DE60025671T2 - Improved subbed polyester support for imaging elements - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION

The The present invention relates to an improved subbed polyester film and such polyester film as a carrier containing imaging materials.

GENERAL STATE OF THE ART

radiation-sensitive Materials based on silver halide chemistry come in one Variety of applications for use, e.g. in photographic Materials for general amateur and professional black and white photography or color photography, for the recording and printing of materials for the motion picture industry, and Materials for the recording and duplication of medical diagnostic images. Other typical materials are for micrography, non-destructive exam and the graphic pre-press has been developed. At graphic Reproduction processes will be the original halftone image either by an optical means in the case of a camera film or by an electronic means in the case of a photosetter film in one Raster method reproduced by a collection of numerous points. Except camera and imagesetter films, there are also so-called contact films, with which raster images can be reproduced. Various photographic Areas, but especially for the graphic pre-press used films, constantly strive a reduction in manufacturing costs, higher opacity and image sharpness and reduced refill rates at. in principle This purpose can be achieved by lowering the silver ratio and the strength the emulsion layer can be achieved, which implies that both the gelatin to silver halide ratio as the strength of the Auxiliary layers are to be lowered, which in turn is due to the setting of a low gelatin ratio amounts. This tendency to low silver and gelatin ratios but can lead to serious problems, as in the following explained becomes.

graphic Photographic materials are usually applied to a polyester support. The most commonly used polyester carrier in the photographic industry a polyethylene terephthalate carrier. A impeccable adhesion of hydrophilic layers such as photographic light-sensitive Emulsion layers of dimensionally stable Polyester film supports, i.e. biaxially stretched hot melt polyester films, becomes known for a long time by using different ones Interlayers between the support and the photosensitive layer (s) Reached emulsion layer (s). In most cases, there will be two intermediate layers needed. A first, as an adhesive layer or primer layer or resin adhesive layer or latex adhesive layer known intermediate layer has a good adhesion on the polyester film and also waits with good marks regarding the Adhesion to the second, known as "gelatin adhesive layer" layer on. The second layer is mainly made of a hydrophilic one Colloid composed like gelatin. A common terminology usage In the following, the first intermediate layer defined above will be described below as a latex adhesive layer and the second intermediate layer as a gelatin adhesive layer designated.

Usually For example, the gelatin adhesive layer becomes some amount of a spacer added so that the surface of the layer given a certain roughness becomes. Without such spacers are a tedious unwinding of the film and later a tedious Winding the ready-to-use polyester film to be expected. Appropriate spacers have to have a certain minimum average particle size, preferably about 3 microns. In the case of a very thin one However, emulsion layer becomes the tip of the spacer particles the surface pierce the emulsion layer. In exposure and development the emulsion layer becomes any pungent through the layer surface Spacer particles one locally limited interruption of the black density of the developed silver cause. At examination In transmitted light, the so-called "speckle" effect can be seen Lowering the spacer quantity or using a spacer facilitated with lower particle size become. However, such measures will turn the unwinding and certainly complicate winding up. Black densities, apart of black density obtained with developed silver can also by use of dispersed in an adhesive composition and, depending on the particle size, if necessary as a spacer acting Russ, as in US-A 4 731 278. This leaves can be seen from US-A 3,615,557, whose teaching describes that in photographic films with biaxially oriented polyester film supports various Pigments and dyes for various purposes can be used, the carrier as Adhesive substrates for Drawing slides thin Layers of a specific three-component copolymer containing the adhesive properties when adhering to a hydrophobic adhesive polyester surface as a polyethylene terephthalate surface.

Another method of obtaining black densities different from black density obtained with developed silver as a conventional black density source, is to produce colored dye mixtures, for example a mixture of a cyan dye, a magenta dye and a yellow dye, as described in EP-A 0 579 299.

It So there is a need for a solution that allows the speck effect to avoid and at the same time the favorable To obtain properties of the use of the spacer.

TASKS OF PRESENT INVENTION

task The present invention is a polyester carrier without To provide unwinding and winding problems.

A Another object of the present invention is to provide imaging elements, like a photographic material, without specking effect after development provide.

SHORT PRESENTATION THE PRESENT INVENTION

Be solved the ones mentioned above Tasks by a polyester film with a top and bottom, the top in turn (a) a latex adhesive layer and (b) contains a gelatin adhesive layer, characterized at least one of the adhesive layers (a) and (b) has a black, preferably in the gelatin adhesive layer (b) incorporated spacer contains wherein the spacer is made with a mixture of one or more Cyan, magenta and yellow dyes loaded hydrophobic polymeric particles where the dyes are used in such relation to each other will get that black. In a further preferred embodiment is the polyester film on its back with an electric conductive latex adhesive layer (c) and a gelatinous antihalation layer (d) coated.

The polyester film according to the invention can be used advantageously as a support for a diversity of Imaging systems, such as a photographic material, a (photo) thermographic Material and an inkjet ink receiving material, used become. Further advantages and embodiments of the present invention The invention will become apparent from the following description.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The various elements which characterize the present invention, will be explained in detail below.

- black spacer

The essential feature of the present invention is the use a black spacer in one of the adhesive layers, whole particularly preferably in the gelatin adhesive layer (b), wherein the black Spacer composed of hydrophobic polymeric particles or beads is that with a mixture of hydrophobic cyan, magenta and yellow dyes loaded in such relation to each other be that the spacer particles look black.

Methods for suitably combining hydrophobic ingredients such as hydrophobic dyes, whiteners and color couplers with hydrophobic polymeric particles are described, for example, in US Pat. No. 4,230,716, US Pat. No. 4,214,047, US Pat. No. 4,247,627, US Pat. US-P 4,304,769 and GB 1 504 949 described.

• – Auflösen der hydrophoben Verbindung in einem wasserunmischbaren Lösungsmittel,
• – Dispergieren der so erhaltenen Lösung in einem wässrigen Medium,
• – Vermischen der erhaltenen Dispersion mit einer Dispersion hydrophober Teilchen in einem anderen wässrigen Medium,
• – Rühren des so erhaltenen Gemisches, damit sich die hydrophobe Verbindung mit den hydrophoben polymeren Teilchen vermischen kann, und
• – Abdampfen des wasserunmischbaren Lösungsmittels.

A particularly preferred method of use in the present invention is disclosed in U.S. Pat EP 483 416 disclosed. This improved process for preparing aqueous dispersions of hydrophobic polymer particles loaded with at least one hydrophobic compound comprises the following steps:

• Dissolving the hydrophobic compound in a water-immiscible solvent,
• Dispersing the solution thus obtained in an aqueous medium,
• Mixing the resulting dispersion with a dispersion of hydrophobic particles in another aqueous medium,
• - Stirring the mixture thus obtained, so that the hydrophobic compound can mix with the hydrophobic polymeric particles, and
• - Evaporation of the water-immiscible solvent.

In practice, any of the numerous combinations of hydrophobic cyan dyes, Magenta dyes and yellow dyes, provided that the dyes can be combined in an appropriate ratio to obtain the black polymeric particles. In a particularly preferred embodiment, a combination of the following dyes is used:

Magentafarbstoff (m1)

Magenta dye (m1)

Gelbfarbstoff (y1)

Yellow dye (y1)

Cyanfarbstoff (c1)

Cyan dye (c1)

Preferred polymer particles which can be loaded include homopolymers or copolymers of acrylic acid, methacrylic acid and its salts and esters, polystyrene, a copolymer of ethyl acrylate and stearyl methacrylate, a copolymer of methacrylic acid, methyl methacrylate and stearyl methacrylate and those mentioned in the above-mentioned US 4,614,708 and U.S. 4,861,808 described polymers.

In a particularly preferred embodiment is used as loadable spacer poly (methyl methacrylate) (PMMA) used.

- Composition of the Polyester film applied layers (a) to (d)

One An essential component of the latex adhesive layer (a) is an adhesion-promoting Latex. One for This preferred class of latex polymers are carboxyl-containing Vinylidene. Typical examples of such polymers are (1) Copolymers of vinylidene chloride and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, (2) Copolymers of vinylidene chloride and a half ester of an unsaturated one carboxylic acid such as the monomethyl ester of itaconic acid, (3) terpolymers of vinylidene chloride, itaconic and an alkyl acrylate or alkyl methacrylate such as ethyl acrylate or Methyl methacrylate and (4) terpolymers of vinylidene chloride, acrylonitrile or methacrylonitrile and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.

In a most preferred embodiment is the latex polymer a copolymer of vinylidene chloride, methyl acrylate and itaconic acid (88% / 10% / 2%). This copolymer is prepared using 0.5% MERSOLAT H (Trade Mark from Bayer AG) as an emulsifier by emulsion polymerization. To achieve a good shelf life, the latex must additional Surfactant, a so-called Nachstabilisator be added. A excellent storage stability by adding 4% ULTRAVON W, trademark of Ciba-Geigy, achieved.

henceforth can the casting solution of Latex adhesive preferably also colloidal silica as a binder be added. A preferred compound is KIESELSOL 100F (Trademark of Bayer AG) with an average particle size between 25 and 30 nm. The ratio the amount of latex to the amount of silica is preferably about 80/20.

The Dry Film Thickness the latex adhesive layer is preferably between about 0.1 mm.

Of the black spacers may indeed be included in the latex adhesive layer but is particularly preferred in the hereinafter described Gelatin adhesive layer incorporated.

The gelatin adhesive layer (b) is applied to the latex adhesive layer (a). In addition to the spacer, the gelatin adhesive layer (b) preferably contains a mixture of gelatin and colloidal silica. A preferred compound is also KIESELSOL 300F (trademark of Bayer AG). Cracking in the dried layer due to excessive shrinkage of the layer during drying can be prevented by using a softening compound. Plasticizers are well known to those skilled in the art. Substances which can be used for this purpose are low molecular weight compounds (eg acetamide, glycerol) and polymeric latices (eg polyethyl acrylate, poly-n.-butyl acrylate). The gelatin adhesive layer may further contain one or more surfactants. Useful surfactants include ULTRAVON ^™ W, an arylsulfonate from CIBA-GEIGY, and ARKOPAL ^™ N060 (formerly HOSTAPAL ^™ W), a nonylphenylpolyethylene glycol from HOECHST.

The Strength the gelatin adhesive layer is preferably between 0.1 and 1 μm.

In a preferred embodiment For example, the polyester film is also backed by a second latex adhesive layer (c) coated. This latex adhesive layer preferably has a similar one Composition like the latex adhesive layer (a) on top. In a particularly preferred embodiment, this contains Layer but a conductive polymer that makes the layer antistatic power. The nature of this conductive connection will now be described in detail explained.

A such a compound, usually a polymer, can be ion-conducting or be electrically conductive.

Indeed the conductivity remains an ionic conductive Polymer containing antistatic layer even after crosslinking still moisture-related. For this reason, conjugated polymers with electronic conductivity been developed. Substances with electronic conductivity instead of ionic conductivity characterized by a non-moisture-related conductivity and are particularly suitable for use in the production of antistatic Layers with permanent and reproducible conductivity.

Lots the known electronically conductive Polymers are strongly colored, making them less suitable for use in photographic materials, however, certain of them are polyarenemethylidenes, e.g. Polythiophene and polyisothionaphthene, translucent without disturbing Staining, at least if she in thin Layers are embedded. Therefore, polythiophene derivatives are one preferred type of conductive Compounds for use in the present invention.

The Production of conductive Polythiophenes is described in the aforementioned book "Science and Applications of Conducting Polymers ", P. 92, mentioned Production literature described.

For environmental reasons, as far as possible, the application of antistatic layers should be carried out from aqueous solutions and the amount of organic solvents should be limited as much as possible. The preparation of antistatic layers of aqueous casting compositions which are dispersions of polythiophenes in the presence of polyanions is disclosed in U.S. Pat EP 0 440 957 described. Thanks to the presence of the polyanion, the polythiophene compound is kept in dispersion.

Preferably, the polythiophene contains thiophene nuclei substituted with at least one alkoxy group or a -O (CH ₂ CH ₂ O) _n CH ₃ group, where n is a number from 1 to 4, or very particularly preferably thiophene nuclei in which a ring closure via two oxygen atoms is obtained to an optionally substituted alkylene group.

in der R¹ und R² jeweils unabhängig voneinander ein Wasserstoffatom oder eine C_1-4-Alkylgruppe oder zusammen eine gegebenenfalls substituierte C_1-4-Alkylengruppe oder eine Cycloalkylengruppe, vorzugsweise eine Ethylengruppe, eine gegebenenfalls alkylsubstituierte Methylengruppe, eine gegebenenfalls C_1-12-alkyl- oder phenylsubstituierte 1,2-Ethylengruppe, eine 1,3-Propylengruppe oder eine 1,2-Cyclohexylengruppe bedeuten.Preferred polythiophenes for use in the present invention contain structural units corresponding to the following general formula:

R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group or together an optionally substituted C _1-4 alkylene group or a cycloalkylene group, preferably an ethylene group, an optionally alkyl-substituted methylene group, an optionally C _1-12 alkyl- or phenyl-substituted 1,2-ethylene group, a 1,3-propylene group or a 1,2-cyclohexylene group.

All especially preferred is poly (3,4-ethylenedioxythiophene) (PEDT) the following formula:

The preparation of the polythiophene and aqueous dispersions containing polythiophene and polymeric polyanion compounds containing the above polythiophene is mentioned in the above EP 0 440 957 described.

suitable polymeric polyanion compounds needed to form the polythiophenes in dispersion are acid polymers in free acidic or neutralized form. The acid polymers are preferably polymeric sulfonic acids. Examples of such polymeric acids are polymers with vinylsulfonic acid and styrenesulfonic acid or mixtures thereof.

The content of anionic groups in the anionic acidic polymers used in combination with the dispersed polythiophene polymer is preferably more than 2% by weight, based on the polymeric compounds, of imparting sufficient stability to the dispersion. Suitable acid polymers or corresponding salts are described, for example, in DE-A 2 541 230, DE-A 2 541 274, DE-A 2 835 856, EP-A 14 921, EP-A 69 671, EP-A 130 115, US Pat 4,147,550, U.S. Patent 4,388,403 and U.S. Patent 5,006,451.

The weight ratio of the polythiophene polymer to the polymeric polyanion compound (s) vary within wide limits, but preferably lies between about 50/50 and 15/85. An especially preferred polymeric polyanion for use in combination with the polythiophene derivative, e.g. PEDT, is polystyrene sulfonate (PSS).

The Dry Film Thickness the conductive one Latex adhesive layer (c) is preferably about 0.1 mm.

In a further preferred embodiment contains the polyester film also on its back one on the second Adhesive layer (c) applied gelatinous antihalation layer (d). Except contains the antihalation dye the casting composition usually gelatin, a matting agent and surfactants.

The presence of an antihalation dye is advantageous when using the subbed polyester film as a support for a radiation sensitive element. Antihalation dyes improve image sharpness by reducing the upward reflection of light through the support into the emulsion layer. As useful dyes that absorb in the visible spectral range, the in US 2,697,037 mentioned colored pigments, which in US 2 274 782 Pyrazonoloxonolfarbstoffe mentioned in US 3,432,207 styryl dyes and butadienyl dyes mentioned in US 2,956,879 mentioned diarylazo dyes used in US 2,527,583 mentioned merocyanine dyes, which in US 3 486 897 . US Pat. No. 3,652,284 and US 3,718,472 mentioned merocyanine dyes and oxonol dyes and the in US 3,976,661 mentioned Enaminhemioxonolfarbstoffe mentioned. Dyes or triphenylmethane-type dyes absorbing in the red spectral region, some of which have an electron-attracting group, are described in, for example, US Pat GB 769 749 . US 2 282 890 . DE 1 038 395 . FR 2 234 585 , JP-A-59-228250, US 2 252 052 and in A. Guyot, Compt. Rend., Vol. 114 (1970), p. 1120. Certain of the compounds described therein contain one or more water-solubilizing groups.

It may be advantageous to use anti-halation dyes which are non-diffusible under normal coating conditions and become diffusible and / or discolored only under alkaline development conditions. Such dyes can be used as dispersions or so-called microcrystalline solid particles. Such non-diffusible or difficult to diffusible dyes are described in, for example US 4 092 168 . EP 274 723 . EP 276 566 . EP 294 461 . EP 299 435 . GB 1 563 809 . EP 015 601 . U.S. 4,857,446 , JP-A 02-259752, JP-A 02-264247, EP 582 753 and EP 587229 ,

The Selection of the color of the antihalation dye depends on the spectral sensitivity distribution of the radiation-sensitive Elements, for that will serve as substrate for the subbed polyester film. Is this radiation-sensitive element, for example one for the red area sensitized photographic film, e.g. a graphic imagesetter film, so a blue antihalation dye is used.

The Dry Film Thickness the gelatinous Antihalation layer is preferably between 0.5 and 4 microns.

- Production the subbed polyester film

The Layers (a) and (b) and the possible layers (c) and (d) can according to any known coating technique, such as dip coating, Air knife coating, cascade coating, curtain coating and extrusion coating, are applied to the film.

In the most preferred embodiment, in which all four layers (a) to (d) are used these layers "on line "in a continuous coating process applied in the production room of the polyester itself on the film. Molten polyester is extruded and longitudinally drawn. Then be the first latex adhesive layer (a) on top and the second, optionally conductive latex adhesive layer (b) on the back appropriate. Thereafter, the subbed polyester is cross-stretched. The layer (b), de optionally the black spacer contains is placed on top and finally the gelatinous antihalation layer (d) on the backing layer applied.

- Image generation systems, the contain the subbed polyester film as a carrier

(a) Carrier for a photographic material

The most important application of the subbed polyester film according to the invention is their use as a carrier a conventional one photographic silver halide material.

It becomes explicit stated that such a photographic material within the Protection of the present invention falls.

In In this application, the gelatin adhesive layer (b) is coated Polyester film with one or more silver halide emulsion layers and one or more protective layers.

The Halide composition of the silver halide emulsions used in the invention is not specifically limited and may be any composition of the group from e.g. Silver chloride, silver bromide, silver iodide, silver chlorobromide, Silver bromide iodide and silver chlorobromoiodide. In a preferred embodiment is the photographic material but a graphic material, whole particularly preferred is a graphic recording material that by definition is suitable for recording raster images, linework and / or text electronically stored in an imagesetter or scanner is suitable. For graphic Recording materials are preferably used emulsions, the Chloride in the largest amount, preferably between 50 mole% and 95 mole%, most preferably between 60 mol% and 89 mol%, a low amount of iodide and as Residual amount of halide containing bromide.

The Preparation of the photographic emulsion (s) may be soluble Silver salts and soluble Halides can be made by various methods, such as e.g. from P. Glafkidès in "Chimie et Physique Photographique " Paul Montel, Paris (1967), by G.F. Duffin in Photographic Emulsion Chemistry, The Focal Press, London (1966), and V.L. Zelikman et al in Making and Coating Photographic Emulsion, The Focal Press, London (1966). You can by mixing the halide and silver solutions under partial or completely controlled conditions of temperature, ratios, order of addition and rate of addition. The cases of Silver halide can be prepared by the single-jet process, the double-jet process, the conversion process or a variation of these different ones Procedure be made.

The Silver halide emulsions can with various metal salts or metal complexes such as rhodium and iridium dopants be doped.

The Emulsion can be according to the usual Method, e.g. by dialysis, flocculation and redispersion, or ultrafiltration, desalted.

The photosensitive silver halide emulsions are preferably chemically sensitized, as described, for example, in the aforementioned "Chimie et Physique Photographique" by P. Glafkides, in the aforementioned "Photographic Emulsion Chemistry" by GF Duffin, in the aforementioned "Making and Coating Photographic Emulsion" by VL Zelikman et al. and in "The Fundamentals of Photographic Processes with Silver Halides," edited by H. Frieser and published by the "Akademische Verlagsgesellschaft" (1968). As described in this literature, chemical sensitization can be carried out by ripening in the presence of small amounts of sulfur-containing compounds, eg, thiosulfate, thiocyanate, thioureas, sulfites, mercapto compounds, and rhodamines. The emulsions may also be treated with gold-sulfur ripening agents, gold-selenium ripening agents, or with the aid of reducing agents, eg, tin compounds as described in U.S. Pat GB 789 823 , Amines, hydrazine derivatives, formamidine sulfinic acids and silane compounds. Chemical sensitization can also be achieved with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt or Au. One can use one of these chemical sensitization methods or a combination thereof.

The Photosensitive silver halide emulsions can be treated with suitable dyes like that of F.M. Hamer in "The Cyanine Dyes and Related Compounds ", 1964, John Wiley & Sons, described spectrally sensitized become. To the for spectral sensitization suitable dyes include cyanine dyes, Merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, Hemicyanine dyes, styryl dyes and hemioxonol dyes. Among the cyanine dyes, merocyanine dyes and merocyanine complex dyes belonging Dyes are especially valuable.

The used according to the invention Silver halide emulsion (s) may contain compounds prevent the fogging or the photographic properties while the production, storage or photographic processing of photographic material Stabilize elements. Many known compounds can be used as Anti-fog or stabilizer of the silver halide emulsion be added. Suitable examples are in Research Disclosure, Essay 36544, September 1994, Chapter VII.

Furthermore Silver halide is another essential part of a photosensitive emulsion layer, the binder. The binder is a hydrophilic colloid, preferably gelatin. Gelatine can, however partially or wholly by synthetic, semi-synthetic or natural polymers be replaced. Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, Poly-N-vinylpyrrolidone, polyvinylimidazole, polyvinylpyrazole, polyacrylamide, polyacrylic acid and their derivatives, especially their copolymers. Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, Saccharides, starch and alginates. Semisynthetic substitutes for gelatin are usually modified natural Products such as e.g. Gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting polymerizable monomers are obtained on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose and cellulose sulfates.

The curing of the binders of the photographic element, particularly when using gelatin as a binder, can be carried out with suitable curing agents, such as those of the epoxide type, the ethyleneimine type, the vinylsulfone type, such as 1,3-vinylsulfonyl-2-propanol , Chromium salts such as chromium acetate and chromium alum, aldehydes such as formaldehyde, glyoxal and glutaraldehyde, N-methylol compounds such as dimethylolurea and methyloldimethylhydantoin, dioxane derivatives such as 2,3-dihydroxydioxane, active vinyl compounds, eg 1,3,5- Triacryloylhexahydro-s-triazine, active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids such as mucochloric acid and mucophenoxychloric acid. These hardeners can be used alone or in combination. The binders may also be treated with fast curing agents such as carbamoylpyridinium salts of US Pat. No. 4,063,952 be hardened type described.

Further can in the photographic invention Material different types of surfactants and lubricants in the photographic emulsion layer or in another hydrophilic Colloid be included. Suitable surfactants and lubricants are described in Research Disclosure, Essay 36544, September 1994, Chapter IX.

The present invention is particularly useful in photographic materials having a thin emulsion layer, eg, less than 2 microns thick, whereby the spacer in the gelatin adhesive layer pierces the surface of this emulsion layer. A particularly preferred embodiment when using such an emulsion layer is a graphic recording material having the following material properties. The emulsion layer present on the gelatin adhesive layer (b) contains 5 g of a low iodide chloride chloride bromide emulsion per square meter of silver (expressed as AgNO ₃ ) and only about 1 g of gelatin / m ² and about 15% of a polymer latex. A first protective layer contains 0.5 g of gelatin / m ² and 0.5 g of a latex. A second protective layer contains 0.5 g gelatin / m ² . The black spacer, which is a mixture of a cyan, magenta, and yellow dye-laden poly (methyl methacrylate) beads, prevents the occurrence of the "streaking" effect after development The black latex adhesive layer is conductive and the gelatinous Antihalation layer contains a blue dye, and more details can be found in the examples below.

(b) support for a (photo) thermographic Material.

One thermosensitive Contains element a substantially light-insensitive silver salt of an organic Carboxylic acid, a reducing agent for it in a thermally effective relationship thereto and a binder. Under "thermal effective relationship " that the reducing agent be so present during the heat development must that it is the particles of the essentially light-insensitive Silver salt of an organic carboxylic acid can diffuse to to effect their reduction. A heat-sensitive element becomes heated by a thermal head.

Contains the heat-sensitive Element further comprises a radiation-sensitive silver halide in catalytic Quantities, the thermographic recording material is a photothermographic Material ("Dry Silver") by irradiation is developed.

Preferred substantially light-insensitive silver salts of an organic carboxylic acid are silver salts of aliphatic carboxylic acids known as fatty acids, in which the aliphatic carbon chain is present preferably contains at least 12 carbon atoms, for example silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, these silver salts are also referred to as "silver soaps". Other silver salts of an organic carboxylic acid as described in GB-P 1 439 478, for example silver benzoate, are also suitable for the preparation of a heat-developable silver image. Combinations of various silver salts of an organic carboxylic acid are also suitable for use in the present invention.

preferred Water-dispersible binders are water-dispersible film-forming Polymers with covalently bonded ionic groups from the group consisting of sulphonate, sulphinate, carboxylate, phosphate, quaternary ammonium groups, tertiary Sulfonium groups and quaternary Phosphonium. Further preferred water-dispersible binders are water-dispersible film-forming polymers with covalently bonded Proportions with one or more acid groups.

The mentioned above Binders or mixtures thereof may be used in combination with waxes or "thermal Solvents ", also referred to as" thermal solvents ", the the reaction rate of the redox reaction at elevated temperature increase, be used.

Suitable organic reducing agents are organic compounds which contain at least one active hydrogen bonded to O, N or C, as is the case with aromatic di- and trihydroxy compounds, aminophenols, METOL ^™ , p-phenylenediamines, alkoxynaphthols, eg 4-methoxy- 1-naphthol, as described in US-P 3,094,41, pyrazolidin-3-one-type reducing agents, for example PHENIDONE ^™ , pyrazolin-5-ones, indane-1,3-dione derivatives, hydroxytetronic acids, hydroxytetronimides, hydroxylamine Derivatives, for example as described in US Pat. No. 4,082,901, hydrazine derivatives and reductones, eg ascorbic acid. It should also be noted that U.S. Patent Nos. 3,074,809, 3,080,254, 3,094,417 and 3,887,378.

Preference is given to reducing agents of the catechol type, ie reducing agents which contain at least one benzene ring with two hydroxyl groups (-OH groups) in the ortho position, such as catechol, 3- (3 ', 4'-dihydroxyphenyl) -propionic acid, 1,2 Dihydroxybenzoic acid, gallic acid, gallic acid esters, eg methyl gallate, ethyl gallate and propyl gallate, tannic acid and 3,4-dihydroxybenzoic acid ester. Particularly preferred reducing agents of the catechol type are disclosed in EP 692,733 and in EP 903 625 described. Other suitable reducing agents are sterically hindered phenols, bisphenols and sulfonamidophenols.

It can also combinations of reducing agents are used, which when heated to participants in the reduction reaction of the essential light-insensitive silver salt of an organic carboxylic acid. Examples are combinations of sterically hindered phenols with Sulfonyl-reducing agents, as described in U.S. Pat. No. 5,464,738, trityl hydrazides and formylphenyl hydrazides, as described in U.S. Pat. No. 5,496,695, trityl hydrazides and formylphenyl hydrazides with various auxiliary reducing agents as described in US-P 5,545,505, U.S. Patent 5,545,507 and U.S. Patent 5,558,983, acrylonitrile compounds, such as described in US Pat. No. 5,545,515 and US Pat. No. 5,635,339, and 2-substituted Malondialdehyde compounds as described in US Pat. No. 5,654,130.

The (photo) thermographic materials may also contain toning agents, Stabilizers, pigments, optical brighteners and surfactants.

It is again to note that the use of the predetermined polyester support according to the invention particularly then advantageous if the heat-sensitive (radiation sensitive) layer a thin layer with a maximum thickness of 2 μm.

(c) Carrier for an ink jet material

inkjet receiving recording materials include a support and an ink-receiving layer. The latter layer contains in the Usually a binder, a pigment, preferably a porous filler and optionally other ingredients such as surfactants, polymeric latices, Plasticizers and mordants that maintain the color of the ink.

Typical binders well known to those skilled in the art include hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, methylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose, water-soluble ethylhydroxyethylcellulose, cellulose sulfate, polyvinyl alcohol, vinyl alcohol copolymers, polyvinyl acetate, polyvinyl acetal, polyvinylpyrrolidone, polyacrylamide, acrylamide / acrylic acid copolymer, stryol / acrylic acid copolymer, Ethylene / vinyl acetate copolymer, vinylmethyl ether / maleic acid copolymer, poly (2-acrylamide-2-methylpropanesulfonic acid), poly (diethylenetriamine-co-adipic acid), polyvinylpyridine, polyvinylimidazole, quaternized polyimidazoline, epichlorohydrin-modified polyethylenimine, ethoxylated polyethylenimine, poly ( N, N-dimethyl-3,5-dimethylene piperidinium chloride), polyethylene oxide, polyurethane, melamine resins, gelatin, carrageenan, dextran, gum arabic, casein, pectin, albumin, starch, collagen derivatives, collodion and agar-agar.

The pigment contained in the ink-receiving layer may be organic Material such as polystyrene, polymethyl methacrylate, silicones, urea-formaldehyde condensation polymers, Be polyester and polyamides. However, an inorganic is preferred porous pigment, like silicic acid, Talc, clay, kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, Aluminum hydroxide, alumina, titania, zinc oxide, barium sulfate, Calcium sulfate, zinc sulfide, satin white, boehmite and pseudo-boehmite.

ink compositions for inkjet printing contain the following ingredients: dyes or pigments, Water and / or organic solvents, Humidifiers such as glycols, detergents, thickeners, polymers Binders, preservatives, etc.

Of the Ink jet printing process can be done by various methods become. In a first process type, the generation of a continuous droplet flow according to a pressure wave pattern. This method is known as a high pressure process. In a first embodiment, the droplet stream becomes in droplets, electrostatically charged, deflected and collected again, and in droplets, remain uncharged, continue to fly in a straight line and create the image, dissolved. In another embodiment The charged deflected droplet stream forms the picture and becomes the uncharged, undeflected stream of droplets collected again. In this variant of high-pressure ink jet method are various Distracted beams at different angles and draw like that the picture on (multiple deflection system).

To a second method the ink droplets are generated "on demand" ("DOD" method or "drop on demand" method), wherein the printing device the droplets only emits when she to serve for imaging on a printing ink receiving material. This adds complexity charging the drops, distracting hardware and resampling the ink avoided. Drop-on-demand can be ink drop generation by a mechanical movement of a piezoelectric Transducer generated pressure wave (the so-called piezoelectric method) or by discrete heat shocks (the so-called "bubble Jet "method or" Thermal Jet "method) become.

Again It should be noted that the use of the substrate according to the invention polyester carrier is particularly advantageous when using a thin ink receiving layer and when printing monochrome black images, e.g. during recording medical diagnostic images by inkjet printing.

EXAMPLES - Preparation a black spacer

4.5 g cyan dye c1, 7.5 g magenta dye ml and 4.5 g yellow dye y1 are dissolved together in 165 ml of ethyl acetate. This solution is stirred for 5 minutes at 1,200 ppm in an aqueous Medium dispersed, the 390 ml of water and 37.5 ml of a 10% solution ANTAROX 880 surfactant, a GAF Co. trademark for a non-ionic Nonylphenyloxypenta (ethyleneoxy) surfactant. The dispersion thus obtained is 1 h with 412.5 g of poly (methyl methacrylate) beads having an average particle size of about Stirred 3 microns. Subsequently, will the ethyl acetate evaporated and the dispersion to a final weight brought from 825 g. 100 g of this dispersion contain 2 g of dye mixture and 10 g of pearls.

- Preparation of a polyethylene terephthalate film with their different adhesive layers and antihalation layers.

in the Hall where the polyethylene terephthalate (PET) film produced molten PET is extruded and longitudinally drawn. Then the PET film in a first coating system with a first latex adhesive layer coated.

After drying of this first adhesive layer, the back of the film is coated with a second adhesive layer. After drying of this second adhesive layer, the double-sided coated film backing is cross-stretched. The thickness of the biaxially stretched film backing thus obtained is 100 μm. The first adhesive layer contains 162 mg / m ^{2 of} the terpolymer of vinylidene chloride, methyl acrylate and itaconic acid (88/10% / 2%) and 40 mg / m ² colloidal silica (specific surface area 100 m ² / g). The second adhesive layer contains 180 mg / m ^{2 of} the terpolymer of vinylidene chloride, methyl acrylate and itaconic acid (88% / 10% / 2%), 20 mg / m ² colloidal silica (specific surface area 100 m ² / g) and 3.15 mg / m ^{2 of} one poly (3,4-ethylenedioxythiophene) / poly (styrene sulphonate) complex. Thereafter, the top of the PET film is coated with a gelatin adhesive layer. The casting solution of this layer contains water, gelatin, KIESELSOL 300F (trademark of Bayer AG), the conventional surfactants ULTRAVON W (trademark of Ciba-Geigy) and ARKOPAL N060 (trademark of Hoechst AG) and the organic solvents hexylene glycol and trimethylolpropane.

In the example of the present invention, the gelatin adhesive layer casting composition further contains the black substance prepared as described above. The final layer contains 1 mg / m ² loaded black PMMA particles.

at in a similar way A manner prepared comparative examples is not one with Dyes laden poly (methyl methacrylate) Abstandshalter or no spacer at all used (see Table 1).

Then is the electrically conductive, applied to the back of the PET film Latex adhesive layer on top with a gelatinous antihalation layer coated. The casting composition this gelatinous Antihalation layer contains Water, gelatin, poly (methyl methacrylate) spacer particles with a mean particle size of 5.9 microns, surfactants and a blue dye of the following formula:

The coating composition contains further, a divinyl sulfone hardener.

- Production a photographic emulsion

In an aqueous sodium chloride-containing gelatin solution (16.7 g gelatin / mol silver) an aqueous silver nitrate solution and an aqueous potassium bromide, sodium chloride, 2.3 × 10 ^-7 mol of Na by double jet ₃ RhCl _{6 /} / mole of silver and 3, 0 × 10 ^-7 mol of Na ₂ IrCl ₆ / mol of silver halide solution stirred. By physical ripening, silver chloride bromide grains having an average particle size of 0.27 μm (coefficient of variation: 19%) and a chloride content of 64 mol% are obtained. After physical ripening of the emulsion, KI is added to stop crystal growth.

D-1 Subsequently, the emulsion is washed according to a conventional flocculation method and then redispersed with 6.67 g of gelatin / mole of silver. The emulsion thus obtained is adjusted to a pH of 5.3 and then chemically sensitized with gold / sulfur at 50 ° C by a 3-hour post-maturation. The emulsion is stabilized with 8.4.times.10.sup.- ³ mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene / mol of silver and with dye D-1 according to the following formula in an amount of 4.0 × 10 ^-4 mol / mol of silver spectrally sensitized

D-1

The thus obtained emulsion has a gelatin / silver ratio of 0.21 on.

- Production photographic materials

A Emulsion layer, an intermediate layer and a protective layer each simultaneously in a three-layer arrangement on layer (b) applied to the various substrated polyethylene terephthalate film supports.

The emulsion layer is applied in a silver ratio of 3.23 g silver / m ² . The top of this layer is then coated with an intermediate layer containing 0.5 g of gelatin / m ² and 0.5 g of latex / m ² (Co [BuMA-AMPS (Na)]) and also stabilizers.

The top of this intermediate layer is coated with a protective layer containing 0.5 g of gelatin / m ² , a hardener, casting additives and a poly (methyl methacrylate) matte. After this coating process, the film samples are dried.

- Exposure and photographic development

Each pattern is exposed behind a step wedge and a filter with a maximum transmission at 622 nm with a xenon flash tube (light emission time: 10 ^-5 s.) And then developed for 15 s at 35 ° C with developer A (with the composition below).

Thereafter, each sample is sequentially fixed in a conventional ammonium thiosulfate-containing fixing bath and finally washed and dried. Development takes place in a Rapiline 66T3 processor (trademark of Agfa-Gevaert NV). Composition of developer A water 800 ml potassium carbonate 29.5 g potassium 34.1 potassium 2.4 diethylene glycol 14 ml hydroquinone 17 Natriumerythrobat 2.5 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0,275 methylbenzotriazole 0.06 Water to fill up 1 l Sodium hydroxide for adjusting the pH on 10.5

- Evaluation of the speckle effect and the maximum density (Dmax)

The speckle effect is evaluated microscopically at a magnification of 200 according to an arbitrarily set qualitative cipher scale. 0 means optimal and 5 means not allowed. Dmax is measured with a Macbeth TD904 densitometer. The hiding power of silver is calculated according to the following formula: Opacity = Dmax / silver application ratio (in g silver / m 2 )

The Data obtained with the samples are listed in Table 1.

TABLE 1

The inventive pattern clearly represents a significant improvement in the Daping effects prove. When using the black PMMA will have the same excellent degree of speckle effect as in the absence achieved this PMMAs. Also, the opacity increases to the same Value as for the carrier containing no PMMA. In summary can be say that using the black spacer the same quality as is achieved in the absence of this spacer. Indeed but becomes in the case of a carrier containing no spacer a received too low carrier roughness and the polyester carrier can not at high coating speeds in the manufacturing facility be handled.

To the detailed description of preferred embodiments of the present invention Invention is likely It should be clear to the experts in this field that here within as defined in the following claims Scope of the present invention numerous modifications possible are.

Claims (13)

A polyester film having a top side and a bottom side, the top side comprising (a) a latex adhesive layer and (b) a gelatin adhesive layer, characterized in that at least one of the adhesive layers (a) and (b) contains a black spacer, the spacer is hydrophobic polymeric particles loaded with a mixture of hydrophobic cyan dyes, magenta dyes and yellow dyes, the dyes being used in such proper proportion to each other that a black spacer is obtained. Polyester film according to claim 1, characterized in that the mixture of dyes contains the following dyes:

(Cyan)

(Magenta dye)

(Yellow dye) Polyester film according to claim 1 or 2, characterized the hydrophobic polymeric particles are poly (methyl methacrylate) beads. Polyester film according to one of claims 1 to 3, characterized in that the black spacer only contained in the gelatin adhesive layer (b). Polyester film according to one of claims 1 to 4, further on its back an electrically conductive latex adhesive layer (c). Polyester film according to claim 5, characterized in that that the electrically conductive latex adhesive layer poly- (3,4-ethylenedioxythiophene) and poly (styrenesulfonate) as an electroconductive complex. A polyester film according to claim 5 or 6, which further on the electrically conductive latex adhesive layer (c) an antihalation dye containing gelatin adhesive layer (d). Polyester film according to one of claims 1 to 7, characterized in that the polyester film is a polyethylene terephthalate film is. A photographic material with a carrier and at least one silver halide emulsion layer, wherein the support has a as in any of the claims 1 to 8 defined polyester film is. A photographic material according to claim 9, characterized characterized in that the dry film thickness of the silver halide emulsion layer at the most 2 μm. A thermographic recording material having a support and a heat-sensitive layer containing an organic silver salt, a binder and a reducing agent in a thermally effective relationship thereto, wherein the support is a polyester film as defined in any one of claims 1 to 8. A photothermographic recording material with a carrier and a radiation-sensitive heat-sensitive layer, the Silver halide, an organic silver salt, a binder and a reducing agent in a thermally effective relationship therewith, wherein the carrier one as in any of the claims 1 to 8 defined polyester film is. An inkjet ink receiving recording material with a carrier and an ink-receiving layer, wherein the support has a as in any of the claims 1 to 8 defined polyester film is.