JP2002128925A - Improved and primed polyester substrate for image- forming element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester substrate having no problem with regard to winding and unwinding, and to provide an image-forming element such as, for example, a photographic material causing no starry night effect after a treatment of the polyester substrate. SOLUTION: A polyester film comprises a latex undercoat at the upper side and a black spacing agent-containing gelatin undercoat. The resulting polyester film is possible to usefully use as the substrate for some image-forming elements, for example, the photographic material, (photo)thermographic material, and an ink jet recording element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to improved subbed polyester films and imaging materials having such polyesters as a support.

[0002]

BACKGROUND OF THE INVENTION Photosensitive materials based on silver halide chemistry are used in many applications, such as black and white or color photographic materials for general amateur and professional photography, recording and printing materials for the motion picture industry, and medical diagnostics. Used in materials for image recording and copying. Other specialty materials have been developed for micrographs, non-destructive testing and graphic arts prepress. In the graphic arts reproduction method, the original image, which appears to have a continuous color gradation, is reproduced in the screening method either by optical means in the case of camera film or electronic means in the case of recorder film by the accumulation of a large number of dots. You. Apart from camera and recorder films, there are also so-called contact films that can reproduce the screened image. In some photographic areas, especially graphic arts prepress films (graphic ar
In ts prepress films, there is always a demand for lower production costs, higher covering power, sharper images, and reduced refill rates. This in principle reduces the silver coverage and thickness of the emulsion layer, which implies a low gelatin / silver halide ratio, and by reducing the thickness of the auxiliary layer, which also implies a low gelatin coverage. Can be achieved. However, this trend to low silver and gelatin coverage can lead to major problems as described below.

Conventionally, graphic arts photographic materials are coated on a polyester support. The most widely used polyester support in the photographic industry is polyethylene terephthalate. To ensure complete adhesion of a hydrophilic layer, such as a photographic emulsion layer, to a dimensionally stable polyester film support, i.e., a biaxially stretched and heat cured polyester film,
It has long been known to provide several interlayers between a support and one or more light-sensitive emulsion layers. In most cases, two intermediate layers are required. The first, known as an adhesive or primer layer or a resin subbing layer or a latex subbing layer, exhibits good adhesion to polyester films and at the same time generally forms a majority of hydrophilic colloids such as, for example, gelatin. It also has good adhesion properties to a second layer known as a "gelatin underlayer" or "gelatin underlayer" or "gel underlayer". For consistency, we refer to the first interlayer as defined above as a latex subbing layer and the second interlayer as a gelatin subbing layer.

[0004] A certain amount of a spacing agent, also called a matting agent, is present in the gelatin subbing layer.
Is generally added to give the surface some roughness. In the absence of such a spacing agent, poor winding and unwinding of the finished polyester would be expected. To be effective, such spacing agents must exhibit some minimum average particle size, preferably about 3 μm. However, if a very thin emulsion layer is used, the top of the spacing agent grains will penetrate the surface of the emulsion layer. If the emulsion layer is exposed and developed, each spacing grain penetration will locally interfere with the black density of the developed silver. When inspecting by light at transmission, this is the so-called "starry night (s
tarry night) effect. This problem can be alleviated by choosing a lower or less spacing agent. However, in that case one would expect the problems with winding and rewinding to be exacerbated. Thus, there is a need for a retained solution that avoids the starry night effect but has the beneficial properties of a spacing agent.

[0005]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a polyester support free of winding and unwinding problems.

It is another object of the present invention to provide an imaging element, such as a photographic material, which is free of starry night effects after processing.

[0007]

SUMMARY OF THE INVENTION The above object has an upper side and a back side,
(A) Latex subbing layer, (b)
This is achieved by providing a polyester film having a gelatin undercoat layer, wherein at least one of the undercoat layers (a) and (b) comprises a black spacing agent. Preferably, a black spacing agent is added in the gelatin subbing layer (b).

In a preferred embodiment, the spacing agent comprises hydrophobic polymer particles filled with one or more mixtures of cyan, magenta and yellow dyes in a relative ratio such that a black color is obtained. In another preferred embodiment, the polyester film has a conductive latex subbing layer (c) and a gelatinous antihalation layer (d) on its backside.

The polyester film according to the present invention can preferably serve as a support for some imaging systems such as photographic materials, (photo) thermographic materials, and ink jet recording materials. Other advantages and embodiments of the present invention will become apparent from the description below.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The various elements making up the present invention will now be described in detail. -Black spacing agent It is the essence of the invention that one of the subbing layers, most preferably the gelatin subbing layer (b), contains a black spacing agent.

In the most preferred embodiment, the black spacing agent comprises hydrophobic polymer particles or beads filled with a mixture of cyan, magenta and yellow hydrophobic dyes in a relative proportion such that the spacing particles appear black.

A hydrophobic component such as a hydrophobic dye, a whitening agent,
And a method for bonding a color coupler with a hydrophobic polymer particle is described in, for example, US Pat. No. 4,230,716, 4,21.
4,047, 4,247,627, 4,304,769 and GB1504949.

A particularly preferred method for use in the present invention is disclosed in EP 483416. This improved method for preparing an aqueous dispersion of hydrophobic polymer particles filled with at least one hydrophobic compound comprises the following steps:-converting the hydrophobic compound into a water-immiscible organic Dissolved in a solvent;-dispersing the resulting solution in an aqueous medium;-mixing the resulting dispersion with a dispersion of the hydrophobic particles in another aqueous medium;-stirring the resulting mixture to produce the hydrophobic compound. Is combined with the hydrophobic polymer particles, and-the water-immiscible solvent is removed by evaporation.

In practice, any of a number of combinations of hydrophobic cyan, magenta and yellow dyes can be used as long as they can be combined in any suitable ratio such that the polymer particles are black. In a particularly preferred embodiment, the following dye combinations are used:

[0015]

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[0016]

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[0017]

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Preferred fillable polymer particles are homopolymers or copolymers of acrylic acid, methacrylic acid, and their salts and esters, polystyrene, copoly (ethyl acrylate / stearyl methacrylate), copoly (methacrylic). Acid / methyl methacrylate / stearyl methacrylate), and the polymers described in US Pat. Nos. 4,614,708 and 4,861,808 above.

In the most preferred embodiment, poly (methyl methacrylate) (PMMA) is used as a fillable spacing agent. -Layer (a) coated on polyester
(D) Composition The essential component of the latex undercoat layer (a) is an adhesion promoting latex. A preferred type of latex polymer for this purpose is a vinylidene chloride-containing copolymer having a carboxyl functionality. Examples of such polymers are
(1) a copolymer of vinylidene chloride and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid; (2) a copolymer of a half ester of vinylidene chloride and an unsaturated carboxylic acid such as a monomethyl ester of itaconic acid;
Terpolymers of vinylidene chloride, itaconic acid and alkyl acrylate or alkyl methacrylate, for example ethyl acrylate or methyl methacrylate, and (4) vinylidene chloride, acrylonitrile or methacrylonitrile and unsaturated carboxylic acids, for example acrylic acid or It is a terpolymer of methacrylic acid.

In the most preferred embodiment, the latex polymer is co (vinylidene chloride-methyl acrylate-itaconic acid: 88% / 10% / 2%). This copolymer was used as an emulsifier in 0.5% MERSOLAT H (Bayer A).
G (trademark). It is necessary to add an additional surfactant, a so-called post-stabilizer, to the latex to ensure good stability on storage. Excellent storage stability is obtained when 4% Ciba-Geigy trademark ULTRAVON W is used.

As another preferred component of the coating solution for the latex subbing layer, colloidal silica can be added as a binder. A preferred compound is KIESELSOL 100F having an average particle size of 25-30 nm.
(Trademark of Bayer AG). The ratio of the amount of latex to silica is preferably about 80/20.

The dry thickness of the latex subbing layer is preferably about 0.1 mm.

The latex subbing layer can contain a black spacing agent, but more preferably this agent is incorporated into the gelatin subbing layer described below.

The gelatin subbing layer (b) is coated on top of the latex subbing layer (a). Apart from the spacing agent, the gelatin subbing layer (b) preferably contains a mixture of gelatin and colloidal silica. The preferred compound is again Kieselsol 300F (Bayer AG
Trademark). Plasticizing compounds can be used to avoid cracking in the dried layer due to excessive shrinkage of the layer during drying. Plasticizers are known in the art. Low molecular weight compounds (eg, acetamide, glycerin) as well as polymeric latex (eg, polyethyl acrylate, poly-n-butyl acrylate) can be used for this purpose. In addition, the gelatin subbing layer may contain one or more surfactants. Useful surfactants are sulfonic acid aryl from CIBA-GEIGY Ultra von ^TM W, nonylphenyl polyethylene from HOECHST - glycolic Arukoparu (ARKOPAL) ^TM N060 (formerly Hosutaparu (hostap
AL) ^TM W).

The thickness of the gelatin subbing layer is preferably 0.5.
It is between 1 and 1 μm.

In a preferred embodiment, the polyester film further has a second latex subbing layer (c) on its back side. This latex subbing layer preferably has the same composition as the upper latex subbing layer (a). However, in a particularly preferred embodiment, the layer further contains a conductive polymer to render the layer antistatic. The properties of this conductive compound will be described in detail below.

Such compounds, generally polymers, can exhibit ionic or electronic conductivity.

However, the conductivity of the antistatic layer containing the ion-conductive polymer is water-dependent even after cross-linking. Accordingly, electron conductive conjugated polymers have been developed. A substance having electronic conductivity instead of ionic conductivity has a conductivity independent of moisture. They are particularly suitable for use in the manufacture of antistatic layers having permanent and reproducible conductivity.

Many of the known electron-conducting polymers are not well suited for use in photographic materials because of their strong coloration, but some of them of the group of polyarenemethylidenes, such as polythiophenes and polyisophenes Tianaphthenic acid is not prohibitively colored and is transparent, at least when coated in a thin layer. As a result, polythiophene derivatives are a preferred type of conductive compound for use in the present invention.

The preparation of conductive polythiophenes is described in the manufacturing literature cited in the above book: "Science and Applications o.
f Conducting Polymers ", p. 92.

For morphological reasons, coating of the antistatic layer should be carried out, where possible, by using as little organic solvent as possible from the aqueous solution. The preparation of antistatic coatings from aqueous coating compositions which are dispersions of polythiophenes in the presence of polyanions is described in EP 0 440 957. Due to the presence of the polyanion, the polythiophene compound is kept in the dispersion.

Preferably, the polythiophene has at least one alkoxy group or —O (CH ₂ CH ₂ O) _n C
H ₃ group [wherein, n is 1-4] thiophene nuclei substituted with or, most preferably, is closed by an alkylene group includes two form substituted on an oxygen atom alkylene group With a thiophene nucleus.

Preferred polythiophenes for use according to the invention have the general formula:

[0034]

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Wherein each of R ¹ and R ² independently represents hydrogen or a C _1-4 alkyl group or, together with an optionally substituted C _1-4 alkylene group or a cycloalkyl group; Alkylene group, preferably ethylene group, optionally alkyl-substituted methylene group, optionally C _1-12 alkyl- or phenyl-optionally substituted 1,2-ethylene group, 1,3-propylene Or a 1,2-cyclohexylene group].

The most preferred compounds have the formula:

[0037]

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Poly (3,4-ethylenedioxy-thiophene), (PEDT).

The preparation of the polythiophene and the aqueous polythiophene-polymeric polyanion dispersion containing the polythiophene is described in EP 0 440 957 cited above.
It is described in.

Suitable polymeric polyanion compounds required to keep the polythiophenes in dispersion are provided by the free acid or neutralized form of the acidic polymer. The acidic polymer is preferably a polymeric sulfonic acid. Examples of such polymeric acids are polymers containing vinyl sulfonic acid and styrene sulfonic acid or mixtures thereof.

In order to ensure sufficient stability of the dispersion, the anionic acidic polymer used together with the dispersed polythiophene polymer preferably has more than 2% by weight of anionic groups with respect to the polymer compound. Having a content of
Suitable acidic polymers or corresponding salts are, for example, DE
-A-25 41 230, DE-A-25 41 27
4, DE-A-28 35 856, EP-A-149
21, EP-A-69 671, EP-A-130 11
5, US-P4,147,550, US-P4,388,4
03 and US-P 5,006,451.

The weight ratio of polythiophene polymer to one or more polymeric polyanion compounds may be, for example, about 5
0/50 to 15/85 can be widely changed.

The most preferred polymeric polyanion for use in combination with a polythiophene derivative, such as PEDT, is polystyrene sulfonate (PSS).

The conductive latex subbing layer (c) preferably has a dry thickness of about 0.1 mm.

In another preferred embodiment, the polyester film further comprises a gelatinous antihalation layer (d) coated on top of the second subbing layer (c) on the back side of the film. Apart from anti-halation dyes,
Coating compositions typically contain gelatin, a matting agent, and a surfactant.

The presence of an antihalation dye is advantageous when the subbed polyester film is used as a support for a photosensitive element. Anti-halation dyes
Improving image sharpness by reducing the upward reflection of light into the emulsion layer by the support. Useful dyes that are absorptive in the visible spectral region include colored pigments of US 2,697,037, pyrazolonol oxonol dyes of US 2,274,782, styryl and butadienyl dyes of US 3,432,207, US 2 , 956,879 diarylazo dyes, US 2,527,583 merocyanine dyes, US
3,486,897, US 3,652,284 and US
3,718,472 merocyanine and oxonol dyes and US 3,976,661 enaminohemioxonol dyes. Dyes, some of which have an electron-withdrawing group, are absorbing in the red spectral region of the di- or triphenylmethane type, for example, GB769949,
US 2,282,890, DE 1038395, FR2,
234,585, JP-A59-228250, US2,
252,052 and A. Guyot, Compt. Rend., Vol 114
(1970), p.1120. Some of the disclosed compounds contain one or more water-soluble groups.

It may be advantageous for the antihalation dye to be non-diffusible under normal coating conditions and to become diffusible and / or discolor only under alkaline processing conditions. Such dyes can be added in dispersion or in the form of so-called microcrystalline solid particles. Non-diffusible or non-diffusible dyes of this type are described, for example, in US Pat.
4,092,168, EP274723, EP27656
6, EP294461, EP299435, GB156
3809, EP015601, US4,857,446,
JP-A02-259752, JP-A02-2642
47, EP582753 and EP587229.

The color of the antihalation dye will be chosen in relation to the spectral sensitivity distribution of the photosensitive element for which the subbed polyester film will serve as a support. For example, if the photosensitive element is a red sensitized photographic film, such as a graphic arts recorder film, then a blue antihalation dye would be added.

The dry thickness of the gelatinous antihalation layer is preferably between 0.5 and 4 μm. Preparation of primed polyester films Layers (a) and (b), and optionally layers (c) and (d), are formed by known coating techniques, such as dip coating, air knife coating, slide hopper coating, and curtains It can be coated by any of the coatings.

In a particularly preferred embodiment in which all four layers (a) to (d) are present, these layers are coated in a continuous "on-line" manner in the production array of the polyester itself. The molten polyester is extruded and stretched in the machine direction. Next, a first latex subbing layer (a) is applied on the top side and a second latex subbing layer (c), which may optionally be conductive, is applied on the backside. The primed polyester is then stretched in the transverse direction. A layer (b), which may optionally contain a black spacing agent, is applied on top, and finally a gelatinous antihalation layer (d) is applied on the back. -Imaging system with primed polyester as support (a) Support for photographic materials The most important use of the primed polyesters according to the invention is as a support for photographic materials of conventional silver halide photographic materials. is there.

It is expressly contemplated that such photographic materials fall within the scope of the present invention.

In this application, one or more silver halide emulsion layers and one or more anti-scratch layers are coated on top of a polyester gelatin subbing layer (b).

The halide composition of the silver halide emulsion used according to the present invention is not particularly limited and includes, for example, silver chloride,
Any composition selected from silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide may be used. However, in a preferred embodiment, the photographic material is a graphic arts material, most preferably a graphic arts recording material, which by definition is used for recording screened images, line drawings and text stored electronically in an image-setter or scanner. Suitable. The graphic arts recording material is preferably
A majority, preferably between 50 mol% and 95 mol%,
Most preferably, use is made of an emulsion containing between 60 mol% and 89 mol% of chloride and a small amount of iodide, the remaining halide being bromide.

One or more photographic emulsions can be obtained from soluble silver salts and soluble halides, for example, by P. Glafkides in "Chimie et Physique Photographique", Paul Mon.
"Photograp" by GF Duffin in tel, Paris (1967)
hic Emulsion Chemistry ", The Focal Press, London (1
966), and by VL Zelikman et al "Making
and Coating Photographic Emulsion ", The Focal Pre
ss, London (1966). They can be made by mixing the halide and silver solutions under partially or completely controlled conditions of temperature, concentration, order of addition, and rate of addition. Silver halide can be precipitated according to the single-jet, double-jet, conversion or alternation of these various methods.

Various metal salts or complexes, such as rhodium and iridium additives, can be incorporated into the silver halide emulsion.

The emulsion is prepared in the usual way, for example by dialysis.
Desalting can be by flocculation and redispersion or by ultrafiltration.

The photosensitive silver halide emulsion preferably comprises
For example, see "Chimie et PhysiquePhotographique" above, P
by P. Glafkides in aul Montel, Paris (1967)
"Photographic Emulsion Chemistry" above, The Foca
l "Making and Coating Photographic Emulsion", GF Duffin, Press, London (1966)
VL Zelikman et al in Focal Press, London (1966)
And edited by H. Frieser and Ak
"Die Grundlagen der Photographischen Prozesse, published by ademische Verlagsgesellschaft (1968)
sensitized chemically as described in "Mit Silberhalogeniden". As described therein,
Chemical sensitization can be carried out by aging in the presence of small amounts of sulfur-containing compounds, such as thiosulfates, thiocyanates, thioureas, sulfites, mercapto compounds, and rhodamines. The emulsion may be prepared with a gold-sulfur ripener, a gold-selenium ripener or a reducing agent such as GB
789,823, tin compounds, amines,
Hydrazine derivatives, formamidine-sulfinic acids,
And sensitization with a silane compound. Chemical sensitization is performed with small amounts of Ir, Rh, Ru, Pb, Cd, H
It can also be performed using g, Tl, Pd, Pt, or Au. One or a combination of these chemical sensitization methods can be used.

The photosensitive silver halide emulsion is, for example, FM
"The Cyanine Dyes and Related Compoun by Hamer
ds ", 1964, John Wiley & Sons. Spectral sensitization with suitable dyes. Dyes which can be used for spectral sensitization purposes include cyanine dyes,
Includes merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

One or more silver halide emulsions for use in accordance with the present invention contain compounds which prevent fogging or stabilize photographic properties during the manufacture or storage of the photographic element or during its photographic processing. Can comprise. Many known compounds can be added to a silver halide emulsion as fog-inhibitors or stabilizers. A good example is Research Disclosure Item 36544, September
1994, Chapter VII.

In addition to silver halide, another essential component of the photosensitive emulsion layer is a binder. The binder is a hydrophilic colloid,
Preferred is gelatin. However, gelatin can be partially or totally replaced by synthetic, semi-synthetic, or natural polymers. Synthetic alternatives to gelatin are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyvinylimidazole, polyvinylpyrazole,
Polyacrylamide, polyacrylic acid, and their derivatives, especially their copolymers. Natural substitutes for gelatin are, for example, other proteins such as zein, albumin and casein, cellulose, sugars, starch, and alginates. Generally, semi-synthetic alternatives to gelatin are obtained by conversion of gelatin using modified natural products, such as alkylating or acylating agents, or by grafting polymerizable monomers onto gelatin. Gelatin derivatives and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulfates.

The binder of the photographic element may be any suitable hardener, for example of the epoxide type, of the ethyleneimine type, especially if the binder used is gelatin.
Of vinylsulfone type, for example 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 Methylol dimethylhydantoin, dioxane derivative such as 2,3-dihydroxy-dioxane, active vinyl compound such as 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compound such as 2,4-dichloro-6-hydroxy It can be hardened with -s-triazine and mucohalic acids such as mucochloric acid and mucophenoxychloric acid. These hardeners can be used alone or in combination. Binders are fast-reacting hardeners, for example US4,
Hardening can also be carried out with carbamoylpyridinium salts as disclosed in U.S. Pat.

The photographic materials of the present invention may further comprise various types of surfactants and lubricants in the photographic emulsion layer or in another hydrophilic colloid layer. Suitable surfactants and lubricants are listed in Research Disclosure Item 3654
4, September 1994, Chapter IX.

The present invention is particularly useful in photographic materials having an emulsion layer in which the spacing agent present in the gelatin subbing is thin enough to penetrate the surface of the emulsion layer, for example, less than 2 μm. A particularly preferred embodiment having such a thin emulsion layer is a graphic arts recording material having the following material characteristics. The emulsion layer on top of the gelatin subbing layer (b) contains only 5 g / m ² of silver (expressed as AgNO ₃ ) in a chlorobromide emulsion containing little iodide, and only about 1 g gelatin / m ² and about 15 g / m ^2. % Polymer latex. The first anti-scratch layer is 0.5
g of gelatin / m ² and 0.5 g of latex. The second antiscratch layer contains 0.5 g gelatin / m ² . The black spacing agent, a poly (methyl methacrylate) bead filled with a mixture of cyan, magenta and yellow dyes, prevents the occurrence of the "starry night" effect after processing. The black latex subbing layer is conductive and the gelatinous antihalation contains a blue dye. Further details are provided in the examples below. (B) Support for (photo) thermographic materials The heat-sensitive element comprises a substantially light-insensitive silver salt of an organic carboxylic acid, a reducing agent therefor in a thermal working relationship therewith and a binder. The mutual thermal relationship is such that during the thermal development step the reducing agent is present in such a way that it can diffuse into the particles of the substantially non-photosensitive silver salt of the organic carboxylic acid and the reduction can take place. Means what you have to do. The heat-sensitive element is exposed using a thermal head in a thermal manner.

If the heat-sensitive element further contains a catalytic amount of light-sensitive silver halide, the thermographic recording material will be a photothermographic material ("dry silver") that will be exposed in an optical manner.

Preferred substantially light-insensitive silver salts of organic carboxylic acids are silver salts of aliphatic carboxylic acids whose aliphatic carbon chain is preferably known as a fatty acid having at least 12 carbon atoms, such as silver laurate, palmitin Silver acid, silver stearate, silver hydroxystearate, silver oleate and silver behenate, and these silver salts are also called "silver soap". Other silver salts of organic carboxylic acids, such as those described in GB-P 1,439,478, such as silver benzoate, can likewise be used to form thermally developable silver images. Combinations of different silver salts of organic carboxylic acids can also be used in the present invention.

Preferred water-dispersible binders include covalently bonded ionic groups selected from the group consisting of sulfonates, sulfinates, carboxylate, phosphate, quaternary ammonium, tertiary sulfonium and quaternary phosphonium groups. Water-dispersible film-forming polymer. Further, preferred water-dispersible binders are water-dispersible film-forming polymers having covalently bonded moieties having one or more acid groups.

The above binders or mixtures thereof may be waxes or “heat solvents”, also called “thermal solvents” or “thermosolvents”, which improve the rate of redox reactions at elevated temperatures. s
olvents) ".

Suitable organic reducing agents are organic compounds containing at least one active hydrogen atom bonded to O, N or C, such as aromatic di- and tri-hydroxy compounds, aminophenols; METOL ^™ P-phenylene-diamines; alkoxynaphthols, for example 4-methoxy-1-naphthol described in US Pat. No. 3,094,41; pyrazolidin-3-one type reducing agents, for example phenidone ^™ ; Pyrazolin-5-ones, indane-1,3-dione derivatives; hydroxytetronic acids; hydroxytetronimides; for example, hydroxylamine derivatives described in US Pat. No. 4,082,901; hydrazine derivatives; and reductones For example, US-P3,074,80
9,3,080,254,3,094,417 and 3,8
See also, 87,378.

Catechol-type reducing agents, ie 2
Reducing agents containing at least one benzene nucleus having two hydroxy groups (-OH) in the ortho position, such as catechol, 3- (3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid, gallic acid and Esters such as methyl gallate, ethyl gallate,
Propyl gallate, tannic acid and 3,4-dihydroxy-benzoic acid esters are preferred, EP 6927
33 and EP903625 are particularly preferred. Other suitable reducing agents are sterically hindered phenols, bisphenols and sulfonamide phenols.

It is also possible to use a combination of a reducing agent which is a reaction partner in the reduction of a silver salt or an organic carboxylic acid which is substantially non-photosensitive upon heating. For example, sterically hindered phenols and sulfonyl hydrazide reducing agents, for example as disclosed in US Pat. No. 5,464,738, for example trityl hydrazides and formyl-phenyl- as disclosed in US Pat. No. 5,496,695. Hydrazides, for example US-P5,545,505, US-P5,
Tritylhydrazides and formyl-phenyl-hydrazides, including various co-reducing agents disclosed in US Pat. No. 545,507 and US Pat.
Acrylonitrile compounds disclosed in US Pat. No. 5,545,515 and US Pat. No. 5,635,339;
There are combinations with 2-substituted malonodialdehyde compounds as disclosed in US Pat.

The (photo) thermographic materials can further contain toning agents, stabilizers, pigments, optical brighteners and surfactants.

The use of a specific polyester support according to the invention is particularly advantageous when the (light) -thermosensitive layer is a thin layer of at most 2 μm. (C) Support for ink jet material The ink jet recording material comprises a support and an ink-receiving layer. This latter layer generally contains binders, pigments, preferably porous filters, and optionally other components such as surfactants, polymer latexes, plasticizers and mordants to hold the dyes of the ink. I do.

Typical binders known in the art include hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, methylcellulose, sodium carboxymethylcellulose, sodium carboxymethylhydroxyethylcellulose, water-soluble ethylhydroxyl. Ethyl cellulose, cellulose sulfate, polyvinyl alcohol, vinyl alcohol copolymer, polyvinyl acetate, polyvinyl acetal, polyvinyl pyrrolidone, polyacrylamide, acrylamide / acrylic acid copolymer, styrene /
Acrylic acid copolymer, ethylene-vinyl acetate copolymer,
Vinyl methyl ether / maleic acid copolymer, poly (2
-Acrylamide-2-methylpropanesulfonic acid),
Poly (diethylenetriamine-co-adipic acid), polyvinylpyridine, polyvinylimidazole, quaternized polyimidazoline, modified polyethyleneimine epichlorohydrin, ethoxylated polyethyleneimine, poly (N, N-dimethyl) Includes -3,5-dimethylenepiperidinium chloride, polyethylene oxide, polyurethane, melamine resin, gelatin, carrageenan, dextran, acacia, casein, pectin, albumin, starch, collagen derivatives, collodion and agar.

The pigments present in the ink receiving layer can be selected from organic substances such as polystyrene, polymethyl methacrylate, silicones, urea-formaldehyde condensation polymers, polyesters and polyamides. However, preferably it is an inorganic porous pigment such as silica, talc, clay, kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, aluminum hydroxide, aluminum oxide, titanium oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, satin White, boehmite and pseudo-boehmite.

The ink composition for an ink jet comprises the following components: dyes or pigments, water and / or organic solvents, wetting agents such as glycols, detergents, thickeners, polymeric binders, preservatives. Agents and the like.

The ink jet printing method can be carried out by several methods. In the first type, a continuous stream of droplets is generated by applying a pressure wave pattern. This method is known as continuous ink jet printing. In a first embodiment, a droplet stream is electrostatically charged, deflected and re-collected droplets which remain unchanged and whose direction is maintained undeflected and forms an image. And split into Alternatively, the charged deflected stream forms an image and the unchanged undeflected jet is recollected. In this variant of continuous ink jet printing, several jet streams are deflected at different angles and consequently record the image (multideflection system).
m)).

According to the second method, the ink droplets can be made "on demand"("DOD" or "drop on demand"), so that the printing device allows the droplets to be imaged on the receiver. Discharges droplets used only during formation, thereby avoiding the complexity of drop charging, deflection hardware and ink recollection. In dropping as needed, the ink droplets are generated by pressure waves generated by the mechanical operation of a piezoelectric transducer (the so-called “piezoelectric method”) or by a separate thermal stimulus (the so-called “bubble jet®” method or “ Heat jet "method).

The use of the primed polyester of the present invention is useful when the ink-receiving layer is a thin layer and when monochrome black images are to be printed, for example for recording medical diagnostic images by ink jet printing. It will also be appreciated that it would be particularly advantageous.

[0079]

EXAMPLES-Preparation of a black spacing agent 4.5 g of cyan dye c1, 7.5 g of magenta dye m1
And 4.5 g of yellow dye y1 together in 165 ml
In ethyl acetate. 1200 times of this solution
Surfactant Antalox (trademark of GAF Co., a nonylphenyloxypenta (ethyleneoxy) nonionic surfactant, 390 ml of water and 37.5 ml of non-ionic surfactant with stirring for 5 min. AN
TAROX) 880 was dispersed in an aqueous medium containing a 10% solution. This dispersion was stirred for 1 hour with 412.5 g of poly (methyl methacrylate) beads having an average particle size of about 3 μm. The ethyl acetate was then evaporated and the dispersion to a final weight of 825g. 100 g of the dispersion contained 2 g of the dye mixture and 10 g of beads. -Preparation of poly (ethylene terephthalate) with different undercoat and anti-halo layers The molten PET was extruded and stretched in the machine direction in a polyethylene terephthalate (PET) production array. A first latex subbing layer was applied to PET at the first coating site. The first subbing layer was dried and a second subbing layer was applied to the other side of the film. The second subbing layer was dried and the film base coated on both sides was stretched in the transverse direction. As a result, the biaxially stretched film base had a thickness of 100 μm. The first subbing layer was a terpolymer of 162 mg / m ² of vinylidene chloride / methyl acrylate / itaconic acid (88% / 1
0% / 2%), and 40 mg / m ² of colloidal silica (100 m ² / g surface area). The second subbing layer was a 180 mg / m ² terpolymer of vinylidene chloride / methyl acrylate / itaconic acid (88% / 10%
/ 2%), 20 mg / m ² colloidal silica (100 m ² / g surface area), and 3.15 mg / m ² poly (3,
4-ethylenedioxythiophene) / poly (styrene sulfonate) complex. Next, a gelatin subbing layer was coated on the upper side of the PET film. The coating solution for this layer is water, gelatin,
OFB (trademark of Bayer AG), Ultrasurf W (trademark of Ciba-Geigy) and Alcopal N060 (trademark of Hoechst AG), which are conventional surfactants, and hexylene glycol and trimethylolpropane, which are organic solvents. I was

In the sample of the present invention, a gelatin undercoat layer
The coating composition of the black is the production method described above
It further contained a color matting agent. The final layer is 1mg
/ M ^TwoOf black PMMA particles filled with.

In the comparative sample manufactured in the same manner,
There was either no dye-loaded poly (methyl methacrylate) spacing agent or no spacing agent (see Table 1).

Next, the gelatinous antihalation layer was
The top of the conductive latex subbing layer on the backside of the T film was coated. This gelatinous antihalation layer coating composition comprises water, gelatin, poly (methyl methacrylate) spacing particles having an average particle size of 5.9 μm, a surfactant and the following formula:

[0083]

Embedded image

A blue dye according to the invention was contained.

In addition, the coating composition may be divinyl
It contained rufone hardener. -Production of photographic emulsion An aqueous gelatin solution containing sodium chloride (16.7 g)
Gelatin / mol silver), aqueous solution of silver nitrate, and bromide
Potassium, sodium chloride, 2.3 × 10^-7Mol / mol
Silver Na_ThreeRhCl₆And 3.0 × 10^-7Mol / mol silver
Na_TwoIrCl ₆Do not stir the aqueous halide solution containing
It was added according to the double jet method. Using physical aging
0.27μm average particle size (coefficient of variation: 19%)
Chlorobromide having a chloride content of 64 mol%
Was formed. After physical ripening of the emulsion, KI is added to form a crystal.
The chief stopped.

The emulsion was then washed using conventional flocculation techniques and then redispersed with 6.67 g / mole silver gelatin. The resulting emulsion was adjusted to pH 5.3 and then chemically sensitized with gold / sulfur at 50 ° C by ripening for 3 hours. 8.4 × 10 ^-3 emulsion
Mol / mol silver of 4-hydroxy-6-methyl-1,3,3
a, stabilized with 7,7-tetraazaindene, 4.0 × 10
^It was spectrally sensitized with the following dye D-1 in an amount of ^-4 mol / mol silver.

[0087]

Embedded image

The emulsion obtained has a gelatin / silver ratio of 0.21. -Preparation of the photographic material The emulsion layer, the intermediate layer and the anti-scratch layer were simultaneously coated on top of layer (b) of a different subbed ethylene polyterephthalate film support using a three-layer arrangement.

3.23 g of emulsion layer per square meter
Of silver. This layer is then
0.5 g gelatin / m ² and 0.5 g latex /
m ² (Co [BuMA-AMPS) Na)]) and overcoated with an intermediate layer further containing a stabilizer. An anti-abrasive layer containing 0.5 g gelatin / m ² , a hardener, a coating aid and a poly (methyl methacrylate) matting agent was applied on top. After coating, the film samples were dried. -Exposure and photographic processing Each sample was subjected to a xenon flash lamp (emission time: 1
0 ^-5 s) exposed through both filters having a peak transmittance step wedge and 622nm by, and then the developer A (composition at 35 ° C. for 15 seconds and developed with see below). Thereafter, each sample was subsequently subjected to fixing in a conventional fixing bath containing ammonium thiosulfate, and finally washed and dried. Processing is Rapiline 66T3 processor (Agfa-Gevaert
Made within the NV trademark). Composition of developer A Water 800 ml Potassium carbonate 29.5 g Potassium sulfite 34.1 Potassium bromide 2.4 Diethylene glycol 14 ml Hydroquinone 17 Sodium erythrobate 2.5 4-Hydroxymethyl-4-methyl-1-phenyl 0.275- 3-pyrazolidone methyl benzotriazole 0.06 Water to adjust the volume to 1 liter Sodium hydroxide to adjust the pH to 10.5-Evaluation of the starry night and maximum concentration (D _max ) At a magnification of 200, evaluated according to an arbitrary qualitative scale, result 0 is optimal and result 5 is prohibitive. _Dmax is a densitometer Macbeth TD9
04. Silver coverage was calculated by the following formula: Coverage = D _max / coated silver coverage (g silver / m ² ).

Table 1 shows the data obtained from the samples.

[0091]

[Table 1]

The samples according to the invention clearly show a great improvement with respect to the starry night effect. Black matting agents achieve the same excellent level of starry night effect as without matting agents. The covering power also increases to the same level as without the matting agent. In summary, the use of a black spacing agent achieves the same quality as without the spacing agent. Without a matting agent, the polyester cannot be handled at high coating speeds in production equipment because the roughness of the support is too low.

Having described the preferred embodiments of the invention in detail, it will now become apparent to those skilled in the art that many modifications may be made without departing from the scope of the invention as defined in the appended claims. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 G03C 1/795 G03C 1/795 1/825 1/825 1/95 1/95 C08L 67: 00 // C08L 67:00 B41M 5/18 H (72) Inventor Etienne van Teiro Belgian 2640 Malt cell Septes Trat 27 Agfa-Gevert na Mrosese Fennent-Jap F-term (reference) 2H023 FA02 FB00 FC10 2H026 AA07 DD42 DD48 DD57 DD58 EE05 FF15 FF17 4F006 AA35 AB02 AB17 AB24 AB65 BA14 CA01 DA04 4J038 BA191 CC032 CD081 CG032 CG142 CH032 CJ132 DK002 EA012 GA06 HA442 JB16 JB18 JC18 KA08 MA08

Claims (3)

[Claims] 1. A polyester film having (a) a latex subbing layer and (b) a gelatin subbing layer in the stated order, said polyester film having an upper side and a back side. A film, wherein at least one comprises a black spacing agent. 2. The black spacing agent according to claim 1, wherein said black spacing agent comprises hydrophobic polymer particles filled with a mixture of cyan, magenta and yellow hydrophobic dyes in an appropriate ratio to provide a black spacing agent. Polyester film. 3. The mixture of dyes comprising the following dyes: ## STR1 ## Embedded image Embedded image The polyester film according to claim 2, comprising: