EP1709095A1 - Polyformals et copolyformals comme couche de protection contre l'hydrolyse appliquee sur du polycarbonate - Google Patents

Polyformals et copolyformals comme couche de protection contre l'hydrolyse appliquee sur du polycarbonate

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Publication number
EP1709095A1
EP1709095A1 EP05700725A EP05700725A EP1709095A1 EP 1709095 A1 EP1709095 A1 EP 1709095A1 EP 05700725 A EP05700725 A EP 05700725A EP 05700725 A EP05700725 A EP 05700725A EP 1709095 A1 EP1709095 A1 EP 1709095A1
Authority
EP
European Patent Office
Prior art keywords
hydroxyphenyl
polycarbonate
bis
mol
hydrolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05700725A
Other languages
German (de)
English (en)
Inventor
Helmut Werner Heuer
Rolf Wehrmann
Ralf Hufen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience 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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1709095A1 publication Critical patent/EP1709095A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D159/00—Coating compositions based on polyacetals; Coating compositions based on derivatives of polyacetals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/60—Bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2459/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only

Definitions

  • the present invention relates to hydrolysis-protected multilayer products, in particular sheets, foils, containers such as e.g. Water bottles, baby bottles or medical articles, comprising at least one layer containing a thermoplastic and at least one layer containing at least one polyformal or copolyformal, and compositions containing polyformals or copolyformals and possible additives, and the use of polyformals and / or copolyformals to produce a hydrolysis protective layer.
  • the present invention relates to a method for producing such multilayer products, such as plates, medical articles or various containers, such as bottle products, baby bottles, water bottles and other products which contain the plates mentioned.
  • Solid or multi-skin sheets for example, are usually provided on one or two sides with UV coextrusion layer (s) on the outside to protect them from damage (e.g. yellowing) by UV light. But other multi-layer products are also protected from damage by UV light.
  • UV coextrusion layer e.g. yellowing
  • other multi-layer products are also protected from damage by UV light.
  • the application of a thermoplastic as a protective layer against hydrolysis damage is not described in the prior art.
  • EP-A 0 110 221 discloses sheets made of two layers of polycarbonate, one layer containing at least 3% by weight of a UV absorber. These plates can be produced according to EP-A 0 110 221 by coextrusion.
  • EP-A 0 320 632 discloses moldings made from two layers of thermoplastic, preferably polycarbonate, one layer containing special substituted benzotriazoles as UV absorbers. EP-A 0 320 632 also discloses the production of these moldings by coextrusion.
  • EP-A 0 247 480 discloses multilayer plates in which a layer of branched polycarbonate is present in addition to a layer of thermoplastic material, the layer of polycarbonate containing special substituted benzotriazoles as UV absorbers. The production of these plates by coextrusion is also disclosed.
  • EP-A 0 500 496 discloses polymer compositions which are stabilized against UV light with special triazines and their use as an outer layer in multilayer systems.
  • Polymers are called polycarbonate, polyesters, polyamides, polyacetals, polyphenylene oxide and polyphenylene sulfide.
  • Water bottles such as B. 5-gallon bottles are not built up in multiple layers according to the prior art (DE 19943642, DE 19943643, EP-A 0411433). The same applies to reusable milk bottles or baby bottles.
  • the polycarbonate containers are manufactured, for example, by the extrusion blow molding process or by the injection blow molding process.
  • the granulate is usually melted with a single-shaft extruder and formed into a free-standing tube through a nozzle, which is then enclosed in a blow mold that squeezes the tube together at the lower end.
  • the tube is inflated within the mold so that the tube is given the desired shape.
  • the mold is opened and the hollow body can be removed (more precisely described, for example, by Brinkschröder, FJ "Polycarbonate” in Becker, Braun, plastic manual, volume 3/1, polycarbonates, polyacetals, polyester, cellulose esters, Carl Hanser Verlag, Kunststoff, Vienna 1992, pages 257 to 264).
  • the injection blow molding process is a combination of injection molding and blow molding.
  • This object is the basis of the present invention.
  • the coatings of products based on the polyformals or copolyformals show a surprising superiority over the prior art in terms of the significantly greater resistance to hydrolysis compared to polycarbonate.
  • polyformals can be regarded as full acetals, which, according to the conventional teaching of the person skilled in the art, should show great sensitivity to hydrolysis, at least in an acidic environment.
  • the polyformal coatings are also hydrolysis-resistant to acidic solutions, even at higher temperatures.
  • the present application thus relates to coatings which contain polyformals or copolyformals of the general formulas (la) and (lb),
  • residues OD-0 and OEO stand for any diphenolate residues in which -D- and -E- are aromatic residues with 6 to 40 C atoms, preferably 6 to 21 C atoms, which contain one or more aromatic or condensed aromatic, possibly containing nuclei containing heteroatoms can and are optionally substituted with C j -C ⁇ alkyl radicals or halogen and may contain aliphatic radicals, cycloaliphatic radicals, aromatic nuclei or heteroatoms as bridging elements and in which k is an integer between 1 and 1500, preferably between 2 and 1000, particularly preferably between 2 and 700 and very particularly preferably between 5 and 500 and particularly preferably between 5 and 300, o represents numbers between 1 and 1500, preferably between 1 and 1000, particularly preferably between 1 and 700 and very particularly preferably between 1 and 500 and particularly preferably between 1 and 300, and m stands for a fractional number z / o and n for a fractional number (oz) / o, where
  • Preferred structural units of the polyformals and copolyformals according to the invention are derived from general structures of the formulas (2a), (2b), (2c) and (2d),
  • brackets describe the underlying diphenolate radicals in which R * and R ⁇ independently of one another are H, linear or branched Cj-Cig alkyl or alkoxy radicals, halogen such as Cl or Br or for an optionally substituted aryl or aralkyl radical, are preferably H or linear or branched C 1 -C 2 alkyl, particularly preferably H or C 8 C 8 alkyl radicals and very particularly preferably H or methyl,
  • X for a single bond, a C - to Cg-alkylene, C2 to C5-alkylidene, C5 to Cg-cycloalkylidene radical, which can be substituted by C ⁇ - to Cg-alkyl, preferably methyl or ethyl radicals, or a Cg to C12 arylene radical, which may contain aroma containing other heteroatoms.
  • table rings can be condensed, where p is an integer between 1 and 1500, preferably between 2 and 1000, particularly preferably between 2 and 700 and very particularly preferably between 5 and 500 and in particular between 5 and 300, p stands for numbers between 1 and 1500, preferably between 1 and 1000, particularly preferably between 1 and 700 and very particularly preferably between 1 and 500 and particularly preferably between 1 and 300, and q for a fraction z / p and r for a fraction (pz) / p stands where z stands for numbers between 0 and p and a part of the residues -ODO- and -OEO- independently of one another also stands for a residue derived from one or more trifunctional compounds, with which then a third linking point, a branching of the Polymer chain occurs
  • the polyformals or copolyformals can accordingly be linear or branched.
  • the bisphenolate residues in the formulas (1) and (2) are particularly preferably derived from the suitable bisphenols mentioned below.
  • Examples of the bisphenols on which the general formula (1) is based are hydroquinone, resorcinol, dihydroxybiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, Bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ketone, bis (hydroxypheny l) sulfone, bis (hy droxyphenyl) sulfoxide, ⁇ , ⁇ '-B is (hy droxypheny l) - diisopropylbenzenes, as well as their ring alkylated and ring halogenated compounds, and also called ⁇ , ⁇ -bis (hydroxyphenyl) polysiloxanes.
  • Preferred bisphenols are, for example, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1- Bis- (4-hy droxypheny l) -3, 3,5-trimethylcyclohexane (bisphenol TMC), l, l-bis- (4-hydroxyphenyl) -cyclohexane, 2,4-bis- (4-hydroxyphenyl) - 2-methylbutane, l, l-bis- (4-hydroxyphenyl) -l-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,
  • bisphenols are, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 1,3 -Up to 2-
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol A
  • 4,4'-dihydroxybiphenyl DOD
  • 4,4'-dihydroxybiphenyl ether DOD ether
  • 1,3 are very particularly preferred -Bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M) and l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol A
  • l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane bisphenol TMC
  • the bisphenols can be used both alone and in a mixture with one another; both homopolyformals and copolyformals are included.
  • the bisphenols are known from the literature or can be prepared by processes known from the literature (see, for example, H. J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348).
  • branching agents can be deliberately and controlledly branched by using small amounts of trifunctional compounds, so-called branching agents.
  • branching agents are: phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2; 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane; 1, 3, 5 -tri- (4-hy droxyphenyl) benzene; 1,1,1-tri- (4-hydroxyphenyl) ethane; Tri- (4-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;
  • branching devices By using such branching devices, corresponding deviations from their idealized structure appear in formulas (1) and (2).
  • structural units derived from the branching agents used have three linking units, which can also be designed as an ester function, inter alia, depending on the branching agent used.
  • the 0.05 to 2 mol.%, Based on diphenols used, of branching agents or mixtures of the branching agents which may also be used can be used together with the diphenols, but can also be added at a later stage in the synthesis.
  • phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof, in amounts of 1-20 mol% 2-10 mol% per mole of bisphenol used. Phenol, 4-tert-butylphenol and cumylphenol are preferred.
  • polyformals and copolyformals of the formulas (la) and (lb) or (2 ad) is carried out, for example, by a solution process, characterized in that bisphenols and chain terminators in a homogeneous solution of methylene chloride or ⁇ , -dichlorotoluene and a suitable high-boiling solvent such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylcaprolactam (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 with methylene chloride or alpha, alpha-dichlorotoluene to be reacted.
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMSO dimethyl
  • Preferred high-boiling solvents are NMP, DMF, DMSO and NMC, particularly preferably NMP, NMC, DMSO and very particularly preferably NMP and NMC.
  • the reaction can also be carried out in several stages. If necessary, the cyclic impurities are separated off after the organic phase has been neutral-washed by a precipitation process in or by a fractional kneading process of the crude product with a solvent which dissolves the cyclic compounds, e.g. Acetone.
  • the cyclic impurities dissolve almost completely in the solvent and can be almost completely removed by kneading and changing the solvent in portions.
  • a content of cycles after kneading can be achieved well below 1%.
  • the cyclic polyformals and copolyformals can also be separated off by a precipitation process in suitable solvents which act as precipitation agents for the desired polymer and as solvents for the undesired cycles.
  • suitable solvents which act as precipitation agents for the desired polymer and as solvents for the undesired cycles. These are preferably alcohols or ketones.
  • the reaction temperature of the polycondensation is 30 ° C. to 160 ° C., preferably 40 ° C. to 100 ° C., particularly preferably 50 ° C. to 80 ° C. and very particularly preferably 60 ° C. to 80 ° C.
  • the present invention thus relates to the use of the polyformals and copolyformals described for the production of multilayer products, for example coextrudates such as multilayer plates, these multilayer plates themselves, and furthermore a process for producing these multilayer plates by coextrusion, and also compositions suitable for coating, containing them Polyformals or copolyformals.
  • the present invention furthermore relates to a product which contains the said multilayer board or other products coated on a polyformal basis.
  • This product which, for example, contains the multilayer plate mentioned or is itself coated, is preferably selected from the group consisting of baby bottles, water bottles or medical products which can be sterilized by steam.
  • the multilayer product according to the invention has numerous advantages.
  • it has the advantage that the polyformal-based hydrolysis protective layer significantly improves long-term stability, in particular hydrolysis resistance to aqueous media.
  • the plate is easy and inexpensive to manufacture, all starting materials are available and inexpensive.
  • the other positive properties of the polycarbonate, for example its good optical and mechanical properties, are not or only insignificantly impaired in the multilayer product according to the invention.
  • the multilayer products according to the invention have further advantages over the prior art.
  • the multilayer products according to the invention such as bottles, can be produced, for example, by coextrusion blow molding. This results in advantages over a product produced by painting. This means that no solvents evaporate during coextrusion, as is the case with coatings.
  • paints require complex technology. For example, they require explosion-proof units when using organic solvents, the recycling of solvents, and thus expensive investments in plants. Coextrusion does not have this disadvantage.
  • a preferred embodiment of the present invention is said multilayer plate or different types of bottles, the base layer being made of polycarbonate and / or
  • the hydrolysis protective layer is 1 to 5000 ⁇ m thick, preferably 5 to 2500 ⁇ m, very particularly preferably 10 to 500 ⁇ m.
  • the panels can be solid panels, multi-skin panels, double-skin panels, triple-skin panels, quadruple-skin panels, etc.
  • the multi-skin sheets can also have different profiles such as Have X profiles or XX profiles.
  • the multi-wall sheets can also be corrugated multi-wall sheets.
  • a preferred embodiment of the present invention is a two-layer plate consisting of a layer made of polycarbonate and a hydrolysis protective layer made of polyformal or copolyformal or a polycarbonate-polyformal blend.
  • Another preferred embodiment of the present invention is a three-layer plate consisting of a layer of polycarbonate as the base layer and two overlying hydrolysis protective layers, each of which, identically or differently, consists of polyformal or copolyformal or a polycarbonate-polyformal blend.
  • bottles e.g. Water bottles (5-gallon bottles), baby bottle ⁇ or reusable milk bottles.
  • Containers for the purposes of the present invention can for the packaging, storage or transport of liquids • be used by solids or gases.
  • Containers for packaging, storing or transporting liquids are preferred, containers for packaging, storing or transporting water (water bottles) are particularly preferred.
  • Containers in the sense of the invention are hollow bodies with a volume of preferably 0.1 1 to 50 1, preferably 0.5 1 to 50 1, very particularly preferred are volumes of 1 1, 51, 121 and 20 1.
  • the containers 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 wall thicknesses of the containers are preferably 0.5 mm to 5 mm, preferably 0.8 mm to 4 mm.
  • Containers in the sense of the present invention have a length of preferably 5 mm to 2000 mm, particularly preferably 100 mm to 1000 mm.
  • the containers have a maximum circumference of preferably 10 mm to 250 mm, preferably from 50 mm to 150 mm and very particularly preferably from 70 to 90 mm.
  • Containers in the sense of the invention preferably have a bottle neck with a length of preferably 1 mm to 500 mm, preferably from 10 mm to 250 mm, particularly preferably from 50 mm to 100 mm and very particularly preferably from 70 to 80 mm.
  • the wall thickness of the bottle neck of the container varies between preferably 0.5 mm to 10 mm, particularly preferably from 1 mm to 10 mm and very particularly preferably from 5 mm to 7 mm.
  • the diameter of the bottle neck varies between preferably 5 mm and 200 mm. 10 mm to 100 mm are particularly preferred and 45 mm to 75 mm are very particularly preferred.
  • the bottle base of the containers according to the invention has a diameter of preferably 10 mm to 250 mm, preferably 50 mm to 150 mm, and very particularly preferably 70 to 90 mm.
  • Containers in the sense of the present invention can have any geometrical shape, e.g. be round, oval or polygonal or angular with for example 3 to 12 sides. Round, oval and hexagonal shapes are preferred.
  • the design of the containers can be based on any surface structure.
  • the surface structures are preferably smooth or ribbed.
  • the containers according to the invention can also have several different surface structures. Ribs or beads can run around the circumference of the container. They can have any distance or several different distances that are different from each other.
  • the surface structures of the containers according to the invention can have roughened or integrated structures, symbols, ornaments, coats of arms, company logos, trademarks, names, manufacturer information, material labeling and or volume information.
  • the containers according to the invention can have any number of handles, which can be located laterally, above or below.
  • the handles can be external and or integrated into the container contour.
  • the handles can be foldable or fixed.
  • the handles can have any contour, for example oval, round or polygonal.
  • the handles preferably have a length of 0.1 mm to 180 mm, preferably of 20 mm to 120 mm.
  • the containers according to the invention can also contain other substances to a lesser extent, for example seals made of rubber or handles made of other materials.
  • the containers according to the invention are preferably produced by the extrusion blow molding process or by the injection blow molding process.
  • polycarbonates according to the invention for producing the containers according to the invention are processed on extruders with a smooth or grooved, preferably a smooth, feed zone.
  • the drive power of the extruder is selected according to the screw diameter. As an example, it should be mentioned that with a screw diameter of 60 mm, the drive power of the extruder is approximately 30 to 40 kW, with a screw diameter of 90 mm approximately 60 to 70 kW.
  • a screw diameter of 50 to 60 mm is preferred for the production of containers of volume 11.
  • a screw diameter of 70 to 100 mm is preferred for the production of containers of volume 20 1.
  • the length of the screws is preferably 20 to 25 times the diameter of the screw.
  • the blow molding tool is preferably tempered to 50 to 90 ° C. in order to obtain a brilliant and high-quality surface of the containers.
  • the base region and the cladding region separately heatable.
  • the blow molding tool is preferably closed with a pinch force of 1000 to 1500 N per cm of pinch seam length.
  • the polycarbonate according to the invention is preferably dried so that the optical quality of the containers is not impaired by streaks 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. is preferred. Lower temperatures do not ensure adequate drying, at higher temperatures there is a risk that the granules of the polycarbonate stick together and are then no longer processable. Dry air dryers are preferred.
  • the preferred melt temperature when processing the polycarbonate according to the invention is 230 ° to 300 ° C.
  • the containers according to the invention can be used for packaging, storage or transport of liquids, solids or gases.
  • the preferred embodiment is as a container, which is used, for example, for packaging, storage or transport of liquids.
  • the embodiment as a water bottle is particularly preferred, which can be used, for example, for packaging, storage or transportation of water.
  • a preferred embodiment of the invention is that in which the containers made of branched polycarbonate are characterized in that the branched polycarbonate contains THPE and / or IBK as branching agent and in which phenol or alkylphenols are used as chain terminators in the production of the branched polycarbonate and where the container is a water bottle.
  • a particularly preferred embodiment of the invention is that in which the container made of branched polycarbonate is characterized in that the branched polycarbonate contains THPE and / or IBK as branching agent and in which phenol is used to produce the branched polycarbonate and in which the polycarbonate is used 260 ° C and a shear rate of 10 s "l has a melt viscosity of 5500 to 7000 Pas and at 260 ° C and a shear rate of 1000 s" 1 a melt viscosity of 900 to 1100 Pas and an MFR (Melt flow index, measured according to ISOl 133) of ⁇ 3.5 g / 10 min and in which the container is a water bottle.
  • MFR Melt flow index
  • the multilayer products are transparent.
  • Both the base material and the hydrolysis protective layer (s) in the multilayer molded parts according to the invention can contain additives.
  • the hydrolysis protective layer can in particular contain UV protection agents or mold release agents.
  • the layers may also contain other customary processing aids, in particular mold release agents and flow agents, and the stabilizers customary in polycarbonates, in particular UV stabilizers, thermal stabilizers, and also colorants and optical brighteners and inorganic pigments.
  • Layers made of all known polycarbonates are suitable as further layers, in addition to the polyformal and copolyformal layers, in particular as the base layer of the multilayer products according to the invention.
  • Suitable polycarbonates are, for example, homopolycarbonates, copolycarbonates and thermoplastic polyester carbonates.
  • M w average molecular weights 18,000 to 40,000, preferably from 26,000 to 36,000 and in particular from 28,000 to 35,000, determined by measuring the relative solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering.
  • the polycarbonates are preferably produced by the phase interface process or the melt transesterification process and are described below by way of example using the phase interface process.
  • Preferred starting compounds are bisphenols of the general formula HO-Z-OH,
  • Z is a divalent organic radical having 6 to 30 carbon atoms and containing one or more aromatic groups.
  • Examples of such compounds are bisphenols which belong to the group of dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, indane bisphenols, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) ketones and ⁇ , ⁇ '-bis (hydroxyphenyl) - belong to diisopropylbenzenes.
  • Particularly preferred bisphenols belonging to the abovementioned connecting groups are bisphenol-A, tetraalkylbisphenol-A, 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 1,1-bis - [2- (4-hydroxyphenyl) -2-propyl] benzene, l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC) and optionally their mixtures.
  • the bisphenol compounds to be used according to the invention are preferably reacted with carbonic acid compounds, in particular phosgene, or with diphenyl carbonate or dimethyl carbonate in the melt transesterification process.
  • Polyester carbonates are preferably obtained by reacting the bisphenols already mentioned, at least one aromatic dicarboxylic acid and optionally carbonic acid equivalents.
  • Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone dicarboxylic acids.
  • Inert organic solvents used in the interfacial process are, for example, dichloromethane, the various dichloroethanes and chloropropane compounds, carbon tetrachloride, trichloromethane, chlorobenzene and chlorotoluene; chlorobenzene or dichloromethane or mixtures of dichloromethane and chlorobenzene are preferably used.
  • phase interface reaction can be accelerated by catalysts such as tertiary amines, in particular N-alkylpiperidines or onium salts.
  • catalysts such as tertiary amines, in particular N-alkylpiperidines or onium salts.
  • Tributylamine, triethylamine and N-ethylpiperidine are preferably used.
  • the catalysts mentioned in DE-A 4 238 123 are preferably used.
  • branching agents allow the polycarbonates to be deliberately and controlled branched.
  • Some suitable branching agents are: phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2; 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane; 1,3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tri- (4-hydroxyphenyl) ethane; Tri- (4-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'-methyl-benzyl) -4-methyl phenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane; Hexa- (4- (4-hydroxyphenyl) -
  • Phenols such as phenol, alkylphenols such as cresol and 4-tert-butylpenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof are preferably used as chain terminators in amounts of 1-20 mol%, preferably 2-10 mol%, per mol of bisphenol. Phenol, 4-tert-butylphenol and cumylphenol are preferred.
  • Chain terminators and branching agents can be added to the syntheses separately or together with the bisphenol.
  • Preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and l, l-Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and 4,4'-dihydroxydiphenyl (DOD).
  • DOD 4,4'-dihydroxydiphenyl
  • the homopolycarbonate based on bisphenol A is particularly preferred.
  • thermoplastics used in the products according to the invention can contain stabilizers.
  • Suitable stabilizers are, for example, phosphines, phosphites or Si-containing stabilizers and further compounds described in EP-A 0 500 496. Examples include triphenyl phosphites, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosponite and triaryl phosphite. Triphenylphosphine and tris (2,4-di-tert-butylphenyl) phosphite are particularly preferred.
  • These stabilizers can be present in all layers of the multilayer products according to the invention. So both in the so-called base and in or in the so-called coex layers. Different additives or concentrations of additives can be present in each layer.
  • the multilayer products according to the invention can contain 0.01 to 0.5% by weight of the esters or partial esters of monohydric to hexavalent alcohols, in particular glycerol, pentaerythritol or Guerbet alcohols.
  • Monohydric alcohols are, for example, stearyl alcohol, palmityl alcohol and Guerbet alcohols.
  • a dihydric alcohol is glycol.
  • a trihydric alcohol is, for example, glycerin.
  • Tetravalent alcohols are, for example, pentaerythritol and mesoerythritol.
  • pentavalent alcohols are arabite, ribite and xylitol.
  • Hexahydric alcohols are, for example, mannitol, glucitol (sorbitol) and dulcitol.
  • the esters are preferably the monoesters, diesters, triesters, tetraesters, pentaesters and hexaesters or their mixtures, in particular statistical mixtures, of saturated, aliphatic Cjo to C36 monocarboxylic acids and optionally hydroxy monocarboxylic acids, preferably with saturated, aliphatic C ⁇ to C 32 monocarboxylic acids and optionally hydroxy monocarboxylic acids.
  • the commercially available fatty acid esters in particular pentaerythritol and glycerol, may contain ⁇ 60% different partial esters due to the manufacturing process.
  • Saturated, aliphatic monocarboxylic acids with 10 to 36 carbon atoms are, for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid and montanic acids.
  • Preferred saturated, aliphatic monocarboxylic acids with 14 to 22 carbon atoms are, for example, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachic acid and behenic acid.
  • Saturated, aliphatic monocarboxylic acids such as palmitic acid, stearic acid and hydroxystearic acid are particularly preferred.
  • the saturated, aliphatic C ] 0 to C 3 6-carboxylic acids and the fatty acid esters as such are either known from the literature or can be prepared by processes known from the literature.
  • Examples of pentaerythritol fatty acid esters are those of the particularly preferred monocarboxylic acids mentioned above.
  • Esters of pentaerythritol and glycerol with stearic acid and palmitic acid are particularly preferred.
  • Esters of Guerbet alcohols and glycerol with stearic acid and palmitic acid and optionally hydroxystearic acid are also particularly preferred. These esters can be present both in the base and in or in the coex layers. Different additives or concentrations can be present in each layer.
  • the multilayer products according to the invention can contain antistatic agents.
  • antistatic agents are cation-active compounds, for example quaternary ammonium, phosphonium or sulfonium salts, anion-active compounds, for example alkylsulfonates, alkylsulfates, alkylphosphates, carboxylates in the form of alkali metal or alkaline earth metal salts, non-ionogenic compounds, for example polyethylene glycol esters, polyethylene glycol ethers, fatty acid esters, ethoxylated ,
  • antistatic agents can be present both in the base and in or in the coex layers. Different additives or concentrations can be present in each layer. They are preferably used in or in the coex layers.
  • the multilayer products according to the invention can contain organic dyes, inorganic color pigments, fluorescent dyes and particularly preferably optical brighteners.
  • colorants can be present both in the base and in or in the coex layers. Different additives or concentrations can be present in each layer.
  • All molding compositions used for the production of the multilayer products according to the invention can be contaminated with corresponding impurities from their production and storage, the aim being to work with starting materials which are as clean as possible.
  • the mixing of the individual constituents in the molding compositions can be carried out in a known manner both successively and simultaneously, both at room temperature and at elevated temperature.
  • the incorporation of the additives into the molding compositions for the products according to the invention is preferably carried out in a known manner by mixing polymer granules with the additives at temperatures of about 200 to 330 ° C. in conventional units such as internal kneaders, single-screw extruders and twin-screw extruders, for example by melt compounding or melt extrusion or by mixing the solutions of the polymer with solutions of the additives and then evaporating the solvents in a known manner.
  • the proportion of additives in the molding composition can be varied within wide limits and depends on the desired properties of the molding composition.
  • the total share the additives in the molding composition is preferably up to about 20% by weight, preferably 0.2 to 12% by weight, based on the weight of the molding composition.
  • Coextrusion as such is known from the literature (see, for example, EP-A 0 110 221 and EP-A 0 110 238).
  • the procedure is preferably as follows.
  • Extruders for producing the core layer and cover layer (s) are connected to a coextrusion adapter.
  • the adapter is designed in such a way that the melt forming the cover layer (s) is adhered to the melt of the core layer as a thin layer.
  • the multilayer melt strand thus produced is then brought into the desired shape (multi-wall or solid sheet) in the nozzle connected subsequently.
  • the melt is then cooled in a known manner by means of calendering (solid plate) or vacuum calibration (multi-wall plate) under controlled conditions and then cut to length. If necessary, a tempering furnace can be installed after the calibration to eliminate stresses.
  • the nozzle itself can also be designed in such a way that the melts are brought together there.
  • multilayer composites can also be produced by extrusion coating, coextrusion and coextrusion blow molding.
  • the batch is washed neutral and salt-free with water (conductivity ⁇ 15 ⁇ S.cm "1 ).
  • the organic phase from the separator is separated off and the solvent exchange methylene chloride for chlorobenzene is carried out in an evaporation kettle.
  • the material is then extruded through a Evaporation extruder ZSK 32 with final granulation at a temperature of 270 ° C. This synthesis procedure is carried out twice, and after discarding the lead material, a total of 9.85 kg of polyformal is obtained as transparent granules which still contain low molecular weight cyclic formals as impurities.
  • the material is divided into two parts and each swollen overnight with about 5 liters of acetone.
  • the batch is washed neutral and salt-free with water (conductivity ⁇ 15 ⁇ S.cm "1 ).
  • the organic phase from the separator is separated off and the solvent exchange methylene chloride for chlorobenzene is carried out in an evaporation kettle.
  • the material is then extruded through a Evaporation extruder ZSK 32 with final granulation at a temperature of 200 ° C. This synthesis procedure is carried out twice, and a total of 11.99 kg of polyformal is obtained as transparent granules after discarding the lead material.
  • the reaction mixture is diluted with 35 1 methylene chloride and 20 1 demineralized water.
  • a separator the batch is washed neutral and salt-free with water (conductivity ⁇ 15 ⁇ S.cm "1 ).
  • the organic phase from the separator is separated off and the solvent exchange methylene chloride for chlorobenzene is carried out in an evaporation kettle.
  • the material is then extruded through a Evaporation extruder ZSK 32 with final granulation at a temperature of 280 ° C.
  • the reaction mixture is diluted with 35 liters of methylene chloride and 20 liters of demineralized water.
  • a separator the batch is washed neutral and salt-free with water (conductivity ⁇ 15 ⁇ S.cm "1 ).
  • the organic phase from the separator is separated off and the solvent exchange methylene chloride for chlorobenzene is carried out in an evaporation kettle.
  • the material is then extruded through a Evaporation extruder ZSK 32 with final granulation at a temperature of 280 ° C.
  • the hydrolysis test is carried out by loading the following hydrolysis media / temperature conditions and time-dependent determination of the change in molecular weight by measuring the relative solution viscosity in methylene chloride (0.5 g / 100 ml solution):
  • Hydrolysis medium 0.1 N HC1 / 80 ° C 0.1 IN NaOH / 80 ° C dest. Water / approx. 100 ° C
  • the hydrolysis test is carried out by exposure to the following hydrolysis media / temperature conditions and time-dependent determination of the change in molecular weight by measuring the relative solution viscosity in methylene chloride (0.5 g / 100 ml solution):
  • Hydrolysis medium 0.1 N HC1 / 80 ° C 0.1 N NaOH / 80 ° C dest. Water / approx. 100 ° C
  • 1.242 / 1.242 (blank) 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
  • the hydrolysis test is carried out by loading the following hydrolysis media / temperature conditions and time-dependent determination of the change in molecular weight by measuring the relative solution viscosity in methylene chloride (0.5 g / 100 ml solution):
  • the hydrolysis test is carried out by loading the following hydrolysis media / temperature conditions and time-dependent determination of the change in molecular weight by measuring the relative solution viscosity in methylene chloride (0.5 g / 100 ml solution):
  • the hydrolysis test is carried out by loading the following hydrolysis media / temperature conditions and time-dependent determination of the change in molecular weight by measuring the relative solution viscosity in methylene chloride (0.5 g / 100 ml solution):
  • the reaction mixture After cooling to 25 ° C., the reaction mixture is diluted with methylene chloride and demineralized water and then washed neutral and salt-free with water (conductivity ⁇ 15 ⁇ S.cm "1 ). The organic phase is separated off. The polymer is isolated by precipitation After washing the product with water and methanol and separating the cycles with acetone and drying at 80 ° C., the polyformal is obtained as white polymer threads.
  • the reaction mixture After cooling to 25 ° C., the reaction mixture is diluted with methylene chloride and demineralized water and then washed neutral and salt-free with water (conductivity ⁇ 15 ⁇ S.cm "1 ). - 35 - phase is separated.
  • the polymer is isolated by precipitation in methanol. After washing the product with water and methanol and separating the cycles with acetone and drying at 80 ° C., the polyformal is obtained as white polymer threads.

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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Wrappers (AREA)
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Abstract

L'invention concerne des produits à couches multiples protégés contre l'hydrolyse qui comprennent au moins une couche qui contient une matière thermoplastique et au moins une couche qui contient au moins un polyformal ou copolyformal, ainsi que des compositions qui contiennent des polyformals ou des copolyformals et des additifs éventuels, et l'utilisation de polyformals et/ou de copolyformals pour produire une couche de protection contre l'hydrolyse.
EP05700725A 2004-01-16 2005-01-07 Polyformals et copolyformals comme couche de protection contre l'hydrolyse appliquee sur du polycarbonate Withdrawn EP1709095A1 (fr)

Applications Claiming Priority (2)

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DE102004002523A DE102004002523A1 (de) 2004-01-16 2004-01-16 Polyformale und Copolyformale als Hydrolyseschutzschicht auf Polycarbonat
PCT/EP2005/000065 WO2005068525A1 (fr) 2004-01-16 2005-01-07 Polyformals et copolyformals comme couche de protection contre l'hydrolyse appliquee sur du polycarbonate

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EP1709095A1 true EP1709095A1 (fr) 2006-10-11

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DE (1) DE102004002523A1 (fr)
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US1924708A (en) * 1930-01-17 1933-08-29 Squibb & Sons Inc Packaging of edible oils
US3134682A (en) * 1960-02-01 1964-05-26 Pittsburgh Plate Glass Co Sanitary coatings compositions
US3547294A (en) * 1968-08-21 1970-12-15 Beverly E Williams Coated plastic containers
JPH05295319A (ja) * 1992-04-17 1993-11-09 Mitsubishi Gas Chem Co Inc 塗料用樹脂組成物
DE19641064A1 (de) * 1996-10-04 1998-04-09 Wacker Chemie Gmbh Modifizierte Polyvinylbutyrale mit niederer Lösungsviskosität
DE10333927A1 (de) * 2003-07-25 2005-02-24 Bayer Materialscience Ag Polyformale als Coextrusionsschutzschicht auf Polycarbonat

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IL176682A0 (en) 2006-10-31
JP2007523972A (ja) 2007-08-23
AU2005205110A1 (en) 2005-07-28
CA2553330A1 (fr) 2005-07-28
TW200604255A (en) 2006-02-01
DE102004002523A1 (de) 2005-08-04
CN1910213A (zh) 2007-02-07

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