyl ether) etc.;
- (d) oligomeric and polymeric flame retardants like e.g. poly(pentabromobenzyl acrylate), poly(dibromophenylene ether) or brominated polystyrene etc.;
- (e) aliphatic brominated compounds like e.g. hexabromocyclododecane; ethylene bis(dibromonorbornane-di-carboximide); dibromoethyl dibromocyclohexane and dibromoneopentyl glycol etc..
- 2-OH-4-methoxy-benzophenone (compound II.1)
- 2,4-di-OH-benzophenone (compound II.2)
- (a) radiation sensitive silver halide emulsion layers, the proviso that these agent(s) has(have) no or a neglectable influence on sensitometric characteristics,
- (b) intermediate layers as e.g. layers between the "subbing unit" and the first light-sensitive silver halide emulsion layer; between two light-sensitive silver halide emulsion layers, between a light-sensitive layer and a protective overcoat layer (e.g. a protective antistress layer)
- (c) protective layer(s)
- (d) overcoat layer(s)
- (e) afterlayer(s)
- (f) one or more backing layer(s).
Exp. No. | Reducing agent | UV-absorber | Laser Power | Evaluation mark |
A | No | No | 4 W | 5 |
B | I.4 | II.1 | 4 W | 1 |
C | I.5 | II.1 | 4 W | 3 |
D | I.1 | II.1 | 4 W | 3 |
E | I.2 | II.1 | 4 W | 2 |
F | I.3 | II.1 | 4 W | 2 |
G | I.4 | II.2 | 4 W | 1 |
H | I.5 | II.2 | 4 W | 1 |
I | I.1 | II.2 | 4 W | 3 |
J | I.2 | II.2 | 4 W | 2 |
K | I.3 | II.2 | 4 W | 2 |
Claims (9)
- A film element wherein said element is a colour photographic motion picture projection film element comprising a transparent thermoplastic film support having a subbing layer unit and coated thereon in succession, a blue-sensitive silver halide emulsion layer comprising a yellow-forming coupler, an intermediate layer, a red-sensitised silver halide emulsion layer comprising a cyan-forming coupler, an intermediate layer, a green-sensitised silver halide emulsion layer comprising a magenta-forming coupler, and an antistress layer characterised in thatat least said subbing layer unit comprises at least one light-stabiliser and at least one chemical compound having reducing properties wherein saidchemical compound having reducing properties is characterised by the property that the sum of its polarographically determined anodic and cathodic potentials is positive and wherein said light-stabiliser is a compound absorbing ultraviolet radiation.
- A film element according to claim 1, wherein between the blue-sensitive silver halide emulsion layer and the transparant support a yellow antihalation undercoat is present, which comprises at least one yellow non-diffusing dye that absorbs blue light and is removable and/or decolourisable in a processing bath.
- A film element according to claim 1 or 2, wherein between said blue-sensitive silver halide emulsion layer and said red-sensitised silver halide emulsion layer a bluish antihalation intermediate layer is provided, which comprises at least one blue non-diffusing dye that absorbs red light and is removable and/or decolourisable in a processing bath.
- A film element according to any of claims 1 to 3, wherein said transparent thermoplastic film support has a polyethylene terephthalate support.
- A film element according to any of claims 1 to 4, wherein said chemical compound is an antioxidant selected from the group of compounds consisting of a phosphite compound, an aminophenol compound, an alkylphenol compound, a di-ester of di-t-butylphenol compound and a 2,5-dialkylester substituted hydroquinone compound.
- A film element according to any of claims 1 to 5, wherein said light-stabilising agent absorbing ultraviolet radiation is selected from the group of agents consisting of aryl-substituted benzotriazole compounds, 4-thiazolidone compounds, benzophenone compounds, cinnamic ester compounds, butadiene compounds, benzoxazole compounds and polymeric stilbene-triazine compounds.
- A film element according to any of claims 1 to 5, wherein said light-stabilising agent absorbing ultraviolet radiation is selected from the group of benzophenone compounds consisting of 2-hydroxy-4-methoxy-benzophenone and 2,4-dihydroxy-benzophenone.
- A film element according to any of claims 1 to 7, wherein said subbing layer unit is substantially composed of at least one hydrophobic polymer layer directly contacting the transparant film support and a hydrophilic colloid layer coated thereupon.
- A film element according to claim 8, wherein said hydrophobic layer has a composition selected from the group consisting of vinylidene chloride and styrene/butadiene copolymers.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19960120156 EP0782045B1 (en) | 1995-12-27 | 1996-12-16 | Silver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95203633 | 1995-12-27 | ||
EP95203633 | 1995-12-27 | ||
EP19960120156 EP0782045B1 (en) | 1995-12-27 | 1996-12-16 | Silver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0782045A1 EP0782045A1 (en) | 1997-07-02 |
EP0782045B1 true EP0782045B1 (en) | 2001-10-24 |
Family
ID=26139963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19960120156 Expired - Lifetime EP0782045B1 (en) | 1995-12-27 | 1996-12-16 | Silver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP0782045B1 (en) |
Family Cites Families (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3091537A (en) | 1959-05-04 | 1963-05-28 | Eastman Kodak Co | Hardening of photographic layers |
US3288775A (en) | 1961-04-07 | 1966-11-29 | Ciba Ltd | Method of hardening gelatin by reacting with conjugated heterocyclic compounds containing halogen atoms and water-solubilizing acid groups |
US3291624A (en) | 1963-08-21 | 1966-12-13 | Eastman Kodak Co | Acetylated derivatives of dialdehydes and of their hemiacetals as gelatin hardeners |
US3325287A (en) | 1963-11-26 | 1967-06-13 | Fuji Photo Film Co Ltd | Photographic gelatin hardening composition |
US3232764A (en) | 1965-05-25 | 1966-02-01 | Eastman Kodak Co | Gelatin compositions adapted for the preparation of hardened coatings |
US3392024A (en) | 1965-06-01 | 1968-07-09 | Eastman Kodak Co | Gelatin silver halide photographic emulsions containing polyfunctional aziridinyl compounds |
US3437484A (en) | 1965-07-26 | 1969-04-08 | Eastman Kodak Co | Antistatic film compositions and elements |
FR1486986A (en) | 1965-07-28 | 1967-06-30 | Eastman Kodak Co | New gelatin compositions and their applications, especially in photography |
GB1146348A (en) * | 1965-12-30 | 1969-03-26 | Fuji Photo Film Co Ltd | Photographic colour elements |
DE1522378A1 (en) | 1966-05-13 | 1969-07-24 | Agfa Gevaert Ag | Process for curing photographic layers containing gelatin |
BE755781A (en) * | 1969-09-05 | 1971-02-15 | Eastman Kodak Co | NEW PHOTOGRAPHIC PRODUCT PROTECTED AGAINST THE EFFECTS OF ELECTROSTATIC DISCHARGE |
US3642486A (en) | 1970-03-19 | 1972-02-15 | Eastman Kodak Co | Vinylsulfonyl-containing compounds as hardening agents |
US3988157A (en) * | 1972-07-17 | 1976-10-26 | Agfa-Gevaert N.V. | Process for adhering hydrophilic layers to dimensionally stable polyester films |
US4116696A (en) * | 1974-02-06 | 1978-09-26 | Fuji Photo Film Co., Ltd. | Photographic material |
GB1533555A (en) | 1975-11-07 | 1978-11-29 | Agfa Gevaert | Dimensionally stable polyester film supports |
JPS57118242A (en) | 1981-01-14 | 1982-07-23 | Fuji Photo Film Co Ltd | Photographic sensitive material |
US4407937A (en) | 1981-03-03 | 1983-10-04 | Fuji Photo Film Co., Ltd. | Silver halide photographic sensitive element containing a fluorine containing compound as an antistatic agent |
US4366238A (en) | 1981-06-25 | 1982-12-28 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
JPS59162546A (en) | 1983-03-07 | 1984-09-13 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
US4587346A (en) * | 1985-01-22 | 1986-05-06 | Ciba-Geigy Corporation | Liquid 2-(2-hydroxy-3-higher branched alkyl-5-methyl-phenyl)-2H-benzotriazole mixtures, stabilized compositions and processes for preparing liquid mixtures |
US4666965A (en) | 1985-01-29 | 1987-05-19 | Mitsubishi Rayon Co., Ltd. | Flame-retardant polyethylene terephthalate resin composition |
FR2580548B1 (en) | 1985-04-19 | 1987-06-26 | Cinema Magnetique Communicatio | MARKED FILMS, METHOD AND APPARATUS FOR MARKING FILMS |
US5135541A (en) | 1986-10-13 | 1992-08-04 | Albright & Wilson Limited | Flame retardant treatment of cellulose fabric with crease recovery: tetra-kis-hydroxy-methyl phosphonium and methylolamide |
JPH0648372B2 (en) * | 1986-11-13 | 1994-06-22 | 富士写真フイルム株式会社 | Silver halide color photographic light-sensitive material |
EP0282611A1 (en) | 1987-03-16 | 1988-09-21 | Moshe Guez | Method and apparatus for writing information on processed photographic film |
DE3730319C2 (en) | 1987-09-10 | 1996-05-09 | Agfa Gevaert Ag | Photographic recording material |
JPH01245052A (en) | 1988-03-26 | 1989-09-29 | Sumitomo Chem Co Ltd | Thermoplastic resin composition |
JPH02116843A (en) | 1988-10-27 | 1990-05-01 | Konica Corp | Silver halide photographic sensitive material subjected to antistatic treatment |
NL8900017A (en) | 1989-01-04 | 1990-08-01 | Metatechnics | METHOD FOR WRITING SIGNS ON A TAPE, AND SYSTEM FOR IMPLEMENTATION OF THIS METHOD |
US5246782A (en) | 1990-12-10 | 1993-09-21 | The Dow Chemical Company | Laminates of polymers having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings |
DE69016438T2 (en) | 1989-07-14 | 1995-05-24 | Dainippon Printing Co Ltd | COVER FILM FOR HEAT TRANSFER. |
US5076970A (en) | 1990-05-29 | 1991-12-31 | Ethyl Corporation | Flame retardant n,n'-bis(tetrabromophthalimide) composition |
US5081176A (en) | 1990-09-24 | 1992-01-14 | General Electric Company | Polyalkylene Terephthalate compositions having improved burning characteristics |
US5219510A (en) | 1990-09-26 | 1993-06-15 | Eastman Kodak Company | Method of manufacture of cellulose ester film |
US5104450A (en) | 1990-09-26 | 1992-04-14 | Eastman Kodak Company | Formulations of cellulose esters with arylene-bis(diaryl phosphate)s |
EP0739933B1 (en) | 1990-11-07 | 1999-03-03 | Teijin Limited | Polyester resin composition |
US5218021A (en) | 1991-06-27 | 1993-06-08 | Ciba-Geigy Corporation | Compositions for polar solvent fire fighting containing perfluoroalkyl terminated co-oligomer concentrates and polysaccharides |
FR2682520B1 (en) | 1991-10-11 | 1994-02-11 | Titra Film Sa | METHOD FOR SUBTITLING CINEMATOGRAPHIC FILMS. |
US5227416A (en) | 1991-12-23 | 1993-07-13 | Ppg Industries, Inc. | Intumescent flame retardant composition |
US5238982A (en) | 1992-09-24 | 1993-08-24 | Basf Corporation | Method for producing polyamide fibers with reduced flammability |
US5378598A (en) | 1992-12-21 | 1995-01-03 | Eastman Kodak Company | Use of acid processed ossein gelatin and chain-extened acid processed ossein gelatin as peptizers in the preparation of photographic emulsions |
DE69316868T2 (en) | 1993-03-08 | 1998-09-03 | Agfa Gevaert Nv | Modified gelatin and hydrophilic elements containing them |
KR960702118A (en) | 1993-04-20 | 1996-03-28 | 워렌 리챠드 보비 | PHOTOGRAPHIC ELEMENTS COMPRISING ANTISTATIC LAYERS |
EP0628860B1 (en) | 1993-06-11 | 1997-10-15 | Agfa-Gevaert N.V. | New type of modified gelatin and its use in a DTR material |
US5395748A (en) | 1993-12-08 | 1995-03-07 | Eastman Kodak Company | Ballasted optical brighteners |
DE4403683A1 (en) | 1994-02-07 | 1995-08-10 | Agfa Gevaert Ag | Photographic silver halide material |
-
1996
- 1996-12-16 EP EP19960120156 patent/EP0782045B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0782045A1 (en) | 1997-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3888678A (en) | Method for adjusting triboelectric charging characteristics of materials | |
US5981155A (en) | Silver halide color photographic film element having a thermoplastic support capable of being marked by means of a laser | |
US4666774A (en) | Static resistant X-ray intensifying screens | |
EP0782045B1 (en) | Silver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser | |
US6171751B1 (en) | Imaging element with hindered amine stabilizer in the base | |
US3849139A (en) | Polyethylene terephthalate film for use as roentgenographic film base | |
GB2343454A (en) | Biaxially oriented polyolefin paperless imaging material | |
JP3416824B2 (en) | Silver halide photographic materials | |
US3911172A (en) | Adhesion of hydrophilic layers on polyester film | |
EP0106464A1 (en) | Tannable imaging element | |
US4363866A (en) | Recording materials | |
EP1184719B1 (en) | Motion picture film element | |
US3331077A (en) | Method and medium for electron beam recording | |
US5955251A (en) | Method for producing information recording medium | |
EP0668534B1 (en) | Silver halide photographic material comprising emulsion layer and backing layer provided on support | |
DE69910936T2 (en) | Transmitted-light photographic display materials with biaxially oriented polyolefin film | |
JP3385484B2 (en) | Silver halide photographic materials | |
EP0664480A2 (en) | Silver halide color photographic material | |
EP0752619A2 (en) | Improved dye imbibition printing blanks and matrix films | |
CA1146751A (en) | Reflex copying process onto light-sensitive recording materials | |
JPH07239528A (en) | Silver halide photographic sensitive material | |
JPH0611803A (en) | Masking material | |
JPH07281357A (en) | Silver halide photographic sensitive material | |
JPH06317876A (en) | Silver halide photographic sensitive material | |
JPH06289536A (en) | Polyester film, laminated film and rolled photographic sensitive material formed by using these films |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE FR GB |
|
17P | Request for examination filed |
Effective date: 19980102 |
|
17Q | First examination report despatched |
Effective date: 19981109 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20011024 |
|
REF | Corresponds to: |
Ref document number: 69616254 Country of ref document: DE Date of ref document: 20011129 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: AGFA-GEVAERT |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20081211 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20081211 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20081210 Year of fee payment: 13 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20091216 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20100831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091216 |