SI22417A - Plates with antinoise and antifragmentation properties based on acrylic glass, process for their preparation and use thereof - Google Patents
Plates with antinoise and antifragmentation properties based on acrylic glass, process for their preparation and use thereof Download PDFInfo
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- SI22417A SI22417A SI200600290A SI200600290A SI22417A SI 22417 A SI22417 A SI 22417A SI 200600290 A SI200600290 A SI 200600290A SI 200600290 A SI200600290 A SI 200600290A SI 22417 A SI22417 A SI 22417A
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F8/00—Arrangements for absorbing or reflecting air-transmitted noise from road or railway traffic
- E01F8/0005—Arrangements for absorbing or reflecting air-transmitted noise from road or railway traffic used in a wall type arrangement
- E01F8/0017—Plate-like elements
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Abstract
Description
Tehnično področje, v katero spada izumTechnical field of the invention
Predloženi izum se nanaša na plošče na osnovi polimetilmetakrilata (t.im. akrilnega stekla) z vključenimi ojačitvenimi polimernimi monofilamentnimi vlakni v obliki tridimenzionalnega prepleta vlaken, pri čemer so ojačitvena polimerna monofilamentna vlakna v polimetilmetakrilatno matrico vključena tako, da so vlakna v njej usmeijena v vse smeri in razporejena navidez enakomerno v vseh smereh, tako da so navidez enakomerno porazdeljena v bistvu skozi celoten prečni prerez plošče oziroma preko njenega celotnega volumna. Predloženi izum se nanaša tudi na postopek izdelave takšnih plošč in njihovo uporabo.The present invention relates to panels based on polymethylmethacrylate (i.e., acrylic glass) incorporating reinforcing polymer monofilament fibers in the form of a three-dimensional fiber interlacing, wherein reinforcing polymer monofilament fibers in the polymethylmethacrylate matrix are incorporated therein so that directions and arranged apparently evenly in all directions, so that they are apparently evenly distributed substantially throughout the entire cross-section of the slab or over its entire volume. The present invention also relates to a process for the manufacture of such panels and their use.
Se zlasti se predloženi izum nanaša na transparentne plošče na osnovi polimetilmetakrilata (PMMA), v katerega so vključena poliamidna monofilamentna vlakna, ki so v obliki tridimenzionalnega prepleta oz. vlaknovine, navidez enakomerno skozi v bistvu celoten prečni prerez plošče oz. preko njenega celotnega voluma. Te plošče so še zlasti primerne kot protihrupni elementi za ograje na avtocestah, mostovih, viaduktih in podobnem, ker imajo poleg protihrupnih lastnosti zaradi vgrajenih ojačitvenih polimernih monofilamentnih vlaken tudi dobre protizlomne in protifragmentacijske lastnosti.In particular, the present invention relates to transparent plates based on polymethylmethacrylate (PMMA), which includes polyamide monofilament fibers, which are in the form of a three-dimensional interlacing. fiber, apparently evenly throughout substantially the entire cross-section of the slab, respectively. across its entire volume. These panels are especially suitable as noise barrier components for highways, bridges, viaducts, and the like, because they have good anti-burglary and anti-fragmentation properties in addition to their noise-canceling properties due to their built-in reinforcing polymer monofilament fibers.
Stanje tehnikeThe state of the art
Protihrupne plošče na osnovi akrilnega stekla z vključenimi ojačitvenimi monofilamentnimi nitmi in njihova izdelava so bile opisane že v EP 0 407 852 A2. V tem dokumentu so opisane plošče, ki imajo, glede na njihov prečni prerez, približno sredinsko nameščene monofilamentne niti iz plastičnega materiala (poliamida) ali iz njih izdelano mrežasto tkanino. Izdelava teh plošč poteka tako, da se monofilamentne niti, ki imajo prednostni premer od 0,2 do 2 mm, napnejo skozi kalup, nakar se vanj vlije predpolimer na osnovi akrilatov. Po eni izvedbi so niti nameščene vzporedno, pri čemer je razdalja med nitmi med 8 in 100 mm, niti pa so lahko tudi v obliki mreže (t.j. niti so nameščene pod kotom 90°).Acrylic-based noise-absorbing panels with reinforcing monofilament yarns included and their manufacture have already been described in EP 0 407 852 A2. This document describes panels which, depending on their cross-section, have approximately centrally-mounted monofilament threads of plastic material (polyamide) or mesh fabric. The production of these sheets is carried out in such a way that the monofilament threads, having a preferred diameter of 0.2 to 2 mm, are threaded through the mold and then the acrylate-based pre-polymer is poured into it. In one embodiment, the threads are arranged in parallel, with the spacing between the threads being between 8 and 100 mm, nor can they be grid-shaped (i.e., the threads are positioned at a 90 ° angle).
V dokumentu EP 0 826 832 A2 so opisane protihrupne plošče s protifragmentacijskimi lastnostmi, izdelane iz akrilnih polimerov in z vključenimi monofilamentnimi nitmi, ki pa niso nameščene sredinsko glede na prečni prerez plošče. V dokumentu je opisano, da so niti nameščene v debelini med 20 in 35 % celotne debeline plošče, in sicer proti površini, nasprotni tisti, ki je izpostavljena naletu vozila oz. udarcu. Iz tega izhaja, da je zaradi lege vlaken pomembno, katera površina plošče je izpostavljena udarcu oz. naletu vozila, zaradi česar lahko ploščo glede na njene mehanske lastnosti opredelimo kot dvostransko - ena stran plošče je v bistvu bolj ojačena za mehanske obremenitve kot druga. Opisano je tudi, da imajo monofilamentne niti splošno premer med 0,1 in 4 mm, prednostno med 2 in 3 mm. Niti ali trakovi, izdelani iz njih, so nameščeni v razdalji od 10 do 100 mm. Tudi v tem primeru gre za v bistvu planamo strukturo vdelanih niti (niti so v eni ravnini) t.j. gre za napete niti, mrežo ali trakove. Monofilamentne niti so napete skoz kalup bodisi vzporedno ali pa v obliki trakov ali mreže. V primeru trakov imajo le-ti širino 5-25 mm in debelino, ki je enaka tisti, ki jo imajo monofilamente niti, iz katerih so izdelani.EP 0 826 832 A2 describes noise-absorbent panels with anti-fragmentation properties made of acrylic polymers and included monofilament threads, which are not centrally located with respect to the cross-section of the panel. The document describes that the threads are located in a thickness between 20 and 35% of the total thickness of the plate, against the surface opposite to the one exposed to the collision of the vehicle or. blow. It follows that, because of the position of the fibers, it is important which surface of the plate is exposed to impact or. when the vehicle is struck, which makes it possible to characterize the plate as two-sided in terms of its mechanical properties - one side of the plate is substantially stronger for mechanical loads than the other. Monofilament filaments are also described to have a general diameter of between 0.1 and 4 mm, preferably between 2 and 3 mm. Threads or strips made of them are located within a distance of 10 to 100 mm. Again, this is basically a planar structure of embedded threads (nor are they in one plane), i.e. they are strained threads, netting or ribbons. Monofilament threads are threaded through the mold either in parallel or in the form of strips or netting. In the case of strips, they have a width of 5-25 mm and a thickness equal to that of the monofilament of the threads from which they are made.
V tem dokumentu ni opisano, na kakšen način se niti vgradijo v ploščo oz. na kakšen način se doseže ustrezna lega vgrajenih niti v teku postopka izdelave plošče oz. ob polimerizaciji PMMA.This document does not describe how they are even installed in the panel or in the panel. how to achieve the proper position of the embedded threads during the process of making the board or. upon polymerization of PMMA.
Tudi EP 1 119 662 BI (WO 00/20690 Al) opisuje protihrupne plošče iz akrilnega stekla, ki imajo v akrilno matrico vključene monofilamentne niti z namenom izboljšati protifragmentacijske lastnosti plošč in ki imajo maksimalno odstopanje 1 mm ali več, prednostno 5 mm, od namišljene ravne črte, ki teče skozi konca te niti. Poliamidne ali polipropilenske niti so lahko vstavljene v ploščo prečno ali vzporedno z ravnino plošče. Niti so lahko vključene tako, da so med seboj vzporedne in tečejo v eni smeri, lahko pa tečejo med seboj vzporedno tudi v več smereh. Premer uporabljenih niti je od 0,2 do 2,0 mm, razdalja med sosednjimi nitmi pa je lahko v območju med 8 in 100 mm. Ena izmed izvedbenih variant je, da so niti vstavljene tako, da je v prečnem prerezu vidna valovita razporeditev niti. Tudi v tem primeru gre za niti, ki so razporejene vzporedno in v bistvu planamo. Iz primerov je razvidno, da so tudi tu v postopku izdelave plošče niti vstavljene v ploščo tako, da so napete skozi kalup.EP 1 119 662 BI (WO 00/20690 Al) also describes acrylic glass noise panels incorporating monofilament threads in the acrylic matrix to improve the anti-fragmentation properties of the panels and having a maximum deviation of 1 mm or more, preferably 5 mm, from the imaginary straight lines running through the ends of this thread. Polyamide or polypropylene threads may be inserted into the plate transversely or parallel to the plane of the plate. The threads can be incorporated in such a way that they are parallel to each other and flow in one direction, or they can flow in parallel in several directions. The diameter of the threads used is 0.2 to 2.0 mm, and the distance between adjacent threads may be in the range of 8 to 100 mm. One embodiment is that the threads are inserted so that a wavy arrangement of the threads is visible in the cross-section. Here again, the threads are arranged in parallel and basically planed. The examples show that even here in the process of making the board, the threads are inserted into the board so that they are tensioned through the mold.
V dosedanjih rešitvah, znanih iz stanja tehnike, se v ploščo na osnovi akrilnih polimerov niti vključijo torej tako, da se jih napne skozi kalup, nakar se v kalup vlije predpolimer, ki tvori polimerno matrico (npr. PMMA). Za napenjanje je potreben mehanizem za vstavljanje in vzdrževanje pozicije niti vse od sestave kalupa do konca udje vanj a polimetilmetakrilata. Niti so napete v nekem točno določenem redu oz. določeni porazdelitvi, kije pogojena med drugim tudi z napenjalnim orodjem, kar ima za posledico neojačene dele med vzporedno razporejenimi nitmi, t.j. na mestih, kjer je samo PMMA. Poleg tega zahteva napenjanje monofilamentnih niti ali mreže ali pasov pri postopku izdelave ojačene akrilne plošče tudi nek določen dodatni čas. Prav tako ni razvidno, da bi bile mnofilamentne niti navidez enakomerno porazdeljene skozi celoten prečni prerez plošče in s tem skozi celoten volumen plošče.In the prior art, the acrylic polymers based on the prior art are thus incorporated into the plate by tensioning them through the mold, after which a pre-polymer forming a polymer matrix (eg PMMA) is poured into the mold. Tensioning requires a mechanism for inserting and maintaining the position of the thread from polymethyl methacrylate to the end of the mold. Neither are strained in some exact order or. certain distributions, which are conditioned, inter alia, by the tensioning tool, which results in non-reinforced parts between parallel threads, i.e. in places where there is only PMMA. In addition, the tensioning of the monofilament threads or the net or straps also requires some additional time in the process of making the reinforced acrylic sheet. It is also not apparent that the multifilament threads are apparently evenly distributed throughout the cross-section of the plate and thus throughout the plate volume.
Rešitev tehničnega problema in podroben opis izumaThe solution of a technical problem and a detailed description of the invention
Predloženi izum se nanaša na plošče na osnovi polimetilmetakrilata s vključenimi ojačitvenimi polimernimi monofilamentnimi vlakni v obliki tridimenzionalnega prepleta vlaken, ki so v polimetilmetakrilatno matrico vključena tako, da so v plošči usmeijena v vse smeri in razporejena navidez enakomerno v vseh smereh, tako da so vlakna navidez enakomerno porazdeljena v bistvu skozi celoten prečni prerez plošče oz. skozi njen celoten volumen.The present invention relates to polymethylmethacrylate-based panels incorporating reinforcing polymer monofilament fibers in the form of a three-dimensional interlacing of fibers which are incorporated into the polymethylmethacrylate matrix in such a way that they are oriented in all directions and arranged in a uniform manner in all directions evenly distributed throughout the entire cross-section of the slab or slab. throughout its entire volume.
Razporeditev skozi v bistvu celoten prečni prerez plošče oz. skozi njen volumen pomeni, da je preplet vlaken razporejen preko vsaj 90 % njenega celotnega prečnega prereza oz. volumna.Arrangement through essentially the entire cross-section of the slab or slab. through its volume means that the fiber interlacing is spread over at least 90% of its total cross-section, or. volume.
Ojačitvena polimerna monofilamentna vlakna so v ploščo v smislu izuma vključena v obliki tridimenzionalnega prepleta vlaken oz. vlaknovine. Torej so plošče v smislu izuma ojačene v vseh (treh) smereh. Do sedaj ni znano, da bi obstajale plošče iz akrilnega stekla s vključenimi tridimezonalnimi prepleti vlaken, kot tudi ne, da bi se pri postopku izdelave ojačenih plošč iz akrilnega stekla za ojačitev in izboljšanje njihovih protifragmentacijskih lastnosti uporabljali tridimenzionalni prepleti polimernih vlaken.Reinforcing polymeric monofilament fibers are included in the plate of the invention in the form of a three-dimensional interlacing of fibers. fiber. Therefore, the panels of the invention are reinforced in all (three) directions. Up to now, it is not known that there are any acrylic sheets with included three-dimensional fiber interlaces, nor that in the process of making reinforced acrylic glass panels, three-dimensional polymer fiber interlaces are used to reinforce and improve their anti-fragmentation properties.
Plošče v smislu izuma so še zlasti primerne kot protihrupni elementi npr. na avtocestah, mostovih, viaduktih, uporabljajo pa se lahko tudi v fasadnih sistemih zgradb, za predelne stene, stopniščne ograje ipd. Zaradi monofolamentnih vlaken, ki so v ploščo vključena preko njenega celotnega prečnega prereza, imajo plošče v smislu izuma izboljšane protizlomne oz. protifragmentacijske lastnosti, saj lahko npr. v primeru naleta vozila v protihrupni element ob cesti preprečijo odpadanje tudi majhnih zlomljenih delcev protihrupnega elementa na cestišče ah v okolje. Plošče v smislu izuma lahko uporabimo tudi pri delovnih napravah in strojih, kjer je potrebna zaščita pred naletavanjem delcev, pri katerih se za tovrstno zaščito sedaj uporabljajo plošče iz neojačenega PMMA ah polikarbonata. V primeru zloma plošče z vgrajenimi polimernimi, prednostno poliamidnimi vlakni v smislu izuma, vgrajena vlakna preprečujejo nastajanje in odpadanje tudi majhnih zlomljenih delcev, saj se le-ti oprimejo vgrajenih poliamidnih vlaken.The panels of the invention are particularly suitable as noise elements e.g. on motorways, bridges, viaducts, and may also be used in facade systems of buildings, partitions, stair railings, etc. Due to the monofilament fibers incorporated into the plate through its entire cross-section, the panels according to the invention have improved anti-burglary and anti-fragmentation properties, since e.g. in the event of a vehicle being hit by a noise element on the side of the road, they also prevent small fractured particles of the noise element from entering the roadway ah into the environment. The panels according to the invention can also be used in work machines and machines which require particle collision protection, in which non-reinforced PMMA ah polycarbonate panels are now used for such protection. In the case of a panel break with embedded polymeric, preferably polyamide fibers according to the invention, the embedded fibers prevent the formation and deposition of even small fractured particles as they adhere to the embedded polyamide fibers.
Predloženi izum se nanaša tudi na nov postopek izdelave plošč na osnovi polimetilmetakrilata s vključenimi ojačitvenimi polimernimi monofilamentnimi vlakni v obliki tridimenzionalnega prepleta vlaken.The present invention also relates to a new process for the manufacture of polymethylmethacrylate based panels with included reinforcing polymer monofilament fibers in the form of a three-dimensional fiber interlacing.
Podrobneje postopek izdelave plošč v smislu izuma poteka tako, daIn more detail, the process of making the panels according to the invention is carried out in such a way that
- se v delno zgotovljen kalup, ki ga na eni strani predstavlja plošča iz kaljenega stekla, na katero je nameščeno ustrezno tesnilo,- into a partially finished mold, represented on one side by a toughened-glass panel, to which a suitable seal is fitted,
- položijo ojačitvena polimerna monofilamentna vlakna v obliki tridimenzionalnega prepleta vlaken, ki ima sposobnost ohraniti obliko skozi dolgo časovno obdobje, pri čemer so vlakna v tem prepletu usmeijena v vse smeri in navidez enakomerno razporejena v vseh smereh, na način, da je preplet vlaken nameščen po celotni površini delno zgo to vij enega kalupa,- lay reinforcing polymer monofilament fibers in the form of a three-dimensional fiber interlacing capable of maintaining shape over a long period of time, with the fibers in this strand being oriented in all directions and apparently evenly spaced in all directions, such that the fiber strand is positioned along the whole surface partly due to the screw of one mold,
- nakar se na tako pripravljeno konstrukcijo položi druga plošča iz kaljenega stekla in kalup fiksira,- a second toughened glass plate is then laid on the structure thus prepared and the mold fixed,
- nato pa se v tako pripravljen kalup vlije predhodno pripravljen ustrezen predpolimer na osnovi metilmetakrilata,- then a pre-prepared methylmethacrylate-based prepolymer is poured into the mold thus prepared,
- čemur sledijo v stroki znane faze polimerizacije in razkaljupljenja, tako da se na koncu dobi polimetilmetakrilatna plošča s vključenimi vlakni.- followed in the art by a known phase of polymerisation and crushing to obtain a polymethylmethacrylate board with fibers included.
Pri postopku v smislu izuma ni potrebno vzdrževanje vstavljenih vlaken v kalupu z namenom zagotoviti enakomerno razporeditev vlaken skozi celoten volumen končne plošče, saj ima uporabljen tridimenzionalni preplet vlaken dovoljšnjo trdnost, da vlakna ostanejo na mestu in se v kalupu zaradi lastne teže ne posedajo. Ustrezna postavitev vlaken skozi celoten prečni presek končne plošče se doseže sama po sebi na račun debeline prepleta poliamidnih vlaken (ki je v bistvu enak debelini končnega produkta), ki so na tak način razporejena v bistvu preko celotnega volumna plošče. Postopek v smislu izuma ne zahteva dodatnih napenjalnih mehanizmov za napenjanje ojačitvenih polimernih monofilamentnih niti, zaradi česar je postopek enostavnejši, saj odpade faza napenjanja niti, hkrati pa je zato tudi krajši.The method of the invention does not require the maintenance of the inserted fibers in the mold in order to ensure a uniform distribution of the fibers throughout the volume of the endplate, since the three-dimensional interlocking of the fibers used is of sufficient strength so that the fibers remain in place and remain in the mold due to their own weight. Proper placement of fibers throughout the cross-section of the endplate is achieved by itself at the expense of the thickness of the interweaving polyamide fibers (substantially equal to the thickness of the final product), which are thus substantially distributed over the entire volume of the panel. The process of the invention does not require additional tensioning mechanisms to strain the reinforcing polymer monofilament threads, which makes the process simpler as the thread tensioning phase is eliminated and therefore shorter.
Primerna ojačitvena monofilamentna polimerna vlakna za uporabo v smislu izuma so lahko polietilenska, polikarbonatna, poliamidna ali polipropilenska vlakna, ki so bila predhodno oblikovana, npr. z ekstrudiranjem, v tridimenzionalni preplet vlaken oz.Suitable reinforcing monofilament polymer fibers for use according to the invention may be polyethylene, polycarbonate, polyamide or polypropylene fibers that have been preformed, e.g. by extrusion, into a three-dimensional interweaving of fibers, respectively.
vlaknovino, ki ima sposobnost ohraniti obliko (debelino in širino) skozi dolgo časovno obdobje. Preplet je narejen v bistvu iz neskončnih vlaken.fiber that has the ability to retain shape (thickness and width) over a long period of time. The braid is made essentially of endless fibers.
V prednostni izvedbi predloženega izuma so v ploščo na osnovi polimetilmetakrilata vključena poliamidna monofilamentna vlakna v obliki tridimenzionalnega prepleta, ki je samostoječa tridimenzionalna tvorba. Vlakna, prednostno poliamidna vlakna, imajo lahko premer od 0,2 do 2 mm, prednostno od 0,5 do 0,8 mm, še zlasti prednostno 0,7 mm.In a preferred embodiment of the present invention, the polymethylmethacrylate-based panel includes polyamide monofilament fibers in the form of a three-dimensional interlacing, which is a self-contained three-dimensional formation. Fibers, preferably polyamide fibers, may have a diameter of 0.2 to 2 mm, preferably 0.5 to 0.8 mm, in particular 0.7 mm.
Masa tridimenzionalnega prepleta polimernih monofilamentnih vlaken, prednostno poliamidnih vlaken, ki se lahko uporablja v smislu predloženega izuma, je lahko med 50 in 1000 g/m2. V prednostni izvedbi ima tridimenzionalni preplet poliamidnih vlaken maso med 300 do 500 g/m .The mass of the three-dimensional interlacing of polymeric monofilament fibers, preferably polyamide fibers, which can be used according to the present invention may be between 50 and 1000 g / m 2 . In a preferred embodiment, the three-dimensional interweaving of the polyamide fibers has a mass between 300 and 500 g / m.
V odvisnosti od končnega namena uporabe plošč v smislu izuma imajo plošče lahko debelino od 3 mm do 100 mm, prednostno od 3 do 25 mm.Depending on the end use of the panels according to the invention, the plates may have a thickness of from 3 mm to 100 mm, preferably from 3 to 25 mm.
V še zlasti prednostni izvedbi plošče v smislu izuma je v ploščo vključen preplet vlaken, v katerem imajo poliamidna vlakna premer 0,7 mm, pri čemer ima preplet debelino 13,5 ± 0,5 mm in maso 380 ± 20 g/m , izgotovljena plošča pa ima debelino okoli 15 mm. V takem primeru predstavlja masa vključenih vlaken približno 2,5 % celotne mase končnega izdelka.In a particularly preferred embodiment of the board of the invention, the board includes a fiber strand in which the polyamide fibers are 0.7 mm in diameter, with a thickness of 13.5 ± 0.5 mm and a mass of 380 ± 20 g / m, made the panel has a thickness of about 15 mm. In such a case, the mass of the fibers involved constitutes approximately 2.5% of the total mass of the finished product.
V plošče v smislu izuma je lahko vključen ojačitveni tridimenzionalni preplet, ki je izdelan iz vlaken vseh barv, pač v odvisnosti od končnega namena uporabe izdelka in tudi želenih dekorativnih učinkov. Prednostno je v plošče vključen preplet vlaken iz brezbarvnih (transparentnih) poliamidnih vlaken. S vključitvijo prepleta iz brezbarvnih poliamidnih vlaken v ploščo zagotovimo, da se skozi ploščo v smislu izuma prepusti vsaj 90 % vpadnega svetlobnega toka, saj se svetloba lahko presvetli tudi skozi ojačitvena vlakna.The panels of the invention may include a reinforcing three-dimensional web made of fibers of all colors, depending on the end use of the product and the desired decorative effects. Preferably, the panels include a combination of colorless (transparent) polyamide fibers. By incorporating colorless polyamide fibers into the panel, it is ensured that at least 90% of the incident light flux is passed through the panel of the invention, since light can also be transmitted through the reinforcing fibers.
Prepuščena svetloba se zaradi različnih lomnih količnikov PMMA matrice in poliamidnih vlaken v izdelku različno lomi. V odvisnosti od tega, kakšen je premer in preplet vlaken v prepletu, ki ga vstavimo v PMMA matrico, lahko z ustrezno dovolj veliko debelino in gostoto vlaken zagotovimo dovolj dobro vidnost ojačitvenega prepleta v plošči, s čimer se lahko, npr. ob njeni uporabi kot protihrupni cestni element, zmanjša verjetnost za zaletavanje ptic v sicer prosojen protihrupni cestni element.Due to the different refractive indexes of the PMMA matrix and the polyamide fibers in the product, the transmitted light is differently refracted. Depending on the diameter and interlacing of the fibers in the interlacing, which is inserted into the PMMA matrix, a sufficiently high thickness and density of fibers can be provided to give sufficient visibility to the reinforcement interlacing in the plate, which can, e.g. when used as an anti-noise road element, it reduces the likelihood of birds hitting an otherwise noisy road element.
Plošča v smislu izuma ima zaradi enakomerne porazdelitve vlaken v vse smeri in v bistvu skozi njen celoten volumen obe strani z v bistvu enakimi mehanskimi lastnostmi. Pri njej se ne pojavlja t.im. dvostranskost, se pravi razlika v lastnostih ene in druge strani plošče, zaradi česar pri montaži plošče na končni objekt, kot npr. protihrupni cestni element, ni potrebno paziti, s katero stranjo je obrnjena proti cestišču.The plate of the invention has both sides with substantially identical mechanical properties due to the uniform distribution of the fibers in all directions and substantially throughout its entire volume. It does not appear so. two-sided, that is, a difference in the properties of one side and the other of the board, resulting in the mounting of the board to the final object, such as a. Noise road element, no need to be careful which side faces the road.
Na račun enakomerne razporeditve niti po celotnem volumnu plošče in na račun enakomernejše gostote vlaken v vsakem kubičnem centimetru plošče se lahko napetosti, ki se pojavijo v materialu pri udarcu v ploščo, prenesejo na večje število vlaken. Poleg tega predvidevamo, da ima plošča večjo trdnost tudi zaradi tega, ker vlakna niso prednapeta oz. v njih ni napetosti kot posledice predhodnega napetja niti na ogrodje oz. kalup z namenom njihove vgradnje v ploščo. Zaradi tega lahko takšna plošča zdrži večje obremenitve, pričakujemo pa lahko, da bodo tudi majhni delci, ki nastanejo pri razbitju plošče, obviseli na vključenih ojačitvenih vlaknih in ob zlomu plošče ne bodo padali v okolico, na primer, v primeru uporabe plošč kot protihrupne ograje ob cestišču, na cestišče.Due to the even distribution of the entire volume of the plate and due to the more uniform fiber density in each cubic centimeter of the plate, the stresses that occur in the material upon impacting the plate can be transferred to a larger number of fibers. In addition, it is assumed that the board has a higher strength also because the fibers are not prestressed. they do not have any voltage as a consequence of the pre-stress, nor on the frame or. mold for the purpose of fitting them into the plate. As a result, such a plate can withstand heavy loads, and it can be expected that even small particles resulting from the breaking of the plate will depend on the reinforcing fibers involved and will not fall into the surroundings when the plate breaks, for example, in the case of panels being used as noise barrier. along the roadway to the roadway.
Ker je v plošči v smislu izuma več ojačitvenih vlaken in so le-ta so v primeijavi s ploščami iz stanja tehnike razporejena enakomerneje preko celotnega volumna plošče, je izboljšana udarna obstojnost plošč. Udarna obstojnost zavzema enakomernejše vrednosti po celotni površini plošče v primerjavi z do sedaj znanimi ploščami, pri katerih so velike neojačene vrzeli med vzporedno razporejenimi nitmi.Because there are several reinforcing fibers in the plate according to the invention and are more evenly distributed over the entire plate volume compared to the prior art plates, the impact resistance of the plates is improved. Impact resistance takes more uniform values over the entire surface of the board compared to the panels known so far, with large non-reinforced gaps between the parallel threads.
Nov postopek izdelave polimetilmetakrilatnih plošč s vključenimi ojačitvenimi poliamidnimi monofilamentnimi vlakni v smislu izuma poteka po prednostni izvedbi izuma podrobneje tako, da se najprej monomer metilmetakrilat in dodatki, ki so običajni v stroki, dozirajo v ustrezen reaktor. Dodatki, ki se uporabijo v majhnih količinah in ki določajo lastnosti akrilnega stekla oz. pomagajo pri sintezi, so: azo in peroksi iniciatorji, redoks iniciatorji, mehčala, barvila (pigmenti, barve), ločilna sredstva, optični belilci, UV stabilizatorji in ostali akrilati in metakrilati, predvsem bultilakrilat, etilakrilat, 2-etilheksilakrilat, akrilna in metakrilna kislina.A new process for the manufacture of polymethylmethacrylate plates incorporating reinforcing polyamide monofilament fibers according to the invention is carried out in a preferred embodiment of the invention by first dosing the methylmethacrylate monomer and additives customary in the art into a suitable reactor. Accessories used in small quantities to determine the properties of acrylic glass or glass. assist in the synthesis of: azo and peroxy initiators, redox initiators, plasticizers, colorants (pigments, dyes), separators, optical brighteners, UV stabilizers and other acrylates and methacrylates, in particular bultyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, acrylic acid .
V reaktorju se pripravi predpolimer tako, da se sproži reakcija polimerizacije metilmetakrilata do ustrezne konverzije, npr. 10 - 30 %, prednostno 15-20 %. Običajno reakcija poteče v 1,5 ure. Nastali predpolimer, ki ima visoko viskoznost, se pretoči v mešalne posode, kamor se po želji vmešajo še barvila in ostali dodatki, kot so peroksi iniciatorji in zamreževalci. Predpolimer je pripravljen za vlivanje.A prepolymer is prepared in the reactor by initiating the polymerization reaction of methyl methacrylate to a suitable conversion, e.g. 10-30%, preferably 15-20%. Typically, the reaction expires in 1.5 hours. The resultant prepolymer, which has a high viscosity, is poured into mixing vessels, which are optionally mixed with dyes and other additives such as peroxy initiators and crosslinkers. The prepolymer is ready for casting.
Kalup za vlivanje predpolimera sestavimo na liniji za sestavo kalupov. Najprej se kaljena stekla, ki so lahko različnih dimenzij, ustrezno očistijo in posušijo. Nato se na mizi za napeljavo tesnila, ki je prednostno na osnovi polivinilklorida (PVC), 3-5 cm od roba stekla namesti polivinilkloridni profil ustrezne debeline, na steklo se položi samostoječ tridimenzionalni ojačitveni preplet polimernih monofilamentnih vlaken, v naslednji fazi pa se na to konstrukcijo položi še eno kaljeno steklo. Tako dobimo steklen kalup, ki ima vstavljen ojačitveni tridimenzionalni preplet vlaken, prednostno iz poliamidnih vlaken, in ob robu nameščeno tesnilo.The pre-polymer casting mold is assembled on the mold assembly line. First, tempered glasses, which can be of different dimensions, are properly cleaned and dried. Subsequently, a polyvinyl chloride profile of appropriate thickness is placed 3-5 cm from the edge of the glass, preferably polyvinyl chloride (PVC) sealing table, on the glass, a freestanding three-dimensional reinforcement of polymer monofilament fibers is placed on the glass, and in the next phase another tempered glass is laid on the structure. This results in a glass mold having a reinforcing three-dimensional fiber interlacing, preferably of polyamide fibers, inserted, and a seal fitted at the edge.
V sestavljene kalupe se glede na želeno in potrebno količino gravimetrično oddozira oz. vlije pripravljen predpolimer. Napolnjene kalupe zlagamo v navpično lego v posebne regale. Ker ima tridimenzionalni preplet dovoljšnjo trdnost vlaken (t.j. je samostoječ), vlakna ostanejo v prvotni legi in ne prihaja do posedanja ali premika vlaken. Regale postavimo v vodne bazene, ki imajo temperaturo 45 - 60 °C. Pri tej temperaturi poteče v obdobju 5-15 ur glavnina polimerizacije.It is gravimetrically dispensed into the composite molds according to the desired and required quantity. poured prepared prepolymer. Fill the molds vertically into special shelves. Because the three-dimensional interlocking has sufficient fiber strength (i.e., it is self-supporting), the fibers remain in their original position and do not cause the fibers to settle or move. The shelves are placed in water basins with a temperature of 45 - 60 ° C. At this temperature, most of the polymerization expires over a period of 5-15 hours.
Sintezo plošč dokončamo v zračni peči pri temperaturi 100 - 130 °C. V tej fazi poteče polimerizacija v obdobju 2-5 ur popolnoma do konca. Po končanem postopku se kalupi ohladijo in plošče vzamejo iz kalupov.The synthesis of the plates is completed in an air oven at 100 - 130 ° C. During this phase, the polymerization proceeds completely over a period of 2-5 hours. After the process is completed, the molds are cooled and the plates are removed from the molds.
Mehanske lastnosti plošč se določajo z v stroki uveljavljenimi standardnimi testi in metodami.The mechanical properties of the panels are determined by standard-established standard tests and methods.
Udarne lastnosti plošč smo določili z ugotavljanjem udarne žilavosti po Charpyju po standardu ISO 179, ki predstavlja energijo, ki je potrebna, da material poči.The impact properties of the panels were determined by determining the Charpy impact strength according to ISO 179, which represents the energy required for the material to burst.
Naše meritve žilavosti po tem standardu za plošče v smislu izuma, ki smo jih izdelali po gornjem novem postopku, so pokazale do 1,7-krat višjo vrednost žilavosti kot pri neojačenem PMMA materialu. Meritve Inštituta za raziskavo cest in mostov IBDiM iz Varšave, Poljska (IBDiM, Instytut Badawczy Drog i Mostow, Varšava, Poljska) so v povprečju pokazale 1,52-krat višjo vrednost žilavosti v primeijavi z običajnimi PMMA ploščami. Absolutna vrednost žilavosti je segala od 19,8 do 22, 3 kJ/m2.Our toughness measurements according to this standard for the panels of the invention made according to the above new procedure showed up to 1.7 times higher toughness values than for non-reinforced PMMA material. IBDiM Road and Bridge Research Institute measurements from Warsaw, Poland (IBDiM, Instytut Badawczy Drog i Mostow, Warsaw, Poland) showed an average of 1.52 times higher toughness compared to conventional PMMA panels. The absolute value of toughness ranged from 19.8 to 22.3 kJ / m 2 .
Zaradi izboljšanja udarnih lastnosti plošč je mogoče sklepati, da plošče v smislu izuma prenesejo višje udarne obremenitve. To pomeni, da kompenzirajo višjo energijo, ki se sprosti ob udarcu ali naletu vozil. Pri naših meritvah, izvedenih po standardu EN 1794-1, Aneks C - Test na odpornost na kamenčke (Impact of stones), smo določili več kot 3x višjo vrednost energije kamenčkov, kot je potrebna glede na standard in glede na neojačene PPM A plošče.In order to improve the impact properties of the panels, it can be concluded that the panels according to the invention withstand higher impact loads. This means that they compensate for the higher energy released on impact or vehicle collision. In our measurements performed according to EN 1794-1, Annex C - Impact of stones test, we have determined more than 3x higher value of pebble energy than is required by standard and non-reinforced PPM A panels.
Na sliki 1 je ponazoijena plošča z vključenimi ojačitvenimi monofilamentnimi poliamidnimi vlakni v obliki tridimenzionalnega prepleta vlaken.Figure 1 illustrates a panel with included reinforcing monofilament polyamide fibers in the form of a three-dimensional fiber interlacing.
Naslednja primera služita zgolj za ponazoritev predloženega izuma in nikakor ne predstavljata omejitve njegovega obsega.The following examples serve merely to illustrate the present invention and do not in any way limit the scope thereof.
Primer 1Example 1
Sinteza laboratorijske ploščeSynthesis of laboratory plate
Kalup smo pripravili iz 2 kaljenih stekel, debeline 5 mm, širine 275 mm in višine 350 mm, in PVC tesnila debeline 17 mm. Tesnilo smo napeljali po samo treh straneh, tako da je bil na vrhu še odprt. Stisnili smo ga s fiksnimi prižemami. V kalup smo vstavili tridimenzionalni preplet brezbarvnih poliamidnih vlaken Geomat Italgrimp proizvajalca Greenvision Ambiente divizione Italdreni, Italija, tako da je preplet v bistvu pokrival celotno površino/volumen kalupa. Preplet je imel debelino 13,5 ± 0,5 mm in površino 200 mm x 200 mm. Debelina posameznih vlaken je bila 0,5 ± 0,03 mm, masa prepleta je bila 350 ± 20 g/m .The mold was made of 2 tempered glasses, 5 mm thick, 275 mm wide and 350 mm high, and PVC seals 17 mm thick. We sealed the gasket only three sides so that the top was still open. We squeezed it with fixed clamps. A three-dimensional colorless polyamide fiber Geomat Italgrimp interlining by Greenvision Ambiente divizione Italdreni, Italy was inserted into the mold, so that the interlining essentially covered the entire surface / volume of the mold. The weave had a thickness of 13.5 ± 0.5 mm and an area of 200 mm x 200 mm. The thickness of the individual fibers was 0.5 ± 0.03 mm and the mass of the weave was 350 ± 20 g / m.
V reaktoiju smo pripravili predpolimer iz 1,5 kg zmesi monomerov metilmetakrilata (MMA) in 2-etilheksilakrilata (2-EHA) ter komercialno dostopnega azo iniciatorja. Zmes smo ob konstantnem mešanju segreli na temperaturo 92°C in to temperaturo ves čas reakcije tudi vzdrževali. Po 15 minutah na temperaturi reakcije smo zmes ob konstantnem mešanju ohladili na sobno temperaturo. Predpolimeru smo izmerili viskoznost po Fordu: čaša po Fordu 0 = 4 mm, iztočni čas predpolimera pri 23 °C je bil 154 s.A 1.5 kg prepolymer of a mixture of methylmethacrylate monomers (MMA) and 2-ethylhexyl acrylate (2-EHA) and a commercially available azo initiator were prepared in the reacto. The mixture was warmed to 92 ° C with constant stirring and maintained at this temperature throughout the reaction. After 15 minutes at the reaction temperature, the mixture was cooled to room temperature with constant stirring. Ford viscosity was measured according to Ford: Ford beaker 0 = 4 mm, pre-polymer efflux at 23 ° C was 154 s.
Tako pripravljen predpolimer smo pretočili v čašo in mu ob konstantnem mešanju dodali komercialno dostopne peroksi iniciatorje in zamreževalec 1,4butandioldimetakrilat (1,4- BDDMA). Dobro premešano zmes smo prefiltrirali in vlili v pripravljen kalup. Kalup smo za 12 ur postavili v vodno kopel pri 52 °C, kjer smo izvajali polimerizacijo.The prepolymer prepared in this way was poured into a beaker and commercially available peroxy initiators and crosslinker 1,4butanedioldimethacrylate (1,4-BDDMA) were added with constant stirring. The well-mixed mixture was filtered and poured into a prepared mold. The mold was placed in a water bath at 52 ° C for 12 hours, where polymerization was performed.
Nato smo ga prenesli v zračno peč pri 130 °C, kjer smo 1 uro izvajali postpolimerizacijo. Po končani reakciji smo kalup ohladili na sobno temperaturo, ga razstavili in izvzeli polimetilmetakrilatno ploščo s vstavljeno ojačitvijo iz poliamidnih vlaken. Izdelana plošča je imela debelino 15 mm.It was then transferred to an air oven at 130 ° C for 1 hour post-polymerization. After completion of the reaction, the mold was cooled to room temperature, disassembled, and the polymethylmethacrylate plate was removed with a reinforced polyamide fiber insert. The manufactured board had a thickness of 15 mm.
Iz plošče smo izrezali epruvete in izmerili žilavost po Charpyju po standardu ISO 179. Vrednost žilavosti je bila 19,8 ± kJ/m2.Tubes were cut from the plate and the Charpy toughness was measured according to ISO 179. The toughness value was 19.8 ± kJ / m 2 .
Primer 2Example 2
Sinteza plošče v proizvodnjiPlate synthesis in manufacturing
Kalupe smo pripravili na liniji za pripravo kalupov iz 2 kaljenih stekel debeline 10 mm in velikosti 2600 mm x 2100 mm, in PVC tesnila debeline 19 mm. Tesnilo smo napeljali po robu spodnjega stekla približno 30 mm od roba in nanj vstavili tridimenzionalni preplet brezbarvnih poliamidnih vlaken Geomat Italgrimp podjetja Greenvision Ambiente divizione Italdreni, tako daje preplet v bistvu pokrival celotno površino kalupa. Preplet je imel debelino 13,5 ± 0,5 mm in površino 2000 mm x 2500 mm. Debelina posameznih vlaken je bila 0,4 ± 0,03 mm in masa prepleta je bila 300 ± 20 g/m . Delno zgotovljene kalupe smo pokrili z drugim kaljenim steklom in kalupe stisnili s fiksnimi objemkami.The molds were prepared on a line for the preparation of molds made of 2 tempered glasses 10 mm thick and 2600 mm x 2100 mm in size, and 19 mm PVC seals. The seal was routed around the bottom glass edge about 30 mm from the edge and a three-dimensional interlining of Geomat Italgrimp colorless polyamide fibers by Greenvision Ambiente divizione Italdreni was inserted into it, so that the interlining essentially covered the entire surface of the mold. The weave had a thickness of 13.5 ± 0.5 mm and an area of 2000 mm x 2500 mm. The thickness of the individual fibers was 0.4 ± 0.03 mm and the mass of the weave was 300 ± 20 g / m. The partially prepared molds were covered with another tempered glass and the molds were pressed with fixed clamps.
Predpolimer smo pripravili v reaktorju volumna 400L, in sicer iz 360 kg zmesi monomerov metilmetakrilata (MMA) in etilakrilata (EA) ter komercialno dostopnega azo iniciatorja. Zmes smo ob konstantnem mešanju segreli na temperaturo 93 °C in to temperaturo ves čas reakcije tudi vzdrževali. Po 10 minutah na temperaturi reakcije smo zmes ob konstantnem mešanju ohladili na sobno temperaturo. Predpolimeru smo izmerili viskoznost po Fordu: čaša po Fordu 0 = 4 mm, iztočni čas predpolimera pri 23 °Cjebil 88 s.The prepolymer was prepared in a 400L volume reactor, from a 360 kg mixture of methylmethacrylate (MMA) and ethylacrylate (EA) monomers and a commercially available azo initiator. The mixture was heated to 93 ° C with constant stirring and maintained at this temperature throughout the reaction. After 10 minutes at the reaction temperature, the mixture was cooled to room temperature with constant stirring. Ford viscosity was measured by Ford viscosity: Ford glass 0 = 4 mm, pre-polymer efflux at 23 ° C for 88 s.
Tako pripravljen predpolimer smo pretočili v mešalno posodo in mu ob konstantnem mešanju dodali komercialno dostopne azo in redoks iniciatoije ter zamreževalec 1,4butandioldimetakrilat (1,4- BDDMA).The prepolymer prepared in this way was poured into a mixing vessel and, with constant stirring, commercially available azo and redox initiates and a crosslinker of 1,4butanedioldimethacrylate (1,4-BDDMA) were added.
Dobro premešano zmes smo na dozirni liniji vlili v pripravljene, na eni strani odprte kalupe. Kalupe smo zložili v regal po več skupaj in jih za 11 ur postavili v vodni bazen pri 54 °C, kjer smo izvajali polimerizacijo.The well-mixed mixture was poured on the dosage line into prepared, open molds on one side. The molds were stacked in several shelves together and placed in a water pool at 54 ° C for 11 hours, where polymerization was carried out.
Nato smo jih prenesli v zračno peč, kjer smo 3 ure izvajali postpolimerizacijo po temperaturnem programu. Po končani reakciji smo kalupe ohladili na sobno temperaturo, jih razstavili in izvzeli plošče s poliamidno ojačitvijo. Izdelana plošča je imela debelino 15 mm.They were then transferred to an air furnace, where post-polymerization was carried out for 3 hours according to a temperature program. After completion of the reaction, the molds were cooled to room temperature, disassembled, and discarded with polyamide reinforcement plates. The manufactured board had a thickness of 15 mm.
Plošče smo uporabili za testiranje po standardih EN 1793 in EN 1794. Plošče odgovaijajo predpisanim vrednostim iz standardov. Test na odpornost na kamenčke je pokazal, da je plošča ostala nepoškodovana celo nad 90 kJ (simulacija energije kamenčkov).The plates were used for testing according to EN 1793 and EN 1794. The plates meet the prescribed values from the standards. A test of pebble resistance showed that the plate remained intact even above 90 kJ (pebble energy simulation).
Claims (21)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI200600290A SI22417A (en) | 2006-12-22 | 2006-12-22 | Plates with antinoise and antifragmentation properties based on acrylic glass, process for their preparation and use thereof |
| PL07468012T PL1936035T3 (en) | 2006-12-22 | 2007-12-07 | Panels with antinoise and antifragmentation properties on the basis of acrylic glass, process for their preparation and use thereof |
| SI200730160T SI1936035T1 (en) | 2006-12-22 | 2007-12-07 | Panels with antinoise and antifragmentation properties on the basis of acrylic glass, process for their preparation and use thereof |
| EP07468012A EP1936035B1 (en) | 2006-12-22 | 2007-12-07 | Panels with antinoise and antifragmentation properties on the basis of acrylic glass, process for their preparation and use thereof |
| DE602007003300T DE602007003300D1 (en) | 2006-12-22 | 2007-12-07 | Blackboard with anti-noise and anti-shatter properties based on synthetic glass, process for its production and use therefor |
| AT07468012T ATE449213T1 (en) | 2006-12-22 | 2007-12-07 | PLATE WITH NOISE AND SHATTER PROTECTION PROPERTIES BASED ON ARTIFICIAL GLASS, METHOD FOR PRODUCTION AND USE THEREOF |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SI200600290A SI22417A (en) | 2006-12-22 | 2006-12-22 | Plates with antinoise and antifragmentation properties based on acrylic glass, process for their preparation and use thereof |
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| Publication Number | Publication Date |
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| SI22417A true SI22417A (en) | 2008-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| SI200600290A SI22417A (en) | 2006-12-22 | 2006-12-22 | Plates with antinoise and antifragmentation properties based on acrylic glass, process for their preparation and use thereof |
| SI200730160T SI1936035T1 (en) | 2006-12-22 | 2007-12-07 | Panels with antinoise and antifragmentation properties on the basis of acrylic glass, process for their preparation and use thereof |
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| SI200730160T SI1936035T1 (en) | 2006-12-22 | 2007-12-07 | Panels with antinoise and antifragmentation properties on the basis of acrylic glass, process for their preparation and use thereof |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1936035B1 (en) |
| AT (1) | ATE449213T1 (en) |
| DE (1) | DE602007003300D1 (en) |
| PL (1) | PL1936035T3 (en) |
| SI (2) | SI22417A (en) |
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| PL2619370T3 (en) | 2010-09-21 | 2016-05-31 | Plazit Iberica Plastic Solutions S A | Reinforced acrylic glass panels |
| SI23477A (en) | 2010-09-23 | 2012-03-30 | Akripol Proizvodnja In Predelava Polimerov D.D. | With fibers reinforced acrylic panel and process for its production |
| EP2824239A1 (en) | 2013-07-10 | 2015-01-14 | Center of Excellence for Polymer Materials and Technologies (PoliMaT) | Reinforced polymeric panels |
| EP3426844B9 (en) | 2016-03-06 | 2020-10-14 | AKRIPOL proizvodnja in predelava polimerov, d.o.o. | Method for panel manufacturing, particularly anti-noise |
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| DE3824077C1 (en) * | 1988-07-15 | 1989-11-09 | Degussa Ag, 6000 Frankfurt, De | |
| DK0407852T3 (en) | 1989-07-13 | 1993-06-14 | Degussa | Suitable acrylic glass panels are suitable for noise insulation elements |
| IT1283844B1 (en) | 1996-08-28 | 1998-04-30 | Atohaas Holding Cv | ANTI-FRAGMENT SHEETS BASED ON ACRYLIC POLYMERS |
| ES2263297T3 (en) | 1998-10-06 | 2006-12-01 | Rohm Gmbh | SUITABLE PLATE AS AN ACOUSTIC PROTECTION WALL. |
| DE29821384U1 (en) * | 1998-11-30 | 1999-02-04 | Polartherm-Flachglas GmbH, 01558 Großenhain | Transparent noise barrier element |
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2006
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2007
- 2007-12-07 AT AT07468012T patent/ATE449213T1/en not_active IP Right Cessation
- 2007-12-07 SI SI200730160T patent/SI1936035T1/en unknown
- 2007-12-07 DE DE602007003300T patent/DE602007003300D1/en active Active
- 2007-12-07 EP EP07468012A patent/EP1936035B1/en active Active
- 2007-12-07 PL PL07468012T patent/PL1936035T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SI1936035T1 (en) | 2010-03-31 |
| PL1936035T3 (en) | 2010-04-30 |
| DE602007003300D1 (en) | 2009-12-31 |
| EP1936035A1 (en) | 2008-06-25 |
| ATE449213T1 (en) | 2009-12-15 |
| EP1936035B1 (en) | 2009-11-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OO00 | Grant of patent |
Effective date: 20070704 |
|
| KO00 | Lapse of patent |
Effective date: 20110809 |