WO1998006787A1 - Procede pour produire un noir de carbone a surface traitee, destine a renforcer les caoutchoucs - Google Patents
Procede pour produire un noir de carbone a surface traitee, destine a renforcer les caoutchoucs Download PDFInfo
- Publication number
- WO1998006787A1 WO1998006787A1 PCT/JP1997/001901 JP9701901W WO9806787A1 WO 1998006787 A1 WO1998006787 A1 WO 1998006787A1 JP 9701901 W JP9701901 W JP 9701901W WO 9806787 A1 WO9806787 A1 WO 9806787A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon black
- rubber
- treated
- black
- organosiloxane
- 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
- 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
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
- Y10T428/2995—Silane, siloxane or silicone coating
Definitions
- the present invention relates to a carbon black having a surface treated with silica, and more particularly to tires and various rubber products having excellent tan 5 temperature dependency of silica, and improved abrasion resistance and electric conductivity.
- the present invention relates to a method for producing a carbon black for use and a rubber composition containing the same. Background art
- Japanese Patent Application Laid-Open Nos. Sho 53-100, 190, Sho 56-38057, and Sho 61-291 609 disclose silicone compounds and carbon black. It is disclosed that the mixture is mixed and dried.
- Japanese Patent Application Laid-Open No. 58-12549 discloses that a carbon black coated on the surface with a silane coupling agent is mixed with a thermoplastic resin. As described above, there is no description on the excellent properties when compounded into rubber.
- Japanese Patent Application Laid-Open No. 4-2339776 discloses a silicon compound having two or less silicon atoms in a molecule and a carbon black as a carbon black chemically modified with an organosilicon compound.
- a method for producing a heated reactant and a rubber composition obtained by mixing the same are disclosed in this example.However, in this case, various organic groups are provided on the surface of a rubber black via an alkoxysilyl group. This is a concept essentially different from the method of attaching silica to a carbon surface as in the present invention. Disclosure of the invention
- the present invention relates to a method for producing a surface black having excellent tan 5 temperature dependency of a silicon force and a surface treatment force suitable for reinforcing rubber having high abrasion resistance and high electrical conductivity, and a compounding method thereof. It is intended to provide a rubber composition.
- the carbon black and the organosiloxane coexist, and then heated at a temperature lower than the temperature at which the carbon black is incinerated and higher than the temperature at which the organosiloxane decomposes.
- a method for producing a surface-treated carbon black comprising attaching a silicon dioxide residue to a surface of a black carbon black.
- the present inventors have found that, as described above, the rubber has excellent tand temperature dependency, has good abrasion resistance, and is suitable for rubber reinforcement without any problems caused by low electrical conductivity.
- the carbon black and the organosiloxane are combined together at a temperature lower than the temperature at which the carbon black surface is oxidized (usually about 200 ° C). below), or the temperature at which the organosiloxane is decomposed or condensed (generally attached about 6 0 ° C or higher) in carbon black click surface silicon dioxide by heating child (S i 0 2) residues It was found that it was possible to produce the desired power black.
- the organoloxane used as a raw material in the present invention is a known organosiloxane, and examples thereof include those having the following structures.
- R 2 , R 3 and R 4 are one or more selected from generally known organic groups and may be the same or all different.
- organic groups include, for example, C, ⁇ ( 4 alkyl groups, C, ⁇ (: 4 alkoxy groups, alkylamino groups (one RNH 2 ,- R d, etc.)
- an alkylphenyl group such as 1 R- ⁇ 0-0H
- an alkylphenyl group such as 1 R- ⁇ 0-0H
- a particularly preferred organosiloxane is an alkoxysilyl group—SiOR (wherein R is a compound containing an alkyl group having 1 to 4 carbon atoms), and 3 to 100 silicon atoms per molecule. It contains 0 or less, preferably 7 or more, and more preferably 10 or more. If the number of silicon atoms is small, it is not preferable because the contact efficiency and the coupling efficiency on the carbon black become poor. 0 0 0 viscosity becomes high when it exceeds, the process Naru rather difficulties.
- the amount of the organosiloxane 0 carbon black click weight in terms of S i 0 2. 1 ⁇ 5 0% by weight is preferable, and 0.5 to 30% by weight is more preferable.If the amount is too small, the desired effect cannot be obtained as a matter of course. I don't like it because it drops.
- carbon black used as a raw material in the present invention any carbon black conventionally used widely for tires and other rubber compositions can be used.
- Preferred carbon blacks are those of SRF to SAF grades, and can be used in various ways and blended in two or more types depending on the use of the rubber composition.
- a predetermined amount of carbon black (preferably unlicensed) is weighed out.
- organosiloxane 0.5 to 50% by weight is used as the amount of silica.
- This is stirred and mixed at room temperature with a closed powder mixer (for example, a universal mixer manufactured by Dalton).
- the organosiloxane may be added after diluting in an appropriate solvent in order to facilitate dispersion.
- the sufficiently stirred mixture of the organosiloxane and the carbon black is heated, for example, on a hot plate at a temperature in the range of 60 ° C to 200 ° C.
- the carbon black for reinforcing surface-treated rubber according to the present invention is blended with any bridgeable rubber component to obtain a rubber composition having excellent abrasion resistance, grip performance, rolling resistance and the like.
- bridgeable rubbers include natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), and butyl rubber.
- IIR halogenated butyl rubber, acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber, styrene Len-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene copolymer rubber, chlorosulfonated polyethylene, acrylyl rubber, epichlorohydrin rubber, polysulfide Rubber, silicone rubber, fluorine rubber, urethane rubber, etc. can be used, and these can be used alone or in any blend. And can and Mochiiruko and are no particular restrictions on the-plane de ratio Waso when used Puren de.
- the surface-treated carbon black is 100 to 200 parts by weight, more preferably 15 to 150 parts by weight, based on 100 parts by weight of the rubber component. It is preferable to mix parts. This amount If the amount is too small, the rubber cannot be satisfactorily reinforced, thereby deteriorating, for example, wear resistance. Conversely, if the content is too large, the practicality as a rubber material may be poor, for example, the hardness becomes too high or the workability is deteriorated. In addition to the surface treatment force black, any carbon black or silica usually blended with the rubber composition can be used in combination with the rubber composition.
- the rubber composition includes, in addition to the rubber and carbon black having silica adhered to its surface, any compounding agent usually used in the rubber industry, for example, sulfur, an organic peroxide, a softener, An antioxidant, a vulcanization accelerator, a filler, a plasticizer, a silane coupling agent, and the like can be appropriately compounded as required within a usual amount.
- any compounding agent usually used in the rubber industry for example, sulfur, an organic peroxide, a softener, An antioxidant, a vulcanization accelerator, a filler, a plasticizer, a silane coupling agent, and the like can be appropriately compounded as required within a usual amount.
- the surface-treated carbon black sample was ashed at 600 in an electric furnace, the ash was fluorinated, and the weight loss was shown as a silica content as a weight fraction relative to the original surface-treated carbon.
- the measurement was performed according to the method of ASTM D3037.
- the surface-treated blacks 1 and 2 according to the present invention were prepared as follows.
- each component excluding the vulcanization system was kneaded for 3 to 5 minutes with a closed mixer of 1.8 liters, and the mixture was added to the master batch released when it reached 1 65 ⁇ 5.
- the sulfur accelerator and sulfur were kneaded with an 8-inch open roll to obtain a rubber composition.
- the unvulcanized vulcanizability of the obtained rubber composition was measured.
- this composition was press-vulcanized at 160 ° C. for 20 minutes in a mold of 15 ⁇ 15 ⁇ 0.2 cm to obtain a target test piece (rubber sheet).
- -G was prepared, and the vulcanization properties were evaluated by the method described above. The results are shown in Table I.
- 0 is an index of cutgrid performance.
- the tan 5 in C is high and is an indicator of rolling resistance of 60. Since tan 5 in C is low, it is possible to provide a rubber composition having both high wet grip properties and low rolling resistance.
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019980702610A KR100265485B1 (ko) | 1996-08-12 | 1997-06-04 | 고무보강용 표면처리 카본블랙을 함유하는 고무조성물 |
EP19970924318 EP0882769B1 (en) | 1996-08-12 | 1997-06-04 | Process for the production of surface-treated carbon black for the reinforcement of rubbers |
DE1997608849 DE69708849T2 (de) | 1996-08-12 | 1997-06-04 | Verfahren zur herstellung von oberflächenbehandeltem russ zur kautschukverstärkung |
US09/043,729 US6020068A (en) | 1996-08-12 | 1997-06-04 | Process for the production of surface-treated carbon black for the reinforcement of rubbers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21276896A JPH1053722A (ja) | 1996-08-12 | 1996-08-12 | ゴム補強用表面処理カーボンブラックの製造方法 |
JP8/212768 | 1996-08-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998006787A1 true WO1998006787A1 (fr) | 1998-02-19 |
Family
ID=16628084
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1997/001901 WO1998006787A1 (fr) | 1996-08-12 | 1997-06-04 | Procede pour produire un noir de carbone a surface traitee, destine a renforcer les caoutchoucs |
Country Status (6)
Country | Link |
---|---|
US (1) | US6020068A (ja) |
EP (1) | EP0882769B1 (ja) |
JP (1) | JPH1053722A (ja) |
KR (1) | KR100265485B1 (ja) |
DE (1) | DE69708849T2 (ja) |
WO (1) | WO1998006787A1 (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6172137B1 (en) | 1997-08-12 | 2001-01-09 | The Goodyear Tire & Rubber Company | Rubber composition and tire having tread thereof |
US6458458B1 (en) * | 1998-10-13 | 2002-10-01 | Cabot Corporation | Polymer coated carbon products and other pigments and methods of making same by aqueous media polymerizations or solvent coating methods |
DE10030703A1 (de) * | 2000-06-23 | 2002-01-10 | Degussa | Ruß |
KR100387296B1 (ko) * | 2000-11-15 | 2003-06-12 | 한국타이어 주식회사 | 스터드리스 타이어 트레드용 고무 조성물 |
US7339068B2 (en) | 2001-01-31 | 2008-03-04 | Momentive Performance Materials Inc. | Nanosized copper catalyst precursors for the direct synthesis of trialkoxysilanes |
US7858818B2 (en) * | 2001-01-31 | 2010-12-28 | Momentive Performance Materials Inc. | Nanosized copper catalyst precursors for the direct synthesis of trialkoxysilanes |
US7294666B2 (en) | 2001-03-16 | 2007-11-13 | The Goodyear Tire & Rubber Company | Tire with component of rubber composition comprised of silica reinforcement and emulsion polymerization derived terpolymer rubber of diene/vinyl aromatic compound which contains pendant hydroxyl groups |
EP1383776A2 (en) * | 2001-04-30 | 2004-01-28 | Crompton Corporation | Hybrid silicon-containing coupling agents for filled elastomer compositions |
JP5037764B2 (ja) * | 2001-08-27 | 2012-10-03 | 電気化学工業株式会社 | 導電性粉末、その製造方法及び用途 |
US6905767B2 (en) * | 2002-02-01 | 2005-06-14 | The Research Foundation Of State University Of New York | Method for enhancing polymer adhesion using filler particle mix and compositions made using the method |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01126375A (ja) * | 1987-11-10 | 1989-05-18 | Mitsubishi Kasei Vinyl Co | 合成樹脂充填材用被覆無機フィラー |
JPH01182368A (ja) * | 1988-01-14 | 1989-07-20 | Shiseido Co Ltd | 疎水性粉体およびこれを含有する化粧料 |
JPH04190839A (ja) * | 1990-11-24 | 1992-07-09 | Kanebo Ltd | 改質粉体 |
JPH09118781A (ja) * | 1995-10-25 | 1997-05-06 | Yokohama Rubber Co Ltd:The | ゴム補強用表面処理カーボンブラック含有ゴム組成物 |
JPH09118780A (ja) * | 1995-10-25 | 1997-05-06 | Yokohama Rubber Co Ltd:The | タイヤ用ゴム組成物 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3290165A (en) * | 1963-04-01 | 1966-12-06 | Huber Corp J M | Surface modified pigments |
JPS53100190A (en) * | 1977-02-15 | 1978-09-01 | Hokuriku Elect Ind | Method of making carbon black having high electric resistivity |
JPS61291659A (ja) * | 1985-06-19 | 1986-12-22 | Kyowa Yuka Kk | カ−ボンブラツクの改質方法 |
DE3684836D1 (de) * | 1985-07-29 | 1992-05-21 | Shiseido Co Ltd | Mit silikonpolymer ueberzogenes pulver oder teilchenfoermiges material. |
US4670059A (en) * | 1986-02-11 | 1987-06-02 | Hewlett Packard Company | Increased solubility of carbon black |
JPH01284564A (ja) * | 1988-05-11 | 1989-11-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | 表面処理されたカーボンブラック、その製造方法及びその用途 |
JP2748158B2 (ja) * | 1989-07-21 | 1998-05-06 | キヤノン株式会社 | 重合トナーの製造方法 |
DE4023537A1 (de) * | 1990-07-25 | 1992-01-30 | Degussa | Mit organosiliciumverbindungen chemisch modifizierte russe, verfahren zu deren herstellung und deren verwendung |
DE4140794C1 (ja) * | 1991-12-11 | 1993-03-11 | Th. Goldschmidt Ag, 4300 Essen, De | |
JP2854787B2 (ja) * | 1993-08-31 | 1999-02-03 | 信越化学工業株式会社 | シリコーンゴム組成物の製造方法 |
US5489328A (en) * | 1994-01-31 | 1996-02-06 | Shin-Etsu Chemical Co., Ltd. | Water repellent agent |
CN1084358C (zh) * | 1996-04-17 | 2002-05-08 | 三菱化学株式会社 | 经过表面处理的炭黑的制备方法及橡胶组合物 |
-
1996
- 1996-08-12 JP JP21276896A patent/JPH1053722A/ja not_active Ceased
-
1997
- 1997-06-04 US US09/043,729 patent/US6020068A/en not_active Expired - Fee Related
- 1997-06-04 WO PCT/JP1997/001901 patent/WO1998006787A1/ja active IP Right Grant
- 1997-06-04 KR KR1019980702610A patent/KR100265485B1/ko not_active IP Right Cessation
- 1997-06-04 DE DE1997608849 patent/DE69708849T2/de not_active Expired - Lifetime
- 1997-06-04 EP EP19970924318 patent/EP0882769B1/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01126375A (ja) * | 1987-11-10 | 1989-05-18 | Mitsubishi Kasei Vinyl Co | 合成樹脂充填材用被覆無機フィラー |
JPH01182368A (ja) * | 1988-01-14 | 1989-07-20 | Shiseido Co Ltd | 疎水性粉体およびこれを含有する化粧料 |
JPH04190839A (ja) * | 1990-11-24 | 1992-07-09 | Kanebo Ltd | 改質粉体 |
JPH09118781A (ja) * | 1995-10-25 | 1997-05-06 | Yokohama Rubber Co Ltd:The | ゴム補強用表面処理カーボンブラック含有ゴム組成物 |
JPH09118780A (ja) * | 1995-10-25 | 1997-05-06 | Yokohama Rubber Co Ltd:The | タイヤ用ゴム組成物 |
Also Published As
Publication number | Publication date |
---|---|
EP0882769A4 (en) | 1999-05-19 |
KR19990064129A (ko) | 1999-07-26 |
EP0882769A1 (en) | 1998-12-09 |
DE69708849D1 (de) | 2002-01-17 |
EP0882769B1 (en) | 2001-12-05 |
DE69708849T2 (de) | 2002-06-20 |
US6020068A (en) | 2000-02-01 |
JPH1053722A (ja) | 1998-02-24 |
KR100265485B1 (ko) | 2000-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO1997015620A1 (en) | Rubber composition comprising carbon black having surface treated with silica | |
JP2011190450A (ja) | タイヤ用ゴム組成物 | |
JP2008503618A (ja) | 乾燥液状改質剤で製造したシリカ強化エラストマーコンパウンド | |
US7144943B2 (en) | Process for production of modified carbon black for rubber reinforcement and process of production of rubber composition containing modified carbon black | |
WO1998006787A1 (fr) | Procede pour produire un noir de carbone a surface traitee, destine a renforcer les caoutchoucs | |
JP2002309002A (ja) | 充填ブチルエラストマーコンパウンドの製造方法 | |
JPH0790123A (ja) | タイヤトレッド用ゴム組成物 | |
US6469089B2 (en) | Elastomeric compounds with improved wet skid resistance and methods to improve wet skid resistance | |
JP3778662B2 (ja) | タイヤトレッド用ゴム組成物 | |
JPH1135735A (ja) | ゴム組成物 | |
JP4318329B2 (ja) | タイヤトレッド用ゴム組成物 | |
JP4076631B2 (ja) | ゴム組成物 | |
JPH10292127A (ja) | 表面処理されたカーボンブラックおよびそれを用いたゴム組成物 | |
JP2006265400A (ja) | ゴム組成物の製造法及びそれを用いた空気入りタイヤ | |
JP2005015695A (ja) | ゴム組成物 | |
JP4063767B2 (ja) | 表面処理カーボンブラックの製造方法並びにその表面処理カーボンブラック及びそれを含むゴム組成物 | |
JPH11189680A (ja) | ゴム組成物 | |
JPH10152582A (ja) | ゴム補強用充填剤及びそれを用いたゴム組成物 | |
JP2004224898A (ja) | ゴム組成物 | |
JPH11263878A (ja) | ゴム製品の製造方法 | |
JP3608857B2 (ja) | ゴム補強用表面処理カーボンブラック含有ゴム組成物 | |
JP3676875B2 (ja) | ゴム補強用表面処理カーボンブラックの製造方法 | |
JP3635164B2 (ja) | シリカ含有加硫性ゴム組成物 | |
JP2004143249A (ja) | タイヤトレッド用ゴム組成物 | |
JPH10330541A (ja) | 変性ポリブタジエンゴム及びそれを含むゴム組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): KR US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09043729 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1997924318 Country of ref document: EP Ref document number: 1019980702610 Country of ref document: KR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 1997924318 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1019980702610 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1019980702610 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1997924318 Country of ref document: EP |