EP0573048B1 - Verfahren zur Herstellung eines Bildes - Google Patents

Verfahren zur Herstellung eines Bildes Download PDF

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Publication number
EP0573048B1
EP0573048B1 EP19930108959 EP93108959A EP0573048B1 EP 0573048 B1 EP0573048 B1 EP 0573048B1 EP 19930108959 EP19930108959 EP 19930108959 EP 93108959 A EP93108959 A EP 93108959A EP 0573048 B1 EP0573048 B1 EP 0573048B1
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EP
European Patent Office
Prior art keywords
silver
dye
image
recording material
group
Prior art date
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Application number
EP19930108959
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English (en)
French (fr)
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EP0573048A2 (de
EP0573048A3 (de
Inventor
Yoshihiko Suda
Nobuyuki Takiyama
Atsushi Tomotake
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0573048A3 publication Critical patent/EP0573048A3/de
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Publication of EP0573048B1 publication Critical patent/EP0573048B1/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/402—Transfer solvents therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/4033—Transferable dyes or precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/4046—Non-photosensitive layers

Definitions

  • the invention relates to a method of image formation using a thermal recording material or heat developable light-sensitive material.
  • thermal recording materials have advantages, such as easy operation and maintenance, feasibility for reduction in equipment size and cost and low running cost.
  • thermal transfer printing has recently been the subject of many research and development activities as can satisfy the requirements for both image quality and cost, in which a thermal transfer ribbon, comprising a support and a layer of dispersion of dye or pigment in binder coated thereon, and recording paper are superposed and heat according to the image information is applied to the back face of the thermal transfer ribbon via a thermal head to record images.
  • the thermal imaging method using a laser beam has also recently been investigated, which is described in an special issue "Imaging Part 2, - Current Hard Copy Printer Technology" of "Shashin Kogyo", pp. 63-113 (published by Shashin Kogyo Shuppansha on July 20, 1988), for instance.
  • silver halide photographic light-sensitive materials have a handling problem of the necessity for use of liquids such as a developer, though they surpass other image recording materials with respect to image quality.
  • the heat development method As a means of solving this problem, what is called the heat development method has been developed, in which exposure is followed by heat development to form images. Details of such a heat development method are given in the proceedings of the 17th symposium of the Society of Photographic Science and Technology of Japan titled “Discussion on Heat Developable Silver Salt Recording System” (May 1987). .
  • silver or dye images are formed by heat treatment and, if necessary, pressure treatment, after imagewise exposure of a heat developable light-sensitive material having a light-sensitive silver halide, a binder and a reducing agent on the support.
  • heat developable light-sensitive materials offer high image quality similarly to silver halide light-sensitive materials, the image quality level is lower than that obtained with conventional liquid processable light-sensitive materials. With this background, further improvements are desired, and development of positive-type heat developable light-sensitive materials is desired.
  • 1,3-sulfur-nitrogen-containing compounds are known to undergo cleavage reaction by the action of silver ion. Attempts have been made to utilize this reaction for imagewise release of reagents in photographic processing.
  • Japanese Patent Examined Publication No. 7576/1980 describes a technology in which a 1,3-sulfur-nitrogen-containing compound is cleaved according to the imagewise distribution of silver ion to release a photographically useful group (hereinafter referred to as PUG), with mention of its applicability to so-called instant photographic materials.
  • photographically useful groups include image forming dyes, their intermediates, antifogging agents and gelatin hardeners.
  • silver ions are supplied in the form of a soluble silver complex ions by the action of a silver halide solvent. An imagewise distribution of silver ions occurs in the unexposed portion.
  • Japanese Patent O.P.I. Publication No. 180548/1984 discloses a method by which a mobile dye is imagewise formed by heating a 1,3-sulfur-nitrogen-containing compound as a dye donator for heat developing type light-sensitive material preferably in the presence of base.
  • the heat developing type light-sensitive material containing a base or base precursor has a drawback of tendency toward maximum density reduction, though it permits fogging reduction in the desired dye image by acceleration of silver development.
  • Particularly recording materials incorporating a hydrophilic binder are normally used after being subjected to aging at a given temperature for a given period to increase the degree of hardening.
  • This aging is carried out at temperatures of normally 25 to 50°C, preferably 30 to 45°C for periods of normally 12 hours to 1 month, preferably 1 day to 2 weeks.
  • a mobile dye forming reaction can take place even during this storage for improvement in the degree of hardening, which leads to a considerable tendency toward image quality deterioration such as increased fogging.
  • the present inventors found that reaction takes place between an organic silver salt and a 1,3-sulfur-nitrogen-containing compound in the presence of a thermal solvent, and substantially in the absence of water and base, and that the use of this reaction makes it possible to obtain a recording material accomplishing the objects described above.
  • the object described above has been accomplished by using a recording material wherein at least a 1,3-sulfur-nitrogen-containing compound capable of being cleaved in the presence of silver ions or water-soluble silver complex salt, an organic silver salt and a thermal solvent are coated on a support.
  • the recording material is capable of forming visible images upon imagewise heating substantially in the absence of water and base.
  • This recording material is embodied as a heat developable light-sensitive material by adding a light-sensitive silver halide.
  • images can be formed by subjecting it to imagewise exposure, after which or simultaneously with which it is subjected to heating substantially in the absence of water and base.
  • the 1,3-sulfur-nitrogen-containing compound used in the present invention is represented by the following formula 1. wherein R 1 and R 2 independently represent a hydrogen atom, aliphatic group, aromatic group or heterocyclic group. R 3 represents a hydrogen atom, aliphatic group, aromatic group, heterocyclic group or acyl group. Z represents a group of non-metallic atoms necessary to form the ring, which ring may have a substituent thereon. Z may cooperate with S-C-N to form a condensed ring.
  • At least one of R 1 , R 2 , R 3 and the substituent on the ring formed by Z is a photographically useful group (PUG) or precursor thereof released upon reaction of the compound of Formula 1 with a silver ion or silver complex ion under heating.
  • PAG photographically useful group
  • Either of R 1 and R 2 is preferably other than a hydrogen atom, and R 3 is preferably other than a hydrogen atom.
  • substituents include carboxyl, sulfo, nitro, hydroxy, halogens such as chlorine, bromine and cyanogen, and hydrocarbon residues including aliphatic, alicyclic and aromatic groups as well as those exemplified for Formulas 1 above.
  • This substituent may have an ethylenic or acetylenic group, and its carbon chain may be interrupted by a hetero atom or hetero atom-containing group such as S, O, N, SO or NH.
  • This substituent may also contain a substituent such as phenylalkyl, alkyl ether, aryl ether, carboalkoxy, carboxyl, hydroxy, sulfo, halogen, cyano, nitro or alkylamino.
  • substituted or unsubstituted alkyl groups such as methyl, ethyl, octyl and dodecyl
  • substituted or unsubstituted cycloalkyl groups such as cyclohexyl, cyclopentyl and cyclooctyl
  • substituted or unsubstituted alkenyl groups such as vinyl, allyl, butenyl, decenyl, octadienyl and hexatrienyl
  • substituted or unsubstituted cycloalkenyl groups such as cyclopentenyl, cycloheptenyl and cyclohexadienyl
  • substituted or unsubstituted alkinyl groups such as ethynyl, hexynyl and octynyl
  • substituted or unsubstituted aryl groups such as phenyl, tolyl, benzyl and naphth
  • 1,3-sulfur-nitrogen-containing compounds which are used in image recording materials are cyclic sulfur-nitrogen-containing compounds having S and N atoms in their ring, specifically thiazolidine and benzothiazolidine. These compounds undergo cleavage reaction at a given rate upon heating in the presence of an organic silver to release a PUG, particularly a dye.
  • These compounds can be used under alkaline to acidic conditions and preferably under neutral to acidic conditions.
  • the photographically useful group (PUG) or precursor thereof is preferably substituted on the carbon atom bound to the sulfur and nitrogen atoms.
  • one of R 1 and R 2 or both in the compound of Formula 1 are preferably PUG.
  • PUG include dyes, developing inhibitors, developing accelerators, fogging agents, developing agents, hardeners, couplers, toning agents and brightening agents.
  • the substances preferably used as PUG are dyes, developing inhibitors and developing accelerators, with preference given to dyes.
  • R 3 and one or more groups substituted on the ring Z are preferably ballast groups which substantially immobilize the compound of Formula 1.
  • the balast groups include ordinarily those having at least 8 carbon atoms and preferably substituted or unsubstituted alkyl groups having 8 to 40 carbon atoms.
  • the balast group may be a polymer residual group.
  • the average molecular weight of the compound represented by Formula 1 is preferably not less than 10,000.
  • preferable compounds are thiazolidine derivatives or benzothiazolidine derivatives and especially preferable ones are thiazolidine derivatives.
  • any conventional dyes known by those skilled in the art including azo, azomethine, indoaniline, oxonol, cyanine, thiazole, anthraquinone, ditriphenylmethane and triphenylmethane dyes can be used.
  • Dye precursor is a compound producing dye molecules by reacting with other molecules or ions, or by heating, after being released.
  • organic silver salts which can be used for the present invention include the silver salts of long-chain aliphatic carboxylic acid and silver salts of carboxylic acid having a heterocyclic ring, such as silver laurate, silver myrystate, silver palmitate, silver stearate, silver arachidonate, silver behenate and silver ⁇ -(1-phenyltetrazolethio)acetate, and the silver salts of aromatic carboxylic acid such as silver benzoate and silver phthalate, described in Japanese Patent Examined Publication No. 4921/1968, Japanese Patent O.P.I. Publication Nos. 52626/1974, 141222/1977, 36224/1978 and 37610/1978, and US Patent Nos.
  • Examples of silver salts having an imino group include benzotriazole silver, which may be substituted or not.
  • substituted benzotriazole silver include alkyl-substituted benzotriazole silver, alkylamidobenzotriazole silver, alkylsulfamoylbenzotriazole silver, halogen-substituted benzotriazole silver salts, alkoxybenzotriazole silver, 5-nitrobenzotriazole silver, 5-aminobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-carboxybenzotriazole silver, 4-sulfobenzotriazole silver and 5-sulfobenzotriazole silver.
  • Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 2-methylbenzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazol silver, 1,2,4-triazole silver, 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver and phthalimide silver, and silver salts of mercapto compound such as 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4-triazole silver, 1-phenyl-5-mercaptotetrazole silver, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,2,4,6-pentazaindene silver.
  • mercapto compound
  • Examples also include the silver salts of carboxylic acid which decarboxylate at high temperatures described in Japanese Patent O.P.I. Publication No. 211454/1985 and the silver salts of acetylene derivative described in Japanese Patent O.P.I. Publication Nos. 226744/1986 and 231542/1986.
  • Silver complex compounds having a stability constant of 4.5 to 10.0 as described in Japanese Patent O.P.I. Publication No. 31728/1977 and silver salts of imidazolinethione as described in US Patent No. 4,168,980 can also be used.
  • silver salts of compounds having an imino group particularly silver salts of benzotriazole derivatives are preferred, with more preference given to silver salts of benzotriazole, 5-methylbenzotriazole and derivatives thereof, sulfobenzotriazole and N-alkylsulfamoylbenzotriazole.
  • organic silver salts described above may be used singly or in combination. They may be used as such after removing soluble salts in an aqueous solution of hydrophilic colloid such as gelatin, or may be used as fine grains of solid obtained by mechanical pulverization and dispersion of the organic silver salt after its isolation.
  • the amount of organic silver salt used is normally 0.01 to 20 g, preferably 0.1 to 5 g per m 2 of recording material.
  • thermal solvent hot melting substance
  • the thermal solvent is a compound which liquifies upon heating and acts to accelerate the image formation. It is preferably in a solid state at normal temperature, and its melting point is preferably 70 to 170°C.
  • the thermal solvent preferably has the following nature.
  • the heating volatility is minimum.
  • Thermal solvents which are preferably used in the recording material of the present invention are described below.
  • the thermal solvent preferably has an i/o value of not less than 0.5 and not more than 4.
  • the i/o value indicates the degree of organicity or inorganicity of compounds, calculated by the method described in "Kagaku no Ryoiki", vol. 11, pp. 719-725 (1957), published by Nankodo Shuppan.
  • hyd represents a group whose ⁇ value is -0.9 to -1.9 ( ⁇ value is a parameter indicating hydrophobicity; the values used were obtained from "Kagaku no Ryoiki", supple. No. 122, “Yakubutsu no Kozo Kassei Sokan” (Nankodo), pp. 96-103.
  • Examples of groups preferred for hyd include -NHCOCH 3 , -CH 2 OH, -NHSO 2 CH 3 , -CONHCH 3 , -NHCONH 2 , -CONH 2 , -NHCSNH 2 , -SO 2 CH 3 , -CH 2 CONH 2 , -SO 2 NH 2 ; -OCONH 2 , -OCH 2 CONH 2 and -N(SO 2 CH 3 ) 2 .
  • R 4 through R 8 in Formula 2 can be selected according to the hyd group so that the i/o value of the compound falls in the range from 1 to 3.
  • R 4 through R 8 include hydrogen atoms, and alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, acyloxy groups and halogen atoms which may have various substituents.
  • thermal solvents which are solid at room temperature and sparingly water-soluble are preferred.
  • thermal solvents which can be used for the present invention, with their i/o values, are given below, but these are not to be construed as limitative.
  • TS-1 HOCH 2 C(CH 3 ) 2 CH 2 OH
  • TS-2 HOCH 2 C(CH 2 ) 4 CH 2 OH
  • the compounds which are most preferably used as thermal solvents for the present invention are the thermal solvents whose i/O value falls in the range from 0.8 to 3, which are solid at room temperature and sparingly water-soluble, specifically TS-10, TS-11, TS-12, TS-13 and TS-14.
  • thermal solvents When added to a recording material comprising a plurality of layers, these thermal solvents may be added to any structural layer.
  • the thermal solvent for the present invention is added at ratios of preferably 10 to 500% by weight, more preferably 20 to 250% by weight of the total amount of binder in the recording material.
  • the thermal solvent used in the present invention is added preferably as a suspension of fine particles in an aqueous colloidal medium using a ball mill, sand mill or another means.
  • the thermal solvents for the present invention may be used in combination of two or more kinds.
  • the recording material used in the present invention is embodied by coating on a support a composition comprising a 1,3-sulfur-nitrogen-containing compound, an organic silver salt and a thermal solvent along with a binder.
  • the desired compound can be formed by heating the coating product using a thermal head or a condensed laser beam or the like to cause reaction between a 1,3-sulfur-nitrogen-containing compound above and silver ion at the heated portion.
  • Imagewise heating makes imagewise formation of the desired compound possible.
  • introducing a dye or a group capable of becoming a dye intermediate to a substituent makes imagewise distribution of the dye.
  • a dye image can be formed, which has a potential for application to a thermal image forming material.
  • the recording material can be embodied as a thermal transfer recording material when the 1,3-sulfur-nitrogen-containing compound used in the present invention is a non-diffusible dye and the product of reaction with organic silver salt is a diffusible dye.
  • the thermal transfer recording material used in the present invention comprises a support and a thermal transfer layer formed thereon which contains the composition used in the present invention.
  • the 1,3-sulfur-nitrogen-containing compound content in the thermal transfer layer is preferably 0.05 to 10 g per m 2 of support.
  • the thermal transfer layer can be formed by dissolving in a solvent one or more kinds of the 1,3-sulfur-nitrogen-containing compound used in the present invention along with a binder or dispersing them in a dispersant in the form of fine grains to yield an ink solution for thermal transfer layer formation, and coating and drying the ink on the support.
  • the dry thickness of the thermal transfer layer is preferably 0.1 to 10 ⁇ m.
  • binders examples include solvent-soluble polymers such as acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyvinylbutyral, polyvinylacetal, nitrocellulose and ethyl cellulose. These binders may be used singly or in combination, and may be used in dispersion in latex as well as in solution in organic solvent.
  • the amount of binder used is preferably 0.1 to 20 g per m 2 of support.
  • organic solvents include alcohols such as ethanol and propanol, cellosolves such as methyl cellosolve, aromatic compounds such as toluene and xylene, esters such as acetates, ketones such as acetone and methyl ethyl ketone and ethers such as tetrahydrofuran and dioxane.
  • any material can be used for the support, as long as it is dimensionally stable and endures heating by thermal head etc. upon recording.
  • preferred materials include thin papers such as condenser paper and glassine paper, and heat stable plastic films such as those of polyethylene terephthalate, polyamide and polycarbonate.
  • the thickness of the support is preferably 2 to 30 ⁇ m, and the support preferably has a subbing layer comprising a polymer selected for the purpose of improving the binder adhesion and preventing dye transfer and deposition on the support.
  • the back face (the side opposite to the thermal transfer layer) of the support may have a slipping layer for the prevention of head cohesion to the support.
  • the thermal transfer recording material for applying the thermal transfer recording material as a thermal recording material permitting full-color image recording, it is preferable to repeatedly coat on a support a total of three layers, namely a magenta thermal transfer layer containing a magenta image forming thermally-diffusible dye, a cyan thermal transfer layer containing a cyan image forming thermally-diffusible dye and a yellow thermal transfer layer containing a yellow image forming thermally-diffusible dye.
  • a total of four layers, namely a thermal transfer layer containing a black image forming substance and the three layers described above may be repeatedly coated on the same surface.
  • the recording material used in the present invention is embodied as a light-sensitive thermal recording material by adding a light-sensitive-containing material to a composition comprising a 1,3-sulfur-nitrogen-containing compound, an organic silver salt and a thermal solvent and coating the mixture along with a binder on the support.
  • a light-sensitive-containing material to a composition comprising a 1,3-sulfur-nitrogen-containing compound, an organic silver salt and a thermal solvent and coating the mixture along with a binder on the support.
  • image recording is achieved optically, wherein images are formed upon uniform heating.
  • This type of materials are referred to as heat developable light-sensitive materials.
  • the heat developable light-sensitive material used in the present invention is described below.
  • a light-sensitive silver halide is used as the light-sensitive material.
  • the organic silver salt described above is reduced with a reducing agent as described below under heating conditions. This reaction is accelerated by so-called latent images formed on the exposed fine grains of silver halide. In other words, in the heat developable light-sensitive material, the organic silver salt undergoes reduction in the exposed portion. Taking place concurrently with this reaction, the reaction of 1,3-sulfur-nitrogen-containing compound and organic silver salt is suppressed in the exposed portion.
  • This principle is applicable to the formation of positive images, for instance.
  • dye transfer occurs in the unexposed portion provided that a dye or a group capable of becoming a dye intermediate is introduced to the substituent for the 1,3-sulfur-nitrogen-containing compound and made non-diffusible and allowed to form a diffusible dye or dye intermediate after reaction with organic silver salt, i.e., positive images can be formed.
  • the compound released in the reverse-imagewise manner is not necessarily a dye; it may be any PUG, such as a developing inhibitor, fogging agent, developing agent, hardener, developing accelerator or brightening agent for controlling the image formed.
  • any material or means can be used. Examples thereof are given in Japanese Patent Application Nos. 256079/1989 (pp. 14-47) and 158931/1990 (pp. 13-41), filed by the present applicants.
  • any known conventional light-sensitive silver halide can be used in the heat developable light-sensitive material to be used in the present invention.
  • Examples of such light-sensitive silver halides include silver chloride, silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide.
  • the reducing agent used in the heat developable light-sensitive material to be used in the present invention is selected as appropriate out of the known conventional reducing agents in use for heat developable light-sensitive materials according to the developing mechanism and dye formation or release mechanism.
  • the reducing agent referred here includes reducing agent precursors which release a reducing agent upon heat development.
  • the heat developable light-sensitive material present invention is employed as a black-and-white or color light-sensitive material.
  • a dye-providing material is used.
  • 1,3-sulfurnitrogen-containing compound used in the present invention may be used in combination with other dye-providing materials.
  • the 1,3-sulfur-nitrogen-containing compound may be designed to release a photographically useful compound other than a dye and may be used to form a color image in the presence of other dye-providing materials.
  • dye-providing materials examples include the diffusible dye forming couplers described in Japanese Patent O.P.I. Publication Nos. 44737/1987, 129852/1987 and 169158/1987 and Japanese Patent Application No. 200859/1989, the leuko dye described in Japanese Patent O.P.I. Publication No. 88254/1986 and the azo dyes used for the heat developable dye bleaching method described in US Patent No. 4,235,957. It is preferable to use a dye-providing material which forms or releases a diffusible dye, with more preference given to a compound which forms a diffusible dye upon coupling reaction.
  • the heat developable light-sensitive material used in the present invention may incorporate various additives as necessary.
  • the heat developable light-sensitive material used in the present invention contains (a) a 1,3-sulfur-nitrogen-containing compound, (b) an organic silver salt, (c) a reducing agent, and (d) a light-sensitive silver halide.
  • a dye-providing material which may be identical to (a) or (c).
  • These substances may be contained in a single photographic component layer or in two or more layers. Specifically, it is possible to add the components (a), (b) and (d) to a single layer and the component (c) to an adjoining layer, or to add (b), (c) and (d) to a single layer and (a) to another layer.
  • Two or more light-sensitive layers may have substantially the same kind of color sensitivity, which layers may be prepared as low and high speed layers, respectively.
  • the heat developable light-sensitive material to be used in the present invention When using the heat developable light-sensitive material to be used in the present invention as a full-color recording material, it usually has three light-sensitive layers with different kinds of color sensitivity, in which respective dyes with different hues are formed or released upon heat development.
  • the blue-sensitive layer (B) contains a yellow dye (Y)
  • the green-sensitive layer (G) contains a magenta dye (M)
  • the red-sensitive layer (R) contains a cyan dye (C), i.e. (B-Y)-(G-M)-(R-C)
  • the present invention is not limited to these combinations, i.e., any combination is acceptable.
  • possible combinations include (B-C)-(G-M)-(R-Y) and (infrared-sensitive layer-C)-(G-Y)-(R-M).
  • These layers may take any configuration, including the layer configurations of R-G-B, G-R-B, R-G-infrared and G-R-infrared as arranged from the support side.
  • the heat developable light-sensitive material used in present invention may be provided with non-light-sensitive layers such as subbing layers, interlayers, protective layers, filter layers, backing layers and peeling layers as well as light-sensitive layers.
  • non-light-sensitive layers such as subbing layers, interlayers, protective layers, filter layers, backing layers and peeling layers as well as light-sensitive layers.
  • the image receiving material comprises a support and an image receiving layer capable of dye reception formed thereon, but the support itself may also serve as an image receiving layer with such capability.
  • the heat developable light-sensitive material present invention can be so-called a mono-sheet type heat developable light-sensitive material wherein a light-sensitive layer and an image receiving layer have previously been laminated on the same support as described in RD No. 15108 and Japanese Patent O.P.I. Publication Nos. 198458/1982, 207250/1982 and 80148/1986 and other publications.
  • the image receiving material for the present invention may incorporate various known additives.
  • additives include antistaining agents, UV absorbents, brightening agents, image stabilizers, developing accelerators, antifogging agents, pH regulators (e.g., acids, acid precursors), thermal solvents, organic fluorine compounds, oil drops, surfactants, hardeners, matting agents, antifungal agents and various metal ions.
  • the heat developable light-sensitive material used in the present invention can be exposed to light in accordance with known exposure means suitable to the color sensitivity of the light-sensitive material.
  • Examples of usable exposure light sources include tungsten lamps, halogen lamps, xenon lamps, mercury lamps, CRT light sources, FO-CRT light sources, light emitting diodes and laser sources (e.g., gas laser, dye laser, YAG laser, semiconductor laser), all of which may be used singly or in combination. It is also possible to use light sources comprising a combination of semiconductor laser and SHG element (second harmonic wave generating element). Also, phosphors excited by electron beams, X-rays, ⁇ -rays or ⁇ -rays can also be used as light sources for exposure.
  • laser sources e.g., gas laser, dye laser, YAG laser, semiconductor laser
  • SHG element second harmonic wave generating element
  • phosphors excited by electron beams, X-rays, ⁇ -rays or ⁇ -rays can also be used as light sources for exposure.
  • a known heating means can be used; for example, it may be brought into contact with a heated heat block, surface heater, heat roller or heat drum, it may be passed through a hot atmosphere, it may be heated using high frequency wave heating, and it may be heated with the Joule heat generated by supplying current to a heat generating electroconductive material like a carbon black layer on the back face of the light-sensitive material or image receiving material.
  • Heating for image formation using a recording material to be used in the invention is carried out substantially in the absence of water and base.
  • the recording material containing a 1,3-sulfur-nitrogen-containing compound contains a base or base precursor
  • a cleavage reaction of the 1,3-sulfur-nitrogen-containing compound proceeds and results in image quality deterioration during long-term storage or high-temperature or high-humidity storage of the recording material.
  • the 1,3-sulfur-nitrogen-containing compound releases a dye, a problem of increased fogging is posed.
  • 1,3-sulfur-nitrogen-containing compounds have been known to be used in the presence of base.
  • the presence of base is unnecessary, on the contrary, the relationship between fog and maximum density improves significantly because 1) reaction is carried out at high temperatures, and 2) the reaction is accelerated by the presence of a thermal solvent.
  • the advantageous effects of the present invention can be ahieved especially noticeably when the formation of image dyes by heat development and the transfer thereof to the image-receiving material are conducted substantially not in the presence of water.
  • a hydrophobic polymer in an image-receiving layer of the image-receiving material.
  • hydrophobic polymers polyvinyl chloride, polycarbonates, polyesters, polyarylates and polystyrene are preferable, and polyvinyl chloride is especially preferable.
  • the film surface pH of the recording layer is not more than 8.0, more preferably not more than 7.0 at 25°C.
  • the film surface pH of the recording layer is preferably kept within the above-mentioned range both before, during and after heating for image formation.
  • the film surface pH of the recording layer can easily be measured by dropwise adding a small amount of pure water onto the surface of the recording layer and applying a flat pH electrode thereon.
  • the pure water used for this purpose is ion exchange water or distilled water whose pH is 5 to 8 and whose electroconductivity is not more than 1 ⁇ s/cm at 25°C.
  • a microsyringe is used to dropwise add about 10 ⁇ l of the pure water onto the surface of the light-layer, and a flat electrode is applied thereto to obtain measurements.
  • aqueous solution containing 300 g of modified gelatin wherein over 90% of the amino groups have been substituted by phenylcarbamoyl groups, 2400 ml of deionized water, 9.18 g of benzotriazole and 51 ml of 28% aqueous ammonia, 1420 ml of another aqueous solution (OB-2) containing 250 g of benzotriazole and 169 ml of 28% aqueous ammonia and 1420 ml of still another aqueous solution (OC-1) containing 360 g of silver nitrate and 336 ml of 28% aqueous ammonia were added at constant flow rate by the double jet precipitation method using the mixer agitator described in Japanese Patent O.P.I.
  • thermal solvent TS-12 25 g was dispersed in 100 ml of a 0.5% aqueous solution of polyvinylpyrrolidone containing 0.04 g of surfactant 1 (Alkanol XC, produced by Du-Pont) to yield 120 ml of a dispersion.
  • the following recording material was prepared using the organic silver salt dispersion, thermal solvent dispersion and 1,3-sulfur-nitrogen-containing compound dispersion prepared above.
  • Gelatin 3.6 g/m 2
  • Compound 37 1.3 g/m 2
  • Silver benzotriazole 0.68 g/m 2 (as silver)
  • Thermal solvent TS-12 6.0 g/m 2
  • Polyvinyl alcohol 0.13 g/m 2
  • the support used was a latex-subbed transparent polyethylene terephthalate film having a thickness of 100 ⁇ m.
  • a recording material 2 was prepared in the same manner as with recording material 1 except that silver benzotriazole was not used.
  • Recording materials 1 (b) and 2 (b) were prepared in the same manner as in Example 1 except that the compound 37 of formula 1 was replaced with the compound 38 of formula 1 for the recording material 1 (b) and silver benzotriazole was not used for the recording material 2 (b).
  • the recording materials 1 (b) and 2 (b) were heated at 120°C for 60 seconds and then uniformly sprayed with a solution of 1% o-dianisidine in acetic acid.
  • the recording material 1 (b) developed an orange color, while the recording material 2 (b) remained colorless.
  • the compound (38) was heated in the presence of benzotriazole silver, a thiazolidine ring was presumably cleaved to form a diffusible aldehyde compound.
  • the recording materials 1 through 19 thus obtained were heated by keeping them in contact with a 120°C hot metal plate for 45 seconds, followed by extraction using the same solvent as in Example 1 and evaluation by thin-layer chromatography.
  • a recording material 20 was prepared with the organic silver salt dispersion, thermal solvent dispersion and 1,3-sulfur-nitrogen-containing compound dispersion prepared in Example 1 and a monodispersed silver iodobromide grain emulsion with an average grain size of 0.25 ⁇ m chemically sensitized with sodium thiosulfate and the following reducing agent 1.
  • the amounts of these components used per m 2 are as follows.
  • Gelatin 3.6 g
  • Compound 37 of the present invention 1.3 g Silver benzotriazole 0.68 g (as silver)
  • Thermal solvent TS-12 6.0
  • Polyvinyl alcohol 0.13
  • Silver iodobromide 0.45 g (as silver) Reducing agent 1 1.02 g
  • the support used was a latex-subbed transparent polyethylene terephthalate film having a thickness of 100 ⁇ m.
  • a recording material 20 (b) was prepared in the same manner as above except that the compound 37 of formula 1 was replaced with the compound 38 of formula 1.
  • the recording materials 20 (a) and 20 (b) were subjected to exposure using a tungsten lamp as the light source.
  • Exposed and unexposed recording materials 20 (a) and 20 (b) were heated, extracted and evaluated by thin-layer chromatography in the same manner as in Examples 1 and 2.
  • the exposed samples yielded an evidently smaller amount of diffusible compounds corresponding to the compounds 37 and 38 of the present invention in comparison with the unexposed samples.
  • the present invention makes it possible to suggest the potential of the present invention for embodiment as a heat developable light-sensitive material.
  • 1,3-sulfur-nitrogen-containing compound of formula 1, as shown in Table 2 and 180 mg of tricresylphosphate were dissolved in 1.2 ml of ethylacetate. Then, the solution was mixed with 6.5 ml of an aqueous solution containing 132 mg of the aforesaid surfactant and 150 mg of gelatin. Then, the mixed solution was emulsified and dispersed with a supersonic homogenizer. After that, ethylacetate was distilled off therefrom and deionized water was added to make 10 g in total. Thus, solutions each containing therein 1,3-sulfur-nitrogen-containing compound were prepared. Compound Addition amount (mg) (41) 672 (42) 318 (45) 612 (47) 360 (58) 491 (65) 716
  • a Dimezone-dispersing solution was prepared by dispersing the mixture of 5.0 g of Dimezone (1-phenyl-4,4-dimethyl-3-pyrazolidone), 5.0 ml of 5 weight % aqueous solution of the above-mentioned surfactant-1 and 40 ml of ion-exchanged water by means of an alumina ball mill.
  • Dimezone was replaced with dimezone-S (4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone)
  • a Dimezone-S dispersion was prepared.
  • Example-1 an organic silver salt emulsion prepared in Example-1 (silver benzotriazole), a thermal solvent dispersion (TS-12) and a silver iodobromide emulsion (an iodide content of 2 mol %), heat developable light-sensitive materials 101 and 102 were prepared.
  • An emulsion layer was coated on a 180 ⁇ m-thick PET support having thereon a subbed layer, and dried.
  • the coating amount of each compound in the emulsion layer is shown as follows: Gelatin 3.0 g/m 2 Polyvinyl pyrrolidone 0.02 g/m 2 Thermal solvent TS-12 1.5 g/m 2 1,3-Sulfur-nitrogen compounds as described in Table 3 Dimezone 2.0 mmol/m 2 Silver iodobromide 2.0 mmol/m 2 Silver benzotriazole 1.0 mmol/m 2 1,2,4-Triazole 24 mmol/m 2 Glyoxal 0.06 g/m 2
  • heat developable light-sensitive materials 101 and 102 were subjected to partial exposure for 10 -3 seconds. Then, each of them was superposed on an image-receiving material, and, they were heated uniformly for 60 seconds while being kept in contact with a metallic heat plate at 120 °C with a pressure of 2 kg/cm 2 .
  • the reflection density of the image was measured using a reflection densitometer PDA-65 (produced by Konica). Results are shown in Table 3. Light-sensitive material Kind and added amount of 1,3-sulfur-nitrogen compound Reflective density Unexposed portion Exposed portion 101 (41) 0.5 mmol/m 2 1.08 0.67 102 (45) 0.5.mmol/m 2 0.51 0.31
  • Example-1 an organic silver salt emulsion prepared in Example-1 (silver benzotriazole), a thermal solvent-dispersion (TS-12), 1,3-sulfur-nitrogen-containing compound dispersion prepared in Example 5, a reducing agent dispersion and a silver iodobromide emulsion (an iodide content of 2 mol %), heat developable light-sensitive materials 201 through 207 having 2-layer constitution were prepared.
  • the first layer (layer-1) was coated on a 180 ⁇ m-thick PET support having thereon a subbed layer, and dried. Then, the second layer (layer-2) was coated thereon and dried.
  • Coating amount of each compound in the first layer and the second layer is shown below.
  • 1,3-Sulfur-nitrogen-containing compound as described in Table 4
  • Thermal solvent TS-12 1.5 g/m 2 Reducing agent as described in Table 4
  • Silver benzotriazole Amount described in Table 4 1,2,4-Triazole 24.0 mmol/m 2 Glyoxal 0.1 g/m 2
  • Heat developable light-sensitive materials 201 through 206 were subjected to light exposure and heat-developing in the same manner as in Example 5, provided that the conditions of heating were changed as shown in Table 4.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Claims (13)

  1. Verfahren zur Bilderzeugung, bei welchem ein Aufzeichnungsmaterial, umfassend einen Schichtträger mit einer darauf befindlichen 1,3-Schwefel-Stickstoff-haltigen Verbindung mit der Fähigkeit, in Gegenwart eines Silberions oder Silberkomplexions gespalten zu werden, einem organischen Silbersalz und einem Wärmelösungsmittel, im wesentlichen in Abwesenheit von Wasser und einer Base oder eines Vorläufers derselben bildgerecht erwärmt wird, wobei die 1,3-Schwefel-Stickstoff-haltige Verbindung der folgenden Formel 1
    Figure 00790001
    worin bedeuten:
    R1 und R2 unabhängig voneinander ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe oder eine heterocyclische Gruppe;
    R3 ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische Gruppe, eine heterocyclische Gruppe oder eine Acylgruppe, und
    Z eine Gruppe von zur Ringbildung erforderlichen nichtmetallischen Atomen, die einen Substituenten enthalten kann, wobei mindestens einer der Reste R1, R2, R3 und des Substituenten am durch Z dargestellten Ring für eine photographisch brauchbare Gruppe oder einen Vorläufer hiervon mit der Fähigkeit, bei der Reaktion mit einem Silberion oder wasserlöslichen Silberkomplex unter Erwärmen freigesetzt zu werden, steht,
    entspricht.
  2. Verfahren nach Anspruch 1, wobei das Aufzeichnungsmaterial gleichzeitig mit oder nach der bildgerechten Belichtung erwärmt wird und zusätzlich ein Reduktionsmittel und ein lichtempfindliches Silberhalogenid enthält.
  3. Verfahren nach Anspruch 2, wobei die photographisch brauchbare Gruppe aus einem Farbstoff, Entwicklungsinhibitor, Entwicklungsbeschleuniger, Verschleierungsmittel, Kuppler, Toner oder Aufheller besteht.
  4. Verfahren nach Anspruch 2, wobei auf den Schichtträger des Aufzeichnungsmaterials eine Wärmeübertragungsschicht mit den in den Ansprüchen 1 oder 2 erwähnten Komponenten aufgetragen ist, die photographisch brauchbare Gruppe aus einem Farbstoff besteht, die Verbindung der Formel 1 als farbstoffliefernde Substanz zur Bildung eines Farbstoffs dient und der gebildete Farbstoff auf ein Bildempfangsmaterial übertragen wird.
  5. Verfahren nach Anspruch 4, wobei die Bildung des Farbstoffs und dessen Übertragung auf das Bildempfangsmaterial jeweils in Abwesenheit von Wasser und einer Base oder eines Vorläufers derselben durchgeführt werden.
  6. Verfahren nach Anspruch 5, wobei das Bildempfangsmaterial einen Schichtträger mit einer darauf befindlichen, ein hydrophobes Polymer enthaltenden Bildempfangsschicht umfaßt.
  7. Verfahren nach Anspruch 6, wobei das hydrophobe Polymer aus Polyvinylchlorid besteht.
  8. Verfahren nach Anspruch 5, wobei das Wärmelösungsmittel aus einer Verbindung der folgenden Formel 2 besteht:
    Figure 00810001
    worin hyd für eine Gruppe, ausgewählt aus -NHCOCH3, -CH2OH, -NHSO2CH3, -CONHCH3, -NHCONH2, -CONH2, -NHCSNH2, -SO2CH3, -CH2CONH2, -SO2NH2, -OCONH2, -OCH2CONH2 und -N(SO2CH3)2, steht und R4 bis R8 jeweils ein Wasserstoffatom, ein Halogenatom oder eine Gruppe, ausgewählt aus Alkyl, Aryl, Alkoxy, Aryloxy, Alkoxycarbonyl und Acyloxy, darstellen.
  9. Verfahren nach Anspruch 5, wobei das Aufzeichnungsmaterial aus einem Schichtträger mit einer darauf befindlichen Schicht mit einem hydrophilen Bindemittel besteht, wobei der Oberflächen-pH-Wert der Schicht nicht mehr als 8,0 bei 25°C beträgt.
  10. Verfahren nach Anspruch 9, wobei der Oberflächen-pH-Wert nicht mehr als 7,0 bei 25°C beträgt.
  11. Verfahren nach Anspruch 5, wobei das Wärmelösungsmittel aus einer Verbindung der in Anspruch 8 beanspruchten Formel 2 besteht und das Aufzeichnungsmaterial eine Schicht mit einem hydrophilen Bindemittel umfaßt und wobei der Oberflächen-pH-Wert der Schicht nicht mehr als 8,0 bei 25°C beträgt.
  12. Verfahren nach Anspruch 11, wobei der erhaltene Farbstoff auf eine ein hydrophobes Polymer umfassende Bildempfangsschicht übertragen wird.
  13. Verfahren nach Anspruch 12, wobei das hydrophobe Polymer Polyvinylchlorid ist.
EP19930108959 1992-06-05 1993-06-03 Verfahren zur Herstellung eines Bildes Expired - Lifetime EP0573048B1 (de)

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US5368979A (en) * 1994-01-27 1994-11-29 Polaroid Corporation Thermally developable photosensitive element
US5667933A (en) * 1996-02-26 1997-09-16 Polaroid Corporation Image-recording element
US5658705A (en) * 1996-02-26 1997-08-19 Polaroid Corporation Image-recording materials with 1,3-sulfur-nitrogen dye releasers
US5716754A (en) * 1996-09-18 1998-02-10 Polaroid Corporation Image-recording materials
US6790569B2 (en) 2000-06-13 2004-09-14 Eastman Kodak Company Color photothermographic elements comprising phenolic thermal solvents
US6465162B1 (en) 2000-08-15 2002-10-15 Eastman Kodak Company Photothermographic materials containing backside image stabilizing compounds
US6368778B1 (en) 2000-08-15 2002-04-09 Eastman Kodak Company Photothermographic materials providing improved image stability and methods of use
US7175977B2 (en) 2003-12-18 2007-02-13 Agfa-Gevaert Stabilizers for use in thermographic recording materials
EP3533619A1 (de) 2018-03-02 2019-09-04 Basf Se Wärmeempfindliches aufzeichnungsmaterial und farbentwickler
CA3149562A1 (en) * 2019-08-30 2021-03-04 Erkan Kocak Heat sensitive recording material with non-phenolic color developers

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JPS59180548A (ja) * 1983-03-31 1984-10-13 Fuji Photo Film Co Ltd 画像形成方法
US4917994A (en) * 1988-03-01 1990-04-17 Eastman Kodak Company Color photographic reflection print material with improved keeping properties
JPH02289853A (ja) * 1989-02-27 1990-11-29 Konica Corp 画像形成方法及び該方法に用いる熱現像カラー感光材料

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