AU746847B2 - Modified impact resistant polymethacrylate moulding material with improved flowability - Google Patents

Modified impact resistant polymethacrylate moulding material with improved flowability Download PDF

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Publication number
AU746847B2
AU746847B2 AU66877/00A AU6687700A AU746847B2 AU 746847 B2 AU746847 B2 AU 746847B2 AU 66877/00 A AU66877/00 A AU 66877/00A AU 6687700 A AU6687700 A AU 6687700A AU 746847 B2 AU746847 B2 AU 746847B2
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Prior art keywords
impact
molding compound
strength
polymethacrylate
molecular weight
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AU6687700A (en
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Klaus Albrecht
Werner Hoss
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
    • C08L2207/324—Liquid component is low molecular weight polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Graft Or Block Polymers (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The invention relates to a modified impact resistant polymethylacrylate moulding material characterized by a Vicat softening temperature according to ISO 306 (B 50) of at least 90 DEG C, a notch impact resistance KSZ (Charpy) according to ISO 179/1eA of at least 3.0 KJ/m<2> at 23 DEG C and a flowability MVR (230 DEG c/3,8 KG) according to ISO 1133 of at least 11 cm<3>/10 min, which can by obtained by mixing a) 80 -98 wt. % of a modified impact resistant polymethacrylate moulding material with b) 20 - 2 wt. % of a low molecular polymethacrylate moulding material in a molten state, whereby the impact-resistant moulding material is 70 - 99 wt. % comprised of a matrix containing 80 - 100 wt. % radically polymerized methylmethacrylate units and optionally 0 20 wt. % other radically polymerizable comonomers and contains 1 -30 wt. % of an impact resistance modifying agent and the low molecular polymethyacrylate moulding material is 80-100 wt. % comprised of radically polymerized methylmethacrylate units and 0-20 wt % other radically polymerizable comonomers and has a viscosity ( eta sp/c) of 25 - 35 ml/g when measured in chloroform according to ISO 1628 part 6.

Description

Impact-strength-modified polymethacrylate molding compound with improved melt volume-flow rate The invention relates to impact-strength-modified polymethacrylate molding compounds with improved melt volume-flow rate.
Prior Art Impact-strength modifiers for polymethacrylate plastics have been known for many years. The manufacture and structure of impact-strength-modified polymethacrylate molding compounds are described in, for example, European Patent Applications EP A 0113924, EP A 0522351, EP A 0465049 and EP A 0683028.
EP A 469521 relates to improvement of flow in the processing of PVC blends to be impact-strengthmodified, for example during injection molding. In this process, polymers based on alkyl methacrylate, comprising at least 50 wt% of methyl methacrylate as well as 2 to 50 wt% of C2 to C8 alkyl methacrylates and having molecular weights (Mw) in the range of 2,000 to 20,000 g/mol are added to PVC-ABS polymer mixtures.
Object and Achievement The object was considered to be to provide an impact-strength-modified polymethacrylate molding compound which has improved melt volume-flow rate at high temperatures, such as are used in the injection-molding process, and which at the same time has high dimensional stability at high temperature and high notched impact strength.
The object is achieved by an impact-strength-modified polymethacrylate molding compound, characterized by a Vicat softening temperature per ISO 306 (B 50) of at least a notched impact strength (Charpy) per ISO 179/leA of at least 3.0 kJ/m 2 at 23 0
C,
and a melt volume-flow rate MVR (230 0 C/3.8 kg) per ISO 1133 of at least 11 cm 3 10 min, obtained by mixing, in the melt, a) 80 to 98 wt% of an impact-strength-modified polymethacrylate molding compound with b) 20 to 2 wt% of a low molecular weight polymethacrylate molding compound [1:\DAYLB\L1BZ105653.doc:am r r~i- the impact-resistant molding compound comprising 70 to 99 wt% of a matrix of 80 to 100 wt% of radical-polymerized methyl methacrylate units and if necessary 0 to 20 wt% of further comonomers that can undergo radical polymerization, and containing 1 to 30 wt% of an impact-strength modifier, and the low molecular weight polymethacrylate molding compound comprising 80 to 100 wt% of radical-polymerized methyl methacrylate units and 0 to 20 wt% of further comonomers that can undergo radical polymerization, and having a viscosity number (qrspi) of 25 to 35 ml/g as measured in chloroform per ISO 1628 Part 6.
It was not foreseeable that the desired characteristics could be achieved by addition of a low molecular weight polymethacrylate molding compound. The new impact-strength-modified molding compound is suitable in particular for use in the injection-molding process, where good melt volume-flow rate is required in order to ensure short cycle times and good filling of the molds. In the process, the other characteristics of the obtained injection-molded articles are not impaired, especially the dimensional stability at high temperature and the notched impact strength.
g~p~g~gp-b~., 4 Description of the Invention Polymethacrylate matrix The impact-resistant molding compound comprises 70 to 99 wt% of a matrix of to 100, preferably 90 to 98 wt% of radical-polymerised methyl methacrylate units and if necessary 0 to 20, preferably 2 to 10 wt% of further comonomers that can undergo radical polymerisation, such as Cl to C4 alkyl (meth)acrylates, especially methyl acrylate, ethyl acrylate or butyl methacrylate. Preferably the average molecular weight Mw of the matrix ranges from 90,000 g/mol to 200,000 g/mol, especially 100,000 g/mol to 150,000 g/mol.
Impact-strength modifier The polymethacrylate matrix contains 1 to 30, preferably 2 to 20, particularly preferably 3 to 15, especially 5 to 12 wt% of an impact-strength modifier, which is an elastomer phase of cross-linked polymer particles. The impact-strength modifier is incorporated in a manner known in itself by bead polymerisation or by emulsion 15 polymerisation.
The simplest case is one in which the cross-linked particles obtainable by means of bead polymerisation have a mean particle size ranging from 50 to 500 pm preferably to 120 tm. They usually comprise at least 40, preferably 50 to 70 wt% of methyl methacrylate, 20 to 40, preferably 25 to 35 wt% of butyl acrylate as well as 0.1 to 2, 20 preferably 0.5 to 1 wt% of a cross-linking monomer, for example a multifunctional (meth)acrylate such as allyl methacrylate and if necessary further monomers such as 0 to 10, preferably 0.5 to 5 wt% of to C4 alky methacrylates, such as ethyl acrylate or *oo 10, preferably 0.5 to 5 wt% of Cl to C4 alkyl methacrylates, such as ethyl acrylate or [R:\LIBH]04068.doc:mrr butyl methacrylate, preferably methyl acrylate, or other monomers that can undergo vinyl polymerization, such as styrene.
Preferred impact-strength modifiers are polymer particles which have a two-layer, particularly preferably a three-layer core-shell structure and which can be obtained by emulsion polymerization (see, for example, EP A 0113924, EP A 0522351, EP A 0465049 and EP A 0683028). Typical particle sizes of these emulsion polymers range from 100 to 500 nm, preferably 200 to 400 nm.
A three-layer or three-phase structure with a core and two shells can be obtained as follows. An innermost (hard) shell can, for example, comprise substantially methyl methacrylate, small proportions of comonomers such as ethyl acrylate, and a proportion of cross-linking agent, such as allyl methacrylate. The middle (soft) shell can, for example, be formed from butyl acrylate and if necessary styrene, whereas the outermost (hard) shell usually corresponds substantially to the matrix polymer, whereby compatibility with the matrix and good bonding thereto are achieved. The polybutyl acrylate proportion in the impact-strength modifier is decisive for the impact-strength effect, and preferably ranges from 20 to 40 wt%, particularly preferably from 25 to 35 wt%.
Impact-strength-modified polymethacrylate molding compounds In the extruder, the impact-strength modifier and matrix polymer can be intermixed in the melt to obtain impact-strength-modified polymethacrylate molding compounds. The discharged material is usually chopped up into the form of granules at first. These can be further processed by means of extrusion or injection molding to obtain molded articles, such as plates or injection-molded parts.
-1 %i "*qjkf 1:r i;i q~ll~i/n Notched impact strengths and melt volume-flow rate of the prior art Molded articles of commercial impact-strength-modified polymethacrylate molding compounds have Charpy notched impact strengths per ISO. 179/leA ranging from kJ/m 2 to 5.0 kJ/m 2 Commercial impact-strength-modified polymethacrylate molding compounds have flow rates MVR (230°C/3.8 kg) ranging from 0.4 to 8.1 cm 3 /10 min per ISO 1133. The melt volume-flow rate of impact-strength-modified polymethacrylate molding compounds must be as high as possible, especially for processing by injection molding. Impactstrength-modified polymethacrylate molding compounds optimised for melt volume-flow rate reach MVR values (230 0 C/3.8 kg, ISO 1133) in the range of about 10.0 cm 3 /10 min at the most.
SLow molecular weight polymethacrylate molding compound The melt volume-flow rate of impact-strength-modified polymethacrylate molding s15 compounds can be increased while maintaining notched impact strength by addition of a low molecular weight polymethacrylate molding compound.
The proportion of low molecular weight polymethacrylate molding compound in the impact-strength-modified polymethacrylate molding compound ranges between 2 and 20, preferably between 3 and 15 wt%.
S 20 The low molecular weight polymethacrylate molding compound comprises 80 to 100 wt% of radical-polymerised methyl methacrylate units and 0 to 20 wt% of further comonomers that can undergo radical polymerisation, for example Cl to C4 alkyl (meth)acrylates, especially methyl acrylate, ethyl acrylate or butyl methacrylate. The low molecular weight polymethacrylate molding compound has a viscosity number (rlsp/c) ranging from 25 to 35 mlg, preferably 27 to 33 mlg as measured in chloroform per ISO 1628 Part 6, corresponding to an average molecular weight Mw (weight average) of 30,000 to 70,000, especially 40,000 to 60,000.
The molecular weight can be determined by methods such as differential scanning chromatography (DSC) or by gel chromatography on the basis of polymethyl methacrylate calibration standards or calibration lines correlated with the viscosity number.
Addition of the low molecular weight polymethacrylate molding compound The low molecular weight polymethacrylate molding compound can be added as 35 j granules during melt processing of impact-strength modifier and polymethacrylate matrix [R:\LIBH]04068.doc:mrr
J
;y in the extruder. In this way the low molecular weight polymethacrylate molding compound is worked into or intermixed with the melt and is then a constituent of the impact-strength-modified molding compound discharged from the extruder. This compound either can be processed directly to molded articles by extrusion or injection molding or can be pellerized first of all to transform it to salable granules.
The low molecular weight polymethacrylate molding compound can also be mixed in the form of granules together with granules comprising impact-strength modifier and polymethacrylate matrix already mixed in the melt (granule mixture) and then processed in the melt.
a.
a.
a.
a aa a a.
a a a a [R:\LIBH]04068.doc:mrr mi Characteristics of the new polymethacrylate molding compound The polymethacrylate molding compound obtained by mixing the low molecular weight polymethacrylate molding compound and the impact-strength-modified polymethacrylate molding compound in the melt is characterized by a Vicat softening temperature per ISO 306 (B 50) of at least a notched impact strength (Charpy) per ISO 179/1eA of at least 3.0 kJ/m 2 at 23 0 C and a melt volume-flow rate MVR (230 0 C/3.8 kg) per ISO 1133 of at least 11 cm 3 /10 min.
~IIIYFi~:
EXAMPLES
An impact-strength-modified molding compound with a content of 7.5 wt% of impact-strength modifier (base emulsion polymer) was homogeneously mixed at 220 0 C in the melt with 5 and 10 wt% of a low molecular weight molding compound in a twin-screw extruder (ZSK 25 of The strands drawn from the extruder were cooled and chopped up to obtain granules. Specimens were made from the resulting granules by means of an injection-molding machine. Various characteristics were measured on the obtained specimens.
Impact-strength-modified molding compound: comprising 92.5 wt% of matrix polymer and 7.5 wt% of impact-strength modifier Matrix polymer: 91 wt% of methyl methacrylate and 9 wt% of methyl acrylate.
Impact-strength modifier: A commercial three-phase (core and two shells) emulsion polymer with a particle size ranging from 300 to 500 nm and a core/shell 1/shell 2 ratio of 1:1:1 with a butyl acrylate proportion of 27 wt% relative to the impact-strength modifier.
EfiffiiffilfiliggJWWW- Core: 95.5 wt% of methyl methacrylate, 4 wt% of ethyl acrylate and 0.5 wt% of 0.5 wt% of allyl methacrylate.
Shell 1: 81.2 wt% of butyl acrylate, 17.5 wt% of styrene, 1.3 wt% of allyl methacrylate.
Shell 2: 96 wt% of methyl methacrylate, 4 wt% of ethyl acrylate.
Low molecular weight molding compound: comprising 85 wt% of methyl methacrylate and 15 wt% of methyl acrylate units with a viscosity number (7sp,c) in the range of 30 ml/g as measured in chloroform per ISO 1628 Part 6, corresponding to an Mw of about 50,000 g/mol.
Rk The results are summarized in the following table. The addition of 5 or 10 wt% of the low molecular weight molding compound leads to a distinct increase of melt volume-flow rate MVR, whereas the dimensional stability at high temperature (VST) and the notched impact strength remain practically unchanged compared with the example without addition of low molecular weight molding compound.
Proportion of low molecular weight molding compound Standard 0 wt% 5 wt% 10 wt%
MVR
(230 0 C/3.8 kg) ISO 1133 8.9 11.1 13.0 in cm 3 /10 min VST (B in °C ISO 306 94.6 94.8 94.2 Notched impact strength (Charpy/23°C) ISO 3.4 3.4 3.4 in kJ/m 2 179/1eA ~s~ll

Claims (6)

1. An impact-strength-modified polymethacrylate molding compound, characterized by a Vicat softening temperature per ISO 306 (B 50) of at least 90 0 C, a notched impact strength (Charpy) per ISO 179/leA of at least 3.0 kJ/m 2 at 23°C, and a melt volume-flow rate MVR (230 0 C/3.8 kg) per ISO 1133 of at least 11 cm 3 /10 min, obtained by mixing, in the melt, a) 80 to 98 wt% of an impact-strength-modified polymethacrylate molding compound with b) 20 to 2 wt% of a low molecular weight polymethacrylate molding compound the impact-resistant molding compound comprising 70 to 99 wt% of a matrix of 80 to 100 wt% of radical-polymerized methyl methacrylate units and if necessary 0 to wt% of further comonomers that can undergo radical polymerization, and containing 1 to wt% of an impact-strength modifier, I. a a [l:\DAYLB\LIBZ]05653.doc:Iam ii; ri~""rs. -Ipb-- 13 and the low molecular weight polymethacrylate molding compound comprising 80 to 100 wt% of radical-polymerised methyl methacrylate units and 0 to 20 wt% of further comonomers that can undergo radical polymerisation, and having a viscosity number (7sp/c) of 25 to 35 ml/g as measured in chloroform per ISO 1628 Part 6.
2. A molding compound according to claim 1, characterised in that the matrix polymer has a molecular weight Mw of 90,000 g/mol to 200,000 g/mol.
3. A molding compound according to claim 1, characterised in that it contains an impact-strength modifier with a polybutyl acrylate proportion of 20 to 40 wt%.
4. An impact-strength-modified polymethacrylate molding compound, o0 substantially as hereinbefore described with reference to any one of the examples.
The use of a molding compound according to one or more of claims 1 to 4 for making molded articles in the injection-molding process.
6. The use according to claim 5, wherein the low molecular weight polymethacrylate molding compound is used as a granule mixture together with the 15 impact-strength-modified polymethacryalte molding compound. Dated 26 June, 2001 Rohm GmbH Co. KG e 20 Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON 0 [R:\LIBH]04068.doc:mrr
AU66877/00A 1999-06-17 2000-06-02 Modified impact resistant polymethacrylate moulding material with improved flowability Ceased AU746847B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19927769A DE19927769A1 (en) 1999-06-17 1999-06-17 Polymethacrylate molding composition, useful for the production of molded articles, is prepared by mixing toughened polymethacrylate and low mol. wt. polymethacrylate
DE19927769 1999-06-17
PCT/EP2000/005051 WO2000078863A2 (en) 1999-06-17 2000-06-02 Modified impact resistant polymethacrylate moulding material with improved flowability

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AU6687700A AU6687700A (en) 2001-01-09
AU746847B2 true AU746847B2 (en) 2002-05-02

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EP (1) EP1189987B1 (en)
JP (1) JP2003503531A (en)
KR (1) KR20020020735A (en)
CN (1) CN1335872A (en)
AT (1) ATE230427T1 (en)
AU (1) AU746847B2 (en)
BG (1) BG106222A (en)
CA (1) CA2374192A1 (en)
CZ (1) CZ20014368A3 (en)
DE (2) DE19927769A1 (en)
HU (1) HUP0201528A3 (en)
MX (1) MXPA01011442A (en)
SK (1) SK18072001A3 (en)
TW (1) TW527393B (en)
WO (1) WO2000078863A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2012244068B2 (en) * 2005-04-25 2015-03-12 Lucite International Uk Limited Acrylic Blends
US9676938B2 (en) 2007-06-08 2017-06-13 Lucite International Uk Limited Polymer composition

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GB9919304D0 (en) 1999-08-17 1999-10-20 Ici Plc Acrylic composition
US6844396B2 (en) * 2002-08-28 2005-01-18 Kaneka Corporation Acrylic resin composition
DE10329938A1 (en) * 2003-07-02 2005-03-17 Röhm GmbH & Co. KG Plastic body with a microstructured surface
DE10349144A1 (en) * 2003-10-17 2005-05-12 Roehm Gmbh Polymer mixture for injection mouldings with a matt surface, e.g. exterior vehicle parts, comprises an acrylic matrix, a crosslinked acrylic impact modifier and plastic particles with a specified range of particle sizes
DE10349142A1 (en) * 2003-10-17 2005-05-12 Roehm Gmbh Polymer blend for production of injection mouldings, e.g. car body parts, contains low-mol. wt. and high-mol. wt. (meth)acrylate (co)polymers and an impact modifier based on crosslinked poly(meth)acrylate
DE102004045296A1 (en) * 2004-09-16 2006-03-23 Röhm GmbH & Co. KG Use of polyalkyl (meth) acrylate bead polymers and molding compound for the production of extruded molded parts with a matted surface
GB0508255D0 (en) * 2005-04-25 2005-06-01 Lucite Int Uk Ltd Acrylic blends
DE102008040152A1 (en) 2008-07-03 2010-01-07 Evonik Röhm Gmbh rheology modifiers
US8759450B2 (en) 2009-07-07 2014-06-24 Evonik Röhm Gmbh Plastics moulding compositions, and mouldings and production processes
DE102011003317A1 (en) 2011-01-28 2012-08-02 Evonik Röhm Gmbh Impact-modified reaction resin
DE102012207100A1 (en) * 2012-04-27 2013-10-31 Evonik Industries Ag Coextruded impact-modified PMMA film
JP2019509389A (en) * 2016-03-25 2019-04-04 アルケマ フランス High melt strength acrylic formulation
FR3053348B1 (en) * 2016-06-29 2020-03-27 Arkema France COMPOSITION COMPRISING A MULTI-PHASE POLYMER AND TWO DIFFERENT (METH) ACRYLIC POLYMERS, METHOD FOR PREPARING THE SAME AND ARTICLE THEREOF
DE102017216789A1 (en) * 2017-09-22 2019-03-28 Tesa Se Laser inscribable foil

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JPH10330576A (en) * 1997-05-30 1998-12-15 Kuraray Co Ltd Methacrylic resin composition
JPH10338792A (en) * 1997-06-05 1998-12-22 Kuraray Co Ltd Methacrylic resin composition and laminate by using the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2012244068B2 (en) * 2005-04-25 2015-03-12 Lucite International Uk Limited Acrylic Blends
AU2012244067B2 (en) * 2005-04-25 2015-03-12 Lucite International Uk Limited Acrylic Blends
US9676938B2 (en) 2007-06-08 2017-06-13 Lucite International Uk Limited Polymer composition

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WO2000078863A3 (en) 2001-07-19
BG106222A (en) 2002-07-31
ATE230427T1 (en) 2003-01-15
AU6687700A (en) 2001-01-09
JP2003503531A (en) 2003-01-28
DE50001014D1 (en) 2003-02-06
TW527393B (en) 2003-04-11
WO2000078863A2 (en) 2000-12-28
CA2374192A1 (en) 2000-12-28
DE19927769A1 (en) 2000-12-21
HUP0201528A2 (en) 2002-08-28
HUP0201528A3 (en) 2004-03-01
MXPA01011442A (en) 2003-08-20
CN1335872A (en) 2002-02-13
EP1189987B1 (en) 2003-01-02
CZ20014368A3 (en) 2002-05-15
EP1189987A2 (en) 2002-03-27
KR20020020735A (en) 2002-03-15
SK18072001A3 (en) 2002-05-09

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