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WO2020084020A1 - Matériau d'enregistrement thermosensible à révélateur chromogène encapsulé - Google Patents

Matériau d'enregistrement thermosensible à révélateur chromogène encapsulé Download PDF

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Publication number
WO2020084020A1
WO2020084020A1 PCT/EP2019/078953 EP2019078953W WO2020084020A1 WO 2020084020 A1 WO2020084020 A1 WO 2020084020A1 EP 2019078953 W EP2019078953 W EP 2019078953W WO 2020084020 A1 WO2020084020 A1 WO 2020084020A1
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WIPO (PCT)
Prior art keywords
heat
sensitive recording
recording material
material according
capsules
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/EP2019/078953
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German (de)
English (en)
Inventor
Nora Wilke
Svenja JENSEN
Martin Schmidt
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.)
Mitsubishi HiTec Paper Europe GmbH
Original Assignee
Mitsubishi HiTec Paper Europe 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
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Publication of WO2020084020A1 publication Critical patent/WO2020084020A1/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
    • B41M5/30—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
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • 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
    • 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
    • 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
    • B41M5/30—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
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • 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
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
    • 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
    • B41M5/3372—Macromolecular compounds

Definitions

  • the present invention relates primarily to a heat-sensitive recording material comprising a carrier substrate and a heat-sensitive recording layer comprising a dye precursor and capsules, the capsules having a core, comprising or consisting of at least one color developer, and a shell which completely or partially surrounds the core.
  • the present invention also relates to the use of the heat-sensitive recording material according to the invention as tickets, labels, receipts and the like.
  • the present invention further relates to a method for producing a heat-sensitive recording material according to the invention and a method for producing capsules which contain at least one color developer in the core.
  • Heat-sensitive recording materials have been known for many years and are extremely popular. This popularity can be attributed, among other things, to the fact that their use is associated with the advantage that the color-forming components are contained in the recording material itself and that printers that are free of toner and color cartridges can therefore be used. It is therefore no longer necessary to or to purchase, store, change or refill color cartridges. This innovative technology has become widely accepted, particularly in public transport and in retail.
  • heat-sensitive recording materials During normal use of heat-sensitive recording materials, they can come into contact with a large number of different substances, which can influence the stability of the thermal printout. In addition to water and organic solvents, these also include fats and oils which are contained, for example, in hand care products and which can be transferred to the heat-sensitive recording material when it is touched. Resistance to fats and oils is therefore particularly relevant.
  • JP H 11-105 431 A describes a heat-sensitive recording material in which acidic color developers are encapsulated in a microcapsule with a particle size of 1 to 10 pm. This is intended to achieve a high color density, good resistance to plasticizers and good storage stability.
  • US 5952 263 A generally describes the encapsulation of a dye precursor and a color developer in order to increase the resistance to organic solvents.
  • heat-sensitive recording materials also meet the high aesthetic requirements of the end customer, that is to say they look high-quality.
  • heat-sensitive recording materials are used as evidence of expensive goods or services, for example As an entry ticket for musical, artistic, cultural or sporting events, the consumer wishes that the receipts are worth the high price of the goods or services.
  • the discoloration can be, for example, a gray color or a pink color of the background, which is dependent on the components of the recording material used. This discoloration not only leads to a decrease in the contrast of the printed image and thus to a poorer legibility of the printed image, but also to a decrease in the aesthetic perception of the recording material by the end customer.
  • the object of the present invention was to provide a heat-sensitive recording material which has an improved resistance to fats and an improved temperature resistance.
  • undesirable discoloration of the heat-sensitive recording material should be reduced or eliminated.
  • a heat-sensitive recording material comprising i) a carrier substrate and ii) a heat-sensitive recording layer comprising a dye precursor and capsules, wherein the capsules have a core, containing or consisting of at least one paint roller, and a shell completely or partially surrounding the core.
  • an encapsulation of the paint roller or the paint roller can improve the fat resistance.
  • the temperature resistance of the heat-sensitive recording material can be improved and an undesirable discoloration of the heat-sensitive recording material can be reduced or completely prevented.
  • the heat-sensitive recording materials can be printed unexpectedly with conventional thermal printers and show a sufficiently high sensitivity for the printing process. It has previously been assumed that encapsulating the color developer means that thermal printing of the recording material is no longer possible or only possible with a high energy input, since a lot of energy must first be used to break open the shell of the capsule.
  • a shell which completely encloses the core is understood to be a shell which encloses the core to more than 97%.
  • a partially enclosing envelope is understood to mean an envelope that encloses the core to more than 40% but less than 97%.
  • the proportion to which the core is enclosed by the shell can be determined on the basis of SEM images, by determining the coated surface and the non-coated surface of the capsule and then calculating the percentage.
  • Heat-sensitive recording materials are preferred according to the invention, the capsules having an average particle size d50, determined using a laser diffraction particle size analysis, in the range from 0.50 to 1.00 pm, preferably in the range from 0.60 to 0.95 pm, particularly preferably in the range from 0.70 to 0.90 pm.
  • heat-sensitive recording materials according to the invention are particularly preferred, the capsules having a particle size d90, determined using a laser diffraction particle size analysis, of less than 2.0 pm, preferably less than 1.75 pm, particularly preferably less than 1.6 pm .
  • heat-sensitive recording materials according to the invention are particularly preferred, the capsules using a laser diffraction particle size analysis have a particular particle size d10 of greater than 0.05 gm gm, preferably greater than 0.10 gm, particularly preferably greater than 0.30 gm.
  • capsules with the size distributions given above lead to particularly good thermal properties of the heat-sensitive recording material.
  • the size of the capsule has an effect on the smoothness of the paper surface. If the capsules are too large, the surface becomes uneven because the capsules can protrude from the surface thereof, particularly if the capsule diameter is greater than the layer thickness of the heat-sensitive recording layer. In the case of capsules which are too small, it has surprisingly been found that the ratio between the core and the shell of the capsule becomes unfavorable and the individual capsules contain too little of the color developer, so that the color formation during printing is impaired.
  • heat-sensitive recording materials are preferred in which the shell of the capsule comprises or consists of a polymer.
  • the polymer is preferably an acrylate.
  • Suitable monomers that can be used to prepare the polymer or copolymer are selected from the groups consisting of (meth) acrylic acids, (meth) acrylamides, alkyl (meth) acrylates, alkenyl (meth) acrylates, aromatic (meth) acrylates, vinyl aromatic monomers, nitrogen-containing compounds and their thio-anogen, and substituted ethylene monomers.
  • Particularly preferred monomers that can be used to produce the polymer or copolymer are selected from the group consisting of ethylene glycol dimethacrylate (“EGDMA”), methyl methacrylate (“MMA”), methyl acrylate, ethyl acrylate, propyl methacrylate, butyl methacrylate (“BMA”), butyl acrylate (“BA”), isobutyl methacrylate (“IBMA”), Hexyl methacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate (“EHA”), 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, isodecyl methacrylate (“IDMA”), undecyl methacrylate, dodecyl methacrylate (also known as lauryl methacrylate methacrylate) (also known as lauryl methacryl
  • crosslinking agents are preferably selected from the group consisting of trivinylbenzene, divinyltoluene, din Divinylpyri-, divinylnaphthalene and divinylxylene, ethyleneglycol diacrylate, trimethylolpropane triacrylate, diethyleneglycol divinyl ether, trivinylcyclohexane, allyl methacrylate, Ethylenglycoldimethac- triacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, trimethylolpropane trimethacrylate, divinylbenzene, Glycidyl methacrylate, 2,2-dimethylpropane-1,3-diacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate,
  • MMA methyl methacrylate
  • diethylene glycol divinyl ether poly(methyl methacrylate-co-diethylene glycol-cold divinyl ether)
  • PMMA-co-EGDAM poly (methyl methacrylate-co-diethylene glycol-cold divinyl ether)
  • heat-sensitive recording materials are preferred, the mass ratio between ethylene glycol dimethacrylate units and methyl methacrylate units in the copolymer being in the range from 1: 3.65 to 1: 7.65, preferably in the range from 1: 4.65 to 1: 6 , 65 is particularly preferably in the range from 1: 5.15 to 1: 6.15. It is particularly preferred according to the invention if, in addition to the ethylene glycol dimethacrylate units and methyl methacrylate units, no further monomers were used to prepare the copolymer.
  • the acrylate polymers are usually prepared from the monomers by radical polymerization. Radical polymerizations can be divided into three steps: start, growth and termination. In most cases, the radicals required for the start must first be formed in situ. According to the invention, the radicals required for starting the chain are preferably formed via the thermal decomposition of potassium peroxodisulfate (KPS).
  • KPS potassium peroxodisulfate
  • Other suitable initiators are, for example, ammonium peroxodisulfate (APS), aza-diisobutyronitrile (AIBN), dibenzoyl peroxide (DBPO) or N, N, N ', N'-tetramethylethylenediamine (TEMEDA).
  • heat-sensitive recording materials are preferred, the color developer being selected from the group consisting of N- (4-methylphenylsulfonyl) -N '- (3- (4-methylphenylsulfonyloxy) phenyl) urea (Pergafast 201), 4-hydroxy-4 '- isopropoxydiphenylsulfone (D8), N- ⁇ 2 - [(phenylcarbamoyl) amino] phenyl ⁇ benzenesulfonamide (NKK), 4,4' -lsopropylidene-di-o-cresol (CAS 79-97-0; bisphenol C), 2 , 4 ' -Dihydroxydiphenylsulfon, 2,4 ' -Sulfonyldiphenol (CAS 5397-34-2; 2,4 ' -Bisphenol S), Bis [4- (2-hydroxy-ethoxy) phenyl] sulfone, 2,2' - [
  • color developers prevents pinking, which can occur when using all or some of these color developers.
  • color developers can also be used in which an unwanted pre-reaction could possibly occur without encapsulation.
  • 3,5-Di (a-methylbenzyl) salicylic acid (CAS 53721-15-6, DMSA-35) has the following structure:
  • heat-sensitive recording materials according to the invention are particularly preferred, in which the color developer is selected from the group consisting of N- (4-methylphenylsulfonyl) -N '- (3- (4-methylphenylsulfonyloxy) phenyl) urea (Pergafast 201), 4-hydroxy-4'-isopropoxydiphenylsulfone (D8), N- ⁇ 2 - [(phenylcarbamoyl) amino] phenyl ⁇ benzenesulfonamide (NKK) and 3,5-di (a-methyl-benzyl) salicylic acid.
  • the color developer is selected from the group consisting of N- (4-methylphenylsulfonyl) -N '- (3- (4-methylphenylsulfonyloxy) phenyl) urea (Pergafast 201), 4-hydroxy-4'-isopropoxydiphenylsulfone (D8), N- ⁇ 2 - [(
  • 3,5-Di (a-methylbenzyl) salicylic acid is a very good color developer, but due to its very pronounced metallophilic property it causes problems when processing or producing heat-sensitive recording materials.
  • the use of 3,5-di (a-methylbenzyl) salicylic acid leads to the heat-sensitive recording layer adhering to the metal roller during calendering, thus detaching from the carrier substrate and no longer detaching from the metal roller without extensive cleaning.
  • the polar forces of attraction between the roller and 3,5-di (a-methylbenzyl) salicylic acid are strong enough to make proper calendering impossible. Calendering is only possible with tools such as an additional release paper on the surface of the thermal paper when inserted into the calender.
  • a heat-sensitive recording material which contains 3,5-di (a-methyl-benzyl) salicylic acid as a color developer tends to cause the background to turn pink.
  • the background does not have a pink color.
  • heat-sensitive recording materials in which the color developer is 3,5-di (a-methylbenzyl) salicylic acid are particularly preferred.
  • heat-sensitive recording materials are preferred, the dye precursor being selected from derivatives of compounds from the group consisting of fluoran, phthalide, lactam, triphenylmethane, phenothiazine and spiropyran.
  • the (non-encapsulated) dye precursors and the (encapsulated) color developers are preferably present next to one another in the heat-sensitive recording layer.
  • a preferred heat-sensitive recording material preferably has, as dye precursor, compounds of the fluorane type selected from the group consisting of 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (3'-methylphenylamino) fluorane ( 6 '- (diethylamino) -3'-methyl-2' - (m-tolylamino) -3H- spiro [isobenzofuran-1, 9'-xanthene] -3-one; ODB-7), 3-di-n- pentylamino-6-methyl-7-anilofluorane, 3- (diethylamino) -6-methyl-7- (3-methylphenylamino) fluorane, 3-di-n-butylamino-7- (2-chloroanilino) fluoran, 3-diethylamino-7- (2-chloroanilino) fluoran, 3-diethylamino-7
  • heat-sensitive recording materials which contain the compounds mentioned in paragraphs [0049] to [0052] of EP 2 923 851 A1 as dye precursors.
  • a heat-sensitive recording material is particularly preferred, the dye precursor being selected from the group consisting of 3-N-di-n-butylamine-6-methyl-7-anilinofluorane (ODB-2) and 3- (N-ethyl-N- isopentylamino) -6-methyl-7-anilinofluoran.
  • ODB-2 3-N-di-n-butylamine-6-methyl-7-anilinofluorane
  • a heat-sensitive recording material is preferred according to the invention, the heat-sensitive recording layer containing a sensitizer.
  • the sensitizer When using a sensitizer, the sensitizer is first melted during the application of heat during the printing process and the melted sensitizer dissolves the color formers and color developers coexisting in the heat-sensitive recording layer and / or lowers the melting temperature of the color formers and color developers in order to bring about a color development reaction.
  • the sensitizer does not participate in the color development reaction itself.
  • a sensitizer is therefore understood to mean substances which serve to adjust the melting temperature of the heat-sensitive recording layer and which can preferably be used to set a melting temperature of approximately 70 to 80 ° C. without the sensitizers themselves being involved in the color development reaction.
  • sensitizers for example fatty acid salts, fatty acid esters and fatty acid amides (eg zinc stearate, stearic acid amide, palmitic acid amide, oleic acid amide, lauric acid amide, ethylene and methylene bisstearic acid amide, methylol stearic acid amide), naphthalene derivatives, biphenalate derivatives and piphenalate derivatives, piphenalate derivatives, and terephthalate derivatives, terephthalate derivatives.
  • fatty acid salts eg zinc stearate, stearic acid amide, palmitic acid amide, oleic acid amide, lauric acid amide, ethylene and methylene bisstearic acid amide, methylol stearic acid amide
  • naphthalene derivatives biphenalate derivatives and piphenalate derivatives, piphenalate derivatives, and terephthalate derivatives, terephthalate derivatives
  • a heat-sensitive recording material is particularly preferred, the sensitizer being selected from the group consisting of 1,2-bis (3-methylphenoxy) ethane, 1,2-diphenoxyethane, 1,2-di (m-methylphenoxy) ethane, 2- (2H-benzotriazol-2-yl) -p-cresol, 2,2'-bis (4-methoxyphenoxy) diethyl ether, 4,4'-diallyloxydiphenyl sulfone, 4-acetylacetophenone, 4-benzybiphenyl, acetoacetic anilides, benzyl 2-naphthyl ether, benzyl naphthyl ether, benzyl 4- (benzyloxy) benzoate, benzyl paraben, bis (4-chlorobenzyl) oxalate ester, bis (4-methoxyphenyl) ether, dibenzyl oxalate, dibenzyl terephthalate, di
  • heat-sensitive recording materials according to the invention which contain the compounds mentioned in paragraphs [0059] to [0061] of EP2923851 A1 as a sensitizer.
  • these sensitizers are used alone, that is, not in combination with the other sensitizers mentioned from the above list.
  • at least two sensitizers, selected from the above list are incorporated into the heat-sensitive recording layer.
  • a heat-sensitive recording material is preferred according to the invention, the sensitizer having a melting point of 60 ° C. to 180 ° C., preferably a melting point of 80 ° C. to 140 ° C.
  • the heat-sensitive recording layer containing a binder, preferably a crosslinked or uncrosslinked binder selected from the group consisting of polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, a combination of polyvinyl alcohol and ethylene-vinyl alcohol -Copolymer, silanol group-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acrylate copolymer and film-forming acrylic copolymers.
  • a binder preferably a crosslinked or uncrosslinked binder selected from the group consisting of polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, a combination of polyvinyl alcohol and ethylene-vinyl alcohol -Copolymer, silanol group-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl
  • the coating composition for forming the heat-sensitive recording layer of the heat-sensitive recording material according to the invention preferably contains, in addition to one or more binders, one or more crosslinking agents for the binder or binders.
  • the crosslinking agent is selected from the group consisting of zirconium, Polyamidaminepichlorhydrinharzen, boric acid, glyoxal, dihydroxy bis (ammonium lactato) titanium (IV); xalderivaten and Glyo- (CAS No. 65104-06-5 Tyzor ® LA.).
  • a heat-sensitive recording material according to the invention whose heat-sensitive recording layer consists of such a coating composition, comprising an o the plurality of binders and one or more crosslinking agents formed for the binder or binders contains, in the heat-sensitive recording layer, one or more binders crosslinked by reaction with one or more crosslinking agents, the crosslinking agent or agents being selected from the group consisting of zirconium carbonate , Polyamide aminepichlorohydrin resins, boric acid, glyoxal, dihydroxy bis (ammonium lactato) titanium (IV) (CAS No. 65104-06-5; Tyzor ® LA) and glyoxal derivatives.
  • Crosslinking agent or agents being selected from the group consisting of zirconium carbonate , Polyamide aminepichlorohydrin resins, boric acid, glyoxal, dihydroxy bis (ammonium lactato) titanium (IV) (CAS No. 65104-06-5; Tyzor ® LA
  • a heat-sensitive recording material is preferred according to the invention, the weight per unit area of the heat-sensitive recording layer being in the range from 1.5 to 6 g / m 2 , preferably in the range from 2.0 to 5.5 g / m 2 , particularly preferably in the range from 2.0 to 4.8 g / m 2 .
  • Image stabilizers, dispersants, antioxidants, mold release agents, defoamers, light stabilizers and brighteners, as are known in the prior art, can additionally be used in recording materials according to the invention.
  • Each of the components is usually used in an amount with a mass fraction of 0.01 to 15%, in particular - with the exception of defoamers - 0.1 to 15%, preferably 1 to 10%, based on the total solids content of the heat-sensitive recording layer.
  • the defoamer can be present in the recording materials according to the invention in amounts with a mass fraction of 0.03 to 0.05%, based on the total solids content of the heat-sensitive recording layer.
  • the heat-sensitive recording layer is completely or partially covered with a protective layer. Due to the arrangement of a protective layer covering the heat-sensitive recording layer, the heat-sensitive recording layer is also shielded from the outside or to the carrier substrate of the next layer within a roll, so that protection against external influences takes place.
  • a protective layer in addition to protecting the heat-sensitive recording layer arranged under the protective layer from environmental influences, such a protective layer often has the additional positive effect of improving the printability of the heat-sensitive recording material according to the invention, in particular in indigo, offset and flexographic printing. For this reason, it may be desirable for certain applications that the heat-sensitive recording material according to the invention has a protective layer, although due to the presence of an encapsulated color developer as defined above in the heat-sensitive recording layer of the heat-sensitive recording material according to the invention, the resistance to fats that can be obtained on a heat-sensitive recording material according to the invention is already sufficient.
  • the protective layer of the heat-sensitive recording material according to the invention preferably contains one or more crosslinked or uncrosslinked binders selected from the group consisting of polyvinyl alcohols modified with carboxyl groups, polyvinyl alcohols modified with silanol groups, acetoacetyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohols, partially and fully hydrolyzed polyvinyl alcohols and film-forming acrylic copolymers.
  • the coating composition contains, in addition to one or more binders, one or more crosslinking agents for the binder or binders to form the protective layer of the heat-sensitive recording material according to the invention.
  • the crosslinking agent is then selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, epichlorohydrin, adipic acid dihydrazide, melamine-formaldehyde, urea, Methylolharn- cloth, ammonium zirconium carbonate, Polyamidepichlorhydrinharzen sodium glyoxylate, calcium ciumglyoxylat and dihydroxybis (ammonium lactato) titanium (IV ) Tyzor ® LA (CAS no. 65104-06-5).
  • a heat-sensitive recording material according to the invention whose protective layer is formed from such a coating composition containing one or more binders and one or more crosslinking agents for the binder or binders, contains one or more binders crosslinked by reaction with one or more crosslinking agents, the or the crosslinking agents are selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, epichlorohydrin, adipic acid dihydrazide melamine formaldehyde, urea, methylol urea, ammonium zirconium carbonate, Polyamidepichlorhydrinhar- zen sodium glyoxylate, Calciumglyoxylat and dihydroxybis (ammonium lactato) titanium (IV) Tyzor ® LA (CAS -No.
  • the protective layer which completely or partially covers the heat-sensitive recording layer is obtainable from a coating composition comprising one or more polyvinyl alcohols and one or more crosslinking agents. It is preferred that the polyvinyl alcohol of the protective layer is modified with carboxyl or in particular silanol groups. Mixtures of different carboxyl groups or silanol-modified polyvinyl alcohols can also be used with preference.
  • a protective layer has a high affinity for the preferably UV-curing printing ink used in the offset printing process. This is crucial to meet the demand for excellent printability within offset printing.
  • the crosslinking agent or agents for the protective layer according to this embodiment variant are preferably selected from the group consisting of boric acid, polyamines, epoxy resins, dialdehydes, formaldehyde oligomers, polyamine epichlorohydrin resin, adipic acid redihydrazide, melamine formaldehyde and dihydroxybis (ammonium lactato) titanium (IV) tyzor ® LA (CAS No. 65104-06-5). Mixtures of different crosslinking agents are also possible.
  • the mass ratio of the modified polyvinyl alcohol to the crosslinking agent in the coating composition for forming the protective layer in accordance with this embodiment variant is in a range from 20: 1 to 5: 1 and particularly preferably in a range from 12: 1 to 7: 1.
  • A is particularly preferred Ratio of the modified polyvinyl alcohol to the crosslinking agent in the range from 100 parts by mass to 8 to 11 parts by mass.
  • the protective layer according to this embodiment variant additionally contains an inorganic pigment.
  • the inorganic pigment is preferably selected from the group consisting of silicon dioxide, bentonite, aluminum hydroxide, calcium carbonate, kaolin and mixtures of the inorganic pigments mentioned.
  • the protective layer according to this embodiment variant with a mass per unit area in a range from 1.0 g / m 2 to 6 g / m 2 and particularly preferably from 1.2 g / m 2 to 3.8 g / m 2 .
  • the protective layer is preferably formed in one layer.
  • the coating composition comprises a water-insoluble, self-crosslinking acrylic polymer as a binder to form the protective layer Crosslinking agent and a pigment component, wherein the pigment component of the protective layer consists of one or more inorganic pigments and is formed with a mass fraction of at least 80% from a highly purified alkaline bentonite, the binder of the protective layer consists of one or more water-insoluble, self-crosslinking acrylic polymers and the binder / pigment ratio is in a range from 7: 1 to 9: 1.
  • a self-crosslinking acrylic polymer within the protective layer according to the second embodiment described here is preferably selected from the group consisting of styrene-acrylic acid ester copolymers, acrylamide group-containing copolymers of styrene and acrylic acid ester and copolymers based on acrylonitrile, methacrylamide and acrylic ester. The latter are preferred.
  • As a pigment alkaline processed bentonite, natural or precipitated calcium carbonate, kaolin, silica or aluminum hydroxide can be incorporated into the protective layer.
  • Preferred crosslinking agents are selected from the group consisting of cyclic urea, methylol urea, ammonium zirconium carbonate and polyamide epichlorohydrin resins.
  • the choice of a water-insoluble, self-crosslinking acrylic polymer as the binder and its mass ratio (i) to the pigment in a range from 7: 1 to 9: 1 and (ii) to the crosslinking agent is greater than 5: 1 for a protective layer with a relatively low mass per unit area a high environmental resistance of the heat-sensitive recording material according to the invention. Such mass ratios are therefore preferred.
  • the protective layer itself can be applied with the aid of conventional coating works, for which purpose a coating color can be used, preferably with a mass per unit area in a range from 1.0 to 4.5 g / m 2 .
  • the protective layer is printed.
  • Protective layers that are curable by actinic radiation are particularly suitable in terms of processing technology and in terms of their technological properties.
  • actinic radiation means UV or ionizing radiation, such as electron beams.
  • the appearance of the protective layer is largely determined by the type of smoothing and the roller surfaces and their materials influencing the friction in the smoothing unit and calender.
  • a roughness (Parker Print Surf roughness) of the protective layer of less than 2.0 pm is regarded as preferred.
  • smoothing units in which NipcoFlex TM or zone-controlled Nipco-P TM rollers are used has proven itself within the scope of the experimental work preceding this invention; however, the invention is not limited to this.
  • the heat-sensitive recording material on the heat-sensitive recording layer or, if a protective layer is arranged, on the protective layer has a Bekk smoothness determined in accordance with ISO 5627 in the range from 10 to 1200 s, preferably in the range from 100 to 1000 s, more preferably in the range from 250 to 900 s.
  • a heat-sensitive recording material additionally comprising an intermediate layer located between the carrier substrate and the heat-sensitive recording layer, the intermediate layer preferably containing pigments.
  • the pigments can be organic pigments, inorganic pigments or a mixture of organic pigments and inorganic pigments. It is preferred according to the invention if the mass per unit area of the intermediate layer is in the range from 5 to 20 g / m 2 , preferably in the range from 7 to 12 g / m 2 .
  • the pigments are organic pigments, preferably organic hollow body pigments.
  • the incorporation of organic pigments in the intermediate layer is advantageous, since organic pigments have a high heat reflectivity.
  • An increased heat reflection of the intermediate layer designed with organic pigments increases the response behavior of the heat-sensitive recording layer to heat, since the radiated heat is at least partially reflected in the heat-sensitive recording layer instead of leading it to the carrier substrate. This significantly increases the sensitivity and the resolving power of the heat-sensitive recording material and also increases the printing speed in the thermal printer.
  • the energy consumption during the printing process can be reduced, which is particularly advantageous in the case of mobile devices.
  • the pigments are inorganic pigments, preferably selected from the list consisting of calcined kaolin, silicon oxide, bentonite, calcium carbonate, aluminum oxide and boehmite .
  • inorganic pigments are incorporated into the intermediate layer between the recording layer and the substrate, these pigments can absorb the components (eg waxes) of the heat-sensitive recording layer that are liquefied by the heat of the thermal head during the formation of the typeface and thus promote an even safer and faster functioning of the heat-induced recording .
  • the inorganic pigments of the intermediate layer cm3 / 100 g, and more preferably 100 cm3 / 100 g, an oil absorption of at least 80, determined according to the Japanese standard JIS K 5101, have.
  • Calcined kaolin has proven particularly useful due to its large absorption reservoir in the cavities. Mixtures of several different types of inorganic pigments are also conceivable.
  • the quantitative ratio between organic and inorganic pigment is a combination of the effects brought about by the two types of pigment, which is particularly advantageously solved if the pigment mixture contains 5 to 30% or better 8 to 20% of organic and 95 to 70% by mass % or better, 92 to 80% consists of inorganic pigment.
  • Pigment mixtures of different organic pigments and / or inorganic pigments are conceivable.
  • the intermediate layer optionally containing at least one binder, in addition to the inorganic and / or organic pigments, preferably based on a synthetic polymer, with styrene-butadiene latex providing particularly good results.
  • a synthetic binder with the admixture of at least one natural polymer, such as particularly preferably starch is a particularly suitable embodiment.
  • a binder-pigment ratio within the intermediate layer between 3: 7 and 1: 9, each based on the mass fraction in% in the intermediate layer, represents a particularly suitable embodiment.
  • Another aspect of the present invention relates to products, preferably admission tickets, TITO tickets (ticket-in, ticket-out), flight, train, boat or bus tickets, gambling receipts, parking tickets, labels, receipts, bank statements, self-adhesive labels, medical and / or technical diagram paper, fax paper, security paper or barcode labels, comprising a heat-sensitive recording material according to the invention.
  • Another aspect of the present invention relates to the use of a heat-sensitive inventive barcode label, self-adhesive ticket, self-adhesive admission ticket, self-adhesive proof of purchase, self-adhesive label, self-adhesive admission ticket, admission ticket, TITO ticket (ticket-in, ticket-out), flight, Train, boat or bus tickets, gambling vouchers, parking tickets, labels, receipts, bank statements, medical and / or technical diagram paper, fax paper or security paper.
  • Another aspect of the present invention relates to a method for producing a heat-sensitive recording material, comprising at least the following method steps: i. Providing or manufacturing a carrier substrate; ii. Providing or producing a coating composition for producing a heat-sensitive recording layer, comprising a color former and capsules, the capsules comprising a core comprising or consisting of at least one color developer, and a core which completely or partially encloses the core
  • a further aspect of the present invention relates to a method for producing capsules each comprising a core, comprising or consisting of at least one color developer, and a shell which completely or partially encloses the core, at least comprising the following method steps: Preparing a paint developer dispersion, preferably an aqueous color developer dispersion;
  • a method according to the invention for the production of capsules is preferred, wherein as the starter of the radical polymerization of potassium peroxodisulfate (KPS), ammonium peroxodisulfate (APS), aza-diisobutyronitrile (AIBN), dibenzoyl peroxide (DBPO) or N, N, N ', N' - Tetramethylethylenediamine (TEMEDA) is added, preferably potassium peroxodisulfate (KPS) is added.
  • KPS potassium peroxodisulfate
  • the statements regarding heat-sensitive recording materials according to the invention apply accordingly.
  • a monomer mixture of the monomers methyl methacrylate (“MMA”) and diethylene glycol divinyl ether is particularly preferred in a process according to the invention.
  • MMA methyl methacrylate
  • diethylene glycol divinyl ether is particularly preferred in a process according to the invention.
  • a mass ratio between ethylene glycol dimethacrylate units and methyl methacrylate units in the copolymer in the range from 1: 3.65 to 1: 7.65 is preferred, preferably in the range from 1: 4.65 to 1: 6.65, particularly preferably in the range from 1: 5.15 to 1: 6.15.
  • a monomer or a monomer mixture to the paint developer dispersion prepared in several steps over a period of 2 to 7 hours or continuously over a period of 2 to 7 hours.
  • a paper web made of bleached and ground hardwood and coniferous cellulose pulps with a mass per unit area of 67 g / m 2 is produced on a Fourdrinier paper machine as carrier substrate with the addition of conventional additives in usual amounts.
  • an intermediate layer comprising cavity pigments and calcined kaolin as a pigment, styrene-butadiene latex as a binder and starch as a cobinder with a mass per unit area of 9 g / m 2 is applied with a roller doctor blade coater and conventionally dried.
  • a recipe shown in Table 3 below is used for the heat-sensitive recording layer.
  • the individual components listed in Table 3 are placed in a 500 ml plastic beaker. The mixture is then mixed with a high-speed stirrer for 30 minutes at room temperature to form a homogeneous dispersion.
  • Table 3 Composition of the coating composition for producing a heat-sensitive recording layer:
  • a heat-sensitive recording layer with a mass per unit area of 6.0 g / m 2 is applied to the intermediate layer with the aid of a doctor blade coater and conventionally dried and calendered after the application (roller pressure 600N / cm 2 at a speed of 25 m / min).
  • Example 2 is repeated, using an uncapsulated 3,5-di (a-methylbenzyl) salicylic acid dispersion instead of the 3,5-di (a-methylbenzyl) salicylic acid dispersion from example 1, the 3,5-di (a-methylbenzyl) salicylic acid content in the dispersion is the same.
  • calendering it is necessary to place a release paper between the heat-sensitive recording layer produced and the metal roller of the calender in order to prevent the heat-sensitive recording layer from sticking.
  • the heat-sensitive recording material produced showed a pink coloring of the background. Determination of the resistance of heat-sensitive recording materials to lanolin (5 minutes):
  • black / white checkered thermal test prints were made using a device of the GebE-Printer Lab type from Gebe on the heat-sensitive recording materials to be tested. After the black and white checkered thermal test prints had been made, the print density was determined using a TECHKON ® SpectroDens Advanced spectral densitometer at three points on the black-colored areas and the unstained areas of the thermal test prints after a rest period of more than 5 minutes. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • the thermal test print of the heat-sensitive recording material to be tested was coated with lanolin. After an exposure time of 5 minutes, the lanolin is carefully wiped off. After 4 hours, a determination of the print density was carried out again with a densitometer TECHKON ® SpectroDens Advanced - spectral densitometer at three points each of the black colored areas and the uncolored areas of the thermal test prints. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • the resistance to lanolin in% corresponds to the quotient of the average pressure density after the lanolin treatment and before the lanolin treatment multiplied by 100.
  • the black colored areas and the unstained areas of the thermal test printout were determined using a TECHKON ® SpectroDens Advanced - Spectral Densitometer densitometer carried out. The mean value was formed from the respective measured values of the black-colored areas and the uncolored areas.
  • a thermal test print was hung in a climate cabinet at 60 ° C. After 24 hours, the thermal paper printout was removed, cooled to room temperature and the print density was again determined at three points on the black-colored areas and the uncolored areas of the thermal test printout using a TECHKON ® SpectroDens Advanced spectral densitometer. The mean value was in each case formed from the respective measured values of black-colored areas and the uncolored areas. The durability of the printed image in% corresponds to the quotient of the mean value of the print density of the colored areas after and before storage in a climatic cabinet multiplied by 100.
  • the encapsulation of the color developer significantly improved the durability of the printed image and the contrast at 60 ° C.
  • the encapsulation of the color developer significantly improved the durability of the printed image and the contrast at 90 ° C.

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

Abstract

La présente invention concerne en premier lieu un matériau d'enregistrement thermosensible comprenant un substrat de support et une couche d'enregistrement thermosensible comprenant un précurseur de colorant et des capsules, les capsules présentant un noyau, contenant au moins un révélateur chromogène ou constitué de celui-ci, et une enveloppe entourant entièrement ou partiellement le noyau. La présente invention concerne en outre l'utilisation du matériau d'enregistrement thermosensible selon l'invention en tant que tickets, étiquettes, ticket de caisse et similaires. La présente invention concerne en outre un procédé de fabrication d'un matériau d'enregistrement thermosensible selon l'invention ainsi qu'un procédé de fabrication de capsules, qui contiennent dans le noyau au moins un révélateur chromogène.
PCT/EP2019/078953 2018-10-26 2019-10-23 Matériau d'enregistrement thermosensible à révélateur chromogène encapsulé Ceased WO2020084020A1 (fr)

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DE102018126744.4 2018-10-26
DE102018126744.4A DE102018126744A1 (de) 2018-10-26 2018-10-26 Wärmeempfindliches Aufzeichnungsmaterial mit verkapseltem Farbentwickler

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0109838A2 (fr) * 1982-11-17 1984-05-30 Fuji Photo Film Co., Ltd. Matériel pour l'enregistrement sensible à la chaleur et à la lumière
JPS61248786A (ja) * 1985-04-26 1986-11-06 Fuji Photo Film Co Ltd 感熱記録材料
EP0727251A2 (fr) * 1995-01-19 1996-08-21 Bayer Ag Microcapsules à paroi constituée par des produits de réaction de polyisocyanates et quanidines
JPH11105431A (ja) 1997-10-02 1999-04-20 Fuji Photo Film Co Ltd 感熱記録材料
US5952263A (en) 1996-10-22 1999-09-14 Ricoh Company, Ltd. Transparent thermosensitive recording material
US20140106963A1 (en) 2008-12-23 2014-04-17 Segan Industries, Inc. Tunable Directional Color Transition Compositions and Methods of Making and Using the Same
EP2923851A1 (fr) 2012-11-21 2015-09-30 Nippon Soda Co., Ltd. Matériau d'enregistrement produit en utilisant un composé non phénolique

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Publication number Priority date Publication date Assignee Title
DE19854866B4 (de) * 1997-11-27 2005-09-08 Mitsubishi Paper Mills Limited Wärmeempfindliches Aufzeichnungsmaterial

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0109838A2 (fr) * 1982-11-17 1984-05-30 Fuji Photo Film Co., Ltd. Matériel pour l'enregistrement sensible à la chaleur et à la lumière
JPS61248786A (ja) * 1985-04-26 1986-11-06 Fuji Photo Film Co Ltd 感熱記録材料
EP0727251A2 (fr) * 1995-01-19 1996-08-21 Bayer Ag Microcapsules à paroi constituée par des produits de réaction de polyisocyanates et quanidines
US5952263A (en) 1996-10-22 1999-09-14 Ricoh Company, Ltd. Transparent thermosensitive recording material
JPH11105431A (ja) 1997-10-02 1999-04-20 Fuji Photo Film Co Ltd 感熱記録材料
US20140106963A1 (en) 2008-12-23 2014-04-17 Segan Industries, Inc. Tunable Directional Color Transition Compositions and Methods of Making and Using the Same
EP2923851A1 (fr) 2012-11-21 2015-09-30 Nippon Soda Co., Ltd. Matériau d'enregistrement produit en utilisant un composé non phénolique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 65104-06-5

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