EP3765303A1 - Revêtements en papier thermoréactifs à base de dérivés de cellulose - Google Patents

Revêtements en papier thermoréactifs à base de dérivés de cellulose

Info

Publication number
EP3765303A1
EP3765303A1 EP19722558.4A EP19722558A EP3765303A1 EP 3765303 A1 EP3765303 A1 EP 3765303A1 EP 19722558 A EP19722558 A EP 19722558A EP 3765303 A1 EP3765303 A1 EP 3765303A1
Authority
EP
European Patent Office
Prior art keywords
heat
recording material
sensitive recording
material according
thermoresponsive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19722558.4A
Other languages
German (de)
English (en)
Other versions
EP3765303B1 (fr
Inventor
Maximilian Nau
Markus BIESALSKI
Michael Horn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technische Universitaet Darmstadt
Koehler Paper SE
Original Assignee
Papierfabrik August Koehler SE
Technische Universitaet Darmstadt
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Papierfabrik August Koehler SE, Technische Universitaet Darmstadt filed Critical Papierfabrik August Koehler SE
Publication of EP3765303A1 publication Critical patent/EP3765303A1/fr
Application granted granted Critical
Publication of EP3765303B1 publication Critical patent/EP3765303B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/366—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using materials comprising a polymeric matrix containing a polymeric particulate material, e.g. hydrophobic heat coalescing particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • 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
    • B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
    • B41M5/361—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties using a polymeric matrix with inorganic particles forming an image by orientation or agglomeration

Definitions

  • the present invention relates to a heat-sensitive recording material, a process for its production and a heat-sensitive recording material obtainable by this process.
  • Heat-sensitive recording materials comprising a support substrate which is black or colored on at least one side, in particular paper, synthetic paper and / or a plastic film which is coated on this black or colored side with an opaque material are known.
  • a support substrate which is black or colored on at least one side, in particular paper, synthetic paper and / or a plastic film which is coated on this black or colored side with an opaque material.
  • the black or colored carrier substrate appears white toward the outside.
  • heat is applied, such as local heat through a thermal printer, the opaque coating loses its opacity at these points and becomes transparent so that the black or colored carrier substrate becomes visible.
  • EP 2 345 678 A1 discloses a heat-sensitive recording material comprising a coating of nanoparticles comprising a shell and a core each have different polymers with different Glasübergangstempe- temperatures.
  • thermosensitive recording material comprising a coating containing an opaque polymer, for example a styrene / acrylate copolymer.
  • the heat-sensitive recording materials known from the prior art have the disadvantage that the structure of the heat-sensitive layer is often quite complex. For example, nanoparticles composed of different layers of different polymers must be provided, which are complex to produce and therefore often expensive. In addition, many of the polymers used are questionable in terms of their sustainability and toxicity. Many heat-sensitive recording materials known from the prior art can also be improved with regard to the sharpness and the contrast of the printed image. In addition, many known thermosensitive recording materials have inadequate storage stability.
  • the object of the present invention is to overcome the above-mentioned disadvantages of the prior art.
  • the object of the present invention is to provide a thermosensitive recording material comprising a thermoresponsive layer which is composed of, for example, sustainable, i. as natural and / or renewable raw materials, constructed, and on the other hand, the lowest possible to no toxicity.
  • the material of the thermoresponsive layer should be able to be provided as simply and easily as possible.
  • the heat-sensitive recording material should enable a sharp and high-contrast print image and, moreover, should not be impaired even with a longer storage time.
  • the heat-sensitive recording material should be produced by a simple and inexpensive method.
  • the melting point of the substances used in the thermoresponsive layer should preferably be above 90.degree. C., so that the process temperatures of up to 90.degree. C. which are customary in the preparation do not have a negative influence on the product.
  • thermoresponsive layer on the at least one black or colored side of the carrier substrate, wherein the thermoresponsive layer comprises nanoparticles of at least one cellulose ester.
  • thermosensitive recording material has the advantage that the thermoresponsive layer contains nanoparticles of modified cellulose, i. of at least one cellulose ester, since the cellulose ester is non-toxic and therefore substantially harmless to health. In addition, this cellulose ester is obtainable relatively cheaply in large quantities.
  • the cellulose ester also has high opacity and, for thermal printing applications, a favorable melting point and glass transition temperature.
  • a heat-sensitive recording material comprising a thermoresponsive layer comprising nanoparticles of at least one cellulose ester is relatively easy and cost-effective to produce. In addition, it has a high storage stability and an excellent print image.
  • the cellulose ester has a relatively high melting point, so that the usual in the preparation of the heat-sensitive recording material process temperatures of up to 90 ° C can be tolerated.
  • the support substrate of the heat-sensitive recording material of the present invention comprises at least one black or colored side.
  • colored side is understood to mean that the side has a color other than white or black, in other words, the heat-sensitive recording material comprises at least one side that is not white the at least one black or colored page has several different colors, also in combination with the color black.
  • thermoresponsive layer comprising nanoparticles of at least one cellulose ester, is applied on this at least one non-white but colored or black side of the carrier substrate.
  • thermoresponsive layer comprising the nanoparticles of at least one cellulose ester is preferably substantially white.
  • Nanoparticles of cellulose esters and methods of preparation are generally known to me.
  • the alcohol groups of cellulose are first esterified.
  • esterifications of cellulose are preferably carried out using the respective acid anhydrides and a catalyst, typically sulfuric acid.
  • a catalyst typically sulfuric acid.
  • the cell is initially suspended in the reaction mixture, but as the acetylation proceeds, the cellulose becomes increasingly soluble in the glacial acetic acid, which causes the homogenization of the reaction mixture.
  • the viscosity of the solution varies and provides information about the degree of substitution (DS).
  • the increasing solution of the polymer chains leads to an increase in the viscosity, which later decreases again due to degradation reactions on the cellulose backbone and thus the reduction of the chain length.
  • the DS and chain length can be controlled on-line by observing the viscosity.
  • cellulose esters are cellulose acetate propionate, cellulose butyrate and cellulose acetate butyrate, which are prepared analogously to the method described above, preferably using the respective acid anhydrides.
  • the procedure is preferably as follows.
  • a solvent for. As dissolved THF, acetone, etc., so that the concentration of the cellulose ester is about 1 to 10 mg / mL.
  • This solution is then dissolved in a non-solvent, e.g. As a mixture of isopropanol and distilled water, like. Either the dissolved cellulose ester may be added to the non-solvent or, conversely, the non-solvent may be added to the solution of the cellulose ester.
  • the resulting suspension is typically stirred for 12 to 24 hours to allow solvent exchange between the still-swollen particles and the precipitating agent.
  • the particles sedimented into the lower quarter of the precipitation mixture and about 4/5 of the solvent mixture is separated.
  • the resulting suspension is centrifuged and the resulting particulate sludge is rinsed to water, and then introduced into coating formulations.
  • Typical yields are between 70 and 80%.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the nanoparticles of the at least one cell osmotic ester number-average particle sizes of 50 to 400 nm, preferably from 160-200 nm (+/- 40 nm), measured by dynamic light scattering (or " dynamic light scattering (DLS) is a technique used to analyze the scattered light of a laser on a dissolved or suspended sample, which is commonly used in polymers and biopolymers
  • DLS dynamic light scattering
  • the number-average particle size was determined in detail as follows: A "Nanophox" from Heribler Sympatec was used. This particle size analyzer uses photon cross-correlation spectroscopy (a statistical analysis method based on DLS) to determine particle sizes and distributions.
  • the temperature during the measurement is kept constant with a thermostat, typically at 20 ° C. Distilled water is usually used as the fluid medium.
  • a large number of scatter events are detected (typically set at 300,000 per second over several minutes).
  • the measured values thus obtained provide information about the Brownian molecular motion of the particles and their diffusion coefficient.
  • thermoresponsive layer has a transparency, measured according to DIN 53147: 1993-01, of less than 35%, preferably less than 30%, particularly preferably less than 25% and most preferably less than 20%, in particular less than 15% or even less than 10%.
  • Transparency is the ability of matter to transmit electromagnetic waves (transmission).
  • Opacity denotes the opposite of transparency, ie lack of transparency or lack of permeability.
  • the opacity is the reciprocal of the transmission.
  • the low transparency preferred according to the invention has the advantage that the black or colored side of the carrier substrate is substantially completely covered and appears at least substantially white to the outside.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the at least one cellulose ester comprises cellulose acetate, cellulose acetate propionate, cellulose butyrate and / or cellulose acetate butylate, preferably cellulose acetate butyrate.
  • cellulose esters are particularly preferred because they have glass transition temperatures (Tg) and melting temperatures (Tm) which are particularly preferred for use in a thermosensitive recording material.
  • nanoparticles of cellulose acetate butyrate are particularly preferred.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the at least one cellulose ester has a Tg of 45 ° C to 150 ° C and / or a Tm of 100 ° C to 185 ° C.
  • Tg and Tm are determined according to DIN 53765: 1994-03 by means of differential scanning calorimetry (DDK or "differential scanning calorimetry” (DSC)).
  • the heat-sensitive recording material according to the invention is characterized in that the at least one cellulose ester is present in an amount of from 35 to 70% by weight, based on the total weight of the thermoresponsive layer, in the thermoresponsive layer.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the thermoresponsive layer also comprises polyvinyl alcohol (PVA).
  • the polyvinyl alcohol is preferably contained in an amount of from 5 to 50% by weight, based on the total weight of the thermoresponsive layer, in the thermo-responsive layer.
  • Polyvinyl alcohol reduces sample viscosity and results in a more homogeneous coating.
  • the precipitating agent in the preparation of the nanoparticles of cellulose esters a small amount, preferably 0.01 to 1 wt .-%, particularly preferably 0.05 to 0.5 wt .-% and most preferably about 0.1 wt .-% of polyvinyl alcohol is added.
  • thermoresponsive layer additionally comprises at least one kaolin, alkali and / or alkaline earth metal salt.
  • the alkali and / or alkaline earth metal salt comprises NaCl, CaCO 3 and / or CaCl 2 .
  • the at least one kaolin, alkali metal and / or alkaline earth metal salt is preferably present in an amount of from 0.05 to 10% by weight, based on the total weight of the thermoresponsive layer, in the thermoresponsive layer.
  • the addition of salt is an advantage because the salt can compensate for surface charges.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the thermoresponsive layer further comprises at least one high molecular weight polyelectrolyte.
  • the at least one high molecular weight polyelectrolyte preferably comprises a poly (vinylamine-vinylformamide) copolymer, as available, for example, under the trade names Lupamin 9010 and Lupamin 4500 from BASF, and / or a cationic polyacrylamide, such as, for example, under the trade name Percol 47 from BASF.
  • the at least one high molecular weight polyelectrolyte is preferably present in an amount of from 5 to 35% by weight, based on the total weight of the thermoresponsive layer, in the thermoresponsive layer.
  • thermoresponsive layer comprises at least one kaolin, alkali and / or alkaline earth salt as defined above and at least one high molecular weight polyelectrolyte as defined above.
  • the heat-sensitive recording material according to the invention is furthermore preferably characterized in that the carrier substrate comprises paper, synthetic paper and / or a plastic film.
  • thermoresponsive layer comprises at least one silicone oil defoamer, preferably in an amount of from 0.05 to 5% by weight, based on the total weight of the thermoresponsive layer.
  • thermoresponsive layer comprises at least one binder, preferably an acrylate binder, which is obtainable, for example, under the trade name Acronal S 360 D from BASF, preferably in an amount of from 0.05 to 5 wt .-%, based on the total weight of the thermoresponsive layer comprises.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the pH of the thermoresponsive layer is 6 to 9.
  • the pH is preferably adjusted by addition of HCl or NaOH.
  • the heat-sensitive recording material according to the invention is preferably characterized in that the heat-sensitive color-forming layer contains conventional additives, such as, for example, stabilizers, release agents, pigments and / or brighteners.
  • thermoresponsive layer comprises polyvinyl alcohol, preferably in an amount of 30 to 60 parts by weight, and 100 parts by weight of nanoparticles of cellulose acetate butyrate, these nanoparticles being obtainable from cellulose acetate butyrate by dissolving cellulose acetate butyrate in an organic solvent, preferably in tetrahydrofuran, and precipitating the nanoparticles of cellulose acetate butyrate by adding this solution of cellulose acetate butyrate to a non-solvent, preferably to a mixture of water and isopropanol, preferably in a mixing ratio of 1 to 4, most preferably from 1.2 to 2.8, wherein the non-solvent preferably additionally polyvinyl alcohol, preferably in an amount of 0.01 to 1 wt .-%, particularly preferably about 0.1 wt -.%, based on the total amount of non-solvent.
  • this heat-sensitive recording material also contains 2 to 10 parts by weight of a binder, 10 to 20 parts by weight of a viscosity regulator and 1 to 5 parts by weight of NaOH.
  • the surface application weight 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 nanoparticles of at least one cellulose ester can be prepared by known methods.
  • nanoparticles of at least one cellulose ester are preferred by a process comprising the steps
  • the method is preferably characterized in that the cellulose ester comprises cellulose acetate, cellulose acetate propionate and / or cellulose acetate butyrate, preferably cellulose acetate butyrate.
  • the method is further preferably characterized in that the non-solvent is water or a mixture of water and at least one organic solvent, preferably in a mixing ratio of 1 to 4, more preferably of 1.2 to 2.8 wherein the at least one organic solvent is preferably isopropanol thereof.
  • non-solvent additionally comprises polyvinyl alcohol, preferably in an amount of from 0.01 to 1% by weight, preferably about 0.1% by weight, based on the total amount of non-solvent, includes.
  • the resulting nanoparticles of at least one cellulose ester in particular the nanoparticles of cellulose acetate butyrate, usually have a mean particle diameter of about 160 to 200 nm with a standard deviation of about 40 nm (measured with DLS, as described above).
  • the heat-sensitive recording material according to the invention can be prepared by conventional methods.
  • the heat-sensitive recording material according to the invention is produced by a process wherein on the at least one black or colored side of the carrier substrate, an aqueous suspension containing the starting materials of the thermoresponsive layer and having a solids content of about 15 to about 60 wt .-%, and wherein the aqueous suspension by coating process, which produce a curtain coater or a leveling coating (blade coater, doctor blade), applied and dried.
  • This method is particularly advantageous from an economic point of view.
  • the value of the solids content of about 15 wt .-% is exceeded, then the economy deteriorates because a large amount of water from the Coating must be removed by gentle drying in a short time, which adversely affects the coating speed. If, on the other hand, the value exceeds 60% by weight, then this only leads to an increased technical outlay in order to ensure the stability of the coating curtain during the coating process.
  • the heat-sensitive recording material according to the invention by means of a process in which the aqueous coating suspension is applied by the curtain coating coating method, preferably at an operating speed of the coating unit of at least about 400 m / min.
  • the so-called curtain-coating method is known to the person skilled in the art and is characterized by the following criteria:
  • a free-falling curtain of a coating dispersion is formed.
  • the coating dispersion in the form of a thin film is "poured" onto a substrate to apply the coating dispersion to the substrate
  • DE 10196052 TI discloses the use of the curtain coating process in the manufacture of information recording materials, including heat-sensitive recording materials.
  • the setting of the operating speed of the coater to at least about 400 m / min has both economic and technical advantages.
  • the operating speed is particularly preferably at least about 750 m / min, very particularly preferably at least about 1000 m / min and very particularly preferably at least about 1500 m / min. It was particularly surprising that even at the latter speed, the resulting heat-sensitive recording material 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 about 150 to about 800 mPas (Brookfield, 100 rpm, 20 ° C). If the value falls below about 150 mPas or exceeds the value of about 800 mPas, then this leads to a poor runnability of the coating on the coating unit. More preferably, the viscosity of the aqueous deaerated coating suspension is about 200 to about 500 mPas.
  • the surface tension of the aqueous application suspension can be from 25 to 60 mN / m, preferably from about 35 to about 50 mN / m (measured according to the static ring method according to Du Noüy, DIN 53914, 1997-07 ).
  • the dried thermoresponsive layer is subjected to a smoothing action. It is advantageous here to adjust the Bekk smoothness, measured to DIN 53107 (2000), to about 100 to about 1200 seconds, preferably to about 300 to about 700 seconds. Bekk smoothing of 100 to 300 sec are measured according to method A of DIN 53107 (2000) and Bekk smoothing of over 300 according to method B of DIN 53107 (2000).
  • the present invention also relates to a heat-sensitive recording material obtainable by the above method.
  • FIG. 1 shows light microscope photographs of a printed heat-sensitive recording material according to the invention.
  • Figure 2 shows an illustration of the opacities. These are the gray values of a horizontal line.
  • the laser power was 70%.
  • the gray value is a value between 0 and 255, with 255 reflecting a completely black pixel and 0 a completely white pixel.
  • An aqueous coating suspension was prepared by mixing 100 parts of cellulose acetate butyrate nanoparticles having a mean particle diameter of about 170 nm ( ⁇ 40 nm) in the presence of 0.1% polyvinyl alcohol, THF as a solvent, and a water / isopropanol mixture in the ratio of 1.2 to 2.8 as non-solvent as described above, mixed with 40 parts of polyvinyl alcohol, 5 parts of Styronal D 517 as binder, 15 parts of Sterocoll as a viscosity regulator and 3 parts of NaOH.
  • the coating formulation a ratio of 11.75% by weight of solids / liquid was selected. This value was chosen because the particles are present after production as ⁇ 15% by weight suspension.
  • the solids contents of the additives and coatings were determined using a dry balance.
  • the polyvinyl alcohol used is 84% saponified polyvinyl acetate (Mn 100,000 g / mol).
  • the sample containers were filled with 100 mg of cellulose acetate butyrate nanoparticles, the respective additives added, and the solids content (FG) adjusted to 11.75 wt% with distilled water. The formulation is then homogenized by Vortex shaker and ultrasonic bath.
  • thermoresponsive layer was 2.5 4 and 6 g / m 2 .
  • the coated substrates were cut in half with scissors.
  • One half of a substrate was tempered for 30 minutes in a drying oven at 70 ° C. in order to simulate simple drying conditions.
  • both samples were "printed” with a 30-watt CO 2 laser (parameter in Tab. 1). In each case 10 different amounts of energy (0.43 - 4.3 mJ / mm 2 ) were deposited and with every amount of energy 12 lines were written into the coating ("printed").
  • the evaluation was done with the open source image analysis program Image! The brightness has been set so that the brightest areas are not actually using the sensor. Based on the Gau values, relative opacities between the melted and non-treated sites could be calculated.
  • the paper strips of formulation 1 showed promising results, which are shown in FIG.
  • the patterns are macroscopically very homogeneous. With a laser power of 70%, sharp line profiles were already recognizable. Increasing the laser power to 80% reduces the distance between the individual lines.
  • FIG. 2 serves to illustrate the opacities. These are the gray values of a horizontal line. The relative opacity reached maximum values of up to 95% for PVA coatings. The thermal treatment showed no negative influence.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Paper (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

L'invention concerne un support d'impression thermosensible comprenant un substrat de support noir ou en couleur sur au moins un côté et une couche thermoréactive sur le ou les côtés noirs ou en couleur du substrat de support. La couche thermoréactive comprend des nanoparticules d'au moins un ester de cellulose. L'invention concerne un procédé de fabrication associé et un support d'impression thermosensible pouvant être obtenu selon ledit procédé.
EP19722558.4A 2018-05-14 2019-05-02 Revêtements en papier thermoréactifs à base de dérivés de cellulose Active EP3765303B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018111495.8A DE102018111495B4 (de) 2018-05-14 2018-05-14 Thermoresponsive Papierbeschichtungen auf Basis von Cellulosederivaten
PCT/EP2019/061187 WO2019219391A1 (fr) 2018-05-14 2019-05-02 Revêtements en papier thermoréactifs à base de dérivés de cellulose

Publications (2)

Publication Number Publication Date
EP3765303A1 true EP3765303A1 (fr) 2021-01-20
EP3765303B1 EP3765303B1 (fr) 2023-06-21

Family

ID=66440017

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19722558.4A Active EP3765303B1 (fr) 2018-05-14 2019-05-02 Revêtements en papier thermoréactifs à base de dérivés de cellulose

Country Status (7)

Country Link
US (1) US11975553B2 (fr)
EP (1) EP3765303B1 (fr)
CN (1) CN112004687B (fr)
DE (1) DE102018111495B4 (fr)
ES (1) ES2954503T3 (fr)
FI (1) FI3765303T3 (fr)
WO (1) WO2019219391A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021115909A1 (de) 2021-06-18 2022-12-22 Koehler Innovation & Technology Gmbh Wärmeempfindliche Aufzeichnungsmaterialien
DE102021133751A1 (de) 2021-12-17 2023-06-22 Koehler Innovation & Technology Gmbh Wärmeempfindliches Aufzeichnungsmaterial
KR20240036602A (ko) 2021-08-11 2024-03-20 쾰러 이노베이션 & 테크놀로지 게엠베하 감열성 기록 재료, 감열성 기록 재료를 탈색시키는 방법, 섬유상 재료 혼합물, 재생지를 제조하는 방법, 및 재생지
DE102021120941A1 (de) 2021-08-11 2023-02-16 Koehler Innovation & Technology Gmbh Wärmeempfindliches Aufzeichnungsmaterial
DE102021133333A1 (de) 2021-12-15 2023-06-15 Koehler Innovation & Technology Gmbh Bahnförmiges wärmeempfindliches Aufzeichnungsmaterial

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1051112B (de) * 1957-08-08 1959-02-19 Fritz Hellige & Co G M B H Fab Verfahren zur Herstellung waermeempfindlicher Registrierpapiere
US3031328A (en) * 1959-11-12 1962-04-24 Ludlow Corp Method and composition for waterresistant recording material
US3320089A (en) * 1964-03-09 1967-05-16 Judson Bigelow Inc Method of making blush coated recording sheet, coated sheet and coating composition
JPH0280288A (ja) 1988-09-19 1990-03-20 Honshu Paper Co Ltd 感熱記録体
US6043193A (en) * 1998-06-23 2000-03-28 Eastman Kodak Company Thermal recording element
DE10196052T1 (de) * 2000-04-11 2003-02-27 Mitsubishi Paper Mills Ltd Verfahren zur Herstellung eines Informationsaufzeichnungsmaterial und Beschichtungslösungen zur Verwendung in diesem Material
CN1705568A (zh) * 2002-10-02 2005-12-07 通用数据公司 热敏记录材料及其制备与使用方法
DE602005010134D1 (de) * 2004-03-03 2008-11-20 Ricoh Kk Reversibles wärmeempfindliches Aufzeichnungsmaterial, Bilderzeugungsvorrichtung und Bilderzeugungsverfahren
JP2006088396A (ja) * 2004-09-21 2006-04-06 Oji Paper Co Ltd 熱転写受容シート
US7425522B2 (en) * 2006-01-18 2008-09-16 Ricoh Company, Ltd. Thermosensitive recording material
US8101334B2 (en) 2008-02-13 2012-01-24 Ricoh Company, Ltd. Image processing method and image processing apparatus
US8054323B2 (en) * 2009-03-31 2011-11-08 Peters Daniel F Reveal substrates and methods of using same
JP2011168045A (ja) * 2010-01-11 2011-09-01 Rohm & Haas Co 記録材料
CN103635329B (zh) 2011-04-20 2016-08-17 罗门哈斯公司 记录材料
DE102013002297A1 (de) 2013-02-08 2014-08-14 Papierfabrik August Koehler Se Wärmeempfindliches Aufzeichnungsmaterial
CN104369564B (zh) * 2013-08-13 2019-06-11 罗门哈斯公司 具有改善的初始对比度的热记录材料
EP2993055B1 (fr) 2014-09-06 2019-04-03 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la chaleur en forme de bande doté d'une couche de protection
CN107107641B (zh) 2014-12-23 2020-04-03 三菱高新技术纸业欧洲有限公司 用于胶版印刷的热敏性记录材料

Also Published As

Publication number Publication date
FI3765303T3 (fi) 2023-09-12
CN112004687A (zh) 2020-11-27
DE102018111495A1 (de) 2019-11-14
ES2954503T3 (es) 2023-11-22
US11975553B2 (en) 2024-05-07
EP3765303B1 (fr) 2023-06-21
US20210213769A1 (en) 2021-07-15
DE102018111495B4 (de) 2020-04-09
WO2019219391A1 (fr) 2019-11-21
CN112004687B (zh) 2023-04-28

Similar Documents

Publication Publication Date Title
DE102018111495B4 (de) Thermoresponsive Papierbeschichtungen auf Basis von Cellulosederivaten
DE69637213T2 (de) Papier für die Tintenstrahlaufzeichnung, gemahlenes ausgefälltes Kalziumkarbonatpigment enthaltend
DE2529427C3 (de) Verfahren zum Herstellen kleiner Polymerkapseln
DE1939624C3 (de) Verfahren zur Herstellung von ölhaltigen Mikrokapseln
DE60207236T2 (de) Tintenstrahlaufzeichnungsmedium mit aminbehandeltem siliziumdioxid
DE3707627A1 (de) Aufzeichnungsblatt fuer tintenstrahldrucker
DE2225274C3 (de) Verfahren zur Herstellung von Mikrokapseln
EP3047068B1 (fr) Matériaux d'emballage, avec un revêtement barrier à base d'amidon et revêtement masse et procede de production de celui
DE2713312A1 (de) Verfahren zur herstellung von gegen wasser unempfindlichen staerkefasern
DE10033054C2 (de) Silicadispersion, Verfahren zu ihrer Herstellung und Verfahren zur Herstellung eines Tintenstrahl-Aufnahmematerials unter Verwendung derselben
EP0114973A2 (fr) Papier photographique résistant à l'eau
DE2531878C3 (de) Mikrokapseln und Verfahren zu ihrer Herstellung
CH666486A5 (de) Formulierung mit hohem feststoffgehalt zur beschichtung von fasrigen, bahnfoermigen produkten, beschichtungsverfahren und beschichtete produkte.
DE4426620A1 (de) Papierträger für den photographischen Druck
DE3131899A1 (de) Waermeempfindliches aufzeichnungsmaterial
DE1906149A1 (de) Streichmittel
DE2556017A1 (de) Streichmassen, damit gestrichene papiere und verfahren zur herstellung gestrichener papiere
EP1994220A1 (fr) Procede de fabrication de substrats peints une ou plusieurs fois
DE3044113A1 (de) Mikrokapseln enthaltende wachsmassen
EP0024602B1 (fr) Dispersions aqueuses, leur préparation et leur utilisation pour préparer des compositions de revêtement
WO2014121788A1 (fr) Matériau d'enregistrement thermosensible
DE2510919C3 (de) Papierstreichmassen und ihre Verwendung
DE2934390C2 (fr)
DE60103096T2 (de) Tintenstrahldruckverfahren
DE60014300T2 (de) Herstellungsverfahren einer stabilen Beschichtungszusammensetzung für ein mit Pigment beschichtetes Tintenstrahlaufzeichnungselement

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20201014

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HORN, MICHAEL

Inventor name: BIESALSKI, MARKUS

Inventor name: NAU, MAXIMILIAN

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230103

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: TECHNISCHE UNIVERSITAET DARMSTADT

Owner name: KOEHLER PAPER SE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230605

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502019008265

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1580670

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230715

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20230621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230921

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2954503

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20231122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231021

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231023

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231021

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502019008265

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20230621

26N No opposition filed

Effective date: 20240322