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HRP20010699A2 - Method of producing self-cleaning detachable surfaces - Google Patents

Method of producing self-cleaning detachable surfaces Download PDF

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Publication number
HRP20010699A2
HRP20010699A2 HR20010699A HRP20010699A HRP20010699A2 HR P20010699 A2 HRP20010699 A2 HR P20010699A2 HR 20010699 A HR20010699 A HR 20010699A HR P20010699 A HRP20010699 A HR P20010699A HR P20010699 A2 HRP20010699 A2 HR P20010699A2
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Croatia
Prior art keywords
hydrophobic material
protrusions
self
hydrophobic
cleaning
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HR20010699A
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English (en)
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Wilhelm Barthlott
Christoph Neinhuis
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Wilhelm Barthlott
Christoph Neinhuis
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7902402&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=HRP20010699(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Wilhelm Barthlott, Christoph Neinhuis filed Critical Wilhelm Barthlott
Publication of HRP20010699A2 publication Critical patent/HRP20010699A2/hr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
    • 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
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/008—Temporary coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B05D1/322—Removable films used as masks
    • B05D1/327—Masking layer made of washable film
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Detergent Compositions (AREA)
  • Paints Or Removers (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Magnetic Heads (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Description

Predmetni izum se odnosi na postupak za proizvodnju samočistećih površina.
Čišćenje površina predmeta ima veliko tehničko i ekonomsko značenje, i to djelomično iz optičkih i estetskih razloga i djelomično iz tehničkih razloga, osobito ako se radi o svjetlopropusnim površinama, koje se za održavanje svojih funkcija povremeno moraju čistiti.
Do sada se pokušavalo više puta izraditi tehničke površine koje odbijaju prljavštinu i/ili koje su samočisteće. Proizvođači polimernih folija ili polimernih ploča su pokušali riješiti taj problem time da su proizvodili prilično glatke površine, koje su izradili ili kao ekstremno hidrofobne ili ekstremno hidrofilne. Primjeri za to su površine iz ekstremno hidrofobnog teflona ili ekstremno hidrofilnih "No-drop" slojeva po kojima voda i prljavština mogu otjecati bez stvaranja kapljica.
Dokument CH-PS-26 82 58 opisuje površine koje odbijaju vodu, koje s vodom tvore kontaktni kut veći od 120°. One se dobivaju nanošenjem prahova kao što su kaolin, talk, glina ili silikagel na podlogu, pri čemu se prethodno pomoću organskih silicijevih spojeva postiže hidrofobnost praha. Nanošenje se vrši zajedno sa smolom koja se može stvrdnuti ili s otopinama s organskim otapalima. Trajne hidrofobne površine se ne mogu tako proizvoditi. Ne postoje uputstva o veličini zrna ili raspodjeli veličine zrna praha. Svojstva tako dobivenih površina se uspoređuju sa površinama listova dragoljuba (Tropaeolum, nap. pr.). Kod te usporedbe treba paziti na to, da pri tome nije niti poznato niti se tehnički moglo analizirati, na čemu se baziraju svojstva površina lista dragoljuba. Sada provedena istraživanja su pokazala da dragoljub ima ekstremno finu ultra strukturu sa elementima strukture manjim od 2 μm.
Dokument US-P-3, 354,022 opisuje površinu koja odbija vodu s povišenjima i udubljejima i sadržajem zraka od najmanje 60%, kod koje se podešava površinski kontaktni kut od više od 90°.
Dokument DE-PS-10 23 217 opisuje jedan oblik za proizvodnju kalupa sa hrapavom površinom. Oblik (kalup) treba služiti za proizvodnju dijela kalupa iz kaučuka ili plastične mase sa hrapavom površinom. Zbog toga se stijenke kalupa prevlače grubim prahom korunda i zapečenim lakom. Kalupi izrađuju proizvode s odgovarajućim udubljenjima i time poboljšanim svojstvima prianjanja. Izbjegava se čak i uobičajena vulkanizacijska fina prevlaka. Na tako dobivenim površinama se dobro može pisati. Proizvodi time nisu samočisteći s tekućom vodom.
Dokument JP-A-62-191447 opisuje postupak za povećanje sposobnosti neke površine da odbija vodu. U tu svrhu se nanosi film plasmapolimera, jetkanjem se postiže njegova hrapavost i nakon toga se nanosi drugi plasmapolimerfilm.
JP-A-3-174279 (Sažetak) opisuje postupak za proizvodnju mat, dekorativnih površina na papirima ili folijama. One se proizvode pomoću lakova koji se stvrdnjavaju pomoću ionizirajućih zraka i u njih se na način koji nije specificiran utiskuju uzorci koji nisu pobliže specificirani. Kasnije se potpuno stvrdnjavaju daljnjim zračenjem.
Detaljna ispitivanja prijavitelja dovela su do neočekivanog rezultata, da je tehnički moguće izvesti umjetno samočisteće površine predmeta, time da se na njima izvede struktura površine koja ima izbočenja i upuštenja, pri čemu treba paziti na to da razmak između izbočenja površine bude u rasponu od 0,1 do 200 μm, po mogućnosti 0,1 do 100 μm a visina povišenja u području od 0,1 do 100 μm, po mogućnosti 0,1 do 50 μm, i pri čemu treba paziti na to, da se ova povišenja sastoje iz hidrofobnih polimera ili održivih hidrofobiranih materijala, te da se vodi računa o tome, da se ta povišenja ne odvajaju u dodiru s vodom ili vodom koja je pomiješana s deterdžentima (usporedi WO 96/04123).
Zadatak predmetnog izuma je pronalaženje postupka za proizvodnju samočistećih površina, pri čemu se one ne odvajaju u dodiru s otopinama deterdženta. Zadatak će se riješiti putem postupka koji ima obilježja navedena u Patentnom zahtjevu 1.
Postupak prema izumu za proizvodnju samočistećih površina, koje imaju povišenja i udubljenja, pri čemu je razmak između povišenja u području 0,1 do 200 μm, a visina izbočenja u rasponu od 0,1 do 100 μm, se bazira na nanošenju hidrofobnog materijala, koji kod isparavanja sredstva za otapanje sam stvara samočisteću površinu na jednoj površini te nakon sušenja, pri čemu se naneseni materijal odvaja s vodenim otopinama deterdženta. Hidrofobni materijal može pri tome imati oblik otopina, disperzija ili emulzija.
Kada se kaže "može se odvojiti s deterdžentima", to znači da se naneseni materijal djelovanjem vodenih otopina deterdženata -barem kod dugoročnog djelovanja - odvajanjem dijelova nanesenog materijala može odvojiti. Takvi naneseni materijali prema izumu se mogu i mehanički uklanjati, primjerice četkanjem, grebanjem ili čišćenjem s vodom pod visokim tlakom.
U jednom obliku izvedbe hidrofobni materijal je vosak, koji sam stvara mikrostrukturiranu samočisteću površinu.
U jednom drugom obliku izvedbe sadrži otopina, disperzija ili emulzija krute djeliće. Oni mogu sami biti hidrofobni ili hidrofilni kada se koriste zajedno s hidrofobnim materijalima kao što je na primjer vosak.
Nanošenje hidrofobnog materijala se može vršiti raspršivanjem, primjerice pomoću doze za raspršivanje ili pomoću pištolja za raspršivanje. Ovisno o vrsti planirane primjene, može biti preporučivo, da hidrofobni materijal dodatno bude oleofoban.
Moguće je, da se hidrofobni materijal transportira zajedno s vodom preko parno propusne površine.
Kao hidrofobni materijal prikladni su u postupku prema ovom izumu dugolančani sekundarni alkoholi i alkandioli, β-diketoni, sekundarni ketoni i dugolančani alkani. Osobito su prikladni nonakosan-10-ol, nonakosan-7,10-diol, nonakosan-5,10-diol, hentriakontan-12,14-dion, hentriakontan-8,10-dion, palmiton i druge hidrofobne supstance koje se otapaju u hlapivim otapalima, i pri njihovom isparavanju tvore hidrofobnu površinu koja odbija vodu.
Tehnički su osobito značajne samočisteće površine predmeta, koje su svjetlopropusne i koje iz optičkih, estetskih ili tehničkih razloga tu nepropusnost svjetla moraju zadržati dulje vrijeme. Ovdje se osobito radi o svjetlopropusnim ostakljivanjima zgrada, vozila, sunčanim kolektorima itd. Mogućnost odvajanja hidrofobnog materijala ima prednosti osobito tada, ako su samočisteća svojstva potrebna samo privremeno, primjerice za vrijeme skladištenja ili transporta, a inače su - primjerice iz estetskih razloga - nepoželjna.
Ekonomsko i tehničko značenje ima proizvodnja samočistećih površina kod kućnih fasada, krovova, spomenika i šatora kao i kod postavljanja unutarnjih slojeva u silosima, spremnicima ili cjevovodima koji sadrže ili vodene otopine ili se lako mogu očistiti bez ostataka tekućom vodom. Značajno je i vanjsko postavljanje slojeva na vozilima, kao što su auti, vlakovi ili avioni.
Optimalni rezultati se postižu tada, kada su povišenja struktura površina postavljena tijesno jedna uz druge, kako bi se preko kapljica vode izbjegao dodir upuštenja koja su izvedena između izbočenja. Ako se izbočenja površinske strukture nalaze međusobno suviše blizu ili ako upuštenja nisu dovoljno duboka, ona ponovno djeluju kao zatvorena površina i na taj način se mogu bolje navlažiti. Zato treba nastojati da se uz povećavanje razmaka izbočenja, također povećava i visina izbočenja od podloge. Dosadašnja mjerenja su pokazala da se unutar zahtjevanih granica za razmak i visinu izbočenja postižu dobri rezultati. Optimalne rezultate daju površine s izbočenjima koja imaju 0,1 do 50 μm i kod kojih razmak između izbočenja iznosi 0,1 do 100 μm.
Izum će se objasniti pomoću slijedećih primjera.
Primjer 1
Hentriakontan-14,16-dion se kao 0,1%-tna otopina u hexanu ili etilacetatu raspršuje na željenu površinu pomoću doze za raspršivanje ili pomoću pištolja za štrcanje. Za vrijeme isparavanja otapala, hentriakontan-14,16-dion stvara samostalno kristale u obliku malih cjevčica, koje u većem broju imaju promjer od 0,2 μm i duljinu od 0,5-5 μm. Zbog prekrivanja tim slojem, površina koja se vlazi postaje hidrofobna i dodirni kut se povećava do 160°. Sa površina takve vrste se zagađene čestice ispiru tekućom vodom, pri čemu se nakon dužeg vremena uklanja i sam sloj. Za povećanje hrapavosti sloja može se u otopinu umiješati hidrofilni (na primjer kvarcno brašno) ili hidrofobni prah (na primjer teflon).
Primjer 2
Komercijalni gips se miješa u omjeru 1:10:2 (težinski postotak) s vodom i silkonatom (Wacker BS 15) i na kraju nanosi pomoću kista ili valjka. Kod sušenja se stvara mikrohrapava površina, čija struktura je određena igličastim kristalima gipsa. Oni su nakon isparavanja vode prekriveni slojem hidrofobnog sredstva. Dodirni kutevi na jednoj takvoj površini iznose iznad 150°.
Primjer 3
Komercijalni gips se miješa u odnosu 1:10:0,5 (težinski postotak) s vodom i jednim silkonatom (Wacker Silkon WI) i konačno se nanosi pomoću pištolja za štrcanje. Kod sušenja se stvara mikrohrapava površina, čija struktura je određena igličastim kristalima gipsa. Oni su nakon isparavanja vode prekriveni slojem hidrofobirajućeg sredstva. Dodirni kutevi na jednoj takvoj površini iznose preko 150°.
Primjer 4
Na jedan polimer propusan za vodenu paru (npr. poliuretan) se s jedne strane nanosi supstanca u obliku voska (na primjer hentriakontan-14,16-dion), koja je karakterizirana sposobnošću stvaranja strukture (vidi primjer 1). Ako se dopusti da voda difundira kroz polimer, tada se vosak transportira zajedno s njom i tvori na površini željene mikrostrukture.
Pomoću dovoljne količine voska može se kod tog sistema postići određena ustrajnost u tom smislu, da se oštećene ili erodirane strukture u određenom periodu mogu obnoviti.

Claims (10)

1. Postupak za proizvodnju samočistećih površina, koje imaju povišenja i udubljenja, naznačen time, da je razmak između povišenja u području od 0,1 do 200 μm, a visina povišenja u području od 0,1 do 100 μm, a otopina, disperzija ili emulzija koja sadrži hidrofobni materijal, koji kod isparavanja otapala sam tvori samočisteću površinu, nanosi se i suši, pri čemu se naneseni materijal može odvajati sa deterdžentima.
2. Postupak prema Patentnom zahtjevu 1, naznačen time, da je hidrofobni materijal vosak.
3. Postupak prema Patentnom zahtjevu 1, naznačen time, da se kao hidrofobni materijal koriste voštane supstancije, kao što su primarni ili sekundarni alkoholi i alkandioli, p-diketoni, sekundarni ketoni i dugolančani alkani.
4. Postupak prema Patentnom zahtjevu 1, naznačen time, da otopina, disperzija ili emulzija sadrži krute čestice.
5. Postupak prema barem jednom od Patentnih zahtjeva l do 4, naznačen time, da se nanošenje otopine, disperzije ili emulzije vrši raspršivanjem.
6. Postupak prema Patentnom zahtjevu 5, naznačen time, da se nanošenje vrši pomoću doze za raspršivanje ili pištolja za raspršivanje.
7. Postupak prema barem jednom od Patentnih zahtjeva 1 do 6, naznačen time, da je hidrofobni materijal dodatno oleofoban.
8. Predmet s površinom, koja ima izbočenja i upuštenja, naznačen time, da se razmak između izbočenja nalazi u području od 0,1 do 200 μm, a visina izbočenja u rasponu od 0,1 do 100 μm, pri čemu su barem izbočenja hidrofobna i sastoje se iz krutih čestica, a površina je prevučena hidrofobnim materijalom.
9. Primjena sekundarnih alkohola i alkandiola, p-diketona, sekundarnih ketona i dugolančanih alkana, naznačena time, da se navedeni koriste kao hidrofobni materijal za proizvodnju samočistećih površina.
10. Primjena prema Patentnom zahtjevu 9, naznačena time, da se kao hidrofobni materijal koristi nonakosan-10-ol, nonakosan-7,10-diol, nonakosan-5,10-diol, hentriakontan-12,14-dion, hentriakontan-8,10-dion ili palmiton.
HR20010699A 1999-03-25 2000-03-18 Method of producing self-cleaning detachable surfaces HRP20010699A2 (en)

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NO20014618L (no) 2001-09-25
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AU765310B2 (en) 2003-09-18
US20070098957A1 (en) 2007-05-03
CA2368204C (en) 2008-09-09
SK13402001A3 (sk) 2002-05-09
PL191143B1 (pl) 2006-03-31
EE200100494A (et) 2002-12-16
US20050136217A1 (en) 2005-06-23
ES2203450T3 (es) 2004-04-16
YU67701A (sh) 2003-08-29
PT1171529E (pt) 2003-12-31
AU4106300A (en) 2000-10-16
KR20020000792A (ko) 2002-01-05
JP2002540283A (ja) 2002-11-26
CZ20013361A3 (cs) 2002-02-13
CN1344297A (zh) 2002-04-10
RU2246514C2 (ru) 2005-02-20
EP1171529B1 (de) 2003-07-23
PL350945A1 (en) 2003-02-24
HUP0200452A2 (en) 2002-11-28
ZA200107800B (en) 2002-05-29
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EP1171529A1 (de) 2002-01-16
DK1171529T3 (da) 2003-11-03
WO2000058410A1 (de) 2000-10-05
ATE245681T1 (de) 2003-08-15
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