IL125779A - Titanium dioxide particles exhibiting anti-uv properties, process for their preparation and cosmetic compositions containing the same - Google Patents
Titanium dioxide particles exhibiting anti-uv properties, process for their preparation and cosmetic compositions containing the sameInfo
- Publication number
- IL125779A IL125779A IL12577997A IL12577997A IL125779A IL 125779 A IL125779 A IL 125779A IL 12577997 A IL12577997 A IL 12577997A IL 12577997 A IL12577997 A IL 12577997A IL 125779 A IL125779 A IL 125779A
- Authority
- IL
- Israel
- Prior art keywords
- titanium dioxide
- properties
- preparation
- dioxide particles
- same
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Birds (AREA)
- General Physics & Mathematics (AREA)
- Epidemiology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Dermatology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Cosmetics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9601850A FR2744914B1 (fr) | 1996-02-15 | 1996-02-15 | Dispersion de dioxyde de titane, poudre a base de dioxyde de titane, leur utilisation dans les formulations cosmetiques |
PCT/FR1997/000266 WO1997030130A1 (fr) | 1996-02-15 | 1997-02-12 | Particules de dioxyde de titane |
Publications (2)
Publication Number | Publication Date |
---|---|
IL125779A0 IL125779A0 (en) | 1999-04-11 |
IL125779A true IL125779A (en) | 2003-09-17 |
Family
ID=9489214
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IL12577997A IL125779A (en) | 1996-02-15 | 1997-02-12 | Titanium dioxide particles exhibiting anti-uv properties, process for their preparation and cosmetic compositions containing the same |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0880564B1 (xx) |
JP (1) | JP3091496B2 (xx) |
CN (1) | CN1083472C (xx) |
AT (1) | ATE192475T1 (xx) |
AU (1) | AU727150B2 (xx) |
BR (1) | BR9707499A (xx) |
CA (1) | CA2253223C (xx) |
DE (1) | DE69701859T2 (xx) |
ES (1) | ES2146083T3 (xx) |
FR (1) | FR2744914B1 (xx) |
IL (1) | IL125779A (xx) |
RU (1) | RU2162443C2 (xx) |
WO (1) | WO1997030130A1 (xx) |
Families Citing this family (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5891857A (en) * | 1996-02-20 | 1999-04-06 | Vanderbilt University | Characterized BRCA1 and BRCA2 proteins and screening and therapeutic methods based on characterized BRCA1 and BRCA2 proteins |
JPH11217219A (ja) * | 1998-01-28 | 1999-08-10 | Nonogawa Shoji Kk | 複合化顔料及びこれを含有する化粧料 |
FR2775981B1 (fr) * | 1998-03-16 | 2000-06-02 | Rhodia Chimie Sa | Composition silicone elastomere reticulant a chaud, thermiquement stable et coloree sans pastellisation |
FR2787797B1 (fr) | 1998-12-23 | 2006-01-06 | Rhodianyl | Procede de fabrication de polyamide |
FR2789997B1 (fr) * | 1999-02-18 | 2004-12-03 | Rhodia Chimie Sa | Composition comprenant une emulsion huile dans l'eau et un agent inorganique |
US6548039B1 (en) | 1999-06-24 | 2003-04-15 | Altair Nanomaterials Inc. | Processing aqueous titanium solutions to titanium dioxide pigment |
US6375923B1 (en) | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
AU776394B2 (en) * | 1999-06-24 | 2004-09-09 | Wrp Technologies, Inc. | Processing aqueous titanium solutions to titanium dioxide pigment |
US6440383B1 (en) | 1999-06-24 | 2002-08-27 | Altair Nanomaterials Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
GB0015381D0 (en) * | 2000-06-26 | 2000-08-16 | Acma Ltd | Particulate metal oxide |
EP1409409B1 (en) | 2001-07-20 | 2004-12-22 | Altair Nanomaterials Inc. | Process for making lithium titanate |
US7285162B2 (en) | 2001-07-30 | 2007-10-23 | Millennium Inorganic Chemicals, Inc. | Titanium dioxide pigment having improved light stability |
US6743286B2 (en) | 2001-07-30 | 2004-06-01 | Millennium Inorganic Chemicals, Inc. | Inorganic particles and methods of making |
JP4111701B2 (ja) * | 2001-10-01 | 2008-07-02 | 触媒化成工業株式会社 | 改質酸化チタン粒子 |
JP3914858B2 (ja) * | 2002-11-13 | 2007-05-16 | 出光興産株式会社 | 熱可塑性樹脂組成物配合用酸化チタン、熱可塑性樹脂組成物及びその成形体 |
JP4105971B2 (ja) * | 2003-03-27 | 2008-06-25 | 株式会社資生堂 | 多孔質酸化チタン粉体及びその製造方法 |
DE10324566A1 (de) | 2003-05-30 | 2004-12-16 | Symrise Gmbh & Co. Kg | Verwendung von Diphenylmethan-Derivaten als Tyrosinase-Inhibitoren |
BRPI0414438A (pt) * | 2003-09-18 | 2006-11-14 | Fmc Corp | método para preparar uma dispersão estável de óxido de metal em água, e, composição |
DE102005010803A1 (de) * | 2005-03-07 | 2006-09-14 | Basf Ag | Kosmetische und dermatologische Zubereitungen, enthaltend transparente oberflächenbeschichtete Titandioxidpartikel |
CN100346874C (zh) * | 2005-03-17 | 2007-11-07 | 华中科技大学 | 二氧化钛为基体的复合型光催化剂的制备方法 |
DE102006013283A1 (de) * | 2006-03-20 | 2007-09-27 | Beiersdorf Ag | Sprühbare Sonnenschutzlotion |
CA2722795C (en) | 2008-05-02 | 2014-04-22 | Eiji Takahashi | Titania fine-particle composite and compositons containing the titania fine-particle composite |
JP5258447B2 (ja) * | 2008-08-11 | 2013-08-07 | 日揮触媒化成株式会社 | 酸化チタン系複合粒子の分散液および該分散液の製造方法 |
PL2411141T3 (pl) | 2009-03-23 | 2014-06-30 | Vaelinge Photocatalytic Ab | Wytwarzanie zawiesiny nanocząsteczek koloidalnych ditlenku tytanu z zachowaniem krystaliczności za pomocą młyna kulkowego z kulkami o rozmiarach mikrometrowych |
JP5397854B2 (ja) * | 2009-07-08 | 2014-01-22 | Nsマテリアルズ株式会社 | 酸化物コーティング酸化チタン含有液及びその製造方法 |
US8545796B2 (en) | 2009-07-31 | 2013-10-01 | Cristal Usa Inc. | Silica-stabilized ultrafine anatase titania, vanadia catalysts, and methods of production thereof |
DE102009056634A1 (de) * | 2009-12-02 | 2011-06-09 | Giesecke & Devrient Gmbh | Festkörperpartikel mit Siliciabeschichtung |
GB0922552D0 (en) * | 2009-12-23 | 2010-02-10 | Croda Int Plc | Particulate titanium dioxide |
EP2729640A4 (en) | 2011-07-05 | 2015-07-08 | Välinge Photocatalytic Ab | COATED WOOD PRODUCTS AND METHOD FOR PRODUCING COATED WOOD PRODUCTS |
JP5794852B2 (ja) * | 2011-07-29 | 2015-10-14 | 石原産業株式会社 | 化粧料用二酸化チタン顔料及びその製造方法 |
JP6049368B2 (ja) * | 2011-09-15 | 2016-12-21 | 日揮触媒化成株式会社 | Al修飾無機酸化物微粒子とその製造方法、分散液、および塗料組成物 |
BR112014021844B1 (pt) | 2012-03-20 | 2021-08-17 | Välinge Photocatalytic Ab | Composição fotocatalítica compreendendo dióxido de titânio e aditivos antifotoacinzentados e painel de construção |
US9375750B2 (en) | 2012-12-21 | 2016-06-28 | Valinge Photocatalytic Ab | Method for coating a building panel and a building panel |
EP3539793A1 (en) | 2013-09-25 | 2019-09-18 | Välinge Photocatalytic AB | A method of applying a photocatalytic dispersion |
CN105131655B (zh) * | 2015-07-20 | 2017-10-24 | 苏州宇希新材料科技有限公司 | 一种液相硅沉积改性的纳米二氧化钛 |
RU2607221C1 (ru) * | 2015-09-09 | 2017-01-10 | Василий Дмитриевич Мушенко | Пигмент белого цвета |
RU2607406C1 (ru) * | 2015-09-09 | 2017-01-10 | Василий Дмитриевич Мушенко | Пигмент белого цвета |
RU2613055C2 (ru) * | 2015-09-09 | 2017-03-15 | Ольга Аркадьевна Орлова | Пигмент белого цвета |
CN111684027B (zh) * | 2018-01-29 | 2023-01-06 | 石原产业株式会社 | 二氧化钛水分散体及其制备方法 |
WO2020170917A1 (ja) * | 2019-02-19 | 2020-08-27 | 昭和電工株式会社 | 酸化チタン |
CN112603840B (zh) * | 2020-12-14 | 2022-09-16 | 上海蔻沣生物科技有限公司 | 化妆料组合物、化妆品 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5813668A (ja) * | 1981-07-15 | 1983-01-26 | Horubein Kogyo Kk | 油彩画用絵具 |
JPS58103668A (ja) * | 1981-12-15 | 1983-06-20 | Sumitomo Electric Ind Ltd | 碍子の分坦電圧検出装置 |
JPS5933364A (ja) * | 1982-08-16 | 1984-02-23 | Sanyo Shikiso Kk | 雲母系真珠顔料の製造法 |
ES2063151T3 (es) * | 1988-03-30 | 1995-01-01 | Rhone Poulenc Chimie | Procedimiento de preparacion de oxido de titanio. |
FR2633605B1 (fr) * | 1988-07-01 | 1991-07-12 | Rhone Poulenc Chimie | Procede de preparation d'oxyde de titane et d'articles a base d'oxyde de titane |
US4923682A (en) * | 1989-03-30 | 1990-05-08 | Kemira, Inc. | Preparation of pure titanium dioxide with anatase crystal structure from titanium oxychloride solution |
GB8908995D0 (en) * | 1989-04-20 | 1989-06-07 | Tioxide Group Plc | Particulate material |
JP2585128B2 (ja) * | 1989-06-02 | 1997-02-26 | テイカ株式会社 | 有色微粒子無機顔料 |
JP2717904B2 (ja) * | 1992-06-04 | 1998-02-25 | 石原産業株式会社 | 鉄含有超微粒子ルチル型二酸化チタン及びその製造方法 |
JPH0649388A (ja) * | 1992-07-31 | 1994-02-22 | Ishihara Sangyo Kaisha Ltd | 二酸化チタン顔料の製造方法 |
FR2735363B1 (fr) * | 1995-06-16 | 1997-07-11 | Oreal | Compositions contenant un derive du dibenzoylmethane et un nanopigment d'oxyde de titane et utilisations |
-
1996
- 1996-02-15 FR FR9601850A patent/FR2744914B1/fr not_active Expired - Lifetime
-
1997
- 1997-02-12 DE DE69701859T patent/DE69701859T2/de not_active Expired - Lifetime
- 1997-02-12 CA CA002253223A patent/CA2253223C/fr not_active Expired - Fee Related
- 1997-02-12 BR BR9707499A patent/BR9707499A/pt not_active IP Right Cessation
- 1997-02-12 JP JP09529047A patent/JP3091496B2/ja not_active Expired - Fee Related
- 1997-02-12 ES ES97905191T patent/ES2146083T3/es not_active Expired - Lifetime
- 1997-02-12 WO PCT/FR1997/000266 patent/WO1997030130A1/fr active IP Right Grant
- 1997-02-12 AT AT97905191T patent/ATE192475T1/de active
- 1997-02-12 RU RU98117089/12A patent/RU2162443C2/ru not_active IP Right Cessation
- 1997-02-12 IL IL12577997A patent/IL125779A/xx not_active IP Right Cessation
- 1997-02-12 CN CN97192296A patent/CN1083472C/zh not_active Expired - Fee Related
- 1997-02-12 EP EP97905191A patent/EP0880564B1/fr not_active Expired - Lifetime
- 1997-02-12 AU AU18834/97A patent/AU727150B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
CA2253223A1 (fr) | 1997-08-21 |
ES2146083T3 (es) | 2000-07-16 |
WO1997030130A1 (fr) | 1997-08-21 |
FR2744914B1 (fr) | 1998-03-20 |
FR2744914A1 (fr) | 1997-08-22 |
IL125779A0 (en) | 1999-04-11 |
EP0880564A1 (fr) | 1998-12-02 |
BR9707499A (pt) | 1999-07-27 |
AU1883497A (en) | 1997-09-02 |
EP0880564B1 (fr) | 2000-05-03 |
DE69701859D1 (de) | 2000-06-08 |
RU2162443C2 (ru) | 2001-01-27 |
CN1083472C (zh) | 2002-04-24 |
AU727150B2 (en) | 2000-12-07 |
JP3091496B2 (ja) | 2000-09-25 |
CA2253223C (fr) | 2002-01-08 |
JPH11506155A (ja) | 1999-06-02 |
CN1211272A (zh) | 1999-03-17 |
DE69701859T2 (de) | 2000-11-09 |
ATE192475T1 (de) | 2000-05-15 |
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Legal Events
Date | Code | Title | Description |
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FF | Patent granted | ||
KB | Patent renewed | ||
KB | Patent renewed | ||
KB | Patent renewed | ||
KB | Patent renewed | ||
EXP | Patent expired |