A masterbatch comprising pigment and demolding agent is provided. The demolding agent is selected from the group comprising low molecular weight polyolefin oils, low molecular weight polyolefin waxes, montan waxes and aliphatic or aromatic carboxylic acid esters of fatty acids and/or fatty alcohols, wherein the pigment content of the masterbatch is from 3 to 70 wt. %, based on the total weight of the masterbatch. The masterbatch is suitable for preparation of a polymer composition having improved pigment dispersion.
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1. An injection molded article produced by a process comprising preparing injection molding a coloured polymer composition by melt-mixing, wherein the coloured polymer composition comprises a melt-mixed coloured polycarbonate composition, comprising:
a) from 40 to 99.96 wt. % of at least one thermoplastic polymer (a), wherein polymer (a) is at least one selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates, wherein the polymer (a) has a weight average molecular weight of 15,000 to 80,000 g/mol, and wherein the polymer (a) is a homopolycarbonate or copolycarbonate containing bisphenol A;
b) from 0.1 to 3 wt. % of at least one pigment component (b);
c) from 0.1 to 3 wt. % of at least one demoulding agent (c) selected from the group consisting of pentaerythritol tetrastearate, glycerol monostearate, and stearyl stearate;
d) from 0 to 60 wt. % of one or more thermoplastic polyesters (d);
e) from 0 to 40 wt. % of one or more elastomers (e) other than component f;
f) from 0 to 40 wt. % of one or more optionally rubber-modified vinyl (co)polymers (f); and
g) from 0 to 10 wt. % one or more further additives;
the process comprising using a masterbatch, wherein the melt-mixed coloured polycarbonate composition comprises a masterbatch consists consisting of the at least one pigment (b) and the at least one demoulding agent (c) in compounding prepared using a shear and mixing unit in a single-shaft extruder, a multi-shaft extruder, an internal mixer, a co-kneader, or a shear roller device,
wherein the demoulding agent is at least one selected from the group consisting of pentaerythritol tetrastearate, glycerol monostearate and stearyl stearate,
wherein the at least one pigment is (b) comprises a carbon-based pigment and the content of pigment in the masterbatch is from 40 to 60 wt. %, based on the total weight of the masterbatch,
wherein the carbon-based pigment is selected from the group consisting of: a) carbon black; b) graphite; c) fullerene; d) graphene; e) activated charcoal; and f) carbon nanotubes, and
wherein the process additionally comprises preparing the masterbatch by using a shear and mixing unit in a single-shaft extruder, multi-shaft extruder, internal mixer, co-kneader or a shear roller device,
wherein the pigment is homogeneously distributed and present in finely dispersed form in the polymer composition,
wherein the produced coloured polymer composition is a polycarbonate composition comprising
a) from 40 to 99.96 wt. % of at least one thermoplastic polymer (a), wherein polymer (a) is at least one selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates, wherein the polymer has a weight average molecular weight of 15,000 to 80,000 g/mol and is a homopolycarbonate or copolycarbonate containing bisphenol A
b) from 0.1 to 3 wt. % of at least one pigment component (b),
c) from 0.1 to 3 wt. % of at least one demoulding agent (c) selected from the group consisting of pentaerythritol tetrastearate, glycerol monostearate and stearyl stearate,
d) from 0 to 60 wt. % of one or more thermoplastic polyesters (d),
e) from 0 to 40 wt. % of one or more elastomers (e) other than component f,
f) from 0 to 40 wt. % of one or more optionally rubber-modified vinyl (co)polymers (f), and
g) from 0 to 10 wt. % one or more further additives.
3. An injection molded article according to
a) metering said demoulding agent and said pigment into said shear and mixing unit,
b) melt-mixing the pigment in the demoulding agent and thereby dispersing the pigment in the demoulding agent to form a melt mixture,
c) optionally filtering the melt mixture,
d) forming melt strands,
e) cooling and granulating the melt strands, and
f) when using underwater or water-ring granulation in step e), drying granules.
4. The injection molded article according to
6. An injection molded article according to
7. An injection molded article according to
8. The injection molded article according to
a) from 50 to 75 wt. % of at least one thermoplastic polymer (a),
b) from 0.1 to 1.5 wt. % of at least one pigment component (b),
c) from 0.1 to 1.5 wt. % of at least one demoulding agent (c),
d) from 20 to 60 wt. % of one or more thermoplastic polyesters (d),
e) from 2 to 20 wt. % of one or more elastomers (e) other than component f,
f) from 3 to 40 wt. % of one or more optionally rubber-modified vinyl (co)polymers (f), and
g) from 0.2 to 10 wt. % one or more further additives.
9. The injection molded article according to
10. An injection molded article according to
11. An injection molded article according to
12. An injection molded article according to
13. An injection molded article according to
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This
wherein R2 is an aliphatic saturated or unsaturated, linear, cyclic or branched alkyl radical and R3 is an alkylene radical of a mono- to tetra-hydric aliphatic alcohol of the formula R3—(OH)o+p. In the compounds of formula (IV), the o radicals R2 in the same molecule can also have different structures.
Particularly preferred for R2 are C1-C30-, particularly preferably C4-C28-, most particularly preferably C12-C24-alkyl radicals. C1-C30-Alkyl represents, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpropyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl or 1-ethyl-2-methylpropyl, n-heptyl and n-octyl, pinacyl, adamantyl, the isomeric menthyls, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Particularly preferred for R3 are C1-C30-, particularly preferably C1-C18-alkylene radicals. Alkylene represents a straight-chained, cyclic, branched or unbranched alkylene radical. C1-C18-Alkylene represents, for example, methylene, ethylene, n-propylene, isopropylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-hexadecylene or n-octadecylene.
In the case of esters of polyhydric alcohols, free, non-esterified OH groups can also be present. Aliphatic carboxylic acid esters which are suitable according to the invention are, for example and preferably, glycerol monostearate (GMS), palmityl palmitate and stearyl stearate. Mixtures of different carboxylic acid esters of formula (IV) can also be used. Carboxylic acid esters which are preferably used are additionally mono- or poly-esters of pentaerythritol, glycerol, trimethylolpropane, propanediol, stearyl alcohol, cetyl alcohol or myristyl alcohol with myristic, palmitic, stearic or montanic acid and mixtures thereof. Pentaerythritol tetrastearate, glycerol monostearate, stearyl stearate and propanediol distearate, or mixtures thereof, are particularly preferred.
A particularly preferred demoulding agent according to the invention is pentaerythritol tetrastearate and glycerol monostearate, in particular pentaerythritol tetrastearate.
Component d
Thermoplastic polyesters according to component d which can be used according to the invention are polyalkylene terephthalates, which can be prepared by methods known in the literature (see e.g. Kunststoff-Handbuch, Volume VIII, p, 695 ff, Carl-Hanser-Verlag, Munich 1973).
In a preferred embodiment, the polyalkylene terephthalates are reaction products of aromatic dicarboxylic acids or reactive derivatives thereof, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, as well as mixtures of these reaction products.
Particularly preferred polyalkylene terephthalates contain at least 80 wt. %, preferably at least 90 wt. %, based on the dicarboxylic acid component, terephthalic acid radicals and at least 80 wt. %, preferably at least 90 mol %, based on the diol component, ethylene glycol and/or 1,4-butanediol radicals.
Particular preference is given to polyalkylene terephthalates which have been prepared solely from terephthalic acid and reactive derivatives thereof (e.g. dialkyl esters thereof) and ethylene glycol and/or 1,4-butanediol, and mixtures of these polyalkylene terephthalates. Polyalkylene terephthalates which are particularly preferably used according to the invention are polybutylene terephthalate (PBT) and polyethylene terephthalate (PET).
Component e
There can be used according to the invention as component e any elastomers other than component f which have a glass transition temperature <10° C., preferably <0° C., particularly preferably <−20° C.
There are preferably used as component e, for example, thermoplastic elastomers such as, for example, olefin-based thermoplastic elastomers (TPO), polyurethane-based thermoplastic elastomers (TPU), and thermoplastic styrene block copolymers (TPS).
Unless expressly described otherwise in the present invention, the glass transition temperature is determined for all components by means of differential scanning calorimetry (DSC) according to DIN EN 61006 at a heating rate of 10 K/min with determination of the Tg as the mid-point temperature (tangent method).
Component f
Rubber-modified vinyl (co)polymers which can be used according to the invention as component fare one or more graft polymers of
The graft base f.2 generally has a mean particle size (d50 value) of from 0.05 to 10.00 μm, preferably from 0.10 to 5.00 μm, more preferably from 0.15 to 1.00 μm and particularly preferably from 0.2 to 0.5 μm.
The mean particle size d50 is the diameter above and below which in each case 50 wt. % of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).
Monomers f.1 are preferably mixtures of
Preferred monomers f.1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, preferred monomers f.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are f.1.1 styrene and f.1.2 acrylonitrile.
Graft bases f.2 suitable for the graft polymers according to component f are, for example, diene rubbers, EP(D)M rubbers, that is to say those based on ethylene/propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene, ethylene/vinyl acetate and acrylate-silicone composite rubbers.
Preferred graft bases f.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with further copolymerisable monomers (e.g. according to f.1.1 and f.1.2), with the proviso that the glass transition temperature of component f.2 is below <10° C., preferably <0° C., particularly preferably <−10° C. Pure polybutadiene rubber is particularly preferred.
The gel content of the graft base f.2 is at least 30 wt. %, preferably at least 40 wt. %, particularly preferably at least 70 wt. % (measured in toluene).
The gel content of the graft base f.2 is determined at 25° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).
Particularly preferred rubber-modified vinyl (co)polymers according to component f are, for example, ABS polymers (emulsion, mass and suspension ABS), as are described, for example, in DE-OS 2 035 390 (=U.S. Pat. No. 3,644,574) or in DE-OS 2 248 242 (=GB-PS 1 409 275) or in Ullmanns, Enzyklopädie der Technischen Chemie, Vol. 19 (1980), p. 280 ff.
The graft copolymers according to component f are prepared by radical polymerisation, for example by emulsion, suspension, solution or mass polymerisation, preferably by emulsion or mass polymerisation, particularly preferably by emulsion polymerisation.
Particularly suitable graft rubbers are also ABS polymers which are prepared by the emulsion polymerisation process by redox initiation with an initiator system comprising organic hydroperoxide and ascorbic acid according to U.S. Pat. No. 4,937,285.
Because it is known that, in the graft reaction, the graft monomers are not necessarily grafted onto the graft base completely, rubber-modified graft polymers according to component f are also understood according to the invention as being those products which are obtained by (co)polymerisation of the graft monomers f.1 in the presence of the graft base f.2 and which also form during working up.
Acrylate rubbers suitable as the graft base f.2 are preferably polymers of acrylic acid alkyl esters, optionally with up to 40 wt. %, based on f.2, of other polymerisable, ethylenically unsaturated monomers. The preferred polymerisable acrylic acid esters include C1- to C8-alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C1-C8-alkyl esters, such as chloroethyl acrylate, as well as mixtures of these monomers.
For crosslinking, monomers having more than one polymerisable double bond can be copolymerised. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having from 3 to 8 carbon atoms and unsaturated monohydric alcohols having from 3 to 12 carbon atoms or saturated polyols having from 2 to 4 OH groups and from 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and tri-vinylbenzenes; but also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate, and heterocyclic compounds which contain at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloyl-hexahydro-s-triazine, triallyl benzenes. The amount of crosslinked monomers is preferably from 0.02 to 5.00 wt. %, in particular from 0.05 to 2.00 wt. %, based on the graft base B.2. In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1 wt. % of the graft base f.2.
Preferred “other” polymerisable, ethylenically unsaturated monomers which can optionally be used in addition to the acrylic acid esters for the preparation of acrylate rubbers suitable as the graft base f.2 are, for example, acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C1-C6-alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as the graft base f.2 are emulsion polymers having a gel content of at least 60 wt. %.
Further suitable graft bases according to f.2 are silicone rubbers having graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
Rubber-free vinyl (co)polymers which can be used according to the invention as component f are, for example and preferably, homo- and/or co-polymers of at least one monomer from the group of the vinyl aromatic compounds, vinyl cyanides (unsaturated nitriles), (meth)acrylic acid (C1-C8)-alkyl esters, unsaturated carboxylic acids, as well as derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.
Particularly suitable are (co)polymers of from 50 to 99 parts by weight, preferably from 60 to 80 parts by weight, in particular from 70 to 80 parts by weight, in each case based on the (co)polymer, of at least one monomer selected from the group of the vinyl aromatic compounds (such as, for example, styrene, α-methylstyrene), vinyl aromatic compounds substituted on the ring (such as, for example, p-methylstyrene, p-chlorostyrene) and (meth)acrylic acid (C1-C8)-alkyl esters (such as, for example, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate), and from 1 to 50 parts by weight, preferably from 20 to 40 parts by weight, in particular from 20 to 30 parts by weight, in each case based on the (co)polymer, of at least one monomer selected from the group of the vinyl cyanides (such as, for example, unsaturated nitriles such as acrylonitrile and methacrylonitrile), (meth)acrylic acid (C1-C8)-alkyl esters (such as, for example, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate), unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids (for example maleic anhydride and N-phenyl-maleimide). The copolymer of styrene and acrylonitrile is particularly preferred.
Such vinyl (co)polymers are known and can be prepared by radical polymerisation, in particular by emulsion, suspension, solution or mass polymerisation.
In an embodiment which is particularly preferred according to the invention, the vinyl (co)polymers have a weight-average molar mass Mw (determined by gel chromatography in dichloromethane with polystyrene calibration) of from 50,000 to 250,000 g/mol, particularly preferably from 70,000 to 180,000 g/mol.
Component g
Additives according to component g which can be used according to the invention are, for example, flameproofing agents (for example halogen compounds or phosphorus compounds such as monomeric or oligomeric organic phosphoric acid esters, phosphazenes or phosphonate amines, in particular bisphenol A diphosphate, resorcinol diphosphate and triphenyl phosphate), flameproofing synergists (for example nano-scale metal oxides), smoke-inhibiting additives (for example boric acid or borates), antidripping agents (for example compounds of the substance classes of the fluorinated polyolefins, of the silicones as well as aramid fibres), antistatics (for example block copolymers of ethylene oxide and propylene oxide, other polyethers or polyhydroxy ethers, polyether amides, polyester amides or sulfonic acid salts), conductivity additives other than the definition of component b, stabilisers (for example UV/light stabilisers, heat stabilisers, antioxidants, transesterification inhibitors, hydrolytic stabilisers), additives having antibacterial action (for example silver or silver salts), additives improving scratch resistance (for example silicone oils or hard fillers such as (hollow) ceramics beads), IR absorbers, optical brightening agents, fluorescent additives, fillers and reinforcing substances other than the definition of component b (for example talc, optionally ground glass fibres, (hollow) glass or ceramics beads, mica, kaolin, CaCO3 and glass flakes), colourings, ground thermoplastic polymers and Brönstedt-acidic compounds as base acceptors, or mixtures of a plurality of the mentioned additives.
The polymer mixtures prepared according to the invention are preferably used in the production of injection-moulded articles or of extrudates in which particular demands are made as regards the homogeneity and freedom from defects of the surfaces.
Examples of moulded articles according to the invention are profiles, films, casing parts of any kind, in particular casing parts for computers, laptops, mobile telephones, television surrounds; for office equipment such as monitors, printers, copiers; for sheets, tubes, conduits for electrical installations, windows, doors and profiles for the construction sector, interior fitting and external applications; in the field of electrical engineering, for example for switches and sockets. The moulded articles according to the invention can also be used for interior fittings for passenger vehicles, railway vehicles, ships, aircraft, buses and other motor vehicles, as well as for automotive bodywork parts. Further moulded articles are food and drinks packaging and structural components which are galvanised or metallised after injection moulding.
a1
Linear polycarbonate based on bisphenol A having a weight-average molecular weight Mw of 17,000 g/mol (determined by GPC in methylene chloride at 25° C. with polycarbonate calibration).
a2
Linear polycarbonate based on bisphenol A having a weight-average molecular weight Mw of 25,000 g/mol (determined by GPC in methylene chloride at 25° C. with polycarbonate calibration).
a3
Linear polycarbonate based on bisphenol A having a weight-average molecular weight Mw of 28,000 g/mol (determined by GPC in methylene chloride at 25° C. with polycarbonate calibration).
a4
Linear polycarbonate based on bisphenol A having a weight-average molecular weight Mw of 30,000 g/mol (determined by GPC in methylene chloride at 25° C. with polycarbonate calibration).
a5
Linear polycarbonate based on bisphenol A having a weight-average molecular weight Mw of 36,000 g/mol (determined by GPC in methylene chloride at 25° C. with polycarbonate calibration)
a6
Linear copolycarbonate of bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane in a mixing ratio of 70 wt. %:30 wt. % having a melt viscosity measured according to ISO 11433 at a temperature of 340° C. and a shear rate of 1000 s−1 of 400 Pas.
a7
Linear polycarbonate of bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane in a mixing ratio of 30 wt. %:70 wt. % having a melt viscosity measured according to ISO 11433 at a temperature of 340° C. and a shear rate of 1000 s−1 of 320 Pas.
a8
Component a2 ground to powder
a9
Linear polycarbonate based on bisphenol A having a weight-average molecular weight Mw of 32,000 g/mol (determined by GPC in methylene chloride at 25° C. with polycarbonate calibration), ground to powder
b1
Black Pearls 800 (Cabot Corporation, Leuven, Belgium): pearled pigment carbon black having a mean primary particle size determined by scanning electron microscopy of 17 nm, a BET surface area determined according to ISO 4652 by nitrogen adsorption of 210 m2/g and an oil adsorption number measured according to ISO 4656 with dibutyl phthalate (DBP) of 65 ml/100 g.
b2
Printex 85 (Evonik Degussa GmbH, Frankfurt/Main, Germany): pigment carbon black having a mean primary particle size determined by scanning electron microscopy of 16 nm, a BET surface area determined according to ISO 4652 by nitrogen adsorption of 200 m2/g and an oil adsorption number measured according to ISO 4656 with dibutyl phthalate (DBP) of 48 ml/100 g.
b3
Chromium rutile pigment
b4
Iron oxide pigment
c1
Pentaerythritol tetrastearate (PETS)
c2
Glycerol monostearate (GMS)
c3
Stearyl stearate
c4
LDPE wax (low-density polyethylene wax)
d1
Linear polyethylene terephthalate having an intrinsic viscosity of 0.665 measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25° C.
d2
Linear polybutylene terephthalate having a melt volume flow rate of 45 cm2/10 min at 250° C. and 2.16 kg load
f1
Emulsion ABS granules with an A:B:S weight ratio of 20:24:56
f2
Mass ABS granules with an A:B:S weight ratio of 25:10:65
f3
Graft polymer consisting of 28 wt. % styrene-acrylonitrile copolymer with a ratio of styrene to acrylonitrile of 71 to 29 parts by weight as shell on 72 wt. % of a particulate graft base as core consisting of 46 parts by weight, based on the graft base, of silicone rubber and 54 parts by weight, based on the graft base, of butyl acrylate rubber, prepared by the emulsion polymerisation process.
f4
Emulsions ABS graft in powder form with an A:B:S weight ratio of 12:58:30
f5
Emulsions ABS graft in powder form with an A:B:S weight ratio of 7:75:18
f6
Polymethyl methacrylate (PMMA)-grafted silicone-butyl acrylate composite rubber graft in powder form, prepared by emulsion polymerisation, consisting of a graft shell of 10 wt. %, based on the graft, of polymethyl methacrylate and 90 wt. %, based on the graft, of particulate silicone-butyl acrylate composite rubber base with a silicone content, based on the silicone-butyl acrylate composite rubber base, of 30 wt. % and a butyl acrylate content, based on the silicone-butyl acrylate composite rubber base, of 70 wt. %.
f7
Styrene-acrylonitrile copolymer (SAN) with an A:S weight ratio of 24:76
g1
Bisphenol A-based oligophosphate
##STR00003##
q=degree of oligomerisation
g2
Polytetrafluoroethylene (PTFE) concentrate consisting of 50 wt. % styrene-acrylonitrile (SAN) copolymer and 50 wt. % PTFE
g3
Stabilisers
g4
Talc with a d50 of 1.2 μm.
g5
Water
A) Carbon Black Masterbatches
The carbon black/demoulding agent masterbatches 1 to 14 listed in table 1 under component B were prepared as described below.
A.1) Mixing Units Used
Test Arrangement 1
A type MDK/E 46 co-kneader from Buss was used.
Test Arrangement 2
As arrangement 1 but without retaining ring 3 (see
Test Arrangement 3
As arrangement 1 but with an additional metering hopper 7 downstream of retaining ring 3 (see
Test Arrangement 4
An Evolum HT32 twin-screw extruder from Clextral with a housing inside diameter of 32 mm, a ratio of screw outside diameter to screw inside diameter of 1.55 and a length-to-diameter ratio of 44 was used. The twin-screw extruder has a housing consisting of 11 parts, in which two co-rotating, intermeshing shafts (not shown) are arranged.
The structure of the extruder used is shown in principle in
Metering of a portion of the pulverulent carbon black and of the pulverulent demoulding agent was carried out by means of differential proportioning weighers (not shown) via the feed hopper 8 into the main intake of the extruder in housing 9 (intake housing).
In the region of housings 9 to 11 there is a feed zone in which the mixture constituents are taken into the extruder in the solid state and conveyed further.
In the region of housing 12 there is a plastification zone, which consists of various conveying double- and triple-threaded kneading blocks of different widths and a return element at the end of the zone.
In the region of housings 13 and 14 there is a mixing zone, which consists of various mixing, kneading and feed elements.
In housing 15, the remaining portion of the pulverulent carbon black is metered into the extruder via a lateral feed device.
In the region of housings 16 and 17 there is a further mixing zone which consists of various mixing, kneading and feed elements.
In housing part 18 (degassing housing) there is the degassing opening 20, which is connected to a suction device (not shown).
In housing 19 (discharge housing) there the pressure build-up zone, which is followed by a spray head (not shown) having a nozzle plate with 6 holes, each of which has a diameter of 3.2 mm.
Test Arrangement 5
A type MDK/E 100 co-kneader from Buss was used. The structure corresponded in principle to the structure of test arrangement 3.
Test Arrangement 6
A shear roller unit was used, as is described, for example, in EP 0707037 B1.
A.2) Preparation of Masterbatches B1-B16
Carbon black/demoulding agent masterbatches B1 to B4 were prepared using the test arrangements, process parameters and formulations indicated in Table 2.
The specific mechanical energy input (SME) indicated in Table 2 was determined according to equation 1.
SME: specific mechanical energy input in kWh/kg
M: torque in Nm
n: speed in l/min
{dot over (m)}: throughput in kg/h
Carbon black/demoulding agent masterbatch B5 was prepared using test arrangement 5 from 58% b1 and 42% c1.
Carbon black/demoulding agent masterbatches B6 and B7 were prepared using test arrangement 6 from 50% b1 and 50% c1 (B6) and 65% b1 and 35% c1 (B7).
Carbon black/demoulding agent masterbatches B8 to B14 were prepared using the test arrangements, process parameters and formulations indicated in Table 3. The specific mechanical energy input (SME) indicated in Table 3 was calculated according to equation 1.
The carbon black/polycarbonate masterbatch B15 was supplied by Color System S.p.a. Carbon black/polycarbonate masterbatch consisting of 15 wt. % b1 and 85 wt. % of a bisphenol A-based polycarbonate having a relative solution viscosity of 1.28 (measured in methylene chloride at 25° C.).
The carbon black/polyethylene masterbatch B16 was supplied by Cabot (trade name: Plasblak PE6130). Carbon black/polyethylene masterbatch containing 50 wt. % carbon black.
B) PC Moulding Compositions
B.1) Mixing Units Used
Test Arrangement 7
An Evolum HT32 twin-screw extruder from Clextral having a housing inside diameter of 32 mm, a ratio of screw outside diameter to screw inside diameter of 1.55 and a length-to-diameter ratio of 36 was used. The twin-screw extruder has a housing consisting of 9 parts, in which two co-rotating, intermeshing shafts (not shown) are arranged.
The structure of the extruder used is shown in principle in
Metering of all the components was carried out by means of differential proportioning weighers (not shown) via the feed hopper 8a into the main intake of the extruder in housing 9a (intake housing).
In the region of housings 9a to 13a there is a feed zone in which the mixture constituents are taken into the extruder in the solid state and conveyed further.
In the region of housings 14a and 16a there is a plastification zone, which consists of various conveying double- and triple-threaded kneading blocks of different widths and a return element at the end of the zone.
In the region of housings 16a and 18a there is a mixing zone which consists of various mixing and feed elements.
In housing part 18a (degassing housing) there is the degassing opening 20a, which is connected to a suction device (not shown).
In housing 19a (discharge housing) there is the pressure build-up zone, which is followed by a spray head (not shown) having a nozzle plate with 6 holes, each of which has a diameter of 3.2 mm.
Test Arrangement 8
As test arrangement 7 but with an injection valve 22 arranged at the end of housing part 21, via which the liquid additive 1 is metered in formulations 20 and 21 (
Test Arrangement 9
A ZSK 25 WLE twin-screw extruder from Coperion Werner & Pfleiderer having a housing inside diameter of 25.2 mm, a ratio of screw outside diameter to screw inside diameter of 1.50 and a length-to-diameter ratio of 48 was used. The twin-screw extruder has a housing consisting of 13 parts, in which two co-rotating, intermeshing shafts (not shown) are arranged. The structure of the extruder used is shown in principle in
Test Arrangement 10
A ZSK 133Sc twin-screw extruder from Coperion Werner & Pfleiderer having a housing inside diameter of 134.4 mm, a ratio of screw outside diameter to screw inside diameter of 1.55 and a length-to-diameter ratio of 31.5 was used. The twin-screw extruder has a housing consisting of 10 parts, in which two co-rotating, intermeshing shafts (not shown) are arranged. The structure of the extruder used is shown in principle in
Test Arrangement 11
A ZSK 92Mc twin-screw extruder from Coperion Werner & Pfleiderer having a housing inside diameter of 92.8 mm, a ratio of screw outside diameter to screw inside diameter of 1.55 and a length-to-diameter ratio of 40 was used. The twin-screw extruder has a housing consisting of 10 parts, in which two co-rotating, intermeshing shafts (not shown) are arranged. The structure of the extruder used is shown in principle in
B.2) Preparation of the PC Moulding Compositions
The process parameters used in the examples for the preparation of PC moulding compositions are shown in Table 4. The specific mechanical energy input (SME) indicated in Table 4 was determined according to equation 1.
The PC moulding composition granules prepared in the examples were processed by an injection moulding process to sheets with a glossy surface having a size of 150 mm×105 mm×3.2 mm and to test specimens having a size of 80 mm×10 mm×4 mm for the Izod notched impact test according to ISO 180/1A.
The sheets with a glossy surface were produced on a type FM160 injection moulding machine from Klöcknrer. This injection moulding machine has a cylinder diameter of 45 mm. To that end, the PC moulding composition granules were predried at 110° C. within a period of 4 hours. Processing by injection moulding was carried out under the conditions characteristic for polycarbonates or polycarbonate/ABS blends or polycarbonate/PET blends. An injection moulding tool with a gloss finish (ISO N1) was used for the production of the sheets.
The number of surface defects on the sheets with a glossy surface was measured as described hereinbefore. 3 plates were measured in each case, and the arithmetic mean was determined from the results.
The Izod notched impact strength of the compound prepared was determined according to ISO 180/1A on the test specimens for the notched impact test. To that end, in each case 10 test specimens were tested, and the arithmetic mean was determined from these results.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 1 (Table 1) using test arrangement 7. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and g (additives) and also a9 given in Table 1 in the mentioned amounts, Mixing of the premix was carried out in a container mixer from Mixaco (type CM30 with Z tool) for 4.5 minutes at a speed of 300 l/min and a degree of filling of the mixer of 80%.
The premix and the remaining mixture constituents listed in Table 1 where then metered separately from one another, in each case by means of a differential proportioning weigher (not shown), via the feed hopper 8a into the main intake into housing 9a of the extruder.
In the plastification zone and the mixing zone in the region of housings 14a, 16a and 18a, the meltable mixture constituents were melted, all the mixture constituents were dispersed and the melt mixture was homogenised, the melt being degassed in the penultimate housing part 18a.
The melt strands emerging from the nozzle plate were cooled in a water bath and then granulated by means of a strand granulator.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, and the measured notched impact strength according to ISO 180/1A are listed in Table 4 under Example 1.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm−1/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 4 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), f (elastomer) and g (additives) given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, and the measured notched impact strength according to ISO 180/1A are listed in Table 4 under Example 2.
A comparison of Example 2 according to the invention with Comparison Example 1 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is markedly smaller and the notched impact strength at 23° C. and at 0° C. is markedly higher than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained almost the same.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 18 cm3/O-min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 18 (see Table 1) using test arrangement 7. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and g (additives) and also f4 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 3.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 18 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 19 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component) and g (additives) and also f4 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 4.
A comparison of Example 4 according to the invention with Comparison Example 3 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is markedly smaller than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained the same. A comparison of Examples 1 to 4 shows that, in the case of elastomer-containing polycarbonate blends with markedly different melt volume flow rates too, the number of surface defects when the carbon black/demoulding agent masterbatch is used is markedly smaller than when the carbon black powder is used.
A flame-protected elastomer-containing polycarbonate blend was prepared according to formulation 20 (see Table 1) using test arrangement 8. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent), g2, g3 and also f4 given in Table 1 in the mentioned amounts. Mixing of the premix was carried out in a container mixer from Mixaco (type CM30 with Z tool) for 4.5 minutes at a speed of 300 l/min degree of filling of the mixer of 80%.
The premix and the remaining mixture constituents listed in Table 1 were then metered separately from one another, in each case by means of a differential proportioning weigher (not shown), via the feed hopper 8b into the main intake into housing 9b of the extruder.
In the plastification zone and the mixing zone in the region of housings 12b and 13b, the meltable mixture constituents were melted, the mixture constituents metered into the main intake were dispersed and the melt mixture was homogenised. The melt was then degassed in housing part 18b. In housing part 21, liquid g1 (flameproofing agent) was added via an injection valve 22 and intimately mixed with the melt in the subsequent mixing zone in housing parts 14b and 19b.
The melt strands emerging from the nozzle plate were cooled in a water bath and then granulated by means of a strand granulator.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, and the measured notched impact strength according to ISO 180/1A are listed in Table 4 under Example 5.
A flame-protected elastomer-containing polycarbonate blend was prepared according to formulation 21 (see Table 1) using test arrangement 8. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), g2, g3 and also f4 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 5.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, and the measured notched impact strength according to ISO 180/1A are listed in Table 4 under Example 6.
A comparison of Example 6 according to the invention with Comparison Example 5 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is markedly smaller and the notched impact strength at 23° C. is higher than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained almost the same. A comparison of Examples 5 and 6 with Examples 1 to 4 shows that, even when a liquid flameproofing agent is added to an elastomer-containing polycarbonate blend, the number of surface defects is markedly smaller when the carbon black/demoulding agent masterbatch is used than when the carbon black powder is used.
A polycarbonate compound having a melt volume flow rate (MVR) of 9.5 cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2 kg) was prepared according to formulation 22 (see Table 1) using test arrangement 7. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and also a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 7.
A polycarbonate compound having a melt volume flow rate (MVR) of 9.5 cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2 kg) was prepared according to formulation 23 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and also a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 8.
A comparison of Example 8 according to the invention with Comparison Example 7 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is smaller than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained almost the same.
A polycarbonate compound having a melt volume flow rate (MVR) of 5 cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2 kg) was prepared according to formulation 24 (see Table 1) using test arrangement 7. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and also a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 9.
A polycarbonate compound having a melt volume flow rate (MVR) of 5 cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2 kg) was prepared according to formulation 25 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and also a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 10.
A comparison of Example 10 according to the invention with Comparison Example 9 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is smaller than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained the same.
A high-temperature-resistant polycarbonate compound (Vicat softening temperature 203° C. measured according to ISO 306 at 50 N; 120° C./h) having a melt volume flow rate (MVR) of 8 cm3/10 min (measured according to ISO 1133 at 330° C. and 2.16 kg) was prepared according to formulation 28 (see Table 1) using test arrangement 7. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and also a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 11.
A high-temperature-resistant polycarbonate compound (Vicat softening temperature 203° C. measured according to ISO 306 at 50 N; 120° C./h) having a melt volume flow rate (MVR) of 8 cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2 kg) was prepared according to formulation 29 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and also a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 12.
A comparison of Example 12 according to the invention with Comparison Example 11 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is markedly smaller than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained the same.
A high-temperature-resistant polycarbonate compound (Vicat softening temperature 184° C. measured according to ISO 306 at 50 N; 120° C./h) having a melt volume flow rate (MVR) of 10 cm3/10 min (measured according to ISO 1133 at 330° C. and 2.16 kg) was prepared according to formulation 30 (see Table 1) using test arrangement 7. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component) and a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 13.
A high-temperature-resistant polycarbonate compound (Vicat softening temperature 184° C. measured according to ISO 306 at 50 N; 120° C./h) having a melt volume flow rate (MVR) of cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2 kg) was prepared according to formulation 31 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component) and a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 14.
A comparison of Example 14 according to the invention with Comparison Example 13 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is markedly smaller than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained almost the same.
A comparison of Examples 7 to 14 shows that, in the case of polycarbonate compounds with markedly different melt volume flow rates and Vicat softening temperatures too, the number of surface defects is markedly smaller when the carbon black/demoulding agent masterbatch is used than when the carbon black powder is used.
A comparison of Examples 7 to 14 with Examples 1 to 4 shows that, even in the case of pure polycarbonate compounds without the addition of elastomer-containing components, the number of surface defects is markedly smaller when the carbon black/demoulding agent masterbatch is used than when the carbon black powder is used.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 17 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 35 (Table 1) using test arrangement 9. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent), g (additives) and f6 given in Table 1 in the mentioned amounts. Mixing of the premix was carried out in a container mixer from Mixaco (type CM30 with Z tool) for 4.5 minutes at a speed of 300 l/min and a degree of filling of the mixer of 80%.
The premix and the remaining mixture constituents listed in Table 1 were then metered separately from one another, in each case by means of a differential proportioning weigher (not shown), via the feed hopper 8c into the main intake into housing 9c of the extruder.
In the plastification zone in the region of housings 12c and 13c, the meltable mixture constituents were melted and all the mixture constituents were dispersed. In the mixing zone in the region of housings 24, 16c, 25 and 17c, the melt mixture was intimately mixed and homogenised. The melt was degassed in the penultimate housing part 18c.
The melt strands emerging from the nozzle plate were cooled in a water bath and then granulated by means of a strand granulator.
The process parameters of the extruder are listed in Table 4 under Example 15. The notched impact strength at different ambient temperatures, measured according to ISO 180/1A, is shown in diagrams
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 17 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 36 (see Table 1) using test arrangement 9. Carbon black/demoulding agent masterbatch granules according to Table 1 which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f6 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 15.
The process parameters of the extruder are listed in Table 4 under Example 16. The notched impact strength at different ambient temperatures, measured according to ISO 180/1A, is shown in diagrams
A comparison of Example 16 according to the invention with Comparison Example 15 shows that, when the carbon black/demoulding agent masterbatch is used, the notched impact strength is markedly higher and the transition from ductile to brittle fracture behaviour occurs at lower temperatures than when the carbon black powder is used. This indicates better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained almost the same.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 17 (see Table 1) using test arrangement 7. B16 (carbon black/polyethylene masterbatch Plasblak PE6130 (50% carbon black) from Cabot) according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 17.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 16 (see Table 1) using test arrangement 7. The carbon black/polycarbonate masterbatch B15 (PC Black 91024 (15% carbon black) from Color Systems) according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and g (additives) and also a9 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 18.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 4 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number; measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 19.
A comparison of Example 19 according to the invention with Comparison Examples 17 and 18 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is markedly smaller than when masterbatches based on polyethylene (B16) or polycarbonate (B15) are used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained almost the same.
An elastomer- and polyester-containing polycarbonate blend having a melt volume flow rate (MVR) of 12 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 32 (Table 1) using test arrangement 10. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and g (additives) and also a8 given in Table 1 in the mentioned amounts. Mixing of the premix was carried out in a container mixer from Mixaco (type CM1000 with MB tool) for 4.5 minutes at a speed of 425 l/min and a degree of filling of the mixer of 80%.
The premix and the remaining mixture constituents listed in Table 1 were then metered separately from one another, in each case by means of a differential proportioning weigher (not shown), via the feed hopper 8d into the main intake into housing 9d of the extruder.
In the plastification zone in the region of housings 12d, 23a and 13d, the meltable mixture constituents were melted and all the mixture constituents were dispersed. In the mixing zone in the region of housings 14d, 24a and 18d, the mixture constituents were intimately mixed and the melt mixture was homogenised. The melt mixture was degassed in the penultimate housing part 8d.
The melt strands emerging from the nozzle plate were cooled in a water bath and then granulated by means of a strand granulator.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 20.
An elastomer- and polyester-containing polycarbonate blend having a melt volume flow rate (MVR) of 12 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 33 (Table 1) using test arrangement 10. B86 (carbon black/polyethylene masterbatch Plasblak PE6130 (50% carbon black) from Cabot) according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and g (additives) and also a8 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 20.
The process parameters of the extruder as well as the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 21.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 12 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 34 (see Table 1) using test arrangement 10. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and g (additives) and also a8 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 20.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 22.
A comparison of Example 22 according to the invention with Comparison Examples 20 and 21 shows that, for elastomer- and polyester-containing polycarbonate blends too, the number of surface defects is markedly smaller when the carbon black/demoulding agent masterbatch is used than when carbon black powder and a carbon black/polyethylene masterbatch according to the prior art are used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) has remained almost the same.
At the same time it is shown that, even with an extruder having a larger screw outside diameter (133 mm), the number of surface defects is markedly smaller when the carbon black/demoulding agent masterbatch is used than when carbon black powder or carbon black masterbatch according to the prior art is used.
A polycarbonate compound having a melt volume flow rate (MVR) of 19 cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2 kg) was prepared according to formulation 26 (see Table 1) using test arrangement 11. Carbon black powder according to Table 1 was added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and g (additives) and also a8 given in Table 1 in the mentioned amounts. Mixing of the premix was carried out in a container mixer from Mixaco (type CM1000 with MB tool). Components b, g and a8 were first introduced into the mixing container and mixed for 2 minutes at a speed of 250 l/min and a degree of filling of the mixer of 80%. Component c was then added to the premixed components in the mixing container and mixed for 1.5 minutes at a speed of 350 l/min.
The premix and the remaining mixture constituents listed in Table 1 were then metered separately from one another, in each case by means of a differential proportioning weigher (not shown), via the feed hopper 8e into the main intake into housing 9e of the extruder.
In the plastification zone and the mixing zone in the region of housings 13e and 14e, the meltable mixture constituents were melted and all the mixture constituents were dispersed. In housing 18e, the melt was degassed. In housing 21a, liquid g1 (flameproofing agent) was injected into the melt via an injection nozzle 22a and intimately mixed with the melt in the subsequent mixing zone in the region of housings 21a, 26 and 19e, and the melt mixture was homogenised.
The melt strands emerging from the nozzle plate were cooled in a water bath and then granulated by means of a strand granulator.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 23.
A polycarbonate compound having a melt volume flow rate (MVR) of 19 cm3/10 min (measured according to ISO 1133 at 30° C. and 1.2 kg) was prepared according to formulation 27 (see Table 1) using test arrangement 11. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), c (demoulding agent) and also a8 given in Table 1 in the mentioned amounts. Mixing of the premix was carried out in a container mixer from Mixaco (type CM1000 with MB tool). Components b, g and a8 were first introduced into the mixing container and mixed for 2 minutes at a speed of 250 l/min and a degree of filling of the mixer of 80%. Component c was then added to the premixed components in the mixing container and mixed for 1.5 minutes at a speed of 350 l/min.
Compounding of the moulding composition was carried out as described in Example 23.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 24.
A comparison of Example 24 according to the invention with Comparison Example 23 shows that, when the carbon black/demoulding agent masterbatch is used, the number of surface defects is markedly smaller than when the carbon black powder is used. Both these findings indicate better dispersion of the carbon black when the carbon black/demoulding agent masterbatch is used, even though the specific mechanical energy input (SME) was higher in Example 23 than in Example 24.
At the same time it is shown that, for a polycarbonate compound too, in an extruder having a larger screw outside diameter (92 mm), the number of surface defects is markedly smaller when the carbon black/demoulding agent masterbatch is used than when carbon black powder is used.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 10 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules containing 40 wt. % carbon black according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 25.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 12 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules containing 45 wt. % carbon black according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
The procedure in the preparation of the polycarbonate blend corresponded to that of Example 25.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 26.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 9 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules containing 50 wt. % carbon black according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
The procedure in the preparation of the polycarbonate blend corresponded to that of Example 25.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 27.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 6 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules containing 58 wt. % carbon black according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
The procedure in the preparation of the polycarbonate blend corresponded to that of Example 25.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 28.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 11 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules containing 60 wt. % carbon black according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
The procedure in the preparation of the polycarbonate blend corresponded to that of Example 25.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 29.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 8 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules containing 65 wt. % carbon black according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
The procedure in the preparation of the polycarbonate blend corresponded to that of Example 25.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 30.
A comparison of Examples 25 to 30 according to the invention with Comparison Example 1 shows that, even when carbon black/demoulding agent masterbatches having carbon black contents varying from 40 wt. % to 65 wt. % are used, the number of surface defects is markedly lower than when carbon black powder is used. With a carbon black content of 65 wt. % in the masterbatch (Example 30), however, the number of surface defects is higher than with 40 wt. % to 60 wt. %, so that 65 wt. % represents the upper carbon black concentration for good dispersion.
In tests with carbon black concentrations less than 40 wt. %, it was not possible to form a strand because the carbon black-demoulding agent composition had too low a viscosity and was tacky. In the tests, therefore, a carbon black concentration of 40 wt. % represented the lower carbon black concentration which could still be processed without problems.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 7 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 31.
A comparison of Examples 2, 27 and 31 according to the invention with Comparison Example 1 shows that, when carbon black/demoulding agent masterbatches produced either using a co-kneader or using a twin-screw extruder or using shear rollers are used, the number of surface defects is markedly smaller than when carbon black powder is used.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 13 (see Table 1) using test arrangement 7. For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 32.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 14 (see Table 1) using test arrangement 7. The procedure in the preparation of the polycarbonate blend corresponded to that of Example 32.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 33.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 15 (see Table 1) using test arrangement 7. The procedure in the preparation of the polycarbonate blend corresponded to that of Example 32.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, are listed in Table 4 under Example 34.
A comparison of Examples 27, 32, 33 and 34 according to the invention with Comparison Example 1 shows that, with c1 or c3 or c4 in the carbon black/demoulding agent masterbatch, when the carbon black/demoulding agent masterbatch so prepared is used, the number of surface defects is markedly smaller than with carbon black powder. Although with c2 in the carbon black/demoulding agent masterbatch, the number of surface defects is larger when the carbon black/demoulding agent masterbatch so prepared is used than with c1, c3 or c4, it is still markedly smaller than with carbon black powder.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 5 (see Table 1) using test arrangement 7. For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, and the measured notched impact strength according to ISO 180/1A are listed in Table 4 under Example 35.
A comparison of Examples 2 and 35 according to the invention with Comparison Example 1 shows that, with both b2 and b1 as carbon black in the carbon black/demoulding agent masterbatch, when the carbon black/demoulding agent masterbatch so prepared is used, the number of surface defects is markedly smaller and the notched impact strength at 23° C. and at 0° C. is markedly higher than with carbon black powder.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 3 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, and the measured notched impact strength according to ISO 180/1A are listed in Table 4 under Example 36.
An elastomer-containing polycarbonate blend having a melt volume flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at 260° C. and 5 kg) was prepared according to formulation 2 (see Table 1) using test arrangement 7. Carbon black/demoulding agent masterbatch granules according to Table 1, which were prepared as described under A.2, were added as the carbon black component.
For the preparation of the compound, a premix was first prepared from components b (carbon black component), g (additives) and f3 given in Table 1 in the mentioned amounts. Preparation of the premix and compounding of the moulding composition were carried out as described in Example 1.
The process parameters of the extruder and the number, measured as described above, of surface defects, based on one square centimeter, and the measured notched impact strength according to ISO 180/1A are listed in Table 4 under Example 37.
A comparison of Examples 2, 36 and 37 according to the invention with Comparison Example 1 shows that, when the carbon black/demoulding agent masterbatches prepared in a co-kneader with different process parameters and test arrangements are used, the number of surface defects is markedly smaller and the notched impact strength at 23° C. and at 0° C. is markedly higher than when the carbon black powder is used.
TABLE 1
(all amounts in wt. %)
95
1
2
3
4
5
6
7
8
all amounts in wt %
Comp.
Invention
Invention
Invention
Invention
Invention
Invention
Invention
a
a1
14.14
a2
42.1
73.3
73.3
73.3
73.3
73.34
73.3
73.3
a3
a4
a5
a6
a7
a8
a9
16.9
B
B1
1.49
B2
1.49
B3
1.49
B4
1.49
B5
1.29
B6
1.49
B7
1.15
B8
B9
B10
B11
B12
B13
B14
B15
B16
b1
0.75
b3
b4
c
c1
0.73
0.16
0.34
d
d1
d2
f
f1
f2
f3
6.89
6.8
6.8
6.8
6.8
6.8
6.8
6.8
f4
f5
f6
f7
17.6
17.52
17.52
17.52
17.52
17.52
17.52
17.52
g
g1
g2
g3
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
g4
g5
Formulation
Component
9
10
11
12
13
14
15
16
17
all amounts in wt %
Invention
Invention
Invention
Invention
Invention
Invention
Invention
Comp.
Comp.
a
a1
a2
73.3
73.21
73.34
73.44
73.21
73.21
73.21
62.58
73.3
a3
a4
a5
a6
a7
a8
a9
4.92
B
B1
B2
B3
B4
B5
B6
B7
B8
1.49
B9
1.9
B10
1.25
B11
1.67
B12
1.9
B13
1.9
B14
1.9
B15
6.53
B16
1.94
b1
b3
b4
c
c1
0.2
0.73
0.72
d
d1
d2
f
f1
f2
f3
6.8
6.8
6.8
6.8
6.8
6.8
6.8
6.82
6.15
f4
f5
f6
f7
17.52
17.2
17.52
17.2
17.2
17.2
17.2
17.54
17
g
g1
g2
g3
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.88
0.89
g4
g5
Formulation
Component
18
19
20
21
22
23
24
25
all amount in wt %
Comp.
acc. to inv.
Comp.
acc. to inv.
Comp.
acc. to inv.
Comp.
acc. to inv.
a
a1
22
21.9
a2
42.2
42.2
a3
59.89
59.89
a4
95
95
a5
95
95
a6
a7
a8
a9
4.44
4.44
4.44
4.44
B
B1
B2
B3
1.5
1
0.32
B4
B5
0.28
B6
B7
B8
B9
B10
B11
B12
B13
B14
B15
B16
b1
0.75
0.5
0.16
0.16
b3
b4
c
c1
0.75
0.4
0.4
0.24
0.4
0.28
d
d1
d2
f
f1
17.1
17.1
f2
8.84
8.84
15.8
15.8
f3
f4
2.95
2.95
3
3
f5
f6
f7
9.4
9.4
g
g1
14.9
14.9
g2
0.8
0.8
g3
0.32
0.32
0.4
0.4
0
0
0
0
g4
g5
Formulation
Component
26
27
28
29
30
31
all amount in wt %
Comp.
acc. to inv.
Comp.
acc. to inv.
Comp.
acc. to inv.
a
a1
36
a2
95.6
a3
62.4
a4
a5
a6
95
95
a7
95
95
a8
3.82
1.04
a9
4.54
4.54
4.84
4.72
B
B1
B2
B3
B4
B5
0.28
0.28
0.28
B6
B7
B8
B9
B10
B11
B12
B13
B14
B15
B16
b1
0.16
0.16
0.16
b3
b4
c
c1
0.4
0.28
0.3
0.18
d
d1
d2
f
f1
f2
f3
f4
f5
f6
f7
g
g1
g2
g3
0.02
0
0
0
0
0
g4
g5
Formulation
Component
32
33
34
35
36
all amount in wt %
Comp.
Comp.
acc. to inv.
Comp.
acc. to inv.
a
a1
a2
48.61
48.76
48.47
a3
74.19
75.11
a4
a5
a6
a7
a8
1.04
0.94
1.03
a9
B
B1
B2
B3
1.8
B4
B5
0.51
B6
B7
B8
B9
B10
B11
B12
B13
B14
B15
B16
0.59
b1
0.3
0.9
b3
0.25
0.25
b4
0.057
0.057
c
c1
0.4
0.2
0.18
0.73
d
d1
31.84
31.75
31.75
d2
0.561
0.5525
0.765
f
f1
f2
f3
f4
f5
14.95
14.91
14.95
f6
8.77
8.75
f7
13.21
13.14
g
g1
g2
g3
0.299
0.2975
0.347
0.89
0.89
g4
2
2
2
g5
1
TABLE 2
Heating temperatures
1st
2nd
Housing
Carbon black/
housing
housing
single-
Co-
demoulding
Test
Through-
half co-
half co-
shaft
Nozzle
kneader
agent master-
arrange-
Formula-
Carbon black
put
Speed
Power
SME
kneader
kneader
extruder
head
shaft
batch no.
ment
tion
metering site
kg/h
min−1
kW
kWh/kg
° C.
° C.
° C.
° C.
° C.
B1
1
50% b1
Feed hopper 1
9
190
3.4
0.378
30
30
40
95
30
50% c1
B2
2
50% b1
Feed hopper 1
12
190
3.3
0.275
90
60
35
130
35
50% c1
B3
3
50% b1
Feed hopper 1: 32%
20
250
3.8
0.190
60
35
75
110
35
50% c1
Feed hopper 7: 18%
B4
3
50% b2
Feed hopper 1: 20%
12
250
2.3
0.192
60
35
75
110
35
50% c1
Feed hopper 7: 30%
TABLE 3
Carbon black/
demoulding
Test
Through-
Spec.
Heating temperatures of the housing parts:
agent master-
arrange-
Formula-
Carbon black
put
Speed
power
9
10
11
batch no.
ment
tion
metering site
kg/h
min−1
kWh/kg
° C.
° C.
° C.
B8
4
50% b1
Feed hopper 8: 25%
25
200
0.084
30
60
65
50% c1
Housing part 15: 25%
B9
4
40% b1
Feed hopper 8: 10%
25
300
0.0096
30
60
65
60% c1
Housing part 15: 30%
B10
4
60% b1
Feed hopper 8: 15%
25
200
0.248
30
60
65
40% c1
Housing part 15: 45%
B11
4
45% b1
Feed hopper 8: 10%
25
300
0.037
30
60
65
55% c1
Housing part 15: 35%
B12
4
40% b1
Feed hopper 8: 20%
25
200
0.032
30
60
65
60% c3
Housing part 15: 20%
B13
4
40% b1
Feed hopper 8: 20%
25
200
0.073
30
60
65
60% c2
Housing part 15: 20%
B14
4
40% b1
Feed hopper 8: 20%
25
200
0.073
30
60
65
60% c4
Housing part 15: 20%
Heating temperatures of the housing parts:
Carbon black/
Nozzle
demoulding
(not
agent master-
12
13
14
15
16
17
18
19
shown)
batch no.
° C.
° C.
° C.
° C.
° C.
° C.
° C.
°C.
° C.
B8
65
65
65
70
50
50
50
35
110
B9
65
65
65
70
50
50
50
35
110
B10
65
65
65
70
50
50
50
35
130
B11
65
65
65
70
50
50
50
35
110
B12
65
65
65
70
50
50
50
35
110
B13
65
65
65
70
50
50
50
35
130
B14
65
65
65
70
50
50
50
35
115
TABLE 4
Surface defects
Notched impact
Notched impact
Test
Through-
per cm2
strength
strength
Formula-
arrange-
put
Speed
SME
Mean of 3
at 23° C.
at 0° C.
Example
tion
ment
kg/h
1/min
kWh/kg
sheets
kJ/m2
kJ/m2
1
Comparison
1
7
103
400
0.129
199
46.9
13.75
2
Invention
4
7
97
400
0.137
19
50.94
15.09
3
Comparison
18
7
92
400
0.145
53
4
Invention
19
7
92
400
0.145
24
5
Comparison
20
8
99
600
0.145
17
12.77
6
Invention
21
8
98
600
0.147
11
13.06
7
Comparison
22
7
62
350
0.188
12
8
Invention
23
7
64
350
0.182
9
9
Comparison
24
7
62
350
0.188
5
10
Invention
25
7
62
350
0.188
4
11
Comparison
28
7
52
350
0.224
257
12
Invention
29
7
52
350
0.224
34
13
Comparison
30
7
58
350
0.201
60
14
Invention
31
7
57
350
0.204
31
15
Comparison
35
9
20
400
0.247
16
Invention
36
9
20
400
0.24
17
Comparison
17
7
73
400
0.131
34
18
Comparison
16
7
73
400
0.131
63
19
Invention
4
7
75
400
0.133
18
20
Comparison
32
10
3100
187
0.131
2191
21
Comparison
33
10
3091
175
0.124
1122
22
Invention
34
10
3092
188
0.131
446
23
Comparison
26
11
2975
493
0.141
247
24
Invention
27
11
3003
485
0.132
11
25
Invention
10
7
95
400
0.14
6
26
Invention
12
7
95
400
0.14
6
27
Invention
9
7
90
400
0.148
10
28
Invention
6
7
95
400
0.14
5
29
Invention
11
7
95
400
0.14
5
30
Invention
8
7
90
400
0.148
21
31
Invention
7
7
90
400
0.148
11
32
Invention
13
7
90
400
0.148
7
33
Invention
14
7
95
400
0.14
48
34
Invention
15
7
95
400
0.14
6
35
Invention
5
7
97
400
0.137
23
56.2
19.22
36
Invention
3
7
97
400
0.137
19
48.3
16.16
37
Invention
2
7
97
400
0.137
17
52.73
15.93
Eckel, Thomas, Rudolf, Reiner, Seidel, Andreas, Thiem, Hans-Jurgen, Reichenauer, Joerg
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