EP3148816B1 - Heat-sensitive recording material - Google Patents
Heat-sensitive recording material Download PDFInfo
- Publication number
- EP3148816B1 EP3148816B1 EP15726926.7A EP15726926A EP3148816B1 EP 3148816 B1 EP3148816 B1 EP 3148816B1 EP 15726926 A EP15726926 A EP 15726926A EP 3148816 B1 EP3148816 B1 EP 3148816B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- heat
- methyl
- recording material
- sensitive
- sensitive recording
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
- B05D1/305—Curtain coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
Definitions
- the invention relates to a heat-sensitive recording material comprising a carrier substrate and a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, a process for its preparation and the use of the phenol-free color developer contained in the heat-sensitive recording material.
- Heat-sensitive recording materials for thermodirect printing which have a heat-sensitive color-forming layer (thermal reaction layer) applied to a carrier substrate, have long been known.
- a color former and a color developer are usually present in the heat-sensitive color-forming layer and react with one another under the influence of heat and thus lead to color development.
- heat-sensitive recording materials which contain a non-phenolic color developer in the heat-sensitive color-forming layer. These have been developed to improve the durability of the typeface, especially when the printed heat-sensitive recording material is stored for a long time or comes into contact with hydrophobic substances such as plasticized materials or oils.
- interest in non-phenolic color developers has increased significantly. The aim here was to avoid the disadvantages of the phenolic color developers, but the performance properties, that can be achieved with phenolic color developers are at least maintained.
- the EP 0 620 122 B1 discloses non-phenolic color developers from the aromatic sulfonyl urea class. These can be used to obtain heat-sensitive recording materials which are notable for high image stability. Furthermore, the heat-sensitive recording materials based on these color developers have a usable thermal sensitivity with good surface whiteness, so that it is comparatively easy to produce high printing densities using commercially available thermal printers if the formulation of the heat-sensitive color-forming layer is designed accordingly.
- B-TUM 4,4'-bis (p-tolylsulfonylureido) diphenylmethane
- TUPH N '- (p-toluenesulfonyl) -N'-phenyl-urea
- N- (p-tolylsulfonyl) -N '- (3-p-tolylsulfonyloxy-phenyl) urea (trade name Pergafast 201®, PF201 BASF) is characterized by the balance of the application technology Properties of the heat-sensitive recording materials produced with this. In particular, these have good dynamic responsiveness and a high resistance of the printout to hydrophobic substances.
- the requirements mentioned under a) relate to the stability or constancy of the composition of the heat-sensitive color-forming layer, in particular the chemical resistance of the color-forming components, even with long-term storage and under more severe climatic conditions
- the requirements mentioned under b) aim at the stability of the during the printing process from the color complex forming the heat-sensitive color-forming layer.
- the post-published WO 2014/080615 A1 discloses a recording material with non-phenolic color developers.
- the post-published WO 2014/189044 A1 discloses heat sensitive recording materials with high recording density.
- the post-published EP 3 053 753 A1 discloses a recording material with non-phenolic color developers.
- the object of the present invention is therefore to remedy the disadvantages of the prior art described above.
- the object of the present invention is to provide a heat-sensitive recording material which also meets the requirements mentioned under a) above, that is to say the functional properties required in terms of application, such as thermal responsiveness and surface whiteness, even when stored for longer periods and under aggravated climatic conditions.
- the task accordingly relates to the property profile of an unprinted, heat-sensitive recording material.
- a heat-sensitive recording material according to claim 1.
- this comprises a carrier substrate and a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, and is characterized in that the at least one color developer is a compound of the formula (I) wherein Ar1 and Ar2 are a phenyl radical and / or a C 1 -C 4 alkyl-substituted phenyl radical, the at least one sensitizing agent being 1,2-diphenoxyethane and the dried heat-sensitive color-forming layer being subjected to such a smoothing measure is that it has a Bekk smoothness of 300 to 700 seconds, measured according to DIN 53107.
- At least one protective layer and / or at least one layer which promotes printability can also be present in the heat-sensitive recording material according to the invention.
- the C 1 -C 4 -alkyl-substituted phenyl radical is preferably a C 1 -alkyl-substituted phenyl radical (ortho-, meta, and / or para-substituted), in particular a para-substituted C 1 -Alkyl-substituted phenyl radical.
- a methyl radical is particularly preferred, a para-methyl radical is very particularly preferred.
- Ar 1 and Ar 2 are a para-methyl-substituted phenyl radical.
- Ar 1 is a phenyl radical and Ar 2 is a para-methyl-substituted phenyl radical.
- Ar 1 and Ar 2 are each a phenyl radical, that is to say the at least one color developer is N- (2- (3-phenylureido) phenyl) benzenesulfonamide.
- the compound of formula (I) is preferably in an amount of about 3 to about 35% by weight, particularly preferably in an amount of about 10 to about 25 % By weight, based on the total solids content of the heat-sensitive layer.
- the selection of the carrier substrate is not critical. However, it is preferred to use paper, synthetic paper and / or a plastic film as the carrier substrate.
- the present invention is likewise not subject to any significant restrictions with regard to the choice of the color former.
- the color former is preferably a dye of the triphenylmethane type, of the fluorane type, of the azaphthalide type and / or of the fluorene type.
- a very particularly preferred color former is a fluoran-type dye because, thanks to the availability and the balanced application-related properties, it enables the provision of a recording material with an attractive price-performance ratio.
- one or more further non-phenolic color developers are present in the heat-sensitive color-forming layer.
- the one or more other non-phenolic color developers are preferably N '- (p-toluenesulfonyl) -N'-phenyl-urea, N- (p-toluenesulfonyl) -N'-3- (p-toluenesulphonyl-oxy phenyl) urea and / or 4,4'-bis (p-tolylsulfonylureido) diphenylmethane.
- the heat-sensitive recording material according to the invention is a heat-sensitive recording material comprising a carrier substrate and at least one color former, at least one phenol-free color developer and at least one heat-sensitive color-forming layer containing sensitizer, characterized in that the at least one color developer is a compound of formula (I) wherein Ar 1 and Ar 2 are a phenyl radical and / or a C 1 alkyl-substituted phenyl radical, the heat-sensitive recording materials 42 and 43 of the WO 2014/080615 are excluded, the carrier substrate being paper, synthetic paper and / or a plastic film, and the at least one color former being a fluoran-type dye.
- Ar 1 and Ar 2 are a phenyl radical and / or a C 1 alkyl-substituted phenyl radical
- the heat-sensitive recording materials 42 and 43 of the WO 2014/080615 are excluded
- the carrier substrate being paper, synthetic paper and / or a plastic film
- the at least one color former
- one or more sensitizing agents can be present in the heat-sensitive color-forming layer, which has the advantage that the control of the thermal pressure sensitivity is easier to implement.
- suitable sensitizers are substances whose melting point is between about 90 and about 150 ° C. and which, in the molten state, dissolve the color-forming components (color formers and color developers) without interfering with the formation of the color complex.
- the sensitizing agent is 1,2-diphenoxyethane.
- Other possible sensitizers are a fatty acid amide, such as stearamide, beheneamide or palmitamide, an ethylene-bis-fatty acid amide, such as N, N'-ethylene-bis-stearic acid amide or N, N'-ethylene-bis-oleic acid amide, a wax, such as polyethylene wax or Montan wax, a carboxylic acid ester such as dimethyl terephthalate, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di- (p-methylbenzyl) oxalate, di- (p-chlorobenzyl) oxalate or di- (p-benzyl) oxalate, an aromatic ether such as 1, 2-di- (3-methylphenoxy) ethane, 2-benzyloxynaphthalene or 1,4-diethoxynaphthalene, an aromatic sulfone such as 1,
- the phenol-free color developer and the sensitizer there is at least one stabilizer (anti-aging agent) in the heat-sensitive color-forming layer.
- the stabilizer is preferably sterically hindered phenols, particularly preferably 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
- 4,4'-dihydroxydiphenyl sulfone such as 4-benzyloxy-4 '- (2-methylglycidyloxy) diphenyl sulfone (trade name NTZ -95®, Nippon Soda Co. Ltd.)
- oligomeric ethers of the general formula (III) (trade name D90®, Nippon Soda Co. Ltd.
- urea-urethane compounds of the general formula (II) are particularly preferred.
- the stabilizer is preferably present in an amount of 0.2 to 0.5 part by weight, based on the at least one phenol-free color developer of the compound of the formula (I).
- At least one binder is present in the heat-sensitive color-forming layer.
- This is preferably water-soluble starches, starch derivatives, methyl cellulose, hydroxyethyl cellulose, carboxymethyl celluloses, partially or completely saponified polyvinyl alcohols, chemically modified polyvinyl alcohols or styrene maleic anhydride copolymers, styrene butadiene copolymers, acrylamide (meth) acrylate copolymers -Methacrylate terpolymers, polyacrylates, poly (meth) acrylic acid esters, acrylate-butadiene copolymers, polyvinyl acetates and / or acrylonitrile-butadiene copolymers.
- At least one release agent (non-stick agent) or lubricant is present in the heat-sensitive color-forming layer.
- These agents are preferably fatty acid metal salts such as e.g. Zinc stearate or calcium stearate, or also behenate salts, synthetic waxes, e.g. in the form of fatty acid amides, e.g. Stearic acid amide and behenic acid amide, fatty acid alkanolamides, e.g.
- Stearic acid methylolamide paraffin waxes of different melting points, ester waxes of different molecular weights, ethylene waxes, propylene waxes of different hardness and / or natural waxes, such as e.g. Carnauba wax or montan wax.
- the heat-sensitive color-forming layer contains pigments.
- pigments The use of these has the advantage, among other things, that they can fix the chemical melt produced in the thermal printing process on their surface. Pigments can also be used to control the surface whiteness and opacity of the heat-sensitive color-forming layer and its printability with conventional printing inks. Finally, pigments have an "extender function", for example for the relatively expensive functional chemicals.
- pigments are inorganic pigments, both of synthetic and natural origin, preferably clays, precipitated or natural calcium carbonates, aluminum oxides, aluminum hydroxides, silicas, diathome earths, magnesium carbonates, talc, but also organic pigments, such as hollow pigments with a styrene / acrylate copolymer wall or urea / formaldehyde condensation polymers.
- optical brighteners can be built into the heat-sensitive color-forming layer. These are preferably stilbenes.
- rheology aids such as thickeners and / or surfactants
- the dried, heat-sensitive, color-forming layer is subjected to a smoothing measure in such a way that the Bekk smoothness appears to be set to about 300 to 700 seconds (measured according to DIN 53107).
- the weight per unit area of the (dry) heat-sensitive layer is preferably about 1 to about 10 g / m 2 , preferably about 3 to about 6 g / m 2 .
- the heat-sensitive recording material is one as claimed in claim 2, a fluran-type dye being used as the color former and, in addition, a sensitizing agent selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers , is present.
- a fluran-type dye being used as the color former and, in addition, a sensitizing agent selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers , is present.
- a sensitizing agent selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers
- the heat-sensitive recording material according to the invention can be obtained using known production processes.
- the recording material according to the invention by a process in which an aqueous suspension containing the starting materials of the heat-sensitive color-forming layer is applied and dried on a carrier substrate, the aqueous application suspension having a solids content of from about 20 to about 75% by weight. , preferably from about 30 to about 50% by weight, and with the curtain coating method at an operating speed of the coating system of at least about 400 m / min is applied and dried and the dried heat-sensitive color-forming layer is subjected to a smoothing measure such that it has a Bekk smoothness of 300 to 700 seconds, measured in accordance with DIN 53107.
- This method is particularly advantageous from an economic point of view.
- the heat-sensitive recording material according to the invention by means of a method in which the aqueous application suspension is applied using the curtain coating method at an operating speed of the coating installation of at least about 400 m / min.
- the so-called curtain coating process is known to the person skilled in the art and is characterized by the following criteria: In the curtain coating process, a free-falling curtain of a coating dispersion is formed. By free fall, the coating dispersion in the form of a thin film (curtain) is "poured" onto a substrate in order to apply the coating dispersion onto the substrate.
- the DE 10196052 T1 discloses the use of the curtain coating process in the production of information recording materials, including heat-sensitive recording materials, multilayer recording layers being carried out by applying the curtain consisting of a plurality of coating dispersion films to substrates (speed max. 200 m / min).
- the operating speed of the coating system is particularly preferably at least approximately 750 m / min, very particularly preferably at least approximately 1000 m / min and very particularly preferably at least approximately 1500 m / min. It was particularly surprising that even at the latter speed, the heat-sensitive recording material obtained is in no way impaired and that the operation is carried out optimally even at this high speed.
- the aqueous deaerated application suspension has a viscosity of approximately 150 to approximately 800 mPas (Brookfield, 100 rpm, 20 ° C.). If the value falls below about 150 mPas or exceeds the value of about 800 mPas, this leads to an unsuitable running ability of the coating composition on the coating unit.
- the viscosity of the aqueous deaerated application suspension is particularly preferably about 200 to about 500 mPas.
- the surface tension of the aqueous application suspension can be adjusted to approximately 25 to approximately 60 mN / m, preferably to approximately 35 to approximately 50 mN / m (measured according to the static ring method according to Du Noüy, DIN 53914) in order to optimize the method ,
- the heat-sensitive color-forming layer can be formed on-line or in a separate coating process off-line. This also applies to layers or intermediate layers that may be applied subsequently.
- the dried, heat-sensitive, color-forming layer is subjected to a smoothing measure, so that the Bekk smoothness, measured in accordance with DIN 53107, is set to 300 to about 700 seconds.
- the present invention also relates to a heat-sensitive recording material which can be obtained by the method described above.
- the invention also relates to the use of the compound of the formula (I) wherein Ar 1 and Ar 2 are a phenyl radical and / or a C 1 -C 4 alkyl-substituted phenyl radical, preferably each a phenyl radical, as non-phenolic Color developer in a heat-sensitive recording material, comprising a carrier substrate and at least one color former, at least one phenol-free color developer and at least one heat-sensitive color-forming layer containing a sensitizer, the at least one sensitizer being 1,2-diphenoxyethane and the dried heat-sensitive color-forming layer being subjected to such a smoothing measure that it has a Bekk smoothness of 300 to 700 seconds, measured according to DIN 53107, as a non-phenolic color developer in a heat-sensitive recording material.
- the heat-sensitive recording material per se.
- the use according to the invention improves the storage stability of the heat-sensitive recording material, in particular the storage stability at high temperatures and high ambient humidity.
- High temperatures are understood to mean temperatures from approximately 25 to approximately 60 ° C., preferably from approximately 30 to approximately 50 ° C.
- High ambient humidity is understood to mean a humidity of approximately 50 to approximately 100%, preferably approximately 70 to approximately 90%.
- the advantages associated with the present invention can be summarized essentially as follows:
- the present invention provides a heat-sensitive recording material which, in addition to a desirable high dynamic pressure sensitivity, also shows an extraordinarily good storage stability, in particular also under conditions of high storage temperature and ambient humidity, without the functional properties necessary for the application, such as surface whiteness and thermal sensitivity, get lost.
- the process described above is advantageous from an economic point of view and permits a high process control of the coating installation even at a speed of more than 1500 m / min, without the process product, that is to say the heat-sensitive recording material according to the invention, being adversely affected.
- the process can be carried out on-line and off-line, which results in a desirable flexibility.
- the heat-sensitive recording material according to the invention is phenol-free and is well suited for POS (point-of-sale) and / or label applications. It is also suitable for the production of tickets, tickets, lottery and betting slips, etc., which can be printed using direct thermal processes and which are highly durable for the images recorded on them under long-term storage, even under more severe climatic conditions with regard to temperature and ambient humidity, and the Contact of the typeface with hydrophobic substances, such as plasticizers, greasy or oily substances, etc., guaranteed.
- the application of an aqueous application suspension to form the heat-sensitive color-forming layer of heat-sensitive recording paper was carried out on a laboratory scale by means of a doctor blade on one side of a synthetic base paper (Yupo® FP680) of 63 g / m 2 . After drying, a thermal recording sheet was obtained.
- the application quantity of the heat-sensitive color-forming layer was between 4.0 - 4.5 g / m2.
- the aqueous application suspension was applied to a paper web with a basis weight of 43 g / m 2 using the curtain coating process.
- the viscosity of the aqueous application suspension was 450 mPas (according to Brookfield, 100 rpm, 20 ° C.) (in the deaerated state). Their surface tension was 46 mN / m (statistical ring method).
- the coating mechanism was arranged in-line. The curtain coating process was operated at a speed of 1550 m / min.
- the coated paper carrier was dried in the usual way.
- the basis weight application of the dry, heat-sensitive layer was 4.0-4.5 g / m 2 .
- a heat-sensitive recording material or thermal paper was produced, the following formulations of aqueous application suspensions being used to form a composite structure on a carrier substrate and subsequently the further layers, in particular a protective layer, being formed in a conventional manner, which is not dealt with separately here shall be.
- An aqueous application suspension was prepared by mixing an aqueous dispersion of the color former by grinding 20 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluorane (ODB-2) with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 (sulfonated polyvinyl alcohol, Nippon Ghosei) was prepared in a bead mill, an aqueous color developer dispersion which was obtained by grinding 40 parts by weight of the color developer together with 66 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 made in the Perl Mill, a dispersion made by grinding 40 parts by weight of sensitizer was prepared in a mill with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266, 189 parts by weight of a 56% PCC dispersion (precipitated calcium carbonate), 50 parts by weight of an aqueous 20% %
- An aqueous application suspension was prepared by mixing an aqueous dispersion of the color former by grinding 20 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluorane (ODB-2) with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a bead mill, an aqueous color developer dispersion which was prepared by grinding 40 parts by weight of the color developer together with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L -3266 was made in the Perl Mill, a dispersion made by grinding 40 parts by weight of sensitizer with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a mill, 200 parts by weight.
- ODB-2 3-Nn-dibutylamine-6-methyl-7-anilinofluorane
- An aqueous application suspension was prepared by mixing an aqueous dispersion of the color former by grinding 20 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluorane (ODB-2) with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 L3266 in a bead mill, an aqueous color developer dispersion obtained by grinding 40 parts by weight of the Color developer together with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in the Perl mill, a dispersion obtained by grinding 40 parts by weight of sensitizer with 33 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in a grinder, a dispersion obtained by grinding 12.5 parts by weight of anti-aging with 10 parts by weight of a 15% aqueous solution of Ghosenex TM L-3266 in one Mill manufactured, 174 parts by weight of a 56% PCC disper
- the grain size (D 4.3 value in ⁇ m) of the ground functional chemicals was set in accordance with Table 3 ( ⁇ 0.1 ⁇ m).
- Table 3 Color formers ( ⁇ m) Color developer ( ⁇ m) Sensitizer ( ⁇ m) Grinding series 1 1.0 0.5 1.0 Grinding series 2 1.0 1.0 1.0 1.0
- the grain size distribution was measured by laser diffraction using a Coulter LS230 device from Beckman Coulter.
- thermal recording materials according to Tables 1, 2 and 3 were evaluated as follows.
- the paper white line was determined in accordance with DIN / ISO 2470 using an Elrepho 3000 spectrophotometer
- the papers (6 cm wide strips) were thermally used using the Atlantek 200 test printer (Atlantek, USA) with a Kyocera print bar of 200 dpi and 560 ohms at an applied voltage of 20.6 V and a maximum pulse width of 0.8 ms printed with a checkerboard pattern with 10 energy levels.
- the image density (optical density, undated) was measured with a Macbeth densitometer RD-914, from Gretag.
- the line components are quantified after HPLC separation using an Agilent 1200 series HPLC device with a DAD detector.
- Sample preparation 2 circular areas are punched out of the paper sample with a punching iron and weighed. The paper samples are extracted with 3 ml of acetonitrile (HPLC quality) in an ultrasonic bath for 30 minutes and the extract is filtered off through a PTFE syringe filter (0.45 ⁇ m).
- HPLC quality acetonitrile
- HPLC separation of the ingredients The above extract was applied to the separation column (Zorbax Eclipse XDB-C18) using an autosampler and eluted with the eluent acetonitrile: THF: H2O (450: 89: 200 parts by weight) with an acetonitrile gradient. Quantitative evaluation of the chromatograms is carried out by comparing the area of the sample peaks assigned over tr times with a calibration line determined using the reference pattern. The measurement error in HPLC quantification is ⁇ 2%.
- Table 4 summarizes the evaluation of the papers according to recipe 1 (table 1), grinding series 1, table 5 the evaluation of the papers according to recipe 1 (table 1), grinding series 2, and table 6 the evaluation of the papers according to recipe 2a or 2b (table 3), meal series 2, together.
- the values of the plasticizer test quantify the durability of the printed image under the influence of dioctyl adipate (representative of hydrophobic agents) based on the% change in the maximum writing power (undated max.) During the test.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
Die Erfindung betrifft ein wärmeempfindliches Aufzeichnungsmaterial, umfassend ein Trägersubstrat sowie eine mindestens einen Farbbildner und mindestens einen phenolfreien Farbentwickler enthaltende wärmeempfindliche farbbildende Schicht, ein Verfahren zu dessen Herstellung sowie die Verwendung des im wärmeempfindlichen Aufzeichnungsmaterial enthaltenen phenolfreien Farbentwicklers.The invention relates to a heat-sensitive recording material comprising a carrier substrate and a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, a process for its preparation and the use of the phenol-free color developer contained in the heat-sensitive recording material.
Wärmeempfindliche Aufzeichnungsmaterialien für die thermodirekt Druckanwendung, die eine auf einem Trägersubstrat aufgebrachte wärmeempfindliche farbbildende Schicht (Thermoreaktionsschicht) aufweisen, sind seit langem bekannt. In der wärmeempfindlichen farbbildenden Schicht liegen üblicherweise ein Farbbildner und ein Farbentwickler vor, die unter Wärmeeinwirkung miteinander reagieren und so zu einer Farbentwicklung führen. Ebenfalls bekannt sind wärmeempfindliche Aufzeichnungsmaterialien, die in der wärmeempfindlichen farbbildenden Schicht einen nicht-phenolischen Farbentwickler enthalten. Diese wurden entwickelt, um die Beständigkeit des Schriftbildes zu verbessern, insbesondere auch dann, wenn das bedruckte wärmeempfindliche Aufzeichnungsmaterial über längere Zeit gelagert wird oder mit hydrophoben Stoffen, wie weichmacherhaltigen Materialien oder Ölen, in Kontakt kommt. Insbesondere vor dem Hintergrund der öffentlichen Diskussionen über das toxische Potenzial von (bis)phenolischen Chemikalien ist das Interesse an nicht-phenolischen Farbentwicklern stark angestiegen. Hierbei war es Ziel, die Nachteile der phenolischen Farbentwickler zu vermeiden, allerdings sollten die Leistungseigenschaften, die mit phenolischen Farbentwicklern erzielt werden können, zumindest beibehalten werden.Heat-sensitive recording materials for thermodirect printing, which have a heat-sensitive color-forming layer (thermal reaction layer) applied to a carrier substrate, have long been known. A color former and a color developer are usually present in the heat-sensitive color-forming layer and react with one another under the influence of heat and thus lead to color development. Also known are heat-sensitive recording materials which contain a non-phenolic color developer in the heat-sensitive color-forming layer. These have been developed to improve the durability of the typeface, especially when the printed heat-sensitive recording material is stored for a long time or comes into contact with hydrophobic substances such as plasticized materials or oils. In particular against the background of public discussions about the toxic potential of (bis) phenolic chemicals, interest in non-phenolic color developers has increased significantly. The aim here was to avoid the disadvantages of the phenolic color developers, but the performance properties, that can be achieved with phenolic color developers are at least maintained.
Die
Die
Ar'-SO2-NH-X-NH-Ar,
wobei Ar durch eine zweiwertige Linkergruppe an weitere aromatische Gruppen geknüpft ist. Ein in der Praxis verbreiteter nicht-phenolischer Entwickler aus dieser Klasse, N-(p-Tolylsulfonyl)-N'-(3-p-tolylsulfonyloxy-phenyl)harnstoff (Handelsname Pergafast 201®, PF201 BASF) zeichnet sich durch die Ausgewogenheit der anwendungstechnischen Eigenschaften der mit diesem hergestellten wärmeempfindlichen Aufzeichnungsmaterialien aus. Insbesondere besitzen diese eine gute dynamische Ansprechempfindlichkeit und eine hohe Beständigkeit des Ausdrucks gegenüber hydrophoben Stoffen.The
Ar'-SO 2 -NH-X-NH-Ar,
where Ar is linked to further aromatic groups by a divalent linker group. A commonly used non-phenolic developer from this class, N- (p-tolylsulfonyl) -N '- (3-p-tolylsulfonyloxy-phenyl) urea (trade name Pergafast 201®, PF201 BASF) is characterized by the balance of the application technology Properties of the heat-sensitive recording materials produced with this. In particular, these have good dynamic responsiveness and a high resistance of the printout to hydrophobic substances.
Hinsichtlich des Haltbarkeitsaspektes wird bei wärmeempfindlichen Aufzeichnungsmaterialien insbesondere auf folgende Gesichtspunkte Wert gelegt:
- a) Die Beständigkeit des unbedruckten ("weißen") wärmeempfindlichen Aufzeichnungsmaterials bei längerfristiger Lagerung und/oder bei verschärften klimatischen Bedingungen, insbesondere hinsichtlich der Beibehaltung der spezifizierten Werte der dynamischen Ansprechempfindlichkeit und der Weiße, und
- b) die Beständigkeit des durch den thermischen Druck generierten Schriftbildes, welches insbesondere der (auch längerfristigen) Einwirkung von Temperatur, Luftsauerstoff, Licht, Feuchte, hydrophoben Agenzien etc. standhalten soll (Archivierungsfähigkeit).
- a) The durability of the unprinted ("white") heat-sensitive recording material after long-term storage and / or under more severe climatic conditions, in particular with regard to the maintenance of the specified values of dynamic response sensitivity and whiteness, and
- b) the durability of the typeface generated by thermal printing, which should withstand the (also longer-term) exposure to temperature, atmospheric oxygen, light, moisture, hydrophobic agents, etc. (archivability).
Während die unter a) genannten Anforderungen die Beständigkeit bzw. Konstanz der Zusammensetzung der wärmeempfindlichen farbbildenden Schicht, insbesondere die chemische Beständigkeit der farbbildenden Komponenten, auch bei längerfristiger Lagerung und unter verschärften klimatischen Bedingungen, betreffen zielen die unter b) genannten Anforderungen auf die Stabilität des sich während des Druckprozesses in der wärmeempfindlichen farbbildenden Schicht ausbildenden Farbkomplexes ab.While the requirements mentioned under a) relate to the stability or constancy of the composition of the heat-sensitive color-forming layer, in particular the chemical resistance of the color-forming components, even with long-term storage and under more severe climatic conditions, the requirements mentioned under b) aim at the stability of the during the printing process from the color complex forming the heat-sensitive color-forming layer.
Die vorstehend erwähnten wärmeempfindlichen Aufzeichnungsmaterialien mit Farbentwicklern auf Basis von Sulfonyl-Harnstoffen erfüllen zwar die unter b) genannten Anforderungen, zeigen jedoch Schwächen hinsichtlich der unter a) aufgeführten Anforderungen. Die Sulfonyl-Harnstoffe sind nämlich chemisch instabil, insbesondere bei Anwesenheit von Wasser. Diese Zersetzungsneigung der Sulfonyl-Harnstoffe über einen weiten pH-Bereich ist bekannt und gut dokumentiert (
Die nachveröffentlichte
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Aufgabe der vorliegenden Erfindung ist es daher, die vorstehend geschilderten Nachteile des Standes der Technik zu beheben. Insbesondere besteht die Aufgabe der vorliegenden Erfindung darin, ein wärmeempfindliches Aufzeichnungsmaterial bereitzustellen, welches auch die vorstehend unter a) genannten Anforderungen, das heißt die anwendungstechnisch erforderlichen funktionellen Eigenschaften, wie thermische Ansprechempfindlichkeit und Oberflächenweisse, erfüllt, und zwar auch bei Lagerung über längere Zeiträume und unter verschärften klimatischen Bedingungen. Die Aufgabe betrifft demnach das Eigenschaftsprofil eines unbedruckten wärmeempfindlichen Aufzeichnungsmaterials.The object of the present invention is therefore to remedy the disadvantages of the prior art described above. In particular, the object of the present invention is to provide a heat-sensitive recording material which also meets the requirements mentioned under a) above, that is to say the functional properties required in terms of application, such as thermal responsiveness and surface whiteness, even when stored for longer periods and under aggravated climatic conditions. The task accordingly relates to the property profile of an unprinted, heat-sensitive recording material.
Erfindungsgemäß wird diese Aufgabe mit einem wärmeempfindlichen Aufzeichnungsmaterial nach Anspruch 1 gelöst. wonach dieses ein Trägersubstrat sowie eine mindestens einen Farbbildner und mindestens einen phenolfreien Farbentwickler enthaltende wärmeempfindliche farbbildende Schicht, umfasst und dadurch gekennzeichnet ist, dass der mindestens eine Farbentwickler eine Verbindung der Formel (I)
Gegebenenfalls liegt zwischen dem Trägersubstrat und der wärmeempfindlichen Schicht mindestens eine weitere Zwischenschicht vor. Auch kann mindestens eine Schutzschicht und/oder mindestens eine die Bedruckbarkeit begünstigende Schicht im erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterial vorliegen.According to the invention this object is achieved with a heat-sensitive recording material according to claim 1. after which this comprises a carrier substrate and a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, and is characterized in that the at least one color developer is a compound of the formula (I)
If appropriate, there is at least one further intermediate layer between the carrier substrate and the heat-sensitive layer. At least one protective layer and / or at least one layer which promotes printability can also be present in the heat-sensitive recording material according to the invention.
Bei dem C1-C4-Alkyl-substituierten Phenyl-Rest handelt es sich vorzugsweise um einen C1-Alkyl-substituierten Phenyl-Rest (ortho-, meta, und/oder para-substituiert), insbesondere einen para-substituierten C1-Alkyl-substituierten Phenyl-Rest. Besonders bevorzugt ist ein Methyl-Rest, ganz besonders bevorzugt ein para-Methyl-Rest.The C 1 -C 4 -alkyl-substituted phenyl radical is preferably a C 1 -alkyl-substituted phenyl radical (ortho-, meta, and / or para-substituted), in particular a para-substituted C 1 -Alkyl-substituted phenyl radical. A methyl radical is particularly preferred, a para-methyl radical is very particularly preferred.
In einer besonders bevorzugten Ausführungsform sind Ar1 und Ar2 ein para-Methyl-substituierter Phenyl-Rest.In a particularly preferred embodiment, Ar 1 and Ar 2 are a para-methyl-substituted phenyl radical.
In einer weiteren besonders bevorzugten Ausführungsform ist Ar1 ein Phenyl-Rest und Ar2 ein para-Methyl-substituierter Phenyl-Rest.In a further particularly preferred embodiment, Ar 1 is a phenyl radical and Ar 2 is a para-methyl-substituted phenyl radical.
In einer ganz besonders bevorzugten Ausführungsform sind Ar1 und Ar2 jeweils ein Phenyl-Rest, das heißt bei dem mindestens einem Farbentwickler handelt es sich um N-(2-(3-phenylureido)phenyl)benzolsulfonamid.In a very particularly preferred embodiment, Ar 1 and Ar 2 are each a phenyl radical, that is to say the at least one color developer is N- (2- (3-phenylureido) phenyl) benzenesulfonamide.
Vorzugsweise liegen etwa 0,5 bis etwa 10 Gew.-Teile, bevorzugt etwa 1,5 bis etwa 4 Gew.-Teile, der Verbindung der Formel (I), bezogen auf den Farbbildner vor. Mengen unter 0,5 Gew.-Teilen haben den Nachteil, dass die gewünschte thermische Druckempfindlichkeit nicht erreicht wird, während Mengen von mehr als 10 Gew.-Teilen dazu führen, dass die Wirtschaftlichkeit des Aufzeichnungsmaterials leidet, ohne dass anwendungstechnische Verbesserungen zu erzielen wären.About 0.5 to about 10 parts by weight, preferably about 1.5 to about 4 parts by weight, of the compound of the formula (I), based on the color former, are preferably present. Amounts of less than 0.5 part by weight have the disadvantage that the desired thermal pressure sensitivity is not achieved, whereas amounts of more than 10 parts by weight lead to the economy of the recording material suffering without improvements in application technology being achievable.
Die Verbindung der Formel (I) liegt vorzugsweise in einer Menge von etwa 3 bis etwa 35 Gew.-%, besonders bevorzugt in einer Menge von etwa 10 bis etwa 25 Gew.-%, bezogen auf den gesamten Feststoffgehalt der wärmeempfindlichen Schicht, vor.The compound of formula (I) is preferably in an amount of about 3 to about 35% by weight, particularly preferably in an amount of about 10 to about 25 % By weight, based on the total solids content of the heat-sensitive layer.
Die Auswahl des Trägersubstrates ist nicht kritisch. Allerdings ist es bevorzugt, als Trägersubstrat Papier, synthetisches Papier und/oder eine Kunststoff-Folie einzusetzen.The selection of the carrier substrate is not critical. However, it is preferred to use paper, synthetic paper and / or a plastic film as the carrier substrate.
Hinsichtlich der Wahl des Farbbildners unterliegt die vorliegende Erfindung ebenfalls keinen wesentlichen Einschränkungen. Bevorzugt ist der Farbbildner jedoch ein Farbstoff vom Triphenylmethan-Typ, vom Fluoran-Typ, vom Azaphthalid-Typ und/oder vom Fluoren-Typ. Ein ganz besonders bevorzugter Farbbildner ist ein Farbstoff vom Fluoran-Typ, da er dank der Verfügbarkeit und der ausgewogenen anwendungsbezogenen Eigenschaften die Bereitstellung eines Aufzeichnungsmaterials mit einem attraktiven Preis-Leistungsverhältnis ermöglicht.The present invention is likewise not subject to any significant restrictions with regard to the choice of the color former. However, the color former is preferably a dye of the triphenylmethane type, of the fluorane type, of the azaphthalide type and / or of the fluorene type. A very particularly preferred color former is a fluoran-type dye because, thanks to the availability and the balanced application-related properties, it enables the provision of a recording material with an attractive price-performance ratio.
Besonders bevorzugte Farbstoffe vom Fluoran-Typ sind:
- 3-Diethylamino-6-methyl-7-anilinofluoran,
- 3-(N-ethyl-N-p-toludinamino)-6-methyl-7-anilinofluoran,
- 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran,
- 3-Diethylamino-6-methyl-7-(o,p-dimethylanilino)fluoran,
- 3-Pyrrolidino-6-methyl-7-anilinofluoran,
- 3-(Cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran,
- 3-Diethylamin-7-(m-trifluoromethylanilino)fluoran,
- 3-N-n-Dibutylamin-6-methyl-7-anilinofluoran,
- 3-Diethylamino-6-methyl-7-(m-methylanilino)fluoran,
- 3-N-n-dibutylamin-7-(o-chloroanilino)fluoran,
- 3-(N-Ethyl-N-tetrahydrofurfurylamin)-6-methyl-7-anilino-fluoran,
- 3-(N-methyl-N-propylamin)-6-methyl-7-anilinofluoran,
- 3-(N-ethyl-N-ethoxypropylamin)-6-methyl-7-anilinofluoran,
- 3-(N-ethyl-N-isobutylamin)-6-methyl-7-anilinofluoran und/oder
- 3-Dipentylamin-6-methyl-7-anilinfluoran.
- 3-diethylamino-6-methyl-7-anilinofluoran,
- 3- (N-ethyl-Np-toludinamino) -6-methyl-7-anilinofluoran,
- 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluoran,
- 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran,
- 3-pyrrolidino-6-methyl-7-anilinofluoran,
- 3- (cyclohexyl-N-methylamino) -6-methyl-7-anilinofluoran,
- 3-diethylamino-7- (m-trifluoromethylanilino) fluoran,
- 3-Nn-dibutyl-6-methyl-7-anilinofluoran,
- 3-diethylamino-6-methyl-7- (m-methylanilino) fluoran,
- 3-Nn-dibutyl-7- (o-chloroanilino) fluoran,
- 3- (N-ethyl-N-tetrahydrofurfurylamine) -6-methyl-7-anilino-fluoran,
- 3- (N-methyl-N-propylamino) -6-methyl-7-anilinofluoran,
- 3- (N-ethyl-N-ethoxypropylamine) -6-methyl-7-anilinofluoran,
- 3- (N-ethyl-N-isobutylamine) -6-methyl-7-anilinofluoran and / or
- 3-dipentylamino-6-methyl-7-anilinofluoran.
In einer besonders bevorzugten Ausführungsform liegen neben dem Farbentwickler der Verbindung der Formel (I) ein oder mehrere weitere nicht-phenolische Farbentwickler in der wärmeempfindlichen farbbildenden Schicht vor.In a particularly preferred embodiment, in addition to the color developer of the compound of the formula (I), one or more further non-phenolic color developers are present in the heat-sensitive color-forming layer.
Bei dem einen oder mehreren weiteren nicht-phenolischen Farbentwicklern handelt es sich vorzugsweise um N'-(p-Toluolsulfonyl)-N'-phenyl-harnstoff, N-(p-Toluolsulfonyl)-N'-3-(p-toluolsulphonyl-oxy-phenyl)-harnstoff und/oder 4,4'-Bis-(p-tolylsulfonylureido)-diphenylmethan.The one or more other non-phenolic color developers are preferably N '- (p-toluenesulfonyl) -N'-phenyl-urea, N- (p-toluenesulfonyl) -N'-3- (p-toluenesulphonyl-oxy phenyl) urea and / or 4,4'-bis (p-tolylsulfonylureido) diphenylmethane.
In einer besonders bevorzugten Ausführungsform handelt es sich bei dem erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterial um ein wärmeempfindliches Aufzeichnungsmaterial, umfassend ein Trägersubstrat sowie eine mindestens einen Farbbildner, mindestens einen phenolfreien Farbentwickler und mindestens ein Sensibilisierungsmittel enthaltende wärmeempfindliche farbbildende Schicht, dadurch gekennzeichnet, dass der mindestens eine Farbentwickler eine Verbindung der Formel (I)
Neben dem mindestens einem Farbbildner und dem mindestens einem Farbentwickler können in der wärmeempfindlichen farbbildenden Schicht ein oder mehrere Sensibilisierungsmittel vorliegen, was den Vorteil hat, dass die Steuerung der thermischen Druckempfindlichkeit leichter zu realisieren ist.In addition to the at least one color former and the at least one color developer, one or more sensitizing agents can be present in the heat-sensitive color-forming layer, which has the advantage that the control of the thermal pressure sensitivity is easier to implement.
Generell kommen als Sensibilisierungsmittel vorteilhafterweise Stoffe in Betracht, deren Schmelzpunkt zwischen etwa 90 und etwa 150°C liegt und die im geschmolzenen Zustand die farbbildenden Komponenten (Farbbildner und Farbentwickler) lösen, ohne die Bildung des Farbkomplexes zu stören.In general, suitable sensitizers are substances whose melting point is between about 90 and about 150 ° C. and which, in the molten state, dissolve the color-forming components (color formers and color developers) without interfering with the formation of the color complex.
Erfindungsgemäß ist das Sensibilisierungsmittel 1,2-Diphenoxyethan. Weitere mögliche Sensibilisierungsmittel sind ein Fettsäureamid, wie Stearamid, Beheneamid oder Palmitamid, ein Ethylen-bis-Fettsäureamid, wie N,N'-Ethylen-bis-stearinsäureamid oder N,N'-Ethylen-bis-ölsäureamid, ein Wachs, wie Polyethylenwachs oder Montanwachs, ein Carbonsäureester, wie Dimethylterephthalat, Dibenzylterephthalat, Benzyl-p-benzyloxybenzoat, Di-(p-methylbenzyl)oxalat, Di-(p-chlorbenzyl)oxalat oder Di-(p-benzyl)oxalat, ein aromatischer Ether, wie 1,2-Di-(3-methylphenoxy)ethan, 2-Benzyloxynaphthalin oder 1,4-Diethoxynaphthalin, ein aromatisches Sulfon, wie Diphenylsulfon, und/oder ein aromatisches Sulfonamid, wie Benzolsulfonanilid oder N-Benzyl-p-toluolsulfonamid.According to the invention, the sensitizing agent is 1,2-diphenoxyethane. Other possible sensitizers are a fatty acid amide, such as stearamide, beheneamide or palmitamide, an ethylene-bis-fatty acid amide, such as N, N'-ethylene-bis-stearic acid amide or N, N'-ethylene-bis-oleic acid amide, a wax, such as polyethylene wax or Montan wax, a carboxylic acid ester such as dimethyl terephthalate, dibenzyl terephthalate, benzyl p-benzyloxybenzoate, di- (p-methylbenzyl) oxalate, di- (p-chlorobenzyl) oxalate or di- (p-benzyl) oxalate, an aromatic ether such as 1, 2-di- (3-methylphenoxy) ethane, 2-benzyloxynaphthalene or 1,4-diethoxynaphthalene, an aromatic sulfone such as diphenyl sulfone and / or an aromatic sulfonamide such as benzenesulfonanilide or N-benzyl-p-toluenesulfonamide.
In einer weiteren bevorzugten Ausführungsform liegt neben dem Farbbildner, dem phenolfreien Farbentwickler und dem Sensibilisierungsmittel mindestens ein Stabilisator (Alterungsschutzmittel) in der wärmeempfindlichen farbbildenden Schicht vor.In a further preferred embodiment, in addition to the color former, the phenol-free color developer and the sensitizer, there is at least one stabilizer (anti-aging agent) in the heat-sensitive color-forming layer.
Bei dem Stabilisator handelt es sich vorzugsweise um sterisch gehinderte Phenole, besonders bevorzugt um 1,1,3-Tris-(2-methyl-4-hydroxy-5-cyclohexyl-phenyl)-butan, 1,1,3-Tris-(2-methyl-4-hydroxy-5-tert-buty|phenyl)-butan, 1,1-Bis-(2-methyl-4-hydroxy-5-tert-butyl-phenyl)-butan.The stabilizer is preferably sterically hindered phenols, particularly preferably 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
Auch Harnstoff-Urethan-Verbindungen der allgemeinen Formel (II), Handelsprodukt UU (Urea-Urethane), oder vom 4,4'-Dihydroxydiphenylsulfon abgeleitete Ether, wie 4-Benzyloxy-4'-(2-methylglycidyloxy)-diphenylsulfon (Handelsname NTZ-95®, Nippon Soda Co. Ltd.), oder oligomere Ether der allgemeinen Formel (III) (Handelsname D90®, Nippon Soda Co. Ltd.) sind als Stabilisatoren im erfindungsgemäßen Aufzeichnungsmaterial einsetzbar.
Besonders bevorzugt sind die Harnstoff-Urethan-Verbindungen der allgemeinen Formel (II).The urea-urethane compounds of the general formula (II) are particularly preferred.
Der Stabilisator liegt vorzugsweise in einer Menge von 0,2 bis 0,5 Gew.-Teilen, bezogen auf den mindestens einen phenolfreien Farbentwickler der Verbindung der Formel (I), vor.The stabilizer is preferably present in an amount of 0.2 to 0.5 part by weight, based on the at least one phenol-free color developer of the compound of the formula (I).
In einer weiteren bevorzugten Ausführungsform liegt in der wärmeempfindlichen farbbildenden Schicht mindestens ein Bindemittel vor. Bei diesem handelt es sich vorzugsweise um wasserlösliche Stärken, Stärkederivate, Methylcellulose, Hydroxyethylcellulose, Carboxymethylcellulosen, partiell- oder vollständig verseifte Polyvinylalkohole, chemisch modifizierte Polyvinylalkohole oder Styrolmaleinsäureanhydrid-Copolymere, Styrolbutadien-Copolymere, Acrylamid-(Meth)-acrylat-Copolymere, Acrylamid-Acrylat-Methacrylat-Terpolymere, Polyacrylate, Poly(meth)-acrylsäureester, Acrylat-Butadien-Copolymere, Polyvinylacetate und/oder Acrylnitril-Butadien-Copolymere.In a further preferred embodiment, at least one binder is present in the heat-sensitive color-forming layer. This is preferably water-soluble starches, starch derivatives, methyl cellulose, hydroxyethyl cellulose, carboxymethyl celluloses, partially or completely saponified polyvinyl alcohols, chemically modified polyvinyl alcohols or styrene maleic anhydride copolymers, styrene butadiene copolymers, acrylamide (meth) acrylate copolymers -Methacrylate terpolymers, polyacrylates, poly (meth) acrylic acid esters, acrylate-butadiene copolymers, polyvinyl acetates and / or acrylonitrile-butadiene copolymers.
In einer weiteren bevorzugten Ausführungsform liegt mindestens ein Trennmittel (Antihaftmittel) oder Gleitmittel in der wärmeempfindlichen farbbildenden Schicht vor. Bei diesen Mitteln handelt es sich vorzugsweise um Fettsäure-Metallsalze, wie z.B. Zinkstearat oder Calciumstearat, oder auch Behenatsalze, synthetische Wachse, z.B. in Form von Fettsäureamiden, wie z.B. Stearinsäureamid und Behensäureamid, Fettsäurealkanolamide, wie z.B. Stearinsäure-methylolamid, Paraffinwachse verschiedener Schmelzpunkte, Esterwachse unterschiedlicher Molekulargewichte, Ethylenwachse, Propylenwachse unterschiedlicher Härten und/oder natürliche Wachse, wie z.B. Carnaubawachs oder Montanwachs.In a further preferred embodiment, at least one release agent (non-stick agent) or lubricant is present in the heat-sensitive color-forming layer. These agents are preferably fatty acid metal salts such as e.g. Zinc stearate or calcium stearate, or also behenate salts, synthetic waxes, e.g. in the form of fatty acid amides, e.g. Stearic acid amide and behenic acid amide, fatty acid alkanolamides, e.g. Stearic acid methylolamide, paraffin waxes of different melting points, ester waxes of different molecular weights, ethylene waxes, propylene waxes of different hardness and / or natural waxes, such as e.g. Carnauba wax or montan wax.
In einer weiteren bevorzugten Ausführungsform enthält die wärmeempfindliche farbbildende Schicht Pigmente. Der Einsatz dieser hat unter anderem den Vorteil, dass diese auf ihrer Oberfläche die im thermischen Druckprozess entstehende Chemikalien-Schmelze fixieren können. Auch kann über Pigmente die Oberflächenweisse und Opazität der wärmeempfindlichen farbbildenden Schicht und deren Bedruckbarkeit mit konventionellen Druckfarben gesteuert werden. Schließlich besitzen Pigmente eine "Extenderfunktion", beispielsweise für die relativ teuren farbgebenden Funktionschemikalien.In a further preferred embodiment, the heat-sensitive color-forming layer contains pigments. The use of these has the advantage, among other things, that they can fix the chemical melt produced in the thermal printing process on their surface. Pigments can also be used to control the surface whiteness and opacity of the heat-sensitive color-forming layer and its printability with conventional printing inks. Finally, pigments have an "extender function", for example for the relatively expensive functional chemicals.
Besonders geeignete Pigmente sind anorganische Pigmente, sowohl synthetischer als auch natürlicher Herkunft, vorzugsweise Clays, gefällte oder natürliche Calciumcarbonate, Aluminiumoxide, Aluminiumhydroxide, Kieselsäuren, Diathomeenerden, Magnesiumcarbonate, Talk, aber auch organische Pigmente, wie Hohlpigmente mit einer Styrol/Acrylat-Copolymer-Wand oder Harnstoff/Formaldehyd-Kondensationspolymere.Particularly suitable pigments are inorganic pigments, both of synthetic and natural origin, preferably clays, precipitated or natural calcium carbonates, aluminum oxides, aluminum hydroxides, silicas, diathome earths, magnesium carbonates, talc, but also organic pigments, such as hollow pigments with a styrene / acrylate copolymer wall or urea / formaldehyde condensation polymers.
Zum Steuern der Oberflächenweisse des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials können optische Aufheller in die wärmeempfindliche farbbildende Schicht eingebaut werden. Bei diesen handelt es sich vorzugsweise um Stilbene.To control the surface whiteness of the heat-sensitive recording material according to the invention, optical brighteners can be built into the heat-sensitive color-forming layer. These are preferably stilbenes.
Um bestimmte streichtechnische Eigenschaften zu verbessern, ist es im Einzelfall bevorzugt zu den zwingenden Bestandteilen des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials weitere Bestandteile, insbesondere Rheologie-Hilfsmittel, wie Verdicker und/oder Tenside, hinzuzufügen.In order to improve certain coating properties, in individual cases it is preferred to add further constituents, in particular rheology aids, such as thickeners and / or surfactants, to the mandatory constituents of the heat-sensitive recording material according to the invention.
Erfindungsgemäß wird die getrocknete wärmeempfindliche farbbildenden Schicht derart einer Glättmaßnahme unterzogen, dass die Bekk-Glätte auf etwa 300 bis 700 sec (gemessen nach DIN 53107), eingestellt wirkt.According to the invention, the dried, heat-sensitive, color-forming layer is subjected to a smoothing measure in such a way that the Bekk smoothness appears to be set to about 300 to 700 seconds (measured according to DIN 53107).
Das Flächenauftragsgewicht der (trocknen) wärmeempfindlichen Schicht beträgt vorzugsweise etwa 1 bis etwa 10 g/m2, bevorzugt etwa 3 bis etwa 6 g/m2.The weight per unit area of the (dry) heat-sensitive layer is preferably about 1 to about 10 g / m 2 , preferably about 3 to about 6 g / m 2 .
In einer besonders bevorzugten Ausführungsform handelt es sich bei dem wärmeempfindlichen Aufzeichnungsmaterial um ein solches nach Anspruch 2, wobei als Farbbildner ein Farbstoff vom Fluran-Typ eingesetzt wird und zusätzlich ein Sensibilisierungsmittel, ausgewählt aus der Gruppe bestehend aus Fettsäureamiden, aromatischen Sulfonen und/oder aromatischen Ethern, vorliegt. In dieser bevorzugten Ausführungsform ist es auch vorteilhaft, dass etwa 1,5 bis etwa 4 Gew.-Teile des phenolfreien Farbentwicklers nach Anspruch 2, bezogen auf den Farbbildner, vorliegen.In a particularly preferred embodiment, the heat-sensitive recording material is one as claimed in claim 2, a fluran-type dye being used as the color former and, in addition, a sensitizing agent selected from the group consisting of fatty acid amides, aromatic sulfones and / or aromatic ethers , is present. In this preferred embodiment, it is also advantageous for about 1.5 to about 4 parts by weight of the phenol-free color developer according to claim 2, based on the color former, to be present.
Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial lässt sich mit bekannten Herstellungsverfahren gewinnen.The heat-sensitive recording material according to the invention can be obtained using known production processes.
Es ist jedoch bevorzugt, das erfindungsgemäße Aufzeichnungsmaterial mit einem Verfahren zu gewinnen, bei dem auf ein Trägersubstrat eine die Ausgangsmaterialien der wärmeempfindlichen farbbildenden Schicht enthaltende wässrige Suspension aufgetragen und getrocknet wird, wobei die wässrige Auftragssuspension einen Feststoffgehalt von etwa 20 bis etwa 75 Gew.-% , bevorzugt von etwa 30 bis etwa 50 Gew.%, aufweist, und mit dem Curtain-Coating-Beschichtungsverfahren bei einer Betriebsgeschwindigkeit der Streichanlage von mindestens etwa 400 m/min aufgetragen und getrocknet wird und die getrocknete wärmeempfindliche farbbildende Schicht derart einer Glättmaßnahme unterzogen wird, dass sie eine Bekk-Glätte von 300 bis 700 sec, gemessen nach DIN 53107, aufweist.However, it is preferred to obtain the recording material according to the invention by a process in which an aqueous suspension containing the starting materials of the heat-sensitive color-forming layer is applied and dried on a carrier substrate, the aqueous application suspension having a solids content of from about 20 to about 75% by weight. , preferably from about 30 to about 50% by weight, and with the curtain coating method at an operating speed of the coating system of at least about 400 m / min is applied and dried and the dried heat-sensitive color-forming layer is subjected to a smoothing measure such that it has a Bekk smoothness of 300 to 700 seconds, measured in accordance with DIN 53107.
Dieses Verfahren ist insbesondere unter wirtschaftlichen Gesichtspunkten vorteilhaft.This method is particularly advantageous from an economic point of view.
Wird der Wert des Feststoffgehaltes von etwa 20 Gew.-% unterschritten, dann verschlechtert sich die Wirtschaftlichkeit, da eine große Menge von Wasser aus dem Strich durch schonende Trocknung in kurzer Zeit entfernt werden muss, was sich nachteilig auf die Streichgeschwindingkeit auswirkt. Wird auf der anderen Seite der Wert von 75 Gew.-% überschritten, dann führt dies lediglich zu einem erhöhten technischen Aufwand, um die Stabilität des Streichfarben-Vorhangs während des Beschichtungsprozesses zu gewährleisten.If the solids content falls below the value of about 20% by weight, then the economy deteriorates, since a large amount of water has to be removed from the coating by gentle drying in a short time, which has a disadvantageous effect on the coating speed. On the other hand, if the value of 75% by weight is exceeded, this only leads to an increased technical outlay in order to ensure the stability of the coating color curtain during the coating process.
Wie vorstehend erwähnt, ist es von Vorteil das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial mittels eines Verfahrens herzustellen, bei dem die wässrige Auftragsuspension mit dem Curtain-Coating-Beschichtungsverfahren bei einer Betriebsgeschwindigkeit der Streichanlage von mindestens etwa 400 m/min aufgetragen wird. Das sogenannte Curtain-Coating-Verfahren ist dem Fachmann bekannt und zeichnet sich durch folgende Kriterien aus:
Beim Curtain-Coating-Beschichtungsverfahren (Vorhangbeschichtungsverfahren) wird ein frei fallender Vorhang einer Beschichtungsdispersion gebildet. Durch freien Fall wird die in Form eines dünnen Filmes (Vorhangs) vorliegende Beschichtungsdispersion auf ein Substrat "gegossen", um die Beschichtungsdispersion auf das Substrat aufzubringen. Die
In the curtain coating process, a free-falling curtain of a coating dispersion is formed. By free fall, the coating dispersion in the form of a thin film (curtain) is "poured" onto a substrate in order to apply the coating dispersion onto the substrate. The
Die Einstellung der Betriebsgeschwindigkeit der Streichanlage auf mindestens etwa 400 m/min hat sowohl betriebswirtschaftliche als auch technische Vorteile. Besonders bevorzugt beträgt die Betriebsgeschwindigkeit mindestens etwa 750 m/min, ganz besonders bevorzugt mindestens etwa 1000 m/min und ganz besonders bevorzugt mindestens etwa 1500 m/min. Es war insbesondere überraschend, dass selbst bei letztgenannter Geschwindigkeit das erhaltene wärmeempfindliche Aufzeichnungsmaterial in keiner Weise beeinträchtigt ist und dass die Betriebsdurchführung selbst bei dieser hohen Geschwindigkeit optimal abläuft.Setting the operating speed of the coating system to at least about 400 m / min has both economic and technical advantages. The operating speed is particularly preferably at least approximately 750 m / min, very particularly preferably at least approximately 1000 m / min and very particularly preferably at least approximately 1500 m / min. It was particularly surprising that even at the latter speed, the heat-sensitive recording material obtained is in no way impaired and that the operation is carried out optimally even at this high speed.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens weist die wässrige entlüftete Auftragssuspension eine Viskosität von etwa 150 bis etwa 800 mPas (Brookfield, 100 U/min, 20 °C) auf. Wird der Wert von etwa 150 mPas unterschritten bzw. der Wert von etwa 800 mPas überschritten, dann führt dies zu einer mangelhaften Lauffähigkeit der Streichmasse am Streichaggregat. Besonders bevorzugt beträgt die Viskosität der wässrigen entlüfteten Auftragssuspension etwa 200 bis etwa 500 mPas.In a preferred embodiment of the process according to the invention, the aqueous deaerated application suspension has a viscosity of approximately 150 to approximately 800 mPas (Brookfield, 100 rpm, 20 ° C.). If the value falls below about 150 mPas or exceeds the value of about 800 mPas, this leads to an unsuitable running ability of the coating composition on the coating unit. The viscosity of the aqueous deaerated application suspension is particularly preferably about 200 to about 500 mPas.
In einer bevorzugten Ausführungsform kann zur Optimierung des Verfahrens die Oberflächenspannung der wässrigen Auftragssuspension auf etwa 25 bis etwa 60 mN/m, bevorzugt auf etwa 35 bis etwa 50 mN/m (gemessen entsprechend der statischen Ringmethode nach Du Noüy, DIN 53914), eingestellt werden.In a preferred embodiment, the surface tension of the aqueous application suspension can be adjusted to approximately 25 to approximately 60 mN / m, preferably to approximately 35 to approximately 50 mN / m (measured according to the static ring method according to Du Noüy, DIN 53914) in order to optimize the method ,
Die Ausbildung der wärmeempfindlichen farbbildenden Schicht kann on-line oder in einem separaten Streichvorgang off-line erfolgen. Dies gilt auch für eventuell nachfolgend aufgetragene Schichten oder Zwischenschichten.The heat-sensitive color-forming layer can be formed on-line or in a separate coating process off-line. This also applies to layers or intermediate layers that may be applied subsequently.
Erfindungsgemäß wird die getrocknete wärmeempfindliche farbbildende Schicht einer Glätt-Maßnahme unterzogen sodass die Bekk-Glätte, gemessen nach DIN 53107, auf 300 bis etwa 700 sec, eingestellt wird.According to the invention, the dried, heat-sensitive, color-forming layer is subjected to a smoothing measure, so that the Bekk smoothness, measured in accordance with DIN 53107, is set to 300 to about 700 seconds.
Die im Zusammenhang mit dem wärmeempfindlichen Aufzeichnungsmaterial aufgeführten bevorzugten Ausführungsformen gelten ebenfalls für das erfindungsgemäße Verfahren.The preferred embodiments listed in connection with the heat-sensitive recording material also apply to the method according to the invention.
Die vorliegende Erfindung betrifft auch ein wärmeempfindliches Aufzeichnungsmaterial, welches mit dem voranstehend geschilderten Verfahren erhältlich ist.The present invention also relates to a heat-sensitive recording material which can be obtained by the method described above.
Die Erfindung betrifft ebenfalls die Verwendung der Verbindung der Formel (I)
Durch die erfindungsgemäße Verwendung kommt es zu einer Verbesserung der Lagerstabilität des wärmeempfindlichen Aufzeichnungsmaterials, insbesondere der Lagerstabilität bei hohen Temperaturen und hoher Umgebungsfeuchte. Unter hohen Temperaturen werden Temperaturen von etwa 25 bis etwa 60°C, bevorzugt von etwa 30 bis etwa 50°C verstanden. Unter hoher Umgebungsfeuchte wird eine Feuchte von etwa 50 bis etwa 100 %, bevorzugt von etwa 70 bis etwa 90% , verstanden.The use according to the invention improves the storage stability of the heat-sensitive recording material, in particular the storage stability at high temperatures and high ambient humidity. High temperatures are understood to mean temperatures from approximately 25 to approximately 60 ° C., preferably from approximately 30 to approximately 50 ° C. High ambient humidity is understood to mean a humidity of approximately 50 to approximately 100%, preferably approximately 70 to approximately 90%.
Die Vorteile, die mit der vorliegenden Erfindung verbunden sind, lassen sich im Wesentlichen wie folgt zusammenfassen:
Die vorliegende Erfindung stellt ein wärmeempfindliches Aufzeichnungsmaterial bereit, welches neben einer wünschenswert hohen dynamischen Druckempfindlichkeit auch eine außerordentlich gute Lagerstabilität, insbesondere auch unter Bedingungen hoher Lagertemperatur und Umgebungsfeuchte, zeigt, ohne dass die für die Anwendung notwendigen funktionellen Eigenschaften, wie beispielsweise Oberflächenweisse und thermische Ansprechempfindlichkeit, verloren gehen.The advantages associated with the present invention can be summarized essentially as follows:
The present invention provides a heat-sensitive recording material which, in addition to a desirable high dynamic pressure sensitivity, also shows an extraordinarily good storage stability, in particular also under conditions of high storage temperature and ambient humidity, without the functional properties necessary for the application, such as surface whiteness and thermal sensitivity, get lost.
Das vorstehend geschilderte Verfahren ist unter wirtschaftlichen Gesichtspunkten vorteilhaft und erlaubt eine hohe Verfahrensführung der Streichanlage sogar bei einer Geschwindigkeit von mehr als 1500 m/min, ohne dass es zu Beeinträchtigungen des Verfahrenserzeugnisses, das heißt des erfindungsgemäßen wärmeempfindlichen Aufzeichnungsmaterials kommt. Die Verfahrensführung kann on-line und off-line erfolgen, was eine wünschenswerte Flexibilität zur Folge hat.The process described above is advantageous from an economic point of view and permits a high process control of the coating installation even at a speed of more than 1500 m / min, without the process product, that is to say the heat-sensitive recording material according to the invention, being adversely affected. The process can be carried out on-line and off-line, which results in a desirable flexibility.
Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial ist phenolfrei, und für POS (point-of-sale) und/oder Etiketten-Anwendungen gut geeignet. Es eignet sich auch zur Herstellung von Fahrkarten, Eintrittskarten, Lotto- und Wettscheinen, etc., welche in Thermodirektverfahren bedruckt werden können und eine hohe Beständigkeit der darauf aufgezeichneten Bilder unter längerfristiger Lagerung, selbst unter verschärften Klimabedingungen hinsichtlich Temperatur und Umgebungsfeuchte, und des in-Kontakt-bringens des Schriftbildes mit hydrophoben Stoffen, wie Weichmachern, fettigen oder öligen Stoffen, etc., gewährleistet.The heat-sensitive recording material according to the invention is phenol-free and is well suited for POS (point-of-sale) and / or label applications. It is also suitable for the production of tickets, tickets, lottery and betting slips, etc., which can be printed using direct thermal processes and which are highly durable for the images recorded on them under long-term storage, even under more severe climatic conditions with regard to temperature and ambient humidity, and the Contact of the typeface with hydrophobic substances, such as plasticizers, greasy or oily substances, etc., guaranteed.
Die Erfindung wird nachfolgend anhand von nicht beschränkten Beispielen im Detail erläutert.The invention is explained in detail below on the basis of non-restricted examples.
Der Auftrag einer wässrigen Auftragssuspension zur Ausbildung der wärmeempfindlichen farbbildenden Schicht eines wärmeempfindlichen Aufzeichnungspapiers erfolgte im Labormaßstabe mittels einer Stabrakel auf eine Seite eines synthetischen Basispapieres (Yupo® FP680) von 63 g/m2. Nach Trocknung wurde ein thermisches Aufzeichnungsblatt erhalten. Die Auftragsmenge der wärmeempfindlichen farbbildenden Schicht lag zwischen 4,0 - 4,5 g/m2.The application of an aqueous application suspension to form the heat-sensitive color-forming layer of heat-sensitive recording paper was carried out on a laboratory scale by means of a doctor blade on one side of a synthetic base paper (Yupo® FP680) of 63 g / m 2 . After drying, a thermal recording sheet was obtained. The application quantity of the heat-sensitive color-forming layer was between 4.0 - 4.5 g / m2.
Im Produktionsmaßstab erfolgte der Auftrag der wässrigen Auftragssuspension auf eine Papierbahn eines Flächengewichtes von 43 g/m2 mittels des Curtain-Coating-Beschichtungsverfahrens. Die Viskosität der wässrigen Auftragssuspension betrug 450 mPas (nach Brookfield, 100 U/min, 20 °C) (im entlüfteten Zustand). Deren Oberflächenspannung betrug 46 mN/m (statistische Ringmethode). Das Streichwerk war in-line angeordnet. Das Curtain-Coating-Beschichtungsverfahren wurde bei einer Geschwindigkeit von 1550 m/min betrieben.On a production scale, the aqueous application suspension was applied to a paper web with a basis weight of 43 g / m 2 using the curtain coating process. The viscosity of the aqueous application suspension was 450 mPas (according to Brookfield, 100 rpm, 20 ° C.) (in the deaerated state). Their surface tension was 46 mN / m (statistical ring method). The coating mechanism was arranged in-line. The curtain coating process was operated at a speed of 1550 m / min.
Nach dem Auftrag der wässrigen Auftragssuspension erfolgte in üblicher Weise der Trocknungsvorgang des beschichteten Papierträgers. Der Flächengewichtsauftrag der trockenen wärmeempfindlichen Schicht betrug 4,0 - 4,5 g/m2.After the application of the aqueous application suspension, the coated paper carrier was dried in the usual way. The basis weight application of the dry, heat-sensitive layer was 4.0-4.5 g / m 2 .
Anhand der vorstehend gemachten Angaben wurde ein wärmeempfindliches Aufzeichnungsmaterial bzw. Thermopapier hergestellt, wobei die folgenden Rezepturen von wässrigen Auftragssuspensionen zur Ausbildung eines Verbundgebildes auf einem Trägersubstrat herangezogen und anschließend in üblicher Weise die weiteren Schichten, insbesondere eine Schutzschicht, ausgebildet wurden, worauf hier nicht gesondert eingegangen werden soll.On the basis of the information given above, a heat-sensitive recording material or thermal paper was produced, the following formulations of aqueous application suspensions being used to form a composite structure on a carrier substrate and subsequently the further layers, in particular a protective layer, being formed in a conventional manner, which is not dealt with separately here shall be.
Eine wässrige Auftragssuspension, wurde hergestellt, indem eine wässrige Dispersion des Farbbildners, die durch Mahlen von 20 Gew.-Teilen 3-N-n-Dibutylamin-6-methyl-7-anilinofluoran (ODB-2) mit 33 Gew.-Teilen einer 15 % wässrigen Lösung von Ghosenex™ L-3266 (sulfonierter Polyvinylalkohol, Nippon Ghosei) in einer Perlen-Mühle hergestellt wurde, eine wässrige Farbentwickler-Dispersion, die durch Mahlen von 40 Gew.-Teilen des Farbentwicklers zusammen mit 66 Gew.-Teilen einer 15 %igen wässrigen Lösung von Ghosenex™ L-3266 in der Perl-Mühle hergestellt wurde, eine Dispersion, die durch Mahlen von 40 Gew.-Teilen Sensibilisierungsmittel mit 33 Gew.-Teilen einer 15 %igen wässrigen Lösung von Ghosenex™ L-3266 in einer Mühle hergestellt wurde, 189 Gew.-Teile einer 56 %igen PCC-Dispersion (präzipitiertes Calciumcarbonat), 50 Gew.-Teile einer wässrigen 20 %igen Zinkstearatdispersion, 138 Gew.-Teile einer 10% igen wässrigen Polyvinylalkohollösung (Mowiol 28-99, Kuraray Europe) gut gemischt wurden.An aqueous application suspension was prepared by mixing an aqueous dispersion of the color former by grinding 20 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluorane (ODB-2) with 33 parts by weight of a 15% aqueous solution of Ghosenex ™ L-3266 (sulfonated polyvinyl alcohol, Nippon Ghosei) was prepared in a bead mill, an aqueous color developer dispersion which was obtained by grinding 40 parts by weight of the color developer together with 66 parts by weight of a 15% aqueous solution of Ghosenex ™ L-3266 made in the Perl Mill, a dispersion made by grinding 40 parts by weight of sensitizer was prepared in a mill with 33 parts by weight of a 15% aqueous solution of Ghosenex ™ L-3266, 189 parts by weight of a 56% PCC dispersion (precipitated calcium carbonate), 50 parts by weight of an aqueous 20% % zinc stearate dispersion, 138 parts by weight of a 10% aqueous polyvinyl alcohol solution (Mowiol 28-99, Kuraray Europe) were mixed well.
Die so erhaltenen wärmeempfindlichen Beschichtungssuspensionen, die sich aus der nachfolgenden Tabelle 1 ergeben, wurden herangezogen, um Verbundgebilde aus Papierträger und Thermoreaktionsschicht herzustellen.
Eine wässrige Auftragssuspension, wurde hergestellt, indem eine wässrige Dispersion des Farbbildners, die durch Mahlen von 20 Gew.-Teilen 3-N-n-Dibutylamin-6-methyl-7-anilinofluoran (ODB-2) mit 33 Gew.-Teilen einer 15 % wässrigen Lösung von Ghosenex™ L-3266 in einer Perlen-Mühle hergestellt wurde, eine wässrige Farbentwickler-Dispersion, die durch Mahlen von 40 Gew.-Teilen des Farbentwicklers zusammen mit 33 Gew.-Teilen einer 15 %igen wässrigen Lösung von Ghosenex™ L-3266 in der Perl-Mühle hergestellt wurde, eine Dispersion, die durch Mahlen von 40 Gew.-Teilen Sensibilisierungsmittel mit 33 Gew.-Teilen einer 15 %igen wässrigen Lösung von Ghosenex™ L-3266 in einer Mühle hergestellt wurde, 200 Gew.-Teile einer 56 %igen PCC-Dispersion (präzipitiertes Calciumcarbonat), 50 Gew.-Teile einer wässrigen 20 %igen Zinkstearatdispersion, 138 Gew.-Teile einer 10%igen wässrigen Polyvinylalkohollösung (Mowiol 28-99) gut gemischt wurden.An aqueous application suspension was prepared by mixing an aqueous dispersion of the color former by grinding 20 parts by weight of 3-Nn-dibutylamine-6-methyl-7-anilinofluorane (ODB-2) with 33 parts by weight of a 15% aqueous solution of Ghosenex ™ L-3266 in a bead mill, an aqueous color developer dispersion which was prepared by grinding 40 parts by weight of the color developer together with 33 parts by weight of a 15% aqueous solution of Ghosenex ™ L -3266 was made in the Perl Mill, a dispersion made by grinding 40 parts by weight of sensitizer with 33 parts by weight of a 15% aqueous solution of Ghosenex ™ L-3266 in a mill, 200 parts by weight. Parts of a 56% PCC dispersion (precipitated calcium carbonate), 50 parts by weight of an aqueous 20% zinc stearate dispersion, 138 parts by weight of a 10% aqueous polyvinyl alcohol solution (Mowiol 28-99) were mixed well.
Eine wässrige Auftragssuspension, wurde hergestellt, indem eine wässrige Dispersion des Farbbildners, die durch Mahlen von 20 Gew.-Teilen 3-N-n-Dibutylamin-6-methyl-7-anilinofluoran (ODB-2) mit 33 Gew.-Teilen einer 15 % wässrigen Lösung von Ghosenex™ L-3266 L3266 in einer Perlen-Mühle hergestellt wurde, eine wässrige Farbentwickler-Dispersion, die durch Mahlen von 40 Gew.-Teilen des Farbentwicklers zusammen mit 33 Gew.-Teilen einer 15 %igen wässrigen Lösung von Ghosenex™ L-3266 in der Perl-Mühle hergestellt wurde, eine Dispersion, die durch Mahlen von 40 Gew.-Teilen Sensibilisierungsmittel mit 33 Gew.-Teilen einer 15 %igen wässrigen Lösung von Ghosenex™ L-3266 in einer Mühle hergestellt wurde, eine Dispersion, die durch Mahlen von 12,5 Gew.-Teilen Alterungsschutz mit 10 Gew.-Teilen einer 15 %igen wässrigen Lösung von Ghosenex™ L-3266 in einer Mühle hergestellt, 174 Gew.-Teile einer 56 %igen PCC-Dispersion (präzipitiertes Calciumcarbonat), 50 Gew.-Teile einer wässrigen 20 %igen Zinkstearatdispersion, 138 Gew.-Teile einer 10%igen wässrigen Polyvinylalkohollösung (Mowiol 28-99) gut gemischt wurden. Die so erhaltenen wärmeempfindlichen Beschichtungssuspensionen, die sich aus der nachfolgenden Tabelle 2 ergeben, wurden herangezogen, um Verbundgebilde aus Papierträger und Thermoreaktionsschicht herzustellen.
*Gew.-Verhältnis 1:1
** DH-43 : 1,1,3-Tris-(2-methyl-4-hydroxy-5-cyclohexyl-phenyl)-butan
* 1: 1 weight ratio
** DH-43: 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane
Die Korngöße (D4,3-Wert in µm) der gemahlenen Funktionschemikalien wurde entsprechend Tabelle 3 eingestellt (± 0,1µm).
Die Messung der Korngrößenverteilung erfolgte durch Laserbeugung mit einem Coulter LS230-Gerät der Fa. Beckman Coulter.The grain size distribution was measured by laser diffraction using a Coulter LS230 device from Beckman Coulter.
Die thermischen Aufzeichnungsmaterialien gemäß den Tabellen 1, 2 und 3 wurden wie nachstehend ausgewertet.The thermal recording materials according to Tables 1, 2 and 3 were evaluated as follows.
Papierweisse strichseitig wurde nach DIN/ISO 2470 mit einem mit Elrepho 3000 Spektralphotometer bestimmtThe paper white line was determined in accordance with DIN / ISO 2470 using an Elrepho 3000 spectrophotometer
Die Papiere (6 cm breite Streifen) wurden thermisch unter Verwendung des Atlantek 200 Testdruckers (Fa. Atlantek , USA) mit einer Kyocera Druckleiste von 200 dpi und 560 Ohm bei einer angelegten Spannung von 20,6 V und einer maximalen Pulsbreite von 0,8 ms mit einem Schachbrett-Muster mit 10 Energieabstufungen bedruckt. Die Bilddichte (optische Dichte, o.D.) wurde mit einem Macbeth-Densitometer RD-914, von Gretag gemessen.The papers (6 cm wide strips) were thermally used using the Atlantek 200 test printer (Atlantek, USA) with a Kyocera print bar of 200 dpi and 560 ohms at an applied voltage of 20.6 V and a maximum pulse width of 0.8 ms printed with a checkerboard pattern with 10 energy levels. The image density (optical density, undated) was measured with a Macbeth densitometer RD-914, from Gretag.
Ein Blatt Aufzeichnungspapier wird in drei identische Streifen geschnitten. Ein Streifen wird gemäß dem Verfahren von (2) dynamisch aufgezeichnete und die Bilddichte bestimmt. Die beiden anderen Streifen werden im unbedruckten (weißen) Zustand für 4 Wochen einem Klima von 40°C und 85% rel. Luftfeuchte (Klima 1) bzw. von 60°C und 50% rel. Luftfeuchte (Klima 2) ausgesetzt. Nach Klimatisierung der Papiere werden sie gemäß dem Verfahren von (2) dynamisch bedruckt und die Bilddichte mit dem Densitometer bestimmt. Die % Veränderung der Schreibleistung beim Bedrucken der gelagerten Muster wurde gemäß der folgenden Gleichung (I) berechnet.
Auf die gemäß dem Verfahren von (2) dynamisch aufgezeichnete Probe des thermischen Aufzeichnungspapiers wurde eine weichmacherhaltigen Frischhaltefolie (PVC - Folie mit 20-25 % Dioctyladipat) unter Vermeiden von Falten und Lufteinschlüssen in Kontakt gebracht, zu einer Rolle gewickelt und 16 Std. bei Raumtemperatur (20-22 °C) gelagert. Nach Abziehen der Folie wurde die Bilddichte (o. D.) gemessen und entsprechend der Formel (II) in Bezug zu den entsprechenden Bilddichtewerten vor der WM-Einwirkung gesetzt.
Probenvorbereitung: Aus dem Papiermuster werden mit einem Stanzeisen 2 Kreisflächen ausgestanzt und gewogen. Die Papierproben werden mit 3 ml Acetonitril (HPLC-Qualität) im Ultraschallbad 30 Min. extrahiert und das Extrakt über ein PTFE-Spritzenfilter (0,45 µm) abfiltriert.Sample preparation: 2 circular areas are punched out of the paper sample with a punching iron and weighed. The paper samples are extracted with 3 ml of acetonitrile (HPLC quality) in an ultrasonic bath for 30 minutes and the extract is filtered off through a PTFE syringe filter (0.45 µm).
HPLC Trennung der Inhaltsstoffe: Mittels Autosampler wurde das obige Extrakt auf die Trennsäule (Zorbax Eclipse XDB-C18) aufgebracht und mit dem Fließmittel Acetonitril:THF:H2O (450:89:200 Gew.-Teile) mit Acetonitril-Gradient eluiert. Quantitative Auswertung der Chromatogramme erfolgt über den Flächenvergleich der über tr-Zeiten zugeordneten Probenpeaks mit einer über die Referenzmuster ermittelten Eichgerade. Der Messfehler bei der HPLC-Quantifizierung beträgt ±2%.HPLC separation of the ingredients: The above extract was applied to the separation column (Zorbax Eclipse XDB-C18) using an autosampler and eluted with the eluent acetonitrile: THF: H2O (450: 89: 200 parts by weight) with an acetonitrile gradient. Quantitative evaluation of the chromatograms is carried out by comparing the area of the sample peaks assigned over tr times with a calibration line determined using the reference pattern. The measurement error in HPLC quantification is ± 2%.
Tabelle 4 fasst die Auswertung der Papiere entsprechend Rezeptur 1 (Tabelle 1), Mahlserie 1, Tabelle 5 die Auswertung der Papiere entsprechend Rezeptur 1 (Tabelle 1), Mahlserie 2, und Tabelle 6 die Auswertung der Papiere entsprechend Rezeptur 2a bzw. 2b (Tabelle 3), Mahlserie 2, zusammen.Table 4 summarizes the evaluation of the papers according to recipe 1 (table 1), grinding series 1, table 5 the evaluation of the papers according to recipe 1 (table 1), grinding series 2, and table 6 the evaluation of the papers according to recipe 2a or 2b (table 3), meal series 2, together.
Verglichen werden die maximal erreichten Bilddichten (o.D. max.) der frischen Papiere mit den entsprechenden Werten nach Bedrucken der gelagerten Papiere unter zwei Klimabedingungen:
- Klima 1: Lagerung der unbedruckten Papiere für 4 Wochen bei 40°C und 85% r.F.
- Klima 2: Lagerung der unbedruckten Papiere für 4 Wochen bei 60°C und 50% r.F..
- Climate 1: Storage of the unprinted paper for 4 weeks at 40 ° C and 85% RH
- Climate 2: Storage of the unprinted papers for 4 weeks at 60 ° C and 50% RH.
Für ausgewählte Papiere wurde auch die quantitative Bestimmung des Farbentwicklers in den frischen und gelagerten Papieren vorgenommen und als Kontrolle die entsprechende Bestimmung des Farbbildners als Strichkomponente die erfahrungsgemäß praktisch keine Veränderung über die Lagerungszeit erfährt.For selected papers, the quantitative determination of the color developer in the fresh and stored papers was also carried out and, as a control, the corresponding determination of the color former as a line component, which experience has shown that there is practically no change over the storage time.
Die Werte des Weichmachertests (WM-Test) quantifizieren die Haltbarkeit des Druckbildes unter dem Einfluss von Dioctyladipat (stellvertretend für hydrophobe Agenzien) anhand der % Veränderung der maximalen Schreibleistung (o.D. max.) während des Tests.The values of the plasticizer test (WM test) quantify the durability of the printed image under the influence of dioctyl adipate (representative of hydrophobic agents) based on the% change in the maximum writing power (undated max.) During the test.
Veränderungen der o.D. von ≤ 10% sind tolerierbar und beeinträchtigen nicht die Anwendungstauglichkeit der Papiere.
*AI-1 = Rezeptur AI (Tabelle 1), Mahlserie 1 (Tabelle 3)
* AI-1 = recipe AI (table 1), grinding series 1 (table 3)
Das wärmeempfindliche Aufzeichnungsmaterial der vorliegenden Erfindung zeigt insbesondere die folgenden vorteilhaften Eigenschaften:
- (1) Das erfindungsgemäße wärmeempfindliche Aufzeichnungsmaterial zeigt praktisch die gleiche Schreibleistung vor und nach der vierwöchigen Lagerung im unbedruckten Zustand bei zwei unterschiedlichen Lagerbedingungen. Der Abfall der max. Druckdichte liegt bei allen Papieren mit dem erfindungsgemäßen Farbentwickler ≤ 10% der Druckdichte der frischen Papieren (CI-1, CII-1, CIII-1, CI-2, CII-2, CIII-2, FI-1, FI-2, FII-1, FII-2, FIII-1, FIII-2).
Demgegenüber zeigen die Vergleichsmaterialien AI-1, AII-1, AIII-1, BI-1, BII-1, BIII-1, DI-1, DII-1, DIII-1, EI-1, EI-2, EII-1, EII-2, EIII-1, EIII-2 deutliche Verluste der Schreibleistung. - (2) Die Abnahme der Farbentwicklerkonzentration in der wärmeempfindlichen farbbildenden Schicht ist minimal für den erfindungsgemäßen Farbentwickler (≤ 7%) und beeinträchtigt die Schreibleistung kaum. Im Gegensatz dazu führt der Einsatz von bekannten nicht-phenolischen Entwicklern zu deutlichen Verlusten der Farbentwicklermenge im Papier und zu einer inakzeptablen niedrigen Schreibleistung nach Lagerung.
- (3) Das aufgezeichnete Bild der erfindungsgemäßen wärmeempfindlichen Papiere mit dem erfindungsgemäßen Farbentwickler weist eine max. Druckdichte auf, die in nichts den Entwicklern der Vergleichsmuster nachsteht (frische max. o.D.-Werte aus Tabellen 4, 5, 6), stabil ist und nach Einwirken von Weichmacher kaum verblasst, vergleichbar der Leistung der bekannten nicht-phenolischen Vergleichsentwicklern (Zeile WM-Test , Tab. 4 und 5)
- (4) Mit typischen Alterungsschutzmittel kann die Lagerungsbeständigkeit der Papiere nicht oder nur ungenügend verbessert werden (E-a Serie vs. E-b, Tabelle 6).
- (5) Die Oberflächenweisse der erfindungsgemäßen Aufzeichnungspapiere ist stabil und zeigt nach den Lagerungsversuchen vergleichbar gute Werte zu den besten Vergleichspapieren und erheblich bessere Werte als jene auf Basis des in der Praxis weit verendeten Pergafast 201®- Entwicklers (D-Serie, Tabelle 4 und 5).
- (6) Mit dem erfindungsgemäßen Herstellungsverfahren lässt sich ein in allen wichtigen anwendungstechnischen Belangen hochwertiges wärmeempfindliches Aufzeichnungsmaterial unter wirtschaftlich vorteilhaften Bedingungen herstellen.
- (1) The heat-sensitive recording material according to the invention shows practically the same writing performance before and after four weeks of storage in the unprinted state under two different storage conditions. The drop in the max. Print density for all papers with the color developer according to the invention is ≤ 10% of the print density of the fresh papers (CI-1, CII-1, CIII-1, CI-2, CII-2, CIII-2, FI-1, FI-2, FII-1, FII-2, FIII-1, FIII-2).
In contrast, the comparative materials show AI-1, AII-1, AIII-1, BI-1, BII-1, BIII-1, DI-1, DII-1, DIII-1, EI-1, EI-2, EII- 1, EII-2, EIII-1, EIII-2 significant loss of write performance. - (2) The decrease in the color developer concentration in the heat-sensitive color-forming layer is minimal for the color developer according to the invention (7 7%) and hardly affects the writing performance. In contrast, the use of known non-phenolic developers leads to significant losses in the amount of color developer in the paper and to an unacceptably low write performance after storage.
- (3) The recorded image of the heat-sensitive papers according to the invention with the color developer according to the invention has a max. Print density, which is in no way inferior to the developers of the comparison samples (fresh max.oD values from Tables 4, 5, 6), is stable and hardly fades after exposure to plasticizer, comparable to the performance of the known non-phenolic comparison developers (line WM- Test, Tab. 4 and 5)
- (4) With typical anti-aging agents, the storage stability of the papers cannot be improved or can only be improved insufficiently (Ea series vs. Eb, Table 6).
- (5) The surface whiteness of the recording papers according to the invention is stable and shows, after the storage tests, comparably good values to the best comparison papers and considerably better values than those based on the Pergafast 201® developer (D series, Tables 4 and 5), which is widely used in practice ).
- (6) With the production method according to the invention, a high-quality heat-sensitive recording material can be produced under economically advantageous conditions in all important application-related matters.
Claims (15)
- Heat-sensitive recording material, comprising a carrier substrate and also a heat-sensitive colour-forming layer containing at least one colour former, at least one phenol-free colour developer and at least one sensitising agent, characterised in that the at least one colour developer is a compound of the formula (I)
- Heat-sensitive recording material according to claim 1, characterised in that Ar1 and Ar2 are each a phenyl radical.
- Heat-sensitive recording material according to either one of claims 1 and 2, characterised in that the carrier substrate is paper, synthetic paper and/or a plastics film.
- Heat-sensitive recording material according to at least one of the preceding claims, characterised in that the at least one colour former is a dye of the triphenylmethane type, of the fluoran type, of the azaphthalide type and/or of the fluorene type, preferably of the fluoran type.
- Heat-sensitive recording material according to at least one of the preceding claims, characterised in that the dye of the fluoran type is selected from the group consisting of
3-diethylamino-6-methyl-7-anilinofluoran,
3-(N-ethyl-N-p-toludinamino)-6-methyl-7-anilinofluoran,
3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran,
3-diethylamino-6-methyl-7-(o,p-dimethylanilino)fluoran,
3-pyrrolidino-6-methyl-7-anilinofluoran,
3-(cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran,
3-diethylamine-7-(m-trifluoromethylanilino)fluoran,
3-N-n-dibutylamine-6-methyl-7-anilinofluoran,
3-diethylamino-6-methyl-7-(m-methylanilino)fluoran,
3-N-n-dibutylamine-7-(o-chloroanilino)fluoran,
3-(N-ethyl-N-tetrahydrofurfurylamine)-6-methyl-7-anilinofluoran,
3-(N-methyl-N-propylamine)-6-methyl-7-anilinofluoran,
3-(N-ethyl-N-ethoxypropylamine)-6-methyl-7-anilinofluoran,
3-(N-ethyl-N-isobutylamine)-6-methyl-7-anilinofluoran and/or
3-dipentylamine-6-methyl-7-anilinofluoran. - Heat-sensitive recording material according to at least one of the preceding claims, characterised in that, in addition to the compound of the formula (I), one or more further non-phenolic colour developers, preferably selected from the group of sulphonylureas, especially preferably N'-(p-toluenesulphonyl)-N'-phenylurea, N-(p-toluenesulphonyl)-N'-3-(p-toluenesulphonyloxyphenyl)-urea and/or 4,4'-bis-(p-tolylsulphonylureido)-diphenylmethane, are present.
- Heat-sensitive recording material according to at least one of the preceding claims, characterised in that from 0.5 to 10 parts by weight, preferably from 1.5 to 4 parts by weight, of the compound of the formula (I), based on the colour former, are present.
- Heat-sensitive recording material according to at least one of the preceding claims, characterised in that the compound of the formula (I) is present in an amount of from 3 to 35 % by weight, preferably from 10 to 25 % by weight, based on the total solids content of the heat-sensitive layer.
- Heat-sensitive recording material according to at least one of the preceding claims, characterised in that the heat-sensitive colour-forming layer contains stabilisers, binders, release agents, pigments and/or brighteners.
- Heat-sensitive recording material according to at least one of the preceding claims, characterised in that the application weight of the dry heat-sensitive layer is from 1 to 10 g/m2, preferably from 3 to 6 g/m2.
- Method of producing a heat-sensitive recording material according to at least one of the preceding claims, characterised in that an aqueous suspension containing the starting materials of the heat-sensitive colour-forming layer is applied to a carrier substrate and dried, wherein the aqueous application suspension has a solids content of from 20 % to 75 % by weight, preferably from 30 % to 50 % by weight, and is applied using the curtain coating method at an operating speed of the coating apparatus of at least 400 m/min, preferably at least 1000 m/min, very especially preferably at least 1500 m/min, and dried, wherein the sensitising agent is 1,2 diphenoxyethane and wherein the dried heat-sensitive colour-forming layer is subjected to a smoothing step to adjust the Bekk smoothness, measured according to DIN 5310, to from 100 to 700 sec.
- Heat-sensitive recording material, obtainable in accordance with the method of claim 12.
- Use of the compound according to formula (I)
- Use according to claim 14 for improving storage stability, especially storage stability at high temperatures and high ambient humidity.
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DE102014107567.6A DE102014107567B3 (en) | 2014-05-28 | 2014-05-28 | Heat-sensitive recording material |
PCT/EP2015/061835 WO2015181291A1 (en) | 2014-05-28 | 2015-05-28 | Heat-sensitive recording material |
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EP (1) | EP3148816B1 (en) |
JP (1) | JP2017521282A (en) |
KR (1) | KR102395673B1 (en) |
CN (1) | CN106536209A (en) |
DE (1) | DE102014107567B3 (en) |
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DE102016113203B4 (en) * | 2016-07-18 | 2018-05-30 | Papierfabrik August Koehler Se | HEAT-SENSITIVE RECORDING MATERIAL |
DE102016219569A1 (en) * | 2016-10-07 | 2018-04-12 | Mitsubishi Hitec Paper Europe Gmbh | Heat-sensitive recording material |
DE102016219567A1 (en) * | 2016-10-07 | 2018-04-12 | Mitsubishi Hitec Paper Europe Gmbh | Heat-sensitive recording material |
US10882348B2 (en) | 2016-10-07 | 2021-01-05 | Mitsubishi Hitec Paper Europe Gmbh | Heat-sensitive recording material |
EP3575100B1 (en) * | 2017-01-30 | 2023-11-15 | Nippon Soda Co., Ltd. | Recording material and recording sheet |
DE102017102702B4 (en) * | 2017-02-10 | 2019-09-12 | Papierfabrik August Koehler Se | Heat-sensitive recording material |
CN109487624A (en) * | 2017-09-12 | 2019-03-19 | 金华盛纸业(苏州工业园区)有限公司 | A kind of heat-sensitive paper and its manufacturing method |
DE102017131276A1 (en) | 2017-12-22 | 2019-06-27 | Mitsubishi Hitec Paper Europe Gmbh | Recyclable release substrate |
DE102018102177A1 (en) | 2018-01-31 | 2019-08-01 | Mitsubishi Hitec Paper Europe Gmbh | Coating composition, heat-sensitive recording layer, thermosensitive recording material, and related uses and methods |
DE102018102180A1 (en) * | 2018-01-31 | 2019-08-01 | Mitsubishi Hitec Paper Europe Gmbh | Heat-sensitive recording material |
DE102018111224B4 (en) | 2018-05-09 | 2020-12-10 | Papierfabrik August Koehler Se | Thermosensitive recording material |
DE102018133168B4 (en) | 2018-12-20 | 2021-02-18 | Papierfabrik August Koehler Se | Thermosensitive recording material |
JP2021146642A (en) * | 2020-03-19 | 2021-09-27 | 株式会社リコー | Thermosensitive recording medium, method for producing thermosensitive recording medium, and article |
EP3885152B1 (en) * | 2020-03-23 | 2022-06-08 | Koehler Innovation & Technology GmbH | Use of n-(p-toluenesulfonyl)-n'-(3-p-toluenesulfonyloxyphenyl)urea as colour developer in a heat-sensitive recording material |
DE102020112411B3 (en) * | 2020-05-07 | 2021-05-27 | Papierfabrik August Koehler Se | Thermosensitive recording material |
EP3957488A1 (en) | 2020-08-19 | 2022-02-23 | Mitsubishi HiTec Paper Europe GmbH | Heat-sensitive recording material and heat-sensitive recording layer and coating composition for its production, uses and methods |
CN112014500A (en) * | 2020-08-24 | 2020-12-01 | 河北建新化工股份有限公司 | Method for measuring content of N-formanilino fluorane |
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Also Published As
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JP2017521282A (en) | 2017-08-03 |
WO2015181291A1 (en) | 2015-12-03 |
KR102395673B1 (en) | 2022-05-09 |
ES2793007T3 (en) | 2020-11-12 |
DE102014107567B3 (en) | 2015-11-05 |
US20170190199A1 (en) | 2017-07-06 |
KR20170010798A (en) | 2017-02-01 |
EP3148816A1 (en) | 2017-04-05 |
CN106536209A (en) | 2017-03-22 |
US10160245B2 (en) | 2018-12-25 |
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