JPH07507404A - Imageable article with dye-selective interlayer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] FIELD OF THE INVENTION Imageable Articles Having a Dye-Selective Interlayer This invention relates to photothermographic materials, particularly dry solver systems (DR) that form colored images. ysilver system).

technology background Imaging systems that develop multiple colors are placed in a barrier to separate adjacent imaging chemicals. It is often influenced by the interlayer. A colored image is formed and diffused into the receiving layer. In the case of imaging systems, the interlayer not only sequesters the imaging chemicals but also absorbs the dyes. It has to be transparent. Imageable articles based on dry silver systems are The article has an imaging system that uses an intermediate layer that performs the following functions.

Dry silver compositions or emulsions are photothermographic compositions that are non-sensitive. Contains a photosensitive reducible silver source, a photosensitive silver source, and a reducing agent for the non-photosensitive reducible silver source . Photosensitive materials generally must be placed in catalytic proximity to a non-photosensitive reducible silver source. It is a photographic silver halide. To bring both materials into catalytic contact By closely physically bonding these materials, fine silver particles or The nucleus is generated by irradiating photographic silver halide with radiation or light. When the nucleus is used as a catalyst in the reduction reaction of the non-photosensitive reducible silver source by a reducing agent. It is necessary to make it work. For a long time, silver halide A photosensitive silver halide catalyst that also produces silver and is considered a reduction catalyst for It was thought that the source could be placed in catalytic proximity to the silver source by seeding methods. . Methods of such catalytic proximity include non-photosensitive methods using halogen-containing sources. partial decomposition of photosensitive reducible silver sources, co-precipitation of silver halide with non-photosensitive reducible silver sources, and and other methods of intimately coupling the silver halide and the silver source.

Exposure of photographic silver halide for both photographic and photothermographic emulsions A small raster of silver atoms is formed. Silver atomic clusters like this The image-wise distribution of In the field, it is known as a latent image. This means that the latent image is Further processing of the photosensitive article so that it cannot be viewed by the viewing means of the mantle This is because a visible image must be formed by this. The visible image is by catalytic reduction of silver ions in catalytic proximity to the silver halide grains that generate the image. It is formed by

In pigmented dry silver imaging systems, leuco dyes or other dye forms The system is used as a reducing agent for a non-photosensitive reducible silver source, and is usually used as a spectral sensitizer for silver halide. Generally, they are contained together. Leuco dyes are oxidized during development, and this A colored image is formed. In the case of all natural color structures, spectrally sensitized milk The agent layer is formed on the substrate and separated by one or more interlayer barrier layers. is common.

In certain colored dry silver constructions known in the art, residual silver Contamination caused by This problem occurs when the developed dye image is Diffusion from the Inruva layer to the image-receiving layer, and then peeling the image-receiving layer from the emulsion layer. It was resolved by In this case, the barrier interlayer protects the chemicals of the adjacent emulsion layer. It must play the role of isolating and diffusing the dye image under heat treatment conditions. No. In addition to the dye image, other components of the emulsion layer also undergo image receptivity under heat processing conditions. Diffuses to the outer layer. In this case, the unoxidized leuco dye diffuses from the emulsion layer to the image-receiving layer. This is because the unoxidized leuco dye oxidizes over time in the image-receiving layer. , resulting in deterioration of printing stability and color separation. Therefore, for the middle class, neutral It is necessary to diffuse the dye image, rather than the leuco dye, into the image-receiving layer.

The best development depends on the specific composition of a given drysilver layer, e.g. It is carried out under subtropical or basic conditions.

When using multiple drysilver layers containing incompatible developer chemicals, one The development conditions within one layer of DryNorver can be used to influence the development of the adjacent layer of DryNorver. It is very difficult to keep it from blurring. Therefore, on the opposite side of the transparent substrate, It is often advantageous to form a single layer of dry silver under different development conditions.

U.S. Pat. No. 4,594,307 discloses that a non-photosensitive reducing organic silver salt and Forms clear and stable dye images through oxidation-reduction reactions with co-dye reducing agents A heat-developable photographic material is disclosed. In this case, the dye formed is Continue heating for development to isolate the silver image from other residual chemicals. Therefore, it is transferred to the image-receiving layer.

Colored dry silver images are described in U.S. Pat. Nos. 4,883,747 and 4,9 No. 23.792 Tri-Pack (yellow/crimson/ cyan blue) by using multilayer structures and microencapsulated structures. It can be formed by In these cited patents, as a barrier intermediate layer, "Gantrez S-97 (trademark)" (polystyrene), " Vinol 523 (trademark) (partially hydrolyzed polyvinyl alcohol) ) and “13utvar B-76 (trademark)” (polyvinylbutvar) Chiral) is used. These structures generally affect the color separation of an image. Contains significant amounts of silver and sensitizer residual contaminants. This contamination problem is The imaged dye image is diffused from the imaging layer to the receiving layer, and the receiving layer is removed from the structure. Solved by peeling off. The success of such an attempt is based on the tri-pack structure A barrier intermediate wall disposed between the imaging layers selectively transfers the image-forming dye. In addition to the movement of other components of the dye-forming layer, especially the unoxidized neutral leuco dye, Thickness (depends on the function to be suppressed).

U.S. Patent Nos. 4.021.240, 4.460.681 and 5.0 No. 77.188 each discloses multiple imaging layers separated by barrier interlayers. The techniques used are disclosed.

Summary of the invention According to this invention, a copolymer of acrylonitrile and vinylidene chloride is Dye-diff image-forming articles using onic dyes and neutral dyes It is useful as an intermediate layer in a usive field (ageable article), and In addition, the copolymer selectively diffuses cationic dyes but neutral leuco dyes. It was found that the diffusion of

According to one aspect of the invention, (a) a compound that produces a cationic dye by oxidation; an image-forming layer containing an ico-dye, (b) an image-receiving layer, and (c) the image-forming layer; an acrylonitrile-vinylidene chloride copolymer disposed between the image-receiving layers; An imageable article having a polymeric interlayer is provided.

According to another aspect of the invention, the image-receiving layer has a substrate coated on one side. An imageable article, the image-receiving layer comprising: a polymeric interlayer forming the image-receiving layer; at least one imaging layer separated from the layers, the polymeric interlayer being active. contains a copolymer of rylonitrile and vinylidene chloride, and the image forming layer Image-forming material containing a neutral leuco dye that produces a cationic dye upon oxidation products will be provided.

According to yet another aspect of the invention, the dye contains a neutral leuco dye and a cationic dye. The mixture is brought into intimate contact with a layer containing a copolymer of acrylonitrile and vinylidene chloride. The cationic dye is diffused through the layer by heating in contact. A method for purifying said mixture comprising separating it from said neutral leuco dye by is provided.

"In close contact" refers to mixtures containing neutral leuco dyes and cationic dyes. The layer (typically containing acrylonitrile-vinylidene chloride copolymer) It means a state in which it is in direct contact with the interlayer). For example, dye-containing mixtures can be It may be coated with a layer of In another possible embodiment, the dye-containing mixture is and a polymer layer is formed on another substrate, and then these two two substrates such that the dye-containing mixture and the polymer layer are in direct contact with each other. Laminate.

Detailed description of the invention This invention includes (a) a neutral leuco dye that produces a cationic dye upon oxidation; (b) an image-receiving layer; and (c) the image-forming layer and the image-receiving layer. in a polymer containing acrylonitrile-vinylidene chloride copolymer disposed between An imageable article with improved image stability having an interlayer is provided.

Although this invention can be applied to single color applications, it can also be applied to multicolor or all-natural color applications. Provides maximum benefits in the application. In the latter case, typically a polymer interlayer a substrate coated with a dye-receiving layer having a plurality of image-forming layers separated by use. At least one layer of the polymeric interlayer comprises acrylonitrile and a salt. Contains a copolymer with vinylidene chloride.

Alternatively, the image-receiving layer may be formed on the second substrate as an external component. this In this case, the second substrate is combined with the first substrate having the imaging layer and the dye during processing. contacting (i.e., laminating) such that the image is transferred from the first substrate to the image-receiving layer; .

The laminate constitutes an image structure according to the invention.

image forming layer The imaging layer is of a type known in the field of imaging technology, i.e. cationic. A colored dye image is formed by oxidation of a neutral leuco dye to produce a neutral dye. Any image forming layer may be used.

In a preferred embodiment, the image forming layer comprises a photosensitive silver halide, a non-photosensitive reducible Silver sources, such as silver salts of organic acids (e.g. silver behenate, silver benzimidazole or or silver saccharin), and a dry silver composition containing an auxiliary reducing agent. include. In this case, the term "auxiliary reducing agent" refers to a substance that acts as a reducing agent for silver ions. Reducing agents other than leuco dyes for additional reduction of non-photosensitive reducible silver sources agents, such as phenol, hindered phenol, methyl gallate, catechol , pyrogallol and hydroquinone. Usually dry silver composition The product further contains a spectral sensitizer. This type of mixture typically uses a solvent as a dispersion medium. The dispersion is prepared as a dispersion and the dispersion is sprayed onto a suitable substrate to form a layer. .

After drying, the layer is exposed to a light image and then redone by heating the coated substrate. Develop the raw image.

The imaging layer according to the invention can be formed in a single coating layer or in a sequential manner in which the various components are dispersed. It may have a plurality of coated lower layers. If the image forming layer has multiple sublayers, In this case, the lower layer containing silver halide is called an emulsion layer.

Silver halides known in the art for photothermographic use may be used in the present invention. It is also useful. Although this type of silver halide is not particularly limited, chloride Silver, silver chloride bromide, silver chloride iodide, silver bromide, silver iodobromide, silver chloride iodobromide and Examples include silver iodide and silver iodide.

The copper halide used in the present invention may be used as it is, but it may be chemically sensitized. agents, such as compounds such as sulfur, selenium or tellurium, gold, platinum, palladium, Compounds such as dium or iridium, reducing agents such as tin halides, or Any mixture of compounds may be used for chemical sensitization. Regarding this, James, T. H.'s paper [[The Theory of the F. Photographic Ink Process (The Theory of the Photo graphic Process) J, 4th edition, published by Macmillan. (1977), pp. 149-169].

The amount of photosensitive silver halide used in the present invention is as follows: Preferably about 0.01 to 15% by weight, based on the total weight of each imaging layer; More preferably, it is 11 to 10% by weight.

victory over Sensitizers added to dry silver compositions are commonly used in the field of photography for halogenated Any dye known to spectrally sensitize silver may be used. use Examples of sensitizing dyes that can be used include, but are not limited to, the following: Anine dyes, merocyanine dyes, cyanine complex dyes, merocyanine anchor ring dyes, Holopolar cyanine dye, hemicyanine dye, styryl dye etc. are exemplified. Among these dyes, cyanine dyes, merocyanine dyes and and merocyanine tin salt dyes are preferred.

A suitable amount of sensitizing dye to be used is generally about IQ-1e per mole of silver halide. ~10-1 mol, preferably 101-101 mol.

Non-photosensitive reducing organic silver salt The non-photosensitive reducing organic silver salt that can be used in the present invention is relatively stable against light. a silver salt, which coexists with the aforementioned leuco compound or optionally with a leuco compound. in the presence of an auxiliary reducing agent and exposed silver halide at a temperature of about 80° C. or higher, preferably It is an organic silver salt that forms a silver image by reacting at a temperature of about 100°C or higher. . Suitable organic silver salts include silver salts of organic compounds having a carboxyl group, preferably Examples include silver salts of aliphatic and aromatic carboxylic acids. aliphatic carboxylic acid Examples of preferred silver salts include the following: silver behenate, silver stearate, Silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate , silver maleate, silver fumarate, silver tartrate, silver linoleate, silver butyrate, camphoric acid silver, and any mixtures of these silver salts, etc. Halogen atom or hydroxyl group Silver salts substituted with are also effective. Aromatic carboxylic acids and other carboxyls Examples of preferable silver salts of group-containing compounds include silver dibenzoate, substituted Silver salts of benzoic acid (e.g. silver 3,5-dihydroxybenzoate, 0-methylbenzoate) Silver acid, silver p-methylbenzoate, silver p-methylbenzoate, 2,4-dichlorobenzoate silver acids, silver acetamidobenzoate, silver p-phenylbenzoate, etc.), silver gallate , silver tannate, silver phthalate, silver terephthalate, lead salicylate, silver phenylacetate , silver pyromellitate, as disclosed in U.S. Pat. No. 3,785,830. Silver salt of una 3-carboxymethyl-4-methyl-4-thiazoline-2-thiones et al., and thiols as disclosed in U.S. Pat. No. 3,330,663. Silver salts of aliphatic carboxylic acids containing ether groups, etc. Contains mercapto or thione group Silver salts of compounds and derivatives thereof can also be used. Preferable compounds of this type Examples of silver salts include: silver 3-mercapto 4-phenyl-1,2 , 4-triazolate, silver 2-mercaptobenzimidazolate, S-alkyl Thioglycolic acid (alkyl group having 12 to 22 carbon atoms) such as silver salt Silver salts of licolic acid, silver salts of dithiocarboxylic acids (e.g., silver dithioacetate, silver thioacetate, Midoate, silver 1-methyl-2-phenyl-4-thiopyridine-5-carboxylate , silver triazine thiolate and silver 2-sulfide benzoxazole), and silver salts such as those disclosed in U.S. Pat. No. 4,123.274. difference Furthermore, silver salts of amino group-containing compounds can also be used. Preferred silver salts of this type of compounds The following are exemplified as silver salts of benzotriazole (e.g. silver pen citriacylate, etc.), silver salts of alkyl-substituted benzotriazoles (e.g., silver metal), tilbencitriacylate, etc.), silver salts of halogen-substituted benzotriazoles (e.g. (e.g., 5-chloropencitriacylate, etc.), carbimidobenzotriazole, etc. 1,2 as disclosed in U.S. Pat. No. 4,220.709. ．． Silver salts of 4-1-lyazole and 1-H-tetrazole, and imidazole silver salt etc.

The silver halide and organic silver salt that initiate development must be present in a state where they can react. No. That is, both are in the same layer, in adjacent layers, or have a thickness of less than 1 micron. They must exist in layers separated from each other by intermediate layers. halogenation Preferably, silver and organic silver salt are present in the same layer.

The silver halide and organic silver salt, which are present in isolation in the binder, must be mixed before use. The coating solution can be prepared by processing both components in a ball mill for an extended period of time. It is also effective to mix the two. Furthermore, halogen-containing compounds are prepared Partially replaces silver in organic silver salts with silver halide by adding It is also effective to use a method that includes

The preparation method of these silver halides and organic silver salts and their compounding method are described in "Res. Research Disclosure + - (Research Disclosure) J, No. 17029 and U.S. Pat. No. 3,700,458. .

The content of the non-photosensitive reducible silver source is determined by the total weight of each imaging layer in which the silver source is present. Preferably 0.1-50% by weight, more preferably 1-5% by weight Ru.

A suitable total coverage of photosensitive silver halide and organic silver salt used in the present invention is: For example, as described in U.S. Pat. No. 4,478,927, 50m g/l is 112 to 10 g/m2.

leuco dye Suitable leuco dyes for use in the present invention are compounds that oxidize to form a dye image. It is. In the practice of the invention, at least one imaging layer is of the leuco type. It must contain a thionic dye and must contain a small amount (at least one other image type). The layer must contain a neutral dye of the leuco type.

Preferred neutral leuco dyes are phenolic leuco dyes, such as 2-(3,5-di -t-butyl-4-hydroxyphenyl)-4,5,3-diphenylimidazo or bis(3,5-di-t-butyl-4-hydroxyphenyl)phenylmethyl Tan et al. This type of phenolic leuco dye useful in the practice of this invention is U.S. Patent No. 4.374.921, U.S. Patent No. 4,460,681, U.S. Patent No. 4,594 , No. 307 and No. 4,780,010.

The leuco dyes used in the present invention can also be colorless, forming visible dyes upon oxidation. or any slightly colored compound. Such compounds are acid It must change to a colored state by oxidation. Both by changes in pH and oxidation. Compounds that change to a colored state upon contact are useful, but are not preferred. On the other hand, changes in pH Compounds that are sensitive only to chemical reactions are not included in the term "leuco dyes." Because this This is because such compounds do not become colored due to oxidation. Various color properties The dyes formed from the leuco dyes in the layers should naturally be different. reflection most Preferably, the difference in large absorbance is at least 60 nm. More preferably, the shape The difference in maximum absorbance of the dyes produced should be at least 80-100 degrees. 3 When forming seed dyes, the difference in maximum absorbance between the two dyes is at least as large as The maximum absorbance of one species should be the minimum value of at least one of the other two species. The maximum absorbance of the species is at least 125, more preferably at least 150 It should be done as follows. As mentioned above, visible dyes are produced by oxidation with silver ions. Any leuco dye that forms is useful in the present invention. Also, US patent No. 3゜442.224, No. 4.021,250, No. 4.022.617 Leuco dyes such as those disclosed in the specifications of No. 1 and No. 4.368.247 are also applicable to this invention. Useful in inventions.

Other leuco dyes, such as those described in U.S. Pat. No. 4,923,792 The image forming layer may also contain benzylidene leuco compounds. dye reduction The compound in this form should exhibit strong absorption in the visible region of the electromagnetic spectrum. oxidation by silver ions to the original colored form of the dye. There must be. Benzylidene dyes are highly pure and low gray level dyes. 1 level). This kind of dyeing materials have large extinction coefficients (typically on the order of 104-105) and good compatibility. Demonstrates solubility and thermal stability. Synthesis of these dyes is easy and The reduced leuco form of the compound is very stable.

Dyes formed from leuco compounds for use in photothermographic elements according to the invention The colors are known and are described, for example, in the following documents: 1) The Color In Dex (The Co1our Index) J, The Society of ・Published by Dice and Colorists (Yorkshire, England) (197 1), Volume 4, Page 4437, 2) Venkatarama The Chemistry of Synthetic Dice ("I 'he Chemistry of 5ynthetic Dyes) J, Aka Published by Demik Press (New York) (1952), Volume 2, Page 1206, 3) U.S. Pat. No. 4,478,927, and 4) Hamer, F., M.), “The Cyanine Dice and Related Compound” The Cyanine Dyes and Re1ated Coa+ Pounds) J, published by Interscience Publishing Yards, New York) (1964), p. 492.

Leuco compounds can be easily synthesized by methods known in the art.

A number of methods are known for synthesis from these precursors. This reaction is a simple two-step process. This is a hydrogen reduction reaction. Suitable synthetic methods are described, for example, in 1) Smith (F, X, Smlth) et al., Tetrahedron Lett, , Vol. 24 (No. 45), pp. 4951-4954 (1983), 2) Huang (X, Huang, L, Xe), Common, Volume 16 (No. 1 3), pp. 1701-1707 (1986), 3) Reimer (H, Z imIIler) et al., J. Org, Chew, vol. 25, p. 1234. ~Page 1235 (1960), 4) Sekiya et al., Chew, Pharm, Bull, Volume 20 (No. 2), page 343 (1972) and Volume 22 (No. 2), No. 448 pages (1974), and 5) Soda (T, 5ohda) et al., Chet Pharm, Bull, 3rd Volume 1 (No. 2), pp. 560-565 (1983).

Furthermore, for other image-forming materials, the mobility of compounds that act as dyes is Materials transformed by high temperature oxidation-reduction reactions with silver halides or organic silver salts may be used (see Japanese Patent Application No. 165054 (1984) specification). ).

For many of the materials listed above, the imagewise distribution of mobile dyes in response to exposure to light is thermally A material in which development is carried out in a photosensitive material. dye image dye The method of obtaining a visible image by transferring it to a fixed material (diffusion transfer method) is as described above. patent specification and Japanese Patent Application No. 168,439 (1984) and No. 182, No. 447 (1984).

The total amount of leuco dye used in the present invention is determined by the total amount of leuco dye used in each layer in which the leuco dye is incorporated. Preferably 1 to 50% by weight, more preferably 5 to 20% by weight It is.

The heat-developable photosensitive material used in the present invention is image-processed in a substantially anhydrous state. When thermally developed after or simultaneously with the exposure, the exposed photosensitive halogen Transfer occurs with formation of a silver image in exposed or unexposed areas with silver oxide. A dynamic dye image is obtained simultaneously.

The photosensitive silver halide and organic silver salt oxidizing agent used in the present invention are as follows: It is generally added to at least one binder. In addition, dye-releasing Disperse the redox component into the binder.

The binders used in the present invention can be used alone or in combination. Vine The polymer may be either hydrophilic or hydrophobic. Typical hydrophilic binder are natural products, such as proteins (e.g. gelatin, gelatin derivatives, etc.), Lulose derivatives, polysaccharides (e.g. starch, gum arabic, pullulan) lulan), dextrin, etc.), and synthetic polymers, such as water-soluble polyvinycin compounds (e.g., polyvinyl alcohol, polyvinylpyrrolidone, allyl transparent or translucent hydrophilic colloids such as mamid polymers, etc.). Other hydrophilic An example of a binder is a binder in which a vinyl compound is dispersed in latex form. As shown, the binder is used to increase the dimensional stability of the photographic material. .

Preferably, the polymeric binder is included in each layer in which the binder is used. 99% by weight, more preferably 20-80% by weight.

The coating amount of the binder used in the present invention is preferably 20g/■2 or less. is 10 g/+s" or less, more preferably 7 g/s" or less. It's below.

A preferred polymer containing photothermographic silver is polyvinyl butyral, but Where appropriate, ethylcellulose, methacrylate, depending on the particular solvent used. copolymers, maleic anhydride copolymers, polystyrene and buta Gen-styrene copolymers can be used.

In the photographic light-sensitive material and dye-fixing material used in the present invention, a photographic emulsion The layer and other binder layers may also contain inorganic or organic hardeners. can be used As a hardening agent, chromium salts (e.g. chromium alum, chromium acetate, etc.), aluminum Dehydes (e.g. formaldehyde, glyoxal, glutaraldehyde, etc.) , N-methylol compounds (e.g. dimethylol urea, methylol dimethyl hydroxide) dioxane derivatives such as 2,3-dihydroxydioxane, etc. ), activated vinyl compounds (e.g. 1,3,5-triacryloylhexahydro- 5-1-riazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halide rogen compounds (e.g., 2,4-dichloro-6-hydroxy-S-triazine, etc.) ) and mucohalogen acids (e.g., mucochloric acid, mucophenoxychloric acid, etc.) Illustrated.

image receiving layer The dyes formed during thermal development of the exposed areas of the emulsion layer are dye receptive under the development conditions. layer and is retained in the receptive layer. The dye-receiving layer has a affinity for the dye used. It may be composed of a polymeric material having compatibility. Of course, The polymer material is selected depending on whether the dye is ionic or neutral. Ru.

The organic polymer materials used in the dye-receiving layer according to the present invention include the following polymers: Examples include: polystyrene (molecular weight: 2.000-85.000), carbon atom Polystyrene derivatives having 4 or less substituents, polyvinylcyclohexene, Polydivinylbenzene, polyvinylpyrrolidine, polyvinylcarbazole, polyvinylbenzene Allylbenzene, polyvinyl alcohol, polyacetal (e.g. polyvinyl formal, polyvinyl butyral, etc.), polyvinyl chloride, chlorinated polyethylene polytrifluoroethylene, polyacrylonitrile, poly(N, N-di methylallylamide), p-cyanophenyl group, pentachlorophenyl group or 2. Polyacrylate with 4-dichlorophenyl group, polyacrylchloro acrylate), poly(methyl methacrylate), poly(ethyl methacrylate) ), poly(propyl methacrylate), poly(isopropyl methacrylate), Poly(isobutyl methacrylate), poly(t-butyl methacrylate), poly (cyclohexyl methacrylate-1-), polyethylene glycol dimethacrylate poly(cyanoethyl methacrylate), polyester (e.g. polyethylene) ntrephthalate, etc.), polysulfone bisphenol A polycarbonate, poly carbonates, polyanhydrides, polyamides and cellulose acetates. " Polymer Handbook” [2nd edition, Brand Lamp (J, B randru p) and Immergut (E, H, Immergut), edited by John Wiley. Also useful are the synthetic polymers described in J.D., & Sons, Inc.]. these These polymers may be used alone, or multiple polymers may be used as copolymers. It may be used in the form of

Shiho! The intermediate layer used in the present invention selectively transmits the dye used to form a developed image. selected from polymeric materials to be formed. The intermediate layer dissolves the previously coated emulsion layer. Preferably, it is coated with a solvent that does not dissolve. The number of intermediate layers used in the present invention One must be a copolymer of acrylonitrile and vinylidene chloride. stomach. The copolymer is either a block copolymer or a random copolymer. You can. The molar ratio of acrylonitrile to vinylidene chloride is approximately 0. 2~ 0.95:1, preferably about 0.4-0.9:1, most preferably about 0.5 ~0.8:1.

The interlayer according to the invention provides a means of improving image stability and further Optionally improve the color separation of cationic dyes. do. Such improvements have made copolymers of acrylonitrile and vinylidene chloride an image forming layer containing a leuco dye that oxidizes to produce a cationic dye; and an image-receiving layer. In this configuration cationic dyes are preferentially image-receiving over neutral non-oxidized leuco dyes. Diffuse into layers.

Long-lasting printing due to the presence of a small amount of neutral leuco dye in the image-receiving layer Stability is improved. In a preferred embodiment of the invention, the first coated intermediate layer is a copolymer of crylonitrile and vinylidene chloride; The layer contains a leuco dye that upon oxidation produces a cationic dye.

These polymers have at least two colors, preferably at least three colors, photothermographic It can be used as an intermediate layer in the construction of a color recording system. This type of construction with appropriate solvent selection In production, it is possible to use simultaneous multiple coating methods that provide good color separation.

This type of configuration also has different chemical properties but similar thermal properties. It is possible to simultaneously thermally develop at least two or more color-forming photothermographic systems with be.

Preferably, the intermediate layer used in the imageable article according to the invention has a coating thereon. Impermeable to solvents used in any subsequent layer to be overlaid. The middle tier is next The impermeability of a layer to a solvent can be tested by a simple method.

First of all, aliphatic carboxylic acids (e.g. having 10 to 32 carbon atoms, preferably 12-28 carboxylic acids) and poly(vinyl butylar) 1) Coating a layer containing the polymer on a suitable substrate. This first coating layer After drying, form a second coating layer containing the selected interlayer polymer. . A third coating layer containing a suitable solvent, color developer and toning agent is then formed. make it happen After drying these coating layers, they are subjected to excessive light irradiation treatment, and then Color development was observed by subjecting to heat treatment at 120°C to 130°C for 60 seconds. If no image is formed or no image is formed, this test result indicates solvent impermeability. I will do it.

Imageable elements according to the invention may optionally be coated with a protective layer. stomach. Suitable materials for the protective layer include, but are not limited to, materials that are insoluble in aqueous systems; Polymers that are soluble in some organic solvents but impermeable to certain other organic solvents can be mentioned. A fourth layer of this barrier preferably containing a color-forming reactive component. The wall layer is usually a polymer of methyl methacrylate [preferably Tu kon) hard polymers or copolymers with a hardness of 20 or more], copolymer polymer or copolymer (e.g. n-butyl acrylate) , butyl methacrylate, or other acrylates, e.g. acrylic acid, methacrylate (copolymers with acrylic acid and acrylic anhydride, etc.), polyethylene, or polyvinyl chloride terpolymer and butadiene-styrene copolymer It is a compound. This barrier layer may also be crosslinked. Crosslinking can be latent or activated It is preferable to add a crosslinking agent. Crosslinking may be done after coating .

The theory of the aforementioned process is that light-sensitive materials containing negative emulsions and direct positive emulsions This is essentially the same as for materials containing agents, except that the area to be developed is They are similar in that one is a light region, while the other is a non-photosensitive region. It's different. Therefore, even if a direct positive emulsion is used, it is different from a negative emulsion. By the same method dye images with good color reproduction can be obtained.

Heating under substantially anhydrous conditions means heating at a temperature of 80°C to 250°C. . "Actual anhydrous conditions" means that the reaction system is in equilibrium with the moisture in the air and the reaction is induced. Alternatively, it means that promoting moisture is not specifically supplied to the reaction system from the outside. this Such conditions are described in “The theory of 'The Photographic Process' (published by Macmillan), 4th edition, 3rd edition It is described on page 74.

In the coating solution used in the present invention, silver halide and organic silver salt oxidizing agent are prepared separately. However, it may be prepared by mixing the two before use. Mixing of both components is done in a bowl. It is effective to do this for a long time in a vacuum cleaner. Another effective method is to prepare organic A halogen-containing compound is added to a silver oxidizing agent, and the halogen-containing compound is dissolved in the oxidizing agent. A method that involves forming silver halide by reacting with silver.

The multiple layers that make up the imageable article according to the invention may be used for various purposes, such as Examples include coating aids, antistatic properties, improved lubricity, emulsification, anti-adhesion, or modification of photographic properties. For example, the following: The following surfactants may be blended as appropriate: 1) Nonionic surfactants, such as saponins (steroids), alkylene oxides side derivatives (e.g. polyethylene glycol/polypropylene glycol condensation) polyethylene glycol alkyl ether, polyethylene glycol alkyl Ruaryl ether, polyethylene glycol ester, polyethylene glycol rusorbitan ester, polyalkylene glycol alkylamine or amino adducts of silicone and polyethylene oxide), glycidol derivatives ( For example, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides ), polyhydric alcohol fatty acid esters, saccharide alkyl esters, etc. 2) Acid groups, such as carboxyl groups, sulfo groups, phospho groups, sulfate groups or is an anionic surfactant having a phosphate group, etc., such as an alkyl carbon acid salt, alkyl sulfonate, alkylbenzene sulfonate, alkyl naphtha Rensulfonate, alkyl sulfate, alkyl phosphate, N-acyl -N-alkyl taurine, sulfoconoyl ester, sulfoalkyl polyoxy Cyethylene alkyl phenyl ether and polyoxyethylene alkyl phosphate ether Stell et al. 3) Amphoteric surfactants, such as amino acids, aminoalkyl sulfonic acids, amino acids Alkyl sulfates or phosphates, alkyl betaines and amine oxides Sid et al. 4) Cationic surfactants, such as alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, heterocyclic quaternary ammonium salts, such as pyridinium salts and aliphatic or heterocyclic phosphonium salts such as Or heterocyclic sulfonium salts, etc.

Among the above surfactants, polyesters having ethylene oxide repeating units in the molecule It is preferable to incorporate a tyrene glycol type nonionic surfactant into the photosensitive material. There are many cases where it is difficult. Among them, 5 or 5 ethylene oxide repeating units in the molecule A polyethylene glycol type having more than that amount is preferred.

The photosensitive material used in the present invention may optionally contain additives for heat-developable photosensitive materials. Various additives known as For example, antistatic layer, conductive layer, protective layer, interlayer, anti-trusion layer and peelable layer. A layer or the like may be used as a component.

Imageable articles according to the invention are coated onto a substrate. A suitable substrate is hard or soft substrates, metal (e.g. steel or aluminum plates, sheets or foils), various film-forming synthetic polymers, e.g. polymers (e.g., polyvinylidene chloride, polyvinyl chloride, polyvinyl acetate, polyvinyl acetate, tyrene, polyisobutylene polymers, and their copolymers) or linear Condensation polymers (e.g. polyethylene terephthalate, polyhexamethylene azide) polyhexamethylene adipamide/adipate, etc.), etc. non-woven substrates based on wood by-products (e.g. Examples include paper, cardboard, etc.) and glass. The substrate is transparent or opaque Ll It may be a deviation.

Particularly useful substrates include cellulose acetate (e.g., cellulose triacetate) and cellulose acetate), polyamides (e.g. heptametal), Polyamide derived from ethylene diamine and terephthalic acid, fluorene dipropylene Polyamides derived from amine and adipic acid, hexamethylene diamine and di Polyamides derived from phenic acid and hexamethylene diamine and isophthales Films made of polyesters (e.g. polyamides derived from acids), polyesters (e.g. diethyl Polyesters and bis derived from lene glycol and diphenylcarboxylic acid -Polyester derived from p-carboquinphenoquine butane and ethylene glycol Stell, etc.) films, polyethylene terephthalate films, and polyethylene terephthalate films. It is a film made of carbonate.

The above film may be modified. For example, cyclohexane, dimethatol, Sophthalic acid, methoxypolyethylene glycol or 1,2-dicarbomethquine Made of polyethylene terephthalate modified with a modifier such as benzenesulfonic acid Film is valid.

The substrate used for the photosensitive material according to the invention has good dimensional stability at processing temperatures. This shows that. For example, as disclosed in U.S. Patent No. 3.634.089, Although polyesters are preferred, more preferred substrates are polyesters. It is a film made of lente phthalate.

If desired, U.S. Patent No. 2.761.791 and British Patent No. 837.095 Even if two or more layers are formed at once, as described in each specification of the good.

In the present invention, the latent image obtained after exposure of a heat-sensitive material is obtained by heating the material to a moderate temperature. , for example, by heating at about 806C to about 250C for about 15 seconds to about 300 seconds. and developed. By extending or shortening the heating time, the heating temperature can be kept within the above range. You can also move it up and down. A temperature range of about 10°C to about 160°C is particularly effective. Canada Heat treatment can be carried out using common heating means, such as hot plates, irons, heated rollers or carbs. This can be done using a heater made of titanium or titanium white.

Imageable articles according to the invention can be coated using coating techniques commonly known in the art. U.S. Pat. No. 4.452.883, U.S. Pat. No. 2.761.791 and Prepared by the method described in British Patent No. 837,095.

The heat treatment for transferring the dye can be carried out using the heating means exemplified in connection with the heat development described above. This can be done using something similar to. Dye image transferred to dye-receiving layer In order to improve image quality, it is necessary to eliminate fog caused by unnecessary development that occurs during dye transfer. Preferably, the increase is prevented. For this purpose, it is necessary to react with silver halide and/or Or add a development stopper and/or anti-fogging agent to a compound capable of adsorbing silver halide. It is especially preferable to include the dye-receiving material as a blocking agent in one of the layers constituting the dye-receiving material. It is valid. This type of compound is disposed in the dye-receiving layer or on top of the dye-receiving layer. It is preferable to include it in a protective layer, for example, a protective layer. This is because the compound Heat can quickly prevent excessive development of the photosensitive layer during the dye transfer process. Therefore, a clear dye image is formed. This type of compound includes A nitrogen-containing heterocyclic compound, preferably a 5-membered or 6-membered nitrogen-containing heterocyclic compound Illustrated.

The following examples are not intended to limit the invention, but rather serve to illustrate the invention. Raw materials used in the examples below, unless otherwise noted, are from standard commercial suppliers, e.g. For example, Aldrich, Chemical Company (Milwaukee, Rice Consin), etc. It was handmade.

The dyes mentioned in the following examples are represented by the following structural formula.

Red sensitizer A (by the method described in U.S. Pat. No. 3,719,495) Prepared) Basic Blue 3 solvent yellow 56 Example 1 This example describes the acrylonitrile-vinylidene chloride copolymer used in the present invention. The method for preparing remer will be explained. The monomers are treated with hydrogenated calcium before being subjected to the polymerization reaction. After treatment with nitrogen, it was distilled under nitrogen atmosphere. Vinylidene chloride 60m1, Acrylic Consisting of 33 ml of lonitrile and 160 mg of azobis(isobutyronitrile) The solution was heated to reflux for 2 days. The resulting solution was dropped into methanol. Thus, the polymer was precipitated. The precipitated polymer was collected by filtration and diluted with tetrahydrofuran. Reconstitute the polymer by redissolving it in methanol and adding the solution to methanol. precipitated. The filtered purified copolymer was dried under vacuum. The resulting copolymer The composition of - is as follows. Acrylonitrile 50 mol% and vinylidene chloride 50 mol%. Monomer conversion was approximately 4%.

Example 2 Diffusion of the dye through the copolymer film according to the invention is carried out by the following method. Ta. A 10% by weight solution of the copolymer in tetrahydrofuran was applied to a transparent substrate [3M Co., Ltd. (St. Bowl, Minnesota) type 0R477400 type undercoated polyester] After coating FJ:]ml), the coating was dried in an oven at 80°C. child The coating layer contains meth containing 10% by weight of poly(vinyl butyral) and 1% by weight of dye. After applying the nol solution and allowing the coating film to dry naturally, it was heated at 140°C for various times. Heated. After measuring the absorbance, use a transparent tape [Scotch Bra manufactured by 3M]. Coating film of Scotch brand Magic J (trademark) The upper layer is removed by repeating the operation of pasting it on and then peeling it off, and then The absorbance of the coated substrate was measured. Diffusivity D (%) of the dye was calculated by the following formula: D (%) = (A’/A) x 100 (In the formula, A indicates the absorbance of the substrate having an upper layer and a lower layer, and Ao excludes the upper layer of the substrate. (shows the absorbance of i&) The dye used for testing the diffusivity of polymers was Oil Blue A (manufactured by DuPont, Wilmington, Plowea), Basic Blue 3 (cationic oxazine dye) and Solvent Yellow 56 (azo dye). obtained for several copolymers. The results are shown in Table 1 below.

A 15% solution of a 9:1 copolymer of vinyl chloride and vinyl acetate in methyl ethyl ketone Coating thickness: 08 m-) on an opaque polyester film substrate. The image is removed by drying the cover film in an oven at 80°C for 5 minutes. An image-receiving layer was formed.

Silver behenate semi-soap (1 mole of silver behenate: 1 mole of behenic acid, solid content 10%) A toluene dispersion was prepared by a homogenization method. 10% dispersion of this semi-soap I After diluting Log with 380 g of ethanol, poly(vinyl 4 g of butyral was added and dissolved. 1.8g of mercuric bromide in methanol 10 ml of the solution dissolved in 100 ml of the solution were added to this dispersion under stirring. Poly (add 2 more poly(vinyl butyral) containing 9-13% vinyl alcohol) 6g was added to this dispersion. The resulting dispersion is hereinafter referred to as “dispersion 1fflA Represented by J.

r3M Fluorad FC-431™ surfactant (stripping agent) 3 drops of fluorochemical coating additive used as a release agent) in Dispersion 1 (kA of The resulting dispersion was added to 25 g of recoat and mixed, and the resulting dispersion was applied onto the image-receiving layer ( Coating thickness: o, osam).

The coated image-receiving layer was dried in an oven at 80°C for 5 minutes. Therefore, a strippable blank emulsion layer was formed.

After coating the following polymer solution on the blank emulsion layer (!!!Fabric thickness: 0.08 g), this blank emulsion layer was placed in an oven in an air atmosphere at 80°C for 5 minutes. An intermediate layer was formed by intermittent drying.

Comparative example A 1:20 copolymer of vinylidene chloride and vinyl chloride (Scientific Polymer Products Co., Ltd.) was dissolved at 3.5% in tetrahydrofuran. Therefore, a coating solution for the intermediate layer was prepared.

Example 3 1=4 copolymer of polyacrylonitrile and vinylidene chloride A coating solution for the interlayer was prepared by dissolving 3.5% in Ran.

Example 4 1:1 copolymer of polyacrylonitrile and vinylidene chloride A coating solution for the interlayer was prepared by dissolving 3.5% in Ran.

Cyan leuco dye rL-704J [3,6-bis(di- 0.3 g of ethylamine)-9-(4-methylbenzoyl)phenoxazine] The solution obtained by dissolving in 3 ml of toluene was mixed with 150 ml of toluene. A solution of 0.005 g of red sensitizing dye A dissolved in a mixed solvent with 5 Q ml of methanol. 1 ml of dispersion A, mixed with 0.1 g of 4-methylphthalic acid and 25 g aliquot of dispersion A. It matched. After applying the obtained mixed dispersion to the intermediate layer (coating thickness: 0.13 mm) , by drying this coated intermediate layer in an oven at 80°C for 5 minutes. A cyan emulsion layer was formed.

The strips cut from the resulting coated sheet were placed in an EG&G sensitometer. Wratten 25 Exposure to light through a red filter for 10-3 seconds A heat-developable latent image was formed in the emulsion layer by this process. The exposed sheet , and was subjected to heat development treatment at 138° C. for 30 seconds on a heating blanket. light A portion of the element, including the thermographic emulsion layer and interlayer, was stripped from the image-receiving layer. C A cyan dye image was transferred to the image-receiving layer corresponding to the areas exposed to the red light of It was observed that

Furthermore, N-bromosuccinic acid was added to a mixed solvent of 50 liters of acetone and 50 liters of toluene. Apply 0.015 μl of a solution containing 0.08 g of acid imide to the non-photosensitive area of the image-receiving layer. dripped into the area. The leuco dye transferred to the image-receiving layer through the emulsion layer and the intermediate layer is - Cyan dye was formed by oxidation with bromosuccinimide solution. .

The treated area was allowed to dry for 30 minutes at room temperature. Oxidation dye oxidized by oxidizing agent The optical density of the material can be measured by a densitometer using a red filter. The diffusion of leuco dye was investigated by The results are shown in Table 2 below.

As is clear from the results in Table 2, the copolymers according to Examples 3 and 4 Compared to copolymers according to A, the diffusion of neutral leuco dyes is reduced, but oxidized The cationic form of the dye is diffused.

The foregoing disclosure of this specification constitutes the art of the present invention as defined by the following claims. may be reasonably modified and transformed without departing from the technical philosophy or scope. Wear.

Continuation of front page (72) Inventor: Ishida, Takuzou Post, St. Paul, Minnesota, 55133-3427, United States ・Office Box No. 33427

Claims (1)

[Claims] 1 Imageable article having layers (a), (b) and (c): (a) an imaging layer containing a neutral leuco dye, thus producing a cationic dye; (b) an image-receiving layer; (c) a layer interposed between the image forming layer and the image receiving layer, the layer comprising acrylonitrile; Polymer interlayer containing a polyvinylidene chloride copolymer. 2. The image forming layer is a non-photosensitive reducible silver source, a photosensitive silver halide, and a polymer binder. The imageable article of claim 1 further comprising a sensitizer and a sensitizer. 3. 3. The method according to claim 2, wherein the non-photosensitive reducible silver source contains a silver salt of an aliphatic carboxylic acid. Imageable article. 4. The image-forming product according to claim 3, wherein the non-photosensitive reducible silver source contains silver behenate. Goods. 5. 3. The imageable article of claim 2, wherein the photosensitive silver halide contains silver bromide. 6. The image-formable article according to claim 2, wherein the image-forming layer further contains a toning agent. 7. The molar ratio of acrylonitrile to vinylidene chloride in the intermediate layer is about 0. 2. The imageable article of claim 1, wherein the ratio is 2 to 0.95:1. 8. The molar ratio of acrylonitrile to vinylidene chloride in the intermediate layer is 0.4. 8. The imageable article of claim 7, wherein the ratio is 0.9:1. 9. Dry silver photothermography having a substrate coated on one side with an image-receiving layer an element for use in an image-receiving layer, wherein the image-receiving layer is separated by a polymeric interlayer. at least one imaging layer separated from the polymeric interlayer; lonitrile-vinylidene chloride copolymer, the image-forming layer is formed by oxidation. Dry silver photothermography containing neutral leuco dyes producing cationic dyes element for. 10. The image forming layer contains a non-photosensitive reducible silver source, a photosensitive silver halide, and a polymer binder. 10. The dry silver photothermographic method according to claim 9, further comprising a primer and a sensitizer. element. 11. Claim 10, wherein the non-photosensitive reducible silver source contains a silver salt of an aliphatic carboxylic acid. Dry silver photothermal photographic element. 12. 12. The dry film according to claim 11, wherein the non-photosensitive reducible silver source contains silver behenate. Ruber photothermal photographic element. 13. The dry silver according to claim 10, wherein the photosensitive silver halide contains silver bromide. Photothermal photography element. 14. The dry silver light according to claim 10, wherein the image forming layer further contains a toning agent. Thermographic element. 15. The molar ratio of acrylonitrile to vinylidene chloride in the intermediate layer is approximately 0. ．． 10. The dry silver photothermographic element of claim 9, wherein the ratio is 2 to 0.95:1. . 16. The molar ratio of acrylonitrile to vinylidene chloride in the intermediate layer is 0. 16. The dry silver photothermographic element of claim 15, wherein the dry silver photothermographic element has a ratio of 4 to 0.9:1. 17. A mixture containing a neutral leuco dye and a cationic dye is mixed with acrylonitrile. - Heating in close contact with the vinylidene chloride copolymer-containing intermediate layer. by diffusing the cationic dye through the intermediate layer. A method for purifying said mixture comprising separating it from the ico-dye. 18. The molar ratio of acrylonitrile to vinylidene chloride in the intermediate layer is 0. 18. The method of claim 17, wherein the ratio is 2 to 0.95:1. 19. The molar ratio of acrylonitrile to vinylidene chloride in the intermediate layer is approximately 0. ．． 19. The method of claim 18, wherein the ratio is 4 to 0.9:1. 20. 18. The method according to claim 17, wherein the heating is carried out at a temperature range of 80<0>C to 250<0>C.