Field of the invention
[0001] The present invention relates to thermographic recording materials with improved
stability to incident light and improved archivability.
Background of the invention.
[0002] Thermal imaging or thermography is a recording process wherein images are generated
by the use of thermal energy. In direct thermal thermography a visible image pattern
is formed by image-wise heating of a recording material containing matter that by
chemical or physical process changes colour or optical density. Such recording materials
become photothermographic upon incorporating a photosensitive agent which after exposure
to UV, visible or IR light is capable of catalyzing or participating in a thermographic
process bringing about changes in colour or optical density.
[0003] Examples of photothermographic materials are the so called "Dry Silver" photographic
materials of the 3M Company, which are reviewed by D.A. Morgan in "Handbook of Imaging
Science", edited by A.R. Diamond, page 43, published by Marcel Dekker in 1991.
[0004] In US 2,910,377 the following statement is made in the description in column 7, lines
23-27: "Stability towards exposure to light is improved by selecting highly purified
materials; freedom from halides and sulphides is particularly important in the case
of compositions involving silver salts". The disclosure in US 2,910,377 concerned
thermographic recording materials coated from solvent media.
[0005] WO 94/16361 discloses a multilayer heat-sensitive material which comprises: a colour-forming
layer comprising: a colour-forming amount of finely divided, solid colourless noble
metal or iron salt of an organic acid distributed in a carrier composition; a colour
developing amount of a cyclic or aromatic organic reducing agent, which at thermal
copy and printing temperatures is capable of a colour-forming reaction with the noble
metal or iron salt; and an image-toning agent; characterized in that (a) the carrier
composition comprises a substantially water-soluble polymeric carrier and a dispersing
agent for the noble metal or iron salt and (b) the material comprises a protective
overcoating layer for the colour-forming layer. WO 94/16361 concerns thermographic
materials coated from aqueous media.
[0006] Ever tighter solvent emission regulations and measures to avoid solvent explosions,
make the avoidance of solvent coating desirable. However, thermographic materials
of the type disclosed in WO 94/16361 while being coatable from aqueous media exhibit
an inadequate archivability for many applications. Furthermore, the presence of chloride
ions in the ingredients has been found to cause poor light stability. There is therefore
a need for thermographic recording materials coatable from aqueous media based on
substantially light-insensitive organic silver salts with improved shelf-life and
stability to light, whose prints exhibit improved archivability and stability to incident
light.
Objects of the invention.
[0007] It is therefore an object of the present invention to provide thermographic recording
materials coated from aqueous media with improved stability to incident light.
[0008] It is therefore another object of the present invention to provide thermographic
recording materials which are capable of producing thermographic prints with improved
archivability and stability to incident light.
[0009] Further objects and advantages of the invention will become apparent from the description
hereinafter.
Summary of the invention
[0010] It is known that conversion of organic silver salts into silver non-fluoro-halides
renders thermographic materials photosensitive, since this is the basis of photothermographic
materials. This conversion would be expected to occur more readily in aqueous media
due to the non-fluoro-halide ions being more mobile in a highly polar medium such
as water. The statement made in US 2,910,377 to the effect that the use of highly
purified materials improves the light-stability of thermographic materials and in
particular freedom from halides and sulphides, concerns thermograpahic materials coated
in solvent media in which the mobility of non-fluoro-halide ions is much lower than
in water.
[0011] It is therefore surprising that in the presence of gelatin and despite the greater
potential for silver halide formation in aqueous media, the expected light instability
due to non-fluoro-halide ions only becomes significant, relative to the general stability
of the material concerned (dependent upon choice of reducing agent and other ingredients),
at non-fluoro-halide ion concentrations above 700ppm with respect to the gelatin present.
This invention enables the use of ingredients in thermographic materials without the
exhaustive removal of non-fluoro-halides.
[0012] The above objects of the present invention are realized by providing a thermographic
recording material comprising a support and a thermosensitive element containing a
substantially light-insensitive silver salt of an organic carboxylic acid, a reducing
agent therefor in thermal working relationship therewith and at least one proteinaceous
binder, characterized in that the thermosensitive element contains between 700ppm
and 5ppm of a non-fluoro-halide ion with respect to the proteinaceous binders in the
thermosensitive element and the thermographic recording material is thermally developable
under substantially water-free conditions.
[0013] A process for producing a thermographic recording material as described above is
further provided by the present invention comprising the steps of: producing an aqueous
dispersion of the substantially light-insensitive silver salt of an organic carboxylic
acid; producing one or more aqueous coating compositions containing together the aqueous
dispersion of the substantially light-insensitive silver salt of an organic carboxylic
acid, the reducing agent and the proteinaceous binder(s); and applying the one or
more aqueous coating compositions to the support thereby forming after drying the
thermosensitive element.
[0014] Preferred embodiments of the present invention are disclosed in the detailed description
of the invention.
Detailed description of the invention.
[0015] In a preferred embodiment the substantially light-insensitive thermographic recording
materials of the present invention are black and white thermographic recording materials.
Definitions
[0016] The term aqueous for the purposes of the present invention includes mixtures of water
with water-miscible organic solvents such as alcohols e.g. methanol, ethanol, 2-propanol,
butanol, iso-amyl alcohol etc.; glycols e.g. ethylene glycol; glycerine; N-methyl
pyrrolidone; methoxypropanol; and ketones e.g. 2-propanone and 2-butanone etc.
[0017] By substantially light-insensitive is meant not intentionally light sensitive. By
substantially solvent-free aqueous medium is meant that solvent, if present, is present
in amounts below 10% by volume of the aqueous medium.
[0018] Heating in a substantially water-free condition as used herein, means heating at
a temperature of 80 to 250°C. The term "substantially water-free condition" 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.
Non-fluoro-halide ion concentration in the thermosensitive element
[0019] According to the present invention a thermographic recording material is provided
comprising a support and a thermosensitive element containing a substantially light-insensitive
silver salt of an organic carboxylic acid, a reducing agent therefor in thermal working
relationship therewith and at least one proteinaceous binder, characterized in that
the thermosensitive element contains between 700ppm and 5ppm of a non-fluoro-halide
ion with respect to the proteinaceous binders in the thermosensitive element. In a
preferred embodiment the non-fluoro-halide ion concentration in the thermosensitive
element is between 500ppm and 5ppm of a non-fluoro-halide with respect to the proteinaceous
binders in the thermosensitive element, with between 300ppm and 5ppm of a non-fluoro-halide
ion with respect to the proteinaceous binders in the thermosensitive element being
particularly preferred and between 150ppm and 5ppm being especially preferred. The
non-fluoro-halide ion is preferably the chloride ion.
Proteinaceous binders
[0020] The non-fluoro-halide ions present in the thermosensitive element may be non-exclusively
or exclusively present in the proteinaceous binder(s) used in the thermosensitive
element of the thermographic and photothermographic recording materials of the present
invention. Therefore the proteinaceous binders in the thermosensitive element may
together contain between 700ppm and 5ppm of non-fluoro-halide ions and preferably
between 500ppm and 5ppm and particularly preferably between 300ppm and 5ppm and especially
between 150ppm and 5ppm.
[0021] The alkali metal ion concentration of the proteinaceous binder(s) used in the thermosensitive
element of the thermographic and photothermographic recording materials of the present
invention together of 100ppm or less.
[0022] Suitable proteinaceous binders include gelatin, modified gelatins such as phthaloyl
gelatin, zein etc, with gelatin being preferred. Table 1 shows that the chloride ion
concentration present in gelatin as determined by ion chromatography using a DIONEX
QIC ANALYSER ion chromatograph varies according to gelatin type from 5300 to 17ppm:
Table 1
GELATIN type |
general description |
chloride ion concentration [ppm] |
sodium ion concentration [ppm] |
GEL01 |
low viscosity |
5300 |
- |
GEL02 |
hydrolyzed gelatin |
2900 |
1700 |
GEL03 |
calcium-free, low viscosity |
1270 |
- |
GEL04 |
calcium-free, medium viscosity |
17 |
<100 |
GEL05 |
calcium-free, low viscosity |
<40 |
2600 |
GEL06* |
calcium-free, low viscosity |
<40 |
<100 |
GEL07 |
calcium-containing, medium viscosity |
≤ 250# |
- |
GEL08 |
calcium-free, high viscosity |
≤ 200# |
- |
GEL09 |
calcium-free, medium viscosity |
≤ 150# |
- |
GEL10 |
calcium-containing, low viscosity |
150-300# |
- |
* type 17881, a gelatin with low potassium ion, sodium ion and chloride-ion concentrations
from AGFA-GEVAERT GELATINEFABRIEK vorm. KOEPFF & SÖHNE |
# specification |
Thermosensitive element
[0023] According to the present invention, a substantially light-insensitive thermographic
recording material is provided comprising a thermosensitive element containing a substantially
light-insensitive silver salt of an organic carboxylic acid, an organic reducing agent
therefor in thermal working relationship therewith and a binder. The thermosensitive
element may comprise a layer system in which the ingredients are dispersed in different
layers, with the proviso that the substantially light-insensitive silver salt of an
organic carboxylic acid and the organic reducing agent are in thermal working relationship
with one another 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 substantially
light-insensitive silver salt of an organic carboxylic acid so that reduction of the
silver salt of an organic carboxylic acid can take place. The thickness of the thermosensitive
element is preferably in the range of 1 to 50 µm.
[0024] In a preferred embodiment of the present invention the thermosensitive element further
contains a photosensitive silver halide, making thermographic recording material photothermographic.
Silver salts of an organic carboxylic acid
[0025] Preferred substantially light-insensitive silver salts of an organic carboxylic acid
used in the present invention are silver salts of aliphatic carboxylic acids known
as fatty acids, 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 salt of an organic carboxylic acids may also be used in the present
invention.
Auxiliary film-forming binders of the thermosensitive element
[0026] Suitable water-dispersible binders for use as auxiliary binders in the thermographic
and photothermographic recording materials of the present invention may be any water-insoluble
polymer It should be noted that there is no clear cut transition between a polymer
dispersion and a polymer solution in the case of very small polymer particles resulting
in the smallest particles of the polymer being dissolved and those slightly larger
being in dispersion. Preferred water-dispersible binders for use according to the
present invention are water-dispersible film-forming polymers with covalently bonded
ionic groups selected from the group consisting of sulfonate, sulfinate, carboxylate,
phosphate, quaternary ammonium, tertiary sulfonium and quaternary phosphonium groups.
Further preferred water-dispersible binders for use according the present invention
are water-dispersible film-forming polymers with covalently bonded moieties with one
or more acid groups.
Thermal solvents
[0027] The above mentioned binders or mixtures thereof may be used in conjunction with waxes
or "heat solvents" also called "thermal solvents" or "thermosolvents" improving the
reaction speed of the redox-reaction at elevated temperature.
Organic reducing agents
[0028] Suitable organic reducing agents for the reduction of silver salt of an organic carboxylic
acid particles are organic compounds containing at least one active hydrogen atom
linked to O, N or C.
[0029] Catechol-type reducing agents, i.e. reducing agents containing at least one benzene
nucleus with two hydroxy groups (-OH) in ortho-position are preferred with those described
in EP-B 692 733 and EP-A 903 625 being particularly preferred. Other suitable reducing
agents are sterically hindered phenols, bisphenols and sulfonamidophenols.
[0030] Combinations of reducing agents may also be used that on heating become reactive
partners in the reduction of the substantially light-insensitive silver salt of an
organic carboxylic acid. For example, combinations of sterically hindered phenols
with sulfonyl hydrazide reducing agents such as disclosed in US-P 5,464,738; trityl
hydrazides and formyl-phenyl-hydrazides such as disclosed in US-P 5,496,695; trityl
hydrazides and formyl-phenyl-hydrazides with diverse auxiliary reducing agents such
as disclosed in US-P 5,545,505, US-P 5.545.507 and US-P 5,558,983; acrylonitrile compounds
as disclosed in US-P 5,545,515 and US-P 5,635,339; and 2-substituted malonodialdehyde
compounds as disclosed in US-P 5,654,130.
Toning agents
[0031] In order to obtain a neutral black image tone in the higher densities and neutral
grey in the lower densities, the thermographic and photothermographic recording materials
according to the present invention may contain one or more toning agents. The toning
agents should be in thermal working relationship with the substantially light-insensitive
silver salt of an organic carboxylic acid and reducing agents during thermal processing.
Any known toning agent from thermography or photothermography may be used. Suitable
toning agents are the phthalimides and phthalazinones within the scope of the general
formulae described in US-P 4,082,901 and the toning agents described in US-P 3,074,809,
US-P 3,446,648 and US-P 3,844,797. Particularly useful toning agents are the heterocyclic
toner compounds of the benzoxazine dione or naphthoxazine dione type described in
GB-P 1,439,478, US-P 3,951,660 and US-P 5,599,647.
Stabilizers and antifoggants
[0032] In order to obtain improved shelf-life and reduced fogging, stabilizers and antifoggants
may be incorporated into the thermographic recording materials of the present invention.
Polycarboxylic acids and anhydrides thereof
[0033] According to the recording material of the present invention the thermosensitive
element may comprise in addition at least one polycarboxylic acid and/or anhydride
thereof in a molar percentage of at least 15 with respect to all the silver salt of
an organic carboxylic acid(s) present and in thermal working relationship therewith.
The polycarboxylic acid may be aliphatic (saturated as well as unsaturated aliphatic
and also cycloaliphatic) or an aromatic polycarboxylic acid. These acids may be substituted
e.g. with alkyl, hydroxyl, nitro or halogen. They may be used in anhydride form or
partially esterified on the condition that at least two free carboxylic acids remain
or are available in the heat recording step.
Surfactants and dispersants
[0034] Surfactants are surface active agents which are soluble compounds which reduce the
interfacial tension between a liquid and a solid. The thermographic and photothermographic
recording materials of the present invention may contain anionic, non-ionic or amphoteric
surfactants e.g.:
- Surfactant Nr. S01
- = ammonium dodecylphenylsulfonate;
- Surfactant Nr. S02
- = N, N-dimethyl-N-hexadecyl-ammonio-acetic acid;
- Surfactant Nr. S03
- = MARLON™ A-365, supplied as a 65% concentrate of a sodium alkyl-phenylsulfonate by
HÜLS.
- Surfactant Nr. S04
- = AKYPO™ OP 80, supplied by CHEMY as an 80% concentrate of an octyl-phenyl-oxy-polyethylene-glycol(EO
8)acetic acid;
- Surfactant Nr. S05
- = hexadecyl-dimethylammonium acetic acid;
- Surfactant Nr. S06
- = acid form of ULTRAVON™ W from CIBA-GEIGY;
- Surfactant Nr. S07
- = ULTRAVON™ W, an aryl sulfonate from CIBA-GEIGY
- Surfactant Nr. S08
- = ARKOPAL™ N060 (previously HOSTAPAL™ W), a nonylphenylpolyethylene-glycol from HOECHST
- Surfactant Nr. S09
- = SAPONINE QUILAYA, containing 10% of saponines, 15% of tannins, 11% of calcium oxalate
and 64% of starch from SCHMITTMANN;
- Surfactant Nr. S10
- = NIAPROOF ANIONIC™ 4, supplied as a 27% concentrate of a sodium 1-(2'-ethylbutyl)-4-ethylhexylsulphate
by NIACET;
- Surfactant Nr. S11
- = ammonium salt of perfluoro-octanoic acid.
[0035] Suitable dispersants are natural polymeric substances, synthetic polymeric substances
and finely divided powders, for example finely divided non-metallic inorganic powders
such as silica.
Other ingredients
[0036] In addition to the ingredients the substantially light-insensitive thermographic
recording material may contain other additives such as free fatty acids, silicone
oil, ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet
radiation reflecting pigments, silica, and/or optical brightening agents.
Support
[0037] The support for the substantially light-insensitive thermographic recording material
according to the present invention may be transparent, translucent or opaque and is
preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper
or 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. The support may be subbed with a subbing layer.
It may also be made of an opacified resin composition.
Protective layer
[0038] In a preferred embodiment of the thermographic recording material according to the
present invented the thermosensitive element is provided with a protective layer.
A 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. In a particularly preferred
embodiment of the thermographic recording material of the present invention, the protective
layer is exclusive of proteinaceous binders.
[0039] The protective layer may comprise a dissolved lubricating material and/or particulate
material, e.g. talc particles, optionally protruding therefrom. Examples of suitable
lubricating materials are a surface active agent, a liquid lubricant, a solid lubricant
or mixtures thereof, which may be used with or without a polymeric binder.
Layer on opposite side of the support to the thermosensitive element
[0040] The thermographic recording material according to the present invention may be provided
with a layer containing a second proteinaceous binder on the opposite side of the
support to the thermosensitive element protective layer.
Photosensitive silver halide
[0041] The photosensitive silver halide used in the present invention may be employed in
a range of 0.1 to 100 mol percent; preferably, from 0.2 to 80 mol percent; particularly
preferably from 0.3 to 50 mol percent; especially preferably from 0.5 to 35 mol %;
and especially from 1 to 12 mol % of substantially light-insensitive organic silver
salt.
[0042] The silver halide may be any photosensitive silver halide such as silver bromide,
silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver
chlorobromide etc. The silver halide may be in any form which is photosensitive including,
but not limited to, cubic, orthorhombic, tabular, tetrahedral, octagonal etc. and
may have epitaxial growth of crystals thereon.
[0043] The silver halide used in the present invention may be employed without modification.
However, it may be chemically sensitized with a chemical sensitizing agent such as
a compound containing sulphur, selenium, tellurium etc., or a compound containing
gold, platinum, palladium, iron, ruthenium, rhodium or iridium etc., a reducing agent
such as a tin halide etc., or a combination thereof. The details of these procedures
are described in T.H. James, "The Theory of the Photographic Process", Fourth Edition,
Macmillan Publishing Co. Inc., New York (1977), Chapter 5, pages 149 to 169.
Spectral sensitization
[0044] The photosensitive silver halide in the photo-addressable thermally developable element
of the photothermographic recording material, according to the present invention,
may be spectrally sensitized with a spectral sensitizer, optionally together with
a supersensitizer.
Antihalation dyes
[0045] The thermographic recording materials used in the present invention may also contain
antihalation or acutance dyes which absorb light which has passed through the photosensitive
thermally developable photographic material, thereby preventing its reflection. Such
dyes may be incorporated into the photosensitive thermally developable photographic
material or in any other layer of the photographic material of the present invention.
Coating
[0046] The coating of any layer of the substantially light-insensitive thermographic recording
materials of 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.
Thermographic printing
[0047] Thermographic imaging is carried out by the image-wise application of heat either
in analogue fashion by direct exposure through an image of 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, or by direct thermal imaging
with a thermal head. Heating takes place in a substantially water-tree condition.
[0048] 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
via the Joule effect into heat, which is transferred to the surface of the thermographic
recording material wherein the chemical reaction resulting in the development of a
black and white image takes place. Such thermal printing heads may be used in contact
or close proximity with the recording layer. 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 1.0 ms, the pressure contact of the thermal printhead with
the recording material being e.g. 200-500g/cm
2 to ensure a good transfer of heat.
[0049] In order to avoid direct contact of the thermal printing heads with a recording layer
not provided with an outermost protective layer, the image-wise heating of the recording
layer 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.
[0050] The image signals for modulating the laser beam or current in the micro-resistors
of a thermal printhead are obtained directly e.g. from opto-electronic scanning devices
or from an intermediary storage means, optionally linked to a digital image work station
wherein the image information can be processed to satisfy particular needs. Activation
of the heating elements can be power-modulated or pulse-length modulated at constant
power. EP-A 654 355 describes 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.
[0051] When used in thermographic recording operating with thermal printheads the thermographic
recording materials are not suitable for reproducing images with fairly large number
of grey levels as is required for continuous tone reproduction. EP-A 622 217 discloses
a method for making an image using a direct thermal imaging element producing improvements
in continuous tone reproduction.
[0052] Image-wise heating of the thermographic recording material can also be carried out
using an electrically resistive ribbon incorporated into the material. Image- or pattern-wise
heating of the thermographic recording material may also proceed by means of pixelwise
modulated ultra-sound, using e.g. an ultrasonic pixel printer as described e.g. in
US-P 4,908,631.
Photothermographic printing
[0053] Photothermographic recording materials, according to the present invention, may be
exposed with radiation of wavelength between an X-ray wavelength and a 5 microns wavelength
with the image either being obtained by pixel-wise exposure with a finely focused
light source, such as a CRT light source; a UV, visible or IR wavelength laser, such
as a He/Ne-laser or an IR-laser diode, e.g. emitting at 780nm, 830nm or 850nm; or
a light emitting diode, for example one emitting at 659nm; or by direct exposure to
the object itself or an image therefrom with appropriate illumination e.g. with UV,
visible or IR light.
[0054] For the thermal development of image-wise exposed photothermographic recording materials,
according to the present invention, any sort of heat source can be used that enables
the recording materials to be uniformly heated to the development temperature in a
time acceptable for the application concerned e.g. contact heating, radiative heating,
microwave heating etc.
Industrial application
[0055] Thermographic recording materials according to the present invention may be used
for both the production of transparencies, for example in the medical diagnostic field
in which black-imaged transparencies are widely used in inspection techniques operating
with a light box, and reflection type prints, for example in the hard copy field.
For such applications the support will be transparent or opaque, i.e. having a white
light reflecting aspect. Should a transparent base be used, the base may be colourless
or coloured, e.g. with a blue colour for medical diagnostic applications.
[0056] The following examples and comparative examples illustrate the present invention.
The percentages and ratios used in the examples and compositions of the ingredients
are by weight unless otherwise indicated.
i) backing layer ingredients:
- KELZAN™ S,
- a xanthan gum from MERCK & CO., Kelco Division, USA, which according to Technical
Bulletin DB-19 is a polysaccharide containing mannose, glucose and glucuronic repeating
units as a mixed potassium, sodium and calcium salt;
- PERAPRET™ PE40,
- a 40% aqueous dispersion of polyethylene latex from BASF;
- LATEX02,
- a 20% by weight dispersion of polymethyl methacrylate with an average particle size
of 88.8nm prepared as described in US-P 5,354,613;
- LATEX03,
- a 15% dispersion of a terpolymer of 18 mol% methyl acrylate, 79 mol% potassium salt
of acrylic acid and 3 mol% TAOE;
- LATEX04,
- a 20% dispersion of a 1µm polymethylmethacrylate latex;
- KIESELSOL™ 100F,
- a colloidal silica from BAYER;
- KIESELSOL™ 300F,
- a colloidal silica from BAYER;
- PLEXIGUM™ M345,
- a polymethylmethacrylate type from ROHM;
ii) thermosensitive element ingredients (in addition to those mentioned above):
- AgBeh
- = silver behenate;
- R01
- = ethyl 3,4-dihydroxybenzoate, a reducing agent containing 470ppm of chloride ions;
- R02
- = propyl gallate, a reducing agent containing 654ppm of chloride ions;
- T01
- = 7-(ethylcarbonato)benzo[e][1,3]oxazine-2,4-dione, a toning agent containing 500ppm
of chloride ions
- T02
- = phthalazinone containing less than 100ppm of chloride ions;
- T03
- = benzo[e][1,3]oxazine-2,4-dione containing 0.7ppm of chloride ions;
- LATEX 01
- = a terpolymer of 42% butyl acrylate, 53% styrene, 2% itaconic acid and 3% of the
ammonium salt of N-[(4'-sulfobenzamido)-oxo-decyl]methacrylamide;
- POLY01
- = POLYVIOL™ WX48 20, a polyvinylalcohol from WACKER CHEMIE, contains 545ppm of chloride
ions;
- POLY02
- = Polyvinylpyrrolidone, contains 1.5ppm of chloride ions;
and
iii) in the protective layer:
- POLYVIOL™ WX48 20, a polyvinylalcohol from WACKER CHEMIE;
- RILANIT™ GMS, a glycerine monotallow acid ester, from HENKEL AG
- MICROACE TALC P3, an Indian talc from NIPPON TALC;
- SERVOXYL™ VPAZ 100, a mixture of monolauryl and dilauryl phosphate, from SERVO DELDEN
B.V.;
- SERVOXYL™ VPDZ 3/100, a mono[isotridecyl polyglycolether (3 EO)] phosphate, from SERVO
DELDEN B.V.;
- 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.
INVENTION EXAMPLES 1 to 3
THERMOGRAPHIC COMPOSITION I
Preparation of silver behenate dispersions
[0057] Silver behenate was added with stirring to an aqueous solution of ammonium dodecylsulfonate
(Surfactant Nr. S01) and the mixtures stirred for 30 minutes with a KOTTHOFF™ stirrer.
The resulting dispersions were then ball-milled to obtain a finely divided 18.5% by
weight aqueous dispersion of silver behenate with 1g of a 0.1g of ammonium dodecylsulfonate
per g silver behenate.
Preparation of the thermographic recording materials
[0058] 3.23g of GEL05 (gelatin) was allowed to swell in 15.986g of deionized water for 30
minutes and the swollen GEL05 was heated up to 36°C. The following ingredients were
then added with stirring: 4.434g of a 20% aqueous solution of T02 followed by 5 minutes
stirring, then 24.20g of the silver behenate dispersion at a temperature of 36°C followed
by 10 minutes stirring, then 11.150g of an aqueous solution containing 5.55% of boric
acid, 8.17% of R01 and 15.23% of ethanol was added and finally 1.0g of an aqueous
solution containing 19.2% of formaldehyde and 6.75% of methanol. The dispersions for
INVENTION EXAMPLES 1 to 3 contained the concentrations of chloride and sodium ions
with respect to the gelatin present given in table 2.
[0059] The resulting silver behenate dispersions were then doctor blade-coated onto a 175µm
thick subbed polyethylene terephthalate support to produce the coating weights of
silver given in table 2.
Thermographic printing
[0060] The printer was equipped with a thin film thermal head with a resolution of 300 dpi
and was operated with a line time of 19ms (the line time being the time needed for
printing one line). During this line time the printhead received constant power. The
average printing power, being the total amount of electrical input energy during one
line time divided by the line time and by the surface area of the heat-generating
resistors was 1.6 mJ/dot being sufficient to obtain maximum optical density in each
of the substantially light-insensitive thermographic recording materials of INVENTION
EXAMPLES 1 to 3.
[0061] The maximum densities, D
max, and minimum densities, D
min, of the prints given in table 2 were measured through visible or blue filters with
a MACBETH™ TR924 densitometer in the grey scale step corresponding to data levels
of 64 and 0 respectively and are given in table 2.
Light box test
[0062] The stability of the image background of the prints made with the substantially light-insensitive
thermographic recording materials of INVENTION EXAMPLES 1 to 3 was evaluated on the
basis of the change in minimum (background) density measured through a blue filter
using a MACBETH™ TR924 densitometer upon exposure on top of the white PVC window of
a specially constructed light-box placed for 3 days in a VÖTSCH conditioning cupboard
set at 30°C and a relative humidity (RH) of 85%. Only a central area of the window
550mm long by 500mm wide was used for mounting the test materials to ensure uniform
exposure.
[0063] The stainless steel light-box used was 650mm long, 600mm wide and 120mm high with
an opening 610mm long and 560mm wide with a rim 10mm wide and 5mm deep round the opening,
thereby forming a platform for a 5mm thick plate of white PVC 630mm long and 580mm
wide, making the white PVC-plate flush with the top of the light-box and preventing
light loss from the light-box other than through the white PVC-plate. This light-box
was fitted with 9 PLANILUX™ TLD 36W/54 fluorescent lamps 27mm in diameter mounted
length-wise equidistantly from the two sides, with the lamps positioned equidistantly
to one another and the sides over the whole width of the light-box and with the tops
of the fluorescent tubes 30mm below the bottom of the white PVC plate and 35mm below
the materials being tested. The results are summarized in table 2.
[0064] The results of the thermographic evaluation of the thermographic recording material
of INVENTION EXAMPLES 1 to 3 show no significant photo-instability in the light-box
test indicating that up to a chloride ion concentration of 201ppm with respect to
the gelatin present there is no adverse effect of the chloride ion content upon the
light stability of thermographic recording materials with the very stable THERMOGRAPHIC
COMPOSITION I used.
Table 2
Invention example number |
AgBeh coverage [g/m2] |
gelatin |
concentrations of ions with respect to gelatin present |
fresh |
Light box: ΔDmax/ΔDmin blue after 3 days at 30°C/85%RH |
|
|
|
[Cl-] [ppm] |
[Na+] [ppm] |
Dmax blue |
Dmin blue |
|
1 |
3.4 |
GEL05 |
201 |
44 |
2.26 |
0.05 |
+0.14/+0.01 |
2 |
3.7 |
GEL05 |
167 |
22 |
2.63 |
0.05 |
-0.07/+0.01 |
3 |
3.7 |
GEL05 |
140 |
4 |
2.43 |
0.05 |
+0.22/+0.02 |
COMPARATIVE EXAMPLES 1 & 2 and INVENTION EXAMPLES 4 to 6
THERMOGRAPHIC COMPOSITION II
Preparation of a tone modifier dispersion
[0065] The tone modifier dispersion was prepared by first dissolving 8.8g of GEL05 in 71.4g
of deionized water by first adding the gelatin, then allowing the gelatin to swell
for 30 minutes and finally heating to 50°C. 20 g of T01 was added with ULTRA-TURRAX™
stirring to this gelatin solution at 50°C, and the stirring continued for a further
5 minutes. Finally the resulting dispersion was pumped through a DYNOMILL™ for 2 hours
to produce the final tone modifier dispersion containing: 20% of T01 and 8.8% of GEL05.
Preparation of thermographic recording materials
[0066] Aqueous silver behenate dispersion was first prepared as described for INVENTION
EXAMPLES 1 to 3 except that the surfactant used was Surfactant Nr. S03 and was present
at a concentration of 0.1g/g silver behenate and the silver behenate concentration
was 16.9%.
[0067] The coating dispersion for the thermosensitive element was produced by first adding
2.059g of gelatin (for the type see table 3) to 7.64g of deionized water or in the
case of COMPARATIVE EXAMPLE 1 2.059g of gelatin (for the type see table 3) together
with 1.949g of GEL02 to 13.11g of deionized water, allowing the gelatin to swell for
30 minutes and then heating the mixture to 36°C then adding the following solutions
and dispersions with stirring while maintaining a temperature of 36°C: 6.93g of the
toner modifier dispersion as flakes (contains GEL05), then for COMPARATIVE EXAMPLE
2 and INVENTION EXAMPLES 4 to 6: 7.430g of a 26.2% dispersion of LATEX 02, then 30.72g
of the aqueous silver behenate dispersion followed by stirring, then 12.35g of an
aqueous solution containing 2.78% of boric acid, 8.17% of R01 and 15.23% of ethanol
and finally 2.88g of a 3.7% aqueous solution of formaldehyde. The chloride and sodium
ions present in the dispersion only arise from the gelatin used.
[0068] The coating dispersion was doctor-blade coated at a pH of Ca. 5.4 onto a 175µm thick
subbed polyethylene terephthalate support to provide, after drying in a drying cupboard
at 50°C, the thermographic recording materials of COMPARATIVE EXAMPLE 1 & 2 and INVENTION
EXAMPLES 4 to 6 with the silver behenate coating weights given in table 3 below.
Table 3
Comparative example number |
AgBeh coverage [g/m2] |
binder % as LATEX 02 |
GELATIN |
total [Cl-] vs gelatin [ppm] |
fresh |
Light box: ΔDmax/ΔDmin blue after 3 days at 30°C/85%RH |
|
|
|
type |
[Cl-] [ppm] |
|
Dmax blue |
Dmin blue |
|
1 |
4.35 |
0 |
(38%) GEL02 |
2900 |
3153 |
3.57 |
0.10 |
+0.52/+0.07 |
|
|
(62%) GEL05 |
<40 |
|
|
|
|
2 |
4.21 |
38 |
GEL03 |
1270 |
1707 |
3.26 |
0.10 |
+0.19/+0.10 |
Invention example number |
|
|
|
|
|
|
|
|
4 |
4.24 |
38 |
(76%) GEL04 |
17 |
454 |
3.15 |
0.10 |
+0.24/+0.01 |
|
|
(24%) GEL05 |
<40 |
|
|
|
|
5 |
4.11 |
38 |
GEL05 |
<40 |
437 |
3.38 |
0.10 |
+0.03/+0.01 |
6 |
4.35 |
38 |
(76%) GEL06 |
<40 |
437 |
3.18 |
0.10 |
+0.17/+0.02 |
|
|
(24%) GEL05 |
<40 |
|
|
|
|
[0069] The results of the thermographic evaluation of the thermographic recording materials
of COMPARATIVE EXAMPLES 1 & 2 show a significant increase in D
min i.e. 0.07 and 0.10 respectively after the light box test as can be seen from table
3, whereas the thermographic recording materials of INVENTION EXAMPLES 4 to 6 show
increases in D
min of 0.02 or less after the light box test indicating that for chloride concentrations
above 1500ppm with respect to gelatin, thermographic recording materials of THERMOGRAPHIC
COMPOSITION II exhibit significant photo-instability in the light-box test, whereas
at chloride ion concentrations of 500ppm or less with respect to gelatin, there is
no significant photo-instability during this test.
COMPARATIVE EXAMPLE 3 and INVENTION EXAMPLE 7
THERMOGRAPHIC COMPOSION III
[0070] Aqueous silver behenate dispersions were prepared as described for INVENTION EXAMPLES
1 to 3 except that the surfactant used was that given in table 3 and was present at
a concentration of 0.1g/g silver behenate and the silver behenate concentration was
21%.
[0071] The coating dispersion for the thermosensitive element was produced by first adding
0.31g of boric acid and 3.942g of gelatin (for the type see table 4) to 19.46g of
deionized water, allowing the gelatin to swell for 30 minutes and then heating the
mixture to 36°C then adding the following solutions and dispersions with stirring
while maintaining a temperature of 36°C: 4.93g of the toner modifier dispersion as
flakes, then a solution of 1g of R01 in 3g of deionized water and 1g of ethanol at
50°C then 1.98g of deionized water and finally by 23.36 of a 21% dispersion of silver
behenate with 0.1g of surfactant/g silver behenate. The chloride and sodium ions present
in the dispersion only arise from the gelatin used.
[0072] The coating dispersion was doctor-blade coated at a pH of ca. 5.0 onto a 175µm thick
subbed polyethylene terephthalate support to provide, after drying in a drying cupboard
at 50°C, the thermographic recording materials of COMPARATIVE EXAMPLE 3 and INVENTION
EXAMPLES 7 with the silver behenate coating weights given below.
Thermographic evaluation
[0073] Thermographic evaluation was carried out as described for INVENTION EXAMPLES 1 to
3 and the results are given in table 4 below. The results of INVENTION EXAMPLE 5 cannot
be directly compared with those of INVENTION EXAMPLE 7, because THERMOGRAPHIC COMPOSITION
II of INVENTION EXAMPLE 4 to 6 and COMPARATIVE EXAMPLES 1 & 2 is more stable than
THERMOGRAPHIC COMPOSITION III of INVENTION EXAMPLE 7 and COMPARATIVE EXAMPLE 3. However,
the trend observed for the results with THERMOGRAPHIC COMPOSITION II is also to be
found in the results obtained with THERMOGRAPHIC COMPOSITION III i.e. that the thermographic
recording material of COMPARATIVE EXAMPLE 3 with a chloride ion concentration greater
than 1500ppm exhibited significant photo-instability in the light-box test, whereas
the thermographic recording material of INVENTION EXAMPLE 7 with less than 500ppm
of chloride ions with respect to the gelatin exhibited no significant photo-instability
in the light-box test in the context of the lower general stability of THERMOGRAPHIC
COMPOSITION III.
Table 4
Comparative example number |
AgBch coverage [g/m2] |
binder % as LATEX 01 |
GELATIN |
total [Cl-] vs gelatin [ppm] |
fresh |
Light box: ΔDmax/ΔDmin blue after 3 days at 30°C/85%RH |
|
|
|
type |
[Cl-] [ppm] |
|
Dmax blue |
Dmin blue |
|
3 |
4.53 |
S03 |
(89%) GEL01 |
5300 |
5544 |
2.66 |
0.10 |
+0.17/+0.63 |
|
|
|
(11%) GEL05 |
<40 |
|
|
|
|
Invention example number |
|
|
|
|
|
|
|
|
7 |
4.40 |
502 |
GEL05 |
<40 |
244 |
2.95 |
0.10 |
+0.02/+0.04 |
INVENTION EXAMPLES 8 and 9
THERMOGRAPHIC COMPOSITION IV
PREPARATION OF SUBBING LAYERS
SUBBING LAYER NUMBER 01:
[0074] A 0.34mm thick polyethylene terephthalate sheet was coated to a thickness of 0.1mm
with a composition which after drying and longitudinal and transverse stretching produced
a 175mm thick support coated with the following subbing-layer composition expressed
as the coating weights of the ingredients present:
# terpolyrner latex of vinylidene chloride/methyl acrylate/itaconic acid (88/10/2): |
162mg/m2 |
# colloidal silica (KIESELSOL™ 100F from BAYER): |
38mg/m2 |
# alkyl sulfonate surfactant (Surfactant Nr. 2): |
0.6mg/m2 |
# aryl sulfonate surfactant (Surfactant Nr. 3): |
4mg/m2 |
SUBBING LAYER NUMBER 02:
[0075] A 0.34mm thick polyethylene terephthalate sheet was coated to a thickness of 0.1mm
with a composition which after drying and longitudinal and transverse stretching produced
a 175mm thick support coated on with the following subbing-layer composition of subbing
layer number 01 expressed as the coating weights of the ingredients present:
# copolymer of terephthalic acid/isophthalic acid/sulfo-isophthalic acid/ethylene
glycol 26.5/20/3.5/50): |
37.0mg/m2 |
# copolymer latex of ethyl acrylate/methacrylic acid (80/20): |
3.0mg/m2 |
# HORDAMER™ PE02: |
1.0mg/m2 |
# PAREZ RESIN™ 707: |
7.0mg/m2 |
Quantity of leachable non-fluoro-halide ions per unit surface of subbing layers
[0076] The chloride-ion content leachable during overcoating with an aqueous dispersion
or solution was simulated by placing a 10 x 5cm
2 piece of subbing layer-coated polyethylene terephthalate in 25mL of deionized water
for a period of 2 hours and determining the quantity of chloride ions leached out
by injecting samples of the leaching water directly into a DIONEX QIK ANALYSER ion
chromatograph The detection limit with these measurements was limited to 0.1ppm by
the deionized water used in the leaching experiments, which had a chloride ion concentration
of 0.02 to 0.06 ppm. The results obtained are given below in table 1:
[0077] Wavelength dispersive X-ray fluorescence (WDXRF) measurements were carried out on
some of the supports to obtain a qualitative estimate of the total chlorine constant
of the supports i.e. both covalently bound chlorine and chloride ions. These showed
no detectable chlorine in an uncoated support, a very small quantity in subbing layer
number 02 and a small quantity in subbing layer 01. The quantity of leachable chloride
ions in the different subbing layers obtained from these measurements are summarized
in table 5:
Table 5
Subbing layer number |
Quantity of leachable chloride ions [mg/m2 surface] |
01 |
0.65 |
02 |
0.3 |
Preparation of the silver behenate dispersion
[0078] The silver behenate dispersion was produced as follows: dispersing 25kg (73.5M) behenic
acid was dispersed with stirring at 80°C in 100L of a 10% solution of Surfactant Nr
5/g behenic acid made up to 250L with deionized water at a temperature of 80°C; then
36.75L of a 2M aqueous solution of sodium hydroxide was added over a period of 10
to 20 minutes to give a clear solution substantially containing sodium behenate; then
25L of a 2.94M aqueous solution of silver nitrate was added with stirring at a rate
of 0.163moles/moles silver behenate·min to convert the sodium behenate completely
into silver behenate; and finally ultrafiltration was carried out with a 500000 MW
polysulfone cartridge filter at room temperature to concentrate the resulting silver
behenate dispersion, the final AgBeh-concentration was 16.7% with 0.07g of Surfactant
Nr 5/g AgBeh, the residual conductivity was 1.0mS/cm.
Preparation of the thermosensitive element
[0079] 175µm thick blue pigmented polyethylene terephthalate supports coated with subbing
layer numbers 01 & 02 were coated with an aqueous coating composition and the following
ingredients so to obtain thereon after drying, a thermosensitive element containing:
- * AgBeh:
- 4.94g/m2
- * GEL05:
- 4.96g/m2
- * formaldehyde
- 0.2g/m2
- * Surfactant Nr. S01
- 0.32g/m2
- * Surfactant Nr. S04
- 0.004g/m2
- * Surfactant Nr. 505
- 0.13g/m2
- * R01
- 1.00g/m2
- * T03
- 0.53g/m2
- * boric acid
- 0.18g/m2
- * ammonium tetraborate
- 0.48g/m2
and to produce the thermographic recording materials of INVENTION EXAMPLES 8 and
9 respectively in which the thermosensitive elements contain, taking into account
the leachable chloride ions from the subbing layers used of 239ppm and 168ppm of chloride
ions with respect to gelatin.
Evaluation
[0080] Thermographic evaluation was carried out as described above for COMPARATIVE EXAMPLES
1 to 3 and INVENTION EXAMPLES 1 & 2 except the archivability tests were carried out
for 4 days at 45°C and 70% relative humidity instead of 3 days at 35°C and 80% relative
humidity. The results are summarized in table 6.
Table 6
Invention example number |
AgBeh coverage [g/m2] |
Total Cl- ions versus gelatin [ppm] |
Leachable Cl--ions from subbing layer |
FRESH |
Archivability: ΔDmin vis/blue after 4d at 45°C/70% RH |
Light box ΔDmin vis/blue after 3d at 30°C/85% RH |
|
|
|
layer nr |
mg/m2 |
Dmax vis/blue |
Dmin vis/blue |
|
|
8 |
4.94 |
239 |
01 |
0.65 |
3.12/3.23 |
0.23/0.10 |
0.01/0.02 |
0.02/0.04 |
9 |
4.94 |
168 |
02 |
0.30 |
2.65/2.71 |
0.21/0.10 |
0.00/0.01 |
0.01/0.01 |
[0081] These results are consistent with those of INVENTION EXAMPLES 1 to 7 and show that
these thermographic recording materials of THERMOGRAPHIC COMPOSITION IV with chloride
ion concentrations below 500ppm (239 and 168ppm respectively) with respect to gelatin
exhibit no significant photo-instability in the light-box test.
INVENTION EXAMPLES 10 to 12 and COMPARATIVE EXAMPLES 4 to 6
THERMOGRAPHIC COMPOSITION V
[0082] 175µm thick polyethylene terephthalate supports coated with subbing layer number
01 was coated with an aqueous coating composition and the following ingredients to
obtain thereon after drying thermosensitive elements compositions of the thermographic
recording materials of COMPARATIVE EXAMPLES 4 to 6 and INVENTION EXAMPLES 10 to 12
as given in table 7:
Table 7
Comparative example nr. |
binder |
AgBeh [g/m2] |
Surfactant Nr S03 [g/m2] |
R01 [g/m2] |
R02 [g/m2] |
tone modifier |
|
type |
coverage [g/m2] |
|
|
|
|
type |
[g/m2] |
4 |
POLY01 |
3.78 |
4.11 |
0.411 |
- |
0.975 |
T01 |
1.038 |
GEL05 |
0.33 |
|
|
|
|
|
|
5 |
POLY01 |
3.83 |
4.16 |
0.416 |
- |
0.986 |
T02 |
0.611 |
GEL05 |
0.33 |
|
|
|
|
|
|
6 |
POLY02 |
3.01 |
4.93 |
0.493 |
1.010 |
- |
T03 |
0.809 |
GEL05 |
0.39 |
|
|
|
|
|
|
Invention example nr. |
|
|
|
|
|
|
|
|
10 |
GEL05 |
4.00 |
4.00 |
0.400 |
- |
0.948 |
T01 |
0.893 |
11 |
POLY02 |
1.93 |
4.48 |
0.448 |
0.917 |
- |
T03 |
0.735 |
GEL05 |
2.55 |
|
|
|
|
|
|
12 |
GEL05 |
3.95 |
3.95 |
0.395 |
- |
0.937 |
T02 |
0.580 |
Thermographic evaluation
[0083] Thermographic evaluation was carried out as described for INVENTION EXAMPLES 1 to
3 and the results are given in table 8.
Table 8
Comparative example number |
AgBeh coverage [g/m2] |
non-gelatin binder |
GELATIN |
total [Cl-] vs gelatin [ppm] |
fresh |
Light box: ΔDmax/ΔDmin blue after 3 days at 30°C/85%RH |
|
|
type |
% |
type |
[Cl-] [ppm] |
|
Dmax blue |
Dmin blue |
|
4 |
4.11 |
POLY01 |
92 |
GEL05 |
<40 |
11717 |
4.00 |
0.17 |
-0.20/+0.43 |
5 |
4.16 |
POLY01 |
92 |
GEL05 |
<40 |
8279 |
3.50 |
0.21 |
+0.20/+0.28 |
6 |
4.93 |
POLY02 |
92.6 |
GEL05 |
<40 |
1680 |
2.90 |
0.13 |
-0.60/+0.41 |
Invention example number |
|
|
|
|
|
|
|
|
|
10 |
4.00 |
- |
- |
GEL05 |
<40 |
429 |
4.10 |
0.12 |
-0.10/+0.08 |
11 |
4.48 |
POLY02 |
43 |
GEL05 |
<40 |
257 |
3.60 |
0.11 |
-0.30/+0.09 |
12 |
3.95 |
- |
- |
GEL05 |
<40 |
320 |
4.10 |
0.08 |
+0.40/+0.06 |
[0084] The light-box results for the thermographic recording materials of COMPARATIVE EXAMPLES
4 to 6 with chloride ion concentrations with respect to gelatin above 1500ppm with
ΔD
min-values of 0.28 to 0.43 show much stronger photo-instability than with the thermographic
recording materials of INVENTION EXAMPLES 10 to 12 with chloride ion concentrations
below 500ppm with respect to gelatin with AD
min-values of 0.06 to 0.09. This is attributable to the higher concentration of chloride
ions therein.
[0085] The photoinstability (ΔD
min increase) in the light-box test with the thermographic recording materials of INVENTION
EXAMPLES 10 to 12, with less than 500ppm of chloride ions with respect to gelatin,
is not dependent upon the chloride ion concentration and hence can be attributed to
the lower stability of the THERMOGRAPHIC COMPOSITION V in general and not to the chloride
ion concentration in particular. Therefore in the context of the lower stability of
THERMOGRAPHIC COMPOSITION V, there is no significant photo-instability attributable
to the chloride ion concentration in the light-box test results for the thermographic
recording materials of INVENTION EXAMPLES 10 to 12 with less than 500ppm of chloride
ions with respect to gelatin.
[0086] Therefore, the trend observed with the results obtained with THERMOGRAPHIC COMPOSITIONS
II and III is also to be found in the results obtained with THERMOGRAPHIC COMPOSITION
V i.e. the thermographic recording materials of COMPARATIVE EXAMPLES 4 to 6 with chloride
ion concentrations greater than 1500ppm with respect to gelatin exhibited significant
photo-instability in the light-box test due to the presence of chloride ions, whereas
there was no photo-instability in the light-box tests for the thermographic recording
materials of INVENTION EXAMPLES 10 to 12 with chloride ion concentrations below 500ppm
with respect to gelatin, which is directly attributable to the presence of chloride
ions.
INVENTION EXAMPLES 14 and 15
Backside layers
[0087] A 175µm thick polyethylene terephthalate support coated on both sides with subbing
layer 01 was coated on one side with backside layer B01 with the following composition:
KELZAN™ S |
10mg/m2 |
polyethylenedioxythiophene |
5mg/m2 |
polystyrene sulfonic acid |
10mg/m2 |
Surfactant Nr. S07 |
21mg/m2 |
PERAPRET™ PE40 |
10mg/m2 |
KIESOLSOL™ 100F |
20mg/m2 |
PMMA latex |
200mg/m2 |
LATEX02 |
30mg/m2 |
[0088] A 175µm thick polyethylene terephthalate support coated on both sides with subbing
layer 01 was also coated on one side with backside layer packet B02. First a layer
with the following composition was coated:
GEL07 |
380mg/m2 |
KIESELSOL 300F |
340.7mg/m2 |
Surfactant Nr S07 |
13.3mg/m2 |
Surfactant Nr. S08 |
6.7mg/m2 |
2-methyl-2,4-pentanediol |
22.2mg/m2 |
Trimethylolpropane |
11.1mg/m2 |
PMMA latex |
1mg/m2 |
then with a layer with the following composition:
GEL05 |
300mg/m2 |
LATEX03 |
450mg/m2 |
Surfactant Nr S10 |
3mg/m2 |
Surfactant Nr S11 |
1mg/m2 |
Polystyrene sulfonic acid |
8mg/m2 |
and finally with a layer of composition:
GEL08 |
1266mg/m2 |
GEL09 |
100mg/m2 |
GEL10 |
130mg/m2 |
Surfactant Nr S09 |
<5 mg/m2 |
Surfactant Nr S10 |
80mg/m2 |
Surfactant Nr S11 |
3mg/m2 |
anti-bacterial agent |
50mg/m2 |
LATEX04 |
100mg/m2 |
PLEXIGUM™ M345 |
50mg/m2 |
dioctadecyl phthalate |
5mg/m2 |
formaldehyde |
106mg/m2 |
sodium sulphate |
1mg/m2 |
Thermosensitive element
[0089] A 175µm thick polyethylene terephthalate support with an uncoated subbing layer 01
on one side and backing layer B01 on the other was used for the thermographic recording
material of INVENTION EXAMPLE 14 and a 175µm thick polyethylene terephthalate support
with uncoated subbing layer 01 on one side and backing layer B02 on the other was
used for the thermographic recording material of INVENTION EXAMPLE 15.
[0090] A thermosensitive element of the following composition was applied in each case to
the side coated with subbing layer 01:
|
thermosensitive element of INVENTION EXAMPLE 14 |
thermosensitive element of INVENTION EXAMPLE 15 |
AgBeh |
5.031g/m2 |
5.268g/m2 |
Surfactant Nr. 1 |
0.503g/m2 |
0.527g/m2 |
GEL05 |
2.66.g/m2 |
2.785g/m2 |
LATEX 01 |
1.843g/m2 |
1.929g/m2 |
R01 |
0.956g/m2 |
1.001g/m2 |
T01 |
1.132g/m2 |
1.185g/m2 |
Boric acid |
0.325g/m2 |
0.340g/m2 |
HCHO |
0.192g/m2 |
0.201g/m2 |
Protective layers
[0091] The thermosensitive elements of the thermographic recording materials of INVENTION
EXAMPLES 14 and 15 were then coated with a protective layer with the following composition:
POLY01 |
2.31g/m2 |
SYLOID™ 72 |
0.08g/m2 |
SERVOXYL™ VPDZ 3/100 |
0.07g/m2 |
SERVOXYL™ VPAZ 100 |
0.07g/m2 |
MICROACE™ TALC P3 |
0.04g/m2 |
RILANIT™ GMS |
0.13g/m2 |
LEVASIL™VP AC 4055 |
0.50g/m2 |
Formaldehyde |
0.52g/m2 |
Curl evaluation experiments
[0092] Curl evaluation experiments were carried out by hanging 24x30 cm
2 sheets for 4 hours at 20°C and 10% and 85% relative humidity respectively in analogy
with ISO Norm 4330 - 1979 (E) and then evaluating the dgree of curl with a curl-meter
The curl values in table 9 are the reciprocal of the curl radius in metres.
Table 9
Invention example number |
Curl at room temperature & 10% RH |
Curl at room temperature & 85% RH |
14 |
10 |
3.3 |
15 |
6.6 |
4.5 |
[0093] From these tests it is clear that the thermographic recording material with the gelatin
backing layer INVENTION EXAMPLE 15 exhibits significantly less curl than the thermographic
recording material with the polymethylmethacrylate-based backing layer of INVENTION
EXAMPLE 14.
[0094] Having described in detail preferred embodiments of the current invention, it will
now be apparent to those skilled in the art that numerous modifications can be made
therein without departing from the scope of the invention as defined in the following
claims.