EP0157639A2 - Matériau à plusieurs couches sensible à la lumière, en couleurs, développable à chaud - Google Patents

Matériau à plusieurs couches sensible à la lumière, en couleurs, développable à chaud Download PDF

Info

Publication number
EP0157639A2
EP0157639A2 EP85302325A EP85302325A EP0157639A2 EP 0157639 A2 EP0157639 A2 EP 0157639A2 EP 85302325 A EP85302325 A EP 85302325A EP 85302325 A EP85302325 A EP 85302325A EP 0157639 A2 EP0157639 A2 EP 0157639A2
Authority
EP
European Patent Office
Prior art keywords
group
heat
sensitive
blue
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP85302325A
Other languages
German (de)
English (en)
Other versions
EP0157639A3 (fr
Inventor
Toyoaki Masukawa
Masaru Iwagaki
Wataru Ishikawa
Tawara Komamura
Kimie Hoshino
Hidenobu Ohya
Shunji Suginaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP6703284A external-priority patent/JPS60209734A/ja
Priority claimed from JP28088284A external-priority patent/JPS61159645A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0157639A2 publication Critical patent/EP0157639A2/fr
Publication of EP0157639A3 publication Critical patent/EP0157639A3/fr
Withdrawn legal-status Critical Current

Links

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
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
    • 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
    • G03C8/4053—Intermediate layers

Definitions

  • This invention relates to a heat-developable multilayered color photo-sensitive material and more particularly to a heat-developable multilayered color photo-sensitive material in which a color contamination is improved.
  • the component layers are multilayered.
  • the typical examples of the layer arrangements include such an arrangement that is provided on a support in order from the support side with a silver halide panchromatic emulsion layer which is sensitive to red-light, a silver halide orthochromatic emulsion layer sensitive to green-light and, on the uppermost, a silver halide regular emulsion layer sensitive to blue-light.
  • the silver halide panchromatic emulsion and silver halide orthochromatic emulsion are spectrally sensitized by making use of such an optical sensitizer as usually called a sensitizing dye, and besides these spectrally sensitized layers, there is provided with the so-called blue-sensitive silver halide emulsion layer having the inherent sensitivity of silver halide itself, that is also called a regular layer.
  • a blue-sensitive silver halide emulsion layer is arranged to the farthest position from a support to serve as the uppermost layer as described above, a color turbidity is caused by overlapping the spectra thereof. Accordingly, in the case of a negative photo-sensitive material, for example, it is usual that the color turbidity is prevented from occurring by interposing a blue-light-absorbing filter layer between a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer.
  • blue-light-absorbing filter layers these are used, a layer comprising silver colloids of the order of from 0.001 to 0.05pm in the particle size, a layer containing such a dye stuff or a dye as flowed into a processing liquid in course of a developing process.
  • Such a blue-light-absorbing filter layer as mentioned may therefore be present only when exposing or sensitizing a photo-sensitive material to light, and if it still remains after completing a development process, an unnecessary absorption will be caused thereby, that is not desirable from the viewpoint of color-reproduction.
  • a silver colloidal layer is advantageous to an ordinary color negative development process because it can readily be removed in a bleaching or fixing step after completing the development process.
  • a silver colloid layer as used in the above-mentioned color negative photo-sensitive material cannot be used.
  • the silver colloid works as a physical developing nucleus for a heat-development as it has the property of a physical developing nucleus, and a reducing agent is oxidized and an organic silver salt is then so reduced as to deposit a metallic silver on the colloidal silver. Resultantly, the oxidants of the reducing agent are diffused into the adjacent layer to cause an undesirable color formation, the increase in fogginess and the lowering of contrast. It is, therefore, not preferable to make the silver colloid layer serve as a blue-light absorbing filter layer.
  • the second object of the invention is to provide a heat-developable multilayered color photo-sensitive material in which fogs are rarely to be caused and the contrast is not lowered.
  • the third object of the invention is to provide a heat-developable multilayered color photo-sensitive material of diffusion-transfer type in which a stain and contrast are improved.
  • a heat-developable multilayered color photo-sensitive material comprising a support having thereon a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer respectively containing at least one selected from (a) a light-sensitive silver halide, (b) an organic silver salt, (c) a developer and, (d) a dye-providing compound (another substance may be contained), wherein a layer containing a diffusionproof blue-light absorbing organic substance is interposed between said blue-sensitive layer and said green-sensitive layer or between said blue-sensitive layer and said red-sensitive layer.
  • a layer containing the blue-light absorbing organic substance to the side of a blue-sensitive emulsion layer opposite to the side thereof to be exposed to light when the photo-sensitive material is exposed to light.
  • the order of arranging a green-sensitive layer and a red-sensitive layer is not always fixed, but is allowed to arranged in reverse order. It is also allowed that only a blue-sensitive layer is also used for a blue-light absorbing filter layer as to a blue-light absorbable organic substance that is a yellow-dye releasing material.
  • the blue-light absorbing organic substances to be used in the invention are those having an absorption property in a visible spectral range of from 400nm to 500nm. It is, further, preferred that they are not diffused to other layers when a photo-sensitive layer is multilayered or preserved, and they do not stain any image when heat-developing or heat-transferring.
  • the characteristics required for the above-mentioned BAOS may somewhat become different in accordance with the conditions of a heat-development process, a post-processing made after the development process, or the like.
  • the dye which does not stain the heat-developed image if it is used for the heat-developable multilayered color photo-sensitive material of the invention either the one which is low in heat-diffusibility to a binder, or the one which is rather high in heat-diffusibility to the binder, but is decolorized by heat or light is cited.
  • the one which is rather high in heat-diffusibility, but has little affinity to the image receiving layer, and therefore does not substantially stain the layer is cited as well.
  • a BAOS means such a degree of diffusion that the BAOS may remain at the most in an adjacent layer even if the BAOS may move out of a layer containing the BAOS itself through a heat-development is made at a usual heat-developing temperature of from 110°C to 170°, and preferably it means such a degree of diffusion that the BAOS will remain in the layer containing the very BAOS. The measurement thereof may be made with the eye.
  • the thickness of a photo-sensitive layer to be used in a heat-developable photo-sensitive material of the invention is from 1pm to 15pm and preferably from 2pm to 10 ⁇ m
  • the thickness of a layer containing BAOS of the invention is from 0.5pm to 10 ⁇ m and more preferably from lpm to 5pm.
  • the thickness thereof is from 0.1 ⁇ m to 20pm and preferably from 0.3pm to 5pm.
  • the preferable thereof are those each having a maximum absorption in a range of from 400nm to 500nm. And, as for the BAOS which are not diffused to other layers when a photo-sensitive layer is multilayered or preserved, and are low in heat-diffusibility in a binder during heat-developing.
  • the molecule of such BAOS has at least one hydrophilic group selected from the group consisting of sulfo, carboxy, sulfino, sulfeno, thiosulfo, dithiosulfo, hydroxysulfonyloxy, hydroxysulfonylthio, thiocarboxy, carboxyimido, hydrazoic acid, carbohydrazoic acid, hydroxime acid, carbohydroxime acid, hydroxame acid, carbohydroxame acid, sulfinimide acid, sulfonimide acid, sulfinohydroxime acid, sulfonohydroxime acid, and sulfamoyl group.
  • hydrophilic group selected from the group consisting of sulfo, carboxy, sulfino, sulfeno, thiosulfo, dithiosulfo, hydroxysulfonyloxy, hydroxysulfony
  • hydrophilic group a sulfo, sulfino, sulfeno, thiosulfo, dithiosulfo, hydroxysulfonyloxy, hydroxysulfonylthio, carboxy and thiocarboxy group are preferable and a sulfo group and a carboxy group are especially preferable.
  • a BAOS having a ballast group is given as an example.
  • Such a preferable BAOS includes those having a large molecular ballast group which are, for example, hydrophobic groups such as a straight or branched alkyl group having not less than 8 carbon atoms, a group containing the above-mentioned alkyl group, an aryl group having a straight or branched alkyl group having not less than 4 carbon atoms and a group containing the above-mentioned aryl group.
  • ballast groups are satisfactorily useful if they have 30 carbon atoms.
  • BOAS having a hydrophobic or hydrophilic chain polymer are preferable in the invention.
  • the dyes having a hydrophilic group when comparing the above-mentioned dyes having a hydrophilic group with the dyes having a ballast group, the latter is preferable, and the dyes having both of the hydrophilic group and a highly hydrophobic ballast group are more preferable.
  • the alkyl group having not less than 8 carbon atoms may be either one of the straight-chained or the branch-chained, and preferable ones have not more than 30 carbon atoms, and more preferable ones have not more than 27 carbon atoms. They include, for example, an n-octyl group, a tert-octyl group, an n-dodecyl group, an n-octadecyl group and the like.
  • an alkoxy group such as dodecyloxy group, an alkylthio group such as dodecylthio group, an alkylsulfonyl group, an alkylamide group such as ⁇ -dodecyloxycarbonylpropioamide group and 2,4-di-tert-amylphenoxyacetamide group, a palmitoylamide group, a dodecylcarbamoyl group, an n-octadecyl succinimide group and the like.
  • the alkyl groups useful in the invention shall not be limited thereto.
  • the groups each containing an aryl group having an alkyl group having not less than 4 carbon atoms include, for example, an aryloxy group substituted by an alkyl group having not less than 4 carbon atoms, and such an arylamide group as 3-palmitoylamidobenzamide group, substituted thereof.
  • the groups useful in the invention shall not be limited thereto.
  • BAOS those having an absorption in a visible spectral range of 400nm to 500nm are arbitrarily selected out of generally known dyes including azo dyes, azomethyne dyes, cyanine dyes, merocyanine dyes, oxonol dyes, styryl dyes, and the like.
  • Typical compounds of such BAOS can be those represented by the following Formula (1) or (2) and the polymers each having a unit induced from monomer represented by the Formula (3); among them, the polymers are more preferable because of the excellent dispersionproof property thereof; where each of R 1 to R 5 is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl, alkoxy, alkylamido, aryl, aryloxy, or arylamido group with 1 to 22 carbon atoms, and any group is also allowed to have a carboxy or sulfo substituent;
  • R 6 is a hydrogen atom, or an alkyl, alkoxy, alkylamido, aryl, anilino, aryloxy, or arylamido group with 1 to 22 carbon atoms, and any group is also allowed to have a substituent.
  • Each of R 7 to R 11 is a hydrogen atom, a halogen atom; or a cyano, nitro, hydroxy, carboxy, or sulfo group; further or a substituted or unsubstituted alkyl, alkoxy, dialkylamino, acyl, alkylamido, or carboalkoxy group with 1 to 22 carbon atoms; R 7 and R 8 are also allowed to combine with each other to form a benzene ring;
  • R 12 and R 13 is a substituted or unsubstituted alkyl group with 1 to 22 carbon atoms such as a methyl, ethyl, propyl, butyl, hydroxyethyl, methoxyethyl, carboxyethyl, sulfopropyl or methanesulfonamidoethyl group; R 12 and R 13 are also allowed to combine with each other to form a piperidine, pyrrolidine or morphorino ring, or the like;
  • Each of R 14 to R 17 is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl, alkoxy, or alkylamido group with 1 to 4 carbon atoms;
  • R 18 is a substituted or unsubstituted alkyl or aryl group;
  • Each of R 19 to R 23 is a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, or a substituted or unsubstituted alkyl, alkoxy, alkylamino, or alkylamido group with 1 to 22 carbon atoms.
  • BAOS to be used in the invention which are represented by General Formula (1) or (2) above-cited, those whose molecule has one or more hydrophilic groups, a greatly hydrophobic alkyl group with 8 or more carbon atoms, or an aryl group having an alkyl group with 4 or more carbon atoms are preferable. Further, those whose molecule has both the above hydrophilic groups and the above hydrophobic group are especially preferable. In addition, compounds whose whole BAOS is polymeric are preferable as well.
  • X represents an ethylenicaly unsaturated group or a group having an ethylene unsaturated group
  • Dye represents a residual group of a blue-light absorbing dye
  • Dye represents a residual group of anyone of generally known dyes having its spectral absorption in a visible spectral range between 400nm and 500nm such as oxonol dyes, styryl dyes and the like including azo dyes, azomethine dyes, cyanine dyes, merocyanine dyes and the like.
  • X represents an ethylenicaly unsaturated group or a group having an ethylenicaly unsaturated group, and preferably those represented by the following Formula (4);
  • R 24 represents hydrogen, a carboxy or alkyl group including, for example, methyl group, ethyl group and the like; the alkyl group is allowed to have such a substituent as a halogen, e.g., fluorine, chlorine and the like, a carboxy group or the like.
  • a halogen e.g., fluorine, chlorine and the like
  • the carboxy group or the carboxy group of a substituent may be allowed to form a salt
  • J 1 and J 2 represent a divalent bonding group, respectively, including, for example, -NHCO-, -CONH-, -COO-, -OCO-, -SCO-, -COS-, -0-, -S-, -SO-, -S0 2 -, and the like
  • X 1 and X 2 represent a divalent hydrocarbon group, respectively, including for example, the divalent hydrocarbon groups include, for example, an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group and an arylenealkylene group
  • the alkylene groups include, for example, methylene group, ethylene group, propylene group and the like
  • the arylene groups include, for example, phenylene group and the like
  • the aralkylene groups include for example, phenylmethylene group and the like
  • the preferable ones are represented by the following Formula (5) or (6);
  • R 25 through R 47 represent respectively hydrogen atom, an alkyl group, an alkenyl group, an cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an amyl group, an acyloxy group, an acylamino group, an alkoxyalkyl group, an aryloxyalkyl group, an alkoxycarbonyloxyl group, an alkoxycarbonylamino group, an alkoxycarbonyl group, an carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a cycloalkylamino group, a halogen atom, cyano group, a acyloxyalkyl group, nitro group, an alkylsulf
  • Each group represented by R 25 through R 47 may further be allowed to have a substituent.
  • two groups adjacent to each other on the benzene ring may be bound to form a carbon ring, and further, R 36 and R37 may be bound each other to form a piperidino ring, a pyrrolidino ring or a morpholino ring.
  • the polymers each having a unit, which are derived from the monomeric compounds of the invention represented by the Formula (3) may be the so-called homopolymers each having a unit, which comprise only one kind of the monomers represented by the Formula (3), or they may be the copolymers each comprising a combination of not less than two kinds of the monomers having the Formula (3), or they may further be copolymers each comprising one or more kinds of other comonomers each having copolymerizable ethylene unsaturated group.
  • the comonomers each having the above-mentioned ethylene unsaturated group which are capable of forming a copolymer with the monomers of the invention having the Formula (3), there may be an ester acrylate, an ester methacrylate, a vinyl ester, an olefin, a styrene, an ester crotonate, a diester itaconate, a diester maleate, a diester fumarate, an acrylamide, an allyl compound, a vinyl ether, a vinyl ketone, a heterocyclic vinyl compound, a glycidyl ester, an unsaturated nitrile, a polyfunctional monomer, a variety of unsaturated acids and the like.
  • esters acrylate include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, cyclohexyl acrylate, cyclohexyl
  • esters methacrylate include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, actyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenyl- aminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate
  • the vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butylate, vinyl isobutylate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate.
  • the olefins include, for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chrolide, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene.
  • the styrenes include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropyl- styrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate.
  • the crotonic acid esters include, for example, butyl crotonate, hexyl crotonate and the like.
  • the diesters itaconate include, for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like.
  • the diesters maleate include, for example, diethyl maleate,. dimethyl maleate, dibutyl maleate and the like.
  • the diesters fumarate include, for example, diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like.
  • An acrylamide such as acrylamide, methylacryl, ethylacrylamide, propylacrylamido, butylacrylamide, tert--butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethyl- aminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, -cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide;
  • a methacrylamide such as methacrylamide methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacryl- amide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, dimethylmethacrylamide, ⁇ -cyanoethylmethacrylamide, N-(2-acetoxyethyl)methacrylamide.
  • the monomer are given as acrylic acid, methacrylic acid, itaconic acid, maleic acid and a monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate; a monoalkyl maleate such as monomethyl meleate, monoethyl maleate, monobutyl maleate; citraconic acid, stylenesulfonic acid, vinylbenzylsulfonic acid, vinylsulfonic acid, an acryloyloxyalkylsulfonic acid such as acryloyloxy- methylsulfonic acid, acryloyloxypropylsulfonic acid; a methacryloxyalkylsulfonic acid such as methacryloyloxy- methylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloylpropylsulfonic acid; an acrylamidoalkylsulfonic acid such as 2-acrylamide
  • These acids may also be such an alkaline metal as Na, K and the like, or an ammonium ion salt.
  • alkaline metal as Na, K and the like
  • ammonium ion salt As for the other comonomers, such a bridged monomer as described in U.S. Patent Nos. 3,459,790, 3,438,708, 3,554,987, 4,215,195 and 4,247,673, and Japanese Patent O.P.I. Publication No. 205735/1982 may be used. To be more concrete, they include, for example, N-(2-acetacetoxy- ethyl)acrylamide, N-(2-(2-acetacetoxyethoxy)ethyl)acrylamide, and the like.
  • a preferable case thereof is that the contents of the repetition unit comprising a monomer having the Formula (3) are from 10 wt% to 90 wt% of the whole polymer, and more preferable case is that the contents thereof are 30 wt% to 70 wt% of the whole polymer.
  • a polymer is prepared in an emulsion--polymerization process or in a solution-polymerization process.
  • the same processes may be applied to the blue-light absorbing dye polymers of the invention having the repetition unit derived from the monomers of the invention having the Formula (3).
  • the emulsion-polymerization processes those described in U.S. Patent Nos. 4,080,211 and 3,370,952 may be applied, and as for the processes in which hydrophobic polymers are dispersed to serve as the latex into an aqueous solution of gelatin, those described in U.S. Patent No. 3,451,820 may be applied.
  • the comonomers thereof may be liquid comonomers which may serve, in a normal state, as a solvent for a stationary monomer, when emulsification--polymerizing.
  • the emulsifying agents include a surface active agent, a macromolecular protective colloid, and a copolymeric emulsifying agent.
  • the surface active agents there include, for example, an anionic active agent, a nonionic active agent, a cationic active agent, and an amphoteric active agent.
  • anionic active agent there are given as the examples, a soap, sodium dodecylbenzene sulfonate, sodium laurylsulfate, sodium dioctylsulfosuccinate, and a sulfuric acid salt of a nonionic active agent.
  • nonionic active agents there include, for example, a polyoxyethylene nonylphenyl ether, a polyoxyethylene stearic acid ester, a polyoxyethylene sorbitan monolaurylic acid ester, a polyoxyethylene-polyoxypropylene block copolymer, and the like.
  • cationic active agents there include, for example, an alkylpyridium salt, tertiary amine and the like.
  • amphoteric active agents there include, for example, a dimethyl alkyl betaine, an alkyl glycine and the like.
  • macromolecular protective colloids there include, for example, a polyvinyl alcohol, hydroxyethyl cellulose and the like. They may be used independently to serve as an emulsifying agent and may also be used in combination with the other surface active agents. The various kinds and functions of these active agents are described in "Belgische Chemische Industrie, 28, 16 - 20 (1963).
  • organic solvents for dissolving the lipophilic polymers there include, for example, methyl acetate, ethyl acetate, propyl acetate, and the like, and an alcohol, a ketone, a halogenated hydrocarbon, an ether, and the like. These organic solvents may be used independently or in combination with two or more kinds of them.
  • the solvents to be used in a polymerization process are a monomer and a well-qualified solvent for blue-light absorbing dye polymers to be produced, and are relatively low in reactivity with a polymerization starting agent.
  • water there include, for example, water, toluene, an alcohol (e.g., methanol, ethanol, iso-propanol, tert-butanol and the like), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethyl formaldehyde, dimethyl sulfoxide, acetonitrile, methylene chloride, and the like; and these solvents may be used independently or in a mixture of two or more kinds thereof.
  • an alcohol e.g., methanol, ethanol, iso-propanol, tert-butanol and the like
  • acetone e.g., methyl ethyl ketone
  • tetrahydrofuran dioxane
  • ethyl acetate dimethyl formaldehyde
  • dimethyl sulfoxide dimethyl sulfoxide
  • the temperatures for a polymerization process are normally within the range of from 30°C to 120°C, though it is necessary to take the kinds of the polymerization starting agents and the solvents into consideration.
  • polymerization starting agents to be used in the emulsification-polymerization process or the solution-polymerization process for preparing a blue-light absorbing dye polymer of this invention, there include the following ones:
  • These polymerization starting agents may be contained in the range of from 0.01 wt% to 10 wt% and more preferably from 0.1 wt% to 5 wt% to the aggregate quantity of monomers in the emulsification-polymerization process or in the solution-polymerization process.
  • the other processes such as a suspension-polymerization process, a block--polymerization and the like may also be applied.
  • this invention there contains every one of the homopolymer of the monomers of the invention having the Formula (1), a copolymer comprising two or more of the monomers in combination, or a copolymer comprising the monomers and at least one kind of the other polymerizable comonomers as the copolymeric components.
  • the synthesizing processes shall not limit to the invention.
  • blue-light absorbing dye polymers of the invention are synthesized in the following two processes;
  • This Compound (A) of 60g were dissolved in 500ml of dioxane at 80°C.
  • the system of reaction was applied with a nitrogen substitution, and 40g of butyl acrylate and 2.7g of azobisisobutylonitrile were added thereto and the resulting solution was stirred for two hours at 80°C. Further, 1.3g of azobisisobutylonitrile were added thereto and stirred for two hours at 80°C.
  • the resulting mixture was poured into 5l of water and was filtrated. Then, 95g of Polymer PM-10 were obtained.
  • a mixture was prepared by mixing 18g of p-methoxy aniline, 32ml of concentrated chloric acid and 450ml of water. The resulting solution was cooled to 0°C and was then dropped therein with a solution of 10.5g of sodium nitrite disslolved in 60ml of water. The resulting solution was stirred for 30 minutes at 0°C was. A solution of a diazonium salt was thus obtained.
  • the molecular weight of a blue-light absorbing dye polymer of the invention is within the range of from 1,500 to 100,000 in term of weight-average molecular weight (Mw).
  • such dyes as above cited are contained by a layer interposed between a blue-sensitive layer and a green-sensitive layer, or between a blue-sensitive layer and a red-sensitive layer.
  • the dyes are ordinarily contained by the layer interposed between the blue-sensitive layer and the green-sensitive layer as shown in the following layer arrangement.
  • Such a layer arrangement as shown above sometimes has, in addition, various other layers (hereinafter called intermediate layer) interposed between the above layers for various specific purposes.
  • intermediate layer various other layers
  • the red-sensitive heat-developable photo-sensitive layer is composed of red-sensitive silver halide, an organic silver salt, a developer, a cyan dye-providing compound, and a binder.
  • the green-sensitive heat-developable photo-sensitive layer is composed of green-sensitive silver halide, an organic silver salt, a developer, a magenta dye-providing compound, and a binder.
  • the blue-sensitive heat-developable photo-sensitive layer is composed of blue-sensitive silver halide, an organic silver salt, a developer, a yellow dye-providing compound, and a binder.
  • a heat-developable multilayered color photo-sensitive material of the invention which is arranged in such a way as described above, releases and forms dyes in course of a heat-developing process, and transfers the dyes onto an image receiving layer.
  • it is necessary to cut off the blue-light from the green-sensitive layer and the red-sensitive layer because both layers are sensitive also to the inherent sensitive range (400nm to 500nm).
  • the above layer containing BAOS functions effectively for this purpose.
  • the BAOS of the invention have not only the property of effectively absorbing the blue light but also an excellent diffusion-resistance as aforementioned, diffusion of the BAOS into farther layers than adjacent layer is prevented substantially. Therefore, not only any fogginess or lowering of contrast, but also any stain are not caused.
  • the above BAOS relevant to the invention are applied ranging from O.Olg/m 2 to 10g/m 2 , preferably from 0.05g/m 2 to 1.5g/m . They can be added to the blue-light-absorbing layer of the heat-developable multilayered color photo-sensitive material by various means according to their structure and properties.
  • the BAOS, together with a binder are dissolved in a certain solvent, and ground with the use of a ball mill, the protect dispersing method that a dispersion is made with the use of a high boiling-point solvent or its combination with a low boiling-point solvent, similarly to the case of dispersion of ordinary couplers, and the Fischer dispersing method that the BAOS are dissolved in a alkaline solution, and then dispersed into a hydrophilic binder.
  • a process as a latex-dispersion process in which the polymers of the invention may be contained in the component layer in such a manner that the polymers are dissolved in a low-boiling solvent such as methanol, ethanol, ethyl acetate or the like, or a high-boiling solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, or the like and the resulted solution is then dispersed by ultrasonic waves; a process in which an polymers are dissolved in an aqueous alkali solution such as an aqueous solution of 10% sodium hydroxide or the like and the resulted solution is neutralizing by a mineral acid such as hydrochloric acid, nitric acid or the like; or a process in which the poly
  • Any blue-light absorbing dye polymer of the invention may be used independently or in combination.
  • the amount thereof to be used is not limited but may be depended upon the kinds of the polymers or whether they are to be used independently or in combination with two or more of them.
  • an amount to be used is from O.Olg to lOg and preferably from 0.05g to 1.5g per square-meter of a support.
  • the photo-sensitive silver halide to be used in the invention include, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and the like.
  • These photo-sensitive silver halide can be prepared in such an arbitrary process in the photographic technical field as a single-jet process, a double-jet process and the like.
  • the desired results are obtained with the use of photo-sensitive silver halide emulsions containing a photo-sensitive silver halide prepared in accordance with an ordinary preparation process of a silver halide gelatin emulsion.
  • the shape of the silver halide particle is allowed to be a regular tetrahedron, regular octahedron, or tetradecahedron, but preferably has at least (1, 1, 1) faces.
  • the particle is allowed to be of core-shell type that the interior and exterior ports are different than each other in halogen composition.
  • Such photo-sensitive silver halide emulsions may preferably be chemically sensitized in an arbitrary process used in the photographic technical field.
  • sensitizing processes there are various processes including, for example, a gold, platinum or palladium sensitization, a sulphur sensitization, a gold-sulphur sensitization, a reduction sensitization, and the like, which may be applied independently or in combination.
  • the photo-sensitive silver halide emulsions prepared as mentioned above can be most preferably applied to a heat-developable photo-sensitive layer that is a component layer of the photo-sensitive materials of this invention.
  • an inorganic halide may be given as the example thereof, including, for example; a halide represented by MXn in which M represents hydrogen, NB 4 group or a metal atom, X represents Cl, Br or I and n is 1 when the M is hydrogen or NH 4 group, and when M is a metal atom, n is the valence thereof, and the metal atoms include those of lithium, sodium, potassium, rubidium, trioum, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thalium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, wolfram, manganese, rhenium, iron, cobalt, nickel, rhodium, paradium, osmium, iridium, platinum, cerium; a halide represented by MXn in which M represents hydrogen, NB 4 group or
  • photo-sensitive silver halide and the photo-sensitive silver salt forming components may be used in combination in various processes.
  • a preferable amount used thereof is from O.OOlg to 50g per sq. meter, and a more preferable amount is from O.lg to lOg per sq. meter.
  • the heat-developable color photo-sensitive materials may also comprise each of blue-light-sensitive, green-light-
  • Each of the blue-light sensitive silver halide emulsion, green-light sensitive silver halide emulsion and red-light silver halide emulsion to be used in the above-mentioned case may be prepared by adding various kinds of spectral sensitization dyes to the silver halide emulsions.
  • the spectral sensitization is made by making use of a sensitizing dye.
  • the spectral sensitization dyes which may typically be used in this invention include, for example, cyanine, merocyanine, a trinuclear or tetranuclear complex cyanine, holopolar cyanine, styryl, hemicyanine, oxonole and the like.
  • cyanine dyes those each having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are preferred to use.
  • Such a nucleus may have an enamine group capable of producing an alkyl group, alkylene group, hydroxyalkyl group, sulfalkyl group, carboxyalkyl group, aminalkyl group, or a condensed carbocyclic or heterocyclic color ring. Also, it may be in the symmetric or unsymmetric form, and the methine chain or the polymethine chain thereof may have an alkyl group, a phenyl group, an enamine group, a heterocyclic substituent.
  • the merocyanine dyes may also have, for example, such an acid nucleus as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolyl acid nucleus, a thiazolinethione nucleus, a malononitrile nucleus, and a pyrazolone nucleus.
  • These acid nuclei may also be substituted by either of an alkyl, alkylene, phenyl, carboxyalkyl, sulfalkyl, hydroxyalkyl, alkoxyalkyl or alkylamine group, or a heterocylic ring nucleus. If required, these dyes may further be used in combination.
  • the amount of these dyes to be added is from 1 x 10 -4 mole to 1 mole per mol of a silver halide or a silver halide forming component, and more preferably, from 1 x 10 -4 mole to 1 x 10 -1 mole.
  • various kinds of organic silver salts may be used if required for increasing the sensitivity and improving the developability of the materials.
  • organic silver salts to be used to the heat-developable color photo-sensitive materials of the invention there may be given as the examples thereof the following; an aliphatic carboxylic acid silver salt such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, silver -(1-phenyltetrazolethio) acetate and the like, as described in Japanese Patent Examined Publication Nos. 4924/1968, 26582/1969, 18416/1970, 12700/1970, and 22185/1970, Japanese Patent O.P.I. Publication No.
  • an aliphatic carboxylic acid silver salt such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, silver -(1-phenyltetrazolethio) acetate and the like, as described in Japanese Patent Examined Publication Nos. 4924/1968, 26582/1969, 18416/1970
  • RD Research Disclosure
  • Nos. 16966 and 16907 British Patent Nos. 1,590,956 and 1,590,957.
  • organic silver salts silver salts of an imino group are preferred to use, especially silver salts of a benzotriazole derivative are preferred, and further, silver salts of a sulfobenzotriazole derivative are more preferred to use.
  • alkyl substitute-bearing benzotriazole silver salts such as, for example, methylbenzotriazole silver; halogen-bearing benzotriazole silver salts such as, for example, bromobenzo- triazole silver, and chlorobenzotriazole silver; amido group-bearing benzotriazole silver such as, for example, 5-acetamidobenzotriazole silver, and the compounds described in the specifications of British Patent Nos.
  • 1,590,956 and 1,590,957 such as, for example, N-[6-chloro-4-N-(3,5-dichloro--4-hydroxy phenyllimino-1-oxo-5-methyl-2,5-cyclohexadiene-2-yll--5-carbamoylbenzotriazole silver salt, 2-benzotriazole-5-ylazo--4-methoxy-l-naphthol silver salt, l-benzotriazole-5-ylazo-2--naphthol silver salt, and N-benzotriazole-5-yl-4-(4-dimethyl- aminophenylazo)benzamide silver salt.
  • N-[6-chloro-4-N-(3,5-dichloro--4-hydroxy phenyllimino-1-oxo-5-methyl-2,5-cyclohexadiene-2-yll--5-carbamoylbenzotriazole silver salt 2-benzotriazole-5-
  • organic silver salts especially useful in the invention are those having a hydrophilic group, for example, those in Japanese Patent O.P.I. Publication No. 118638/1983.
  • organic salts are cited: 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sulfonic acid sodium, benzotriazole silver-5-sulfonic acid sodium, benzotriazole silver-4-sulfonic acid potassium, benzotriazole silver-5-sulfonic acid potassium, benzotriazole silver-4-sulfonic acid ammonium, benzotriazole silver-5-sulfonic acid ammonium, 4-carboxybenzotriazole silver, 5-carboxybenzotriazole silver, benzotriazole silver-4--carboxylic acid sodium, benzotriazole silver-5-carboxylic acid sodium, benzotriazole silver-4-carboxylic acid potassium, benzotriazole silver-5-carboxylic acid potassium, benzotriazole silver-4-carboxylic acid ammonium, benzotriazole silver-5
  • the salt may be isolated, and dispersed into a binder for the photo-sensitive layers by an appropriate means for its use.
  • the salt may be prepared in such a binder for the photo-sensitive layers, and directly used without isolation.
  • the applying amount of the organic silver salt ranges preferably from 0.05g to 10.Og per sq. meter of the support or from 0.01 mole to 500 mole per mole of a photo-sensitive layer halide, and more preferably from 0.2g to 5.0g per sq. meter of the support or from 0.1 mole to 100 mole per mole of the photo-sensitive silver halide.
  • developers to be used in a heat-developable color photo-sensitive material of the invention such developing agents as described, for example, in the specifications of U.S. Patent Nos. 3,531.286; 3,761,270; and 3,764,328; in RD Nos. 12146, 15108, and 15127; and in Japanese Patent O.P.I. Publication No. 27132/1981; that is, developing agents of p-phenylenediamine type, p-aminophenol type, phosphoroamido- phenol type, and sulfonamidophenol type; and color developing agents of hydrazone type are advantageously applicable in the case of heat-transferable dye-providing materials described, for example, in Japanese Patent O.P.I. Publication No.
  • the particularly preferable reducing agents may be given those represented by the following Formula (23) appeared in Japanese Patent O.P.I. Publication No. 146133/1981:
  • R 48 and R 49 each represent hydrogen or an alkyl group which is allowed to have a substituent and has one to 30 carbon atoms and preferably one to four carbon atoms, and the R 48 and R 49 may close a ring so as to form heterocyclic ring;
  • R 50 , R 51 , R 52 and R 53 each represent hydrogen, a halogen, a hydroxy group, an amino group, an alkoxy group, an acylamide group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group which is allowed to have a substituent and has one to 30 carbon atoms, and preferably, one to four carbon atoms, and the R 50 and R48, and the R 52 and R 49 each may close a ring so as to form a heterocyclic ring, respectively; and M represents an alkaline metal atom or a compound containing an ammonium group, a nitrogen-containing organic base or a quaternary nitrogen atom.
  • the nitrogen-containing organic base in the Formula (7) is an organic compound containing a nitrogen atom which is capable of producing an inorganic acid and a salt and displays a basicity.
  • the particularly essential organic bases include, for example, an amine compound.
  • Chain amine compounds include, for example, primary amine, secondary amine, and tertiary amine, and cyclic amine compounds include pyridine, quinoline, piperidine, imidazole and the like as the famous examples of the typical heterocyclic organic bases.
  • a compound as hydroxylamine, hydrazine, amidine and the like is also useful for a chain amine.
  • the salts of nitrogen-containing organic bases such an inorganic acid salt as a chloride, a sulfate, a nitrate or the like of the organic bases is preferably used.
  • the compounds each containing quaternary nitrogen in the formula above there include, for example, a salt or hydroxide of a nitrogen compound having a quatrivalent covalent bond.
  • the reducing agents represented by Formula (7) may be synthesized in such a well-known process as described in, for example, Houben-Weyl, Methoden der Organischen Chemie, B and XI/2, pp. 645 - 703.
  • phenols including p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, and N-methyl-p-aminophenol
  • sulfonamidophenols for example, 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, and 2,6-dibromo-4-(p-toluenesulfonamido)phenol
  • polyhydroxybenzenes for example, hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, and 3-carboxycatechol
  • naphthols for example, K-naphthol, 9-naphthol, 4-aminonap
  • the applying amount depends on types of organic silver salt, photo-sensitive silver salt and other ingredients to be used, or the like, but ranges ordinarily from 0.05 moles to 10 moles, preferably from 0.1 mole to 3 moles per mole of organic silver salts, respectively.
  • dye-providing compounds to be used in a heat-developable color photo-sensitive material of the invention the ones of both dye-releasing type and dye-forming type are applicable, and there are cited compounds described, for example, in Japanese Patent O.P.I. Publication Nos. 179840/1982, 186744/1982, 123533/1983, 149046/1983, and 149047/1983, 12431/1984, 716648/1984, 95529/1984, 116740/1984, 124327/1984, 124329/1984, 159159/1984 and the like.
  • dye-providing compounds described in the specifications of the above Japanese Patent O.P.I. Publication Nos. 124339/1984 and 1591591984 it is preferable that, their molecule has either a hydrophilic groups such a sulfo or carboxy group, or a ballast group as a large-molecular hydrophobic group, and thereby can be immobilized in photo-sensitive layers, and that the dyes formed therefrom are heat-transferable.
  • the dye-providing materials may be classified, depending on the reaction forms, into two types, that is, one is a negative type dye-providing material which works on a positive function, namely, thereby a negative dye image is formed when the negative type silver halide is used; and the other is a positive type dye-providing material which works on a negative fuction, namely, thereby a positive dye image is formed when a negative type silver halide is used. Further, the negative type dye-providing material may be classified in the following;
  • reducible dye releasing compounds there may be given a compound represented by Formula (5) as the example thereof.
  • Car represents a reducible substrate, i.e., the so-called Carrier, which is capable of releasing an oxidized dye when a photo-sensitive silver halide and/or an organic silver salt to be used if required; and Y represents a diffusible dye residual group.
  • a 1 and A 2 each represent hydrogen or a hydroxy or amino group; and Y is similar to the Y previously represented in Formula (8).
  • Cp l represents an organic group, i.e., the so-called coupler residual group, which is capable of releasing a diffusible dye upon reacting with the oxidation products of a reducing agent
  • J represents a divalent coupling group, and the coupling of Cp 1 to J is cleaved by the reaction of J with the oxidation product of the reducing agent
  • n is an integer of 0 or 1
  • Y is similar to the Y represented in Formula (8). It is preferred that Cp l is substituted by one of various ballast groups so as to make the coupling dye releasing type compound non-diffusible.
  • the ballast groups are an organic group having not less than 8 carbon atoms and more preferably not less than 12 carbon atoms; a hydrophilic group such as a sulfo group, a carboxy group or the like; and a group having not less than 8 carbon atoms and more preferably not less than 12 carbon atoms, and a hydrophilic group such as a sulfo group, a carboxy group or the like, together, which are suitably used according to characters of photo-sensitive materials.
  • the other ballast groups which are particularly preferable may include a chain polymer.
  • A' represents a hydrophobic coupler residue.
  • A' has no group such as a sulfo, carboxy or thiosulfo group, which makes the dye-providing compound immobile in heat-developable
  • B' represents a group releasible from a coupler by a coupling reaction.
  • B' has a sulfo, carboxy, or thiosulfo group; a large-molecular hydrophobic group, for example, an alkyl group having 8 or more carbon atoms, or an aryl group having an alkyl group with 4 or more carbon atoms; a group which can make dye-providing compounds such as hydrophilic and hydrophobic polymer residues immobile in heat-developable photo-sensitive layers.
  • Such a dye-providing compound is that which yeilds a hydrophilic heat-transferable dye through coupling reaction with the oxidant of a color developing agent in course of heat-development.
  • A' in the above General Formula (11) can be represented, for example, by the following General Formulas (12) to (16).
  • each of R 54 , R 55 , R 56 and R 57 is a hydrogen atom, a halogen atom (preferably a chlorine, bromine or iodine atom), an alkyl group (preferably an alkyl group with 1 to 24 carbon atoms, for example, a methyl, ethyl, butyl, t-octyl, n-dodecyl, n-pentadecyl, or cyclohexyl group; or an alkyl group with an aryl substituent, for example, a benzyl or phenethyl group as well), a substituted, or unsubstituted aryl group, (for example, a phenyl, naphthyl, tolyl, or methyl group), an acyl group (for example, an acetyl, tetradecanoyl, or pivaloyl group, or a substituted or unsubstituted benzoyl group),
  • Each of R 581 R 59 and R 60 is a hydrogen atom, a halogen atom (preferably a chlorine, bromine or iodine atom), an alkyl group (preferably an alkyl group with 1 or 2 carbon atoms, that is, a methyl or ethyl group), an alkoxy group (preferably an alkoxy group with 1 or 2 carbon atoms, that is, a methoxy or ethoxy group), a substituted or unsubstituted alkylamido group (for example, a laurylamido group or the like), a substituted or unsubstituted phenoxyacetamido group (for example, a phenoxyacetamido group with an alkyl substituent, or the like), or a substituted or unsubstituted arylamido group.
  • a halogen atom preferably a chlorine, bromine or iodine atom
  • an alkyl group preferably an alkyl group with
  • R 61 is an alkyl group (preferably an alkyl group with 1 to 24 carbon atoms, for example, a methyl, butyl or heptadecyl group), an alkoxy group (preferably an alkoxy group with 1 to 18 carbon atoms, for example, a methoxy, ethoxy or octadecyloxy group), an arylamino group (for example, an anilino group, or further-an anilino group with a halogen atom, or an alkyl, amido or imido group as substituent), a substituted or unsubstituted alkylamido group (for example, a laurylamido group, a substituted or unsubstituted phenoxyacetamido group, or a phenoxybutaneamido group), or a substituted or unsubstituted arylamido group (for example, a benzamido group, or a benzamido group with
  • R 62 is an alkyl group (preferably an alkyl group with 1 to 18 carbon atoms), or a substituted or unsubstituted aryl group (for example, a phenyl, tolyl, or methoxyphenyl group, or the like).
  • R 63 is an arylamino group (for example, an anilino group, or an anilino group with a halogen atom, or an alkyl, alkoxy, alkylamido, arylamido, or imido group, or the like as substituent).
  • R 64 and R 65 represents the same group as the one represented by above-mentioned R 54 , R 55 , R 56 or R 57 .
  • each of the substituents R 54 to R 56 as coupler residues which are represented by A' are desirable to have an aryl group having either an alkyl group with 8 or more carbon atoms, or an aryl group with an alkyl group of 4 or more carbon atoms so as not to hinder the heat-transferability of formed dyes.
  • B' represents a hydrophilic group such as a sulfo group or a carboxyl group, or a group represented by -J-Y (where J is a divalent combined group, and Y is a substituted or unsubstituted alkyl or aryl group).
  • J is a divalent combined group
  • Y is a substituted or unsubstituted alkyl or aryl group.
  • the alkyl or aryl group represented by Y it is preferable to be an alkyl or aryl group having a hydrophilic substituent such as a sulfo or carboxy group.
  • an alkyl group having a substituted or unsubstituted alkylcarbamoyl or arylcarbamoyl substituent an alkyl group having a carboalkoxy, or carboaryloxy substituent; an alkyl group having a halogen substituent; an aryl group having a alkylamido, alkylsulfonamido, arylamido, or arylsulfonamido substituent; an aryl group having a substituted or unsubstituted alkylcarbamoyl, alkylsulfamoyl, arylcarbamoyl, or arylsulfamoyl substitutent or a substituted or unsubstituted alkyl substituent with 1 to 22 carbon atoms; an aryl group having a substituted or unsubstituted alkyl substituent with 1 to 22 carbon atoms; an aryl group having an alkyl group having an alky
  • the active-position substituent represented by B' in Formula (11) it is preferable to have an alkyl group or the like having a hydrophilic group such as a sulfo or carboxy group, an alkyl group with 8 or more carbon atoms, or an aryl group with an alkyl group of 4 or more carbon atoms as a group immobilizable against heat in the heat-developable photo-sensitive layer. It is especially preferable to have both the hydrophilic group and the hydrophobic group mentioned above.
  • a sulfo, sulfino, sulfeno, thiosulfo, dithiosulfo, hydroxylsulfonyloxy, hydroxysulfonylthio, carboxy, or thiocarboxy group is cited.
  • C P2 represents an organic group capable of forming a diffusible dye upon reaction with, i.e., coupling to, the oxidation product of a reducing agent, that is, the so-called coupler residual group;
  • X3 represents a divalent coupling group; and
  • Q represents a ballast group.
  • the molecular weight of the coupler residual group represented by C P2 is preferably not more than 700 and more preferably not more than 500, because of the diffusivity of the formed dye.
  • a preferable ballast group is the one similar to the ballast groups defined by Formula (10), and more preferable one is a group having not less than 8 carbon atoms and more preferably not less than 12 carbon atoms and a hydrophilic group such as a sulfo group, a carboxy group or the like together, and a further preferable one is a chain polymer.
  • the preferable ones are those having a repetition unit, which are represented by Formula (18) below;
  • C P2 and X 3 each represent the same reference characters defined in Formula (17);
  • X 4 represents an alkylene, allylene or aralkylene group, or a divalent organic group; and
  • L represents an ethylene unsaturated group or a group having the ethylene unsaturated group; and each of L and l 3 is 0 or 1.
  • Coupler residual groups defined by Cp 1 and C P2 each in Formulas (10), (17) and (18) above are preferable.
  • R 66 , R 67 , R 68 and R 69 represent hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, carbamoyl group, sulfamoyl group, an acyloxy group, amino group, an alkoxy group, aryloxy group, cyano group, ureido group, an alkylthio group, an arylthio group, carboxy group, sulfo group, or a heterocyclic residual group, and they may further be substituted with hydroxy group, carboxy group, sulfo group, an alkoxy group, cyano group, nitro group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group,
  • substitutions may be selected in accordance with the purposes of Cp 1 and Cp 2 , and in Cp l , as described above, it is preferred that one of the substituents is a ballast group, and in Cp 2 , it is preferred to select a substituent so that the molecular weight thereof may be not more than 700 and more preferably not more than 500, because the diffusibility of dyes to be formed is to be improved.
  • W 1 represents a group of atoms necessary for forming a quinone ring on which a substituent may be taken place;
  • R 70 represents an alkyl group or hydrogen;
  • E represents -SO 2 - or in which R 71 represents an alkyl group or hydrogen, and R 72 represents oxygen or r is 0 or 1;
  • Y is synonymous with the Y previously defined in Formula (8).
  • the examples of the compounds are described in Japanese Patent O.P.I. Publication Nos. 166954/1984, 154445/1984 and the like. They include, for example, the following compounds; Exemplified dye-providing materials:
  • the other positive type dye-providing materials there includes a compound which is deprived of a dye releasing function when it is oxidized, that is typified by the compound represented by Formula (30) below;
  • W represents a group of atoms necessary for forming a benzene ring on which a substitutent may be taken place; and R 70 , E, and Y each are synonymous with those defined in Formula (29), respectively.
  • R 70 , E, and Y each are synonymous with those defined in Formula (29), respectively.
  • the examples of these compounds are described in Japanese Patent O.P.I. Publication Nos. 124329/1984, 154445/1984 and the like. The following compounds are given as the examples;
  • W, R 70 and Y each are synonymous with those defined in Formula (30).
  • the examples of the compounds are described in Japanese Patent O.P.I. Publication No. 154445/1984, and the following compounds are given as the examples;
  • the preferable residual groups of such diffusible dyes are of not more than 800 in molecular weight and more preferably not more than 600 because of improving the diffusibility of the dyes, and the examples of such residual groups are given these of an azo dye, azomethine dye, anthraquinone dye, napthoquinone dye, styryl dye, nitro dye, quinoline dye, carbonyl dye, phthalocyanine dye and the like.
  • These residual groups of dyes may also be in the recolorable and temporarily short-waved form when heat-developing or image-transferring.
  • a chelatable dye residual group is in the preferable form to answer the requirements for improving light resistance of an image.
  • dye-providing materials may be used independently or in combination with two or more of them.
  • the amount was is not limited but may be determined according to the kinds of dye-providing materials, whether they are used independently or in combination, or whether the photographic component layer of a photo-sensitive material of the invention comprises a single layer or two or more multilayers.
  • the amount thereof to be used is, for example, 0.005g to 50g per square-meter and preferably from O.lg to lOg per square meter.
  • any arbitrary process may be applied to contain dye-providing material to be used in the invention in the photographic component layers of a heat-developable color photo-sensitive material.
  • the polymers of the invention may be contained in the component layer in such a manner that the polymers are dissolved in a low-boiling solvent such as methanol, ethanol, ethyl acetate or the like, or a high-boiling solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, or the like and the resulted solution is then dispersed by ultrasonic waves; that the polymers are dissolved in an aqueous alkali solution such as an aqueous solution of 10% sodium hydroxide or the like and the resulted solution is neutralized by a mineral acid such as chloric acid, nitric acid or the like; or that the polymers are dispersed together with an aqueous solution of a suitable polymer such as polyvinyl butyral, poly
  • various other additives than the components mentioned above can be added as occasion calls.
  • development accelerators alkali-releasing agent described in the specifications of U.S. Patent Nos. 3,220,846; 3,531,285; 4,012,260; 4,060,420; 4,088,496; and 4,207,392; and in RD Nos. 15733, 15734, and 15776; organic acids described in Japanese Patent Examined Publication No. 12700/1970; -CO-, -S0 2 - ' or -SO- group-bearing nonaqueous polar solvents described in U.S. Patent No.
  • anti-fogging agents there are cited compounds for example, described in Japanese Patent Examined Publication No. 11113/1974; in Japanese Patent O.P.I. Publication Nos. 90118/1974, 10724/1974, 97613/1974, 101019/1975, 130720/1974, 123331/1975, 47419/1976, 57435/1976, 78227/1976, 104338/1976, 19825/1978, 20923/1978, 50725/1976, 3223/1976, 42529/1976, 81124/1976, 51821/1979, and 93149/1980; in the specification of British Patent No. 1,455,271; in the specifications of U.S. Patent Nos.
  • a printout inhibiting agent is allowed to be used in combination especially against printout after the heat-developing treatment.
  • halogenated hydrocarbons described in, for example, Japanese Patent O.P.I. Publication Nos. 45288/1973, 119624/1975, 120328/1975, and 46020/1978; that is, tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolysulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, and 2,4-bis(tribromo- methyl)-6-methyltriazine.
  • spectral sensitizing dyes including spectral sensitizing dyes, anti-halation dyes, fluorescent sensitizers, film-hardening agents, anti-static agents, plasticizers, and extenders at need.
  • hydrophilic binders are usually preferable. However, certain hydrophobic binders are allowed to be used in partial combination of such hydrophilic binders. Binders in the invention are referred to as binders soluble in water, or in mixtures of water and freely water-soluble organic solvents.
  • proteins such as gelatine and gelatine derivatives; cellulose derivatives; polysaccharides such as dextran; natural substances such as gum arabic; and synthetic polymers such as polyvinyl acetals (for example, polyvinyl butyral, preferably acetalized by 20% or less), polyacrylamide, polyvinyl pyrrolidone, ethyl cellulose, and polyvinyl alcohol (preferably saponified by 75% or more).
  • binders to be used in the invention are not limited thereto. These may be used in combination of two or more types if necessary, and the combination of gelatine and other water-soluble polymers which is described in the specifications of Japanese Patent O.P.I. Publication Nos.
  • This binder contains gelatin and vinyl pyrrolidone polymer.
  • the vinyl pyrrolidone polymer may be a polyvinyl pyrrolidone which is a homopolymer of vinyl pyrrolidone or may be a copolymer, including a graft copolymer, of vinyl pyrrolidone and one or two of the other monomers capable of polymerizing with the vinyl pyrrolidone. These polymers may be used regardless of any polymerization degree thereof.
  • the polyvinyl pyrrolidone may be a substituted polyvinyl pyrrolidone, and a preferred polyvinyl pyrrolidone has a molecular weight of from 1,000 to 400,000.
  • vinyl monomers including, for example, a (metha) acrylic ester such as acrylic acid, methacrylic acid and the alkyl esters thereof, a vinyl alcohol, a vinyl imidazol, a (metha)'acrylamide, a vinyl carbinol, a vinyl alkyl ether and the like. It is preferred that at least 20% by weight of the composition thereof (hereinafter a percentage by weight will be referred simply to as "%") is polyvinyl pyrrolidone. In the preferred examples of such polymers, their molecular weight each are from 5,000 to 400,000.
  • the gelatines may be treated in a liming or acidizing process, and they may also be an ossein gelatin, a pig-skin gelatin, a hide gelatin or a denatured gelatin in which the above-mentioned gelatin is esterified, or phenylcarbamoylated.
  • a gelatin amount to the total binder amount is preferably from 10% to 90% and more preferably from 20% to 60%, and a vinyl pyrrolidone amount thereto is preferably from 5% to 90% and more preferably from 10% to 80%.
  • binders may contain other high molecular substances, and the preferred binders comprise, for example, gelatin and a mixture of vinyl pyrrolidone of from 1,000 to 400,000 in molecular weight and one or more than two of other high molecular substances, or they comprise gelatin and a mixture of a vinyl pyrrolidone copolymer of from 5,000 to 400,000 in molecular weight and one or more than two of other high molecular substances.
  • polyvinyl alcohol polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, a polyethylene glycol ester, or a natural substance including, for example, a protein such as a cellulose derivative, and a polysaccharide such as starch and gum arabic.
  • the contents thereof may be from 0 to 85% and preferably from 0 to 70%.
  • the above-mentioned vinyl pyrrolidone polymers may also be a cross-linked polymers, and if this is the case, it is preferred to make them cross-link after they are coated on a support.
  • This case include the case where a cross-linking reaction is progressed in nature.
  • the amount of the binders used therein is normally from 0.05g to 50g per square meter of each layer, and more preferably from O.lg to 10g.
  • the binders are to be used preferably in the amount of from O.lg to 10 9 per gram of a dye-providing material monomer, and more preferably in the amount of from 0.25g to 4g.
  • Photo-sensitive layer ranges from 1/10 to 10 weight parts, preferably 1/4 to 4 weight parts per weight part of organic silver salt.
  • binders to be used in every layer (hydrophilic colloid) other than photo-sensitive layers of a heat-developable multilayered color photo-sensitive material of the invention there is no limitation, but varied binders are applicable. However, the arbitrary use of certain hydrophilic or hydrophobic binders according to the purpose is preferable.
  • Such binders include, for example, proteins such as gelatine, gelatine derivatives, casein, casein sodium, albumin; cellulose derivatives such as ethyl cellulose; polysaccharides such as dextran and agar-agar; natural substances such as gum arabic, and tragacanth gum; synthetic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and water-soluble polyvinyl acetal; latex-state vinyl compounds which improve the dimentional stability of photographic material; and other synthetic polymers such as follows.
  • suitable synthetic polymers there are cited those described in the specifications U.S. Patent Nos.
  • water-insoluble polymers composed of alkyl acrylate or methacrylate, acrylic acid, or sulfoalkyl acrylate or methacrylate.
  • polyvinyl butyral polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinylpyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-styrene copolymer, vinyl chloride--vinyl acetate copolymer, vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propionate, and cellulose acetate phthalate. They may be used in combination of two or more types if necessary.
  • the heat-developable photo-sensitive multilayer of a heat-developable multilayered color photo-sensitive material of the invention is basically constituted three layers which is photo-sensitive in the blue color range, the green color range, and the red color range, respectively, that is, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. These individual layers release and form dyes which correspond to the three primary colors of yellow, magenta, and cyan, respectively.
  • each of the above individual photo-sensitive layers may be divided into two layers - a high-sensitive layer and a low-sensitive layer - which are applied separately, or further may be divided into three or more layers, and applied.
  • a heat-developable multilayered color photo-sensitive material of the invention there are provided, in addition to the photo-sensitive layers, with varied photograph-constituting layers such as an overcoating layer, an undercoating layer, a backing layer, intermediate layers and filter layers according to purposes.
  • the heat-developable photo-sensitive layers and other photograph-constituting layers relevant to the invention are applied on varied supports.
  • material to be used as a support in the invention there are cited plastic films such as cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polyamide film, polyethylene film, polyethylene terephthalate film, and polycarbonate film; metals such as aluminum; baryta paper and synthetic paper.
  • a heat-developable multilayered color photo-sensitive material of the invention gives color images to an image-receiving element through heat-transfer onto the image-receiving element which is layed under the heat-developable photo-sensitive material.
  • a certain, known thermal solvent is allowed to be added for the purpose of balancing of the above solution physical development ratio, color development reaction ratio and diffusion transfer ratio.
  • thermal solvents there are cited urea derivatives, amide derivatives, polyethylene glycols, and polyhydric alcohols.
  • polyethyleneglycols these having a molecular weight between 62 to 10,000 are preferable.
  • urea derivatives there are cited, besides urea itself, thiourea, 1,3-dimethylurea, 1,3-diethylurea, diethyleneurea, 1,3-diisopropylurea, 1,3-dibutylurea, 1,1-dimethylurea, 1,3-dimethoxyethylurea, 1,3-dimethylthiourea, 1,3-dibutylthiourea, tetramethylthiourea, phenylurea, tetramethylurea, and tetraethylurea.
  • acetamide As for concrete instances of the amide derivatives, there are cited acetamide, propionamide, n-butylamide, i-butylamide, benzamide, diacetamide, dimethylformamide, acetanilide, ethylacetamidoacetate, malonamide, 2-chloroproionamide, 3-chloropropionamide, phthalimide, succinimide, and N,N-dimethylacetamide.
  • an encapsulated, water-immiscible auxiliary agent for diffusion described in Japanese Patent O.P.I. Publication No. 174949/1983 can be added.
  • any layer may do, so long as it is composed of a substance which receives the diffusible black dye released or formed through heat-development.
  • the layer is formed by a mordant used in a photo-sensitive material of diffusion-transfer type, and a heat-resistant organic polymer having a glass transition point between 40°C and 250°C, described in Japanese Patent O.P.I. Publication No. 207250/1982, etc.
  • nitrogen--containing secondary and tertiary amines nitrogen-containing heterocyclic compounds, and their quaternary cationic compounds are well-known, and effectively applicable to the invention as well.
  • dialkylamino group-containing polymer as mordant is disclosed in U.S. Patent No. 2,675,316.
  • Aminoguanidine derivatives are disclosed in U.S. Patent No. 2,882,156.
  • Mordants of aqueous sol type are disclosed in U.S. Patent Nos. 3,958,995 and 2,721,852.
  • Water-insoluble mordants are disclosed in Japanese Patent O.P.I. Publication No. 61228/1975.
  • polystyrenes with 2000 to 85,000 molecular weight; derivatives of poly-styrene bearing a substituent with 4 or less carbon atoms; polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinylalchol; polyvinylacetals such as polyvinylformal and polyvinylbutyral; polyvinyl chloride, chlorinated polyethylene, polytrichlorofluoroethylene, polyacrylonitrile, poly-N,N-dimethylacrylamide; polyesters, whose unit bears a p-cyanophenyl, pentachlorophenyl, or 2,4-dichlorophenyl group, such as polyacrylate, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate,
  • cellulose acetates such as triacetate and diacetate
  • polyamides for example, by combination of heptamethylenediamine and terephthalic acid, fluorenedipropylamine and adipic acid, hexamethylenediamine and diphenic acid, or hexamethylendiamine and isophthalic acid
  • polyesters for example by combination of diethylene glycol and diphenylcarboxylic acid, or bis-p-carboxyphenoxybutane and ethylene glycol
  • polyethylene terephthalate and polycarbonate.
  • polyethylene terephtalate modified making use of cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, or 1,2-dicarbomethoxy-4-benzenesulfonic acid also effective.
  • the polymer may be either applied on a support such as paper, glass and metal to form an image-receiving layer, or processed in the form of film or sheet to function also as a support in itself.
  • the support may be formed by either a single layer, or several layers.
  • the support may have a titanium white-containing part or layer as a white color-reflecting layer therein or thereon.
  • the compound to be used as the mordant afore-mentioned also is applied on an appropriate support singly or in combination with another polymer.
  • exposing means are applicable.
  • the latent image is obtained with image exposure to a radiation including visible rays.
  • light sources for the ordinary color printing such as a tungsten lamp, mercury lamp, xenon lamp, laser, CRT and LED are available as light source.
  • images which are cast by a video camera or the like, and image information which is transmitted from a TV station are directly produced by CRT or OFT, and that such images are formed on a heat-developable photo-sensitive material by means of contact or lens.
  • LEDs which have been markedly improved in recent years are being used as exposing or displaying means in various instruments.
  • a system is designed so that LEDs may emit the green light, the red light, and the infrared radiation, respectively, and layers which are sensitive to such lights and radiation, may provide yellow, magenta, and cyan dyes, respectively. That is, the green-, red- and infrared-sensitive layers may be to contain yellow, magenta, and cyan dye-providing compounds, respectively.
  • the original drawing is read by a light-receiving element such a phototube and CCD, and inputted into a memory of a computer or the like, and that such information is image-treated at need, reproduced by CRT, and then utilized as a image-like light source, or, on the basis of the treated information, the three LEDs are made to emit and expose.
  • a light-receiving element such as a phototube and CCD
  • the heat-transfer from a heat-developable multilayered color photo-sensitive material of the invention to an image receiving layer (element) for heat-transfer is conducted when the heat-developable multilayered color photo-sensitive material of the invention is heat-developed or is reheated after the completion of the heat-development.
  • Heating for heat-transfer may be conducted making use of any means applicable to ordinal heat-developable photo-sensitive materials. For example, it may be useful to make the material contact with a heated block or blade, to make use of high-frequency heating, and further to provide a conductive layer within the heat-developable multilayered color photo-sensitive material of the invention, or within the image-receiving layer (element), and ultilize Joule heat generated by conduction or an intensive magnetic field therefrom.
  • the heating pattern there is no special limitation, but it is possible to reheat after preheating, to heat for a short time at high temperature or for a long time at low temperature, including continuously raising or lowering the temperature, repeatedly if necessary, or to heat discontinuously.
  • certain simple heating patterns are preferable.
  • the heating termperature for heat-transfer ranges from 80°C to 200°C, preferably from 100°C to 180°C, and the heating time ranges from 1 second to 5 minutes, preferably from 5 seconds to 3 minutes.
  • a coating liquid compound of the below components was prepared, and applied onto a 100pm-thick support of transparent polyethylene terephthalate film provided with treatment of photographic undercoating:
  • an intermediate layer (I) composed of polyvinylpyrrolidone and gelatine was applied.
  • the applying amounts were 0.4g/m 2 for gelatine, and 1.0g for polyvinyl-pyrrolidone, but, besides, 0.7g/m 2 of 1.6-hexanediol was added to.
  • another coating liquid having the same composition as the above coating liquid, except for substituting a green-sensitive silver halide emulsion (An aged silver iodobromide emulsion, containing 4 mole% of silver iodide, composed of cubic particles with an average grain size of 0.15,u, and added to with 500mg per mole% Ag of 3,3'--carboxyethyl-5,5'-dichloro-oxacarbocyanine.) for the said red-sensitive silver halide emulsion, and using 0.63g of ⁇ , ⁇ - ⁇ ', ⁇ '-tetrakis(1-phenyl-3-isopropanamido-pyrazoline-5-one--4-yl)-m-xylene as dye-providing material, was applied.
  • a green-sensitive silver halide emulsion An aged silver iodobromide emulsion, containing 4 mole% of silver iodide, composed of cubic particles with
  • Another intermediate layer (II) composed of polyvinylpyrrolidone and gelatine was applied.
  • the applying amounts were 0.4g/m 2 for gelatine, l.Og/m 2 for polyvinylpyrrolidone, but, besides, 0.7g/m 2 of 1,6-hexanediol was added to.
  • the obtained samples 1 to 11 of heat-developable multilayered color photo-sensitive materials were exposed to the blue light and then the green light through a step wedge, respectively.
  • an image-receiving element was prepared by applying a solution of polyvinyl chloride (polymerization degree: about 1100; mfd. by Wako Pure Chemical Industries) in tetrahydrofuran so that the thickness of the formed layer of polyvinyl chloride may fall on 15um. Then the image-receiving element was laid over the above heat-developable multilayered color photo-sensitive material, heated for 1 minute at 140°C, and immediately stripped. Thus a diffusion-transfer image was produced on the image-receiving layer. Obtained results are shown in Table 2 at every sample.
  • the transfer image of the Control II was evenly developed, being low in contrast with high Dmin of both yellow and magenta images. (The reason of this is presumably that colloidal silver contained in the intermediate layer as blue light-absorbing layer functioned as nucleus of physical development.)
  • the transfer images of the Controls III to V was stained, having high Dmin of the yellow component of the magenta image. (The reason of this is presumably that the dyes in the blue-light-absorbing dye layer were diffused to transfer to the image receiving layer.)
  • the transfer images of the Samples I to VI by the invention were not stained with good filter effects, being low in Dmin and Dmax of the yellow component of the magenta image, because dyes were not diffusion-transferred.
  • a coating liquid compound of the below components was prepared, and applied onto a 100pm-thick support of transparent polyethylene terephthalate film provided with treatment of photographic undercoating:
  • Gelatine Surface active agent
  • Gelatin--hardening agent Gelatin-hardening agent
  • the applying amounts of main components were 1.2g/m 2 for Ag, 1.25g/m 2 for gelatine, and 2.9g/m 2 for poly(4-vinyl--pyrrolidone), respectively.
  • an intermediate layer (I) composed of polyvinylpyrrolidone and gelatine was applied.
  • the applying amounts were 0.4g/m 2 for gelatine, and l.Og/m 2 for polyvinyl-pyrrolidone, but, besides, 0.7g/m 2 of 1.6-hexanediol was added to.
  • another coating liquid having the same composition as the above coating liquid, except for substituting a green-sensitive silver halide emulsion (An aged silver iodobromide emulsion, containing 4 mole% of silver iodide, composed of cubic particles with an average grain size of 0.15 ⁇ m, and added to with 500mg per mole of Ag of 3,3'-carboxyethyl-5,5'-dichloro-oxacarbocyanine.) for the red-sensitive silver halide emulsion, and using 1.47g of exemplified dye-providing material (12) as a dye-providing material, was applied.
  • a green-sensitive silver halide emulsion An aged silver iodobromide emulsion, containing 4 mole% of silver iodide, composed of cubic particles with an average grain size of 0.15 ⁇ m, and added to with 500mg per mole of Ag of 3,3'-carboxyethyl-5,5
  • Another intermediate layer (II) composed of polyvinylpyrrolidone and gelatine was applied.
  • the applying amounts were 0.4g/m 2 for gelatine, 1.0g/m 2 for polyvinylpyrrolidone, but, besides, 0.7g/m 2 of 1,6-hexanediol was added to.
  • the obtained samples 23 to 33 of heat-developable multilayered color photo-sensitive materials were exposed to the blue light and then the green light through a step wedge, respectively.
  • an image-receiving element was prepared by applying a solution of polyvinyl chloride in tetrahydrofuran so that the thickness of the formed layer of polyvinyl chloride may fall on l5um. Then the image-receiving element was laid over the above heat-developable multilayered color photo-sensitive material, heated for 1 minute at 140°C, and immediately stripped. Thus a diffusion-transfer image was produced on the image-receiving layer. Obtained results are shown in Table 5 at every sample.
  • the transfer image of the Control II was evenly developed, being low in contrast with high Dmin of both yellow and magenta images. (The reason of this is presumably that colloidal silver contained in the intermediate layer as blue light-absorbing layer functioned as nucleus of physical development.)
  • the transfer images of the Controls III to V was stained, having high Dmin of the yellow component of the magenta image. (The reason of this is presumably that the dyes in the blue-light-absorbing dye layer were transferred in themselves.)
  • the transfer images of the Samples I to VI by the invention were not stained with good filter effects, being low in Dmin and Dmax of the yellow component of the magenta image, because dyes were not diffusion-transferred.
  • a heat-developable multilayered color photo-sensitive material in which an intermediate layer containing a blue-light absorbing dye relevant to the invention, which is a compound represented by Formula (1) or (2) or a polymer having a unit derived rom a monomer represented by Formula (3) is interposed between the blue-sensitive layer and its adjacent layer does not cause fogs and lowering of contrast, and enables diffusion--transferred unturbid images.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP85302325A 1984-04-03 1985-04-02 Matériau à plusieurs couches sensible à la lumière, en couleurs, développable à chaud Withdrawn EP0157639A3 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP6703284A JPS60209734A (ja) 1984-04-03 1984-04-03 熱現像多層カラ−感光材料
JP67032/84 1984-04-03
JP28088284A JPS61159645A (ja) 1984-12-29 1984-12-29 熱現像カラ−感光材料
JP280882/84 1984-12-29

Publications (2)

Publication Number Publication Date
EP0157639A2 true EP0157639A2 (fr) 1985-10-09
EP0157639A3 EP0157639A3 (fr) 1987-05-06

Family

ID=26408238

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85302325A Withdrawn EP0157639A3 (fr) 1984-04-03 1985-04-02 Matériau à plusieurs couches sensible à la lumière, en couleurs, développable à chaud

Country Status (1)

Country Link
EP (1) EP0157639A3 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195979A2 (fr) * 1985-03-23 1986-10-01 Agfa-Gevaert AG Matériau d'enregistrement phtographique en couleurs développable à la chaleur
EP0628869A2 (fr) * 1993-05-31 1994-12-14 Fuji Photo Film Co., Ltd. Matériau couleur sensible à la lumière du type diffusion-transfert développable par la chaleur et procédé de préparation d'une image en couleur
US6413699B1 (en) 1999-10-11 2002-07-02 Macdermid Graphic Arts, Inc. UV-absorbing support layers and flexographic printing elements comprising same
CN110441954A (zh) * 2019-08-01 2019-11-12 深圳市华星光电技术有限公司 显示面板及显示装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2124565A1 (fr) * 1971-02-09 1972-09-22 Fuji Photo Film Co Ltd
FR2226692A1 (fr) * 1973-04-21 1974-11-15 Fuji Photo Film Co Ltd
GB2105482A (en) * 1981-09-12 1983-03-23 Agfa Gevaert Ag A photographic recording material with a precursor compound for a yellow mask coupler
GB2136980A (en) * 1983-02-08 1984-09-26 Kodak Ltd Sensitive silver halide photothermographic materials for producing dye images

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2124565A1 (fr) * 1971-02-09 1972-09-22 Fuji Photo Film Co Ltd
FR2226692A1 (fr) * 1973-04-21 1974-11-15 Fuji Photo Film Co Ltd
GB2105482A (en) * 1981-09-12 1983-03-23 Agfa Gevaert Ag A photographic recording material with a precursor compound for a yellow mask coupler
GB2136980A (en) * 1983-02-08 1984-09-26 Kodak Ltd Sensitive silver halide photothermographic materials for producing dye images

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0195979A2 (fr) * 1985-03-23 1986-10-01 Agfa-Gevaert AG Matériau d'enregistrement phtographique en couleurs développable à la chaleur
EP0195979A3 (fr) * 1985-03-23 1987-05-13 Agfa-Gevaert AG Matériau d'enregistrement phtographique en couleurs développable à la chaleur
EP0628869A2 (fr) * 1993-05-31 1994-12-14 Fuji Photo Film Co., Ltd. Matériau couleur sensible à la lumière du type diffusion-transfert développable par la chaleur et procédé de préparation d'une image en couleur
US5478693A (en) * 1993-05-31 1995-12-26 Fuji Photo Film Co., Ltd. Diffusion transfer heat-developable color photographic light-sensitive material and process for forming color image
EP0628869A3 (fr) * 1993-05-31 1997-02-05 Fuji Photo Film Co Ltd Matériau couleur sensible à la lumière du type diffusion-transfert développable par la chaleur et procédé de préparation d'une image en couleur.
US6413699B1 (en) 1999-10-11 2002-07-02 Macdermid Graphic Arts, Inc. UV-absorbing support layers and flexographic printing elements comprising same
USRE39835E1 (en) * 1999-10-11 2007-09-11 Rustom Sam Kanga UV-absorbing support layers and flexographic printing elements comprising same
CN110441954A (zh) * 2019-08-01 2019-11-12 深圳市华星光电技术有限公司 显示面板及显示装置
CN110441954B (zh) * 2019-08-01 2022-03-29 Tcl华星光电技术有限公司 显示面板及显示装置

Also Published As

Publication number Publication date
EP0157639A3 (fr) 1987-05-06

Similar Documents

Publication Publication Date Title
US4584267A (en) Thermally developable, light-sensitive material
US4656124A (en) Heat-developable color photo-sensitive material
EP0131161A2 (fr) Matériel photosensible pour couleurs développable par la chaleur
EP0144087B1 (fr) Matériel photosensible pour la couleur développable à chaud
EP0157639A2 (fr) Matériau à plusieurs couches sensible à la lumière, en couleurs, développable à chaud
US5071740A (en) Heat developable color photosensitive material
US4631251A (en) Heat-developable color photo-sensitive material with polymeric coupler
EP0186494B1 (fr) Matériau photosensible en couleurs développable à chaud
JP3163203B2 (ja) 熱現像カラー感光材料およびこれを用いるカラー画像形成方法
JP3239305B2 (ja) 熱現像カラー感光材料およびその製造方法
JPH0573223B2 (fr)
JPH0439660B2 (fr)
JPS61177451A (ja) 熱現像カラ−感光材料
JPS61175637A (ja) 熱現像カラ−感光材料
JPH0477892B2 (fr)
JPH0588818B2 (fr)
JPS61210351A (ja) 熱現像カラ−感光材料
JPH029333B2 (fr)
JPH0682204B2 (ja) 新規なシアン色素供与物質を含有する熱現像感光材料
JPH0146057B2 (fr)
JPS625238A (ja) 熱現像感光材料
JPH0535858B2 (fr)
JPH0573224B2 (fr)
JPS62129850A (ja) 熱現像カラ−感光材料
JPH029332B2 (fr)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19871009

17Q First examination report despatched

Effective date: 19880422

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19881103

RIN1 Information on inventor provided before grant (corrected)

Inventor name: OHYA, HIDENOBU

Inventor name: KOMAMURA, TAWARA

Inventor name: MASUKAWA, TOYOAKI

Inventor name: IWAGAKI, MASARU

Inventor name: ISHIKAWA, WATARU

Inventor name: HOSHINO, KIMIE

Inventor name: SUGINAKA, SHUNJI