EP0600068A1 - Procede et feuille receptrice pour impression par transfert thermique. - Google Patents

Procede et feuille receptrice pour impression par transfert thermique.

Info

Publication number
EP0600068A1
EP0600068A1 EP93913368A EP93913368A EP0600068A1 EP 0600068 A1 EP0600068 A1 EP 0600068A1 EP 93913368 A EP93913368 A EP 93913368A EP 93913368 A EP93913368 A EP 93913368A EP 0600068 A1 EP0600068 A1 EP 0600068A1
Authority
EP
European Patent Office
Prior art keywords
dye
receiver sheet
receiver
sheet
receptive
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
EP93913368A
Other languages
German (de)
English (en)
Other versions
EP0600068B1 (fr
Inventor
Kenneth West Dysert Colch Hutt
Ian Richard Stephenson
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.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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
Priority claimed from GB929212630A external-priority patent/GB9212630D0/en
Priority claimed from GB9216277A external-priority patent/GB9216277D0/en
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0600068A1 publication Critical patent/EP0600068A1/fr
Application granted granted Critical
Publication of EP0600068B1 publication Critical patent/EP0600068B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • B41M5/46—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 the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays

Definitions

  • This invention relates to a thermal transfer printing method and to an imaged receiver sheet produced by the method.
  • Thermal transfer printing is a printing process in which a dye is caused, by thermal stimuli, to transfer from a dyesheet to a receiver sheet.
  • the dyesheet and receiver sheet are placed in intimate contact, the thermal stimuli are applied to the dyesheet and the dyesheet and receiver sheet are then separated.
  • the thermal stimuli By applying the thermal stimuli to pre-determined areas in the dye-sheet, the dye is selectively transferred to the receiver to form the desired image.
  • Receiver sheets conventionally comprise a substrate with a dye-receiving polar surface on one side, into which a dye is thermally transferable and retainable. Where the substrate is itself polar and capable of receiving a dye, the dye may be transferred directly to a surface of the substrate.
  • receiver sheets typically comprise a substrate supporting a receiver layer specifically tailored to receive the dye.
  • Receiver sheets may also comprise a backcoat to impart desirable characteristics including improved handling properties and to provide for improved ease of lamination. It is known to use polar polymers, for example, polyester and polyvinyl alcohol/polyvinylchloride copoly er, in the receiver layer as such polymers provide for good dye compatibility.
  • polar polymers we mean a polymer comprised of monomeric units which have a significant dipole moment.
  • Dye sheets conventionally comprise a substrate having on one side thereof, a dye layer comprising a thermally transferable dye dissolved and/or dispersed in a polymeric binder, which again is a polar polymer.
  • a polymeric binder which again is a polar polymer.
  • a light-absorbing material which may be present in the dye coat or may be present in a separate layer preferably located between the dye coat and the substrate in order to allow absorption of the inducing light.
  • problems with the dyesheet and receiver sheet are employed, problems with
  • release agents include silicone polymers for example siloxanes.
  • a receiver layer on the substrate allows a release agent to be incorporated in the dye-receptive surface but may lead to an increase in the cost of production of receiver sheets. Further, the presence of a release agent as an extra component in a receiver layer may also complicate the formulation and coating of the receiver layer onto the substrate.
  • thermal transfer printing is in the preparation of prints from images generated by a colour video camera.
  • quality of such prints be equal to that of prints provided by conventional silver halide photographic methods.
  • a reflective optical density of at least 1.6 is required for commercial acceptance.
  • a thermal transfer print has the same feel as a photographic print.
  • photographic prints are produced on paper having a surface coating of a polyolefin. Such paper is relatively cheap, is readily available and would, of course give the same feel as photographic prints.
  • polyolefins are apolar polymers( ie polymers comprised of monomeric unit which do not have a significant dipole moment) any tendency to bond to the polar material of the dye sheet is likely to be less.
  • GB Patent Specification No 2 217 866 does, in fact, disclose the use of such paper for thermal transfer prints using a heated print head as the source of the thermal stimuli.
  • the maximum O.D. achievable is only circa 50Z of the commercially acceptable value.
  • the prints have a tendency to fade with time.
  • the use of such paper with "conventional" thermal transfer printing is not viable.
  • a method of light-induced thermal transfer printing which comprises providing a receiver 15 sheet having a dye-receptive surface and a dye sheet having a light absorbing material for converting the inducing light into thermal energy and a dye coat comprising a binder and a dye, arranging the dyesheet on the receiver sheet such that dye coat and the said surface are adjacent, preferably in intimate contact, applying inducing light to the dyesheet which is absorbable by the ⁇ ⁇ light absorbing material to produce thermal stimuli in pre-determined areas of the dye sheet thereby to cause dye to transfer from the dye coat to the surface and separating the dyesheet and the receiver sheet wherein the said surface contains, as a dye-receptive medium, a substantially apolar organic polymeric material. 5
  • dye-receptive surface we mean the volume of the receiver sheet defined by at least part of the surface thereof and the depth of the sheet at that surface to which a dye may be transferred in a thermal transfer printing process.
  • the substantially apolar material comprises an organic 0 polymer having monomeric units a significant proportion of which do not comprise halogens and/or functional moieties comprising heteroatoms.
  • the invention further provides an imaged receiver sheet comprising a substrate optionally supporting a receiver layer which substrate (or, if present, receiver layer) has a dye-receptive surface which contains, as a 5 dye-receptive medium, a substantially apolar polymeric organic material containing a thermally transferable dye defining an image wherein the said dye is transferred to said dye-receptive surface by means of a light induced thermal transfer printing process.
  • a method and imaged receiver sheet according to the invention is advantageous as it enables a dye to be retained in the substantially apolar material of the receiver sheet without the need for the presence of a polar material to provide the appropriate dye compatibility and a dye image of acceptable quality may be secured.
  • the substantially apolar polymeric material in the receiver sheet has less of a tendency to stick to the dye sheet with which it is in contact during printing hence there is no need for a release agent as may be required with conventional receiver sheets to facilitate the release of the two sheets.
  • a further benefit of the invention, as a consequence of not requiring a release agent, is that it is not necessary to provide a separate receiver layer (in which the release agent is typically located) on the substrate.
  • An additional important advantage is that the feel of the final print will be substantially the same as a photographic print.
  • a receiver layer is present on the substrate of a receiver sheet of the invention provided that the said layer contains, as a dye-receptive medium, a substantially apolar polymeric organic material.
  • the presence of a receiver layer is optional rather than being necessary to accommodate a release agent.
  • the nature of the receiver layer need not be constrained by the requirement that it be compatible with a release agent.
  • the substantially apolar material contained in the dye-receptive surface suitably comprises a polyolefin, a mixture and/or a block or random copolymer of polyolefins.
  • Preferred polyolefins include polypropylene and polyethylene, isotactic polypropylene being particularly preferred.
  • a blend of polyolefins may be employed, and the relative amounts of the components of the blend may be selected to provide desirable porosity and surface gloss characteristics.
  • the substantially apolar material may be solid, porous or voided as desired.
  • the substantially apolar polymeric organic material is present in the dye-receptive surface in an amount by weight greater than any other organic component in the surface, preferably in an amount of at least 50Z, especially at least 802 and desirably substantially 1002 by weight of organic components in the said surface.
  • the dye-receptive surface preferably also comprises an inorganic filler to impart opacity which is especially desirable if the receiver sheet comprises a substrate without any receiving layer and to provide improved wear characteristics and optical density.
  • Suitable fillers include alumina, silica and particularly titanium dioxide.
  • a particularly preferred receiver sheet according to the invention comprises an isotactic polypropylene substrate having a filler comprising titanium dioxide.
  • the inorganic filler may be present in an amount of 0.5 to 50 2 and preferably 1 to 202 by weight of the dye-receptive surface.
  • the dye-receptive surface may comprise other organic materials, ⁇ as a minor proportion of the total organic materials in the dye-receptive surface, in addition to the substantially apolar material in order to impart desired characteristics to the surface.
  • Suitable organic materials include polymers for example polyvinyl chloride, polyacrylonitrile, polystyrenes and polyesters, and also include the monomeric compounds of suitable polymers including acrylonitrilebutylstyrene (ABS).
  • ABS acrylonitrilebutylstyrene
  • the apolar material is present in the dye receptive surface in an amount of at least 502 and preferably at least 802 by weight of the total organic components in the said surface.
  • the receiver sheet comprises a substrate having a dye-receptive surface without a separate receiver layer
  • the substrate is desirably adapted by the provision of a smooth surface texture.
  • the substrate may have a receiver layer on one side of the substrate, which layer comprises a dye-receptive surface comprising a substantially apolar polymeric organic material into which thermally ⁇ transferable dyes can readily pass in a TTP process. It is not necessary for the receiver layer to contain a material which acts as a release agent, preferably the receiver layer is substantially free of a release agent.
  • the receiver sheet comprises a substrate and a receiver layer having a dye-receptive surface
  • substrates known in the art may be employed in the present invention including cellulose fibre paper, synthetic paper for example TYVE synthetic paper, thermoplastic films for example polyethylene terephthalate (desirably biaxially orientated), filled and/or voided thermoplastic films for example pearl film, and laminates of two or more substrate materials.
  • the dye-receptive surface of the receiver layer comprises a substantially apolar organic polymeric material.
  • that part of the receiver layer which does not function as the dye-receptive surface may comprise a conventional receiver layer material for example polar polymers as described herein.
  • the substrate may also have a back coat on the opposite side to the dye-receiving surface, if desired, to impart desirable properties for example, to improve handling characteristics and to aid adhesion of a protective cover sheet to the receiver sheet.
  • the back coat if present, comprises a cross-linked polymer binder and is provided to impart desirable properties to the receiver sheet for example improved handling characteristics and reduced tendency to retransfer the dye at low temperatures.
  • the back coat may have a textured surface which may be imparted by a filler material or by the polymer per se.
  • a receiver sheet made according to the present invention may be laminated with a cover sheet on both sides to provide protection for the image on the sheet so that the receiver sheet is suitable for use asfor example as a security or identity badge.
  • the cover sheet may be the same or different on the different sides of the sheet and is preferably transparent on at least one side of the sheet.
  • the cover sheet suitably comprises a thermoplastic film, for example polyvinyl chloride, polyethylene terephthalate and polycarbonate compositions. When used in such a way, the receiver sheet may be in the form of a film of apolar polymeric material.
  • the inducing light is desirably a laser, for example Nd:YAG, Argon ion and Ti:sapphire and preferably a laser diode.
  • a laser for example Nd:YAG, Argon ion and Ti:sapphire
  • organic materials known to absorb at the laser wavelengths. Examples of such materials include the substituted phthalocyanines described in EP-B-157,568, which can readily be selected to match laser diode radiation at 750-900 nm, for example and carbon black pigment which has a broad absorption spectrum and is thus useful for a wide range of visible light and infra red emitting lasers.
  • Also of importance is the provision of sufficient absorber for the system used. It is desirable to use sufficient to absorb at least 502 of the incident inducing light. We prefer to use sufficient to absorb at least 902 of the inducing light, to obtain an optical density of 1 in transmission, although higher proportions may be used if desired.
  • a variety of materials can be used for the dyesheet substrate, including transparent polymer films of polyesters, polyamides, polyimides, polycarbonates, polysulphones, polypropylene and cellophane, for example.
  • Biaxially orientated polyester film is the most preferred, in view of its mechanical strength, dimensional stability and heat resistance.
  • the thickness of the substrate is suitably 1-50 ⁇ m, and preferably 2-30 ⁇ m. Any dye capable of being thermally transferred may be selected as required.
  • Dyes known to thermally transfer come from a variety of dye classes, eg from such nonionic dyes as azo dyes, anthraquinone dyes, azomethine dyes, methine dyes, indoaniline dyes, naphthoquinone dyes, quinophthalone dyes and nitro dyes.
  • the dyecoat binder can be selected from such known polymers as polycarbonate, polyvinylbutyral, and cellulose polymers, such as methyl cellulose, ethyl cellulose and ethyl hydroyethyl cellulose, for example, and mixtures of these.
  • the dyecoat may also include dispersing agents, antistatic agents, antifoaming agents, and oxidation inhibitors, and can be coated onto the absorber layer as described for the formation of the latter.
  • the thickness of the dyecoat is suitably 0.1-5 ⁇ m, preferably 0.5-3 ⁇ m.
  • the dyesheet may be elongated in the form of a ribbon and housed in a cassette for convenience, enabling it to be wound on to expose fresh areas of the dyecoat after each print has been made.
  • Dyesheets designed for producing multicolour prints have a plurality of panels of different uniform colours, usually three: yellow, magenta and cyan, although the provision of a fourth panel containing a black dye, has also previously been suggested.
  • these different panels When supported on a substrate elongated in the form of a ribbon, these different panels are suitably in the form of transverse panels, each the size of the desired print, and arranged in a repeated sequence of the colours employed.
  • panels of each colour in turn are held against a dye-receptive surface of the receiver sheet, as the two sheets are imagewise selectively heated the first colour being overprinted by each subsequent colour in turn to make up the full colour image.
  • a coating In applying a coating to a substrate, either for the dye sheet or the receiver sheet, various coating methods may be employed including, for example, roll coating, gravure coating, screen coating and fountain coating. After removal of any solvent, the coating can be cured for example by heating or by irradiation with for example ultra violet light, electiron beams and gamma rays.
  • a receiver sheet according to the invention was prepared by coating isotactic polypropylene onto a paper substrate to a coat weight of 15gsm.
  • a selection of dye sheets were prepared as follows: Dyesheets 1. 2. 3
  • polyester film having a back coat and a sub-coat was coated to a dry coat thickness of approximately l ⁇ m by gravure printing (yellow and magenta) and 2.5 ⁇ m using a Meyer bar (cyan) with the following dye compositions (amounts are in kg unless otherwise stated) and the compositions were dried by heating in air for about 15 seconds at 110°C:
  • Dyesheet 1 Dyesheet 2
  • Dyesheet 3 Yellow Ma enta Cyan
  • Yl was Cl solvent yellow 1.41; Y2 was Cl disperse yellow 126; Ml was 3-methyl-4(3-methyl-4-cyanoisothiazol-5-ylazo)-N-ethyl-N-acetoxyethyl aniline; M2 was Cl disperse red 60; Cl was
  • the prepared dyesheets were each brought into contact with a sample of the receiver sheet according to the invention by application of 1 atmosphere pressure.
  • An STC LT-100 laser diode operating at 807nm was collimated and then focused using a 160mm achromat lens.
  • the incident laser power at the dyesheet was about 60mW and the laser spot (full width at half maximum power) was about 30x20 ⁇ m.
  • the laser spot was scanned by a galvanometer scanner.
  • the dyesheet and receiver sheet were held on an arc which allowed focus to be retained throughout the scan length.
  • the scanning equipment addressed the laser to locations 20xl0 ⁇ m apart giving a good overlap of adjoining pixels.
  • the laser was pulsed for a a specific time of between 100 and 600 ⁇ s according to the desired optical density of the pixel to provide high resolution dye pixels on the receiver sheets.
  • the optical density of the transmitted dye was recorded using a Sakura densitometer operating in reflection mode and the results are listed in Table 1.
  • Example 2 The test carried out in Example 1 was repeated using the same dye-sheets and printing process with a receiver sheet comprising isotactic polypropylene filled with 32 by weight of the receiver sheet of titanium dioxide (rutile form).
  • the optical density of the transmitted dye was recorded using a Sakura densitometer operating in reflection mode and the results are listed in Table 1.
  • Example 1 The test carried out in Example 1 was repeated using the same dye-sheets and printing process and using a polyethylene based synthetic paper (TYVEK) as a receiver sheet.
  • TYVEK polyethylene based synthetic paper
  • the optical density of the transmitted dye was recorded using a Sakura densitometer operating in reflection mode and the results are listed in Table 1.
  • Example 1 was repeated except that the printing of the magenta dye was carried using a progammable print head supplying heat pulses of 2 to 10 ms (ie 2000 to 10,000 ⁇ s) .
  • the results are shown in Figure 1 and the results for magenta from Example 1 are shown in Figure 2.
  • An increase in maximum O.D. of from 0.8 to 2 ( i ⁇ an increase of 2502) is apparent, whereas Figures 3 and 4, which show the measured O.D. for magenta using a conventional receiver sheet printed by in both ways, shows an increase in maximum O.D. of from 2 to 3 ( ie an increase of only 502) .
  • Example 5 Ageing characteristics were investigated by storing the prints under ambiant conditions for circa one year and then remeasuring the O.D.
  • Figure 5 shows the results for prints made by the conventional print head method
  • Figure 6 shows the results for prints made in accordance with the invention.
  • O.D. there is an appreciable drop in O.D. at original levels as low as 0.3 wheras with printing in accordance with the invention there is no drop until an O.D. of 1.2.
  • conventional prints suffer a drop in maximum O.D. of 302 whereas prints according to the invention only drop by 102.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

Procédé d'impression par transfert thermique photo-induit, consistant à effectuer l'impression directement sur un matériau sensiblement apolaire, par exemple une polyoléfine, sans qu'il soit nécessaire d'utiliser un agent de séparation dans la surface de réception de colorant. L'invention se rapporte également à des feuilles réceptrices exposées à une image et comprenant une surface de réception de colorant contenant un matériau sensiblement apolaire.
EP93913368A 1992-06-15 1993-06-15 Procede et feuille receptrice pour impression par transfert thermique Expired - Lifetime EP0600068B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB929212630A GB9212630D0 (en) 1992-06-15 1992-06-15 Thermal transfer printing receiver sheet and method
GB9212630 1992-06-15
GB9216277 1992-07-30
GB9216277A GB9216277D0 (en) 1992-07-30 1992-07-30 Thermal transfer printing receiver sheet and method
PCT/GB1993/001267 WO1993025392A1 (fr) 1992-06-15 1993-06-15 Procede et feuille receptrice pour impression par transfert thermique

Publications (2)

Publication Number Publication Date
EP0600068A1 true EP0600068A1 (fr) 1994-06-08
EP0600068B1 EP0600068B1 (fr) 1997-08-13

Family

ID=26301066

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93913368A Expired - Lifetime EP0600068B1 (fr) 1992-06-15 1993-06-15 Procede et feuille receptrice pour impression par transfert thermique

Country Status (4)

Country Link
EP (1) EP0600068B1 (fr)
JP (1) JPH06509760A (fr)
DE (1) DE69313081T2 (fr)
WO (1) WO1993025392A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6228555B1 (en) * 1999-12-28 2001-05-08 3M Innovative Properties Company Thermal mass transfer donor element

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2217866B (en) * 1988-04-15 1992-02-12 Oji Paper Co Thermal transfer image-receiving sheet
GB8824366D0 (en) * 1988-10-18 1988-11-23 Kodak Ltd Method of making colour filter array
US5143904A (en) * 1989-07-18 1992-09-01 Oji Paper Co., Ltd Thermal transfer dye image-receiving sheet
US5126760A (en) * 1990-04-25 1992-06-30 Eastman Kodak Company Direct digital halftone color proofing involving diode laser imaging

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9325392A1 *

Also Published As

Publication number Publication date
WO1993025392A1 (fr) 1993-12-23
DE69313081D1 (de) 1997-09-18
DE69313081T2 (de) 1997-12-11
JPH06509760A (ja) 1994-11-02
EP0600068B1 (fr) 1997-08-13

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