Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate

Definitions

• the present invention relates to compositions comprising a polymer selected from the group consisting of polycarbonate, a transparent polycarbonate-polyester blend, a copolyester carbonate and a transparent polyester and ester of branched alcohols and carboxylic acids, the carboxylic acids in turn carrying esterified OH functions, and Products made from these compositions, in particular plates.
• compositions containing polycarbonate are used in many fields.
• panels made from compositions containing polycarbonate are used, for example, for roofing or glazing.
• the compositions containing polycarbonate usually contain additional substances such as e.g. Lubricant (also called mold release agent).
• Lubricant also called mold release agent.
• Carboxylic acid esters for example, are used as lubricants.
• compositions containing polycarbonate and Guerbet alcohols are known.
• Guerbet alcohols are the products of the Guerbet reaction and can be produced, for example, by the Guerbet reaction.
• the Guerbet reaction is the self-condensation of alcohols under the influence of sodium or copper at approx. 200 ° C and elevated pressure.
• Polycarbonate sheets are known, for example, from EP A 0 110 221 and are provided for a large number of applications.
• the sheets are produced, for example, by extrusion of compositions containing polycarbonate. If necessary, coextrusion can be carried out with further compositions which contain polycarbonate and which additionally contain an increased proportion of UV absorbers.
• a recurring problem in the extrusion of such sheets is the settling of volatile constituents from the composition on the calibrator (in the case of multi-wall sheets) or on the rollers (in the case of solid sheets), which can lead to surface defects on the sheets.
• Volatile components are, for example, UV absorbers, mold release agents and other low molecular components of the composition.
• EP A 0 320 632 describes coextruded sheets from compositions which contain polycarbonate, which contain a UV absorber and can contain a lubricant.
• the disadvantage is that with a longer extrusion time, the surface of the plates by evaporation from the melt of the composition, especially in the
• the increased evaporation of the UV absorber from the melt of the composition leads to the formation of deposits on the calibrator or the rollers and finally to the formation of defects on the plate surface (e.g. white spots, waviness, etc.).
• the polycarbonate abrasion on the calibrator also leads to powdery deposits on the polycarbonate plates.
• Esters of Guerbet alcohols in polycarbonates are also known, for example EP-A 0 390 994 describes compositions which contain polycarbonate and which additionally contain special fatty acid esters of Guerbet alcohols as mold release agents.
• EP-A 0 390 994 does not mention the use of the molding compositions for coextrusion.
• the mold release agents according to the invention are suitable for applications in coextrusion together with higher amounts of UV
• WO 01/62851 and WO 01/25334 describe in the examples the use of Lubril JK, which is one of the embodiments of EP-A 0 390 994, in special polycarbonate ABS blends. Coextrusion is not mentioned here either.
• WO 01/74935 teaches that mixtures of the esters of fatty acids and Guerbet alcohols and fatty acids and linear alcohols can improve the process for the production of plastic sheets by coxtrusion, in particular if the process is carried out over a long period of time (improvement of the long-term coextrusion behavior).
• the present invention is therefore based on the object of providing compositions which contain polycarbonate which do not have the disadvantages of the prior art in the production of sheets by extrusion of these compositions.
• composition comprising a polymer selected from the group consisting of polycarbonate, a transparent polycarbonate-polyester blend, a copolyester carbonate and a transparent polyester and a compound of the formula (I)
• homologous compounds of the formula (II) are distinguished by different values of n and where for the compounds of the formula (I) and for the compounds of the formula (H):
• the proportion by weight of the compounds of the formula (I) and of the compounds of the formula (LT) is preferably 0.02 to 1.0, particularly preferably 0.1 to 0.5% by weight in total (I and II).
• the ratio of the proportion by weight of the compound of the formula I in the composition according to the invention to the proportion by weight of all compounds of the formula II in the composition according to the invention is 1: 0.001 to 1: 1.2, preferably 1: 0.005 to 1: 1.
• the polymer which is selected from the group consisting of polycarbonate, a transparent polycarbonate-polyester blend, a copolyester carbonate and a transparent polyester is polycarbonate.
• the polymer which is selected from the group consisting of polycarbonate, a transparent polycarbonate-polyester blend, a copolyester carbonate and a transparent polyester is a transparent polyester.
• This transparent polyester is available from diacids and diols.
• the diacids are at least one or more diacids selected from the group consisting of terephthalic acid, isophthalic acid and cyclohexane-1,4-dicarboxylic acid.
• the diols are at least one or more diols selected from the group consisting of ethylene glycol, butane-1,4-diol, cyclohexane-1,4-dimethanol, diethylene glycol and neopentyl glycol.
• compositions according to the invention are provided by the compositions according to the invention, the compositions additionally containing 0.1 to 15 parts by weight of UV absorber.
• the UV absorber is preferably selected from the group consisting of (bis [2-hydroxy-5-tert-octyl-3-
• a preferred embodiment of the present invention is a composition according to the invention, the composition additionally 10 to
• thermal stabilizers are preferably selected from the group consisting of tris (2,4-di-tert-butylphenyl) phosphate, triphenylphosphine and 3.9 to [2,4-bis (1-methyl-1-phenylethyl) phenoxy ] -2,4,8, 10-tetraoxa-3,9-diphosphaspiro [5.5] undecane and 5-butyl-5-ethyl-2- [2,4,6-tris (l, l-dimethylethyl) phenoxy] -l, 3,2-dioxaphosphorinanes.
• the object according to the invention is further achieved by the use of the compositions according to the invention for the production of any desired products.
• the production is preferably carried out by extrusion.
• the object according to the invention is achieved by products containing the compositions according to the invention.
• these products are single-layer or multi-layer plates, one or more of the layers of the plates containing a composition according to the invention.
• Multilayer plates made of at least three layers are preferred, one or both of the outer layers of the multilayer plates containing a composition according to the invention.
• compositions according to the invention preferably additionally contain 0.1 to 15 parts by weight, particularly preferably 1 to 15 parts by weight, very particularly preferably 3 to 8 parts by weight of UV absorber.
• the preferred polycarbonate according to the invention is bisphenol A homopolycarbonate.
• the compositions according to the invention can contain further customary processing aids, in particular further mold release agents and flow agents.
• compositions according to the invention can contain conventional stabilizers for polycarbonates, in particular conventional thermal stabilizers.
• the relative proportions by weight of the compounds of the formula I and formula II can be determined, for example, by HPLC.
• Rhodia Rhodia GmbH, Städelstrasse 10, D-60596 Frankfurt
• Lubril JK Lubril JK
• the compounds of formula (I) and the compounds of formula (II) can be prepared by known methods. For example, they can be produced as described in EP A 0 390 994. Additives of the formula (I) are commercially available, for example Lubril JK from Rhodia, and are normally used for cosmetics. They are typically present in a mixture with compounds of the formula (II).
• compositions according to the invention have proven to be particularly advantageous. They can be processed without any problems and show no impairments in the products obtained as a product. Surprisingly, it has been found that when these compounds are used, additives of compositions which contain polycarbonate and which are known to be volatile no longer lead to the problems described at the outset.
• Thermoplastic, aromatic polycarbonates for the compositions according to the invention are homopolycarbonates, copolycarbonates and thermoplastic polyester carbonates. They preferably have average molecular weights M w of 18,000 to 40,000 g / mol, preferably of 26,000 to 36,000 g / mol and in particular of
• the melt viscosity of the compositions should preferably be less than that of the substrate to which they are applied when producing multilayer products.
• examples include “Schnell”, Chemistry and Physics of Polycarbonates, Polymer
• Compounds which are preferably to be used as starting compounds are bisphenols of the general formula HO-Z-OH, in which Z is a divalent organic radical having 6 to 30 carbon atoms and containing one or more aromatic groups.
• 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) ) -diisopropylbenzenes belong.
• bisphenols belonging to the abovementioned connecting groups are bisphenol-A, tetraalkylbisphenol-A, 4,4- (meta-phenylenediisopropyl) diphenol (bisphenol M), 4,4- (para-phenylenediisopropyl) diphenol, 1,1 -Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC) and, if appropriate, their mixtures.
• Homopolycarbonates based on bisphenol-A and copolycarbonates based on the monomers bisphenol-A and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane are particularly preferred.
• the bisphenol compounds to be used according to the invention are reacted with carbonic acid compounds, in particular phosgene or, in the melt transesterification process, diphenyl carbonate or dimethyl carbonate.
• Polyester carbonates are obtained by reacting the bisphenols already mentioned, at least one aromatic dicarboxylic acid and optionally carbonic acid equivalents.
• aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and
• Benzophenone A part, up to 80 mol%, preferably from 20 to 50 Mol% of the carbonate groups in the polycarbonates can be replaced by aromatic dicarboxylic acid ester groups.
• 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 42 38 123 are used.
• the polycarbonates can be branched deliberately and in a controlled manner by using small amounts of 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-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'-methylbenzyl) -4-methylphenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane; Hexa- (4- (4-hydroxyphenyl-
• 2,4-dihydroxybenzoic acid trimesic; cyanuric chloride; 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole; l, 4-bis (4 ', 4 "-dihydroxytriphenyl) methyl) benzene and in particular: l, l, l-tri- (4-hydroxyphenyl) ethane and bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
• the optionally used 0.05 to 2 mol%, based on the diphenols used, of branches or mixtures of the branchers can be used together with the diphenols but can also be added at a later stage in the synthesis.
• Chain breakers can be used.
• Phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, 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.
• compositions according to the invention are also referred to as coextrusion compositions.
• compositions according to the invention can also contain UV absorbers.
• Suitable UV absorbers for the coextrusion compositions according to the invention are preferably those compounds which, because of their absorption capacity, are below
• 400 nm are able to effectively protect polycarbonate from UV light and have a molecular weight of more than 370, preferably 500 and more.
• UV absorbers which can be used according to the invention are described below.
• R 3 and R 4 are also the same or different and are H, C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, benzyl or C 6 -C 14 aryl.
• n 1, 2, 3 or 4.
• Ri, R2, m and n have the meaning given for formula (II), and in which p is an integer from 0 to 3, q is an integer from 1 to 10,
• Y equals -CH 2 -CH 2 -, - (CH 2 ) 3 -, - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 -, or CH (CH 3 ) -CH 2 - is and R 3 and R 4 have the meaning given for formula (II).
• Preferred ranges 0.00001 - 1.5% by weight and 2-20% by weight, particularly preferably 0.01 - 1.0% by weight and 3-10% by weight, very particularly preferably 0.1 - 0.5% by weight and 4-8% by weight
• Rl, R2, R3, R4 in formula (TV) are the same or different and are H or alkyl or CN or halogen or O-alkyl and X is alkyl.
• X octyl
• R 1 is C j alkyl to C 17 alkyl
• R 2 is H or C j -alkyl to - alkyl and n is 0 to 20.
• Preferred ranges 0.00001 - 1.0% by weight and 1.5-10% by weight, particularly preferably 0.01 - 0.8% by weight and 2-8% by weight>, very particularly preferably 0.1 - 0.5% by weight and 3-7% by weight
• R 1 to R 40 may be the same or different and denote H, alkyl, CN or halogen.
• UV absorbers mentioned in claim 1 of US Pat. No. 5,959,012 are also suitable.
• the UV absorbers are incorporated into the compositions of the plates according to the invention to be used by customary methods, for example by mixing solutions of the UV absorbers with solutions of the plastics in suitable organic solvents such as CH 2 C1 2 , haloalkanes, halogen aromatics and chlorobenzene and xylenes.
• suitable organic solvents such as CH 2 C1 2 , haloalkanes, halogen aromatics and chlorobenzene and xylenes.
• the solution mixtures are removed in a known manner, for example compounded, by evaporation of the solvent and subsequent extrusion.
• Suitable stabilizers for the polycarbonates for the compositions according to the invention 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-diphosphonite and triaryl phosphite.
• Triphenylphosphine and tris (2,4-di-tert-butylphenyl) phosphite are particularly preferred.
• antistatic agents are cation-active compounds, for example quaternary ammonium, phosphonium or sulfonium salts, anion-active compounds, for example alkyl sulfonates, alkyl sulfates, alkyl phosphates, carboxylates in the form of
• nonionic compounds for example polyethylene glycol esters, polyethylene glycol ethers, fatty acid esters, ethoxylated fatty amines.
• Preferred antistatic agents are nonionic compounds.
• All starting materials and solvents used for the synthesis of the compositions 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 individual constituents can be mixed in a known manner both successively and simultaneously, both at room temperature and at elevated temperature.
• the additives are preferably incorporated into the compositions according to the invention in a known manner by mixing polymer granules with the additives at temperatures of approximately 200 to 380 ° 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 subsequent evaporation of the solvents in a known manner.
• the proportion of additives in the composition can be varied within wide limits and depends on the desired properties of the molding composition.
• the total proportion of additives in the composition is approximately up to 20% by weight, preferably 0.2 to 12% by weight, based on the weight of the compositions.
• the use of the composition according to the invention offers a significant advantage on any polycarbonate molding compositions as the base material.
• the plate base material is also equipped with the mold release agent of the composition according to the invention.
• the invention therefore furthermore relates to moldings which have been produced using the compositions according to the invention.
• the compositions can be used to produce solid plastic sheets and so-called multi-skin sheets (eg double skin sheets).
• the plates therefore also include those which have an additional cover layer with the composition according to the invention with an increased UV absorber content on one or both sides.
• the compositions according to the invention make it easier to manufacture products, in particular panels and products made from them, such as glazing for greenhouses, winter gardens, bus stops, billboards, signs, protective windows, automobile glazing, windows and roofing.
• Subsequent processing of the products coated with the composition according to the invention such as Deep drawing or surface processing such as Finishing with scratch-resistant lacquers, water-spreading layers and the like are possible and the products produced by these processes are also the subject of the patent.
• Extruders for producing the core layer and cover layer (s) are connected to a coextrusion adapter.
• the adapter is constructed in such a way that the melt forming the cover layers) 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 after calibration
• the nozzle itself can also be designed such that the melts are brought together there.
• the thickness of the coex layer is approximately 50 ⁇ m in each case.
• the facility consisted of
• the main extruder with a screw with a length of 33 D and a diameter of 70 mm with degassing the coex adapter (feedblock system) a coextruder for applying the top layer with a screw with a length of 25 D and a diameter of 30 mm the special slot die with a width of 350 mm to the calibrator the roller conveyor of the take-off device - the cutting device (saw) the deposit table.
• the polycarbonate granulate of the base material was fed to the hopper of the main extruder, the UV coextrusion material to that of the coextruder.
• the respective material was melted and conveyed in the respective plasticizing system cylinder / screw. Both material melts were combined in the coex adapter led and form a composite after leaving the nozzle and cooling in the calibrator.
• the other facilities served to transport, cut to length and lay down the extruded sheets.
• Coextrusion with D - no deposits over a test period of 5 hours after 90 minutes, light transverse waves occurring at irregular intervals, which have a slightly negative effect on the plate quality.
• Coextrusion with E no deposits over a test period of 5 hours. The cross waviness is so low that the plate quality is not negatively affected - grade: very good

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Extrusion Moulding Of Plastics Or The Like (AREA)

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• 2002
  • 2002-02-05 DE DE10204524A patent/DE10204524A1/de not_active Withdrawn
• 2003
  • 2003-01-24 DE DE50306903T patent/DE50306903D1/de not_active Expired - Lifetime
  • 2003-01-24 ES ES03737272T patent/ES2285137T3/es not_active Expired - Lifetime
  • 2003-01-24 EP EP03737272A patent/EP1474472B1/de not_active Expired - Lifetime
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  • 2003-01-24 MX MXPA04007549A patent/MXPA04007549A/es active IP Right Grant
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