JPH10115889A - Sensitivity enhancing method and recording method for photosensitive thermally developable photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the photographic sensitivity of a photographic material by executing an exposure stage according to information during a heating stage while keeping the photographic material existing in one identical holding or guide means during both of the exposure stage and the heating stage according to the information. SOLUTION: The exposure stage is started after the heating stage is started and a preliminary heating stage is executed before the exposure stage. Besides, it is prefereble that the duration of the exposure stage is under 1/10 of that of the heating stage. It is specially preferable that the duration of the exposure stage is under 1/100 of that of the heating stage. The exposure stage corresponding to the information of the photosensitive thermal developing feasible photographic material and the thermal developing stage thereof are executed in the midst of the heating stage. Then, a visible image is formed from a latent image obtained on the exposure stage. Besides, the heating stage is started before the exposure stage is started and finished after the thermal developing stage for forming the visible image is finished. Thus, the photographic sensitivity is enhanced while enabling a simple photothermography processor to be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a sensitivity-enhancing recording method for photographic materials in which an informed exposure occurs during heating.

[0002]

BACKGROUND OF THE INVENTION Thermal imaging or thermography is a recording method in which an image is formed by the use of image-wise modulated thermal energy.

[0003] Three methods are known in thermography: Image-wise or information-wise transfer of components necessary for a chemical or physical process to effect a change in color or optical density to a receptor element.

[0004] 2. Thermal dye transfer printing in which a visible image pattern is formed by the transfer of colored species from an imagewise heated donor element to a receiver element.

[0005] 3. Direct thermal formation of a visible image pattern by image-wise or information-wise heating of a recording material containing a substance whose color or optical density changes by a chemical or physical process.

[0006] Type 3 thermographic materials contain photosensitive reagents that can catalyze or participate in thermographic processes that result in a change in color or optical density after exposure to UV light, visible light or IR light. If so, it becomes a photothermographic material.

An example of a photothermographic material is 3M
Company is a so-called “dry silver” photothermographic material, which is a “Handbook”
og Imaging Science ”, edit
ed by A. R. Diamond, page 4
3, published by Marcel Dek
ker in 1991. A. Morgan
Are discussed.

[0008] DOS 2 248 545 provides a uniform auxiliary surface at a temperature within a suitable development temperature range for the photosensitive material, prior to the full implementation of the exposure, to the thermally developable photosensitive silver material. A copying method is disclosed which is subjected to thermal treatment and after exposure to thermal development; and in a subclaim, the photosensitive material can be subjected to auxiliary heating during its exposure. The description and the examples of the invention do not indicate the efficiency of auxiliary heating during exposure.

[0009] Yu. E. FIG. Usanov, T .; B. Kol
esova, L .; P. Burleva, M .; R. V. S
ahyun and D.A. R. Whitcomb is C
ambridge, Massachusetts, US
S held at A in May 18-23, 1997
ocityy for Imaging Science
e and Technology (IS &
T. ) 50th Annual Conference
Preliminaries, pp. 42-45: Experiments performed using thermally developed Dry Silver ^™ 7858 type photothermographic materials and spectrally sensitized model photothermographic materials from 3M were performed using flash lamp or sensitometer exposure. Preheating above 100 ° C. before cooling and then cooling showed that the rate during development was reduced. Eventually, a decrease in light sensitivity was observed. Exposure of the material during the preheating process gave similar results. Preheating temperature is 100
The higher the temperature, the longer the preheating time, the lower the photosensitivity of the material. It has been determined that this phenomenon does not depend on the composition of the silver halide or its method of insertion into the thermally developable composition.

It is desirable to improve the photosensitivity of the photosensitive thermally developable photographic material so that a lower power heat source can be used. For example, DE-A 196 36
It is also desirable to achieve such an increase in photosensitivity, while allowing for simplification of the photothermographic processor, as described in 253.0.

[0011]

OBJECTS OF THE INVENTION It is therefore an object of the present invention to provide a method for improving the photosensitivity of a photosensitive thermally developable photographic material.

It is yet another object of the present invention to provide an improved recording method which allows for the use of a simple photothermographic processor while increasing sensitivity.

[0013] Other objects and advantages of the present invention will become apparent from the further description and examples.

[0014]

SUMMARY OF THE INVENTION An imagewise exposure of a photosensitive thermally developable photographic material to radiation, thereby forming a latent image; and heating the photosensitive thermally developable photographic material, comprising the steps of: The thermally developable photographic material is on one and the same holding or guiding means during both the informational exposure step and the heating step; the informational exposure step is performed during the heating step A recording method is provided.

The photosensitive thermally developable photographic material is on the same one holding or guiding means during both the informational exposure step and the heating step; the heating step is prior to the informational exposure step and / or In the meantime, there is provided a method for improving the photosensitivity of a photosensitive thermally developable photographic material, which is performed.

Preferred embodiments of the present invention are disclosed in the detailed description of the invention.

[0017]

DETAILED DESCRIPTION OF THE INVENTION Surprisingly, the inventors of the present invention have found that preheating the material requires less exposure than using prior art methods in which the unheated material is exposed to recording radiation. It has been found that a short time results in a thermally developable photographic material. This indicated that when heated, the material became more sensitive to the recording radiation and the device could be simplified.

However, prolonged preheating reduces the sensitivity of the photosensitive thermally developable photographic material to spectrally sensitized wavelengths and in some cases completely destroys the U.S.C.
V-sensitivity, the intrinsic sensitivity, remains substantially unchanged in all cases. This indicates that the spectral sensitizer alone or together with the supersensitizer cannot, for any reason, sensitize the material to IR radiation after prolonged preheating. ing.

Recording Method for Photosensitive Thermally Developable Photographic Materials and Method for Enhancing Its Photosensitivity In a preferred embodiment of the invention, the exposure step is started after the start of the heating step.

The photographic material can be preheated before exposure in a further step of the recording method and the method of the present invention for improving the photosensitivity of the photographic material.

According to the invention, the duration of the exposure phase is preferably less than one tenth of the duration of the heating phase, and the duration of the exposure phase is 100 times the duration of the heating phase.
It is particularly preferred that it is less than one part.

In a particular embodiment of the present invention, the intellectual exposure and thermal development of the photosensitive thermally developable photographic material takes place during the heating step, during which the latent image obtained from the exposure step is A visible image is formed.

In a particularly preferred embodiment of the invention, the heating step starts before the start of the exposure step and ends after the thermal development for forming a visible image is completed.

According to the present invention, the photographic material and the photosensitive thermally developable photographic material can be exposed to radiation at a wavelength between the X-ray wavelength and the 5 micron wavelength so that the image is finely focused. Light source, eg, CRT light source; UV, visible or IR wavelength laser, eg, 780 nm, 830 n
e.g. a He / Ne-laser or IR-laser diode emitting at m or 850 nm; or by pixel-wise exposure using a light-emitting diode such as, for example, one emitting at 659 nm; or using the subject itself or suitable illumination, for example UV , Obtained by direct exposure to an image therefrom using visible or IR light. Exposure using infrared light or visible light is preferable.
Visible light in the wavelength range of 0 nm is particularly preferred. According to the present invention, exposure using an infrared emitting laser diode is preferred.

The photosensitive thermally developable photographic material can be heated by the same heating means during exposure and subsequent heating. In addition, the photosensitive thermally developable photographic material can be heated by the same heating means before, during, and during heating following exposure. A heating drum is the preferred conventional heating means.

[0026] For the thermal development of the informed light-sensitive thermally developable photographic material according to the recording method of the present invention, the recording material is brought to the development temperature within the time acceptable for the relevant application. Any type of heat source that allows for heating can be used, for example, contact heating, radiation heating or microwave heating using a heating roller, heating drum, or thermal head. The preferred temperature of the photosensitive thermally developable photographic material during thermal development is 110 ° C.
~ 130 ° C.

In the preferred recording method of the present invention, at least two radiation beams move simultaneously on the photosensitive thermally developable photographic material, and the first of the radiation beams follows the information of the photosensitive thermally developable photographic material. The second is to heat the informed photosensitive thermally developable photographic material to a uniform development temperature.

Photosensitive thermally developable photographic material The photosensitive thermally developable photographic material preferably contains an infrared sensitizer or a visible light sensitizer, and further comprises a photosensitive silver halide, an organic reducing agent and a binder. It is particularly preferred to include an agent.

In the present invention, it is preferable to use a photosensitive thermally developable photographic material containing a gelatinous silver halide emulsion layer. A substantially light-insensitive organic silver salt in which the photosensitive silver halide is catalytically associated, and an organic reducing agent in thermal relation therewith for the substantially light-insensitive organic silver salt; It is particularly preferred to use a photosensitive thermally developable photographic material further comprising in the present invention. Photosensitive thermally developable photographic materials can have a layer system in which the components are dispersed in various layers, where the imaging process can take place.

For example, in the case of a photosensitive thermally developable photographic material containing a photosensitive silver halide and an organic reducing agent and optionally further containing a substantially light-insensitive organic silver salt, the photosensitive silver halide Or, if present, the substantially light-insensitive organic silver salt must be in a thermal working relationship with the organic reducing agent, i.e., during the thermal development process,
It must be present in such a way that it can diffuse into the light-sensitive silver halide or substantially light-insensitive organic silver salt grains and cause the reduction of the silver halide or organic silver salt to take place; The silver, if present, must be in catalytic association with the substantially light-insensitive organic silver salt.

Photosensitive Silver Halide The photosensitive silver halide used in the present invention can be used substantially within the range of 0.1 to 100 mole percent of the non-photosensitive organic silver salt. A range of 80 mole percent is preferred, a range of 0.3 to 50 mole percent is particularly preferred, 0.5 to 35 mole percent is particularly preferred,
1-12 mol% is very preferred.

The silver halide can be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide and the like. . Silver halide can be in any form that is photosensitive, including but not limited to cubic, oblique, plate-like, tetrahedral, octagonal, etc., and can have epitaxial growth of crystals thereon. it can.

The silver halide used in the present invention can be used without modification. However, chemical sensitizers, for example, compounds containing sulfur, selenium, tellurium or the like, or compounds containing gold, platinum, palladium, iron, ruthenium, rhodium or iridium, reducing agents such as tin halides or the like The combination can be used to chemically sensitize it. Details of these methods can be found in T.W. H. James, "The Theor
y of the PhotographicProc
ess ”, Fourth Edition, Macmi
lan Publishing Co. Inc. , N
ew York (1977), Chapter 5, p
Ages 149-169.

Spectral Sensitizer The photosensitive thermally developable photographic material of the present invention can contain an infrared sensitizer or a visible light sensitizer. Suitable sensitizers include cyanine, mesocyanin, styryl, hemicyanine,
Oxonol, hemioxonol and xanthene dyes are included. Useful cyanine dyes include those having a basic nucleus, such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Preferred merocyanine dyes include those having not only the above basic nucleus, but also an acid nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinone nucleus, a malononitrile nucleus and a pyrazolone nucleus. Is included. Among the above-mentioned cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly preferred.

Suitable infrared sensitizers include EP-A's 4
65 078, 559 101, 616 014 and 6
35 756, JN's 03-080251, 03-
163440, 05-01943, 05-07266
2 and 06-003763, and US-P's
4,515,888, 4,639,414,4,71
3,316, 5,258,282 and 5,441,86
6 are included.

For use in the photosensitive thermally developable photographic material used in the present invention, the general formula (I) having an anion if necessary for charge compensation:

[0037]

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Wherein Z ¹ and Z ² independently represent S, O or Se; R ¹ and R ¹³ independently represent an alkylene chain; X ¹ and X ² independently represent-(C ＯO) -R ¹⁸ ,-(S
O ₂₎ -R ¹⁹ or - (indicates S = O) -R ²⁰ group wherein alkoxy R ^18, R ¹⁹ and R ²⁰ are independently -, aryloxy -, amino - group - or a substituted amino R ² ,
R ³ , R ⁴ , R ⁵ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently hydrogen, chlorine, bromine, fluorine, iodine or keto-, sulfo-, carboxy-, ester-, sulfonamide-, Amido-, dialkylamino-, nitro-, cyano-, alkyl-, alkenyl-, hetero-aromatic, aryl-,
Alkoxy - or aryloxy - represents a group, which groups can be substituted; or together with R ² is R ³ independently, R ³ together with R ^4, R ⁴ is R ⁵ together with, R ¹⁴ together with R ^15, R ¹⁵ is can the and R ¹⁶ together with R ¹⁶ constitute the atoms necessary to complete a benzene ring which may be substituted with R ¹⁷ Can;
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently represent hydrogen, chlorine, bromine, fluorine, iodine, an alkyl group, a substituted alkyl group, an alkoxy group, an aryloxy group, a thioalkyl group , A disubstituted amino group, wherein the substituents can constitute the atoms necessary for completion of the 5- or 6-ring atom heterocycle, or each independently represents R ⁶
5 which may be the to together with R ⁸ is R ¹⁰ together with R ^8, R ¹⁰ together with R ^12, R ⁷ together with R ^9, and R ⁹ is substituted with R ¹¹ -Atoms or atoms necessary for the completion of a 6-atom carbocyclic or heterocyclic ring; each independently R ¹ together with R ⁶ and R ¹³ can be R ¹²
5- or 6-ring atoms which may be substituted together with the atoms necessary for the completion of the heterocyclic ring].

In the general formula (I), R ¹⁸ , R ¹⁹ and R
^The substituted amino group represented by the ²⁰ groups includes -N
^{H- (C = O) -R 21} , -NH- (SO 2) -R 22, -
^{NH- (S = O) -R 23} , -N - -CN, -N - - (C =
^{O) -R 24, -N - -} (SO 2) -R 25, -N - - (S =
O) -R ²⁶ and ^-N - containing -CN groups, can be any substituent of possible amino group, wherein R ^21,
R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently alkyl,
Indicates a substituted alkyl, aryl or substituted aryl group.

In the particularly preferred dyes corresponding to the general formula (I) used according to the invention, R ¹⁸ , R ¹⁹ and R
²⁰ can be independently deprotonated -N
^{H- (C = O) -R 21} , -NH- (SO 2) -R 22, -
NH- indicates the (S = O) -R ²³ or -NH-CN group, wherein R ^21, R ²² and R ²³ are independently represents an alkyl, substituted alkyl, aryl or substituted aryl group.

Suitable IR-sensitizing dyes of the general formula (I) for use according to the invention are:

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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Is as follows.

Supersensitizers According to the present invention, the photosensitive thermally developable photographic material further comprises a supersensitizer.

Preferred supersensitizers are selected from the group consisting of: mercapto compounds, disulfide compounds, stilbene compounds, organic borate compounds and styryl compounds. Supersensitizers suitable for use with infrared spectral sensitizers are EP-A 559 228, EP-A 587.
338, US-P 3,877,943, US-P
4,873,184 and unpublished European patent application EP
96202107.7.

Substantially non-photosensitive organic silver salt The substantially non-photosensitive organic silver salt preferably used in the photosensitive thermally developable photographic material used in the present invention preferably has an aliphatic carbon chain. Is at least 12-
Silver salts of aliphatic carboxylic acids known as fatty acids having a C atom, such as silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and behen whose silver salts are also called "silver soaps" Silver acid; US
-P4,504,575; silver dodecylsulfonate; and di- (2) described in EP-A 227141.
-Ethylhexyl) -silver sulfosuccinate. For example, aliphatic carboxylic acids modified with thioether groups described in GB-P 1,111,492 and GB-P
Other organic silver salts described in 1,439,478, such as silver benzoate and silver phthalazinone, can likewise be used to form heat-sensitive silver images. Silver imidazolate and US-
The substantially light-insensitive inorganic or organic silver salt complexes described in P 4,260,677 are also suitable.

For the purposes of the present invention, the term substantially light-insensitive organic silver salt also includes mixtures of organic silver salts.

Emulsions of Organic Silver Salts and Photosensitive Silver Halides Silver halides are photosensitive and thermally developable in any manner which places them in catalytic proximity to a substantially light insensitive organic silver salt. Can be added to photographic materials. The light-sensitive silver halide and the substantially light-insensitive organic silver salt, which are separately formed in the binder, i.e., externally generated or "preformed", can be mixed before use to prepare a coating solution. However, it can be blended for a long time before use. A particularly preferred manner of preparing an emulsion of an organic silver salt and a photosensitive silver halide for coating a photosensitive thermally developable photographic material from a solvent medium according to the present invention is disclosed in U.S. Pat. No. 3,839,049. But the Research Disclosure
Re, June 1978, item 17029 and U.S. Pat. No. 3,700,458 can be used.

Organic Reducing Agents Organic reducing agents suitable for use in the photosensitive thermally developable photographic material used in the present invention include mono-, bis-, tris- or tetrakis-phenol;
Di- or polyhydroxy-naphthalene; di- or polyhydroxybenzene; hydroxymonoethers such as alkoxynaphthols, for example 4-methoxy-1-naphthol as described in US Pat. No. 3,094,41; Pyrazolidin-3-one type reducing agents such as PHENIDONE ^™ ; pyrazolin-5-one; indan-1,3-dione derivative; hydroxytetronic acid; hydroxytetronimide; 3-pyrazolin; pyrazolone; reducing sugars;
For example, METOL ^™ ; for example, US-P 4,082,9
P-phenylenediamine as described in No. 01,
Hydroxylamine derivatives; reductones, such as ascorbic acid; hydroxamic acid; hydrazine derivatives; amidoximes;
Organic compounds containing at least one active hydrogen atom bonded to O, N or C, US Pat.
4,809, 3,080,254, 3,094,417
And 3,887,378. Particularly preferred catechol type reducing agents are EP-A 692 733 and E
P-A 599 369.

Polyphenols such as bisphenol used in 3M Dry Silver ^™ materials, sulfonamide phenols such as those used in Kodak Dacomatic ^™ materials, and naphthols can be used as silver halide / organic silver salt / reduced Particularly preferred for photosensitive thermally developable photographic materials based on agents.

Auxiliary reducing agent The above reducing agent, which is considered as a primary reducing agent or a main reducing agent,
It can be used together with a so-called auxiliary reducing agent. Auxiliary reducing agents that can be used together with the above-mentioned primary reducing agents are described in Periodical Research Disclosur.
e, February 1979, item 1784
2, US-P 4,360,581 and 4,782,0
04, as well as sulfonamidophenols as described in EP-A 423 891. Other auxiliary reducing agents which can be used together with the above-mentioned primary reducing agents are hydrazides as disclosed in EP-A 762 196, sulfonyl hydrazides as disclosed in US-P 5,464,738. Reducing agent; US-P
US Pat. No. 5,496,695; trityl hydrazide and formyl-phenyl-hydrazide as disclosed in US Pat.
P 5,545,505, US-P 5.5545.50
7 and formyl-phenyl-hydrazide with various co-reducing agents as disclosed in US-P 5,558,983; US-P 5,5
Acrylonitrile compounds as disclosed in US Pat. No. 45,515 and US Pat. No. 5,635,339; and organic reducing metal salts such as US Pat. No. 3,460,946.
And tin stearate as described in US Pat.

Binder The binder for the photosensitive thermally developable photographic material used in the present invention can be coatable from a solvent or an aqueous dispersion and must itself be film-forming. Or it must be used together with a film-forming binder.

It can be coated from a solvent dispersion,
Film-forming binders useful in the present invention include all types of natural, modified natural or synthetic resins or mixtures of such resins in which the organic silver salt can be uniformly dispersed; for example, polyurethanes, polyesters ,polyamide,
Polycarbonates and polymers derived from α, β-ethylenically unsaturated compounds, polyvinyl acetals, preferably polyvinyl butyral, and acrylonitrile, acrylamide, methacrylamide, methacrylate, acrylate, methacrylic acid, acrylic acid, vinyl ester, styrene and alkene Homopolymers and copolymers prepared using monomers selected from the group consisting of; or a mixture thereof.

The film-forming binder which can be coated from the aqueous dispersion medium used in the present invention is any kind of transparent or translucent water-dispersible or water-soluble, in which the organic silver salt can be dispersed uniformly. Natural, modified natural or synthetic resins, or mixtures of such resins, such as proteins, such as gelatin and gelatin derivatives;
Cellulose derivative; polysaccharide; galactomannan; polyvinyl alcohol; polyvinylpyrrolidone; polyurethane; polyester;
Polymers derived from α, β-ethylenically unsaturated compounds, for example polyvinyl acetal, preferably polyvinyl butyral, and acrylonitrile, acrylamide, methacrylamide, methacrylate, acrylate, methacrylic acid, acrylic acid, vinyl ester, styrene and alkene Homopolymers and copolymers produced using monomers selected from the group; latexes of water-dispersible polymers with or without hydrophilic groups, or mixtures thereof.

The above-mentioned binder or a mixture thereof can be used together with wax or "heat solvent", which is also called "thermal solvent" or "thermo-solvent", to increase the reaction rate of the redox reaction at high temperature.

Polycarboxylic Acids and Anhydrides The photosensitive thermally developable photographic materials used according to the present invention comprise at least one polycarboxylic acid and / or anhydride at least based on the total organic silver salt present. 20
It can also be present in mole percent and in thermal working relationship therewith. Preferred aromatic polycarboxylic acids are ortho-phthalic acid and 3-nitro-phthalic acid, tetrachlorophthalic acid, melitic acid, pyromellitic acid and trimellitic acid, and their anhydrides.

Toning Agents To obtain neutral black image tones at high densities and neutral grays at low densities, the photosensitive thermally developable photographic material is mixed with an organic silver salt and a reducing agent, It preferably contains so-called toning agents known from thermography or photothermography. Suitable toning agents are succinimides, phthalazines and phthalimides, and phthalazinones within the general formula described in US Pat. No. 4,082,901, and US Pat. No. 3,074,
809, US-P 3,446,648 and US-P
3,844,797. Particularly useful toning agents are GB-P 1,439,478, and US-P 3,951,660 and US-P.
And benzoxazinedione or naphthooxazinedione type heterocyclic toner compounds as described in US Pat.

Antihalation Dye The photosensitive thermally developable photographic material used in the present invention, in addition to the components, absorbs light that has passed through the photosensitive thermally developable photographic material, thereby preventing its reflection or preventing its reflection. An acutance dye can also be included. Such dyes can be inserted into the photosensitive thermally developable photographic material or into any other layer of the photographic material of the present invention.

Other Additives In addition to these components, the photosensitive thermally developable photographic materials used in the present invention include other additives, such as free fatty acids, surfactants, silicone oils, such as BAYSILONEEOL A
(From BAYER AG, GERMANY), ultraviolet light absorbing compounds; silica; colloidal silica; fine polymer particles, such as particles of poly (methyl methacrylate); and / or optical brighteners.

Support The support for the photosensitive thermally developable photographic material used in the present invention can be transparent, translucent, or opaque, for example having a white light reflecting surface, such as paper. , Polyethylene coated paper or cellulose esters such as cellulosic triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylate, polycarbonate or polyester, for example polyethylene terephthalate or GB 1,29
3,676, GB 1,441,304 and GB 1,
Thin flexible carriers made from a transparent resin material made from polyethylene naphthalate as disclosed in 454,956 are preferred.

The support can be in the form of a sheet, ribbon or web and can be subbed if needed to improve adhesion to the heat-sensitive recording layer coated thereon. One or more backing layers can be provided to control physical properties such as curl or charge.

Protective Layer The outermost layer on the photosensitive side of the photosensitive thermally developable photographic material avoids local deformation of the photosensitive thermally developable photographic material and improves its resistance to abrasion. Can be a protective layer.

The protective layer preferably contains a binder, which can be hydrophobic (solvent-soluble) or, for example, EP-A 614.
769 can be hydrophilic (water-soluble). However, a hydrophilic binder is preferred for the protective layer, which can be coated from an aqueous composition, by mixing the hydrophilic protective layer and the layer directly below by using a hydrophobic bond in the layer immediately below. Because it can be avoided.

The protective layer used in the present invention can also contain at least one solid lubricant having a melting point lower than 150 ° C. and at least one liquid lubricant, and at least one of the lubricants is phosphoric acid. A derivative; may further contain dissolved lubricating and / or particulate materials, such as talc particles, which may optionally protrude from the outermost layer. Lubricants can be applied with or without a polymeric binder.

Such a protective layer is made of a particulate material such as W
It can also contain talc particles, which can optionally protrude from the protective outermost layer, as described in O 94/11198. Other additives, for example colloidal particles such as colloidal silica, can also be inserted into the protective layer.

Antistatic Layer The photosensitive thermally developable photographic material used in the present invention may further contain an antistatic layer. Suitable antistatic layers are EP-A's 444 326, 534006 and 644 456, US-P's 5,364,752.
And 5,472,832, and DOS 41257
58. Particularly preferred antistatic layers are E
PA-628 560, US-P 5,354,61
3, US-P 5,372,924, US-P 5,3
70,981 and U.S. Pat. No. 5,391,472.

Coating Coating of any of the layers of the photosensitive thermally developable photographic material used in the present invention can be performed by thin-film coating methods known in the art. For the coating of web-type supports for photographic materials, slide hopper coating is preferred, but other coating methods such as dip coating and air knife coating can also be used. For more information on such coating methods, see “Modern Coa
ting and DryingTechnology
y "by Edward D. Cohen and E
dgar B. Gutoff, published b
y VCH Publishers Inc. 220
East 23rd Street, Suite909
New York, NY 10010.

Industrial Use The photosensitive thermally developable photographic material used in the present invention can be used for both transparency and reflection type printing. This means that the support will be transparent or opaque, for example with a white light reflecting surface.
For example, there are paper-based substrates that can contain white reflective pigments, which can optionally also be applied to an interlayer between the recording material and the paper-based substrate. If a transparent base is used, the base can be colorless or colored, for example, having a blue color.

In the field of graphics hardcopy, photosensitive heat developable photographic materials on a white opaque base are used, whereas in the field of medical diagnostics, a black-imaging transformer is used in an inspection method operated with a light box. Parity is widely used.

The following components were used in the inventive and comparative examples of the present invention: a) Antihalation / antistatic layer components: D01:

[0076]

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KELZAN ^™ S: Technical
According to Bulletin DB-19, mannose,
MERCK & CO., A polysaccharide containing glucose and glucuronic acid repeating units as mixed potassium, sodium and calcium salts. , Kelco Divis
ion, USA; xanthan gum from USA; PT-dispersion: prepared by polymerization of 3,4-ethylenedioxy-thiophene in the presence of polystyrenesulfonic acid and ferric sulfate as described in US-P 5,354,613. Dispersion of poly (3,4-ethylenedioxy-thiophene) / polystyrenesulfonic acid to be prepared; ULTRAVON ^™ W: aryl sulfonate from CIBA-GEIGY; PERAPRET ^™ PE40: 40% aqueous dispersion of polyethylene wax from BASF; KIESELSOL ^™ 100F: 36% aqueous dispersion of colloidal silica from BAYER; MAT01: Methyl methacrylate (98% by weight) having an average particle size of 5.9 μm, prepared as described in US Pat. No. 4,861,812. ) -Stearyl methacrylate ( % By weight)-20% aqueous dispersion of particles of copolymer beads; LATEX01: 12% by weight of polymethyl methacrylate having an average particle size of 88.8 nm, prepared as described in US-P 5,354,613. B) photosensitive layer: i) silver behenate / silver halide emulsion layer: GEL: phthaloyl gelatin type 16875 from ROUSESELOT; Butvar ^™ B76: polyvinyl butyral from MONSANTO; LOWINOX ^™ 22IB46: CHEM. WERK
2-propyl-bis (2-hydroxy-3,5-ditylphenyl) methane from E LOWI; TMABP: tetramethylammonium bromide perbromide TMPS: tribromomethylbenzenesulfinate; MBI: 2-mercaptobenzimidazole; SENSI : SENSI 01 ii) Protective Layer: CAB: Cellulose Acetate Butyrate CAB from EASTMAN
-171-15S; PMMA: Polymethylmethacrylate Acryloid ^™ K120N from ROHM & HAAS.

LOWINOX ^™ 22IB46: CHE
M. 2-propyl-bis (2-hydroxy-3,5-ditylphenyl) methane from WERKE LOWI.

The following examples illustrate, but do not limit, the invention. All percentages, parts and ratios are by weight unless otherwise stated.

[0080]

【Example】

Comparative Example 1 and Examples 1-4 of the Invention Photothermographically developable photographic material Support Polyethylene terephthalate (PE) colored with blue pigment
T) The foil is first coated on both sides with a subbing layer consisting of a terpolymer latex of vinylidene chloride-methyl acrylate-itaconic acid (88/10/2) mixed with colloidal silica (surface area 100 m ² / g) did. After stretching the foil in the transverse direction, the foil has a thickness of 175 μm,
And PET- respectively as a subbing layer on each side of the foil having a coverage of terpolymer and silica 170 mg / m ² and 40 mg / m ^2.

Antihalation / Antistatic Layer First, 55 / g of polymethyl methacrylate
mg of D01 dissolved in ethyl acetate and adding the antihalation dye D onto the polymethyl methacrylate particles of LATEX01 by evaporating the ethyl acetate.
By adsorbing 01, an antihalation / antistatic layer was formed.

On one side of the thus subbed PET-foil, 0.30 g of KELZAN ^™ S were then added.
22.4 mL of N-methylpyrrolidone in 0.8 mL of deionized water, 0.84 g of ULTRAVON ^™ W, 1
g PERAPRET ^™ PE 40 and 2.22 g K
Dissolve in the stirring mixture of IESELSOL 100F, then with stirring: 0.2 mL of 25% NaOH, 0.1 mL.
6 g dry PT-dispersion, LATEX01 after adsorption of 66.7 mL D01, 1.2 mL MAT01 and 30
After coating the antistatic composition obtained by adding mL of 2-propanol and drying at 120 ° C .: KELZAN ^™ S: 7.5 mg / m ² dry PT-dispersion: 15 mg / m ² ULTRAVON ^™ W: 21 mg / m ² polyethylene wax (from PERARET ^™ PE40): 10 mg / m ² colloidal silica (from KIESELSOL ^™ 100F): 20 mg / m ² 5.9 μm beads of cross-linked methyl methacrylate-stearyl methacrylate copolymer (from MAT01): A layer consisting of 6 mg / m ² polymethyl methacrylate (from LATEX01): 200 mg / m ² antihalation dye D01: 11 mg / m ² was obtained.

Silver halide emulsion 3.1 consisting of 97 mol% silver bromide and 3 mol% silver iodide in deionized water and having a weight average particle size of 50 nm.
A silver halide emulsion containing 1% by weight of silver halide grains and 0.47% by weight of GEL as a dispersant was prepared, for example, by the method of T.I.
H. James, “The Theory of th
e Photographic Process ", F
orth Edition, Macmillan Pu
flushing Co. Inc. , New York
(1977), Chapter 3, pages 88-
No. 104, using a conventional silver halide manufacturing method.

Silver Behenate / Silver Halide Emulsion A solution of 6.8 kg of behenic acid in 67 L of 2-propanol was placed in a 400 L vessel heated at 65 ° C. to maintain the temperature of the contents at 65 ° C. In addition, 96% of the behenic acid is converted to sodium behenate by adding 76.8 L of 0.25 M sodium hydroxide in deionized water with stirring, and then at 40 ° C. at 10.5 kN.
A silver behenate / silver halide emulsion was prepared by adding g of the above silver halide emulsion with stirring and finally adding 48 L of a 0.4 M solution of silver nitrate in deionized water with stirring. When the addition of silver nitrate was completed, the contents of the vessel were cooled, the precipitate was filtered, washed, slurried with water, filtered again and finally dried at 40 ° C. for 72 hours.

Then, 7 kg of the dry powder containing 9 mol% of silver halide and 4 mol% of behenic acid, based on silver behenate, are added to a solution of 700 g of Butvar ^™ B76 in 15.6 kg of 2-butanone. By using a conventional dispersion method, a dispersion of 33% by weight was obtained. Then 7.4
kg of 2-butanone were added and the resulting dispersion was homogenized in a microfluidizer. Finally, 2.8 kg of Butvar ^™ B76 was added with stirring to obtain a 31% by weight solids dispersion.

Coating and Drying of Silver Behenate / Silver Halide Emulsion Layer An emulsion layer coating composition for a photosensitive heat developable photographic material was prepared by adding 40.86 g of the above described silver behenate / silver halide emulsion to the following: Prepared by adding the solution or liquid with stirring in the following order: 10.87 g of 2-butanone, 0.7 of a 9% solution of TMABP in methanol.
5 g, followed by stirring for 2 hours, 1.3 g of 2-butanone,
0.2 g of an 11% solution of potassium bromide in methanol and 1.3 g of 2-butanone, followed by stirring for 30 minutes,
0.21 g LOWINOX ^™ 22IB46, 0.5
g of TMPS and 9.24 g of 2-butanone, followed by stirring for 10 minutes, 1.84 g of a 0.11% solution of SENSI in methanol, followed by stirring for 30 minutes, and finally 4.35 g of Butvar. ^TM B76 was added, followed by stirring for 45 minutes, then 4.79 g of 2-butanone.

The PET-foil, primed and coated with an antihalation / antistatic layer as described above, is then coated with the coating composition at a blade setting of 150 μm on the uncoated side of the foil backing layer. Doctor blade-coat to a wet layer thickness of 80 μm and place it on an aluminum plate in a drying cabinet
Dry at 0 ° C. for 5 minutes.

Protective Layer A protective layer coating composition for a photosensitive thermally developable photographic material was prepared by adding 36.3 g of 2-butanone and 4.16 g.
4.08 g CAB and 0.16 g P in methanol
Prepared by dissolving MMA and adding the following solids or solutions with stirring in the following order: 0.5 g phthalazine, 0.2 g 4-methylphthalic acid, 0.1 g tetrachlorophthalic acid, 0.1 g 2 g of tetrachlorophthalic anhydride and 2.55 g of LOWINOX ^™ 22
A solution consisting of IB46 and 5.95 g of 2-butanone.
Then, the protective layer coating composition was added to the emulsion layer by 100 μm.
Doctor blade-coating at a blade setting of m to a wet layer thickness of 57 μm, which after drying for 8 minutes at 80 ° C. on an aluminum plate in a drying cabinet gave a layer having the following composition: CAB 4.08 g / m ² PMMA 0.16g / m ² phthalazine 0.50g / m ² 4- methyl phthalic acid 0.20 g / m ² tetrachlorophthalic acid 0.10 g / m ² tetrachlorophthalic acid anhydride 0.20g / m ² LOWINOX ^TM 22IB46 2.55 g / m ² Informational Exposure and Heat Treatment A sheet of photosensitive thermally developable photographic material having a diameter of 198
mm is exposed in the same manner and thermally developed on a device capable of performing informational exposure and thermal development on the same heatable drum of mm, and heat-developable photosensitive heat-developable photographic material. The antihalation layer was brought into contact with the drum, ie, transported at a rate of 20.73 mm / sec with the protective layer for the silver behenate / silver halide emulsion layer as the outermost layer.

Exposure according to information is 200 mW from SDL
Using a laser diode at a speed of 20.73 mm / sec, at 10.85 lines / mm, a maximum laser intensity of 71 mW / spot (120 μm diameter)
20. Exposure for each 55.6 × 431.8 mm ² sheet.
It took 8 seconds. Thermal development is performed at 121 ° C. for 15 seconds, and a drum capable of heating a sheet and 311.
It was contacted over 02 mm. In Comparative Example 1, the sheet was not heated before or during exposure, and in Examples 1-4 of the present invention, the sheet was preheated via a drum for various times and heated during exposure.

The optical density of the resulting image was measured in transmission using a MacBeth ^™ TR924 densitometer through a visible filter to generate a sensitometric curve for the photosensitive thermally developable photographic material, from which the maximum and minimum were determined. Optical density, D _max and D _min , and D
The relative photosensitivity for _min + 1.0 was determined.

[0091] The photosensitive thermally developable photographic material was exposed information-wise, D _max obtained by heat-treating - and D _min - value and the relative sensitivity of the values for obtaining the optical density of D _min +1.0 Are summarized in Table 1 together with the preheating and heat treatment conditions used.

[0092]

[Table 1]

The sensitivities obtained by heating during exposure under various preheating conditions were compared with the results obtained in Comparative Example 1 in which exposure was performed using a cold material and preheating was not performed. _Shows a significant increase in _{Dmax for} the same exposure, and a significant improvement in light sensitivity. Furthermore, this improvement in photosensitivity has been achieved using one and the same holding or guiding means, in this case a photosensitive thermally developable photographic material on a drum, with exposure during heating, which is more concise. It is possible to use a simple processing device.

Comparative Example 2 and Example 5 of the Present Invention In Example 5 of the present invention, DRYV from IMATION was used.
The IEW ^™ photosensitive thermally developable photographic material was used in place of the photosensitive thermally developable photographic material in Comparative Example 1 and Examples 1-4 of the present invention. DRYVIEW ^™ materials are based on the usual silver halide / silver behenate / reducing agent concept and are spectrally sensitized to infrared. Exposure and heat treatment according to the information were performed in Comparative Example 1 and Example 1 of the present invention.
In this case, the thermal development was performed using the same apparatus as used in the cases (1) to (4).
17.5 at 123.9 ° C instead of 15-5 seconds at 1 ° C
Seconds.

[0095] The photosensitive thermally developable photographic material was exposed information-wise, D _max obtained by heat-treating - and D _min - value and the relative sensitivity of the values for obtaining the optical density of D _min +1.0 Are summarized in Table 2 together with the preheating and heat treatment conditions used.

[0096]

[Table 2]

The sensitivities obtained by preheating and heating during the exposure were compared with the results obtained in Comparative Example 2 in which the exposure was performed using a cold material and no preheating was performed.
The increase in _Dmax and the improvement in photosensitivity for the same exposure are shown. Again, this improvement in photosensitivity has been achieved using one and the same holding or guiding means, in this case a photosensitive thermally developable photographic material on a drum, with exposure during heating, which is more pronounced. It allows the use of simple processing equipment.

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Jacobs Bossierz Belgium B 2640 Malt Cell Septes Trat 27 Agfa-Gevert na Mrose Fennoutjapp (72) Inventor Robert Obermere Belgium B 2640 Malt Cell・ Septes Trat 27 ・ Agfa-Gevert Na Murose Fennojasjap (72) Inventor Eday Demus Belgium ・ B 2640 Maltcell Septestrat 27 ・ Agfa-Gevert Na Mulose Fuennajasjap (72) Inventor Leo Elbrandt Belgium B 2640 Maltcell Septes Trat 27 Agfa-Gevuert na Mrose Huenno In the Sharp (72) Inventor Hans Streakers Belgium Bee 2640 Malt Cell Septes Trat 27 Agfa-Gevert Na Mrose Fennaut In the Sharp (72) Inventor Thomas Zetetmeier Germany D-85646 Neufarn Dol Feltbeek 6 (72) Inventor Jürgen Müller Germany Day-81545 Miyunchen Bottsu Alice Schüterse 7 (72) Inventor Friedrich Schuttoopf Germany Day-81541 Miyunchen Hohen Baldeck Kashutraße 30 (72) Inventor Gerald Halbettle Germany Day-82258 Eberswach Gietorngsbeek 16

Claims (2)

[Claims] 1. The method according to claim 1, further comprising the step of exposing the photosensitive thermally developable photographic material to radiation in an informational manner, thereby forming a latent image; and heating the photosensitive thermally developable photographic material. The thermothermally developable photographic material is on one and the same holding or guiding means during both the informational exposure step and the heating step; the informational exposure step is performed during the heating step Recording method characterized by that. 2. The photothermographically developable photographic material is on one and the same holding or guiding means during both the informational exposure step and the heating step; A method for improving the photosensitivity of a photosensitive thermally developable photographic material, which is performed before and / or during the step.