EP0775595A1 - Matériaux pour l'enregistrement par la chaleur avec un dérivé de l'acide phosphorique comme lubrifiant - Google Patents
Matériaux pour l'enregistrement par la chaleur avec un dérivé de l'acide phosphorique comme lubrifiant Download PDFInfo
- Publication number
- EP0775595A1 EP0775595A1 EP96203127A EP96203127A EP0775595A1 EP 0775595 A1 EP0775595 A1 EP 0775595A1 EP 96203127 A EP96203127 A EP 96203127A EP 96203127 A EP96203127 A EP 96203127A EP 0775595 A1 EP0775595 A1 EP 0775595A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording material
- outermost layer
- material according
- lubricant
- thermal
- 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
Links
- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000000314 lubricant Substances 0.000 title claims abstract description 48
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- 229910000147 aluminium phosphate Inorganic materials 0.000 title 1
- 239000010410 layer Substances 0.000 claims abstract description 60
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- 239000010687 lubricating oil Substances 0.000 claims abstract description 22
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 17
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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Classifications
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- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
- G03C2001/7488—Sliding layers or means
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
- G03C2001/7628—Back layer
Definitions
- the present invention relates to a thermographic material suitable for thermal development in dynamic contact with a heat source.
- it concerns improvements in imaging properties due to its surface in contact with the heat source having a particular composition.
- Thermal imaging or thermography is a recording process wherein images are generated by the use of imagewise modulated thermal energy.
- Direct thermal thermography is concerned with materials which are substantially not photosensitive, but are sensitive to heat or thermosensitive. Imagewise applied heat is sufficient to bring about a visible change in a thermosensitive imaging material.
- thermographic recording materials are of the chemical type. On heating to a certain conversion temperature, an irreversible chemical reaction takes place and a coloured image is produced.
- a typical heat-sensitive (thermographic) copy paper includes in the heat-sensitive layer a thermoplastic binder, e.g ethyl cellulose, a water-insoluble silver salt, e.g. silver stearate and an appropriate organic reducing agent, of which 4-methoxy-1-hydroxy-dihydronaphthalene is a representative.
- a thermoplastic binder e.g ethyl cellulose
- a water-insoluble silver salt e.g. silver stearate
- an appropriate organic reducing agent of which 4-methoxy-1-hydroxy-dihydronaphthalene is a representative.
- a heterocyclic organic toning agent such as phthalazinone is added to the composition of the heat-sensitive layer.
- Thermo-sensitive copying paper is used in "front-printing” or “back-printing” using infra-red radiation absorbed and transformed into heat in contacting infra-red light absorbing image areas of an original as illustrated in Figures 1 and 2 of US-P 3,074,809.
- WO 94/11199 attempts to solve the white line problem and teaches that a recording material comprising on a support (i) a heat sensitive layer comprising a substantially light insensitive organic silver salt, (ii) a protective layer containing a thermomeltable particle dispersed in a binder and (iii) a reducing agent being present in the heat sensitive layer and/or another layer on the same side of the support carrying the heat sensitive layer. It also teaches that the protective layer may further comprise a lubricant or a lubricant may be present on top of the protective layer.
- thermomeltable wax particles more preferably with melting points of at least 150°C, dispersed in a binder optionally together with a lubricant
- improved slip properties can be achieved by incorporating at least one solid lubricant (thermomeltable wax) with a melting point below 150°C and at least one liquid lubricant at least one of which being a phosphoric acid derivative.
- a recording material comprising at least one thermosensitive element, comprising a substantially light-insensitive organic silver salt and an organic reducing agent therefor in thermal working relationship therewith, on a support, characterized in that an outermost layer of the recording material comprises at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of the lubricants is a phosphoric acid derivative.
- thermo image forming process comprising the steps of: (i) bringing an outermost layer of the above described recording material into contact with a heat source; (ii) applying heat from the heat source imagewise to said recording material while maintaining mutual contact to but with relative movement between said recording material and the heat source; and (iii) separating the recording material from the heat source.
- a third lubricant is present in the surface layer.
- This third lubricant may be a phosphoric acid ester and is preferably a solid lubricant.
- liquid lubricant is a phosphoric acid derivative.
- the solid lubricant with a melting point below 150°C is a phosphoric acid ester.
- a thermal image forming process is realized, wherein the heat source is a thin film thermal head.
- suitable solid lubricants have a melting point below 150°C.
- solid lubricants having a melting point below 110°C with solid lubricants with a molecular weight below 1000 being particularly preferred.
- solid lubricants are defined as those lubricants being solid at room temperature.
- Solid lubricants which can be used according to the present invention are polyolefin waxes e.g. polypropylene waxes, ester waxes e.g. fatty acid esters, polyolefin-polyether block copolymers, amide waxes e.g. fatty acid amides, polyglycols e.g. polyethylene glycol, fatty acids, fatty alcohols, natural waxes and solid phosphoric acid derivatives.
- polyolefin waxes e.g. polypropylene waxes
- ester waxes e.g. fatty acid esters
- polyolefin-polyether block copolymers amide waxes e.g. fatty acid amides
- polyglycols e.g. polyethylene glycol
- fatty acids fatty alcohols
- natural waxes and solid phosphoric acid derivatives.
- Preferred solid lubricants are selected from the group consisting of fatty acid esters, polyolefin-polyether block copolymers and fatty acid amides.
- Preferred fatty acid esters are glycerine monostearate, glycerine monopalmitate and mixtures of glycerine monostearate and glycerine monopalmitate.
- Preferred fatty acid amides are selected from the group consisting of ethylenebisstearamide, stearamide, oleamide, myristamide and erucamide.
- Suitable solid non-phosphoric acid derivative lubricants according to the present invention with their melting points are: Melting point [°C] SL01: ethylenebisstearamide (CeridustTM 3910 from Hoechst AG) 141 SL02: myristamide 106 SL03: stearamide 104 SL04: glycerine monostearate 81 SL05: erucamide 80 SL06: oleamide 73 SL07: glycerine tristearate 55-73 SL08: MobilcerTM Q (a paraffin wax) 67 SL09: glycerine monotallow acid ester (RilanitTM GMS from Henkel AG) 55-60 SL10: sorbitan monostearate (SPANTM 60 from ICI PLC) 55 SL11: sorbitan tristearate (SPANTM 65 from ICI PLC) 48-53 SL12: sorbitan monopalmitate (SPANTM 40 from ICI PLC) 44-47 SL13
- PSL phosphoric acid derivative solid lubricants
- PSL01 Melting point [°C]
- PSL01 ServoxylTM VPAZ 100 from Servo Delden BV (mixture of monolauryl and dilauryl phosphates)
- PSL02 ServoxylTM VPRZ 100 from Servo Delden BV (mixture of monocetyl and monostearyl phosphates)
- PSL03 potassium alkyl phosphate (CrafolTM AP37 from Henkel AG) 62
- non-phosphoric acid derivative liquid lubricants (LL) examples are:
- PLL phosphoric acid derivative liquid lubricants
- the outermost layer of the recording material may in different embodiments of the present invention be the outermost layer of the thermosensitive element, a protective layer applied to the thermosensitive element or a layer on the opposite side of the support to the thermosensitive element.
- the outermost layer surface layer of the recording material according to the present invention may be a protective layer applied to the thermosensitive element to avoid local deformation of the thermosensitive element and to improve resistance against abrasion.
- the protective layer preferably comprises a binder, which may be hydrophobic (solvent soluble) of hydrophilic (water soluble).
- a binder which may be hydrophobic (solvent soluble) of hydrophilic (water soluble).
- hydrophobic binders polycarbonates as described in EP-A 614 769 are particularly preferred.
- hydrophilic binders are preferred for the protective layer, as coating can be performed from an aqueous composition and mixing of the hydrophilic protective layer with the immediate underlayer can be avoided by using a hydrophobic binder in the immediate underlayer.
- a protective layer according to the present invention may comprise in addition at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of the lubricants is a phosphoric acid derivative, further dissolved lubricating material and/or particulate material, e.g. talc particles, optionally protruding from the outermost layer.
- suitable lubricating materials are surface active agents, liquid lubricants, solid lubricants which do not melt during thermal development of the recording material, solid lubricants which melt (thermomeltable) during thermal development of the recording material or mixtures thereof.
- the lubricant may be applied with or without a polymeric binder.
- the surface active agents may be any agents known in the art such as carboxylates, sulfonates, aliphatic amine salts, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, fluoroalkyl C 2 -C 20 aliphatic acids.
- Examples of liquid lubricants include silicone oils, synthetic oils, saturated hydrocarbons and glycols.
- solid lubricants include various higher alcohols such as stearyl alcohol and fatty acids.
- Such protective layers may also comprise particulate material, e.g. talc particles, optionally protruding from the protective outermost layer as described in WO 94/11198.
- Other additives can also be incorporated in the protective layer e.g. colloidal particles such as colloidal silica.
- the outermost layer of the recording material may comprise a hydrophilic binder.
- Suitable hydrophilic binders for the outermost layer are, for example, gelatin, polyvinylalcohol, cellulose derivatives or other polysaccharides, hydroxyethylcellulose, hydroxypropylcellulose etc., with hardenable binders being preferred and polyvinylalcohol being particularly preferred.
- the outermost layer according to the present invention may be crosslinked.
- Crosslinking can be achieved by using crosslinking agents such as described in WO 95/12495 for protective layers, e.g. tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamine resins etc., with tetraalkoxysilanes such as tetramethylorthosilicate and tetraethylorthosilicate being preferred.
- the outermost layer of the recording material according to the present invention may comprise a matting agent.
- Suitable matting agents are described in WO 94/11198 and include e.g. talc particles and optionally protrude from the outermost layer.
- thermosensitive element comprises a substantially light-insensitive organic silver salt and an organic reducing agent therefor in thermal working relationship therewith.
- the element may comprise a layer system in which the ingredients may be dispersed in different layers, with the proviso that the substantially light-insensitive organic silver salt and the organic reducing agent are in thermal working relationship with one another i.e. during the thermal development process the reducing agent must be present in such a way that it is able to diffuse to said substantially light-insensitive organic silver salt particles so that reduction of the organic silver salt can take place.
- Preferred organic silver salts according to the present invention are silver salts of aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, with silver behenate being particularly preferred.
- Such silver salts are also called "silver soaps”.
- the silver image density depends on the coverage of the above defined reducing agent(s) and organic silver salt(s) and has to be preferably such that, on heating above 100 °C, an optical density of at least 2.5 can be obtained.
- Suitable organic reducing agents for the reduction of said substantially light-insensitive organic silver salts are organic compounds containing at least one active hydrogen atom linked to O, N or C, such as is the case with, aromatic di- and tri-hydroxy compounds; aminophenols; METOL (tradename); p-phenylenediamines; alkoxynaphthols, e.g. 4-methoxy-1-naphthol described in US-P 3,094,41; pyrazolidin-3-one type reducing agents, e.g.
- PHENIDONE (tradename); pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids; hydroxytetronimides; hydroxylamine derivatives such as for example described in US-P 4,082,901; hydrazine derivatives; and reductones e.g. ascorbic acid; see also US-P 3,074,809, 3,080,254, 3,094,417 and 3,887,378.
- aromatic di- and tri-hydroxy compounds having at least two hydroxy groups in ortho- or para-position on the same aromatic nucleus
- aromatic nucleus e.g. benzene nucleus, hydroquinone and substituted hydroquinones, catechol, pyrogallol, gallic acid and gallic acid esters
- polyhydroxy spiro-bis-indane compounds especially these corresponding to the following general formula (I):
- polyhydroxy-spiro-bis-indane compounds described in US-P 3,440,049 as photographic tanning agent, more especially 3,3,3',3'-tetramethyl-5,6,5',6'-tetrahydroxy-1,1'-spiro-bis-indane (called indane I) and 3,3,3',3'-tetramethyl-4,6,7,4',6',7'-hexahydroxy-1,1'-spiro-bis-indane (called indane II).
- Indane is also known under the name hydrindene.
- catechol-type reducing agents i.e. reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position
- catechol 3-(3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid, gallic acid and esters e.g. methyl gallate, ethyl gallate, propyl gallate, tannic acid, and 3,4-dihydroxy-benzoic acid esters.
- catechol-type reducing agents are benzene compounds in which the benzene nucleus is substituted by no more than two hydroxy groups which are present in 3,4-position on said nucleus and have in the 1-position of said nucleus a substituent linked to said nucleus by means of a carbonyl group.
- the silver image density depends upon the coverage of reducing agent and organic silver salt and has preferably to be such that upon heating an optical density of at least 2.5 can be obtained. Preferably at least 0.10 moles of reducing agent per mole of organic silver salt is used.
- auxiliary reducing agents are e.g. sterically hindered phenols, that on heating become reactive partners in the reduction of the substantially light-insensitive organic silver salt such as silver behenate, such as described in US-P 4,001,026; or are bisphenols, e.g. of the type described in US-P 3,547,648.
- the auxiliary reducing agents may be present in the imaging layer or in a polymeric binder layer in thermal working relationship thereto.
- auxiliary reducing agents are sulfonamidophenols corresponding to the following general formula : Aryl-SO 2 -NH-Arylene-OH in which :
- auxiliary reducing agents that may be used in conjunction with the above mentioned primary reducing agents are organic reducing metal salts, e.g. stannous stearate described in US-P 3,460,946 and 3,547,648.
- thermosensitive element Film-forming binders of the thermosensitive element
- the film-forming binder of the thermosensitive element containing the substantially light-insensitive organic silver salt may be all kinds of natural, modified natural or synthetic resins or mixtures of such resins, wherein the organic silver salt can be dispersed homogeneously: e.g. cellulose derivatives such as ethylcellulose, cellulose esters, e.g.
- cellulose nitrate carboxymethylcellulose, starch ethers, galactomannan
- polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
- a particularly suitable polyvinyl butyral containing a minor amount of vinyl alcohol units is marketed under the trade name BUTVAR B79 of Monsanto USA and provides a good adhesion to paper and properly subbed polyester supports
- the binder to organic silver salt weight ratio is preferably in the range of 0.2 to 6, and the thickness of the recording layer is preferably in the range of 5 to 50 ⁇ m.
- the layer containing the organic silver salt is commonly coated onto a support in sheet- or web-form from an organic solvent containing the binder dissolved therein, but may be applied from an aqueous medium as a latex, i.e. as an aqueous polymer dispersion.
- a latex the dispersible polymer has preferably some hydrophilic functionality.
- Polymers with hydrophilic functionality for forming an aqueous polymer dispersion (latex) are described e.g. in US-P 5,006,451, but serve therein for forming a barrier layer preventing unwanted diffusion of vanadium pentoxide present as an antistatic agent.
- binders or mixtures thereof may be used in conjunction with waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the reaction speed of the redox-reaction at elevated temperature.
- heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state in the recording layer at temperatures below 50°C but becomes a plasticizer for the recording layer in the heated region and/or liquid solvent for at least one of the redox-reactants, e.g. the reducing agent for the organic silver salt, at a temperature above 60°C.
- redox-reactants e.g. the reducing agent for the organic silver salt
- the recording layer contains preferably in admixture with said organic silver salts and reducing agents a so-called toning agent known from thermography or photothermography.
- Suitable toning agents are the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901. Further reference is made to the toning agents described in US-P 3,074,809, 3,446,648 and 3,844,797.
- Other particularly useful toning agents are the heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type within the scope of following general formula : in which: X represents O or N-alkyl; each of R 1 , R 2 , R 3 and R 4 (same or different) represents hydrogen, alkyl, e.g.
- C1-C20 alkyl preferably C1-C4 alkyl, cycloalkyl, e.g. cyclopentyl or cyclohexyl, alkoxy, preferably methoxy or ethoxy, alkylthio with preferably up to 2 carbon atoms, hydroxy, dialkylamino of which the alkyl groups have preferably up to 2 carbon atoms or halogen, preferably chlorine or bromine; or R 1 and R 2 or R 2 and R 3 represent the ring members required to complete a fused aromatic ring, preferably a benzene ring, or R 3 and R 4 represent the ring members required to complete a fused aromatic aromatic or cyclohexane ring. Toners within the scope of said general formula are described in GB-P 1,439,478 and US-P 3,951,660.
- a toner compound particularly suited for use in combination with polyhydroxy benzene reducing agents is 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine described in US-P 3,951,660.
- the recording layer may contain in addition to the ingredients mentioned above other additives such as free fatty acids, surface-active agents, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, silicone oil, e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY), ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, silica, and/or optical brightening agents.
- antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
- silicone oil e.g. BAYSILONE ⁇ l A (tradename of BAYER AG - GERMANY)
- ultraviolet light absorbing compounds e.g. BAYSILONE ⁇ l A (tradename of BAYER AG
- the support for the thermal imaging material according to the present invention may be transparent, translucent or opaque, e.g. having a white light reflecting aspect and is preferably a thin flexible carrier made e.g. from paper, polyethylene coated paper or transparent resin film, e.g. made of a cellulose ester, e.g. cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate.
- a paper base substrate is present which may contain white reflecting pigments, optionally also applied in an interlayer between the recording material and said paper base substrate.
- the support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive recording layer.
- the support may be made of an opacified resin composition, e.g. polyethylene terephthalate opacified by means of pigments and/or micro-voids and/or coated with an opaque pigment-binder layer, and may be called synthetic paper, or paperlike film; information about such supports can be found in EP's 194 106 and 234 563 and US-P's 3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent base be used, said base may be colourless or coloured, e.g. having a blue colour.
- an antistatic layer is applied to the outermost layer not comprising at least one solid lubricant having a melting point below 150°C and at least one liquid lubricant in a binder, wherein at least one of said lubricants is a phosphoric acid derivative.
- Suitable antistatic layers therefor are described in EP-A 440 957.
- any layer of the recording material of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, NY 10010, U.S.A.
- thermal printing image signals are converted into electric pulses and then through a driver circuit selectively transferred to a thermal printhead.
- the thermal printhead consists of microscopic heat resistor elements, which convert the electrical energy into heat via Joule effect.
- the electric pulses thus converted into thermal signals manifest themselves as heat transferred to the surface of the thermal paper wherein the chemical reaction resulting in colour development takes place.
- the operating temperature of common thermal printheads is in the range of 300 to 400°C and the heating time per picture element (pixel) may be 50ms or less, the pressure contact of the thermal printhead with the recording material being e.g. 100-500g/cm 2 to ensure a good transfer of heat.
- the direct thermal image-wise heating of the recording material proceeds by Joule effect heating in that selectively energized electrical resistors of a thermal head array are used in contact or close proximity with said recording layer.
- Suitable thermal printing heads are e.g. a Fujitsu Thermal Head (FTP-040 MCS001), a TDK Thermal Head F415 HH7-1089 and a Rohm Thermal Head KE 2008-F3.
- the image signals for modulating the current in the micro-resistors of a thermal printhead are obtained directly e.g. from opto-electronic scanning devices or from an intermediary storage means, e.g. magnetic disc or tape or optical disc storage medium, optionally linked to a digital image work station wherein the image information can be processed to satisfy particular needs.
- an intermediary storage means e.g. magnetic disc or tape or optical disc storage medium
- Direct thermal imaging can be used for both the production of transparencies and reflection type prints.
- hard copy field recording materials on a white opaque base are used, whereas in the medical diagnostic field black-imaged transparencies are widely used in inspection techniques operating with a light box.
- a subbed polyethylene terephthalate support having a thickness of 175 ⁇ m was doctor blade-coated with a coating composition containing butanone as a solvent and the following ingredients so as to obtain thereon, after drying for 1 hour at 50°C, a layer containing: silver behenate 4.74g/m 2 polyvinylbutyral (ButvarTM B79 from Monsanto) 18.92g/m 2 silicone oil (BaysiloneTM from Bayer AG) 0.043g/m 2 benzo[e][1,3]oxazine-2,4-dione, a toning agent 0.260g/m 2 7-(ethylcarbonato)-benzo[e][1,3]oxazine-2,4-dione, a toning agent (see formula II below) 0.133g/m 2 butyl 3,4-dihydroxybenzoate, a reducing agent 1.118g/m 2 tetrachlorophthalic anhydride 0.151g/m 2 pi
- thermosensitive element with a surface protective layer
- thermosensitive element was then coated with different aqueous compositions with the following basic composition expressed as weight percentages of ingredients present:
- thermo head printer After hardening, a commercially available AGFA DRYSTARTM 2000 (thermal head) printer with a maximum electrical input energy per dot of 63mW was used to produce an image over the whole width of the thermal head consisting of 11 blocks each printed at different electrical energies per dot and each with a non-printed strip in the middle thereof 2mm wide in the printing direction and 18cm long lateral to the printing direction, while printing the 2mm wide and 2cm long strips either side thereof. The degree to which the print obtained distinguished between these 2mm wide laterally adjoining non-printed and printed strips was used as a measure of the image quality attained i.e.
- Comparative example 13 teaches that a combination of a solid lubricant and a liquid lubricant when neither is a phosphoric acid derivative, as disclosed in WO 94/11199, results in a very poor image quality.
- the recording materials of invention examples 3 to 22 were produced as described for invention examples 1 to 2 except that an additional solid lubricant was incorporated into the protective layer.
- the recording materials of invention examples 23 to 26 were produced as described for invention examples 1 to 2 except that an additional liquid lubricant was incorporated into the protective layer.
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- General Physics & Mathematics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP19960203127 EP0775595B1 (fr) | 1995-11-27 | 1996-11-08 | Matériaux pour l'enregistrement par la chaleur avec un dérivé de l'acide phosphorique comme lubrifiant |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP95203246 | 1995-11-27 | ||
EP95203246 | 1995-11-27 | ||
EP19960203127 EP0775595B1 (fr) | 1995-11-27 | 1996-11-08 | Matériaux pour l'enregistrement par la chaleur avec un dérivé de l'acide phosphorique comme lubrifiant |
Publications (2)
Publication Number | Publication Date |
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EP0775595A1 true EP0775595A1 (fr) | 1997-05-28 |
EP0775595B1 EP0775595B1 (fr) | 1999-09-15 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US6207614B1 (en) * | 1999-01-06 | 2001-03-27 | Agfa-Gevaert | Substantially light-insensitive black and white monosheet thermographic recording material with improved image tone |
EP1186947A1 (fr) * | 2000-09-11 | 2002-03-13 | Agfa-Gevaert | Matériaux photothermographiques d'enregistrement à stabilité améliorée |
US6558895B2 (en) | 2000-09-11 | 2003-05-06 | Agfa-Gevaert | Photothermographic recording materials with improved stability |
WO2005073802A2 (fr) * | 2004-01-28 | 2005-08-11 | Eastman Kodak Company | Materiaux pour thermographie directe comprenant des couches protectrices ameliorees |
CN111471508A (zh) * | 2020-05-09 | 2020-07-31 | 中国乐凯集团有限公司 | 润滑剂及其制备方法、直接热成像材料及其制备方法 |
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US4001026A (en) | 1972-06-13 | 1977-01-04 | Agfa-Gevaert N.V. | Method and materials for thermoplastic recording |
US4082901A (en) | 1973-04-04 | 1978-04-04 | Agfa-Gevaert N.V. | Thermographic material |
US4187113A (en) | 1975-11-05 | 1980-02-05 | Imperial Chemical Industries Limited | Voided films of polyester with polyolefin particles |
US4260677A (en) | 1976-03-12 | 1981-04-07 | Minnesota Mining And Manufacturing Company | Thermographic and photothermographic materials having silver salt complexes therein |
US4360581A (en) | 1979-11-24 | 1982-11-23 | Agfa-Gevaert Aktiengesellschaft | Color photographic recording material containing non-diffusing electron donor compounds |
DE3339810A1 (de) | 1982-11-05 | 1984-05-10 | Fuji Photo Film Co., Ltd., Minami Ashigara, Kanagawa | Waermeentwickelbares farbphotographisches material |
EP0119615A2 (fr) | 1983-03-16 | 1984-09-26 | Fuji Photo Film Co., Ltd. | Procédé de formation d'images à sec |
EP0122512A2 (fr) | 1983-03-25 | 1984-10-24 | Fuji Photo Film Co., Ltd. | Procédé de formation d'images à sec et matériau à cet effet |
US4504575A (en) | 1983-10-31 | 1985-03-12 | E. I. Du Pont De Nemours And Company | Heat-developable film containing silver sulfonate physical developer |
EP0194106A2 (fr) | 1985-02-28 | 1986-09-10 | Dai Nippon Insatsu Kabushiki Kaisha | Feuille pour transfert par la chaleur et procédé l'utilisant |
EP0227141A1 (fr) | 1985-11-26 | 1987-07-01 | Agfa-Gevaert N.V. | Méthode pour la production d'un matériau photothermographique |
EP0234563A2 (fr) | 1986-02-25 | 1987-09-02 | Dai Nippon Insatsu Kabushiki Kaisha | Feuille pour transfert sensible à la chaleur |
US4740446A (en) | 1985-11-12 | 1988-04-26 | Agfa Gevaert Aktiengesellschaft | Heat development process and color photographic recording material suitable for this process |
US4780402A (en) | 1975-10-23 | 1988-10-25 | Imperial Chemical Industries, Plc | Films of a light sensitive element having a support polyethylene terephthalate containing barium sulfate particles |
US4782004A (en) | 1985-11-16 | 1988-11-01 | Fuji Photo Film Co., Ltd. | Method for developing a heat-developable photosensitive material comprising a dye providing compounds and an auxiliary developing agent |
US5006451A (en) | 1989-08-10 | 1991-04-09 | Eastman Kodak Company | Photographic support material comprising an antistatic layer and a barrier layer |
EP0423891A1 (fr) | 1989-10-20 | 1991-04-24 | Agfa-Gevaert N.V. | Méthode pour enregistrer et déceler un modèle de rayonnement ionisant |
EP0440957A2 (fr) | 1990-02-08 | 1991-08-14 | Bayer Ag | Dispersions de polythiophènes nouvelles, leur préparation et leur utilisation |
US5059579A (en) | 1988-06-30 | 1991-10-22 | Imperial Chemical Industries Plc | Receiver sheet |
WO1994011198A1 (fr) | 1992-11-16 | 1994-05-26 | Agfa-Gevaert Naamloze Vennootschap | Support de thermo-imagerie directe |
WO1994011199A1 (fr) | 1992-11-16 | 1994-05-26 | Agfa-Gevaert Naamloze Vennootschap | Produit pour une thermographie directe |
WO1994014618A1 (fr) * | 1992-12-18 | 1994-07-07 | Agfa-Gevaert Naamloze Vennootschap | Imagerie thermique directe |
EP0614769A1 (fr) | 1993-03-08 | 1994-09-14 | Agfa-Gevaert N.V. | Matériau sensible à la chaleur contenant une couche protectrice pour l'enregistrement direct d'images |
EP0622217A1 (fr) | 1993-04-27 | 1994-11-02 | Agfa-Gevaert N.V. | Méthode pour la production d'une image avec des éléments thermosensibles pour emploi direct |
WO1995012495A1 (fr) | 1993-11-06 | 1995-05-11 | Agfa-Gevaert Naamloze Vennootschap | Procede de thermographie directe au moyen d'un materiau d'enregistrement thermosensiblle et protege |
EP0692733A2 (fr) | 1994-07-07 | 1996-01-17 | Agfa-Gevaert N.V. | Procédé directe pour l'enregistrement thermique |
-
1996
- 1996-11-08 EP EP19960203127 patent/EP0775595B1/fr not_active Expired - Lifetime
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US4001026A (en) | 1972-06-13 | 1977-01-04 | Agfa-Gevaert N.V. | Method and materials for thermoplastic recording |
US3944699A (en) | 1972-10-24 | 1976-03-16 | Imperial Chemical Industries Limited | Opaque molecularly oriented and heat set linear polyester film and process for making same |
US3951660A (en) | 1972-12-16 | 1976-04-20 | Agfa-Gevaert, A.G. | Dry copying material |
GB1439478A (en) | 1972-12-16 | 1976-06-16 | Agfa Gevaert Ag | Dry copying material |
US4082901A (en) | 1973-04-04 | 1978-04-04 | Agfa-Gevaert N.V. | Thermographic material |
US3887378A (en) | 1973-04-16 | 1975-06-03 | Agfa Gevaert | Image recording and receiving materials |
US4780402A (en) | 1975-10-23 | 1988-10-25 | Imperial Chemical Industries, Plc | Films of a light sensitive element having a support polyethylene terephthalate containing barium sulfate particles |
US4187113A (en) | 1975-11-05 | 1980-02-05 | Imperial Chemical Industries Limited | Voided films of polyester with polyolefin particles |
US4260677A (en) | 1976-03-12 | 1981-04-07 | Minnesota Mining And Manufacturing Company | Thermographic and photothermographic materials having silver salt complexes therein |
US4360581A (en) | 1979-11-24 | 1982-11-23 | Agfa-Gevaert Aktiengesellschaft | Color photographic recording material containing non-diffusing electron donor compounds |
DE3339810A1 (de) | 1982-11-05 | 1984-05-10 | Fuji Photo Film Co., Ltd., Minami Ashigara, Kanagawa | Waermeentwickelbares farbphotographisches material |
EP0119615A2 (fr) | 1983-03-16 | 1984-09-26 | Fuji Photo Film Co., Ltd. | Procédé de formation d'images à sec |
EP0122512A2 (fr) | 1983-03-25 | 1984-10-24 | Fuji Photo Film Co., Ltd. | Procédé de formation d'images à sec et matériau à cet effet |
US4504575A (en) | 1983-10-31 | 1985-03-12 | E. I. Du Pont De Nemours And Company | Heat-developable film containing silver sulfonate physical developer |
EP0194106A2 (fr) | 1985-02-28 | 1986-09-10 | Dai Nippon Insatsu Kabushiki Kaisha | Feuille pour transfert par la chaleur et procédé l'utilisant |
US4740446A (en) | 1985-11-12 | 1988-04-26 | Agfa Gevaert Aktiengesellschaft | Heat development process and color photographic recording material suitable for this process |
US4782004A (en) | 1985-11-16 | 1988-11-01 | Fuji Photo Film Co., Ltd. | Method for developing a heat-developable photosensitive material comprising a dye providing compounds and an auxiliary developing agent |
EP0227141A1 (fr) | 1985-11-26 | 1987-07-01 | Agfa-Gevaert N.V. | Méthode pour la production d'un matériau photothermographique |
EP0234563A2 (fr) | 1986-02-25 | 1987-09-02 | Dai Nippon Insatsu Kabushiki Kaisha | Feuille pour transfert sensible à la chaleur |
US5059579A (en) | 1988-06-30 | 1991-10-22 | Imperial Chemical Industries Plc | Receiver sheet |
US5006451A (en) | 1989-08-10 | 1991-04-09 | Eastman Kodak Company | Photographic support material comprising an antistatic layer and a barrier layer |
EP0423891A1 (fr) | 1989-10-20 | 1991-04-24 | Agfa-Gevaert N.V. | Méthode pour enregistrer et déceler un modèle de rayonnement ionisant |
EP0440957A2 (fr) | 1990-02-08 | 1991-08-14 | Bayer Ag | Dispersions de polythiophènes nouvelles, leur préparation et leur utilisation |
WO1994011198A1 (fr) | 1992-11-16 | 1994-05-26 | Agfa-Gevaert Naamloze Vennootschap | Support de thermo-imagerie directe |
WO1994011199A1 (fr) | 1992-11-16 | 1994-05-26 | Agfa-Gevaert Naamloze Vennootschap | Produit pour une thermographie directe |
WO1994014618A1 (fr) * | 1992-12-18 | 1994-07-07 | Agfa-Gevaert Naamloze Vennootschap | Imagerie thermique directe |
EP0614769A1 (fr) | 1993-03-08 | 1994-09-14 | Agfa-Gevaert N.V. | Matériau sensible à la chaleur contenant une couche protectrice pour l'enregistrement direct d'images |
EP0622217A1 (fr) | 1993-04-27 | 1994-11-02 | Agfa-Gevaert N.V. | Méthode pour la production d'une image avec des éléments thermosensibles pour emploi direct |
WO1995012495A1 (fr) | 1993-11-06 | 1995-05-11 | Agfa-Gevaert Naamloze Vennootschap | Procede de thermographie directe au moyen d'un materiau d'enregistrement thermosensiblle et protege |
EP0692733A2 (fr) | 1994-07-07 | 1996-01-17 | Agfa-Gevaert N.V. | Procédé directe pour l'enregistrement thermique |
Non-Patent Citations (1)
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6207614B1 (en) * | 1999-01-06 | 2001-03-27 | Agfa-Gevaert | Substantially light-insensitive black and white monosheet thermographic recording material with improved image tone |
EP1186947A1 (fr) * | 2000-09-11 | 2002-03-13 | Agfa-Gevaert | Matériaux photothermographiques d'enregistrement à stabilité améliorée |
US6558895B2 (en) | 2000-09-11 | 2003-05-06 | Agfa-Gevaert | Photothermographic recording materials with improved stability |
WO2005073802A2 (fr) * | 2004-01-28 | 2005-08-11 | Eastman Kodak Company | Materiaux pour thermographie directe comprenant des couches protectrices ameliorees |
WO2005073802A3 (fr) * | 2004-01-28 | 2005-10-13 | Eastman Kodak Co | Materiaux pour thermographie directe comprenant des couches protectrices ameliorees |
CN111471508A (zh) * | 2020-05-09 | 2020-07-31 | 中国乐凯集团有限公司 | 润滑剂及其制备方法、直接热成像材料及其制备方法 |
CN111471508B (zh) * | 2020-05-09 | 2022-11-01 | 乐凯医疗科技有限公司 | 润滑剂及其制备方法、直接热成像材料及其制备方法 |
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