NO139962B - PROCEDURE FOR IMPROVING THE SURFACE PROPERTIES OF OBJECTS MANUFACTURED BY POLYSTYRENE, POLYAMIDE OR POLYCARBONATE FOR USE IN CULTIVATION OF LIVING CELLS OR TISSUE - Google Patents
PROCEDURE FOR IMPROVING THE SURFACE PROPERTIES OF OBJECTS MANUFACTURED BY POLYSTYRENE, POLYAMIDE OR POLYCARBONATE FOR USE IN CULTIVATION OF LIVING CELLS OR TISSUE Download PDFInfo
- Publication number
- NO139962B NO139962B NO171/73A NO17173A NO139962B NO 139962 B NO139962 B NO 139962B NO 171/73 A NO171/73 A NO 171/73A NO 17173 A NO17173 A NO 17173A NO 139962 B NO139962 B NO 139962B
- Authority
- NO
- Norway
- Prior art keywords
- polystyrene
- cultivation
- objects
- polycarbonate
- polyamide
- Prior art date
Links
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 11
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 10
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 6
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 5
- 239000004952 Polyamide Substances 0.000 title claims abstract description 4
- 229920002647 polyamide Polymers 0.000 title claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 210000004102 animal cell Anatomy 0.000 claims description 4
- 241001465754 Metazoa Species 0.000 claims description 3
- 210000005260 human cell Anatomy 0.000 claims description 3
- 210000001519 tissue Anatomy 0.000 claims description 3
- 239000004033 plastic Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000005855 radiation Effects 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
Abstract
Fremgangsmåte for å forbedre overflateegenskapene hos gjenstander fremstilt av polystyren, polyamid eller polykarbonat for anvendelse ved dyrking av levende celler eller vev.Method for improving the surface properties of articles made from polystyrene, polyamide or polycarbonate for use in the cultivation of living cells or tissues.
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for å for- The present invention relates to a method for
bedre overflateegenskapene hos gjenstander fremstilt av polystyren, polyamid eller polykarbonat for anvendelse ved dyrking av levende animalske eller menneskeceller eller -vev, hvorved gjenstandenes overflater gjøres hydrofile, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at overflaten av gjenstandene bringes i kontakt med et medium omfattende vann og oksygen under samtidig bestråling med UV-lys med dominerende bølgelengde 2540 Å. improve the surface properties of objects made of polystyrene, polyamide or polycarbonate for use in the cultivation of living animal or human cells or tissues, whereby the surfaces of the objects are made hydrophilic, and the distinctive feature of the method according to the invention is that the surface of the objects is brought into contact with a medium comprising water and oxygen under simultaneous irradiation with UV light with a dominant wavelength of 2540 Å.
Ved en særlig foretrukket utførelsesform av fremgangsmåten i henhold til oppfinnelsen bringes gjenstandene i kontakt med atmosfærisk luft inneholdende vanndamp. In a particularly preferred embodiment of the method according to the invention, the objects are brought into contact with atmospheric air containing water vapour.
Gjenstander fremstilt av plast, f.eks. fremstilt av polystyren, Objects made of plastic, e.g. made of polystyrene,
har vist seg uegnet til dyrking av levende animalske eller menneskeceller eller -vev på grunn av at disse materialers overflate-egenskaper forhindrer væsker med høye overflatespenninger, have proven unsuitable for the cultivation of live animal or human cells or tissues due to the fact that the surface properties of these materials prevent liquids with high surface tensions,
spesielt vandige oppløsninger, i å henge fast ved overflatene. Videre er levende celler og vev ikke i stand til å vokse som especially aqueous solutions, in sticking to the surfaces. Furthermore, living cells and tissues are unable to grow as
et monolag på overflaten av slike gjenstander men krøller sammen til dannelse av klumper som ikke kan undersøkes på passende måte. a monolayer on the surface of such objects but crumples to form clumps that cannot be suitably examined.
Det er blitt forsøkt å forbedre overflateegenskapene hos gjenstander av plastmaterial til bruk til medisinske formål ved å underkaste disse gjenstander en sterk gammabestråling til opp-nåelse av en strålingsdose på minst 5 megarad. En slik fremgangsmåte er beskrevet i britisk patentskrift 1.036.237. I praksis har det.imidlertid vist seg at det kreves en strålingsdose på ca. 10,5 megarad og selv når det anvendes en så stor strålingsdose har det vist seg vanskelig å oppnå reproduserbare resultater. Videre har man konstatert at det ved så store strålingsdoser dannes stoffer som er giftige overfor de følsomme celler og vev. Dette viser seg særlig ved langtidsdyrking (opptil 30 døgn) hvor det ved anvendelse av slike bestrålte gjenstander ikke er mulig å opprettholde et ønsket cellelag. Dessuten resulterer den kraftige bestråling i en gulfarging av materialet. Attempts have been made to improve the surface properties of objects made of plastic material for use for medical purposes by subjecting these objects to strong gamma irradiation to achieve a radiation dose of at least 5 megarads. Such a method is described in British patent document 1,036,237. In practice, however, it has been shown that a radiation dose of approx. 10.5 megarad and even when such a large radiation dose is used, it has proved difficult to achieve reproducible results. It has also been established that with such large doses of radiation, substances are formed which are toxic to the sensitive cells and tissues. This is particularly evident in long-term cultivation (up to 30 days) where, when such irradiated objects are used, it is not possible to maintain a desired cell layer. In addition, the strong irradiation results in a yellowing of the material.
Det har nå vist seg at overflaten av gjenstander av de ovennevnte plastmaterialer kan gjøres tilstrekkelig hydrofil til at vev eller celler kan vokse derpå i form av et monolag ved en behandling av overflaten som ikke fører til dannelse av giftige stoffer og som ikke medfører de øvrige ovennevnte ulemper ved tidligere kjente fremgangsmåter. It has now been shown that the surface of objects made of the above-mentioned plastic materials can be made sufficiently hydrophilic so that tissue or cells can grow thereon in the form of a monolayer by treating the surface which does not lead to the formation of toxic substances and which does not entail the other above-mentioned disadvantages of previously known methods.
Når overflaten av en plastgjenstand utsettes for bestråling med ultrafiolett lys under tilstedeværelse av vann og oksygen, dannes store mengder ozon. Ozonet synes å være et viktig mellom-produkt ved reaksjonen med plastmaterialet, og for å øke mengden av dannet ozon er det hensiktsmessig at den ultrafiolette strålingskilde slås på noen tid før behandlingen av plastgjen-standen påbegynnes. When the surface of a plastic object is exposed to ultraviolet light in the presence of water and oxygen, large amounts of ozone are formed. Ozone appears to be an important intermediate in the reaction with the plastic material, and in order to increase the amount of ozone formed, it is appropriate that the ultraviolet radiation source is switched on some time before the treatment of the plastic object begins.
Ozon dekomponeres ved bestråling med et kvanteutbytte på 0,62 mol ozon pr. lyskvantum. Tilstedeværelsen av vann forøker i vesentlig grad dette kvanteutbytte. Ozone is decomposed by irradiation with a quantum yield of 0.62 mol ozone per light quantum. The presence of water substantially increases this quantum yield.
Når en blanding av ozon og vann bestråles kan man iaktta dannelse av fri hydroksylradikaler. Disse hydroksylradikaler omdannes som følge av dekomponeringen av ozon til et oksygenmolekyl og et oksygenatom, hvorav sistnevnte reagerer med vann til dannelse av to hydroksylradikaler. When a mixture of ozone and water is irradiated, the formation of free hydroxyl radicals can be observed. These hydroxyl radicals are converted as a result of the decomposition of ozone into an oxygen molecule and an oxygen atom, the latter of which reacts with water to form two hydroxyl radicals.
Det antas at en av de følgende reaksjoner deretter foregår: It is assumed that one of the following reactions then takes place:
1. Noen av hydroksylradikalene reagerer direkte med plastmaterialet til dannelse av et hydrofilt produkt. Når det dreier seg om polystyren reagerer hydroksylradikalene med en særlig reaktiv form av polystyrenet, som dannes som følge av bestrålingen med ultrafiolett lys. Det har imidlertid vist seg at det også skjer en reaksjon med polystyrenet selv om polystyrenet ikke er blitt omdannet til en slik reaktiv form. 2. Hydroksylradikalene slutter seg sammen i par under dannelse av hydrogenperoksyd som også dekomponerer ved bestråling til dannelse av hydroksylradikaler som deretter kan reagere med plastmaterialet. 1. Some of the hydroxyl radicals react directly with the plastic material to form a hydrophilic product. When it comes to polystyrene, the hydroxyl radicals react with a particularly reactive form of the polystyrene, which is formed as a result of the irradiation with ultraviolet light. However, it has been shown that a reaction also takes place with the polystyrene even if the polystyrene has not been converted into such a reactive form. 2. The hydroxyl radicals join together in pairs to form hydrogen peroxide which also decomposes upon irradiation to form hydroxyl radicals which can then react with the plastic material.
Betydningen av at bestrålingen av gjenstandenes overflate skjer under samtidig tilstedeværelse av vann og oksygen er blitt demonstrert ved noen laboratorieforsøk. The importance of the irradiation of the object's surface taking place in the simultaneous presence of water and oxygen has been demonstrated in some laboratory experiments.
Ved disse laboratorieforsøk ble petriskåler av styren bestrålet med en 15 watt UV-lavtrykkslampe anbragt i en hul sylinder med huller til petriskåler med en diameter på 5 cm. Laboratorie-apparaturen var videre slik innrettet at det gjennom sylinderen kunne føres en gassblanding med gitt sammensetning. De omhand-lede petriskåler ble bestrålt med UV-lys i et tidsrom på 5 min. ved en temperatur på 40°C. De således behandlede petriskåler ble deretter undersøkt til bestemmelse av om de var egnet til dyrking av levende animalske celler eller vev. In these laboratory experiments, petri dishes made of styrene were irradiated with a 15 watt UV low-pressure lamp placed in a hollow cylinder with holes for petri dishes with a diameter of 5 cm. The laboratory equipment was also arranged in such a way that a gas mixture with a given composition could be passed through the cylinder. The treated Petri dishes were irradiated with UV light for a period of 5 min. at a temperature of 40°C. The Petri dishes thus treated were then examined to determine whether they were suitable for growing living animal cells or tissues.
Ved forsøket ble følgende gasser anvendt: The following gases were used in the experiment:
1) tørt nitrogen 1) dry nitrogen
2) fuktig nitrogen 2) moist nitrogen
3) tørt oksygen 3) dry oxygen
4) fuktig oksygen 4) moist oxygen
Uttrykket "fuktig" betyr at gassen var mettet med vanndamp ved 40°C. The term "moist" means that the gas was saturated with water vapor at 40°C.
Undersøkelsene av de behandlede petriskåler viste at de petriskåler som var blitt bestrålt med UV-lys under tilstedeværelse av tørt nitrogen, fuktig nitrogen og tørt oksygen, i motsetning til de skåler som var blitt bestrålt under tilstedeværelse av fuktig oksygen, ikke var egnet til dyrking av celler eller vev. The investigations of the treated petri dishes showed that the petri dishes that had been irradiated with UV light in the presence of dry nitrogen, moist nitrogen and dry oxygen, in contrast to the dishes that had been irradiated in the presence of moist oxygen, were not suitable for the cultivation of cells or tissues.
I stedet for å anvende en oksygenholdig gass inneholdende vanndamp kan vannet påsprøytes eller på annen måte påføres gjen-standens overflate til dannelse av et vannlag på denne. Instead of using an oxygen-containing gas containing water vapour, the water can be sprayed on or otherwise applied to the object's surface to form a water layer on it.
Oksygenet tilveiebringes -som nevnt fortrinnsvis i form av atmosfærisk luft. The oxygen is provided - as mentioned, preferably in the form of atmospheric air.
Når det som UV-strålingskilde anvendes en 15 watt lavtrykks-kvikksølvlampe oppnås en vesentlig virkning på polystyren i løpet av et tidsrom på omtrent 2,5 min. When a 15 watt low-pressure mercury lamp is used as the UV radiation source, a significant effect on the polystyrene is achieved within a period of approximately 2.5 minutes.
Den hydrofile karakter av overflaten av plastgjenstander, som er blitt behandlet ved hjelp av fremgangsmåten i henhold til oppfinnelsen, kommer til uttrykk ved at vinkelen mellom vann-overflaten og overflaten av plastgjenstandene, hvorpå vann er blitt påført, er nesten null, når vinkelen er over null, er overflaten mer eller mindre hydrofob. The hydrophilic character of the surface of plastic objects, which have been treated using the method according to the invention, is expressed by the fact that the angle between the water surface and the surface of the plastic objects, on which water has been applied, is almost zero, when the angle is above zero, the surface is more or less hydrophobic.
Oppfinnelsen skal i det følgende illustreres mer detaljert under henvisning til følgende utførelseseksempler: In the following, the invention will be illustrated in more detail with reference to the following design examples:
EKSEMPEL 1 EXAMPLE 1
Med vann besprøytede polystyrenskåler ble innført i en strøm Polystyrene bowls sprayed with water were introduced into a stream
av atmosfærisk luft mettet med vann ved en temperatur på 40°C og ble bestrålt ved hjelp av en UV-lampe som utsendte lys med en dominerende bølgelengde på 2540 Ångstrøm i 3 min. Den således behandlede overflate var hydrofil. Et ESCA-spektrum av overflaten viser at den inneholder oksygen. of atmospheric air saturated with water at a temperature of 40°C and was irradiated using a UV lamp emitting light with a dominant wavelength of 2540 Angstroms for 3 min. The thus treated surface was hydrophilic. An ESCA spectrum of the surface shows that it contains oxygen.
EKSEMPEL 2 EXAMPLE 2
En med vann besprøytet plate av nylon ("Maranyl F 10 3" (ICI) A water-sprayed sheet of nylon ("Maranyl F 10 3" (ICI)
på kaprolaktambasis (nylon-6)) ble innført i en strøm av vann-mettet atmosfærisk luft ved 35°C og bestrålt ved hjelp av en UV-lampe, som utsendte lys med en dominerende bølgelengde på 2540 Å i 65 min. Den således behandlede overflate var hydrofil. on a caprolactam base (nylon-6)) was introduced into a stream of water-saturated atmospheric air at 35°C and irradiated by means of a UV lamp, which emitted light with a dominant wavelength of 2540 Å for 65 min. The thus treated surface was hydrophilic.
EKSEMPEL 3 EXAMPLE 3
En med vann besprøytet plate av polykarbonat ("Makrolon" (Bayer) på bisfenolbasis) ble innført i en med vann mettet strøm av atmosfærisk luft ved en temperatur på 35°C og bestrålt ved hjelp av en UV-lampe som utsendte lys med en dominerende bølgelengde på 2540 Å i 65 min. Den således behandlede overflate var hydrofil. A water-sprayed sheet of polycarbonate ("Makrolon" (Bayer) on a bisphenol basis) was introduced into a water-saturated stream of atmospheric air at a temperature of 35°C and irradiated by means of a UV lamp emitting light with a dominant wavelength of 2540 Å for 65 min. The thus treated surface was hydrophilic.
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB181872A GB1414671A (en) | 1972-01-14 | 1972-01-14 | Method of improving the surface properties of articles made from a plastics material |
GB3788572 | 1972-08-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
NO139962B true NO139962B (en) | 1979-03-05 |
NO139962C NO139962C (en) | 1979-06-13 |
Family
ID=26237006
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO171/73A NO139962C (en) | 1972-01-14 | 1973-01-12 | PROCEDURE FOR IMPROVING THE SURFACE PROPERTIES OF OBJECTS MANUFACTURED BY POLYSTYRENE, POLYAMIDE OR POLYCARBONATE FOR USE IN CULTIVATION OF LIVING CELLS OR TISSUE |
Country Status (15)
Country | Link |
---|---|
JP (1) | JPS4881966A (en) |
AR (1) | AR197209A1 (en) |
BE (1) | BE793952A (en) |
CA (1) | CA1016332A (en) |
CH (1) | CH571036A5 (en) |
DD (1) | DD106854A5 (en) |
DE (1) | DE2301073A1 (en) |
ES (1) | ES410622A1 (en) |
FR (1) | FR2168013B1 (en) |
GB (1) | GB1414671A (en) |
IE (1) | IE37054B1 (en) |
IL (1) | IL41223A (en) |
IT (1) | IT978154B (en) |
NL (1) | NL7300431A (en) |
NO (1) | NO139962C (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53129263A (en) * | 1977-04-19 | 1978-11-11 | Toshiba Corp | Production of chemical plating substrate |
US6528292B1 (en) * | 1987-05-29 | 2003-03-04 | Aventis Pharmaceuticals Holdings Inc. | Derivatized polystyrene and other polymer supports for spectroscopic studies |
EP0852598A1 (en) * | 1995-09-28 | 1998-07-15 | Kimberly-Clark Worldwide, Inc. | Sulfonated polymers and method of sulfonating polymers |
US5798078A (en) * | 1996-07-11 | 1998-08-25 | Kimberly-Clark Worldwide, Inc. | Sulfonated polymers and method of sulfonating polymers |
AT408227B (en) * | 1999-07-22 | 2001-09-25 | Wolfgang Dr Kern | METHOD FOR MODIFYING POLYMER SURFACES |
FR2891834B1 (en) * | 2005-10-11 | 2007-12-14 | Alchimer Sa | PROCESS FOR MODIFYING SURFACES OF POLYMERS, IN PARTICULAR HYDROXYLATION OF POLYMER SURFACES, AND PRODUCTS SUCH AS OBTAINED |
WO2012048275A2 (en) | 2010-10-08 | 2012-04-12 | Caridianbct, Inc. | Configurable methods and systems of growing and harvesting cells in a hollow fiber bioreactor system |
JP6633522B2 (en) | 2013-11-16 | 2020-01-22 | テルモ ビーシーティー、インコーポレーテッド | Cell growth in bioreactors |
WO2015148704A1 (en) | 2014-03-25 | 2015-10-01 | Terumo Bct, Inc. | Passive replacement of media |
JP6830059B2 (en) | 2014-09-26 | 2021-02-17 | テルモ ビーシーティー、インコーポレーテッド | Scheduled cell feeding |
WO2017004592A1 (en) | 2015-07-02 | 2017-01-05 | Terumo Bct, Inc. | Cell growth with mechanical stimuli |
WO2017205667A1 (en) | 2016-05-25 | 2017-11-30 | Terumo Bct, Inc. | Cell expansion |
US11104874B2 (en) | 2016-06-07 | 2021-08-31 | Terumo Bct, Inc. | Coating a bioreactor |
US11685883B2 (en) | 2016-06-07 | 2023-06-27 | Terumo Bct, Inc. | Methods and systems for coating a cell growth surface |
US11624046B2 (en) | 2017-03-31 | 2023-04-11 | Terumo Bct, Inc. | Cell expansion |
US11629332B2 (en) | 2017-03-31 | 2023-04-18 | Terumo Bct, Inc. | Cell expansion |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE540128A (en) * | 1954-12-27 | |||
US3418066A (en) * | 1966-11-08 | 1968-12-24 | Eastman Kodak Co | Surface oxidation and treatment of polymers |
-
0
- BE BE793952D patent/BE793952A/en unknown
-
1972
- 1972-01-14 GB GB181872A patent/GB1414671A/en not_active Expired
-
1973
- 1973-01-02 IL IL41223A patent/IL41223A/en unknown
- 1973-01-03 IE IE9/73A patent/IE37054B1/en unknown
- 1973-01-10 CH CH222475A patent/CH571036A5/xx not_active IP Right Cessation
- 1973-01-10 DE DE2301073A patent/DE2301073A1/en not_active Withdrawn
- 1973-01-11 AR AR246078A patent/AR197209A1/en active
- 1973-01-11 NL NL7300431A patent/NL7300431A/xx not_active Application Discontinuation
- 1973-01-12 CA CA161,106A patent/CA1016332A/en not_active Expired
- 1973-01-12 NO NO171/73A patent/NO139962C/en unknown
- 1973-01-12 FR FR7301030A patent/FR2168013B1/fr not_active Expired
- 1973-01-12 DD DD168219A patent/DD106854A5/xx unknown
- 1973-01-13 ES ES410622A patent/ES410622A1/en not_active Expired
- 1973-01-15 IT IT19207/73A patent/IT978154B/en active
- 1973-01-16 JP JP48007303A patent/JPS4881966A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
IE37054B1 (en) | 1977-04-27 |
CA1016332A (en) | 1977-08-30 |
NO139962C (en) | 1979-06-13 |
DE2301073A1 (en) | 1973-07-19 |
IL41223A0 (en) | 1973-03-30 |
BE793952A (en) | 1973-05-02 |
ES410622A1 (en) | 1976-01-01 |
FR2168013A1 (en) | 1973-08-24 |
IT978154B (en) | 1974-09-20 |
GB1414671A (en) | 1975-11-19 |
AR197209A1 (en) | 1974-03-22 |
FR2168013B1 (en) | 1976-11-05 |
CH571036A5 (en) | 1975-12-31 |
JPS4881966A (en) | 1973-11-01 |
NL7300431A (en) | 1973-07-17 |
DD106854A5 (en) | 1974-07-05 |
IL41223A (en) | 1977-01-31 |
IE37054L (en) | 1973-07-14 |
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