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WO1996036653A2 - Materiau d'arret resistant a l'eau - Google Patents

Materiau d'arret resistant a l'eau Download PDF

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Publication number
WO1996036653A2
WO1996036653A2 PCT/EP1996/001862 EP9601862W WO9636653A2 WO 1996036653 A2 WO1996036653 A2 WO 1996036653A2 EP 9601862 W EP9601862 W EP 9601862W WO 9636653 A2 WO9636653 A2 WO 9636653A2
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WO
WIPO (PCT)
Prior art keywords
barrier
barrier material
hydrocolloids
material according
substituted
Prior art date
Application number
PCT/EP1996/001862
Other languages
German (de)
English (en)
Other versions
WO1996036653A3 (fr
Inventor
Wilfried Babel
Ralf PÖRSCHKE
Klaus BRÄUMER
Reiner Mehnert
Tom Scherzer
Rudolf Hinterwaldner
Original Assignee
Deutsche Gelatine-Fabriken Stoess Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Deutsche Gelatine-Fabriken Stoess Ag filed Critical Deutsche Gelatine-Fabriken Stoess Ag
Priority to EP96919668A priority Critical patent/EP0826010A2/fr
Priority to AU58135/96A priority patent/AU5813596A/en
Priority to JP8534505A priority patent/JPH11500484A/ja
Publication of WO1996036653A2 publication Critical patent/WO1996036653A2/fr
Publication of WO1996036653A3 publication Critical patent/WO1996036653A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather

Definitions

  • the invention relates to a water-resistant barrier material, which in particular for finishing, forming or building protective, adhesive and intermediate layers or films or for producing carrier-free films with excellent barrier properties against gaseous and / or liquid ambient media, in particular oxygen, air , Water vapor and the like.
  • the barrier material according to the invention can be used to equip or coat both flat substrates and moldings made of metal, plastic, cellulose material and / or inorganic materials, and also to bond them.
  • the equipping of flat substrates, the coating of shaped bodies with or the formation of barrier layers when building up composite materials or laminates by gluing is a known and material-related necessity in the art, so that objects are protected against environmental influences and the service life is extended. Protection against environmental influences has a high priority in the national economy. When it comes to packaging, especially for the food and pharmaceutical sectors, but also for other high-quality goods, particularly high demands are placed on the barrier equipment.
  • the barrier materials In the case of fillings from the food and pharmaceutical sectors in particular, the barrier materials must be chemically and physically inert and must not release any toxic, taste and odor-influencing substances or experience sensory changes through them. Furthermore, they may not trigger so-called "scalping" effects in direct or indirect product contacts.
  • solvent, water and / or monomer-containing barrier materials such as coating compositions, lacquer, must predominantly be used.
  • the solvents are important auxiliaries, for example to obtain barrier materials in solid, processable aggregate states from solid polymers and / or resins in order to be able to wet the material surfaces to be coated in order to develop adhesion.
  • the solvents required for this are not water or monomers (reactive diluents), are aliphatic and aromatic, such as esters, ketones, toluene, xylene and the like, and must be removed from the barrier materials after use.
  • the released solvents must be disposed of or recycled using costly techniques in accordance with emissions legislation and TA-Luft.
  • aqueous barrier materials up to 20% of organic solvents are added to the solvent "water”, which, after removal, must also be disposed of according to the TA-Luft.
  • Solvent-free coating or barrier compositions have also become known in recent times. Instead of inert solvents, such compositions contain so-called reactive diluents or monomers, which integrate into the polymer matrix during curing or crosslinking. Since these are relatively low molecular weight compounds, they are not only physiologically questionable, but also have characteristic, intense, negative taste and smell notes. The one that can be achieved
  • the degree of crosslinking is often only ⁇ 90%, so that they are not suitable, among other things, for equipping packaging materials for food and pharmaceuticals.
  • too low a degree of networking can also lead to problems in technical areas, especially in terms of resistance to environmental influences.
  • the reactive thinners have the disadvantage that if residues thereof, even in the ppm range, are not crosslinked, they adversely affect the adhesion (adhesion) at the interface, because they can stray like inert solvents.
  • polymerizable barrier materials that can be hardened by means of ionizing rays, in particular electron beams and UV rays, have also been known for several years.
  • Photoinitiators and possibly so-called synergists are added to the UV-curable barrier masses so that they polymerize under UV rays.
  • these photosensitive additives remain in the barrier layers after curing and contaminate the environment both when stacked and when they come into contact with filling goods and are therefore unsuitable for food and pharmaceutical packaging materials because they are physiologically classified as questionable.
  • contamination problems do not arise when curing or crosslinking with ionizing radiation.
  • the radiation-curable barrier compositions known according to the current state of the art have the disadvantage overall that they have a relatively high proportion for processing reasons
  • barrier materials described above will make it difficult for an expert in the future, either from an economic or technical point of view, to provide barrier layer equipment under environmentally friendly and optimal hygienic conditions, because the state of the art does not offer total solutions that meet all requirements.
  • high demands are made, as is only the case from the recommendations of the federal government health office (BGA) "plastics in food traffic” or from the legal provisions of the Food and Drug Administration (FDA) and the individual environmental laws.
  • BGA federal government health office
  • FDA Food and Drug Administration
  • barrier materials can only be used to a limited extent, with the food and pharmaceuticals area being completely excluded. This is due to the fact that the contents are influenced by sensors, ie taste and smell.
  • sensors ie taste and smell.
  • post-curing it is also possible to achieve qualitative improvements in non-thermosensitive substrates, but these are often not sufficient to achieve the required minimum standard. Added to this are the additional cost burdens for end products due to such post-treatment measures. For this reason, efforts were made to develop better technical solutions using radiation curing, which at the same time also ensure cost-effectiveness. Because of the minimum degree of networking that cannot be achieved under economic conditions - as already mentioned above - it was possible to use these radiation-curable coating materials are not the hoped for
  • Another European patent application 0 184 345 describes radiation-curable, thermoplastic coating compositions for wood and other substrates which consist of copolymerizable ethylenically unsaturated polyesters and thermoplastic polymers.
  • monomers or reactive thinners and / or inert organic solvents are necessary.
  • This presents coating compositions which, although they can provide good final properties, are associated with the problems of evaporation of the inert solvents and those of the residual solvent and monomer contents.
  • hot melt coatings are based on inert resins, waxes, thermoplastics and / or elastomers.
  • inert resins waxes
  • thermoplastics thermoplastics
  • elastomers elastomers
  • Hot melt adhesives related to the hot melt have become very important in many industries, the hot melt has remained relatively insignificant, apart from some areas of application, such as corrosion protection films.
  • These anti-corrosion films are made from a hot-dip material that includes consists of cellulose esters, plasticizer mixtures and mineral oil additives, e.g. if Dip tool parts, machine parts into the hot mass and then let them cool down. The film or coating that forms can later be removed without residue.
  • thermoplastic base materials including the resins and plasticizers are thermosensitive and exposed to thermal oxidation, particularly in the presence of atmospheric oxygen. This not only changes the product properties, it also creates crack products that are physiologically questionable. This associated thermal problem is described in international terminology with the term "heat history”. While with the
  • Hot melt adhesives can be worked with stabilizers and antioxidants, they can only be used in the melt masses if they are used in the technical field. Covering with protective gases such as nitrogen (N 2 ) can also reduce thermo-oxidative degradation.
  • Another disadvantage of the thermoplastic melt coating compositions is the relatively low softening points, which are preferably below + 150 ° C., in particular below + 120 ° C.
  • Another disadvantage is that the backbone polymers are already in their final state as a macromolecule and therefore very high processing temperatures of + 180 ° C to + 270 ° C are necessary to achieve adequate wetting and thus adhesion to the different substrate surfaces. Certainly there are masses melting even at low temperatures, but they do not have heat resistance and the chemical resistance is not always sufficient.
  • Such melt coating compositions are described, inter alia, in DE-OS 24 25 395, which are formulated on the basis of ethylene-vinyl acetate copolymers. Further enamel masses are in the monograph R. Jordan
  • polyester melt compositions which are based on linear copolyesters of terephthalic and / or isophthalic acid and can be from amorphous to crystalline (DE-OS 24 14 287).
  • DE-OS 19 17 788 and 31 06 570 describe radiation-sensitive telomerized or acryloxy- or methacryloxy-terminated polyesters, which are preferably made from aliphatic and cycloaliphatic and only partially from aromatic polycar bonic acids and polyhydric aliphatic alcohols. They are very linear and can only be hardened with rays under difficult conditions. Since the relative distances between the acrylic and methacrylic groups increase with increasing molecular weights in the case of linear molecules, the energy requirement required for crosslinking or curing also increases. Despite this increased energy requirement, good cross-linking is not guaranteed so that a degree of cross-linking of less than 90% is achieved.
  • a further significant disadvantage is the thermal sensitivity and the rheological properties, especially when it comes to high molecular weight linear polyesters. Because these decompose very oxidatively with increasing temperature.
  • Melt can be processed at temperatures below ⁇ 150 ° C, in particular ⁇ 100 ° C and can thus be functionally handled at an early stage, but their cross-linking function is only triggered by the ambient humidity. This is it preferably around moisture-curing polyurethane systems. Depending on the layer thickness and ambient humidity, curing takes between 1 and 96 hours. For an industrial production an undiscutable hardening phase, apart from the fact that uncrosslinked hardener parts can migrate.
  • European patent 0 270 831 describes solvent-free, low-monomer or non-polymerizable, meltable masses based on (meth) acrylated cellulose esters and polyesters, which may include can be used to form barrier layers on flat substrates. But now an effective barrier layer against oxygen and
  • layer thicknesses of ⁇ 50 ⁇ m, in particular ⁇ 100 ⁇ m, are required.
  • these layer thicknesses e.g. the oxygen permeability only by a factor of 10 to 20 on substrates made of polyethylene and / or polypropylene.
  • substrates made of polyesters e.g. Melinex
  • Enamel materials were also designed for other tasks. Since these enamels are also processed at temperatures ⁇ 80 ° C, especially ⁇ 140 ° C, they are also thermosensitive.
  • barrier polymers can be classified according to Römpps Chemie-Lexikon, 9th edition, volume 1, page 349 - as follows:
  • the barrier polymers are processed using various process technologies, e.g. by injection molding, compression molding, blow molding, rotary molding, thermoforming and the like. Since individual barrier polymers rarely have multiple barrier properties, so-called “composite films” or “composite laminates” have to be produced from different substrates by coextrusion and / or gluing.
  • barrier polymers The specific properties of the individual barrier polymers are adequately described in the relevant literature.
  • a current overview of barrier polymers is provided by William J. Korosin "Barrier Polymers and Structures", ACS Symposium Series 423, Washington, DC, 1990, ISBN 0-8412-1762-9.
  • EP-A1-0 547 551 describes edible films (edible films) which consist of modified starches, gelatin, plasticizers, lipids and water. These films are said to have physical or microbial barrier properties in food against water, solutes, gas and water vapor. Depending on the type, content and film thickness
  • the permeability of the barrier polymers to water vapor and gases is of particular importance for the durability of perishable goods. This permeability is not a leak in the classic sense of porosity and / or capillary holes, but the so-called
  • Solid Diffusion the gas dissolves in the barrier polymer like in a liquid, migrates through it and emerges as gas on the other side. This diffusibility does not depend on the thickness of the barrier layer, but only on the barrier polymer. The thickness of the polymer barrier layer is only a time factor.
  • barrier polymers such as polyamide, cellulose acetate
  • the barrier polymers are assessed according to their permeability coefficients.
  • the known barrier polymers have very different barrier properties, especially against oxygen and water vapor. Only in a few applications do they meet the required barrier properties as a simple layer. In order to be able to meet the catalog of requirements of the packaging industry, which does not only include the barrier properties, so-called multiple coatings, composite films or laminates have to be produced from the barrier polymers and / or the surfaces thereof have to be metallized. Only through these measures can barrier properties be achieved that are comparable to those of aluminum foils. However, such multilayer connections are subject to technical and economic limits because - The packaging weight and thus the barrier polymer requirement increases
  • barrier polymers especially when used as packaging materials for everyday consumer goods, are the legal requirements and / or self-restrictions of manufacturers and consumers on ecology and the environment. This fact has already resulted in e.g. Polyvinyl halogens, e.g. PVC and PVDC, as barrier polymers in packaging materials are no longer permitted.
  • PVC and PVDC Polyvinyl halogens
  • the measure reduces the number of barrier polymers that can be used, the spectrum that is available in practice cannot be covered with the remaining barrier materials. This is especially true when very high barrier properties, i.e. e.g. very low oxygen and water vapor permeability values are required. In practice, there are a multitude of needs where the requirements - even of high-quality barrier polymers - can no longer be met.
  • the object of the present invention is to provide barrier materials which avoid the above disadvantages and which meet the requirements defined in Table 1 with only a single layer.
  • a water-resistant barrier material which comprises natural, biodegradable hydrocolloids which are mono- or polysubstituted by ethylenically unsaturated and / or epoxy-containing radicals, and the hydrocolloids are hardened and / or crosslinked by means of a polyreaction which relates to the radicals .
  • high-quality barrier materials with superior, advantageous properties are produced from hydrocolloids curable or crosslinkable by a polyreaction, in particular polymerization and / or polyaddition, which are substituted with mono- or poly-ethylenically unsaturated and / or epoxy group-containing residues to let.
  • the adhesive starting materials according to the invention based on natural, biodegradable hydrocolloids which are mono- or polysubstituted by ethylenically unsaturated and / or epoxy group-containing residues include water-soluble, biodegradable hydrocolloids or backbone polymers A, which come, inter alia, from the following polymer families: - proteins
  • Polypeptides especially those of collagen origin, e.g. Gelatin; animal glues; Collagens; Whey proteins, caseins; Plant proteins, especially soybean, rapeseed and cereal proteins and / or their hydrolysates.
  • Cellulose and its derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc., starch and starch derivatives, glycogen, alginic acid and derivatives including salts, agar agar, hetero-polysaccharides, heteroglycans, hemicelluloses and their derivatives, chitin, gum arabic and the like.
  • the barrier materials according to the invention are preferably hydrocolloidal compounds of the general formula (I) wherein A is a hydrocolloid of the above meaning, preferably with a molecular weight of about 500 to about 2,000,000,
  • R 1 is the hydrocarbon radical of an ethylenically unsaturated, optionally hydroxy, nitrile, halogen and / or C 1 -C 4 alkyl-substituted carboxylic acid, preferably an acrylic, methacrylic and / or crotonic acid and / or with an ⁇ , ⁇ -epoxy group with 2 to 10 carbon atoms
  • X -O-, -N (R 2 ) -, -NH-C (O) - and / or the group R 1 -C (O) -X- stands for an ethylenically unsaturated dicarboximide residue, preferably maleimide residue,
  • R 2 is optionally hydroxy, amino, multiple R 1 -C (O) -X-, C 1 -C 8 alkyl-, C 1 -C 8 alkoxy- and / or oxyalkyl- substituted, saturated or unsaturated hydrocarbon residue, preferably an aliphatic hydrocarbon residue and optionally -C (O) -O-, -OC (O) -O-, -O- C (O) -, -O-, -C ( O) -, -NH-C (O) -NH-,
  • R 3 H, RC (O) -, R 2 - Y - A and / or C 1 -C 4 alkyl,
  • the barrier materials according to the invention are based on functionalized hydrocolloids.
  • the starting materials include known and conventional hydrocolloids or their basic raw materials.
  • the chemical modification of the starting materials takes place by introducing reactive and / or functional groups into the main molecular chains without changing or damaging the colloid chemical and water-soluble properties.
  • the barrier materials according to the invention are reactive, biodegradable hydrocolloids or backbone polymers. They are essentially reaction products from a non-radical reaction between polypeptides and / or polysaccharides, their functional groups, e.g. Hydroxyl, amino, imino, thiol and / or carboxyl groups are at least partially derivatized with a polymerized residue.
  • the barrier materials according to the invention are thus derivatives of esters of unsaturated carboxylic acids
  • hydrocolloidal compounds which correspond to the above formula (I) are particularly preferred. In the hydrocolloidal compounds of the formula
  • R 1 can be the hydrocarbon radical, for example methacrylic, chloracrylic, cyanoacrylic acid and the like, with the acrylic and methacrylic acid radical being particularly preferred. Furthermore, R 1 can also be an epoxy group-bearing hydrocarbon radical having 2 to 10 carbon atoms, the epoxy groups preferably being arranged in the ⁇ or ⁇ position.
  • R 2 contains at least one R 1 -C (O) -X group, in which R 1 and X can have the meaning given above and in the case of several R 1 - (C) -
  • radicals within a molecule the radicals R 1 or X can in each case be the same or different. Possibly existing ones
  • Bridge members of the radical R 2 can be arranged both within the radical, in particular in the case of aliphatic radicals, R 2 and / or at one or both ends as bridge members of the radical R 2 to form X, Y or A. In a very particularly preferred
  • Embodiment R 2 is an at least divalent, optionally substituted glycol or polyol residue with 2 to 6 C atoms, the divalent residue of an aliphatic oxyarboxylic acid with 2 to 18 C atoms or the divalent residue of a carboxylic acid -C 2 -C 6 - Is glycol or C 6 -C 80 polyalkylene glycol ester.
  • R 2 can, for example, also be a C 1 -C 4 alkylene group which is optionally substituted with lower alkyl groups.
  • the general formula (II) has a further group of usable, highly suitable ethylenically unsaturated substituted compounds: (R 1 - X) n - (R 2 ) m - Y - A (II), in which R 1 is an allyl or vinyl group and / or an ⁇ -, ß-
  • R 4 can be the same or different and can be branched and unbranched and cyclic alkylene radicals having 1 to 20, preferably 1 to 10 carbon atoms, arylene radicals, aralkylene radicals and / or acyl radicals having 1 to 20 C atoms,
  • R 5 H, Cl, CN, OH, C 1 -C 4 alkyl
  • the derivatization can take place by non-radical reaction or by grafting reactions on the backbone polymers.
  • the reactive groups introduced into the main molecular chains of the hydrocolloids A according to the present invention are ethylenically unsaturated and / or epoxy group-bearing radicals. These can be connected to the hydrocolloids directly or via the radical R 2 , for example a divalent, optionally substituted hydrocarbon or polyol radical.
  • the curing or polymerization is carried out by means of the reaction initiators, hardeners and / or by high-energy radiation which are customary for compounds of this type.
  • the barrier materials can also contain further known constituents, such as accelerators, stabilizers, rheology-influencing agents, fillers, pigments and / or further polymerisable compounds or compounds which can be copolymerized with the abovementioned ethylenically unsaturated and / or epoxy group-bearing hydrocolloids, in particular compounds which carry water-soluble and / or active hydrogen atoms and the like.
  • the functionalized backbone polymers or hydrocolloids in which the reactive groups have been introduced into the main molecular chains via a non-radical reaction. They contribute significantly to a homogeneous barrier material, as has surprisingly been found.
  • These functionalized products are produced, inter alia, as described in DE-A-42 10334.
  • Functional residues in the hydrocolloid are ⁇ 0.1 mass% (m%).
  • the particularly preferred contents are between 1 and 50 m%, in particular between 5 and 35 m%.
  • Functionalized hydrocolloids which have at least 10 curable or crosslinkable groups per 1000 amino acid or monosaccharide units have proven to be particularly advantageous barrier materials.
  • a large number of ethylenically unsaturated and / or epoxy group-bearing compounds according to the above formulas are suitable for functionalizing the hydrocolloids A.
  • Reactive radicals which, inter alia, from the groups of
  • ethylenically unsaturated compounds e.g. Acrylic acid glycidyl ester, methacrylic acid glycidyl ester, acryloxypropionic acid glycidyl ester, methacryloxypropionic acid glycidyl ester, maleic acid monomethylacryloxyethyl ester, urethane methacrylate, allyl glycidyl carbonate, (meth) acrylamide, 2-acrylamido-2-methyl-epoxydyl-methoxyl-acrylate, vinyl-methoxyl-oxy-acrylate-methyl-oxy-oxy-oxy-acrylate,
  • Epoxy group-bearing compounds such as epichlorohydrin, butyl diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopen tylglycol diglycidyl ether, polypropylene glycol diglycidyl ether, vinylcyclohexene diepoxide, are introduced into the hydrocolloid A.
  • Compounds which are water-soluble and / or readily dispersible in water are particularly preferred for functionalization.
  • the polymerization required for curing can be carried out as a pure homopolymerization of a derivative containing the above radicals, but also by copolymerization of a mixture of such derivatives.
  • the hydrocolloids according to the invention can also copolymerize with water-soluble or water-dispersible unsaturated and / or epoxy group-bearing monomers, oligomers and / or polymers.
  • these co-reactants include the function of a crosslinker.
  • These cross-linking connections can be, for example, the above ones used for functionalization or others.
  • compounds are suitable which have active H atoms in the molecule and e.g.
  • connections include Polyamines, polyimines, polyamides, polyamidoamines, polysulfides, silicon-hydrogen compounds and the like.
  • Polyols in particular water-soluble polyols, are also suitable for the cationic polymerization, which additionally have a "softening" or
  • the curing or polymerization of the barrier materials according to the invention itself takes place via a) in the case of ethylenically unsaturated residues by free-radical polymerization
  • reaction initiators 1. inorganic peroxides, such as alkali and / or
  • Alkaline earth metal peroxides, and hydrogen peroxide Alkaline earth metal peroxides, and hydrogen peroxide
  • Peroxyacids and their salts e.g. Peroxodisulfuric acid, sodium peroxodisulfate (persulfate); - Actinic light, especially UV rays in the
  • Wavelength range 380 to 100 nm in the presence of photoinitiators e.g. Benzophenone, benzoin ether, Michler 's ketone, methylthioxanthone, ketals and
  • synergists e.g. Amines, tert. Amino alcohols and / or - using electron beams in low energy
  • Acceleration range from 150 to 300 keV and a preferred, effective penetration depth of 3 to 400 g / m 2 , as well as a dose distribution from 5 Kgy to 100 Kgy, in particular 10 to 70 Kgy and a dose spread of approx. ⁇ 3%. b) in the case of residues carrying epoxy groups - by polyaddition with active H atoms
  • Crosslinkers mentioned, e.g. Isophoronediamine, diethylenetriamine, 4, 4-diaminodiphenylmethane - by cationic polymerization and actinic light in the presence of Lewis and Bronsted acids,
  • Carbonium ions and trialkyloxonium salts such as, for example, bis- [4- (diphenylsulphono) phenyl] sulfite bis-hexafluorophosphate, ⁇ -2,4- (cyclopentadienyl) [1,2,3,4,5,6- ⁇ ) - (methylethyl) benzene] iron (II) hexafluorophosphate.
  • the polymerization and copolymerization can be accelerated by adding an accelerator after adding one or more reaction initiators, especially if curing is carried out at temperatures 25 25 ° C.
  • Accelerators based on tertiary amines such as diethylaniline, diethyl p-toluidine, triethylene amine, heavy metal salts such as cobalt acetylacetonate are suitable for this purpose.
  • Carbon dioxide (CO 2 ) and / or noble gas to suppress oxygen inhibition If, on the other hand, layers, coatings, films and foils or the like made of the aqueous barrier materials according to the invention are cured or crosslinked before dehydration or drying, an inert protective gas atmosphere can be dispensed with, as has surprisingly been found. Because the existing water content creates its own self-sufficient protection zones against molecular oxygen (O 2 ). This procedure also has the further advantage that the subsequent dehydration or drying can be made technically simpler and thus more economical.
  • additional reactive groups can be cross-linked in the main molecular chains of the hydrocolloids.
  • Suitable for this purpose include bi- and / or polyfunctional isocyanates and the like, but also aldehydes, such as glutaraldehyde.
  • aldehydes such as glutaraldehyde.
  • dual and hybrid curing can also be carried out with the barrier materials according to the invention, provided that the functional groups for this have been functionalized with the appropriate radicals and / or contain other reactive links in the main molecular chain.
  • This group includes, among others aliphatic and / or cycloaliphatic urethane (meth) acrylates, polyether (meth) acrylates, acrylamido-2-methylpropanesulfonic acid. If these compounds are not water-soluble, they are advantageously added to the barrier materials according to the invention in the form of aqueous dispersions. Already additions from
  • the barrier materials according to the invention can optionally be modified by further additives.
  • known additives are pigments to give the barrier materials a colored appearance.
  • the term “pigments” is understood in general to mean dyes, coloring compounds, fillers and extenders of all types, which provide the inventive barrier materials with additional solids and, if appropriate, also make them printable. At the same time, they give the barrier materials a number of specific properties.
  • the content of pigments and fillers can be between 0.5 and 80, preferably 1.0 and 70% by weight.
  • the barrier materials can also contain plasticizers. Particularly suitable plasticizers are water-soluble products, such as polyols, such as, for example, diols, glycols, glycerol, sorbitol, inositol and other sugar alcohols, which may have reactive groups according to the above formula.
  • the barrier materials according to the invention can contain further additives, e.g. Stabilizers, antioxidants, leveling and wetting agents are added.
  • additives e.g. Stabilizers, antioxidants, leveling and wetting agents are added.
  • the barrier materials according to the invention offer a further advantage when processing and producing barrier layers and films because they remain water-soluble or water-dispersible. Only through hardening or crosslinking are these properties partially or completely eliminated, depending on the content of reactive groups. Thus, the person skilled in the art is provided with a barrier material with which he is familiar and whose properties he knows.
  • the barrier materials according to the invention are in solid form as powders, granules and the like or as aqueous gels, solutions and / or dispersions. For processing they have to
  • the hydrocolloids according to the invention are particularly environmentally friendly from this point of view.
  • crosslinking co-reactants reaction initiators and optionally other additives and / or additives are also added and incorporated in an aqueous, liquid phase in the hydrocolloids according to the invention.
  • simple mixing containers with suitable mixing tools can be used, which, if necessary, must be heated to melt the gels.
  • the preparation and processing can also be carried out continuously, which includes Extruders, mixing screws are suitable.
  • barrier materials according to the invention include gases, e.g. Air, must be degassed with a vacuum before application.
  • Another object of the invention is the equipping of substrates with the polymerizable barrier materials according to the invention or the production of self-supporting barrier films.
  • the polymerizable barrier materials according to the invention are used, inter alia, to form layers for flat substrates and moldings. out
  • Cellulose materials such as Paper, cardboard and cardboard of all kinds,
  • Plastics such as foils and sheets made of polyvinyl alcohol, polyethylene, polypropylene, polycarbonate, polyester, polyvinyl esters, polyamides, polyvinyl halides and their copolymers, as well as fiber composites Thermoplastics and thermosets, but also
  • the barrier materials according to the invention are also particularly suitable as so-called top coats of substrate surfaces equipped with vapor deposition layers of metals or oxides of silicon (Si), aluminum (Al) and / or magnesium (Mg), because they have their gas and Improve water vapor impermeability values again by very high factors.
  • barrier properties of the barrier materials according to the present invention can be varied within wide limits.
  • the barrier properties of the barrier materials according to the present invention can be varied within wide limits.
  • the barrier properties are essentially determined by the type of hydrocolloids according to the invention and their dehydration behavior, as has surprisingly been found.
  • Particularly high permeation reductions are provided by hydrocolloids which, from their aqueous solutions and / or gels, do not dehydrate or dry via pores or capillary activities, but rather via diffusion processes.
  • hydrocolloids according to the invention which form gels or are subjected to a sol / gel transformation in the uncrosslinked state and have a content of reactive groups of between 20 and 50% by weight.
  • those hydrocolloids according to the invention which are of collagenic origin, for example gelatin, are suitable.
  • the barrier properties of the hydrocolloids according to the invention can optionally be further improved if
  • crosslinking agents are also used and / or
  • the dehydration or drying of the uncrosslinked and crosslinked layers, coatings, films, foils or the like also has an influence on the polymer network formations and their barrier layer properties.
  • the dehydration or drying is therefore carried out under conditioned climates, with pre-dried air with a relative humidity of ⁇ 40% and low temperatures ⁇ 100 ° C. being particularly preferred.
  • the cured or crosslinked barrier materials, films and / or films according to the invention have a dependency
  • barrier layers with excellent functionalities against a variety of gases, vapors and / or liquids, e.g. Oxygen-containing gases and vapors, but also water vapor and volatile vapors form a focus.
  • the barrier materials according to the invention also have good resistance to organic solvents, such as alcohols; Oils and fats; as well as a variety of weak acids and bases.
  • the chemical resistance is essentially influenced by the basic hydrocolloid, the degree of crosslinking and the crosslinking density.
  • the hardened or crosslinked barrier materials according to the invention have greatly reduced requellabilities, which may also have a positive effect on the barrier properties, as has surprisingly been found.
  • barrier layers can be produced with the barrier materials according to the present invention.
  • These barrier layers according to the invention provide barrier factors which can be up to 10 7 higher than their unmodified basic hydrocolloids. These potential improvements were surprising because the barrier factors of the unmodified hydrocolloids are generally ⁇ 10 2 .
  • permeation values can be determined, among other things
  • the barrier materials according to the invention adhere to a large number of substrate surfaces.
  • a surface pretreatment may be necessary to improve the wetting and adhesion of the surfaces to be coated. This is particularly the case when these surfaces are non-polar, such as with polyolefinic substrates. Flame treatment, corona discharge, low-pressure plasma and / or adhesive primer are suitable for surface pretreatment.
  • Self-supporting barrier films and foils can be made from the barrier materials according to the invention, among others. by pouring onto an adhesive base, then hardening or crosslinking and dehydrating. The process conditions are analogous to the above.
  • the hydrocolloids according to the invention lose their hydrocolloidal properties as a result of curing, crosslinking and / or polymerizing. That the layers, coatings, films, foils and the like produced in this way are no longer water-soluble and / or water-dispersible, but instead deliver, inter alia, boiling water-resistant and possibly sterilization-proof network polymers. Furthermore, the temperature-dependent reversible transforms into an irreversible sol / gel transformation. In water, the polymer networks can still have a relatively weak self-swelling.
  • the new polymer networks include resistant to water, water-containing media, salt solutions, weak acids and bases, sugar solutions, fruit juices, milk, alcoholic beverages, soft drinks, milk and milk products, oils, fats, organic solvents and are therefore particularly suitable for equipping packaging materials and packaging materials made of different materials .
  • sensor-sensitive products such as Coffee, fruit powder and the like offer excellent protection to the barrier layers because they are diffusion-tight against a large number of aromatic media.
  • the hardened barrier layers, coatings, films and foils are sensor-neutral and do not have or have a so-called "scalping effect" against any filling goods or the like.
  • the barrier materials according to the invention hardened by means of UV and electron beams are additionally sterile.
  • the new polymer networks which were formed by curing, crosslinking and / or polymerizing the barrier materials according to the invention, have furthermore remained biodegradable, as has surprisingly been found.
  • the hardened barrier materials can be broken down in an acidic or alkaline environment within a few days. When buried in the ground or when composting, biodegradation takes several days to a few weeks.
  • Special areas of application for additive-, monomer-free, polymerizable barrier materials according to the present invention are the packaging and packaging areas for food and pharmaceutical products.
  • they In order to be able to provide packaging and packaging materials for these fields of application in the future, they not only have to be manufactured and processed under stricter legal requirements, but they also have to meet the increased requirements of food and pharmaceutical legislation in terms of their physiological and sensory behavior.
  • new barrier materials as coating compositions are necessary, which are based on other innovative, new technologies. According to the present invention, this object can be successfully achieved technically and economically with the, in particular additive and monomer-free, polymerizable barrier materials because:
  • barrier materials according to the present invention can be used to produce porous and / or absorbent substrates, such as e.g. Impregnate cellulose materials, in particular paper, cardboard, cardboard, wood, wood-based materials and the like, in order to give them highly functional barrier properties.
  • porous and / or absorbent substrates such as e.g. Impregnate cellulose materials, in particular paper, cardboard, cardboard, wood, wood-based materials and the like, in order to give them highly functional barrier properties.
  • barrier materials are created which are not comparable to the known barrier polymers. This not only largely eliminates the described and other known disadvantages, but also completely new barrier polymers and materials are provided which are better able to cope with current and future aspects and requirements, particularly in the food and pharmaceutical sectors.
  • This new class of barrier polymers according to the present invention offers the following advantages, among others: - natural polymers available from national resources
  • the starting hydrocolloids are preferably foods or approved additives for foods
  • the barrier materials according to the present invention are potentially superior to them and thus make essential contributions to improving the ecology, environment and waste disposal and are physiologically and toxicologically much safer.
  • Derivatized high-blooming type A gelatin gels (20% W / W) of the types given in Table 2 were applied to 210 g / m 2 cardboard by hand knife and irradiated with 180 keV electrons.
  • the radiation dose was 40 kGy.
  • N 2 permeability of the cardboard coated with cross-linked gelatin The ratio becomes the barrier factor for O 2 Q 2 permeability of the substrate
  • Films with a thickness of 25 ⁇ m were applied and irradiated with 180 keV electrons.
  • the radiation dose was 40 kGy. Permeabilities and barrier factors were measured.
  • Derivatized high-blooming type A gelatin of the type given in Table 4 was applied with a hand knife to polyester film precoated with SiOx and irradiated with 180 keV electrons.
  • the radiation dose was 40 kGy.
  • the oxygen permeability of the gelatin-coated film was measured.
  • Derivatized Type A gelatin of the types listed in Table 5 was mixed with aqueous dispersions of various monomeric and oligomeric acrylates such as TMPTA, polyether acrylates and polyester acrylates.
  • the acrylic concentration was between 1 and 10% by weight.
  • the mixtures were applied to 60 g / m 2 paper with a hand knife and irradiated with 180 keV electrons.
  • the radiation dose was 40 kGy.
  • Table 5 shows barrier factors and O 2 permeabilities of the coated ones
  • the biodegradability of the irradiated, i.e. cross-linked coating material was tested by in vivo and in vitro tests.
  • the in vitro test includes the treatment of the coating material in the form of films with a thickness of 20 ⁇ m with the protease pepsin at 37 ° C. over a period of 7 days.
  • the radiation intensity used for the crosslinking there are different mass changes, based on the starting mass after the enzymatic hydrolysis.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour objet un nouveau type de matériau d'arrêt résistant à l'eau, destiné en particulier à être utilisé pour le garnissage, le formage ou la structure de couches ou de films de protection, adhésifs ou intermédiaires ou pour la production de feuilles sans supports, doté de remarquables propriétés d'arrêt vis-à-vis de milieux ambiants gazeux et/ou liquides, en particulier oxygène, air, vapeur d'eau et analogue. Une simple couche d'un tel matériau présente des degrés de perméabilité à l'oxygène et à l'eau extrêmement faibles.
PCT/EP1996/001862 1995-05-18 1996-05-04 Materiau d'arret resistant a l'eau WO1996036653A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96919668A EP0826010A2 (fr) 1995-05-18 1996-05-04 Materiau d'arret resistant a l'eau
AU58135/96A AU5813596A (en) 1995-05-18 1996-05-04 Water-resistant barrier material
JP8534505A JPH11500484A (ja) 1995-05-18 1996-05-04 耐水性遮断剤の使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995118247 DE19518247A1 (de) 1995-05-18 1995-05-18 Wasserresistentes Barrierematerial
DE19518247.2 1995-05-18

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WO1996036653A2 true WO1996036653A2 (fr) 1996-11-21
WO1996036653A3 WO1996036653A3 (fr) 1997-01-09

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EP (1) EP0826010A2 (fr)
JP (1) JPH11500484A (fr)
AU (1) AU5813596A (fr)
CA (1) CA2219628A1 (fr)
DE (1) DE19518247A1 (fr)
WO (1) WO1996036653A2 (fr)

Cited By (5)

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WO1999008717A2 (fr) * 1997-08-15 1999-02-25 Surmodics, Inc. Polymeres reactifs latents avec fractions biologiquement actives
WO1999058331A1 (fr) * 1998-05-13 1999-11-18 Tetra Laval Holdings & Finance S.A. Lamine impermeable au gaz a base d'amidon pour conditionnement, procede de production de ce lamine et recipients de conditionnement
US6506895B2 (en) 1997-08-15 2003-01-14 Surmodics, Inc. Photoactivatable nucleic acids
US6667082B2 (en) 1997-01-21 2003-12-23 Cryovac, Inc. Additive transfer film suitable for cook-in end use
US7812224B2 (en) 1997-04-04 2010-10-12 Board Of Regents Of University Of Nebraska Methods and materials for making and using transgenic dicamba-degrading organisms

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DE19746750A1 (de) * 1997-10-23 1999-05-12 Volker Schneck Strangförmiges Dichtband zum Einlegen in Trennfugen eines Betonmauerwerks
DE10012686A1 (de) * 2000-03-15 2001-09-27 Apack Ag Bio Verpackungen Beschichtung von biologisch abbaubaren Formkörpern
DE10032361A1 (de) * 2000-07-04 2002-01-24 Fraunhofer Ges Forschung Verbundsystem aus Trägermaterial und mindestens einer eine Barrierematerial enthaltenden Schicht
WO2002094555A1 (fr) * 2001-05-22 2002-11-28 Membrana Gmbh Lamine, procede de production du lamine et vetement contenant ce lamine
DE102005031250A1 (de) * 2005-07-04 2007-01-18 Richard Dr. Shah Alam Cropp Kollagenbeschichtung von Einmalfaserverpackungen und Lebensmittelbehältern
SE0700404L (sv) * 2007-02-19 2008-08-20 Xylophane Ab Polymerfilm eller -beläggning innefattande hemicellulosa
CN103757983A (zh) * 2014-02-17 2014-04-30 陕西科技大学 一种改性水解胶原蛋白固体施胶剂及其制备方法
DE102022119507A1 (de) * 2022-08-03 2024-02-08 Gelita Ag Verfahren zur Herstellung eines Papiers mit einer verbesserten Fett- und Öldichtigkeit, hergestelltes Papier und dessen Verwendung

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US4142013A (en) * 1974-10-07 1979-02-27 Hoechst Aktiengesellschaft Shaped article of cellulose hydrate with a coating of plastic material of chemically modified protein and process for the production thereof
GB1544155A (en) * 1977-08-24 1979-04-11 Fuji Oil Co Ltd Method for preparing protein-coated film
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EP0649870A1 (fr) * 1993-10-20 1995-04-26 Kureha Kagaku Kogyo Kabushiki Kaisha Film de barrière aux gaz et sa production

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6667082B2 (en) 1997-01-21 2003-12-23 Cryovac, Inc. Additive transfer film suitable for cook-in end use
US7183006B2 (en) 1997-01-21 2007-02-27 Cryovac, Inc. Additive transfer film suitable for cook-in end use
US7812224B2 (en) 1997-04-04 2010-10-12 Board Of Regents Of University Of Nebraska Methods and materials for making and using transgenic dicamba-degrading organisms
US8119380B2 (en) 1997-04-04 2012-02-21 Board Of Regents Of University Of Nebraska Methods and materials for making and using transgenic dicamba-degrading organisms
US8629323B2 (en) 1997-04-04 2014-01-14 Board Of Regents Of The University Of Nebraska Methods and materials for making and using transgenic dicamba-degrading organisms
WO1999008717A2 (fr) * 1997-08-15 1999-02-25 Surmodics, Inc. Polymeres reactifs latents avec fractions biologiquement actives
WO1999008717A3 (fr) * 1997-08-15 1999-05-06 Surmodics Inc Polymeres reactifs latents avec fractions biologiquement actives
US6121027A (en) * 1997-08-15 2000-09-19 Surmodics, Inc. Polybifunctional reagent having a polymeric backbone and photoreactive moieties and bioactive groups
US6506895B2 (en) 1997-08-15 2003-01-14 Surmodics, Inc. Photoactivatable nucleic acids
US6514734B1 (en) 1997-08-15 2003-02-04 Surmodics, Inc. Polybifunctional reagent having a polymeric backbone and latent reactive moieties and bioactive groups
WO1999058331A1 (fr) * 1998-05-13 1999-11-18 Tetra Laval Holdings & Finance S.A. Lamine impermeable au gaz a base d'amidon pour conditionnement, procede de production de ce lamine et recipients de conditionnement
US6692801B1 (en) 1998-05-13 2004-02-17 Tetra Laval Holdings & Finance S.A. Starch based gas barrier laminate

Also Published As

Publication number Publication date
EP0826010A2 (fr) 1998-03-04
JPH11500484A (ja) 1999-01-12
DE19518247A1 (de) 1996-11-21
AU5813596A (en) 1996-11-29
CA2219628A1 (fr) 1996-11-21
WO1996036653A3 (fr) 1997-01-09

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