Fluorinated polyether-silane

ES 2 320 134 T3

DESCRIPTION

Fluorinated polyether silane.

The present invention relates to a polyether isocyanate derivative fluorinated silane, a composition and method for treating substrates, in particular substrates having a hard surface such as ceramic or glass, to make them impervious to water, oil, stains, and dirt. The present invention also relates to compositions for use in said method.

The use of fluorinated silanes, that is, silane compounds having one or more fluorinated groups, is known to render substrates such as glass or ceramics impervious to oil and water. For example, US 5,274,159 describes fluorinated alkoxy silane destructible surfactants that can be applied from an aqueous solution. WO 02/30848 describes compositions comprising fluorinated polyether silanes to render ceramics impervious to oil and water.

EP 797111 describes compositions of alkoxysilane compounds containing perfluoropolyether groups to form antifouling layers on optical components. Additionally, the U.S. Patent No. 6,200,884 describes perfluoropolyether modified aminosilane compositions that polymerize into films having improved water and oil repellency and anti-stain properties.

EP 789050 describes the use of polyether fluorinated silanes to make film coatings of compounds. US 3,646,085 teaches polyether fluorinated silanes for rendering glass or metal surfaces impermeable to oil and water. WO 99/37720 describes fluorinated polyether silanes for providing anti-reflective surfaces with an anti-dirt coating on substrates such as glass or plastic. US 3,950,588 describes the use of fluorinated polyether silanes to make ceramic surfaces, such as bathroom tiles or kitchen utensils, impervious to water and / or oil.

Although many fluorinated silane compositions are known in the prior art for treating substrates to make them impervious to oil and water, there remains a desire to provide more improved compositions for treating substrates, in particular substrates having a hard surface such as ceramics, glass and stone, in order to make them impervious to water and oil and easy to clean. There is also a need to treat glass and plastics as a hard surface, particularly in the ophthalmic field, in order to make them resistant to stains, dirt and dust. It is desired that such compositions and methods using them can produce coatings having improved properties. In particular, it would be desirable to improve the durability of the coating, including better abrasion resistance of the coating. In addition, improving the cleanability of such substrates while using less detergents, water or manual labor, is not only a wish for the end consumer, but also has a positive impact on the environment. In particular, it is also desired that the coatings show good chemical resistance, particularly when exposed to various cleaning compositions with a pH greater than 9. The compositions can be conveniently applied in an easy and safe manner and be compatible with existing manufacturing methods. Preferably, the compositions will fit easily into the manufacturing processes that are practiced to produce the substrates to be treated. The compositions preferably also avoid the use of ecologically offensive components.

The present invention provides in one aspect a composition for treating a substrate that includes a mixture of: 1) a fluorinated polyether isocyanate derivative silane or a mixture thereof that includes the reaction product of (i) a fluorinated polyether compound of the formula.

T '_k-Q '_Y) -R_F-QT_k (I) where R_F is a monovalent or divalent polyfluoropolyether group; Q and Q 'are independently a chemical bond, a divalent linking organic group or a trivalent linking organic group; T and T 'are each NCO or a reactive isocyanate group; k 'is an integer from 0 to about 5; k is at least 2; and y is 0 or 1; and (ii) a silane compound of the formula

T ”-Q” -Yes (Y3__x) R '_x (II) where T "is -NCO or a reactive isocyanate group; Q "is a divalent linking organic group; R 'is an alkyl group, for example, a C alkyl group₁-C₄, or an aryl group, such as, for example, phenyl, naphthyl, or substituted phenyl or naphthyl, where the phenyl or naphthyl is substituted by one or more substituents such as C-alkyl₁-C₄, C alkoxy₁ -C₄, halo, nitro, and the like; Y is a hydrolyzable group; and x is 0 or 1; where at least one of the T or T "is -NCO where the reactive isocyanate group is -C (O) N (R¹) (R²), where R¹ and R² they are independently hydrogen, hydroxyalkyl or polyalkylenepolyamine 2) an organic solvent; and, optionally, 3) a surfactant, such as a hydrocarbon, silicone or fluorinated surfactant or a mixture thereof.

ES 2 320 134 T3

It has been found that when an isocyanate-derived polyether fluorinated silane, for example an isocyanate-derived polyether fluorinated silane, as defined above, is applied from a solution containing an organic solvent, waterproof coatings can be obtained. to oil and water that have excellent abrasion resistance and chemical resistance and very good easy-to-clean properties, in particular when exposed to various cleaning compositions with a pH greater than 9. Furthermore, the compositions spread well on the substrate to be treated with the result that uniform properties can be achieved over the entire surface of the treated surface.

By the term "solution", in relation to the present invention, it is meant that the composition is stable, that is, precipitation does not occur, for at least the amount of time necessary to prepare the composition and apply it to the substrate. Generally, this means that the composition will be stable for at least one hour. Compositions of the invention were generally found to have a stability of about 1 day or even longer.

Advantageously, the compositions of the invention are prepared by diluting a concentrated solution of the fluorinated silane derived from polyether isocyanate as defined above. For example, a concentrated solution of at least 25% by weight of a fluorinated silane derived from polyether isocyanate in an organic solvent is diluted by adding additional organic solvent (s) to said solution in order to prepare a solution containing between about 0.01 and 5.0% by weight of the polyether isocyanate derivative fluorinated silane.

In another aspect, the present invention also provides a method of treating a substrate, including the step of applying the composition of the invention as defined above to the substrates. Preferably, the coating obtained on the substrate is cured, generally at a temperature of about 20 to 300 ° C, depending on the chosen cure catalyst. The substrate can be preheated in order to cause the composition to cure when applied, or alternatively the heating can take place simultaneously with or subsequent to application of the composition to the substrate.

In still another aspect, the invention provides novel polyether isocyanate derived fluorinated silanes prepared from the reaction product of a composition including a mixture of polyether isocyanate derived fluorinated silane or a mixture thereof that includes the reaction product of :

(i) a fluorinated polyether compound of the formula

T'k-Q ') and-Rf-Q-Tk (I) where R_F is a monovalent or divalent polyfluoropolyether group; Q and Q 'is independently a chemical bond, a divalent linking organic group or a trivalent linking organic group; T and T 'are -NCO or a reactive isocyanate group; k 'is an integer from 0 to about 5; k is at least 2; and y is 0 or 1; and (ii) a silane compound of formula

T ”-Q” -Yes (Y₃__x) R '_x (II) where T "is each independently selected from the group consisting of -NCO, and reactive isocyanate groups; Q "is a divalent linking organic group; R 'is an alkyl group or an aryl group; Y is a hydrolyzable group; and x is 0 or 1, and where at least one of T or T "is -NCO where the reactive isocyanate group is -C (O) N (R¹) (R²), where R¹ and R² they are independently hydrogen, hydroxyalkyl or polyalkylenepolyamine.

Also, the fluorochemical compositions of the present inventions are generally environmentally friendly in that the compositions that can be obtained are substantially free of fluorochemical components that are slowly eliminated from the body of living organisms. Furthermore it is believed that fluorochemical breakdown products, which can also form, are well removed from the body of living organisms. In particular, the evidence shows that fluorinated polyether compounds having a perfluorinated polyether moiety having a molecular weight of at least 750 g / mol and perfluorinated polyether degradation products that can be formed therefrom could be further removed. effectively from the body of living organisms. In particular, there are indications that fluorinated polyether compounds having a fluorinated polyether moiety derived from a polycondensation of hexafluoropropylene oxide and having a molecular weight of at least 750 g / mol could be more efficiently removed from the body of living organisms in comparison with long chain perfluoroaliphatic compounds having, for example, 8 perfluorinated carbons.

In still another aspect, the invention provides articles, for example, glass or ceramic substrates having protective coatings on at least a portion of the surface thereof wherein the coatings comprise a fluorinated silane derived from polyether isocyanate as described herein. present memory.

The monovalent or divalent polyfluoropolyether group Rf in formula I above can include linear, branched and / or cyclic structures, which can be saturated or unsaturated. It is a perfluorinated group (that is, all

ES 2 320 134 T3 CH bonds are replaced by CF bonds). In one embodiment, the perfluorinated polyether group corresponds to the formula

- ((R3f) q-R2f-O) x-R1f- (O-R2f- (R3f) q) x- (III) where Rf¹ is a perfluorinated alkyl or perfluorinated alkylene group, Rf² is a perfluorinated polyalkyleneoxy group consisting of perfluorinated alkyleneoxy groups having 1, 2, 3, or 4 carbon atoms or a mixture of said perfluorinated alkyleneoxy groups; Rf³ is a perfluorinated alkylene group or a substituted perfluorinated alkyl group; q and q 'are independently chosen from 0 or 1; z is 4 to 30, and z 'is 0 to 30. The perfluorinated alkyl or alkylene group R¹f in formula (II) can be linear, branched or cyclic and can contain stranded heteroatoms, such as N, O or S, and can contain 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. R²f and R³f are repeating perfluorinated units and combinations thereof. For example, R³f is - (C_BF_2n) -o- (CF (Z)) - R²_F, for example, includes perfluorinated repeating units such as - (C_nF_2nO) -, - (CF (Z) O) -; - (CF (Z) C_nF_2nO) -, - (C_nF_2nCF (Z) O-, - (CF₂CF (Z) O) -, and combinations thereof. In these repeating units Z is a perfluoroalkyl group, a substituted perfluoroalkyl group, an oxygen substituted perfluoroalkyl group, a perfluoroalkoxy group or an oxygen substituted perfluoroalkoxy group, all of which may be linear, branched or cyclic and preferably have about 1 to about 9 carbon atoms and 0 to about 4 oxygen atoms. Examples of polyfluoropolyethers containing polymeric moieties made from these repeating units are described in US Patent No. 5,306,758.

Typical approximate average structures for a divalent perfluoropolyether group include -CF₂O (CF₂OR)_m(C₂F₄OR)_pCF₂-, where an average value for myp is 0 to 50, provided that myp are not simultaneously 0, -CF (CF₃) OR (CF (CF₃) CF₂OR)_pCf (CF₃) -, -CF₂O (C₂F₄OR)_pCF₂-, and - (CF₂)₃O (C₄F₈OR)_p(CF₂)₃-, where an average value for p is 3 to 50. Of these, particularly preferred approximate average structures are -CF₂O (CF₂OR)_mC₂F₄OR)_pCF₂-, -CF2O (C2F4O) pCF2-, y-CF (CF3) (OCF2 (CF3) CF) pO (CF2) mO (CF (CF3) CF2O) pCF (CF3) -.

Typical approximate average structures for a monovalent perfluoropolyether group, R_F, include CF₃CF₂O (CF2O) m (C2F4O) pCF2-, CF3CF2O ^ F4O) pCF2-, CF3O (CF2O) m (C2F4O) pCF2-, CF3CF2CF2O (CF (CF3) CF2O) pCF (CF3) -, or combinations thereof; where an average value for myp is 0 to 50 and myp are not independently 0.

When synthesized, these compounds typically include a mixture of polymers. The approximate average structure is the approximate average of the polymer blend.

Examples of linking groups Q, Q 'and / or Q "include organic groups comprising aromatic or aliphatic groups that can be interrupted by O, N, or S and that can be substituted, alkylene groups, oxy groups, thio groups, and / or carbonyl groups. Q and Q 'are each independently a chemical bond or a divalent or trivalent linking organic group for example as mentioned above. In compounds of formula I, k is at least 2, T and T 'are as mentioned above and each T or T' can be chosen independently, and y is 0 or 1. According to a particular embodiment, the moiety -T or -T 'is a remainder of the formula -CO-N (R¹) (R²), where R¹ it is for example -CH2CH2OH. -CH2CH2NHCH2CH2NH2 or -CH2CH2NHCH2CH2NHCH2CH2NH2. and R² is for example hydrogen or R¹.

In formula II above, T "is a group as defined for T above. In one embodiment T "includes at least one -NCO group. When T "is not -NCO, then T includes at least one -NCO group.

The divalent linking group Q "in formula (II) above can include linear, branched or cyclic structures, which can be saturated or unsaturated. The group Q "may contain one or more heteroatoms (eg, oxygen, nitrogen, or sulfur) or functional groups (eg, carbonyl, amido, urethanylene, or sulfonamido). Preferably, the divalent linking group Q "is a hydrocarbon group, preferably a linear hydrocarbon group, optionally containing heteroatoms or functional groups. Examples of Q "groups include -CH2O (CH2) 3-, -CH2OC (O) N (R) (CH2) 3-, where R is H or a lower alkyl group, - (CnH2n) -N (H) -C (O) O- and - (CnH2n) -, where n is about 2 to about 6. A preferred Q "linking group is -CH₂CH₂CH₂-.

Y represents a hydrolyzable group in formula (II) such as for example a halide, a C alkoxy group₁-C₄, an acyloxy group or a polyoxyalkylene group, such as the polyoxyethylene groups described in US 5,274,159. Specific examples of hydrolyzable groups include methoxy, ethoxy, and propoxy groups. R 'independently represents a C alkyl group₁-C₄, such as, for example, methyl and ethyl groups.

Compounds of formula I suitable for compositions for treating substrates of the present invention have an average molecular weight (weight average) of at least about 200, and preferably, at least about 800. Preferably, they are not greater than about 10,000.

The values ​​of m and p illustrated above for isocyanate derived fluorinated silanes can vary. Typically, an average value of m is within a range of about 1 to about 50, and an average value of p is within a range of about 4 to about 40. Since these are oligomeric or polymeric materials, such compounds exist as mixtures. after synthesis, which are suitable for

ES 2 320 134 T3 its use. These mixtures can also contain perfluoropolyether chains without bearing functional groups (inert liquids) or more than two terminal groups (branched structures) as a consequence of the methods used in their synthesis. Typically, mixtures of oligomeric or polymeric materials can be used that contain less than about 10% by weight of non-functional polymers (eg, those without urethane silane groups). In addition, mixtures of any of the individually listed compounds of formula I can be used.

As a specific example, the isocyanate component to make the fluorinated compound of the fluorochemical composition is of the formula OCN-Q "-SiY_3-xR¹_x as defined above or (T '_k, _Q ')_Y-R_FQT_k as defined above where T includes one to three isocyanate groups, OCN.

The isocyanate compound can be aliphatic or aromatic and is conveniently a non-fluorinated compound. Generally, the molecular weight of the polyisocyanate compound will not be more than 1500 g / mol. Examples include, for example, stearyl isocyanate, phenylisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,2-ethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclic trimer of hexamethylene diisocyanate, and cyclic trimer of hexamethylene diisocyanate. isophorone diisocyanate (isocyanurates); Aromatic polyisocyanates such as 4,4'-methylene diphenylene diisocyanate, 4,6-di- (trifluoromethyl) -1,3-benzene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, o-, m- diisocyanate, and p-xylylene, 4,4'-diisocyanatodiphenyl ether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3 '-dimethyl-4,4'-diisocyanatodiphenyl, 1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate, 4-chloro-1,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and 1,8-dinitro-2,7-naphthylene diisocyanate. Still other isocyanates that can be used to prepare the fluorinated compound include cyclic diisocyanates. Also useful are isocyanates containing internal isocyanate-derived moieties such as azetedinedione containing diisocyanates such as that available from Bayer as DESMODUR ™ TT. Also suitable are other di- or tri-isocyanates such as those available from Bayer as DESMODUR ™ L, DESMODUR ™ N, and DESMODUR ™ W, tri- (4-isocyanatophenyl) -methane (available from Bayer as DESMODUR ™ R) and DDI 1410 (available from Henkel). Diisocyanates can first be condensed with the fluorinated moiety (eg polyether dialcohols) or with the appropriate alkoxy silane (eg aminoalkylalkoxysilanes, such as aminopropyltrimethoxysilane or aminopropyltriethoxysilane, or mercaptoalkylsilanes, such as mercaptopropyltriethoxysilane).

Silanes derived from isocyanate perfluoropolyether can be prepared using standard techniques. Generally, one or more compounds of formula I are reacted with one or more compounds of formula II. For example, commercially available or newly synthesized perfluoropolyether diols can be combined with an isocyanate alkoxysilane, such as 3- (triethoxysilyl) propyl isocyanate, commercially available from Aldrich Chemicals, Milwaukee, WI, by known methods, which are described in the examples. Such materials may or may not need to be purified before use in a treatment composition.

Alternatively, isocyanate perfluoropolyether derived silanes can be synthesized first by reacting one or more isocyanate-containing compounds of formula I with isocyanate-reacting material (s), followed by condensation of residual isocyanate groups with reagents that they contain a silane functionality, for example aminopropyltriethoxysilane or mercaptopropyltriethoxysilane.

The compounds according to formula (I) can be obtained, for example, by oligomerization of hexafluoropropylene oxide, which results in a perfluoropolyether carbonyl fluoride. This carbonyl fluoride can be converted to an acid, acid salt, ester, amide, or alcohol by reactions well known to those skilled in the art. The carbonyl fluoride or acid, ester or alcohol derived therefrom can further be further reacted to introduce the desired reactive groups according to known procedures. For example, EP 870 778 describes suitable methods for producing compounds according to formula (I) having the residues -QT_k desired. Compounds having the moiety -CON (R1) (CH₂)_nOH listed above can be obtained by reacting the methyl ester derivative of a fluorinated polyether with an amino alcohol. For example, 2-aminoethanol can produce a compound having the moiety -CONHCH2CH2OH. In the same way, the methyl ester of a fluorinated polyether can be reacted with diethylenetriamine or triethylenetetraamine to form -CONHCH2CH2NHCH2CH2NH2 and -CONHCH2CH2NHCH2CH2NH-CH2CH2NH2 moieties respectively.

Furthermore other examples of compounds according to formula (I) above are described in EP 870 778 US 3,536,710.

A composition of the present invention includes one or more organic solvents. The preferred organic solvent or mixture of organic solvents should be capable of dissolving at least 0.01% of the polyether isocyanate derivative fluorinated silane as defined above. In addition, the organic solvent makes the surfactant (s) and the fluorinated silane (s) compatible (in case they are not compatible in the absence of the organic solvent), and decreases the viscosity. of the dilutable nonaqueous concentrate Suitable organic solvents, or solvent mixtures are polar organic solvents and can include aliphatic alcohols, such as methanol, ethanol, isopropyl alcohol; ketones such as acetone or methyl ethyl ketone; esters, such as ethyl acetate, methylformate, and ethers, such as diisopropyl ether, 1,4-dioxane, and diethylene glycol dimethyl ether; and amides, such as N-methylpyrrolidinone, and N, N-dimethylformamide, and mixtures thereof. Fluorinated solvents such as, for example, heptafluorobutanol, trifluoroethanol and hexafluoroisopropanol, can be used alone or in combination with other organic solvents that do not contain fluorine, in order to improve the solubility of the polyether isocyanate derivative fluorinated silane.

ES 2 320 134 T3

Preferred organic solvents are aliphatic alcohols. Some examples of preferred aliphatic alcohols are ethanol, and isopropyl alcohol.

Preferably the organic solvent is miscible with water. Also, preferably, the organic solvent has a boiling point that is below 200 ° C.

Optionally, the composition of this invention may also include surfactants to make the composition water soluble or water dispersible.

A surfactant is defined as “a substance which, when present at low concentration in a system, has the property of adsorbing onto the surfaces or interfaces of the system and of altering, to a marked degree, the surface or interfacial free energies of these surfaces. " (Milton J. Rosen, "Surfactants and Interfacial Phenomena," Second Ed., John Wiley & Sons, New York, NY, 1989, page 1). These surfactants have “a characteristic molecular structure consisting of a structural group that has very little attraction to [a] solvent, known as a lyophobic group, together with a group that has a strong attraction to [a] solvent, called the lyophilic group. .... ”(Milton J. Rosen,“ Surfactants and Interfacial Phenomena, ”Second Ed., John Wiley & Sons, New York, NY, 1989, pages 3-4). When the solvent is aqueous, the lyophobic group is typically a non-polar group such as alkyl or fluorinated alkyl, while the lyophilic group is a polar group.

The term "fluorinated" (as the term fluorinated surfactant) indicates that at least about 75 percent, preferably at least about 85 percent, more preferably at least about 95 percent, of the hydrogen atoms of the alkyl moiety are replaced by fluorine atoms. Optionally, the remaining hydrogen atoms can be replaced by other halogen atoms, such as chlorine atoms.

Fluorinated surfactant acts to stabilize an emulsion (that is, droplets of a liquid phase dispersed in another liquid phase) or dispersion, and can aid in the solubility or compatibility of the fluorinated silane (s) and the ) organic cosolvent (s) (if there is one or more organic cosolvent (s)) of the dilutable nonaqueous concentrate.

Fluorinated surfactants useful in this invention are amphiphilic materials, comprising one or more hydrophobic fluorochemical segments and one or more solubilizing and hydrophilic segments. Such materials are described in "Fluorinated Surfactants and Repellents", Second Edition, by E. Kissa, Surfactant Science Series, Volume 97, Marcel Dekker, Inc .: New York, 2001, pp. 1- 21. Fluorinated surfactants have a fluorine content by weight of at least 10%. These fluorinated surfactants can be monomeric or polymeric, with molecular weights between about 300 and about 100,000 grams per mole, preferably between about 400 and about 20,000 grams per mole. Hydrophobic fluorochemical groups can be, for example, perfluoroalkyl containing between about 3 and about 20 carbon atoms, or a mono- or divalent perfluoropolyether group with molecular weight between about 300 and about 10,000 grams per mole. Hydrophilic groups in fluorinated surfactants can be anionic (such as carboxylate), cationic (such as quaternary ammonium), nonionic (such as oligo (oxyethylene)), or amphoteric (such as amine oxide) as long as they do not contain functionalities that cause instability in the concentrates of this invention, for example strongly acidic groups, strongly basic groups, or contamination by fluorine ions.

Representative fluorinated surfactants include, but are not limited to, the following:

C₇F₁₅CO₂-NH4⁺

C₈F₁₇SW₂N (C₂H₅) C₂H4O)₇CH3

C₈Fi7 (C₂H4O) iqH (C4 F₉SO2) 2N^-NH4⁺

C4F₉SO2N (CH₃) (C2H4O)_nCH3 (where n_approx-7) C₃F7O (CF (CF₃) CF2O)_nCF (CF₃) CO2-NH4⁺ (where_approx-13)

Examples of these and other fluorinated surfactants of the present invention are described, for example, in US Patent Nos. 3,772,195 (Francen), 4,090,967 (Falk), 4,099,574 (Cooper et al.) , 4,242,516 (Mueller), 4,359,096 (Berger), 4,383,929 (Bertocchio et al.), 4,472,286 (Falk), 4,536,298 (Kamei et al.), 4,795,764 (Alm et al. ), 4,983,769 (Bertocchio et al.) And 5,085,786 (Alm et al.). Some of these fluorinated surfactants are commercially available from Minnesota Mining and Manufacturing Company (St. Paul, Minnesota), which carry the FLUORAD ™ trademark, or commercially available from EI DuPont de Nemours and Co. (Wilmington, Delaware), which have the trademark ZONYL^TM.

Polymeric fluorinated surfactants can also be used in the present invention. Examples of polymeric fluorinated surfactants that can be used in the present invention are found in US Patent Nos. 3,787,351 (Olson), 4,668,406, and International PCT Application WO 01/30873.

ES 2 320 134 T3

Examples of polymeric fluorinated surfactants that may be used include random copolymer fluorinated surfactants. Examples of random copolymer fluorinated surfactants include the following structures:

<img file="ES2320134T3_D0001.tif" />

Where the molar ratio of a: b: c is about 30: about 1: about 32, and where the molecular weight of the surfactant is about 1,000 to about 4,000 grams per mole; Y

<img file="ES2320134T3_D0002.tif" />

where the molar ratio of a ': b': c 'is about 3: about 3: about 1, and where the molecular weight of the surfactant is about 2,000 to about 40,000 grams per mole.

The surfactant can also be a hydrocarbon or silicone surfactant, which is not reactive with the isocyanate-derived silane. The hydrocarbon surfactant may be a cosurfactant with a fluorinated surfactant mentioned above. Typically, a hydrocarbon surfactant includes, for example, nonionic surfactants, such as Triton ™ X-305, Surfynol ™ 465 or Tween.^TM 80, cationic surfactants such as Arquad ™ 2C-75 and anionic surfactants such as Witcolate^TM 4085.

The surfactant or surfactant mixture is generally included in the concentrate in an amount up to about 50% by weight, preferably up to about 30% by weight,

Suitable substrates that can be treated in a particularly effective manner with the isocyanate polyether-derived fluorinated silane mixture of this invention include substrates having a hard surface preferably with functional groups capable of reacting with the isocyanate-derived fluorinated silane of the invention. . Preferably, said substrate surface reactivity is provided by active hydrogen atoms. When such active hydrogen atoms are not present, the substrate must first be treated in an oxygen-containing plasma or corona atmosphere or treated with a primer, such as a SiO2 layer to make it reactive to the fluoropolyether silane.

Treatment of substrates results in treated surfaces holding less dirt and easier to clean due to the oil and water impervious nature of the treated surfaces. These desirable properties are maintained despite extended exposure or use and repeated cleaning, due to the high degree of durability of the treated surface as can be obtained by the compositions of this invention.

Preferably, the substrate should be cleaned before applying the compositions of the invention in order to obtain optimal characteristics, particularly durability. That is, the surface of the substrate to be coated should be substantially free of organic and inorganic contamination prior to coating. Cleaning techniques depend on the type of substrate and include, for example, a solvent wash step with an organic solvent, such as acetone or ethanol, or a reactive gas phase treatment such as UV / ozone.

ES 2 320 134 T3

Useful substrates include ceramics, glazed ceramics, glass, metals (such as aluminum, iron, stainless steel, copper, and the like), natural and artificial stone, thermoplastic materials (such as poly (meth) acrylate, polycarbonate, polystyrene, styrene copolymers such such as styrene / acrylonitrile copolymers, and polyesters such as polyethylene terephthalate), and wood. Additionally, the compositions of the invention can also be added to paints (such as those based on acrylic resins), and powder coatings (such as polyurethane, epoxy or hybrid powder coatings) for application to the substrates listed above.

Particularly preferred substrates include those siliceous substrates including ceramics, glazed ceramics, glass, concrete, mortar, grout, and natural and artificial stone. Various articles can be effectively treated with the fluorochemical solution of the present invention to provide an oil and water repellent coating thereon. Examples include ceramic tiles, bathtubs or toilets, glass shower panels, building glass, various parts of a vehicle (such as the rear view mirror or windshield), and glazed porcelain or ceramic materials. Treatment of glass used for ophthalmic uses, for example glass lenses, with the composition of the present invention is especially advantageous.

Another preferred substrate is an anti-reflective substrate. Anti-reflective (AR) surfaces are substrates prepared by vacuum spraying thin metal oxide films onto substrates made of glass or plastic and are particularly useful in ophthalmic devices and electronic equipment display devices. Said metal oxide films are relatively porous and consist of a group of particles that form a relatively rough profile. These coatings help reduce glare and reflection. When used in ophthalmic glasses they reduce asthenopia or visual fatigue. When they are conductive coatings, they also help reduce static discharge and electromagnetic emission. Thus, one application for these coatings is to provide increased contrast and anti-reflective properties to improve the readability of display devices, such as computer monitors. In US document 5,851,674 discloses anti-reflective substrates.

Powdered metal oxide anti-reflective coatings are generally durable and uniform. Furthermore, their optical properties are controllable, which makes them desirable. They also have very high surface energies and refractive indices. However, the high surface energy of a powdered metal oxide surface makes it prone to contamination by organic impurities (such as skin oils). The presence of surface contaminants results in further degradation of the anti-reflective properties of metal oxide coatings. Furthermore, due to the high refractive indices, surface contamination becomes extremely noticeable to the end user.

The present invention provides a protective coating on an anti-reflective surface that is relatively durable, and more resistant to contamination and easier to clean than the anti-reflective surface itself. The present invention provides in one embodiment a method and composition for use in preparing an anti-reflective article comprising a substrate having an anti-reflective surface and an anti-soiling coating of about less than 200 Angstroms thick deposited thereon. The anti-fouling coating comprises an isocyanate-derived fluorinated siloxane film of a thickness that substantially does not change the anti-reflective characteristics of the anti-reflective article.

Preferably, the overall thickness of the anti-fouling coating is greater than a monolayer (which is typically greater than about 15 Angstroms thick). That is, preferably, an anti-fouling coating of the present invention is at least about 20 Angstroms thick, and more preferably, at least about 30 Angstroms thick. Preferably, it is less than about 200 Angstroms thick, and more preferably, less than about 100 Angstroms thick. The coating material is typically present in an amount that does not substantially change the anti-reflective characteristics of the anti-reflective article.

The coating composition is typically a relatively dilute solution, containing between 0.01 and 5 percent by weight inclusive of the fluorinated silane derived from polyether isocyanate, more preferably, between 0.01 and 3 percent by weight inclusive of the fluorinated silane. derived from polyether isocyanate, and most preferably, between 0.02 and 0.2 percent by weight inclusive of the silane.

For ease of manufacture and for cost reasons, the compositions of the present invention can be prepared immediately prior to use by diluting a concentrate of one or more of the polyether isocyanate derived fluorinated silanes. The concentrate will generally comprise a concentrated solution of the polyether isocyanate derivative fluorinated silane in an organic solvent. The concentrate will be stable for several weeks, preferably at least 1 month, more preferably at least 3 months. It has been found that the polyether isocyanate derivative fluorinated silane can be easily dissolved in an organic solvent at high concentrations. In particular, it has been found that at amounts of at least 25% by weight, it becomes easier to dissolve the fluorinated compound of this invention in an organic solvent and concentrated solutions are obtained which are generally crystalline and stable for a long period. This is surprising since cloudy solutions of limited stability can be obtained at low concentrations, while at high concentrations in the same organic solvent, clear solutions with high stability are obtained. For example, at room temperature, stable transparent solutions in ketones and alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol and isopropanol, fluorinated solvents such as hydrofluorocarbons can be obtained at a concentration of at least 10%, by weight of the silane fluorinated polyether isocyanate derivative, while at a concentration of only 0.1% in organic solvents

ES 2 320 134 T3 are not halogenated, the solution tends to be opaque and of limited stability. On the other hand, in hydrofluoroethers, a fluorinated solvent, the solutions containing 0.1% or more of the fluorinated silane derived from isocyanate polyether were clear.

In a preferred embodiment of the present invention, the fluorochemical composition will be free of or substantially free of perfluorinated polyether moieties having a molecular weight of less than 750 g / mol and / or perfluoroaliphatic groups of more than 5 or 6 carbons. By the term "perfluoroaliphatic groups" is meant groups consisting of carbon and fluorine without including perfluoro end groups of the perfluoro polyether moieties. By the term "substantially free of" it is meant that the particular perfluorinated polyether moieties are present in amounts of not more than 10% by weight, preferably not more than 5% by weight, and most preferably not more than 1% by weight. weight based on the total weight of the perfluoropolyether moieties in the composition and that particular perfluoroaliphatic groups having more than 5 or 6 carbons are present in amounts of not more than 10% by weight, preferably not more than 5% by weight and most preferably not more than 1% by weight based on the total weight of perfluoroaliphatic groups in the composition. Compositions that are free of or substantially free of these moieties or groups are preferred due to their environmentally beneficial properties.

Thus, according to a preferred embodiment, the compositions for application to a substrate are prepared by diluting a concentrate comprising a solution of at least 10% by weight of a fluorinated polyether compound in an organic solvent, adding an organic solvent to the concentrate. or mixed solvents. A freshly diluted solution thus prepared will generally be stable for about 1 day. A wide variety of coating methods can be used to apply a composition of the present invention, such as brushing, spraying, dipping, rolling, and the like. Additionally, these materials can be applied using super critical fluids such as compressed liquid carbon dioxide, as described in US Patent Application No. 09 / 838,415, filed 4/19/2001 (US-A - 2002/0192380).

A preferred coating method for applying a polyether isocyanate derived fluorinated silane of the present invention includes spray application. A substrate to be coated can typically be contacted with the treatment composition at room temperature (typically, about 20 ° C to about 25 ° C). Alternatively, the mixture can be applied to substrates that are preheated to a temperature of, for example, between 60 ° C and 150 ° C. This is of particular interest for industrial production, where, for example, ceramic tiles can be treated immediately after the firing oven at the end of the production line. After application, the treated substrate can be dried and cured at room or elevated temperature, for example 40 to 300 ° C and for a sufficient drying time. The procedure may also require a buffing step to remove excess material.

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ES 2 320 134 T3

Glossary

<td>Designator</td><td>Name, Structure and / or Formula</td><td>Availability</td>

<td>aminoethanol</td><td>NH₂CH₂CH₂Oh</td><td>Sigma-Aldrich Milwaukee, Wl</td>

<td>APD^: ......................................................................</td><td>2-amino-1,3-propanediol; HOCH₂CH (NH₂) CH₂Oh</td><td>Sigma-Aldrich</td>

<td>APTES</td><td>Aminopropyltriethoxysilane NH₂(CH₂)₃Yes (OCH₂CH₃)₃</td><td>Sigma-Aldrich</td>

<td>chloropropylsilane</td><td>CI (CH₂)₃Yes (OCH₃)₃</td><td>Sigma-Aldrich</td>

<td>DESMODUR ™ N 100</td><td>Polyfunctional isocyanate resin averaging ~ 3.5 NCO groups per molecule</td><td>Bayer, Pittsburgh, PA</td>

<td>DBTDL</td><td>Dibutyltin dilaurate; [CH₃(CH₂)₁₀CO₂]₂Sn [(CH₂)₃CH₃]₂</td><td>Sigma-Aldrich</td>

<td>DETA</td><td>diethylenetriamine; NH₂CH₂CH₂NHCH₂CH₂NH₂</td><td>Sigma-Aldrich</td>

<td>FS-1</td><td>Fluorinated surfactant</td><td>As prepared in WO 01/30873 A1; Example 4</td>

<td>FOMBLIN Z-DEAL ™</td><td>CH₃OC (O) CF₂(CF₂OR)_n(CF₂CF₂OR)_mCF₂C (O) O CH₃; where_avg, m_avg= ~10 -12</td><td>Ausimont, Thorofare, NJ</td>

<td>oligomeric ester HPFO</td><td>CF₃CF₂CF₂(CF (CF₃) CF₂OR)_nCF (CF₃) COOCH₃; where n = 3 to 20; MW_avg -1232</td><td>3M, St Paul, MN</td>

<td>MPTMS</td><td>3-mercaptopropyltrimethoxysilane; HS (CH₂)₃Yes (OCH₃)₃</td><td>Sigma-Aldrich</td>

<td>NCO-silane</td><td>3- (triethoxysilyl) propyl isocyanate; OCN (CH₂)₃Yes (OC₂H₅)₃</td><td>Sigma-Aldrich</td>

<td>octadecanol</td><td>CH₃(CH₂)₁₇Oh</td><td>Sigma-Aldrich</td>

<td>Sodium borohydride</td><td>NaBH₄</td><td>Sigma-Aldrich</td>

ES 2 320 134 T3

<td>i ------------------------------------------------- -------------------------------------------------- ----------------- | Designator</td><td>Name, Structure and / or Formula</td><td>Availability</td>

<td>| TEGME</td><td>tri (ethylene glycol) monomethyl ether, CH₃(OCH₂CH₂)₃Oh</td><td>Sigma-Aldrich</td>

<td>| TEH</td><td>tin (ll) 2-ethylhexanoate; [CH₃(CH₂)₃CH (C₂H₅)CO₂]₂Sn</td><td>Sigma-Aldrich,</td>

<td>| TIT</td><td>triethylenetetraamine; NH₂CH₂CH₂NHCH₂CH₂NHCH₂CH₂NH₂</td><td>Sigma-Aldrich</td>

<td>| TFSD</td><td>tetrafluorosuccinyl difluoride; FOCCF₂CF₂COF</td><td>3M</td>

Sample preparation and test methods

Coating method

In a first stage, the substrates (white sanitary tiles available from Sphinx, the Netherlands) were cleaned and degreased with acetone. After cleaning, the polyether fluorinated silanes in solvent mixtures as given in the respective examples were applied to the substrates by spraying at about 20 ml / minute. The substances were stored at room temperature before coating. Alternatively, the substrates were preheated prior to coating. The coated samples were dried at room temperature or force dried in an air oven at 120 ° C for 30 minutes. Then the excess product was removed using a dry cloth.

Abrasion / scrub method

The abrasion test was carried out using an Erichsen cleaning machine (available from DCI, Belgium), a 3M cloth^TM HIGH PERFORMANCE ™ (available from 3M Co., St. Paul, Minnesota) and a CIF cleansing cream^TM(available from Lever Faberge, France), using 40 cycles.

Base Treatment

White toilets (tiles available from Sphinx, The Netherlands), coated as described above, were subjected to basic pH conditions using the following method. A stainless steel ring (7.6 cm diameter) was stamped to the glazed surface of the sanitary tiles using epoxy, and a 15 mL aliquot of NaOH (5% aqueous solution) was charged to the ring. After 24 hours, the basic solution was removed, the tile was washed with deionized water, and contact angle measurements were made to the surface of the tile that was in contact with the solution.

Contact angle measurement

The treated substrates were analyzed for their contact angles against water (W) and n-hexadecane (O) using an Olympus TGHM goniometer (Olympus Corp, Pompano Beach, FL). Contact angles were measured before (initial) and after abrasion (abrasion), unless otherwise noted. The contact angles with water and hexadecane were measured at least 24 hours after application or after abrasion. Values ​​are the mean values ​​of 4 measurements and are indicated in degrees. The minimum value that could be measured for a contact angle was 20. A value &lt;20 means that the liquid spreads on the surface.

Examples

Preparation 1

Oligomeric Ester-HFPO / Succinyl Fluoride (HFPO-SF)

It can be prepared essentially according to US Patent No. 4,647,413, Examples 1 and 9.

ES 2 320 134 T3

Example 1

Preparation of FOMBLIN Z-DEAL^TM/ APD / NCO-Silane; 1/2/4

A 100 mL three-neck round bottom flask fitted with a stirrer, heating mantle, thermometer, and condenser was charged with FOMBLIN Z-DEAL.^TM (19.6 g, 0.01 mol) and APD (1.8 g, 0.02 mol). The reaction was carried out under nitrogen. The temperature of the mixture was raised to 40 ° C and held for 4 hours. Then, NCO-silane (9.9 g, 0.04 mol) was added along with a drop of TEH (approximately 0.05 g) and the resulting mixture was heated overnight at 80 ° C. The reaction was examined for residual isocyanate using standard IR techniques. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

Example 2

Preparation of FOMBLINZ-DEAL^TM/ TETA / NCO-silane, 1/2/6

A 100 mL three-neck round bottom flask fitted with a stirrer, heating mantle, thermometer, and condenser was charged with FOMBLIN Z-DEAL.^TM (19.6 g, 0.01 mol) and TETA (2.9 g, 0.02 mol). The reaction was carried out under nitrogen. The temperature of the mixture was raised to 40 ° C and held for 4 hours. Then, NCO-silane (14.8 g, 0.06 mol) was added and the resulting mixture was heated overnight at 40 ° C. The reaction was examined for residual isocyanate using standard IR techniques. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

Example 3

Preparation of the oligomeric ester-HFPO / APD / NCO-silane; 1/1/2

A 100 mL three-neck round bottom flask fitted with a stirrer, heating mantle, thermometer, and condenser, was charged with oligomeric diester HFPO (12.3 g, 0.01 mol) and APD (0.9 g, 0). , 01 mol). The reaction was carried out under nitrogen. The temperature of the mixture was raised to 40 ° C and held for 16 hours. Then, NCO-silane (5.0 g, 0.02 mol) was added along with a drop of TEH (about 0.05 g) and the resulting mixture was heated overnight at 80 ° C. The reaction was examined for residual isocyanate using standard IR techniques. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

Example 4

Preparation of oligomeric ester-HFPO / DETA / NCO-silane; 1/1/2

A 100 mL round bottom three neck flask fitted with a stirrer, heating mantle, thermometer and condenser was charged with oligomeric ester hFpO (12.3 g, 0.01 mol) and DETA (11 mol). The reaction was carried out under nitrogen. The temperature of the mixture was raised to 40 ° C and held for 16 hours. Then, NCO-silane (5.0 g, 0.02 mol) was added and the resulting mixture was heated overnight at 40 ° C. The reaction was examined for residual isocyanate using standard IR techniques. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

Example 5

Preparation of HFPO / TETA / NCO-silane oligomeric ester: 1/1/3

A 100 mL round bottom three neck flask fitted with a stirrer, heating mantle, thermometer, and condenser was charged with HFPO oligomeric ester (12.3 g, 0.01 mol) and TETA (1.5 g, 0 , 01 mol). The reaction was carried out under nitrogen. The temperature of the mixture was raised to 40 ° C and held for 4 hours. Then, NCO-silane (7.4 g, 0.03 mol) was added and the resulting mixture was heated overnight at 40 ° C. The reaction was examined for residual isocyanate using standard IR techniques. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

Example 6

Preparation of oligomeric ester-HFPO / TETA / NCO-silane, 2/1/2

A 100 mL three-neck round bottom flask fitted with a stirrer, heating mantle, thermometer, and condenser, was charged with HFPO-SF (24.6 g, 0.02 mol) and TETA (1.5 g, 0). , 01 mol). The reaction was carried out

ES 2 320 134 T3 under nitrogen. The temperature of the mixture was raised to 40 ° C and held for 4 hours. Then, NCOsilane (5.0 g, 0.02 mol) was added and the resulting mixture was heated overnight at 40 ° C. The reaction was examined for residual isocyanate using standard IR techniques. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

Example 7

Preparation of HFPO-SF / APD / NOC-silane; 1/2/4

The process described in Example 3 was continued by replacing HFPO-oligomeric ester with an equimolar amount of diester HFPO-SF as described in Preparation 1 and with adequate amounts of other materials to achieve the 1/2/4 molar ratio.

Example 8

Preparation of HFPO-SF / DETA / NCO-silane; 1/2/6

The process described in Example 4 was continued by replacing HFPO-oligomeric ester with an equimolar amount of HFPO-SF as described in Preparation 1 and with adequate amounts of other materials to achieve the 1/2/6 molar ratio.

Example 9

Preparation of oligomeric ester-HFPO / TETA / NCO-silane / chloropropylsilane: 1/1/2/1

The procedure described in Example 5 was continued by substituting a combination of NCO-silane (5.0 g, 0.02 mol) and chloropropylsilane (2.0 g, 0.01 mol) for NCO-silane.

Example 10

Preparation of Fomblin ZDEAL^TM/ Aminoethanol / DESMODUR^TM N-100 / APTES; 1/2/2/4

A 100 ml three-necked flask equipped with a stirrer, heating mantle, thermometer, and condenser, was charged with Fomblin Z-DEAL^TM (19.6 g, 0.01 mol) and aminoethanol (1.4 g, 0.02 mol), and heated at 40 ° C under nitrogen for 4 hours. To this mixture was added methyl ethyl ketone (30.0 g), DeSmODUR ™ N-100 (6.6 g 0.02 mol) and a drop of TEH (approximately 0.05 g). The resulting mixture was heated overnight at about 80 ° C under nitrogen. The reaction was then cooled to about 30 ° C and APTES (7.2 g, 0.04 mol) was added and heated to about 40 ° C for 2 hours. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

Example 11

Preparation of Fomblin Z-DEAL^TM/ Aminoethanol DESMODUR ™ N-100 / APTES / Octadecanol; 1/2/2/3/1

The procedure described in Example 10 was continued by substituting APTES (5.4 g, 0.03 mol), and octadecanol (2.7 g, 0.01 mol) for APTES.

Example 12

Preparation of oligomeric ester-HFPO / Aminoethanol DESMODUR^TM N-100 / Aminopropylsilane; 1/1/1/2

A 100 mL three-necked flask, equipped with a stirrer, a condenser, and a thermometer, was charged with oligomeric ester-HFPO (12.3 g, 0.01 mol) and aminoethanol (0.7 g, 0.01 mol). The mixture was reacted for 4 hours at 60 ° C under nitrogen; DESMODUR ™ N-100 (3.3 g; 0.01 mol), methyl ethyl ketone (30 g) and a drop of TEH (approximately 0.05 g). The mixture was heated at 80 ° C overnight under nitrogen. The resulting mixture was cooled to 40 ° C and APTES (3.5 g; 0.02 mol) was added and further reacted for 4 hours at 40 ° C. The reaction was examined for residual isocyanate. A viscous liquid was obtained, and this viscous liquid (0.1 g) was then diluted with ethanol (95.4 g), water (3.0 g) and acetic acid (1.5 g) before application.

ES 2 320 134 T3

Example 13

Preparation of ester-HFPO / Aminoethanol DESMODUR ™ N-100 / MPTMS: 1/1/1/2

The process described in Example 12 was continued by substituting APTES for MPTMS (4.0 g, 0.02 mol).

Example 14

Preparation of oligomeric ester-HFPO / TETA / NO C-silane - TEGME; 1/1/3 and alkoxy exchange with TEGME

The process described in Example 5 was followed except that after examining the residual isocyanate, TEGME (42.4 g) was added to the reaction mixture, a Dean-Stark separator was mounted, and the mixture was heated for 2 hours. at 120 ° C and 3 hours at 140 ° C. A clear, slightly brown liquid was obtained; An aliquot of this liquid (0.1 g) was diluted in ethanol (95.4 g), water (3.0 g) and 1.5 g of acetic acid (1.5 g) before application.

Example 15

Preparation of a water-dilutable concentrate using FS-1

The product prepared in Example 3 (3.0 g) was mixed with FS-1 (1.0 g) and isopropanol (12.0 g) in a 30 ml glass vial with stirring. As a result, a crystalline solution was given, which was diluted 0.1% in ethanol (100.0 g), water (3.0 g) and acetic acid (1.5 g) before application.

Comparative Example C1

Comparative Example C1 was prepared according to the process described in WO 02/30848, Example 50.

Comparative Example C2

Untreated tile.

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ES 2 320 134 T3

<td>Examples</td><td>Material</td><td>Initial Water Contact Angle (°) (Hexadecane)</td><td>Angle of Water contact after abrasion (°) (hexadecane)</td><td>Angle of Water contact after the base (°) (hexadecane)</td>

<td> 1</td><td>Z-Deal / APD / NCO- silane 1/2/4</td><td> 100 (65)</td><td> 85 (53)</td><td> 92 (56)</td>

<td> 2</td><td>Z-Deal / TETA / NCO- silane 1/2/6</td><td> 105 (63)</td><td> 83 (51)</td><td> 90 (58)</td>

<td> 3</td><td>HFPO / ester AMPD / NCO- silane 1/1/2</td><td> 112(72)</td><td> 80 (50)</td><td> 95 (62)</td>

<td> 4</td><td>HFPO / ester DETA / NCO- silane 1/1/2</td><td> 111 (68)</td><td> 82 (52)</td><td> 97(56)</td>

<td> 5</td><td>HFPO / ester TETA / NCO- silane 1/1/3</td><td> 106 (69)</td><td> 80 (48)</td><td> 92 (55)</td>

<td> 6</td><td>HFPO / ester TETA / NCO- silane 2/1/2</td><td> 114(72)</td><td> 84 (53)</td><td> 95 (60)</td>

<td> 7</td><td>diester HFPO- SF / APD / NCO-silane</td><td> 108 (67)</td><td> 86 (55)</td><td> 90 (55)</td>

<td> 8</td><td>diester HFPO- SF / DETA / NCO-silane</td><td> 105 (65)</td><td> 84 (53)</td><td> 90(56)</td>

<td> 9</td><td>HFPO / TETA / NCOsilane / chloropropylsila oligomeric ester no</td><td> 105 (63)</td><td> 78 (48)</td><td> 83(50)</td>

<td> 10</td><td>Fomblin Z DEALTM / Aminoetan ol / DESMOD URTM N-100 / APTES</td><td> 110 (65)</td><td> 85 (53)</td><td> —</td>

ES 2 320 134 T3

<td>Examples</td><td>Material</td><td>Initial Water Contact Angle (°) (Hexadecane)</td><td>Angle of Water contact after abrasion (°) (hexadecane)</td><td>Contact Angle Water after the base (°) (hexadecane)</td>

<td> 11</td><td>Fomblin Z-DEALTM / Aminoethanol / DESMODURTM N10O / APTES / Octade canol</td><td> 108 (63)</td><td> 90 (50)</td><td> —</td>

<td> 12</td><td>oligomeric ester HFPO / Aminoethanol / N-100 / APTES</td><td> 105 (69)</td><td> 82 (52)</td><td> 90 (54)</td>

<td> 13</td><td>oligomeric ester HFPO / aminoethanol / N-100 / MPTMS</td><td> 112(71)</td><td> 83 (55)</td><td> 90(54)</td>

<td> 14</td><td>HFPO / TETA / NCOsilane / TEGME oligomeric ester</td><td> 103 (65)</td><td> 85 (50)</td><td> 88(54)</td>

<td> 15</td><td>Example 3 / FC- 4430 / IPA = 3/1/12</td><td> 107(70)</td><td> 83(55)</td><td> 85 (52)</td>

<td>C1</td><td>See WO 02/3848; Ex. 50</td><td> 105 (64)</td><td> 88 (57)</td><td> 61 (38)</td>

<td>C2</td><td>Not treated</td><td> 35 (&lt;20)</td><td> 25 (&lt;20)—</td><td> 22 (&lt;20)—</td>