EP2329959A1 - Heat-sensitive recording material with barrier coating - Google Patents
Heat-sensitive recording material with barrier coating Download PDFInfo
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- EP2329959A1 EP2329959A1 EP09177678A EP09177678A EP2329959A1 EP 2329959 A1 EP2329959 A1 EP 2329959A1 EP 09177678 A EP09177678 A EP 09177678A EP 09177678 A EP09177678 A EP 09177678A EP 2329959 A1 EP2329959 A1 EP 2329959A1
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- Prior art keywords
- heat
- sensitive recording
- recording material
- recording layer
- material according
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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
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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
- B41M5/30—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
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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
- B41M5/30—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
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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
- B41M5/41—Base layers supports or substrates
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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
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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
- B41M2205/04—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
- B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/10—Watermarks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
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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
- B41M5/30—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
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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
- B41M5/30—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
- B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
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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
- B41M5/30—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
- B41M5/3375—Non-macromolecular compounds
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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
- B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
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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
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
Definitions
- the invention relates to a heat-sensitive recording material having a substrate which carries on the front side at least one heat-sensitive recording layer, which in turn has at least one dye precursor and at least one color acceptor, which react color-forming with one another under the action of heat.
- the heat-sensitive recording layer is generically covered with a protective layer.
- the thermosensitive recording material has a barrier coating capable of protecting the thermosensitive recording layer from backward penetration of chemicals capable of causing uncontrolled desensitization and color reactions in the thermosensitive recording layer.
- thermosensitive recording material is just as from EP 2 033 802 A1 according to which the recording material comprises a substrate, on the front side a protective layer coated with heat-sensitive recording layer is applied and the back has a backside coating, the backside coating comprises in addition to pigments and binders acting as a crosslinking component based on polyurethane.
- thermosensitive recording materials have proven themselves on the market quite well and solve the problem of a plasticizers, oils and fats protective backing coating quite outstanding. Both writings However, there is no indication as to how the heat-sensitive recording layer is to be protected against chemicals which can either cause an undesired color-forming reaction in the recording layer or a weakening or erasure of a typeface to be formed or formed in the recording layer and which, even in larger quantities, contained in the substrate and / or applied to the back of the substrate. The achievement of this task was preceded by the time-consuming analysis of numerous defective productions, which made it necessary to put the formulation of the task also the usual basic process for the production of heat-sensitive recording materials to the test.
- the heat-sensitive recording layer is shielded toward the substrate by the barrier layer containing ethylene-vinyl alcohol copolymer (EVOH) a perfect and - very much - lasting protection against organic solvents. Even a long-term exposure of organic solvents from the direction of the substrate is able to keep the barrier coating containing ethylene-vinyl alcohol copolymer (EVOH) from the heat-sensitive recording layer.
- EVOH ethylene-vinyl alcohol copolymer
- the heat-sensitive recording material of the present invention is produced by the roll and then stored, the front and back sides of the recording material in the roll come into contact, respectively.
- a protective layer covering the heat-sensitive recording layer, the heat-sensitive recording layer is also shielded to the outside of the next layer within a roll by the protective layer, which is also to be formed to provide good organic solvent protection.
- the barrier coating of the heat-sensitive recording material according to the invention preferably comprises at least 90 wt .-%, most preferably at least 98 wt .-% - each based on the total weight of Barrier coating, the ethylene-vinyl alcohol copolymer.
- Further constituents of this barrier coating are, for example, defoamers and / or agents for stabilizing the color curtain in the case of a possible application of the coating composition for the barrier coating by means of curtain or slide coaters.
- the coating weight for the barrier coating is preferably in a range from 0.9 to 5.0 g / m 2 , very particularly preferably in a range from 1.5 to 3.5 g / m 2 .
- Particularly suitable brushing compositions for the application of this barrier coating are, in particular, contactless application devices such as air brushes and curtain coater or slide coater, without being restricted in any way.
- a protective layer covering the heat-sensitive recording layer is of integral importance to the present invention.
- a protective layer which is the same as the barrier coating based on ethylene-vinyl alcohol copolymer (EVOH) is prepared and then preferably at least 90 wt .-%, most preferably at least 98 wt .-% - in each case based
- modified polyvinyl alcohol wherein the two values relate to the wt .-% on the total content of binder in the protective layer.
- a protective layer constructed in this way is considered to be preferred in the context of the present invention.
- the thus preferred protective layer of the heat-sensitive recording material according to the invention in addition to the diacetone-modified polyvinyl alcohol in a first possible embodiment, further binders, in particular mixtures of different carboxyl or silanol-modified polyvinyl alcohols have. These then make up a maximum of 40 wt .-%, more preferably only a maximum of 15 wt .-%, again, based on the total amount of binder in the protective layer.
- the protective layer of the heat-sensitive recording material according to the invention has as binders exclusively diacetone-modified polyvinyl alcohol.
- diacetone-modified polyvinyl alcohol is the sole binder in the protective layer covering the heat-sensitive recording layer
- Suitable crosslinking aids in the protective layer are, in particular, those selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
- the ratio of the weight percent of the binder, in particular of the diacetone-modified polyvinyl alcohol, to the crosslinking aid is in a range from 20: 1 to 5: 1 and more preferably in a range from 12: 1 to 7 : 1 is.
- the protective layer additionally contains an inorganic pigment.
- the inorganic pigment is selected from the group comprising silica, aluminum hydroxide, bentonite, calcium carbonate, kaolin or a mixture of said inorganic pigments.
- roller coater, knife coater, curtain coater or air brush are particularly suitable as coating devices for applying the protective layer covering the heat-sensitive recording layer.
- the basis weight of the protective layer is preferably between 1.0 and 3.0 g / m 2 and more preferably between 1.6 and 2.3 g / m 2 .
- the configuration of the heat-sensitive recording layer is less limited.
- the recording layer may initially include all known dye precursors in principle, and combinations of several dye precursors are possible.
- the heat-sensitive recording layer has at least 33% by weight, based on the total amount of color acceptors in the heat-sensitive recording layer, as color acceptor, N- (p-toluenesulphonyl) -N'-3- (p-toluenesulphonyl-oxy-phenyl) urea according to the following formula (1), wherein the two CH 3 end molecules are also often omitted in the literature.
- N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea is known as Pergafast ® 201 from Ciba Specialty Chemicals Inc.
- N- (p-toluenesulphonyl) -N ' -3- (p-to! Uensulphonyl-oxy-phenyl) -urea is the sole color acceptor. Based on the total weight of the recording layer, the color acceptor then makes up to 32% by weight, but preferably in the range of 18 to 30% by weight and more preferably 20 to 28.5% by weight of the heat-sensitive recording layer ,
- the recording layer of the heat-sensitive recording material of the present invention within this first embodiment may preferably also contain sensitizers to increase the thermal responsiveness.
- Sensitisers are on the one hand the substances listed in paragraph [0033];
- 2- (2H-benzotriazol-2-yl) -p-cresol according to the following formula (2) is particularly preferred, although here too the CH 3 end molecule is frequently omitted from the literature:
- 2- (2H-benzotriazol-2-yl) -p-cresol of formula (2) available as Tinuvin® from CIBA Specialty Chemicals Inc., may be used as the sole sensitizer or in combination with the sensitizers mentioned in paragraph [0033] the recording layer of the recording material according to the invention are used.
- the heat-sensitive recording layer as color acceptor is at least 66 2/3% by weight, based on the total amount of color acceptors in the heat-sensitive Recording Layer - 4,4'-Dihydroxydiphenylsulfone.
- 4,4'-Dihydroxydiphenylsulfone is also commonly referred to as 4,4'-sulfonyldiphenol and is also known under the tradename 4,4 Bisphenol S.
- 4,4'-Dihydroxydiphenylsulfone has the chemical formula C12H1004S and can be represented as the following formula (3):
- the above color acceptors are preferably incorporated into this heat-sensitive recording layer to a maximum of 10% by weight, based on the total amount of color acceptors in the heat-sensitive recording layer, the remainder being 4,4'-dihydroxydiphenylsulfone.
- 4,4'-dihydroxydiphenylsulfone is the sole color acceptor in the thermosensitive recording layer is considered to be most preferred.
- thermosensitive recording material as the dye precursor in the thermosensitive recording layer preferably comprises at least one substance selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3 (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N- cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran and 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl- 7-anilinofluoran.
- Very particular preference is given to 3-dibutylamino-6-methyl-7-anilinofluoran - also known as ODB
- thermosensitive recording layer has more than one dye precursor each selected from the dye precursors listed in the above paragraph.
- the recording material according to the invention may further comprise, in addition to these substances mentioned as dye precursors, one or more of the following compounds absorbing in the near infrared range:
- the recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness.
- Such sensitizers are, for example: benzyl p-benzyloxybenzoate, methylolstearamide, stearic acid amide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl oxalate, Benzylnaphthylether, dimethyl terephthalate and diphenylsulfone, with methylolstearamide, and in particular stearic acid amide and dimethyl terephthalate are considered to be very preferred.
- Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate Terpolymers and alkali salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers also offer themselves as binders for incorporation into the heat-sensitive recording layer at.
- water-soluble binders such as starch, hydroxy
- polyvinyl alcohol ethylene-vinyl alcohol copolymers or polyvinyl alcohol in conjunction with ethylene-vinyl alcohol copolymers as particularly preferred binders which together, based on the total weight of the recording layer, in a range of 10 to 20 wt .-% in the heat-sensitive recording layer is incorporated.
- the coating composition for forming the heat-sensitive recording layer may further contain lubricants and release agents such as metal salts higher fatty acids, for example, zinc stearate, calcium stearate, and waxes, such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides, and castor wax.
- lubricants and release agents such as metal salts higher fatty acids, for example, zinc stearate, calcium stearate, and waxes, such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides, and castor wax.
- pigments preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silicic acid and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 0 to 28% by weight, based on the total weight of the recording layer, should be included in the recording layer, as is preferred.
- inorganic pigments such as, for example, aluminum (hydr) oxide, silicic acid and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 0 to 28% by weight, based on the total weight of the recording layer, should be included in the recording layer, as is preferred.
- the heat-sensitive recording layer - offer in particular roller blade coater, knife coater, curtain coater or air brush.
- the coating composition used to form the recording layer is aqueous.
- the subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes.
- the basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.2 to 4.8 g / m 2 .
- the heat-sensitive recording material according to the invention comprises a pigment-containing intermediate layer, which is arranged between the barrier coating and the heat-sensitive recording layer.
- Suitable pigments of the intermediate layer are both organic void pigments and inorganic pigments, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite.
- organic void pigments and inorganic pigments the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite.
- such an intermediate layer can make a positive contribution to the leveling of the surface to be coated, which reduces the amount of coating color necessarily to be applied for the heat-sensitive recording layer. For this reason, offer to coat the pigment-containing intermediate layer leveling coating, such as Walzenstreichwerke, doctor blade and (roll) doctor blade coating.
- the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording.
- the basis weight of the pigment-containing intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
- paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention.
- the barrier coating between the substrate and heat-sensitive recording layer it is possible due to the arrangement of the barrier coating between the substrate and heat-sensitive recording layer, to use those substrates that would rather prohibit due to their ingredients and their negative influence on the heat-sensitive recording layer such as films or films coated papers in which the respective films Contain larger amounts of plasticizers, or papers from recycled fibers of the lowest quality.
- the proposed heat-sensitive recording material has a coating of a tincture applied to the substrate in the form of at least one character or in the form of a pattern, the tincture comprising at least one organic solvent. It is also possible that the tincture comprises a mixture of several organic solvents. In a preferred Embodiment are also included in the tincture other ingredients such as fluorescent fibers and / or pigments.
- Applying the tincture with at least one organic solvent to the substrate formed to form the paper authentication feature causes the opacity of the substrate to change at the sites wetted with the tincture relative to the non-wetted areas of the substrate. If one keeps the thus treated, here proposed heat-sensitive recording material against a light source, makes the change in transparency in the review sharp-edged as easily recognizable image or pattern.
- analog printing methods such as, for example, the flexographic and gravure printing methods are particularly suitable.
- the tincture is applied by means of digital printing methods. If the order of tincture digital printing technology, which is considered preferable and what is given, inter alia, in the inkjet printing process, the formation of an individual authentication feature per single section of the proposed here heat-sensitive recording material is made possible. If the heat-sensitive recording material proposed here is used as a ticket and / or in particular as an admission ticket, each individual ticket can be provided with an individual authentication feature.
- the heat-sensitive recording material proposed here as a ticket, very particularly preferably as an admission ticket.
- a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 130 g / m 2 with the addition of conventional additives in conventional amounts is first prepared on a fourdrinier paper machine as a substrate. From the paper web 3 sample rolls are cut for further treatment.
- the coating material used for the heat-sensitive recording layer essentially contains the following components: Dye precursors: 3-dibutylamino-6-methyl-7-anilinofluoran, that is ODB-2; color acceptor: N- (p-toluensulphonyl) -N '-3- (p-toluensulphonyl-oxy-phenyl) -urea, which is Pergafast® 201; sensitizer: Benzylnaphthyl ether, that is BNE; Binder: polyvinyl alcohol; co-binders: Acrylate copolymer; Pigment: Calcium carbonate.
- a protective layer of 2.0 g / m 2 is applied to the heat-sensitive recording layer by means of air brushing in each case for all 3 pattern rolls.
- a coating composition which essentially contains the following components: Binder: Diacetone-modified polyvinyl alcohol; 61.3% by weight (atro) crosslinkers: adipic; 6.0% by weight (atro) Pigment: Kaolin; 16.6% by weight (atro) Lubricant: Hidorin Z-7-30; 8.1% by weight (atro) aids: pH regulator, optical brightener; 8.0% by weight (atro)
- the desired barrier effect of the barrier layer against organic solvents should then be investigated.
- 0.5 ml of ethanol is applied to the respective reverse side of test strips from the 3 sample rolls corresponding to Example 1 according to the invention and the two comparative examples 2 and 3 using a pipette. After a respective exposure time of 10 minutes, the ethanol is completely absorbed. The effect of the solvent application on the heat-sensitive recording layer is visually evaluated.
- the heat-sensitive recording layer of Inventive Example 1 shows no thermal reactions at all, the present invention is excellently confirmed in terms of quality.
- Comparative Example 2 shows an intense thermoreactions, this barrier coating is not at all suitable to develop a far-reaching protective effect against organic solvents from the direction of the substrate over a longer exposure time.
- Comparative Example 3 there are scattered color reaction points on the heat-sensitive recording layer: below these colored dots, the barrier coating of the coating composition BS3 has cracks and voids due to the too high viscosity of the silanized polyvinyl alcohol. Again, the barrier effect against organic solvents is not convincing, because not without flaws.
- thermosensitive recording material finally expected by the inventors.
Abstract
Description
Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial mit einem Substrat, das vorderseitig mindestens eine wärmeempfindliche Aufzeichnungsschicht trägt, die ihrerseits mindestens einen Farbstoffvorläufer und mindestens einen Farbakzeptor aufweist, welche unter Einwirkung von Wärme farbbildend miteinander reagieren. Die wärmeempfindliche Aufzeichnungsschicht ist gattungsgemäß mit einer Schutzschicht überzogen. Ferner weist das wärmeempfindliche Aufzeichnungsmaterial eine Barrierebeschichtung auf, welche in der Lage ist, die wärmeempfindliche Aufzeichnungsschicht vor einem rückseitigen Eindringen von Chemikalien, die unkontrollierte Desensibilisierungs- und Farbreaktionen in der wärmeempfindlichen Aufzeichnungsschicht bewirken können, zu schützen.The invention relates to a heat-sensitive recording material having a substrate which carries on the front side at least one heat-sensitive recording layer, which in turn has at least one dye precursor and at least one color acceptor, which react color-forming with one another under the action of heat. The heat-sensitive recording layer is generically covered with a protective layer. Further, the thermosensitive recording material has a barrier coating capable of protecting the thermosensitive recording layer from backward penetration of chemicals capable of causing uncontrolled desensitization and color reactions in the thermosensitive recording layer.
Ein solches wärmeempfindliches Aufzeichnungsmaterial ist beispielsweise aus der
- Stärke,
- ein keine Styrol- oder Vinylacetatkomponenten umfassendes Acrylatcopolymer mit einer Filmbildungstemperatur kleiner 5°C und bevorzugt kleiner 2°C
- sowie einen alkalischen Katalysator, wie beispielsweise Calciumcarbonat, enthält. Die Rückseitenbeschichtung des bekannten wärmeempfindlichen Aufzeichnungsmaterials soll eine gute Sperrwirkung gegenüber den im Offset- und Flexodruck verwendeten Substanzen, insbesondere organischen Lösungsmitteln, sowie gegenüber Weichmachern, Ölen und Fetten gewährleisten.
- Strength,
- an acrylate copolymer comprising no styrene or vinyl acetate components and having a film-forming temperature of less than 5 ° C and preferably less than 2 ° C
- and an alkaline catalyst such as calcium carbonate. The backside coating of the known heat-sensitive recording material is intended to ensure a good barrier effect with respect to the substances used in offset and flexographic printing, in particular organic solvents, as well as to plasticizers, oils and fats.
Ein gattungsgemäßes wärmeempfindliches Aufzeichnungsmaterial ist genauso aus der
Beide wärmeempfindliche Aufzeichnungsmaterialien haben sich auf dem Markt durchaus bewährt und lösen das Problem einer gegenüber Weichmachern, Ölen und Fetten schützenden Rückseitenbeschichtung ganz hervorragend. Beide Schriften geben jedoch keinen Hinweis darauf, wie die wärmeempfindliche Aufzeichnungsschicht gegenüber Chemikalien zu schützen ist, die entweder eine ungewollte farbbildende Reaktion in der Aufzeichnungsschicht oder aber eine Schwächung bzw. Löschung eines in der Aufzeichnungsschicht auszubildenden oder ausgebildeten Schriftbildes bewirken können und die - auch in größeren Mengen - in dem Substrat enthalten und/oder auf der Rückseite des Substrats aufgebracht sind. Der Gewinnung dieser Aufgabenstellung war die zeitintensive Analyse zahlreicher Fehlproduktionen vorausgegangen, die es erforderlich machten, bei der Formulierung der Aufgabenstellung auch die üblichen Grundverfahren zur Herstellung von wärmeempfindlichen Aufzeichnungsmaterialien auf den Prüfstand zu stellen.Both thermosensitive recording materials have proven themselves on the market quite well and solve the problem of a plasticizers, oils and fats protective backing coating quite outstanding. Both writings However, there is no indication as to how the heat-sensitive recording layer is to be protected against chemicals which can either cause an undesired color-forming reaction in the recording layer or a weakening or erasure of a typeface to be formed or formed in the recording layer and which, even in larger quantities, contained in the substrate and / or applied to the back of the substrate. The achievement of this task was preceded by the time-consuming analysis of numerous defective productions, which made it necessary to put the formulation of the task also the usual basic process for the production of heat-sensitive recording materials to the test.
Bei einer solchen Aufgabenstellung spielt insbesondere die Dichtigkeit von Schichten gegenüber organischen Lösungsmitteln eine besonders herausragende Rolle. Nach zahlreichen Vorversuchen mussten die Erfinder überdies erkennen, dass viele der bekannten oder nahe liegenden Rezepturen zur Ausbildung einer Schutzbeschichtung bei der Handhabung innerhalb der Produktion ganz häufig zu Verarbeitungsschwierigkeiten durch rheologische Besonderheiten der in der Regel selbstvernetzenden Beschichtungsmassen führen. Diese Verarbeitungsschwierigkeiten führen insbesondere zu Beschichtungsfehlern durch zu hoch viskose Streichmassenbestandteile und in einer schleichenden Verstopfung in den Rohrzuleitungen hin zu den Beschichtungsaggregaten.In such a task, in particular the tightness of layers over organic solvents plays a particularly prominent role. After numerous preliminary experiments, the inventors also had to realize that many of the known or obvious formulations for the formation of a protective coating during handling within the production quite often lead to processing difficulties due to rheological characteristics of the generally self-crosslinking coating compositions. These processing difficulties lead, in particular, to coating defects due to overly viscous coating composition components and in a creeping obstruction in the pipe supply lines to the coating units.
Zur Lösung dieser anstehenden Aufgaben wird ein wärmeempfindliches Aufzeichnungsmaterial vorgeschlagen, mindestens aufweisend:
- ein Substrat,
- eine auf der Vorderseite des Substrates angeordnete wärmeempfindliche Aufzeichnungsschicht mit mindestens einem Farbstoffvorläufer und mindestens einem Farbakzeptor, wobei Farbstoffvorläufer und Farbakzeptor unter Einwirkung von Wärme farbbildend miteinander reagieren,
- eine die wärmeempfindliche Aufzeichnungsschicht abdeckende Schutzschicht,
- eine Barrierebeschichtung, geeignet zum Schutz der wärmeempfindlichen Aufzeichnungsschicht vor einem Eindringen von unkontrollierte Desensibilisierungs- und Farbreaktionen in der wärmeempfindlichen Aufzeichnungsschicht bewirkenden Chemikalien,
dadurch gekennzeichnet, - dass die Barrierebeschichtung zwischen Substrat und wärmeempfindlicher Aufzeichnungsschicht angeordnet ist und
- dass die Barrierebeschichtung Ethylen-Vinyl-Alkohol-Copolymer (EVOH) enthält.
- a substrate,
- a heat-sensitive recording layer arranged on the front side of the substrate and having at least one dye precursor and at least one color acceptor, the dye precursor and color acceptor reacting in color forming form under the action of heat,
- a protective layer covering the heat-sensitive recording layer,
- a barrier coating suitable for protecting the thermosensitive recording layer from penetration of uncontrolled desensitizing and dyeing reactions in the thermosensitive recording layer causing chemicals;
characterized, - that the barrier coating is disposed between the substrate and the heat-sensitive recording layer, and
- in that the barrier coating contains ethylene-vinyl alcohol copolymer (EVOH).
Ausschließlich ein wärmeempfindliches Aufzeichnungsmaterial mit der erfindungsgemäßen Anordnung von
- Substrat
und den in dieser Reihenfolge auf der Vorderseite des Substrates vorzusehenden, mindestens notwendigen - Barrierebeschichtung,
- wärmeempfindliche Aufzeichnungsschicht
- und Schutzschicht
- substratum
and the at least necessary to be provided in this order on the front side of the substrate - Barrier coating,
- heat-sensitive recording layer
- and protective layer
Bei der erfindungsgemäßen Anordnung von Substrat und den in dieser Reihenfolge auf der Vorderseite des Substrates vorzusehenden, mindestens notwendigen Barrierebeschichtung, wärmeempfindliche Aufzeichnungsschicht und Schutzschicht ist die wärmeempfindliche Aufzeichnungsschicht zum Substrat hin durch die Ethylen-Vinyl-Alkohol-Copolymer (EVOH) enthaltende Barrierebeschichtung abgeschirmt, die einen perfekten und - ganz wesentlich - dauerhaften Schutz vor organischen Lösungsmitteln darstellt. Selbst eine lang andauernde Exposition von organischen Lösungsmitteln aus Richtung des Substrates vermag die Ethylen-Vinyl-Alkohol-Copolymer (EVOH) enthaltende Barrierebeschichtung von der wärmeempfindlichen Aufzeichnungsschicht fernzuhalten.In the inventive arrangement of the substrate and the at least necessary barrier coating, heat-sensitive recording layer and protective layer to be provided in this order on the substrate, the heat-sensitive recording layer is shielded toward the substrate by the barrier layer containing ethylene-vinyl alcohol copolymer (EVOH) a perfect and - very much - lasting protection against organic solvents. Even a long-term exposure of organic solvents from the direction of the substrate is able to keep the barrier coating containing ethylene-vinyl alcohol copolymer (EVOH) from the heat-sensitive recording layer.
Da das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial rollenweise produziert und anschließend gelagert wird, kommen jeweils Vorder- und Rückseite des Aufzeichnungsmaterials in der Rolle in Kontakt. Durch die Anordnung einer die wärmeempfindliche Aufzeichnungsschicht abdeckenden Schutzschicht ist die wärmeempfindliche Aufzeichnungsschicht auch nach außen bzw. zum Substrat der nächsten Lage innerhalb einer Rolle hin durch die Schutzschicht abgeschirmt, die ebenfalls so auszubilden ist, dass sie eine guten Schutz vor organischen Lösungsmitteln darstellt.Since the heat-sensitive recording material of the present invention is produced by the roll and then stored, the front and back sides of the recording material in the roll come into contact, respectively. By disposing a protective layer covering the heat-sensitive recording layer, the heat-sensitive recording layer is also shielded to the outside of the next layer within a roll by the protective layer, which is also to be formed to provide good organic solvent protection.
In verschiedenen Versuchen stellte sich eine besonders überzeugende Überlegenheit einer Barrierebeschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer heraus. Einerseits verglichen mit einer Beschichtung auf der Basis von üblichem Polyvinylalkohol bildet eine Beschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer eine gegenüber organischen Lösemitteln wesentlich verbesserte Barrierewirkung. Soll hingegen andererseits eine Barrierebeschichtung beispielsweise auf der Basis von hochmolekularem silanisiertem Polyvinylalkohol ausgebildet werden, spielen die sehr großen Verarbeitungsschwierigkeiten dieses silanisierten Polyvinylalkohols unter anderem in Folge seiner hohen Viskosität eine entscheidende Rolle:
- Wird eine starke wässerige Verdünnung des hochmolekularen Polyvinylalkohols
innerhalb der Streichmasse zur Ausbildung der Barrierebeschichtung gewählt, ist deren Verarbeitung gut möglich, aber eine zufriedenstellende Abschirmung der wärmeempfindlichen Aufzeichnungsschicht zum Substrat hin ist nicht gegeben: es kommt bei einer Exposition mit organischen Lösungsmitteln zu unkontrollierbaren Desensibilisierungs- oder Farbreaktionen in der wärmeempfindlichen Aufzeichnungsschicht.
- Will a strong aqueous dilution of high molecular weight polyvinyl alcohol
within the coating composition for forming the barrier coating, its processing is quite possible, but satisfactory shielding of the heat-sensitive recording layer from the substrate is not possible: uncontrollable desensitization or color reactions occur in the thermosensitive recording layer upon exposure to organic solvents.
Die Barrierebeschichtung des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials umfasst bevorzugt zu mindestens 90 Gew.-%, ganz besonders bevorzugt zu mindestens 98 Gew.-% ― jeweils bezogen auf das Gesamtgewicht der Barrierebeschichtung, das Ethylen-Vinyl-Alkohol-Copolymer. Weitere Bestandteile dieser Barrierebeschichtung sind dann beispielsweise Entschäumer und/oder Mittel zur Stabilisierung des Farbvorhangs bei einem möglichen Auftrag der Beschichtungsmasse für die Barrierebeschichtung mittels Curtain- bzw. Slide-Coaters.The barrier coating of the heat-sensitive recording material according to the invention preferably comprises at least 90 wt .-%, most preferably at least 98 wt .-% - each based on the total weight of Barrier coating, the ethylene-vinyl alcohol copolymer. Further constituents of this barrier coating are, for example, defoamers and / or agents for stabilizing the color curtain in the case of a possible application of the coating composition for the barrier coating by means of curtain or slide coaters.
Das Auftragsgewicht für die Barrierebeschichtung liegt bevorzugt in einem Bereich von 0,9 bis 5,0 g/m2, ganz besonders bevorzugt in einem Bereich von 1,5 bis 3,5 g/m2. Als zum Auftrag dieser Barrierebeschichtung besonders geeignete Streichwerke kommen insbesondere kontaktlose Auftragsvorrichtungen wie Luftbürste sowie Curtain- bzw. Slide-Coater in Betracht, ohne darauf in irgendeiner Art und Weise beschränkt zu sein.The coating weight for the barrier coating is preferably in a range from 0.9 to 5.0 g / m 2 , very particularly preferably in a range from 1.5 to 3.5 g / m 2 . Particularly suitable brushing compositions for the application of this barrier coating are, in particular, contactless application devices such as air brushes and curtain coater or slide coater, without being restricted in any way.
Entsprechend den obigen Ausführungen in den Absätzen [0007] und [0009] ist die Ausbildung einer die wärmeempfindliche Aufzeichnungsschicht abdeckenden Schutzschicht von integraler Bedeutung für die vorliegende Erfindung. Neben einer Schutzschicht, die genauso wie die Barrierebeschichtung auf der Basis von Ethylen-Vinyl-Alkohol-Copolymer (EVOH) hergestellt ist und die dann bevorzugt zu mindestens 90 Gew.-%, ganz besonders bevorzugt zu mindestens 98 Gew.-% ― jeweils bezogen auf das Gesamtgewicht einer solchen Schutzschicht, das Ethylen-Vinyl-Alkohol-Copolymer enthält, konnten auch sehr gute Ergebnisse erzielt werden mit einer Schutzschicht, die als Bindemittel zu mindestens 60 Gew.-%, besonders bevorzugt zu mindestens 85 Gew.-% Diaceton-modifizierten Polyvinylalkohol aufweist, wobei sich die beiden Werte zu den Gew.-% auf den Gesamtanteil an Bindemittel in der Schutzschicht beziehen. Eine derart aufgebaute Schutzschicht gilt als bevorzugt im Sinne der vorliegenden Erfindung.According to the above explanations in paragraphs [0007] and [0009], the formation of a protective layer covering the heat-sensitive recording layer is of integral importance to the present invention. In addition to a protective layer, which is the same as the barrier coating based on ethylene-vinyl alcohol copolymer (EVOH) is prepared and then preferably at least 90 wt .-%, most preferably at least 98 wt .-% - in each case based On the total weight of such a protective layer containing ethylene-vinyl alcohol copolymer, very good results could also be achieved with a protective layer containing at least 60% by weight, particularly preferably at least 85% by weight, of diacetone as binder. modified polyvinyl alcohol, wherein the two values relate to the wt .-% on the total content of binder in the protective layer. A protective layer constructed in this way is considered to be preferred in the context of the present invention.
Die derart bevorzugte Schutzschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kann neben dem Diaceton-modifizierten Polyvinylalkohol in einer ersten möglichen Ausführungsform weitere Bindemittel, insbesondere Mischungen verschiedener Carboxylgruppen- oder Silanol-modifizierter Polyvinylalkohole, aufweisen. Diese machen dann maximal 40 Gew.-%, besonders bevorzugt nur maximal 15 Gew.-%, aus, erneut bezogen auf den Gesamtanteil an Bindemittel in der Schutzschicht. In einer zweiten möglichen Ausführungsform weist die Schutzschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials als Bindemittel ausschließlich Diaceton-modifizierten Polyvinylalkohol auf. Insbesondere wenn Diaceton-modifizierter Polyvinylalkohol alleiniges Bindemittel in der die wärmeempfindliche Aufzeichnungsschicht abdeckenden Schutzschicht ist, gilt es als ganz besonders bevorzugt, wenn der Bindemittelanteil in der Schutzschicht in einem Bereich von 35 bis 65 Gew.-% liegt, bezogen auf das Gesamtgewicht der Schutzschicht.The thus preferred protective layer of the heat-sensitive recording material according to the invention, in addition to the diacetone-modified polyvinyl alcohol in a first possible embodiment, further binders, in particular mixtures of different carboxyl or silanol-modified polyvinyl alcohols have. These then make up a maximum of 40 wt .-%, more preferably only a maximum of 15 wt .-%, again, based on the total amount of binder in the protective layer. In a second possible embodiment, the protective layer of the heat-sensitive recording material according to the invention has as binders exclusively diacetone-modified polyvinyl alcohol. In particular, when diacetone-modified polyvinyl alcohol is the sole binder in the protective layer covering the heat-sensitive recording layer, it is considered to be particularly preferable that when the binder content in the protective layer is in a range of 35 to 65% by weight based on the total weight of the protective layer.
Als Vernetzungshilfsmittel in der Schutzschicht bieten sich insbesondere solche an, die ausgewählt sind aus der Gruppe umfassend: Borsäure, Polyamin, Epoxyharz, Dialdehyd, Formaldehydoligomere, Epiochlorhydrinharz, Adipinsäuredihydrazid, Dimethylharnstoff, Melaminformaldehyd. Auch Mischungen verschiedener Vernetzungshilfsmittel sind möglich.Suitable crosslinking aids in the protective layer are, in particular, those selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, adipic dihydrazide, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
Es ist bevorzugt, wenn innerhalb der Schutzschicht das Verhältnis der Gew.- % des Bindemittels, insbesondere des Diaceton-modifizierten Polyvinylalkohols zu dem Vernetzungshilfsmittel in einem Bereich von 20 : 1 bis 5 : 1 und besonders bevorzugt in einem Bereich von 12 : 1 bis 7 : 1 liegt.It is preferred if, within the protective layer, the ratio of the weight percent of the binder, in particular of the diacetone-modified polyvinyl alcohol, to the crosslinking aid is in a range from 20: 1 to 5: 1 and more preferably in a range from 12: 1 to 7 : 1 is.
Besonders gute Ergebnisse wurden erzielt, wenn die Schutzschicht zusätzlich ein anorganisches Pigment enthält. Dabei empfiehlt es sich besonders, wenn das anorganische Pigment ausgewählt ist aus der Gruppe umfassend Siliziumdioxid, Aluminiumhydroxid, Bentonit, Kalziumkarbonat, Kaolin oder einer Mischung aus den genannten anorganischen Pigmenten. Dabei ist insbesondere ein Verhältnis Pigment und hier ganz besonders bevorzugt von Kaolin zu dem Diaceton-modifizierten Polyvinylalkohol in einem Bereich von 1 : 1,5 bis 1 : 4,5 einzustellen, die Verhältniswerte dabei bezogen auf die jeweiligen Gew.-% von Pigment und Polyvinylalkohol in der Schutzschicht.Particularly good results have been achieved if the protective layer additionally contains an inorganic pigment. It is particularly recommended that the inorganic pigment is selected from the group comprising silica, aluminum hydroxide, bentonite, calcium carbonate, kaolin or a mixture of said inorganic pigments. In this case, in particular, a ratio of pigment and here very particularly preferably of kaolin to the diacetone-modified polyvinyl alcohol in a range of 1: 1.5 to 1: 4.5 set, the ratio here based on the respective wt .-% of pigment and Polyvinyl alcohol in the protective layer.
Als Beschichtungsvorrichtung zum Auftrag der die wärmeempfindliche Aufzeichnungsschicht abdeckenden Schutzschicht bieten sich insbesondere Rollrakelstreichwerk, Messerstreichwerk, Vorhangbeschichter oder Luftbürste an. Die flächenbezogene Masse der Schutzschicht liegt bevorzugt zwischen 1,0 und 3,0 g/m2 und noch besser zwischen 1,6 und 2,3 g/m2.Roller coater, knife coater, curtain coater or air brush are particularly suitable as coating devices for applying the protective layer covering the heat-sensitive recording layer. The basis weight of the protective layer is preferably between 1.0 and 3.0 g / m 2 and more preferably between 1.6 and 2.3 g / m 2 .
Die Ausgestaltung der wärmeempfindlichen Aufzeichnungsschicht ist weniger limitiert. Hier erkannten die Erfinder mit Bezug auf die gestellte Aufgabe, dass die Aufzeichnungsschicht zunächst grundsätzlich alle bekannten Farbstoffvorläufer beinhalten kann, wobei auch Kombinationen mehrerer Farbstoffvorläufer möglich sind.The configuration of the heat-sensitive recording layer is less limited. Here, the inventors recognized with reference to the stated object that the recording layer may initially include all known dye precursors in principle, and combinations of several dye precursors are possible.
Allgemein ist als möglicher Farbakzeptor insbesondere mindestens eine der Substanzen möglich, ausgesucht aus der Liste, umfassend:
- ■ 2,2 bis (4-hydroxyphenyl)-propan,
- ■ 4-[(4-(1-methylethoxy)phenyl)sulfonyl]phenol,
- ■ 4,4'-Dihydroxydiphenylsulfon,
- ■ N-(p-toluensulphonyl)-N'-(3-p-toluensulphonyl-oxy-phenyl)-harnstoff,
- ■ 2,4'-dihydroxy-diphenylsulfon,
- ■ N-(2-hydroxyphenyl)-2-[(4-hydroxyphenyl)thio]acetamid,
- ■ 2,2 bis (4-hydroxyphenyl) -propane,
- ■ 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol,
- 4,4'-dihydroxydiphenyl sulfone,
- N- (p-toluenesulphonyl) -N '- (3-p-toluenesulphonyl-oxy-phenyl) -urea,
- ■ 2,4'-dihydroxydiphenyl sulfone,
- N- (2-hydroxyphenyl) -2 - [(4-hydroxyphenyl) thio] acetamide,
In einer ersten bevorzugten Ausführungsform gemäß dieses Absatzes sowie der nächstfolgenden Absätze [0022] bis [0025] weist die wärmeempfindliche Aufzeichnungsschicht als Farbakzeptor zu mindestens 33⅓Gew.-%, bezogen auf den Gesamtanteil an Farbakzeptoren in der wärmeempfindlichen Aufzeichnungsschicht, N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß der folgenden Formel (1) auf, wobei die beiden CH3-Endmoleküle in der Literatur auch häufig weggelassen werden.
N-(p-toluensulphonyl)-N'-3-(p-toluensulphonyl-Oxy-phenyl)-harnstoff gemäß obiger Formel (1) ist bekannt als Pergafast® 201 der Firma CIBA Speciality Chemicals Inc.N- (p-toluensulphonyl) -N'-3- (p-toluensulphonyl-oxy-phenyl) -urea according to the above formula (1) is known as Pergafast ® 201 from Ciba Specialty Chemicals Inc.
Als ganz besonders bevorzugt innerhalb dieser ersten Ausführungsform gilt es, wenn N-(p-toluensulphonyl)-N'-3-(p-to!uensulphonyl-Oxy-phenyl)-harnstoff gemäß der Formel (1) alleiniger Farbakzeptor ist. Bezogen auf das Gesamtgewicht der Aufzeichnungsschicht macht dann der Farbakzeptor bis zu 32 Gew.-%, bevorzugt jedoch einen Anteil in einem Bereich von 18 bis 30 Gew.-% und noch besser zwischen 20 und 28,5 Gew.-% der wärmeempfindlichen Aufzeichnungsschicht aus.As very particularly preferred within this first embodiment, it is when N- (p-toluenesulphonyl) -N ' -3- (p-to! Uensulphonyl-oxy-phenyl) -urea according to the formula (1) is the sole color acceptor. Based on the total weight of the recording layer, the color acceptor then makes up to 32% by weight, but preferably in the range of 18 to 30% by weight and more preferably 20 to 28.5% by weight of the heat-sensitive recording layer ,
Die Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials innerhalb dieser ersten Ausführungsform kann zur Erhöhung der thermischen Ansprechempfindlichkeit bevorzugt auch Sensibilisatoren enthalten. Derartige Sensibilisatoren sind zum einen die im Absatz [0033] aufgeführten Substanzen; besonders bevorzugt ist jedoch innerhalb dieser ersten Ausführungsform 2-(2H-benzotriazol-2-yl)-p-cresol gemäß der folgenden Formel (2), wobei auch hier das CH3-Endmolekül in der Literatur häufig weggelassen wird:
2-(2H-benzotriazol-2-yl)-p-cresol gemäß Formel (2), erhältlich als Tinuvin® der Firma CIBA Speciality Chemicals Inc., kann als alleiniger Sensibilisator oder in Kombination mit den in Absatz [0033] genannten Sensibilisatoren in der Aufzeichnungsschicht des erfindungsgemäßen Aufzeichnungsmaterials eingesetzt werden.2- (2H-benzotriazol-2-yl) -p-cresol of formula (2), available as Tinuvin® from CIBA Specialty Chemicals Inc., may be used as the sole sensitizer or in combination with the sensitizers mentioned in paragraph [0033] the recording layer of the recording material according to the invention are used.
In einer zweiten ebenfalls bevorzugten Ausführungsform gemäß dieses Absatzes und der nächstfolgenden Absätze [0027] bis [0029] und [0034] weist die wärmeempfindliche Aufzeichnungsschicht als Farbakzeptor zu mindestens 66 2/3 Gew.-% - bezogen auf den Gesamtanteil an Farbakzeptoren in der wärmeempfindlichen Aufzeichnungsschicht - 4,4'-Dihydroxydiphenylsulfon auf.In a second likewise preferred embodiment according to this paragraph and the following paragraphs [0027] to [0029] and [0034], the heat-sensitive recording layer as color acceptor is at least 66 2/3% by weight, based on the total amount of color acceptors in the heat-sensitive Recording Layer - 4,4'-Dihydroxydiphenylsulfone.
4,4'-Dihydroxydiphenylsulfon wird auch häufig als 4,4'-Sulfonyldiphenol bezeichnet und ist genauso unter der Handelsbezeichnung 4,4 Bisphenol S bekannt. 4,4'-Dihydroxydiphenylsulfon weist die chemische Summenformel C12H1004S auf und ist darstellbar als folgende Formel (3):
Die wärmeempfindliche Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials innerhalb dieser zweiten Ausführungsform kann neben 4,4'-Dihydroxydiphenylsulfon weitere Farbakzeptoren aufweisen, ausgesucht aus der Liste, umfassend
- 2,2 bis (4-hydroxyphenyl)-Propan - auch bekannt als Bisphenol A,
- 4-[(4-(1-methylethoxy)phenyl)sulfonyl]-Phenol - auch bekannt als D8 sowie
- Pergafast® 201.
- 2,2 bis (4-hydroxyphenyl) propane - also known as bisphenol A,
- 4 - [(4- (1-methylethoxy) phenyl) sulfonyl] phenol - also known as D8 as well
- Pergafast® 201.
Bevorzugt sind die obigen Farbakzeptoren, einzeln oder auch untereinander kombiniert, zu maximal 10 Gew.-% ― bezogen auf den Gesamtanteil an Farbakzeptoren in der wärmeempfindlichen Aufzeichnungsschicht - in dieser wärmeempfindlichen Aufzeichnungsschicht eingebunden, den Rest bildet 4,4'-Dihydroxydiphenylsulfon. Schließlich gilt eine Ausführungsform, bei der 4,4'-Dihydroxydiphenylsulfon einziger Farbakzeptor in der wärmeempfindlichen Aufzeichnungsschicht ist, als ganz besonders bevorzugt.The above color acceptors, individually or else combined with one another, are preferably incorporated into this heat-sensitive recording layer to a maximum of 10% by weight, based on the total amount of color acceptors in the heat-sensitive recording layer, the remainder being 4,4'-dihydroxydiphenylsulfone. Finally, an embodiment in which 4,4'-dihydroxydiphenylsulfone is the sole color acceptor in the thermosensitive recording layer is considered to be most preferred.
Das wärmeempfindliche Aufzeichnungsmaterial weist als Farbstoffvorläufer in der wärmeempfindlichen Aufzeichnungsschicht bevorzugt mindestens eine Substanz aus, die ausgesucht ist aus der Liste, umfassend: 3-diethylamino-6-methyl-7-Anilinofluoran, 3-dibutylamino-6-methyl-7-Anilinofluoran, 3-(N-methyl-N-propyl)amino-6-methyl-7-Anilinofluoran, 3-(N-ethyl-N-isoamyl)amino-6-methyl-7-Anilinofluoran, 3-(N-methyl-N-cyclohexyl)amino-6-methyl-7-Anilinofluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-Anilinofluoran und 3-(N-ethyl-N-tetrahydrofuryl)amino-6-methyl-7-Anilinofluoran. Ganz besonders bevorzugt ist dabei 3-dibutylamino-6-methyl-7-Anilinofluoran - auch bekannt als ODB-2.The thermosensitive recording material as the dye precursor in the thermosensitive recording layer preferably comprises at least one substance selected from the list comprising: 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3 (N-methyl-N-propyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilinofluoran, 3- (N-methyl-N- cyclohexyl) amino-6-methyl-7-anilinofluoran, 3- (N-ethyl-N-tolyl) amino-6-methyl-7-anilinofluoran and 3- (N-ethyl-N-tetrahydrofuryl) amino-6-methyl- 7-anilinofluoran. Very particular preference is given to 3-dibutylamino-6-methyl-7-anilinofluoran - also known as ODB-2.
Es ist möglich, dass die wärmeempfindliche Aufzeichnungsschicht mehr als einen Farbstoffvorläufer aufweist, jeweils ausgesucht aus den im obigen Absatz aufgelisteten Farbstoffvorläufern. Das erfindungsgemäße Aufzeichnungsmaterial kann jedoch neben diesen als Farbstoffvorläufer angegebenen Substanzen weiterhin auch eine oder mehrere der folgenden, im nahen Infrarot-Bereich absorbierenden Verbindungen enthalten:It is possible that the thermosensitive recording layer has more than one dye precursor each selected from the dye precursors listed in the above paragraph. However, the recording material according to the invention may further comprise, in addition to these substances mentioned as dye precursors, one or more of the following compounds absorbing in the near infrared range:
3,6-Bis(dimethylamino)fluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3,6-Bis(diethylamino)-fluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Dibutylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3-Dibutylamino-6-diethylaminofluoren-9-spiro-3'-(6'-dimethylaminophthalid), 3,6-Bis(dimethylamino)fluoren-9-spiro-3'-(6'-diethylamino-phthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3-Dibutylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3,6-Bis-(diethylamino)fluoren-9-spiro-3'-(6'-diethylaminophthalid), 3,6-Bis-(dimethylamino)-fluoren-9-spiro-3'-(6'-dibutylaminophthalid), 3-Dibutylamino-6-di-ethylaminofluoren-9-spiro-3'-(6'-diethylaminophthalid), 3-Diethylamino-6-dimethylaminofluoren-9-spiro-3'-(6'-dibutylaminophthalid), 3,3-Bis[2-(4-dimethylamino-phenyl)-2-(4-methoxyphenyl)-ethenyl]-4,5,6,7-tetrachlorophthalid.3,6-Bis (dimethylamino) fluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dimethylaminophthalide), 3.6- Bis (diethylamino) -fluorene-9-spiro-3 '- (6'-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dimethylaminophthalide), 3-dibutylamino-6-diethylaminofluorene -9-spiro-3 '- (6'-dimethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9-spiro-3' - (6'-diethylamino-phthalide), 3-diethylamino-6-dimethylaminofluorene-9 -spiro-3 '- (6'-diethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-diethylaminophthalide), 3,6-Bis (diethylamino) fluorene-9-spiro-3 '- (6'-diethylaminophthalide), 3,6-bis (dimethylamino) -fluorene-9-spiro-3' - (6'-dibutylaminophthalide) , 3-Dibutylamino-6-dimethylaminofluorene-9-spiro-3 '- (6'-diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3' - (6'-dibutylaminophthalide), 3,3 bis [2- (4-dimethylamino-phenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalid.
Die Aufzeichnungsschicht des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kann zur Erhöhung der thermischen Ansprechempfindlichkeit bevorzugt auch Sensibilisatoren mit einem Schmelzpunkt idealerweise von 60°C bis 180°C, besonders bevorzugt mit einem Schmelzpunkt von 80°C bis 140°C, enthalten. Derartige Sensibilisatoren sind beispielsweise: Benzyl-p-benzyloxy-benzoat, Methylolstearamid, Stearinsäureamid, p-Benzylbiphenyl, 1,2-Di(phenoxy)-ethan, 1,2-Di(m-methylphenoxy)ethan, m-Terphenyl, Dibenzyloxalat, Benzylnaphthylether, Dimethylterephtalat und Diphenylsulfon, wobei Methylolstearamid, und insbesondere Stearinsäureamid und Dimethylterephtalat als ganz bevorzugt gelten.The recording layer of the heat-sensitive recording material of the present invention may also preferably contain sensitisers having a melting point of preferably from 60 ° C to 180 ° C, more preferably having a melting point of from 80 ° C to 140 ° C, to increase the thermal responsiveness. Such sensitizers are, for example: benzyl p-benzyloxybenzoate, methylolstearamide, stearic acid amide, p-benzylbiphenyl, 1,2-di (phenoxy) ethane, 1,2-di (m-methylphenoxy) ethane, m-terphenyl, dibenzyl oxalate, Benzylnaphthylether, dimethyl terephthalate and diphenylsulfone, with methylolstearamide, and in particular stearic acid amide and dimethyl terephthalate are considered to be very preferred.
In zahlreichen Versuchen zur zweiten bevorzugten Ausführungsform betreffend die wärmeempfindliche Aufzeichnungsschicht zeigte sich, dass ein auf die Gew.- % innerhalb der Aufzeichnungsschicht bezogenes Verhältnis
- Farbakzeptorgesamt : Sensibilisatorgesamt und insbesondere
- 4,4'-Dihydroxydiphenylsulfon : Sensibilisator, ausgesucht aus der Liste umfassend Methylolstearamid, Stearinsäureamid, und Dimethylterephtalat
ganz besonders bevorzugt in einem Bereich von 1 : 0,8 bis 1 : 1,4, liegt.In numerous experiments on the second preferred embodiment relating to the heat-sensitive recording layer, it was found that a ratio based on the weight% within the recording layer
- Total color acceptor : total sensitizer and in particular
- 4,4'-Dihydroxydiphenylsulfone: Sensitizer selected from the list consisting of methylolstearamide, stearic acid amide, and dimethyl terephthalate
most preferably in a range of 1: 0.8 to 1: 1.4.
Geeignete Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht sind beispielsweise wasserlösliche Bindemittel wie Stärke, Hydroxyethylzellulose, Methylzellulose, Carboxymethylzellulose, Gelatine, Kasein, Polyvinylalkohole, modifizierte Polyvinylalkohole, Ethylen-Vinylalkohol-Coplymere, Natriumpolyacrylate, Acrylamid-Acrylat-Copolymere, Acrylamid-Acrylat-Methacrylat-Terpolymere sowie Alkalisalze von Styrol-Maleinsäureanhydrid-Copolymer oder Ethylen-Maleinsäureanhydrid-Copolymer, wobei die Bindemittel allein oder in Kombination untereinander eingesetzt werden können; auch wasserunlösliche Latexbinder wie Styrol-Butadiene-Copolymere, Acrylnitril-Butadien-Copolymere und Methyl-Acrylat-Butadien-Copolymere bieten sich als Bindemittel zur Einbindung in die wärmeempfindliche Aufzeichnungsschicht an. Im Sinne der vorliegenden Erfindung gelten Polyvinylalkohol, Ethylen-Vinylalkohol-Coplymere oder Polyvinylalkohol in Verbindung mit Ethylen-Vinylalkohol-Coplymeren als besonders bevorzugte Bindemittel, die zusammen, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in einem Bereich von 10 bis 20 Gew.-% in die wärmeempfindliche Aufzeichnungsschicht eingebunden sind.Suitable binders for incorporation into the heat-sensitive recording layer are, for example, water-soluble binders such as starch, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, polyvinyl alcohols, modified polyvinyl alcohols, ethylene-vinyl alcohol copolymers, sodium polyacrylates, acrylamide-acrylate copolymers, acrylamide-acrylate-methacrylate Terpolymers and alkali salts of styrene-maleic anhydride copolymer or ethylene-maleic anhydride copolymer, which binders can be used alone or in combination with one another; Water-insoluble latex binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and methyl acrylate-butadiene copolymers also offer themselves as binders for incorporation into the heat-sensitive recording layer at. For the purposes of the present invention are polyvinyl alcohol, ethylene-vinyl alcohol copolymers or polyvinyl alcohol in conjunction with ethylene-vinyl alcohol copolymers as particularly preferred binders which together, based on the total weight of the recording layer, in a range of 10 to 20 wt .-% in the heat-sensitive recording layer is incorporated.
Zur Vermeidung des Klebens an einem Thermokopf und zur Vermeidung einer übermäßigen Abnutzung des Thermokopfes kann die Beschichtungsmasse zur Ausbildung der wärmeempfindlichen Aufzeichnungsschicht - allgemein sowie innerhalb der ersten bevorzugten wie auch innerhalb der zweiten bevorzugten Ausführungsform bereffend die wärmeempfindliche Aufzeichnungsschicht - weiterhin Gleit- und Trennmittel enthalten wie Metallsalze höherer Fettsäuren, zum Beispiel Zinkstearat, Kalziumstearat sowie Wachse, wie zum Beispiel Paraffin, oxidiertes Paraffin, Polyethylen, Polyethylenoxid, Stearamide und Kastorwachs. Weitere Bestandteile der Aufzeichnungsschicht sind gegebenenfalls beispielsweise Pigmente, bevorzugt anorganische Pigmente wie beispielsweise Aluminium(hydr)oxid, Kieselsäure und Kalziumkarbonat, wobei hier insbesondere Kalziumkarbonat, das bevorzugt in einer Menge von 0 bis 28 Gew.-%, bezogen auf das Gesamtgewicht der Aufzeichnungsschicht, in die Aufzeichnungsschicht eingebunden sein soll, als bevorzugt gilt.In order to prevent sticking to a thermal head and to avoid excessive wear of the thermal head, the coating composition for forming the heat-sensitive recording layer, generally and within the first preferred as well as the second preferred embodiment, the heat-sensitive recording layer, may further contain lubricants and release agents such as metal salts higher fatty acids, for example, zinc stearate, calcium stearate, and waxes, such as paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearamides, and castor wax. Further constituents of the recording layer are optionally, for example, pigments, preferably inorganic pigments such as, for example, aluminum (hydr) oxide, silicic acid and calcium carbonate, in which case in particular calcium carbonate, preferably in an amount of from 0 to 28% by weight, based on the total weight of the recording layer, should be included in the recording layer, as is preferred.
Als Beschichtungsvorrichtung zum Auftrag der wärmeempfindlichen Aufzeichnungsschicht - allgemein sowie innerhalb der ersten bevorzugten wie auch innerhalb der zweiten bevorzugten Ausführungsform bereffend die wärmeempfindliche Aufzeichnungsschicht - bieten sich insbesondere Rollrakelstreichwerk, Messerstreichwerk, Vorhangbeschichter oder Luftbürste an. Entsprechend einer bevorzugten Ausführungsform ist die zur Ausbildung der Aufzeichnungsschicht genutzte Beschichtungsmasse wässerig. Die anschließende Trocknung der Beschichtungsmasse geschieht üblicherweise durch ein Verfahren, bei dem Wärme zugeführt wird, wie es durch Heißluft-Schwebetrockner oder auch Kontakttrockner geschieht. Bewährt ist auch eine Kombination aus den aufgeführten Trockenverfahren. Die flächenbezogene Masse der wärmeempfindlichen Aufzeichnungsschicht liegt bevorzugt zwischen 2 und 6 g/m2 und noch besser zwischen 2,2 und 4,8 g/m2.As a coating device for applying the heat-sensitive recording layer - in general as well as within the first preferred as well as within the second preferred embodiment, the heat-sensitive recording layer - offer in particular roller blade coater, knife coater, curtain coater or air brush. According to a preferred embodiment, the coating composition used to form the recording layer is aqueous. The subsequent drying of the coating composition is usually done by a method in which heat is supplied, as is done by hot-air floating dryer or contact dryer. Proven is also a combination of the listed dry processes. The basis weight of the heat-sensitive recording layer is preferably from 2 to 6 g / m 2, and more preferably from 2.2 to 4.8 g / m 2 .
In einer ganz besonders bevorzugten Ausführungsform weist das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial eine pigmenthaltige Zwischenschicht auf, welche zwischen Barrierebeschichtung und wärmeempfindlicher Aufzeichnungsschicht angeordnet ist.In a very particularly preferred embodiment, the heat-sensitive recording material according to the invention comprises a pigment-containing intermediate layer, which is arranged between the barrier coating and the heat-sensitive recording layer.
Als Pigmente der Zwischenschicht bieten sich sowohl organische Hohlraum-Pigmente wie auch anorganische Pigmente an, letztere bevorzugt ausgewählt aus der Gruppe, umfassend natürliches wie kalziniertes Kaolin, Siliziumoxid und hier besonders Bentonit, Kalziumkarbonat sowie Aluminiumhydroxid und hier besonders Böhmit. Eine solche Zwischenschicht kann zum einen einen positiven Beitrag zur Egalisierung der zu beschichtenden Oberfläche leisten, womit sich die Menge an notwendigerweise aufzubringender Streichfarbe für die wärmeempfindliche Aufzeichnungsschicht reduziert. Aus diesem Grund bieten sich zum Auftrag der pigmenthaltigen Zwischenschicht egalisierende Streichwerke an, wie beispielsweise Walzenstreichwerke, Streichmesser- und (Roll-)Rakelstreichwerke. Zum anderen können die Pigmente dieser Zwischenschicht die durch Hitzeeinwirkung verflüssigten Wachsbestandteile der wärmeempfindlichen Aufzeichnungsschicht bei der Schriftbildausbildung aufnehmen und begünstigen so eine sichere und schnelle Funktionsweise der wärmeinduzierten Aufzeichnung. Die flächenbezogene Masse der pigmenthaltigen Zwischenschicht liegt bevorzugt zwischen 5 und 20 g/m2 und noch besser zwischen 7 und 11 g/m2.Suitable pigments of the intermediate layer are both organic void pigments and inorganic pigments, the latter preferably selected from the group comprising natural and calcined kaolin, silica and in particular bentonite, calcium carbonate and aluminum hydroxide and here especially boehmite. On the one hand, such an intermediate layer can make a positive contribution to the leveling of the surface to be coated, which reduces the amount of coating color necessarily to be applied for the heat-sensitive recording layer. For this reason, offer to coat the pigment-containing intermediate layer leveling coating, such as Walzenstreichwerke, doctor blade and (roll) doctor blade coating. On the other hand, the pigments of this intermediate layer can absorb the heat-liquefied wax constituents of the thermosensitive recording layer in the typeface formation and thus promote a safe and rapid operation of the heat-induced recording. The basis weight of the pigment-containing intermediate layer is preferably between 5 and 20 g / m 2 and more preferably between 7 and 11 g / m 2 .
Auch wenn nicht auf Papier als Substrat beschränkt, ist Papier das Substrat, die sich am Markt auch mit Blick auf die gute Umweltverträglichkeit wegen der guten Recyclingfähigkeit durchgesetzt hat und die im Sinne der Erfindung bevorzugt ist. Es ist aber möglich aufgrund der Anordnung der Barrierebeschichtung zwischen Substrat und wärmeempfindlicher Aufzeichnungsschicht, auch solche Substrate zu verwenden, die sich aufgrund ihrer Inhaltsstoffe und deren negativer Einflussnahme auf die wärmeempfindliche Aufzeichnungsschicht eher verbieten würden wie beispielsweise Folien oder Folien beschichtete Papiere, bei denen die jeweiligen Folien größere Mengen an Weichmachern enthalten, oder auch Papiere aus recycelten Fasern niedrigster Qualitäten.Although not limited to paper as a substrate, paper is the substrate that has prevailed on the market with regard to the good environmental compatibility because of good recyclability and is preferred in the context of the invention. However, it is possible due to the arrangement of the barrier coating between the substrate and heat-sensitive recording layer, to use those substrates that would rather prohibit due to their ingredients and their negative influence on the heat-sensitive recording layer such as films or films coated papers in which the respective films Contain larger amounts of plasticizers, or papers from recycled fibers of the lowest quality.
Die herausragende Beständigkeit des vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials gegenüber organischen Lösungsmitteln ermöglicht die Ausbildung eines völlig neuartigen Authentifikationsmerkmals in Form eines unechten Wasserzeichens. In diesem Sinne und im Rahmen einer ganz bevorzugten Ausführungsvariante weist das vorgeschlagene wärmeempfindliche Aufzeichnungsmaterial eine rückseitig auf das Substrat in Form von mindestens einem Zeichen oder in Form eines Musters aufgetragene Beschichtung aus einer Tinktur auf, wobei die Tinktur mindestens ein organisches Lösungsmittel umfasst. Es ist auch möglich, dass die Tinktur eine Mischung aus mehreren organischen Lösungsmitteln umfasst. In einer bevorzugten Ausführungsform sind in der Tinktur auch weitere Bestandteile enthalten wie beispielsweise fluoreszierende Fasern und/oder Pigmente.The outstanding resistance of the proposed thermosensitive recording material to organic solvents enables the formation of a completely novel authentication feature in the form of a spurious watermark. In this sense and within the scope of a very preferred embodiment, the proposed heat-sensitive recording material has a coating of a tincture applied to the substrate in the form of at least one character or in the form of a pattern, the tincture comprising at least one organic solvent. It is also possible that the tincture comprises a mixture of several organic solvents. In a preferred Embodiment are also included in the tincture other ingredients such as fluorescent fibers and / or pigments.
Der Auftrag der Tinktur mit mindestens einem organischem Lösungsmittel auf das zur Ausbildung des Authentifikationsmerkmals aus Papier bestehende Substrat bewirkt eine Änderung der Opazität bzw. der Transparenz des Substrates an den mit der Tinktur benetzten Stellen im Vergleich zu den nicht benetzten Stellen des Substrates. Hält man das derart behandelte, hier vorgeschlagene wärmeempfindliche Aufzeichnungsmaterial gegen eine Lichtquelle, macht sich die Transparenzänderung in der Durchsicht scharfkantig als leicht zu erkennendes Bild oder Muster aus.Applying the tincture with at least one organic solvent to the substrate formed to form the paper authentication feature causes the opacity of the substrate to change at the sites wetted with the tincture relative to the non-wetted areas of the substrate. If one keeps the thus treated, here proposed heat-sensitive recording material against a light source, makes the change in transparency in the review sharp-edged as easily recognizable image or pattern.
Zum Auftrag der das Authentifikationsmerkmal ausbildenden Tinktur bieten sich insbesondere analoge Druckverfahren, wie beispielsweise das Flexo- und das Tiefdruckverfahren an. In einer ganz besonders bevorzugten Ausführungsform ist die Tinktur mittels digitaler Druckverfahren aufgebracht. Sofern der Auftrag der Tinktur digitaldrucktechnisch erfolgt, was als bevorzugt gilt und was unter anderem im Inkjet-Druckverfahren gegeben ist, wird die Ausbildung eines individuellen Authentifikationsmerkmals pro Einzelabschnitt des hier vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials ermöglicht. Wird das hier vorgeschlagene wärmeempfindliche Aufzeichnungsmaterial als Ticket und/oder insbesondere als Eintrittskarte verwendet, kann jede einzelne Eintrittskarte mit einem individuellen Authentifikationsmerkmal versehen werden. Im Falle einer Eintrittskarte beispielsweise für ein Fußballspiel können Veranstalter, Veranstaltungsort, Veranstaltungszeit, gegeneinander antretende Fußballmannschaften, Verkaufsort und Verkaufszeit des Tickets und vielleicht noch eine fortlaufende Kontrollziffer als individuelles Authentifikationsmerkmal auf das hier vorgeschlagene wärmeempfindliche Aufzeichnungsmaterial ausgebildet werden. Die Verfälschung eines solchen Authentifikationsmerkmals ist schwierig und mit entsprechender Kontrolle am Veranstaltungsort aussichtslos.For the order of the tincture that forms the authentication feature, analog printing methods, such as, for example, the flexographic and gravure printing methods are particularly suitable. In a very particularly preferred embodiment, the tincture is applied by means of digital printing methods. If the order of tincture digital printing technology, which is considered preferable and what is given, inter alia, in the inkjet printing process, the formation of an individual authentication feature per single section of the proposed here heat-sensitive recording material is made possible. If the heat-sensitive recording material proposed here is used as a ticket and / or in particular as an admission ticket, each individual ticket can be provided with an individual authentication feature. For example, in the case of a ticket for a football match, organizer, venue, event time, soccer teams opposing each other, place of sale and time of sale of the ticket, and perhaps a continuous check digit may be formed as an individual authentication feature on the heat-sensitive recording material proposed herein. The falsification of such an authentication feature is difficult and hopeless with appropriate control at the venue.
Entsprechend den obigen Ausführungen gilt es also als besonders bevorzugt, das hier vorgeschlagene wärmeempfindliche Aufzeichnungsmaterial als Ticket, ganz besonders bevorzugt, als Eintrittskarte zu verwenden.According to the above statements, it is therefore particularly preferred to use the heat-sensitive recording material proposed here as a ticket, very particularly preferably as an admission ticket.
Die Erfindung soll anhand des nachfolgenden erfindungsgemäßen Beispiels 1 sowie der beiden Vergleichsbeispiele 2 und 3 weiter verdeutlicht werden:The invention will be further elucidated on the basis of the following inventive example 1 and the two comparative examples 2 and 3:
Zu diesem Zweck wird zunächst auf einer Langsieb-Papiermaschine als Substrat eine Papierbahn aus gebleichten und gemahlenen Laub- und Nadelholzzellstoffen mit einer flächenbezogenen Masse von 130 g/m2 unter Zusatz üblicher Zuschlagstoffe in üblichen Mengen hergestellt. Aus der Papierbahn werden 3 Musterrollen zur Weiterbehandlung geschnitten.For this purpose, a paper web of bleached and ground deciduous and softwood pulps with a basis weight of 130 g / m 2 with the addition of conventional additives in conventional amounts is first prepared on a fourdrinier paper machine as a substrate. From the paper web 3 sample rolls are cut for further treatment.
Zur Ausbildung des einen erfindungsgemäßen Beispiels und der beiden vergleichenden Beispiele werden drei verschiedene Streichmassen für eine vorderseitige Beaufschlagung des jeweiligen Substrates der 3 Musterrollen mit jeweils einer Barrierebeschichtung vorbereitet:
- ■ Streichmasse BS1(für Beispiel 1) enthält zu 99,5 Gew.-% Ethylen-Vinyl-Alkohol-Copolymer (EVOH) , genauer Exceval HR 3010 (Kuraray), weitere Bestandteile von Streichmasse BS1 sind in erster Linie Entschäumer.
- ■ Streichmasse BS2(für Vergleichsbeispiel 2) enthält zu 99,5 Gew.-% üblichen Polyvinylalkohol, genauer Gohsenol NM 11 (Nippon Gohsei), weitere Bestandteile von Streichmasse BS2 sind in erster Linie Entschäumer.
- ■ Streichmasse BS3(für Vergleichsbeispiel 3) enthält zu 99,5 Gew.-% silanisierten Polyvinylalkohol, genauer R 1130 (Kuraray), weitere Bestandteile von Streichmasse BS3 sind in erster Linie Entschäumer.
- Coating composition BS1 ( for Example 1 ) contains 99.5% by weight of ethylene-vinyl alcohol copolymer (EVOH), more precisely Exceval HR 3010 (Kuraray), further constituents of coating composition BS1 are primarily defoamers.
- Coating composition BS2 ( for Comparative Example 2 ) contains 99.5% by weight of conventional polyvinyl alcohol, more specifically Gohsenol NM 11 (Nippon Gohsei), further constituents of coating composition BS2 are primarily defoamers.
- Coating composition BS3 ( for Comparative Example 3) contains 99.5% by weight silanized polyvinyl alcohol, more precisely R 1130 (Kuraray), further constituents of coating composition BS3 are primarily defoamers.
Die drei Streichmassen werden zum beabsichtigten Auftrag mittels Luftbürste auf einen Feststoffgehalt von 12 % mit Wasser verdünnt. Anschließend werden die jeweiligen Viskositäten der Streichmassen nach Brookfield (Spindel 3 / 100 rpm / 23 °C) bestimmt, es ergeben sich die Messwerte:
- ■ Streichmasse BS1: 750,
- ■ Streichmasse BS2: 690,
- ■ Streichmasse BS3: 2780 (Fraktionsbildung, kein sauberes Verstreichen möglich).
- ■ coating weight BS1: 750,
- ■ coating BS2: 690,
- ■ Coating weight BS3: 2780 (formation of fractions, no clean spreading possible).
Zur Ausbildung des erfindungsgemäßen Beispiels 1 sowie der beiden Vergleichsbeispiele 2 und 3 werden die drei Streichmassen nunmehr vorderseitig mittels Luftbürste auf das jeweilige Substrat der 3 Musterrollen mit einer jeweiligen flächenbezogenen Masse von 2,8 g/m2 aufgetragen.For the formation of Inventive Example 1 and the two Comparative Examples 2 and 3, the three coating compositions are now applied front side by means of air brush on the respective substrate of the 3 pattern rolls with a respective basis weight of 2.8 g / m 2 .
Auf die getrocknete Barrierebeschichtung wird jeweils bei allen 3 Musterrollen innerhalb von einem Durchgang durch die zur Anwendung kommenden Mehrkopf-Streichmaschine
- mittels Rollrakel-Streichwerk eine hauptsächlich kalziniertes Kaolin und organische Hohlraum-Pigmente als Pigmentmischung, Styrolbutadienlatex als Bindemittel und Stärke als Cobinder aufweisende Zwischenschicht von 8 g/m2 und anschließend
- mittels Rollrakel-Streicheinrichtung eine wärmeempfindliche Aufzeichnungsschicht mit einer flächenbezogenen Masse von 4,2 g/m2
- by means of roller blade coating a mainly calcined kaolin and organic void pigments as a pigment mixture, styrene butadiene latex as a binder and starch as cobinder-containing intermediate layer of 8 g / m 2 and then
- by means of roller blade coating device, a heat-sensitive recording layer having a basis weight of 4.2 g / m 2
Die für die wärmeempfindliche Aufzeichnungsschicht zum Einsatz kommende Streichmasse enthält im wesentlichen die folgenden Komponenten:
Auf die wärmeempfindliche Aufzeichnungsschicht wird schließlich mittels Luftbürste jeweils bei allen 3 Musterrollen eine Schutzschicht von 2,0 g/m2 aufgetragen. Dafür kommt eine Streichmasse zum Einsatz, die im wesentlichen die folgenden Komponenten enthält:
Bei allen 3 Musterrollen soll alsdann die erwünschte Sperrwirkung der Barriereschicht gegenüber organischen Lösemitteln untersucht werden. Zu diesem Zweck wird auf die jeweilige Rückseite von Probestreifen aus den 3 Musterrollen entsprechend des erfindungsgemäßen Beispiels 1 sowie der beiden Vergleichsbeispiele 2 und 3 mit einer Pipette 0,5 ml Ethanol aufgegeben. Nach einer jeweiligen Einwirkzeit von 10 Minuten ist das Ethanol vollständig aufgesaugt. Die Auswirkung des Lösemittelauftrags auf die wärmeempfindliche Aufzeichnungsschicht wird visuell beurteilt.For all 3 sample rolls, the desired barrier effect of the barrier layer against organic solvents should then be investigated. For this purpose, 0.5 ml of ethanol is applied to the respective reverse side of test strips from the 3 sample rolls corresponding to Example 1 according to the invention and the two comparative examples 2 and 3 using a pipette. After a respective exposure time of 10 minutes, the ethanol is completely absorbed. The effect of the solvent application on the heat-sensitive recording layer is visually evaluated.
Die wärmeempfindliche Aufzeichnungsschicht des erfindungsgemäßen Beispiels 1 zeigt überhaupt keine Thermoreaktionen, die vorliegende Erfindung wird hinsichtlich ihrer Güte hervorragend bestätigt. Bei dem Vergleichsbeispiel 2 zeigt sich eine intensive Thermoreaktionen, diese Barrierebeschichtung ist überhaupt nicht geeignet, eine weitreichende Schutzwirkung gegenüber organischen Lösemitteln aus Richtung des Substrates über eine längere Einwirkzeit zu entfalten. Bei dem Vergleichsbeispiel 3 ergeben sich vereinzelte Farbreaktionspunkte auf der wärmeempfindlichen Aufzeichnungsschicht: unterhalb dieser farbigen Punkte weist die Barrierebeschichtung aus der Streichmasse BS3 Risse und Fehlstellen infolge der zu hohen Viskosität des silanisierten Polyvinylalkohols auf. Auch hier ist die Barrierewirkung gegenüber organischen Lösemitteln nicht überzeugend, weil nicht ohne Fehlstellen.The heat-sensitive recording layer of Inventive Example 1 shows no thermal reactions at all, the present invention is excellently confirmed in terms of quality. In Comparative Example 2 shows an intense thermoreactions, this barrier coating is not at all suitable to develop a far-reaching protective effect against organic solvents from the direction of the substrate over a longer exposure time. In Comparative Example 3, there are scattered color reaction points on the heat-sensitive recording layer: below these colored dots, the barrier coating of the coating composition BS3 has cracks and voids due to the too high viscosity of the silanized polyvinyl alcohol. Again, the barrier effect against organic solvents is not convincing, because not without flaws.
Damit kann die schließlich seitens der Erfinder erwartete Überlegenheit des vorgeschlagenen wärmeempfindlichen Aufzeichnungsmaterials bestätigt werden.Thus, the superiority of the proposed thermosensitive recording material finally expected by the inventors can be confirmed.
Claims (17)
dadurch gekennzeichnet, dass
characterized in that
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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ES09177678T ES2394407T3 (en) | 2009-12-01 | 2009-12-01 | Heat sensitive record material with barrier coating |
EP20090177678 EP2329959B1 (en) | 2009-12-01 | 2009-12-01 | Heat-sensitive recording material with barrier coating |
PCT/EP2010/063412 WO2011067004A1 (en) | 2009-12-01 | 2010-09-13 | Heat-sensitive recording material with barrier coating |
US13/512,979 US9050844B2 (en) | 2009-12-01 | 2010-09-13 | Heat-sensitive recording material with barrier coating |
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EP20090177678 EP2329959B1 (en) | 2009-12-01 | 2009-12-01 | Heat-sensitive recording material with barrier coating |
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EP2329959A1 true EP2329959A1 (en) | 2011-06-08 |
EP2329959B1 EP2329959B1 (en) | 2012-08-29 |
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EP20090177678 Not-in-force EP2329959B1 (en) | 2009-12-01 | 2009-12-01 | Heat-sensitive recording material with barrier coating |
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US (1) | US9050844B2 (en) |
EP (1) | EP2329959B1 (en) |
ES (1) | ES2394407T3 (en) |
WO (1) | WO2011067004A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019141751A1 (en) * | 2018-01-18 | 2019-07-25 | Mitsubishi Hitec Paper Europe Gmbh | Heat-sensitive recording material comprising a plurality of submicrometre particles with a monomodal particle size distribution |
CN111778773A (en) * | 2020-05-26 | 2020-10-16 | 湖南天琪智慧印刷有限公司 | Thermal sensitive paper with high retention rate and ethanol resistance and manufacturing method thereof |
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DE102015014036A1 (en) * | 2015-10-30 | 2017-05-04 | Giesecke & Devrient Gmbh | security element |
US10653136B2 (en) * | 2016-07-11 | 2020-05-19 | Covestro Llc | Aqueous compositions for treating seeds, seeds treated therewith, and methods for treating seeds |
US10653135B2 (en) * | 2016-07-11 | 2020-05-19 | Covestro Llc | Methods for treating seeds with an aqueous composition and seeds treated therewith |
JP6865656B2 (en) * | 2017-08-31 | 2021-04-28 | 三光株式会社 | Thermal recording material |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5641724A (en) | 1994-09-29 | 1997-06-24 | Ricoh Company, Ltd. | Reversible thermosensitive coloring composition and a thermosensitive recording medium using thereof |
US5804529A (en) | 1996-05-10 | 1998-09-08 | Mitsubishi Paper Mills Ltd. | Heat-sensitive recording material and process for the production thereof |
EP0938419B1 (en) | 1997-09-12 | 2000-11-15 | Mitsubishi HiTec Paper Flensburg GmbH | Thermo-sensitive printing sheet comprising a back coating containing starch, an acrylate copolymer and an alkaline catalyst |
US6150067A (en) | 1998-04-02 | 2000-11-21 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
EP2033802A1 (en) | 2007-09-10 | 2009-03-11 | Mitsubishi HiTec Paper Flensburg GmbH | Heat sensitive recording material with reverse coating |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0844097B1 (en) | 1996-11-21 | 2001-07-18 | Ncr International Inc. | Thermal paper with security features and security ink therefor |
DE69908989T2 (en) * | 1998-02-02 | 2004-05-19 | NCR International, Inc., Dayton | Heat sensitive recording material |
DE19842866A1 (en) * | 1998-09-19 | 2000-03-30 | Stora Spezialpapiere Gmbh | Thermographic material useful e.g. for travel ticket or receipt has (ir)regular pattern of reagent fluorescing in ultraviolet light and invisible in daylight as security mark on back |
FR2828897B1 (en) * | 2001-08-21 | 2004-01-23 | Danel | FILIGRAN PRINTING ARTICLE, PARTICULARLY FOR THERMAL PRINTER |
ES2265300B1 (en) | 2006-07-17 | 2008-02-01 | Antonio Oliva Gurgui | "DERIVATIVES OF POLYURETHANS AND CORRESPONDING USES AND PROCEDURES OF MANUFACTURE OF BRANDS TO WATER". |
ES2294965B1 (en) | 2007-05-07 | 2009-04-16 | Antonio Oliva Gurgui | "DERIVATIVES OF URETANS AND OLIGOURETHANS AND CORRESPONDING USES AND PROCEDURES OF MANUFACTURING BRANDS TO WATER THROUGH THE OFFSET PRINTING TECHNIQUE". |
-
2009
- 2009-12-01 EP EP20090177678 patent/EP2329959B1/en not_active Not-in-force
- 2009-12-01 ES ES09177678T patent/ES2394407T3/en active Active
-
2010
- 2010-09-13 WO PCT/EP2010/063412 patent/WO2011067004A1/en active Application Filing
- 2010-09-13 US US13/512,979 patent/US9050844B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5641724A (en) | 1994-09-29 | 1997-06-24 | Ricoh Company, Ltd. | Reversible thermosensitive coloring composition and a thermosensitive recording medium using thereof |
US5804529A (en) | 1996-05-10 | 1998-09-08 | Mitsubishi Paper Mills Ltd. | Heat-sensitive recording material and process for the production thereof |
EP0938419B1 (en) | 1997-09-12 | 2000-11-15 | Mitsubishi HiTec Paper Flensburg GmbH | Thermo-sensitive printing sheet comprising a back coating containing starch, an acrylate copolymer and an alkaline catalyst |
US6150067A (en) | 1998-04-02 | 2000-11-21 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording material |
EP2033802A1 (en) | 2007-09-10 | 2009-03-11 | Mitsubishi HiTec Paper Flensburg GmbH | Heat sensitive recording material with reverse coating |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019141751A1 (en) * | 2018-01-18 | 2019-07-25 | Mitsubishi Hitec Paper Europe Gmbh | Heat-sensitive recording material comprising a plurality of submicrometre particles with a monomodal particle size distribution |
CN111778773A (en) * | 2020-05-26 | 2020-10-16 | 湖南天琪智慧印刷有限公司 | Thermal sensitive paper with high retention rate and ethanol resistance and manufacturing method thereof |
Also Published As
Publication number | Publication date |
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US9050844B2 (en) | 2015-06-09 |
WO2011067004A1 (en) | 2011-06-09 |
EP2329959B1 (en) | 2012-08-29 |
US20140274681A1 (en) | 2014-09-18 |
ES2394407T3 (en) | 2013-01-31 |
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