KR930002391A - 재분산 가능한 코어-셀(core-shell) 폴리머 분말의 제조방법 - Google Patents
재분산 가능한 코어-셀(core-shell) 폴리머 분말의 제조방법 Download PDFInfo
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- KR930002391A KR930002391A KR1019920012262A KR920012262A KR930002391A KR 930002391 A KR930002391 A KR 930002391A KR 1019920012262 A KR1019920012262 A KR 1019920012262A KR 920012262 A KR920012262 A KR 920012262A KR 930002391 A KR930002391 A KR 930002391A
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- 229920000642 polymer Polymers 0.000 title claims 21
- 239000000843 powder Substances 0.000 title claims 14
- 239000011258 core-shell material Substances 0.000 title claims 12
- 238000004519 manufacturing process Methods 0.000 title claims 8
- 238000000034 method Methods 0.000 claims 15
- 239000000203 mixture Substances 0.000 claims 13
- 239000000178 monomer Substances 0.000 claims 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 9
- 150000001875 compounds Chemical class 0.000 claims 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 4
- 239000000839 emulsion Substances 0.000 claims 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- -1 alkyl methacrylate Chemical compound 0.000 claims 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 3
- 239000000920 calcium hydroxide Substances 0.000 claims 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- 150000008064 anhydrides Chemical class 0.000 claims 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000011398 Portland cement Substances 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000003926 acrylamides Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 150000008378 aryl ethers Chemical class 0.000 claims 1
- 229910001567 cementite Inorganic materials 0.000 claims 1
- 239000012986 chain transfer agent Substances 0.000 claims 1
- 229960002887 deanol Drugs 0.000 claims 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 claims 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 1
- 239000001530 fumaric acid Substances 0.000 claims 1
- GENANDRSSKIPII-UHFFFAOYSA-N furan-2,5-dione;3-methylideneoxolane-2,5-dione Chemical compound O=C1OC(=O)C=C1.C=C1CC(=O)OC1=O GENANDRSSKIPII-UHFFFAOYSA-N 0.000 claims 1
- 238000005227 gel permeation chromatography Methods 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 150000003440 styrenes Chemical class 0.000 claims 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Developing Agents For Electrophotography (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
- Polyesters Or Polycarbonates (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Dental Preparations (AREA)
- Medicinal Preparation (AREA)
- Liquid Crystal (AREA)
Abstract
Description
Claims (18)
- 2단계 수용성 에멀죤 연속 중합공정으로 재분산가능한 코어-셀 폴리머 분말을 제조하는 방법에 있어서, (a) 제1단계에서 카복실산 또는 무수물 약 5내지 40%알킬 아크릴레이트 또는 아릴테르 또는 아크릴아미드 또는 메타아크릴아미드 약 0 내지 30%로 이루어진 모노머 혼합용을 형성시키고, (b) 혼합물을 중합하여 셀 폴리머를 형성시키고, (c) 셸을 아민 또는 염기로 중화하고, 그리고 제2단계에서, (d)게산된 Tg가 -65 내지 +35℃가 되도록 알킬 아크릴레이트 또는 메타크릴레이트 또는 스티렌 약70 내지 약 100%및 카복실산의 히드록시알킬 에스테르 또는 알크릴아미드 또는 메타크릴아미드 약 0 내지 약 30%로 이루어진 모노머의 혼합물을 형성시키고, (e) 제2단계 모노머를 제1단계에서 중화한 폴리머와 혼합하고, (f) 제2단계의 혼합된 모노머를 중합하여 수용성 에멀죤 코어-셸 폴리머를 형성시키고, (g)수용성 에먼죤 코어-셸 폴리머를 스프레이-건조에 의해 재분산 가능한 폴리머 분말로 전환하는 것으로 이루어지는 2단계 수용성 에멀죤 연속 중합공정에 의한 재분산 가능한 코어-셸 폴리머 분말의 제조방법.
- 제1항에 있어서, 코어 대 셸의 중향비가 약 95 : 5 내지 약 60 : 40이고, 겔 투과 크로마토 그래피로 측정시, 가수분해된 셸에 있어서 코어의 평균분자량은 100,000 이상이고 셸의 평균분자량은 약 2500 내지 약 12,000인 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제2항에 있어서, 셸의 Tg가 약60℃이상, 바람직하게는 약80℃이상이고, 코어의 Tg는 약-65내지 약+35℃, 바람직하기는 약-40내지 약+25℃인 방법.
- 제1항에 있어서, 셸 및 코어를 구성하는 모노머 혼합물이 메틸아크릴레이트, 에틸 아크릴레이트, 부틸 아크릴레이트, 2-에틸헥실 아크릴레이트, 데실 아크릴레이트, 메틸 메타아크릴레이트, 에틸 메타아크릴레이트, 히드록시에틸 메타아크릴레이트, 히드록시프로필 아크릴레이트, 히드록시프로필 메타아크릴레이트, 부틸 메타아크릴레이트, 아크릴로니트릴, 아크릴산, 메타아크릴산, 이타콘산, 말레산, 푸마르산, 아크릴산 무수물, 메타아크릴산 무수물, 말레산 무수물, 이타콘산 무수물, 푸마르산 무수물, 스티렌, 치환된 스티렌, 비닐 아세트이트 및 다른 C1내지 C12알킬 아크릴레이트 및 메나아크릴레이트, 아크릴아미드, 메타아클릴아미드, N-메틸을 메타아크릴아미드 및 N-메틸을 메타아크릴아미드 및 N-메틸을 아크릴아미드로 구성된 그룹에서 선택되는 재분산 가능한 코어-셸 폴리머 분말의 제조방법.
- 제4항에 있어서, 셸을 구성하는 모노머 혼합물이 셸 총중량 기준으로 카복실산 또는 무수물 약5내지 약40% 및 알킬 아크릴레이트 또는 알킬 메타아크릴레이트 또는 스티렌 약60내지 약95%인 재분산가능한 코어-셀폴리머 분말의 제조방법.
- 제5항에 있어서, 셸을 구성하는 바람직한 모노머 혼합물을 메틸 메타아크릴레이트 및 메타아크릴산인 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제6항에 있어서, 셸을 구성하는 모노머 혼합물을 암모니아, 트리에틸아민, 모에탄올아민, 디메틸아미노에탄올, 수산화나트륨 및 수산화칼슘과 다른 모든 IA 및 IIA족 수산화물등으로 구성된 그룹에서 선택된 염기로 중화하는 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제7항에 있어서, 염기가 중화되는 산의 총당량을 기준하여, 수산화칼슘 약30내지 60% 및 수산화나트륨 약40 내지 70%, 바람직하기는 수산화칼슘 약35내지 50%및 수산화나트륨 약50내지 60%인 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제7항에 있어서, 염기가 암모니아 100%인 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제4항에 있어서, 코어를 구성하는 모노머 혼합물이 코어 총중량 기준으로 카복실산 또는 무수물 또는 아크릴아미드 약0내지 약5%및 알킬아크릴레이트 또는 알킬 메타아크릴레이트 또는 스티렌 약95내지 약100%인 재분산 가능한 코어-셸 폴리머 분말의 제조방법.
- 제10항에 있어서, 코어를 구성하는 바람직한 모노머 혼합물이 부틸아크릴레이트 및 메틸 메타아크릴레이트인 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제10항에 있어서, 코어를 구성하는 바람직한 모노머 혼합물이 부틸아크릴레이트 및 스트레인 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제10항에 있어서, 제1단계 모노머 혼합물을 셀 모노머 형성하도록 다작용성 화합물 존재하에 중합하는 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제13항에 있어서, 다작용성 화합물이 둘이상의 불포화 부위를 갖는 다작용성 화합물, 둘 이상의 분리가능한 원자를 갖는 반응성 쇄 전이제, 하나이상의 불포화 부위와 하나이상의 분리가능한 원자를 갖는 하브리드 다작용성 화합물로 구성된 그룹에서 선택되는 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제14항에 있어서, 다작용성 화합물이 알릴 메타아크릴레이트인 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 제13항에 있어서, 다작용성 화합물이 셸 총중량 기준으로 약 5%미만, 바람직하기는 약 0.5 내지 3.0%로 포함되는 재분산가능한 코어-셸 폴리머 분말의 제조방법.
- 알칼리-가용성 에멀죤 폴리머 셸 및 수-불용성 에멀죤 폴리머 코어를 갖는 코어-셸 폴리머 분말로 이루어지고, 코어 및 셸 폴리머가 다작용성 화합물에 의해 화학적으로 그래프트된, 제1항의 방법으로 제조된 물품.
- 포틀랜드 시멘트 유효량을 제1항의 코어-셸 폴리머 분말 유효량과 혼합하여 이루어지는 시멘타이트 조성물의 개질방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US728,398 | 1991-07-11 | ||
US07/728,398 US5403894A (en) | 1991-07-11 | 1991-07-11 | A redispersible core-shell polymer powder |
Publications (2)
Publication Number | Publication Date |
---|---|
KR930002391A true KR930002391A (ko) | 1993-02-23 |
KR0149877B1 KR0149877B1 (ko) | 1999-05-15 |
Family
ID=24926690
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1019920012262A Expired - Fee Related KR0149877B1 (ko) | 1991-07-11 | 1992-07-10 | 재분산 가능한 코어-셸 폴리머 분말의 제조방법 |
Country Status (25)
Country | Link |
---|---|
US (1) | US5403894A (ko) |
EP (1) | EP0522791B1 (ko) |
JP (1) | JPH05194681A (ko) |
KR (1) | KR0149877B1 (ko) |
CN (1) | CN1042435C (ko) |
AT (1) | ATE135019T1 (ko) |
AU (1) | AU657965B2 (ko) |
BR (1) | BR9202580A (ko) |
CA (1) | CA2073154A1 (ko) |
CZ (1) | CZ217092A3 (ko) |
DE (1) | DE69208754T2 (ko) |
ES (1) | ES2086657T3 (ko) |
FI (1) | FI923192L (ko) |
HK (1) | HK160996A (ko) |
HU (1) | HU214105B (ko) |
IE (1) | IE922267A1 (ko) |
IL (1) | IL102469A (ko) |
MX (1) | MX9204036A (ko) |
NO (1) | NO922664L (ko) |
NZ (1) | NZ243439A (ko) |
PL (1) | PL171898B1 (ko) |
SI (1) | SI9200144A (ko) |
SK (1) | SK217092A3 (ko) |
TW (1) | TW219367B (ko) |
ZA (1) | ZA924957B (ko) |
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-
1991
- 1991-07-11 US US07/728,398 patent/US5403894A/en not_active Expired - Lifetime
-
1992
- 1992-06-30 AU AU18693/92A patent/AU657965B2/en not_active Ceased
- 1992-07-01 DE DE69208754T patent/DE69208754T2/de not_active Expired - Fee Related
- 1992-07-01 EP EP92306097A patent/EP0522791B1/en not_active Expired - Lifetime
- 1992-07-01 AT AT92306097T patent/ATE135019T1/de not_active IP Right Cessation
- 1992-07-01 ES ES92306097T patent/ES2086657T3/es not_active Expired - Lifetime
- 1992-07-03 NZ NZ243439A patent/NZ243439A/en unknown
- 1992-07-03 CA CA002073154A patent/CA2073154A1/en not_active Abandoned
- 1992-07-03 ZA ZA924957A patent/ZA924957B/xx unknown
- 1992-07-07 NO NO92922664A patent/NO922664L/no unknown
- 1992-07-09 MX MX9204036A patent/MX9204036A/es not_active IP Right Cessation
- 1992-07-10 CZ CS922170A patent/CZ217092A3/cs unknown
- 1992-07-10 SI SI19929200144A patent/SI9200144A/sl unknown
- 1992-07-10 KR KR1019920012262A patent/KR0149877B1/ko not_active Expired - Fee Related
- 1992-07-10 IE IE226792A patent/IE922267A1/en not_active Application Discontinuation
- 1992-07-10 FI FI923192A patent/FI923192L/fi not_active Application Discontinuation
- 1992-07-10 HU HU9202284A patent/HU214105B/hu not_active IP Right Cessation
- 1992-07-10 JP JP4184088A patent/JPH05194681A/ja active Pending
- 1992-07-10 PL PL92295245A patent/PL171898B1/pl unknown
- 1992-07-10 SK SK2170-92A patent/SK217092A3/sk unknown
- 1992-07-10 BR BR929202580A patent/BR9202580A/pt not_active IP Right Cessation
- 1992-07-10 IL IL10246992A patent/IL102469A/en not_active IP Right Cessation
- 1992-07-11 CN CN92105647A patent/CN1042435C/zh not_active Expired - Fee Related
- 1992-08-15 TW TW081106460A patent/TW219367B/zh active
-
1996
- 1996-08-29 HK HK160996A patent/HK160996A/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FI923192L (fi) | 1993-01-12 |
ES2086657T3 (es) | 1996-07-01 |
JPH05194681A (ja) | 1993-08-03 |
MX9204036A (es) | 1993-01-01 |
SI9200144A (en) | 1993-03-31 |
ZA924957B (en) | 1993-03-31 |
DE69208754T2 (de) | 1996-09-19 |
DE69208754D1 (de) | 1996-04-11 |
KR0149877B1 (ko) | 1999-05-15 |
AU1869392A (en) | 1993-01-14 |
CN1042435C (zh) | 1999-03-10 |
HU9202284D0 (en) | 1992-10-28 |
US5403894A (en) | 1995-04-04 |
CA2073154A1 (en) | 1993-01-12 |
TW219367B (ko) | 1994-01-21 |
EP0522791A1 (en) | 1993-01-13 |
HU214105B (en) | 1997-12-29 |
SK217092A3 (en) | 1995-02-08 |
HK160996A (en) | 1996-09-06 |
ATE135019T1 (de) | 1996-03-15 |
HUT63864A (en) | 1993-10-28 |
AU657965B2 (en) | 1995-03-30 |
IL102469A0 (en) | 1993-01-14 |
IE922267A1 (en) | 1993-01-13 |
FI923192A0 (fi) | 1992-07-10 |
IL102469A (en) | 1995-03-30 |
NZ243439A (en) | 1994-10-26 |
CZ217092A3 (en) | 1993-01-13 |
PL295245A1 (en) | 1993-04-05 |
NO922664L (no) | 1993-01-12 |
CN1068337A (zh) | 1993-01-27 |
NO922664D0 (no) | 1992-07-07 |
BR9202580A (pt) | 1993-03-16 |
PL171898B1 (pl) | 1997-06-30 |
EP0522791B1 (en) | 1996-03-06 |
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