ULTRA-THIN HYDROPHOBIC AND OLEOPHOBIC LAYER, ITS METHOD OF MANUFACTURE AND USE IN MECHANICS AS A BARRIER FILM

Abstract
The invention relates to a novel ultra-thin hydrophobic and oleophobic layer, formed by self-assembly on a solid substrate surface, of compounds of the general formula
Description

The present invention relates to a novel ultra-thin hydrophobic and oleophobic layer, formed by self-assembly on a solid substrate surface, of compounds based on catechol, a method of preparing this ultra-thin layer and the use thereof as a barrier film, an anti-migration film or an anti-wetting film, which will be referred to in the disclosure below as an “epilame” by analogy with the watchmaking sector.


The proper functioning of a mechanical movement depends among other things on its lubrication. The durability of the lubricant depends particularly on its being maintained in the functioning area; however, a drop of lubricant rapidly spreads on a clean part. The deposition of a layer of epilame, generally in the form of an invisible hydrophobic and oleophobic molecular, layer, enables the spread of the lubricant and its components to be avoided.


The spread of a liquid depends on the forces of interaction between the liquid, the surface and the surrounding air (cf. J. C. Berg, “Wettability”, Marcel Dekker, New York, 1993 and A. W. Adamson, “Physical Chemistry of Surfaces”, Wiley). The parameter that characterises the forces of interaction between a liquid and air is the surface tension, γLV. Similarly, a surface energy γSV is defined between a solid and the surrounding air and a parameter γLS between the solid and the liquid. For a drop of liquid in equilibrium on a surface, Young's equation stipulates that γSV−γLSLV·cos θ, where θ is the contact angle of the drop of liquid in relation to the surface. Young's equation also shows that, if the surface tension of the liquid is lower than the surface energy, the contact angle is zero and the liquid, wets the surface. This is what happens for a lubricant deposited on a clean metallic surface, since a lubricant has a surface tension of 35-40 mN/m whereas a common metallic surface has a higher surface energy.


The surface energy depends on several factors (J. P. Renaud and P. Dinichert, 1956, “Etats de surface et étalement des huiles d'horlogerie”, Bulletin SSC III page 681):

    • the chemical composition and crystallographic structure of the solid, and in particular of its surface,
    • the geometric characteristics of the surface and its roughness (and therefore the defects and/or the state of polishing),
    • the presence of molecules physically adsorbed or chemically bonded to the surface, which can easily mask the solid and significantly modify its surface energy.


The surface energy is often determined by the last atomic or molecular layer. The chemical nature of the solid is of little importance in relation to the state of its surface and the contamination covering it. On a clean metallic surface free from organic contamination, the advancing contact angle with a drop of water is less than 10°. With a molecule forming self-assembled monomolecular layers (SAM: Self-Assembled Monolayers) having an —OH functional group (e.g. HOC11H22SH), this contact angle is about 30°, whereas it is about 110° for a —CH3 functional group (e.g. C12H25SH) and about 118° for a —CF3 functional group (e.g. C10F17H4SH).


The manufacturing techniques used in mechanical engineering up to the 1930s left a surface state that minimised the spread of lubricants by means of the presence of a film that lowered the surface energy (M. Osowiecki, 1957, “Un nouvel épilame résistant aux lavages”, Bulletin SSC III, page 735). This film disappeared with, the improvements made to washing techniques, causing more or less rapid spread, of the lubricants. In 1930, P. Woog of the Compagnie Francaise de Raffinage developed an anti-migration product based on stearic acid, which he called “epilame”. This was used in various branches of industry until the end of the 1960s. The name remained, and refers in watchmaking to any product used to guarantee that lubricants are retained on a surface.


The deposition of a compound on a functional surface in order to reduce surface energy and to control wettability and adhesion is a fairly widespread process. However, its application as a barrier film or anti-migration film is limited to watchmaking (M. Massin, “Epilames et lubrifiants associés à haute stabilité: propriétés, technologie d'application et résultats en horlogerie”, Actes du congrès de Chronométrie Franco-Allemand, page 85, 1970, and “Conception de la lubrification en micromécanique: réalisations nouvelles par préparation des surfaces associées à des fluides silicones”, Actes du congrès des Sociétés Allemande et Francaise de Chronométrie, page 95, 1971), the space industry (M. Marchetti, “Aspects globaux at locaux de la mise en oeuvre de la lubrication fluide en ambiance spatiale”, doctoral theais, INSA, Lyon, 2000) and electronics. Common to the first two sectors is the difficulty in replacing a used or exhausted lubricant.


Products based on stearic acid diluted in toluene were used in watchmaking until the 1970s (M. Osowiecki, see reference above, and P. Ducommun, 1956, “Les huiles d'horlogerie synthétiques”, J. Suisse Horl. Bij. 9-10, 117). Research undertaken in the late 1960s led to two important developments. On the one hand, a silicone-based product was developed (P. Massin, see references above) but met with only limited success. On the other hand, fluorinated polymer-based products were introduced during the 1970s and are still in use today.


Currently, the great majority of epilames available on the market, such as Fixodrop FK-BS from Moebius or the Fluorad product range (FC-722 and others) from 3M, consist of a fluorinated polymer dissolved in a perfluorinated solvent.


The coating of the components on the substrate takes place by dipping the latter in a solution of perfluorinated solvent loaded with polymer. The solvent used is generally tetradecafluorohexane (C6F14) which, once volatilised, is a greenhouse gas since it remains stable in air for 3200 years and has a global warming potential of 7400 CO2 equivalents.


The object of the invention is to propose compounds which can be used as an epilame and are capable of being fixed to a solid substrate surface without the use of environmentally toxic fluorinated solvents.


These objects are achieved by the invention as defined in the attached set of claims.


The invention proposes a novel ultra-thin hydrophobic and oleophobic layer, formed by self-assembly on a solid substrate surface, of compounds based on catechol and a method of preparing this ultra-thin layer which uses an environmentally friendly non-fluorinated solvent, e.g. a mixture of water and 2-propanol. Owing to the catechol base of the compounds used, this ultra-thin layer is firmly attached to the solid substrate surface. This ultra-thin layer has satisfactory properties for use as an epilame, in particular an, advancing contact angle with water and a spread of a drop, entirely comparable with that of the layer obtained from the commercial reference product, Fixodrop FK-BS.


The invention thus makes an important contribution to the eco-friendly preparation of epilames.


The catechol-based compounds have the general formula





A-B


in which


A represents a group of the formula







in which

    • Z represents C or N+,
    • X represents C—H or C-L, L being an electron-attracting group selected from F, Cl, Br, I, CF3, NO2 and N(CH3)3+,
    • Y represents H or CH3, or Y forms a 5- or 6-atom heterocycle with X,
    • T represents NH, NH—CO, NH—CO—NH or NH2+U, U being a soluble anion such as e.g. F, Cl, Br, I, OH, NO3, HSO4, SO42−, CO32−, HCO3 or SCN, and
    • B represents a C1-C20 linear aliphatic alkyl group partially or completely substituted with F.


The group A is used particularly to enable the attachment of the compounds to the surface of the solid substrate owing to the catechol group and the solubilisation of the amphiphilic molecule A-B in the dipping solution.


The group B provides the ultra-thin layer with its hydrophobic and oleophobic properties.


The group B is preferably a linear aliphatic alkyl group perfluorinated in its terminal section, e.g. with the formula





(CH2)n—(CF2)mCF3


in which n is 1 to 5, particularly 1 to 3, and m is 4 to 11, particularly 5 to 9.


Groups A of interest are those selected from one of the following groups:







A particularly useful compound is N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluorcundecanamide







(SuSoS2).


The compounds of formulae A-B can be obtained from known compounds using techniques and reactions well known to the organic chemist.


For example, N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecanamide can be obtained by reacting N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoate and 3-hydroxytyrosine hydrochloride in solution in DMF in the presence of N-methylmorpholine.


3-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-Heptadecafluoro-undecanamido)-6,7-dihydroxy-1,1-dimethyl-1,2,3,4-tetrahydroquinolinium







(SuSoS 3)

can be prepared from ANACAT and N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoic acid by processes similar to those described by Y. Bethuel, K. Gademann, J. Org. Chem. 2005, 70, 6258; Zürcher, S.; Wäckerlin, D.; Bethuel, Y.; Malisova, B.; Textor, M.; Tosatti, S.; Gademann, K. Journal of the American Chemical Society 2006, 128, 1064-1065.


1-(2-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-Heptadeca-fluoroundecanamido)ethyl)-3,4-dihydroxypyridinium







(SuSoS4)

can also be prepared by processes similar to those mentioned above from 1-(2-aminoethyl)-3,4-dihdyroxypyridinium and from N-succinimidyl 2H,2H,3H,3H-perflucroundecanoic acid.


N-(3,4-Dihydroxyphenethyl)-3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecan-1-aminium







(SuSoS5) can also be prepared by processes similar to those mentioned above from 3-hydroxytyrosine hydrochloride and 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-iodo-decane.


N-(4,5-Dihydroxy-2-nitrophenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadeca-fluoroundecanamide







(SuSoS6) can also be prepared by processes similar to those mentioned above from 4-(2-aminoethyl)-5-nitro-benzene-1,2-diol and N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoic acid.


The solid substrate on the surface of which the self-assembly takes place may be any solid substrate involved in the functioning of a mechanical movement, particularly composed of a material selected from gold, silver, steel, aluminium, brass, bronze, copper-beryllium, titanium dioxide, ruby, sapphire, as well as other metallic surfaces such as iron, chromium, tantalum, yttrium, silicon, germanium, copper, platinum, nickel and nickel-phosphorus, and metal oxides or ceramics, such as zirconia, or niobia (niobium oxide), this list being non-limitative. It is also possible to use as the substrate polymers such as polyethylenes, polystyrenes, polyamides, polydimethyl-siloxanes, polyvinyl chlorides or epoxy resins, this list also being non-limitative. The substrate may also be a substrate made of one of these materials or another, the surface of which has been covered or coated, for example by an electroplating of gold, of gold-copper-cadmium and of gold, of nickel, of rhodium, of tin-nickel, or treated by anodising, as in the case of parts made of aluminium alloy or titanium alloy, or modified by a surface treatment such as oxidation, carburisation or nitriding.


The thickness of the ultra-thin layer, measured by ellipsometry, is generally 0.5 to 10 nm, the upper value that will be used for the definition of ultra-thin, preferably 1 to 4 nm.


In order to be effective as an epilame, i.e. satisfactorily to prevent the spread of oil, the advancing contact angle with water must generally be at least 100°.


The ultra-thin, layer of formula A-B preferably remains effective as an epilame after two washing operations.


The invention also relates to a mechanical part characterised in that it comprises an ultra-thin layer as defined above.


The invention also relates to a method of preparing the ultra-thin layer defined above, characterised in that it comprises the immersion of the substrate in a solution of the compound of formula A-B, for example in water or a mixture of water and protic solvent such as, for example, 2-propanol. This method does not use any fluorinated solvent and is therefore environmentally friendly.


The invention will be better understood with the aid of the following examples, which are illustrative in nature and non-restrictive.







EXAMPLE 1
Synthesis of N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecanamide (SuSoS2)
Synthesis of N-succinimidyl 2H,2H,3H,3H-perfluoroundecanoate

2H,2H,3H,3H-Perfluoroundecanoic acid (1.354 g, 2.75 mmol), N-hydroxysuccinimide (348 mg, 3.02 mmol) and dicyclohexylcarbodiimide (622 mg, 3.02 mmol) were dissolved in ethyl acetate (120 ml) and stirred for 18 hours at ambient temperature. The white precipitate which formed (dicyclohexylurea, DCU) was filtered and the remaining solution was evaporated to dryness. The residue was recrystallised twice from ethyl acetate. Yield 1.00 g (62%) containing traces of DCU.



1H NMR (CDCl3, 300 MHz, ppm): 3.0 (m, 2H CH2), 2.88 (s, 4H CH2 NHS), 2.6 (m, 2H CH2).


Synthesis of N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecanamide

3-Hydroxytyrosine hydrochloride (257.5 mg, 1.35 mmol) and N-methylmorpholine (241 μl) were dissolved in DMF (8 ml). The NHS perfluoro ester (800 mg) was added and the mixture was stirred under a nitrogen atmosphere overnight. Water (40 ml) was added and the precipitate that formed was filtered and washed with water. The solid was dissolved in ethyl acetate and the organic phase was dried with magnesium sulfate. The solvent was evaporated and the residue recrystallised from chloroform (30 ml, 4° C.) Yield 752 mg (88%).


Molecular weight: 627.29%


% by weight: C, 36.38; H, 2.25; F 51.49; N 2.23; O 7.65 without H: C 47.5; F 42.5; N 2.5; O 7.5 1H NMR (CDCl3, 300 MHz, ppm): 8.7 (s broad, 2H OH), 8.08 (t, 1H NH), 6.7-6.4 (m, 3H dopamine), 3.2 (q, 2H CH2), 2.7-2.3 (m, 6H CH2),


corresponding to N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecanamide







EXAMPLE 2
Preparation of Dipping Solutions and Immersion of Various Substrates Therein
Preparation of Dipping Solution of SuSoS2

33 mg of SuSoS2 (0.052 mmol) were dissolved in 35 ml of 2-propanol in a 100 ml graduated flask and shaken until completely dissolved. Ultrapure water was added up to the mark and the solution was again shaken vigorously, which caused an increase in the temperature of the solution. After the solution returned to ambient temperature, a few drops of water were added to adjust the volume to 100 ml. The solution was subjected to ultrasound for 10 seconds to degas it and to allow complete mixing of the water and the 2-propanol.


Immersion of Substrates of Gold, Polished Steel, Aluminium, Titanium Oxide and Ruby in the Dipping Solutions

The samples of gold, polished steel, aluminium, titanium oxide and ruby were cleaned in a UV/ozone chamber for 30 minutes and immersed overnight in the solution of SuSoS2. The samples were then immersed in 2-propanol for 10 seconds, rinsed with additional 2-propanol and dried with a nitrogen flow. In the case of steel, the surfaces were lightly polished with a cloth soaked in 2-propanol, rinsed with additional 2-propanol and dried with a nitrogen flow.


EXAMPLE 3
Analysis of the Ultra-thin Layers Formed by Self-assembly on Various Substrates

The monolayers formed by self-assembly on the various substrates were analysed by

    • variable angle spectroscopic ellipsometry (VASE; cf. Feller et al. (2005), “Influence of poly(propylene sulfide-block-ethylene glycol) di- and triblock copolymer architecture on the formation of molecular adlayers on gold surfaces and their effect on protein resistance: A candidate for surface modification in biosensor research”, Macromolecules 38 (25): 10503-10510,
    • dynamic contact angle measurement (dCA; cf. Tosatti et al. (2002) “Self-Assembled Monolayers of Dodecyl and Hydroxy-dodecyl Phosphates on Both Smooth and Rough Titanium and Titanium Oxide Surfaces”, Langmuir 18(9): 3537-3548), as follows: the surface wettability was determined by measuring the advancing and the receding contact angles on a sessile drop (of water) (Contact Angle Measuring System, G2/G40 2.05-D, Krüss GmbH, Hamburg, Germany); the experiment was conducted automatically, increasing and reducing the size of the drop at a rate of 15 ml per minute; 480 values were measured for the advancing contact angle and 240 for the receding contact angle, at 3 different positions for each sample); the data collected were analysed using the tangent method 2 (adjustment routine of the prop-Shape Analysis program, version DSA 1.80.0.2 for Windows 9×/NT4/2000, (c) 1997-2002 KRUESS”), and
    • X-ray spectroscopy (XPS; Tosatti et al. above).


The various substrates used are

    • plates of silicon covered with a fine layer of gold
    • disks of polished steel
    • disks of polished ruby
    • plates of aluminium
    • plates of silicon covered with a fine layer of titanium dioxide


The main parameters measured by VASE and CA are compiled in Table 1 below.









TABLE 1







Thickness measured by ellipsometry and


advancing contact angles with water












Thickness measured
Advancing contact


Substrate
Modification
by ellipsometry (nm)
angle with water [°]





Gold
Clean

approx. 50



SuSoS2
0.7
115.6 ± 0.8


Polished
Clean

<10


steel
SuSoS2
3.3
116.8 ± 2.5


Aluminium
Clean
not measured
<10



SuSoS2
not measured
126.2 ± 1.9


Titanium
Clean

<10


dioxide
SuSoS2
1.4
116.5 ± 0.6


Ruby
Clean
not measured
<10



SuSoS2
not measured
109.9 ± 2.1









Analysis by X-ray photoelectron spectroscopy (XPS) shows that the SuSoS2 molecules are present on all the surfaces by detection of the elements N and F.


These results show that an ultra-thin layer of SuSoS2, whose thickness, measured by ellipsometry, does not correspond exactly to the expected thickness of a well-ordered monolayer, is obtained on all the substrates tested.


Nevertheless, the advancing contact angle values with water are satisfactory for use as an epilame (greater than 100°).


EXAMPLE 4
Comparison of Ultra-fine Layers Formed by Self-assembly of SuSoS2 and Fixodrop FK-BS on Surfaces of Gold, Polished Steel and Ruby
1) Preparation of Ultra-fine Layers of SuSoS2 and Fixodrop on the Surfaces of the Various Substrates

Surfaces of substrates of gold, polished steel and ruby are covered with an ultra-fine layer of SuSoS2 as described in example 2. The surface appearance is excellent for gold and ruby; the layer is invisible and no mark resulting from the deposit can be distinguished.


Surfaces of substrates of gold, polished steel and ruby are covered with an ultra-fine layer of Fixodrop EK-BS in accordance with the manufacturer's instructions by dipping the substrates in a solution of tetradeca-fluorohexane.


The thickness of this layer measured by ellipsometry on gold is 0.7 nm for SuSoS2 and 1.7 nm for Fixodrop.


2) Measurement of Contact Angles with Different Solvents and Determination of Surface Energies

The advancing contact angles with water, hexadecane, diiodomethane and ethylene glycol were measured by dynamic contact angle measurement using a goniometric technique similar to that used in example 3.


The dispersive and polar components of the surface energy were deduced from these measurements using the Owens-Wendt model (Owens D. K. and Wendt R. C., 1969, Journal of Applied Polymer Science, 13, 8, p. 1741).


The main results obtained are compiled in table 2 below.









TABLE 2







Contact angles and surface energies with various solvents












Steel
Ruby
Gold
Gold


Liquid
SuSoS2
SuSoS2
SuSoS2
Fixodrop














Contact angle [°]






Hexadecane
64.1
56.8
47.3
56.8


Diiodomethane
90.4
84.4
77.8
78.0


Ethylene glycol
93.2
87.2
84.9
88.4


Water
103.0
113.8
104.8
104.2


Surface energy [mJ/m2]


Dispersive
12.5
16.3
18.6
16.8


Polar
2.2
0.2
0.8
0.4


Total
14.6
16.6
19.4
17.3









For gold, steel and ruby, these contact angles with water, hexadecane, diiodomethane and ethylene glycol are acceptable for use as an epilame, comparable with those measured for Fixodrop.


For gold, steel and ruby, the layer formed with SuSoS2 exhibits only a dispersive nature, as expected for a molecule of this type. The surface energy seems to vary with the material, but is in all cases less than 20 mJ/m2. The lowest energy and therefore in principle the best behaviour) is obtained for steel, followed by ruby and gold.


3) Measurement of Lubricant Spread

The spread of lubricants on a surface is characterised by measuring the average diameter of a drop of typically 0.5 mm in diameter immediately after depositing the drop and after 20 minutes. The spread corresponds to the relative variation in the average diameter after 20 minutes. A good lubricant behaviour corresponds to a spread of 2% or less. A spread greater than 10% can be observed by the naked eye and is not acceptable. The oils used for the tests are a watchmakers' oil “941” (Moebius et Fils, mixture of alkyl-aryl-monooleate and two C10-C13 diasters, viscosity of 110 cSt at 20° C., surface tension of 32.8 mN/m) and a CESNIII test oil (Laboratoire Suisse de Recherches Horlogères, silicone oil, surface tension of 23.1 mN/m, “La Suisse Horlogère” No 43, 7.11.1974).


The spread obtained on surfaces of steel, ruby and gold coated with the SuSoS2 molecule, and a gold surface coated with the commercial product Fixodrop PK-BS from Moebius et Fils in accordance with the manufacturer's instructions, is compared. For the SuSoS2 molecule, the spread is less than 1% in all cases and is comparable to that measured for Fixodrop, as shown by the table below.









TABLE 3







Lubricant spread













Ultra-
Moebius
CESNIII



Surface
thin layer
941 oil
oil
















Steel
SuSoS2
0.11%
0.92%



Ruby
SuSoS2
0.37%
0.46%



Gold
SuSoS2
0.30%
0.14%



Gold
Fixodrop FK-BS
−0.90% 
0.86%










4) Conclusion

For all the surfaces investigated, the contact angle obtained on the ultra-thin layers formed with the SuSoS2 molecule is greater than 100°, the surface energy is less than 20 mJ m−2 and the spread is less than 1%.


The layers display good resistance to washing treatments on ruby, but less good on gold and steel.


The properties of the ultra-thin SuSoS2 layer are equivalent to those obtained with the commercial product Fixodrop.

Claims
  • 1. An ultrathin hydrophobic and oleophobic layer, formed by self-assembly on a solid substrate surface, of compounds of the general formula, A-Bin whichA represents a group of the formula
  • 2. An ultra-thin layer as claimed in claim 1, wherein B is a linear aliphatic alkyl group perfluorinated in its terminal section, having the formula (CH2)n—(CF2)mCF3 in which n is from 1 to 5 and m is from 4 to 11.
  • 3. An ultra-thin layer as claimed in claim 2, wherein n is from 1 to 3 and m from 5 to 9.
  • 4. An ultra-thin layer as claimed in claim 1, wherein A is selected from one of the following groups:
  • 5. An ultra-thin layer as claimed in claim 1, wherein it is obtained from N-(3,4-dihydroxyphenethyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecanamide.
  • 6. An ultra-thin layer as claimed in claim 1, wherein the solid substrate is composed of a material selected from gold, silver, steel, aluminium, brass, bronze, copper-beryllium, titanium dioxide, ruby, sapphire, silicon, nickel and nickel phosphorus, as well as other metallic surfaces such as iron, chromium, tantalum, yttrium, germanium, copper, platinum, and metal oxides or ceramics, such as zirconia or niobia (niobium oxide), or polymers such as polyethylenes, polystyrenes, polyamides, polydimethylsiloxanes, polyvinyl chlorides, epoxy resins, or a substrate made of one of these materials or another, the surface of which has been covered or coated, for example by an electroplating of gold, of gold-copper-cadmium and of gold, of nickel, of rhodium, of tin-nickel, or treated by anodising, as in the case of parts made of aluminium alloy or titanium alloy, or modified by a surface treatment such as oxidation, carburisation or nitriding.
  • 7. An ultra-thin layer as claimed in claim 1, wherein its advancing contact angle with water is at least 100°.
  • 8. An ultra-thin layer as claimed in claim 1, wherein its thickness measured by ellipsometry is from 0.5 to 10 nm.
  • 9. A mechanical party wherein it comprises an ultra-thin layer as claimed in claim 1.
  • 10. A method of preparing an ultra-thin layer as claimed in claim 1, wherein it comprises the immersion of the substrate in a solution of the compound of formula A-B in water or a mixture of water and protic solvent.
  • 11. A method as claimed in claim 10, wherein the protic solvent is 2-propanol.
  • 12. Use of an ultra-thin layer as claimed in claim 1 as a barrier film.
Priority Claims (1)
Number Date Country Kind
06405505.6 Dec 2006 EP regional
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/CH07/00603 11/29/2007 WO 00 7/6/2009