EP0715964B2 - Wärmeempfindliches Aufzeichnungsmedium - Google Patents

Wärmeempfindliches Aufzeichnungsmedium Download PDF

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Publication number
EP0715964B2
EP0715964B2 EP95109213A EP95109213A EP0715964B2 EP 0715964 B2 EP0715964 B2 EP 0715964B2 EP 95109213 A EP95109213 A EP 95109213A EP 95109213 A EP95109213 A EP 95109213A EP 0715964 B2 EP0715964 B2 EP 0715964B2
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EP
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Prior art keywords
thermosensitive recording
recording medium
organic solvent
fluoran
protective layer
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English (en)
French (fr)
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EP0715964A2 (de
EP0715964A3 (de
EP0715964B1 (de
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Hiroshi Goto
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Ricoh Co Ltd
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Ricoh Co Ltd
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Priority claimed from JP6331852A external-priority patent/JPH07223364A/ja
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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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds

Definitions

  • the present invention relates to a thermosensitive recording medium which uses a color development reaction occurring between an electron donative coloration compound and an electron acceptor compound.
  • the electron donative coloration compound may be simply referred to as a color coupler, hereinafter.
  • the electron acceptor compound may be referred to as a developer, hereinafter.
  • the present invention relates to the thermosensitive recording medium which is useful as a film sheet for image forming in an overhead projector (which will be abbreviated to an OHP, hereinafter), as a film sheet for image forming in a CAD (computer aided designing, and as a film for a video printer.
  • OHP overhead projector
  • thermosensitive recording medium which uses the color development reaction occurring between the color coupler and the developer has been well-known.
  • thermosensitive recording medium for the OHP or as a a diazo mother print or as a design drawing.
  • Japanese Patent Application No.61-121875 and Japanese Laid-Open Application No.1-99873 propose transparent thermosensitive recording media, it being possible that a thermal head directly prints on the transparent thermosensitive recording media.
  • a problem is present in manufacturing the transparent thermosensitive recording media.
  • the color coupler is micro-capsulated, while the developer is dissolved in organic solvent which is slightly soluble or insoluble in water.
  • emulsion dispersion substance is obtained and an application liquid consisting of emulsion dispersion substance is thus obtained.
  • the thus-obtained application liquid is applied or coated on a transparent carrier and thus the transparent thermosensitive recording medium is obtained.
  • the manufacturing process is considerably complicate.
  • another problem of the transparent thermosensitive recording media is that the transparency of the transparent thermosensitive recording media is insufficient.
  • An object of the present invention is to solve the above-mentioned problems present in the prior art and thus to provide the thermosensitive recording media, which use the reaction occurring between the color coupler and the developer and which has improved thermosensitivity, an improved color development image forming property, and, in particular, improved transparency.
  • an irreversible thermosensitive recording medium as defined in claim 1 which medium has a thermosensitive recording layer on a carrier body.
  • the thermosensitive recording layer has main ingredients consisting of the electron donative coloration compound and the electron acceptor compound together with binder resin.
  • the thermosensitive recording medium includes 500 through 5,000 ppm of organic solvent.
  • the organic solvent has a dielectric constant of 2.0 through 25.0 at 20°C, and has vapor pressure of 1333 to 26660 Pa (10 through 200 mmHg) at 20°C.
  • the irreversible thermosensitive recording medium has the thermosensitive recording layer on the carrier body, a main ingredient of the carrier body being resin.
  • the thermosensitive recording layer has main ingredients consisting of the electron donative coloration compound and the electron acceptor compound together with binder resin.
  • the thermosensitive recording medium includes 500 through 5,000 ppm of organic solvent.
  • the organic solvent has dielectric constant of 2.0 through 25.0 at 20°C, and has vapor pressure of 1333 to 26660 Pa (10 through 200 mmHg) at 20°C.
  • thermosensitive recording medium A major amount of the organic solvent included in the thermosensitive recording medium according to the present invention is present in the thermosensitive recording layer.
  • a protective layer of the recording medium has an amount of the organic solvent present therein.
  • making the organic solvent be included in the thermosensitive layer is effective for controlling the optical density of a fresh recording medium to be low.
  • the carrier body is a carrier which is insoluble in the organic solvent, little amount of the organic solvent is present in the carrier body. Therefore, a content of the organic solvent included in the recording medium accordingly tells a content of the organic solvent which is included in the thermosensitive layer and protective layer but is not included in the carrier body.
  • a considerably large portion of cause which results in the optical density of a fresh thermosensitive recording medium according to the present invention to be high depends on the organic solvent included in the thermosensitive layer and protective layer. If the content of the organic solvent is lower than the above-mentioned 500 ppm, the optical density of a fresh recording medium is relatively high so that no significant effect can be obtained even if the above-mentioned aging is performed thereon. Further, if the content of the organic solvent exceeds the above-mentioned 5,000 ppm, it is possible to control the optical density of a fresh recording medium to be low.
  • the organic solvent exceeds the above-mentioned 5,000 ppm, an image, which has been obtained as a result of color development image forming on the recording medium, can not be well preserved. Therefore, the content of the organic solvent is limited within an extent between 500 through 5,000 ppm.
  • the present invention uses the organic solvent having dielectric constant of 2.0 through 25.0 at 20°C, and having vapor pressure of 1333 to 26660 Pa (10 through 200 mmHg) at 20°C, as will be mentioned later.
  • thermosensitive recording medium will now be described in detail. It is noted that the above-described effect obtained from the organic solvent remarkably appears in particular if the thermosensitive recording medium is an irreversible transparent thermosensitive recording medium which is obtained as a result of stacking of recording layer and protective layer on a transparent one of the carrier body. The above-mentioned irreversible transparent thermosensitive recording medium will now be described.
  • the color coupler used in the present invention is dye precursor which is colorless or light color in itself and is not specifically limited.
  • Well-known compounds which can be used for the color coupler are, for example: triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, leuco auramine compounds, rhodamine lactam compounds, spiro pyran compounds, indolino phthalide compounds.
  • the fluoran compounds are specially preferable to be used as the color coupler used in the present invention. Specific examples are listed below:
  • Organic phosphorus compounds are used as the developer for color developing of the above-mentioned color coupler in the present invention.
  • phosphonic acid expressed by the following general chemical formula (I) or (II) is used: (In the above formula, the sign 'R' is referred alkyl group having 16 through 24 carbons.)
  • the developer which developer consists of a single compound or consisting of mixture of a plural types of compounds.
  • the color coupler is used, which color coupler may consist of a single compound or mixture of a plural types of compounds.
  • a substance having an index of refraction of an extent between 1.45 through 1.60 in normal temperature and having a hydroxyl group in its molecule is used as the binder resin used in the thermosensitive recording layer.
  • binder resin examples include poly(vinyl butyral), poly(vinyl acetal), epoxy resin, ethyl cellulose, cellulose acetate, hydroxy propyl cellulose, ethyl hydroxy cellulose, and so forth.
  • thermosensitive recording layer in order to improve a coating property or a recording property, for example, dispersing agent, high-molecular cationic electrically conductive agent, color development image stabilizing agent, or the like may be included in the thermosensitive recording layer.
  • thermosensitive recording layer may be included in the thermosensitive recording layer.
  • Ultraviolet ray absorbing agent, oxidation inhibiter, quencher of singlet oxygen, quencher of superoxido anion may be used as the above-mentioned light stabilization agent used in the present invention.
  • the carrier body of the thermosensitive recording medium according to the present invention is a carrier body mainly formed of a synthetic paper sheet, a metallic foil, and/or synthetic resin.
  • a transparent or opaque carrier body is used as the carrier body, the transparent or opaque carrier body consisting of one of a polyester film such as that of poly(ethylene terephthalate), poly(butylene terephthalate), or the like, a cellulose derivative film such as that of cellulose triacetate, or the like, a polyolefine film such as that of polypropylene, polyethylene, or the like, and a polystyrene film.
  • the transparent or opaque carrier body is obtained as a result of pasting some of the above-listed films with one another.
  • thermosensitive recording medium which does not have the protective layer therein, of the thermosensitive recording medium according to the present invention will now be described.
  • the developer is dispersed in the binder resin.
  • the dispersion is not uniform in a surface portion and an internal portion of the layer.
  • voids are present in the recording layer and thus air present in the voids has an index of refraction different from an index of refraction of the recording layer itself and the refraction index difference causes light scattering.
  • the recording layer is opaque.
  • Such voids may be formed, for example, as a result of the organic solvent present in the recording layer being transformed into gas and then removed therefrom, or as a result of a space being defined between adjacent developer particles.
  • the voids present in and unevenness present on the recording layer are eliminated and thus the surface thereof is smoothed.
  • the above-mentioned resin has an index of refraction of 1.45 through 1.60 in normal temperature, the extent of which index is the same as that of the index of the binder resin.
  • the protective layer is formed. The thus-formed protective layer not only contributes for making the recording medium be transparent but also has great effect to improve a chemical resistant property, a water proof property, a friction resistant property, a light proof property and a head matching property.
  • the good head matching property means a state of a surface of the recording medium such as that a thermal head can smoothly slides on the surface of the recording medium. Further, the good head matching property means a state of the surface of the recording medium such that no sticking occurs, that is, the thermal head running on the surface of the recording medium does not cause the protective layer to be shaped nor cause the protective layer to crack.
  • the protective layer is an essential element to obtain the transparent thermosensitive recording medium having a superior property.
  • the following elements are included: a coat mainly formed of watersoluble resin and hydrophobic resin, a coat mainly formed of ultraviolet ray setting resin or electron ray setting resin, and so forth.
  • a coat mainly formed of watersoluble resin and hydrophobic resin By forming such a protective layer, it is possible to obtain the recording medium which does not create substantial problems even after coming into contact with organic solvent, plasticizer, oil, sweat, water or the like.
  • organic or inorganic filler and lubricant be included in the protective layer, it is possible to eliminate problems of sticking which may occur as a result of a thermal head or the like coming into contact with the recording medium. Therefore, it is possible to obtain the thermosensitive recording medium having improved reliability and an improved head matching property.
  • the color coupler used in the present invention is not specifically limited and may consist of one which was described in the description of the transparent thermosensitive recording medium.
  • Compounds which may be used as the developer are, other than the organic phosphorus compounds described above, phenyl compounds which are relatively unlikely to be dissolved in the organic solvent.
  • Specific examples thereof are derivatives of bis(hydroxyphenyl) acetic acid and derivatives of gallic acid.
  • Substance to be used as the binder resin used in the thermosensitive recording medium may consist of resin which is dissolved in the organic solvent and becomes a film when it is coated and dried.
  • poly(vinyl chloride) resin ethylene - vinyl acetate copolymer, polystyrene, poly(vinyl acetate) resin, vinyl chloride- acetate copolymer, saturated polyester resin, polyurethan acryl resin, polycarbonate resin, and so forth.
  • poly(vinyl chloride) resin ethylene - vinyl acetate copolymer
  • polystyrene poly(vinyl acetate) resin
  • vinyl chloride- acetate copolymer vinyl chloride- acetate copolymer
  • saturated polyester resin polyurethan acryl resin
  • polyurethan acryl resin polycarbonate resin
  • thermosensitive recording medium it is possible to add additives which were described in the description of the transparent thermosensitive recording medium, if it is necessary.
  • the carrier body used in the present invention may consist of not only the transparent carrier body described above but also a synthesis paper sheet using a resin film, a white polyester film having inorganic substance added thereto, a foamed white polyester film or the like.
  • the protective layer in the present invention may also use the resins and additives described in the description of the transparent thermosensitive recording medium.
  • the organic solvent for dissolving the binder resin has dielectric constant of 2.0 through 25.0 at 20°C, and has vapour pressure of 1333 to 26660 Pa (10 through 200 mmHg) at 20°C.
  • Specific examples of the organic solvent are listed below: kinds of ether such as dibutyl ether, isopropyl ether, dioxane, tetrahydrofuran, or the like, kinds of ketone such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone or the like, kinds of ester such ethyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate, or the like, kinds of aromatic hydrocarbon such as benzene, toluene, xylene, or the like. In practice, one of them alone is used as the organic solvent for dissolving the binder resin, or combination of
  • an extent of coating thickness mentioned below is considered. That is, if the extent of coating thickness is such that the protective layer formed on the recording medium as a result of coating has a thickness in an extent between 0.1 ⁇ m and 20 ⁇ m, preferably a thickness in an extent between 0.5 ⁇ m and 10 ⁇ m, the desirable performance of the protective layer can be sufficiently exhibited and thus the desirable performance of the recording medium can be ensured.
  • thermosensitive recording medium according to the present invention can be used for any image forming method of those such as a method using a heat pen, a method using a thermal head, a method using laser heating, a method using a thermal etching technique using light and so forth.
  • the image forming method, for which the thermosensitive recording medium according to the present invention can be used is not specifically limited to the above-mentioned methods.
  • the thermosensitive recording medium according to the present invention is useful for being used in the image forming method using the thermal head and that using the thermal etching technique using light (white light including visible light and infrared light).
  • FIG.1 shows evaluation results obtained from samples in embodiments according to the present invention and comparison examples.
  • each of units 'part' and '%' is that of weight basis.
  • Substance having the following composition will be dispersed through a portable ball mill and thus an average particle diameter of octadecyl phosphonic acid reaches approximately 0.4 ⁇ m: 3-dimethylamino-6-methyl-7-anilino fluoran 10 parts, octadecyl phosphonic acid 30 parts, poly(vinyl butyral) (Denka butyral #3000-2, manufactured by Denki Kagaku Kogyo Company) 15 parts, and toluene/methyl ethyl ketone (1/1) mixture liquid 285 parts.
  • a coating liquid of the recording layer is thus prepared.
  • the thus-prepared coating liquid of the recording layer is coated on a foamed white polyethylene film of 100 ⁇ m using a wire bar so as to result in a coated film thickness of approximately 6.0 ⁇ m, and the thus-coated liquid is dried.
  • the thermosensitive recording medium is produced. While drying, the conditions in which the above-mentioned coated liquid is dried to provide the recording layer are adjusted so that a content of the organic solvent in the recording layer is approximately 1,000 ppm.
  • Substance having the following composition will be dispersed through a portable ball mill and thus an average mote diameter of bis(P-hydroxyphenyl) methyl ester acetate reaches approximately 1.2 ⁇ m: 3-di-n-butylamino-6-methyl-7-anilino fluoran 10 parts, bis(P-hydroxyphenyl) methyl ester acetate 30 parts, poly(vinyl acetate) 25 parts, and xylene/methyl isobutyl ketone (7/3) mixture liquid 275 parts.
  • a coating liquid of the recording layer is thus prepared.
  • a coating liquid of the protective layer is prepared: butyl acetate solution having therein 75% urethane acrylate ultraviolet ray setting resin, which consists of 25% of the butyl acetate solution and 75% of urethane acrylate ultraviolet ray setting resin (Unidick C7-157 manufactured by Dainippon Ink Kagaku Company) 100 parts, xylene solution having therein 52% silicon resin, which consists of 48% of xylene solution and 52% of silicone resin (Byk-344 manufactured by Big Chemy Japan Company) 4.5 parts, and ethyl acetate 50 parts.
  • urethane acrylate ultraviolet ray setting resin which consists of 25% of the butyl acetate solution and 75% of urethane acrylate ultraviolet ray setting resin (Unidick C7-157 manufactured by Dainippon Ink Kagaku Company) 100 parts
  • xylene solution having therein 52% silicon resin which consists of 48% of xylene solution and 52% of silicone resin (B
  • the transparent thermosensitive recording medium is produced as described below.
  • the coating liquid of the recording layer is coated on a transparent polyester film of 100 ⁇ m using a wire bar so as to result in a coated film thickness of approximately 7.5 ⁇ m, and the thus-coated liquid is dried.
  • the thermosensitive recording layer is formed.
  • thermosensitive recording layer upon the thus-formed thermosensitive recording layer, the coating liquid of the protective layer is coated using a wire bar and dried. After that, a thus-coated and dried film is cured using an 80 W/cm ultraviolet ray lamp. Thus, a coated film thickness of approximately 5 ⁇ m constituting the protective layer is formed on the thermosensitive recording layer. Thus, the transparent thermosensitive recording medium is produced.
  • the conditions in which the above-mentioned coated liquids are dried to provide the recording layer and protective layer are adjusted so that a content of the organic solvent in the recording layer and protective layer is approximately 2,000 ppm.
  • Substance having the following composition will be dispersed through a portable ball mill and thus an average particle diameter of octadecyl phosphonic acid reaches approximately 0.3 ⁇ m (not including a particle having a diameter thereof equal to or larger than 1 ⁇ m): 3-diethylamino-6-methyl-7-anilino fluoran 10 parts, octadecyl phosphonic acid 30 parts, poly(vinyl butyral) (Denka butyral #3000-2, manufactured by Denki Kagaku Kogyo Company) 15 parts, and toluene/methyl ethyl ketone (1/1) mixture liquid 285 parts. A coating liquid of the recording layer is thus prepared.
  • a coating liquid of the protective layer is prepared: 75% butyl acetate solution having therein urethane acrylate ultraviolet ray setting resin (Unidick C7-157 manufactured by Dainippon Ink Kagaku Company) 100 parts, 52% xylene solution having therein silicone resin (Byk-344 manufactured by Big Chemy Japan Company) 4 parts, and ethyl acetate 50 parts.
  • the transparent thermosensitive recording medium is produced as described below.
  • the coating liquid of the recording layer is coated on a transparent polyester film of 100 ⁇ m using a wire bar so as to result in a coated film thickness of approximately 6.0 ⁇ m, and the thus-coated liquid is dried.
  • the thermosensitive recording layer is formed.
  • thermosensitive recording layer upon the thus-formed thermosensitive recording layer, the coating liquid of the protective layer is coated using a wire bar and dried by heating. After that, a thus-coated and dried film is cured using an 80 W/cm ultraviolet ray lamp. Thus, a coated film thickness of approximately 5 ⁇ m constituting the protective layer is formed on the thermosensitive recording layer. Thus, the transparent thermosensitive recording medium is produced.
  • the conditions in which the above-mentioned coated liquids are dried to provide the recording layer and protective layer are adjusted so that a content of the organic solvent in the recording layer and protective layer is approximately 2,200 ppm.
  • thermosensitive recording medium in the above-described third embodiment is then preserved in a thermostat for 12 hours under 40°C.
  • the transparent thermosensitive recording medium in the fourth embodiment is obtained.
  • the coating liquids are prepared and the recording medium is produced.
  • the conditions in which the above-mentioned coated liquids are dried to provide the recording layer and protective layer are differently adjusted so that a content of the organic solvent in the recording layer and protective layer is approximately 4,300 ppm.
  • the transparent thermosensitive recording medium in the fifth embodiment is produced.
  • the transparent thermosensitive recording medium in the above-described fifth embodiment is then preserved in a thermostat for 12 hours under 40°C.
  • the transparent thermosensitive recording medium in the sixth embodiment is obtained.
  • the coating liquid is prepared and the recording medium is produced.
  • the conditions in which the above-mentioned coated liquid is dried to provide the recording layer are differently adjusted so that a content of the organic solvent in the recording layer is approximately 350 ppm.
  • the thermosensitive recording medium in the first comparison example is produced.
  • the coating liquids are prepared and the recording medium is produced.
  • the conditions in which the above-mentioned coated liquids are dried to provide the recording layer and protective layer are differently adjusted so that a content of the organic solvent in the recording layer and protective layer is approximately 450 ppm.
  • the transparent thermosensitive recording medium in the second comparison example is produced.
  • the coating liquids are prepared and the recording medium is produced.
  • the conditions in which the above-mentioned coated liquids are dried to provide the recording layer and protective layer are differently adjusted so that a content of the organic solvent in the recording layer and protective layer is approximately 480 ppm.
  • the transparent thermosensitive recording medium in the third comparison example is produced.
  • thermosensitive recording medium in the above-described third comparison example is then preserved in a thermostat for 12 hours under 40°C.
  • the transparent thermosensitive recording medium in the fourth comparison example is obtained.
  • the coating liquids are prepared and the recording medium is produced.
  • the conditions in which the above-mentioned coated liquids are dried to provide the recording layer and protective layer are differently adjusted so that a content of the organic solvent in the recording layer and protective layer is approximately 6,000 ppm.
  • the transparent thermosensitive recording medium in the fifth comparison example is produced.
  • the coating liquids are prepared and the recording medium is produced, except for the following matter:
  • toluene/methyl ethyl keton (1/1) mixture liquid toluene/ethanol (with a dielectric constant of 27.0 at 20°C and with a vapour pressure of 5866 Pa (44 mmHg) at 20°C) (1/1) mixture liquid is used.
  • the thermosensitive recording medium in the sixth comparison example is produced.
  • the coating liquids are prepared and the recording medium is produced, except for the following matter:
  • n-hexane with a dielectric constant of 1.85 at 20°C and with a vapour pressure of 20660 Pa (155 mmHg) at 20°C)
  • n-butanol with a dielectric constant of 19.2 at 20°C and with a vapour pressure of 733 Pa (5.5 mmHg) at 20°C
  • thermosensitive recording medium in the seventh comparison example is produced.
  • thermosensitive recording medium in each of the above-described first, second, third, fourth, fifth, sixth embodiments according to the present invention, and first, second, third, fourth, and fifth comparison examples.
  • the evaluation test is such that a printing device using a thermal head of 8 dots/mm prints an image on the thermosensitive recording medium. In the printing, energy is applied to the recording medium such that power of 0.7 W/dot is applied and the power is applied for each pulse span of 0.5 msec. Items of the evaluation test will now be described.
  • An image part (optical) density and a background part (optical) density are measured immediately after the printing using a transmission density meter, X-Rite 310TR (manufactured by XRITE COMPANY).
  • thermosensitive recording medium a fixed content of the organic solvent is included in the recording layer and protective layer of the thermosensitive recording medium.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (8)

  1. Irreversibles wärmeempfindliches Aufzeichnungsmaterial, umfassend einen Trägerkörper und eine auf dem Trägerkörper vorgesehene wärmeempfindliche Aufzeichnungsschicht;
    wobei das wärmeempfindliche Aufzeichnungsmaterial dadurch gekennzeichnet ist, dass:
    die wärmeempfindliche Aufzeichnungsschicht hauptsächlich aus Elektronen abgebender Farbgebungs-Verbindung und Elektronenakzeptor-Verbindung zusammen mit Bindemittel-Harz zusammengesetzt ist; und
    das wärmeempfindliche Aufzeichnungsmaterial 500 bis 5000 ppm organisches Lösungsmittel einschließt,
    wobei das organische Lösungsmittel eine Dielektrizitätskonstante von 2,0 bis 25,0 bei 20°C aufweist und einen Dampfdruck bei 20°C von 1333 bis 26660 Pa (10 bis 200 mmHg) aufweist.
  2. Wärmeempfindliches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass das wärmeempfindliche Aufzeichnungsmaterial weiter eine auf der wärmeempfindlichen Aufzeichnungsschicht vorgesehene Schutzschicht umfasst.
  3. Wärmeempfindliches Aufzeichnungsmaterial nach Anspruch 2, dadurch gekennzeichnet, dass das organische Lösungsmittel in der wärmeempfindlichen Schicht und der Schutzschicht eingeschlossen ist.
  4. Wärmeempfindliches Aufzeichnungsmaterial nach den Ansprüchen 1 - 3, dadurch gekennzeichnet, dass:
    die Elektronenakzeptor-Verbindung eine organische Phosphor-Verbindung umfasst, die ausgedrückt wird durch eine allgemeine Formel (I):
    Figure 00130001
    wobei R eine Alkylgruppe mit 16 bis 24 Kohlenstoffatomen darstellt, oder eine allgemeine Formel (II):
    Figure 00140001
    wobei R1 eine Alkylgruppe mit 13 bis 23 Kohlenstoffatomen darstellt.
  5. Wärmeempfindliches Aufzeichnungsmaterial nach den Ansprüchen 1 - 4, dadurch gekennzeichnet, dass der Trägerkörper in dem organischen Lösungsmittel unlöslich ist.
  6. Wärmeempfindliches Aufzeichnungsmaterial nach den Ansprüchen 1 - 5, dadurch gekennzeichnet, dass der Trägerkörper eine transparente Harzfolie mit einem Brechungsindex bei Normaltemperatur zwischen 1,45 und 1,60 umfasst.
  7. Wärmeempfindliches Aufzeichnungsmaterial nach den Ansprüchen 1 - 6, dadurch gekennzeichnet, dass das Bindemittel-Harz der wärmeempfindlichen Aufzeichnungsschicht ein transparentes Harz mit einem Brechungsindex bei Normaltemperatur zwischen 1,45 und 1,60, das in seinem Molekül eine Hydroxylgruppe oder eine Carboxylgruppe aufweist, ist.
  8. Wärmeempfindliches Aufzeichnungsmaterial nach den Ansprüchen 2 - 7, dadurch gekennzeichnet, dass die Schutzschicht ein Harz als Hauptkomponente derselben umfasst, wobei das Harz einen Brechungsindex bei Normaltemperatur zwischen 1,45 und 1,60 aufweist.
EP95109213A 1994-12-09 1995-06-14 Wärmeempfindliches Aufzeichnungsmedium Expired - Lifetime EP0715964B2 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP331852/94 1994-12-09
JP33185294 1994-12-09
JP6331852A JPH07223364A (ja) 1993-12-15 1994-12-09 感熱記録媒体
US355974 1994-12-14
US08/355,974 US5532201A (en) 1993-12-15 1994-12-14 Thermosensitive recording medium

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EP0715964A2 EP0715964A2 (de) 1996-06-12
EP0715964A3 EP0715964A3 (de) 1996-07-10
EP0715964B1 EP0715964B1 (de) 1998-09-09
EP0715964B2 true EP0715964B2 (de) 2002-10-30

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63315290A (ja) † 1987-06-18 1988-12-22 Toppan Printing Co Ltd 感熱記録材
EP0492628A1 (de) † 1990-12-26 1992-07-01 Ricoh Company, Ltd Reversible wärmeempfindliche Aufzeichnungszusammensetzung, Aufzeichnungsmedium, Aufzeichnungsverfahren und Anzeigevorrichtung, die das Aufzeichnungsmedium verwendet
JPH05104859A (ja) † 1991-10-15 1993-04-27 Ricoh Co Ltd 透明感熱記録媒体

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH659975A5 (en) * 1983-05-16 1987-03-13 Ciba Geigy Ag Pressure-sensitive or heat-sensitive recording material
JPS61121875A (ja) 1984-11-12 1986-06-09 チヤネルロツク　インコ−ポレイテツド すべり接続プライヤ
JPH074986B2 (ja) * 1986-05-26 1995-01-25 富士写真フイルム株式会社 感熱記録材料
DE3781259T2 (de) * 1986-12-25 1993-03-11 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur herstellung eines waermeempfindlichen aufzeichnungsmaterials.
JPH0825335B2 (ja) 1987-10-13 1996-03-13 富士写真フイルム株式会社 感熱記録材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63315290A (ja) † 1987-06-18 1988-12-22 Toppan Printing Co Ltd 感熱記録材
EP0492628A1 (de) † 1990-12-26 1992-07-01 Ricoh Company, Ltd Reversible wärmeempfindliche Aufzeichnungszusammensetzung, Aufzeichnungsmedium, Aufzeichnungsverfahren und Anzeigevorrichtung, die das Aufzeichnungsmedium verwendet
JPH05104859A (ja) † 1991-10-15 1993-04-27 Ricoh Co Ltd 透明感熱記録媒体

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DE69504627T3 (de) 2003-02-27
DE69504627T2 (de) 1999-03-11
EP0715964A2 (de) 1996-06-12
DE69504627D1 (de) 1998-10-15
EP0715964A3 (de) 1996-07-10
EP0715964B1 (de) 1998-09-09

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