WO1994016904A1 - Element pour former une image thermosensible - Google Patents
Element pour former une image thermosensible Download PDFInfo
- Publication number
- WO1994016904A1 WO1994016904A1 PCT/EP1993/003635 EP9303635W WO9416904A1 WO 1994016904 A1 WO1994016904 A1 WO 1994016904A1 EP 9303635 W EP9303635 W EP 9303635W WO 9416904 A1 WO9416904 A1 WO 9416904A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- imaging element
- film layer
- amino
- methyl
- image
- Prior art date
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
- B41M5/42—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
-
- 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
- B41M5/40—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
- B41M5/41—Base layers supports or substrates
-
- 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
- B41M2205/04—Direct thermal recording [DTR]
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- 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
- B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
-
- 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
- B41M5/337—Additives; Binders
- B41M5/3372—Macromolecular compounds
Definitions
- This invention relates to an imaging element that can be imaged by means of heat, and to a method of protecting said imaging elements, and more particularly to imaging elements for the preparation of negative copies of graphic images.
- the invention relates to coloured imaging products which are decolourised by brief heating to thermographic copying temperatures. Such products are useful e.g. in the preparation of negative colour projection transparencies, e.g. by thermal printers.
- the coloured reaction product can be decolourized simply by heating, the acid component being readily removed and the coloured imaging body becomes returned to a colourless or leuco state.
- the above imaging elements are inherently unstable and are difficult to store both before use, and after receiving a graphic image.
- the present invention provides a more stable thermographic imaging element containing a heat-decomposable coloured reaction product of a dye precursor and a volatizable organic acid.
- an imaging element comprising a support having a colour layer of polymeric binder including a reaction product of a dye-precursor and a volatizable organic acid, characterised in that the colour layer is covered by a transparent polymeric film layer containing compounds having amino groups.
- the film layer polymer and/or copolymer has a glass transition temperature (Tg) of at least 60° C and preferably about 80° C.
- Tg glass transition temperature
- the film layer is formed from amino modified polysaccharide for example, amino modified dextran or an amino modified pullulan as disclosed in EP-A-514990.
- Pullulan is a polysaccharide that is produced by micro-organisms of the Aureobasidium pullans type (Pullaria pullulans) and that contains maltotriose repeating units connected by an «_ -1,6 glycosidic bond. Pullulan is generally produced on an industrial scale by the fermentation of partially hydrolysed starch or by bacterial fermentation of sucrose . Pullulan is commercially available from Shodex Pharmacosmos.
- amino containing materials are amino modified cellulose (both natural and synthetic ) , homo- and co-polymers of vinylmonomers having an amino group, amino modified methacrylates e.g. a methacrylate co-polymer including at least 25% by weight of N-tert-butylamino ethyl methacrylate. Low molecular weight amino group containing compounds may also be added to the polymeric film layer.
- the cover layer may contain additives such as matting agents, ultra-violet radiation absorbers, and anti-oxidants.
- an imaging element comprising a support having a colour layer of polymeric binder including a reaction product of a dye precursor and a volatizable organic acid, characterised in that the colour layer is coated with a polymeric film layer containing compounds having amino groups.
- the film layer is applied as an aqueous dispersion or solution of polymeric material.
- triarylmethanelactone compounds such as 3,3-bis (p-dimethylaminophenyl)-6- dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl)phthalide, 3- (p-dimethylaminophenyl) 3-(1,2-dimethylindole-3-yl)phthalide, 3-(p- dimethylaminophenyl) -3-(2-methylindole-3-yl)phthalide, 3,3-bis (1,2- dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-bis (1,2- dimethylindole-3-yl)-6-dimethylaminophthalide, 3,3-bis (9- ethylcarbazole-3-yl) -6-dimethylaminophthalide, 3,3-bis (2- phenylindole-3-yl)-6-d
- Still further dye precursors for use in connection with the present invention are disclosed in e.g. US-P-4.803.148, EP-A-302529, DE-A-3.807.744, DE-A-3.942.227, DE-A-3.810.207, US-P4.753.759 and the references cited therein.
- the dye precursors may be used either solely or in combination.
- the dye precursor and colour developer are arranged in a polymeric layer on the support of the imaging element.
- binders for these layers there can be used e.g. polyesters, polyamides, e.g. N-methoxymethyl polyhexamethylene adipamide, vinylidene chloride copolymers, e.g. vinylidene chloride/acrylonitrile, vinylidene chloride/methylacrylate and vinylidene chloride/vinylacetate copolymers etc., ethylene/vinyl acetate copolymers, cellulosic ethers, e.g. methyl cellulose, ethyl cellulose and benzyl cellulose, polyethylene, synthetic rubbers, e.g.
- butadiene/acrylonitrile copolymers and chloro-2-butadiene-l,3 polymers, cellulose esters, e.g. cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate, cellulose nitrate, polyvinyl esters, e.g. polyvinyl acetate/acrylate, polyvinyl acetate/methacrylate and polyvinyl acetate, polyacrylate and alpha-alkyl polyacrylate esters, e.g. polymethyl methacrylate and polyvinyl acetate, high molecular weight polyethylene oxides of polyglycols having average molecular weights from about 4,000 to 1, 000, 000,.
- cellulose esters e.g. cellulose acetate, cellulose acetate succinate and cellulose acetate butyrate, cellulose nitrate
- polyvinyl esters e.g. polyvinyl acetate/acrylate, polyvinyl acetate/
- polyvinyl chloride and copolymers e.g. polyvinyl chloride/acetate, polyvinylchloride/acetate/alkohol, polyvinyl acetal, e.g. polyvinyl butyral, polyvinyl formal, polyformaldehydes, polyurethanes and copolymers, polycarbonate and copolymers, polystyrenes and copolymers e.g.
- polystyrene/acrylonitrile polystyrene/acrylonitrile/butadiene
- polyvinyl alcohol polystyrene/acrylonitrile
- cellulose polystyrene/acrylonitrile/butadiene
- polyvinyl alcohol polyvinyl alcohol
- cellulose anhydrous gelatin
- phenolic resins and melamine-formaldehyde resins etc. or mixtures of one ore more of the above polymers.
- Suitable supports for the imaging element in connection with the present invention are supports that are stable at the heating temperatures used for image-wise or overall heating the imaging element to obtain an image.
- useful supports are e.g. polyester film supports e.g. polyethylene terephthalate, glass, wood, paper, polyethylene coated paper, cellulose esters e.g. cellulose acetate, cellulose propionate, cellulose butyrate, poly carbonate, polyvinyl chloride, polyimide, polypropylene etc.
- An adhesive layer (sometimes called a subbing layer ) may be placed between the support and the colour layer.
- the colour layer may be imaged under thermographic copying procedures in which the colour disappears at the heated image areas. This may be achieved by use of a thermal head , or by using laser techniques together with an imaging element capable of converting light into heat by use of a suitable colour complex in the colour layer or an additional light sensitive substance.
- Leuco dye L-2 (formula see below) 2.50%
- Copolymer (vinyl chloride/vinyl acetate) (SOLVIC 560 RA, Solvay) 1.50%
- Leuco dye L-3 (formula see below) 2.50%
- Polymer dispersion F (water) 3.00%
- Polymer dispersion G (water) 3.00% Copolymer of 75% methyl methacrylate 25% ethyl methacrylate
- the dye solution and the polymer solution or dispersion respectively were coated with a wet film thickness of 50 ⁇ each in the described order on a polyethylene terephthalate base with a thickness of 63 ⁇ m and dried at 50° C to leave a coloured coating or layer.
- Each of the samples was imaged with a thermal head, causing the coloured layer to discolour in the heat imaged areas ,in a Hitachi VY 100 videoprinter.
- the density in the image-areas (Dmax) and non- image areas (Dmin) of each of the obtained images was then measured.
- the polymeric protection film prevents escape of the acid which can then re-react with the dye precursor to maintain the coloured layer.
- the amino groups in the polymer reacts with any released acid to tip the equilibrium and cause a faster imaging reaction to give improved images.
- the protective film layer becomes sufficiently porous to allow volatilization of the acid to form the image.
- reaction between the acid and the amino polymer help create an additional barrier to the volatilization of the acid during 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)
Abstract
Un élément pour former une image comprenant un support ayant une couche colorée de liant polymère contenant le produit de réaction d'un précurseur de colorant et d'un acide organique volatilisable. Lorsqu'on le soumet à une formation d'image thermique durant la copie thermographique, le composé coloré se décompose et l'acide libéré se volatilise en laissant une image claire et transparente. L'image peut être stabilisée en couvrant la couche colorée d'une couche d'un film polymère clair et transparent contenant des composés ayant des groupes amino, par exemple des polysaccharides à modification amino.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93200214 | 1993-01-28 | ||
EP93200214.0 | 1993-01-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994016904A1 true WO1994016904A1 (fr) | 1994-08-04 |
Family
ID=8213590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1993/003635 WO1994016904A1 (fr) | 1993-01-28 | 1993-12-16 | Element pour former une image thermosensible |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO1994016904A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1065049A1 (fr) * | 1999-06-29 | 2001-01-03 | Agfa-Gevaert N.V. | Elément formateur d'image sensible à la chaleur avec une couche protectrice pour la fabrication de plaques d'impression lithographiques |
US6503684B1 (en) | 1999-06-29 | 2003-01-07 | Agfa-Gevaert | Processless thermal printing plate with cover layer containing compounds with cationic groups |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0179492A2 (fr) * | 1984-10-25 | 1986-04-30 | Kanzaki Paper Manufacturing Company Limited | Matériel pour l'enregistrement thermosensible |
EP0400485A2 (fr) * | 1989-05-24 | 1990-12-05 | Kanzaki Paper Manufacturing Co., Ltd. | Matériau d'enregistrement thermosensible |
EP0492628A1 (fr) * | 1990-12-26 | 1992-07-01 | Ricoh Company, Ltd | Composition colorante thermosensible et réversible, matériau d'enregistrement, méthode d'enregistrement et appareil pour l'affichage d'images utilisant le matériau d'enregistrement |
-
1993
- 1993-12-16 WO PCT/EP1993/003635 patent/WO1994016904A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0179492A2 (fr) * | 1984-10-25 | 1986-04-30 | Kanzaki Paper Manufacturing Company Limited | Matériel pour l'enregistrement thermosensible |
EP0400485A2 (fr) * | 1989-05-24 | 1990-12-05 | Kanzaki Paper Manufacturing Co., Ltd. | Matériau d'enregistrement thermosensible |
EP0492628A1 (fr) * | 1990-12-26 | 1992-07-01 | Ricoh Company, Ltd | Composition colorante thermosensible et réversible, matériau d'enregistrement, méthode d'enregistrement et appareil pour l'affichage d'images utilisant le matériau d'enregistrement |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1065049A1 (fr) * | 1999-06-29 | 2001-01-03 | Agfa-Gevaert N.V. | Elément formateur d'image sensible à la chaleur avec une couche protectrice pour la fabrication de plaques d'impression lithographiques |
US6503684B1 (en) | 1999-06-29 | 2003-01-07 | Agfa-Gevaert | Processless thermal printing plate with cover layer containing compounds with cationic groups |
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