US20200332128A1 - Edible Functional Coatings And Hybrid Polymer-Based Coatings For Pharmacy And Food - Google Patents

Edible Functional Coatings And Hybrid Polymer-Based Coatings For Pharmacy And Food Download PDF

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US20200332128A1
US20200332128A1 US16/095,763 US201716095763A US2020332128A1 US 20200332128 A1 US20200332128 A1 US 20200332128A1 US 201716095763 A US201716095763 A US 201716095763A US 2020332128 A1 US2020332128 A1 US 2020332128A1
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coating composition
groups
coating
organic groups
silicic acid
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Sabine Amberg-Schwab
Daniela Collin
Anika Deinhardt
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P20/00—Coating of foodstuffs; Coatings therefor; Making laminated, multi-layered, stuffed or hollow foodstuffs
    • A23P20/10—Coating with edible coatings, e.g. with oils or fats
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P20/00—Coating of foodstuffs; Coatings therefor; Making laminated, multi-layered, stuffed or hollow foodstuffs
    • A23P20/10—Coating with edible coatings, e.g. with oils or fats
    • A23P20/105—Coating with compositions containing vegetable or microbial fermentation gums, e.g. cellulose or derivatives; Coating with edible polymers, e.g. polyvinyalcohol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/24—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing atoms other than carbon, hydrogen, oxygen, halogen, nitrogen or sulfur, e.g. cyclomethicone or phospholipids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/28—Dragees; Coated pills or tablets, e.g. with film or compression coating
    • A61K9/2806—Coating materials
    • A61K9/282—Organic compounds, e.g. fats
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular

Definitions

  • the present invention relates to the use of a composition containing silicic acid (hetero) polycondensate modified with organic groups, as coating of medicines and food.
  • the present invention relates to a method for producing a coating product and a coating product.
  • PVDC polyvinylidene chloride
  • aluminum composite films have been used so that the active ingredients can be sufficiently protected from moisture, oxygen, UV radiation and mechanical damage.
  • PVDC or PVC are used as a composite foil.
  • the water permeability of a composite foil is, for flat films, usually between 0.09 g/m 2 ⁇ d (e. g. for 51 ⁇ m PCTFE (polychlorotrifluoro ethylene) on PVC and 4 g/m 2 ⁇ d (e.g. for 250 ⁇ m thick PVC). After thermoforming, it increases to about 2.5 3.5 times.
  • Coatings for tablets and medicines generally have very different functions. They serve e.g.:
  • the selection of the polymer film used for the coating of pharmaceuticals depends, inter alia, on where and in what time span the active substance is to be released. If a fast release (fast release) is desired, the nuclei can be coated with polymers soluble in gastric juice that dissolve in a pH environment of 1-3.5. On the other hand, sustained-release or gastric acid-sensitive drugs are coated with polymer layers that dissolve or swell at a pH of 6.5 8.0 to allow the drug to diffuse through the swollen film.
  • Dragées, tablets, capsules, pellets and granules coated with enteric coatings have long played a major role in the group of solid oral dosage forms.
  • Common film coatings are based, for example, on methyl cellulose or other cellulose derivatives with different gastric juice solubilities.
  • cellulose derivatives are also used. These coatings allow controlled drug release by controlled degradation.
  • Modified PVA has a very good initial water vapor barrier.
  • the material nevertheless has a water absorption capacity, whereby the coating swells and loses barrier when it is exposed to a moist environment for a long time.
  • EP 0 839 008 B1 describes an edible inorganic coating on foods and pharmaceutical products, as well as the production of these.
  • This inorganic coating (constituents: SiO 2 , SiO, CaO, ZnO, TiO 2 , MnO) serves as a barrier layer against water vapor and oxygen. It is said to improve storage stability but not affect the taste and texture of the actual product. Disadvantages of this vacuum deposited coating, on the one hand, are that it has to be very thin (ideally between 0.0005-0.02 ⁇ m) in order to avoid cracking or flaking off and, on the other hand, the coating process by sputtering or CPD is very expensive, complex and time consuming.
  • US 3 471 304 A, U.S. Pat. Nos. 4 661 359 A and 4 710 228 A disclose edible moisture barrier coatings of shellac and also cellulose ethers, monoglycerol, metal salts and fatty acids as coating agents for food products and as enteric-coated coating compositions for sustained release or for release in the intestine. These do not meet the necessary barrier requirements for the pharmaceutical industry.
  • lipids, fats, oils and fatty acids are disclosed as moisture barrier additives. These already have a natural hydrophobic effect. However, the barrier effect is far from being comparable with the ORMOCER® barrier coatings and is therefore not sufficient on its own.
  • the specified water absorption is, for example, max. 1% if stored at 40° C. and 75% relative moisture for 30 min.
  • this can be stearic acid (obtained by saponification from vegetable and animal oils and fats), or act as a moisture scavenger, such as microcrystalline cellulose, which acts like a molecular sponge in contact with water.
  • stearic acid obtained by saponification from vegetable and animal oils and fats
  • microcrystalline cellulose acts like a molecular sponge in contact with water.
  • the disadvantages of this development is, first, that the incorporation of microcrystalline cellulose the coating becomes opaque or white, respectively.
  • the layer thickness with 100-200 ⁇ m is very uninteresting from the economic point of view.
  • the water vapor barrier improved only slightly.
  • WO 12/16814 describes the deposition of inorganic layers, such as metal oxides, on pharmaceutical products by means of ALD (atomic layer deposition).
  • ALD atomic layer deposition
  • US 2015/0250731 A1 describes a method for tablet coating and for a pharmaceutical formulation.
  • the coating is applied to the pharmaceutical substrates by means of ALD (atomic layer deposition).
  • ALD atomic layer deposition
  • MLD molecular layer deposition
  • Inorganic oxides are used as precursors.
  • Biomaterials such as hydroxyapatite, polymers, sugars, nanolaminates and the like may also be deposited thereover.
  • the desired precursors are simply mixed in the desired ratio.
  • barrier layers For food, there are different coating concepts compared to medicines, as the requirements are often very diverse and specific. In general, however, there is also the need and desire to improve the shelf life of the products by means of suitable barrier layers. For example, oxygen entering through the barrier layer leads to oxidation of fats (“rancidity”), to vitamin depletion and to flavor destruction. The entry of water vapor can lead to loss of crispiness, clumping of hygroscopic products and growth of microorganisms.
  • the coatings can be applied to the food by various methods, such as by dipping, spraying, brushing and panning, followed by a drying process.
  • Edible coatings have been divided into four categories: polysaccharides, lipids, proteins and composites.
  • Composites are edible films and coatings and often consist of a mixture of polysaccharides, proteins and/or lipids.
  • WO 2013/087757 A1 discloses an edible coating wherein the first layer consists of an edible oil and a second layer of hydrophobic edible particles (diameter 20 nm-500 ⁇ m).
  • the particles consist of either an inorganic core material and a hydrophobic shell (fats, oils, etc.) or entirely one hydrophobic material such as wax.
  • Applications are for potato chips, biscuits, cornflakes, fruits, ice cream waffles etc. As a result, cornflakes, for example, do not absorb milk so quickly and still have a very good crunch.
  • U.S. Pat. No. 5 741 505 A discloses an inorganic coating on foods and pharmaceutical products as a moisture/gas barrier.
  • These inorganic coating materials include SiO 2 , SiO, MgO, CaO, TiO 2, ZnO and MnO.
  • the coating should be thinner than 0.05 ⁇ m. These thin layers improve the haptics problem, which has sometimes resulted from thick organic coatings. Cornflakes that do not soak up in milk so fast are mentioned as a possible application.
  • WO 2003/007736 A1 discloses a continuous fat layer with 1-15% water-insoluble and fat-insoluble particles (diameter 0.05-100 ⁇ m). These particles are inorganic components SiO 2 , silicates, talcum, clay materials and phosphates. In addition, organic materials such as microcrystalline cellulose and insoluble cellulose derivatives can be used.
  • US 2010 062 116 discloses a coating of microwaveable foods for crispy appearance. Incorporation of a susceptor in the coating, which converts the microwave radiation into heat. Hereby, the mechanism of microwave heating is transformed into one that is comparable to a conventional oven heating process.
  • the composition of the coating contains at least one prolamine and at least one hydrocolloid or gelling agent.
  • Enteric coated coated dragées, tablets, capsules, pellets and granules have long played a major role in the group of solid oral dosage forms. Enteric resistance is achieved today by coating the dosage form with acidic polymers which are protonated in the stomach and are insoluble in this form. The acidic groups only dissociate in the neutral to weakly basic environment of the thin or large intestine, thereby converting the polymer into its ionic and therefore soluble form. Enteric coatings serve to protect the stomach lining from aggressive drugs, to prevent the premature inactivation of acid-labile drugs, to release drugs targeted in the small or large intestine or to cover unpleasant taste and odor properties of drugs. Coatings on foods can prevent the release of odors from them and, moreover, protect the food from moisture and undesirable oxidation reactions causing oxygen.
  • the problem to be solved is to achieve excellent barrier values, which are necessary for the protection of medicines or food, while eliminating the need for chlorine-containing or aluminum-containing packaging and coatings and to be able to dispense with other expensive or questionable procedures.
  • Another object is to provide moisture barrier layers that have a good balance between a low permeability to water vapor and rapid dissolubility in the body and therefore have good water solubility.
  • a further object of the present invention is to prepare medicaments and foods such that the packaging materials which can be used for them do not necessarily have to have particularly good barrier properties, while the medicaments or foods are still sufficiently protected against moisture and gases such as oxidizing oxygen. Because packaging materials are often subjected to a deep-drawing process. However, deep-drawn packaging materials have less good barrier properties than non-thermoformed ones.
  • Another object of the present invention is to provide a material for the food and pharmaceutical industry which is a functional coating.
  • the material or the layer composite can be biodegradable and develop an antimicrobial effect only on contact with moisture, this coating preferably having good barrier properties against the passage of oxygen and water vapor, in order to protect the contents e.g. from oxidative processes.
  • the above object is achieved in that the advantageous and desired properties are already realized in a coating of the drug or the food.
  • the present invention provides the use of a composition containing silicic acid (hetero) polycondensate modified with organic groups as a coating of a substrated selected from a drug and food or as a component of such a coating, wherein the organic groups of the silicic acid (hetero) polycondensate are at least partially biodegradable.
  • the present invention also provides a method for producing a coating product comprising the following steps:
  • composition which is optionally present in a diluent and/or solvent and contains silicic acid (hetero) polycondensate modified with organic groups, on a substrated selected from a drug and food;
  • composition used in the preparation of the coating product is preferably the composition used in connection with the use according to the invention.
  • the present invention also provides a coating product obtained by the above-mentioned method and a coating product comprising a substrate selected from a drug and food and a coating applied to the substrate, the coating having a composition containing silicic acid (hetero) polycondensate modified with organic groups.
  • substrate as used herein is not particularly limited and means any drug or food that can be coated.
  • the prerequisite for the coatability is a solid state or a state in which at least one defined and stable surface is present.
  • pharmaceutical or “drug” refers to any pharmaceutical or drug for humans and animals that meets the stated substrate requirements.
  • a drug includes both prescription drugs and over-the-counter remedies, such as cough drops.
  • the inclusion in the human or animal body includes not only the oral inclusion and subsequent swallowing, but also the inclusion via the nose or other body orifices and the intake into the mouth and the subsequent sucking or dissolving in the mouth or chewing without swallowing.
  • the inclusion of another body opening is, for example, the rectal uptake of suppositories.
  • Typical examples of drugs are solid peroral dosage forms such as enteric coated coated tablets, tablets, capsules, pellets and granules.
  • the term “food” refers to any food or food for humans or animals or other means of incorporation into the human or animal body which meets the stated substrate requirements. Another means is, for example, a dietary supplement or other supplements, such as vitamins or minerals. Intake into the human or animal body involves not only oral ingestion and subsequent swallowing, but also ingestion into the mouth and subsequent suckling or chewing without swallowing.
  • the terms “coating” or “covering” or “to coat” or “to cover” refer to the application of a substance to the surface of a substrate, wherein the surface of the substrate may be completely or partially covered.
  • the thickness of the coating or covering is not limited and varies depending on the size of the substrate, the nature of the surface of the substrate, and the use of the coating. A typical range of thickness is 1 ⁇ m to 1 mm.
  • the coating materials of the invention are biodegradable; they behave safely in the body and are easily metabolized. With the materials according to the invention it is therefore possible to provide layers in the field of tablet coatings or food coatings for the first time.
  • desired properties of the layers e.g. barrier properties
  • desired properties of the layers can be set. This is accomplished, inter alia, by a combination of one or more layers of the inventive material with one or more very thin, purely inorganic layers that are e.g. sputtered.
  • the solubility of the layers in the stomach or in the small intestine can also be adjusted.
  • the Si—O—Si bonds of the condensates according to the invention are usually acid stable, but base labile, so that the product coated therewith, when the coating is complete, passes through the stomach undigested, but is degraded in the small intestine. This is important for a number of tablet applications.
  • such condensates can also be modified to be acid labile. This is achieved by the modification with suitable groups bonded to silicon via carbon, as is known to the person skilled in the art.
  • the acid lability can also be adjusted by a reduction of the degree of crosslinking, especially of the degree of inorganic crosslinking (i. e. the Si—O—Si or Si—O-metal bonds).
  • the coating materials according to the invention can be applied as lacquers. They are particularly favorable because they can achieve barrier properties with respect to water vapor and oxygen.
  • the coating can be converted by metabolic processes into natural metabolic products, such as CO 2 or H 2 O. Also, degradation products can be introduced into human metabolism. The only remains are essentially only the inorganic constituents of the previous hybrid material (e.g. SiO 2 ), which already occur in nature in the form of natural minerals and excreted by the organism.
  • natural metabolic products such as CO 2 or H 2 O.
  • degradation products can be introduced into human metabolism. The only remains are essentially only the inorganic constituents of the previous hybrid material (e.g. SiO 2 ), which already occur in nature in the form of natural minerals and excreted by the organism.
  • the coating applicable according to the invention With the help of the coating applicable according to the invention, excellent barrier values for water vapor and oxygen can be achieved, which are necessary to protect the pharmaceutical products, in particular tablets, drug and the like, or food.
  • the protection of pharmaceutical products and food can thus be partially or completely realized by such a coating, which makes an often chlorine-containing or aluminum-containing packaging superfluous or allows a waiver of other expensive or questionable procedures.
  • the coating according to the invention is produced by applying a corresponding coating varnish to the desired pharmaceutical, in particular a tablet, or the desired foodstuff. If it contains solvents, it can be removed if necessary.
  • the inorganic component of the coating lacquer according to the invention consists of silicon cations, optionally in combination with other cations such as aluminum, zirconium, titanium or boron, and combinations thereof, which are linked together via oxygen bridges and thereby form a network.
  • This is an organically modified silicic acid or, in the case of the presence of other metal ions, an organically modified silicic acid hetero-polycondensate.
  • An example of such a heteropolycondensate is a condensate containing silicon and aluminum and optionally further cations.
  • silicic acid (hetero) polycondensate is used as a common term for the pure silicic acid polycondensates and heteroatoms-containing polycondensates.
  • the organically modified silicic acid (hetero) polycondensate is usually produced by hydrolytic condensation of silanes, optionally in combination with co-condensable compounds of other metal ions.
  • silanes may carry carbon-bonded organic groups in addition to hydrolyzable groups such as alkoxides or hydroxide groups. These groups remain attached to the respective silicon atoms in the hydrolytic condensation, and the polycondensate is suitably modified with them.
  • biodegradable organic groups are preferably present in the condensate at least partially via Si—C bonds.
  • this does not exclude the possibility of using polycondensates with oxygen-bonded biodegradable organic groups.
  • Such polycondensates are known to the person skilled in the art.
  • Biodegradable groups are integrated in the silicic acid (hetero) polycondensate of the present invention as mentioned organic. With respect to these groups, those skilled in the art can refer to materials known in the art. Various types of substances, including oligo- and polymers, which can be used in the present invention, are mentioned below.
  • HPMC hydroxypropylmethylcelluloses
  • MC methylcelluloses
  • NaCMC sodium carboxymethylcellulose
  • HEC hydroxyethylcellulose
  • HPC hydroxypropylcellulose
  • PVP polyvinylpyrrolidone
  • PVA polyvinyl alcohol
  • HPMC forms highly water soluble films that tend to be brittle.
  • MC is a water-soluble polymer.
  • NaCMC is a widely used and highly water-soluble polymer with a strong thickening effect.
  • a significant disadvantage is the partially insufficient mechanical properties of the films of NaCMC.
  • HEC is rarely used as a film coating because of its high tack but is more commonly used as a primer.
  • HPC is an extremely tacky polymer that forms mechanically stable films.
  • HPC alone is hardly used, but much better to process as co-polymer.
  • PVP alone forms a sticky solution and a brittle film, but increases gloss and color homogeneity with HPMC.
  • PVA as a polymer alone is very sticky. It improves the mechanical properties as a co-polymer (Kollicoat/BASF).
  • Polysaccharides which can be used as the modifying organic groups in the present invention and are already used in the art for edible coatings or coatings include cellulose, starch derivatives, pectin derivatives, seaweed extracts, gum arabic and chitosan. Polysaccharides are usually very hydrophilic and have poor water vapor and gas barrier properties. They are mainly used as sacrificial layers for food products.
  • Cellulose and derivatives thereof provide good film-forming properties which are odorless, tasteless, flexible and transparent. They have a moderate strength and are resistant to oils and fats, but have poor water vapor barrier properties.
  • Chitosan can form partially permeable coatings so that the internal atmosphere can be modified. This delays the ripening and degradation process in fruits and vegetables. Coatings made of chitosan are transparent, robust, flexible and have good oxygen barrier properties. CO 2 permeability could be improved by methylation of the polymers. They are biodegradable, biocompatible and chemically inert and also relatively cheap.
  • Starch is used in industrially produced foods because it is biodegradable and edible, is abundant, low in cost, non-allergenic, and easy to process. Coatings with high amylose content have a good oxygen barrier, are flexible, resistant to oil. They are odorless, tasteless, transparent, bioabsorbable, semipermeable for CO 2 .
  • Carrageenan involves a gelling mechanism which forms a 3-dimensional network of polysaccharide double helixes in a moderate drying process. This solid film is used for desserts, ice cream, milkshakes, salad dressings, condensed milk and sauces to increase the viscosity. It is also used in beer, toothpaste, soy milk and many other products.
  • Acetylated glycerol monostearates can be stretched to 800% of their original length.
  • the moisture barrier is significantly worse than the polysaccharides. They are used for poultry and meat products to the minimize fluid loss during storage.
  • the abovementioned materials can be used as such to be bound to suitable silanes or already hydrolytically condensed silicic acid homo- and/or heteropolycondensates and thus to incorporate biodegradable groups into the condensate.
  • ingredients thereof or degradation products thereof, such as individual sugar components may be used therefor.
  • the materials or groups preferably require at least one free OH or carboxylic acid group, which can be bound e.g. via a silicon-bonded, isocyanate- or epoxy-containing group, as explained in more detail below.
  • Edible films and coatings consist of a mixture of polysaccharides, proteins and/or lipids. The goal is to produce such composite films that have improved barrier or mechanical properties depending on the application.
  • organic monomers, oligomers or polymers such as caprolactone/caprolactam polymers, for example polycaprolactone, polycaprolactone triol or derivatives of polycaprolactone triol, polylactic acid, biobased waxes such as cutins, chitosan or hem icelluloses or celluloses, including cellulose derivatives and/or cellulose building blocks.
  • cellulose building blocks is intended to mean all monomers, oligomers and polymers which have at least two ⁇ -D-glucose units having a ⁇ -1,4-glycosidic bond and at least one OH group.
  • groups are those whose hydrocarbon chains are interrupted by one or more ester and/or amide and/or ether and/or urethane groups such that only a few carbon atoms directly follow one another.
  • organic polymers both bio-based biodegradable natural products and natural product derivatives such as chitosan, cellulose, cellulose derivatives and/or cellulose building blocks, as well as petroleum-based biodegradable starting materials, e.g. polycaprolactone triol (PCL-T).
  • PCL-T polycaprolactone triol
  • PCL polycaprolactone
  • the polyester is prepared from the cyclic c-caprolactone by a ring-opening polymerization reaction.
  • the thermoplastic has a low glass transition temperature of ⁇ 60° C., giving it a waxy consistency.
  • the good water, oil and solvent resistance makes PCL suitable for applications of all kinds, such as for packaging or as a carrier material for cells in tissue engineering interesting.
  • PCL can be biodegraded by the enzyme lipase.
  • the optimum degradation temperature of PCL is 50° C. (RUDNIK, E.: Compostable Polymer Materials. Amsterdam: Elsevier, 2008).
  • the polymer chains of the PCL contain a maximum of 5 carbon atoms, each located between a carboxy group and an ether group (or a terminal OH group), and thus fall within the above definition of groups having carbon chains that are interrupted by one or more ester and/or amide and/or ether and/or urethane group(s).
  • the molecule is cleaved to give 6-hydroxycaproic acid, which is completely metabolized in the citric acid cycle.
  • the organic, biodegradable groups of the coating material which can be used according to the invention is bound to a silicon atom via a carbon atom in each case.
  • the connection is formed in a simple manner e.g. by reaction with silanes bearing a silicon-bonded group substituted with an isocyanate group. Isocyanate groups can react both hydroxy groups (to form a urethane group) and with carboxylic acid groups (to form an amide group and free CO 2 ).
  • Suitable isocyanate silanes are alkoxysilanes of the formula R a SiX 4-a , where X is a hydrolysis-sensitive group or a hydroxy group, in particular an alkoxy group, more preferably methoxy or ethoxy.
  • R represents an isocyanatoalkyl group, and a is 1 or 2, with 1 being preferred.
  • the isocyanatoalkyl group may be the isocyanatopropyl group.
  • the common isocyanatopropyltriethoxysilane is a suitable silane for the purposes of the invention.
  • silanes having caprolactone derivatives are produced via the coupling reaction with the isocyanate group.
  • an organic, biodegradable group containing at least two short carbon chains in a branched position as defined above is selected.
  • Polycaprolacton-triol (PCL-T) proved to be particularly suitable for this embodiment. It is a PCL derivative based on three PCL chains linked by a 1,1,1-trimethylolpropane moiety:
  • the liquid that is highly viscous at room temperature (molecular mass about 300 g/mol) is biodegradable. All existing hydroxy groups of the PCL-T are equally reactive with respect to the reaction partner used, i. e. the isocyanate silane. The number of silanes that can be attached to one molecule of PLC-T is therefore controlled by stoichiometry. According to the invention, the functionalization of one or two hydroxy groups has proved favorable. Depending on the choice of the index a in the compound R a SiX 4-a , the result is a mono- or disilane, wherein the silane atoms carry two or three hydrolysis-sensitive groups.
  • a triethoxysilane was used, that is, a silane of the formula R a SiX 4-a , where R is ethoxy and a is 1.
  • R and a can also have different meanings as explained above.
  • Each of the hydroxy groups of the PLC-T can be linked with a silyl radical via a Si—C bond, for example via the above-mentioned isocyanate coupling.
  • the reaction scheme for preparing the silyl-functionalized PLC-T can be represented as follows:
  • the silyl group-functionalized PLC-T is hereinafter referred to as PCL-T-1/3-triethoxysilane, and the two silyl groups-functionalized PLC-T will be referred to as PCL -T-2/3-triethoxysilane.
  • cellulose can be incorporate into the inorganic network instead of PLC-T.
  • cellulose was functionalized with epichlorohydrin to give epoxy- or diol-functionalized cellulose.
  • Cellulose can be integrated in the silicic acid (hetero) polycondensate through a crosslinking reaction with an epoxy group-containing silicic acid (hetero) polycondensate.
  • the two reaction variants show two of the many possibilities of incorporation of the biodegradable groups: In the former case, these groups are linked via an Si—C bond, in the latter case via a connection to the organic network.
  • the hydrolytic condensation of the silanes modified with organic, biodegradable substituents as described above can be carried out in the presence of further hydrolytically condensable compounds of the formula M b (X) b where M is selected from a metal which can be incorporated, as described above, via oxygen atoms in the inorganic network of the silicic acid (hetero) polycondensate.
  • M is selected from Al, Si, Zr, Ti, B, while b represents the formal oxidation state of this metal and X means, as described for the silanes, a hydrolysis-sensitive group or a hydroxy group.
  • the latter may be complexed to slow the hydrolytic condensation reaction of this component in sol-gel formation, resulting in the formation of broader network structures.
  • the coating lacquer which can be used according to the invention has good coating properties.
  • one or more components which positively influence the coating (film formation) and/or barrier properties can be, for example, organic components or components with an organic content that can be organically polymerized and thus form an additional organic network to increase the barrier effect of the coating, and/or have polar groups to improve the adhesion to the substrate.
  • Suitable organically polymerizable groups are groups having reactive rings such as epoxy groups or having non-aromatic C ⁇ C double bonds such as (meth)acrylic groups, in particular (meth)acrylate groups. Thermal organic polymerization is superior to organic polymerisation by light, because thermal curing is technically very easy to realize.
  • epoxy groups are particularly preferred not only because they can be subjected to heat-induced polymerization, but also because hydroxy groups are formed during polymerization, which ensure good adhesion to the substrate.
  • the component which positively influences the coating properties is preferably an inorganic component having an organic portion, namely a silane having a carbon-bonded radical bearing an organically polymerizable group, for example, an epoxy silane or a (meth)acrylic silane.
  • An alkoxy-modified epoxysilane e.g. of (3-glycidyloxypropyl) trimethoxysilane, known by the abbreviation GLYMO, can be suitably use.
  • This silane, together with the silane carrying the biodegradable component and optionally one or more hydrolytically condensable compounds of the formula M b (X) b may be subjected to a hydrolytic condensation reaction.
  • the layers obtained by application of the lacquer have good barrier properties with respect to the passage of oxygen and water vapor.
  • good barrier effects to oxygen and water vapor are accompanied by barrier effects, as compared to other gases, vapors and odors. This is e.g. very important if the tablets to be coated are to be protected from such gases, vapors or odors, or to prevent the release of odors or to reduce odors that come from food to be coated.
  • the coating material suitable for coating food or tablets according to the invention can be prepared as follows:
  • the layer deposited from the gas phase can be applied directly to the substrate and overcoated with the coating material according to the invention, or vice versa.
  • Particularly favorable are layer combinations in which a layer according to the invention is applied via a layer deposited from the gas phase or lies between two such layers.
  • Substrates coated with the above-mentioned combinations again show improved barrier values, even with a relatively thin hybrid polymer layer (in particular below 10 ⁇ m, e.g. in the range of 1 to 5 ⁇ m).
  • the substrates coated with a combination of a SiO, layer and a layer according to the invention showed barrier values with respect to the passage of oxygen and water vapor, which were far below the values required for food packaging.
  • lacquers described above can be applied to the drug cores or food.
  • the application can be made by a variety of application techniques (for example, by spraying).
  • barrier coatings for the tablets or food are obtained after the organic crosslinking of the lacquer.
  • the application amount is preferably between 3 and 10% by mass.
  • the layer thickness can preferably be adjusted to ranges between 1 to 250 ⁇ m, more preferably to 5 to 100 ⁇ m.
  • inert fillers in the coating is known from the prior art. These should not be chemically reactive, non-hygroscopic, dispersible and have a particle size that does not affect the visual appearance of the coating.
  • Typical fillers are starch, chemically modified starch, dextrin, microcrystalline cellulose, insoluble cellulose derivatives, and inorganic compounds (e.g. talcum, TiO 2 , SiO 2 , silicates, clay materials, insoluble carbonates and phosphates).
  • the proportion of the filler (preferably in an amount of 1-25% of the coating) depends on the material.
  • Starch or dextrin improve the mechanical properties and facilitate processability.
  • Inorganic fillers such as silicates improve the moisture barrier. According to the invention, it is found that the silicic acid (hetero) polycondensates with incorporated PCL-T have good adhesion to various substrates and are transparent and biodegradable.
  • Epoxy-functionalized alkoxysilane GLYMO
  • two more metal alcoholates aluminum tri-sec. butoxide, AsB and a tetraalkoxysilane, usually tetramethoxysilane
  • ammonium chloride ammonium hydroxide
  • ethanol complexing agent
  • isocyanate-containing alkoxysilane isocyanatopropyltriethoxysilane
  • polycaprolactone-triol hydrochloric acid 0, 1 M.
  • PCL-T polycaprolactone-triol
  • the product was characterized by IR transmission (Nicolet 6700, Thermo Fisher Scientific, resolution: 4 cm ⁇ 1 , measuring range: 4000 cm ⁇ 1 to 400 cm ⁇ 1 ) and NMR spectroscopy (DPX400, Bruker). By calculating the integrals in the 1 H NMR spectrum, it could be shown that the single functionalization led to 100% of the singly functionalized product and the twofold functionalization gave an almost equally high yield.
  • an epoxy group-containing silicic acid polycondensate prepared by the prior art was mixed with the functionalized cellulose; the mixture was subjected to a polymerization reaction.
  • a standard varnish was prepared using the following components:
  • GLYMO preferably in an amount of 40 80 mol %, based on all silicon-containing starting materials
  • TMOS preferably in an amount of 20-60 mol %, based on all silicon-containing starting materials
  • aluminum tert-butylate complexed with ethyl acetoacetate preferably in an amount of 1 and 30 mol %, based on the molar amount of GLYMO plus TMOS.
  • the complexation of the aluminum tert-butylate serves to slow the hydrolysis and condensation of the aluminum compound to prevent a rapid growth of the oxide network.
  • the comparative example was repeated with the proviso that part of the GLYMO was replaced by Si-functionalized PCL-T (one-third of the hydroxy groups replaced) such that the mass fraction of the functionalized PCL-T (based on solids) was 16% by weight.
  • the durability of the lacquer systems was tested both by Raman spectroscopy and by determination of the kinematic viscosity (Ubbelohdeviskosimeter type AVS 410 of Schott/SI Analytics GmbH).
  • the determination of the solids content of the lacquer systems was carried out by baking at 200° C. for one hour. In each case a double determination was carried out.
  • the coating of the lacquers was carried out by Erichsen Spiral Squeegee (Model 358) and Coatmaster 509 MC film applicator from Erichsen. It was worked with a spiral squeegee with a film width of 220 mm and a wire winding of 20 ⁇ m. The resulting wet film thicknesses were thus in the range of 20 ⁇ m. The application speed was 12.5 mm/s.
  • the substrate was PLA film (30 ⁇ m) or Cellophane film (45 ⁇ m, 20 ⁇ 27 cm) and, for the solid-state NMR samples, a Teflon plate. A PET film (100 ⁇ m) was used for the measurements of biodegradation.
  • the substrates were pretreated with corona.
  • the curing of the coatings took place at 100° C. for 1 h (PLA films) or 130° C. for 1 h (PET films and Teflon plate) in a convection oven U 80 from Memmert GmbH+Co. KG. After curing, a thickness of the coating of about 5 ⁇ m was measured.
  • Comparably thick coatings can be achieved with conventional methods for tablet coatings.
  • the resulting coatings were examined for their appearance and their adhesion to polylactate (PLA) and polyethylene terephthalate (PET) films.
  • the visual appearance was evaluated with the naked eye.
  • the adhesion was determined by means of a tape test, which is derived from the cross-cut technique with adhesive tear (DIN EN ISO 2409).
  • the adhesion of the layer to the substrate is evaluated using the categories TT 0 (the layer is not detached from the substrate by the test) to TT 5 (the layer is completely detached from the substrate).
  • an adhesive tape with a defined bond strength was glued bubble-free on the coating and pressed. After a period of 1 min, the adhesive tape was peeled off within one second at an angle of about 60° to the pulling direction and then the adhesion was evaluated.
  • the biodegradability of the coatings produced was tested according to standard ISO 14885 1:2005 and by storage of the samples in a compost.
  • the coated PET films were clamped in a slide frame for the compost test and connected at the back with a non-degradable control sample (coating on PET film).
  • the samples were then placed vertically in the compost so that the entire sample was covered by soil.
  • the compost was made from so-called dry active compost of Kompostwerke WUrzburg GmbH, water (approx. 50% by weight, based on the dry compost) and Radivit® compost accelerator from Neudorff (about 5 g per liter of compost).
  • the microorganisms of the compost and the compost accelerator are active for about two to three weeks.
  • the compost was changed every 3 weeks and all samples were carefully cleaned and photographed. With visible signs of biodegradation, the samples were examined by laser scanning microscopy (VK-X200 from Keyence Corporation).
  • the inorganic network density of the cured coating systems was investigated by 29 Si solid-state HPDEC/MAS NMR spectroscopy. By assigning the T and Q groups, it was possible to ensure that all participating precursors were integrated into the inorganic network.
  • the inorganic network density could be estimated from the intensity ratios of the T groups.
  • Table 1 shows the network density of the different lacquer systems in comparison.
  • SiO x layers on polyethylene terephthalate (PET/SiO x ) applied by means of PVD have water vapor permeabilities (WVTR) in the range of 0.12 g/m 2 /d. Their oxygen permeabilities (OTR) are about 0.23 cm 3 /m 2 /d/bar. These values are slightly above the values required for food packaging of 0.10 g/m 2 /d for the WVTR and of 0.1 cm cm 3 /m 2 /d/bar for the OTR.
  • the coatings according to the invention are suitable for the production of coating materials for food and pharmaceutical products.
  • the attached FIG. 1 shows the determined values.
  • the “prior art ORMOCER®” herein means a lacquer made of a hybrid material according to the above-described comparative example.
  • the coating referred to as “45% by weight of PCL-T content” is approximately equivalent to Example 3-PCL-T-1/3 above, except that a slightly larger proportion of GLYMO was replaced with PCL-T such that the content of PCL-T was increased from 41 to 45 wt.-%.
  • the coating referred to as “15% by weight of PCL-T” corresponds approximately to Example 1 above -PCL-T-1/3, i. e. the reference lacquer, but with slightly less GLYMO replaced with PCL-T so that its content is only 15% by weight.
  • Tablet coatings require extremely good barrier properties against odors, water vapor and oxygen, when oxygen or water-vapor-sensitive agents are involved.
  • inorganic oxide layers such as SiO x (1.5 ⁇ x ⁇ 1.8) to achieve very good barrier values [Amberg-Schwab, S.: Handbook of Sol-Gel Science and Technology, Vol. 3, Ed.: S. Sakka, Kluwer Academic Publishers, Norwell, Chap. 21 (2004), p. 455].
  • the applied hybrid polymer layer reduces micro- and nanoporosity.
  • the combination with an inorganic oxide layer may constitute a functional coating.
  • the material used according to the invention can be present in a layer composite with one or more other, preferably inorganic, layers.
  • the layer composite is edible.
  • the oxygen permeability and the water vapor permeability, each with and without hybrid polymer barrier coating were examined.
  • the investigation of the oxygen permeability was carried out according to DIN 53 380 (23° C., 50% rh, relative humidity), the investigation of the water vapor permeability was carried out according to DIN 53 122 (23° C., 85% rh, relative humidity).
  • the substrate showed an oxygen permeability of 160 cm 3 mM 2 ⁇ d ⁇ bar, for the substrate coated with hybrid polymer an oxygen permeability of 10 cm 3 /m 2 ⁇ d ⁇ .
  • the biodegradable model substrate had a value of 140 g/m 2 ⁇ d, and for the hybrid polymer-coated biodegradable model substrate a value of 30 g/m 2 ⁇ d.
  • FIG. 1 shows the oxygen (OTR, at 50% RH and 23° C.) and water vapor transmission rate (WVTR, at 90% RH and 38° C.) of the developed chitosan and PCL-T containing coatings in a layer system of PET film and SiO x layer.
  • OTR oxygen
  • WVTR water vapor transmission rate
  • FIGS. 2 and 3 show the in vitro cytotoxicity of some PCL-T materials.
  • FIG. 2 In vitro cytotoxicity of glass slides coated with the lacquer usable according to the invention
  • the cytotoxicity can be determined from OD 450 : A sample is considered non-cytotoxic if OD 450 is ⁇ 80% of the blank Nc2 value (the black line indicates this area).
  • FIG. 3 In vitro cytotoxicity of glass slides coated with the lacquer which can be used according to the invention.
  • Silicic acid polycondensate extracts were obtained by shaking the sterile with the silicic acid polycondensate coated glass plates for 24 h in a cell culture medium (DMEM—Dulbecco's Modified Eagle Medium) under physiological and aseptic conditions. Subsequently, the subconfluent cell cultures (L929) were incubated in undiluted extraction solutions for 24 h and prepared analogously to the previous film to determine OD 450 . “Ormocer” refers to the reference lacquer.
  • the figures show that the two coating materials which can be used according to the invention are not cytotoxic to mammalian cells since they reach the minimum value. Therefore, these compositions can be used as coatings for medicines and foods.
  • Extract from contact with organically modified silicic acid polycondensate without biodegradable groups is weakly cytotoxic. Due to a biodegradable, harmless coating on the tablets, which have excellent barrier properties, it is possible to replace PVDC and aluminum with alternative packaging materials that do not have any outstanding barrier effect, but are deep-drawable. In addition, alternative, simpler packaging concepts are conceivable, for example, a waiver of the separation in blister packs.
  • the properties of the highly functional coating materials can be adjusted, combined and customized in addition to the barrier effects.
  • the coatings are, for example, stable in an acidic environment, but can also be adjusted so that they dissolve already in the stomach.
  • the composition of the coating can be chosen so that it behaves harmlessly in the body.
  • the barrier coating also improves the shelf life of pharmaceutical products and food.
  • the use according to the invention makes it possible to produce products which are edible coatings and have the following properties:
US16/095,763 2016-04-26 2017-04-26 Edible Functional Coatings And Hybrid Polymer-Based Coatings For Pharmacy And Food Abandoned US20200332128A1 (en)

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US3471304A (en) 1966-03-07 1969-10-07 Archer Daniels Midland Co Edible coating compositions
US4661359A (en) 1985-06-03 1987-04-28 General Mills, Inc. Compositions and methods for preparing an edible film of lower water vapor permeability
US4710228A (en) 1985-10-16 1987-12-01 General Mills, Inc. Edible coating composition and method of preparation
US5741505A (en) 1995-01-20 1998-04-21 Mars, Incorporated Edible products having inorganic coatings
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US7906134B2 (en) * 2005-12-21 2011-03-15 Abbott Laboratories Room temperature-curable polymers
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CA2828754A1 (fr) 2011-03-03 2012-09-07 Merck Patent Gmbh Preparation pharmaceutique solide enrobee
EP2790517A1 (fr) 2011-12-14 2014-10-22 Unilever N.V. Enrobage comestible et produit alimentaire enrobé
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