[go: up one dir, main page]

EP2864522B1 - Verfahren zur herstellung hydrophober und oleophober beschichtungen auf metallischen substraten - Google Patents

Verfahren zur herstellung hydrophober und oleophober beschichtungen auf metallischen substraten Download PDF

Info

Publication number
EP2864522B1
EP2864522B1 EP13756700.4A EP13756700A EP2864522B1 EP 2864522 B1 EP2864522 B1 EP 2864522B1 EP 13756700 A EP13756700 A EP 13756700A EP 2864522 B1 EP2864522 B1 EP 2864522B1
Authority
EP
European Patent Office
Prior art keywords
coating
treatment
metal surfaces
treated
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP13756700.4A
Other languages
English (en)
French (fr)
Other versions
EP2864522A2 (de
Inventor
Mariarosa RAIMONDO
Federica Bezzi
Magda Blosi
Claudio MINGAZZI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA
Consiglio Nazionale delle Richerche CNR
Original Assignee
Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA
Consiglio Nazionale delle Richerche CNR
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA, Consiglio Nazionale delle Richerche CNR filed Critical Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA
Priority to PL13756700T priority Critical patent/PL2864522T3/pl
Publication of EP2864522A2 publication Critical patent/EP2864522A2/de
Application granted granted Critical
Publication of EP2864522B1 publication Critical patent/EP2864522B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material

Definitions

  • the present invention relates to a method for the treatment of metal surfaces.
  • hydrophobicity of a surface depends by the appropriate combination between the structural characteristics, in terms of size of the roughness, and the energy of the same surface, in turn linked to the chemistry.
  • a surface is defined hydrophobic when the contact angle ( ⁇ ) that the same form with a drop of water is greater than 90°, hydrophobicity is said gradually increasing as the contact angle ⁇ goes beyond this threshold.
  • the super hydrophobicity is achieved when the contact angle of the surface with a drop of water is greater than 150°.
  • the higher the contact angle that the surface forms with a drop of oil the higher is the degree of oleophobicity.
  • the dynamic hydrophobicity is related to the ability of a drop of water to "roll” or “slide” along a surface, and then leave the same once the angle of inclination starts to increase.
  • the dynamic hydrophobicity can be expressed in two ways, by means of the minimum value of the angle of inclination that the surface must present in order to cause the "rolling" or the “sliding” of a drop of known size, or by means of the measurement of the hysteresis value (difference) between the contact angle with which a drop of known volume advances ( ⁇ A ) on an inclined plane and the angle of recession ( ⁇ R ).
  • the pertinent literature shows how the relationship between static hydrophobicity and dynamic hydrophobicity is complex and, in many cases, even if the static contact angle is sufficiently high (> 150°), it does not correspond to a sufficient dynamic hydrophobicity. This is because if the interaction of the droplet with the surface depends in a more or less direct manner from the surface roughness and energy, its movement on the same is affected by additional parameters, such as physical inhomogeneity, differences in chemistry and composition, particle size, etc., the influence of which is difficult to interpret.
  • oleophobicity Another functional property of great interest for the metal surfaces is oleophobicity, ie the repellency against oils, fats, etc.
  • the provision of this additional property to a metal surface allows to physically prevent the adhesion of dirt and grease particles, in order to further implement the performance of "self-cleaning".
  • the degree of oleophobicity of a surface depends strongly on the energy of the surface itself, or better, on the difference between the surface tension of the oily substance and the energy of the surface itself; the lower will be the latter, the greater the repellency of the surface towards adhesion of substances with higher surface tension.
  • DE102007029668 A method for coating metal substrates according to the prior art is disclosed in DE102007029668 , wherein an alkaline catalyst is disclosed and vapour is used for forming hydroxyl groups in a step of functionalization.
  • Working in basic catalysis, according to DE102007029668 there is the need to create such conditions which can lead to the densification of the coating.
  • D1 discloses (paragraph 0055) a heat treatment at growing temperatures, in controlled environment (air or inert at high temperature).
  • DE1020077526 , DE102010011185 , WO2005066388 , WO2008083310 and EP1142845 disclose similar methods for coating a metal substrate comprising sol-gel coating with a metal alkoxide with an acid catalyst; consolidating in two steps the obtained layer, the first step involving a treatment with water; and further treatments with solutions containing alkylsilane compounds.
  • Purpose of the present invention is to provide metal surfaces presenting a high hydrophobicity and oleophobicity without compromising their realization on an industrial scale.
  • Object of the present invention is a method for the treatment of metal surfaces, characterised in that it comprises in succession:
  • the method includes a third step of consolidation, in which, after being treated with an alkylsilane compound, the said coating is subjected to a temperature comprised between 50 °C and 300 °C.
  • the step of deposition provides that said sol is deposited by dipcoating or spray coating or spin-coating.
  • said coating has a thickness comprised between 50 and 500nm.
  • said coating is treated with a fluorinated compound by dipcoating or spray coating or spin-coating.
  • said fluorinated compound is a fluorine alkyl silane.
  • a further object of the present invention is a metal component having a surface coating made by the method forming object of the present invention.
  • the metal surface used is aluminum
  • the ceramic surface used is porcelain stoneware and the glass surface is a sodium-calcium glass (Superfrost-Carlo Erba), all suitably degreased and pretreated.
  • a colloidal suspension of alumina was prepared by peptization of aluminum tri-sec butoxide 0.5M in aqueous solution in the presence of nitric acid as the acid catalyst.
  • the reactions of hydrolysis and condensation which lead to the formation of the sol occur keeping the system under stirring at 80 °C.
  • the molar ratios of the sol are as follows:
  • the surfaces takeb ubder examination (metal, ceramic and glass) were subjected to an operation of "dip coating” in the sol at room temperature.
  • the operation of "dip coating” was realized with a speed of immersion and emersion of 120 mm/min and a soak time in the sol of 5 seconds. Once every single substrate has emerged from the sol, the solvent water is evaporated promoting the transition to the state of gel formed by nano particles of partially hydrolyzed Al 2 O 3 .
  • the substrates were heat treated in an oven at 400 °C for 10 minutes in order to remove organic residues and promote the densification of the formed coating.
  • the substrate is preferably cleaned and activated, for example by means of acid/basic attacks of the surfaces, heat treatment in air, machining or other.
  • the treated surfaces were immersed in boiling water for 30 minutes and again thermally treated in an oven at 400 °C for 10 minutes.
  • the treated surfaces were subjected to a further operation of "dip coating" in a solution containing an alkylsilane compound.
  • the compound used is a fluorine alkyl silane marketed by the company EVONIK with the code F8263.
  • the treated surfaces were kept in a stove at 150 °C for 15 minutes in order to promote the chemical activation of the surface of the film of alumina.
  • the abrasion was carried out by simulating the standardized operating procedure in the case of coated glass for buildings (UNI EN 1096-2, Appendix E: Test of resistance to abrasion).
  • UNI EN 1096-2 Appendix E: Test of resistance to abrasion.
  • an abrasive felt rotating pad (thickness 10 mm ⁇ 1 mm) with a diameter of 5,0 cm ⁇ 0,5 cm and operated at a speed of 30 rounds/minute.
  • the felt pad was applied to the treated surfaces with a force equal to 4N and for a time equal to 30 seconds.
  • Table I shows the measured values of the above characteristics.
  • the values of dynamic hydrophobicity which can be found on metal surfaces treated with the method of the present invention are such as to ensure high repulsion to dirt and contaminants of various kinds, also of biological origin, avoid in adverse environmental conditions the formation of ice and frost, effectively limiting phenomena of wear and corrosion, reduce, or even avoid, phenomena of fouling due to different agents, allow more favorable fluid dynamic conditions in the vicinity of the surface, with consequent gains in terms of energy.
  • the surfaces indicated as SM1 and SM2 were tested for freezing/unfreezing according to UNI EN 539-2 (2006).
  • the surfaces SM1 and SM2 have been subjected to successive cycles of freezing/unfreezing in a climatic chamber in which continuous thermal excursions from +11 °C to -17 °C occurs and in which the step of unfreezing occurs by means of immersion in water and the subsequent phase of freezing occurs after the water has been drained from inside the climatic chamber.
  • the number of cycles of freezing/unfreezing to which the surfaces SM1 and SM2 were subjected was equal to: 36, 119, 234, 345, 447.
  • the evaluation of the resistance to cycles of freezing/unfreezing is based on the measures of static hydrophobicity (static contact angle) and dynamic hydrophobicity (hysteresis) after each of the said cycles of freezing/unfreezing.
  • Table II are reported the detected values of static contact angle and hysteresis.
  • Table II Number of cycles Static contact angle (°) Hysteresis (°) 36 145 ⁇ 3 12 ⁇ 3 119 140 ⁇ 2 12 ⁇ 2 234 140 ⁇ 5 11 ⁇ 3 345 140 ⁇ 5 19 ⁇ 5 447 134 ⁇ 3 7 ⁇ 4

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Surface Treatment Of Glass (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (10)

  1. Verfahren zur Behandlung von Metallflächen zum Verleihen einer hohen sowohl statischen als auch dynamischen Hydrophobizität und Oleophobizität, dadurch gekennzeichnet, dass es nacheinander Folgendes umfasst:
    - einen Schritt des Abscheidens einer Beschichtung aus Metalloxid, wobei auf eine Metallfläche ein Sol abgeschieden wird, das aus einer kolloidalen Suspension von einem oder mehreren Metallalkoxiden M(OR)n in Anwesenheit eines sauren Katalysators in Wasser besteht,
    wobei:
    M in der Gruppe bestehend aus Al, Ti, Si, Y, Zn, Zr enthalten ist;
    R eine lineare oder verzweigte aliphatische Kette C1-C4 ist;
    und wobei der Übergang von Sol zu Gel durch Verdampfen des Wassers aus der Beschichtung gefördert wird;
    - einen Schritt des Verfestigens, wobei die Beschichtung einer Temperatur zwischen 150 °C und 400 °C ausgesetzt wird;
    - einen Schritt des Funktionalisierens, wobei die Beschichtung mit kochendem Wasser für die Realisierung der Hydroxylgruppen und zum Modulieren der Oberflächenrauheit auf der Nanometerskala behandelt wird;
    - einen zweiten Schritt des Verfestigens, wobei die Beschichtung einer Temperatur zwischen 150 °C und 400 °C ausgesetzt wird, und
    - einen Schritt des chemischen Aktivierens der Oberfläche, wobei die Beschichtung mit einer Alkylsilan-Verbindung behandelt wird.
  2. Verfahren zur Behandlung von Metallflächen nach Anspruch 1, dadurch gekennzeichnet, dass in dem Schritt des Abscheidens M Al ist.
  3. Verfahren zur Behandlung von Metallflächen nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass in dem Schritt des Funktionalisierens die Beschichtung über eine Zeit von mindestens 30 min mit kochendem Wasser behandelt wird.
  4. Verfahren zur Behandlung von Metallflächen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass in dem Schritt des chemischen Aktivierens der Oberfläche die Alkylsilan-Verbindung fluoriniert wird.
  5. Verfahren zur Behandlung von Metallflächen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es einen dritten Schritt des Verfestigens umfasst, wobei nach Behandlung mit einer Alkylsilan-Verbindung die Beschichtung einer Temperatur zwischen 50 °C und 300 °C ausgesetzt wird.
  6. Verfahren zur Behandlung von Metallflächen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Schritt des Abscheidens vorsieht, dass das Sol mittels Tauchbeschichtung oder Sprühbeschichtung oder Rotationsbeschichtung abgeschieden wird.
  7. Verfahren zur Behandlung von Metallflächen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Beschichtung eine Dicke zwischen 50 und 500 nm aufweist.
  8. Verfahren zur Behandlung von Metallflächen nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass in dem Schritt des chemischen Aktivierens der Oberfläche die Beschichtung mit einer fluorinierten Verbindung mittels Tauchbeschichtung oder Sprühbeschichtung oder Rotationsbeschichtung behandelt wird.
  9. Verfahren zur Behandlung von Metallflächen nach Anspruch 8, dadurch gekennzeichnet, dass die fluorinierte Verbindung ein Fluoralkylsilan ist.
  10. Metallisches Element mit einer durch das Verfahren nach einem der vorhergehenden Ansprüche hergestellten Oberflächenbeschichtung.
EP13756700.4A 2012-06-21 2013-06-21 Verfahren zur herstellung hydrophober und oleophober beschichtungen auf metallischen substraten Not-in-force EP2864522B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13756700T PL2864522T3 (pl) 2012-06-21 2013-06-21 Sposób obróbki powierzchni metalowych dla nadania im dużej hydrofobowości i oleofobowości

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000291A ITRM20120291A1 (it) 2012-06-21 2012-06-21 Metodo per il trattamento di superfici metalliche per conferire alle stesse una elevata idrofobicita' ed oleofobicita'
PCT/IT2013/000175 WO2013190587A2 (en) 2012-06-21 2013-06-21 Method for the treatment of metal surfaces for bestowing thereon a high hydrophobicity and oleophobicity

Publications (2)

Publication Number Publication Date
EP2864522A2 EP2864522A2 (de) 2015-04-29
EP2864522B1 true EP2864522B1 (de) 2016-09-07

Family

ID=46584172

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13756700.4A Not-in-force EP2864522B1 (de) 2012-06-21 2013-06-21 Verfahren zur herstellung hydrophober und oleophober beschichtungen auf metallischen substraten

Country Status (5)

Country Link
EP (1) EP2864522B1 (de)
ES (1) ES2605999T3 (de)
IT (1) ITRM20120291A1 (de)
PL (1) PL2864522T3 (de)
WO (1) WO2013190587A2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3670740A1 (de) 2018-12-20 2020-06-24 European Central Bank Amphiphobe cellulosehaltige materialien, deren herstellung und verwendung

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202200024981A1 (it) 2022-12-05 2024-06-05 Johnson Screens Inc Piastre metalliche filtranti rivestite da nanorivestimenti multifunzionali

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001287971A (ja) * 2000-03-31 2001-10-16 Matsushita Electric Ind Co Ltd 防汚性被膜及びその製造方法、それを用いた自動車用防汚ガラス及びその製造方法、並びにそれを用いた自動車
DE102004001097B4 (de) * 2004-01-05 2014-06-05 Epg (Engineered Nanoproducts Germany) Ag Metallische Substrate mit verformbarer glasartiger Beschichtung
CN101573471A (zh) * 2006-12-29 2009-11-04 3M创新有限公司 固化含有金属烷氧化物的膜的方法
DE102007007526A1 (de) * 2007-02-15 2008-08-21 Epg (Engineered Nanoproducts Germany) Ag Feinste Interferenzpigmente enthaltende Glasschichten auf Metall-, Glas- und Keramikoberflächen und Verfahren zu deren Hersstellung
DE102007029668A1 (de) * 2007-06-27 2009-01-08 Epg (Engineered Nanoproducts Germany) Ag Ultraharte Kompositschichten auf Metalloberflächen und Verfahren zu ihrer Herstellung
DE102010011185A1 (de) * 2010-03-12 2011-09-15 Epg (Engineered Nanoproducts Germany) Ag Metallische Oberflächen mit dünner, glas- oder keramikartiger Schutzschicht mit hoher chemischer Beständigkeit und verbesserten Antihaft-Eigenschaften

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3670740A1 (de) 2018-12-20 2020-06-24 European Central Bank Amphiphobe cellulosehaltige materialien, deren herstellung und verwendung

Also Published As

Publication number Publication date
EP2864522A2 (de) 2015-04-29
ITRM20120291A1 (it) 2013-12-22
WO2013190587A2 (en) 2013-12-27
WO2013190587A3 (en) 2014-03-13
ES2605999T3 (es) 2017-03-17
PL2864522T3 (pl) 2017-06-30

Similar Documents

Publication Publication Date Title
Lomga et al. Fabrication of durable and regenerable superhydrophobic coatings with excellent self-cleaning and anti-fogging properties for aluminium surfaces
JP5086238B2 (ja) マグネシウムおよびマグネシウム合金について視認可能な非クロメート化成被覆を形成する方法
EP1963550B1 (de) Verfahren zur verringerung der porosität
Raimondo et al. Wetting behavior and remarkable durability of amphiphobic aluminum alloys surfaces in a wide range of environmental conditions
Zandi-Zand et al. Organic–inorganic hybrid coatings for corrosion protection of 1050 aluminum alloy
JP6502905B2 (ja) 腐食防止コーティング
Mandal et al. Green manufacturing of nanostructured Al-Based sustainable self-cleaning metallic surfaces
JP4995428B2 (ja) 酸化チタン塗膜形成方法
JP2008536013A5 (de)
JP2011526835A5 (de)
KR101847786B1 (ko) 친수 및 오염방지 기능을 갖는 투명방음벽용 나노세라믹 코팅 접합유리 제조방법
WO2021119373A1 (en) Selectively applied gradient coating compositions
US20140147598A1 (en) Coating method and coating for a bearing component
Laroche et al. Silicone nanofilaments grown on aircraft alloys for low ice adhesion
JP2015063061A (ja) 防汚体及びその製造方法
KR101769228B1 (ko) 부착 오염에 대한 자기 세정 능력이 우수한 피막을 형성하는 수계 친수성 도료 조성물 및 부착 오염에 대한 자기 세정 능력이 우수한 피막을 형성한 표면 처리재
EP2864522B1 (de) Verfahren zur herstellung hydrophober und oleophober beschichtungen auf metallischen substraten
WO2017095987A1 (en) Glass article having coating with interpenetrating polymer network
KR101940924B1 (ko) 친수 및 오염방지 기능을 갖는 나노세라믹 코팅유리 제조방법
Power et al. Versatile Self‐Cleaning Coating Production Through Sol–Gel Chemistry
Karimi et al. Synthesis and characterization of anti-scratch and anti-corrosion hybrid nanocomposite coatings based on Sol-Gel process
EP2766508B1 (de) Verfahren zur korrosionsschutzbehandlung fester metallsubstrate
EP2681347B1 (de) Verfahren zur behandlung von keramischen oberflächen zur verleihung von hoher hydrophobie und oleophobie
US10450469B2 (en) Transparent self-healing oleophobic and hydrophobic coatings
Doodman et al. Alumina nanostructured coating for corrosion protection of 316L stainless steel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150120

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160323

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 826943

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161015

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013011184

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161207

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161208

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2605999

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170317

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170107

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161207

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170109

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013011184

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

26N No opposition filed

Effective date: 20170608

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20170623

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170621

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170621

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130621

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 826943

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160907

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20200512

Year of fee payment: 8

Ref country code: CH

Payment date: 20200616

Year of fee payment: 8

Ref country code: DE

Payment date: 20200609

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20200610

Year of fee payment: 8

Ref country code: IT

Payment date: 20200610

Year of fee payment: 8

Ref country code: NL

Payment date: 20200615

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20200526

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20200701

Year of fee payment: 8

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602013011184

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20210701

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 826943

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210621

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210621

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220101

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210621

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210701

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210621

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220926

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210622