JPH1073900A - Photothermographic recording material containing sensitizing dye and recording method for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photothermographic recording material having high IR sensitivity and superior image forming property. SOLUTION: This photothermographic recording material contains a substrate and a photo-addressable heat-developable element contg. a practically nonphotosensitive org. silver salt, a reducing agent for the org. silver salt associated with the org. silver salt in thermal action, photosensitive silver halide spectrally sensitized with a dye represented by the formula and catalytically associated with the org. silversalt and a binder. The dye may have an anion if necessary so as to attain charge compensation. In the formula, each of Z<1> and z<2> is S, O or Se, each of R<1> -R13 is an alkylene chain and each of X<1> and X<2> is -(C=O)-R$<18> -(SO2 )-R<19> or -(S=O)-R<20> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photothermographic recording material containing a photosensitive silver halide spectrally sensitized with a specific dye and a recording method therefor.

[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: 1. Direct thermal formation of a visible image pattern by image-wise heating of a recording material containing a substance whose color or optical density changes by a chemical or physical process; 2. Image-wise transfer of components necessary for a chemical or physical process to effect a change in color or optical density to a receiving element; 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.

[0004] Type 1 thermographic materials contain photosensitive reagents that can catalyze or participate in a thermographic process that results in a change in color or optical density after exposure to UV, visible or IR light. If you do
It becomes a photothermographic material.

An example of a photothermographic material is 3M
Company's so-called "dry silver" photographic material, which is a "Handbook of Image"
ngScience ", edited by AR.
Diamond, page43, published
by Marcel Dekker in 1991. A. Morgan.

The most widely used radiation-sensitive salt in such materials is silver halide, which is in catalytic association with an organic silver salt and the species formed upon exposure are exposed to light. It must be able to catalyze the thermal imaging process. Silver halide must be spectrally sensitized with dyes to extend its sensitivity range to the infrared region of actinic radiation.

Various types of benzoxazole, benzothiazole and benzoselenazole cyanine spectral sensitizers have been disclosed for use in infrared-sensitive photothermographic materials based on organic silver salt / silver halide / reducing agent systems. US-P 4,835,096 has the general formula:

[0008]

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Wherein R ₁ represents a lower alkyl group having 1 to 5 carbon atoms and X ⁻ represents an anion. JN03 discloses a photothermographic element comprising a dye; 163440A has at least one formula (I):

[0010]

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Wherein Z ₁ and Z ₂ are each S, O or Se; R ₁ ＨH, alkyl or alkoxy;
R ₂ = carboxyalkyl or — (CH ₂ ) _n COOH; n = 1 to 4; X = Cl, Br or I]. U.S. Pat. No. 5,441,866 preferably has a central core of a hydrophobic binder, a supersensitizer and a spectral sensitizer:

[0012]

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Wherein R ¹ is (C) having 1 to 20 carbon atoms.
H _{2) n} -COO ^- group or a carbon atoms an alkyl group having 1 to 20; n is heat comprises an infrared absorbing dye having an integer from 1 to 20 - discloses a developable photothermographic element And EP-A 616 014 is characterized in that both nitrogen atoms of the cyanine chromophore have five carboxyalkyl substituents comprising an alkyl chain having at least 5 carbon atoms, and 2-mercaptobenzimidazole, metal Disclosed are heptamethine cyanine dyes that can be used with chelators and supersensitizers such as pyridine, pyrimidine and triazine derivatives.

All of these IR-spectral sensitizers have been shown to exhibit acceptable spectral sensitization of light-sensitive silver halides.
It requires the presence of a supersensitizer in a concentration of 3-50 moles per mole of spectral sensitizer. The presence of such large amounts of extra components is disadvantageous both from an economic point of view and from the risk of conflict with functional components.

[0015]

OBJECTS OF THE INVENTION It is a first object of the present invention to provide a photothermographic recording material having high infrared sensitivity and excellent image-forming properties.

A second object of the present invention is to provide a substantially light-insensitive organic silver salt, an organic reducing agent for an organic silver salt, and a catalytically insoluble organic silver salt, Photothermographic recording materials containing photo-addressable thermally developable elements based on photosensitive silver halide spectrally sensitized with a dye that does not require the presence of a supersensitizer to exhibit spectral sensitization It is to provide.

A third object of the present invention is to provide a photo-forming device having excellent image-forming properties which can be coated from an aqueous medium.
It is to provide an addressable thermally developable element.

Yet another object of the present invention is to provide a recording method for a photothermographic recording material having the above-mentioned improved properties.

Further objects and advantages of the present invention will become clear from the description hereinafter.

[0020]

SUMMARY OF THE INVENTION In accordance with the present invention, a substantially light-insensitive organic silver salt, a reducing agent therefor in thermal action therewith, a dye are spectrally sensitized and substantially light-insensitive. A photothermographic recording material comprising a photo-addressable thermally developable element comprising a photosensitive silver halide and a binder catalytically associated with an organic silver salt, wherein the dye is required for charge compensation. Is a general formula (I) having an anion:

[0021]

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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 ³ is R ⁴ together with R ² is R ³ each independently, 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
Together with R ^8, R ⁸ is together with R ^10, R ¹⁰ together with R ^12, R ⁷ is and R ⁹ together with R ⁹ may be substituted with R ¹¹ 5 -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
A 5- or 6-ring atom which can be substituted together with the atoms necessary for the completion of the heterocyclic ring].

Preferred embodiments of the invention are disclosed in the dependent claims.

[0024]

DETAILED DESCRIPTION OF THE INVENTION

[0025]

IR-Spectral Sensitizing Dyes In accordance with the present invention, the photo-addressable thermally developable element is a compound in which the R ¹⁸ , R ¹⁹ and R ²⁰ groups are substituted amino groups, ie all possible substitutions of amino groups, including ^{-NH- (C = O) -R 21} , -N
^{_{H- (SO 2) -R 22,}} -NH- (S = O) -R 23, -
^{N - -CN, -N - - (} C = O) -R 24, -N - - (S
O ₂ ) -R ²⁵ , -N ^-- (S = O) -R ²⁶ and -N ^-- C
N represents a group, wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ independently represent a dye corresponding to the general formula (I) representing an alkyl, substituted alkyl, aryl or substituted aryl group. Including.

[0026] In a preferred embodiment of the present invention, the dye may be R ^18, R ¹⁹ and R ²⁰ are independently deprotonated ^{-NH- (C = O) -R 21} , -NH- (S
O ₂ ) -R ²² , -NH- (S = O) -R ²³ or -NH-
Represents a CN group, wherein R ²¹ , R ²² and R ²³ independently correspond to formula (I) representing an alkyl, substituted alkyl, aryl or substituted aryl group.

In a further preferred embodiment of the invention,
The dye exists as an amine salt.

In a particularly preferred embodiment of the invention, the dye is of the formula

[0029]

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Corresponding to

In a further particularly preferred embodiment of the invention, the dye is of the formula

[0032]

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Corresponding to

In an even more particularly preferred embodiment of the invention, the dye is of the formula

[0035]

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Corresponding to

In an even more particularly preferred embodiment of the present invention, the dye is of the formula

[0038]

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Corresponding to FIG.

Suitable IR-sensitizing dyes according to the invention are:

[0041]

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[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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Is as follows.

SENSI 01 was produced as described in Example 1 of the present invention. The method described in Example 1 of the present invention and M. Hamer, "The Cyanin
eDyes and Related Component
ds ", Interscience Publisher
rs, New York (1964), using a synthesis method similar to that described in other IRs used in accordance with the present invention.
Sensitizing dyes can be synthesized.

The sensitivity of the photothermographic recording material containing the IR-sensitizing dye used according to the present invention is
It will depend on the choice of sensitizing dye, its concentration, the manner in which the IR-sensitizing dye is inserted, and the exact composition of the photothermographic recording material.

For the purposes of the present invention, the term infrared light means light having a wavelength in the range from 700 nm to 1000 μm.

[0051]

Supersensitizer According to a preferred embodiment of the present invention, the photo-addressable element further comprises a supersensitizer. In a particularly preferred embodiment of the invention, the supersensitizer is selected from the group of compounds consisting of: mercapto compounds, disulfide compounds, stilbene compounds, organic borate compounds and styryl compounds.

The choice of the supersensitizer and the molar ratio of the supersensitizer to the IR-sensitizing dye is such that the layer of the IR-sensitizing dye and then the photo-addressable thermally developable element is coated. Depends on the choice of media to be made. Supersensitizers suitable for use in accordance with the present invention include:

[0053]

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SS-02: 2-mercapto-benzimidazole SS-03: 2-mercaptobenzothiazole-5
[N- (4′-chlorophenyl)] sulfonamide.

Supersensitizer Versus I Used According to the Invention
The molar ratio of R-sensitizing dye will depend on the desired improvement in photothermographic performance, such as increased sensitivity, reduced _Dmin , and the like.

[0056]

Photo-Addressable Thermally Developable Element The photo-addressable thermally developable element of the present invention comprises a substantially light-insensitive organic silver salt, a photosensitive halide catalytically associated therewith. Silver and an organic reducing agent that is in a thermal working relationship with the substantially light-insensitive organic silver salt, and a binder. The element is in silver halide, catalytically associated with a substantially light-insensitive organic silver salt, in sensitized association with silver halide grains, optionally in spectral sensitization with a supersensitizer. Agents and other components active in the course of thermal development or before or after development of the element in the same layer or other layers, provided that the organic reducing agent and
The toning agent, if present, is substantially in thermal relationship with the light-insensitive organic silver salt, i.e., during the thermal development process, the reducing agent and, if present, the toning agent are substantially Can diffuse into the light-insensitive organic silver salt.

[0057]

Substantially light-insensitive organic silver salts The preferred substantially light-insensitive organic silver salts of the present invention are known as organic carboxylic acids, especially fatty acids whose aliphatic carbon chain preferably has at least 12-C atoms. Silver salts of aliphatic carboxylic acids such as silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, the silver salts of which are also called "silver soaps"; US-P 4, 5
No. 04,575; silver di- (2-ethylhexyl) -sulfosuccinate described in EP-A 227 141. For example, GB-P
1,111,492 and modified aliphatic carboxylic acids having a thioether group and GB-P 1,43
Other organic silver salts described in 9,478, such as silver benzoate and silver phthalazinone, can also be used to form thermally developable silver images. Further are mentioned silver imidazolates and the substantially light-insensitive inorganic or organic silver salt complexes described in U.S. Pat. No. 4,260,677.

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

[0059]

[Sensitive Silver Halide] The photosensitive silver halide used in the present invention is substantially 0.1 to less than a light-insensitive organic silver salt.
It can be used within the range of 35 mole percent,
A range of 5 to 20 mole percent is preferred, and a range of 1 to 12 mole percent is particularly 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.

[0062]

[Emulsion of organic silver salt and photosensitive silver halide]
A suspension of particles containing a silver salt of an insensitive organic carboxylic acid is an aqueous solution or suspension of an organic carboxylic acid or a salt thereof, as described in EP-A 754 969; Can be obtained using a method comprising simultaneously metering in an aqueous liquid.

The silver halide can be added to the photo-addressable, thermally developable element in any manner that places it in catalytic proximity to a substantially light-insensitive organic silver salt. Produced separately in the binder,
That is, the external or "preformed" silver halide and the substantially light-insensitive organic silver salt can be mixed prior to use to prepare a coating solution, but both are blended for an extended period of time. Is also effective. In addition, US
-P 3,457,075, comprising adding a halogen-containing compound to an organic silver salt and partially converting the substantially light-insensitive organic silver salt to silver halide. It is effective to use.

In accordance with the present invention, a particularly preferred manner of preparing an emulsion of an organic silver salt and a photosensitive silver halide for coating a photo-addressable, thermally developable element from a solvent medium is described in US Pat. 839,049, but with a Research Disc.
loss, June 1978, item 170
Other methods such as those described in US Pat. No. 29 and US Pat. No. 3,700,458 can also be used for preparing the emulsion.

A particularly preferred manner of preparing an emulsion of an organic silver salt and a light-sensitive silver halide for coating a photo-addressable thermally developable element from an aqueous medium according to the present invention is described in the unpublished PCT patent. Application PCT / EP
/ 96/02580, comprising a substantially light-insensitive organic silver salt, a photosensitive silver halide in catalytic association with a substantially light-insensitive organic silver salt, substantially A photo-addressable thermally developable element comprising a reducing agent and a binder in thermal communication with the light-insensitive organic silver salt, wherein the binder is a water-soluble polymer, a water-dispersible polymer or a water-soluble polymer. Containing a mixture of a photosensitive polymer and a water-dispersible polymer, wherein the photosensitive silver halide grains are photo-
Non-aggregating in the addressable, thermally developable element, substantially uniformly distributed over and between the particles of the light-insensitive organic silver salt, at least 8 of the particles by number
A photothermographic recording material is disclosed wherein 0% has a diameter of ≦ 40 nm as measured by transmission electron microscopy.

Organic Reducing Agent for Photo-Addressable Thermally Developable Element Coated from Non-Aqueous Medium Substantially light in photo-addressable thermally developable element coated from non-aqueous medium Suitable organic reducing agents for the reduction of insensitive organic heavy metal salts are mono-, bis-, tris- or tetrakis-phenol; mono- or bis-naphthol; di- or polyhydroxy-naphthalene; di- or polyhydroxybenzene. Hydroxy monoethers such as alkoxynaphthols such as 4-methoxy-1-naphthol described in US Pat. No. 3,094,41; pyrazolidin-3-one type reducing agents such as PHENIDONE (trade name); pyrazoline-5 -One; indane-1,3-dione derivative; Ron acid; hydroxy tetronic imide; pyrazoline; pyrazolones; reducing sugars; aminophenols, e.g. METOL (tradename); for example US
-P- as described in P 4,082,901
Phenylenediamines, hydroxyamine derivatives; reductones such as ascorbic acid; hydroxamic acids; hydrazine derivatives; amidoximes; at least one active hydrogen atom bonded to O, N or C, as in the case of n-hydroxyurea and the like. Organic compounds containing
US-P 3,074,809, 3,080,254,
See also 3,094,417 and 3,887,378.

Polyphenols such as bisphenol used in 3M Dry Silver ^™ materials, sulfonamide phenols such as those used in Kodak Dacomatic ^™ materials, and naphthols are photosensitive silver halides / organic silver salts / Particularly preferred for photothermographic recording materials having photo-addressable thermally developable elements based on reducing agents.

Photo-coated from aqueous medium
Organic Reducing Agents for Addressable Thermally Developable Elements Organic reducing agents suitable for the reduction of substantially light-insensitive organic heavy metal salts in photo-addressable thermally developable elements coated from aqueous media are: , O, N or C is an organic compound containing at least one active hydrogen atom. Organic reducing agents particularly suitable for the reduction of substantially light-insensitive organic silver salts in such photo-addressable thermally developable elements are non-sulfo-substituted 6-membered aromatics having at least three substituents. A ring or heteroaromatic ring compound, wherein one of the three substituents is a hydroxy group on the first carbon atom, the second of which is a hydroxy or amino-group substituted on the second carbon atom; ,
Three or five ring atoms are removed from the first carbon atom of the compound in a conjugated double bond system, wherein (i) the third substituent is part of an annealed carbocyclic or heterocyclic ring system (Ii) the third or higher substituent is not an aryl- or o | o-aryl-group in which the aryl group is substituted with a hydroxy-, thiol- or amino-group; iii) The third or higher substituent is a non-sulfo-electron withdrawing group when the second substituent is an amino-group.

Particularly preferred reducing agents are substituted catechols or substituted hydroquinones, 3- (3 ', 4'-dihydroxyphenyl) -propionic acid, 3', 4'-dihydroxy-butyrophenone, methyl gallate, gallic acid Ethyl and 1,5-dihydroxy-naphthalene are particularly preferred.

[0070]

Reducing Agent Insertion During the thermal development process, the reducing agent is present in such a way that it can substantially diffuse into the light-insensitive organic silver salt particles and reduction of the organic silver salt can occur. There must be.

[0071]

[Auxiliary reducing agent] The above reducing agents regarded as primary reducing agents or main reducing agents can be used together with so-called auxiliary reducing agents. Auxiliary reducing agents that can be used together with the above primary reducing agents include sulfonyl hydrazide reducing agents as disclosed in US Pat. No. 5,464,738, US-P.
Tritylhydrazide and formyl-phenyl-hydrazide as disclosed in US Pat. No. 5,496,695, and organic reducing metal salts such as US Pat.
No. 0,946 and 3,547,648.

[0072]

Binder The film-forming binder for the photo-addressable thermally developable element of the present invention can be coatable from a solvent or an aqueous dispersion medium.

The film-forming binder for the photo-addressable thermally developable element of the present invention can be coatable from a solvent dispersing medium and, according to the present invention, provides a uniform dispersion of the organic silver salt. All types of natural, modified natural or synthetic resins, or mixtures of such resins; polymers derived from α, β-ethylenically unsaturated compounds, such as polyvinyl chloride,
Post-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, made from polyvinyl alcohol as a starting compound, repeating vinyl alcohol units Is a polyvinyl acetal, preferably polyvinyl butyral, a copolymer of acrylonitrile and acrylamide, a polyacrylate, a polymethacrylate, a polystyrene, and a polyethylene, or a mixture thereof, in which only a part of the aldehyde can be reacted with the aldehyde. Can be. A particularly suitable polyvinyl butyral containing a small amount of vinyl alcohol units is MONSANTO US
A: Trade name BUTVAR ^™ B76 and BUTVA
Are sold under the R ^TM B79, it gives paper and appropriately good adhesion to primed polyester support.

The film-forming binder for the photo-addressable thermally developable element that can be coated from the aqueous dispersion medium of the present invention can be any type of transparent material in which the organic silver salt can be uniformly dispersed. Or translucent water-dispersible or water-soluble natural, modified natural or synthetic resins, or mixtures of such resins, such as proteins, such as gelatin and gelatin derivatives (eg, phthaloyl gelatin), cellulose derivatives, such as carboxymethyl cellulose, Polysaccharides such as dextran, starch ether, galactomannan, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer,
Homo- or co-polymerized acrylic or methacrylic acid,
It may be a latex of a water-dispersible polymer with or without a hydrophilic group, or a mixture thereof. Polymers having a hydrophilic functional group for forming an aqueous polymer dispersion (latex) include, for example, U
No. 5,006,451, which works for the formation of a barrier layer to prevent the undesired diffusion of vanadium pentoxide, which is present as an antistatic agent.

[0075]

Ratio of binder to organic silver salt: The weight ratio of binder to organic heavy metal salt is preferably in the range of 0.2 to 6, and the thickness of the photo-addressable, thermally developable element is in the range of 1 to 50 µm. Is preferred.

[0076]

[Thermal Solvent] The above-mentioned binder or mixture thereof can be used together with wax or "heat solvent" which is also called "thermal solvent" or "thermo-solvent" which improves the reaction rate of oxidation-reduction reaction at high temperature. .

In the present invention, the term “heat solvent” is a solid state in the recording layer at a temperature lower than 50 ° C., but becomes a plasticizer for the recording layer in a heated region at a temperature higher than 60 ° C. And / or at least one of the redox reactants, such as a non-hydrolyzable organic material that becomes a liquid solvent for the reducing agent for the organic heavy metal salt.

[0078]

Toner To obtain a neutral black image tone at high density and a neutral gray at low density, the photo-addressable thermally developable element is mixed with an organic heavy metal salt and a reducing agent, It preferably contains so-called toning agents known from thermography or photothermography.

Suitable toning agents are succinimides and phthalimides and phthalazinones within the general formula described in US Pat. No. 4,082,901. Furthermore, US-P 3,074,809, US-P 3,4
46,648 and U.S. Pat. No. 3,844,797. Other particularly useful toning agents are GB-P 1,439,478 and US-P 3,
Benzoxazinedione or naphthooxazinedione type heterocyclic toner compounds as described in US Pat.

[0080]

Stabilizers and Antifoggants Stabilizers and antifoggants can be incorporated into the photothermographic materials of this invention to improve shelf life and reduce fog. Examples of suitable stabilizers and antifoggants, which can be used alone or in combination, and precursors thereof, include US-P 2,131,038 and 2,694,
No. 716; US-P 2,88
Azaindenes described in 6,437 and 2,444,605; Urazoles described in U.S. Pat. No. 3,287,135; Sulfocatechols described in U.S. Pat. No. 3,235,652; GB-P 623,448 Oximes described in US-P 3,220,839; thyuronium salts described in US-P 3,220,839; US-P 2,566,263 and 2,59
Platinum and gold salts described in 7,915; US-P 3,70
U.S. Pat. No. 0,457, the tetrazolyl-thio-compounds;
-P 4,404,390 and 4,351,896, a mesoionic 1,2,4-triazolium-3-thiolate stabilizer precursor; a tribromomethyl ketone compound described in EP-A 600 587; EP- A 600
No. 586, combinations of isocyanates and halogenated compounds; vinyl sulfone and β-halosulfone compounds described in EP-A 600 589;
aging Processes and Mater
ials, Neblette's 8th edition
n ", by D. Kloosterboer, edit
ed by J. Sturge, V .; Walworth
and A. Shepp, page 279, Van
Nostrand (1989) in Chapter 9;
rch Disclosure 17029 publ
The compounds cited in this regard are included in ised in June 1989; as well as in the references cited in all of these references.

[0081]

Surfactant For the preparation of a dispersion of substantially light-insensitive organic silver salt particles in an aqueous medium and for dispersing a water-dispersible binder such as a polymer latex in an aqueous medium. Non-ionic, cationic or anionic surfactants can be used in accordance with the present invention. Mixtures of non-ionic and anionic surfactants, non-ionic and cationic surfactants, cationic and anionic surfactants, or non-ionic, cationic and anionic surfactants Can also be used according to the present invention.

[0082] In one embodiment of the present invention, the surfactant is an anionic surfactant. In a preferred embodiment of the present invention, the anionic surfactant is a sulfonate,
For example, alkyl, aryl, alkaryl or aralkyl sulfonates, alkyl and alkaryl sulfonates, such as: sodium salts of alkyl sulfonates from MERSOLAT ^™ H, BAYER ULTRAVON ^™ W, sodium salts of aryl sulfonates from CIBA-GEIGY are particularly preferred. .

In another embodiment of the present invention, the ionic surfactant is a non-ionic surfactant, such as an alkyl,
Aryl, alkaryl or aralkyl polyethoxyethanol. Preferred non-ionic surfactants of the present invention are alkoxy-polyethoxyethanol and alkaryloxy-polyethoxyethanol.

[0084]

In addition to the other additives Component, photo - addressable thermally developable element may contain other additives such as free fatty acids, surface active agents, antistatic agents, for example _{F 3 C (CF 2) 6} CON
Non containing fluorocarbon group as in _{H (CH 2 CH 2 O)} -H - ionic antistatic agent, silicone oil,
For example, BAYSILONE oel A (BAYERA
G-GERMANY (trade name), an ultraviolet light absorbing compound,
It may contain white light reflecting and / or ultraviolet light reflecting pigments, silica, colloidal silica, fine polymer particles [eg, of poly (methyl methacrylate)], and / or optical brighteners.

[0085]

Antihalation Dye According to a preferred embodiment of the present invention, the photothermographic recording material further comprises an antihalation or acutance dye that absorbs light transmitted through the photosensitive layer and thereby prevents its reflection. Such dyes can be inserted into the photo-addressable thermally developable element or into any other layer making up the photothermographic recording material of the present invention. The antihalation dye may also be thermally bleached during the thermal development process or photo-bleached after the thermal development process, which is contained in a layer that can be removed following the exposure process. Can be. Antihalation dyes suitable for use in the case of infrared light are EP-A's 377 961 and 652 473, EP-B's 101 646 and 1
02 781, and US-P's 4,581,3
25 and 5,380,635.

[0086]

Support The support for the photothermographic recording material of the present invention may be transparent, translucent or opaque, for example, a white light reflecting surface (white light reflex).
It can have a ting aspect), for example paper, polyethylene coated paper, or cellulose esters such as, for example, cellulose triacetate, corona and flame treated polypropylene, polystyrene, polymethacrylate, polycarbonate or polyester, for example polyethylene terephthalate or GB1, 293,
676, GB 1,441,304 and GB 1,45
Thin flexible carriers made from a transparent resin fill made from polyethylene naphthalate as disclosed in US Pat. No. 4,956 are preferred. For example, there are paper-based substrates which can contain white reflective pigments, which can optionally also be applied to an intermediate layer between the recording material and the paper-based substrate.

The support may be in the form of a sheet, ribbon or web, and may be subbed if needed to improve adhesion to the heat-sensitive recording layer coated thereon. The support can be made of an opaque resin composite, for example using pigments and / or micropores, or from opaque polyethylene terephthalate coated with an opaque pigment-binder layer, synthetic paper or paper. Can be called like film;
Information on such supports can be found in EP's 1941.
06 and 234 563, and US-P's 3,
944,699, 4,187,113, 4,780,4
02 and 5,059,579.
If a transparent base is used, the base can be colorless or colored, for example, having a blue color.

One or more backing layers can be provided to control physical properties such as curl or charge.

[0089]

Protective Layer According to a preferred embodiment of the photothermographic recording material of the present invention, the photo-addressable thermally developable element includes a photo-addressable thermally developable element to avoid local deformation of the photo-addressable thermally developable element. A protective layer is provided to improve its resistance to abrasion and to prevent its direct contact with components of the equipment used for thermal development.

This protective layer has the same composition as the anti-stick coating or slip layer applied behind the dye donor material in the thermal dye transfer material, or the protective layer used in the material for direct thermal recording. be able to.

The protective layer preferably contains a binder, which can be solvent-soluble (hydrophobic), solvent-dispersible, water-soluble (hydrophilic) or water-dispersible. Among the hydrophobic binders, cellulose acetate butyrate, polymethyl methacrylate and polycarbonates as described, for example, in EP-A 614 769 are particularly preferred. Suitable hydrophilic binders are, for example, gelatin, polyvinyl alcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose, etc .; hardenable binders are preferred, with polyvinyl alcohol being particularly preferred.

The protective layer of the photothermographic recording material according to the invention can be crosslinked. Crosslinking is as described in WO 95
/ 12495 can be carried out using a cross-linking agent for the protective layer as described in, for example, tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins, etc. Silicates and tetraethyl orthosilicate are preferred.

The protective layer of the present invention comprises at least one solid lubricant having a melting point lower than 150 ° C. and at least one liquid lubricant in a binder, wherein at least one of the lubricants is a phosphoric acid derivative. Alternatively, it may further comprise dissolved lubricating and / or particulate material, such as talc particles, which may optionally protrude from the outermost layer. Examples of suitable lubricating materials are surfactants, liquid lubricants,
A solid lubricant that does not melt during the thermal development of the recording material, a solid lubricant that melts during the thermal development of the recording material (thermal melting), or a mixture thereof. Lubricants can be applied with or without a polymeric binder.

Such a protective layer is made of a particulate material such as W
It may also include talc particles, which may 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.

[0095]

Antistatic layer In a preferred embodiment of the recording material of the present invention, an antistatic layer is applied to the outermost layer of the support on the side of the support which is not coated with the photo-addressable thermally developable element. A suitable antistatic layer therefor is EP
-A's 444 326, 534 006 and 644
456, US-P's 5,364,752 and 5,
472, 832, and DOS 4125758.

[0096]

Coating The coating of any layer of the photothermographic recording material of the present invention may be, for example, a Modern
Coating and Drying Techn
logic, edited by Edward D.
Cohen and Edgar B. Gutoff,
(1992) VCH Publishers In
c. 220 East 23rd Street, Su
item 909 New York, NY 1001
0, U.S. S. A. This can be done by any coating method as described in

[0097]

Photothermographic recording method The photothermographic materials of the present invention can be exposed using infrared light at wavelengths between 700 and 1100 nm, and the images are precisely focused light sources such as IR wavelength lasers or 7
I emitting at 80 nm, 830 nm or 850 nm
Obtained by R-pixel-by-pixel exposure using a laser diode; or by direct exposure to the object itself or to an image therefrom using IR light.

For the thermal development of the image-wise exposed photothermographic recording material according to the invention, in a time which is acceptable for the relevant application, for example contact heating, radiant heating, microwave heating, etc. Any type of heat source that allows the recording material to be heated uniformly to the development temperature can be used.

According to the present invention: (i) exposing the photothermographic recording material described above image-wise with actinic radiation to which the photothermographic recording material is sensitive;
(Ii) There is also provided a photothermographic recording method comprising thermally developing an image-wise exposed photothermographic recording material.

[0100]

[Application] The photothermographic recording material of 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 which can contain white reflective pigments, which can optionally also be applied to an intermediate layer 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 hard copy, photothermographic recording materials on a white opaque base are used,
In the field of medical diagnostics, black-imaging transparency is widely used in tests operated with light boxes.

While the invention will be described below in connection with preferred embodiments thereof, it will be understood that it is not intended to limit the invention to those embodiments. On the contrary, the intent is to cover all alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.

In addition to the above components, the following components were used in the photothermographic recording materials of the inventive and comparative examples: a) Antistatic layer component: KELZAN ^™ S: Technical Bullet
According to tin DB-19, MERC is a polysaccharide containing mannose, glucose and glucuronic acid repeating units as mixed potassium, sodium and calcium salts
K & CO. , Kelco Division, US
Xanthan gum from A; PT-dispersion: prepared by polymerization of 3,4-ethylenedioxy-thiophene in the presence of polystyrenesulfonic acid and ferric sulfate as described in US Pat. No. 5,354,613. Dispersion of poly (3,4-ethylenedioxy-thiophene) / polystyrenesulfonic acid; ULTRAVON ^™ W: arylsulfonate 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), prepared as described in US Pat. No. 4,861,812, having an average particle size of 5.9 μm. Stearyl methacrylate (2% by weight) 20% aqueous dispersion of particles of polymer beads; LATEX01: US-P 5,354,613 was prepared as described in 12 wt% dispersion of polymethyl methacrylate having an average particle size of 88.8nm;

[0104]

Embedded image

B) Photo-addressable, thermally developable element component BINDER 01 for coating the element from an aqueous medium: consisting of 45% by weight of methyl methacrylate, 45% by weight of butadiene and 10% by weight of itaconic acid. Copolymer.

SENSI C01 (US-P 5,44)
IR-sensitizing dyes according to 1,866):

[0107]

Embedded image

SENSI C02 (EP-A 616)
IR-sensitizing dyes according to 014):

[0109]

Embedded image

SENSI C03 (EP-A 616)
IR-sensitizing dyes according to 014):

[0111]

Embedded image

C) Photo-addressable, thermally developable elemental components for coating elements from non-aqueous media: i) Silver behenate / silver halide emulsion layer: GEL: Phthaloyl gelatin 16875 from ROUSSELOT 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 PHP: pyridinium hydrobromide perbromide; TMPS: tribromomethylbenzenesulfinate; SENSI C01: see above SENSI C02: see above SENSI C03: see above ii) Protective layer: CAB: cellulose acetate butyrate CAB from EASTMAN
-171-15S; PMMA: Polymethylmethacrylate Acryloid ^™ K120N from ROHM & HAAS.

The following examples and comparative examples illustrate the invention. The percentages and ratios used in the examples and comparative examples are by weight unless otherwise indicated.

[0114]

【Example】

[0115]

[Example 1 of the present invention] Synthesis of SENSI 01: Synthesis of SENSI 01
It involves the coupling of two intermediates A and B, which themselves are synthesized from a sequence of intermediates in a synthesis ladder.

Synthesis of Intermediate A: The first step in the synthesis of Intermediate A was the synthesis of D. D was prepared according to the following reaction scheme:

[0117]

Embedded image

10 L of butyl acetate, 2425 g of F and 3038 g of E were added to the flask, and the mixture was heated to reflux temperature and then at reflux temperature for a further 8 hours. Subsequently, upon cooling to room temperature, the product precipitated. It is then filtered and washed with butyl acetate to give a 74% yield of intermediate D
Was manufactured.

Intermediate A was then synthesized according to the following reaction scheme:

[0120]

Embedded image

294 g of intermediate D, 343 g of intermediate C
And 600 mL of sulfolane were added to the flask and heated on an oil bath with stirring at 125 ° C. for 24 hours.
Then the reaction mixture was cooled to 60 ° C. and 1200 mL of acetone was added. The resulting suspension was then stirred at room temperature for 1 hour, after which it was filtered and washed well with acetone to produce 51% yield of intermediate A.

Synthesis of Intermediate B: The first step in the synthesis of Intermediate B was the preparation of Intermediate H according to the following synthetic formula:

[0123]

Embedded image

2 L of ethanol, 5.5 g of sodium ethoxide and 759 mL of diethyl malonate were added to the flask, the mixture was cooled to -30 ° C and the atmosphere above the mixture was changed to nitrogen. Then 758 mL of acrolein dissolved in 750 mL of ethanol was added over 60 hours while maintaining the temperature of the reaction mixture at 0-5 <0> C. When the addition of acrolein is complete, raise the temperature to room temperature,
8 g sodium ethoxide dissolved in 180 mL ethanol was added. After standing overnight, 19 mL of acetic acid was added and the reaction mixture was evaporated under reduced pressure. The liquid residue was then distilled under reduced pressure to produce 26% yield of intermediate H.

Then, using the intermediate H, the intermediate G was prepared according to the following synthetic formula:

[0126]

Embedded image

162 g of Intermediate H, 162 mL of ethanol and 0.16 g of p-toluenesulfonic acid monohydrate were added to the flask and mixed well at room temperature. Then 20
6 mL of Intermediate I was added with stirring, then the stirred reaction mixture was heated to 30-40 ° C. until the reaction was complete. Then 0.33 mL of 33% odium methoxide
The solution was added and the mixture was stirred at 30-40 <0> C for another 15 minutes. Finally, the reaction mixture was vacuum distilled to produce 99% yield of intermediate G.

Then, using the intermediate G, the intermediate B was prepared according to the following reaction formula:

[0129]

Embedded image

[0130] 73 mL of dimethylformamide in the flask was cooled to 0 ° C. Then 59 mL of phosphoryl chloride was added with stirring and the mixture was stirred at room temperature for another hour. Then 98 g of intermediate G were added with stirring and the mixture was stirred at room temperature for a further 90 minutes. Then 7
20 mL of ethanol and 33 mL of deionized water were added and the mixture was stirred at room temperature for another 30 minutes. Then 2
73 mL of aniline was added with stirring and the mixture was stirred at room temperature for another 30 minutes. Finally, 3000 mL of a 6N solution of hydrochloric acid were added and the mixture was stirred at room temperature for another 15 minutes. The resulting precipitate was filtered and washed with a warm mixture of methanol and ethyl acetate to produce 86% yield of intermediate B.

Synthesis of SENSI 01: SENSI 0
1 was prepared according to the following reaction scheme:

[0132]

Embedded image

28 g of intermediate B, 180 mL of N, N-
Dimethylacetamide, 11 mL acetic anhydride and 37 m
1-8 diazabicyclo [5,4,0] undec-7 of L
The ene was added to the flask and mixed at room temperature to produce an orange solution. Then 39 g of intermediate A was added to the reaction mixture and then stirred at room temperature for 2.5 hours. Then an additional 9 mL of 1-8 diazabicyclo [5,4,0] undec-7ene was added and the mixture was stirred at room temperature for another hour. Finally, 360 mL of acetone was added to precipitate the product, which was filtered, washed and dried to give a 62% yield of SEN.
SI 01 was manufactured.

[0134]

[Examples 1 to 10 of the present invention and Comparative Examples 1 to 9]

[0135]

[Silver Behenate Dispersion] Dissolve 34 g (0.1 mol) of behenic acid in 340 mL of 2-propanol at 65 ° C. and add 400 mL of 0.24 M to a stirred behenic acid solution.
The behenic acid is converted to sodium behenate by adding aqueous sodium hydroxide solution and finally 250 mL of 0.1 mL of 0.1 wt.
Silver behenate was produced by adding a 4M aqueous solution of silver nitrate to precipitate silver behenate. This was filtered and washed with a mixture of 10% by volume of 2-propanol and 90% by volume of deionized water to remove residual sodium nitrate.

After drying at 45 ° C. for 12 hours, silver behenate is added to the anionic dispersants Ultravon ^™ W and Mer.
The paste was dispersed in deionized water using Solat ^™ H and rapidly mixed using a high-speed impingement mill (rotor-stator mixer) to obtain a paste.
after homogenization using a microfluidizer)
20% by weight of silver behenate, 2.1% by weight of Ultrav
on ^™ W and 0.203% by weight of Mersolat ^™
A finely divided stable dispersion containing H was obtained. The pH of the resulting dispersion was adjusted to about 6.5.

Then the following components: 2.22% by weight of 2 g
An aqueous solution of 3- (triphenyl-phosphonium) propionic bromide (PC02), corresponding to a concentration of 8 mol% of PC02 relative to silver behenate, was added to 3.0 g of silver behenate dispersion at pH 4 with stirring. In addition, in-situ conversion of silver behenate to some silver bromide was performed. After stirring for a further 10 minutes, the supersensitizer is added with stirring as a solution in water and / or methanol as specified in Table 1,
Immediately afterwards the IR-spectral sensitizer was added as a solution or dispersion in water and / or methanol as specified in Table 1. After stirring for a further 15 minutes, 2 g of 30% strength by weight B
An aqueous dispersion of INDER 01 was added with stirring at pH 4, followed by 2 g of 4.5% by weight of 3- (3 ',
An aqueous solution of 4'-dihydroxyphenyl) propionic acid was added.

[0138]

[Table 1]

[0139]

[Coating and drying of photothermographic materials]
A silver behenate / silver bromide dispersion is applied to an undercoated polyethylene terephthalate support having a thickness of 100 μm,
Doctor blade-coated at 0 μm blade setting. After drying on the coating bed at 40 ° C. for several minutes, the emulsion layer was dried in a hot air oven at 40 ° C. for 1 hour.

[0140]

[Image-wise exposure and heat treatment] Examples 2-1 of the present invention
The photothermographic materials of 0 and Comparative Examples 1-9 were prepared with a nominal power of 12.8 mW focused to give a point diameter (1 / e ² ) of 115 μm, 63 μm.
836 nm from HITACHI scanned at a speed of 5 m / sec with a pitch of m and 30% overlap
Diode laser HL type 8318G beam,
Exposure was through a wedge filter having an optical density varying between 0 and 3.3 with an optical density step of 0.15. The maximum exposure (filter optical density = 0) is about 50 J /
m ² .

The heat treatment is performed for 15 seconds at 105 ° C. on the side of the support on which the silver behenate / silver halide emulsion layer is not provided.
In contact with the heated metal block. The optical density of the image was measured using a MacBeth ^™ TR924 densitometer in transmission through a visible filter to obtain a sensitometric curve for the photothermographic recording material, from which the maximum and minimum optical densities, D
_The exposure required to obtain an optical density of _max and D _min , and D _min +0.5 was determined.

Examples 2 to 10 of the present invention and Comparative Example 1
-9 were exposed image-wise and heat treated to obtain _Dmax- and _Dmin -values, and the exposure values required to obtain an optical density of _Dmin + 0.5 were determined by IR Table 2 summarizes the sensitizer, supersensitizer, molar ratio of supersensitizer to IR-sensitizer and the heat treatment conditions used.

The results in Table 2 show that there is a supersensitizer (Example 9 of the present invention) and no supersensitizer (Examples 2 to 2 of the present invention).
8) both show effective IR-sensitization of the photothermographic recording material using the IR-sensitizing dye of the present invention. By comparison, SENSI C01, disclosed as an IR-sensitizing dye for photothermographic materials in US-P 5,441,866, and EP
-SENSI C02 and SENSIC03 disclosed as IR-sensitizing dyes in A 616 014
Do not show IR-sensitization in the absence of supersensitizer within the exposure range investigated.

[0144]

[Table 2]

[0145]

[Examples 11 to 17 of the present invention]

[0146]

[Support] Polyethylene terephthalate (PET) foil is firstly coated on both sides with colloidal silica (surface area: 100
A subbing layer consisting of a terpolymer latex of vinylidene chloride-methyl acrylate-itaconic acid (88/10/2) mixed with m ² / g) was coated. After stretching the foil in the transverse direction, the foil has a thickness of 175 μm, and 170 mg / m ² and 4 respectively on each side of the PET-foil.
We had a coverage of terpolymer and silica in the subbing layer of 0 mg / m ^2.

[0147]

[Antihalation / antistatic layer] Embodiment 11 of the present invention
The anti-halation / antistatic layer of the ~ 17 photothermographic recording material was prepared by first adding 55 mg D01 dissolved in ethyl acetate per gram of polymethyl methacrylate and allowing the ethyl acetate to evaporate.
It was produced by adsorbing an antihalation dye D01 onto polymethyl methacrylate particles of LATEX01.

On one side of the thus-primed 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.

[0149]

Silver halide emulsion 3.11% by weight of silver halide grains consisting of 97 mol% of silver bromide and 3 mol% of silver iodide in deionized water and having a weight average particle diameter of 50 nm.
A silver halide emulsion containing 0.47% by weight of GEL as a dispersant was prepared, for example, by T.I. H. James, "The T
heavy of the Photographic
Process ", Forth Edition, M
acmillan Publishing Co. In
c. , New York (1977), Chapter
3, pages 88-104, using conventional silver halide production methods.

[0150]

Silver Behenate / Silver Halide Emulsion A solution of 6.8 kg of behenic acid in 67 L of 2-propanol is added at 65 ° C. to a heated 400 L vessel to maintain the temperature of the contents at 65 ° C. Convert 96% of the behenic acid to sodium behenate by adding, with stirring, 76.8 L of 0.25 M sodium hydroxide in deionized water, then 10.5 kg of the above silver halide emulsion at 40 ° C. Was added with stirring, and finally 48 L of a 0.4 M solution of silver nitrate in deionized water was added with stirring to prepare a silver behenate / silver halide emulsion.
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.

7 kg of dry powder containing 9 mol% of silver halide and 4 mol% of behenic acid, based on silver behenate, is then 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 was added and the resulting dispersion was homogenized in a microfluidizer. Finally, 2.8kg of But
Var ^™ B76 was added with stirring to give a 31% by weight solid dispersion.

[0152]

Coating and Drying of Silver Behenate / Silver Halide Emulsion Layer The emulsion layer coating composition for the photothermographic recording materials of Examples 11 to 17 of the present invention was prepared as follows.
Prepared by adding the following solutions or liquids to 0.86 g of the above silver behenate / silver halide emulsion with stirring in the following order: 10.87 g of 2-butanone, 9% solution of TMABP in methanol Of 0.75 g, followed by stirring for 2 hours, 1.3 g of 2-butanone, 0.2 g of a 11% solution of potassium bromide in methanol and 1.3 g of 2-butanone, followed by stirring for 30 minutes, And 0.2
1 g LOWINOX ^™ 22IB46, 0.5 g T
A solution consisting of MPS and 9.24 g of 2-butanone, followed by stirring for 10 minutes. A particular weight of a particular concentration of a particular IR-sensitizing dye solution, which can also contain a particular supersensitizer at a particular concentration, specified in Table 3 for a particular embodiment of the invention. Addition was followed by stirring for 30 minutes. Finally, 4.35 g of Butvar ^™ B76 was added, followed by stirring for 45 minutes, then 2-butanone was added to a total weight of up to 76 g.

The PET-foil, primed and coated with an antistatic layer as described above, is then coated with a coating composition of 80 μm wet on a non-static layer-coated side of the foil at a blade setting of 150 μm. Doctor blade-coating to layer thickness, which was dried on an aluminum plate in a drying cabinet at 80 ° C. for 5 minutes.

[0154]

[Table 3]

[0155]

Protective Layer The protective layer coating composition for the photothermographic recording materials of Examples 11 to 17 of the present invention was
Prepared by dissolving 4.08 g CAB and 0.16 g PMMA in 36.3 g 2-butanone and 4.16 g methanol and adding the following solids or solutions with stirring in the following order: 5 g of phthalazine, 0.
A solution consisting of 2 g of 4-methylphthalic acid, 0.1 g of tetrachlorophthalic acid, 0.2 g of tetrachlorophthalic anhydride, and 2.55 g of LOWINOX ^™ 22IB46 and 5.95 g of 2-butanone.

The emulsion layer was then doctor blade-coated with a protective layer coating composition at a blade setting of 100 μm to a wet layer thickness of 57 μm, which after drying on an aluminum plate in a drying cabinet at 80 ° C. for 8 minutes, It gave a layer having a ^{composition: CAB 4.08g / 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 anhydride 0.20 g / m ² LOWINOX ^™ 22IB46 2.55 g / m ²

[0157]

[Image-wise exposure and heat treatment] Examples 11 to 11 of the present invention
Seventeen photothermographic recording materials were focused to give a point diameter (1 / e ² ) of 28 μm, 61 mW of which had a nominal power of 100 mW actually reaching the recording material, 50 m / s at a pitch of 14 μm. An 849 nm single-mode diode laser beam from SPECTRA DIODE LABS scanned at a speed of 0.25 nm was exposed through a wedge filter having an optical density varying between 0 and 4.2 in 0.20 optical density steps.

The heat treatment is carried out for 10 or 14 seconds, as specified in Table 4, by contacting the side of the support with the silver behenate / silver halide emulsion layer with a drum heated to a temperature of 121 ° C. Let's go. The optical density of the image is Mac
Using a Beth ^™ TR924 densitometer, measured in transmission through a visible filter, to obtain a sensitometric curve for the photothermographic recording material,
The exposure required to obtain a maximum and minimum optical density, _Dmax and _Dmin , and an optical density of _Dmin + 1.0 was then determined.

[0159] The photothermographic recording materials of Examples 11 to 17 of the present invention the image - exposing the street, obtained by heat treatment D _max - and D _min - value, and D _min +1.0
Exposure value required to obtain the optical density of the IR-sensitizer,
Table 4 summarizes the supersensitizers, the molar ratio of the supersensitizer to the IR-sensitizer and the heat treatment conditions used.

From the results shown in Table 4, the spectral sensitization of the photothermographic recording material using the IR-sensitizing dye of the present invention was as follows.
It is clear that effective spectral sensitization occurs in the infrared region of the spectrum. In the case of spectral sensitization with SENSI 03, the presence of the supersensitizer SS-02 indicates that the resulting D
_min − value is significantly reduced, but the sensitivity is reduced (= D _min +
At the expense of increased exposure required to obtain an optical density of 1.0).

[0161]

[Table 4]

[0162]

[Examples 18 to 20 of the present invention]

[0163]

[Silver Behenate / Silver Halide Emulsion] Example 11 of the Present Invention
7 kg containing 9 mol% of silver halide and 4 mol% of behenic acid prepared as described in cases 17 to 17
Of 648 in 29.9 kg of 2-butanone
g of Butvar ^™ B79 was dispersed using a microfluidizer to give a 20% by weight solid dispersion. Then 6.5 kg Butvar ^™ B79 was added and 32
A weight percent solid dispersion was obtained.

[0164]

Coating and Drying of Silver Behenate / Silver Halide Emulsion Layer The emulsion layer coating composition for the photothermographic recording materials of Examples 18 to 20 of the present invention was prepared as follows.
Prepared by adding the following solutions or liquids to 3.61 g of the above silver behenate / silver halide emulsion with stirring in the following order: 10 g of 2-butanone, a 11.5% solution of PHP in methanol 0.8 g, followed by stirring for 2 hours, 1 g of 2-butanone and 0.2 g of a 11% solution of potassium bromide in methanol, followed by stirring for 30 minutes. A particular weight of a particular concentration of a particular IR-sensitizing dye solution, which may also contain a particular supersensitizer at a particular concentration, specified in Table 5 for particular embodiments of the invention. Addition was followed by stirring for 30 minutes. Then 2.4 g of LOWINOX ^™ 22IB46 and 0.5
g of TMPS, followed by 2-butanone.
Total weight up to g.

The PET-foil, primed and coated with an antistatic layer as described above, is then coated with a coating composition of 85 μm on a non-static layer-coated side of the foil at a blade setting of 150 μm. Doctor blade-coating to layer thickness, which was dried on an aluminum plate in a drying cabinet at 80 ° C. for 5 minutes.

[0166]

[Table 5]

[0167]

Protective Layer The protective layer coating composition for the photothermographic recording materials of Examples 18 to 20 of the present invention was
4. In 47 g of 2-butanone and 4.4 g of methanol.
Prepared by dissolving 08 g CAB and 0.16 g PMMA and adding the following solids with stirring in the following order: 0.5 g phthalazine, 0.2 g 4-methylphthalic acid, 0.1 g tetra Chlorophthalic acid and 0.1.
2 g of tetrachlorophthalic anhydride.

The emulsion layer was then doctor blade-coated with a protective layer coating composition at a blade setting of 100 μm to a wet layer thickness of 60 μm, which was dried on an aluminum plate in a drying cabinet at 80 ° C. for 8 minutes before It gave a layer having a ^{composition: CAB 4.08g / 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 anhydride 0.20 g / m ²

[0169]

[Image-wise exposure and heat treatment] Examples 18 to 18 of the present invention
Twenty photothermographic recording materials were focused 15 to give a point diameter (1 / e ² ) of 10 μm.
It has a nominal power of 0 mW and 8.8 at a pitch of 5.9 μm
SPECTRADIO scanned at a speed of m / s
An 830 nm single mode diode laser beam from DE LABS was exposed through a filter having an optical density varying between 0 and 4.2 in 0.15 optical density steps.

The heat treatment, and the exposure required to obtain an optical density of D _min +1.0, and the evaluation of the resulting wedge images to determine the D _max -and D _min -values are described in Examples of the invention. Performed as described for photothermographic recording materials 11-17.

[0171] The photothermographic recording materials of Examples 18-20 of the present invention the image - exposing the street, obtained by heat treatment D _max - and D _min - value, and D _min +1.0
The exposures necessary to obtain the optical densities of the above are summarized in Table 6 together with the IR-sensitizer, the supersensitizer, the molar ratio of the supersensitizer to the IR-sensitizer and the heat treatment conditions used.

[0172]

[Table 6]

From the results shown in Table 6, the spectral sensitization of the photothermographic recording material using the IR-sensitizing dye of the present invention was as follows.
It is clear that effective spectral sensitization occurs in the infrared region of the spectrum. In the case of spectral sensitization with SENSI 02, the presence of the supersensitizer SS-02 appears to significantly reduce the D _min − value, but a significant decrease in sensitivity (= D _min +1.0 Increase in exposure required to obtain optical density).

Having described the preferred embodiments of the invention in detail, those skilled in the art will now appreciate that numerous modifications can be made without departing from the scope of the invention, which is limited by the following claims. It will be clear that modifications can be made therein.

The main features and aspects of the present invention are as follows.

1. A support, as well as a substantially light-insensitive organic silver salt, a reducing agent therefor in thermal working relationship therewith, a dye that is spectrally sensitized with the dye and catalytically reacted with the substantially light-insensitive organic silver salt; A photothermographic recording material comprising a photo-addressable thermally developable element comprising a photosensitive silver halide and a binder associated with
The general formula (I) wherein the dye has an anion if necessary for charge compensation:

[0177]

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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
Together with R ^8, R ⁸ together with R ^10, R ¹⁰ together with R ^12, R ⁷ is together and R ⁹ and R ⁹ together with R ^11, which may optionally be substituted The 5-atom or 6-atom carbon atoms or the atoms necessary for the completion of the heterocycle can be constituted; each independently R ¹ together with R ⁶ and R ¹³ independently R ¹²
Or a 6-ring atom or a 6-ring atom which can be substituted together with an atom necessary for the completion of the heterocyclic ring.].

[0179] 2. The dye may be -NH- (C, wherein R ¹⁸ , R ¹⁹ and R ²⁰ may each be deprotonated.
ＯO) —R ²¹ , —NH— (SO ₂ ) —R ²² , —NH—
(S = O) -R ²³ or indicates -NH-CN group, wherein R
²¹ , R ²² and R ²³ are independently alkyl, substituted alkyl,
2. The photothermographic recording material according to claim 1, which corresponds to formula (I) representing an aryl or substituted aryl group.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Ivan Hogue Martens Belgium B 2640 Malt cell Septes Trat 27 Agfa-Gevert na Mrose Fennoutjaps (72) Inventor Hans Streakers Belgium B 2640 Maltcell Septes Trat 27, Agfa-Gevuert Na, in Mrose-Fennoutjap

Claims (1)

[Claims] 1. A support, and substantially light-insensitive.
Organic silver salts and their reduction in thermal action
Sensitized with the agent, dye and said substantially light-insensitive
Photosensitive halogenation catalytically associated with a receptive organic silver salt
Photo-addressable thermally developable containing silver and binder
A photothermographic recording material comprising a functional element,
The dye has an anion if necessary for charge compensation
General formula (I):[Wherein, Z¹And Z^TwoIndependently represents S, O or Se;
R¹And R¹³Independently represents an alkylene chain; X¹And X
^TwoIs independently-(C = O) -R¹⁸,-(SO_Two) -R¹⁹or
Is-(S = O) -R²⁰Where R is¹⁸, R¹⁹as well as
R²⁰Are independently alkoxy-, aryloxy-, amido
R represents a no- or substituted amino-group;^Two, R^Three, R^Four, R^Five,
R¹⁴, R^Fifteen, R¹⁶And R¹⁷Is independently hydrogen, chlorine, odor
Element, fluorine, iodine or keto-, sulfo-, carboxy
-, Ester-, sulfonamide-, amide-, dial
Killamino-, nitro-, cyano-, alkyl-, al-
Kenyl-, hetero-aromatic, aryl-, alkoxy- also
Or an aryloxy group, which groups are substituted
Or each independently R^TwoIs
R^ThreeWith, R^ThreeIs R^FourWith, R^FourIs R^Fivealong with,
R¹⁴Is R^FifteenWith, R^FifteenIs R¹⁶With and R¹⁶Is R
¹⁷Of the benzene ring which can be substituted together with
The atoms necessary for the conclusion can be made;⁶, R⁷,
R⁸, R⁹, R^Ten, R ¹¹And R¹²Is independently hydrogen, chlorine,
Bromine, fluorine, iodine, alkyl group, substituted alkyl group,
An alkoxy group, an aryloxy group, a thioalkyl group,
Denotes a substituted amino group, wherein the substituent is a 5-ring atom or
Represents the atoms necessary for completing the 6-ring heterocycle
Or independently of each other R⁶Is R⁸With
And R⁸Is R^TenWith, R^TenIs R¹²With, R⁷Is R
⁹With and R⁹Is R¹¹May have been replaced with
5- or 6-atom carbocyclic or heterocyclic ring
Atoms necessary for the completion of
Stand up R¹Is R⁶With and R¹³Is R¹²Replaced with
5- or 6-ring atoms that can be
Can form the atoms needed to complete the ring]
Photothermographic recording material characterized by
Fees.