WO2023134835A1 - Papiers couchés comportant une couche de peinture semi-cristalline servant de matériau d'emballage - Google Patents

Papiers couchés comportant une couche de peinture semi-cristalline servant de matériau d'emballage Download PDF

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Publication number
WO2023134835A1
WO2023134835A1 PCT/DE2023/200013 DE2023200013W WO2023134835A1 WO 2023134835 A1 WO2023134835 A1 WO 2023134835A1 DE 2023200013 W DE2023200013 W DE 2023200013W WO 2023134835 A1 WO2023134835 A1 WO 2023134835A1
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Prior art keywords
weight
coated paper
coating color
lignin
range
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PCT/DE2023/200013
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German (de)
English (en)
Inventor
Kerstin BARTELS
Simon Trosien
Markus BIESALSKI
Markus WILDBERGER
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Koehler Innovation & Technology Gmbh
Technische Universitaet Darmstadt, Koerperschaft Des Oeffentlichen Rechts
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Publication of WO2023134835A1 publication Critical patent/WO2023134835A1/fr

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/22—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper

Definitions

  • the invention relates to a coated paper with a high barrier performance for use as a packaging material for food.
  • Packaging accounts for a large proportion of global plastic waste pollution, which is why the search for alternatives made from biodegradable materials is being driven forward.
  • Packaging materials for food often consist of plastics, for example polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE) and polypropylene (PP), since these have good barrier properties, low weight and high mechanical stability.
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • PE polyethylene
  • PP polypropylene
  • Paper-based packaging materials have many advantages over plastic materials, such as renewability, recyclability and compostability. However, their application is limited due to the often poor barrier properties and high sensitivity to moisture. In order to improve the barrier properties, the paper-based packaging material can be laminated with aluminum or petroleum-based polymers such as PE, EVOH and PVC derivatives. However, these coatings complicate waste sorting and therefore recycling, and reduce compostability. Therefore, the use of barrier layers based on naturally bio-based polymers or the replacement of the conventional metal or plastic-based layer is very desirable from an ecological point of view. Examples of natural polymers that have been tested for packaging applications are chitosan, hemicelluloses, microfibrillated cellulose and starch. However, many of the natural polymers are hydrophilic and the films made from these materials are often hygroscopic, resulting in a partial loss of their barrier properties at high humidity.
  • lignin has been used in papermaking.
  • WO 2021/191097 A1 describes a method for producing paper. This process includes a wet phase and a dry phase.
  • the wet phase involves making a fiber slurry with fibers in water, where the fibers are selected from the group of lignocellulose, hemicellulose and cellulose.
  • An additive comprising enzymatically oxidized lignin is added in the wet phase. This is intended to improve the moisture resistance of the paper, in particular the compressive strength in the presence of moisture.
  • a fatty acid such as stearic acid
  • lignin as a hydrophobic biopolymer, suggests itself for use as a barrier layer on paper, research is still poor.
  • a coating color layer based on lignin alone does not have sufficient barrier properties. For this reason, various attempts have been made in the prior art to improve the properties of lignin to such an extent that they remain sufficiently tight even in a humid environment, such as in food packaging.
  • the lignin esterified with the long-chain palmitic acid had better barrier properties against water vapor than the lignin esterified with lauric acid.
  • the best barrier performance was achieved with a layer of hardwood lignin esterified with palmitic acid.
  • DE 10 2017 108 577 A1 relates to coatings comprising at least one polymer and at least one crystallizable material and methods for their production.
  • the polymer should have a maximum viscosity of 10 12 mPa s at the melting point of the crystallizable material. In this way layers are obtained which are superhydrophobic and regenerable. However, these layers only have very low gas barrier properties.
  • the present invention is based, inter alia, on the surprising finding that the barrier effect of a coating color layer based on a natural polymer, for example lignin or lignin stearate, can be significantly increased by inducing semicrystallinity, ie both crystalline and amorphous areas. This is achieved by adding a crystallizable organic compound, for example stearic acid, to the coating color.
  • a coated paper according to the invention produced with this coating color layer has an adequate barrier effect for use in the food industry and is nevertheless biodegradable and recyclable.
  • the present invention relates to a coated paper, comprising a base paper and at least one semi-crystalline coating color layer applied directly or indirectly to the base paper and having amorphous areas and crystalline areas:
  • amorphous regions contain one or more natural polymers and/or one or more derivatives of natural polymers
  • the crystalline regions comprise one or more crystallizable organic compounds; and • wherein the permeability of the coated paper to at least one gas is reduced compared to the base paper.
  • the invention relates to a coating color for coating papers, containing at least one solvent, at least one crystallizable organic compound and at least one natural polymer and/or derivative of a natural polymer,
  • crystallizable organic compound is selected from fatty acids, hydroxy fatty acids or dicarboxylic acids or their esters, amides or salts;
  • the natural polymer is selected from polysaccharides such as alginate, agar-agar, cutin, suberin, lignin, cellulose, chitosan, and starch, hydrocarbons such as rubber or balata, proteins such as collagen, keratin, fibroin, nucleic acids, lipids, polylactide (PLA ), polyhydroxybutyrate (PHB), and polyhydroxyalconoate (PHA); and
  • solvent selected from water, tetrahydrofuran (THF), toluene, ethyl acetate, and alcohols.
  • the invention relates to a method for producing a coated paper with a base paper and a semi-crystalline coating color layer, comprising the steps: a) producing a coating color according to a second aspect by melt dispersion, high-pressure dispersion, or spray drying and subsequent mechanical dispersion of the components ; b) providing a base paper; c) application of the coating color to the base paper, and d) curing of the coating color with formation of the semi-crystalline coating color layer.
  • the invention relates to packaging for foodstuffs comprising the coated paper according to the first aspect.
  • Fig. 1 shows an elugram of Kraft lignin labeling the number average molar mass Mn and the weight average molar mass Mw.
  • Fig. 2 shows a 31 P-NMR spectrum of Kraft lignin.
  • Signal A internal standard
  • signal group B aliphatic and phenolic hydroxy groups
  • signal C carboxy group
  • Fig. 3 shows a 31 P-NMR spectrum of the lignin ester.
  • Signal A internal standard
  • signal group B hydroxy groups
  • signal group C carboxy groups.
  • FIG. 4 shows an IR spectrum of lignin stearate (bottom) in comparison with the educt Kraft lignin (top) and stearic acid (middle).
  • WD stands for "working distance” and refers to the distance between the objective of the scanning electron microscope and the sample being examined.
  • EHT stands for "high tension” and refers to the high voltage used to accelerate the electrons in the scanning electron microscope.
  • B) shows an enlargement of a 4 pL drop of water on the lignin stearate-stearic acid coating recorded with Dataphysics OCA35 including a tiltable stage under constant temperature and humidity (23 °C, 50 % relative humidity).
  • FIG. 9 shows a diagram of the roll-off angle of water droplets on the surface of a lignin stearate-stearic acid coating as a function of the droplet volume.
  • WVTR water vapor transmission rate
  • coating color refers to paints containing or consisting of binders, Additives and, if necessary, pigments or matrix pigments that are applied (“coated") to the paper surface with special coating devices for surface finishing or modification of a base paper. Papers made in this way are referred to as "coated papers”.
  • a “coated paper” is understood to mean a base paper which comprises one or more layers applied by coating, ie coating color layers. Possible layers of such a coated paper substrate are functional layers and structure-forming layers (such as leveling layers for smoothing the surface).
  • coating color is used as a generic term for all spreadable coating compositions, preparations and/or solutions in the paper industry for treating, modifying or finishing a paper surface.
  • Coating color layer means the coating color that has been applied to the base paper and has hardened.
  • Paper is a flat material consisting essentially of fibers of plant origin and formed by dewatering a fiber suspension on a wire. The resulting fiber fleece is compacted and dried.
  • the two-dimensional materials “cardboard” and “cardboard” produced in the same way are also subsumed under paper. Distinguishes between paper, board and paperboard only on the basis of basis weight, where paperboard has a grammage greater than 600 g/ m2 , paperboard has a grammage greater than 150 and less than or equal to 600 g/ m2 and paper has a grammage of less than or equal to 150 g/m 2 .
  • semicrystalline and “partially crystalline” generally refer to a solid and in particular a layer which contains both crystalline and amorphous areas (domains).
  • a semi-crystalline layer usually contains a large number of individual amorphous and crystalline areas.
  • crystallinity is synonymous with "degree of crystallinity” or “degree of crystallization” and describes that portion of a partially crystalline solid that is crystalline.
  • the most common methods for determining the degree of crystallization at Polymers are density measurement, differential scanning calorimetry (DSC), X-ray diffraction (XRD), IR spectroscopy or NMR spectroscopy. The measured value determined depends on the measurement method used. According to the invention, the crystallinity of the coating color is determined by means of XRD measurements.
  • natural polymer synonymous with “biogenic biopolymer” is a polymer that is synthesized in the cell of a living being.
  • the natural polymer is therefore also biodegradable.
  • the natural polymer is in particular a natural polymer within the meaning of Directive (EU) 2019/904 of the European Parliament and of the Council of June 5, 2019 on reducing the impact of certain plastic products on the environment (see Article 3 No.1 Exclusion in the definition of plastic).
  • derivatives of natural polymers is understood to mean polymers produced by the further processing of biopolymers. These are also referred to as chemically modified polymers. Examples of derivatives of natural polymers are lignin derivatives, e.g., lignin esters, cellulose derivatives and starch derivatives.
  • a “crystallizable organic compound” is to be understood as meaning those organic compounds which attach themselves to a crystallization nucleus in a regular, substance-specific form and can form a nucleus or crystal.
  • the “melting temperature” (T m ) is the temperature at which a substance melts, ie changes from the solid to the liquid state of aggregation.
  • the melting temperature for polymers and crystallizable materials can be determined using differential scanning calorimetry according to DIN EN ISO 11357-3: 2013. A heating or cooling rate of 10 K/min is preferably used.
  • the "glass transition temperature” is the temperature at which polymers or plastics (although only fully or partially amorphous polymers) change from the liquid or rubber-elastic, flexible state to the glassy or hard-elastic, brittle state, it is therefore also called “softening point". At this temperature, the polymer has a viscosity of 1012 mPas. For polymers that do not have a melting temperature, the glass transition temperature takes the place of the melting temperature.
  • the glass transition temperatures can be determined, for example, by means of dynamic differential thermal analysis (differential scanning calorimetry DSC) according to DIN EN ISO 11357-2: 2014.
  • the “contact angle” of a drop of liquid on a surface is understood to mean the angle that the line of intersection between the base of the drop and the surface forms with the horizontal. It is measured in degrees and depends on various factors such as the surface tension of the liquid and the properties of the surface.
  • roll-off angle is understood to mean the angle of inclination of a surface at which a drop rolls off it. It is usually used to characterize superhydrophobic surfaces with a very high contact angle, where the droplet is approximately spherical. With smaller contact angles, a drop can also move from the surface, but is usually first deformed and then slides over the surface. With a roll-off angle of 180°, the water drop does not roll off, but sticks to the coating color layer, even if the drop hangs down.
  • surfaces with contact angles of 145° or more with respect to water are referred to as “superhydrophobic”.
  • superhydrophobic surfaces are characterized by a roll-off angle of less than 10°.
  • the present invention relates to a coated paper, comprising a base paper and at least one semi-crystalline coating color layer applied directly or indirectly to the base paper and having amorphous areas and crystalline areas: • wherein the amorphous regions contain one or more natural polymers and/or one or more derivatives of natural polymers;
  • crystalline regions comprise one or more crystallizable organic compounds
  • the permeability for at least one gas with the same total applied amount is lower than the permeability of a coated paper with the same base paper and one coating color layer made of the natural polymer or its derivative and one coating color layer made of the crystallizable organic compound.
  • the permeability of the coated paper is reduced for at least one compared to the base paper.
  • This can be oxygen (O2), nitrogen (N2), carbon dioxide (CO2), methane (CH4), hydrogen (H2), water vapor or a mixture thereof, for example air.
  • O2 oxygen
  • N2 nitrogen
  • CO2 carbon dioxide
  • CH4 methane
  • H2 hydrogen
  • WVTR water vapor transmission rate
  • the barrier performance or permeability is directly dependent on the crystallinity in the system according to the invention.
  • this effect is based on the embedding of crystallites formed from the crystallizable component in an amorphous matrix of natural polymer.
  • the crystallites are impermeable to gases, especially polar molecules such as water in the vapor phase, due to the high packing density.
  • the gases In order to permeate through the thin, semi-crystalline coating color layer, the gases have to take a further route “around the crystallites”, which directly reduces the permeation coefficient and the semi-crystalline layer thus acts as a water vapor barrier.
  • This theory behind the effect is also supported by the computer-aided model described by Müller-Plathe for diffusion through semi-crystalline and filled polymers (see Müller-Plate habilitation thesis ETH Zurich 1993, page 67 ff.).
  • Pure layers of natural polymer eg lignin
  • Pure layers of crystallizable organic Connection Stearic acid layers which have open areas due to free volumes between the crystallite structures, through which gases can permeate.
  • the permeability, in particular the WVTR, can thus be adjusted for each system according to the invention by selecting the crystallinity. Below 10% crystallinity, a semi-crystalline system typically has little measurable impact on the WVTR of the coated paper compared to a comparable non-crystalline layer. According to one embodiment, the crystallinity of the semi-crystalline coating color layer is in the range from 10% to 90%. A crystallinity above 90% does not generally lead to any change in the barrier effect, but to various structural disadvantages, such as disrupting the integrity of the film. For example, the crystallinity can be 10%, 12%, 14%, 16%,
  • the crystallinity ranges from 10% to 40%. A slight reduction in gas permeability can still be achieved above 40%. In a particularly preferred embodiment, the crystallinity ranges from 15% to 25%.
  • the coating color that is used to form the semi-crystalline coating color layer preferably contains no crystalline elements, and the crystallizable organic compound is also preferably not present in the coating color in crystalline form.
  • the fatty acid molecules may also be present in crystalline form to a small extent. Especially when the fatty acid melts in the presence of water and then disperses and cools. This state is referred to herein as being essentially non-crystalline.
  • the crystallizable organic compound in the coating color is essentially in non-crystalline form. It is therefore not a coating color comprising crystalline fillers in amorphous binders.
  • Such a coating color layer is also referred to as a granular crystalline coating color layer to distinguish it from the semicrystalline coating color layer according to the invention.
  • the semi-crystallinity according to the invention is therefore not granular crystallinity.
  • the crystallinity preferably only occurs with the application of the coating color layer.
  • the form crystalline areas during application of the coating color to the base paper In a further embodiment, the crystalline areas form during the hardening of the coating color. According to one embodiment, the crystalline areas form both during the application of the coating color to the base paper and during the curing of the coating color.
  • a coated paper with a high barrier performance, in particular a very low WVTR, can be achieved with the coating color according to the invention.
  • the WVTR is not more than 40 g m- 2 d 1 for a coating color basis weight of 10 ⁇ 1 gm 2 .
  • the WVTR of the coated paper according to the invention can be, for example, 40 g be.
  • a WVTR of no more than 20 g nr 2 d- 1 , or even no more than 10 gm 2 d- 1 can be achieved.
  • the melting temperature T m of the at least one crystallizable organic compound is preferably lower than the glass transition temperature T g of the at least one natural polymer and/or the at least one derivative of a natural polymer.
  • Example 9 also in a system according to the invention with the derivative of a natural polymer, namely lignin stearate, and a fatty acid, the use of a fatty acid such as suberic acid with a melting temperature which is higher than the glass transition temperature of the lignin stearate leads to significantly poorer results Results in water vapor barrier performance than using a fatty acid such as stearic acid with a melting temperature lower than the glass transition temperature of the lignin stearate.
  • a fatty acid such as suberic acid with a melting temperature which is higher than the glass transition temperature of the lignin stearate
  • the melting temperature Tm of the at least one crystallizable organic compound should be at least 1°C lower than the glass transition temperature Tg of the at least one natural polymer and/or the derivative of a natural polymer.
  • the melting temperature Tm of the crystallizable organic compound may be 1°C, 2°C, 3°C, 4°C, 5°C, 7°C, 10°C, 12°C, 15°C, 17°C, 20°C, 22°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75° C, or 80 °C lower than the glass transition temperature T g of the at least one natural polymer and/or the derivative of a natural polymer.
  • the melting temperature Tm of the at least one crystallizable organic compound is at least 5°C lower than the glass transition temperature Tg of the at least one natural polymer and/or the derivative of a natural polymer. According to one embodiment, the melting temperature Tm of the at least one crystallizable organic compound is at least 10°C lower than the glass transition temperature Tg of the at least one natural polymer and/or the derivative of a natural polymer. According to one embodiment, the melting temperature Tm of the at least one crystallizable organic compound is at least 20°C lower than the glass transition temperature Tg of the at least one natural polymer and/or the derivative of a natural polymer.
  • the melting temperature T m of the at least one crystallizable organic compound is at least 30° C. lower than the glass transition temperature T g of the at least one natural polymer and/or the derivative of a natural polymer.
  • the melting temperature of stearic acid is about 40°C below the glass transition temperature Tg of lignin stearate.
  • the melting temperature Tm of the at least one crystallizable organic compound is at least 50°C lower than the glass transition temperature Tg of the at least one natural polymer and/or the derivative of a natural polymer.
  • the surface of the coating color layer is not superhydrophobic.
  • the coating color layer therefore has a contact angle of no more than 150° with respect to water.
  • the contact angle can be, for example, 80°, 85°, 90°, 95°, 100°, 105°, 110°, 115°, 120°, 125°, 130°, 135°, 140°, or 145°. Even with over 145°, surfaces are still considered superhydrophobic. Accordingly, the contact angle is preferably not more than 145°. According to one embodiment, the contact angle is no more than 130°. According to one embodiment, the contact angle is no more than 115°.
  • the coating color layer preferably has a roll-off angle of more than 10° with respect to a drop of water with a volume of 4 pL.
  • the roll-off angle can be, for example, 10°, 15°, 20°, 25°, 30°, 35°, 40°, 45°, 50°, 55°, 60°, 65°, 70°, 75°, 80°, 85 °, 90°, 95°, 100°, 105°, 110°, 115°, 120°, 125°, 130°, 135°, 140°, 145°, 150°, 155°, 160°, 165°, 170°, 175°, 180°.
  • the roll-off angle is more than 20°.
  • the roll-off angle is more than 40°.
  • the roll-off angle is more than 60°.
  • the proportion of the crystallizable organic compounds, based on the total mass of the coating color layer is in the range from 1 to 60% by weight. Below 1% by weight, no measurable crystallinity can be generated, but the entire coating color layer remains amorphous. If more than 60% crystallizable organic compound is used, the film becomes too inhomogeneous and holes can form, which limit the barrier performance.
  • the crystalline organic compound can be a proportion of 1% by weight, 2% by weight, 4% by weight, 5% by weight, 6% by weight, 8% by weight, 10% by weight, 12% by weight, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt% -%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 46 wt% , 48% by weight, 50% by weight, 52% by weight, 54% by weight, 56% by weight, 58% by weight, or 60% by weight in the coating color layer.
  • the proportion of the crystalline organic compound is in the range from 3 to 50% by weight.
  • the proportion of the crystalline organic compound is in the range from 5 to 40% by weight.
  • the proportion of the crystalline organic compound is in the range from 25 to 35% by weight.
  • the crystallizable organic compounds are preferably at least partially chain hydrocarbons, which are preferably branched.
  • the addition of similar chains of such chain-like hydrocarbons allows crystal or crystallite formation.
  • crystallizable organic compounds that can be used according to the invention are fatty acids, fatty acid amides, fatty acid esters, salts of fatty acids, hydroxy fatty acids, hydroxy fatty acid amides, hydroxy fatty acid esters, salts of hydroxy fatty acids, or dicarboxylic acids and their dicarboxylic esters, dicarboxylic acid amides or salts of dicarboxylic acids.
  • dicarboxylic acids which can be used according to the invention are tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, icosanedioic acid or docosanedioic acid.
  • the crystallizable organic compound is preferably not starch.
  • the crystallizable organic compound is preferably not suberic acid, especially when the natural polymer is lignin or lignin stearate.
  • the fatty acid used as the crystallizable organic compound can be a saturated or unsaturated fatty acid having 12 to 40 carbon atoms. Examples of saturated fatty acids are lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, lacceric acid, geddic acid.
  • unsaturated fatty acids are myristoleic acid, palmitoleic acid, margaroleic acid, petroselinic acid, oleic acid (OA), elaidic acid, vaccenic acid, gadoleic acid, gondoic acid, cetolic acid, erucic acid, and nervonic acid.
  • unsaturated fatty acids are linoleic acid (LA), a-linolenic acid (ALA), y-linolenic acid (GLA), calendulic acid, punicic acid, alpha-eleostearic acid, beta-eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid (timnodonic acid, EPA), docosadienoic acid, docosatetraenoic acid (adrenic acid, ADA), docosapentaenoic acid, (clupa(no)donic acid), (DPA-3) docosahexaenoic acid (cervonic acid, clupanodonic acid, DHA) and tetracosahexaenoic acid (nisic acid).
  • LA linoleic acid
  • ALA a-linolenic acid
  • GLA y-linolenic acid
  • the fatty acid used as the organic compound to crystallize has 16 to 18 carbon atoms and 0 or 1 double bond.
  • the fatty acid is selected from margaric acid, stearic acid, palmitic acid, linoleic acid, ⁇ -linolenic acid, ⁇ -linolenic acid.
  • the crystallizable organic compound is stearic acid or its amide or salt.
  • Fatty acid salts according to the invention are chromium(III) chloride complexes with fatty acids, and aluminium, calcium, sodium, potassium and ammonium salts.
  • Preferred fatty acid salts are monovalent salts of sodium, potassium or ammonium ions.
  • the at least one crystallizable organic compound can be present in the coating color as a fatty acid mixture or wax.
  • suitable waxes include carnauba wax, candelilia wax, beeswax and Japan wax.
  • the fatty acid mixture is a mixture of stearic acid, palmitic acid, oleic acid, linoleic acid and/or linolenic acid.
  • fatty acid mixtures are a mixture of stearic acid, palmitic acid and oleic acid, a mixture of stearic, linoleic and linolenic acids, a mixture of stearic, palmitic and linoleic acids, a mixture of stearic, palmitic and linolenic acids, a mixture of stearic, oleic and linoleic acids, a mixture of stearic, oleic and linolenic acids, a mixture from stearic acid, linoleic acid and linolenic acid.
  • the proportion of the natural polymers or their derivatives can be in the range from 40 to 99% by weight. Only one polymer or its derivative can be used, but also mixtures of natural polymers, mixtures of derivatives of natural polymers or mixtures of natural derivatives and derivatives of natural polymers. Without wishing to be bound by theory, the natural polymers or their derivatives form the amorphous areas on the one hand and are involved in the formation of the crystalline areas on the other. It is assumed that the natural polymers form the amorphous matrix in which the crystalline areas are embedded. The proportion of the natural polymers depends on the proportion of the crystallizable organic compound(s) and the presence of other possible components.
  • the natural polymers or their derivatives can have a proportion of 40% by weight, 42% by weight, 44% by weight, 46% by weight, 48% by weight, 50% by weight, 52% by weight -%, 54 wt%, 56 wt%, 58 wt%, 60 wt%, 62 wt%, 64 wt%, 66 wt%, 68 wt% , 70 wt%, 72 wt%, 74 wt%, 76 wt%, 78 wt%, 80 wt%, 82 wt%, 84 wt%, 86 wt% -%, 88% by weight, 90% by weight, 92% by weight, 94% by weight, 96% by weight, 98% by weight, or 99% by weight.
  • the proportion of the natural polymers is in the range from 50 to 95% by weight. According to one embodiment, the proportion of the natural polymers is in the range from 60 to 90% by weight. According to one embodiment, the proportion of the natural polymers is in the range from 65 to 75% by weight.
  • Natural polymers that can be used according to the invention are, for example, hydrocarbons such as rubber or balata, proteins such as collagen, keratin, fibroin, nucleic acids, polysaccharides such as alginate, agar-agar, cutin, suberin, lignin, cellulose, chitosan, and starch, lipids, polylactide (PLA) , polyhydroxybutyrate (PHB), and polyhydroxyalconoate (PHA).
  • hydrocarbons such as rubber or balata
  • proteins such as collagen, keratin, fibroin, nucleic acids, polysaccharides such as alginate, agar-agar, cutin, suberin, lignin, cellulose, chitosan, and starch
  • lipids such as polylactide (PLA) , polyhydroxybutyrate (PHB), and polyhydroxyalconoate (PHA).
  • Derivatives according to the invention are cellulose derivatives such as methyl cellulose (MC) and hydroxypropylmethyl cellulose (HPMC), methyl hydroxyethyl cellulose (MHEC), starch derivatives such as methylated starch, ethylated starch; Hydroxyethyl starch, hydroxypropyl starch, carboxymethyl starch, starch formate, starch acetate, starch propionate, or starch butyrate, suberin derivatives, cutin derivatives, or lignin derivatives. It is believed that these natural polymers and their derivatives are capable of forming an amorphous matrix around a crystallizable organic compound.
  • the crystallizable organic compound is preferably not identical to the natural polymer or its derivative. Consequently, the crystalline and amorphous areas of the coating color layer according to the invention are not just different states of a substance.
  • the fatty acids are considered absolutely harmless for the human organism and are listed under the designation E 570 on the list of ingredients for food, so they are suitable for food ("dual-use substance").
  • E 570 on the list of ingredients for food, so they are suitable for food ("dual-use substance").
  • the natural polymer is suberin.
  • Suberin is a plant biopolymer that is embedded in cell walls. Suberinized cells are found both in the secondary closure tissue and in subterranean plant organs. Suberin is named after the cork oak tree (Quercus subet. Suberin can be divided into two different domains: a polyphenolic and a polyaliphatic domain. Dicarboxylic acids, hydroxy acids, long-chain fatty acids and hydroxycinnamic acids were found in the polyaliphatic fraction. Current research also provides evidence that Glycerol is also a very prominent monomer of the compound. The phenolic part shows a similarity to lignin. However, the proportion of monolignols is significantly lower than that of lignin.
  • the natural polymer is lignin.
  • Lignin is a high-molecular, aromatic substance that fills the spaces between the cell membranes in woody plants and turns them into wood. Lignin can be regarded as a higher-molecular (MR approx. 5000 to 10000) derivative of phenylpropane which, depending on the type of wood, is composed of structures which can be traced back to coumaryl alcohol, coniferyl alcohol or sinapyl alcohol.
  • the lignin of different types of wood or plants differs in the percentage of alcohol.
  • the components network with each other in a variety of ways (ether and CC bonds) and thus form a three-dimensional network.
  • the lignin of different wood and plant species also differs in the proportion of alcohols or the phenyl residues derived from them: softwood lignin contains predominantly coniferyl units (about 90%), which have a guaiacyl residue (3-methoxy -4-hydroxy-phenyl radical) and is therefore referred to as G-lignin.
  • Hardwood lignin contains varying proportions of guaiacyl residues and sinapyl elements containing a syringyl residue (3,5-methoxy-4-hydroxy-phenyl residue).
  • the syringyl content can be between 5 and 65 percent, the resulting lignins are called GS lignins.
  • the lignin of partially woody grasses and other monocots is characterized by a high proportion of about 15 to 35 percent cumaryl elements, which form the para-hydroxyphenylpropane, along with an equal amount of syringyl and a guaiacyl proportion of 50 to 70 percent that form HGS lignins
  • the lignin can be obtained from conifers, deciduous trees, grass plants or annual plants. According to one embodiment, the lignin is obtained from softwoods. According to a further embodiment, it is lignin made from deciduous trees.
  • the lignin is obtained from softwoods using the Kraft process. These methods are described in Nitz et al. summarized in 2001. According to one embodiment, the lignin is obtained from hardwoods using the Kraft process.
  • the derivative of a natural polymer is an ester of a natural polymer. Esters of natural polymers which are suitable according to the invention are cellulose esters, starch esters, cutin esters, suberin esters and lignin esters. According to one embodiment, it is an ester of lignin and one or more fatty acids, hydroxy fatty acids or dicarboxylic acids.
  • the acid used for the esterification of the lignin preferably has a similar chain length and degree of branching as the acid used as the crystallizable organic compound.
  • the chain length of the two acids should not differ by more than 8 carbon atoms.
  • the chain length preferably differs by no more than 5 carbon atoms.
  • the difference in chain length is particularly preferably not more than 3 carbon atoms.
  • the number of double bonds, i.e. the degree of saturation should match between the acid used for the esterification of the lignin and the acid used as the crystallizable organic compound.
  • the coating color or the coating color layer contains an ester of a natural polymer, the fatty acid being identical to at least one fatty acid used as a crystallizable organic compound.
  • the selection of identical fatty acids offers the best conditions for the formation of the crystals in the semi-crystalline coating color layer.
  • the coating color or the coating color layer contains a lignin fatty acid ester, the fatty acid being identical to at least one fatty acid used as a crystallizable organic compound. Another advantage of using identical fatty acids is that the excess fatty acid that did not react during the esterification can be used. This saves one process step.
  • the crystallizable organic compound is stearic acid and the natural polymer derivative is lignin stearate.
  • the synthesis of the ester of the natural polymer can be carried out according to the principle of a Schotten-Baumann esterification (see example 2). Suitable reaction conditions are known to those skilled in the art and can be found in Example 2.
  • the lignin stearate can be obtained by reacting stearic acid chloride with Kraft lignin.
  • the lignin stearate used according to the invention to produce the coated paper can have an esterification number of at least 40%.
  • the esterification number can be, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%. According to the embodiment, the esterification number is at least 90%.
  • the lignin stearate preferably has a softening point Tg in the range from 70 to 140.degree. Above 140 °C, there might be problems in the technical application, since the processing (melt dispersion, drying and filming) would probably be problematic. Below about 70 °C, the matrix can still remain too soft after drying and, for example, when the paper webs are rolled up, the coating can “stick” and later detach when the webs are unwound.
  • the temperature can be 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 120°C, 125°C, 130° C, 135 °C or 140 °C. Even more preferably, the lignin stearate has a softening point Tg in the range of 120 to 140°C.
  • the coating color layer can contain one or more other ingredients, for example a protective colloid or a filler.
  • Protective colloids are particularly suitable for keeping the particles stable in aqueous dispersion and thus enabling the paper to be coated homogeneously.
  • Suitable protective colloids are polyvinyl alcohol, polysorbates, PEG alkoxylates and sorbitan fatty acid esters (SPAN).
  • Suitable fillers are in particular pigments such as nanoclay. Nanoclay is used as an accelerator for crystallization.
  • Both the natural polymer used or its derivative and the crystallized organic compound can contain impurities that are caused by extraction or production.
  • impurities are, for example, non-esterified lignin polymers, but also polysaccharides such as celluloses and xylans. These impurities preferably make up only a very small part of the coating color and thus of the resulting coating color layer.
  • the proportion of impurities is in the Coating color layer based on the total mass of the coating color layer below 1% by weight.
  • the coating color does not contain any synthetic polymer that is petroleum-based and non-biodegradable.
  • Coated paper is biodegradable due to the materials present in the coating color layer.
  • Biodegradability refers to the ability of organic chemicals to be broken down biologically, i.e. by living beings or their enzymes. In the ideal case, this chemical metabolism proceeds completely up to mineralization, but it can also stop in the case of transformation products that are stable in degradation.
  • the guidelines for the testing of chemicals from the OECD, which are also used in the context of chemical approval, are generally recognised.
  • the tests of the OECD test series 301 (A-F) demonstrate rapid and complete biodegradation (ready biodegradability) under aerobic conditions. Different test methods are available for readily or poorly soluble as well as for volatile substances.
  • Biodegradable or “biodegradable” in the sense of the present invention refers to papers that have a biodegradability measured according to OECD 301 F of at least 40% or measured according to OECD 302 C (MITI-II test) of at least 20% and thus have a inherent or fundamental degradability. This corresponds to the limit value for the OECD 302 C according to "Revised Introduction to the OECD Guidelines for testing of Chemicals, Section 3, Part 1 , dated 23 March 2006". From a limit value of at least 60% measured according to OECD 301 F, microcapsule walls are also referred to as rapidly biodegradable.
  • the coated paper has ready biodegradability according to OECD 301.
  • the coated paper is recyclable. Paper recycling is the dissolving and processing of waste paper, used cardboard and cardboard in plants of the paper industry with the aim of producing new paper, cardboard and cardboard from it. To a small extent, waste paper pulp is first produced as pulp from the recovered paper, which is only later used for Production of new paper is used. Ink removal or deinking is the key process in paper recycling to remove ink from printed waste paper. The evaluation of the recyclability can be carried out with the INGEDE method 11, for example.
  • the coated paper according to the invention achieves a deinkability score of over 50 using the INGEDE method 11. The deinkability score is preferably over 70.
  • the coated paper can be approved for direct or indirect food contact.
  • it is suitable for approval in accordance with the guidelines of the European Food Safety Authority.
  • the base paper has a basis weight of less than 150 g rrr 2
  • the basis weight can be, for example, 150 g rrr 2 , 145 g rrr 2 , 140 gm 2 , 135 gm 2 , 130 gm 2 , 125 gm 2 , 120 gm 2 , 115 gm 2 , 110 gm 2 , 105 gm 2 , 100 gm 2 , 95 g nr 2 , 90 g nr 2 , 85 g nr 2 , 80 g m- 2 , 75 g nr 2 , 70 g nr 2 , 65 g m- 2 , 60 g nr 2 , 55 g nr 2 , 50 g nr 2 , 45 g nr 2 , 40 g m- 2 , 35 gm 2 or 30 gm 2 .
  • the basis weight is below 100 g
  • the coated paper can contain further layers in addition to the semi-crystalline coating color layer.
  • the coated paper contains a further layer selected from a coating color, an ink, a sealing medium and an adhesive.
  • the further layer can be arranged on the semi-crystalline coating color layer, between base paper and semi-crystalline coating color layer or on the side of the base paper opposite the semi-crystalline coating color layer.
  • the semi-crystalline coating color layer can therefore be applied directly to the base paper.
  • the semi-crystalline coating color layer is in direct contact with the base paper. Indirect application means that there are one or more layers between the coating color and the base paper.
  • Additional layers can, in particular, further reduce the permeability of the coated paper for at least one gas compared to the base paper or form barriers for liquids or viscous substances such as fats, oils, hydrocarbons.
  • a further layer can in particular: a) comprise at least one hydrophobic polymer, eg based on a polyacrylate, a styrene-Zbutadiene copolymer and/or a polyolefin b) comprise at least one hydrophilic polymer, eg based on a polyvinyl alcohol c) comprise at least one inorganic pigment , eg a platelet-shaped pigment, eg a layered silicate such as kaolin, d) comprise at least one inorganic pigment and a binder, e) comprise amorphous and crystalline areas, eg the coating color composition according to the invention, f) contain or consist of substances which are selected from the group lipophilic substances, paraffins, in particular hard paraffins, waxes, in particular microcrystalline waxes, waxes based on vegetable oils or fats, waxes based on animal oils or fats, vegetable waxes, animal waxes, low molecular weight polyolefins
  • substances according to point e) above for example to prevent or reduce the transfer of substances from underlying layers to a food, in particular a fatty food, h) comprise or consist of at least one metal, eg aluminum, gold, and/or a metal oxide, eg aluminum oxide, in particular be a metallized layer, i) be at least hot- or cold-sealable, j) at least comprise its adhesive, k) at least comprise or consist of a thermoplastic material, in particular as a heat-sealable material.
  • the base paper can be a base paper coated on one or both sides or an uncoated base paper.
  • coated base paper In the case of coated base paper, the surface is finished with a coating color containing a binder. Coating color is used as the material for the binder application, the main component of which can be starch, starch derivatives, chalk, kaolin, casein or plastic dispersion. This gives the base paper a more closed, smoother and more stable surface.
  • uncoated base paper can also be surface-treated and contain up to 5 g/m 2 of pigments.
  • the coated paper has a width-related breaking strength in the fiber direction in the range from 3.0 to 6.0 kN-rrr 1 .
  • the width-related breaking force in the fiber direction can be, for example, 3.0 kN-rrr 1 , 3.2 kN-rrr 1 , 3.4 kN-rrr 1 , 3.5 kN-rrr 1 , 3.6 kN-rrr 1 , 3.8 kN-rrr 1 , 4.0 kN-rrr 1 , 4.2 kN nr 1 , 4.4 kN nr 1 , 4.5 kN nr 1 , 4.6 kN nr 1 , 4.8 kN nr 1 , 5, 0 kN nr 1 , 5.2 kN-rrr 1 , 5.4 kN-rrr 1 , 5.5 k
  • the broad-based breaking strength in the fiber direction is in the range from 3.5 to 5.5 kN rrr 1 . According to one embodiment, the broad-based breaking strength in the fiber direction is in the range of 4.0 to 5.0 kN rrr 1 .
  • the induced semi-crystallinity according to the invention was achieved, for example, with a coating color containing a fatty acid as a crystallizable organic compound in combination with the derivative of a natural polymer, in particular lignin. Consequently, according to a second aspect, the invention relates to a coating color for coating papers, containing at least one solvent, at least one crystallizable organic compound and at least one natural polymer and/or derivative of a natural polymer.
  • the crystallizable organic compound is preferably selected from fatty acids, hydroxy acids or dicarboxylic acids or their esters, amides or salts. Furthermore, the crystallizable organic compound is present in the coating color in non-crystalline form. Since the coating color is the starting material for the formation of the coating color layer, the definitions of the crystallizable organic compound in the first aspect of the invention also apply here.
  • the natural polymer is selected in particular from hydrocarbons such as rubber or balata, proteins such as collagen, keratin, fibroin, nucleic acids, polysaccharides such as alginate, agar-agar, cutin, suberin, lignin, cellulose, chitosan, and starch, lipids, polylactide (PLA) , polyhydroxybutyrate (PHB), and polyhydroxyalconoate (PHA).
  • hydrocarbons such as rubber or balata
  • proteins such as collagen, keratin, fibroin, nucleic acids, polysaccharides such as alginate, agar-agar, cutin, suberin, lignin, cellulose, chitosan, and starch
  • lipids such as polylactide (PLA) , polyhydroxybutyrate (PHB), and polyhydroxyalconoate (PHA).
  • PHA polylactide
  • PHB polyhydroxybutyrate
  • PHA polyhydroxyalcono
  • the coating color also contains at least one solvent.
  • Suitable solvents are water, tetrahydrofuran (THF), toluene, ethyl acetate, and alcohols such as ethanol or isopropanol.
  • the solvent is preferably water.
  • At least one fatty acid in the ester of the natural polymer, in particular in the lignin ester, is identical to at least one fatty acid used as a crystallizable organic compound.
  • the crystallizable organic compound is stearic acid and the natural polymer derivative is lignin stearate.
  • the proportion of natural polymers and/or their derivatives in the coating color differs from the proportion in the coating color layer.
  • the proportion of natural polymers and/or their Derivatives based on the total mass of the coating color in the range from 6 to 30% by weight.
  • the proportion can be, for example, 6% by weight, 8% by weight, 10% by weight, 12% by weight, 14% by weight, 16% by weight, 18% by weight, 20% by weight -%, 22%, 24%, 26%, 28%, or 30% by weight.
  • the proportion is in the range from 8 to 25% by weight.
  • the proportion is in the range from 15 to 25% by weight.
  • the proportion of the crystallizable organic compounds, based on the total mass of the coating color is in the range from 2 to 15% by weight.
  • the proportion can be, for example, 2% by weight, 4% by weight, 6% by weight, 8 10%, 12%, 13%, 14%, or 15% by weight.
  • the proportion is in the range from 4 to 12% by weight.
  • the proportion is in the range from 5 to 8% by weight.
  • the proportion of the solvent, based on the total mass of the coating color is in the range from 60 to 95% by weight.
  • the proportion can be, for example, 60% by weight, 62% by weight, 64% by weight, 66% by weight, 68% by weight, 70% by weight, 72% by weight, 74% by weight -%, 76 wt%, 78 wt%, 80 wt%, 82 wt%, 84 wt%, 86 wt%, 88 wt%, 90 wt% 92%, 94% or 95% by weight.
  • the proportion is in the range from 70 to 90% by weight. In one embodiment, the proportion ranges from 75 to 85% by weight.
  • the proportion of polymer is preferably in the range from 6.5% by weight to 7.5% by weight and the proportion of crystallizable organics Compound in the range of 2.5% to 3.5% by weight.
  • the proportion of polymer is preferably in the range from 9.8% by weight to 11.3% by weight and the proportion of crystallizable organics Compound in the range of 3.8% to 5.3% by weight.
  • the proportion of polymer is preferably in the range from 16.3% by weight to 18.8% by weight and the proportion of crystallizable organics Compound in the range of 6.3% to 8.8% by weight.
  • the proportion of polymer is preferably in range from 16.3% to 18.8% by weight and the proportion of crystallizable organic compound in the range from 6.3% to 8.8% by weight.
  • the proportion of polymer is preferably in the range from 26.0% by weight to 30.0% by weight and the proportion of crystallizable organics compound in the range of 10.0% to 14.0% by weight.
  • the invention relates to a method for producing a coated paper with a base paper and a semi-crystalline coating color layer, comprising the steps: a) producing a coating color according to a second aspect by melt dispersion, high-pressure dispersion, or spray drying and subsequent mechanical dispersion of the components ; b) providing a base paper; c) application of the coating color to the base paper, and d) curing of the coating color with formation of the semi-crystalline coating color layer.
  • the coating color is applied to the base paper, preferably by means of a curtain or doctor blade method.
  • the method according to the invention can be used to adjust the crystallinity of the semicrystalline coating color layer by the proportion of crystallizable organic compounds based on the total mass of the coating color.
  • the curing temperature, curing time and curing pressure have an impact on the crystallinity.
  • the curing temperature is in the range from 20 to 300°C.
  • the curing temperature is in the range from 120 to 140°C.
  • the curing time is in the range from 10 s to 15 minutes. According to one embodiment of the method, the curing time is in the range from 1 to 3 minutes.
  • the curing pressure is in the range from 0.2 bar to 3 bar. According to one embodiment of the method, the curing pressure is in the range from 0.9 bar to 1.1 bar.
  • the invention also relates to a coated paper produced by the method according to the second aspect.
  • the invention relates to packaging for foodstuffs comprising the coated paper according to the first aspect.
  • This may be, for example, packaging for dried food, food sold cold that requires further preparation, packaging containing food in single-serving portions for more than one person, or packaging containing food in single-serving portion sizes for more than one person unit is sold, act.
  • Stand-up pouch packaging, tubular pouch packaging or packaging paper can be used as packaging, for example.
  • the packaging is a tubular bag packaging.
  • Example 1 Characterization of the lignin
  • the main focus of the characterization of the lignin is the molar mass of the lignin and the number of hydroxyl groups.
  • Molar mass The molar mass is determined by means of GPC.
  • FIG. 1 shows an example of a Kraft lignin used.
  • the number of hydroxy groups can be determined by titration and by means of 31 P-NMR.
  • the OH number of Kraft lignin (KL) is determined according to DIN EN ISO 4629-1.
  • the phosphorylation of the lignin derivatives is carried out according to the instructions of Granata et al. carried out.
  • 25 mg of the dry lignin are first dissolved in 150 pL DMF.
  • 100 pL pyridine, 200 pL of a solution of the internal standard endo-N-hydroxy-5-norbomene-2,3-dicarboximide (25.0 mmol*L-1 in pyridine/CDCl3 1.6:1) and 50 pL of a solution of chromium(III) acetylacetonate (32.64 mmol/L, in pyridine/CDCl3 1.6:1) were added.
  • the amount of hydroxy groups can be calculated from the integrals of the signals.
  • a hydroxy group level of 6.18 mmol/g and a carboxy group level of 0.5 mmol/g are obtained.
  • the synthesis of the lignin stearate was carried out according to the principle of a Schotten-Baumann esterification of the stearic acid chloride with Kraft lignin.
  • reaction solution was then poured into 3 L of water and stirred for 2 hours.
  • the precipitate is filtered off (Po.2), washed with water and dried at 40° C. in a vacuum drying cabinet.
  • the solid was added to 1 L of ethanol and heated to boiling for 6 h. After cooling to room temperature, the mixture was centrifuged (4,700 rpm, 10 min). The supernatant was decanted off and the solid was again placed in 200 mL ethanol, stirred at 60° C. for about 1 h, allowed to cool to room temperature and centrifuged. This step was repeated about 2 to 3 times.
  • the solid is dried at 40° C. in a vacuum drying cabinet. To remove any insoluble residues, the solid is dissolved in a little THF, the solution is centrifuged, the decanted solution is spun off in a rotary evaporator and the product is obtained in this way.
  • the synthetic procedure was repeated with stearic acid amide from Croda, candelilla wax and carnauba in place of the stearic acid.
  • the most important factor characterizing the lignin ester is the degree of esterification. This was determined by means of 31 P NMR spectroscopy and by means of titration. 31 P NMR spectroscopy
  • the degree of esterification can be calculated from the mole fractions of the hydroxyl groups of the lignin ester (nLE) and the Kraft lignin (nKL) used.
  • the total amount of hydroxyl groups nKL (-OH and -COOH) in the Kraft lignin used is 6.68 mmol per gram of lignin (see example 1).
  • the amount of hydroxyl groups in the lignin ester can be determined analogously. The spectrum obtained is shown in FIG.
  • the amount of hydroxyl groups (-OH) is therefore: 1.10 mmol*g- 1
  • the softening point of the lignin ester is determined optically.
  • a small amount of powdered lignin esters is placed on a watch glass and placed in a convection oven. The oven temperature is increased in 10°C increments and the temperature at which the powder melts into a droplet is noted.
  • the softening point of lignin stearate is around 130°C
  • Figure 4 shows the IR spectrum of lignin stearate in comparison with kraft lignin and stearic acid.
  • Figure 5 shows the 1 H-NMR spectrum of lignin stearate.
  • the solids content of a coating color was between 10 and 25 percent by weight.
  • the preparation was repeated with stearic acid amide, carnauba wax and candelilla wax in place of stearic acid.
  • the solvent mixture was varied to ensure solubility and subsequent wettability on the paper to be coated.
  • the lignin stearate/carnauba wax and lignin stearate/candelilla wax coating colors were prepared in a 2:1 mixture of THF/EE.
  • the solids content of a coating color was between 10 and 25 percent by weight.
  • 3.75 g of spray-dried lignin stearate-stearic acid mixture (1:1) was dispersed in 15 mL of a solution of 1% SPAN-60 in water using an ultrathorax.
  • the preparation was repeated with stearic acid amide, carnauba wax and candelilla wax in place of stearic acid.
  • An RK K303 Multicoater (see Table 1) was used to coat the papers.
  • the base paper was placed on the waste paper in such a way that the standard K-bar to be clamped rests on the base paper.
  • the corresponding bar is clamped in the Multicoater.
  • a weight was placed on the paper behind the stick.
  • the desired spreading speed was set (from organic medium 10-20 m/min, from aqueous dispersion 3 m/min).
  • the coating color (approx.
  • the water vapor permeability is determined based on DIN 53122-1 as a gravimetric method. Round test specimens with a diameter of 6.3 cm are punched out of the papers to be examined. A desiccant (e.g. silica gel beads) is placed in a measuring vessel. A sealing ring is placed on the edge of the vessel, the test specimen is placed on the sealing ring with the side of the water vapor barrier facing the drying agent, another sealing ring and a metal ring are placed on the test specimen. The jar is sealed with a lid having a hole 5.7 cm in diameter. The diagram of such a measurement setup in cross section can be seen in the figure.
  • a desiccant e.g. silica gel beads
  • the measuring vessel prepared in this way is placed in a climatic chamber in which a temperature of 38 °C and relative humidity of >90% prevail. After conditioning in the chamber for around 16 hours, the measuring vessel is weighed. At intervals of 2-3 hours, new weighings are carried out until at least three measurement results are available. The measuring vessel is stored in the climatic chamber between the weighings.
  • the water vapor permeability in grams per square meter per day (g*nr 2 *d- 1 ) can be calculated from the mass gain. At least two test specimens are measured per barrier to be examined.
  • a WVTR of 17.1 ⁇ 1.0 g nfr 2 day- 1 can be achieved with a proportion of 30% by weight. If the proportion of stearic acid is further increased, the WVTR increases again and the barrier performance deteriorates.
  • Example 7 (Comparison) - Investigation of the surface structure and WVTR of a superhydrophobic layer not according to the invention according to DE 10 2017 108 577
  • a base paper was coated with a superhydrophobic layer according to example 1 from DE 10 2017 108 577.
  • the area weight of this application was 10 g/m 2 .
  • the polymer CSE3 is a fully substituted cellulose ester (DS:3) of stearic acid.
  • the substrate was heated to 120 °C in a drying cabinet for 5 minutes and then cooled under laboratory conditions (22 ⁇ 3 °C / 35% relative humidity, RH).
  • the melting temperature of AKD determined by means of differential scanning calorimetry (DSC) was -60 °C, that of the polymer CSE3 at -55 °C.
  • the contact angle was determined with a Dataphysics OCA35 including a tiltable table under constant temperature and humidity (23°C, 50% relative humidity). The contact angle is calculated from the images using the SCA 4.5.2 Build 1052 software. No enlargement is given. The contact angle of a 4 ⁇ l drop of water was 159 ⁇ 3° (see FIG. 7B).
  • Example 3 a coating color based on a mixture of lignin stearate and stearic acid (7:3, i.e. 30% stearic acid content) was produced. For this purpose, 1 g of the mixture was weighed into a 5 mL vessel with a lid and dissolved in 3 mL of a mixture of THF and EA (1:2).
  • This coating color was applied to CCK-coated paper made from hardwood and softwood pulps with a total weight per unit area of 63 g/m 2 as described in Example 3 (application rate: 5 g/m 2 ). After coating, the paper was transferred to a cardboard backing, fixed at the corners to prevent it from curling up and dried in an oven at 130° C. for 10 minutes.
  • the glass transition temperature (T g ) of lignin stearate is around 130°C.
  • the melting point of stearic acid is 69 °C, well below the T g of lignin stearate. Consequently, the formation of a superhydrophobic layer was not to be expected.
  • the contact angle of a 4 ⁇ l drop of water was 103.2 ⁇ 1.4° (see FIG. 8B). As expected due to the low contact angle, the roll-off angle could not be easily determined.
  • the roll-off angle (RoA) of a 4 pL water droplet was not measurable because the device can only achieve a 70° tilt, and no roll-off was observed at this tilt. Therefore, different droplet volumes were applied and the roll-off angles were determined. The results are shown in the graph of FIG.
  • the theoretical roll-off angle of a 4 pL water droplet on the lignin stearate-stearic acid layer was calculated by fitting a curve (see Table 2).
  • the calculated roll-off angle of the 4 pL drop exceeds 180°. Thus, there is no unrolling.
  • coatings of either stearic acid or suberic acid as the crystallizable organic compound and lignin stearate as the natural polymer were prepared as described in Example 8. The proportion of fatty acids was varied. A mixture of THF and methanol (1:1) was used to produce the coating colors containing suberin.
  • Stearic acid has a melting temperature T m ⁇ 69 °C and thus well below the glass transition temperature of lignin stearate T g - 130 °C.
  • the melting temperature T m suberic acid has a T m ⁇ 140 °C above the glass transition temperature of lignin stearate.
  • the coating colors were prepared as described in Example 8, but with varying amounts of stearic acid or suberic acid.
  • the proportion of the fatty acid was 20%, 30%, 40%, 50% or 60% by weight.
  • Example 8 these coating colors were applied to a corresponding base paper. Upon completion, the WVTR of the coated papers was determined as described in Example 6. The result is shown in FIG.
  • suberic acid lignin stearate lines have significantly higher WVTR values with a minimum of about 200 gm 2 d- 1 at a 30% by weight content of suberic acid.
  • the values of the coatings with stearic acid were significantly lower with a minimum of 24 gm 2 d- 1 , also with a proportion of 30% by weight.

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Abstract

L'invention concerne un papier couché comprenant un papier de base et au moins une couche de peinture semi-cristalline à zones amorphes et cristallines appliquée directement ou indirectement sur le papier de base, les zones amorphes comprenant un ou plusieurs polymères naturels et/ou un ou plusieurs dérivés de polymères naturels ; les zones cristallines comprenant un ou plusieurs composés organiques cristallisables ; et la perméabilité d'au moins un gaz à travers le papier couché étant réduite par rapport au papier de base. L'invention concerne également la sauce de couchage utilisée pour la fabrication du papier couché, un procédé de fabrication ainsi qu'un emballage alimentaire.
PCT/DE2023/200013 2022-01-17 2023-01-17 Papiers couchés comportant une couche de peinture semi-cristalline servant de matériau d'emballage WO2023134835A1 (fr)

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DE102022200463.9A DE102022200463A1 (de) 2022-01-17 2022-01-17 Gestrichene Papiere mit einer semikristallinen Streichfarbenschicht als Verpackungsmaterial

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DE102017108577A1 (de) 2017-04-21 2018-10-25 Technische Universität Darmstadt Regenerierbare superhydrophobe Beschichtung
DE102019114196A1 (de) * 2019-05-27 2020-12-03 Mitsubishi Hitec Paper Europe Gmbh Barrierematerial, insbesondere Barrierepapier, umfassend mindestens ein lipophiles organisches Material, sowie Zwischenprodukte und Verfahren zu seiner Herstellung
WO2021191097A1 (fr) 2020-03-26 2021-09-30 Metgen Oy Procédé de fabrication de papier résistant à l'humidité

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DE102017108577A1 (de) 2017-04-21 2018-10-25 Technische Universität Darmstadt Regenerierbare superhydrophobe Beschichtung
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