TW201315770A - Polymer composition having a filler content and coextruded sheet obtainable therefrom - Google Patents

Abstract

The present invention relates to a polymer composition containing polycarbonate with a weight-average molecular weight Mw of from 24, 000 to 33, 000 and 5.0 wt.% to 20.0 wt.% (based on the total amount of the composition) of glass hollow spheres with an alkalinity of less than 1.0 meq/g. The present invention furthermore provides coextruded sheets in which the coextruded layer contains this polymer composition, and shaped articles produced therefrom, in particular containers and pieces of luggage, very particularly suitcases. Sheets which are obtainable with the polymer composition according to the invention have a high mechanical stability, a high scratch resistance, pleasant haptic properties and an excellent homogeneous external visual impression. The present invention furthermore relates to a process for the preparation of these polymer compositions and a process for production of the sheets according to the invention.

Description

Polymer composition having a filler component and a coextruded sheet obtainable therefrom

The present invention relates to a polymer composition, a coextruded sheet of which the coextruded layer comprises such a polymer composition, and articles formed therefrom, in particular containers and luggage pieces, and in particular luggage. The shaped article can be produced, for example, by thermoforming. Coextruded sheets obtainable with the polymer composition according to the present invention have high mechanical stability, high scratch resistance, pleasant touch, and good uniform external appearance. The present invention is directed to a method of preparing such a polymer composition and a method of producing a coextruded sheet according to the present invention.

Some combinations of devices for providing materials with high mechanical stability and corresponding surface characteristics are described in the prior art. In these prior art it has been primarily resorted to the use of strengthening materials to treat plastic compositions.

US 20080132617 A1 thus describes a polycarbonate blend comprising hollow glass spheres with improved flow, high rigidity, low shrinkage and high scratch resistance.

WO2007025663 A1 describes a polymer composition comprising a specific polyolefin and polycarbonate or with other thermoplastic materials, and a glass filler. A soft touch material having high scratch resistance can be obtained by this specific mixture.

JP 72-58528 A discloses a polycarbonate having a surface treated hollow glass sphere as a filler. Polycarbonate has good Mechanical properties.

No. 5,334,427 A discloses a thermoplastic sheet of at least three layers. In this context, a glass fiber mat is bonded to a base layer comprising at least two different fillers by a chemical bonding layer. This sheet can be embossed and is particularly mechanically stable.

GB 1585327 and GB 1585338 have described the use of glass spheres to make sheets.

No. 4,849,265 A describes a flexible PC film in which a surface-twisted glass sphere is embedded in a layer of a particular material, which is not a polycarbonate.

WO 1996007525 A1 describes an embedded moulding comprising a thin polycarbonate moulding of glass spheres for the manufacture of a scratch-resistant surface.

No. 6,204,971 B1 describes a projection screen in which a hollow glass sphere is pressed into an opaque layer which is then applied to a transparent polycarbonate sheet in such a way as to achieve the highest possible diffusion of light.

WO 2002062877 A1 describes the improvement of the scratch resistance and other properties of PET and other plastics, such as mechanical properties and fire resistance, by means of glass materials in the form of particles or fibers. It further describes the manufacture of an extruded sheet in which a material comprising glass is applied to one or both sides of the sheet as a coextruded layer.

However, up to now, there has been a need for a coextruded sheet having high mechanical stability, high scratch resistance, a pleasant touch, and especially a further uniform appearance with a further greatly improved appearance.

It is therefore an object of the present invention to provide a polymer composition and a coextruded sheet comprising the polymer composition in a layer, preferably in a layer applied by coextrusion, which has high mechanical stability and high Scratch resistance, pleasant touch and a good uniform external look.

Surprisingly, the above objects are achieved by means of a polymer composition comprising a polycarbonate and a specific hollow glass sphere. The coextruded sheet according to the present invention has a desired property comprising: a base layer; and coextrusion applied to at least one side of the base layer (preferably applied to one side of the base layer) and comprising the polymer composition according to the present invention Out of layer. The melt flow rate (MVR) of the polycarbonate of the base layer and the coextruded layer is preferably different.

The invention therefore provides that the polymer composition P) comprises a polycarbonate having a weight average molecular weight Mw of from 24,000 to 33,000 g/mol and preferably a melt flow rate of from 8 to 16 cm ³ /min, a basicity of less than 1.0 meq/g. And a hollow glass sphere of 5.0% by weight to 20.0% by weight (based on the total amount of the composition) and a conventional additive which does not additionally comprise a thermoplastic polymer.

The invention further provides a sheet comprising two layers A) and B), wherein layer A) comprises (as described above and in the claims) a polymer composition, layer B) comprises a melt flow rate (MVR) from 3 Polycarbonate to 9 cm ³ /10 min preferably from 4 to 9 cm ³ /10 min, wherein the polycarbonate in layer A) has a melt flow rate from 8 to 16 cm ³ /10 min (MVR ). Preferably, the base layer and the extruded layer polycarbonate have different melt flow rates.

The invention further provides a preparation method of the polymer composition P) according to claim 1, wherein the polycarbonate and the hollow glass sphere are mixed on a twin-screw extruder, characterized in that the hollow glass beads are directly directly fed through the side feed port. The melt was introduced into a melt having a temperature from 320 ° C to 360 ° C, the extruder speed was from 300 rpm to 500 rpm, and the polycarbonate had a melt flow rate (MVR) of from 8 to 16 cm ³ /10 min.

The polymer composition P) preferably comprises from 8.0% to 15.0% by weight, particularly preferably from 9.0% to 12.0% by weight, of hollow glass spheres.

The hollow glass spheres according to the invention are preferably made of a low alkali glass, preferably a borate glass.

Particularly preferred hollow glass spheres are characterized in that the alkalinity of the uncoated hollow glass spheres (measured according to ASTM D3100) is less than 1.0 meq/g, preferably less than 0.8 meq/g, particularly preferably Ground below 0.6 meq/g. The alkalinity of the hollow glass spheres used can be further reduced by applying a suitable coating.

Preferably, the hollow glass spheres have from 0.2 g/cm ^{3 to} 0.8 g/cm ³ , preferably from 0.4 g/cm ^{3 to} 0.7 g/cm ³ , particularly preferably from 0.55 g/cm ^{3 to} 0.65 g/cm ³ The particle density, and an average particle size (d ₅₀ ) of from 1 μm to 70 μm, preferably from 5 μm to 50 μm, more preferably from 5 μm to 30 μm, particularly preferably from 8 μm to 20 μm. The average particle size d ₅₀ is a diameter number (average volume diameter) above which both particles and particles below this number account for 50% by weight.

In particular, an insulating glass having a high uniform pressure compressive strength is preferred. ball. In the present invention, hollow glass spheres having a pressure equalization compressive strength of from 500 bar to 2,500 bar, preferably from 1,000 bar to 2,200 bar, particularly preferably from 1,900 bar to 2,100 bar, are used.

The compressive strength is the impedance that keeps at least 80% of the spheres from damage when the sphere is exposed to the pressure in the liquid column.

The hollow glass spheres according to the present invention may be surface treated, such as decaneized, to ensure better compatibility with the polymer.

Hollow glass spheres are commercially available, in particular from 3M Deutschland GmbH (for example, product number iM30K or S60HS) and from Potters Industries Inc., Malvern, PA (USA) (product name 110P8). . Uncoated (untreated) forms and coated (surface treated) forms of such commercially available products are available. In the context of the present invention, a coated product is preferably used.

In a preferred embodiment, the coextruded layer does not contain other fillers or glass reinforcing materials such as glass fibers other than the hollow glass spheres according to the present invention.

The base layer of polycarbonate may similarly comprise fillers and reinforcing materials, such as glass-containing fillers (such as glass fibers, glass spheres or hollow glass spheres) or talc, especially when filler-containing recycled polycarbonate is used as the base layer. When using materials. However, the filler content of the base layer should be at most 20% of the filler content of the coextruded layer. The base layer may comprise from 0.0 to 2.0% by weight, preferably from 0.0% to 1.5% by weight, particularly preferably 0.0% by weight, of untreated or surface treated filler and reinforcing material. However, the base layer is preferably free of fillers and reinforcing materials.

The polymer composition or coextruded layer may comprise as a further additive: a) from 0.000% to 0.050% by weight of a monoprotic or polyprotic acid, phosphorous acid and phosphoric acid, particularly preferably 85% strength orthophosphoric acid. Aqueous solution. If present, the amount is preferably from 0.001% by weight to 0.010% by weight, particularly preferably from 0.003% by weight to 0.006% by weight, and b) from 0.0% by weight to 10.0% by weight, preferably from 0.0% by weight to 8.0% by weight, particularly preferably from 0.1% to 7.0% by weight, of at least one or more UV absorbers, the data of which corresponds to the total amount of all UV absorbers.

The thermoplastic material for the base layer is a polycarbonate having an MVR of from 3 to 9 cm ³ /10 min. The amount of transparent thermoplastic material contained in the composition is such that the sum of the transparent thermoplastic material and other remaining components (e.g., additives) is 100% by weight.

The polymer composition of the base layer may comprise from 0.00% by weight to 0.50% by weight, preferably from 0.05% by weight to 0.4% by weight, particularly preferably from 0.1% by weight to 0.35% by weight, of at least one or more UV absorbers, by weight The data corresponds to the total amount of all UV absorbers.

The following additives are suitable as additional additives to the polymer composition of the coextruded layer and the base layer: c) from 0.00% to 0.20% by weight, preferably from 0.01% by weight, based on the total of the heat or processing stabilizer 0.10% by weight of one or more heat or processing stabilizers, preferably selected from the group consisting of phosphines, phosphites, phenolic antioxidants and mixtures thereof, the above weight % pairs It should be from 0.0000% to 5.000% by weight, preferably from 0.00001% to 10.000% by weight, based on the total amount of all heat and processing stabilizers, d) based on the total amount of the additives.

The polymer composition may also further comprise a release agent. Conventional release agents are used in amounts of from 0.00% by weight to 1.00% by weight, preferably from 0.01% by weight to 0.50% by weight, particularly preferably from 0.01% by weight to 0.40% by weight. Preferably, the coextruded layer or coextruded layer and the polymer composition of the base layer do not comprise a release agent.

The amounts of the above individual additives are each based on the sum of the polymer compositions of both the coextruded layer and the base layer. In each case, the additives may be used singly or in the form of a combination of two or more.

The polycarbonates in the present invention are all homopolycarbonates, copolycarbonates and polyester carbonates. Particularly preferred polycarbonates in the context of the invention are homopolycarbonates based on bisphenol A, and bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-three. The monomer of methylcyclohexane is a matrix copolycarbonate, preferably in a weight ratio of from 9:1 to 3:7. The polycarbonate can be linear or branched in a known manner.

Polycarbonates are prepared in a known manner from bisphenols, carbonic acid derivatives, selective chain terminators and branching agents. The detailed preparation of polycarbonate has been disclosed in many patent specifications for nearly 40 years. For example, the following literature can be found in Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, PRMüller, H. Nouvertne, BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Vol. 11, No. 2, 1988, Pp. 648-718; last reference to Dres.U.Grigo, K. Kirchner and PRMüller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pp. 117-299.

Bisphenols suitable for the preparation of polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl) sulfide, Bis(hydroxyphenyl)ether, bis(hydroxyphenyl)ketone, bis(hydroxyphenyl)hydrazine, bis(hydroxyphenyl)arylene, alpha, alpha'-bis(hydroxyphenyl)diisopropylbenzene, and from blush or Benzyl decylamine derived from a phenolphthalein derivative, and its nuclear alkylation and nuclear halogenated compound.

Preferred bisphenols are 4,4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-p-dipropylbenzene, 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, double- (3,5-Dimethyl-4-hydroxyphenyl)indole, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-di- (3,5-Dimethyl-4-hydroxybenzene)-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-di- (3,5-Dibromo-4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

Particularly preferred bisphenols are 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis-(3 , 5-dichloro-4-hydroxyphenyl)propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)propane, 1,1-bis-(4-hydroxyphenyl)cyclohexane, And 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

For example, US-A 3 028 635, US-A 2 999 825, US-A 3 148 172, US-A 2 991 273, US-A 3 271 367, US-A 4 982 014 and US-A 2 999 846 In DE-A 1 570 703, DE-A 2063 050, DE-A 2 036 052, DE-A 2 211 956 and DE-A 3 832 396, in FR-A 1 561 518, in "H. Schnell, Such and other suitable diphenols are described in the literature of Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" and in JP-A 62039/1986, JP-A 62040/1986 and JP-A 105550/1986.

Only one bisphenol can be used when using homopolycarbonate, but a plurality of bisphenols can be used when using a copolycarbonate.

Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.

Suitable chain terminators which can be used in the preparation of the polycarbonate are both monophenols and monocarboxylic acids. Suitable monophenols are phenol itself, alkylphenols such as cresol, p-tert-butylphenol, cumene phenol, p-n-octyl phenol, p-isooctyl phenol, p-n-nonyl phenol and P-isodecyl phenol, halogen phenol such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, 2,4,6-triiodophenol, p- Iodine and its mixture.

Preferred chain terminators are phenol, cumene phenol and/or p-tert-butyl phenol.

Suitable monocarboxylic acids are more benzoic acid, alkylbenzoic acid and halobenzoic acid.

Preferred chain terminators are more preferably substituted one or more times by linear or branched C1-C30 alkyl groups. Preferred alkyl groups are unsubstituted or have a third butyl substitution.

The chain termination dose used is preferably between 0.1 and 5 mole %, based on the number of moles of the particular bisphenol used. The chain terminator can be added before, during or after the phosgene reaction.

Suitable branching agents are trifunctional or trifunctional based compounds known in polycarbonate chemistry, especially compounds having three or more phenolic OH groups.

Suitable branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4, 6-tris(4-hydroxyphenyl)-heptane, 1,3,5-tris(hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)benzene Methane, 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, hexa(4-(4-hydroxybenzene) Isopropyl) phenyl)-o-terephthalate (hexa-(4-(4-hydroxyphenylisopropyl)-phenyl)-orthoterephthalic acid ester), tetrakis(4-hydroxyphenyl)methane, tetrakis(4-( 4-hydroxyphenylisopropyl)phenoxy)methane and 1,4-bis((4',4"-dihydroxytriphenyl)methyl)benzene and 2,4-dihydroxybenzoic acid, 1,2 , 5-benzenetricarboxylic acid, melamine chloride and 3,3-bis-(3-methyl-4-hydroxybenzene)-2-oxo-2,3-dihydroindole.

According to the molar amount of the specific bisphenol used, the selective use The amount of the branching agent is preferably from 0.05 mol% to 2.00 mol%.

The branching agent may be introduced as an aqueous alkaline phase initially with the bisphenol and the chain terminator, or may be added as a solution in an organic solvent prior to the phosgene reaction. The branching agent is used with bisphenol during the transesterification process.

If polycarbonate is used as the thermoplastic material in the coextruded layer A), it has from 24,000 to 33,000, preferably from 25,000 to 32,000, more preferably from 25,000 to 30,000, particularly preferably from 25,000 to The weight average molecular weight Mw of 27,000 g/mol includes the upper and lower limits in each range. The melt flow rate MVR (measured according to DIN EN ISO 1133 at 300 ° C and 1.2 kg load) is preferably from 1.5 cm ³ /10 min to 22.5 cm ³ /10 min, particularly preferably 8 cm ³ /10 Min to 16 cm ³ /10 min.

If polycarbonate is used as the thermoplastic material in the base layer, it has a weight average molecular weight of from 26,000 to 35,000, preferably from 28,000 to 33,000, particularly preferably from 29,000 to 32,000, and is included in each range. The value of the lower limit. The melt flow rate MVR (measured according to DIN EN ISO 1133 at 300 ° C and 1.2 kg load) is preferably from 1.5 cm ³ /10 min to 16 cm ³ /10 min, particularly preferably 3 cm ³ /10 Min to 9 cm ³ /10 min.

In each of the above cases, the weight average molecular weight was determined by colloidal osmometry and polycarbonate standard calibration.

In a particular embodiment of the invention, a homopolycarbonate based on 2,2-bis-(4-hydroxyphenyl)-propane is used in each case as the base polymer composition and coextruded. Layer polymer composition Both thermoplastic materials. Such homopolycarbonates are preferably linear, i.e. they do not comprise any branching agents.

In the context of the present invention, a single protic or polyprotic acid stands for, for example, ethylene phosphate, citric acid, phosphorous acid and phosphoric acid. Particularly preferred is an 85% strength aqueous orthophosphoric acid.

In the context of the present invention, a mold release or release agent is a commercially available product, commercially available as a neopentyltetrastearate (PETS) as a % substrate, such as Loxiol® VPG from Emery Oleochemicals Europe, Düsseldorf, Germany. 861;- commercially available products based on glyceryl monostearate such as Loxiol® EP 129 from Emery Oleochemicals Europe, Düsseldorf, Germany or Dimodan HAB from Danisco, Copenhagen, Denmark; - 2-octyl ten Commercially available products of dialkyl stearate as a substrate such as Loxiol® 3820 from Emery Oleochemicals Europe, Düsseldorf, Germany; commercially available as a branched ester mixture (CAS 573991-39-6) Obtained products such as Lubril® JK from Rhodia GmbH, Frankfurt, Germany; - commercially available products based on ester waxes such as Loxiol® G 32 from Emery Oleochemicals Europe, Düsseldorf, Germany; the above release agents can be used alone or Use as a mixture. In the context of the present invention, it is preferably used alone or in a mixture. A stripping agent based on neopentyl alcohol tetrastearate or 2-octyldodecanol stearate.

The UV absorbers that can be used in the base layer and in the coextruded layer in the present invention are those having a minimum permeable wavelength below 400 nm and a maximum permeable wavelength above 400 nm. Such compounds and their preparation are known from the literature, for example in EP-A 0 839 623, WO-A 96/15102 and EP-A 0 500 496. Examples of such UV absorbers are benzotriazole, three , diphenyl ketone and / or aromatized cyanoacrylate.

The benzotriazole-based UV absorber is, for example, preferably 2-(3',5'-bis-(1,1-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole (Tinuvin). ® 234, BASF SE, Ludwigshafen), 2-(2'-hydroxy-5'-(t-octyl)-phenyl)-benzotriazole (Tinuvin® 329, BASF SE, Ludwigshafen), 2-(2 '-Hydroxy-3'-(2-butyl)-5'-(t-butyl)-phenyl)-benzotriazole (Tinuvin® 350, BASF SE, Ludwigshafen) and bis-(3-(2H) - benzotriazolyl)-2-hydroxy-5-(trioctyl)methane (Tinuvin® 360, BASF SE, Ludwigshafen).

three The UV absorber of the kind is preferably (2-(4,6-diphenyl-1,3,5-three) -2-yl)-5-(hexyloxy)-phenol (Tinuvin® 1577, BASF SE, Ludwigshafen) and 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6 -di-(4-phenyl)phenyl-1,3,5-three (CGX UVA 006 or Tinuvin® 1600, BASF SE, Ludwigshafen).

The diphenyl ketone UV absorber is preferably, for example, 2,4-dihydroxydiphenyl ketone (Chimasorb® 22, BASF SE, Ludwigshafen) and 2-hydroxy-4-(octyloxy)-diphenyl ketone. (Chimasorb® 81, BASF SE, Ludwigshafen).

More preferably, a UV absorber selected from the group consisting of cyanoacrylates and malonic esters, for example, 1,3-bis-[(2'-cyanide-3',3'-diphenylpropenyl) is preferred. Oxy]-2,2-bis-{[(2'-cyanide-3',3'-diphenylpropenyl)oxy]methyl}-propane (Uvinul® 3030, BASF SE Ludwigshafen) or tetraethyl Base 2,2'-(1,4-phenylene dimethylene)-dipropionate (Hostavin® B-Cap, Clariant AG).

In a particular embodiment of the invention, the polymer composition of the coextruded layer comprises one or more UV absorbers, but no benzotriazole UV absorber is present.

A preferred UV absorber for the coextruded layer is 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3, 5-three (CGX UVA 006 or Tinuvin® 600, BASF SE, Ludwigshafen) or (2-(4,6-diphenyl-1,3,5-three) 2-yl)-5-(hexyloxy)-phenol (Tinuvin® 1577, BASF SE, Ludwigshafen).

In another particular embodiment of the invention, the coextruded layer does not use any UV absorber.

In the context of the present invention, phosphites, phosphonites and phosphines are especially suitable as heat or processing stabilizers.

For example, triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, and tris (phosphoric acid) Octaalkyl) ester, distearyl neopentyl alcohol diphosphite, tris(2,4-di-tert-butyl-phenyl) phosphite, diisodecyl neopentyl alcohol diphosphoric acid Ester, bis(2,4-di-tert-butyl-phenyl) pentaerythritol diphosphite, bis(2,4-diisopropylphenylphenyl)neopentanol diphosphite, Bis(2,6-di-t-butyl-4-ethylphenyl)neopentitol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4- Di-t-butyl-6-methylphenyl)-neopentitol diphosphite, bis(2,4,6-paran (t-butylphenyl)neopentitol diphosphite, Tristearyl sorbitol triphosphite, bismuth (2,4-di-t-butylphenyl)-4,4'-diphenylene diphosphinate, 6-isooctyloxy-2, 4,8,10-tetra-t-butyl-12H-biphenyl [d,g]-1,3,2-di phosphorus (6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocine), bis(2,4-di-t-butyl- 6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10 -tetra-tert-butyl-12-methyl-biphenyl [d,g]-1,3,2-di phosphorus (6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocine), 2,2',2"-nitrogen- [Triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1'-diphenyl-2,2'-diyl) phosphite], 2-ethyl Hexyl (3,3',5,5'-t-butyl-butyl-1,1'-diphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl -2-(2,4,6-tri-t-butylphenoxy)-1,3,2-di phosphorus (5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dio xaphosphirane), bis(2,6-di-t-butyl-4- Ethylphenyl) pentaerythritol diphosphite, triphenylphosphine (TPP), trialkylphenylphosphine, bis(diphenylphosphino)ethane or trinaphthylphosphine.

It is especially preferred to use triphenylphosphine (TPP), Irgafos® 168 (see (2,4-di-t-butyl-phenyl)phosphite) and hexamethylenephenyl phosphite or a mixture thereof.

More phenolic antioxidants such as alkylated monophenols, alkylated thiophenols, hydroquinones and alkylated hydroquinones can be used. Especially preferred is Irganox® 1010 (neopentitol 3-(4-hydroxy-3,5-di-t-butylphenyl)propionate; CAS: 6683-19-8) and Irganox 1076® ( 2,6-Di-t-butyl-4-(octadecyloxyethyl)phenol).

Further additives in the context of the invention are, for example, antistatic agents, inorganic pigments, organic dyes, flame retardants, IR absorbers or optical brighteners. In this context, inorganic pigments and/or organic dyes may be added during the kneading and preferably during the extrusion of the sheet. In the case of the extrusion period, the addition is preferably carried out by a masterbatch containing a high concentration of the above additives in the polycarbonate carrier matrix. Inorganic pigments and/or organic dyes can be used in both the base layer and the coextruded layer.

It has been found that in order to achieve the object according to the invention it is important to maintain the coextruded sheet according to the invention at a specific layer thickness. In particular, the thickness of the coextruded sheet comprising hollow glass spheres must be maintained within a narrow defined range so that a good uniform external appearance can be achieved in addition to a high scratch resistance and a pleasant touch. .

In the context of the present invention, the coextruded layer has a layer thickness of from 50 μm to 300 μm, preferably from 90 μm to 250 μm, more preferably from 100 μm to 200 μm, particularly preferably from 120 μm to 170 μm. . Here, the thickness of the coextruded layer is defined as two measured values (based on the width of the film, one measurement is taken at the center of the sheet, and the other measured value is taken at the distance side). The average of the edge 10 cm). The film thickness of the coextruded layer was measured by means of an optical microscope. In the context of the present invention, the total thickness of the sheet comprising the base layer and the coextruded layer is from 1 mm to 8 mm, preferably from 1 mm to 5 mm, particularly preferably from 2 mm to 4 mm.

The preparation of the molding composition for the coextruded layer is preferably carried out by a kneading method known per se using a twin screw extruder. However, it has proven to be advantageous to set specific processing parameters. These include metering into the hollow glass spheres by direct feed into the melt, the melt having an optimized melt temperature and extruder speed configuration. The temperature of the melt is from 320 ° C to 380 ° C, preferably from 330 ° C to 360 ° C, particularly preferably from 330 ° C to 355 ° C. The extruder speed is from 300 rpm to 500 rpm, preferably from 360 rpm to 500 rpm.

Coextruded sheets are made by conventional coextrusion processes using, for example, coextrusion adapters or coextrusion dies. A coextrusion die is preferably used.

Example

In order to produce coextruded sheets, various polymer compositions for coextruded layers are prepared by kneading in the present invention. The equipment for mixing includes:

‧ Four weight scales from K-Tron

‧ Evolum 32HT co-rotating twin-screw extruder from Clextral with a screw diameter of 32 mm

‧ an orifice mold for shaping the melt tow

‧Water bath for cooling and curing the tow

‧ Granulation equipment

‧Selective auxiliary extruder on the drum 5 (lateral feed port)

‧Extruder with 11 barrels at 4D length

‧ The vacuum devolatization yield by the water ring pump on the drum 10 is 50 kg/h.

The polymer composition used to prepare the coextruded layer and the selected kneading conditions are described in more detail below.

In this method, the 85% strength orthophosphoric acid used in all cases (analytical grade EMSURE® ACS, ISO, reag. Ph Eur) is fed from the feed port in the form of a mixture with polycarbonate powder. 1) added.

The polycarbonate pellets are metered in analogly from the feed port at the tank 1.

The hollow glass spheres are metered from the transverse feed port at the drum 5 or from the feed port at the drum 1. If added by a lateral feed port (also referred to as an auxiliary extruder), this addition is "unpressurized".

The hollow glass spheres used in the examples are characterized as follows: 3M Experimental Glass Bubbles, amorphous vermiculite treated with iM30K from 3M Deutschland GmbH, Neuss, Germany, alkalinity 0.5 meq/g and an average particle size d ₅₀ of 17 μm (volume diameter). The pressure equalization compressive strength is 2,000 bar.

The UV absorber is CGX UVA 006 from BASF SE, Ludwigshafen, which is -[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-bis(4-phenyl)phenyl-1 , 3,5-three .

TPP is triphenylphosphine.

Uvitex OB is 2,5-thiophenediyl-bis(5-t-butyl-1,3-benzo) Oxazole), an optical brightener from BASF SE, Ludwigshafen.

Co-extruded polymer composition of layer A: kneaded the following: 85.000% Makrolon® 3100 000000 (a thermally stable linear polycarbonate from Bayer MaterialScience AG, Leverkusen with a melt flow rate MVR of 6 cm ³ /10 Min (bisphenol A based on DIN EN ISO 1133 at 1.2 kg load and 300 °C); 10.000% hollow glass spheres and 4.940% Makrolon® 3108 powder premix (from Bayer MaterialScience AG, Leverkusen linear polycarbonate with a melt flow rate MVR of 6 cm ³ /10 min (measured according to DIN EN ISO 1133 at 1.2 kg load and 300 ° C) of bisphenol A); 0.030% CGX UVA 006; 0.025% TPP; and 0.0050% phosphoric acid.

Mixing conditions of A: speed: 450 rpm, melt temperature 370 °C.

Tank temperature: 80 ° C in Zone 1; 220-223 ° C in Zone 2; temperature range from 310 to 349 ° C in each of the following zones.

The hollow glass spheres are added by a lateral feed port at the barrel 5.

Co-extruded polymer composition of layer B: kneaded the following: 85.000% Makrolon® 2600 000000 (a thermally stable linear polycarbonate from Bayer MaterialScience AG, Leverkusen with a melt flow rate MVR of 12.5 cm ³ /10 Min (bisphenol A based on DIN EN ISO 1133 at 1.2 kg load and 300 °C); pre-mixture of 10.0000% hollow glass spheres and 4.940% Makrolon® 3108 powder (from Bayer MaterialScience AG, Leverkusen linear polycarbonate with a melt flow rate MVR of 6 cm ³ /10 min (measured according to DIN EN ISO 1133 at 1.2 kg load and 300 ° C) of bisphenol A); 0.030% CGX UVA 006; 0.025% TPP; and 0.0050% phosphoric acid.

Blending conditions for B: speed: 450 rpm, melt temperature 345 °C.

Tank temperature: 78-80 ° C in Zone 1; 200-205 ° C in Zone 2; temperature range 270 to 327 ° C in each of the following zones.

The hollow glass spheres are added by a lateral feed port at the barrel 5.

Co-extruded polymer composition of layer C: kneaded the following: 85.000% Makrolon® 2600 000000 (a thermally stable linear polycarbonate from Bayer MaterialScience AG, Leverkusen with a melt flow rate MVR of 12.5 cm ³ /10 Min (bisphenol A based on DIN EN ISO 1133 at 1.2 kg load and 300 °C); pre-mixture of 10.0000% hollow glass spheres and 4.970% Makrolon® 3108 powder (from Bayer MaterialScience AG, Leverkusen's linear polycarbonate with a melt flow rate MVR of 6 cm ³ /10 min (measured according to DIN EN ISO 1133 at 1.2 kg load and 300 ° C) of bisphenol A); 0.025% TPP ; and 0.0050% phosphoric acid.

C mixing conditions: speed: 450 rpm, melt temperature 339 ° C.

Tank temperature: 79-80 ° C in Zone 1; 200-218 ° C in Zone 2; temperature range 270 to 318 ° C in each of the following zones.

The hollow glass spheres are added by a lateral feed port at the barrel 5.

Co-extruded polymer composition of layer D: kneaded the following: 85.000% Makrolon® 2600 000000 (a thermally stable linear polycarbonate from Bayer MaterialScience AG, Leverkusen with a melt flow rate MVR of 12.5 cm ³ /10 Min (bisphenol A based on DIN EN ISO 1133 at 1.2 kg load and 300 °C); pre-mixture of 10.0000% hollow glass spheres and 4.970% Makrolon® 3108 powder (from Bayer MaterialScience AG, Leverkusen's linear polycarbonate with a melt flow rate MVR of 6 cm ³ /10 min (measured according to DIN EN ISO 1133 at 1.2 kg load and 300 ° C) of bisphenol A); 0.025% TPP ; and 0.0050% phosphoric acid.

Blending conditions for D: speed: 325 rpm, melt temperature 342 °C.

Tank temperature: 78-80 ° C in Zone 1; 200-216 ° C in Zone 2; temperature range 308 to 326 ° C in each of the following zones.

The hollow glass sphere is added by the feed port at the tank 1.

Co-extruded polymer composition of layer E: Blending the following: 85.000% Makrolon® 3100 000000 (a thermally stable linear polycarbonate from Bayer MaterialScience AG, Leverkusen with a melt flow rate MVR of 6 cm ³ /10 Min (bisphenol A based on DIN EN ISO 1133 at 1.2 kg load and 300 °C); 10.000% hollow glass spheres and 4.950% Makrolon® 3108 powder premix (from Bayer MaterialScience AG, Leverkusen's linear polycarbonate with a melt flow rate MVR of 6 cm ³ /10 min (measured according to DIN EN ISO 1133 at 1.2 kg load and 300 ° C) of bisphenol A); 0.025% TPP ; 0.02% by weight of Uvitex® OB; and 0.0050% phosphoric acid.

Mixing conditions for E: speed: 225 rpm, melt temperature 335 °C.

Tank temperature: 80 ° C in Zone 1; 198 ° C in Zone 2; temperature range from 298 to 321 ° C in each of the following zones.

The hollow glass spheres are added by a lateral feed port at the barrel 5.

Co-extruded polymer composition of layer F: kneaded the following: 85.000% Makrolon® 3100 000000 (a thermally stable linear polycarbonate from Bayer MaterialScience AG, Leverkusen with a melt flow rate MVR of 6 cm ³ /10 Min (bisphenol A based on DIN EN ISO 1133 at 1.2 kg load and 300 °C); premix of 10.000% hollow glass spheres and 4.750% Makrolon® 3108 powder (from Bayer MaterialScience AG, Leverkusen linear polycarbonate with a melt flow rate MVR of 6 cm ³ /10 min (measured according to DIN EN ISO 1133 at 1.2 kg load and 300 ° C) of bisphenol A); 0.200% by weight Tinuvin® 360; 0.025% TPP; 0.020% by weight Uvitex® OB; and 0.0050% phosphoric acid.

Mixing conditions for F: speed: 226 rpm, melt temperature 336 °C.

Tank temperature: 80 ° C in Zone 1; 201 ° C in Zone 2; temperature range from 298 to 318 ° C in each of the following zones.

The hollow glass spheres are added by a lateral feed port at the barrel 5.

The polymer composition of coextruded layers E and F was made using an extruder configuration that was compatible with the mixing example A-D.

Coextruded sheets produced using E and F comprise agglomerates of hollow glass spheres. A comparison of the MVR values of E and F shows that 0.2% of Tinuvin® 360 has a detrimental effect on molecular weight (increased MVR).

Coextruded polycarbonate sheets are made hereinafter using the polymer compositions described above for the coextruded layers. The processing variables used in this method are explained below.

Extrusion method (mold method): The polycarbonate solid sheet is manufactured with the assistance of the following machines and equipment:

- Single-screw extruder (de-evaporation extruder, single-screw Breyer, Singen/Germany with screw diameter 60 mm and length 33 D) with vacuum melt de-evaporation unit.

- MAAG melt pump

- Single-layer solid sheet extrusion die (from Breyer, Singen/Germany) with a width of 400 mm (for solid sheets from 1 to 10 mm)

- 3-zone co-extrusion machine with a diameter of 30 mm and a length of 25D

- Horizontal three-roll extruder with a width of 500 mm and a diameter of 300 mm (Breyer, Singen/Germany)

- Roller conveyor, length (compression machine / cutting station distance) 6 m

- Output wheel

- Transverse cutting device (circular saw)

- Stacking table

A solid sheet having a coextruded layer on one side (thin sheets 1-7, see Table 1) was produced in the following manner: polycarbonate pellets for the base layer in a non-dry state in each case (in the following) Known as PC-1) (linear polycarbonate based on bisphenol A, melt flow rate MVR of 6.0 cm ³ /10 min (measured according to DIN EN ISO 1133 at 1.2 kg load and 300 °C) 0.1% by weight of Tinuvin® 360 was used as a UV absorber and 0.05% by weight of triphenylphosphine) was fed to the tank of the main extruder and conveyed by a drum/screw melt. The temperature of each of the main extruders was between 280 and 290 ° C, so the resulting melt temperature was 300 °C. The pumping speed of the melt was set at 42 rpm and the resulting screw speed was between 54 and 56 rpm. The polymer composition for the coextruded layer AF was used in each case as the material for the one side coextruded layer, in each case in a pre-dried state (in a dry air drying apparatus at 120 ° C 4 Hours) These materials are fed into the slots of the co-extrusion machine. The co-extruder barrel temperature is 180 to 240 ° C and the melt temperature is about 240 ° C. The screw speed is 45 rpm.

The melt of the two materials was mixed in a co-extrusion die and then conveyed to a sheet mold designed to have a 2.8 mm exit gap. The output speed is 1.22 m/min. The roll temperatures of rolls 1, 2 and 3 of the extruder were 115°, 125° and 135 ° C, respectively, and the roll pitch was set to produce a sheet of 2.0 mm thick.

Other plant equipment is used for transportation, cutting to specificity and stacking multiple sheets.

The sheet produced in this way has a total thickness of 2.0 mm and a sheet width of 400 mm. The upper layer (from co-extrusion) contained compositions A-F having an average thickness of 100 μm or 150 μm (see Table 1).

Determination of the film thickness of the coextruded layer: The film thickness of the coextruded layer was measured by optical microscopy from an Axioplan microscope from Zeiss, which has a zoomed eyepiece, magnified 50x and 200x objective lenses and used from Philips' HBO 50 W mercury vapor lamp.

For measurement, a sample piece 1 cm long and 0.5 cm wide was cut at several selected positions of the sheet to be studied. Thin sections of sample pieces having a thickness of 20 μm were cut along the cross section of the sheet using a HM 355 S microtome from Thermo Fisher Scientific. The film thickness of the coextruded layer was then visually observed by optical microscopy using the apparatus described above, which is the difference in μm between the interface of the base layer/coextruded layer and the interface of the coextruded layer/air.

It can be seen from the table that the polymer compositions B), C) and D) according to the invention exhibit good surface uniformity, but the polymer compositions of the comparative examples A), E) and F) only exhibit an average to Poor uniformity even some obvious visible agglomerates of hollow glass spheres.

Table 1 further shows that the sheet having the polymer composition according to the invention as layer A) has good surface uniformity (sheets 2, 3, 4 and 5).

It is evident from Table 1 that it is compared to mixing by ordinary feed ports (thin plates 4 and 5) or by using lateral feed ports but at lower speeds (thin plates 6 and 7) or by using lateral feed ports and higher Speed but higher material temperature (sheet 1), if higher speed is used, using the transverse feed port of the extruder instead of the ordinary feed port, and in the polymer composition for layer A) according to the invention The use of a predetermined material temperature (also using the term melt temperature as a synonym for the kneading) greatly improves the uniformity of the surface of the sheet. Specific improvements in uniformity can be similarly applied to the polymer composition in accordance with specific processing parameters.

Scratch resistance was determined by pencil hardness tester according to ISO 15184 or ASTM D3363: a small piece was sawed from a specific sheet or thermoformed work piece and fixed to a glass plate to prepare a test sample. Pencil hardness was determined using a BYK-Gardner Wolf-Wilburn pencil hardness tester and a pencil from Cretacolor. In this test, according to ISO 15184, the name of the pencil that no longer damaged the surface in the test configuration of 750 g pressure and 45° angle was recorded.

The center of the sheet was measured in each test, and the values of the sheets 3 and 4 were 2B.

The coextruded sheets according to the present invention produced in the above manner are suitable for the production of semi-finished products by thermoforming.

For the thermoforming according to the prior art, a thin plate 3 having a size of 1.9 x 400 x 500 mm sawed from the extrusion plate was thermoformed on an Illig thermoforming unit (U60 SB53C).

The sheet was first dried at 125 ° C for 4 hours.

The pre-dried warm film is placed in a fixing frame of the thermoforming unit in a co-extruded face-up manner, sandwiched, and irradiated from the upper side with an IR lamp (set at 500 ° C) to a desired forming temperature of 210 ° C. It is thermoformed. The warm-up time here is 92 seconds.

The forming mold used was a rectangular stepped pyramid having a total height of 15 cm and 6 vertical steps, and its temperature was controlled at 80 ° C for processing. The size of the mold is 16 x 23 cm.

The hot forming process using the film 3 proceeds smoothly. A uniform surface of good quality is still obtained after hot forming.

Anti-scratch test on thermoformed products

Scratch resistance tests were performed on different steps of the stepped pyramid on the thermoformed product.

Substrate: at least 2B

At least the first step: at least 2B

Second step on the thin plate side: at least 2B

In the third step: at least 2B

Fourth step on the side of the thin plate: at least 2B

In the fifth step: at least 2B

Claims (14)

A polymer composition P) comprising: a polycarbonate having a weight average molecular weight Mw of from 24,000 to 33,000 g/mol and a melt flow rate of from 8 to 16 cm ³ /min; a basicity of less than 1.0 meq/g and 5.0% by weight Hollow glass spheres up to 20.0% by weight (based on the total amount of the composition); and conventional additives which do not additionally comprise a thermoplastic polymer. The polymer composition of claim 1 includes polycarbonate and hollow glass spheres as well as conventional additives. The polymer composition of claim 1 or 2, wherein the additive is selected from at least one of the group consisting of a single proton or a polyprotic acid, a thermal or processing stabilizer, a UV absorber, a phenolic antioxidant , release agents, antistatic agents, inorganic pigments, organic dyes, flame retardants, IR absorbers and optical brighteners. The polymer composition of claim 1, wherein the hollow glass sphere is contained in an amount of from 8.0% by weight to 15.0% by weight. The polymer composition of claim 1 or 2, wherein the hollow glass sphere has a compressive strength of from 500 bar to 2,500 bar. The polymer composition of any one of claims 1 to 3, which comprises from 0.000% by weight to 0.050% by weight of a single proton or a polyprotic acid. Use of a polymer composition as claimed in any one of claims 1 to 6 for the manufacture of an extruded sheet. A sheet comprising two layers A) and B), wherein layer A) comprises a polymer composition as in claim 1 and layer B) comprises a melt flow rate (MVR) from 3 to 9 cm ³ /10 min Polycarbonate wherein the polycarbonate in layer A) has a melt flow rate (MVR) from 8 to 16 cm ³ /10 min. A sheet according to item 7 of the patent application, wherein the thermoplastic material in the layer B) is a polycarbonate or a copolycarbonate having a molecular weight (weight average) of from 26,000 to 33,000 g/mol. a sheet according to one or more of claims 7 to 8, wherein the layer A) has a layer thickness of 50 μm to 300 μm and the layer comprising the layers A) and B) has a layer thickness of 1 mm to 8 mm, the sheet was prepared by co-extrusion. A shaped article comprising a film as one or more of items 7 to 9 of the patent application. For example, the container and baggage parts of claim 10 of the patent application. A method of preparing a polymer composition P) according to claim 1, wherein the polycarbonate and the hollow glass sphere are mixed on a twin-screw extruder, characterized in that it is directly introduced by a side feed port The hollow glass sphere is introduced into a melt having a temperature of from 320 ° C to 360 ° C, and the speed of the extruder is from 300 rpm to 500 rpm and the polycarbonate has a melt of from 8 to 16 cm ³ /10 min. Flow rate (MVR). The method of claim 12, wherein the extruder speed is from 300 rpm to 500 rpm.