US3924041A - Heat-sensitive recording material and process for producing same - Google Patents

Heat-sensitive recording material and process for producing same Download PDF

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Publication number
US3924041A
US3924041A US454534A US45453474A US3924041A US 3924041 A US3924041 A US 3924041A US 454534 A US454534 A US 454534A US 45453474 A US45453474 A US 45453474A US 3924041 A US3924041 A US 3924041A
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heat
support
sensitive
layer
transfer layer
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Masuo Miyayama
Mineyuki Murase
Harumi Shiraiwa
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Kohjin Holdings Co Ltd
Kohjin Co
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Kohjin Co
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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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick

Definitions

  • ADHESION TEMPERATURE (c) HEAT-SENSITIVE RECORDING MATERIAL AND PROCESS FOR PRODUCING SAME BACKGROUND OF THE INVENTION 1.
  • Field of the Invention The present invention relates to a heat-sensitive recording material and a process for producing the same.
  • a so-called transfer-type heat-sensitive copying method in which a transfer sheet having a heat-sensitive transfer layer and a receiving sheet are superposed on each other and heat is imagewise applied to the heat-sensitive layer of the heat-sensitive transfer sheet to imagewise soften and melt this layer, thus imagewise transferring the transfer layer onto the receiving layer to obtain a copy, as disclosed, for example, in US. Pat. No. 2,769,391.
  • the heat-sensitive copying material to be used therefor comprises two independent sheets, i.e., a receiving sheet and a transfer sheet. These two sheets are superposed over each other for use in duplication.
  • insufficient contact between the receiving sheet and the transfer sheet results in an insufficient and non-uniform transfer of the transfer layer to the receiving sheet upon application of heat. If the transfer layer is increased in thickness than is necessary to achieve duplication so as to improve the above defect, the transfer layer spreads too widely in lateral direction upon transfer, which results in obtaining discontinuous, broad or distorted images only.
  • the transfer layer must possess additional properties such as coloring properties when used for copying documents, or an affinity for an ink when used for producing a master for offset printing, as well as the heat-sensitive property, depending upon the end use to which the assembly is put. Since a conventional transfer layer has had to possess a plurality of properties as described above, it has been difficult to obtain a transfer layer capable of satisfying all of these requirements.
  • An object of the present invention is to obtain a novel heat-sensitive recording material without the defects which have been encountered with the abovedescribed conventional heat recording materials.
  • Another object of the present invention is to provide a heat-sensitive recording material which can be handled with ease and stably provide a sharp and distinct copied image with no distortion, no broadened areas and discontinuous areas, and to provide a process for producing the same.
  • the material of the present invention can be applied to various heat-sensitive copying or recording methods.
  • the heat-sensitive recording material of the present invention comprises support A having thereon transfer layer B and support C in order, these sheets having the property that before heating the adhesion strength between transfer layer B and support C is less than the adhesion strength between transfer layer B and support A and is larger than 0.1 g/cm but, after heating to a temperature higher than the heat sensitive temperature of transfer layer B, the adhesion strength between transfer layer B and support C becomes greater than the adhesion strength between support A and transfer layer B, with the transfer B comprising, at least at the side thereof in contact with support C, a heat-sensitive composition containing as a major component a mixture of a heat-sensitive substance which becomes fluid at the heat-sensitive temperature of the heat-sensitive substance and an adhesiveness-imparting agent which can adhere to support C at a temperature not higher than the heat-sensitive temperature of the heat-sensitive substance.
  • the recording material can be handled integrally as one sheet by adhering the transfer layer B on support A to the receiving support C with an appropriate degree of strength.
  • FIG. 1 is a cross-sectional view showing one embodiment of the heat-sensitive recording material of the present invention.
  • FIG. 2 is a cross-sectional view showing another embodiment of the heat-sensitive recording material of the present invention in which transfer layer B comprises a colored layer or an ink-receptive layer B-1 and a heat-sensitive layer B-2.
  • FIF. 3 shows the condition of duplication using reflection exposure method with the heat-sensitive recording material 1 of the present invention, in which numeral 2 denotes an original and 3 an image area.
  • FIG. 4 shows the condition of the material after copying, in which delamination occurs between transfer layer B and support C at the non-image area B and, at image area B, delamination occurs between support A and transfer layer B.
  • FIG. 5 shows the relationship between the press-contacting temperature and the peel strength required between the transfer layer B and support C, in one example of the heatsensitive recording material of the present invention, in the case of press-contacting support C onto transfer B formed on support A.
  • the transfer layer B of the present invention must comprise, at least at one side thereof which is in contact with support C, a heat-sensitive composition containing as a major component a mixture of a heatsensitive substance and an adhesiveness-imparting agent.
  • a heat-sensitive composition containing as a major component a mixture of a heatsensitive substance and an adhesiveness-imparting agent.
  • the number of layers forming the transfer layer B is not particularly limited.
  • the transfer layer B can be formed as one layer comprising a composition containing as a major component a mixture of a heat-sensitive substance and an adhesiveness-imparting agent. It can further contain a coloring agent such as an oil-soluble dye, a water-soluble dye, an alcohol-soluble dye or a disperse dye, or an organic or inorganic pigment if it is to have end-use applications for copying documents, a spirit dye if it is to have end-use applications for preparing a spirit master,
  • a coloring agent such as an oil-soluble dye, a water-soluble dye, an alcohol-soluble dye or a disperse dye, or an organic or inorganic pigment if it is to have end-use applications for copying documents, a spirit dye if it is to have end-use applications for preparing a spirit master,
  • a suitable amount of these addenda can range from about 2 to 80, preferably 5 to 60, percent by weight of the layer.
  • the transfer layer can comprise two layers: one layer being a colored or ink-receptive layer B-l in contact with support A; and the other layer being a heat-sensitive layer B-2 in contact with support C, containing as a major component a mixture of a heat-sensitive substance and an adhesiveness-imparting agent.
  • the transfer layer B must substantially transmit the ligth used for exposure, while where a stencil transmission method is used, the transfer layer B must possess a component which absorbs the light used for exposure to generate heat.
  • the heat-sensitive substance must become fluid at the heat-sensitive temperature employed upon heatsensitive duplication.
  • the heat-sensitive temperature is preferably not less than about 40C and not higher than about 200C, most preferably 50 to 150C.
  • the heat-sensitive substance those which exhibit almost no fluidity at a temperature lower than the heatsensitive temperature but become fluid very quickly at the heat-sensitive temperature, that is, those substances which exhibit the characteristics as graphically shown, e.g., by XYZ, in FIG. 5 are preferable.
  • Suitable examples of such heat-sensitive substances are paraffins having a variety of melting points, e.g. (50 to 75C); waxes such as candelilla wax (m.p. 60 80C), bees wax (m.p. 60 66C), montan wax (m.p. 65 105C), ceresine wax (m.p. 65- 85C), carnauba wax (m.p. 75 86C), etc.; wax analogs such as stearic acid, stearyl alcohol, etc.; synthetic resins such as coumarone-indene resins, phenolic resins, e.g., novalac (m.p. 50 150C), alkylphenolic resins (m.p.
  • petroleum resins e.g., comparatively low molecular weight polystyrene (e.g., having a number mean molecular weight about 300 to 200,000, having a melting point of about 50 to 150C), aliphatic hydrocarbon polymers (e.g., having an number mean molecular weight of about 500 to 2,000 and a melting point of about 50 to 130C), etc.; natural resins and modified ones thereof such as rosin, ester gum, hydrogenated rosin, etc., these materials can be used either alone or in combination.
  • polystyrene e.g., having a number mean molecular weight about 300 to 200,000, having a melting point of about 50 to 150C
  • aliphatic hydrocarbon polymers e.g., having an number mean molecular weight of about 500 to 2,000 and a melting point of about 50 to 130C
  • natural resins and modified ones thereof such as rosin, ester gum, hydrogenated rosin, etc., these materials can be used either alone or in combination
  • the adhesiveness-imparting agent must impart adhesivity to the mixture of the adhesiveness-imparting agent and the heat-sensitive substance upon mixing such that the mixture can adhere to support C at a temperature less than the heat-sensitive temperature of the heat-sensitive substance.
  • adhesiviness-imparting agent which can be used and which satisfy the abovedescribed requirement are a variety of rubbers and resins having a glass transition point or a softening point less than the heat-sensitive temperature of the heatsensitive substance, preferably a softening point or glass transition point of more than 5 less than the heatsensitive temperature from a practical standpoint.
  • rubbers such as natural rubber, polyisobutylene, butadiene rub ber, styrene-butadiene rubber, nitrile rubber, etc.; pol- 4 yvinyl chloride and the copolymers thereof (e.g., vinyl chloride-vinyl acetate, vinyl chloride-vinyl propionate, vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate-maleic anhydride, etc.); polyvinylidene chloride and copolymers thereof (e.g., vinylidene chloridemethyl acetate, vinylidene chloride-ethyl acetate, vinylidene chloride-acrylonitrile, vinylidene chloridevinyl chloride, etc.); polyvinyl acetate and the copolymers thereof (e.g., vinyl acetate-methyl acrylate, vinyl acetate-ethyl acrylate, etc.); polymethacrylates and
  • the amount of the adhesiveness-imparting agent employed can be appropriately selected depending upon the combination of the heat-sensitive substance and the adhesiveness-imparting agent used or the desired degree of adhesion strength between, e.g., the transfer layer B and support C.
  • the proportion of the adhesiveness-imparting agent in the heat-sensitive layer is about 1 to 90 percent by weight, preferably 5 to percent by weight and, more preferably, 20 to 50 percent by weight.
  • Transfer layer B can comprise two layers, i.e., a colored or ink-receptive layer B-l in contact with support A and a heat-sensitive layer B-2 in contact with support C.
  • a colored layer B-l those layers which are prepared by incorporating in the heat-sensitive composition a variety of dyes such as oil-soluble dyes (e.g., Oil Black, Oil Blue, Oil Red, Oil Yellow, etc.), water-soluble dyes (e.g., Methylene Blue, Congo Red, etc.), alcohol-soluble dyes (e.g., Rhodamine, Safranine, Victoria Green, Crystal Violet, etc.) and disperse dyes; various organic or inorganic pigments such as carbon black, titanium oxide, zinc oxide, red iron oxide, Phthalocyanide Blue and Phthalocyanine Green in a suitable amount, or those which are prepared by incorporating the coloring agent in thermoplastic resins such as polyvinyl chloride or a copolymer thereof, polyvinylidene chloride or a copo
  • the use of a colored or ink-receptive layer B-l which is heat-insensitive at a heat-sensitive temperature of the heat-sensitive layer B-2 has the advantage of providing better copied images, because an excessive fluidity of the transfer layer upon heat sensitization can be controlled and the adhesion strength between the support A and transfer layer B is made constant regardless of the temperature.
  • heat-sensitive substance which forms the conventional heat-sensitive transfer stratum comprising a transfer sheet and a receiving sheet
  • those heat-sensitive substances which do not exhibit any fluidity when the temperature is increased to a certain point but become fluid very quickly at the heat-sensitive temperature such as carnauba wax, are preferable.
  • transfer layer B comprising such a substance to support C
  • layer B will not adhere to support C at all, while when the temperature is increased to or higher than the heat-sensitive temperature, layer B adheres to support C so strongly, due to the fluidity of the heat-sensitive layer B, that the relative relationship in adhesion strength between these sheets is not satisfactory.
  • support A those supports which are not melted by the heat applied upon heat-sensitive duplication, such as paper, plastic films, and the like, can be used.
  • the support A can be appropriately selected depending upon the end-use application and the copying method employed. For example, in using the reflection exposure method as the copying method, support A must substantially transmit the light used.
  • An appropriate thickness of support A is a thickness of about 5 to 500 u, preferably 5 to u.
  • plastic films are plastic films of polypropylene, polyethylene, polyvinyl chloride; polyvinylidene chloride, polymethyl methacrylate, polyvinyl alcohol, polystyrene, polycarbonate, polyester, nylon, polyurethane, cellulose derivatives, and the like.
  • the choice of such a film will be dependent upon the purpose for use.
  • these sheets can be subjected to a surface treatment such as corona discharge, flame treatment, chemical treatment, etc. or a coating treatment to appropriately adjust the adhesivity of the support.
  • support C those examples suitable for support A, such as paper and plastic films can be selected depending upon the end use.
  • support C can be also subjected to, if desired, a surface treatment or a coating treatment as described previously for support A to appropriately adjust the adhesivity to the support C.
  • the absolute values of the adhesion strength between these supports are not particularly limited so long as the above-described relative and the condition in which the adhesion'strength between layer B and support C before heating is greater than zero are satisfied.
  • the peel strength between support A and transfer layer B is about 1 to g/cm, preferably 2 to 50 g/cm
  • the peel strength between layer B and support C is about 0.1 to 50 g/cm before heating and, after heating, is not less than about 2 g/cm, preferably not less than 20 g/cm as measured as described hereinafter.
  • the adhesion strength between layer B and support C is greater than zero. That is, transfer layer B adheres to support C with a certain degree of strength. Therefore, even when the thickness of the transfer layer is reduced, transfer can be effected in high yield and the material can be handled as one sheet. In addition, good copied images with no distortion and image broadening, which have been defects in conventional materials, can be obtained with stability.
  • transfer layer (B) itself or the adhesion strength between the colored or inkreceptive layer B-1 and the heat-sensitive layer B-2 must be greater than both the adhesion strength between transfer layer B and support C before heat sensitizing and the adhesion strength between transfer layer B and support A after heat sensitizing, whereas the cohesion strength must be of such degree that, upon separating support A from support C after copying, transfer layer B can be severed in an imagewise manner.
  • the transfer layer B can be formed as a discontinuous layer comprising fine particles, e.g., having a particle size ranging from about 0.1 to 100 1.1..
  • the process for producing the heat-sensitive recording material of the present invention which comprises support A, transfer layer B and support C comprises press-contacting support C onto the surface of transfer layer B formed on support A, each support having the property such that 1 before heating, the adhesion strength between support A and layer B is greater than the adhesion strength between transfer layer B and support C is greater than 0, and 2 this relation is changed by heating to a temperature not less than the heat sensitive temperature of the transfer layer B so that the adhesion strength between transfer layer B and support C becomes greater than the adhesion strength between support A and transfer layer B.
  • the transfer layer B comprises, at least at one one side in contact with support C, a heat-sensitive composition containing a major component a mixture of a heat-sensitive substance and an adhesiveness-imparting agent, this heat-sensitive substance exhibiting fluidity at a heat-sensitive temperature upon duplication and this adhesiveness-imparting agent imparting sufficient adhesiveness so that adherence to support C at a temperature less than the heat-sensitive temperature of the heat-sensitive substance occurs.
  • Support C is presscontacted onto the surface of heat-sensitive composition of the transfer layer B comprising the heat-sensitive composition at a temperature not higher than the heat-sensitive temperature of the heat-sensitive composition and at a temperature not lower than the adhesiveness-generating temperature thereof.
  • transfer layer B on support A can be employed, e.g., a method of applying a solution in water or an organic solvent, a dispersion in water or an organic solvent or a melt of the heat-sensitive composition to support A, followed by drying, or a method of forming a heat-sensitive composition layer on a separate temporary support, bringing this heatsensitive composition layer into contact with support A and then removing the temporary support.
  • organic solvents which can be used as described hereinbefore are alcohols such as methanol, ethanol, butanol and isopropyl alcohol, aromatic hydrocarbons such as toluene, benzene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, etc.
  • alcohols such as methanol, ethanol, butanol and isopropyl alcohol
  • aromatic hydrocarbons such as toluene, benzene and xylene
  • esters such as ethyl acetate and butyl acetate
  • ketones such as methyl ethyl ketone
  • transfer layer (B) comprising a colored or ink-receptive layer B-1 and a heatsensitive layer B-2
  • various methods can be employed, for example, a method of forming on support A a col- )I'Cd or ink-receptive layer B-1 and a heat-sensitive ayer B-2 in turn, a method of forming a heat-sensitive ayer 8-2 on a separate temporary support, bringing :his layer into contact with a colored or ink-receptive ayer 8-1 on support A previously formed, and then renoving the temporary support, or a method of forming )n a separate temporary support a heat-sensitive layer 3-2 and a colored or ink-receptive layer 8-1 in turn, )ringing it into contact with support A, and then renoving the temporary support.
  • the thickness of transfer layer B can be appropriately selected depending upon the end use purpose. However, generally the thickness ranges from about 0.3 to 18 u, more preferably 0.5 to 51.1.. in order to obtain good copied images, the transfer layer should be as thin as possible. Where the layer B comprises two layers, a suitable thickness for transfer layer B-l ranges from about 0.5 to 17 ,u. and for B-2 ranges from about 0.5 to 15 u, preferably 0.5 to 5 ,u..
  • transfer layer B comprises two layers, i.e., a colored or ink-receptive layer B-1 and a heat-sensitive layer
  • support C is press-contacted onto the surface of the transfer layer B comprising the heat-sensitive composition.
  • Thepress-contacting temperature should not be higher than the heat-sensitive temperature of the heat-sensitive composition and should not be lower than the adhesiveness-generating temperature.
  • a suitable press-contacting temperature can range from room temperature (about 20 30C) to about lC, preferably 50C to C.
  • the press-contacting temperature is not higher than the adhesiveness-generating temperature, adherence of transfer layer B to support C is impossible, while if the press-contacting temperature is not lower than the heat-sensitive temperature, the heat-sensitive substance is converted to a heat-sensitized state and the adhesion strength between the transfer layer B and support C becomes so great that relative relationship in the adhesion strength between the supports is not satisfied, resulting in a destruction of copying ability.
  • the adhesion strength between transfer layer B and support C can usually be about 0.1 to 50 g/cm, which can be highly controlled by selecting the press-contacting temperature, the application pressure, the time, the kind of adhesivenessimparting agent, the compounds amount, and the like.
  • Various press-contacting method can be employed, e.g., a method of passing two superposed supports through two press rollers maintained at an appropriate temperature, or a method of press-contacting the two supports to each other using parallel heating plates.
  • press-contacting support A, transfer layer B and support C can be different from that described above.
  • the combination of support A, transfer layer B and support C in the present invention includes, for example, polyester-(montan wax (this first listed component in the parentheses here and in the examples hereinafter being a heat sensitive substance), polyisoprene (this second listed component in the parentheses here and in the examples hereinafter being an adhesiveness-imparting agent))-cellulose acetate, polypropylene-(carnauba wax, styrene-butadiene copolymer rubber)-polyvinyl chloride, nylon- (montan wax-polybutadiene)polypropylene, nylon-(montan wax, low molecular weight polyethylene a non-crystalline polyester)-polystyrene, polypropylene-(montan wax, ethylene-vinyl acetate copolymer)-cellulose acetate, polyethylene terephthalate-(montan wax, polyvinyl butyral, ethylenevinyl acetate copolymer)-cellulose acetate, polyethylene ter
  • FIG. 1 is an enlarged cross-sectional view showing configuration 1 of the heat-sensitive copying material in accordance with the present invention, wherein A, B and C represent support A, transfer layer B and support C, respectively.
  • FIG. 2 is anenlarged cross-sectional view showing another configuration 1 of the heat-sensitive copying material in accordance with the present invention, wherein B-l represents a colored or ink-receptive layer 3-], and 8-2 a heat-sensitive layer B-2.
  • FIG. 3 shows the condition of copying employing a reflection exposure method using the heat-sensitive copying material 1 of the present invention, wherein numeral 2 denotes an original and 3 denotes an image area.
  • numeral 2 denotes an original
  • 3 denotes an image area.
  • image area 3 which travels in the order of support A and transfer layer B, and thus the temperature of transfer layer B corresponding to the image area reaches the heat-sensitive temperature.
  • the adhesion strength between portion B' and support C becomes greater than the adhesion strength between support A and portion B after heating, the former having been less than the latter before heating.
  • a positive copied image B corresponding to the image area is formed on support C while a negative copied image is formed on support A. Because no heating occurred in the non-image area, delamination occurs between transfer layer B and sup port C since the adhesion strength between support A and the transfer layer B is greater than the adhesion strength between transfer layer B and support C, whereas in the image area B, delamination occurs between support A and transfer layer B since the adhe- 10 sion strength between transfer layer B and support C is greater than the adhesion strength between support A and transfer layer B.
  • FIG. 5 shows the relationship between the press-contacting temperature and the adhesion strength between transfer layer B and support C in conducting the presscontacting at a pressure of 3 kg/cm for 2 seconds, in which a heat-sensitive composition provided on a polyethylene terephthalate film [support A is brought into Contact with a cellulose acetate film [support C with this composition containing montan wax as a heat-sensitive substance and ethylene-vinyl acetate copolymer (vinyl acetate content: 40 percent by weight) as an adhesiveness-imparting agent in a weight proportion of 30.
  • X represents the point at which adhesiveness appears, transfer layer B being capable of adhering to support C at a temperature higher than this temperature.
  • Y represents the heat sensitive temperature, the adhesion strength of transfer layer B to support C sharply increasing at a temperature higher than this temperature.
  • the adhesiveness-generating temperature of the heat-sensitive composition can be room temperature (about 20 30C) or less than that, it is preferably higher than room temperature to stabilize the adhesion strength with the lapse of time.
  • This temperature difference is preferably less than about 20C, e.g., a difference of 0C to 20C with a smaller difference being preferred.
  • adhesion strength between support A and transfer layer B can be varied somewhat depending upon the temperature as long as the adhesion strength is intermediate in strength between the adhesion strengths corresponding to Y and Z at least in the heat-sensitive temperature range Y to Z.
  • the adhesion strength between support A and transfer layer B can be adjusted by an appropriate selection of the material of support A or transfer layer B, by using a support A which has been surface treated and by a selection of laminating conditions of transfer layer B onto support A.
  • the heat-sensitive recording material of the present invention can be employed in various heat-sensitive copying or recording methods.
  • the heat-sensitive recording material of the present invention can be used in a reflection or transmission exposure method wherein an original having an image capable of absorbing infrared rays or visible light and generating heat is superposed on the heat-sensitive copying material and the assembly is irradiated with infrared rays or visible light; a stencil transmission copying method wherein a stencil bearing image areas capable of transmitting infrared rays or visible light and nonimage areas capable of reflecting infrared rays or visible light is superposed on the copying material containing a substance capable of absorbing infrared rays or visible light and generating heat, and infrared rays or visible light are applied thereto from the stencil side; or a heat-printing method using an imagewise heated plate or a heating pen.
  • a suitable exposure can be radiation of a wave length ranging from about 400 to 10,000 m preferably 700 to 3,000 mg, for an exposure time of less than 1 second, generally 0.5 to 0.001 second.
  • the heat-sensitive recording material of the invention can be used in the following applications.
  • It can be used as an intermediate original for use in diazo copying, for photographing film, or as an intermediate original for preparing an original printing plate, by using transparent plastic films as support A and support C and incorporating a coloring agent in the transfer layer or providing a colored layer.
  • It is usable as a lithographic printing master by using an ink-receptive or oleophilic light-sensitive substance such as wax or providing an ink-receptive layer and using, as support C, a support which, on at least the surface, is inkrepellent or can be rendered hydrophilic.
  • the heat-sensitive layer-coated surface of the thus prepared configuration of support A/colored layer B- l/heat-sensitive layer 8-2 was brought into contact with support C and passed through two press rollers heated to C to obtain a heat-sensitive copying material. Additionally, a comparative sample was prepared for comparison using montan wax alone as a heat-sensitive composition.
  • the peel strength between the layers as measured in a manner similar to ASTM D 1876-61T are as shown in Table l, but using 2 cm wide test sample and a head speed of 100 mm/min.
  • heat-sensitive copying materials obtained by the process of the present invention can be handled as one sheet and, when copying was conducted superposing the material on an original using a reflection exposure method using a commercially available heat-sensitive copying machine, black, negative and positive copied sheets were obtained in a simple copying operation.
  • the resulting copied sheets were favorably used as transparencies for an overhead projector, as an intermediate original for preparing a printing original plate and as an intermediate original for use in diazo copying.
  • EXAMPLE 3 In a manner analogous to Example 1 except for changing the composition of the heat-sensitive layer B-2 in Example I to (50 parts of carnauba wax 50 parts of Evaflex No. and changing support C and the press roll temperature as shown in Table 3, heatsensitive copying materials were obtained. The results thus obtained are shown in Table 3.
  • Table 3 tive copying material was obtained. With this sample, the peel strength between support A and layer B-l was 5 g/cm and the peel strength layerB-2 and support C was 0.5 g/cm.
  • the resulting heat-sensitive copying materials obtained in the present invention were handled as one sheet and showed good copying properties.
  • the sample in which vinylidene chloride copolymer-coated paper was used as support C was used as a document copy by conducting duplication according to a transmission exposure method.
  • Camauba Wax (mp. 84C) 35 parts Evaflex No. 40 35 Oil Black 2H8 30
  • a toluene solution (heated to 60C) of the transfer layer composition was coated onto support A in an amount of 2 g/m on a solid basis, and dried at 1 10C. Then, the transfer layer-coated surface was brought into contact with support C and pressure was applied 15 thereto at 65C to obtain an integral heat-sensitive copying material.
  • the peel strength between support A/layer B was 10 g/cm and the peel strength between layer B/support C was 1 g/cm.
  • This heat-sensitive copying material was easy to handle, showed good copying properties and was advantageously used for projection and as an intermediate original.
  • Support C an offset master for direct drawing (made by Fuji Photo Film Co., Ltd)
  • a heat-sensitive copying material was obtained for use as an offset master.
  • the peel strength between layer B and support C was 2 g/cm.
  • the surface of the resulting offset master plate having an ink-receptive wax image was desensitized and mounted on an offset printer. Upon conducting printing, good impressions were obtained.
  • EXAM PLE '7 Configuration Support A/Colored Layer B-l/Heatsensitive Layer B-Z/Support C Support (A) Stretched nylon film (15 1. thick) Support (C) Internally plasticized polyvinyl chloride film (100 ,u. thick) A toluene solution (heated to 60C) of the colored layer composition was coated onto support A in an amount of 1.5 g/m on a solid basis, and dried at l C. Then, a toluene solution (heated to 60C) of the heatsensitive layer composition was coated on the colored layer-coated surface in an amount of 2 g/m on a solid basis, and dried at l 10C. The heat-sensitive layercoated surface of the thus prepared constitution of support A/colored layer B-l/heat-sensitive layer B-2 was brought into contact with support C, pressure being applied thereto at 60C, to obtain an integral heat-sensitive copying material.
  • the peel strength between support A and layer 8-1 was 10 g/cm and the peel strength between layer B-2 and support C was 0.2 g/cm.
  • the resulting heat-sensitive copying material was easy to handle, showed good copying properties, and was advantageously used for projection and as an intermediate original.
  • a heat-sensitive recording material comprising a support (A) having thereon a transfer layer (B) and a support (C) in turn, said supports having the property that before heating the adhesion strength between the transfer layer (B) and the support (C) is smaller than the adhesion strength between the transfer layer (B) and support (A) and larger than 0.1 g/cm but, after heating to a temperature higher than the heat-sensitive temperature of the transfer layer (B), the adhesion strength between the transfer layer (B) and support (C) becomes greater than the adhesion strength between support (A) and transfer layer (B), and said transfer layer (B) comprising, at least on the side thereof in contact withsupport (C), a heat-sensitive composition containing as a major component a mixture of a heat-sensitive substance which becomes fluid at the heat-sensitive temperature of the heat-sensitive substance and an adhesiveness-imparting agent which can adhere to support (C) at a temperature not higher than the heat-sensitive temperature of said heat-sensitive substance.
  • thermosensitive recording material as described in claim ll, wherein said heat-sensitive substance is a wax and said adhesiveness-imparting agent is an ethylene-vinyl acetate copolymer.
  • a process for producing a heat-sensitive recording material which comprises applying support (A) and support (C) onto opposite sides of transfer layer (B) at a temperature, for support (C), not higher than the heat-sensitive temperature of said heat-sensitive composition of layer (B) and not lower than the adhesiveness-generating temperature of layer (B), said support (A), transfer layer (B) and support (C) having the property that before heating the adhesion strength between layer (B) and support (C) is less than the adhesion strength between support (A) and layer (B) and greater than 0.1 g/cm but, after heating to a temperature higher than the heat-sensitive temperature of the transfer layer (B), the adhesion strength between layer (B) and support (C) becomes greater than the adhesion strength between support (A) and layer (B), and said transfer layer (B) comprising at least at the side thereof in contact with support (C) a heat-sensitive composition containing as a major component a mixture of a heat-sensitive substance which becomes fluid at the heat-sensitive temperature of the heat-
  • transfer layer (B) by first forming a colored layer on support (A) and then forming a heat-sensitive layer thereon, and press-contacting support (C) onto the heat-sensitive layer of transfer layer (B).
  • transfer layer (B) by first forming an inkreceptive layer on support (A) and then forming a heat-sensitive layer on said ink-receptive layer and press-contacting support (C) onto the heat-sensitive layer of transfer layer (B).

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Manufacture Or Reproduction Of Printing Formes (AREA)
  • Laminated Bodies (AREA)
US454534A 1973-03-23 1974-03-25 Heat-sensitive recording material and process for producing same Expired - Lifetime US3924041A (en)

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4066810A (en) * 1975-04-01 1978-01-03 Toyo Soda Manufacturing Co., Ltd. Heat printing sheet and heat printing method
US4074003A (en) * 1974-11-05 1978-02-14 Weber Marking Systems, Inc. Thermographic stencil sheet, assembly and method of making an imaged stencil sheet
US4104067A (en) * 1974-01-29 1978-08-01 Agfa-Gevaert, Ag Polymer binder
US4131695A (en) * 1975-02-27 1978-12-26 Ciba-Geigy Corporation Azo color former containing heat-sensitive recording material
FR2395151A1 (fr) * 1977-06-23 1979-01-19 Minnesota Mining & Mfg Feuille colorante transferable par thermographie, avec un liant de caoutchouc
US4157412A (en) * 1977-10-25 1979-06-05 Minnesota Mining And Manufacturing Company Composite material for and method for forming graphics
US4173677A (en) * 1976-06-21 1979-11-06 Sekisui Kagaku Kogyo Kabushiki Kaisha Electro-thermosensitive recording materials
US4189171A (en) * 1977-03-01 1980-02-19 Sterling Drug Inc. Marking systems containing 3-aryl-3-heterylphthalides and 3,3-bis(heteryl)phthalides
US4244605A (en) * 1977-10-25 1981-01-13 Minnesota Mining And Manufacturing Company Material for forming graphics
EP0042954A2 (en) * 1980-06-26 1982-01-06 International Business Machines Corporation Correctable thermal transfer printing ribbon
US4349620A (en) * 1979-06-15 1982-09-14 E. I. Du Pont De Nemours And Company Solvent developable photoresist film
US4474898A (en) * 1982-07-16 1984-10-02 Mitsubishi Paper Mills, Ltd. Pressure-sensitive copying paper of "transfer to plain paper" type
US4576831A (en) * 1982-08-23 1986-03-18 Fuji Photo Film Co., Ltd. Process for producing heat-sensitive recording paper
WO1989010845A1 (en) * 1988-05-10 1989-11-16 Ncr Corporation Thermal transfer ribbon
US4981746A (en) * 1987-08-27 1991-01-01 Dai Nippon Insatsu Kabushiki Kaisha Heat-sensitive stencil sheet
US5024989A (en) * 1990-04-25 1991-06-18 Polaroid Corporation Process and materials for thermal imaging
US5155003A (en) * 1990-11-21 1992-10-13 Polaroid Corporation Thermal imaging medium
US5200297A (en) * 1990-11-21 1993-04-06 Polaroid Corporation Laminar thermal imaging mediums, containing polymeric stress-absorbing layer, actuatable in response to intense image-forming radiation
US5229247A (en) * 1991-11-27 1993-07-20 Polaroid Corporation Method of preparing a laminar thermal imaging medium capable of converting brief and intense radiation into heat
US5270073A (en) * 1988-12-02 1993-12-14 Konica Corporation Heat sensitive recording material, its manufacturing method and image forming process
US5275914A (en) * 1992-07-31 1994-01-04 Polaroid Corporation Laminar thermal imaging medium comprising an image-forming layer and two adhesive layers
US5279889A (en) * 1991-11-27 1994-01-18 Polaroid Corporation Imaging laminate with improved tab for delamination
US5342731A (en) * 1990-11-21 1994-08-30 Polaroid Corporation Laminar thermal imaging medium actuatable in response to intense image-forming radiation utilizing polymeric hardenable adhesive layer that reduces tendency for delamination
US5393639A (en) * 1992-11-25 1995-02-28 Polaroid Corporation Imaging laminate
US5514525A (en) * 1993-09-23 1996-05-07 Polaroid Corporation Method of preparing a laminar thermal imaging medium
US6245479B1 (en) 1986-12-09 2001-06-12 Polaroid Corporation Thermal imaging medium

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JPS54143303A (en) * 1978-04-28 1979-11-08 Nippon Telegraph & Telephone Method of making printing plate by thermal copying
JPS56126194A (en) * 1980-03-07 1981-10-02 Mitsubishi Paper Mills Ltd Fixing type heat-sensitive recording paper
JPS57105382A (en) * 1980-12-24 1982-06-30 Fujitsu Ltd Ink sheet
US4453839A (en) * 1982-06-15 1984-06-12 International Business Machines Corporation Laminated thermal transfer medium for lift-off correction and embodiment with resistive layer composition including lubricating contact graphite coating
JPS58133458U (ja) * 1982-12-27 1983-09-08 内外カ−ボンインキ株式会社 単体感圧複写紙
JPS59164187A (ja) * 1983-03-09 1984-09-17 Honshu Paper Co Ltd 熱転写記録媒体
JPS61162387A (ja) * 1985-01-11 1986-07-23 Alps Electric Co Ltd 感熱転写媒体
JPS61162394A (ja) * 1985-01-11 1986-07-23 Alps Electric Co Ltd 感熱転写媒体
JPS6227179A (ja) * 1985-07-29 1987-02-05 Oji Paper Co Ltd 熱転写プリンタ−用インクシ−ト
JPS6227180A (ja) * 1985-07-29 1987-02-05 Oji Paper Co Ltd 熱転写プリンタ−用インクシ−ト
JPH01258989A (ja) * 1988-04-08 1989-10-16 Union Kemikaa Kk 熱転写インクシート
GB9113427D0 (en) * 1991-06-21 1991-08-07 Erba Carlo Spa Penem derivatives
JP4910580B2 (ja) * 2006-09-07 2012-04-04 ヤマハ株式会社 フィルタ制御装置およびプログラム
JP4830736B2 (ja) * 2006-09-07 2011-12-07 ヤマハ株式会社 フィルタ制御装置およびプログラム

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US2769391A (en) * 1951-11-14 1956-11-06 Dick Co Ab Method of manufacturing imaged hectograph spirit master
US2974585A (en) * 1958-07-07 1961-03-14 Columbia Ribbon & Carbon Duplicating
US3311489A (en) * 1965-09-24 1967-03-28 Oxford Paper Co Transfer sheet and method of preparing
US3751318A (en) * 1971-01-25 1973-08-07 Columbia Ribbon Carbon Mfg Thermographic transfer process
US3852091A (en) * 1971-01-25 1974-12-03 Columbia Ribbon Carbon Mfg Thermographic transfer sheets

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US2769391A (en) * 1951-11-14 1956-11-06 Dick Co Ab Method of manufacturing imaged hectograph spirit master
US2974585A (en) * 1958-07-07 1961-03-14 Columbia Ribbon & Carbon Duplicating
US3311489A (en) * 1965-09-24 1967-03-28 Oxford Paper Co Transfer sheet and method of preparing
US3751318A (en) * 1971-01-25 1973-08-07 Columbia Ribbon Carbon Mfg Thermographic transfer process
US3852091A (en) * 1971-01-25 1974-12-03 Columbia Ribbon Carbon Mfg Thermographic transfer sheets

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4104067A (en) * 1974-01-29 1978-08-01 Agfa-Gevaert, Ag Polymer binder
US4074003A (en) * 1974-11-05 1978-02-14 Weber Marking Systems, Inc. Thermographic stencil sheet, assembly and method of making an imaged stencil sheet
US4131695A (en) * 1975-02-27 1978-12-26 Ciba-Geigy Corporation Azo color former containing heat-sensitive recording material
US4066810A (en) * 1975-04-01 1978-01-03 Toyo Soda Manufacturing Co., Ltd. Heat printing sheet and heat printing method
US4173677A (en) * 1976-06-21 1979-11-06 Sekisui Kagaku Kogyo Kabushiki Kaisha Electro-thermosensitive recording materials
US4189171A (en) * 1977-03-01 1980-02-19 Sterling Drug Inc. Marking systems containing 3-aryl-3-heterylphthalides and 3,3-bis(heteryl)phthalides
FR2395151A1 (fr) * 1977-06-23 1979-01-19 Minnesota Mining & Mfg Feuille colorante transferable par thermographie, avec un liant de caoutchouc
US4244605A (en) * 1977-10-25 1981-01-13 Minnesota Mining And Manufacturing Company Material for forming graphics
US4157412A (en) * 1977-10-25 1979-06-05 Minnesota Mining And Manufacturing Company Composite material for and method for forming graphics
US4349620A (en) * 1979-06-15 1982-09-14 E. I. Du Pont De Nemours And Company Solvent developable photoresist film
EP0042954A2 (en) * 1980-06-26 1982-01-06 International Business Machines Corporation Correctable thermal transfer printing ribbon
EP0042954A3 (en) * 1980-06-26 1982-07-14 International Business Machines Corporation Correctable thermal transfer printing ribbon
DK152346B (da) * 1980-06-26 1988-02-22 Ibm Farvebaand til korrigerbar, termisk overfoeringstrykning
US4474898A (en) * 1982-07-16 1984-10-02 Mitsubishi Paper Mills, Ltd. Pressure-sensitive copying paper of "transfer to plain paper" type
US4576831A (en) * 1982-08-23 1986-03-18 Fuji Photo Film Co., Ltd. Process for producing heat-sensitive recording paper
US6245479B1 (en) 1986-12-09 2001-06-12 Polaroid Corporation Thermal imaging medium
US4981746A (en) * 1987-08-27 1991-01-01 Dai Nippon Insatsu Kabushiki Kaisha Heat-sensitive stencil sheet
WO1989010845A1 (en) * 1988-05-10 1989-11-16 Ncr Corporation Thermal transfer ribbon
US5270073A (en) * 1988-12-02 1993-12-14 Konica Corporation Heat sensitive recording material, its manufacturing method and image forming process
US5024989A (en) * 1990-04-25 1991-06-18 Polaroid Corporation Process and materials for thermal imaging
US5342731A (en) * 1990-11-21 1994-08-30 Polaroid Corporation Laminar thermal imaging medium actuatable in response to intense image-forming radiation utilizing polymeric hardenable adhesive layer that reduces tendency for delamination
US5200297A (en) * 1990-11-21 1993-04-06 Polaroid Corporation Laminar thermal imaging mediums, containing polymeric stress-absorbing layer, actuatable in response to intense image-forming radiation
US5426014A (en) * 1990-11-21 1995-06-20 Polaroid Corporation Method for preparing a laminar thermal imaging medium actuatable in response to intense image-forming radiation including a polymeric hardenable adhesive layer that reduces delamination tendency
US5155003A (en) * 1990-11-21 1992-10-13 Polaroid Corporation Thermal imaging medium
US5229247A (en) * 1991-11-27 1993-07-20 Polaroid Corporation Method of preparing a laminar thermal imaging medium capable of converting brief and intense radiation into heat
US5279889A (en) * 1991-11-27 1994-01-18 Polaroid Corporation Imaging laminate with improved tab for delamination
US5328798A (en) * 1991-11-27 1994-07-12 Polaroid Corporation Laminar thermal imaging medium containing photohardenable adhesive layer and polymeric elastic and non-brittle barrier layer
US5389180A (en) * 1991-11-27 1995-02-14 Polaroid Corporation Imaging laminate with improved tab for delamination
US5275914A (en) * 1992-07-31 1994-01-04 Polaroid Corporation Laminar thermal imaging medium comprising an image-forming layer and two adhesive layers
US5387490A (en) * 1992-07-31 1995-02-07 Polaroid Corporation Method of preparing a laminar thermal imaging medium
US5393639A (en) * 1992-11-25 1995-02-28 Polaroid Corporation Imaging laminate
US5514525A (en) * 1993-09-23 1996-05-07 Polaroid Corporation Method of preparing a laminar thermal imaging medium
US5552259A (en) * 1993-09-23 1996-09-03 Polaroid Corporation Adhesive composition, and imaging medium comprising this adhesive composition

Also Published As

Publication number Publication date
JPS49122344A (ja) 1974-11-22
JPS5129949B2 (ja) 1976-08-28

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