US3912844A - Thermal recording method - Google Patents

Thermal recording method Download PDF

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Publication number
US3912844A
US3912844A US36601073A US3912844A US 3912844 A US3912844 A US 3912844A US 36601073 A US36601073 A US 36601073A US 3912844 A US3912844 A US 3912844A
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Prior art keywords
vinyl
methyl
polymer
copolymers
maleic acid
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Ichiro Endo
Hiroshi Matsuno
Hiroshi Kokado
Eiichi Inoue
Katsuhiko Nishide
Kikuo Kinjo
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Canon Inc
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Canon Inc
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Priority to US36601073 priority Critical patent/US3912844A/en
Priority to BE131894A priority patent/BE800470A/fr
Priority to DE19732328900 priority patent/DE2328900C3/de
Priority claimed from DE19732328900 external-priority patent/DE2328900C3/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/368—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties involving the creation of a soluble/insoluble or hydrophilic/hydrophobic permeability pattern; Peel development
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • thermal recording sheet produced by coating onto a substrate finely divided particles of a hydrophobic high polymer having a glass transition point of less than 40C such as polyethylene latex dispersed in a hydrophilic high polymer such as gelatin, casein, polyvinyl alcohol (PVA) andthe like.
  • a thermal pattern is applied to this sheet to cause fusing of the hydrophobic resin particles at a high temperature portion resulting in change of various properties of the sheet surface such as mechanical strength, solubility, dye acceptability, inking property and the like.
  • It is also possible to produce relief images or dye images by washing with water or soaking in an aqueous solution of dye after applying a thermal pattern or to use directly an offset printing plate.
  • the above mentioned thermal recording methods and thermal recording sheets used therefor are disclosed in M. N. Vrancken: SPBE 2nd Symposium on Unconventional Photographic Systems (1967) and Japanese Patent Publication No. 1743/ 1964.
  • a polyester sheet covered with a hydrophobic resin emulsion and a pigment dispersed in an aqueous resin is exposed to a thermal pattern and washed with water wherein the portion subjected to high temperature to form a pigment image.
  • thermal recording sheet capable of producing a visible image only by applying a thermal pattern without a developing treatment.
  • thermal recording sheets have a thermal recording layer composed of at least two kinds of solid reaction components capable of releasing active components as the result of melting or decomposing at a temperature corresponding to a high temperature portion of the thermal pattern,dispersed in a binder resin, and capable of producing a colored matter by reaction when heated.
  • reaction components are physically separated so that no reaction occurs at room temperature.
  • one of them is heated to the melting point or decomposition temperature, there is caused contact between both of them or the released active components to initiate the reaction and produce a colored matter.
  • reaction components and combinations thereof There have been known many kinds of reaction components and combinations thereof.
  • a Representative one is a combination of a long chain fatty acid metal salt with a chelating agent or an organic reducing agent.
  • Representative chelating agents are tannic acid, pyrogallol and spiropyrans, and a representative reducing agent is hydroquinone. As the result of mutual reaction, there is formed a visible image composed of metal chelate or metal.
  • the above-mentioned prior arts have many drawbacks.
  • the image is composed of a pigment, metal chelate, metal and the like so that it is not possible to ob tain transparency, light color and high purity.
  • These drawbacks are disadvantageous especially when the thermal recording sheet is used for a overhead projector or regeneration of color by a thermal recording method.
  • thermal recording sheets for converting a physical or chemical change caused by a thermal pattern to a visible image.
  • This common drawback is that the production of the thermal recording sheet is carried out at a temperature lower than the heat response temperature (heat sensitive temperature) of the sheet.
  • the heat sensitive temperature is a temperature which is sufficient to produce a visible image and generally ranges from C to 150C, preferably from C to C.
  • the coating and drying should be naturally carried out at 15 60C for safety.
  • the heat sensitive temperature when wetted with a solvent is lower than that of the dried coating so that it is more necessary to oper ate at low temperatures.
  • the above difficulty is mainly due to irreversibility of response of the thermal recording sheet to heat or thermal response.
  • thermal recording methods and sheets having reversible thermal response.
  • a dielectric high polymer film is uniformly charged and then exposed to a thermal pattern.
  • the electrostatic charge is decayed at a high temperature portion of the thermal pattern to produce an electrostatic pattern, which is then developed with a charged toner to produce a visible image.
  • This method is published in P. M. Cassiers: Photogr', Sci, & Eng, 4, p. 199 1960) and is called electrothermography.
  • the present inventors have now found that a thin film composed of a certain kind of high polymer complex shows a peculiar thermal behavier.
  • This thin film is uniform and transparent and can not be dyed with a dye liquid developer at room temperature, but when heated at a temperature higher than a certain temperature, it can accept a dye from the dye liquid developer and be dyed.
  • This property can be directly used for production of the thermal recording sheet and the thermal recording method.
  • the high polymer complex thin film prosuch acceptability. in other words the heat response of the thermal recording sheet according to the present invention is reversible.
  • the image portion capable of accepting a dye when exposed to a high temperature is hereinafter called a latent image in the present invention. It has also now been found that the latent image and other portions of the sheet exhibit differences in solubility and differences in gas permeability as well dye acceptability.
  • An object of this invention is to provide a novel thermal recording method and a novel thermal recording sheet therefor.
  • Another object of this invention is to provide a novel method of converting a thermal pattern to a visible image and a recording sheet therefor.
  • a further object of this invention is to provide a novel method of converting a thermal pattern applied to a thermal recording sheet to a reversible latent image and then converting the resulting reversible latent image to an everlasting image.
  • Still another object of this invention is to provide a novel method of producing a transparent, light and highly pure color image.
  • a still further object of this invention is to provide a novel thermal recording method and a material therefor for producing multicolor images.
  • Still another object of this invention is to provide a novel thermal recording method and a material therefor for regenerating a continuous tone.
  • a still further object of this invention is to provide a novel thermal recording method and a material therefor for applying a thermal pattern to a thermal recording sheet and then forming a latent image which can be eliminated if desired.
  • Still another object of this invention is to provide a novel thermal recording method and a material therefor in which add-on is possible.
  • a still further object of this invention is to provide an inexpensive thermal recording sheet and a process for production thereof.
  • a thermal recording method which comprises applying a thermal pattern to a recording member having a recording layer composed of at least a polymer complex to produce a reversible latent image capable of being visualized.
  • thermo recording method as mentioned above in which the polymer complex has a weak bond capable of being dissociated at a temperature ranging from 50C to l2O"C.
  • thermo recording method mentioned above in which the resulting latent image is visualized with a dye liquid developer.
  • thermo recording method as mentioned 4 above in which the latent image is visualized by utilizing difference of solubility.
  • thermo recording method mentioned above in which the resulting latent image is visualized by utilizing difference of gas permeability.
  • a thermal recording method which comprises applying a thermal pattern to a recording member having a heat sensitive layer comprising a complex of polymers which are selected from polymers and copolymers of N-vinyl lactams, N-vinyl cyclic carbamates, N-vinyl imidazoles, 2-vinylpyridine, alkylene oxides, 4-vinyl-pyridine and acrylamide, to form a reversible latent image capable of being visualized.
  • thermo recording method as mentioned above in which the resulting latent image is visualized with a dye liquid developer.
  • thermo recording method as mentioned above in which the resulting latent image is visualized by utilizing difference of solubility.
  • a thermal recording member used for the thermal recording method mentioned above which comprises a heat sensitive layer containing, as an active component, a polymer complex having a weak bond capable of being dissociated at a temperature ranging from 50C to 120C.
  • a thermal recording member used for the thermal recording method as mentioned above which comprises a. heat sensitive layer containing a complex composed of a low molecular weight compound or a polymer with a polymer selected from polymers and copolymers of N-vinyl lactams, N-vinyl cyclic carbak mates, N-vinyl imidazoles, 2-vinyl pyridines, alkylene oxides, 4-vinyl pyridines and acrylamide.
  • thermo recording member used for the thermal recording method mentioned above which comprises a heat sensitive layer containing a polymer complex and a proton acceptor or a proton donor.
  • a thermal recording member used for the thermal recording method as mentioned above which comprises a heat sensitive layer containing a proton acceptor or proton donor and a complex composed of a low molecular weight compound or a polymer with a polymer selected from polymers and copolymers of N- vinyl lactams, N-vinyl cyclic carbamates, N-vinyl imidazoles, 2-vinyl pyridines, alkylene oxides, 4-vinyl pyridines and acrylamide.
  • a thermal recording member used for the thermal recording methodas mentioned above which comprises a heat sensitive layer containing an aliphatic or aromatic ketone which is non-volatile at room temperature and a complex composed of a low molecular weight compound or a polymer with a polymer selected from polymers and copolymers of N-vinyl lactams, N- vinyl cyclic carbamates, N-vinyl imidazoles, 2-vinyl pyridines, alkylene oxides, 4-vinyl pyridines and acrylamide.
  • a thermal recording member used for the thermal recording method as mentioned above which comprises a heat sensitive layer containing benzophenone and a complex composed of a low molecular weight compound or a polymer with a polymer selected from polymers and copolymers of N-vinyl lactams, N- vinyl cyclic carbamates, N-vinyl imidazoles, 2-vinyl pyridines, alkylene oxides, 4-vinyl pyridines and acrylamide.
  • FIG. 1 shows a combination of an infrared absorption spectrum of PVP and that of ES-425 at a range of 1600 l800 cm;
  • FIG. 2 shows an infrared absorption spectrum of a complex of PVP and ES-425
  • FIG. 3 shows an infrared absorption spectrum directly after heating the complex in FIG. 2.
  • a thermal recording method which comprises applying a thermal pattern to a thermal recording sheet to form a latent image, and contacting with a dye liquid developer, washing off with'a solvent, or utilizing the difference of gas permeability to convert the latent image to a visible image.
  • the thermal pattern may be applied by a known method.
  • Representative methods for applying a thermal pattern are as follows.
  • a thermal recording sheet surface is partly and selectively heated by a heat stylus, a heat typewriter, a thermal printing head, or a scanning beam such as laser and electron beam.
  • a stylus heated by a nichrome wire is driven in accordance with an input signal to scan the surface of the thermal recording sheet and there is obtained a recording corresponding to the trace of the stylus.
  • a thermal printing head is composed of a matrix of minorheating dots and the dots are selectively heated byapplying an electric current from a controlling circuit.
  • a thermal recording sheet contacting the head is heated in accordance with the letter [or sign pattern to produce a record. Details and specifications of such thermal printing heads are disclosed in ⁇ U.S. Pat. No. 3,161,457 (National Cash Register) and Japanese Patent Publication No. 23520/1970. These "thermal printing heads may be used in the thermal re- 'ii cordingmethods of this invention.
  • An original having a letter or sign pattern capable of absorbing a radiation is placed in contact with a thermal recordingsheet in a thermal conductive position and irradiated with a strong radiation such as an incanldescent tungsten lamp.
  • the letter or sign portion of the i original absorbs more radiation than the background ruon and is more heated to raise the temperature -Qand thereby there is formed a thermal pattern, which is [then transferred to a thermal recording sheet by conduction' of heat.
  • Athermal recording sheet having a radiation g -'absorption property is used and subjected to an extremely strong radiation for a short time by using a Tflashing discharging lamp as the radiation source for 6 heating, there can be effected a negative-positive reproduction.
  • a thermal recording sheet is contacted with a negative image of a silver salt film and exposed to a flash discharging lamp on the film side, the radiation passing through transparent portions of the film is converted to heat in the thermal recording sheet to produce a thermal pattern.
  • a thermal recording sheet having radiation absorption property absorbing said laser light wave length in this case).
  • a thermal pattern is applied to a thermal recording sheet of the present invention by a method as mentioned above to produce a reversible latent image and then the resulting latent image is converted to a visible image within a period of life time.
  • the life time of the latent image is a parameter showing reversibility of the latent image and is defined as a period of time from applying a thermal pattern to the maximum time at which any substantial lowering of density is not observed when developed, or a period of time from the application of a thermal pattern to a time at which the latent image is almost eliminated down to a fog density.
  • One of these two definitions is used for each particular purpose.
  • a thermal recording sheet is contacted with a dye liquid developer to convert a latent image to a visible image.
  • the sheet is soaked in a dye liquid developer, or the sheet surface is wetted with a sponge, felt, roller or belt impregnated with a liquid developer, or a liquid developer is sprayed onto the sheet surface.
  • a simple developing device such as a wet diazo copying machine and a developing device for a copier of a diffusion transferring reversing method, which may be used without any particular modification.
  • Necessary developing time varies depending upon the type, composition or temperature of the liquid developer or the mechanical conditions.
  • the developing time may be selected with a considerable latitude, but is in general, about 5 seconds taking into consideration rapid and access or about one minute for the purpose of reproduction of a continuous tone in the following examples.
  • the image is already produced at a portion corresponding to the high temperature portion of the thermal pattern.
  • the recording is finished with or without washing with water to remove excess liquid developer. If desired, additional treatments of the images such as dry-- ing, chelating the dye image to improve the durability may be applied.
  • Latent images on one thermal recording sheet may be developed with two or more dye liquid developers to form each different colored image.
  • the latent image may be visualized by utilizing'a difference of solubility in a solvent or a difference of gas permeability. Increase in solubility in a certain solvent of the latent image portion according to the present invention is observed.
  • the recording sheet in a gas suchas ammonia gas after forming the latent image and forming color of a visible image forming component, in or under the recording layer, capable of forming color by alkali.
  • the visible image forming component capable of forming color by alkali- may be a pH indicator or a combination of an aromatic diazo compound and a coupler.
  • the thermal recording sheet may be produced by providing on a support a thin film composed of a high polymer complex having a weak bond capable of being dissociated at 50C 120C. 7
  • polymer complex is meant a complex compound of at least two kinds of polymer compounds, or at least one polymer and at least one low molecular weight compound having a moiety as described in Table l and Table 3 and there exists a weak bond between these components, and further, physical or chemical property of one or more of the components is remarkably changed. If there exists no bond among such components at all, the physical property of the mixture of the components is a simple sum of the physical or chemical properties of each component- The weak bond changes the physical or chemical properties of the components, but does not change the intrinsic chemical structure of each component substance.
  • the polymer complex includes a polymer having at least two kinds of moieties as shown in Table l and Table 3 in the same molecular chain.
  • a polymer shows physical or chemical properties similar to a complex produced by mixing polymers having each moiety.
  • polymer complex in the present invention may be defined as follows:
  • polymer having a proton donative group and a proton acceptive group 4. polymer having a proton donative group and a proton acceptive group.
  • the proton donative moiety and the proton acceptive moiety are selected from moieties as shown in Table l and Table 3.
  • the cause of the weak bond has not yet been deter- I mined, but it is considered that the weak bond is caused by the complicated combination of electrostatic forces between ions, hydrogen bonds, van der Waals forces, electrostatic forces caused by partial transferring of electric charge or a spacial intertwinement of high polymer chains and segments.
  • an important factor of the complex of the present invention is hydrogen bonding or a spacial configuration based on entwinement of hydrogen bonding and molecular chains.
  • Table 1 illustrates atoms and atomic groups participating in the formation of the hydrogen bond.
  • Table 1 illustrates atoms and atomic groups participating in the formation of the hydrogen bond.
  • the polymer chains probably delay the thermal dissociation speed of the weak bond to extend the life of the latent image enough to retain the life up to'the developing step, and when the latent image is maintained at a temperature higher than the temperature at which the polymer chain is frozen the latent image disappears gradually as the result of Brownian motion of the polymer chain. Room temperature is generally higher than the polymer chain freezing temperature.
  • Table 2 shows energy of typical hydrogen bonds. Since the energy value is about several Kcal./mole, it is clear that the bond can be easily cut by thermal energy.
  • the thermal recording sheet of the present invention may be produced by providing on a support a thin film composed of at least a polymer (A) selected from polymers and copolymers of N-vinyl lactams, N-vinyl cyclic carbarnate, N-vinyl imidazole, 2-vinyl pyridines, 4-vinyl pyridines, alkylene oxides and acryl amide and a polymer (B) capable of forming a complex with the polymer (B).
  • the polymer (A) as mentioned above can form a complex with other many substances.
  • the resulting film shows such a peculiar physical property, but when the film is treated with an acid or alkali or the pH is changed, the original components, that is, the polymer (A) and the polymer (B), can be recovered again from the thin film or gel. This factindicates the presence of a weak bond.
  • the polymer (B) capable of forming such a weak bond with the polymer (A) may be selected from many high polymers as mentioned later. The formation of the complex may be judged based on the above mentioned matter upon selectingpolymer (B).
  • the complex When the above mentioned complex is heated to a temperature higher than a certain temperature, the complex can be dyed by the liquid developer.
  • This mechanism is not yet clear, but may be considered follows.
  • the polymer complex composed of a polymer (A) and a polymer (B) is stable at room temperature and the dye acceptability of the polymer (A) is masked and cannot be dyed by the dye liquid developer.
  • the complex is dissociated to each component substance at a certain temperature or higher than said temperature and the physical properties of each component substance appear again to recover the dye acceptability of the polymer (A).
  • the dissociation to each component seems to be accompanied simultaneously by separation of micro phase.
  • the high polymer components thus dissociated coagulate each other by the self coagulation force and there is formed an island structure of one of them in a sea of the other (seaisland structure of a blend polymer), and thereby there is provided a surface sufficient to accept a dye from the dye liquid developer.
  • Representative polymers (A) in this invention are: l. N-vinyl lactam polymer Polymers such as N-vinyl pyrrolidone, N-vinyl-3- methyl pyrrolidone, N-vinyl-S-methyl pyrrolidone, N- vinyl-3,3,5-trimethyl pyrrolidone, N-vinyl-3-benzylpyrrolidone, N-vinyl piperidone, N-vinyl-4-methyl piperidone, N-vinyl caprolactam (N-vinylhexahydro-2l-l-adipin-Z-one), N-vinyl capryllactam, N-vinyl-3-morpholinone, N-vinyl thiopyrrolidone, N-vinyl-Z-pyridone and the like.
  • N-vinyl lactam polymer Polymers such as N-vinyl pyrrolidone, N-vinyl-3- methyl pyrrolidone
  • the above-mentioned monomers are known materials and processes for the polymerization thereof are also known. Particularly important and commercially available homopolymers are poly-N-vinyl pyrrolidone, poly-N-vinyl piperidone, poly-N-vinyl caprolactam and poly-N'vinyl morpholinone. Copolymers of said monomers with each other or of said monomers with other vinyl monomers are also useful.
  • the other vinyl monomer may be methacrylates, acrylates, acrylamides, acrylonitrile, vinyl ethers, vinyl acetate, vinylimidazoles,
  • copolymers with vinyl acetate are commercially available.
  • the copolymer may include graft-copolymers, for example graft-copolymers of monomers such as formaldehyde, vinyl chloride, acrylamide, vinyl pyridine and the like onto poly-N-vinyl pyrrolidone.
  • N-vinyl cyclic carbamate polymer Polymers of monomers such as N-viny1-2-oxazolidone, N-vinyl--methyl-2-oxazolidone, N-vinyl-S- ethy1-2-oxazolidone, N-vinyl-4-methyl-2-oxazolidone, N-vinyl-2-thiooxazolidone, N-vinyl-2-mercaptobenzothiazole and the like.
  • Homopolymers of the above mentioned monomers or copolymers of the above mentioned monomers with styrene, vinyl acetate, methacrylate, vinyl ether, N- vinylpyrrolidone and the like are also included.
  • Homopolymers of monomers such as N-vinyl-2-oxazolidone and N-vinyl-S-methyl-2-oxazolidone, or copolymers of these monomers with vinyl acetate are particularly important.
  • N-vinyl imidazoles Copolymers of monomers such as N-vinyl imidazole, N-vinyl-2-methyl imidazole and N-vinyl-4-methyl imidazole, with other vinyl monomers such as styrene, acrylonitrile, methyl methacrylate, N-vinylpyrrolidone and the like.
  • 2-, or 4-Vinylpyridine polymer 5.
  • Alkylene oxide polymer Polyethylene oxide, polypropylene oxide and the like.
  • a thin layer of a homopolymer of N-vinyl lactam, N- vinyl cyclic carbamate, N-vinylimidazoles, 2- or 4- vinylpyridine, alkyleneoxide or acryl amide as mentioned above can be dyed by a dye liquid developer of this invention.
  • the type of partner monomer and the composition ratio should be carefully selected to impart a suitable capacity of accepting a dye from a dye liquid developer.
  • monomer such vinyl acetate giving a water insoluble polymer, the developing speed by a dye liquid developer in the copolymer is retarded.
  • the composition ratio of N-vinyl lactam/vinyl acetate preferably ranges from about 60 40 to 90 10.
  • N-vinyl imidazole, N-vinyl pyridine and the like are copolymerized with N-vinyl lactam, the developing speed by a dye liquid developer is accelerated.
  • the developing speed or image density and the like may be controlled by appropriately selecting the partner monomer in copolymerization.
  • Polymers of N-vinyl lactam, N-vinyl cyclic carbamate, N-vinyl imidazole, 2- or 4-vinyl pyridine, alkylene oxide or acrylamide as aforementioned are made into a thin layer by combining with a polymer (B) forming the complex.
  • Polymer (B) may be selected from high polymers of various kinds. Particularly, high polymers having carboxylic acid radicals, sulfonic acid radicals or OH radicals are preferable.
  • Combination of polymer (A) and polymer (B) may be effected based on a standard that a complex is formed between them (the 12 examination of complex formation is disclosed previously). It is desirable to satisfy at least the following conditions. i
  • the high polymer complex obtained is soluble in 5 usual solvents. This property enable one to form a thin layer of the complex from the solvent solution. 2.
  • a homogeneous and substantially transparent layer is formed without separating the components from each other.
  • Polyesters obtained by reacting an excess of aliphatic polyhydric carboxylic acid such as citric acid, tartaric acid and the like with diols such as ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol and the like.
  • polyvinyl hydrogen oxalate polyvinyl hydrogen malonate, polyvinyl hydrogen glutarate, polyvinyl hydrogen adipate, polyvinyl hydrogen suberate, polyvinyl hydrogen maleate, polyvinyl hydrogen undecenyl succinate, polyvinyl hydrogen isophthalate, polyvinyl hydrogen terephthalate, polyvinyl hydrogen hexahydrophthalate, polyvinyl- O-carboxymethylphenyl acetate, polyvinyl-P-carboxymethylphenyl acetate, polyvinyl-O-carboxyphenyl acetate, polyvinyl hydrogen succinate polyvinyl hydrogen phthalate (90/10), polyvinyl hydrogen oxalate polyvinyl hydrogen isophthalate (50/50), polyvinyl hydrogen maleate [polyvinyl hydrogen adipate 10/90), polyvinyl acetate polyvinyl hydrogen succinate 13 (70/30), polyvinyl be
  • Acrylic acid and methacrylic acid polymer There may be mentioned, for example, polyacrylic acid, partially hydrolyzed product of polymethacrylic acid-n-butyl, partially hydrolyzed product of polyacryl- N-n-propylamide and the like.
  • E. a,B-Unsaturated acid polymer There may be mentioned, for example, polymers of a,B-unsaturated acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, diester fumarate and the like, or copolymers of the a,B-unsaturated acid as mentioned above with other vinyl monomers.
  • Vinyl monomers to be copolymerized with the acid anhydride monomer preferably include vinyl esters such as vinyl acetate andthe like and vinyl ethers.
  • Vinyl monomers to be copolymerized with diester fumarate is preferably include acrylamide, vinyl esters, vinyl ethers, ethylene, styrene, acrylic esters and the like.
  • the above mentioned polymer is disclosed in Murahashi, lnoue and Tani, Gosei Kobunshi [111], Asakura Shoten, 1971, pages 250-257 and pages 374-380.
  • a particularly useful polymer is maleic anhydride copolymer since it is not expensive.
  • a carboxylic acid radical existing in the copolymer forms the derivatives such as the mono ester of dicarboxylic acid, mono amide and the like by reacting with a compound having active hydrogen such as alcohol, ammonia, primary and secondary amines and the like.
  • the derivatives thereof are useful in this invention. Processes for producing some of them are disclosed in the following US. Patents.
  • Acid polyvinyl alcohol derivatives For example, polyviny1-0-su1fobenzoate, polyvinyl-B- sulfopropionate, polyvinyl-B-sulfovarate, polyvinyl-P- sulfophenyl acetate, polyvinyl acetate polyvinyl-O-sulfobenzoate (50/50), polyvinyl benzoate polyvinyl-ysulfopropionate (50/50), polyvinyl acetate polyvinyl crotonate polyvinyl-2-sulfo-4-carboxybenzoate (40/30/30), polyvinyl formal polyvinyl butyral polyvinyl-p-sulfobenzal (/60/30), polyvinyl formal polyvinyl acetate polyvinyl-O-sulfobenzal (60/20/20), polyvinyl alcohol polyvinyl acetate polyvinyl formal polyvinyl-O-sulfo
  • ethyl cellulose ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxyethyl ethyl cellulose, hydroxyethyl benzyl cellulose and the like.
  • Polymer (A) and polymer (B) as mentioned above are properly selected and combined in accordance with the aforementioned conditions. That is, at least a high polymer selected from the polymer (A) group and at least a high polymer selected from the polymer (B) group are mixed in a solution form and the complex thus formed is separated (when the solvent is water, alcohol, ketones and the like, the complex may be normally separated as gel), dissolved in a solvent for the complex, thereafter coated on a support and dried to form a thin layer. Alternatively, from the first each high polymer is dissolved and mixed in a solvent for the complex, coated on a support and dried to form a thin layer. In order to improve various responses to heat or a physical property of the film of the thermal recording layer, a third inert polymer or plasticizers may be added. These substances are selected from known materials.
  • Example 7 For the purpose of facilitating the selection of the high polymers, combinations of high polymers and various embodiments of heat sensitive sheets made therefrom are shown in Example 7.
  • An example of polymer (B) giving a preferable result when combined with a polymer (A) is a,B-unsaturated acid polymer, particularly, a copolymer of an alkyl vinyl ether and maleic anhydride.
  • Thee combination of the above-mentioned polymer (B) and the polymer (A) provides a thermal recording sheet having excellent film physical proper- 16 ties such as flexibility, mechanical strength and the like and satisfyingrequiredcharacteristics such as heat sensitive temperature, image density, contrast, clearness of background and the like without adding any other third component.
  • v 1 A
  • ether and maleic anhydride are mono esters [l], mono ammonium salts [11] and mono amides [111] of vinyl ethers having alkyl radical of C -C maleic anhydride copolymer (copolymerization ratio being 'about 1:1).
  • copolymerization ratio being 1:1, the unit structure is represented as follows:
  • R and R are alkyl radicals having C C R R is hydrogen or an alkyl radical having C C and the total carbon atoms of R R, and R and R R is not more than 19.
  • 11 1 EZTEZTF Examples of suitable alkyl vinyl ethers are shown below. Only the alkyl radical R is illustrated. The number in the parentheses is the boiling point: methyl (6.0), ethyl (35.5), n-propyl (655), i-propyl (55), n-butyl (94), i-butyl (83), t-butyl i-amyl (109), nhexyl (143), n-octyl (58, 44 mmHg), 2-ethyl hexyl (177), n-decyl (101, 11 mmHg), n-dodecyl (126, 3 mmHg), n-octadecyl (182, 3 mmHg). Some of them are already commercially available.
  • Alkyl vinyl ether maleic anhydride copolymer [V] is reacted with an alcohol under moderate conditions to produce a monoester.
  • methyl vinyl ether maleic acid mono ether copolymers are supplied by: General Aniline and Film Corp, for example, Gantrez ES Resin.
  • Mono ammonium salts [II] are obtained by neutralizing with ammonia or the corresponding alkyl amine after hydrolyzing the copolymer [V] and mono amides [III] are obtained by reacting ammonia or the corresponding primary or secondary alkyl amine with the copolymer [V].
  • n-butyl vinyl ether maleic anhydride copolymer [VI] Desiccated refined benzene 1000 ml.) is poured in a three-necked flaskequipped with an agitator and a tube introducing nitrogen, and maleic anhydride 134 g.) and 135 g. of n-butyl vinyl ether (a reagent manufactured by Tokyo Kasei Kogyo K.K.) are dissolved therein, thereafter the substitution of nitrogen is carried out.
  • Benzoyl peroxide 1.7 g.) is added thereto, ag itated for 4 hours at 50C 60C, then for hours at A gelatinous polymer is obtained and benzene is removed therefrom.
  • the resulting matter iswashed sufficiently with ethylene dichloride and dried by removing water to produce 260 g. of a flocculent product.
  • copolymers of approximately l/l ratio are obtained from i-butyl vinyl ether, i-octyl vinyl ether or noctadecyl ether and maleic anhydride.
  • mono-N-methyl amide copolymer [XI] is obtained by using methyl amine as a substi- 2.
  • Methyl vinyl ether maleic anhydride copolymer 10 g. (trade name, Gantrez A N 139, manufactured by General Aniline and Film Corp.) is dissolved in a solution of pyridine (100 ml.) in n-octyl alcohol (8.5 g.), agitated for 5 hours at 100C, poured into water, and
  • the aforementioned layer comprising the complex of polymer (A) and polymer (B) is manufactured by coating the solvent solution on a suitable support and drying.
  • the complex may be produced by mixing the polymer (A) solution with the polymer (B) solution and recovering the separated complex. It is economical, however, that the polymer (A) and the polymer (B) are mixed, dissolved in a solvent capable of dissolving the complex, and directly used as a coating solution.
  • additives 19 20 other than the complex of polymer (A) and polymer FH HQ] RCOO C H QH CSH'SNHCOCH, (B) may be added.
  • the additives there may be men- RCONHR, ROH, C H NHC H RCONH H O, tioned a flattening agent of the coating such as silica C1 CH aerogel (finely divided powder of SiO titaniumoxide 7 powder and the like, and an image property controlling 5 agent. It has been now found that some compounds have a powerful effect on the image property of this recording complex. In general, certain kinds of proton fi s 4; 5-.
  • donors and proton acceptors may contribute to l reducing the back ground density, (2) decreasing the 10 NH image density and contrast, and (3) decreasing the de- (H2 veloping speed. Further, as these contribute to improvement in regeneration of the image and sharpness 5 z- CGHBCH2NH2- thereof, controlling the vanishing speed of the latent Proton accepting capacity: (arranged in order of inimage, and reducing the aging period after coating and tensity) R Gill-[Q RCON RCONHR' drying the recording sheet, and therefore the recording Ha- 2 nBt-O- RCHO. cu properties are improved.
  • Proton donative ca acit arra 55 p y nged in order of in z CHaCH CH CHO tensity) c c R' I cH cooc H c CH 000 wherein R, R',R" and the like are alkyl or aryl.
  • the complex used for the present invention may be produced by combining one of the polymers (A) and the polymers (B) with a low molecular weight compound capable of forming a complex by combining with such polymers.
  • the low molecular weight compound may be selected from compounds having a structure similar to the structure of the proton donative or proton acceptive monomer of the polymer (A) or (B).
  • the dyeability of the polymer is a very important factor so that the polymer should be selected from polymers having dyeability.
  • a polymer (A) and a polymer (8') can form a complex, there may be often used a copolymer having monomer structures which constitute the polymer (A) and the polymer (B).
  • the latent image of the thermal recording sheet according to this invention is dyed by accepting selectively the dye from the dye liquid developer.
  • dye liquid developer suitable for this invention
  • relatively water-soluble means to be soluble in water alone or a mixture of water and an organic solvent miscible with water such as alcohol, lower ketone, dioxane, benzyl alcohol and the like.
  • Triphenylmethane dye such as Rhoduline Blue 6GA, Brilliant Green, Malachite Green, Para Rosaniline,
  • anthraquinone dye such as Alizarine Astrol B, Alizarine Pure Blue B, Alizarine Cyanine Green G, Anthraquinone Violet, Anthraquinone Blue and the like;
  • ketoimine type dye such as Auramine O and Auramine G.
  • aqueous solution of these dyes or an aqueous solution containing alcohol, lower ketone, dioxane and benzyl alcohol of these dyes may be used as a dye liquid developer.
  • a buffer solution for adjusting pH, or an inorganic salt such as sodium sulfate, sodium chloride and the like for controlling the dyeing capacity, or an organic mordant such as poly-N-vinyl pyridinium quaternary salt and the like other than the dye may be added to the dye liquid developer.
  • the complex obtained from a N-vinly lactam polymer and the like has an anionic radical such as a carboxylic acid radical or a sulfonic acid radical and the like, it is desirable that the pH value is neutral or acid for the purpose of decreasing the background density as far as possible.
  • an oil type dye such as Oil Brown N, Oil Red 0, Solvent Blue 16, Solvent Violet l7, Solvent Black 12 and the like.
  • a negative image is generally obtained by using an oil type dye.
  • the dye used for a dye liquid developer according to this invention is not limited only to a colored substance, but may include a substance such as a fluorescent substance, an ultraviolet ray absorber, an electron ray absorber and the like which produce an image by irradiation with ultraviolet rays and electron rays, and the like. Further, it should be understood that a liquid developer containing a substance capable of forming a colored substance by reaction with a third substance incorporated in the thermal recording layer is also within the scope of the dye liquid developer of the present invention.
  • thermo recording layer There may be mentioned, for example, a combination of a metal salt and a chelating agent and a combination of a diazo compound and an azo coupler (one of them is incorporated in either the thermal recording layer or the liquid developer). It is very easy to select a substance which is inert and not heat sensitivity when incorporated in the thermal recording layer.
  • EXAMPLE 1 30 g. of methyl vinyl ether maleic acid mono n-butyl ester copolymer [trade name: Gantrez ES-425 manufactured by GAF (General Aniline and Film Corp); solid content: 50%] was added to a solution of g. of poly-N-vinyl pyrrolidone (trade name: PVP, [(-90 manufactured by GAF) in 150 g. of alcohol and stirred to obtain a gel-like high polymer complex. 150 g. of dimethyl formamide was added to said gel-like complex to dissolve said gel-like matter and obtain a homogeneous and clear solution.
  • PVP poly-N-vinyl pyrrolidone
  • a polyester film of 70 microns in thickness subjected to a treatment of imparting a hydrophilic property was coated with said solution and dried by hot air at 70 80C (the thickness of said coating was 2 microns after drying).
  • the properties of said film such as its heat sensitive temperature or contrast may be stabilized after standing at room temperature (about C) for several days.
  • Said produced thermal recording sheet was contacted with a thermal wedge composed of aluminum hot plates set at temperatures between 40C and 150C at intervals of 10C for about 3 seconds, then dipped in a dye liquid developer D-l (a solution of 0.5 g. of Crystal Violet in 100 ml. of distilled water) and washed with water.
  • D-l a solution of 0.5 g. of Crystal Violet in 100 ml. of distilled water
  • the process for preparing said high polymer complex solution is fairly optional.
  • the polyester film coated with a solution of a copolymer of poly-N-vinyl pyrrolidone and mono-n-butyl ester in a mixture of 150 g. of alcohol and 150 g. of dimethyl formamide was a thermal recording sheet having the same properties as that of the above mentioned one.
  • the film surface of said thermal recording sheet was closely contacted with one side of a manuscript printed on both sides and passed through a Thermofax copying machine (Secretary type, manufactured by Minesota Mining and Manufacturing Co.). A visible change was scarcely found on said surface at this stage. A clear violet image appeared on the portion corresponding to letter portions of the manuscript when the thermal recording sheet was dipped in a dye liquid developer D-l (liquid temperature: 20C) and pulled up, and said image was fixed firmly on the sheet without any further treatment. Said image density was 1.54 (measured by a red filter) and the background density was 0.02. A transparent image having high contrast was formed by projecting said sheet using an overhead projector.
  • Table 6 shows the relation between standing time and image density when the thermal recording sheet of this Example was passed through a Thermofax copying machine with a black colored manuscript, allowed to stand at 20C (room temperature) for a predetermined time and then developed with said dye liquid developer D- 1.
  • Table 6 shows the reversibility of a latent image formed on the recording sheet of this invention. It is found in Table 6 that the recording sheet of this invention can be used once more and add-on of other images is possible after standing for about 24 hours since the latent image disappears almost completely after standing for about 24 hours, and that it is possible to stock copies since the image density hardly changes at standing times of 10 30 minutes.
  • Table 7 shows the image characteristic when the solution of the high polymer complex of this Example was applied to a polyester sheet under the above conditions, dried and then allowed to stand at 20C (room temperature). The background density after standing at various times and developing in a dye liquid developer D] was measured (developed without passing through Thermofax copying machine).
  • Table 8 shows that various dye liquid developers may be used for the sheet of this Example.
  • FIG. 1 the infrared absorption spectrum of the complex of polyvinyl pyrrolidone (PVP) and methy vinyl ether maleic acid mono-n-butyl ester copolymer (ES-425) is shown.
  • PVP polyvinyl pyrrolidone
  • ES-425 methy vinyl ether maleic acid mono-n-butyl ester copolymer
  • a gel-like product is precipitated by mixing PVP and ES-425 in alcohol, washed with alcohol several times and dried to produce a white powdered complex.
  • the complex always shows a constant elementary analysis regardless of the molar ratio of PVP to ES-425.
  • the elementary analysis is as follows: C 58.02%, H 7.64%, N 4.71%.
  • the molar ratio of PVP in said complex calculated value of the elementary analysis is 55%.
  • absorption of carbonyl radical of pvp, 1680 cm and absorption of carboxylic acid of ES-425, 1715 cm", as illustrated in FIG. I disappear, and a new broad absorption having the peak at 1660 cm appears.
  • Said new adsorption is considered to be the adsorption due to the shifting of the proton of carboxylic acid and carbonyl radical to the side of low wave member as the result of hydrogen bonding of proton of carboxylic acid and carbonyl radical. Hydrogen bonding is considered to contribute to the formation of said complex as shown in the following scheme.
  • the physical and/or chemical properties of the heated portion are different from those of the portions which are not heated.
  • the complex produced from PVP and ES- 425 is formed by hydrogen bonding of the carbonyl radical of PVP and the carboxylic acid of ES-425 and thereby an absorption appears at 1660 cm" in an infrared absorption spectrum.
  • FIG. 3 shows an infrared ab- .sorption spectrum directly after heating the complex. When the complex is heated, the absorption at 1660 cm changes to two sbsorptions at 1680 cm and 1640 cm", and a shoulder of absorption appears at 1715 cm.
  • EXAMPLE 2 15g. of poly-N-vinyl pyrrolidone (trade name: PVP K-) and 14g. of methyl vinyl ether/maleic acid mono-N-n-hexylamide [XIV] were dissolved in a mixture of g. of alcohol and 150g. of dimethyl formamide. The resulting solution was applied to a semitransparent tracing paper (of a thickness of about 30 microns) in a thickness of about 2 microns and dried. Since the heat sensitivity of said product is stabilized after about 10 days, the said product was allowed to stand for said period, cut into a tape for contact with a heated printing head(a small computer manufactured by Canon Co., trade name: pocketronic) and the latter operated.
  • a heated printing head a small computer manufactured by Canon Co., trade name: pocketronic
  • EXAMPLE 3 This Example relates to a sheet for stylus recording used in oscillograph recording. N-vinyl pyrrolidone polymer and vinyl ether/maleic acid copolymer at compounding amounts as shown in Table 10 were dissolved in 300g. of a mixture of alcohol and dimethyl formamide of the same amount as that of alcohol- Said solution was applied to an opaque tracing paper and dried in hot air at 90 100C (thickness of film after drying: 2 microns).
  • polymer (g) PVPK-90 Methyl vinyl ether/maleic acid 1 l g.) mono-n-octyl ester copolymer [Vlll] (15 g.) PVPK-90 Methyl vinyl ether/maleic acid 2 12 g.) mono-n-octadceyl ester copolymer l l g-) PVP/VAE- n-butyl vinyl ether/maleic acid 3 735* mono amide copolymer (1 g) [X1 g) PVPK-90 n-butyl vinyl ether/malcic acid 4 (14 g.) mono-N-l-propyl amide compolymer [XII] (15 g.) PVPK-90 Methyl vinyl ether/maleic acid 5 12 g.) mono N-methyl-N-octadecyl amide copolymer [XV] 15 g.) PVP/VAE- n-butyl vinyl e
  • EXAMPLE 4 polymer [Vll] were dissolved in 300g. of a mixture of alcohol and dimethyl formaldehyde l l The resulting solution was applied vto a polyester sheet at the thickness of about 3 microns (after drying) and dried to obtain a master. The master after standing for 10 days at room temperature can be used stably. The master was cut in the dimension of a cabinet and a small hole was provided in said master for registration.
  • black-white originals corresponding to each of three colors for regeneration of said three colors were prepared, and each original was passed through a Thermofax copying machine with said master for exposure.
  • the master was developed by the following liquid developer corresponding to each color, and lightly washed with water to obtain masters of cyan, magenta and yellow.
  • a baryta paper coated with gelatine was mordanted as follows:
  • the coloring matters were transferred to said baryta paper by laying one color master upon the others in predetermined positions respectively on said baryta paper and squeezing to obtain color prints of cyan, 'magenta and yellow.
  • the black-white original for printing of a master may be produced easily by a known method.
  • the black-white intermediate original for regenerating yellow, magenta and cyan may be obtained by laying each filter of blue green and red on a colored original respectively and copying by an electrophotographic copying machinev on a panchromatically-sensitized ZriO electrophotographic paper. Since the toner developer used for electrophotographic copying paper absorbs effectively the light from the light souce of a Thermofax copying machine, the intermediate original thus obtained may be utilized to produce a master.
  • Cyans v mono ester copolymer Speed density Patent Blue c n 5 Z-cthylhexyl low low B illi Bl 6 n-decyl low low Alizarme Blue (AB) 7 mlddk 0w Fast And Green B I I "(iantrcz ESE-Z25 (manufactured by (iAF) Mlgentds' i r *Gantrez PIS-3354 (manufactured by ()AF) Acid Magenta 28 cone. ""(ianlrez F5425 (manufactured by GAF) Fast Fuchsine Fast Crimson 6 BL Violamine RR EXAMPLE 6 Yellow! l5g.
  • an organic solvent miscible two Solutions Selected therefrom were i d i h h with water such as alcohol, acetone; methyl ethyl keother for a gel time test. tone, dioxane and the like to a dye liquid developer to A mixture f two Compounds i h Same amount was increase the image y- 40 dissolved in a suitable solvent for coating, and said solution was applied to a polyester film at the thickness of a Table l l 2 4 microns (after drying) .and' dried to prepare a sam- Samplc Ester radicals of methyl Developing Back P The heat n ty tested wlth'respectto S'ald No.
  • Example 9 an original picture different from the first original pic- This example relates to a method for preparing and ture was printed onto said film and then said printed for using the thermal recording sheet suitable for refilm was developed in the liquid developer of Crystal generating the negative-positive image.
  • Said gel was dissolved in a mixture of alcohol and dimethyl formamide l 1 and 10g. (solid content: 5g.) of N-vinyl pyridine/vinyl acetate copolymer (trade name: PVP/VAE-735) was added. The resulting solution was applied to a polyester sheet at the thickness of 3 microns (after drying) and dried. The resulting film contained silver colloid and was light brown and had infrared absorbing properties. After stabilizing by standing at room temperature, said sheet was contacted with a negative photography image and exposed to a Xenon flashing discharge lamp (trade mark: Press-150 manufactured by Minicham) at a short distance and immediately developed in the dye liquid developer D-ll to obtain a clear positive image. Said sheet was printed by a step wedge having 2 step and was developed. The maximum density was 1.5 (green filter) and the back ground density was 0.25. Eight steps are observed between the maximum density and the background density.
  • Said thermal recording sheet may be used for recording by laser scanning.
  • the laser ray having a wave length of 6328 A, spot diameter of 2 microns on the sheet and an intensity of 10 milliwatt
  • EXAMPLE 10 This example relates to the effect of an agent used to control the properties of the image.
  • PVP/ES-425 is 4/6 (molar ratio)
  • a solution comprised of 8.0g. of poly-N-vinyl pyrrolidone (trade name: PVP K- manufactured by GAF Co), 24g. of methyl vinyl ether/maleic acid mono-nbutyl ester copolymer (50% solution) (trade name: Gantrez ES-425 manufactured by GAF Co), g. of ethanol, 50g. of dimethylformaldehyde and 10g. of an addition agent was applied on a polyester film and dried. After standing for 7 days at room temperature. said thermal recording sheet was passed through a Tharmafax copying machine with a manuscript and developed by machine under the following conditions.
  • Image Density-Background Density Developing by the machine disclosed above is the developing method using the following developing machine.
  • the developing is conducted in such a way that a film transferred by a field roller provides aberration of position to an actuator, a photoswitch connects by said aberration of position, said film is put between crip plates connecting to the comfollower on the film conveyer to be fixed, said film is treated by fountain development, and excess liquid developer scraped off with a blade.
  • Tables 13 and 14 show that the most effective additive is 9-fluorene carboxylic acid in 1 and benzophenone in (2). The results show that weak mutual action among high polymer (A), high polymer (B) and the additive provides an influence on the image property.
  • EXAMPLE 11 15g. of polyvinyl pyrrolidone (trade name: PVP K-90, manufactured by GAF)'was dissolved in 150 g. of alcohol and g. of methyl vinyl ether/maleic acid mono-n-butyl ester copolymer(trade name: Gantrez ES-425, manufactured by GAF) (solid content: was added to. said solution and permitted to stand to obtain a gel-like high polymer complex.
  • 150g. of dimethyl formamide was added to said gel-like Complex to obtain a homogeneous and clear solution.
  • Said solution was applied to a polyester film at a thickness of microns (the film having been subjected to a treatment imparting a hydrophilic property) dried by hot air'at 70: C.
  • thermo recording sheet is EXAMPLE 12
  • a latent image formed on a thermal recording sheet prepared by the methodof Example ll except adding a small amount of phenolphthalein to the composition of Example 1 l was exposed to ammonia vapor for 10 minutes, a reddish rose color was formed at the portion of the latent image. Thus a visible image was obtained.
  • EXAMPLE I 3 Silver behenate (25g) and hydroquinone lg.) were added to and dispersed in a solution of theco mplex obtained in Example I in dimethylformamide, coated on a polyester film of 70 microns in thickness and dried at room temperature. The resulting thermal recording sheet was contacted with a first original and passed through a copier which was adjusted to give a thermal pattern of C. to produce a dark brown image due to the reduction of the silver behenate. Then a portion of the thermal recording member having no image was contacted with a second original and passed through a copier adjusted to give a thermal pattern of 60-80. The silver behenate did not react with the complex under such temperature conditions and failed to produce any image of the second original.
  • the resulting sheet was developed with the dye liquid developer D-l in Example I and there was obtained an image of the second original.
  • a thermal recording member useful for forming a reversible latent image by heating which is capable of being developed into a permanent visible image
  • said recording member comprising a support having thereon a uniform and transparent recording layer composed of a heat-sensitive composition which comprises a polymer complex including a polymer moiety which is normally dyeable at room temperature but which, in the polymer complex, is dyeable only after heating the complex to an elevated temperature.
  • said polymer complex is acomplex of a polymer (A) and a polymer (B); and wherein said polymer (A) is a dyeable polymer selected from the group consisting of homopolymers and copolymers of N-vinyl lactams, N-vinylcyclic carbamates, N-vinyl imidazoles, vinyl pyridines, alkylene oxides and acrylamides; and
  • polymer (B) is selected from the group consisting of polymers having a carboxylic acid radical, a sulfonic acid radical or an OH radical.
  • a thermal recording member according to claim 1 wherein said polymer (A) is a homopolymer of one of said group, a copolymer of morethan one of said group or, a copolymer of one of said group with a different vinyl monomer.
  • a thermal recording member in which said polymer ('8) is selected from the group consisting of polyesters obtained by reacting an aliphatic polyhydric carboxylic acid and diols, acid'cellulose derivatives, an acid polyvinyl polymer, an acrylic acid polymer, a methacrylic'acid polymer, an a, [3- unsaturated acid polymer, acid polyvinyl alcohol derivatives, cellulose ethers, a phenolic'resin, a cresol-formaldehyde resin and a phenoxyacetici acidformaldehyde resin. 7 6.
  • a thermal recording member according to claim-l in which said polymer (B) is selected from the group consisting of homopolymers and copolymers of maleic anhydride, maleic anhydride mono-esters and maleic anhydride mono-amides.
  • a thermal recording member in which said polymer (B) is selected from the group consisting of copolymers of l) and a, B-unsaturated acid selected from the group consisting of maleic anhydride, maleic anhydride mon-esters, maleic anhydride mono-amides, itaconic anhydride, citraconic anhydride and diester fumarate, and (2) a vinyl monomer selected from the group consisting of vinyl acetate, vinyl ethers,

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  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
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Cited By (15)

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Publication number Priority date Publication date Assignee Title
US4654677A (en) * 1982-04-07 1987-03-31 Hitachi, Ltd. Recording apparatus
US4734359A (en) * 1985-11-07 1988-03-29 Canon Kabushiki Kaisha Thermal recording material for display and image display device utilizing the same
US4783395A (en) * 1987-02-17 1988-11-08 Hoechst Celanese Corporation Desensitizing solution for lithographic printing plates
US4960670A (en) * 1987-05-13 1990-10-02 Fuji Photo Film Co., Ltd. Formulation of barcodein microencapsulated diazo thermodevelopable photo-recording method utilizing electric current activated minute matrixes to light record
US5045440A (en) * 1990-02-07 1991-09-03 Hoechst Celanese Corp. Stabilization of optical information storage media by incorporation of nitrogen containing compounds
US5300952A (en) * 1990-10-25 1994-04-05 Ricoh Company, Ltd. Thermal image forming equipment forms image directly on image carrier or paper sheet
US5650329A (en) * 1990-08-23 1997-07-22 Awc. Inc. Acid indicators
EP1031414A1 (fr) * 1999-02-22 2000-08-30 Fuji Photo Film Co., Ltd. Précurseur de plaque d'impression lithographique
US6136751A (en) * 1998-01-29 2000-10-24 Ricoh Company, Ltd. Reversible thermosensitive recording medium, and image forming and erasing method
US6773764B2 (en) * 2002-01-03 2004-08-10 Hitachi Global Storage Technologies Netherlands B.V. Method of forming a patterned magnetic recording medium
EP1738900A1 (fr) * 2005-06-30 2007-01-03 Agfa-Gevaert Précurseur de plaque d'impression lithographique thermosensible
US20070003875A1 (en) * 2005-06-30 2007-01-04 Agfa-Gevaert Method for preparing a lithographic printing plate precursor
US20070003869A1 (en) * 2005-06-30 2007-01-04 Agfa-Gevaert Heat-sensitive lithographic printing plate-precursor
US20070003870A1 (en) * 2005-06-30 2007-01-04 Agfa-Gevaert Heat-sensitive lithographic printing plate precursor
US10101672B2 (en) 2015-05-27 2018-10-16 Suss Microtec Lithography Gmbh Device for treating a disc-shaped substrate and support adapter

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US3476937A (en) * 1963-12-05 1969-11-04 Agfa Gevaert Nv Thermographic recording method employing a recording material comprising a uniform layer of discrete hydrophobic thermoplastic polymer particles
US3679410A (en) * 1966-01-11 1972-07-25 Agfa Gevaert Heat-sensitive recording material
US3694246A (en) * 1969-06-24 1972-09-26 Ncr Co Method of using display device utilizing polymer-polymer miscibilities
US3708323A (en) * 1970-12-28 1973-01-02 Ncr Couplet transparency manufacturing process
US3764335A (en) * 1971-08-02 1973-10-09 Eastman Kodak Co Image forming compositions including an azide and transition metal complexes of triorganophosphines

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Publication number Priority date Publication date Assignee Title
US3476937A (en) * 1963-12-05 1969-11-04 Agfa Gevaert Nv Thermographic recording method employing a recording material comprising a uniform layer of discrete hydrophobic thermoplastic polymer particles
US3679410A (en) * 1966-01-11 1972-07-25 Agfa Gevaert Heat-sensitive recording material
US3694246A (en) * 1969-06-24 1972-09-26 Ncr Co Method of using display device utilizing polymer-polymer miscibilities
US3708323A (en) * 1970-12-28 1973-01-02 Ncr Couplet transparency manufacturing process
US3764335A (en) * 1971-08-02 1973-10-09 Eastman Kodak Co Image forming compositions including an azide and transition metal complexes of triorganophosphines

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654677A (en) * 1982-04-07 1987-03-31 Hitachi, Ltd. Recording apparatus
US4734359A (en) * 1985-11-07 1988-03-29 Canon Kabushiki Kaisha Thermal recording material for display and image display device utilizing the same
US4783395A (en) * 1987-02-17 1988-11-08 Hoechst Celanese Corporation Desensitizing solution for lithographic printing plates
US4960670A (en) * 1987-05-13 1990-10-02 Fuji Photo Film Co., Ltd. Formulation of barcodein microencapsulated diazo thermodevelopable photo-recording method utilizing electric current activated minute matrixes to light record
US5045440A (en) * 1990-02-07 1991-09-03 Hoechst Celanese Corp. Stabilization of optical information storage media by incorporation of nitrogen containing compounds
US5650329A (en) * 1990-08-23 1997-07-22 Awc. Inc. Acid indicators
US5300952A (en) * 1990-10-25 1994-04-05 Ricoh Company, Ltd. Thermal image forming equipment forms image directly on image carrier or paper sheet
US6136751A (en) * 1998-01-29 2000-10-24 Ricoh Company, Ltd. Reversible thermosensitive recording medium, and image forming and erasing method
EP1031414A1 (fr) * 1999-02-22 2000-08-30 Fuji Photo Film Co., Ltd. Précurseur de plaque d'impression lithographique
US6509132B1 (en) 1999-02-22 2003-01-21 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
US6773764B2 (en) * 2002-01-03 2004-08-10 Hitachi Global Storage Technologies Netherlands B.V. Method of forming a patterned magnetic recording medium
EP1738900A1 (fr) * 2005-06-30 2007-01-03 Agfa-Gevaert Précurseur de plaque d'impression lithographique thermosensible
US20070003875A1 (en) * 2005-06-30 2007-01-04 Agfa-Gevaert Method for preparing a lithographic printing plate precursor
US20070003869A1 (en) * 2005-06-30 2007-01-04 Agfa-Gevaert Heat-sensitive lithographic printing plate-precursor
US20070003870A1 (en) * 2005-06-30 2007-01-04 Agfa-Gevaert Heat-sensitive lithographic printing plate precursor
US7678533B2 (en) 2005-06-30 2010-03-16 Agfa Graphics, N.V. Heat-sensitive lithographic printing plate precursor
US10101672B2 (en) 2015-05-27 2018-10-16 Suss Microtec Lithography Gmbh Device for treating a disc-shaped substrate and support adapter

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BE800470A (fr) 1973-10-01
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