EP0512476A1 - Aufzeichnungsmittel mit verringerter Farbstoffdiffusion - Google Patents

Aufzeichnungsmittel mit verringerter Farbstoffdiffusion Download PDF

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Publication number
EP0512476A1
EP0512476A1 EP92107576A EP92107576A EP0512476A1 EP 0512476 A1 EP0512476 A1 EP 0512476A1 EP 92107576 A EP92107576 A EP 92107576A EP 92107576 A EP92107576 A EP 92107576A EP 0512476 A1 EP0512476 A1 EP 0512476A1
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EP
European Patent Office
Prior art keywords
color
forming
layer
diffusion
imaging medium
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Granted
Application number
EP92107576A
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English (en)
French (fr)
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EP0512476B1 (de
Inventor
Peter R. Hagerty
Edward P. Lindholm
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Polaroid Corp
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Polaroid Corp
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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
    • 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
    • B41M5/305—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers with reversible electron-donor electron-acceptor compositions

Definitions

  • This invention relates to a imaging medium with reduced dye diffusion, and to an imaging process using such an imaging medium.
  • Imaging media which have at least one color-forming layer comprising a color-forming composition adapted to undergo a rapid change of color (from colorless to colored, from colored to colorless, or from one color to another) upon increase in the temperature of the color-forming layer above a color-forming temperature for a color-forming time.
  • the color change in such media need not be supplied by applying heat directly to the medium;
  • the color-forming composition may comprise a color-forming compound which undergoes a change of color upon heating above a color-forming temperature, and an absorber capable of absorbing actinic radiation and thereby generating heat in the color-forming layer.
  • thermal imaging media When such a medium is exposed to appropriate actinic radiation, this radiation is absorbed by the absorber, thereby heating the color-forming compound and causing it to undergo its color change.
  • thermal imaging media have the advantage over conventional silver halide media of not requiring a post-exposure developing step. Such thermal imaging media also have the advantage that they are essentially insensitive to visible light, so that they can be handled under normal lighting conditions.
  • U.S. Patents Nos. 4,602,263 and 4,826,976 both describe thermal imaging systems for optical recording and particularly for forming color images. These thermal imaging systems rely upon the irreversible unimolecular fragmentation of one or more thermally unstable carbamate moieties of an organic compound to effect a visually discernible color shift.
  • U.S. Patent No. 4602,263 and 4,826,976 both describe thermal imaging systems for optical recording and particularly for forming color images. These thermal imaging systems rely upon the irreversible unimolecular fragmentation of one or more thermally unstable carbamate moieties of an organic compound to effect a visually discernible color shift.
  • the color-developing component is a substantially colorless di- or triarylmethane imaging compound possessing within its di- or triarylmethane structure an aryl group substituted in the ortho position to the meso carbon atom with a moiety ring-closed on the meso carbon atom to form a 5- or 6-membered ring, said moiety possessing a nitrogen atom bonded directly to the meso carbon atom and the nitrogen atom being bound to a group with a masked acyl substituent that undergoes fragmentation upon heating to liberate the acyl group for effecting intramolecular acylation of the nitrogen atom to form a new group in the ortho position that cannot bond to the meso carbon atom, whereby the di- or triarylmethane compound is rendered colored.
  • thermal imaging systems using di- or triarylmethane compounds are described in U.S. Patents Nos. 4,720,450 and 4,960,901, while U.S. Patent No. 4,745,046 describes a thermal imaging system using as color-forming co-reactants a substantially colorless di- or triarylmethane compound possessing on the meso carbon atom within its di- or triarylmethane structure an aryl group substituted in the ortho position with a nucleophilic moiety which is ring-closed on the meso carbon atom, and an electrophilic reagent which upon heating and contacting the di- or triarylmethane compound undergoes a bimolecular nucleophilic substitution reaction with the nucleophilic moiety to form a colored, ring-opened di- or triarylmethane compound.
  • the color-forming component is a colorless precursor of a preformed image dye substituted with (a) at least one thermally removable protecting group that undergoes fragmentation from the precursor upon heating and (b) at least one leaving group that is irreversibly eliminated from the precursor upon heating, provided that neither the protecting group nor the leaving group is hydrogen, said protecting and leaving groups maintaining the precursor in its colorless form until heat is applied to effect removal of the protecting and leaving groups, whereby the colorless precursor is converted to an image dye.
  • the aforementioned patents describe a preferred form of imaging medium for forming multicolor images; in this preferred imaging medium, three separate color-forming layers, capable of forming yellow, cyan and magenta dyes respectively, are superposed on top of one another. Each of the three color-forming layers has an infra-red absorber associated therewith, these absorbers absorbing at differing wavelengths, for example 760, 820 and 880 nm. This medium is imagewise exposed simultaneously to three lasers having wavelengths of 760, 820 and 880 nm. (In the present state of technology, solid state diode lasers emitting at about 760 to 1000 nm provide the highest output per unit cost.
  • the color-forming materials also hereinafter referred to as "leuco dyes", with the understanding that the leuco dye may comprise more than one compound
  • the infra-red absorbers with the leuco dyes in order to ensure efficient absorption of the laser radiation and hence efficient heating of the leuco dye.
  • the resultant imagewise heating of the color-forming layers causes the leuco dyes to undergo color changes in the exposed areas, thereby producing a multicolored image, which needs no development.
  • This preferred type of imaging medium is capable of very high resolution images; for example, the medium can readily be imaged using a laser to produce a 2000 line 35 mm slide.
  • the sharpness of the image degenerates; for example, narrow lines with sharp, well-defined edges in the original image may become broader and show fuzzy edges after the image has been stored at room temperature for weeks or months.
  • Such fuzziness in the image is of course highly undesirable in a high resolution imaging system.
  • this invention provides an imaging medium comprising: a color-forming layer comprising a thermal color-forming composition adapted to undergo a change of color upon increase in the temperature of the color-forming layer above a color-forming temperature for a color-forming time, the color-forming composition being dispersed in a first polymer having a glass transition temperature of at least 50°C; and a diffusion-reducing layer in contact with one face of the color-forming layer, the diffusion-reducing layer comprising a second polymer, having a glass transition temperature of at least 50°C, and being essentially free from the color-forming composition.
  • This invention also provides a process for forming and storing a image, the process comprising: providing an imaging medium of the invention; imagewise heating the color-forming layer above the color-forming temperature for the color-forming time, thereby causing the color-forming composition to undergo the change of color in heated regions, produce a colored material in these heated regions, and thereby form an image; storing the image for a period of at least about one week without substantial diffusion of the colored material outwith the color-forming layer and the diffusion-reducing layer.
  • the imaging medium of the present invention comprises a color-forming layer comprising a color-forming composition dispersed in a first polymer having a glass transition temperature of at least 50°C, and a diffusion-reducing layer in contact with one face of the color-forming layer, having a glass transition temperature of at least 50°C, and being essentially free from the color-forming composition.
  • the color-forming composition desirably comprises a color-forming compound which undergoes a change of color upon heating above a color-forming temperature, and an absorber capable of absorbing actinic radiation and thereby generating heat in the color-forming layer.
  • This type of imaging medium can be imaged by actinic radiation rather than by direct heating, and a high resolution image is more easily achieved using actinic radiation, for example a focussed laser.
  • one or more than one color-forming layer may be provided with a diffusion-reducing layer or layers in accordance with the present invention.
  • the first polymer used in the imaging medium of the present invention desirably has a glass transition temperature of at least 75°C, and preferably at least 95°C.
  • This polymer is preferably an acrylic polymer, desirably poly(methyl methacrylate), which has a glass transition temperature of about 110°C.
  • the or each diffusion-reducing layer desirably has a glass transition temperature of at least 55°C, and preferably comprises an acrylic polymer, styrene-acrylic polymers being especially preferred.
  • Appropriate styrene-acrylic polymers are readily available commercially, and good results have been obtained using the acrylic latices sold as Joncryl 138 and 538 by S.C. Johnson & Son, Inc., Racine WI 53403, United States of America.
  • the glass transition temperatures of the diffusion-reducing layer can be higher than those of these specific polymers, difficulties may be encountered in producing media containing a plurality of adjacent layers, all of which have very high glass transition temperatures, and such media may not be very stable against cracking during storage, and thus it is generally convenient to use a very high glass transition temperature material (T g > 95°C) for the color-forming layer and a material of lower glass transition temperature (T g ⁇ 75°C) for the diffusion-reducing layer or layers.
  • T g > 95°C for the color-forming layer
  • T g ⁇ 75°C material of lower glass transition temperature
  • the or each diffusion-reducing layer must of course be thick enough to ensure that the color-forming composition cannot diffuse therethrough and thus migrate to other layers of the imaging medium where it may produce undesirable effects. On the other hand, it is desirable to avoid excessively thick diffusion-reducing layers, since such thick layers may adversely affect the resolution of the imaging medium.
  • the optimum thickness of diffusion-reducing layer in any specific imaging medium may readily be determined empirically. In general, it is preferred that the diffusion-reducing layer have a thickness of at least 1 ⁇ m.
  • the image-receiving layer should normally have a low glass transition temperature so that dye can readily diffuse thereinto.
  • the advantages of the present invention are not achieved simply by placing the color-forming composition in a layer of a polymer having a high glass transition temperature; provision of the diffusion-reducing layer having a glass transition temperature of at least about 50°C is also necessary to substantially reduce or overcome the problem of post-imaging diffusion of colored material.
  • the diffusion-reducing layer or layers should also be essentially free from (and preferably completely free from) the color-forming composition, since any color-forming composition present in the diffusion-reducing layer(s) may tend to migrate laterally during storage after imaging, with deleterious effects on the sharpness of the image produced.
  • the color-forming composition used in the present imaging medium may be any of those described in the aforementioned patents, or in various copending Applications.
  • the color-forming composition may be:
  • a multicolor imaging medium having two or more (usually three) different color-forming layers which produce different colors.
  • the color-forming layers are separated by solvent-resistant interlayers.
  • a preferred form of the present imaging medium comprises: a support; a first color-forming layer superposed on the support; a diffusion-reducing layer superposed on the first color-forming layer; a second color-forming layer superposed on the second diffusion-reducing layer, the second color-forming layer comprising a second color-forming composition adapted to undergo a change of color upon increase in the temperature of the color-forming layer above a second color-forming temperature for a second color-forming time, the color change undergone by the second color-forming layer being different from that undergone by the other color-forming layer; and an interlayer interposed between the diffusion-reducing layer and the second color-forming layer, the interlayer having a glass transition temperature less than 50°C.
  • the heat-sensitive element contains an infra-red absorbing substance for converting infra-red radiation into heat, which is transferred to the leuco dye to initiate the color-forming reaction and effect the change in the absorption characteristics of the leuco dye from colorless to colored.
  • the infra-red absorber should be in heat-conductive relationship with the leuco dye, for example, in the same layer as the leuco dye or in an adjacent layer.
  • the infra-red absorbers are desirably selected such that they absorb radiation at different predetermined wavelengths above 700 nm sufficiently separated so that each color-forming layer may be exposed separately and independently of the others by using infra-red radiation at the particular wavelengths selectively absorbed by the respective infra-red absorbers.
  • the color-forming layers containing yellow, magenta and cyan leuco dyes may have infra-red absorbers associated therewith that absorb radiation at 760 nm, 820 nm and 880 nm, respectively, and may be addressed by laser sources, for example, infra-red laser diodes emitting at these respective wavelengths so that the three color-forming layers can be exposed independently of one another. While each layer may be exposed in a separate scan, it is usually preferred to expose all of the color-forming layers simultaneously in a single scan using multiple laser sources of the appropriate wavelengths.
  • the leuco dyes and associated infra-red absorbers may be arranged in an array of side-by-side dots or stripes in a single recording layer.
  • the imaging medium may be heated prior to or during exposure. This may be achieved using a heating platen or heated drum or by employing an additional laser source or other appropriate means for heating the medium while it is being exposed.
  • the imaging medium of the present invention may comprise additional layers, for example, a subbing layer to improve adhesion to a support, interlayers for thermally insulating the color-forming layers from each other, an anti-abrasive topcoat layer, an ultra-violet screening layer having an ultraviolet absorber therein, or other auxiliary layers.
  • a subbing layer to improve adhesion to a support
  • interlayers for thermally insulating the color-forming layers from each other
  • an anti-abrasive topcoat layer an ultra-violet screening layer having an ultraviolet absorber therein, or other auxiliary layers.
  • ultra-violet screening layers are desirably provided on both sides of the color-forming layer(s); conveniently, one of the ultra-violet screening layers is provided by using as the support a polymer film containing an ultra-violet absorber, and such absorber-containing films are available commercially.
  • the leuco dyes are selected to give the desired color or combination of colors, and for multicolor images, the compounds selected may comprise the subtractive primaries yellow, magenta and cyan or other combinations of colors, which combinations may additionally include black.
  • the leuco dyes generally are selected to give the subtractive colors cyan, magenta and yellow, as commonly employed in photographic processes to provide full natural color.
  • the support employed may be transparent or opaque and may be any material that substantially retains its dimensional stability during image formation.
  • Suitable supports include paper, paper coated with a resin or pigment, such as calcium carbonate or calcined clay, synthetic papers or plastic films, such as polyethylene, polypropylene, polycarbonate, cellulose acetate, poly(ethylene terephthalate) and polystyrene. If it is desired to image through the support, the support must of course be sufficiently transparent that it does not interfere with the imaging process, and in this case it is also desirable that the support be substantially non-birefringent.
  • the or each color-forming layer contains a binder and is formed by combining the leuco dye, the infra-red absorber and the binder in a common solvent, applying a layer of the coating composition to the support and then drying. Rather than a solution coating, the layer may be applied as a dispersion or an emulsion.
  • the coating composition also may contain dispersing agents, plasticizers, defoaming agents, hindered amine light stabilizers and coating aids. In forming the color-forming layer(s) and the interlayers or other layers, temperatures should be maintained below levels that will cause the color-forming reaction to occur rapidly so that the leuco dyes will not be prematurely colored or bleached.
  • binders examples include poly(vinyl alcohol), poly(vinyl pyrrolidone), methyl cellulose, cellulose acetate butyrate, styrene-acrylonitrile copolymers, copolymers of styrene and butadiene, poly(methyl methacrylate), copolymers of methyl and ethyl acrylate, poly(vinyl acetate), poly(vinyl butyral), polyurethane, polycarbonate and poly(vinyl chloride).
  • the binder selected should not have any adverse effect on the leuco dye incorporated therein and may be selected to have a beneficial effect.
  • the binder should be substantially heat-stable at the temperatures encountered during image formation and it should be transparent so that it does not interfere with viewing of the color image. Where electromagnetic radiation is employed to induce imagewise heating, the binder also should transmit the light intended to initiate image formation.
  • the imaging medium (generally designated 10) shown in the drawing is intended for use in the production of transparencies and comprises a substantially transparent support 12 formed of 4 mil (101 ⁇ m) poly(ethylene terephthalate) (PET) film incorporating an ultra-violet absorber.
  • PET poly(ethylene terephthalate)
  • Appropriate PET films are readily available commercially, for example as P4C1A film from DuPont de Nemours., Wilmington, Delaware, United States of America.
  • the imaging medium 10 also comprises a diffusion-reducing subcoat 14 approximately 1 ⁇ m thick formed from a 10:1 w/w mixture of a water-dispersible styrene acrylic polymer (Joncryl 538 sold by S.C. Johnson & Son, Inc., Racine WI 53403, United States of America) and a water-soluble acrylic polymer (Carboset 526 sold by The B.F. Goodrich Co., Akron Ohio 44313, United States of America). As explained above, the presence of the minor proportion of water-soluble acrylic polymer reduces the tendency for the layer 14 to crack during the coating process.
  • a diffusion-reducing subcoat 14 approximately 1 ⁇ m thick formed from a 10:1 w/w mixture of a water-dispersible styrene acrylic polymer (Joncryl 538 sold by S.C. Johnson & Son, Inc., Racine WI 53403, United States of America) and a water-soluble acrylic polymer (Carboset 526 sold by The B.F.
  • the diffusion-reducing subcoat 14 which has a glass transition temperature of approximately 55°C, and serves the function of a conventional subcoat, namely increasing the adhesion of the color-forming layer 16 (described in detail below) to the support 12.
  • the subcoat 14 also serves to reduce or eliminate migration of colored material from the color-forming layer 16 after imaging; as noted above, if a conventional subcoat were employed in place of the diffusion-reducing subcoat 14, diffusion of the colored material from the layer 16 into the subcoat after imaging might cause loss of sharpness of the image.
  • the subcoat 14 is coated onto the support 12 from an aqueous medium containing the water-dispersible and water-soluble polymers.
  • a yellow color-forming layer 16 is in contact with the diffusion-reducing subcoat 14.
  • This color-forming layer 16 is approximately 5 ⁇ m thick and comprises approximately 47.5 parts by weight of the aforementioned Leuco Dye A, 1.6 parts by weight of an infra-red absorber of the formula: (which may be prepared by a process analogous to that described in U.S. Patent No. 4,508,811 using the 2,6-bis(1,1-dimethylethyl)-4-methylselenopyrylium salts described in the copending Application No. * (Attorney's ref.
  • the color-forming layer 16 is applied by coating from a mixture of heptanes and methyl ethyl ketone.
  • a second solvent-resistant interlayer 24 which is formed from the same material, and coated in the same manner as, the solvent-resistant interlayer 20.
  • the transparent bubble-suppressant layer 32 is a 1.75 mil (44 ⁇ m) PET film, a preferred film being that sold as ICI 505 film by ICI Americas, Inc., Wilmington, Delaware, United States of America.
  • the bubble-suppressant layer 32 prevents the formation of bubbles in the imaging medium 10 during imaging, and thus helps to ensure that the colors in the imaged medium are not affected by bubble formation.
  • the adhesive layer which is approximately 2 ⁇ m thick, is formed of a water-dispersible styrene acrylic polymer (Joncryl 138 sold by S.C. Johnson & Son, Inc., Racine WI 53403, United States of America) and is coated on to the ultraviolet filter layer 30 from an aqueous dispersion.
  • a water-dispersible styrene acrylic polymer (Joncryl 138 sold by S.C. Johnson & Son, Inc., Racine WI 53403, United States of America)
  • the entire structure containing these three layers is laminated under heat (approximately 225°F, 107°C) and pressure to the structure containing the layers 12-26 to form the complete imaging medium 10.
  • the imaging medium 10 may be provided with additional layers, for example an anti-abrasion layer, superposed on the bubble-suppressant layer 32.
  • diffusion-reducing layers are present only on either side of the yellow color-forming layer 16, and only this color-forming layer comprises a polymer having a glass transition temperature of 50°C.
  • this color-forming layer comprises a polymer having a glass transition temperature of 50°C.
  • this medium After imaging in the same manner as in Example 1, this medium showed a overall transmission optical density in blue light of 0.45. After the post-imaging storage, this density increased to 1.10, showing the extreme diffusion of color materials experienced with a low glass transition temperature binder in a color-forming layer.
  • the present invention is effective in preventing diffusion of the colored materials formed during imaging when the image is stored for substantial periods, and hence permits one to obtain sharp, well-defined images which do not suffer substantial loss of sharpness after storage.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP19920107576 1991-05-06 1992-05-05 Aufzeichnungsmittel mit verringerter Farbstoffdiffusion Expired - Lifetime EP0512476B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69619691A 1991-05-06 1991-05-06
US696196 1991-05-06

Publications (2)

Publication Number Publication Date
EP0512476A1 true EP0512476A1 (de) 1992-11-11
EP0512476B1 EP0512476B1 (de) 1995-07-12

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EP19920107576 Expired - Lifetime EP0512476B1 (de) 1991-05-06 1992-05-05 Aufzeichnungsmittel mit verringerter Farbstoffdiffusion

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EP (1) EP0512476B1 (de)
JP (1) JPH05127336A (de)
CA (1) CA2068024A1 (de)
DE (1) DE69203381T2 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0663301A1 (de) * 1994-01-14 1995-07-19 Agfa-Gevaert N.V. Aufzeichnungsmaterial für ein Direktbildverfahren durch Wärme
US9045654B2 (en) 2008-05-15 2015-06-02 3M Innovative Properties Company Multilayer articles capable of forming color images

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0231257A1 (de) * 1985-07-12 1987-08-12 The Upjohn Company Chemische verbindungen mit substituierten phenylringen

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 123 (M-581)(2570) 17 April 1987 & JP-A-61 263 795 ( CANON K.K. ) 21 November 1986 *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 21 (M-661)(2868) 22 January 1988 & JP-A-62 179 985 ( OJI PAPER K.K. ) 7 August 1987 *
PATENT ABSTRACTS OF JAPAN vol. 6, no. 210 (M-166)(1088) 22 October 1982 & JP-A-57 116 692 ( RICOH K.K. ) 20 July 1982 *
PATENT ABSTRACTS OF JAPAN vol. 8, no. 249 (M-338)(1686) 15 November 1984 & JP-A-59 124 890 ( KONISHIROKU SHASHIN KOGYO K.K. ) 19 July 1984 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0663301A1 (de) * 1994-01-14 1995-07-19 Agfa-Gevaert N.V. Aufzeichnungsmaterial für ein Direktbildverfahren durch Wärme
US9045654B2 (en) 2008-05-15 2015-06-02 3M Innovative Properties Company Multilayer articles capable of forming color images

Also Published As

Publication number Publication date
DE69203381D1 (de) 1995-08-17
DE69203381T2 (de) 1995-12-07
JPH05127336A (ja) 1993-05-25
EP0512476B1 (de) 1995-07-12
CA2068024A1 (en) 1992-11-07

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