EP1431059A1

EP1431059A1 - Barrier layers for use in substantially light-insensitive thermographic recording materials

Info

Publication number: EP1431059A1
Application number: EP03104491A
Authority: EP
Inventors: Ingrid c/o AGFA-GEVAERT Geuens; Frank c/o AGFA-GEVAERT LOUWET; Peter c/o AGFA-GEVAERT Michiels
Original assignee: Agfa Gevaert NV; Agfa Gevaert AG
Current assignee: Agfa Gevaert NV; Agfa Gevaert AG
Priority date: 2002-12-19
Filing date: 2003-12-02
Publication date: 2004-06-23
Anticipated expiration: 2023-12-02
Also published as: EP1431059B1

Abstract

A substantially light-insensitive black and white monosheet thermographic recording material has a support and on one side of the support comprises a thermosensitive element, a barrier layer and an outermost protective layer, the thermosensitive element being exclusive of a high contrast agent and containing at least one substantially light-insensitive silver salt of a carboxylic acid, at least one reducing agent therefor in thermal working relationship therewith, at least one toning agent and at least one binder, characterized in that the at least one reducing agent is an ortho-dihydroxy-benzene derivative and the barrier layer comprises a copolymer comprising vinyl chloride units and vinyl acetate and/or vinyl alcohol units, a copolymer comprising styrene units and acrylonitrile units, a copolymer comprising cationic units and/or a copolymer comprising styrene units and maleic acid units.

Description

FIELD OF THE INVENTION

The present invention concerns barrier layers for use in substantially light-insensitive thermographic recording materials.

BACKGROUND OF THE INVENTION

Thermography is an image-forming process including a heating step and hence includes photothermography in which the image-forming process includes image-wise exposure and direct thermal processes in which the image-forming process includes an image-wise heating step. In direct thermal printing a visible image pattern is produced by image-wise heating of a recording material.
US 3,832,186 discloses in EXAMPLE 9 a heat developing-out photosensitive material obtained by coating a polyethylene terephthalate film support with a composition comprising polyvinyl butyral, silver benzotriazole, mercuric bromide, a benzoxazolidene thiohydantoin sensitising dye, ascorbic acid monomyristate as reducing agent and 3-mercapto-5-phenyl-4-phenyl-1,2,4-triazole and overcoating this composition with a vinyl chloride-vinyl acetate copolymer (weight ratio 85:15).
US 3,933,508 discloses a heat developable light-sensitive material comprising, on a support, (1) an organic silver salt, (2) a light-sensitive silver halide or silver-halide prepared by reacting the organic silver salt with a halide, (3) a reducing agent, (4) a binder, and (5) an overcoat layer overlying components (1)-(4); said components (1)-(4) occurring in a single coated layer consisting essentially of a polymer having a refractive index greater than about 1.45 at 20°C, having heat resistance to temperatures greater than about 46°C, being colorless and soluble in organic solvents, and providing increased transparency for said overcoat layer. Examples of polymers used for the overcoat layer according to US 3,933,508, which are preferably heat-resistant, colorless and soluble in solvents, are polyvinyl chloride, polyvinyl acetate, copolymers of vinyl chloride and vinyl acetate containing more than 50 mol% vinyl chloride but insufficient vinyl chloride to lower the heat resistance, polyvinyl butyral, polystyrene, polymethyl methacrylate, benzyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose acetate, polyvinylidene chloride, polyvinyl pyrrolidone, cellulose propionate, polyvinyl formal, cellulose acetate phthalate, polycarbonates and cellulose acetate propionate. Moreover, gelatin, gelatin derivatives such as phthalated gelatin, acrylamide polymers, polyisobutylene, butadiene-styrene copolymers (no limitation on monomer proportions) and polyvinyl alcohol are preferred. EXAMPLES 5, 10, 12 and 18 exemplify an overcoat comprising a vinyl chloride-vinyl acetate copolymer (95 wt% vinyl chloride, 5wt% vinyl acetate).
GB-A 1,422,057 discloses a heat-developable photosensitive material comprising, coated on a support, a layer of (1) an organic silver salt, (2) a light-sensitive silver halide as grains of which at least 30 mole % is silver iodide, (3) a reducing agent and (4) a spectrally sensitising dye adsorbed on the surface of the silver halide grains, which sensitizing dye has an oxidation potential not exceeding 1.00 volt and difference in values between its oxidation potential and its reduction potential of at least 2.00 volts. EXAMPLE 4 discloses a silver benzotriazolate-containing heat-developable photosensitive layer with a top-coat of a vinyl chloride-vinyl acetate copolymer (85:15 by weight).
DE-A 24 39 460 discloses a thermally developable photosensitive material, comprising coated on a support, (a) an organic silver salt, (b) a catalytic quantity of a silver halide or photosensitive silver-halide prepared by reacting the organic silver salt with a halide, (c) a reducing agent and (d) a binder, and an overcoat, which comprises a polymer layer with kaolin dispersed therein. DE-A 24 39 460 discloses the following overcoat polymers: (a) copolyesters; (b) nylon compounds; (c) vinylidene dichloride copolymers; (d) ethylene-vinyl acetate-copolymers; (e) cellulose ethers; (f) polyethylene; (g) synthetic rubbers; (h) cellulose esters; (i) polyvinylesters; (j) polyacrylates and α-alkyl-polyacrylate esters; (k) high molecular weight polyethylene oxides of polyglycols with an average molecular weight of about 4000 to 1,000,000; (1) polyvinyl chloride and copolymers; (m) polyvinyl acetals; (n) polyformaldehydes; (o) polyurethanes; (p) polycarbonates; (q) polystyrenes; (r) gelatins and their derivatives; (s) polyvinyl alcohol; (t) naturally occurring colloids. EXAMPLE 4 discloses an overcoat layer comprising a vinyl chloride-vinyl acetate copolymer (95:5 by weight).
US 4,197,131 discloses a light-sensitive composition comprising an intimate mixture of a substantially light-sensitive silver compound which upon reduction gives a visible change and sufficient of a silver halide to catalyse said reduction to give a visible change in those areas where the silver halide has been exposed to light and when the mixture is heated in the presence of a reducing agent, and as a yellow acutance dye a 1-alkyl-4-nitromethylene-quinolane, the alkyl substituent containing 1 to 4 carbon atoms. The EXAMPLES disclose overcoating of the light-sensitive dispersion with a layer comprising a vinyl chloride-vinyl acetate copolymer available from Union Carbide under the name VYNS.
The EXAMPLES of US 4,450,229 disclose the overcoating of a photothermographic element comprising a binder, light sensitive silver halide in catalytic proximity to a light insensitive silver source material in said element which contains a reducible source of silver ions, a reducing agent for silver ion and an effective latent image stabilizing of a particular class of compounds, with a layer comprising a vinyl acetate-vinyl chloride copolymer (80 wt% vinyl acetate, 20wt% vinyl chloride).
US 4,558,003 discloses an unexposed photothermographic article comprising a support, a silver containing layer comprising a binder, a silver compound having reducible silver ions, silver halide in catalytic proximity to said silver compound, and a reducing agent for silver ion, said binder comprising at least 25 percent by weight of a poly(vinyl acetal), said article being characterized by the presence of an amount of borate ion, a boric acid salt, or a boric acid, alone, or in combination with an isocyanate, sufficient to harden said binder. EXAMPLE 1 exemplifies a top coat of a poly(vinyl acetate)/poly(vinyl chloride)copolymer (80/20).
US 4,460,681 discloses a color photothermographic imageable article comprising a substrate, a photothermographic emulsion layer, and organic solvent soluble barrier layer, a second photothermographic emulsion layer on a polymeric cover layer, wherein each of the photothermographic layers comprise a reducible silver source, photosensitive silver halide, a reducing agent for silver ion and solvent soluble binder, and further wherein each photothermographic layer is sensitized to a portion of the spectrum at least 60 nm different from the other photothermographic layer and each photothermographic layer contains a leuco dye which when oxidized forms a feasible dye having a maximum absorbance at least 60 nm different from that of the dye formed in the at least one other photosensitive layer, and the barrier layer is between said photothermographic layers and is impermeable to the solvent contained in the second photothermographic layer. Second layer "barrier" polymers may, according to US 4,460,681, be maleic anhydride/vinyl methyl ether copolymers, polyvinylidene chloride (SARAN™), or polyvinylpyrrolidone, with maleic acid copolymers such as alkyl monoesters of poly(methyl vinyl ether/maleic acid) being preferred. The "barrier" polymer, which is the fourth layer and preferably contains the color reactants, is normally a methyl methacrylate polymer (preferably a hard polymer with a Tukon hardness of 20 or more), copolymer, or blend with other polymers or copolymers (e.g. copolymer with n-butyl acrylate, butyl methacrylate, and other acrylates such as acrylic acid, methacrylic acid, acrylic anhydride, and the like), polystyrene, or a combination of a polyvinyl chloride tripolymer with a butadiene-styrene copolymer. The preferred polymer is a hard methyl methacrylate homopolymer blended with soft methyl methacrylate copolymers. In EXAMPLE 5, a yellow/magenta barrier coating is disclosed of a butadiene/styrene copolymer and a polyvinyl chloride/acetate/alcohol) polymer (VAGH).
EP-A 0 536 955 discloses a heat developable photothermographic article comprising: (a) an image-receiving element comprising a polymeric image-receiving layer; and (b) strippably adhered to said image-receiving element, an imageable photothermographic element comprising a plurality of emulsion layers, each of which emulsion layers comprises a binder, a silver source material, and a leuco dye, and interposed between each pair of said emulsion layers a dye-permeable interlayer. EP-A 0 536 955 further discloses that the first interlayer must be impermeable to solvents to be used for applying the subsequent coating; however, the polymer for forming the first interlayer can be applied from any organic solvent. The polymer of the first interlayer is preferably a thermoplastic polymer. Homopolymers of vinyl chloride or copolymers of vinyl chloride, preferably having a glass transition temperature greater than 80°C, for example, a copolymer of vinyl chloride (96%) and vinyl acetate (4%), a blend of poly(vinyl chloride)(90%) and poly(vinyl acetate)(10%), can be used to form the first interlayer. EXAMPLE 1 exemplifies an interlayer comprising a terpolymer of vinyl chloride(83%), vinyl acetate(16%) and maleic acid(1%).
US 4,942,115 discloses a thermally processable imaging element comprising a support bearing a thermally processable hydrophobic imaging layer and, on the side of the imaging layer away from the support, an overcoat layer comprising poly(silicic acid) and a hydrophilic monomer or polymer, wherein the element comprises a polymeric adhesion promoting layer between the overcoat and the imaging layer. US 4,942,115 discloses that polymers that are useful in the polymeric adhesion promoting layer are: (1) terpolymers of 2-propenenitrile, 1,1-dichloroethene, and propenoic acid, such as disclosed in US 3,271,345; and (2) terpolymers of 2-propenoic acid, methyl ester, 1,1-dichloroethene and itaconic acid as disclosed in, for example, US 3,437,484, with a polymeric adhesion layer comprising poly(2-propenenitrile co-1,1-dichloroethene-co-2-propenoic acid) or poly(2-propenoic acid, methyl-ester-co-1,1dichloroethene-co-itaconic acid) being preferred and poly(2-propenenitrile co-1,1-dichloroethene-co-2-propenoic acid) being exemplified.
US 6,352,819 discloses a high contrast black-and-white photothermographic material comprising a support having thereon: (a) a thermally developable, high contrast imaging layer(s) comprising a binder and in reactive association, photosensitive silver halide, a non-photosensitive source of reducible silver ions, a reducing composition for said non-photosensitive source reducible silver ions, and a high contrast agent, and (b) a barrier layer that is on the same side but farther from said support than said high contrast imaging layer(s), said barrier layer comprising a film-forming polymer and being impermeable to or reactive with any components that are diffusible from said image-forming layer(s) at a temperature greater than 80°C. US 6,352,819 further discloses but does not claim a high contrast black-and-white thermographic material comprising a support having thereon: (a) a thermally developable and non-photosensitive, high contrast imaging layer(s) comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, a reducing composition for said non-photosensitive source reducible silver ions, and a high contrast agent, and (b) a barrier layer that is farther from the support than the high contrast imaging layer(s), the barrier layer comprising a film-forming polymer and being impermeable to or reactive with any components that are diffusible from said image-forming layer(s) at a temperature greater than 80°C. The term thermographic material is a generic term which includes photothermographic materials and the recitation of the high contrast thermographic material does not exclude the presence of photosensitive species such as photosensitive silver halide. There is therefore no specific disclosure in US 6,352,819 concerning substantially light-insensitive thermographic materials and moreover US 6,352,819 contains no examples devoted to substantially light-insensitive thermographic materials. Some particularly useful barrier materials, according to US 6,352,819, include polyvinyl alcohol, a styrene polymer (including polymers of styrene derivatives), a vinyl halide polymer, a vinyl acetate polymer [such as polyvinyl acetate, poly(ethylene-co-vinyl acetate) or a copolymer of a vinyl halide and vinyl acetate], a polyvinyl pyrrolidone, a water-soluble or water-dispersible polyester, and gelatin (including deionised and acid processed gelatin) or a gelatin derivative (such as phthalated gelatin and carbamoylated gelatin, with the styrene polymers, vinyl acetate polymers and polyvinyl alcohol being preferred. EXAMPLE 12 discloses a barrier layer comprising poly(vinyl chloride-co-vinyl acetate), EXAMPLE 32 discloses a barrier layer comprising poly(styrene-co-acrylonitrile) (75:25 weight), EXAMPLE 33 discloses a barrier layer comprising U CAR VYNS poly(vinyl chloride-co-vinyl acetate) from Union Carbide and EXAMPLE 34 discloses a barrier layer comprising U CAR VAGH poly(vinyl chloride-co-acetate-co-vinyl alcohol) from Union Carbide.
It has been found that, in order to achieve a neutral image tone in substantially light-insensitive black and white monosheet thermographic materials, reducing agents and toning agents are required which diffuse to the surface of the material despite the presence of an outermost protective layer both during storage before printing and after printing and results, in extreme cases, in the user visually observing deposits of reducing agents, toning agents and reaction products of the imaging-forming process on the surface of the materials. Substantially light-insensitive black and white monosheet thermographic materials are therefore required which exhibit an acceptably neutral image tone, but do not exhibit the formation of such deposits of reducing agents, toning agents and reaction products of the imaging-forming process.

ASPECTS OF THE INVENTION

It is therefore an aspect of the present invention to provide a substantially light-insensitive black and white monosheet thermographic material, which exhibits acceptably neutral image tone, but do not exhibit the formation of surface deposits comprising, for example, reducing agent, toning agent and carboxylic acid.
Further aspects and advantages of the invention will become apparent from the description hereinafter.

SUMMARY OF THE INVENTION

US 6,352,819 teaches the barrier layer comprises a film-forming polymer(s) that reacts with or acts as a physical barrier to diffusible by-products resulting from the presence of high contrast agents such as acrylonitrile co-developers, hydrazide co-developers and isoxazole codevelopers. It has been surprisingly found that prints of substantially light-insensitive black and white monosheet thermographic materials with thermosensitive elements not containing a high contrast agent and containing at least one substantially light-insensitive silver salt of a carboxylic acid, ortho-dihydroxy-benzene derivatives as reducing agents in combination with a barrier layer comprising a copolymer comprising vinyl chloride units and vinyl acetate units and/or vinyl alcohol units and/or a copolymer comprising styrene units and acrylonitrile units inserted between the outermost protective layer and the thermosensitive element exhibit acceptably neutral image tones, as characterized by CIELAB a* and b* values, and that surface deposits are neither formed prior to printing nor after printing. The L*, a* and b* CIELAB-values were determined by spectrophotometric measurements according to ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90.
Aspects of the present invention are realized with a substantially light-insensitive black and white monosheet thermographic recording material has a support and on one side of the support comprises a thermosensitive element, a barrier layer and an outermost protective layer, the thermosensitive element being exclusive of a high contrast agent and containing comprising a substantially light-insensitive silver salt of a carboxylic acid, at least one reducing agent therefor in thermal working relationship therewith, at least one toning agent and a binder, characterized in that the at least one reducing agent is an ortho-dihydroxy-benzene derivative and the barrier layer comprises a copolymer comprising vinyl chloride units and vinyl acetate units and/or vinyl alcohol, a copolymer comprising styrene units and acrylonitrile units, a copolymer comprising cationic units and/or a copolymer comprising styrene units and maleic acid units.
Preferred embodiments of the present invention are disclosed in the detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

The term alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
The term acyl group as used in disclosing the present invention means -(C=O)-aryl and -(C=O)-alkyl groups.
The L*, a* and b* CIELAB-values are defined in ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90.
Substantially light-insensitive means not intentionally light sensitive.
The term "high contrast agent", which are sometimes identified as "co-developers" or "auxiliary developers", have as their main function an increase in the contrast of the material by reducing most or all of the reducible silver ions in the substantially light-insensitive silver salt of a carboxylic acid in the radiation-exposed areas e.g. acrylonitrile co-developers, hydrazide co-developers and isoxazole co-developers as disclosed in US 6,352,819 herein incorporated by reference.
Heating in association with the expression a substantially water-free condition as used herein, means heating at a temperature of 80 to 250°C. The term "substantially water-free condition" as used herein means that the reaction system is approximately in equilibrium with water in the air, and water for inducing or promoting the reaction is not particularly or positively supplied from the exterior to the element. Such a condition is described in T.H. James, "The Theory of the Photographic Process", Fourth Edition, Macmillan 1977, page 374.

Thermosensitive element

The term thermosensitive element as used herein is that element which contains all the ingredients, which contribute to image formation. According to the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the thermosensitive element contains at least a substantially light-insensitive silver salt of a carboxylic acid, an ortho-dihydroxy-benzene derivative reducing agent therefor in thermal working relationship therewith, a toning agent and a binder. The thermosensitive element may comprise a layer system in which the above-mentioned ingredients may be dispersed in different layers, with the proviso that the substantially light-insensitive silver salt of a carboxylic acid is in reactive association with the ortho-dihydroxy-benzene derivative reducing agent i.e. during the thermal development process the reducing agent must be present in such a way that it is able to diffuse to the particles of the substantially light-insensitive silver salt of a carboxylic acid, so that reduction to silver can occur. Such materials include the possibility of the substantially light-insensitive silver salt of a carboxylic acid and/or the ortho-dihydroxy-benzene derivative reducing agent therefor being encapsulated in heat-responsive microcapsules, such as disclosed in EP-A 0 736 799 herein incorporated by reference.

Substantially light-insensitive silver salt of a carboxylic acid

According to a first embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the substantially light-insensitive silver salt of a carboxylic acid is not a double organic salt containing a silver cation associated with a second cation e.g. magnesium or iron ions.
According to a second embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, said substantially light-insensitive silver salt of an carboxylic acid is a substantially light-insensitive silver salt of an aliphatic carboxylic acids known as a fatty acid, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called "silver soaps". Other silver salts of an organic carboxylic acid as described in GB-P 1,439,478, e.g. silver benzoate, may likewise be used to produce a thermally developable silver image. Combinations of different silver salts of an organic carboxylic acids may also be used in the present invention, as disclosed in EP-A 964 300 herein incorporated by reference.

Ortho-dihydroxy-benzene derivative

According to a third embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the ortho-dihydroxy-benzene derivative is selected from the group consisting of catechol, 3-(3,4-dihydroxyphenyl) propionic acid, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid esters, gallic acid, gallic acid esters, e.g. methyl gallate, ethyl gallate and propyl gallate, 3,4-dihydroxy-benzaldehyde, 3,4-dihydroxy-acetophenone, 3,4-butyrophenone, 3,4-dihydroxy-benzophenone, 3,4-dihydroxybenzophenone derivatives, 3,4-dihydroxy-benzonitrile, and tannic acid, as disclosed in EP-A 0 692 733, EP-A 0 903 625, EP-A 1 245 403 and EP-A 1 245 404 herein incorporated by reference.
Combinations of reducing agents may also be used that on heating become reactive partners in the reduction of the one or more substantially light-insensitive organic silver salt. For example, combinations of sterically hindered phenols with sulfonyl hydrazide reducing agents such as disclosed in US 5,464,738; trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in US 5,496,695; trityl hydrazides and formyl-phenyl-hydrazides with diverse auxiliary reducing agents as disclosed in US 5,545,505, US 5,545,507 and US 5,558,983; acrylonitrile compounds as disclosed in US 5,545,515 and US 5,635,339; and 2-substituted malonodialdehyde compounds as disclosed in US 5,654,130.

Toning agent

According to a fourth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the at least one toning agent is selected from the group consisting of phthalazinone, phthalazinone derivatives, benzoxazine dione, benzoxazine dione derivatives, naphthoxazine dione and naphthoxazine derivatives, pyridazone, pyridazone derivatives, compounds represented by formula (I) :
wherein R¹ is an alkyl group optionally substituted with a hydroxy, carboxy, carboxy ester, acyl or carbonate group; X is S, O or N-R⁶; R⁶ is an optionally substituted alkyl group; R², R³, R⁴ and R⁵ independently represent a hydrogen atom, a halogen atom or an alkyl, an alkoxy, a thio-alkoxy, a nitro, a cyano, a carboxy, a carboxy ester, an acyl, an aldehyde, an acylamido, a sulphonamido, an acylamino, a carbonate, a hydroxy or an aryl group or at least one of R² and R³, R³ and R⁴ and R⁴ and R⁵ independently represent the atoms necessary to form a carbocyclic or heterocyclic group or at least one of R¹ and R⁵ and R² and R⁶ independently represent the atoms necessary to form a heterocyclic ring; compounds represented by formula (II) :
wherein R⁷ is an optionally substituted alkyl group; Y is S, O or N-R¹⁰ ; R¹⁰ is an optionally substituted alkyl group; R⁸ and R⁹ independently represent a hydrogen atom, a halogen atom or an alkyl, an alkoxy, a thio-alkoxy, a nitro, a cyano, a carboxy, a carboxy ester, an acyl, an aldehyde, an acylamido, a sulphonamido, an acylamino, a carbonato, a hydroxy or an aryl group or R⁸ and R⁹ represent the atoms necessary to form a heterocyclic or a nonaromatic carbocyclic ring or at least one of R⁸ and R¹⁰ and R⁹ and R⁷ independently represent the atoms necessary to form a heterocyclic ring; and both R⁸ and R⁹ cannot both be an alkyl group; and compounds represented by formula (III):
wherein R¹¹ is a hydrogen atom or a C1 to C3 alkyl, a C1 to C3 alkenyl, a C1 to C3 alkynyl, a cycloalkyl, an alkaryl, an aryl, a heterocyclic or a heteroaryl group all of which may be optionally substituted; with the proviso that R¹¹ may not be a hydrogen atom if both R¹² and R¹³ are both hydrogen atoms; R¹² and R¹³ are independently a hydrogen atom or an amide, ester, carboxy, carbonato, alkyl, alkenyl, alkynyl, cycloalkyl, alkaryl, aryl, heterocyclic or heteroaryl group all of which may be optionally substituted; R¹² and R¹³ may together represent the atoms necessary to complete an alicyclic, a heterocyclic or a heteroaromatic ring which all may be optionally substituted; and X is a carbonyl group, or is -N-R¹⁴, where R¹⁴ is an alkyl group.
Suitable optional substituents for the alkyl groups of R¹, R⁶, R⁷ and R¹⁰ are independently include carboxy and carboxy ester groups. Suitable substituted alkyl groups include: -CH₂COOH, -C₂H₄COOH and -C₂H₄COOC₂H₅.
Suitable benzoxazine dione toning agents for use in the thermographic material, according to the present invention, are disclosed in GB 1,439,478, US 3,951,660 and US 5,599,647, herein incorporated by reference.

Binder of the thermosensitive element

The film-forming binder of the thermosensitive element may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, in which the at least one organic silver salt can be dispersed homogeneously either in aqueous or solvent media: e.g. cellulose derivatives, starch ethers, galactomannan, polymers derived from α,β-ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylates, polymethacrylates, polystyrene and polyethylene or mixtures thereof.
Suitable water-soluble film-forming binders for use in thermographic recording materials according to the present invention are: polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyethyleneglycol, proteinaceous binders, polysaccharides and water-soluble cellulose derivatives. A preferred water-soluble binder for use in the thermographic recording materials of the present invention is gelatine.
The binder to organic silver salt weight ratio is preferably in the range of 0.2 to 7, and the thickness of the thermosensitive element is preferably in the range of 5 to 50 µm. Binders are preferred which do not contain additives, such as certain antioxidants (e.g. 2,6-di-tert-butyl-4-methylphenol), or impurities which adversely affect the thermographic properties of the thermographic recording materials in which they are used.

Barrier layer

Aspects of the present invention are realized with substantially light-insensitive black and white monosheet thermographic recording material has a support and on one side of the support comprises a thermosensitive element, a barrier layer and an outermost protective layer, the thermosensitive element being exclusive of a high contrast agent and containing at least one substantially light-insensitive silver salt of a carboxylic acid, at least one reducing agent therefor in thermal working relationship therewith, at least one toning agent and a binder, characterized in that the at least one reducing agent is an ortho-dihydroxy-benzene derivative and the barrier layer comprises a copolymer comprising vinyl chloride units and vinyl acetate and/or vinyl alcohol units, a copolymer comprising styrene units and acrylonitrile units, a copolymer comprising cationic units and/or a copolymer comprising styrene units and maleic acid units.
According to a fifth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the barrier layer is interposed between the thermosensitive element and the outermost protective layer.
The mechanism of the restraining influence of the barriers layers, according to the present invention, upon the diffusion of ingredients and reaction products of the imaging forming process to the surface of the protective layer is unknown, but it is believed that these layers may perform a dual role in providing an impervious barrier for certain of the ingredients and reacting with others of the diffusing species. The copolymers used in the barrier layer of the thermographic material, according to the present invention, all have a more polar species, e.g. vinyl chloride, acrylonitrile, maleic acid and cationic units, and less polar species, e.g. styrene and vinyl acetate. Such polar species could represent a barrier to the diffusion of non-polar species.
According to a sixth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the copolymer comprising vinyl chloride units and vinyl acetate units contains up to 95% by weight of vinyl chloride. The weight ratio of vinyl chloride to vinyl acetate has not been found to be critical. Further comonomers may be present, but have not been found to be critical to the performance of the copolymer as a barrier to diffusion of ingredients or reaction products from the image-forming process.
According to a seventh embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the copolymer comprising styrene units and acrylonitrile units contains between 20 and 60% by weight of acrylonitrile.
According to an eighth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the copolymer containing cationic units contains quaternary ammonium, quaternary phosphonium or ternary sulphonium units.
According to a ninth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the copolymer containing cationic units contains methacrylamidopropyltrimethylammonium chloride or dimethyl-diallylammonium chloride units.
It has been found that the barrier layers exhibit an optimal restraining influence upon the diffusion of ingredients and reaction products of the imaging forming process when coated from coating solutions containing 5 to 20% by weight of the copolymer and/or with wet layer thicknesses of 5 to 20 µm.

Suitable copolymers for use in the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, include:

Copolymer nr.	Copolymer composition
1	VINNOL™ E15 45, a vinyl chloride-vinyl acetate-copolymer (85:15 by weight) from Wacker Chemie
2	VINNOL™ E15 45M, a vinyl chloride-vinyl acetate-maleic acid anhydride-copolymer (80.9:18.5:0.6 by weight) from Wacker Chemie
3	VINNOL™ E15 45A, a vinyl chloride-vinyl alcohol-copolymer (83.5:16.5 by weight) from Wacker Chemie
4	VINNOL™ H40 60, a vinyl chloride-vinyl acetate-copolymer (60:40 by weight) from Wacker Chemie
5	VINYLITE™ VAGD, a vinyl chloride-vinyl acetate-vinyl alcohol-copolymer (91:3:6 by weight) from Rohm and Haas Company
6	LUSTRAN™ SAN28, a styrene-acrylonitrile-copolymer (75:25 by weight) from BAYER
7	LURAN™ 378P, a styrene-acrylonitrile-copolymer (67.5:32.5 by weight) from BASF
8	LURAN™ 388S natur, a styrene-acrylonitrile-copolymer (67.8:32.2 by weight) from BASF
9	LURAN™ 358N, a styrene-acrylonitrile-copolymer (64:36 by weight) from BASF
10	LUSTRAN™ SAN CN25, a styrene-acrylonitrile-copolymer (54:46 by weight) from BAYER
11	POVAL CM318, methacrylamidopropyl trimethylammonium chloride-vinyl acetate-vinyl alcohol-copolymer, 88.5 mol% gehydrolyseerd with 2.5 mol% N⁺, from Kuraray
12	POVAL C118, a methacrylamidopropyl trimethylammoniumchloride-vinyl acetate-vinylalcohol-copolymer, 99.4 mol% hydrolyzed with 0.5 mol% N⁺ from Kuraray
13	POVAL C506, a 75.5% hydrolyzed methacrylamidopropyl trimethylammoniumchloride-vinyl alcohol-vinyl acetate-copolymer with 0.5 mol% N⁺ from Kuraray
14	a styrene-maleic acid copolymer (50/50 mol%) as a 10% by weight aqueous solution with pH 7
15	GOSHEFIMER K210, a 85.8-88% hydrolyzed vinyl acetate-vinyl alcohol with ca. 1 mol% dimethyl-diallylammonium chloride-copolymer from Nippon Goshei

Protective layer

In general the outermost protective layer protects the thermosensitive element from atmospheric humidity and from surface damage by scratching etc. and prevents direct contact of printheads or heat sources with the recording layers. Protective layers for thermosensitive elements which come into contact with and have to be transported past a heat source under pressure, have to exhibit resistance to local deformation and good slipping characteristics during transport past the heat source during heating. A slipping layer, being the outermost layer, may comprise a dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer.
Examples of suitable lubricating materials are a surface-active agent, a liquid lubricant, a solid lubricant or mixtures thereof, with or without a polymeric binder.
According to a tenth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the outermost protective layer comprises the reaction product of at least one hydrolyzed polyalkoxysilane and a hydroxy-group containing polymer.
According to an eleventh embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the outermost protective layer comprises the reaction product of a hydrolyzed tetra-alkoxysilane, e.g. tetramethoxysilane or tetra-ethoxysilane, and polyvinyl alcohol.

Stabilizers

According to a twelfth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the thermosensitive element further contains a stabilizer.
According to a thirteenth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the thermosensitive element further contains a stabilizer selected from the group consisting of benzotriazole; substituted benzotriazoles; aromatic polycarboxylic acid, such as ortho-phthalic acid, 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid and anhydrides thereof; 1-phenyl-5-mercapto-tetrazole compounds in which the phenyl group is substituted with a substituent containing an optionally substituted aryl group, 1-(5-mercapto-1-tetrazolyl)-acetyl compounds represented by formula (IV):
wherein R¹⁵ is -NR¹⁶R¹⁷, -OR¹⁸ or an optionally substituted aryl or heteroaryl group; R¹⁶ is hydrogen or an optionally substituted alkyl, aryl or heteroaryl group; R¹⁷ is an optionally substituted aryl or heteroaryl group; and R¹⁸ is an optionally substituted aryl group; and compounds with two or more groups represented by formula (V) :
where Q comprises the necessary atoms to form a 5- or 6-membered unsaturated heterocyclic ring, A is hydrogen, a counterion to compensate the negative charge of the thiolate group or two or more A groups provide a linking group between the two or more groups represented by formula (V).
According to a fourteenth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the thermosensitive element further contains at least one optionally substituted aliphatic or carbocyclic polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 15 with respect to all the organic silver salt(s) present and in thermal working relationship therewith. The polycarboxylic acid may be used in anhydride form or partially esterified on the condition that at least two free carboxylic acids remain or are available during the heat recording step.

Surfactants and dispersants

Surfactants and dispersants aid the dispersion of ingredients, which are insoluble in the particular dispersion medium. The substantially light-insensitive thermographic material used in the present invention may contain one or more surfactants, which may be anionic, non-ionic or cationic surfactants and/or one or more dispersants. Suitable dispersants are natural polymeric substances, synthetic polymeric substances and finely divided powders, e.g. finely divided non-metallic inorganic powders such as silica. It has been found that the addition of a silicone oil to the coating solution of the Copolymer endowed the barrier coating solution with improved wetting properties.
According to a fifteenth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the barrier layer contains a silicone oil.

Support

According to a sixteenth embodiment of the substantially light-insensitive black and white monosheet thermographic recording material, according to the present invention, the support is transparent or translucent. It is preferably a thin flexible carrier made transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate. The support may be in sheet, ribbon or web form and subbed if needs be to improve the adherence to the thereon coated thermosensitive element. The support may be dyed or pigmented to provide a transparent coloured background for the image.

Coating techniques

The coating of any layer of the substantially light-insensitive thermographic material used in the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc., 220 East 23rd Street, Suite 909 New York, NY 10010, USA. Coating may proceed from aqueous or solvent media with overcoating of dried, partially dried or undried layers.

Thermographic processing

Thermographic imaging is carried out by the image-wise application of heat either in analogue fashion by direct exposure through an image or by reflection from an image, or in digital fashion pixel by pixel either by using an infra-red heat source, for example with a Nd-YAG laser or other infra-red laser, with a substantially light-insensitive thermographic material preferably containing an infra-red absorbing compound, or by direct thermal imaging with a thermal head.
In thermal printing image signals are converted into electric pulses and then through a driver circuit selectively transferred to a thermal printhead. The thermal printhead consists of microscopic heat resistor elements, which convert the electrical energy into heat via Joule effect. The operating temperature of common thermal printheads is in the range of 300 to 400°C and the heating time per picture element (pixel) may be less than 1.0ms, the pressure contact of the thermal printhead with the recording material being e.g. 200-1000g/linear cm, i.e. with a contact zone (nip) of 200 to 300 µm a pressure of 5000 to 50,000 g/cm², to ensure a good transfer of heat.
In order to avoid direct contact of the thermal printing heads with the outermost layer on the same side of the support as the thermosensitive element when this outermost layer is not a protective layer, the image-wise heating of the recording material with the thermal printing heads may proceed through a contacting but removable resin sheet or web wherefrom during the heating no transfer of recording material can take place.
Activation of the heating elements can be power-modulated or pulse-length modulated at constant power. EP-A 654 355 discloses a method for making an image by image-wise heating by means of a thermal head having energizable heating elements, wherein the activation of the heating elements is executed duty cycled pulsewise. EP-A 622 217 discloses a method for making an image using a direct thermal imaging element producing improvements in continuous tone reproduction.
Image-wise heating of the recording material can also be carried out using an electrically resistive ribbon incorporated into the material. Image- or pattern-wise heating of the recording material may also proceed by means of pixel-wise modulated ultrasound.

Industrial application

Thermographic imaging can be used for the production of reflection type prints and transparencies, in particular for use in the medical diagnostic field in which black-imaged transparencies are widely used in inspection techniques operating with a light box.

The invention is illustrated hereinafter by way of comparative examples and invention examples. The percentages and ratios given in these examples are by weight unless otherwise indicated.
Subbing layer Nr. 01 on the emulsion side of the support has the composition:

copolymer of 88% vinylidene chloride, 10% methyl acrylate and 2% itaconic acid	79.1 mg/m²
Kieselsol® 100F, a colloidal silica from BAYER	18.6 mg/m²
Mersolat® H, a surfactant from BAYER	0.4 mg/m²
Ultravon® W, a surfactant from CIBA-GEIGY	1.9 mg/m²

Ingredients in the thermosensitive element in addition to the above-mentioned ingredients:

BL5HP	S-LEC BL5HP, a polyvinyl butyral from SEKISUI;
Oil	BAYSILON, a silicone oil from BAYER;
VL	DESMODUR VL, a 4,4'-diisocyanatodiphenylmethane from BAYER

Reducing agents:

R01	3,4-dihydroxybenzonitrile;
R02	3,4-dihydroxybenzophenone;
R03	ethyl 3,4-dihydroxybenzoate

Stabilizers:

S01	glutaric acid
S02	tetrachlorophthalic acid anhydride
S03	benzotriazole
S04	adipic acid

Compositions of thermosensitive elements used:

	Thermosensitive element types
	1	2	3	4	5
AgBeh [g/m²]	3.94	4.150	3.960	4.15	4.42
BL5HP [g/m²]	15.32	16.601	15.841	16.60	16.796
R01 [g/m²]	0.595	0.439	-	-	0.618
R02 [g/m²]	0.566	0.894	-	-	-
R03 [g/m²]	-	-	0.940	0.845	0.515
BOD01 [g/m²]	-	-	0.216	-	-
BOD02 [g/m²]	0.111	-	0.111	0.116	0.226
BOD03 [g/m²]	0.156	0.246	-	-	-
BOD04 [g/m²]	-	-	-	0.269	-
S01 [g/m²]	0.256	0.294	0.283	0.297	0.287
S02 [g/m²]	0.126	0.130	0.125	0.132	0.139
S03 [g/m²]	0.105	0.109	0.103	0.110	0.116
VL [g/m²]	0.175	0.190	-	-	-
Oil [g/m²]	0.035	0.037	0.035	0.037	0.039

Ingredients in the barrier layers:

Polymer nr	Copolymer composition
1	reaction product of hydrolyzed tetramethoxy-silane and polyvinyl alcohol (ERCOL™ 48 20) [0.166:2 by weight]
2	reaction product of hydrolyzed tetramethoxy-silane and polyvinyl alcohol (ERCOL™ 48 20) [1.690:2 by weight]
3	reaction product of hydrolyzed tetramethoxy-silane and polyvinyl alcohol (ERCOL™ 48 20) [3.379:2 by weight]
4	reaction product of hydrolyzed tetramethoxy-silane and polyvinyl alcohol (ERCOL™ 48 20) [5.069:2 by weight]
5	cellulose acetate butyrate
6	S-LEC BL5HP, a polyvinyl butyral from Sekisui
7	S-LEC BL16, a polyvinyl butyral from Sekisui
8	S-LEC B DSG12, a polyvinyl butyral from Sekisui
9	S-LEC KW23, a vinyl butyral-vinyl acetate-vinyl alcohol terpolymer from Sekisui
10	S-LEC KW3, a vinyl butyral-vinyl acetate-vinyl alcohol terpolymer from Sekisui
11	ALMACRYL™ EB56, an isophthalic acid/adipic acid/ethylene glycol polymer (75-80:25-20:100 on molar basis) from Image Polymers
12	DEGALAN™ M345, a poly(methyl methacrylate) from Degussa
13	JAGOTEX EM2245, a polyacrylate from E. Jäger Fabrik GmbH
14	SARAN™ F2202, a vinylidene chloride-acrylonitrile-copolymer [80/20 by weight] from Dow Chemical Co.
15	HIMER™ ST95, a polystyrene from Sanyo Chemical Industries
16	Polystyrene 158K, a polystyrene from BASF
17	ERCOL™ 48 20, a polyvinylalcohol from ACETEX EUROPE
18	CELVOL™ 203, a polyvinyl alcohol from Celanese Chemicals
19	POVAL™ R2105, a 98% hydrolyzed silanol-modified vinyl alcohol-vinyl acetate-copolymer from Kuraray
20	POVAL™ R2130, a silanol-modified vinyl alcohol-vinyl acetate-copolymer from Kuraray
21	POVAL™ 405, a vinyl alcohol-vinyl acetate-copolymer from Kuraray

Ingredients in the protective layer:

ERCOL™ 48 20	a polyvinylalcohol from ACETEX EUROPE;
LEVASIL™ VP AC 4055	a 15% aqueous dispersion of colloidal silica with acid groups predominantly neutralized with sodium ions and a specific surface are of 500 m²/g, from BAYER AG has been converted into the ammonium salt;
ULTRAVON™ W	75-85% concentrate of a sodium arylsulfonate from Ciba Geigy converted into acid form by passing through an ion exchange column;
SYLOID™ 72	a silica from Grace;
SERVOXYL™ VPDZ 3/100	a mono[isotridecyl polyglycolether (3 EO)] phosphate, from SERVO DELDEN B.V.;
SERVOXYL™ VPAZ 100	a mixture of monolauryl and dilauryl phosphate, from SERVO DELDEN B.V.;
MICROACE TALC P3	an Indian talc from NIPPON TALC;
RILANIT™ GMS	a glycerine monotallow acid ester, from HENKEL AG
TMOS	tetramethylorthosilicate hydrolyzed in the presence of methanesulfonic acid.

COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31

The substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 were prepared by coating a dispersion with the following ingredients of thermosensitive element type 1 in 2-butanone onto a 175µm thick blue-pigmented polyethylene terephthalate support with CIELAB a*-and b*-values of -9.5 and -17.9 respectively subbed on the emulsion-coated side with subbing layer 01 giving type 1 thermosensitive elements after drying at 50°C for 1h in a drying cupboard, for composition see above. The type 1 thermosensitive elements were then coated with a barrier layer from a 2-butanone solution, for type of copolymer used and coating weight see Tables 1A and 1B. The barrier layers were then further coated with an aqueous composition with the following ingredients, which was adjusted to a pH of 3.8 with 1N nitric acid, to a wet layer thickness of 85 µm and then dried at 50°C for 15 minutes to produce a protective layer PRO-L with the composition:

ERCOL™ 48 20	2.1g/m²
LEVASIL™ VP AC 4055	1.05g/m²
ULTRAVON™ W	0.075g/m²
SYLOID™ 72	0.09 g/m²
SERVOXYL™ VPDZ 3/100	0.075g/m²
SERVOXYL™ VPAZ 100	0.075g/m²
MICROACE TALC P3	0.045g/m²
RILANIT™ GMS	0.15g/m²
TMOS	0.87g/m² (assuming that the TMOS was completely converted to SiO₂)

After coating the protective layer was hardened by heating the substantially light-insensitive thermographic material at 45°C for 7 days at a relative humidity of 70%.

Thermographic printing

The substantially light-insensitive thermographic recording materials of COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 were printed using a DRYSTAR™ 4500 printer from AGFA-GEVAERT with a resolution of 508 dpi which had been modified to operate at a printing speed of 14 mm/s and a line-time of 3.5 ms instead of 7.1 ms and in which the 75 µm long (in the transport direction) and 50 µm wide thermal head resistors were power-modulated to produce different image densities. The maximum densities of the images (D_max) measured through a visible filter with a MACBETH™ TR924 densitometer were all greater than 2.0.
Assessment of diffusion of ingredients and reaction products of the imaging forming process to protective layer surface

The diffusion of ingredients and reaction products of the imaging forming process to the surface of the protective layer was assessed visually according to a scale of 0 to 5 with the following criteria:

diffusion assessment of 0:	no diffusion
diffusion assessment of 1:	first indication of diffusion upon examination under an intense lighting after rubbing with a paper tissue
diffusion assessment of 2:	visible in daylight after rubbing with a paper tissue
diffusion assessment of 3:	just visible in daylight without rubbing with a paper tissue
diffusion assessment of 4:	moderately strong deposition without rubbing with a paper tissue
diffusion assessment of 5:	very strong deposition without rubbing with a paper tissue

The results for unprinted and printed materials after different times under ambient conditions (25°C) are given in Tables 1A and 1B below for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 respectively.

Comparative Example Nr.	Polymer	Assessment of diffusion
	nr	coverage [g/m²]	prior to printing	after printing
			0 d	10 d	20 d	30 d	0 d	10 d	20 d	30 d
1	-	-	5	5	5	5	3	5	5	5
2	-	-	0	0	0	0	0	1	1	2
3	1	1	0	0	0	0	0	0	2	3
4	2	2	0	0	0	0	1	2	2	2
5	3	2	0	0	0	0	1	3	3	3
6	4	2	0	0	0	0	1	2	2	2
7	5	2	0	0	0	0	0	1	2	2
8	6	2	0	0	0	0	0	2	2	2
9	7	2	0	0	0	0	0	2	2	2
10	8	2	0	0	0	0	0	3	2	3
11	9	2	0	0	1	1	0	3	3	3
12	10	2	0	0	0	0	0	3	3	3
13	11	2	0	0	0	0	2	2	2	2
14	12	2	0	0	0	0	0	2	2	2
15	13	2	0	0	0	0	0	1	2	2
16	14	2	0	0	0	0	0	1	2	2
17	15	2	0	0 0		0	1	2	2	2
18	16	2	0	0	0	0	0	2	2	2
19	18	2	0	0	0	1	0	3	4	3
20	18	1	0	0	0	1	0	3	3	4
21	19	2	0	0	0	0	0	0	2	2
22	19	1	0	0	0	0	0	1	2	3
23	20	2	0	0	0	0	2	2	2	2
24	21	1	0	0	0	0	0	3	4	4

Invention Example nr.	Copolymer	Assessment of diffusion
	nr	coverage [g/m²]	prior to printing	after printing
			0 d	10 d	20 d	30 d	0 d	10 d	20 d	30 d
1	1	2.0	0	0	0	0	0	1	1	1
2	1	1.0	0	0	0	0	0	1	1	1
3	1	0.5	0	0	0	0	0	0	0	0
4	1	0.25	0	0	0	0	0	0	0	0
5	2	2.0	0	0	0	0	0	1	1	1
6	2	1.0	0	0	0	0	0	1	1	1
7	2	0.5	0	0	0	0	0	0	0	0
8	2	0.25	0	0	0	0	0	0	0	0
9	3	2.0	0	0	0	0	0	0	1	1
10	3	1.0 0	0	0	0	0	0	1	1	1
11	3	0.5	0	0	0	0	0	0	0	0
12	3	0.25	0	0	0	0	0	0	0	0
13	6	2.0	0	0	0	0	0	1	1	1
14	6	1.0	0	0	0	0	0	1	1	1
15	6	0.5	0	0	0	0	0	0	0	0
16	6	0.25	0	0	0	0	0	0	0	0
17	7	2.0	0	0	0	0	0	1	1	1
18	7	1.0	0	0	0	0	0	1	1	1
19	7	0.5	0	0	0	0	0	0	0	0
20	7	0.25	0	0	0	0	0	0	0	0
21	8	2.0	0	0	0	0	0	1	1	1
22	8	1.0	0	0	0	0	0	1	1	1
23	8	0.5	0	0	0	0	0	0	0	0
24	8	0.25	0	0	0	0	0	0	0	0
25	11	2	0	0	0	0	0	0	0	0
26	11	1	0	0	0	0	0	0	0	0
27	12	2	0	0	0	0	0	0	0	0
28	12	1	0	0	0	0	0	0	0	0
29	13	2	0	0	0	0	0	0	0	0
30	14	2	0	0	0	0	0	0	0	0
31	14	1	0	0	0	0	0	0	0	0

The results of COMPARATIVE EXAMPLE 1 show that there is very considerable diffusion of ingredients and reaction products of the imaging forming process to the surface even prior to printing. The results for COMPARATIVE EXAMPLE 2 show that the protective layer used based on the reaction product of polyvinyl alcohol with hydrolyzed tetramethoxysilane was able to prevent further transport to the surface of the protective layer prior to printing, but after printing considerable diffusion of ingredients and reaction products of the imaging forming process could be detected after 20 days.
The results of COMPARATIVE EXAMPLES 3 to 24 show that the ability of barrier layers of Polymer nr. 1 to 21, all outside the scope of the present invention, to prevent diffusion to the surface of the protective layer was inferior to the situation without a barrier layer. It is notable that Polymer nr. 1 to 4 together with a protective layer based on the reaction product of polysilicic acid and a hydroxy-containing polymer was reported in US 5,264,334 to provide an effective barrier to ingredient diffusion.
The results for INVENTION EXAMPLES 1 to 31, on the other hand, show that Copolymers nr. 1 to 3, 6 to 8 and 11 to 14, according to the present invention, are surprisingly able, at coverages from below 0.25 g/m² to above 2 g/m², to prevent diffusion of ingredients and reaction products of the imaging forming process to the surface of the protective layer over periods of 30 days under ambient conditions (25°C) both before and after printing.
These copolymers can be grouped into copolymers comprising vinyl chloride and vinyl acetate units (Copolymers nr. 1 to 3), copolymers comprising styrene-acrylonitrile (Copolymers nr. 6 to 8), copolymers with cationic units (Copolymers nr. 11 to 13) and styrene-maleic acid copolymers (Copolymer nr. 14).

COMPARATIVE EXAMPLES 25 to 29 and INVENTION EXAMPLES 32 to 38

The substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 25 to 29 and INVENTION EXAMPLES 32 to 38 were prepared as described for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 except for the barrier layers, which are given in Tables 2A and 2B for COMPARATIVE EXAMPLES 25 to 29 and INVENTION EXAMPLES 32 to 38 respectively.
The diffusion of ingredients and reaction products of the imaging forming process to the protective layer surface for COMPARATIVE EXAMPLES 25 to 29 and INVENTION EXAMPLES 32 to 38 was assessed as described for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 prior to printing and after printing as described for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31. The results of the diffusion experiments are also given in Table 2.

The results of the diffusion experiments in Table 2 confirm the findings of INVENTION EXAMPLES 1 to 31, that copolymers 1 to 3 and 6 to 8 are able to prevent diffusion of ingredients and reaction products of the imaging forming process to the surface of the thermographic material both before and after printing for a period of 30 days under ambient conditions (25°C).

Comparative Example nr.	Polymer	Assessment of diffusion
	nr	coverage [g/m²]	prior to printing	after printing
			0 d	10 d	20 d	30 d	0 d	10 d	20 d	30 d
25	-	-	0	0	0	0	0	1	2	2
26	-	-	0	0	0	1	0	1	2	2
27	6	2	0	0	0	0	0	3	2	3
28	17	1	0	0	0	0	1	1	2	2
29	17	2	0	0	1	1	1	2	1	2
Invention Example nr.	Copolymer
	nr	coverage [g/m²]
32	1	2	0	0	0	0	0	0	0	0
33	1	2	0	0	0	0	0	0	0	0
34	2	2	0	0	0	0	0	0	0	0
35	3	2	0	0	0	0	0	0	0	0
36	6	2	0	0	0	0	0	0	0	0
37	7	2	0	0	0	0	0	0	0	0
38	8	2	0	0	0	0	0	0	0	0

Evaluation of thermographic properties

For a barrier layer to be usable in substantially light-insensitive thermographic materials, it is important that it is not only able to restrain the diffusion of ingredients and reaction products of the imaging forming process to the surface of the protective layer but also has no adverse effect on the image tone of the prints.
The image tone of fresh prints made with the substantially light-insensitive thermographic recording materials of COMPARATIVE EXAMPLES 25 to 29 and INVENTION EXAMPLES 32 and 38 was assessed on the basis of the L*, a* and b* CIELAB-values at optical densities, D, of 1.0 and 1.5 and the results are given in Table 3.

The results in Table 3 show that barrier layers of copolymer nr. 1 to 3 and 6 to 8 shifted the CIELAB b*-values of fresh prints with barrier layers slightly negatively with respect to the corresponding thermographic material of COMPARATIVE EXAMPLES 25 and 26, which renders the image tone more acceptable to a radiologist.

Comparative Example nr.	Copolymer	CIELAB values of fresh print at
	nr	coverage [g/m²]	D = 1.0	D = 1.5
			a*	b*	a*	b*
25	-	-	-4.12	-4.45	-2.62	-4.92
26	-	-	-4.44	-4.44	-2.71	-4.53
27	6	2	-4.41	-3.69	-2.58	-3.97
28	17	1	-4.19	-4.85	-2.56	-3.94
29	17	2	-4.33	-3.57	-2.39	-2.75
Invention Example nr.	Copolymer
	nr	coverage [g/m²]
32	1	2	-4.72	-6.29	-3.12	-5.65
33	1	2	-4.56	-5.74	-2.95	-5.86
34	2	2	-4.61	-6.76	-3.01	-6.24
35	3	2	-4.65	-6.24	-3.15	-5.99
36	6	2	-4.68	-6.97	-3.06	-6.36
37	7	2	-4.73	-6.94	-3.08	-6.19
38	8	2	-4.74	-6.90	-3.01	-6.21

COMPARATIVE EXAMPLE 30 and INVENTION EXAMPLES 39 to 50

The substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLE 30 and INVENTION EXAMPLES 39 to 50 were prepared by coating a dispersion with the ingredients of thermosensitive element type 2 in 2-butanone onto a 175µm thick blue-pigmented polyethylene terephthalate support with CIELAB a*-and b*- values of -9.5 and -17.9 respectively subbed on the emulsion-coated side with subbing layer 01 giving type 2 thermosensitive elements after drying at 85°C for 3 minutes in a drying cupboard, for composition of the type 2 thermosensitive element see above. The type 2 thermosensitive elements were then coated with a barrier layer from a 2-butanone solution, for copolymer type used and coating weight see Table 4. The barrier layers were then provided with the same protective layer as for the substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31.

The diffusion of ingredients and reaction products of the imaging forming process to the protective layer surface for COMPARATIVE EXAMPLE 30 and INVENTION EXAMPLES 39 to 50 was assessed as described for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 after subjecting prints to 3, 6, 9, 12, 15 and 18 days at 57°C and 34% relative humidity, which provided a more rigorous test of the ability of these barrier layers to restrain diffusion of ingredients and reaction products of the imaging forming process to the surface. The results of these diffusion experiments are also given in Table 4.

Comparative Example nr.	Polymer	Assessment of diffusion for
	nr	coverage [g/m²]	prints subjected to 57°C/34%RH for
				3 d	6 d	9 d	12 d	15 d	18 d
30	-	-		2	2	4	5	5	5
Invention Example nr.	Copolymer
	nr	wet layer thickness [µm]	coverage [g/m²]
39	2	45	1	0	1	-	-	-	-
40	2	20	1	0	0	-	-	-	-
41	2	20	0.5	0	0	-	-	-	-
42	2	20	1	0	0	0	0	0	0
43	2	20	0.6	0	0	0	0	0	0
44	2	20	0.5	0	0	0	0	0	0
45	2	20	0.4	0	0	0	0	0	1
46	2	20	0.3	0	0	0	0	0	2
47	7	50	1	0	0	-	-	-	-
48	7	45	1	0	1	-	-	-	-
49	7	20	1	0	0	-	-	-	-
50	7	20	0.5	0	0	-	-	-	-

The results in Table 4 show that barrier layers of Copolymer nr. 2, a vinyl chloride-vinyl acetate-maleic acid anhydride copolymer, provides excellent restraint of the diffusion of ingredients and reaction products of the imaging forming process to the surface even under these more rigorous conditions and that barrier layers of Copolymer nr. 7, a styrene-acrylonitrile copolymer, also provided satisfactory restraint of the diffusion of ingredients and reaction products of the imaging forming process to the surface under these conditions.

Evaluation of thermographic properties

For a barrier layer to be usable in substantially light-insensitive thermographic materials, it is important that it is not only able to restrain the diffusion of ingredients and reaction products of the imaging forming process to the surface of the protective layer but also has no adverse effect on the image tone of the prints.

The image tone of fresh prints made with the substantially light-insensitive thermographic recording materials of COMPARATIVE EXAMPLE 30 and INVENTION EXAMPLES 39 to 50 was assessed on the basis of the L*, a* and b* CIELAB-values at optical densities, D, of 1.0 and 1.5 and the results given in Table 5.

Comparative Example nr.	Polymer	CIELAB values of fresh print
	nr	wet layer	coverage	D = 1.0	D = 1.5
		thickness [µm]	[g/m²]	a*	b* -7.07	a*	b*
30	-		-	-4.95		-3.26	-5.74
Invention Example nr.	Copolymer
	nr	wet layer thickness [µm]	coverage [g/m²]
39	2	45	1	-5.31	-8.99	-4.04	-8.75
40	2	20	1	-5.49	-8.98	-4.19	-8.54
41	2	20	0.5	-5.35	-9.40	-3.78	-9.06
42	2	20	1	-5.53	-9.15	-4.10	-8.03
43	2	20	0.6	-5.43	-8.99	-4.03	-8.14
44	2	20	0.5	-5.42	-8.93	-4.07	-8.09
45	2	20	0.4	-5.36	-8.72	-3.93	-7.88
46	2	20	0.3	-5.03	-7.78	-3.22	-6.83
47	7	50	1	-5.16	-8.90	-3.45	-8.61
48	7	45	1	-5.19	-8.71	-3.40	-8.36
49	7	20	1	-5.43	-8.85	-3.85	-8.43
50	7	20	0.5	-5.18	-8.83	-3.72	-8.60

The results in Table 5 show that barrier layers of copolymer nr. 2 and 7 shifted the CIELAB b*-values of fresh prints with barrier layers slightly negatively with respect to the corresponding thermographic material of COMPARATIVE EXAMPLE 30, which rendered the image tone more acceptable to a radiologist. Furthermore, it was found that the attainable D_max decreased for a given barrier layer coverage with decreasing wet layer thickness i.e. with increasing concentration of the Copolymer in the coating solution. A wet layer thickness above 30µm had no further influence upon D_max for copolymer-coverages of less than 0.4 g/m² and a wet layer thickness of 20µm was possible for copolymer-coverages of less than 0.3 g/m².

COMPARATIVE EXAMPLE 31 and INVENTION EXAMPLES 51 to 62

The substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLE 31 and INVENTION EXAMPLES 51 to 62 were prepared as described for COMPARATIVE EXAMPLE 30 and INVENTION EXAMPLES 39 to 50 except that type 2 thermosensitive elements were used and for the barrier layers, which are given in Table 6.

Comparative Example nr.	Polymer	assessment of diffusion for prints subjected to 57°C/34%RH for 3d
	nr	coverage [g/m²]
31	-	-	5
Invention Example nr.	Copolymer
	nr	coverage [g/m²]
51	2	1	0
52	3	1	0
53	4	1	0
54	5	1	0
55	5	1	0
56	6	1	0
57	7	1	0
58	9	1	0
59	10	1	0
60	11	1	0
61	12	1	0
62	14	1	0

The diffusion of ingredients and reaction products of the imaging forming process to the protective layer surface for COMPARATIVE EXAMPLE 31 and INVENTION EXAMPLES 51 to 62 was assessed as described for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 after subjecting prints to 3 days at 57°C and 34% relative humidity. The results are also given in Table 6.
No diffusion of ingredients and reaction products of the imaging forming process to the surface was observed in the case of barrier layers of Copolymers nr. 2 to 7, 9 to 12 and 14 with a coverage of 1g/m². Most of these barrier layers were applied from 2-butanone solutions, but barrier layers of Copolymer nr. 11, 12 and 14 were applied from aqueous solutions. These copolymers can mainly be grouped into copolymers comprising vinyl chloride and vinyl acetate units (Copolymers nr. 1 to 5), copolymers comprising styrene-acrylonitrile (Copolymers nr. 6 to 10) and copolymers with cationic units (Copolymers nr. 11 and 12).

Evaluation of thermographic properties

The image tone of fresh prints made with the substantially light-insensitive thermographic recording materials of COMPARATIVE EXAMPLE 31 and INVENTION EXAMPLES 51 to 62 was assessed on the basis of the L*, a* and b* CIELAB-values at optical densities, D, of 1.0 and 1.5 and the results given in Table 7.

Comparative Example nr.	Polymer	CIELAB values of fresh print
	nr	coverage [g/m²]	D = 1.0	D = 1.5
			a*	b*	a*	b*
31	-	-	-2.67	-9.42	-0.45	-9.22
Invention Example nr.	Copolymer
	nr	coverage [g/m²]
51	2	1	-2.58	-11.15	-0.82	-10.6
52	3	1	-2.68	-11.14	-0.63	-10.5
53	4	1	-3.04	-10.39	-0.8	-9.41
54	5	1	-3.05	-11.27	-1.32	-10.86
55	5	1	-2.17	-10.15	+0.54	-9.7
56	6	1	-2.34	-10.63	-0.03	-10.1
57	7	1	-2.4	-10.41	+0.16	-9.81
58	9	1	-2.54	-10.58	+0.12	-10.04
59	10	1	-2.53	-10.2	-0.15	-9.68
60	11	1	-2.32	-8.3	+0.33	-7.15
61	12	1	-2.14	-8.85	+0.77	-8.35
62	14	1	-2.73	-8.87	-0.14	-8.76

The results in Table 7 show that certain barrier layers of copolymer nr. 2 to 7, 9 to 12 and 14 shifted the CIELAB b*-values of fresh prints with barrier layers slightly negatively with respect to the corresponding thermographic material of COMPARATIVE EXAMPLE 31 (e.g. barrier layers of Copolymer nr. 2 to 7 and 9 and 10), which enhances the image tone, and others shifted the CIELAB b*-values slightly positively with respect to the corresponding thermographic material of COMPARATIVE EXAMPLE 31 (e.g. barrier layers of Copolymer nr. 11, 12 and 14, all coated from aqueous solutions).
he composition of barrier layers of copolymers containing vinyl chloride and vinyl acetate units with various weight percentages of vinyl chloride and vinyl acetate units (Copolymer nr. 2 to 5) did not have a significant influence upon image tone i.e. for weight percentages of vinyl chloride units between 60 and 91 and for weight percentages of vinyl acetate between 3 and 15.
The composition of barrier layers of copolymers containing styrene and acrylonitrile with various weight percentages of styrene and acrylonitrile (Copolymer nr. 6, 7, 9 and 10) did not have a significant influence upon image tone i.e. for weight percentages of styrene units between 54 and 75 and for weight percentages of acrylonitrile between 25 and 46.

COMPARATIVE EXAMPLES 32 to 39 and INVENTION EXAMPLES 63 to 74

The substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 32 to 39 and INVENTION EXAMPLES 63 to 74 were prepared by coating dispersions containing the ingredients for the appropriate thermosensitive element type (see Table 8 for the thermosensitive element type used for the particular COMPARATIVE or INVENTION EXAMPLE) in 2-butanone onto the support described for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 giving the particular type of thermosensitive element for the particular COMPARATIVE or INVENTION EXAMPLE after drying at 85°C for 3 minutes in a drying cupboard with the compositions given above. The thermosensitive elements were then optionally coated with a barrier copolymer from a 2-butanone solution, see Table 8 for copolymer type and coating weight. The barrier layers were then provided with the same protective layer as for the substantially light-insensitive thermographic materials of COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31.

The diffusion of ingredients and reaction products of the imaging forming process to the protective layer surface for COMPARATIVE EXAMPLES 32 to 39 and INVENTION EXAMPLES 63 to 74 was assessed as described for COMPARATIVE EXAMPLES 1 to 24 and INVENTION EXAMPLES 1 to 31 after subjecting fresh material and prints to different tests: 3 days and 6 days at 57°C and 34% relative humidity; and 7 days at 45°C and 70% relative humidity. The results are given in Table 8.

Comparative Example nr.	thermosensitive element type	Polymer	Assessment of diffusion to material surface
		nr	coverage	fresh material after 57°C/ 34%RH/	prints after 57°C/ 34%RH/	fresh material after 45°C/70%RH/
			[g/m²]	3 d	6 d	3 d	6 d	7 d
32	2	-	-	0	0	5	5	5
33	2	-	-	0	0	5	5	5
34	3	-	-	0	0	5	5	5
35	3	-	-	0	0	5	5	3
36	4	-	-	0	0	5	5	5
37	4	-	-	0	0	5	5	0
38	5	-	-	0	0	5	5	5
39	5	-	-	0	0	5	5	5
Invention Example nr.		Copolymer
		nr	wet layer thickness [µm]	coverage [g/m²]
63	2	6	10	0.79	0	0	0	0	0
64	2	6	20	0.79	0	0	0	0	0
65	2	6	30	0.79	0	0	0	0	0
66	2	6	40	0.79	0	0	0	0	0
67	2	6	50	0.79	0	0	0	0	0
68	2	6	50	0.79	0	0	0	0	0
69	3	6	50	0.79	0	0	0	0	0
70	3	6	50	0.79	0	0	0	0	0
71	4	6	50	0.79	0	0	0	0	0
72	4	6	50	0.79	0	0	0	0	0
73	5	6	50	0.79	0	0	0	0	0
74	5	6	50	0.79	0	0	1	1	0

The experiments disclosed in Table 8 show whether the barrier layers of the present invention could be used with different thermosensitive elements with different compositions. On the basis of these experiments with a barrier layer of Copolymer nr. 6 with a coverage of 0.79 g/m², it can be seen that this barrier layer provides an excellent restraint of the diffusion of ingredients and reaction products of the imaging forming process to the surface of the thermographic material. Moreover, the results for INVENTION EXAMPLES 63 to 67, 69, 71 and 73 show that the barrier layer as such provides this restraint, which means that the choice of protective layer is not critical with respect to restraining ingredient diffusion and that the protective layer can be solely designed to optimise the mechanical interaction to the thermal printing head and the adhesion to the barrier layer.
The present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof irrespective of whether it relates to the presently claimed invention. In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.

Claims

A substantially light-insensitive black and white monosheet thermographic recording material has a support and on one side of said support comprises a thermosensitive element, a barrier layer and an outermost protective layer, said thermosensitive element being exclusive of a high contrast agent and containing at least one substantially light-insensitive silver salt of a carboxylic acid, at least one reducing agent therefor in thermal working relationship therewith, at least one toning agent and at least one binder, characterized in that said at least one reducing agent is an ortho-dihydroxy-benzene derivative and said barrier layer comprises a copolymer comprising vinyl chloride units and vinyl acetate and/or vinyl alcohol units, a copolymer comprising styrene units and acrylonitrile units, a copolymer comprising cationic units and/or a copolymer comprising styrene units and maleic acid units.
Substantially light-insensitive black and white monosheet thermographic recording material according to claim 1, wherein said barrier layer is interposed between said thermosensitive element and said outermost protective layer.
Substantially light-insensitive black and white monosheet thermographic recording material according to claim 1 or 2, wherein said copolymer comprising vinyl chloride units and vinyl acetate units contains up to 95% by weight of vinyl chloride.
Substantially light-insensitive black and white monosheet thermographic recording material according to claim 1 or 2, wherein said copolymer comprising styrene units and acrylonitrile units contains between 20 and 60% by weight of acrylonitrile.
Substantially light-insensitive black and white monosheet thermographic recording material according to claim 1 or 2, wherein said copolymer containing cationic units contains quaternary ammonium, quaternary phosphonium or ternary sulphonium units.
Substantially light-insensitive black and white monosheet thermographic recording material according to claim 5, wherein said quaternary ammonium units are methacrylamidopropyl-trimethylammonium chloride or dimethyl-diallylammonium chloride units.
Substantially light-insensitive black and white monosheet thermographic recording material according to any of the preceding claims, wherein said toning agent is selected from the group consisting of naphthoxazine dione, naphthoxazine derivatives, 7-methyl-benzo[e][1,3]oxazine-2,4-dione, 7-methoxy-benzo[e][1,3]oxazine-2,4-dione and 7-(ethylcarbonato)-benzo[e][1,3]oxazine-2,4-dione.
Substantially light-insensitive black and white monosheet thermographic recording material according to any of the preceding claims, wherein said ortho-dihydroxy-benzene derivative is selected from the group consisting of catechol, 3-(3,4-dihydroxyphenyl) propionic acid, 3,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid esters, gallic acid, gallic acid esters, 3,4-dihydroxy-benzaldehyde, 3,4-dihydroxy-acetophenone, 3,4-butyrophenone, 3,4-dihydroxy-benzophenone, 3,4-dihydroxybenzophenone derivatives, 3,4-dihydroxy-benzonitrile, and tannic acid.
Substantially light-insensitive black and white monosheet thermographic recording material according to any of the preceding claims, wherein said outermost protective layer comprises the reaction product of at least one hydrolyzed polyalkoxysilane and a hydroxy-group containing polymer.
Substantially light-insensitive black and white monosheet thermographic recording material according to any of the preceding claims, wherein said outermost protective layer comprises the reaction product of a hydrolyzed tetra-alkoxysilane, e.g. tetramethoxysilane or tetra-ethoxysilane, and polyvinyl alcohol.