WO1999001457A1 - Photochromatic compounds, process for their preparation and their use in polymeric materials - Google Patents

Photochromatic compounds, process for their preparation and their use in polymeric materials Download PDF

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Publication number
WO1999001457A1
WO1999001457A1 PCT/EP1998/003994 EP9803994W WO9901457A1 WO 1999001457 A1 WO1999001457 A1 WO 1999001457A1 EP 9803994 W EP9803994 W EP 9803994W WO 9901457 A1 WO9901457 A1 WO 9901457A1
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WIPO (PCT)
Prior art keywords
group
general formula
groups
branched
linear
Prior art date
Application number
PCT/EP1998/003994
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English (en)
French (fr)
Inventor
Luciana Crisci
William Giroldini
Vincenzo Malatesta
Maria Lucia Wis
Original Assignee
Great Lakes Chemical (Europe) Gmbh
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 Great Lakes Chemical (Europe) Gmbh filed Critical Great Lakes Chemical (Europe) Gmbh
Priority to US09/446,904 priority Critical patent/US6414057B1/en
Priority to EP98939568A priority patent/EP0994879B1/en
Priority to JP50632199A priority patent/JP2002507980A/ja
Priority to KR1019997012438A priority patent/KR100569654B1/ko
Priority to AU88033/98A priority patent/AU8803398A/en
Priority to DE69818471T priority patent/DE69818471T2/de
Priority to AT98939568T priority patent/ATE250613T1/de
Publication of WO1999001457A1 publication Critical patent/WO1999001457A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-condensed systems
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances

Definitions

  • the present invention relates to photochromatic compounds . More specifically, the present invention relates to photochromatic compounds belonging to the group of spiro-isoindolino-oxazines, a process for their preparation and their use in polymeric materials.
  • a further object of the present invention relates to polymeric compositions containing said photochromatic compounds and the photochromatic articles obtained from their processing.
  • Photochromatic compounds are substances which have the characteristic of reversibly changing colour and/or degree of light transmission when exposed to solar or artificial light in the band ranging from UV to visible, or to some types of electromagnetic radiation, returning to their original state of colour and transmission when the initial light source is Z removed .
  • organic photochromatic compounds those belonging to the groups of spiro-indolino-oxazines, spiro-pyranes and chromenes, are particularly known and used.
  • the above compounds are capable of giving photochromatic characteristics to polymerized organic materials used, for example, in the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications.
  • the Applicant has now found photochromatic compounds belonging to the group of spiro-isoindolino- oxazines which have excellent photochromatic character- istics, excellent stress resistance and high dyability characteristics .
  • the present invention therefore relates to photochromatic compounds belonging to the group of spiro- isoindolino-oxazines having general formula (I) :
  • R represents a linear or branched ⁇ -C ⁇ alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched C 1 -C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2, 2, 6, 6-tetrame- thylpiperidine group; a linear or branched C 2 -C 6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched (C 1 -C 6 ) alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C 1 -C 6 ) amine groups; a benzyl group; R 1 and R 2 , the same or different, represent a linear or branched C.,-C 10 alkyl group, said alkyl group
  • Preferred compounds having general formula (I) for the purposes of the present invention are those in which:
  • R represents one of the following groups: methyl, ethyl, isopropyl, 2-allyl, 2-hydroxyethyl, 2-car- boxy ethyl, phenyl, 4-N,N-dimethylaminoaniline, 4-methoxybenzene, 4-cyanobenzene;
  • R 1 and R j represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group;
  • - R 3 , R 4 , R 5 and R 6 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, ethoxyl, N,N-dime- thylamine, piperidine, morpholine, carboxyl, carboxymethyl , N,N-dimethylcarboxyamide, cyano, nitro
  • R 44 and R 47 , R 48 and R ⁇ , R 58 and R 67 independently represent the condensation point with the oxazine ring and the other substituents each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, 2-hydroxy- ethyl, 2-allyl, piperidine, morpholine, N,N- dimethylamine, carboxyl, carboxymethyl, N,N- dimethylcarboxyamide, cyano, nitro, ethylke- tone, ethylketone, phenylketone, methylthiol ; ii) two adjacent substituents between R g and R 13 , R 14 and R ⁇ , R 22 and R 2S , R 30 and R 35 , 36 and R 41 , R 44 and R 47 , R 4g and R ⁇ , R gg and R 67 , different from
  • a xurther obj ect of "the present .invention relates -to a. process _for the preparation of the photochromatic compounds having general ⁇ ormula (J) .
  • photochromatic compounds having general formula (I) can be prepared y the condensation of isoindoline compounds having general formula (X) :
  • reaction product is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropa- nol, toluene, or a mixture of these solvents, at a temperature ranging from 50 °C to 100 "C, preferably between 60 'C and 75 °C, for a time ranging from 1 hour to 10 hours, preferably between 2 hours and 5 hours.
  • an inert organic solvent such as, for example, ethyl alcohol, isopropa- nol, toluene, or a mixture of these solvents
  • reaction product is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropa- nol, toluene, or a mixture of these solvents, and in the presence of aqueous ammonia at 30%, at a temperature ranging from 50°C to 100 °C, preferably between 60 °C and 75 "C, for a time ranging from 1 hour to 10 hours, preferably between 2 hours and 3 hours.
  • the reaction product thus obtained is, generally, purified by elution on a silica column and subsequent crystallization from a solvent such as, for example, acetone, toluene, heptane.
  • the isoindoline compounds having general formula (X) can be prepared according to procedures known in the art and described, for example, in: “Tetrahedron” (1966), Vol. 22, page 2481; “Journal of Organic Chemistry” (1979), Vol. 44, page 1519; “Angewandte Chemie International (1968), Vol. 7, page 373.
  • the isoindoline compounds having general formula (X) are usually kept in the form of salts such as, for example, iodides, bromides, chlorides, as the free base is easily oxidated by the air.
  • nitrous compounds having general formula (XI) can be prepared by the reaction of phenol compounds with nitrous acid or butyl nitrite, as described, for example, in Italian patent 1.176.858.
  • isoindoline compounds having general formula (X) are the following, represented by formula (Xa) corresponding to 1, 1,2, 4 ,7-pentamethyl-3- methylene-isoindoline and formula (Xb) corresponding to
  • nitrous compounds having general formula (XI) are the following, represented by formula (XIa) corresponding to l-nitrous-2-naphthol, by formula (Xlb) corresponding to 2-nitrous-1-naphthol, by formula (XIc) corresponding to 5-nitrous-6-hydroxy- quinoline, by formula (Xld) corresponding to 1-nitrous- 2-naphthol-6-propan(l) one and by formula (Xle) corresponding to 10-nitrous-9-phenanthrol:
  • aromatic 1,2-quinone compounds having general formula (XII) are the following, represented by formula (Xlla) corresponding to 1,2- naphthoguinone-4-morpholine, by formula (Xllb) corre- sponding to 1, 2-naphthoguinone- -piperidine and by formula (XIIc) corresponding to 1, 2-naphthoquinone-4- (di ethylaniline) :
  • the photochromatic compounds having general formula (I) of the present invention are colourless or slightly yellowish crystalline products.
  • Their solutions in common organic solvents such as, for example, benzene, toluene, methanol, when not exposed to light sources are colourless or slightly yellow. These solutions, if exposed to a light source, either visible or UV, become blue-coloured, either sky- blue or blue-green. The colouring quickly diminishes when the light source is removed.
  • the photochromatic compounds having general formula (I) can be applied to the surface or incorporated in mass into the desired articles, using tech- niques already known in the art and described hereun- der.
  • Some polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which the photochromatic compound having formula (I) is homogeneously dispersed in mass.
  • the photochromatic compound having general formula (I) can be dissolved in a solvent, together with the polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
  • the mixture thus obtained is deposited on a transparent carrier to form, after evaporation of the solvent, a photochromatic coating.
  • (I) can also be added to a polymerizable monomer such as, for example, a meth(acrylic) or allyl carbonate monomer, so that, after polymerization carried out in the presence of a suitable initiator such as, for example, azo-bis (isobutyronitrile) in the case of the meth(acrylic) monomer or a peroxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
  • a suitable initiator such as, for example, azo-bis (isobutyronitrile) in the case of the meth(acrylic) monomer or a peroxyketal in the case of the allyl carbonate monomer
  • the photochromatic compound having general formula (I) can be applied to a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethylene glycol bis (allyl carbonate) , by surface impregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing the photochro- matic compound having general formula (I) , operating according to the method described, for example, in U.S. patent 5.130.353.
  • the photochromatic compounds having general formula (I) of the present invention have the characteristic of being able to be incorporated in mass or using one of the techniques described above, into various organic polymers such as, for example, high density polyethylene, low density polyethylene, ethyl- ene-vinylacetate copolymer, polyether amides, polypropylene, polymethylmethacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, epoxy, polysiloxane or urethane resins, polycarbonate, polydiethylene glycol bis(allyl carbonate), polyamides, polyesters, polystyrene, vinyl polychloride, polymethy- lacrylate, polyethylacrylate, siliconic polymers.
  • organic polymers such as, for example, high density polyethylene, low density polyethylene, ethyl- ene-vinylacetate copolymer, polyether amides, polypropylene, polymethylmethacrylate, polyvin
  • the photochromatic compounds having general formula (I) of the present invention can be optionally used in the presence of the usual additives for organic polymers such as, for example, phenol antioxidants, sterically hindered amines, benzotriazoles, phosphites or phosphonites.
  • organic polymers such as, for example, phenol antioxidants, sterically hindered amines, benzotriazoles, phosphites or phosphonites.
  • a further object of the present invention therefore relates to polymeric compositions comprising the above polymeric materials and the above photochromatic compounds having general formula (I) , optionally in the presence of the above polymeric additives, and the photochromatic articles obtained from their processing.
  • the photochromatic compounds having general formula (I) of the present invention have a photochromatic activity also at room temperature and, surprisingly, in some cases, their photochromatic activity is higher than that of products belonging to the group of spiro-indolino-oxazines .
  • the photochromatic compounds having general formula (I) of the present invention can be used as such, mixed with each other, or combined with other suitable organic photochromatic compounds to obtain, after activation, the formation of different colourings such as, green, brown and grey.
  • Photochromatic compounds belonging to the group of spiro-indolino-oxazines or spiro-pyranes described in the art such as, for example, in U.S. patent 5.066.818, are particularly useful for the purpose.
  • the examples provided hereunder for a better understanding of the present invention and for its embodiment are purely illustrative and in no way limit the scope of the invention itself.
  • EXAMPLE 1 Preparation of 1 , 1,2 ,4,7-pentamethyl-3-methylene- isoindoline iodide.
  • the above mixture is heated to 80 °C, under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane.
  • the aqueous phase obtained is treated with sodium hydroxide at 30% until pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 10 ml of hexane.
  • the product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 23.5 g.
  • a quantity equal to 23.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 16 g of methyliodide.
  • the autoclave is heated to 85 °C and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours.
  • the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane.
  • the above mixture is heated to 80"C, under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane.
  • the aqueous phase obtained is treated with sodium hydroxide at 30% until a pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 20 ml of hexane.
  • the product is dried under vacuum and conserved in a nitrogen atmosphere: the yield is 44 g.
  • a quantity equal to 25 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 18 g of methyliodide.
  • the autoclave is heated to 85 °C and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours.
  • the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane.
  • 24 g of product are obtained, corresponding to 1,1,4, 7-tetramethyl-N-phenyl-3-methylene-isoindoline iodide.
  • the NMR data are indicated in Table 2.
  • the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
  • the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
  • the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
  • the dry residue obtained is dissolved in 20 ml of isopropanol to which 2 ml of triethylamine and 3.4 g of l-nitrous-2-naphthol-6-propan(l)one [Compound (Xld)] are added: the mixture is heated to 70 "C and maintained at this temperature, under stirring, under a nitrogen atmosphere, for three hours.
  • the reaction raw product obtained is then purified by passage on a silica gel column eluating with a mixture of heptane/toluene in a ratio of 1/1.
  • the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
  • the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
  • the photochromatic activity is evaluated in methanol and toluene, at 20 °C, of Compounds (la) -(If) obtained as described above in Examples 3-8. Solutions are prepared at a concentration equal to about 10 '4 M (the exact concentrations are indicated in Table 9) of the various Compounds (la) -(If) in the two solvents and subsequently 1.3 ml of each solution is placed, individually, in a 1 cm quartz cell having a square base inlet.
  • the quartz cell containing the solution is introduced into a Peltier temperature control system (HP accessory - HP 89090A) , with the possibility of magnetic stirring during the measuring, and is irradiated from above with a Philips UVA lamp with an irradiance equal to 9 Watt/cm 2 supported on the cell itself.
  • the irradiance time varies from sample to sample (60"-180") to guarantee the maximum degree of colouring of the solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Eyeglasses (AREA)
PCT/EP1998/003994 1997-07-03 1998-07-01 Photochromatic compounds, process for their preparation and their use in polymeric materials WO1999001457A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US09/446,904 US6414057B1 (en) 1997-07-03 1998-07-01 Photochromatic compounds, process for their preparation and their use in polymeric materials
EP98939568A EP0994879B1 (en) 1997-07-03 1998-07-01 Photochromatic compounds, process for their preparation and their use in polymeric materials
JP50632199A JP2002507980A (ja) 1997-07-03 1998-07-01 ホトクロミック化合物、それらの製造方法及びポリマー材料でのそれらの使用
KR1019997012438A KR100569654B1 (ko) 1997-07-03 1998-07-01 포토크로마틱 화합물, 이의 제조 방법 및 중합체물질에서의 이의 용도
AU88033/98A AU8803398A (en) 1997-07-03 1998-07-01 Photochromatic compounds, process for their preparation and their use in polymeric materials
DE69818471T DE69818471T2 (de) 1997-07-03 1998-07-01 Photochromatische verbindungen, verfahren zu ihrer herstellung und ihre verwendung in polymere zusammensetzungen
AT98939568T ATE250613T1 (de) 1997-07-03 1998-07-01 Photochromatische verbindungen, verfahren zu ihrer herstellung und ihre verwendung in polymere zusammensetzungen

Applications Claiming Priority (2)

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ITMI97A01573 1997-07-03
IT97MI001573A IT1292461B1 (it) 1997-07-03 1997-07-03 Composti fotocromatici,procedimento per la loro preparazione e loro utilizzo in materiali polimerici

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WO1999001457A1 true WO1999001457A1 (en) 1999-01-14

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PCT/EP1998/003994 WO1999001457A1 (en) 1997-07-03 1998-07-01 Photochromatic compounds, process for their preparation and their use in polymeric materials

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AR (1) AR010923A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AT (1) ATE250613T1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
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DE (1) DE69818471T2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999057219A1 (en) * 1998-05-07 1999-11-11 Great Lakes Chemical (Europe) Gmbh Photochromic compounds, process for their preparation and their use in polymeric materials
WO2001077112A3 (en) * 2000-04-06 2002-04-18 Yeda Res & Dev Photochromic spiro(indoline)naphthoxazines
US11492365B2 (en) 2020-02-07 2022-11-08 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists
US12291529B2 (en) 2023-02-16 2025-05-06 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists

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MY149850A (en) * 2003-09-29 2013-10-31 Ciba Holding Inc Stabilization of photochromic systems
ATE406413T1 (de) * 2006-01-27 2008-09-15 Ems Chemie Ag Photochrome formmassen und daraus hergestellte gegenstände
US20210284778A1 (en) 2020-03-11 2021-09-16 Alcon Inc. Photochromic polydiorganosiloxane vinylic crosslinkers
US11999908B2 (en) 2020-06-02 2024-06-04 Alcon Inc. Method for making photochromic contact lenses
HUE069854T2 (hu) 2020-10-28 2025-04-28 Alcon Inc Eljárás fotokróm kontaktlencsék elõállítására
HUE070248T2 (hu) 2020-11-04 2025-05-28 Alcon Inc Eljárás fotokróm kontaktlencsék elõállítására
HUE069913T2 (hu) 2020-11-04 2025-04-28 Alcon Inc Eljárás fotokróm kontaktlencsék elõállítására
KR20230131494A (ko) 2021-03-08 2023-09-13 알콘 인코포레이티드 광기능성 콘택트 렌즈의 제조 방법
KR20230144634A (ko) 2021-04-01 2023-10-16 알콘 인코포레이티드 광변색성 콘택트 렌즈의 제조 방법
EP4514597A1 (en) 2022-04-28 2025-03-05 Alcon Inc. Method for making uv and hevl-absorbing ophthalmic lenses

Citations (4)

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EP0134633A2 (en) * 1983-08-08 1985-03-20 American Optical Corporation Photochromic composition
EP0432841A2 (en) * 1989-12-12 1991-06-19 GREAT LAKES CHEMICAL ITALIA S.r.l. Spiro-indoline-oxazine compounds with photochromatic and photosensitizing characteristics and the process for their preparation
EP0508219A2 (de) * 1983-12-16 1992-10-14 Optische Werke G. Rodenstock Photochrome Substanzen
EP0524692A1 (en) * 1991-07-24 1993-01-27 GREAT LAKES CHEMICAL ITALIA S.r.l. Photochromatic and thermochromatic compounds and their application in polymeric materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0134633A2 (en) * 1983-08-08 1985-03-20 American Optical Corporation Photochromic composition
EP0508219A2 (de) * 1983-12-16 1992-10-14 Optische Werke G. Rodenstock Photochrome Substanzen
EP0432841A2 (en) * 1989-12-12 1991-06-19 GREAT LAKES CHEMICAL ITALIA S.r.l. Spiro-indoline-oxazine compounds with photochromatic and photosensitizing characteristics and the process for their preparation
EP0524692A1 (en) * 1991-07-24 1993-01-27 GREAT LAKES CHEMICAL ITALIA S.r.l. Photochromatic and thermochromatic compounds and their application in polymeric materials

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999057219A1 (en) * 1998-05-07 1999-11-11 Great Lakes Chemical (Europe) Gmbh Photochromic compounds, process for their preparation and their use in polymeric materials
WO2001077112A3 (en) * 2000-04-06 2002-04-18 Yeda Res & Dev Photochromic spiro(indoline)naphthoxazines
US6891038B2 (en) 2000-04-06 2005-05-10 Yeda Research And Development Co. Ltd. Photochromic spiro(indoline)naphthoxazines
US11492365B2 (en) 2020-02-07 2022-11-08 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists
US11926643B2 (en) 2020-02-07 2024-03-12 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists
US12291529B2 (en) 2023-02-16 2025-05-06 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists

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AR010923A1 (es) 2000-07-12
EP0994879A1 (en) 2000-04-26
JP2002507980A (ja) 2002-03-12
DE69818471T2 (de) 2004-07-01
EP0994879B1 (en) 2003-09-24
ATE250613T1 (de) 2003-10-15
KR20010020559A (ko) 2001-03-15
AU8803398A (en) 1999-01-25
DE69818471D1 (de) 2003-10-30
ZA985807B (en) 1999-01-26
ITMI971573A0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1997-07-03
ITMI971573A1 (it) 1999-01-03
IT1292461B1 (it) 1999-02-08
KR100569654B1 (ko) 2006-04-11
US6414057B1 (en) 2002-07-02

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