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WO1992018337A1 - Materiau d'enregistrement thermosensible - Google Patents

Materiau d'enregistrement thermosensible Download PDF

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Publication number
WO1992018337A1
WO1992018337A1 PCT/EP1991/000763 EP9100763W WO9218337A1 WO 1992018337 A1 WO1992018337 A1 WO 1992018337A1 EP 9100763 W EP9100763 W EP 9100763W WO 9218337 A1 WO9218337 A1 WO 9218337A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat
sensitive recording
layer
recording layer
recording material
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.)
Ceased
Application number
PCT/EP1991/000763
Other languages
German (de)
English (en)
Inventor
Andrea Richter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Renker & Co KG GmbH
Original Assignee
Renker & Co KG GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Renker & Co KG GmbH filed Critical Renker & Co KG GmbH
Publication of WO1992018337A1 publication Critical patent/WO1992018337A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B41M5/26—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
    • B41M5/405—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 characterised by layers cured by radiation
    • 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 invention relates to a heat-sensitive recording material whose heat-sensitive recording layer contains a special color precursor compound and which has a protective layer covering the recording layer, the film-forming agents of which are polymers produced from electron beams from oligomers.
  • Heat-sensitive recording materials with a protective layer protecting the recording layer and hardened by means of an electron beam are known from DE-A-3312716.
  • the protective layer with a basis weight of
  • 0.1 to 20 g per m 2 which can contain 5 to 300 parts by weight of pigment per 100 parts by weight of film-forming resin, is formed from oligomers liquid at room temperature with at least one ethylenically unsaturated bond per molecule and the oligomers are converted into polymers by curing with electron beams.
  • the formation of the heat-sensitive layer is not critical, and as a color Ending reactants can be used both metal salts of higher fatty acids, such as iron III stearate and gallic acid or other polyhydric phenols, and weakly basic dye precursor compounds in combination with organic acidic substances. 3-Dibutylamino-6-methyl-7-anilinofluoran is not mentioned among the numerous dye precursor compounds based on fluoranes.
  • EP-A-306916 discloses a particularly storage-stable, heat-sensitive recording material in which 3-dibutylamino-6-methyl-7-anilinofluorane and 3-dibutylamino-7-chloroanilinofluorane in combination with bis- (3-allyl-4 -hydroxyphenyl) sulfone and dibenzylo: xalate can be used as acidic reactants.
  • the special combination of dye precursor compound with the special acidic color-developing compounds results in a storage-stable material whose heat-sensitive recording layer can optionally be covered with a protective layer made of a water-soluble polymer.
  • the object of the invention is to provide a heat-sensitive recording material whose recording layer has a lower tendency to gray the background of the image than the known recording materials.
  • a heat-sensitive recording material having a heat-sensitive recording layer which is arranged on a carrier material and which contains a weakly basic color precursor compound and acidic organic compounds (as a color-developing reactant) and that an agent is applied over the recording layer
  • Has electron beam cured protective layer of crosslinked polymers which is characterized in that the Recording layer as the basic color precursor compound contains 3-dibutylamino-6-methyl-7-anilinofluoran in an amount of 2 to 100 g per 100 g of color-developing organic compounds.
  • the protective layer covering the heat-sensitive recording layer is produced from one or more oligomers which are liquid at room temperature and have at least one ethylenically unsaturated bond per molecule, the oligomers being polymerized and crosslinked by means of electron beams, so that a water-insoluble and solvent-insoluble protective layer is formed.
  • an intermediate layer of polymers hardened and crosslinked by means of electron beams is present between the carrier material and the heat-sensitive recording layer.
  • the intermediate layer is formed with a basis weight of 1 g per m 2 to 10 g per m 2 .
  • the formation of such an intermediate layer has the advantage that the influence of the carrier material on the color formation reaction and the contrast of the resulting recording is suppressed with respect to the image background.
  • any coating base papers can be used. Backing papers with special surface smoothness are not required.
  • the intermediate layer prevents the coating composition for the recording layer from penetrating too deeply into the carrier material and reduces the outflow of heat into the carrier material during use.
  • plastic films can also be used as the carrier material.
  • Coating base papers suitable as a carrier material preferably have a surface sizing which contains polymers which, under the influence of electron radiation, adhere
  • graft copolymerization are capable of graft copolymerization with the oligomers of the intermediate layer. Such a graft copolymerization can also occur with plastic films as the carrier material and improve the adhesion of the intermediate layer.
  • the heat-sensitive recording layer contains as film-forming binder at least one synthetic polymer which is capable of a graft copolymerization, so that under the action of the electron beams when the liquid oligomers harden, a graft copolymerization of the oligomers with the or Polymers of the binder system of the heat sensitive
  • EP - A - 306916 as a color-developing compound bis (3'-allyl-4'-hydroxyphenyl) sulfone and or dibenzyl oxalate or derivatives thereof are required to achieve advantageous results, other organic acidic developers can also be used according to the invention.
  • Materials are used that can form a color image with the special dye precursor. These include organic acidic materials such as phenolic compounds, e.g. B.
  • benzoic acid p-tert-butylbenzoic acid, trichlorobenzoic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert- Butyl salicylic acid, 3-benzylsalicylic acid, 3- ( ⁇ -methylbenzyl) salicylic acid, 3-chloro-5 ( ⁇ -methylbenzyl) salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5- ( ⁇ , ⁇ -dimethylbenzyl) salicylic acid, 3,5-di ( ⁇ -methylbenzyl) salicylic acid and terephthalic acid; furthermore the salts of such phenolic compounds or aromatic carboxylic acids with polyvalent metals such as e.g.
  • the recording layer is formed by applying a coating composition which, in addition to the special fluorane derivative, also contains the acidic developer compound in addition to the customary auxiliaries for this layer.
  • the heat-sensitive recording layer contains starch as a binder.
  • the binder content is 2 to 40, preferably 5-25 percent by weight, based on the total solids of the heat-sensitive recording layer.
  • the heat-sensitive recording layer particularly preferably contains at least one synthetic polymer which is capable of graft copolymerization.
  • Particularly suitable synthetic polymers are polyacrylates, polymethacrylates, polyacrylamides, polymethacrylamides, polystyrene copolymers, polyacrylonitrile, polymethacrylonitrile, polyvinylidene chloride, polyvinyl alcohols, polyvinolpyrrolido.n, polyvinyl acetals, cellulose derivatives.
  • the chemical valence bonds in these film-forming polymers are activated by high-energy electron beams to the extent that they are capable of reactions, in the presence of monomers and oligomers, in particular of graft copolymerization and crosslinking.
  • the binder system of the recording layer preferably contains a proportion of such
  • meltable compounds such as amide waxes, fatty acid amides, carnauba wax, paraffin wax, calcium stearate, ester waxes, dimethyltherephthalate and p-benzylbiphenyl are used to adjust the heat sensitivity of the recording layer.
  • the recording layer can also contain inorganic pigments such as kaolin, clay, calcium carbonate, titanium dioxide, silicon dioxide.
  • the amount of inorganic pigments in the recording layer can be 10 to 60 percent by weight based on the total weight of the coating composition.
  • auxiliaries can be added to the heat-sensitive coating composition, such as dispersants, anti-foaming agents, UV absorbers, stabilizers.
  • the amount of meltable compounds such as waxes, amides or organic compounds with melting ranges from 60 ° to 180 ° C. is generally 10 to 1000 parts by weight per 100 parts by weight of color-forming compounds.
  • the components of the coating composition are dispersed using water as the dispersing medium with the aid of suitable dispersing devices.
  • the reactants can be dispersed both separately and together, with separate dispersing being preferred. So-called agitator ball mills are particularly preferred as the dispersing device.
  • the composition for the heat-sensitive recording layer can be applied using customary methods of paper coating technology.
  • the amount of coating is generally 2 to 12 g per m 2 , preferably 3 to 10 g per m 2 , the values relating to the dry weight.
  • the polymer layer crosslinked by the electron radiation is then formed on the dried, heat-sensitive recording layer as a protective layer.
  • the protective layer is made from a coating composition containing one or more oligomers with at least one ethylenically unsaturated bond in the molecule.
  • the oligomers which are liquid at room temperature can be used as oligomers or a mixture and generally have a molecular weight of up to 50,000. It is essential that the oligomers may be combined so that the viscosity of the coating composition allows the application of a uniform liquid film.
  • dibasic acids phthalic acid and ethylene glycol or other dihydric alcohols.
  • Polyester acrylates or polyester methacrylates such as condensation products of phthalic acid, maleic acid, fumaric acid or other dibasic acids, ethylene glycol, glycerin, pentaerythritol or other polyhydric alcohols with acrylic acid or methacrylic acid.
  • Urethane acrylates or urethane methacrylates ie condensation products of ethylene glycol or other polyhydric alcohols, adipic acid and other dibasic acids, polyisocyanates, especially di-isocyanates and acrylic acid or methacrylic acid.
  • epoxy acrylates or epoxymethacrylates these are reaction products of an epoxy resin with acrylic acid or
  • Silicone acrylates or silicone methacrylates that is
  • Polybutadiene acrylates or polybutadiene methacrylates that are reaction products of a polybutadiene oligomer of a polyisocyanate and hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
  • meltamine acrylates or melamine methacrylate these are condensation products of methylolmelamine and hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
  • the same oligomers can also be used to form an intermediate layer between the support material and the heat-sensitive recording layer.
  • the protective layer and the intermediate layer can also contain pigments in addition to the film-forming polymer.
  • Suitable pigments are inorganic pigments such as calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, barium sulfate, zinc sulfate, caolin, clay, calcined clay.
  • organic pigments such as polystyrene, microspheres, nylon powder, polyethylene powder, zinc stearate, magnesium stearate, calcium stearate and barium stearate can also be used. Suitable pigments have one
  • Particle size of 0.3 - 5 microns and can be used in amounts of 0.2 to 300 parts by weight per 100 parts by weight of polymer component. Amounts of 0.2 to 4.5 parts by weight per 100 parts by weight of the polymer component of the resin layer are particularly preferred.
  • the protective layer is applied in amounts of 1 g per m 2 to 10 g per m 2 (as a crosslinked polymer coating). Amounts of 2 to 5 g per m 2 , based in each case on the weight of the crosslinked protective layer, are particularly preferred.
  • Electron beam accelerators suitable for hardening the protective layer or the intermediate layer are commercially available.
  • the oligomer layer is irradiated with the electron beam of a suitable dosage, the dosage being based on the
  • Requirements of the special oligomer or the oligomer mixture are adapted such that the oligomers are polymerized and crosslinked to form a water-insoluble and solvent-insoluble layer.
  • the radiation dose required is 0.1 Mrad to 20 Mrad, preferably 3 to 10 Mrad. If, according to a preferred embodiment of the invention, a graft copolymerization between monomers and oligomers and a synthetic polymer is desired in the recording layer at the interfaces between the recording layer and the protective layer and / or the intermediate layer, a somewhat higher radiation dose is used than for crosslinking and curing the oligomers to activate the synthetic polymers in the recording layer to the extent that the desired graft copolymerization occurs.
  • the yield of free radicals and graft copolymers formed by radiation can be expressed by a so-called G value, where
  • the G value is an expression of the yield of the
  • the heat sensitive coating compositions are applied to uncoated paper with a weight of 70 g / m 2 in an amount of 5 g / m 2 and then dried.
  • Example 1 The resin mentioned in Example 1 is applied to the heat-sensitive recording material 2 and treated as above.
  • Example 1 The resin mentioned in Example 1 is applied to the heat-sensitive recording material 3 and treated as above.
  • Example 2 The resin mentioned in Example 2 is applied to the heat-sensitive recording material 2 and treated as above.
  • Example 2 The resin mentioned in Example 2 is applied to the heat-sensitive recording material 3 and treated as above.
  • the background whiteness and the color intensity produced by an energy supply of 12.6 to 37.8 mJ / mm 2 , were measured with a Macbeth densitometer model RD 920 without color filter.
  • Tab. 1 shows the results.
  • the polyester acrylate oligomer from Example 2 is applied in an amount of 5 g / m 2 to the support (an uncoated paper with a weight of 70 g / m 2 ) and cured with the aid of an electron beam.
  • Example 1 applied in an amount of 5 g / m 2 and dried.
  • the resin from Example 2 is again applied to this recording material in an amount of 5 g / m 2 and cured with an electron beam.
  • the heat-sensitive recording material according to Example 3 is without color development and after color formation at 120 ° C for 1 min. measured the optical density. The material is then placed in water at 20 ° C for 24 h (Tab. 3). Furthermore, from d. heat-sensitive recording material according to Example 4 the dyn. Sensitivity in an energy range of 12.6 to 37.8 mJ / mm 2 determined and compared with the pattern without an intermediate resin layer.

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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)

Abstract

Matériau d'enregistrement thermosensible qui présente une couche d'enregistrement thermosensible disposée sur un support, laquelle contient du 3-dibutylamino-6-méthyl-7-anilinofluorane servant de composé précurseur colorant faiblement basique et un composé organique acide servant de partenaire réactionnel chromogène, et qui présente, au-dessus de la couche d'enregistrement, une couche protectrice durcie par un rayonnement électronique et constituée de polymères réticulés. La quantité de composés précurseurs de couleur est de 2 à 100 g pour 100 g de composés organiques chromogènes dans la couche d'enregistrement.
PCT/EP1991/000763 1990-04-14 1991-04-20 Materiau d'enregistrement thermosensible Ceased WO1992018337A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19904012186 DE4012186C1 (fr) 1990-04-14 1990-04-14

Publications (1)

Publication Number Publication Date
WO1992018337A1 true WO1992018337A1 (fr) 1992-10-29

Family

ID=6404489

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/000763 Ceased WO1992018337A1 (fr) 1990-04-14 1991-04-20 Materiau d'enregistrement thermosensible

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DE (1) DE4012186C1 (fr)
WO (1) WO1992018337A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4812438A (en) * 1986-05-29 1989-03-14 Kanzaki Paper Mfg. Co., Ltd. Heat-sensitive recording material
EP0306916A2 (fr) * 1987-09-08 1989-03-15 Mitsubishi Paper Mills, Ltd. Matériau d'enregistrement sensible à la chaleur
EP0339670A2 (fr) * 1988-04-28 1989-11-02 Kanzaki Paper Manufacturing Co., Ltd. Matériaux d'enregistrement thermosensibles
DE3935070A1 (de) * 1988-10-21 1990-04-26 Dainippon Ink & Chemicals Waermeempfindliches wiedergabemedium und harzzusammensetzung fuer einen deckueberzug dafuer
DE4012185C1 (fr) * 1990-04-14 1991-05-23 Renker Gmbh & Co Kg, 5160 Dueren, De
DE4012184C1 (fr) * 1990-04-14 1991-05-29 Renker Gmbh & Co Kg, 5160 Dueren, De

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4484204A (en) * 1982-04-10 1984-11-20 Kanzaki Paper Manufacturing Co., Ltd. Heat-sensitive record material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4812438A (en) * 1986-05-29 1989-03-14 Kanzaki Paper Mfg. Co., Ltd. Heat-sensitive recording material
EP0306916A2 (fr) * 1987-09-08 1989-03-15 Mitsubishi Paper Mills, Ltd. Matériau d'enregistrement sensible à la chaleur
EP0339670A2 (fr) * 1988-04-28 1989-11-02 Kanzaki Paper Manufacturing Co., Ltd. Matériaux d'enregistrement thermosensibles
DE3935070A1 (de) * 1988-10-21 1990-04-26 Dainippon Ink & Chemicals Waermeempfindliches wiedergabemedium und harzzusammensetzung fuer einen deckueberzug dafuer
DE4012185C1 (fr) * 1990-04-14 1991-05-23 Renker Gmbh & Co Kg, 5160 Dueren, De
DE4012184C1 (fr) * 1990-04-14 1991-05-29 Renker Gmbh & Co Kg, 5160 Dueren, De

Also Published As

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DE4012186C1 (fr) 1991-05-16

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