MXPA06007904A - Polyformals and copolyformals as a protective layer against hydrolysis on polycarbonate - Google Patents

Abstract

The invention relates to a multilayered products which are protected against hydrolysis, comprising at least one layer containing a thermoplast and at least one layer containing at least one polyformal or copolyformal, in addition to compositions containing polyformal or copolyformals and possible additives, in addition to the use of polyformals or copolyformals in the production of a layer which protects against hydrolysis.

Description

POLIFORMAL AND IFORMAL COPOINTS AS A LAYER FOR THE PROTECTION AGAINST HYDROLYSIS ON POLYCARBONATE DESCRIPTION OF THE INVENTION The present invention deals with multi-layer products protected against hydrolysis, in particular sheets, films, containers such as for example water bottles, baby bottles or medical articles, comprising at least one layer containing a thermoplastic material and at least one layer containing at least one polyformal or copolyformal, and polyformal or copolyformable containing compositions and possible additives, and the use of polyformals and / or copolyformals to produce a layer for protection against hydrolysis. The present invention also relates to a process for producing these multilayer products, such as sheets, medical articles or various containers, such as bottle products, baby bottles, water bottles and other products containing said sheets. The solid or multi-walled sheets are generally coated, for example, on one or two sides with coextrusion layer (s) for UV light on the outer sides, to protect them from damage (eg yellowing) by UV light. However, other multi-layer products are also protected in the same way REF: 173991 of damage by UV light. In contrast, the application of a thermoplastic material as a layer that provides protection against hydrolytic damage is not described in the prior art. The prior art with regard to multi-layer protected products is summarized below: EP-A 0 110 221 discloses sheets comprising two layers of polycarbonate, a layer containing at least 3% by weight of a UV light absorber. These sheets can be produced by means of coextrusion according to EP-A 0 110 221. EP-A 0 320. 632 describes molded articles comprising two layers of thermoplastic polymer, preferably polycarbonate, a layer containing benzotriazoles substituted especially as UV light absorbers. EP-A 0 320 632 also describes the production of these molded articles by co-extrusion. EP-A 0 247 480 discloses multilayer sheets in which in addition to a sheet made of thermoplastic polymer, a sheet made of branched polycarbonate is present, the sheet made of polycarbonate contains benzotriazoles substituted especially as UV light absorbers. In the same way, the production of these sheets is described by co-extrusion.

EP-A 0 500 496 discloses polymeric compositions stabilized with special triazines against UV light and their use as an outer layer in multilayer systems. Polycarbonate, polyesters, polyamides, polyacetals, polyphenylene oxide and polyphenylene sulfide are cited as polymers. According to the prior art, water bottles, such as for example 19 liter bottles (5 gallons), do not have a multi-layer construction (DE 19943642, DE-19943643, EP-A 0411433). The same applies to milk bottles or reusable baby bottles. Polycarbonate containers are produced, for example, by means of extrusion blow molding or air blow molding. In extrusion-air blow molding, the granules are generally melted with an individual screw extruder and are molded through a nozzle to form a self-standing parison, which is then enclosed by an insufflation mold which compresses the parison together at the lower end. Inside the mold, the parison is inflated to give it the desired shape. After a period of cooling, the mold is opened and the molded article by blowing air can be removed (described in greater detail for example in Brinkschroder, F. J. "Polycarbonate" in Becker, Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag, Munich, Vienna 1992, pages 257 to 264). For extrusion-blow molding it is advantageous to use a highly pseudoplastic polycarbonate in order to obtain a high stability of the molten material.

The branched polycarbonates are particularly pseudoplastic. Injection-insufflation molding is a combination of injection molding and air insufflation molding. The process takes place in three steps: 1) Injection molding of the parison in the plastic temperature range of the polycarbonate 2) Parison in the thermoplastic polycarbonate range (the core of the injection mold is also the mandrel, insufflation) 3) Removal of the molded article by air insufflation and optional air cooling of the insufflation mandrel (described in greater detail for example in Anders, S., Kaminski, A., Kappenstein, R., "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Cari Hanser Verlag, Munich, Vienna 1992, pages 223 to 225).

However, none of the products known in the prior art achieves satisfactory results in each respect, particularly as far as long-term stability in relation to hydrolysis is concerned. Water damages polycarbonate above 60 ° C. Prolonged contact with boiling water leads to molecular weight reduction, which is further accelerated in the presence of thermal stabilizers such as organic phosphites. In addition, the polycarbonates can be hydrolyzed preferably under alkaline conditions. Microwave radiation further accelerates this degradation. In the prior art patents there is never mention of layers for protection against hydrolysis to overcome this disadvantage. Therefore, starting from the prior art, the objective was to provide a multilayer sheet or coated containers such as, for example, water bottles or medical articles, which must be able to be sterilized in superheated steam, which exhibits improved properties compared to the prior art, such as improved long-term stability with respect to hydrolysis in water, even at elevated temperatures, and in the acidic environment and also the basic environment. This is the fundamental objective of the present invention.

This object is surprisingly achieved by means of coatings containing certain polyformals or copolyformables such as the polymer base. The coatings of products based on polyformals or copolyformals exhibit a surprising superiority over the prior art in terms of markedly superior resistance to hydrolysis compared to polycarbonate. This is particularly surprising because the polyformals can be considered as complete acetals, which, according to the current doctrine that is maintained by the person skilled in the field, must exhibit a high sensitivity to hydrolysis, at least in the acidic environment. . However, in contrast to this, coatings made from polyformals are resistant to hydrolysis even in relation to acid solutions and even at elevated temperatures. Thus, the present application provides polyformal or copolyformable containing coatings having the general formulas (a) or (lb), 1a 1b where the radicals O-D-0 and O-E-0 represent any diphenolate radical, in which -D- and -E- are aromatic radicals having from 6 to 40 carbon atoms, preferably from 6 to 21 carbon atoms, which may contain one or more condensed aromatic or aromatic nuclei, containing optionally heteroatoms and are optionally substituted by alkyl radicals of 1 to 12 carbon atoms or halogen and may contain aliphatic radicals, cycloaliphatic radicals, aromatic nuclei or heteroatoms as connecting bonds and in which k represents an integer between 1 and 1500, preferably between 2 and 1000, particularly preferably between 2 and 700 and more preferably between 5 and 500 and especially preferably between 5 and 300 or represents numbers between 1 and 1500, preferably between 1 and 1000, particularly preferably between 1 and 700 and more preferably between 1 and 500 and especially preferably between 1 and 500 300 ym represents a fraction z / oyn represents a fraction (oz) / o, where z represents the numbers between O and ó. The preferred structural units of the polyformals and copolyformals according to the invention are derived from general structures having the formulas (2a), (2b), (2c) and (2d), (2d) wherein the parentheses describe the fundamental diphenolate radicals, in which R1 and R2, independently of one another, represent H, linear or branched alkyl or alkoxy radicals of 1 to 18 carbon atoms, halogen such as Cl or Br or represent an aryl radical or optionally substituted aralkyl, preferably represents H or straight or branched alkyl of 1 to 12 carbon atoms, particularly preferably represents H or alkyl radicals of 1 to 8 carbon atoms and more preferably represents H or methyl, X represents an individual bond, an alkylene radical of 1 to 6 carbon atoms, alkylidene of 2 to 5 carbon atoms carbon, cycloalkylidene of 5 to 6 carbon atoms, which can be substituted by alkyl of 1 to 6 carbon atoms, preferably methyl or ethyl radicals or an arylene radical of 6 to 12 carbon atoms, which can be optionally condensed with other aromatic rings containing heteroatoms, where p represents an integer between 1 and 1500, preferably between 2 and 1000, particularly preferably between 2 and 700, and more preferably between 5 and 500 and especially between 5 and 300, p represents numbers between 1 to 1500, preferably between 1 and 1000, particularly preferably between 1 and 700 and more preferably between 1 and 500 and especially preferably between 1 and 300 and q represents a fraction z / p and y represents a fraction (pz) / p, where z represents the numbers between 0 and p, and a part of the radicals -ODO- and -0-EO-independently of each other also represent a radica The derivative of one or more trifunctional compounds, as a result of which a third binding site, a branch of the polymer chain, occurs at this point. In this way, the polyformals or copolyformals can be linear or branched. The bisphenolate radicals in formulas (1) and (2) are particularly preferably derived from the suitable bisphenols mentioned below.

Hydroquinone, resorcinol, dihydroxybiphenyls, bis- (hydroxyphenyl) -alkanes, bis- (hydroxyphenyl) -cycloalkanes, bis- (hydroxyphenyl) -sulfides, bis- (hydroxy-phenyl) -ethers, bis- (hydroxyphenyl) -ketones, bis- (hydroxyphenyl) -sulfones, bis- (hydroxyphenyl) -sulphoxides, a, a '-bis- (hydroxyphenyl) -diisopropyl-benzenes and alkylated compounds in the ring and halogenated in the ring thereof and also a,? - bis- (hydroxyphenyl) -polysiloxanes are mentioned by way of example for the basic bisphenols of the general formula (1). Preferred bisphenols are, for example, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (ether-DOD), 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A), , 1-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane (bisphenol TMC), 1,1-bis- (4-hydroxyphenyl) -cciohexane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -1- phenylethane, 1,4-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis- [2 - (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) propane , bis- (3, 5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis- (3, 5-dimethyl-4-hydroxyphenyl) propane, bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2, -bis- (3, 5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 2,2-bis- (3, 5-dichloro-4-hydroxyphenyl) propane and 2, 2-bis- (3 , 5-dibromo-4-hydroxyphenyl) -propane. Particularly preferred bisphenols are, for example, 2, 2-bis- (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3, 5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis- (4-hydroxyphenyl) -1-phenylethane , - 2, 2-bis- (3, 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 1,1-bis- (4- hydroxyphenyl) -cciohexane and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane (bisphenol TMC). More particularly preferred are 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M) and 1,1-bis- (4-) hydroxyphenyl) -3,3,5-trimethyl-cyclohexane (bisphenol TMC). Particularly preferred are 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A) and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane (bisphenol TMC). The bisphenols can be used either alone or in a mixture with each other; both homopoliformal and copoliformal are included. The bisphenols are known from the literature or can be produced by methods known from the literature (see for example HJ Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Edition, Vol. 19, page 348). The polyformals according to the invention can be deliberately branched in a controlled manner by the use of small amounts of trifunctional compounds which are known as "branching agents." Some suitable branching agents are: phloroglycinol, 4,6-dimethyl-2,4,6-tri- ( 4-hydroxyphenyl) hepteno-2,4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -butyl, 1,3,5- tri (4-hydroxyphenyl) benzene; 1,1-, tri- - (-hydroxyphenyl) ethane; tri- (4-hydroxyphenyl) phenylmethane; 2,2-bis- [4, 4-bis- (4-hydroxyphenyl) cyclohexyl] propane; 2,4-bis- (4-hydroxyphenylisopropyl) phenol 2, 6-bis- (2-hydroxy-5'-methyl-benzyl) -4-methylphenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane; - (4-hydroxyphenylisopropyl) phenyl) orthothetaphthalic, tetra- (4-hydroxyphenyl) methane; tetra- (4- (4-hydroxyphenyl-isopropyl) phenoxy) methane; a, a, a "-tris- (4-hydroxyphenyl) - 1,3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3, 3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole; . 1, 4-bis- (4 ', 4"-dihydroxytriphenyl) methyl) benzene and in particular: 1,1, 1-tri- (4-hydroxyphenyl) ethane and bis- (3-methyl-4-hydroxyphenyl) -2 -oxo-2,3-dihydroindole The use of these branching agents leads to corresponding deviations in formulas (1) and (2) of their idealized structure, which means that according to the amount of branching agent used, may producing structural units having three linking units, which can also be formed as ester functions, etc., depending on the branching agent used, which are derived from the branching agents used. 0.05 to 2% by mol of branching agents or mixtures of branching agents that can optionally be incorporated, in relation to the diphenols used, can be added together with the diphenols but can also be added in a last stage of the synthesis. Phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof are preferably used as chain terminators for polyformals used as materials in the coextruded coating, in amounts of 1-20% in mol, preferably 2-10% in mol, per mol of bisphenol. Preferred are phenol, 4-tert-butyl-phenol or cumyl-phenol. The polyformals and copolyformals having the formulas (la) and (lb) or (2 ad) are produced, for example, by means of a solution process, characterized in that the bisphenols and chain terminators are reacted with methylene chloride or alpha, alpha-dichlorotoluene in a homogeneous solution of methylene chloride or, a-dichlorotoluene and a suitable solvent with high boiling, such as for example N-methyl-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-caprolactam (NMC), chlorobenzene, dichlorobenzene, trichlorobenzene or tetrahydrofuran (THF) in the presence of a base, preferably sodium hydroxide or potassium hydroxide, at temperatures between 30 and 160 ° C. Preferred solvents with high boiling point are NMP, DMF, DMSO and NMC, particularly preferably NMP, NMC, DMSO and more preferably NMP and NMC. The reaction can also be carried out in several stages. The separation of the cyclic impurities that is optionally necessary takes place after washing under neutral conditions of the organic phase by means of a precipitation process in or by means of the fractional combination of the crude product with a solvent that dissolves the cyclic compounds, by acetone example. The cyclic impurities dissolve almost completely in the solvent and can be almost completely separated by the combination in portions and the change of the solvent. After the combination, a content of cyclic compounds well below 1% can be achieved by using for example about 10 liters of acetone, which is added for example in 5 portions to a polyiforinal amount of about 6 kg. The polyformal and cyclic copolyformals can also be separated by means of a precipitation process in suitable solvents, which act as precipitants for the desired polymer and as solvents for the undesirable cyclic compounds. Preferably, these are alcohols or ketones. The reaction temperature for the polycondensation is from 30 ° C to 160 ° C, preferably from 40 ° C to 100 ° C, particularly preferably from 50 ° C to 80 ° C and more particularly preferably from 60 ° C to 80 ° C. The present invention thus provides the use of the described polyformals and copolyformals for the production of multilayer products, for example coextruded products such as multilayer sheets, these same multilayer sheets and also a process for the production of these multilayer sheets by co-extrusion, and to coat suitable compositions containing these polyformals or copolyformals. The present invention also provides a product containing the aforementioned multilayer sheet or other coated products that are based on polyformals. This product, which, for example, contains the above-mentioned multilayer film or which is coated itself, is preferably selected from the group consisting of baby bottles, water bottles or medical articles that can be sterilized in superheated steam. The multi-layer product according to the invention has numerous advantages. In particular, it has the advantage that a clear improvement in long-term stability is achieved, in particular in the stability towards hydrolysis in relation to aqueous media, through the layer for protection against hydrolysis which is based on polyformals. In addition to the fact that the sheet can be produced in an easy and inexpensive way, all the starting materials are available and are economical. In addition, the other positive properties of the polycarbonate, for example its good optical and mechanical properties, are not deteriorated or only insignificantly deteriorated in the multilayer product according to the invention. The multilayer products according to the invention have additional advantages compared to the prior art. The multilayer products according to the invention, such as bottles, can be produced, for example, by coextrusion-insufflation molding. This leads to advantages over a product obtained by the coating. For example, solvents do not evaporate in co-extrusion as is the case with coating systems. In addition, the coatings have a limited storage capacity. The - coextrusion does not have this disadvantage. In addition, coatings require technology complex For example, they require explosion-proof units if organic solvents are used, the recycling of solvents and therefore an expensive investment in the equipment. Coextrusion does not have this disadvantage. A preferred embodiment of the present invention is the aforementioned multi-layered sheet or various types of bottles, the base layer consisting of polycarbonate and / or copolycarbonate and / or polyester and / or copolyester and / or. polyester and / or polymethyl methacrylate carbonates and / or polyacrylates and / or mixtures of polycarbonate and polymethyl polyesters and / or methacrylates and the coextruded layer consists of polyformals or co-polyformals or mixtures thereof with (co) polycarbonate and / or (co) polyesters. According to the invention, multilayer products are preferred in which the layer for protection against hydrolysis is from 1 to 5000 μm in thickness, preferably from 5 to 2500 μm, more preferably from 10 to 500 μm. . The sheets can be solid sheets, multi-wall sheets, double-walled sheets, triple-walled sheets, four-walled sheets, and so on. The multilayer sheets may also have several profiles, such as for example X profiles or XX profiles. In addition, multiple-wall sheets can also be sheets of multiple corrugated walls.

A preferred embodiment of the present invention is a two-layer sheet consisting of a polycarbonate layer and a layer for protection against polyformal or copolyformal hydrolysis or a polycarbonate-polyformal mixture. A further preferred embodiment of the present invention is a three layer sheet consisting of a polycarbonate layer as the base sheet and two superimposed layers for protection against hydrolysis, which are the same or different and consist of polyformal or copolyformal or a polycarbonate-polyformal mixture. As an embodiment of the present invention, various types of containers are likewise preferred, such as bottles, for example, water bottles (5 gallon bottles), baby bottles or reusable milk bottles. The containers within the meaning of the present invention can be used for packing, storing or transporting liquids, solids or gases. Preferred are containers for the packaging, storage or transport of liquids (containers for liquids), containers for packaging, storage or transport of water (water bottles) are particularly preferred. The containers within the meaning of the invention are blown containers having a volume of preferably 0. 1 to 50 1, preferably from 0.5 to 50 1, the volumes of 1 1, 5 1, 12 1 and 20 1 are most particularly preferred. Water bottles having a volume of 11.4 to 19 1 (3 to 5 gallons) are most particularly preferred. The packages have an empty weight of preferably 0.1 g to 3000 g, preferably 50 g to 2000 g and particularly preferably 650 g to 900 g. The thickness of the wall of the containers is preferably 0.5 mm to 5 mm, preferably 0.8 mm to 4 mm. The containers within the meaning of the present invention have a length of preferably 5 mm to 2000 mm, particularly preferably 100 mm to 1000 mm. The packages have a maximum perimeter of preferably 10 mm to 250 mm, preferably 50 mm to 150 mm and much more preferably 70 to 90 mm. The containers within the meaning of the invention preferably have a bottle neck of a length of preferably 1 mm to 500 mm, preferably 10 mm to 250 mm, particularly preferably 50 mm to 100 mm and much more particularly preferable from 70 to 80 mm.

The thickness of the bottleneck wall of the containers varies between preferably 0.5 mm and 10 mm, particularly preferably between 1 mm and 10 mm and much more preferably between 5 mm and 7 mm. The diameter of the bottle neck varies between preferably 5 mm and 200 mm. Particularly preferred is from 10mm to 100mm and it is much more preferable from 45mm to 75mm. The bottle base of the packages according to the invention has a diameter of preferably 10 mm to 250 mm, preferably from 50 mm to 150 mm and much more preferably from 70 to 90 mm. The containers within the meaning of the present invention can have any geometric shape, they can be for example round, oval or polygonal or angular with for example from 3 to 12 sides. Round, oval and hexagonal shapes are preferred. The design of the containers can be based on any surface texture. The textures of the surface are preferably smooth or ribbed. The packages according to the invention can also exhibit several different surface textures. The ribs or ribs can run around the perimeter of the containers. They can also be separated by some distance or they can be separated by several different distances.

The surface textures of the containers according to the invention may exhibit rough or integrated textures, symbols, ornaments, national shields, company logos, trademarks, monograms, manufacturer's instructions, material descriptions and / or volume information. The containers according to the invention can 'exhibit any variety of handholds, which may be located on the side, top or bottom. The handles can be external or they can be integrated in the contour of the container. The handles can be bent or fixed. The handles can be of any shape, for example oval, round or polygonal. The length of the handles is preferably from 0.1 mm to 180 mm, preferably from 20 mm to 120 mm. In addition to the polycarbonate according to the invention, the packages according to the invention can also contain other substances to a small degree, for example seals made of rubber or handles made of other materials. The packages according to the invention are preferably produced by means of extrusion molding - air insufflation or injection molding - air insufflation. In a preferred embodiment of the process for producing the packages according to the invention, the polycarbonates according to the invention are processed in extruders having a smooth or notched feed section, preferably a smooth feed section. The drive power of the extruder is selected according to the screw diameter. As an example, with a spindle diameter of 60 mm, the extruder drive power is approximately 30 to 40 kW, with a spindle diameter of 90 mm is approximately 60 to 70 kW. The three-section, universal spindles conventionally used in the processing of industrial thermoplastic products are suitable. For the production of packages having a volume of 1 1, a screw diameter of 50 to 60 mm is preferred. For the production of packages having a volume of 20 1, a spindle diameter of 70 to 100 mm is preferred. The length of the spindles is preferably 20 to 25 times the diameter of the spindle. In the case of blow molding, the inflation mold is preferably heated to 50 to 90 ° C to obtain a high-quality flashing package surface. To ensure uniform and effective heating of the insufflation mold, the base area and the sleeve area They can be heated separately. The insufflation mold is preferably closed with a compressive force of 1000 to 1500 N per cm of throttle welding length. Prior to processing, the polycarbonate according to the invention is preferably dried so that the optical quality of the packages is not diminished by striations or bubbles and the polycarbonate is not hydrolytically degraded during processing. The residual moisture content after drying is preferably less than 0.01% by weight. A drying temperature of 120 ° C. The lower temperatures do not guarantee adequate drying, while at higher temperatures there is a risk that the polycarbonate granules will stick together and can no longer be processed. Dry air dryers are preferred. The temperature of the preferred molten material during the processing of the polycarbonate according to the invention is 230 ° to 300 ° C. The containers according to the invention can be used for packing, storing or transporting liquids, solids or gases. The method is preferred so that the containers are used for example for packing, storing or transporting liquids. Particularly preferred is the modality for a bottle for water it can be used, for example, for packing, storing or transporting water. A preferred embodiment of the invention is one wherein the containers made of polycarbonate Branched are characterized in that the branched polycarbonate contains THPE and / or IBC as the branching agent and wherein the phenol or alkyl phenols are used as chain terminators in the production of the branched polycarbonate and wherein the container is a bottle for water. A particularly preferred embodiment of the invention is that wherein the package made of branched polycarbonate is characterized in that the branched polycarbonate contains THPE and / or IBC as a branching agent and wherein the phenol is used for the production of the branched polycarbonate and wherein polycarbonate has a melt viscosity of 5500 to 7000 Pas at 260 ° C and a shear rate of 10 s "1 and a melt viscosity of 900 to 1100 Pas at 260 ° C and a shear rate of 1000 s "1 and has a melt flow index (MFR), measured in accordance with ISO 1133) of <; 3.5 g / 10 minutes and where the container is a bottle for water. In a particular embodiment, the multi-layer products are transparent. Both the base material and the layer (s) for the protection against hydrolysis in the multilayer molded articles according to the invention may contain additives. Depending on the area of application, the layer for protection against hydrolysis may contain, in particular, UV light stabilizers or mold release agents. The layers may also contain other conventional processing aids, particularly mold release agents and flow control agents and stabilizers conventionally used in polycarbonates, particularly UV light stabilizers, heat stabilizers, as well as dyes and optical brighteners and pigments. inorganic Layers made of all known polycarbonates are suitable as additional layers, in addition to the polyformal and copolyformable layers, particularly as a base layer of the multilayer products according to the invention. Suitable polycarbonates are, for example, homopolycarbonates, copolycarbonates and thermoplastic polyestercarbonates. These preferably have average molecular weights M p of 18,000 to 40,000, preferably of 26,000 to 36,000 and particularly of 28,000 to 35,000, determined at measuring the relative solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering. With respect to the preparation of polycarbonates, reference is made by way of example to "Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience 'Publishers, New York, London, Sydney, 1964" and "DC PREVORSEK, -BT DEBONA and Y. KESTEN, Corporate Research Center, "Allied Chemical Corporation, Moristown, New Jersey 07,960. "Synthesis of Poly (ester) Carbonate Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, 75-90 (1980) "and a" D. Freitag, U. Grigo, P.R. Müller. N. Nouvertne, BAYER AG,? Polycarbonates' in Encyclopedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pages 648-718"and finally to" Drs. U. Grigo, K. Kircher and P.R. Müller? olycarbonate 'in Becker / Braun, Kunststoff-Handbuch, Vol. 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-229. "The production of the polycarbonates is preferably carried out by means of the process of interfacial polycondensation or the interesterification process of molten material and is described below using the interfacial polycondensation process as an example. starting compounds are bisphenols having the general formula HO-Z-OH, wherein Z is an organic, bivalent radical having from 6 to 30 carbon atoms and containing one or more aromatic groups. Examples of these compounds are bisphenols belonging to the group of dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, indane-bisphenols, bis- (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) ketones, a'bis (hydroxyphenyl) ) -diisopropyl-benzenes. Particularly preferred bisphenols belonging to the above-mentioned groups of compounds are bisphenol A, tetraalkyl bisphenol A, 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] enne (bisphenol M), 1, 1 -bis- [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,1-bis- (4-hydroxyphenyl) -3,3,3-trimethylcyclohexane (BP-TMC) and optionally mixtures thereof. The bisphenol compounds to be used according to the invention are preferably reacted with carbonic acid compounds, in particular phosgene, or in the case of the interesterification process of molten material with diphenyl carbonate or dimethyl carbonate.

The polyester carbonates are preferably obtained by reacting the bisphenols mentioned above, at least one aromatic dicarboxylic acid and optionally carbonic acid equivalents. Examples of aromatic dicarboxylic acidsSuitable are phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone dicarboxylic acids. A part, up to 80% by mol, preferably from 20 to 50% by mol of the carbonate groups in the polycarbonates can be replaced by aromatic dicarboxylic acid ester groups. Examples of organic, inert solvents used in the interfacial polycondensation process are dichloromethane, the various dichloroethanes and chloropropane compounds, tetrachloromethane, trichloromethane, chlorobenzene and chlorotoluene; it is preferred to use chlorobenzene or dichloromethane or mixtures of dichloromethane and chlorobenzene. The interfacial polycondensation reaction can be accelerated by means of catalysts such as tertiary amines, in particular N-alkyl-piperadines or onium salts, Tributylamine, triethylamine and N-ethylpiperidine are preferably used. When the polymer is melted, the catalysts mentioned in DE-A 4 238 123 are preferably used.

The polycarbonates can be intentionally branched in a controlled manner by using small amounts of branching agents. Some suitable branching agents are: phloroglucinol, 4,6-dimethyl-2,4,6-tri- (-hydroxyphenyl) -heptene-2; 4,6-dimethyl-2,4,6,6-tri- (4-hydroxyphenyl) -heptane; 1,3,5-tri- (4-hydroxyphenyl) -benzene; 1,1, 1-tri- (4-hydroxyphenyl) -ethane; tri- (-hydroxyphenyl) -phenylmethane; 2,2-bis- [4, 4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane; 2, 4-bis- (4-hydroxyphenyl-isopropyl) -phenol; 2,6-bis- (2-hydroxy-5'-methylbenzyl) -4-methylphenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane; hexa- (4- (4-hydroxyphenyl-isopropyl) -phenyl) -ortoterephthalic acid ester; tetra- (4-hydroxyphenyl) -methane; tetra- (4- (4-hydroxyphenyl-isopropyl) -phenoxy) -methane; a, a, a '-tris- (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3, 3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole; 1,4-bis- (4 ', 4"-dihydroxytriphenyl) methyl) -benzene and in particular 1,1, 1-tri- (4-hydroxyphenyl) -ethane and bis- (3-methyl-4-hydroxyphenyl) - 2-oxo-2, 3-dihydroindole 0.05 to 2 mol% of the branching agents or mixtures of branching agents, which can optionally be incorporated, with respect to the diphenols used, can be added together with the diphenols, but it can also be added in the last stage of the synthesis.

Phenols such as phenol, alkylphenols such as cresol and 4-tere-butyl-phenol, chlorophenol, bromophenol, cumyl-phenol or mixtures thereof are preferably used as chain terminators, in amounts of 1-20% mol. preferably 2-10% in mol, per mol of bisphenol. Preferred are phenol, 4-tert-butyl-phenol or cumyl-phenol. The chain terminators and branching agents can be added to the synthesis either separately or together with the bisphenol. The production of polycarbonates by the interesterification process of molten material is described in DE-A 42 38 123 by way of example. Preferred polycarbonates are the bisphenol A-based homopolycarbonate, the 1,1-bis- (4-hydroxyphenyl) -3,3,3-trimethyl-cyclohexane-based homopolycarbonate and the copolycarbonates based on the two bisphenol A and 1, 1 monomers. -bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane and the copolycarbonates based on the two monomers bisphenol A and 4,4'-dihydroxydiphenyl (DOD). Particularly preferred is bisphenol A-based homopolycarbonate. All thermoplastic materials that are used in the products according to the invention may contain stabilizers. The adequate stabilized are, for example, stabilizers containing phosphines, phosphites or Si and other compounds described in EP-A 0 500 496. Examples which may be mentioned include triphenyl phosphites, diphenylalkyl phosphites, phenyldialkyl phosphites, tris- (nonylphenyl). phosphite, tetracis- (2,4-di-tert-butylphenyl) -4,4 '-biphenylene diphosphonite and triarylphosphite .. Triphenyl phosphite and tris- (2,4-di-tert-butylphenyl) are particularly preferred. phosphite. These stabilizers may be present in all layers of the multilayer products according to the invention. In other words, both in the so-called base and in the commonly called coextruded layer or layers. Different additives or additive concentrations may be present in each layer. The multilayer products according to the invention may also include from 0.01 to 0.5% by weight of esters or partial esters of monohydric to hexahydric alcohols, in particular of glycerol, pentaerythritol or Guerbet alcohols. The monohydric alcohols are, for example, stearyl alcohol, palmityl alcohol and Guerbet alcohols. An example of a dihydric alcohol is glycol. An example of trihydric alcohol is glycerin. Examples of tetrahydric alcohols are pentaerythritol and mesoerythritol.

Examples of pentahydric alcohols are arabitol, ribitol and xylitol. Examples of hexahydric alcohols are mannitol, glucitol (sorbitol) and dulcitol. The esters are preferably monoesters, diesters, triesters, tetraesters, pentaesters and hexaesters or mixtures thereof, in particular random mixtures of monocarboxylic, aliphatic, saturated acids of 10 to 36 carbon atoms and optionally hydroxymonocarboxylic acids, preferably with "monocarboxylic acids". , aliphatic, saturated of 14 to 32 carbon atoms and optionally hydroxy monocarboxylic acids Commercially available fatty acid esters, in particular of pentaerythritol and glycerol, may contain <60% of various partial esters as a consequence of their Production process The monocarboxylic, aliphatic, saturated acids having from 10 to 36 carbon atoms are, for example, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, stearic acid, hydroxystearic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacos acid anoic and octacosanoic acid Preferred monocarboxylic, aliphatic, saturated acids having from 14 to 22 carbon atoms are for example tetradecanoic acid, hexadecanoic acid, acid stearic acid, hydroxystearic acid, eicosanoic acid and docosanoic acid. The monocarboxylic, aliphatic, saturated acids, such as hexadecanoic acid, stearic acid and hydroxystearic acid are particularly preferred. The carboxylic, aliphatic, saturated acids of 10 to 36 carbon atoms and the fatty acid esters are either known per se from the literature or can be produced by methods known from the literature. Examples of pentaerythritol fatty acid esters are those of the particularly preferred monocarboxylic acids that were specified above. The esters of pentaerythritol and glycerol with stearic acid and hexadecanoic acid are particularly preferred. The esters of Guerbet alcohols and of glycerol with stearic acid and hexadecanoic acid and optionally with hydroxystearic acid are also particularly preferred. These esters may be present both in the base and in the co-extruded layer or layers. Different additives or concentrations may be present in each layer. The multilayer products according to the invention may contain antistatic agents.

Examples of antistatic agents are cationic compounds, for example quaternary ammonium, phosphonium or sulfonium salts, anionic compounds, for example alkyl sulfonates, alkyl sulfates, alkyl phosphates, carboxylates in the form of alkali metal salts or salts of alkaline earth metals, non-ionogenic compounds, for example polyethylene glycol esters, polyethylene glycol ethers, fatty acid esters, ethoxylated fatty amines. These antistatic agents can be present both in the base and in the coextruded layer or layers. Different additives or concentrations may be present in each layer. These are preferably used in the coextruded layer or layers. The multilayer products according to the invention may contain organic dyes, inorganic color pigments, fluorescent dyes and particularly preferably optical brighteners. These dyes may be present both in the base and in the coextruded layer or layers. Different additives or concentrations may be present in each layer. All the molding compositions that are used for the production of the multilayer products according to the invention, the raw materials and the solvents therein, can be contaminated with impurities As a result of the preparation and storage conditions, the objective is to work with starting materials that are as clean as possible. The individual components of the molding compositions can be mixed by a known means, both successively and simultaneously and both at room temperature and at elevated temperature. The additives, in particular the additives mentioned above, are preferably incorporated into the molding compositions for the products according to the invention by a known means by mixing the polymeric granules with the additives at temperatures of about 200 to 330 ° C in conventional units , such as internal mixers, single-screw extruders and two-rotor extruders, for example when combining the molten material or the extrusion of the molten material or when mixing the solutions of the polymer with solutions of the additives, followed by the evaporation of the solvents by a known means. The content of additives in the molding composition can be varied within wide limits and is controlled by the desired properties of the molding composition. The total content of additives in the molding composition is preferably up to about 20% by weight, preferably from 0.2 to 12% by weight, relative to the weight of the molding composition. Coextrusion is known per se from the bibliography (see for example EP-A 0 110 221 and EP-A 0 110 238). In the present case, the process is preferably carried out as follows. The extruders are connected to a coextrusion adapter to produce the core and the outer layer (s). The adapter is designed in such a way that the molten materials forming the outer layer (s) are adhesively applied as a thin layer to the molten material of the core. The multilayer fused material strand that is produced in this manner is then transferred to the adjacent nozzle in the desired shape (multi-walled sheet or solid sheet). The molten material is then cooled under conditions controlled by a known means by calendering (solid sheet) or vacuum calibration (multiwall sheet) and then cut into sections. A conditioning oven may optionally be connected after the calibration step to eliminate the voltage. Instead of connecting an adapter before the nozzle, the nozzle itself can also be designed in such a way that the materials. Fused join there. Multilayer compositions can also be produced according to the prior art by extrusion coating, coextrusion and coextrusion-air blowing molding. The invention is further explained by the following examples without being limited thereto. The examples according to the invention describe only the preferred embodiments of the present invention.

EXAMPLES Example 1 Synthesis of homopoliformal from bisphenol TMC: 7 kg (22.55 mol) of the TMC bisphenol, 2,255 kg (56.38 mol) of sodium hydroxide pellets and 51.07 g (0.34 mol) of finely ground p-tert-butyl-phenol (Aldrich) in 500 ml of methylene chloride are added. add to a solvent mixture consisting of 28.7 kg of methylene chloride and 40.18 kg of N- methyl-2-pyrrolidone (NMP) under nitrogen protective gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred for one hour at this temperature. After cooling to 25 ° C, the reaction batch is diluted with 35 1 of methylene chloride and 20 1 of demineralized water. The batch is washed with water in a separator until it is neutral and free of salts (conductivity <15 μS.cirf1). The organic phase of the separator is separated and the solvent exchange of methylene chloride by chlorobenzene is carried out in an evaporator. The material is then extruded by means of a ZSK 32 evaporation extruder at a temperature of 270 ° C with subsequent granulation. This synthesis procedure • is carried out twice. After discarding the feedstock, a total of 9.85 kg of polyformal is obtained as clear granules. It still contains low molecular weight cyclic formals as an impurity. The material is divided into two parts and each one is left to expand overnight with approximately 5 1 of acetone. The obtained products are combined with empty portions of fresh acetone until no cyclic compounds can be detected. After combining the purified material and dissolving it in chlorobenzene, it is again extruded through the evaporating extruder at 280 ° C. After discarding the feedstock, a total of 7.31 kg of polyformal is obtained as clear granules.

Analysis: • Molecular weight Pm = 38345, Mn = 20138, D = 1.90 by means of the calibration against polycarbonate (GPC, for its acronym in English). • Vitreous transition temperature. Tg = 170.8 ° C • Viscosity of relative solution in methylene chloride (0.5 g / 100 ml of solution) = 1.234 • Confirmation of the freedom of the polymer of cyclic compounds by means of the GPC (oligomers in a lower molecular weight range) and MALDI-TOF (the molecular weight of the cyclic compounds compared to the molecular weight of the open chain analogues).

Example 2 Homopolif or al from bisphenol A: 7 kg (30.66 mol) of bisphenol A (Bayer AG), 3.066 kg (76.65 mol) of sodium hydroxide pellets and 69.4 g (0.462 mol) of finely ground p-tert-butyl-phenol (Aldrich) in 500 ml of Methylene chloride is added to a mixture of solvents consisting of 28.7 kg of methylene chloride and 40.18 kg of N-methyl-2-pyrrolidone (NMP) under a nitrogen blanketing gas with stirring. After homogenization, the mixture is heated to reflux. (78 ° C) and stirred for one hour at this temperature. After cooling to 25 ° C, the reaction batch is diluted with 20 1 of methylene chloride and 20 1 of demineralized water. The batch is washed with water in a separator until it is neutral and free of salts (conductivity <15 μS.cm "1) .The organic phase of the separator is separated and solvent exchange of methylene chloride by chlorobenzene is carried out The material is then extruded by means of an evaporation extruder ZSK 32 at a temperature of 200 ° C with subsequent granulation.This synthesis procedure is carried out twice. , a total of 11.99 kg of polyformal is obtained as transpt granules.

Analysis: • Molecular weight Pm = 31732, Mn = 3465 by means of the calibration against polycarbonate (GPC). The compounds cyclicals did not separate in this case. It is not possible to expand the material with acetone, which means that the separation of the cyclic compounds is not possible either. • Vitreous transition temperature Tg = 89 ° C • Viscosity of relative solution in methylene chloride (0.5 g / 100 ml of solution) = 1.237 / 1.239 (double determination).

Example 3 a) Synthesis of the copoliformal to bisphenol TMC and bisphenol A part: . 432 kg (17.5 mol) of TMC bisphenol (x = 70 mol%), 1,712 kg (7.5 mol) of bisphenol A (y = 30 mol%), 2.5 kg (62.5 mol) of sodium hydroxide pellets and 56.33 g (0.375 mol) of finely ground p-tert-butyl-phenol (Aldrich) in 500 ml of methylene chloride added to a solvent mixture consisting of 28.7 kg of methylene chloride and 40.18 kg of N-methyl-2-pyrrolidone (NMP) under a protective nitrogen gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred for one hour at this temperature. After cooling to 25 ° C, the reaction batch is diluted with 35 1 of methylene chloride and 20 1 of demineralized water. The batch is washed with water in a separator until it is neutral and free of salts (Conductivity <15 μS.cm "1) The organic phase of the separator is separated and the solvent exchange of methylene chloride by chlorobenzene is carried out in an evaporator.The material is then extruded by means of an extruder of ZSK 32 evaporation at a temperature of 280 ° C with subsequent granulation.After discarding the feed material, a total of 5.14 kg of copolyformal is obtained as transpt granules.This still contains low molecular weight cyclic compounds as an impurity. The product obtained is combined with several portions of fresh acetone until no cyclic compounds can be detected.The purified material dissolves in chlorobenzene and is extruded again at 270 ° C through of the evaporation extruder. After discarding the feedstock, 3.11 kg of polyformal obtained as transpt granules.

Analysis: • Molecular weight Pm = 39901, Mn = 19538, D = 2.04 by means of the calibration against polycarbonate (GPC). • Vitreous transition temperature Tg = 148.2 ° C • Viscosity of relative solution in methylene chloride (0.5 g / 100 ml of solution) = 1.244 / 1.244 (granules) • MN- ^? in CDC13 shows the expected insertion ratio x / y = 0.7 / 0.3 of the TMC / BPA monomers (integral of the chemical changes of aliphatic, cyclic groups (TMC) to methyl groups (BPA)) b) a) Synthesis of copolyformals from bisphenol TMC and bisphenol A with a variable composition: The additional copolyformals are produced in the same manner as the synthesis in Example 3a) (see Table 1).

Example no. TMC [mol%] BPA [mol%] Tg [° C] 3b) 30 70 115 3c) 35 65 120 3d) 40 60 124 3e) 50 50 132 3f) 55 45 137 3g) 70 30 149 3h) 80 20 158 3i) 90 10 165 EXAMPLE 4 Synthesis of the copolyformal from the bisphenol TMC and the 4,4'-dihydroxybiphenyl (DOD): 3. 749 kg (12.07 mol) of TMC bisphenol (x = 90% by mol), 0.2497 kg (1.34 mol) of 4, 4'-dihydroxybiphenyl (DOD) (y = 10% by mol), 1339 kg (33.48 mol) of pellets Sodium hydroxide and 20.12 g (0.134. mo-1) of finely ground p-tert-butylphenol (Aldrich) in 200 ml of methylene chloride are added to a mixture of solvents consisting of 12.0 1 methylene chloride and 22.25 kg of N-methyl-2-pyrrolidone (NMP) under a nitrogen blanketing gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred for one hour at this temperature. After cooling to 25 ° C, the reaction batch is diluted with 35 1 of methylene chloride and 20 1 of demineralized water. The batch is washed with water in a separator until it is neutral and free of salts (conductivity <15 μS.cm "1) The organic phase of the separator is separated and the solvent exchange of methylene chloride by chlorobenzene is carried out in an evaporator.The material is then extruded by means of an evaporation extruder ZSK 32 at a temperature of 280 ° C with subsequent granulation After the feed material is discarded, a total of 2.62 kg of copolyformable is obtained as transparent granules.This still contains low molecular weight cyclic compounds as an impurity. let it expand overnight with approximately 5 1 acetone.The product obtained is combined with several portions of fresh acetone until no cyclic compounds can be detected.The purified material is dissolved in chlorobenzene and extruded again at 240 ° C through the evaporation extruder. After discarding the feedstock, the polyformal is obtained as transparent granules. Analysis: • Molecular weight Pm = 44287, Mn = 17877, D = 2.48 by means of the calibration against polycarbonate (GPC). • Vitreous transition temperature Tg = 167 ° C.

Example 5 Synthesis of the copolyformal from bisphenol A and 4,4'-dihydroxybiphenyl (DOD): 22. 37 g (0.0098 mol) of bisphenol A (x = 70% in mol), 7.82 g (0.0042 mol) of 4,4 '-dihydroxybiphenyl (DOD) (y = 30% in mol), 14.0 g (0.35 mol) of sodium hydroxide pellets and 0.21 g (0.0014 mol) of finely ground p-tert-butyl-phenol (Aldrich) are added to a mixture of solvents consisting of 125 ml of sodium chloride. methylene and 225 ml of N-methyl-2-pyrrolidone (NMP) under a nitrogen protective gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred at this temperature for one hour. After cooling to 25 ° C, the reaction batch is diluted with methylene chloride and demineralized water. It is then washed with water until it is neutral and free of salts (conductivity <15 μS.cm "1) .The organic phase is separated.The polymer is isolated by precipitating it in methanol.After washing the product with water and methanol and drying at 80 ° C, the polyformal is obtained as white filaments of polymers.

Analysis: • Molecular weight Pm = 19057, Mn = 4839, D = 3.94 by means of the calibration against polycarbonate (GPC).

Example 6 Hydrolysis test of the BPA polyformal Example 2 The hydrolysis test is carried out by loading with the following hydrolysis / temperature conditions and determining the change in molecular weight to over time by measuring the viscosity of relative solution in methylene chloride (0.5 g / 100 ml of solution): Hydrolysis medium: 0.1 N HCl / 80 ° C 0.1 N / 80 ° C NaOH distilled water / approx. 100 ° C The following results are obtained up to a total load period of 21 days (multiple determinations in each case): _ a) Hydrolysis medium: 0.1 N HCl / 80 ° C Time [days] Relative solution viscosity? Re? 0 1,237 / 1,239 (reference sample) 7 1,237 / 1,238 / 1,236 / 1,237 / 1,237 / 1,238 14 1,237 / 1,237 / 1,236 / 1,237 / 1,237 / 1,237 21 1,236 / 1,239 / 1,235 / 1,236 / 1,235 / 1,235 a) Hydrolysis medium: 0.1 N NaOH / 80 ° C Time [days] Relative solution viscosity? Re? 0 1,237 / 1,239 (reference sample) 7 1,237 / 1,238 / 1,237 / 1,237 / 1,236 / 1,237 14 1,237 / 1,237 / 1,236 / 1,236 / 1,236 / 1,236 21 1,236 / 1,236 / 1,236 / 1,236 / 1,236 / 1,235 a) Hydrolysis medium: distilled water / approx. 100 ° C Time [days] Relative solution viscosity? Re? 0 1,237 / 1,239 (reference sample) 7 1,238 / 1,237 / 1,238 / 1,237 / 1,237 / 1,237 14 21,238 / 1,237 / 1,237 / 1,237 / 1,237 / 1,235 were not measured Example 7 TMC / BPA copolyformation hydrolysis test (70/30) of example 3: The hydrolysis test is carried out by loading with the following hydrolysis / temperature conditions and the determination of molecular weight change over time by measuring the viscosity of the relative solution in methylene chloride (0.5 g / 100 ml of solution): Hydrolysis medium: 0.1 N HCl / 80 ° C 0.1 N / 80 ° C NaOH distilled water / approx. 100 ° C The following results were obtained up to a total load period of 21 days (multiple determinations in each case): a) Hydrolysis medium: 0.1 N HCl / 80 ° C Time [days] Relative solution viscosity? Re? 0 1,242 / 1,242 (reference sample, after spraying on the 80x10x4 test piece) 7 - 1,242 / 1,242 / 1,243 / 1,243 / 1,242 / 1,243 14 1,240 / 1,241 / 1,240 / 1,242 / 1,241 / 1,241 21 1,243 / 1,243 / 1,243 / 1,242 / 1,243 / 1,243 a) Hydrolysis medium: NaOH 0.1 N / 80 ° C Time [days] Relative solution viscosity? re? 0 1,242 / 1,242 (reference sample) 7 1,243 / 1,242 / 1,243 / 1,243 / 1,243 / 1,243 14 1,240 / 1,241 / 1,241 / 1,241 / 1,242 / 1,242 21 1,242 / 1,242 / 1,243 / 1,242 / 1,243 / 1,242 a) Hydrolysis medium: distilled water / approx. 100 ° C Time [days] Relative solution viscosity r \ rsl 0 1,242 / 1,242 (reference sample) 7 1,242 / 1,243 / 1,242 / 1,243 / 1,243 / 1,242 14 1,241 / 1,241 / 1,241 / 1,242 / 1,241 / 1,241 21 1,242 / 1,243 / 1,242 / 1,241 / 1,244 / 1,243 Example 8 Hydrolysis test of a TMC polyformal: (same as that of example 1, but with greater weight molecular) • Molecular weight Pm = 50311, Mn = 21637, D = 2.32 by means of the calibration against polycarbonate (GPC). • Vitreous transition temperature Tg = 172 ° C. • Viscosity of relative solution in methylene chloride (0.5 g / 100 ml of solution) = 1.288 / 1.290. The hydrolysis test is carried out by loading with the following hydrolysis media / temperature conditions and by determining the molecular weight change over time by measuring the relative solution viscosity in methylene chloride (0.5 g / 100 ml of solution): Hydrolysis medium: 0.1 N HCl / 80 ° C 0.1 N / 80 ° C NaOH distilled water / approx. 100 ° C The following results are obtained up to a total load period of 21 days (multiple determinations in each case): a) Hydrolysis medium: 0.1 N HCl / 80 ° C Time [days] Relative solution viscosity? re? 0 1,288 / 1,290 (reference sample, after spraying on the 80x10x4 test piece) 7 1,291 / 1,290 / 1,289 / 1,288 / 1,288 / 1,290 14 1,288 / 1,288 / 1,289 / 1,289 / 1,288 / 1,288 21 1,288 / 1,288 / 1,289 / 1,289 / 1,289 / 1,289 a) Hydrolysis medium: NaOH 0.1 N / 80 ° C Time [days] Relative solution viscosity? rel 0 1,288 / 1,290 (reference sample) 7 1,289 / 1,289 / 1,290 / 1,290 / 1,289 / 1,289 14 1,287 / 1,289 / 1,288 /1.289/1.286/1.287 21 1.287 / 1.288 / 1.294 / 1.294 / 1.288 / 1.288 a) Hydrolysis medium: distilled water / approx. 100 ° C Time [days] Relative solution viscosity? Re? 0 1,288 / 1,290 (reference sample) 7 1,285 14 1,281 21 1,284 EXAMPLE 9 Hydrolysis test of Makrolon 2808 ^ polycarbonate, Bayer AG (comparative experiments): The hydrolysis test is carried out by loading with the following hydrolysis media / temperature conditions and by determining the molecular weight change through of time when measuring the viscosity of Relative solution in methylene chloride (0.5 g / 100 ml of solution): Hydrolysis medium: 0.1 N HCl / 80 ° C 0.1 N / 80 ° C NaOH distilled water / approx. 100 ° C The following results are obtained up to a total load period of 21 days (multiple determinations in each case): a) Hydrolysis medium: 0.1 N HCl / 80 ° C Time [days] Relative solution viscosity? ReX 0 1,284 / 1,289 (reference sample, after spraying on the 80x10x4 test piece) 7 1,282 / 1,280 / 1,281 / 1,283 / 1,278 / 1,280 14 1,280 / 1,281 / 1,278 / 1,279 /1.280/1.280 21 1.275 / 1.276 / 1.276 / 1.276 / 1.277 / 1.277 a) Hydrolysis medium: 0.1 N NaOH / 80 ° C Time [days] Relative solution viscosity? Rel 0 1,284 / 1,289 (reference sample) 7 1,279 / 1,280 / 1,279 / 1,279 / 1,280 / 1,280 14 1,277 / 1,277 / 1,277 / 1,277 / 1,279 / 1,279 21 1,277 / 1,277 / 1,274 / 1,274 / 1,279 / 1,282 a) Hydrolysis medium: distilled water / approx. 100 ° C Time [days] Relative solution viscosity? R &? 0 1,284 / 1,289 (reference sample) 7 1,272 14 1,273 21 1,273 It can be clearly seen that after the hydrolysis charge the solution viscosity of the polycarbonate drops more abruptly than in the case of the polyformals. This means that the polycarbonate can degrade more easily and, therefore, is less stable than the polyformal. In this way, a coextrusion layer made of polyformal acts as a protective layer against premature damage of the sheet or the container.

EXAMPLE 10 Synthesis of the copoliformal from the TPC bisphenol and the resorcinol: 39. 1 g (0.126 mol) of the TMC bisphenol (x = 90% in mol), 1. 542 g (0.014 mol) of resorcinol (y = 10% in mol), 14.0 g (0.35 mol) of sodium hydroxide pellets and 0.21 g (0.0014 mol) of finely ground p-tert-butyl phenol (Aldrich) are added to a solvent mixture consisting of 125 ml of methylene chloride and 225 ml of N-methyl-2-pyrrolidone.

(NMP) under a nitrogen protective gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred at this temperature for one hour.

After cooling to 25 ° C, the reaction batch is diluted with methylene chloride and demineralized water, and then washed with water until neutral and free of salts (conductivity <15 μS.cirf1). The organic phase To stop. The polymer is isolated by precipitating it in methanol. After washing the product with water and methanol and separating the cyclic compounds with acetone and drying at 80 ° C, the polyformal is obtained as white polymer filaments.

Analysis: • Molecular weight Pm = 32008, Mn = 12251, D = 2.6 by means of the calibration against polycarbonate (GPC). • Vitreous transition temperature Tg = 163 ° C.

Example 11 Synthesis of the copoliformal from bisphenol TMC and m, p-bisphenol A: 14. 84 g (0.065 mol) of TMC bisphenol (x = 50 mol%), 20.18 g (0.065 mol) of m, p-bisphenol A (3,4-isopropylidene diphenol) (y = 50 mol%), 14.0 g (0.35 mol) of sodium hydroxide pellets and 0.21 g (0.0014 mol) of finely ground p-tert-butyl phenol (Aldrich) are added to a mixture of solvents consisting of 125 ml of methylene chloride and 225 ml of N-methyl-2-pyrrolidone (NMP) under a nitrogen protective gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred at this temperature for one hour. After cooling to 25 ° C, the reaction batch is diluted with methylene chloride and demineralized water and then washed with water until neutral and free of salts (conductivity <15 μS.cm "1). The organic phase is separated. The polymer is isolated by precipitating it in methanol. After washing the product with water and methanol and separating the cyclic compounds with acetone and drying at 80 ° C, the polyformal is obtained as white polymer filaments.

Analysis: • Molecular weight Pm = 28254, Mn = 16312, D = 1.73 by means of the calibration against polycarbonate (GPC). • Glass transition temperature Tg = 92 ° C.

Example 12 'Synthesis of the copoliformal from bisphenol A and from 4,4' sulfone-diphenol: 36. 29 g (0.145 mol) of 4,4 '-sulfone-diphenol (x = 50 mol%), 33.46 g (0.145 mol) of bisphenol A (y = 50 mol%), 28.8 g (0.72 mol) of pellets of sodium hydroxide and 0.436 g (0.0029 mol) of finely ground p-tert-butyl-phenol (Aldrich) are added to a mixture of solvents consisting of 300 ml of methylene chloride and 570 ml of N-methyl-2- pyrrolidone (NMP) under a nitrogen protective gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred at this temperature for one hour. After cooling to 25 ° C, the reaction batch is diluted with methylene chloride and demineralized water and then washed with water until neutral and free of water. salts (conductivity < 15 μS.crrf1). The organic phase is separated. The polymer is isolated by precipitating it in methanol. After washing the product with water and methanol and separating the cyclic compounds with acetone and drying at 80 ° C, the polyformal is obtained as white polymer filaments.

Analysis: • Molecular weight Pm = 21546, Mn = 7786, D = 2.76 by means of the calibration against polycarbonate (GPC). • Vitreous transition temperature Tg = 131 ° C.

Example 13 Synthesis of polyformal • from 4,4'-dihydroxyethyl ether: 28 30 g (0.14 mol) of ether 4, 4'-dihydroxy-enyl (Bayer AG), 14.0 g (0.35 mol) of sodium hydroxide pellets and 0.21 g (0.0014 mol) of finely ground p-tert-butyl-phenol (Aldrich) are added to a mixture of solvents consisting of 125 ml of methylene chloride and 225 ml of N-methyl-2-pyrrolidone (NMP) under nitrogen blanketing gas with stirring. After homogenization, the mixture is heated to reflux (78 ° C) and stirred at this temperature for one hour. After cooling to 25 ° C, the reaction batch is diluted with methylene chloride and demineralized water and then washed with water until neutral and free of salts (conductivity <15 μS.cm "1). The polymer is isolated by precipitating it in methanol, after washing the product with water and methanol and separating the cyclic compounds with acetone and drying at 80 ° C, the polyformal is obtained as white polymer filaments.

Analysis: • Molecular weight Pm = 24034, Mn = 9769, D = 2.46 by means of the calibration against polycarbonate (GPC). • Vitreous transition temperature Tg = 57 ° C.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (2)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. The use of at least one polymorph or .copoliformal to produce a coating for protection against hydrolysis for packaging. 2. The use according to claim 1, wherein the polyformals or copolyformals have the general formulas (la) or (lb), 1a 1b wherein the radicals ODO and OEO represent any diphenolate radical, in which -D- and -E- are aromatic radicals having from 6 to 40 carbon atoms, which may contain one or more condensed aromatic or aromatic nuclei, containing optionally heteroatoms and are optionally substituted by alkyl radicals of 1 to 12 carbon atoms or halogen and may contain aliphatic radicals, cycloaliphatic radicals, aromatic nuclei or heteroatoms as connecting bonds and in which k represents an integer between 1 and 1500 and m represents a fraction z / oyn represents a fraction (oz) / o, where z represents the numbers between 0 and a part of the radicals -ODO- and -OEO- independently of each other also represent a radical derived from one or more trifunctional compounds, as a result of which a third binding site, a branching occurs at this point of the polymer chain. 3. The containers, characterized in that they exhibit a coating for protection against hydrolysis according to claim 1 or 2. _ 4. Water bottles, bottles and medical articles, characterized in that they exhibit a coating for protection against water. hydrolysis according to claim 1 or
2. 2.