EP2699659A1 - Fluorinated phosphates as surface active agents - Google Patents

Fluorinated phosphates as surface active agents

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Publication number
EP2699659A1
EP2699659A1 EP12709446.4A EP12709446A EP2699659A1 EP 2699659 A1 EP2699659 A1 EP 2699659A1 EP 12709446 A EP12709446 A EP 12709446A EP 2699659 A1 EP2699659 A1 EP 2699659A1
Authority
EP
European Patent Office
Prior art keywords
formula
coating
coating composition
linear
present
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.)
Withdrawn
Application number
EP12709446.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Sheng Peng
Allison Mary Yake
Xianjun Jean Meng
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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
Priority claimed from US13/372,032 external-priority patent/US20130210976A1/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2699659A1 publication Critical patent/EP2699659A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/004—Surface-active compounds containing F
    • C11D1/006—Surface-active compounds containing fluorine and phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only

Definitions

  • the field of invention is related to the use of fluorochemical surfactants in coating compositions to impart surface effects to substrates coated with such compositions.
  • fluoroalkyl phosphate surfactants and surface treatment agents contain multiple fluorochemical chains, containing a higher percentage of fluorine at a given concentration and are typically used because they are thought to provide better performance.
  • the fluorinated starting materials are more expensive and in short supply. Reduction of the amount of the fluorinated starting material in these surfactants while maintaining the same or better performance is desirable. Reducing the amount of the fluorinated starting component needed would not only reduce the cost, but also shorten the cycle time as fewer steps are needed in the production of the surfactants and less energy is required. Reducing the fluorine content would reduce the cost, but it is necessary to maintain product performance.
  • Brace and Mackenze describe their use as an oil repellent, particularly when y is 2.
  • the present invention provides a method to increase surfactant performance and to impart improved surface effects to a coated surface while utilizing less fluorinated starting material.
  • the present invention comprises an improved method for lowering the surface tension of coating compositions wherein a surfactant is contacted with said coating composition, wherein the improvement comprises contacting said coating compositions with a surfactant comprising formula I and formula II
  • Rf is a Ci to CQ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
  • A is (CH 2 CF2) m (CH 2 )n, (CH 2 )oSO2N(CH 3 )(CH2)p,
  • n 0 to 4.
  • n, o, p, and r are each independently 2 to 20;
  • E is a C 2 to C 2 Q linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a CQ to Cio ary! group;
  • M is a Group I metal or an ammonium cation (NH x R2y) + , wherein R2 is a Ci to C4 alkyl; x is 1 to 4; y is 0 to 3; and x + y is 4; and
  • the present invention further comprises a method of increasing the oil contact angle of a coating composition applied to a surface comprising contacting the surface with a coating composition comprising formula I and formula II as defined above wherein formula I is present at greater than or equal to 50 mol%.
  • the present invention further comprises a method of imparting surface effects to a coated substrate comprising contacting all or a portion of a surface of the substrate with a coating composition comprising formula I and formula II as defined above wherein formula I is present at greater than or equal to 50 mol%.
  • the present invention further comprises a coating composition and substrate from any of the above methods.
  • the present invention comprises an improved method for lowering the surface tension of coating compositions wherein a surfactant is contacted with said coating composition, wherein the improvement comprises contacting said coating compositions with a surfactant comprising formula I and formula II
  • Rf is a Ci to C6 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
  • A is (CH 2 CF2) m (CH 2 )n, (CH 2 )oSO2N(CH 3 )(CH2)p,
  • n 0 to 4.
  • n, o, p, and r are each independently 2 to 20;
  • E is a C 2 to C 2 Q linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a CQ to Cio ary! group;
  • M is a Group I metal or an ammonium cation (NH x R2y) + , wherein R2 is a Ci to C4 alkyl; x is 1 to 4; y is 0 to 3; and x + y is 4; and wherein formula (I) is present at greater than or equal to 50 mol%.
  • R2 is a Ci to C4 alkyl
  • x is 1 to 4
  • y is 0 to 3
  • x + y is 4
  • formula (I) is present at greater than or equal to 50 mol%.
  • Compounds of formula I and formula II useful in the present invention can be prepared according to methods described by Longoria, et al., in U.S. Patent 6,271 ,289, and Brace and Mackenzie, in U.S.
  • Patent 3,083,224 Typically, either phosphorus pentoxide (P2O5) or phosphorus oxychloride (POCI3) is reacted with fluorinated alkyl alcohol or fluorinated alkyl thiol to give mixtures of the mono- and bis- (fluoroalkyl) phosphoric acids.
  • the product is then neutralized using common bases such as ammonium or sodium hydroxides, or alkanol amines, such as, diethanolamine (DEA), to provide a mixture of the corresponding phosphates. Excess unreacted alcohol is removed via vacuum distillation.
  • the ratio of fluorinated alcohol or fluorinated alkyl thiol with P2O5 is controlled to provide a composition useful as a surfactant in the present invention wherein the amount of compounds of formula I
  • formula I and formula II are present at a mol ratio of formula I to formula II of at least 2:1 . More preferably, formula I and formula II are present at a mol ratio of formula I to formula II of at least 3:1 .
  • the fluoroalkyl alcohol or fluoroalkyl thiol used as a reactant in the preparation of the surfactant useful in the present invention comprises compounds as described below for various embodiments.
  • the surfactant comprises compounds of formula I and formula II wherein A is
  • Rf, R1 , m, n, and M are as defined above.
  • Preferred compounds of formula la and formula lla include those wherein Rf is a C4 or CQ perfluoroalkyl, and n is 2.
  • VDF vinylidene fluoride
  • RfCH2CF2 linear or branched perfluoroalkyl iodides
  • telomer iodides Balague, et al, "Synthesis of fluorinated telomers, Part 1 , Telomerization of vinylidene fluoride with perfluoroalkyl iodides", J. Flour Chem. (1995), 70(2), 215-23.
  • the specific telomer iodides are isolated by fractional distillation.
  • the telomer iodides can be treated with ethylene by
  • telomer ethylene iodides wherein n is 1 to 3 or more.
  • the telomer ethylene iodides can be treated with oleum and hydrolyzed to provide the corresponding telomer alcohols according to procedures disclosed in WO 95/1 1877 (Elf Atochem S.A.).
  • the telomer ethylene iodides can be treated with a variety of reagents to provide the corresponding thiols according to procedures described in J. Fluorine Chemistry, 104, 2 173-183 (2000).
  • One example is the reaction of the telomer ethylene iodides with sodium thioacetate, followed by hydrolysis.
  • the surfactant employed comprises compounds of formula I and formula II wherein A is (CH2)oSO2N(CH3)(CH2)p, herein denoted as formula lb and formula Mb,
  • Rf, o, p, and M are as defined above in formula I.
  • Preferred compounds of formula lb and formula Mb include those wherein o and p are each 2, and Rf is a C4 or CQ linear or branched perfluoroalkyl.
  • the fluoroalkyl alcohol used to prepare compounds of formula lb and Mb are available from E. I. du Pont de Nemours and Company, Wilmington DE.
  • the surfactant employed comprises compounds of formula I and formula II wherein A is 0(CF2)q(CH2) r , herein denoted as formula Ic and lie,
  • Rf, q, r, and M are as defined above in formula I.
  • Preferred compounds of formula Ic and formula lie include those wherein q and r are each 2, and Rf is C3 linear or branched perfluoroalkyl.
  • the perfluoroalkyl ether iodide is then reacted with an excess of ethylene at an elevated temperature and pressure. While the addition of ethylene can be carried out thermally, the use of a suitable catalyst is preferred.
  • the catalyst is a peroxide catalyst such as benzoyl peroxide, isobutyryl peroxide, propionyl peroxide, or acetyl peroxide. More preferably the peroxide catalyst is benzoyl peroxide.
  • the temperature of the reaction is not limited, but a temperature in the range of 1 10°C to 130°C is preferred.
  • the reaction time can vary with the catalyst and reaction conditions, but 24 hours is usually adequate.
  • the product is purified by any means that separates unreacted starting material from the final product, but distillation is preferred. Satisfactory yields up to 80% of theory have been obtained using about 2.7 mols of ethylene per mole of perfluoroalkyl ether iodide, a temperature of 1 10°C and autogenous pressure, a reaction time of 24 hours, and purifying the product by distillation.
  • the perfluoroalkylether ethylene iodides are then treated with oleum and hydrolyzed to provide the corresponding alcohols according to procedures disclosed in WO 95/1 1877 (Elf Atochem S.A.).
  • the perfluoroalkylether ethyl iodides can be treated with N-methyl formamide followed by ethyl alcohol/acid hydrolysis.
  • a temperature of about 130° to 160°C is preferred.
  • the telomer ethylene iodides are treated with a variety of reagents to provide the corresponding thiols according to procedures described in J.
  • telomer ethylene iodides reaction of the telomer ethylene iodides with sodium thioacetate, followed by hydrolysis.
  • the telomer ethylene iodide can also be treated to provide the corresponding thioethanols or thioethylamines by conventional methods.
  • the surfactant comprises compounds of formula I and formula II wherein A is
  • Rf, E and M are as defined above in formula I. Preferred
  • compounds of formula Id and formula lid include those wherein Rf is a C3 linear or branched perfluoroalkyl.
  • the fluoroalcohols used as starting materials to make the compounds of formula Id and formula lid are prepared by reacting a dioxane, a fluoroalkyi containing at least 1 unsaturated bond, and a diol in the presence of an alkali metal compound.
  • a dioxane a fluoroalkyi containing at least 1 unsaturated bond
  • the present invention comprises an improved method for lowering the surface tension of coating compositions wherein a surfactant is contacted with said coating composition, wherein the improvement comprises contacting said coating compositions with a surfactant comprising formula I and formula II, as defined above, and wherein formula I is present at greater than or equal to 50 mol%.
  • a surfactant comprising formula I and formula II, as defined above, and wherein formula I is present at greater than or equal to 50 mol%.
  • U.S. Patents 3,083,224 and 4,145,382 disclose that surfactants containing a higher ratio of bis(fluoroalkyl)phosphates to mono(fluoroalkyl)phosphate are desirable and would perform better resulting in lower surface tensions. While this may be generally true for aqueous systems, surprisingly, the same does not prove to be true for coating compositions defined infra.
  • the improved method of the present invention results in lowering of the surface tension of a coating composition with which a surfactant comprising formula I and formula II is contacted when more of formula I is present. This is due to the surface altering properties of the surfactant of formula I and formula II wherein the ratio of compounds of formula I to formula II present is greater than or equal to 50 mol%, when compared to surfactants containing more formula II (bis(fluoroalkyl)phosphate) than formula I (mono(fluoroalkyl) phosphate).
  • Leveling refers to the uniformity of coverage of the coating when applied to a substrate. It is undesirable to have streaking, surface defects, or withdrawal of the coating from the substrate surface at the edges or otherwise. An even coating will provide a superior dried coating on the substrate surface.
  • Weight is the spreading of a coating composition over a surface.
  • Uniformity in spreading is desirable to provide a superior dried uniform surface.
  • contacting the surfactant, as defined above, with the coating composition is typically achieved by simply blending with or adding the surfactant to the coating composition.
  • the contacting of the surfactant to the coating composition can occur prior to applying the coating composition to a substrate, or can occur after applying the coating composition to a substrate.
  • a low concentration of about 0.1 % by weight of surfactant is sufficient to lower surface tension of a coating composition to less than about 18 dyne/cm ⁇ . Concentrations as low as 0.01 % by weight of the surfactant in the coating composition are effective to achieve a surface tension of less than about 25 dyne/cm ⁇ .
  • Suitable coating compositions include a composition, typically a liquid formulation, of an alkyd coating, Type I urethane coating, unsaturated polyester coating, or water-dispersed coating, and are applied to a substrate for the purpose of creating a lasting film on a substrate surface.
  • coating composition typically a liquid formulation, of an alkyd coating, Type I urethane coating, unsaturated polyester coating, or water-dispersed coating, and are applied to a substrate for the purpose of creating a lasting film on a substrate surface.
  • coating compositions typically a liquid formulation, of an alkyd coating, Type I urethane coating, unsaturated polyester coating, or water-dispersed coating
  • alkyd coating as used herein is meant a conventional liquid coating based on alkyd resins, typically a paint, clear coating, or stain.
  • the alkyd resins are complex branched and cross-linked polyesters containing unsaturated aliphatic acid residues.
  • Conventional alkyd coatings utilize, as the binder or film-forming component, a curing or drying alkyd resin.
  • Alkyd resin coatings contain unsaturated aliphatic acid residues derived from drying oils. These resins spontaneously polymerize in the presence of oxygen or air to yield a solid protective film.
  • drying or "curing” and occurs as a result of autoxidation of the unsaturated carbon-carbon bonds in the aliphatic acid component of the oil by atmospheric oxygen.
  • drying oils have been used as raw materials for oil-based coatings and are described in the literature.
  • urethane coating as used hereinafter is meant a conventional liquid coating based on Type I urethane resins, typically a paint, clear coating, or stain.
  • Urethane coatings typically contain the reaction product of a polyisocyanate, usually toluene diisocyanate, and a polyhydric alcohol ester of drying oil acids. Urethane coatings are classified by ASTM D-1 into five categories. Type I urethane coatings contain a pre-reacted autoxidizable binder as described in Surface Coatings Vol. I, previously cited.
  • uralkyds urethane-modified alkyds
  • oil-modified urethanes urethane oils
  • urethane alkyds are the largest volume category of polyurethane coatings and include paints, clear coatings, or stains.
  • the cured coating is formed by air oxidation and polymerization of the unsaturated drying oil residue in the binder.
  • unsaturated polyester coating as used hereinafter is meant a conventional liquid coating based on unsaturated polyester resins, dissolved in monomers and containing initiators and catalysts as needed, typically as a paint, clear coating, or gel coat formulation.
  • Unsaturated polyester resins contain as the unsaturated prepolymer the product obtained from the condensation polymerization of a glycol such as 1 ,2- propylene glycol or 1 ,3-butylene glycol with an unsaturated acid such as maleic (or of maleic and a saturated acid, e. g., phthalic) in the anhydride form.
  • the unsaturated prepolymer is a linear polymer containing unsaturation in the chain. This is dissolved in a suitable monomer, for instance styrene, to produce the final resin.
  • the film is produced by copolymerization of the linear polymer and monomer by means of a free radical mechanism.
  • the free radicals can be generated by heat, or more usually by addition of a peroxide, such as benzoyl peroxide, separately packaged and added before use.
  • a peroxide such as benzoyl peroxide
  • Such coating compositions are frequently termed "gel coat" finishes.
  • the decomposition of peroxides into free radicals is catalyzed by certain metal ions, usually cobalt.
  • the solutions of peroxide and cobalt compound are added separately to the mix and well stirred before application.
  • the unsaturated polyester resins that cure by a free radical mechanism are also suited to irradiation curing using, for instance, ultraviolet light. This form of cure, in which no heat is produced, is particularly suited to films on wood or board.
  • Other radiation sources, for instance electron-beam curing are also used.
  • water-dispersed coatings as used herein is meant coatings intended for the decoration or protection of a substrate composed of water as an essential dispersing component such as an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous phase.
  • Water-dispersed coating is a general classification that describes a number of formulations and includes members of the above described classifications as well as members of other classifications. Water- dispersed coatings in general contain other common coating ingredients. Water-dispersed coatings are exemplified by, but not limited to, pigmented coatings such as latex paints, automotive base coats, industrial
  • a water dispersed coating optionally contains surfactants, protective colloids and thickeners, pigments and extender pigments, preservatives, fungicides, freeze-thaw stabilizers, antifoam agents, agents to control pH, coalescing aids, and other ingredients.
  • the film forming material is a latex polymer of acrylate acrylic, vinyl-acrylic, vinyl, or a mixture thereof.
  • dried coating as used herein is meant the final decorative and/or protective film obtained after the coating composition has dried, set or cured.
  • a final film can be achieved by, for non- limiting example, curing, coalescing, polymerizing, interpenetrating, radiation curing, UV curing or evaporation.
  • Final films can also be applied in a dry and final state as in dry coating.
  • Floor waxes, polishes, or finishes are generally water based or solvent based polymer emulsions.
  • the surfactants used in the methods of the present invention are suitable for use in such floor finishes.
  • Commercially available floor finish compositions typically are aqueous emulsion-based polymer compositions comprising one or more organic solvents, plasticizers, coating aides, anti-foaming agents, surfactants, polymer emulsions, metal complexing agents, and waxes.
  • the particle size range and solids content of the polymer are usually controlled to control the product viscosity, film hardness and resistance to deterioration.
  • Polymers containing polar groups function to enhance solubility and may also act as wetting or leveling agents providing good optical properties such a high gloss and distinctness of reflected image.
  • Preferred polymers for use in floor finishes include acrylic polymers, polymers derived from cyclic ethers, and polymers derived from vinyl substituted aromatics.
  • Acrylic polymers include various poly(alkyl acrylates), poly(alkyl methacrylates), hydroxyl substituted poly(alkyl acrylates) and poly(alkyl methacrylates).
  • Commercially available acrylic copolymers used in floor finishes include, for example, methyl
  • MMA/BA MAA methacrylate/butyl acrylate/methacrylic acid
  • MMA/BA AA methyl methacrylate/butyl acrylate/acrylic acid
  • commercially available styrene-acrylic copolymers include styrene/methyl methacrylate/butyl acrylate/methacrylic acid
  • Polymers derived from cyclic ethers usually contain 2 to 5 carbon atoms in the ring with optional alkyl groups substituted thereon. Examples include various oxiranes, oxetanes, tetrahydrofurans, tetrahydropyrans, dioxanes, trioxanes, and caprolactone. Polymers derived from vinyl substituted aromatics include for example those made from styrenes, pyridines, conjugated dienes, and copolymers thereof. Polyesters, polyamides, polyurethanes and polysiloxanes are also used in floor finishes.
  • the waxes or mixtures of waxes that are used in floor finishes include waxes of a vegetable, animal, synthetic, and/or mineral origin.
  • Representative waxes include, for example, carnuba, candelilla, lanolin, stearin, beeswax, oxidized polyethylene wax, polyethylene emulsions, polypropylene, copolymers of ethylene and acrylic esters, hydrogenerated coconut oil or soybean oil, and the mineral waxes such as paraffin or ceresin.
  • the waxes typically range from 0 to about 15 weight percent and preferably from about 2 to about 10 weight percent based on the weight of the finish composition.
  • the surfactants as defined above are effectively introduced to the coating composition by thoroughly stirring it in at room or ambient temperature. More elaborate mixing can be employed such as using a mechanical shaker or providing heat or other methods.
  • the surfactants generally are added at about 0.001 weight % to about 5 weight % by dry weight of the coating composition of the invention in the wet composition. Preferably about from about 0.005 weight % to about 2 weight %, more preferably from about 0.005 weight % to about 0.5 weight %, and even more preferably from about 0.01 weight % to about 0.05 weight % is used.
  • Floor waxes or polishes are water based, solvent based and polymer.
  • the surfactants used in the present invention are suitable for use with any of these.
  • Water-based and polymer waxes dry to a high gloss without buffing; solvent-based wax requires vigorous buffing.
  • Water- based wax is recommended for asphalt, vinyl, vinyl asbestos and rubber- tiled floors; solvent-based waxes produce a hard, shiny finish and are best for wood, cork and terrazzo floors.
  • Self-polishing waxes, such as polymer or resin will yellow or discolor and wear off in heavy traffic areas; they should be stripped off and reapplied after three or four coats.
  • the surfactant comprising compounds of formula I and formula II, as defined above, are effectively contacted with the coating composition by thoroughly stirring it in at room or ambient temperature. More elaborate mixing can be employed such as using a mechanical shaker or providing heat or other methods. Such methods are not necessary and do not substantially improve the final composition.
  • the surfactants comprising compounds of formula I and formula II are generally contacted at about 0.001 weight % to about 5 weight % by dry weight of the in the wet paint. Preferably about from about 0.01 weight % to about 1 weight %, and more preferably from about 0.1 weight % to about 0.5 weight % is used.
  • the present invention further comprises a method for increasing the contact angle of a coating composition applied to a surface comprising contacting the surface with a coating composition comprising formula I and formula II (RfAO)P(0)(0 " M )2 (formula I)
  • Rf, A, m, n, o, p, r, q, E , M, R 2 , x, y, and the coating composition are as defined above; and wherein formula (I) is present at greater than or equal to 50 mol%.
  • formula I and formula II are present at a mol ratio of formula I to formula II of at least 2:1 . More preferably, formula I and formula II are present at a mol ratio of formula I to formula II of at least 3:1 .
  • Rf is C4 to CQ linear or branched perfluoroalkyl.
  • the increase of the contact angle of the coated surface is due to the surface altering properties of the coating composition comprising compounds of formula I and formula II wherein the ratio of compounds of formula I to formula II present is greater than or equal to 50 mol% when compared to surfactants containing more bis(fluoroalkyl)phosphate than mono(fluoroalkyl) phosphate.
  • the increasing of the contact angle of the coating composition results in increased anti-blocking, oil repellency, and resistance to dirt pickup in the dried coating.
  • resistance to dirt pickup or "dirt pickup resistance” is used herein to mean resistance by the dried coating to soiling. It is particularly applicable to coatings exposed to weather in that the coating resists soiling from dirt, debris, mold, and other conditions encountered in normal weather throughout the year. The level of dirt pickup resistance is indicated by the measurement of advancing oil contact angle. "Blocking” is the undesirable sticking together of two coated surfaces when pressed together, or placed in contact with each other for an extended period of time, after the coating has dried. When blocking occurs separation of the surfaces can result in disruption of the coating on one or both surfaces. Thus anti-blocking, also referred to as resistance to blocking, is beneficial in many situations where two coated surfaces need to be in contact, for example on window frames.
  • Oil repellency is the ability of a surface coated with a coating composition according to the method of the present invention to not allow oil globules to spread. Oil repellency is determined by measuring the advancing angle when a drop of oil is placed in contact with a surface coated with a coating composition described above for use in the above described methods of the present invention.
  • Rf is a Ci to CQ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
  • A is (CH 2 CF2) m (CH 2 )n, (CH 2 )oSO2N(CH 3 )(CH2)p,
  • n 0 to 4.
  • n, o, p, and r are each independently 2 to 20;
  • E is a C 2 to C 2 o linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C6 to Ci o aryl group;
  • M is a Group I metal or an ammonium cation (NH x R2y) + , wherein
  • R2 is a Ci to C4 alkyl; x is 1 to 4; y is 0 to 3; and x + y is 4; and
  • the contacting of the coating composition with all or a portion of a surface of the substrate is achieved by conventional means.
  • Non-limiting examples include application by brush, cloth, pad, spray, doctor blade, or other known means.
  • the amount of compounds of formula I is equal to or greater than 50 mol% relative to the amount of compounds of formula II (bis(fluoroalkyl)phosphate) in the coating composition.
  • formula I and formula II are present at a mol ratio of formula I to formula II of at least 2:1 . More preferably, formula I and formula II are present at a mol ratio of formula I to formula II of at least 3:1 .
  • the compounds of formula I and formula II are added to the coating composition, typically as a mixture, as previously described.
  • the surfactants comprising compounds of formula I and formula II are generally present at about 0.001 weight % to about 5 weight % by dry weight of the in the wet paint. Preferably about from about 0.01 weight % to about 1 weight %, and more preferably from about 0.1 weight % to about 0.5 weight % is used.
  • the surface properties imparted to the coated substrate are improved compared to a substrate coated with a composition containing a surfactant that comprises more bis(fluoroalkyl)phosphate than
  • the improved surface properties provided by the method of the present invention result from using a coating composition containing a surfactant having a greater amount of formula I than formula II.
  • Such improved properties include a smoother more uniform coating due to increased wetting and leveling of the coating composition, and increased resistance to blocking, oil repellency, and dirt pickup resistance in the dried coating.
  • the present invention comprises a coating composition having improved wetting and leveling comprising a coating base and a surfactant of formula I and formula II
  • Rf, A, m, n, o, p, r, q, E , M, R 2 , x, y, and the coating composition are as defined above; and wherein formula (I) is present at greater than or equal to 50 mol%.
  • formula (I) is present at greater than or equal to 50 mol%.
  • the present invention further comprises a substrate treated according to any of the above-described methods of the present invention.
  • One or more surfaces of the substrate have been contacted with a coating composition containing a surfactant comprising formula I and formula II
  • Rf, A, m, n, o, p, r, q, E , M, R 2 , x, y, and the coating composition are as defined above; and wherein formula (I) is present at greater than or equal to 50 mol%.
  • Typical substrates include a wide variety of surfaces on which coating compositions are normally used. These include various
  • the hard surface substrates include porous and non-porous mineral surfaces, such as glass, stone, masonry, concrete, unglazed tile, brick, porous clay and various other substrates with surface porosity.
  • Specific examples of such substrates include unglazed concrete, brick, tile, stone including granite, limestone and marble, grout, mortar, statuary, monuments, wood, composite materials such as terrazzo, and wall and ceiling panels including those fabricated with gypsum board.
  • plastics, metals, ceramics, and other hard surfaces are included in the present invention.
  • substrates include fibrous substrates. Most any fibrous substrate is suitable for treatment by the methods of the present invention. Such substrates include fibers, yarns, fabrics, fabric blends, textiles, carpet, rugs, nonwovens, leather and paper.
  • the term "fiber” includes fibers and yarns, before and after spinning, of a variety of compositions and forms, and includes pigmented fibers and pigmented yarns.
  • fabrics is meant natural or synthetic fabrics, or blends thereof, composed of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon, and aramids such as “NOMEX” and "KEVLAR".
  • fabric blends is meant fabric made of two or more different fibers.
  • these blends are a combination of at least one natural fiber and at least one synthetic fiber, but also can be a blend of two or more natural fibers and/or of two or more synthetic fibers.
  • the methods of the present invention are useful in improving the surface effects of various coating compositions and treated substrates.
  • the methods of the present invention are useful in coating compositions, such as floor finishes and paints.
  • the methods of the present invention produce superior surface altering performance, such as, but not limited to wetting, leveling, resistance to blocking, oil repellency, and dirt pickup resistance, of coating compositions while requiring less fluorinated starting material as does the prior art compositions. This improved performance results in a reduced cost of raw materials and manufacturing as well as decreases cycle time.
  • formulation N-29-1 is available from Dow Coating Materials, Midland, Ml.
  • Sherwin Williams MAB 024-1501 semi-gloss paint is commercially available from Sherwin Williams, Cleveland Ohio. That used in the Examples was purchased locally at Wilmington, DE. Test Method 1 - Surface Tension Measurement
  • Results were in dynes/cm (mN/m) with a Standard Deviation of less than 1 dyne/cm.
  • the tensiometer was used according to the manufacturer's recommendations.
  • a stock solution was prepared for the highest concentration of surfactant in the coating composition to be analyzed.
  • the concentration of the solution was by mol percent of the surfactant in a commercially available floor polish (RHOPLEX® 3829, Formulation N-29-1 ).
  • the solutions are stirred overnight (for approximately 12 hours) to ensure complete mixing.
  • Lower concentrations of the stock solution for each example were made by diluting the original stock solution.
  • the floor polish is used for applications in the consumer, institutional, and industrial cleaning segments for demonstration of providing surface effects to substrates. Lower surface tension results indicate superior performance. Test Method 2 - Contact Angle
  • Example 1 characterized as having a ratio of mono(fluoroalkyl) phosphate to bis(fluoroalkyl)phosphate of greater than 9 to 1 .
  • a sample of the product of Example 1 was added to RHOPLEX 3829 floor polish and tested according to Test Method 1 for surface tension at various concentrations.
  • a sample of the product of Example 1 was also added to Sherwin Williams MAB 024-1501 semi-gloss paint and tested according to Test Method 2 for contact angle measurement. Test results are listed in Tables 2 and 3.
  • Example 2 to 4 were prepared as described in Example 1 , with different ratios of POCI3 to C6F13CH2CH2OH, and produced products having the ratios of mono(fluoroalkyl)phosphates to bis(fluoroalkyl)phosphates as listed in Table 1 .
  • a sample of the product of each of Examples 2 to 4 was added to RHOPLEX 3829 floor polish and tested according to Test Method 1 for surface tension at various concentrations.
  • a sample of the product of each of Examples 2 to 4 was also added to Sherwin Williams MAB 024-1501 semi-gloss paint and tested according to Test Method 2 for contact angle measurement. Test results are listed in Tables 2 and 3.
  • Comparative Examples A to C were prepared as described in Example 1 , with different ratios of POCI3 to C6F13CH2CH2OH, and produced products having ratios mono(fluoroalkyl)phosphates to

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
EP12709446.4A 2011-04-18 2012-03-02 Fluorinated phosphates as surface active agents Withdrawn EP2699659A1 (en)

Applications Claiming Priority (3)

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US201161476498P 2011-04-18 2011-04-18
US13/372,032 US20130210976A1 (en) 2012-02-13 2012-02-13 Fluorinated phosphates as surface active agents
PCT/US2012/027504 WO2012145078A1 (en) 2011-04-18 2012-03-02 Fluorinated phosphates as surface active agents

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CN (1) CN103649288A (enrdf_load_stackoverflow)
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JP2016074828A (ja) * 2014-10-07 2016-05-12 三菱マテリアル株式会社 親水撥油剤、表面被覆材、塗布膜、樹脂組成物、油水分離濾材及び多孔質体
US9920219B2 (en) * 2015-06-22 2018-03-20 Awi Licensing Llc Soil and dirt repellent powder coatings
KR102149221B1 (ko) * 2015-10-02 2020-08-31 더 케무어스 컴퍼니 에프씨, 엘엘씨 소수성 화합물을 포함하는 코팅
BR112018006546B1 (pt) * 2015-10-02 2022-12-13 Dsm Ip Assets B.V. Uso de uma partícula revestida
AU2017290253B2 (en) 2016-06-29 2021-11-25 Armstrong World Industries, Inc. High performance coatings for building panels

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3083224A (en) 1961-12-08 1963-03-26 Du Pont Polyfluoroalkyl phosphates
CA1023768A (en) 1972-12-21 1978-01-03 Horst Jager Polyfluoroalkyl iodides, process for their manufacture, and their use
JPS5377015A (en) 1976-12-16 1978-07-08 Asahi Glass Co Ltd Preparation of fluorine-containing phosphoric acid ester
US4144185A (en) * 1978-02-24 1979-03-13 The United States Of America As Represented By The Secretary Of The Interior Method and composition for removing calcium sulfate scale deposits from surfaces
US5330883A (en) * 1992-06-29 1994-07-19 Lsi Logic Corporation Techniques for uniformizing photoresist thickness and critical dimension of underlying features
WO1995004020A1 (en) 1993-07-29 1995-02-09 E.I. Du Pont De Nemours And Company Process for the preparation of perfluoroalkyl iodide
WO1995011877A1 (fr) 1993-10-27 1995-05-04 Elf Atochem S.A. Alcools polyfluores et leurs procedes de preparation
IT1269886B (it) 1994-06-14 1997-04-15 Ausimont Spa Processo per il trattamento superficiale di materiali cellulosici, metallici,vetrosi,oppure cementi,marmi,graniti e simili
US5879623A (en) * 1995-12-27 1999-03-09 Buckman Laboratories International Inc. Methods and compositions for controlling biofouling using fluorosurfactants
CN1217013A (zh) * 1996-04-29 1999-05-19 纳幕尔杜邦公司 十氟戊烷组合物
US5908822A (en) * 1997-10-28 1999-06-01 E. I. Du Pont De Nemours And Company Compositions and processes for drying substrates
US6271289B1 (en) 1999-11-16 2001-08-07 E. I. Du Pont De Nemours And Company Stain resistant compositions
US20050107645A1 (en) 2002-06-27 2005-05-19 Asahi Glass Company Limited Fluorine-containing alcohol and method for its production
BE1014987A6 (nl) * 2002-10-07 2004-07-06 Vandersteen Anne Marie Reiningsmiddel.
US20110091408A1 (en) * 2009-10-20 2011-04-21 E. I. Du Pont De Nemours And Company Methods of using fluoroalkyl phosphate compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012145078A1 *

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WO2012145078A1 (en) 2012-10-26
JP2014515781A (ja) 2014-07-03
KR20140027259A (ko) 2014-03-06
CN103649288A (zh) 2014-03-19
AU2012246727A2 (en) 2013-08-22

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