[go: up one dir, main page]

WO2000055249A1 - Composition de moulage pigmentee, stable a la fusion, a base de polycarbonate - Google Patents

Composition de moulage pigmentee, stable a la fusion, a base de polycarbonate Download PDF

Info

Publication number
WO2000055249A1
WO2000055249A1 PCT/US2000/005860 US0005860W WO0055249A1 WO 2000055249 A1 WO2000055249 A1 WO 2000055249A1 US 0005860 W US0005860 W US 0005860W WO 0055249 A1 WO0055249 A1 WO 0055249A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
bis
hydroxyphenyl
amount
stabilizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2000/005860
Other languages
English (en)
Inventor
Sivaram Krishnan
James B. Johnson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Bayer Corp
Original Assignee
Bayer AG
Bayer Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG, Bayer Corp filed Critical Bayer AG
Priority to AU37273/00A priority Critical patent/AU3727300A/en
Publication of WO2000055249A1 publication Critical patent/WO2000055249A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • thermoplastic molding compositions and more particularly to molding compositions that contain pigments or dyes.
  • thermoplastic polycarbonate resin (ii) about 3 to 20 percent, relative to the total weight of (i) and (ii), of titanium dioxide, and (iii) a stabilizer, the molecular structure of which features at least one benzofuran-2-one group per molecular chain.
  • the amount of the stabilizer incorporated in the composition is that which is sufficient to improve the resistance of the composition to thermal degradation.
  • TECHNOLOGICAL BACKGROUND Color concentrates are well known in the art. These are blends which contain a relatively high concentration of a functional additive may be used advantageously in admixture with, for instance, virgin resin or with virgin blends in preparing molding compositions containing effective amounts of the functional additive.
  • Molders use color concentrates as means to minimizing inventory of pre-colored materials. Use of concentrates also provided for ease in handling, and maintaining cleanliness in work areas. For example, a molder requiring a large number of compositions differing in their color, may inventory lower volumes of each of these in the form of color concentrates and dilute them as needed with natural resins at the molding or extrusion machines to produce colored articles. Color concentrates containing 10 to 20% of the pigment are common in the industry. Titanium dioxide is a known pigment that is often useful in making white or opaque articles. Color concentrates containing polycarbonate resin and a high loading of titanium dioxide are therefore useful and desirable. Unfortunately, degradation of polycarbonate resin often results in the course of processing of such concentrates. There is a need in providing polycarbonate/titanium dioxide concentrates, which will offer greater resistance to thermal degradation.
  • U.S. Patent 4,325,863 disclosed benzofuranone compound useful as stabilizer for organic materials.
  • the organic polymeric materials stabilized by this compound are said to include polycarbonates and poiyamides as well as copolymers of styrene and acrylonitrile.
  • U.S. Patent 4,338,244 which disclosed benzofuran(2)one to be a useful stabilizer for organic materials.
  • Polycarbonates, poiyamides and SAN copolymers are mentioned among the many resins said to be stabilized by the incorporation of this compound.
  • Patents 5,175,312 and 5,607,624 which disclosed 3-phenyl-3H-benzofuran-2-ones and 3-arylbenzofuranones respectively, said to be suitable as stabilizing agents for organic materials against oxidative, thermal or light induced degradation.
  • the present invention resides in the findings that polycarbonate color concentrates that contain a high loading of titanium dioxide are rendered more resistant to thermal degradation by the incorporation of a stabilizing amount of a stabilizer the molecular structure of which contains at least one benzofuran-2-one group.
  • thermoplastic polycarbonate resin (i) thermoplastic polycarbonate resin
  • Suitable polycarbonate resins for preparing the copolymer of the present invention are homopolycarbonates and copolycarbonates and mixtures thereof.
  • the polycarbonates generally have a weight average molecular weight of 10,000 to 200,000, preferably 20,000 to 80,000 and their melt flow rate, per ASTM D-1238 at 300°C, is about 1 to about 65 g/10 min., preferably about 2 to 24 g/10 min.
  • They may be prepared, for example, by the known diphasic interface process from a carbonic acid derivative such as phosgene and dihydroxy compounds by polycondensation (see German Offenlegungsschriften 2,063,050; 2,063,052; 1 ,570,703; 2,211 ,956; 2,211 ,957 and 2,248,817; French Patent 1 ,561 ,518; and the monograph by H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York, New York, 1964, all incorporated herein by reference).
  • dihydroxy compounds suitable for the preparation of the polycarbonates of the invention conform to the structural formulae (1 ) or (2).
  • A denotes an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cycloalkylene group with 5 to 15 carbon atoms, a cycloalkylidene group with 5 to 15 carbon atoms, a carbonyl group, an oxygen atom, a sulfur atom, -SO- or -S0 2 or a radical conforming to
  • e and g both denote the number 0 to 1 ;
  • Z denotes F, Cl, Br or C ⁇ -C 4 -alkyl and if several Z radicals are substituents in one aryl radical, they may be identical or different from one another; d denotes an integer from 0 to 4; and f denotes an integer from 0 to 3.
  • dihydroxy compounds useful in the practice of the invention are hydroquinone, resorcinol, bis-(hydroxyphenyl)-alkanes, bis- (hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)- sulfoxides, bis-(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)-sulfones, dihydroxydiphenyl cycloalkanes, and ⁇ , ⁇ -bis-(hydroxyphenyl)-diisopropyl- benzenes, as well as their nuclear-alkylated compounds.
  • aromatic dihydroxy compounds are described, for example, in U.S.
  • bisphenols are 2,2-bis-(4-hydroxy- phenyl)-propane (bisphenol A), 2,4-bis-(4-hydroxyphenyl)-2-methyl- butane, 1 ,1-bis-(4-hydroxyphenyl)-cyclohexane, ⁇ , ⁇ '-bis-(4-hydroxy- phenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)- propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4- hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfide, bis-(3,5-dimethyl-4-hydroxy- phenyl)-sulfoxide, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfox
  • aromatic bisphenols examples include 2,2,-bis- (4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)- propane, 1 ,1-bis-(4-hydroxyphenyl)-cyclohexane and 1 ,1-bis-(4- hydroxyphenyl)-3,3,5-trimethylcyclohexane.
  • the most preferred bisphenol is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).
  • bisphenol A 2,2-bis-(4-hydroxyphenyl)-propane
  • the polycarbonates of the invention may entail in their structure units derived from one or more of the suitable bisphenols.
  • resins suitable in the practice of the invention is phenolphthalein-based polycarbonate, copolycarbonates and terpolycarbonates such as are described in U.S. Patents 3,036,036 and 4,210,741 , both incorporated by reference herein.
  • the polycarbonates of the invention may also be branched by condensing therein small quantities, e.g., 0.05 to 2.0 mol % (relative to the bisphenols) of polyhydroxy compounds.
  • polyhydroxy compounds which may be used for this purpose: phloroglucinol; 4,6-dimethyl-2,4,6-tri-(4-hydroxy- phenyl)-heptane; 1 ,3,5-tri-(4-hydroxyphenyl)-benzene; 1 ,1 ,1-tri-(4- hydroxyphenyl)-ethane; tri-(4-hydroxyphenyl)-phenylmethane; 2,2-bis-[4,4- (4,4'-dihydroxydiphenyl)]-cyclohexyl-propane; 2,4-bis-(4-hydroxy-1- isopropylidine)-phenol; 2,6-bis-(2'-dihydroxy-5'-methylbenzyl)-4-methyl- phenol; 2,4-dihydroxybenzoic acid; 2-(4-hydroxyphenyl)-2-(2,4-dihydroxy- phenyl)-propane and 1 ,4-bis-(4,4'-dihydroxy
  • Some of the other polyfunctional compounds are 2,4-dihydroxy-benzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(4-hydroxyphenyl)-2-oxo- 2,3-dihydroindole.
  • the preferred process for the preparation of polycarbonates is the interfacial polycondensation process.
  • Other methods of synthesis in forming the polycarbonates of the invention such as disclosed in U.S. Patent 3,912,688, incorporated herein by reference, may be used.
  • Suitable polycarbonate resins are available in commerce, for instance, Makrolon FCR, Makrolon 2600, Makrolon 2800 and Makrolon 3100, all of which are bisphenol based homopolycarbonate resins differing in terms of their respective molecular weights and characterized in that their melt flow indices (MFR) per ASTM D-1238 are about 16.5 to 24, 13 to 16, 7.5 to 13.0 and 3.5 to 6.5 g/10 min., respectively. These are products of Bayer Corporation of Pittsburgh, Pennsylvania.
  • a polycarbonate resin suitable in the practice of the invention is known and its structure and methods of preparation have been disclosed, for example, in U.S.
  • Titanium dioxide pigment in particulate form is well known to the art- skilled. It has been widely used as a pigmenting additive in molding composition and it is readily available in commerce.
  • the stabilizer suitable in the context of the invention is a compound, the structure of which contains at least one benzofuran-2-one group per molecule.
  • the compound conforms structurally to
  • R-i is an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system, and where in the embodiment where n is 2, R-i is unsubstituted or C- - alkyl or hydroxy substituted phenylene or naphthylene, and
  • R 2 , R 3 , 4 and R5 independently of one another are hydrogen, C- ⁇ - 25 -alkyl groups or phenyl.
  • a preferred compound is represented by 5,7-di-tertiary-butyl -3-(3,4 di-methylphenyl)-3H-benzofuran-2-one which is depicted as:
  • the stabilizer suitable in the context of the invention is characterized in that it melts at a temperature equal to or lower than the melt temperature of polycarbonate. This characteristic enables the compounding of the stabilizer with the polycarbonate resin in their molten state.
  • the stabilizer of the invention is added to the composition in an amount sufficient to improve the resistance of the composition against thermal degradation, as such is evidenced by decrease in the molecular weight of the polycarbonate resin.
  • the improvement is determined by comparing the resistance to a correspondingly pigmented composition which contains no stabilizer.
  • the stabilizer is present in an amount of 2 to 20%, more preferably 2 to 10% relative to the weight of the titanium dioxide present in the composition.
  • the stabilization characterizing the inventive composition may be determined by measuring its melt flow rate (MFR).
  • MFR melt flow rate
  • ASTM D-1238 under the conditions stated in the table below.
  • Stabilized compositions have a lower MFR than do corresponding, un-stabilized compositions under similar thermal conditions.
  • the stabilized compositions of the invention may contain other conventional additives which are known for their art-recognized functions. These include dyes, other pigments, reinforcing agents and fillers, flame- retardants and hydrolysis and UV stabilizers, plasticizers and mold release agents.
  • compositions of the invention are conventional.
  • the invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
  • compositions in accordance with the invention have been prepared and their properties determined.
  • the table below provides a summary of the makeup of the compositions and their properties.
  • the polycarbonate used was Makrolon 3100, a homopolycarbonate based on Bisphenol A, a product of Bayer Corporation, having a MFR of about 5- 6 gm/10 minutes.
  • the stabilizer was 5,7-di-tertiary-butyl-3-(3,4 di- methylphenyl)-3H-benzofuran-2-one.
  • the MFR values on molded parts was determined on parts molded at the indicated temperature.
  • the amount of stabilizing compound is represented as percent relative to the weight of titanium dioxide (TiO 2 ) 'Per ASTM D 1238, @ 300°C, 1.2 kg load
  • Example E shows the relative stability of polycarbonate in terms of its resistance to thermal degradation.
  • the MFR values of the resin remains fairiy constant even at a molding temperature of 700°F.
  • the incorporation of 5% of titanium oxide in the resin results in a considerable increase in the MFR values, an indication of degraded resin.
  • a more severe degradation results upon the incorporation of a greater amount of titanium oxide (Example C).
  • Examples B and D demonstrate the beneficial stabilizing effect imparted to the material system of polycarbonate and titanium oxide upon the addition of the inventive stabilizer. This performance is indicative of the greater resistance to thermal degradation.
  • Polyamide Caprolactam based ** The amount of stabilizing compound is represented as percent relative to the weight of titanium dioxide (TiO 2 )
  • the conditions for determining the melt flow rates of Examples A, B and C were 300°C, 1.2 kg load; Examples D, E and F were 230°C, 3.8 kg load; Examples G, H and I were 235°C, 2.16 kg load

Landscapes

  • 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)

Abstract

L'invention porte sur une composition thermoplastique présentant une meilleure résistance à la dégradation thermique de la résine. Cette composition comprend (i) une résine de polycarbonate thermoplastique, (ii) environ 3 à 20 % par rapport au poids total de (i) et (ii), de dioxyde de titane, et (iii) un stabilisant dont la structure présente au moins un groupe de benzofuran-2-one par molécule. La quantité de (iii) est la quantité suffisante pour améliorer la résistance de la composition à la dégradation thermique.
PCT/US2000/005860 1999-03-15 2000-03-07 Composition de moulage pigmentee, stable a la fusion, a base de polycarbonate Ceased WO2000055249A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37273/00A AU3727300A (en) 1999-03-15 2000-03-07 Melt-stable, pigmented polycarbonate molding composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26811599A 1999-03-15 1999-03-15
US09/268,115 1999-03-15

Publications (1)

Publication Number Publication Date
WO2000055249A1 true WO2000055249A1 (fr) 2000-09-21

Family

ID=23021529

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/005860 Ceased WO2000055249A1 (fr) 1999-03-15 2000-03-07 Composition de moulage pigmentee, stable a la fusion, a base de polycarbonate

Country Status (2)

Country Link
AU (1) AU3727300A (fr)
WO (1) WO2000055249A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004094518A1 (fr) * 2003-04-03 2004-11-04 Dow Global Technologies Inc. Polycarbonate contenant un sulfonamide aromatique comme inhibiteur d'inflammation
EP1882718A4 (fr) * 2005-05-19 2008-07-09 Teijin Chemicals Ltd Composition de résine de polycarbonate
WO2013152292A1 (fr) * 2012-04-05 2013-10-10 Sabic Innovative Plastics Ip B.V. Polycarbonate à réflectance élevée
US9090759B2 (en) 2012-04-05 2015-07-28 Sabic Global Technologies B.V. High reflectance polycarbonate
US9287471B2 (en) 2012-02-29 2016-03-15 Sabic Global Technologies B.V. Polycarbonate compositions containing conversion material chemistry and having enhanced optical properties, methods of making and articles comprising the same
US9290618B2 (en) 2011-08-05 2016-03-22 Sabic Global Technologies B.V. Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions
US9346949B2 (en) 2013-02-12 2016-05-24 Sabic Global Technologies B.V. High reflectance polycarbonate
US9821523B2 (en) 2012-10-25 2017-11-21 Sabic Global Technologies B.V. Light emitting diode devices, method of manufacture, uses thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2281910A (en) * 1993-09-17 1995-03-22 Ciba Geigy Ag 3-Arylbenzofuranone stabilisers
DE19728214A1 (de) * 1996-07-05 1998-01-08 Ciba Geigy Ag Phenolfreie Stabilisierung von Polyolefinfasern
GB2322861A (en) * 1997-03-06 1998-09-09 Ciba Sc Holding Ag Stabilising polycarbonates, polyesters and polyketones
WO1999003915A1 (fr) * 1997-07-14 1999-01-28 Dover Chemical Corporation Melanges lactones/phosphites

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2281910A (en) * 1993-09-17 1995-03-22 Ciba Geigy Ag 3-Arylbenzofuranone stabilisers
DE19728214A1 (de) * 1996-07-05 1998-01-08 Ciba Geigy Ag Phenolfreie Stabilisierung von Polyolefinfasern
GB2322861A (en) * 1997-03-06 1998-09-09 Ciba Sc Holding Ag Stabilising polycarbonates, polyesters and polyketones
WO1999003915A1 (fr) * 1997-07-14 1999-01-28 Dover Chemical Corporation Melanges lactones/phosphites

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004094518A1 (fr) * 2003-04-03 2004-11-04 Dow Global Technologies Inc. Polycarbonate contenant un sulfonamide aromatique comme inhibiteur d'inflammation
EP1882718A4 (fr) * 2005-05-19 2008-07-09 Teijin Chemicals Ltd Composition de résine de polycarbonate
US7939591B2 (en) 2005-05-19 2011-05-10 Teijin Chemicals, Ltd. Polycarbonate resin composition
US9290618B2 (en) 2011-08-05 2016-03-22 Sabic Global Technologies B.V. Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions
US9957351B2 (en) 2011-08-05 2018-05-01 Sabic Global Technologies B.V. Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions
US9299898B2 (en) 2012-02-29 2016-03-29 Sabic Global Technologies B.V. Polycarbonate compositions containing conversion material chemistry and having enhanced optical properties, methods of making and articles comprising the same
US9287471B2 (en) 2012-02-29 2016-03-15 Sabic Global Technologies B.V. Polycarbonate compositions containing conversion material chemistry and having enhanced optical properties, methods of making and articles comprising the same
WO2013152292A1 (fr) * 2012-04-05 2013-10-10 Sabic Innovative Plastics Ip B.V. Polycarbonate à réflectance élevée
US9090759B2 (en) 2012-04-05 2015-07-28 Sabic Global Technologies B.V. High reflectance polycarbonate
US9315675B2 (en) 2012-04-05 2016-04-19 Sabic Global Technologies B.V. High reflectance polycarbonate
CN104220502B (zh) * 2012-04-05 2017-08-25 沙特基础全球技术有限公司 高反射率聚碳酸酯
CN104220502A (zh) * 2012-04-05 2014-12-17 沙特基础创新塑料Ip私人有限责任公司 高反射率聚碳酸酯
US9821523B2 (en) 2012-10-25 2017-11-21 Sabic Global Technologies B.V. Light emitting diode devices, method of manufacture, uses thereof
US9346949B2 (en) 2013-02-12 2016-05-24 Sabic Global Technologies B.V. High reflectance polycarbonate

Also Published As

Publication number Publication date
AU3727300A (en) 2000-10-04

Similar Documents

Publication Publication Date Title
CA2014931C (fr) Compositions de polycarbonates resistants aux rayons gamma
CA1335221C (fr) Compositions de polycarbonate resistant aux radiations gamma
US6069225A (en) Polycarbonate composition useful in optical storage applications
CA2069595C (fr) Composition a base de polycarbonate resistante aux rayons gamma
US5187211A (en) Gamma radiation resistant polycarbonate compositions
WO2000055249A1 (fr) Composition de moulage pigmentee, stable a la fusion, a base de polycarbonate
CA2176302C (fr) Composition de moulage thermoplastique a tenacite amelioree
US5681905A (en) Gamma radiation-resistant blend of polycarbonate with polyester
EP1274781B1 (fr) Composition de polycarbonate resistant au rayonnement gamma
US5405892A (en) Melt-stable, pigmented polycarbonate composition
US5086097A (en) Ultraviolet stabilizer for polycarbonate compositions
CA1335222C (fr) Compositions de polycarbonate stables hydrolytiquement
US20100036014A1 (en) Stabilized antimicrobial polycarbonate compositions
US6153685A (en) Melt-stable pigmented polycarbonate molding composition
US6197853B1 (en) Polycarbonate composition resistant to gamma radiation
US5856413A (en) Polycarbonate compositions having mold-release properties
US6046301A (en) Polycarbonate compositions having reduced tendency to splay
EP1791908B1 (fr) Compositions de moulage a base de polycarbonate thermoplastique, ignifuges
US20030105209A1 (en) Flame retardant polycarbonate composition
US20140005311A1 (en) Polycarbonate composition with low static performance
CA2475583A1 (fr) Compositions de moulage a base de polycarbonate thermoplastiques ignifuges
HK1056189A (zh) 耐γ射线的聚碳酸酯组合物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase