EP1040933B1 - Beidseitiges Aufzeichnungsmedium - Google Patents

Beidseitiges Aufzeichnungsmedium Download PDF

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Publication number
EP1040933B1
EP1040933B1 EP20000302517 EP00302517A EP1040933B1 EP 1040933 B1 EP1040933 B1 EP 1040933B1 EP 20000302517 EP20000302517 EP 20000302517 EP 00302517 A EP00302517 A EP 00302517A EP 1040933 B1 EP1040933 B1 EP 1040933B1
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EP
European Patent Office
Prior art keywords
polyvinyl alcohol
recording medium
double
heat
recording
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP20000302517
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English (en)
French (fr)
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EP1040933A1 (de
Inventor
Masaki Nishimura
Hiromasa Kondo
Takaaki Koro
Koichi Ishida
Ritsuo Mando
Hideyuki Suzuki
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New Oji Paper Co Ltd
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Oji Paper Co Ltd
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Classifications

    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • 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
    • 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
    • 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
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the 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
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B41M5/443—Silicon-containing polymers, e.g. silicones, siloxanes

Definitions

  • the present invention relates to a recording medium, more particularly to a double-side recording medium, one side of which has an ink jet recording ability and the other side of which has a heat-sensitive recording ability.
  • the ink jet recording system which makes use of a water-base ink has been applied to printers for terminal devices, facsimiles, plotters, ledger paper printing devices or the like, because of such reasons that the system does not generate so much noises during recording operations, makes it easy to carry out color printing or recording and permits high-speed recording. Since the wood free paper and coated paper used in the usual printing are inferior in ink-absorptive capacity, printed ink remains on the paper surface over a long period of time without being dried, this in turn leads to the contamination of the printing device and printed sheets and/or the contamination of printed images and therefore, such paper is less practicable.
  • J.P. KOKAI Japanese UnExamined Patent Publication
  • base paper in which an urea-formalin resin is incorporated with a water-soluble polymer
  • J.P. KOKAI No. Sho 53-49113 there has also been disclosed recording paper whose surface is coated with a variety of porous inorganic pigments including amorphous silica in order to improve the color-developing ability of an ink and reproducibility of images.
  • J.P. KOKAI No. Hei 4-16379 proposes the use of at least two porous pigments, which have different fine pore sizes, in combination and this would be successful to some extent.
  • the ink jet recording method is one in which recording is performed by impacting ejected ink drops against the surface of a recording medium. Accordingly, the impact precision should be improved in order to obtain recorded materials having high precision and excellent reproducibility. For this reason, the direction, in which an ink is discharged from a printer head, is limited to that along which the gravity acts on it, i.e., the direction from upward to downward. Thus, it is difficult to simultaneously record the both sides of a recording medium. In addition, it is possible to once record one side of a recording medium, to have then the recording medium turned over and to thus record the other side of the medium. However, this never allows the speeding-up of the printing or recording operations and rather makes the mechanism of the printer more complicated and also makes the size of the printer larger. Therefore, this method is not practically acceptable.
  • the high-speed recording technique is badly needed in cases where a large quantity of double-side printed materials should be printed, while taking into consideration the practical method of using printers.
  • This corresponds to the cases where New Year's cards, letters of inquiry after health in the hot season, invitation cards, and greeting cards are printed in general family.
  • various designs and/or letters are recorded on the back side thereof, but only addresses are printed on the front face thereof and therefore, monochromatic printing is sufficient in most of the cases. If these printing operations are carried out simply by an existing ink jet printer, however, all the printing medium should be reset on the printer after the completion of the printing operation on one side of the medium to thus record images on the other side thereof.
  • Another object of the present invention is to provide a double side recording medium, which does not cause any bleeding on a heat-sensitive recording layer due to the solvent present in an ink jet ink, which does not cause any discoloration of the printed letters on the heat-sensitive recording layer and which permits both heat-sensitive recording and ink jet recording.
  • the inventors of this invention have conducted various studies to achieve the foregoing objects, have found a recording medium, which can satisfy the foregoing requirements.
  • the present invention provides a double-side recording medium, according to claims 1 to 9 of this document.
  • pulp for paper used in the present invention as the substrate, there may be listed.
  • chemical pulp such as soft-wood bleached kraft pulp (hereunder referred to as "NBKP") and hardwood bleached kraft pulp (hereunder referred to as "LBKP”); mechanical pulp such as GP, BCTMP and MP; pulp obtained from raw materials other than wood such as kenaf; and paper-making pulp represented by DIP pulp or the like.
  • polyolefinic fibers such as polyethylene, polypropylene, ethylene-propylene copolymer, polystyrene and ethylene-vinyl acetate copolymer; halogen atom-containing polymers such as polyvinyl chloride and polyvinylidene chloride; polyamide type fibers such as 6-nylon and 66-nylon; aliphatic polyester fibers such as polyethylene succinate, polycaprolactone, polylactic acid and polyhydroxy butyrate-valylate copolymer; and/or vinylon fibers.
  • polyolefinic fibers such as polyethylene, polypropylene, ethylene-propylene copolymer, polystyrene and ethylene-vinyl acetate copolymer
  • halogen atom-containing polymers such as polyvinyl chloride and polyvinylidene chloride
  • polyamide type fibers such as 6-nylon and 66-nylon
  • aliphatic polyester fibers such as polyethylene succinate, polycaprol
  • fillers for instance, inorganic pigments such as talc, kaolin, calcined kaolin, calcium carbonate, white carbon, amorphous silica, diatomaceous earth, titanium oxide, activated china clay and barium sulfate; and/or organic pigments such as urea-formalin resin, nylon powder and polyethylene powder and the substrate can be prepared by the acidic or neutral paper-making process according to the usual method.
  • inorganic pigments such as talc, kaolin, calcined kaolin, calcium carbonate, white carbon, amorphous silica, diatomaceous earth, titanium oxide, activated china clay and barium sulfate
  • organic pigments such as urea-formalin resin, nylon powder and polyethylene powder and the substrate can be prepared by the acidic or neutral paper-making process according to the usual method.
  • base paper which contains or is provided thereon with a sizing agent represented by rosin type sizes, alkenyl succinic acid anhydride and alkyl ketene dimers; starches such as oxidized starch, enzyme-modified starch, cation-modified starch, esterified starch and etherified starch; cellulose derivatives such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, methoxy cellulose and hydroxy cellulose; polyvinyl alcohols such as completely or partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol; water-soluble polymers such as polyacrylamide, polyvinyl pyrrolidone, acrylic acid amide-acrylic acid ester copolymer, acrylic acid amide-acrylic acid ester-methacrylic acid copolymer, alkali salts of styrene-maleic anhydride copolymer, alkali salt
  • an inkjet receiving layer containing dialkylamine epichlorohydrin polycondensate is provided.
  • a base material for paper is coated with or impregnated with a cationic resin and/or a water-soluble resin or a water-dispersible resin (wood free paper type one).
  • a pigment-containing layer is preferred to the base material from the viewpoint of the ink-absorbing ability.
  • an ink-receiving layer containing a xerogel type porous pigment to one side of the recording medium.
  • the order of the ink-receiving layer and the heat-sensitive layer to be applied is not restricted to any specific one, but it is preferred that the ink-receiving layer be first applied to the base material before the step for the application of the heat-sensitive layer since contamination upon color development due to, for instance, rubbing of the heat-sensitive layer can be reduced to a level of as low as possible.
  • pigments to be incorporated into the ink-receiving layer include inorganic pigments such as amorphous silica, alumina, calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, white carbon, alumina and aluminum hydroxide; and organic pigments such as styrenic, acrylic, urea resin type, melamine resin type and benzoguanamine type ones.
  • xerogel type porous pigments which can be prepared using a variety of known methods such as those listed below and have already been put on the market:
  • silica type pigments are silica type pigments, because they are excellent in the ink receiving ability and can ensure a high recording density due to their characteristic properties such as relatively low refractive index, and easy controllability of the porous structure.
  • a pigment having a particle size of not more than 1 ⁇ m permits the preparation of an ink-receiving layer having excellent surface gloss.
  • the resins (which serve as binders) may appropriately be selected from any known ones.
  • aqueous solutions or aqueous dispersions of, for instance, starch and derivatives thereof; cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; natural or semisynthetic polymers such as casein, gelatin and soybean protein; polyvinyl alcohol derivatives such as polyvinyl alcohol, silyl-modified polyvinyl alcohol and cation-modified polyvinyl alcohol; vinylic copolymer resins such as polyvinyl butyral resin, polyethyleneimine type resin, polyvinyl pyrrolidone type resin, poly(meth)acrylic resin, acrylic acid ester type resin, polyamide type resin, polyacrylamide type resin, polyester resin, urea resin, melamine resin, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer and ethylene-vinyl acetate copolymer
  • the resins it is also preferable to use sell-emulsifiable cationic resins containing no emulsifier.
  • the self-emulsifiable cationic resins By employment of the self-emulsifiable cationic resins, both anti-graying of background properties of heat sensitive recording layer and reduction of the color forming ability are small, and there can be obtained superior effects in terms of water resistance and recorded image quality of the ink jet recording portion.
  • an emulsion polymerization type latex When an emulsion polymerization type latex is used as the resin, there are some cases where an anionic, cationic or nonionic emulsifier reduces adhesion properties and water resistance of ink jet recording portion or where bleedings occur on ink jet recording portion. Furthermore, there are some possibilities in that such an emulsifier lowers anti-graying of background and color formation properties of heat-sensitive recording layer.
  • self-emulsifiable cationic resins include copolymers obtained by soap free polymerization of monomers such as styrene butadiene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, a cationic functional group being bonded to at least one part of the monomers.
  • Examples of the cationic functional groups include thirdly amino group, quaternary ammonium group and the like but are not limited to them.
  • An amount of the self-emulsifiable cationic resins is not limited but preferably 1 to 30 wt %, more preferably, 3 to 15 wt % relative to an amount of an aqueous ink receiving layer.
  • the method for the production of the sell-emulsifiable cationic resins is not limited, but includes, for example, seed polymerization method, reactive emulsion method or oligomer method.
  • cationic polymer compounds such as polyethyleneimine type resin, polyamine type resin, polyamide type resin, polyamide epichlorhydrin type resin, polyamine epichlorhydrin type resin, polyamide polyamine epichlorhydrin type resin, polydiallylamine type resin, and dicyan-diamide condensate, in order to improve the water resistance of images printed with a water-based ink.
  • dialkylamine • epichlorohydrin polycondensate is incorporated into the ink receiving layer.
  • dialkylamine in the polycondensate alkyl group having 1 to 4 carbon atoms is preferable and in particularly, dimethylamine • epichlorohydrin polycondensate is preferable.
  • dialkylamine • epichlorohydrin polycondensate improves water resistance of ink jet recorded parts and does not lower the color formation properties of the heat sensitive recording layer even if it is subjected to high temperature and high humidity condition.
  • the ink receiving layer contain at least 0.1 wt %, more preferably 1 to 50 wt %, most preferably 3 to 30 wt % of dialkylamine ⁇ epichlorohydrin polycondensate.
  • a cationic substance such as polyvinyl pyridine, polydialkyl aminoethyl methacrylate, polydialkyl aminoethyl acrylate, polydialkyl aminoethyl methacrylamide, polydialkyl aminoethyl acrylamide, polyepoxy amine, polyamideamine, dicyanediamide • formalin condensate, dicyanediamide polyalkyl • polyalkylene polyamine condensate, polydiallyldimethylammonium chloride, polyvinyl amine, polyallylamine, acrylamide • diallylamine hydrochloric acid copolymer and modified product thereof.
  • a cationic substance such as polyvinyl pyridine, polydialkyl aminoethyl methacrylate, polydialkyl aminoethyl acrylate, polydialkyl aminoethyl methacrylamide, polydialkyl aminoethyl acrylamide, polyepoxy amine, polyamideamine, dicyanediamide • formalin con
  • a pigment dispersant e.g., a thickening agent, an anti-foaming agent, a foam-inhibitor, a foaming agent, a releasing agent, a penetrating agent, a wetting agent, a thermal gelling agent, a lubricant and/or other various kinds of auxiliary agents known in the art.
  • the means for applying an ink-receiving layer to the base material for paper may be appropriately be selected from those usually employed such as size press, gate roll, roll coater, bar coater, air-knife coater, rod blade coater and blade coater.
  • a heat-sensitive recording ability is imparted to the side opposite to the side to which the ink jet recording ability is imparted.
  • the heat-sensitive recording in general comprises the steps of heating a heat-sensitive recording layer, which mainly comprises a colorless or pale colored leuco dye and a developer, which can cause the coloration of the dye upon heating, through a heating head to thus cause a reaction between the leuco dye and the developer and to thus perform recording through the coloration of the dye.
  • a heat-sensitive recording layer which mainly comprises a colorless or pale colored leuco dye and a developer, which can cause the coloration of the dye upon heating, through a heating head to thus cause a reaction between the leuco dye and the developer and to thus perform recording through the coloration of the dye.
  • Such a method has suitably been used in, for instance, various kinds of printers and facsimiles, since the maintenance of these apparatuses is quite easy.
  • the heat-sensitive recording is not limited in the relative positions of the recording head and the recording layer, unlike
  • the leuco dyes to be incorporated into the heat-sensitive recording layer there may be listed, for instance, triphenylmethane type, fluoran type and diphenylmethane type compounds and can be selected from those conventionally known in this art.
  • the leuco dye may be at least one member selected from the group consisting of 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, Crystal Violet Lactone, 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-(o,p-dimethylanilino) fluoran, 3-(N-ethyl-N-p-toluidino)-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-
  • the developer to be incorporated into the heat-sensitive recording layer may be, for instance, at least one member selected from the group consisting of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl)-1-phenylethane, 1,4-bis (1-methyl-1-(4'-hydroxyphenyl) ethyl) benzene, 1,3-bis (1-methyl-1-(4'-hydroxyphenyl) ethyl) benzene, dihydroxy diphenyl ether, benzyl p-hydroxy benzoate, bisphenol S, 4-hydroxy-4'-isopropyloxy diphenyl sulfone, 1,1-di-(4-hydroxyphenyl) cyclohexane, 1,7-di-(4-hydroxyphenylthio)-3,5-dioxaheptane, 3,3'-diallyl-4,4'-dihydroxy diphenyl sulfone, N-(p-tolu
  • organic acid substances for example, phenol compounds such as 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 4,4'-dihydroxyphenylsulfide, hydroguinone monobenzylether, 2,4'-dihydroxybenzophenone, 2,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4'-methyldiphenyl sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, 2,4-bis(phenylsulphonyl) phenol, bis(p-hydroxyphenyl) methyl acetate, 1,4-bis[ ⁇ -methyl- ⁇ -(4'-hydroxyphenyl) ethyl]benzene, 1,3-bis[ ⁇ -methyl- ⁇ -(4'-hydroxyphenyl) ethyl]benzene, di(4-hydroxy-3-
  • sulfonyl group in their molecule such as 4-hydroxy-4'-isopropyloxy diphenyl sulfone, 3,3'-diallyl-4,4'-dihydroxy diphenyl sulfone, 4-hydroxy-4'-methyldiphenyl sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, 2,4-bis(phenylsulfonyl) phenol, N-(p-trylsulfonyl) carbamoic acid p-cmylphenylester, N-(p-trylsulfonyl) carbamoic acid p-benzyloxyphenyl ester, N-(o-toluoyl)-p-torylsulfonamide, N-(p-toluenesulfonyl)-N'-(p-to-tol
  • 4-hydroxy-4'-isopropyloxy diphenyl sulfone and 3,3'-diallyl-4,4'-dihydroxy diphenyl sulfone are preferable since storability and recording sensitivity of heat sensitive recording portion becomes good by use of one of these.
  • a ratio of leuco dye and developer is optimally determined based on the kind of the using leuco dye and developer, and is not limited. However, it is preferable that the weight ratio of leuco dye to developer be 1:1 to 1:10, more preferably 1:2 to 1:6.
  • binders usable herein are, for instance, polyvinyl alcohols having a variety of molecular weights; starch and derivatives thereof; cellulose derivatives such as methoxy cellulose, carboxymethyl cellulose, methyl cellulose and ethyl cellulose; water-soluble polymer materials such as sodium polyacrylate, polyvinyl pyrrolidone, acrylic acid amide/acrylic acid ester copolymers, acrylic acid amide/acrylic acid ester/methacrylic acid terpolymers, alkali salts of styrene/maleic anhydride copolymers, polyacrylamide, sodium alginate, gelatin and casein; and latexes such as polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer, polybutyl methacrylate, ethylene/vinyl acetate copolymer,
  • the heat-sensitive recording layer may comprise heat-fusible substance (so-called sensitizer) in combination with the foregoing components.
  • the sensitizers usable herein may be heat-fusible organic compounds having a melting point ranging from 50 to 150°C and specific examples thereof include 1-hydroxy-2-naphthoic acid phenyl ester, benzyl naphthyl ether, dibenzyl terephthalate, benzyl p-benzyloxy benzoate, diphenyl carbonate, ditolyl carbonate, m-terphenyl, 1,2-bis (phenoxy) ethane, 1,2-bis (m-tolyloxy) ethane, 1,5-bis (p-methoxyphenoxy)-3-oxapentane, oxalic acid diesters, 1,4-bis (p-tolyloxy) benzene, benzene-sulfoanilide, 2-chloroacetoacetoanilide, 4-ethoxy
  • the heat-sensitive recording layer of the present invention may likewise comprise a pigment and/or waxes.
  • Such pigments may be, for instance, inorganic fine powder such as calcium carbonate, silica, zinc carbonate, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, calcined clay, talc, and surface-treated calcium carbonate and silica; and organic fine powder such as urea-formalin resin, styrene/methacrylic acid copolymer and polystyrene resin.
  • inorganic fine powder such as calcium carbonate, silica, zinc carbonate, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, calcined clay, talc, and surface-treated calcium carbonate and silica
  • organic fine powder such as urea-formalin resin, styrene/methacrylic acid copolymer and polystyrene resin.
  • oil-absorptive pigments whose oil absorption is not less than 70 ml/100 g.
  • the waxes usable herein may be, for instance, known ones such as paraffins, amide type waxes, bisimide type waxes, and metal salts of higher fatty acids.
  • heat-sensitive recording layer may if necessary comprise a storage stabilizer, a coloring agent and/or other auxiliary agents.
  • a primer coating layer may be arranged below the heat-sensitive recording layer in order to improve the sensitivity of the recording layer and to prevent any formation of scum on the printer head and it is also possible to apply a protective layer on the heat-sensitive recording layer for the purpose of improving the storability and printability of the resulting recording medium.
  • the printer used in the present invention is preferably one that possesses two recording units, i.e., an ink jet recording unit and a heat-sensitive recording unit.
  • Each of these recording units may be a usual separate recording unit.
  • the ink jet recording unit may be a commercially available usual recording unit for the ink jet printer and the heat-sensitive recording unit may likewise be the usual recording unit for the heat-sensitive recording printer. That is, they are not necessarily specially designed ones, respectively.
  • the head of the heat-sensitive recording unit is desirably arranged upwardly or faces sideways and further the heat-sensitive recording unit is preferably positioned in front of the ink jet recording unit. This is because if the heat-sensitive recording unit faces downward, it is necessary to have the recording paper turned inside out for the ink jet recording, for the reason described above.
  • the ink jet recording unit is positioned in front of the heat-sensitive recording unit, the heat-sensitive recording is carried out after the ink jet recording operations.
  • heat-sensitive recording it is necessary to arrange a platen roll at the position against which the head of the recording unit is pressed and the nipping of the recording paper immediately after the ink jet recording between the platen roll and the head of the heat-sensitive unit may cause contamination of the platen roll with the undried ink on the paper.
  • the recording paper gets swollen as it absorbs water-based ink and as a result, the surface thereof is not smooth, the paper may, for instance, wrinkle.
  • the recording heads of the both ink jet and heat-sensitive recording units may be a serial head or a line head, with the line head being desirable for high-speed recording operations.
  • the ink jet recording unit of the printer used in the present invention may be one similar to those of the presently commercially available ink jet printers, as has been discussed above.
  • the recording head may be either a serial head or a line head, with the line head being preferred for high-speed recording operations.
  • the ink used is not limited to any specific one.
  • the water-based ink used in the present invention comprises, as a dye, at least one member selected from the group consisting of water-soluble direct dyes, water-soluble acid dyes and colored pigments and other optional components such as a wetting agent, a dye-solubilizing agent, an antiseptic and/or an anti-fungus agent.
  • water-soluble direct dyes include, but are not limited to, CI. Direct Black, CI. Direct Yellow, CI. Direct Blue, and Ci.
  • Direct Red and examples of water-soluble acid dyes include, but are not limited to, CI. Acid Black, CI. Acid Yellow, CI. Acid Blue, and CI. Acid Red.
  • wetting agents and dye-solubilizing agents there may be listed, for instance, alcohols and derivatives thereof such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol and glycerin; nitrogen atom-containing compounds such as formamide, dimethyl acetamide and N-methyl-2-pyrrolidone; and sulfur atom-containing compounds such as dimethyl sulfoxide and sulfolane.
  • alcohols and derivatives thereof such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol and glycerin
  • nitrogen atom-containing compounds such as formamide, dimethyl acetamide and N-methyl-2-pyrrolidone
  • sulfur atom-containing compounds such as dimethyl sulfoxide and sulfolane.
  • substances capable of inducing color development of the heat-sensitive recording layer may be included and therefore, the wetting agent, dye-solubilizing agent or the like present in the ink penetrate into the heat-sensitive recording layer to thus induce the color development of the recording layer and, in turn, sometimes results in the so-called phenomenon: fog, if the base material is susceptible, to the penetration of the foregoing components of the ink.
  • some of the components of the ink such as the wetting agent and the dye-solubilizing agent may induce the discoloration of the color-developed portion of the heat-sensitive recording layer and thus they may often induce the discoloration of images developed on the heat-sensitive recording layer. Therefore, it is necessary to inhibit any penetration of the solvents for these wetting agent and dye-solubilizing agent or the like into the heat-sensitive recording layer.
  • any penetration of the solvent can substantially be inhibited.
  • the time is preferably not less than 35 seconds.
  • a 10% polyethylene glycol aqueous solution (0.5 ml) is dropwise added to the side to which the ink jet recording ability is imparted using a micro-syringe, followed by observing the droplet from the side of the heat-sensitive recording layer and then determining the time required till three transparent spots appear.
  • the time is defined to be its resistance to solvent-permeation.
  • the penetration time to a level of not less than 30 seconds, there can be used various means such as an increase in the thickness of the base material (basis weight is preferably 30 to 300 g/m 2 ), improvement of the degree of sizing, and appropriate selection of the kind and amount of the resin incorporated into the ink-receiving layer (the first embodiment of the present invention).
  • said penetrating time can be controlled in 30 seconds or more by adjusting the Stockigt sizing degree (specified by JIS P 8122) of the base paper to 30 seconds or more.
  • the present invention positions or arranges an intermediate layer free of any solvent-penetration between the heat-sensitive recording layer and the base material. If the intermediate layer is arranged between the ink jet recording layer and the substrate, the resulting recording medium often has a reduced ink jet ink-absorptive capacity and accordingly, ink jet-recorded images may be accompanied by bleeding. For this reason, the intermediate layer is between the substrate and the heat-sensitive recording layer in the recording medium of the present invention.
  • the resin included in the intermediate layer may be appropriately selected from those.known ones, for instance, aqueous solutions or aqueous dispersions of, for instance, starch and derivatives thereof; cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; naturally occurring or semisynthetic polymers such as casein, gelatin and soybean protein; polyvinyl alcohol derivatives such as polyvinyl alcohol, silyl-modified polyvinyl alcohol and cation-modified polyvinyl alcohol; vinylic copolymer resins such as polyvinyl butyral resin, polyethyleneimine type resin, polyvinyl pyrrolidone type resin, poly(meth)acrylic resin, acrylic acid ester type resin, polyamide type resin, polyacrylamide type resin, polyester resin, urea resin, melamine resin, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer and ethylene-vinyl acetate copolymer; or modified poly
  • those excellent in the solvent-penetration-inhibitory effect are polyvinyl butyral resin, styrene-butadiene copolymer and polyvinyl alcohols, preferably having an average degree of polymerization of not less than 500 and they can preferably be used in the invention.
  • the intermediate layer of the present invention may if necessary comprise a pigment and examples thereof usable herein are inorganic pigments such as calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, white carbon, alumina and aluminum hydroxide; and organic pigments such as styrenic, acrylic, urea resin type, melamine resin type and benzoguanamine resin type pigments.
  • inorganic pigments such as calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, white carbon, alumina and aluminum hydroxide
  • organic pigments such as styrenic, acrylic, urea resin type, melamine resin type and benzoguanamine resin type pigments.
  • the amount of the intermediate layer to be applied ranges, in terms of the weight of the solid content, from 2 to 15 g/m 2 , preferably 4 to 8 g/m 2 . This is because if the coated amount is less than 2 g/m 2 , it is difficult to achieve the intended effect of inhibiting solvent-penetration, while if the amount exceeds 15 g/m 2 , the resistance to solvent-penetration is satisfied, but the resulting recording medium is often unfavorable from the viewpoint of recording operations or preparation operations and production cost.
  • the base paper In cases of using the intermediate layer, it is preferable that the base paper have a basis weight of 30 to 300 g/m 2 , more preferably 50 to 250 g/m 2 .
  • the intermediate layer In cases of using the intermediate layer, there can be obtain advantages in that it is not necessary to adjust the sizing degree of the base paper or the oil absorption of pigment contained in the ink jet recording layer.
  • the Stockigt sizing degree of the base paper may be 30 seconds or less, and it is preferable that the oil absorption of the ink jet recording layer be in the range of about 200 to 350.
  • a resin-containing protective layer onto the heat-sensitive recording layer would serve to inhibit any possible adverse effect of the ink, present on the ink jet recording layer on the neighboring heat-sensitive recording layer even when the recording mediums are put in layers after recording operations.
  • an acetoacetyl-modified polyvinyl alcohol or a polyvinyl alcohol, more preferably having an average degree of polymerization of not less than 500 is incorporated into the protective layer. This permits the achievement of quite excellent resistance to ink jet ink and therefore, the heat-sensitive recording layer is never adversely affected by the high-speed double-side recording operations.
  • the ink solvent may sometimes undergo the inter-recording medium transfer from the surface of the ink jet recording layer to that of the heat-sensitive recording layer and this would leads to graying of the heat-sensitive recording layer and/or discoloration of recorded images.
  • the recording medium is set on a recording apparatus in the form of a roll and then wound up in a roll immediately after ink jet recording operations, the heat-sensitive recording layer undergoes conspicuous graying and/or discoloration. To prevent such graying and discoloration due to the action of the ink solvent, it is quite effective to apply a protective layer onto the heat-sensitive recording layer.
  • cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose; casein; gum arabic; starches such as oxidized starch, etherified starch, dialdehyde starch and esterified starch; completely or partially saponified polyvinyl alcohol; polyvinyl alcohols or those modified with a variety of functional groups such as acetoacetyl-modified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silyl-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, pyrrolidone-modified polyvinyl alcohol and silicon-modified polyvinyl alcohol, with acetoacetyl-modified polyvinyl alcohol and polyvinyl
  • a polyvinyl alcohols selected from the group consisting of acetoacetyl-modified polyvinyl alcohols, carboxyl-modified polyvinyl alcohol, silyl-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, olefin-modified polyvinyl alcohol, nitrile-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, and polyvinyl alcohol.
  • a curing agent may be incorporated into the coating solution for forming a protective layer.
  • curing agents there may be listed, for instance, glyoxal, methylolmelamine, potassium persulfate, ammonium persulfate, sodium persulfate, ferric chloride, magnesium chloride, boric acid, alum and ammonium chloride.
  • a pigment may if necessary be added to the protective layer.
  • pigments are inorganic pigments such as calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, barium sulfate, zinc sulfate, talc, kaolin, clay, calcined kaolin and colloidal silica; and organic pigments such as styrene micro-balls, nylon powder, polyethylene powder, urea-formalin resin filler and raw starch particles.
  • the protective layer may if necessary comprise various kinds of auxiliary agents, for instance, a lubricant such as zinc stearate, calcium stearate, stearic acid amide, polyethylene wax, carnauba wax, paraffin wax or ester wax; a surfactant such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium salt of lauryl alcohol sulfate, alginic acid salts or metal salts of fatty acids; a UV absorber such as benzophenone type or triazole type one; an anti-foaming agent, a fluorescent dye, and/or a colored dye.
  • a lubricant such as zinc stearate, calcium stearate, stearic acid amide, polyethylene wax, carnauba wax, paraffin wax or ester wax
  • a surfactant such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenes
  • the amount of the protective layer to be applied ranges, in terms of the solid content, from 0.1 to 10 g/m 2 and preferably 0.5 to 5 g/m 2 . This is because if it is less than 0.1 g/m 2 , the intended effect, i.e., the resistance to solvent-penetration is insufficient, while if it exceeds 10 g/m 2 , the resulting recording medium may cause a decrease in the sensitivity upon heat-sensitive recording operations.
  • the recording medium of the present invention can be used not only for the simultaneous high-speed ink jet recording and heat-sensitive recording, but also in the recording operations wherein an ink jet printer and a heat-sensitive printer are used independently.
  • the recording medium of the present invention can be used as papers for ballot, tickets, tags, papers for printer, postcards, paper for various forms, cards, postal matters and the likes.
  • words or marks are, in advance, printed on the surface of ink jet recording layers of the recording medium of the present invention and then figures or other marks are printed on the surface of heat sensitive layer.
  • the recording medium of the present invention permits high-speed double-side recording and at least one side of the recording medium is favorable for color ink jet recording, while the other side has a heat-sensitive recording ability.
  • the recording medium of the present invention is one that permits both ink jet recording and heat-sensitive recording.
  • the medium never causes any bleeding on the ink jet recording side, any graying of the heat-sensitive recording layer due to the action of the solvent present in the ink jet ink and never undergoes any discoloration of the printed matter on the heat-sensitive recording layer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (9)

  1. Zweiseitiges Aufnahmemedium, das ein hauptsächlich Pulpe enthaltendes Papierausgangsmaterial umfasst, dessen eine Seite eine Tintenstrahlaufnahmeschicht und dessen andere Seite eine hitzeempfindliche, einen Leukofarbstoff und einen Entwickler enthaltende Aufnahmeschicht aufweist, wobei
    i) eine ein Harz enthaltende Zwischenschicht zwischen dem Papierausgangsmaterial und der hitzeempfindlichen Aufnahmeschicht angeordnet ist und
    ii) die Tintentstrahlaufnahmeschicht Dialkylamin-Epichlorhydrin-Polykondensat enthält.
  2. Zweiseitiges Aufnahmemedium gemäß Anspruch 1, wobei das Ausgangsmaterial eine flächenbezogene Masse zwischen 50 und 300 g/m2 hat.
  3. Zweiseitiges Aufnahmemedium gemäß Anspruch 1, wobei das Ausgangsmaterial eine flächenbezogene Masse zwischen 50 und 100 g/m2 hat.
  4. Zweiseitiges Aufnahmemedium gemäß Anspruch 1, wobei das Ausgangsmaterial ein Bindemittel darin enthalten hat und der Stockigt-Leimungsgrad des Ausgangsmaterials 30 Sekunden oder mehr ist.
  5. Zweiseitiges Aufnahmemedium gemäß Anspruch 1, wobei das in der Zwischenschicht enthaltene Harz ein Mitglied ausgewählt aus der Gruppe bestehend aus Polyvinylalkohol, silylmodifizierter Polyvinylalkohol, Polyvinylbutyralharze, Polyvinylpyrrolidon, Styrol-Butadien-Copolymere, Carboxymethylzellulose und Stärke umfasst.
  6. Zweiseitiges Aufnahmemedium gemäß Anspruch 1, wobei das Gewicht des Feststoffgehaltes der Zwischenschicht im Bereich von 2 bis 15 g/m2 ist.
  7. Zweiseitiges Aufnahmemedium gemäß Anspruch 1, wobei eine Harz enthaltende Schutzschicht auf der hitzeempfindlichen Aufnahmeschicht gebildet wird.
  8. Zweiseitiges Aufnahmemedium gemäß Anspruch 7, wobei das in der Schutzschicht enthaltene Harz ein Polyvinylalkohol ausgewählt aus der Gruppe bestehend aus acetoacetylmodifizierten Polyvinylalkoholen, carboxylmodifiziertem Polyvinylalkohol, silylmodifiziertem Polyvinylalkohol, sulfonsäuremodifiziertem Polyvinylalkohol, olefinmodifiziertem Polyvinylalkohol, nitrilmodifiziertem Polyvinylalkohol, amidmodifiziertem Polyvinylalkohol und Polyvinylalkohol umfasst.
  9. Zweiseitiges Aufnahmemedium gemäß Anspruch 7, wobei das Gewicht des Feststoffgehaltes der Schutzschicht in dem Bereich von 0,1 bis 10 g/m2 ist.
EP20000302517 1999-03-29 2000-03-28 Beidseitiges Aufzeichnungsmedium Expired - Lifetime EP1040933B1 (de)

Applications Claiming Priority (2)

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JP08617099A JP4038929B2 (ja) 1999-03-29 1999-03-29 両面記録媒体
JP8617099 1999-03-29

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EP1040933A1 EP1040933A1 (de) 2000-10-04
EP1040933B1 true EP1040933B1 (de) 2004-03-03

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN101687424B (zh) * 2007-05-10 2013-08-07 日本制纸株式会社 热敏记录体

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Publication number Priority date Publication date Assignee Title
JP3895931B2 (ja) * 2001-01-15 2007-03-22 大日本印刷株式会社 複合記録用熱転写受像媒体
EP1543984B1 (de) * 2003-12-18 2009-02-25 Mitsubishi Hitec Paper Flensburg GmbH Wärmempfindliches Aufzeichnungsmaterial zur beidseitigen Bedruckung
JP2006021831A (ja) * 2004-06-08 2006-01-26 Oji Paper Co Ltd 小判断裁紙堆積体の包装体
US7618922B2 (en) 2005-01-13 2009-11-17 Nippon Paper Industries Co., Ltd. Thermally-sensitive recording medium
WO2006077858A1 (ja) * 2005-01-18 2006-07-27 Oji Paper Co., Ltd. 光沢インクジェット記録用紙
JP2006224457A (ja) * 2005-02-17 2006-08-31 Nisshinbo Ind Inc インクジェット記録用シート
EP2855162B1 (de) 2012-06-04 2016-11-16 Hewlett-Packard Development Company, L.P. Gewebedruckmedien

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JPH0725191B2 (ja) * 1989-03-17 1995-03-22 日本製紙株式会社 インクジェット記録シート
JP2762879B2 (ja) * 1992-12-07 1998-06-04 日本製紙株式会社 感熱孔版印刷用記録シート
JPH0725148A (ja) * 1993-07-13 1995-01-27 Mitsubishi Paper Mills Ltd 可逆感熱系複合記録材料
JP2840042B2 (ja) * 1995-03-29 1998-12-24 日本製紙株式会社 インクジェット記録用両面記録紙及びその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101687424B (zh) * 2007-05-10 2013-08-07 日本制纸株式会社 热敏记录体

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EP1040933A1 (de) 2000-10-04
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JP4038929B2 (ja) 2008-01-30
DE60008610D1 (de) 2004-04-08

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