EP0499369A1 - Bildempfangsmaterial für thermische Farbstoffübertragungen - Google Patents

Bildempfangsmaterial für thermische Farbstoffübertragungen Download PDF

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Publication number
EP0499369A1
EP0499369A1 EP92300627A EP92300627A EP0499369A1 EP 0499369 A1 EP0499369 A1 EP 0499369A1 EP 92300627 A EP92300627 A EP 92300627A EP 92300627 A EP92300627 A EP 92300627A EP 0499369 A1 EP0499369 A1 EP 0499369A1
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EP
European Patent Office
Prior art keywords
cross
receiver
dye
backcoat
receiver sheet
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.)
Granted
Application number
EP92300627A
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English (en)
French (fr)
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EP0499369B1 (de
Inventor
John Anthony Pope
Richard Anthony Hann
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication date
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Publication of EP0499369A1 publication Critical patent/EP0499369A1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/02—Dye diffusion thermal transfer printing (D2T2)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36—Backcoats; Back layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes

Definitions

  • the invention relates to thermal transfer printing, and especially to receivers having backcoats which provide a surface that can effectively be written on using aqueous inks, and to which water-activated adhesives can adhere.
  • Thermal transfer printing is a generic term for processes in which one or more thermally transferable dyes are caused to transfer from a dyesheet to a receiver in response to thermal stimuli.
  • a dyesheet comprising a thin substrate supporting a dyecoat containing one or more such dyes uniformly spread over an entire printing area of the dyesheet
  • printing can be effected by heating selected discrete areas of the dyesheet while the dyecoat is pressed against a dye-receptive surface of a receiver sheet, thereby causing dye to transfer to corresponding areas of that receiver.
  • the shape of the pattern transferred is determined by the number and locations of the discrete areas which are subjected to heating.
  • Full colour prints can be produced by printing with different coloured dyecoats sequentially in like manner, and the different coloured dyecoats are usually provided as discrete uniform print-size areas in a repeated sequence along the same dyesheet.
  • High resolution photograph-like prints can be produced by thermal transfer printing using appropriate printing equipment, such as a programmable thermal print head or laser printer, controlled by electronic signals derived from a video, computer, electronic still camera, or similar signal generating apparatus.
  • a typical thermal print head for example, has a row of individually operable tiny heaters spaced to print six or more pixels per millimetre, by providing very short hot pulses according to the electronic signals.
  • Receiver sheets comprise a substrate with a dye-receiving surface on one side.
  • the surface may simply be adapted by provision of a particularly smooth surface texture.
  • receiver sheets comprise a substrate supporting a receiver coat of a dye-receptive composition containing a material having an affinity for the dye molecules, and into which they can readily diffuse when an area of dyesheet pressed against it is heated during printing.
  • thermoplastic films such as biaxially orientated polyethyleneterephthalate film, filled and/or voided thermoplastic films such as pearl film, and laminates of two or more such sheets.
  • receiver sheets also have one or more polymer backcoats on the side of the substrate remote from the image-receiving side. These may be provided to fulfil a number of different roles, including improvement of handling properties to enable adjacent sheets to slide more easily over one another instead of sticking together. Good handling properties are particularly important in automatic printers where sheets are to be fed individually to the printing station from a cassette or stack of such sheets, and such improved handling may be achieved by applying an antistatic backcoat comprising a cross-linked polymer matrix doped with an antistatic agent.
  • the receiver may have a backcoat with a textured surface to reduce blocking, typically by having particulate material partially embedded in a cross-linked polymer matrix, suitably one doped with an antistatic agent as above. Examples of very effective antistatic backcoats are described, for example, in EP-A-409,526.
  • the photograph-like images that can be obtained with thermal transfer printing open up many of the photography markets to the versatile techniques of electronic imaging.
  • immediate printing capability for example, is useful for instant photograph booths, recording criminal or scientific evidence, or other occasional small quantity uses.
  • Displays and holiday postcards can also take advantage of the ability to mix signals in electronic imaging, enabling portraits to be superimposed on prerecorded backgrounds, for example.
  • the hydrophobic nature of the back of many current receiver sheets can be infuriating to the user, in their inability to accept aqueous-based inks and adhesives.
  • Antistatic backcoats described EP-A-409,526 comprise various crosslinked polymer matrices doped with alkali metal salt antistatic agents.
  • some (but not all) of the cross-linked polymer matrices referred to therein also provide backcoats having good writability with aqueous inks and stickability with aqueous-based adhesives.
  • cross-linked polymers that give good writability there is generally surprisingly little (if any) deterioration in handling properties when the alkali metal salts are omitted (though that is not true for other matrices described therein), and that such omission may also bring a surprising benefit in improved retransfer resistance.
  • a receiver sheet for thermal transfer printing comprises a substrate having a dye-receiving surface on one side and supporting a backcoat on the other, characterised in that the backcoat comprises a cross-linked organic polymer which is a reaction product of a polyalkylene glycol and a polyfunctional organic cross-linking agent reactive with the terminal hydroxyl groups of the polyalkylene glycol, said backcoat being free from alkali metal salts.
  • dye diffusion thermal transfer relies on dyes being sufficiently mobile to diffuse from one polymer environment into another when heat is applied by the printer.
  • backcoats are generally polymer-based, and when they are held in contact with dye-containing prints for extended periods, eg during storage, some retransfer of the dye may occur, wherein dye molecules forming the printed image rediffuse out of the dye-receiving surface and into the backcoat of an adjacent sheet against which it is held during storage. This can happen even at the relatively low temperatures of ambient conditions, and is an unwanted side effect commonly observed when thermal transfer prints are stored in contact with each other, eg in an envelope, paper wallet or box.
  • polyethylene glycols are polyethylene glycols. We have also obtained useful results with polypropylene glycols, but as the series progresses, the moisture resistance is reduced and the strength of the coating decreases.
  • Polyethylene glycols are readily available in molecular weights up to about 35,000 (weight average), but for the present application we prefer to use polyethylene glycols of average molecular weights of about 10,000 and under, to avoid coating problems that can occur with higher molecular weight materials, and we particularly prefer molecular weights of about 2,000 or less, to maintain a high level of cross-linking. (By "about” we mean to include such ranges as may be included by the manufacturers on either side of the nominal figure quoted.) Very low molecular weight polyethylene glycols, especially diethylene glycol and triethylene glycol are particularly suitable.
  • cross-linking agents capable of reacting with terminal hydroxyl groups of polyalkylene glycols, tend to be very reactive compounds with generally low shelf lives, though some may be functionally blocked.
  • a readily available range of cross-linking agents which we find to be particularly effective and also user-friendly is the polyfunctional N-(alkoxymethyl)amino resins.
  • polyfunctional N-(alkoxymethyl)amino resins include alkoxymethyl derivatives of urea, guanamine and melamine resins.
  • Lower alkyl compounds ie up to the C4 butoxy derivatives
  • the methoxy derivative is much preferred because of the greater ease with which its more volatile by-product (methanol) can be removed afterwards.
  • hexamethoxymethylmelamines examples of the latter which are sold by American Cyanamid in different grades under the trade name Cymel, are the hexamethoxymethylmelamines, suitably used in a partially prepolymerised (oligomer) form to obtain appropriate viscosities.
  • Hexamethoxymethylmelamines are 3-6 functional, depending on the steric hindrance from substituents and are capable of forming highly cross-linked materials using suitable acid catalysts, eg p-toluene sulphonic acid (PTSA).
  • PTSA p-toluene sulphonic acid
  • Our preferred backcoats are textured, the texture being provided by particulate material within the size range 2 to 10 ⁇ m in diameter, embedded in the cross-linked polymer.
  • the particulate material preferably comprises a mixture of small and large particles, at least 90% of the particles being within the size ranges 2-3 ⁇ m and 7-10 ⁇ m, with the particles distributed between the two size ranges according to a ratio of smaller to larger in the range 2:1 to 1:5.
  • Such textured surfaces can improve tooth to give writability with pencils and ball-point pens. They can also bring advantages during manufacture, to the winding characteristics of long webs of receiver sheet. The roughness of such surfaces may also help to reduce slip when receiver sheets are being transported by the printer during printing, and improve handling properties by facilitating sliding of cut receiver sheets, one over the other, when stacked before or after printing.
  • the proportion of particulate material to the polymer matrix of the backcoat (which may include thermoplastic polymers in addition to the cross-linked thermoset material) can be varied over a considerable range and still provide a beneficial effect.
  • a suitable range is from 0.5 to about 50% by weight of the total polymer content of the composition. Quantities less than 0.5% tend to have little effect, and we prefer a well loaded composition, the upper limit being determined by the required strength of the coating. Such coatings become crumbly if too much is added, and the optimum will vary with the particulate material used. Increasing the loading of the small size particles gives an increasingly mat finish, and good ink-absorption properties, while increasing the larger particles gives greater tooth, as described above.
  • receiver sheets are those in which the backcoat has a textured surface and consists essentially of
  • the polymer composition can include other polymeric materials, including both thermoset and thermoplastic polymers; but to maintain the writability and stickability of the resulting backcoat, the cross-linked polyalkylene glycol reaction product preferably provides about half or more of the polymer composition.
  • the polymer constituent of the backcoat shall consist entirely of the cross-linked reaction products of the polyalkylene glycols, thereby to maximise the benefits thereof.
  • retransfer is a problem associated with dye-diffusion thermal transfer technology, which relies on dyes being able to diffuse into the receiver, and hence being susceptible to diffusion out of it again. It is thus a problem that is not experienced in other forms of thermal transfer, such as sublimation transfer in which dye vapour condenses from the surrounding atmosphere onto a receiving surface, or melt transfer (sometimes referred to as mass transfer) in which an ink sheet has an ink coat of a dye or pigment dispersed in a meltable resin, which when melted carries the dye or pigment with it onto the receiver surface. Because dye-diffusion transfer requires this ability to diffuse through the receiver, most receivers differ from those used for such other techniques by the provision of a special receiver coat having such diffusion properties.
  • Such dye-diffusion can be driven by a concentration gradient, so the resistance of the present backcoat to retransfer of the dye molecules, is particularly pertinent to receiver sheets specifically adapted for dye-diffusion transfer by the provision of a receiver coat.
  • our preferred receiver is one wherein the dye-receiving surface is provided by a receiver coat supported on the substrate, the receiver coat comprising a dye-receptive composition containing a material having an affinity for the dye molecules, and through which they can diffuse when driven by a concentration gradient.
  • Receiver sheets according to the first aspect of the invention are particularly suited to use in the configuration of long strips wound as a roll onto a core, eg in a cassette from which the printer may withdraw appropriate lengths as required.
  • Most of the present receiver sheets can also be cut into individual print size portions, and sold as a stack of receivers, whether in a cartridge adapted for an automatic feed printer, or as a refill pack.
  • the backcoat polymeric material is predominantly, or preferably entirely, consisting of the cross-linked polyalkylene glycols.
  • a receiver sheet according to the first aspect of the invention having the configuration of an elongated strip of multiple-print length, wound into a roll and packaged for use in a continuous feed thermal transfer printer.
  • This enables the receiver sheet to be fed to the printing station as required, without precut sheets having to slide one over the other, and sticking and jamming the printer; and once printed taking advantage of the lower retransfer properties obtained in the absence of alkali metal antistatic agents according to the present invention.
  • the present backcoat enables the backs of the prints to be individually endorsed with aqueous inks immediately they emerge from the printer, or indeed at any time later.
  • a receiver sheet as described above, wherein the dye-receiving surface is provided by a dye-receptive composition, characterised in that the receiver has been printed by dye-diffusion thermal transfer printing and as a consequence the dye-receptive composition contains transferred image-forming dyes diffused therein.
  • the sheet shown in Fig 1 has a substrate of biaxially orientated polyethyleneterephthalate film 1. Coated onto one side of this (ie the dye-receiving side) is a conducting undercoat 2, overlain by a receptive layer 3. On the other side remote from the dye-receiving side is a backcoat 4 according to the present invention.
  • a strip 21 of the same sheet is shown wound around a core 22, to form a roll 23 suitable for use in a printer with a continuous receiver feed mechanism.
  • the invention is illustrated by a series of receiver sheets using various coating compositions, the receiver sheets being cut lengths of that shown in the drawings.
  • the substrate was a large web of opaque white Melinex 990 biaxially orientated polyester film (ICI).
  • ICI biaxially orientated polyester film
  • a backcoat was first applied, followed by a conductive undercoat and its overlying receiver layer on the other side, as described below.
  • the first coat to be applied to the web was the backcoat.
  • One surface of the web was first chemically etched to give a mechanical key, and (for Example 1) a backcoat coating composition prepared from the following: (Gasil EBN and Syloid 244 are brands of silica particles sold by Crosfield and Grace respectively, and Diakon MG102 is a polymethylmethacrylate sold by ICI).
  • the backcoat composition was prepared as two solutions, these being a thermoset precursor solution, and a filler dispersion containing the acid catalyst. Shortly before use, the two solutions were mixed to give the above composition. This was then machine coated onto the etched surface, dried and cured to form a 1.5-2 ⁇ m thick backcoat.
  • a conductive undercoat composition was prepared consisting of: (K-Flex is a polyester polyol sold by King Industries and PVP is polyvinyl pyrrolidone, both being added to adjust the coating properties.)
  • This composition was prepared initially as separate solutions of the reactive ingredients, these being mixed shortly before use. This composition was then machine coated onto the opposite side of the substrate from the backcoat, dried and cured at 110°C to give a dry coat thickness of about 1 ⁇ m.
  • the receiver layer coating composition also used Cymel 303 and an acid catalysed system compatible with the conductive undercoat, and consisted of: (Tegomer HSi 2210 is a bis-hydroxyalkyl polydimethylsiloxane, cross-linkable by the Cymel 303 under acid conditions to provide a release system effective during printing, being sold by Th Goldschmidt.)
  • This coating composition was made by mixing three functional solutions, one containing the dye-receptive Vylon and the Tinuvin UV absorber, a second containing the Cymel cross linking agent, and the third containing both the Tegomer silicone release agent and the Nacure solution to catalyse the crosslinking polymerisation between the Tegomer and Cymel materials.
  • the receiver composition was coated onto the conductive undercoat, dried and cured 140°C to give a dye-receptive layer about 4 ⁇ m thick.
  • Example 1a a further receiver web was also prepared in the manner of the above, except that the backcoat composition comprised three elements, the third being a solution of lithium nitrate sufficient to contribute 1 part by weight of lithium nitrate in the total composition.
  • Each of the receiver webs was cut into standard sizes, and fed through a thermal transfer printer from a stack. Single sheets were fed from the stack in turn, and printed with a full colour image. No handling problems were experienced during printing, and any subjective handling improvements which may have been noticed when changing from Example 1 to 1a, or from 2 to 2a, was small.
  • postage stamps were moistened, and applied to the backcoats. When dry they could not readily be removed without damage.
  • compositions In the table below are provided further backcoat compositions. These have been selected to show a wide range of polyalkylene glycols that can be used, including polypropylene glycol and a series of polyethylene glycols ranging from those having a high molecular weight, down to diethylene glycol. The percentages quoted are by weight of the composition including the antistatic agent but excluding the acid catalyst.
  • preparing the compositions for Examples 3 to 9 separate solutions of the polyalkylene glycol and the polyfunctional cross-linking agent were made up and mixed just before use, in the manner of the previous Examples. For the comparative Examples 3a to 9a, a further solution containing the alkali metal salt was also prepared and mixed with the other two just before use.
  • PPG polypropylene glycol
  • PEG polyethylene glycol
  • Trigol triethylene glycol
  • Digol diethylene glycol
  • Triflate is lithium trifluoro methane sulphate
  • KFBS potassium nona fluoro-1-butane sulphonate
  • PTSA is p-toluene sulphonic acid (amine blocked).
  • compositions shown in the above table provide the basic polymer precursors, antistatic agents for the comparison Examples, and acid catalysts used in the composition.
  • a filler dispersion when the solutions are mixed shortly before coating onto the receiver substrate and drying.
  • the filler may be a mixture of species as shown in Example 1, or a single species.
  • the backcoat composition (which again is applied, dried and cured first) has the following composition:
  • Pergopak M3 is a micronised urea formaldehyde polymer, manufactured by Martinswerk, and provides the bulk of the particulate filler.
  • some of the larger silica particles (Gasil EBN) have been retained to give sufficient tooth for effectiove writing with pencils and ball point pens.
  • the good aqueous wettability of such compositions again provides a surface that can effectively be written on using aqueous inks, and to which water-activated adhesives can adhere.
EP92300627A 1991-02-11 1992-01-24 Bildempfangsmaterial für thermische Farbstoffübertragungen Expired - Lifetime EP0499369B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9102801 1991-02-11
GB919102801A GB9102801D0 (en) 1991-02-11 1991-02-11 Thermal transfer printing receiver

Publications (2)

Publication Number Publication Date
EP0499369A1 true EP0499369A1 (de) 1992-08-19
EP0499369B1 EP0499369B1 (de) 1995-06-14

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EP92300627A Expired - Lifetime EP0499369B1 (de) 1991-02-11 1992-01-24 Bildempfangsmaterial für thermische Farbstoffübertragungen

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EP (1) EP0499369B1 (de)
JP (1) JPH0640176A (de)
AT (1) ATE123709T1 (de)
DE (1) DE69202874T2 (de)
GB (1) GB9102801D0 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0709230A1 (de) * 1994-10-27 1996-05-01 Dai Nippon Printing Co., Ltd. Bildempfangsschicht für thermische Übertragung
US6660397B2 (en) * 2002-02-21 2003-12-09 Toray Plastics (America), Inc. Thermoplastic sheet with scratch resistant surface and method of making same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5462911A (en) 1993-09-24 1995-10-31 Dai Nippon Printing Co., Ltd. Thermal transfer image-receiving sheet
KR102020485B1 (ko) 2013-01-11 2019-09-11 삼성디스플레이 주식회사 블록 공중합체, 그 형성 방법 및 패턴 형성 방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0409526A2 (de) * 1989-07-21 1991-01-23 Imperial Chemical Industries Plc Empfangsmaterial für die thermische Farbstoffübertragung
EP0444588A1 (de) * 1990-02-27 1991-09-04 Eastman Kodak Company Empfangselement für die thermische Farbstoffübertragung mit Polyethylenoxidrückschicht

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0409526A2 (de) * 1989-07-21 1991-01-23 Imperial Chemical Industries Plc Empfangsmaterial für die thermische Farbstoffübertragung
EP0444588A1 (de) * 1990-02-27 1991-09-04 Eastman Kodak Company Empfangselement für die thermische Farbstoffübertragung mit Polyethylenoxidrückschicht

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0709230A1 (de) * 1994-10-27 1996-05-01 Dai Nippon Printing Co., Ltd. Bildempfangsschicht für thermische Übertragung
US5943084A (en) * 1994-10-27 1999-08-24 Dai Nippon Printing Co., Ltd. Thermal transfer image-receiving sheet
US6660397B2 (en) * 2002-02-21 2003-12-09 Toray Plastics (America), Inc. Thermoplastic sheet with scratch resistant surface and method of making same

Also Published As

Publication number Publication date
GB9102801D0 (en) 1991-03-27
DE69202874T2 (de) 1995-11-16
ATE123709T1 (de) 1995-06-15
JPH0640176A (ja) 1994-02-15
EP0499369B1 (de) 1995-06-14
DE69202874D1 (de) 1995-07-20

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