WO1992018336A1 - Wärmeempfindliches aufzeichnungsmaterial mit pigmentierter schutzschicht - Google Patents

Wärmeempfindliches aufzeichnungsmaterial mit pigmentierter schutzschicht Download PDF

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Publication number
WO1992018336A1
WO1992018336A1 PCT/EP1991/000762 EP9100762W WO9218336A1 WO 1992018336 A1 WO1992018336 A1 WO 1992018336A1 EP 9100762 W EP9100762 W EP 9100762W WO 9218336 A1 WO9218336 A1 WO 9218336A1
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WO
WIPO (PCT)
Prior art keywords
heat
sensitive recording
layer
protective layer
weight
Prior art date
Application number
PCT/EP1991/000762
Other languages
German (de)
English (en)
French (fr)
Inventor
Walter Von Wirth
Andrea Richter
Original Assignee
Renker Gmbh & Co. Kg
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 Gmbh & Co. Kg filed Critical Renker Gmbh & Co. Kg
Publication of WO1992018336A1 publication Critical patent/WO1992018336A1/de

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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
    • B41M5/40—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
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes

Definitions

  • the invention relates to a heat-sensitive recording material whose protective layer covering the recording layer and having a film-forming agent made of polymers produced with electron beams from oligomers has a low pigment content.
  • 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 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 which are liquid at room temperature and have at least one ethylenically unsaturated bond per molecule and which Oligomers converted to polymers by electron beam curing.
  • the formation of the heat-sensitive layer is not critical, and 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 can be used as color-forming reactants become. It is stated in the publication that a proportion of pigments in the protective layer of less than 5 parts by weight per 100 parts by weight of polymer does not lead to any remarkably improved resistance to water, plasticizers, oils and organic solvents.
  • EP-A-339679 describes a heat-sensitive recording material in which a first protective layer composed of an aqueous coating composition with a film-forming resin as the main component is first applied to the recording layer. Thereafter, a composition curable by electron beams is applied as a further protective layer which, in addition to the resin curable by electron beams, also has a macromonomer containing organopolysiloxane.
  • the top protective layer can contain 1-15% by weight of pigments based on the total solids of the layer.
  • the object of the invention is to provide a heat-sensitive recording material, the recording layer of which has a lower tendency to gray the image background and a higher contrast than the known recording materials and whose resistance to environmental influences is improved.
  • a heat-sensitive recording material with a heat-sensitive recording layer arranged on a carrier material, which contains color precursor compounds and acidic organic compound (s) as color-developing reaction partner (s), and that a single electron directly above the recording layer ⁇ radiation-cured pigmented protective layer of crosslinked polymers is arranged, which contains 0.02 to 4.5 parts by weight of one or more pigments per 100 parts by weight of polymer.
  • 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.
  • the recording material has a good recordability without disturbances on the thermal head.
  • the change in the pigment content does not lead to a reduction in the stability of the material against water, plasticizers, oils and organic solvents.
  • 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 into the carrier material and reduces the outflow of heat into the carrier material during use.
  • 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 polymer (s) of the binder system of the heat-sensitive coating ⁇ drawing layer takes place at the boundary layer between the protective layer and / or the intermediate layer. This leads to a stronger bond between the layers.
  • the protective layer also contains a small proportion of pigments.
  • pigments can be used. Suitable pigments are inorganic pigments such as calcium carbonate, zinc oxide, aluminum oxide, titanium dioxide, silicon dioxide, aluminum hydroxide, barium sulfate, zinc sulfate, kaolin, clay, calcined clay. However, 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 a particle size of 0.3-5 ⁇ and are only used in amounts of 0.02 to 4.5 parts by weight per 100 parts by weight of the polymer component of the protective layer.
  • 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.
  • the pigments mentioned above can also be incorporated into the intermediate layer.
  • 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 adapted to the requirements of the special oligomer or the oligomer mixture in such a way 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 the synthetic polymers in the recording layer is desired at the interfaces between the recording layer and the protective layer and / or intermediate layer, a somewhat higher one becomes Radiation dose used to decompose and harden the oligomers in order to activate the synthetic polymers in the recording layer to such an 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 chemical reactions caused by radiation between the oligomers among one another and the polymers in the adjacent recording layer.
  • Suitable substrates are both paper and plastic films.
  • Suitable coating base papers preferably have a surface sizing onto the polymers which, under the influence of the electron radiation, are capable of graft copolymerizing 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 polymer layer crosslinked by the electron radiation is then formed on the dried, heat-sensitive recording layer as a protective layer. Before the heat-sensitive recording layer is applied to the carrier material, it is preferred to form an intermediate layer which likewise contains polymers crosslinked by electron radiation.
  • 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 as 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.
  • Unsaturated polyesters such as condensation products of maleic acid, fu aric acid and other unsaturated 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, glycerol, 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 that are reaction products of an epoxy resin with acrylic acid or methacrylic acid.
  • Silicone acrylates or silicone methacrylates that are reaction products of an acryloyl- or methacryloyl-alkoxysilane and an organopolysiloxane.
  • Polybutadiene acrylates or polybutadiene methacrylates these are reaction products of a polybutadiene oligomer of a polyisocyanate and hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
  • Polyether acrylates or polyether methacrylates are condensation products of acrylic acid or methacrylic acid and addition products of trimethylol, propane, pentaerythritol and other polyhydric alcohols and alkylene oxide.
  • meltamine acrylates or melamine methacrylate these are condensation products of methylolmelamine and hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
  • the heat-sensitive recording layer contains so-called color precursor compounds, preferably weakly basic color precursor compounds, which form a color with acidic organic compounds as reactants.
  • Suitable color formers are, for example: Dyes based on triarylmethane, for example 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindole-3-3> -l.
  • Phthalide 3- (p-Dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2- dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6 -dimethylamino-phthalide, 3,3-bis- (4-dimethylaminophenyl) -6-dimethylamino-phthalide and 3-p-dimethylaminophenyl-3- (l-methylpyrrol-3-yl) - 6-dimethylaminophthalide; diphenylmethane, 4,4 -Bis-dimethylamino-benzhydryl-benzyl
  • Color precursor compounds based on metal salts for example Fe salts, metal salts of higher fatty acids, which form a color with acidic reactants.
  • color development materials which, when heated and in contact with the colorless or light-colored basic dye or metal salts, give a color
  • inorganic acidic materials including active clay, acid clay, attapulgite, bentonite, colloidal silica and aluminum silicate and organic ones acidic materials including phenol compounds such as 4-tert-butylphenol, 4-tert-octylphenol, 4-phenylphenol, 4-acetylphenol, * -naphthol, p -naphthol, hydroquinone, 2,2'-dihydroxydiphenyl, 2,2 ' -Methylene bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis - (4-chlorophenol) -4,4'-dihydroxy-diphenylmethane, 4,4'-isopropylidene diphenol ( Bisphenol A), 4,4 * -isopropylidene-bis (2-tert-butylphenol, 4,4
  • Aromade monobenz ether, novolac phenolic resins and phenolic polymers aromatic carboxylic acids such as benzoic acid, p-tert.-butylbenzoic acid, trichlorobenzoic acid, 3-sec.-butyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, salicylic acid, 3-isopropylsalicylic acid, 3-tert.-butyl salic acid, 3-benzyl salicylic acid, 3- (• i.-ethylbenzyl) salicylic acid, 3-chloro-5-W-methylbenzyl) salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-phenyl-5 - (- i ⁇ C-dimethylbenzyl) salicylic acid, 3,5-di - (.- methylbenzyl) salicylic acid and terephthalic acid; furthermore the salts of such phenolic compounds or aromatic carboxylic acids with poly
  • the recording layer is formed by applying a coating composition which, in addition to the special one Fluoran derivative still contains the acidic development compound in addition to the usual auxiliaries for this layer.
  • the heat-sensitive recording layer contains starch, hydroxyethyl cellulose, methyl cellulose, CMC, casein, polyvinyl alcohol,
  • the binder content is 2 to 40, preferably 5-25 percent by weight, based on the total solids of the heat-sensitive recording layer.
  • Suitable 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.
  • auxiliary agents can be added to the heat-sensitive coating composition, such as dispersing agents, anti-foaming agents, UV absorbers, stabilizers, etc.
  • 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, separate dispersion 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 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.
  • the samples obtained have the designations 4/1, 4/2 and 4/3.
  • SiO 2 (4A) 5 parts by weight of SiO 2 (4A) are introduced into 95 parts by weight of oligomer in the protective layer according to Example 4 and 10 parts by weight of SiO 2 (4B) to 90 parts by weight of oligomer.
  • the protective layers 4A and 4B are applied in an amount of 5 g / m 2 to the heat-sensitive layers according to Examples 1-3 and, as already mentioned under Example 4, hardened.
  • the samples obtained have the designations 4A1, 4A2, 4A3 and 4B1, 4B2, 4B3.
  • 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 paper with the colored image was immersed in water for 5 minutes and then rubbed with gauze five times. Then the image density was measured.
  • a plasticized film acts on the colored image under a pressure of 5 g / cm 2 for 24 hours at 40 ° C. Then the image density is measured.
  • the polyester acrylate oligomer from Example 4 is applied to the layer carrier (an uncoated paper with a weight of 70 g / m 2 ) in an amount of 5 g / m 2 without pigment addition and cured with the aid of an electron beam.
  • the heat-sensitive recording recipe from Example 1 is applied to this resin layer in an amount of 5 g / m 2 and dried.
  • the resin is applied to this recording material with 2% by weight SiO 2 from Example 4 in an amount of 5 g / m 2 and hardened with an electron beam.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
PCT/EP1991/000762 1990-04-14 1991-04-20 Wärmeempfindliches aufzeichnungsmaterial mit pigmentierter schutzschicht WO1992018336A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19904012184 DE4012184C1 (enrdf_load_stackoverflow) 1990-04-14 1990-04-14

Publications (1)

Publication Number Publication Date
WO1992018336A1 true WO1992018336A1 (de) 1992-10-29

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WO (1) WO1992018336A1 (enrdf_load_stackoverflow)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4012186C1 (enrdf_load_stackoverflow) * 1990-04-14 1991-05-16 Renker Gmbh & Co Kg, 5160 Dueren, De
DE4012184C1 (enrdf_load_stackoverflow) * 1990-04-14 1991-05-29 Renker Gmbh & Co Kg, 5160 Dueren, De
DE4235127A1 (de) * 1992-10-17 1994-04-21 Renker Gmbh & Co Kg Lichtpausfähiges wärmeempfindliches Aufzeichnungsmaterial

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61279590A (ja) * 1985-06-06 1986-12-10 Fuji Photo Film Co Ltd 感熱記録紙
EP0264827A2 (en) * 1986-10-16 1988-04-27 Kanzaki Paper Manufacturing Company Limited Heat-sensitive recording material
JPH01210381A (ja) * 1988-02-19 1989-08-23 Kanzaki Paper Mfg Co Ltd 感熱記録体
DE4012185C1 (enrdf_load_stackoverflow) * 1990-04-14 1991-05-23 Renker Gmbh & Co Kg, 5160 Dueren, De
DE4012184C1 (enrdf_load_stackoverflow) * 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
JPH07119149B2 (ja) * 1988-04-28 1995-12-20 新王子製紙株式会社 感熱記録体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61279590A (ja) * 1985-06-06 1986-12-10 Fuji Photo Film Co Ltd 感熱記録紙
EP0264827A2 (en) * 1986-10-16 1988-04-27 Kanzaki Paper Manufacturing Company Limited Heat-sensitive recording material
JPH01210381A (ja) * 1988-02-19 1989-08-23 Kanzaki Paper Mfg Co Ltd 感熱記録体
DE4012185C1 (enrdf_load_stackoverflow) * 1990-04-14 1991-05-23 Renker Gmbh & Co Kg, 5160 Dueren, De
DE4012184C1 (enrdf_load_stackoverflow) * 1990-04-14 1991-05-29 Renker Gmbh & Co Kg, 5160 Dueren, De

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 146 (M-587)(2593) 13. Mai 1987 & JP,A,61 279 590 ( FUJI PHOTO FILM COMPANY LIMITED ) 10. Dezember 1986 siehe Zusammenfassung *
PATENT ABSTRACTS OF JAPAN vol. 13, no. 519 (M-895)(3867) 20. November 1989 & JP,A,01 210 381 ( KANZAKI PAPER MANUFACTURING COMPANY LIMITED ) 23. August 1989 siehe Zusammenfassung *

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