KR20140027259A - Fluorinated phosphates as surface active agents - Google Patents

Abstract

Contacting a surface active agent and a coating composition in the method for lowering the surface tension of the coating composition, the coating _{composition, (R f AO) P (} O) (O - M +) 2 ( Formula I) and (R _f AO) ₂ P (O) (O ^- M ⁺ ) wherein R _f is C ₁ to C ₆ linear or branched perfluoro optionally interrupted by one, two or three ether oxygen atoms Alkyl; A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n , (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , O (CF ₂ ) _q (CH ₂ ) _r , or OCHFCF ₂ OE ; m is from 0 to 4; n, o, p, and r are each independently 2-20; q is 2; E is a C ₂ to C ₂₀ linear or branched alkyl group optionally interrupted by an oxygen, sulfur, or nitrogen atom; Cyclic alkyl groups, or C ₆ to C ₁₀ aryl groups; M is a Group I metal or ammonium cation (NH _x R ² _y ) ⁺ (where R ² is C ₁ to C ₄ alkyl; x is 1 to 4; y is 0 to 3; x + y is 4 ); Formula (I) is present in at least 50 mol%], comprising contacting with a surfactant comprising: a substrate treated with said coating composition.

Description

Fluorinated phosphate as surface active agent {FLUORINATED PHOSPHATES AS SURFACE ACTIVE AGENTS}

FIELD OF THE INVENTION The field of the present invention relates to the use of fluorochemical surfactants in coating compositions to impart surface effects to substrates coated with such compositions.

Typically, fluoroalkyl phosphate surfactants and surface treatment agents are typically used because they contain a high percentage of fluorine containing a large number of fluorinated compound chains at a given concentration and are considered to provide better performance. However, fluorinated starting materials are more expensive and lack in supply. It is desirable to reduce the amount of fluorinated starting materials in these surfactants while maintaining the same or better performance. Reducing the amount of required fluorinated starting components not only reduces the cost, but also shortens the cycle time, because fewer steps are required to produce the surfactant and less energy is needed. Reducing the fluorine content will reduce costs, but it is necessary to maintain product performance.

Brace and Mackenzie, in US Pat. No. 3,083,224, have the general formula [C _m F _{2m +1} C _n H _2n O] _y PO (OM) _3-y , wherein m is 4 to 12 , n is 1 to 16, and y is on average 1.0 to 2.5). Braces and mackenzies describe their use as oil emulsions, especially when y = 2.

Montagna et al., In EP 0 687 533, describe poly-perfluoroalkyleneoxide monophosphate esters for use as oil repellents and water repellents in various ceramics.

It is desirable to improve surfactant performance while using less fluorinated starting materials, particularly in reducing surface tension in coating compositions. It is also desirable to impart an improved surface effect to the coated surface. The present invention provides a method of increasing surfactant performance and imparting improved surface effects to the coated surface while using less fluorinated starting materials.

The present invention provides a method of lowering the surface tension of a coating composition by contacting a surfactant with the coating composition, wherein the coating composition is represented by the following formulas (I) and (II):

(I)

(R _f AO) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID = 0.0 &

(R _f AO) ₂ P (O) (O ^- M ⁺ )

[In the above formula,

R _f is C ₁ to C ₆ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;

A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n , (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , O (CF ₂ ) _q (CH ₂ ) _r , or OCHFCF ₂ OE ;

m is from 0 to 4;

n, o, p, and r are each independently 2-20;

q is 2;

E is a C ₂ to C ₂₀ linear or branched alkyl group optionally interrupted by an oxygen, sulfur, or nitrogen atom; Cyclic alkyl groups, or C ₆ to C ₁₀ aryl groups;

M is a Group I metal or ammonium cation (NH _x R ² _y ) ⁺ (where R ² is C ₁ to C ₄ alkyl; x is 1 to 4; y is 0 to 3; x + y is 4 );

Formula I is present in greater than 50 mole%].

The present invention provides a method of increasing the oil contact angle of a coating composition applied to a surface, wherein the surface comprises a coating composition comprising Formula I and Formula II as defined above, wherein Formula I is present in at least 50 mole percent. It further comprises a method comprising the step of contacting with.

The present invention provides a method of imparting a surface effect to a coated substrate, wherein all or part of the surface of the substrate comprises Formula I and Formula II as defined above (Formula I is present at least 50 mol%). And further comprising contacting with the coating composition.

The invention further comprises a coating composition and a substrate from any of the above methods.

Trademarks are capitalized herein.

The present invention provides a method of lowering the surface tension of a coating composition by contacting a surfactant with the coating composition, wherein the coating composition is represented by the following formulas (I) and (II):

(I)

(R _f AO) P (O) (O ^- M ⁺ ) ₂

≪ RTI ID = 0.0 &

(R _f AO) ₂ P (O) (O ^- M ⁺ )

[In the above formula,

R _f is C ₁ to C ₆ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;

A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n , (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , O (CF ₂ ) _q (CH ₂ ) _r , or OCHFCF ₂ OE ;

m is from 0 to 4;

n, o, p, and r are each independently 2-20;

q is 2;

E is a C ₂ to C ₂₀ linear or branched alkyl group optionally interrupted by an oxygen, sulfur, or nitrogen atom; Cyclic alkyl groups, or C ₆ to C ₁₀ aryl groups;

M is a Group I metal or ammonium cation (NH _x R ² _y ) ⁺ (where R ² is C ₁ to C ₄ alkyl; x is 1 to 4; y is 0 to 3; x + y is 4 );

Formula I is present in greater than 50 mole%].

Compounds of formula (I) and formula (II) useful in the present invention may be prepared according to the methods described in Longoria et al., US Pat. No. 6,271,289, and Brace and McKenzie, US Pat. No. 3,083,224. Typically, either phosphorus pentoxide (P ₂ O ₅ ) or phosphorus oxychloride (POCl ₃ ) is reacted with a fluorinated alkyl alcohol or a fluorinated alkyl thiol to provide a mixture of mono- and bis- (fluoroalkyl) phosphoric acid do. The product is then neutralized with a common base such as ammonium hydroxide or sodium hydroxide, or an alkanol amine such as diethanol amine (DEA) to provide a mixture of the corresponding phosphates. Vacuum distillation removes excess unreacted alcohol. By controlling the ratio of fluorinated alcohol or fluorinated alkyl thiol to P ₂ O ₅ Provided are compositions useful as surfactants in the present invention wherein the amount of the compound of formula I (mono (fluoroalkyl) phosphate) is at least 50 mol% relative to the amount of the compound of formula II (bis (fluoroalkyl) phosphate). . Preferably, Formula I and Formula II are present in a molar ratio of Formula I to Formula II of 2: 1 or greater. More preferably, Formula I and Formula II are present in a molar ratio of Formula I to Formula II of at least 3: 1.

Fluoroalkyl alcohols or fluoroalkyl thiols used as reactants in the preparation of surfactants useful in the present invention include compounds as described below for various embodiments. Preferred are surfactants comprising compounds of formula (I) and formula (II), wherein R _f is a C ₃ to C ₆ linear or branched perfluoroalkyl, m is 1 to 4. More preferred are surfactants comprising compounds of formula (I) and formula (II) wherein R _f is a C ₂ to C ₄ linear or branched perfluoroalkyl, m is 1-3.

In one embodiment of the invention, the surfactant comprises a compound of formula (I) and formula (II), wherein A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n- , wherein :

(Ia)

(R _f CH ₂ CF ₂ ) _m (CH ₂ ) _n O) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID = 0.0 &

(R _f CH ₂ CF ₂ ) _m (CH ₂ ) _n O) ₂ P (O) (O ^- M ⁺ )

(Wherein,

R _f , R ¹ , m, n, and M are as defined above).

Preferred compounds of formula (Ia) and formula (IIa) include compounds in which R _f is C ₄ or C ₆ perfluoroalkyl and n is 2.

Fluorinated alcohols useful in the preparation of surfactants for use in various embodiments, including compounds of formula (Ia) and formula (IIa), are available by synthesis according to the following scheme:

The telomerization of vinylidene fluoride (VDF) and linear or branched perfluoroalkyl iodides is well known and has the formula (R _f CH ₂ CF ₂ ) _m I wherein m is 1 to 3 or more , R _f is a C ₁ to C ₆ linear or branched perfluoroalkyl group. See, eg, Balague, et al, "Synthesis of fluorinated telomers, Part 1, Telomerization of vinylidene fluoride with perfluoroalkyl iodides", J. Flour Chem. (1995), 70 (2), 215-23. Certain telomer iodides are isolated by fractional distillation. The telomer iodide is treated with ethylene by the procedure described in US Pat. No. 3,979,469 (Ciba-Geigy, 1976) to give telomer ethylene iodide, where n is 1-3 or more. Can provide. The telomer ethylene iodide is treated with fuming sulfuric acid and hydrolyzed according to the procedure disclosed in WO 95/11877 (Elf Atochem SA) to give the corresponding telomer alcohol. Can provide. Higher homologs of telomer ethylene iodide (n = 2, 3) are available with excess ethylene at high pressure. Telomere ethylene iodide is described in J. Fluorine Chemistry, 104, 2 173-183 (2000)] to give the corresponding thiol. An example is the reaction of telomerethylene iodide with sodium thioacetate followed by hydrolysis.

In a further embodiment of the invention, the surfactants used include compounds of Formula I and Formula II wherein A is (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , which are used herein Formula Ib and Formula IIb:

(Ib)

(R _f (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p O) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID =

(R _f (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p O) ₂ P (O) (O ^- M ⁺ )

(Wherein,

R _f , o, p, and M are as defined above in formula (I). Preferred compounds of formula (Ib) and formula (IIb) include those wherein o and p are each 2 and R _f is a linear or branched perfluoroalkyl of C ₄ or C ₆ . The fluoroalkyl alcohols used to prepare the compounds of Formulas (Ib) and (IIb) are described in E. Wilmington, Delaware, USA. children. Available from EI du Pont de Nemours and Company.

In a further embodiment of the invention, the surfactants used include compounds of formula (I) and formula (II) wherein A is O (CF ₂ ) _q (CH ₂ ) _r , which are described herein below:

(Ic)

(R _f O (CF ₂ ) _q (CH ₂ ) _r O) P (O) (O ^- M ⁺ ) ₂

And

(IIc)

(R _f O (CF ₂ ) _q (CH ₂ ) _r O) ₂ P (O) (O ^- M ⁺ )

(Wherein,

R _f , q, r, and M are as defined above in formula (I). Preferred compounds of formulas (Ic) and (IIc) include those wherein q and r are each 2 and R _f is a linear or branched perfluoroalkyl of C ₃ .

Fluoroalcohols used as starting materials for the preparation of compounds of formulas (Ic) and (IIc) are available by the following series of reactions:

Starting perfluoroalkyl etheriodide of formula R _f OCF = CF ₂ is an implementation of US Pat. No. 5,481,028 which discloses the preparation of a compound of formula R _f OCF ₂ CF ₂ I from perfluoro-n-propyl vinyl ether. It may be prepared by the procedure described in Example 8.

The perfluoroalkyl ether iodide is then reacted with excess ethylene at elevated temperature and elevated pressure. The addition of ethylene can be carried out thermally, but it is preferred to use a suitable catalyst. Preferably, 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 reaction temperature is not limited, but a temperature in the range of 110 ° C to 130 ° C is preferred. The reaction time may vary depending on the catalyst and reaction conditions, but usually 24 hours is suitable. The product is purified by any means of separating the unreacted starting material from the final product, but distillation is preferred. A satisfactory yield of up to 80% of theory is obtained by using about 2.7 moles of ethylene per mole of perfluoroalkyl ether iodide, a temperature of 110 ° C. and autogenous pressure, a reaction time of 24 hours and distillation to purify the product. lost.

Perfluoroalkylether ethylene iodide is then treated with fuming sulfuric acid and hydrolyzed according to the procedure disclosed in WO 95/11877 (Elf Atochem S. A.) to give the corresponding alcohols. Alternatively, perfluoroalkylether ethyl iodide can be treated with N-methyl formamide followed by ethyl alcohol / acid hydrolysis. A temperature of about 130 ° C. to 160 ° C. is preferred. Higher homologs of telomer ethylene iodide (q = 2, 3) are available with excess ethylene at high pressure.

Telomere ethylene iodide is described in J. Fluorine Chemistry, 104, 2 173-183 (2000), is treated with various reagents to provide the corresponding thiols. One example is the reaction of telomer ethylene iodide with sodium thioacetate followed by hydrolysis. Telomere ethylene iodide can also be treated in a conventional manner to provide the corresponding thioethanol or thioethylamine.

In a further embodiment of the invention, the surfactant comprises a compound of formula (I) and formula (II) wherein A is —OCHFCF ₂ OE—, wherein

(Id)

(R _{f -} OCHFCF ₂ OE-O) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID = 0.0 &

(R _{f -} OCHFCF ₂ OE-O) ₂ P (O) (O ^- M ⁺ )

(Wherein,

R _f , E and M are as defined above in formula (I). Preferred compounds of formula (Id) and formula (IId) include Included are those wherein R _f is a linear or branched perfluoroalkyl of C ₃ .

Fluoroalcohols used as starting materials for preparing compounds of formula (Id) and formula (IId) are prepared by reacting dioxane, fluoroalkyl containing at least one unsaturated bond, and diol in the presence of an alkali metal compound. For example, in a sealed stainless steel reaction vessel, for about 8 hours at about 70 ° C., in the presence of an alkali metal such as KOH, 1,4-dioxane and the compound of formula R _f OCF = CF ₂ are replaced with HO ( React with a diol such as CH ₂ ) ₂ OH. Further details are provided in US Patent Application No. 2005/0107645, which is incorporated herein by reference.

The present invention relates to a method of lowering the surface tension of a coating composition by contacting a surfactant with the coating composition, wherein the coating composition is present in formula (I) and formula (II) as defined above at least 50 mol%. A method comprising contacting with a surfactant comprising a). U.S. Patent Nos. 3,083,224 and 4,145,382 indicate that surfactants containing a higher proportion of bis (fluoroalkyl) phosphate relative to mono (fluoroalkyl) phosphate are preferred and work better to result in lower surface tension. It starts. This may generally be the case for aqueous systems, but surprisingly, the same is not true for coating compositions defined below. The improved process of the present invention results in a decrease in the surface tension of the coating composition in contact with a surfactant comprising formula l and formula ll when more formula l is present. This is because the ratio of the compound of formula (I) to the compound of formula (II) present when compared to a surfactant containing formula (ll) (bis (fluoroalkyl) phosphate) more than formula l (mono (fluoroalkyl) phosphate) This is because of the surface alteration properties of the surfactants of formula (I) and formula (II), which are at least 50 mol%.

The lowering of the surface tension of the coating composition to which such surfactants containing more formula l are added results in an increase in wetting and leveling. As used herein, "leveling" refers to the uniformity of coverage of a coating when applied to a substrate. It is undesirable to have streaking, surface defects, or detachment of the coating from the substrate surface at the edges, and the like. The flat coating will provide an excellent dried coating on the substrate surface. "Wet" is the spreading of a coating composition onto a surface. It is desirable for the spread to be uniform in order to provide an excellent dried uniform surface.

In the process of the invention, the step of contacting the surfactant with the coating composition as defined above is typically accomplished by simply blending or adding the surfactant to the coating composition. Contact of the surfactant to the coating composition may occur before applying the coating composition to the substrate or may occur after applying the coating composition to the substrate. In the present invention, a low concentration of surfactant of about 0.1% by weight is sufficient to lower the surface tension of the coating composition to less than about 1.8 Pa (18 dyne / cm 2). Surfactants at concentrations as low as 0.01% by weight in the coating composition are effective to achieve surface tensions below 25 dyne / cm 2.

Suitable coating compositions, referred to herein as "coating compositions" or "coating bases," are compositions of alkyd coatings, type I urethane coatings, unsaturated polyester coatings, or water-dispersible coatings, typically in liquid formulations. It is applied to the substrate for the purpose of producing a durable film on the substrate surface. These are conventional paints, stains, polishing agents, floor finishes, and similar coating compositions.

As used herein, the term "alkyd coating" means a conventional liquid coating, typically paint, clear coating, or colorant, based on alkyd resins. Alkyd resins are complex branched and crosslinked polyesters containing unsaturated aliphatic acid residues. Conventional alkyd coatings utilize cured or dry alkyd resins as binders or film-forming components. Alkyd resin coatings contain unsaturated aliphatic acid residues derived from dry oils. These resins spontaneously polymerize in the presence of oxygen or air to produce a solid protective film. Polymerization is called "drying" or "curing" and occurs as a result of the self-oxidation of unsaturated carbon-carbon bonds in the aliphatic acid component of the oil by atmospheric oxygen. When applied to the surface as a thin liquid layer of formulated alkyd coatings, the cured films formed are relatively hard, non-melt, and many organic solvents that act as solvents or diluents for non-oxidized alkyd resins or dry oils. In fact it is insoluble. Such dry oils have been used as raw materials for oil based coatings and are disclosed in the literature.

As used herein, the term "urethane coating" refers to conventional liquid coatings of type I urethane resins, typically paints, clear coatings, or colorants. Urethane coatings typically contain the reaction product of polyisocyanates, typically toluene diisocyanates, and polyhydric alcohol esters of dry oil acids. Urethane coatings fall into five categories by ASTM D-1. Type I urethane coatings are described in Surface Coatings Vol. It contains a pre-reacted autooxidative binder as described in I]. These are also known as uralkyds, urethane-modified alkyds, oil-modified urethanes, urethane oils, or urethane alkyds, and are the largest category of polyurethane coatings and include paints, clear coatings, or colorants. The cured coating is formed by air oxidation and polymerization of unsaturated dry oil residues in the binder.

The term " unsaturated polyester coating " as used hereinbelow means a conventional liquid coating, typically a paint, clear coating, or gel coat formulation, containing an initiator and a catalyst, if necessary, dissolved in a monomer and based on an unsaturated polyester resin. . Unsaturated polyester resins are obtained from condensation polymerization of glycols such as 1,2-propylene glycol or 1,3-butylene glycol and unsaturated acids such as maleic acid in the form of anhydrides (or maleic and saturated acids, for example phthalic acid). The product is contained as an unsaturated prepolymer. Unsaturated prepolymers are linear polymers containing an unsaturated compound in the chain. It is dissolved in a suitable monomer, for example styrene, to produce the final resin. The film is produced by copolymerization of a linear polymer with a monomer by a free radical mechanism. Free radicals may be produced by heat or, more commonly, by the addition of peroxides such as benzoyl peroxide, and may be packaged separately and added before use. Such coating compositions are often referred to as "gel coat" finishes. When curing the coating at room temperature, the decomposition of the peroxide into free radicals is catalyzed by certain metal ions, typically cobalt. The solution of peroxide and cobalt compound is added separately to the mixture and stirred well before application. Unsaturated polyester resins cured by free radical mechanisms are also suitable for irradiation curing, for example, with ultraviolet light. This type of cure that produces no heat is particularly suitable for films on wood or board. Other radiation sources, such as electron-beam curing, are also used.

The term "water-dispersed coating" as used herein is intended for the decoration or protection of a substrate, consisting of water as an essential dispersion component, such as emulsions, latexes or suspensions of film-forming materials dispersed in an aqueous phase. Means a coated coating. "Water-dispersed coating" is a generic classification that describes a number of formulations and includes members of other classes as well as members of the aforementioned classes. Water-dispersed coatings generally include other conventional coating components. The water-dispersed coating can be colored, for example latex paint, automotive base coat, industrial maintenance paint, uncoloured coating, for example clear wood sealer ), Colorants, and finishes, high gloss clear coatings for industrial and automotive, coatings for masonry and cement, and aqueous asphalt emulsions. The water-dispersed coating optionally contains surfactants, protective colloids and thickeners, pigments and extender pigments, preservatives, fungicides, freeze-thaw stabilizers, antifoams, pH adjusters, coalescing aids, and other ingredients. In the case of latex paint, the film-forming material is a latex polymer of acrylate acrylic, vinyl-acrylic, vinyl, or mixtures thereof. Such water-dispersed coating compositions are described in C. R. Martens, "Emulsion and Water-Soluble Paints and Coatings", Reinhold Publishing Corporation, New York, NY, 1965.

As used herein, the term "dry coating" refers to the final decorative and / or protective film obtained after the coating composition is dried, solidified or cured. Such final films can be achieved by non-limiting examples, for example, by curing, coalescing, polymerization, interpenetrating, radiation curing, UV curing or evaporation. The final film may also be applied in a dried final state, such as in a dry coating.

Floor waxes, polishes, or finishes (hereinafter "floor finishes") are generally aqueous or solvent-based polymer emulsions. The surfactants used in the process of the invention are suitable for use in such floor finishes. Commercially available floor finish compositions are typically aqueous emulsion-based polymer compositions that include one or more organic solvents, plasticizers, coating aids, antifoams, surfactants, polymer emulsions, metal complexing agents, and waxes. The particle size range and solids content of the polymers are usually controlled to control product viscosity, film hardness and thermal resistance. Polymers comprising polar groups can serve to improve solubility and can also act as wetting or leveling agents to provide excellent optical properties such as high gloss and distinctness of the 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 for use in floor finishes include, for example, methyl methacrylate / butyl acrylate / methacrylic acid (MMA / BA / MAA) copolymers; Methyl methacrylate / butyl acrylate / acrylic acid (MMA / BA / AA) copolymers and the like. Commercially available styrene-acrylic copolymers include styrene / methyl methacrylate / butyl acrylate / methacrylic acid (S / MMA / BA / MMA) copolymers; Styrene / methyl methacrylate / butyl acrylate / acrylic acid (S / MMA / BA / AA) copolymers and the like. Polymers derived from cyclic ethers usually contain from 2 to 5 carbon atoms in the ring substituted with optional alkyl groups. These examples include various oxiranes, oxetane, tetrahydrofuran, tetrahydropyrans, dioxane, trioxane and caprolactone. Polymers derived from vinyl substituted aromatics include, for example, those made from styrene, pyridine, conjugated dienes, and copolymers thereof. Polyesters, polyamides, polyurethanes and polysiloxanes are also used in floor finishes.

Waxes or wax mixtures used in floor finishes include waxes of 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, hydrogenated coconut oil or soybean oil, and broad wax (mineral waxes) such as paraffin or cerasin. These waxes typically range from 0 to about 15 weight percent, preferably from about 2 to about 10 weight percent, based on the weight of the finish composition.

If the coating composition is a floor finish, the surfactant as defined above is effectively introduced into the coating composition by thoroughly stirring at room temperature or ambient temperature. More sophisticated mixing may be employed, such as the use of a mechanical shaker or the provision of heat or other methods. If the coating composition is a floor finish, the surfactant is generally added at about 0.001% to about 5% by weight based on the dry weight of the coating composition of the present invention in the wet composition. Preferably from about 0.005% to about 2%, more preferably from about 0.005% to about 0.5%, even more preferably from about 0.01% to about 0.05% by weight.

Bottom waxes or varnishes are water based, solvent based and polymer. Surfactants used in the present invention are suitable for use with any of these. Aqueous and polymeric waxes are dried to high gloss without buffing; Solvent-based waxes require vigorous buffing. Water based waxes are recommended for asphalt, vinyl, vinyl asbestos and rubber tile floors; Solvent-based waxes produce a hard, glossy finish and are best for wood, cork, and terrazzo floors. Self-polishing waxes such as polymers or resins will yellow or discolor and wear in areas of high traffic volume; After three or four coatings, they must be peeled off and reapplied.

Surfactants comprising compounds of formula (I) and formula (II) as defined above are in effective contact with the coating composition by thorough stirring at room temperature or ambient temperature. More sophisticated mixing may be employed, such as the use of a mechanical shaker or the provision of heat or other methods. Such a method is not essential and does not substantially improve the final composition. When the coating composition is a latex paint, the surfactants comprising the compounds of formula (I) and formula (II) are generally contacted at from about 0.001% to about 5% by weight, based on the dry weight in the wet paint. Preferably, about 0.01% to about 1% by weight, more preferably about 0.1% to about 0.5% by weight is used.

The present invention provides a method of increasing the contact angle of a coating composition applied to a surface, the surface of which is represented by the formulas (I) and (II):

(I)

(R _f AO) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID = 0.0 &

(R _f AO) ₂ P (O) (O ^- M ⁺ )

(Wherein,

R _f , A, m, n, o, p, r, q, E, M, R ² , x, y and the coating composition are as defined above; Formula (I) is present in an amount greater than 50 mol%), further comprising contacting with a coating composition. Preferably, Formula I and Formula II are present in a molar ratio of Formula I to Formula II of 2: 1 or greater. More preferably, Formula I and Formula II are present in a molar ratio of Formula I to Formula II of at least 3: 1. Preferably, R _f is C ₄ to C ₆ linear or branched perfluoroalkyl. The increase in the contact angle of the coated surface results in a ratio of the compound of formula (I) to the compound of formula (II) being 50 compared to the surfactant containing more bis (fluoroalkyl) phosphate than mono (fluoroalkyl) phosphate. This is because of the surface modifying properties of the coating composition comprising the compounds of formula (I) and formula (II), which are at least mole%. Increasing the contact angle of the coating composition causes an increase in anti-blocking, oil repellency, and resistance to dirt pickup in the dried coating.

The term "resistance to dirt pickup" or "dirt pickup resistance" is used herein to mean the resistance of the dried coating to contamination. It is particularly applicable to climate exposed coatings in that the coating resists dirt, debris, mold, and contamination from other conditions encountered in normal weather throughout the year. The level of dirt pickup resistance is indicated by the measurement of the forward oil contact angle. "Blocking" is that after the coating has dried, the two coated surfaces are undesirably sticked together if they are pressed together or laid in contact with each other for a long time. If blocking occurs, separation of the surfaces may cause breakage of the coating at one or both surfaces. Thus, antiblocking, also referred to as resistance to blocking, is advantageous in many situations where two coated surfaces need to be contacted, for example in window frames. "Oil repellent" is the ability of a surface coated with a coating composition according to the method of the present invention to not spread oil droplets. Oil repellency is determined by measuring the advancing angle when the oil droplet is placed in contact with the surface coated with the coating composition described above for use in the method of the invention described above.

The present invention provides a method for imparting a surface effect to a substrate, wherein all or part of the surface of the substrate is represented by the following general formulas (I) and (II):

(I)

(R _f AO) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID = 0.0 &

(R _f AO) ₂ P (O) (O ^- M ⁺ )

[In the above formula,

R _f is C ₁ to C ₆ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;

A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n , (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , O (CF ₂ ) _q (CH ₂ ) _r , or OCHFCF ₂ OE ;

m is from 0 to 4;

n, o, p, and r are each independently 2-20;

q is 2;

E is a C ₂ to C ₂₀ linear or branched alkyl group optionally interrupted by an oxygen, sulfur, or nitrogen atom; Cyclic alkyl groups, or C ₆ to C ₁₀ aryl groups;

M is a Group I metal or ammonium cation (NH _x R ² _y ) ⁺ (where R ² is C ₁ to C ₄ alkyl; x is 1 to 4; y is 0 to 3; x + y is 4 );

Formula (I) is present at least 50 mol%; further comprising contacting with a coating composition containing a surfactant.

Contact of the coating composition with all or part of the surface of the substrate is accomplished by conventional means. Non-limiting examples include application by brush, cloth, pad, spray, doctor blade, or other known means.

The amount of the compound of formula I (mono (fluoroalkyl) phosphate) is at least 50 mol% relative to the amount of the compound of formula II (bis (fluoroalkyl) phosphate) in the coating composition. Preferably, Formula I and Formula II are present in a molar ratio of Formula I to Formula II of 2: 1 or greater. More preferably, Formula I and Formula II are present in a molar ratio of Formula I to Formula II of at least 3: 1. Compounds of formula l and compounds of formula ll are added to the coating composition, typically as a mixture, as described above. If the coating composition is a latex paint, the surfactants comprising the compounds of formula (I) and formula (II) are generally present at from about 0.001% to about 5% by weight, based on the dry weight in the wet paint. Preferably, about 0.01% to about 1% by weight, more preferably about 0.1% to about 0.5% by weight is used.

The surface properties imparted to the coated substrates are improved compared to substrates coated with compositions containing surfactants comprising more bis (fluoroalkyl) phosphates than mono (fluoroalkyl) phosphates. The improved surface properties provided by the process of the invention result from the use of coating compositions containing surfactants in amounts greater than formula ll. Such improved properties include smoother and more uniform coatings due to increased wetting and leveling of the coating composition, and increased blocking resistance, oil repellency, and dirt pickup resistance in dried coatings.

The present invention includes a coating composition with improved wetting and leveling comprising a coating base and a surfactant of Formula I and Formula II:

(I)

(R _f AO) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID = 0.0 &

(R _f AO) ₂ P (O) (O ^- M ⁺ )

Wherein R _f , A, m, n, o, p, r, q, E, M, R ² , x, y and the coating composition are as defined above; Formula I is at least 50 mol% Exists). The improvement in wetting and leveling provided by the present invention utilizes a coating composition containing a surfactant in an amount greater than Formula ll compared to a coating composition containing a surfactant in an amount greater than Formula l. It comes from doing.

The present invention further includes a substrate treated according to any of the foregoing methods of the present invention. At least one surface of the substrate may be represented by Formula I and Formula II:

(I)

(R _f AO) P (O) (O ^- M ⁺ ) ₂

And

≪ RTI ID = 0.0 &

(R _f AO) ₂ P (O) (O ^- M ⁺ )

Wherein R _f , A, m, n, o, p, r, q, E, M, R ² , x, y and the coating composition are as defined above; Formula I is present at least 50 mol% And a coating composition containing a surfactant.

Typical substrates include a wide variety of surfaces on which coating compositions are commonly used. These include various building materials, typically hard surface treated materials. Hard surface substrates include porous and nonporous mineral surfaces such as glass, stone, masonry, concrete, unglazed tiles, bricks, porous clays, and various other substrates having surface porosity. Specific examples of such substrates include unglazed concrete, bricks, tiles, stones (including granite, limestone and marble), grouts, mortars, statues, monuments, wood, composite materials, for example Wall and ceiling panels, including terrazzo, and those made of gypsum board. In addition to plastics, metals, ceramics, and other hard surfaces are included in the present invention. They are buildings, siding, roads, parking ramps, driveways, floors, fireplaces, fireplace hearth, counter tops, walls, ceilings, decks, patios. Used in the construction of furniture, fixtures, appliances, molded articles, shaped articles, decorative articles, and other articles for interior and exterior applications.

Other substrates include fibrous substrates. Most optional fibrous substrates are suitable for treatment by the process of the present invention. Such substrates include fibers, yarns, fabrics, cloth blends, textiles, carpets, rugs, nonwovens, leather and paper. The term “fiber” includes fibers and yarns, before and after spinning, in various compositions and forms, and includes colored fibers and colored yarns. "Cloth" consists of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefin, nylon, and aramids, such as "NOMEX" and "KEVLAR", Natural or synthetic cloth, or blends thereof. "Fabric blend" means a fabric made of two or more different fibers. Typically, these blends are a combination of at least one natural fiber and at least one synthetic fiber, but may be a blend of two or more natural fibers and / or two or more synthetic fibers.

The method of the present invention is useful for improving the surface effects of various coating compositions and treated substrates. In particular, the method of the present invention is useful for coating compositions such as floor finishes and paints. The process of the present invention requires, but is not limited to, the wetting, leveling, blocking resistance, oil repellency, and dirt pick-up resistance of the coating composition, while requiring fewer fluorinated starting materials than the prior art compositions require. Provides excellent surface modification performance, which is not limited. This improved performance not only reduces raw material costs and manufacturing costs, but also reduces cycle times.

Material and test method

The following materials were used in the examples herein.

C ₆ F ₁₃ CH ₂ CH ₂ OH and POCl ₃ are available from Sigma Aldrich, St. Louis, MO.

RHOPLEX 3829 floor polish, formulation N-29-1 is available from Dow Corning Materials, Midland, Michigan.

Sherwin Williams MAB 024-1501 semi-gloss paint is available from Sherwin Williams, Cleveland, Ohio. Used in the examples was purchased locally in Wilmington, Delaware, USA.

Test Method 1-Surface Tension Measurement

Bill according to the equipment manual from the KRUSS K11 Version 2.501 Tension Meter (KRUSS USA, Matthews, NC) in accordance with the American Society for Testing and Materials ASTM # D1331-56. Surface tension was measured using the Wilhelmy plate method. A perimeter-aware vertical plate was attached to the scale and the force due to wetting was measured. Each example to be tested was added to the coating composition based on the weight of solids of the additive in deionized water. Several different concentrations were prepared. Ten replicates were tested for each dilution and the following machine settings were used:

Method: Plate Method SFT

Thickness: 1.0 s

Wet Length: 40.2 mm

Reading limit: 10

Minimum standard deviation: 2 dynes / cm

Gravity Acceleration: 9.80665 m / s ²

The results were in mN / m (dyne / cm) and the standard deviation was less than 1 dyne / cm. The tension meter was used according to the manufacturer's recommendation.

The stock solution was prepared with the highest concentration of surfactant in the coating composition to be analyzed. The concentration of the solution was based on the mole percent of surfactant in commercially available floor polish (Roflex® 3829, Formulation N-29-1). The solution is stirred overnight (approximately 12 hours) to ensure complete mixing. The original stock solution was diluted to produce lower concentrations of the stock solution for each example. To demonstrate providing surface effects to substrates, floor polishes were used for applications in consumer, public agency, and industrial cleaning segments. Lower surface tension results indicate better performance.

Test Method 2-Contact Angle

Oil contact angles are described in A. W. Adamson in The Physical Chemistry of Surfaces, Fifth Edition, Wiley & Sons, New York, NY, 1990, was measured by the Sessile Drop method. For additional information on equipment and procedures for contact angle measurement, see R. H. Dettre et al. in "Wettability ", Ed. by J. C. Berg, Marcel Dekker, New York, NY, 1993).

광학 벤치(미국 뉴저지주 마운틴 레이크스 블룸필드 43번가 소재의 레임-하트 인코포레이티드

로부터 입수가능함)를 사용하여 기재를 수평 위치로 유지하였다. 동일한 제조업자로부터의 망원 각도계(telescoping goniometer)를 이용하여 소정의 온도에서 헥사데칸을 사용하여 접촉각을 측정하였다. MAB 페인트에, 시험하고자 하는 각각의 실시예를, 페인트 중 첨가제의 고형물을 기준으로 0.018 중량%로 첨가하였다. 시험 액체 한 방울을 폴리에스테르 스크럽 시험 패널(레네타(Leneta) P-121 무광 흑색(dull black) 또는 균등물, 미국 뉴저지주 마와 소재의 레네타 컴퍼니(Leneta Company)) 상에 놓고 방울과 표면 사이의 접촉 지점에서 탄젠트를 정밀하게 결정하였다. 액체 방울의 크기를 증가시킴으로써 전진각을 결정하였다. 데이터를 전진 접촉각으로서 제공하였다. 사용한 액체 또는 오일은 n-헥사데칸이었다.In the cecil drop method, the lame-heart

Optical Bench (Lame-Heart Incorporated, Bloomfield 43, Mountain Lakes, NJ, USA

Available from) to maintain the substrate in a horizontal position. The contact angle was measured using hexadecane at a predetermined temperature using a telescoping goniometer from the same manufacturer. To the MAB paint, each example to be tested was added at 0.018% by weight, based on the solids of the additives in the paint. A drop of the test liquid was placed on a polyester scrub test panel (Leneta P-121 dull black or equivalent, the Leneta Company, Mawa, NJ) and placed on a drop and surface. The tangent was precisely determined at the point of contact between them. The advancing angle was determined by increasing the size of the liquid drop. Data was provided as forward contact angle. The liquid or oil used was n-hexadecane.

Example

Example 1

In a round bottom 100 ml flask equipped with thermocouple and magnetic stir bar, POCl ₃ (0.61 g, 4 mmol) was dissolved in anhydrous THF (25 ml). Then a solution containing C ₆ F ₁₃ CH ₂ CH ₂ OH (2.93 g, 8 mmol), and triethylamine (1 g, 10 mmol) in dry THF (15 mL) was slowly added to the reactor. The reaction was kept at 0 ° C. for 1-2 h and stirred at rt overnight. The solid was then filtered off and the solvent was evaporated by high vacuum. The resulting oil was diluted with aqueous NH ₄ OH solution (30% NH ₃ , 4 mmol) and the pH adjusted to 8-8.5. Samples of the product of Example 1 were characterized by a ratio of mono (fluoroalkyl) phosphate to bis (fluoroalkyl) phosphate of greater than 9 to 1. Samples of the product of Example 1 were added to Roflex 3829 floor polish and tested according to Test Method 1 for surface tension at various concentrations. Samples of the product of Example 1 were also added to Sherwin Williams MAB 024-1501 semi-gloss paint and tested according to Test Method 2 for contact angle measurements. The test results are listed in Tables 2 and 3.

Examples 2-4

By varying the ratio of POCl ₃ to C ₆ F ₁₃ CH ₂ CH ₂ OH, Examples 2 to 4 were prepared as described in Example 1, which was mono (fluoroalkyl) phosphate to bis (fluoroalkyl The proportion of phosphate produced the product as listed in Table 1. Examples 2-4 Samples of each product were added to Roflex 3829 floor polish and tested according to Test Method 1 for surface tension at various concentrations. Samples of each product of Examples 2-4 were also added to Sherwin Williams MAB 024-1501 semi-gloss paint and tested according to Test Method 2 for contact angle measurements. The test results are listed in Tables 2 and 3.

Comparative Examples A to C

By varying the ratio of POCl ₃ to C ₆ F ₁₃ CH ₂ CH ₂ OH, Comparative Examples A to C were prepared as described in Example 1, which produced mono (fluoroalkyl) phosphate to bis (fluoroalkyl). The proportion of phosphate produced the product as listed in Table 1. These examples contained higher amounts of bis (fluoroalkyl) phosphates. Samples of each of Comparative Examples A-C were added to the Roflex 3829 floor polish and tested according to Test Method 1 for surface tension at various concentrations. Samples of the products of each of Comparative Examples A to C were also added to Sherwin Williams MAB 024-1501 semi-gloss paint and tested according to Test Method 2 for contact angle measurements. The test results are listed in Tables 2 and 3.

Coating composition containing a surfactant having a ratio of mono (fluoroalkyl) phosphate to bis (fluoroalkyl) phosphate from 1: 1 to> 9: 1 (roplex 3829) (Example 1, for the tested concentrations) The surface tension of Example 4) was lower compared to the coating composition (Comparative Examples A to C) where the amount of bis (fluoroalkyl) phosphate was higher. Lower surface tension showed better wetting and leveling properties.

Coating composition containing a surfactant having a ratio of mono (fluoroalkyl) phosphate to bis (fluoroalkyl) phosphate of 1: 1 to> 9: 1 (Sherwin Williams MAB 024-1501 semi-gloss paint) (Example 1 The contact angle of Example 4) was higher compared to the coating composition (Comparative Examples A to C) where the amount of bis (fluoroalkyl) phosphate was higher. Larger oil contact angles resulted in better antiblocking, oil repellency, and dirt pick-up resistance.

Claims (20)

In a method of lowering the surface tension of a coating composition by contacting a surfactant with the coating composition,
The coating composition is formula (I) and (II)
(I)
(R _f AO) P (O) (O ^- M ⁺ ) ₂ , and
≪ RTI ID = 0.0 &
(R _f AO) ₂ P (O) (O ^- M ⁺ )
[In the above formula,
R _f is C ₁ to C ₆ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n , (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , O (CF ₂ ) _q (CH ₂ ) _r , or OCHFCF ₂ OE ;
m is from 0 to 4;
n, o, p, and r are each independently 2-20;
q is 2;
E is a C ₂ to C ₂₀ linear or branched alkyl group optionally interrupted by an oxygen, sulfur, or nitrogen atom; Cyclic alkyl groups, or C ₆ to C ₁₀ aryl groups;
M is a Group I metal or ammonium cation (NH _x R ² _y ) ⁺ (where R ² is C ₁ to C ₄ alkyl; x is 1 to 4; y is 0 to 3; x + y is 4 );
Formula I is present in at least 50 mole%]. The method of claim 1, wherein Formula I and Formula II are present in a molar ratio of Formula I to Formula II of at least 2: 1. The method of claim 1 wherein Formula I and Formula II are present in a molar ratio of Formula I to Formula II of at least 3: 1. The method of claim 1, wherein R f is C ₄ to C ₆ linear or branched perfluoroalkyl. The method of claim 1, wherein the coating composition is selected from the group consisting of alkyd coatings, type I urethane coatings, unsaturated polyester coatings, or water-dispersed coatings. The method of claim 5, wherein the coating composition is a floor finish, a polishing agent, a floor polish, or a paint. The method of claim 1, wherein the coating composition is applied to the substrate prior to contact with the surfactant. A method of increasing the contact angle of a coating composition applied to a surface, the method comprising the following formulas (I) and (II):
(I)
(R _f AO) P (O) (O ^- M ⁺ ) ₂ , and
≪ RTI ID = 0.0 &
(R _f AO) ₂ P (O) (O ^- M ⁺ )
[In the above formula,
R _f is C ₁ to C ₆ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n , (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , O (CF ₂ ) _q (CH ₂ ) _r , or OCHFCF ₂ OE ;
m is from 0 to 4;
n, o, p, and r are each independently 2-20;
q is 2;
E is a C ₂ to C ₂₀ linear or branched alkyl group optionally interrupted by an oxygen, sulfur, or nitrogen atom; Cyclic alkyl groups, or C ₆ to C ₁₀ aryl groups;
M is a Group I metal or ammonium cation (NH _x R ² _y ) ⁺ (where R ² is C ₁ to C ₄ alkyl; x is 1 to 4; y is 0 to 3; x + y is 4 );
Formula (I) is present at at least 50 mol%). The method of claim 8, wherein Formula I and Formula II are present in a molar ratio of Formula I to Formula II of at least 2: 1. The method of claim 8, wherein R _f is C ₄ to C ₆ linear or branched perfluoroalkyl. The method of claim 8, wherein the coating composition is selected from the group consisting of alkyd coatings, type I urethane coatings, unsaturated polyester coatings, or water-dispersed coatings. The method of claim 11, wherein the coating composition is a floor finish, polishing agent, floor polish, or paint. The method of claim 8, wherein the contacting step increases the wetting and leveling of the coating composition. As a method for imparting a surface effect to a substrate, all or part of the surface of the substrate is represented by the following formulas (I) and (II):
(I)
(R _f AO) P (O) (O ^- M ⁺ ) ₂ , and
≪ RTI ID = 0.0 &
(R _f AO) ₂ P (O) (O ^- M ⁺ )
[In the above formula,
R _f is C ₁ to C ₆ linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
A is (CH ₂ CF ₂ ) _m (CH ₂ ) _n , (CH ₂ ) _o SO ₂ N (CH ₃ ) (CH ₂ ) _p , O (CF ₂ ) _q (CH ₂ ) _r , or OCHFCF ₂ OE ;
m is from 0 to 4;
n, o, p, and r are each independently 2-20;
q is 2;
E is a C ₂ to C ₂₀ linear or branched alkyl group optionally interrupted by an oxygen, sulfur, or nitrogen atom; Cyclic alkyl groups, or C ₆ to C ₁₀ aryl groups;
M is a Group I metal or ammonium cation (NH _x R ² _y ) ⁺ (where R ² is C ₁ to C ₄ alkyl; x is 1 to 4; y is 0 to 3; x + y is 4 );
Formula (I) is present at at least 50 mole percent; and contacting with a coating composition containing a surfactant. The method of claim 14, wherein Formula I and Formula II are present in a molar ratio of Formula I to Formula II of at least 2: 1. The method of claim 14, wherein R _f is C ₄ to C ₆ linear or branched perfluoroalkyl. The method of claim 14, wherein the coating composition is selected from the group consisting of alkyd coatings, type I urethane coatings, unsaturated polyester coatings, or water-dispersed coatings. 15. The method of claim 14, wherein the surface effect is resistance to blocking, oil repellent, or dirt pickup resistance. A coating composition treated according to the method of claim 1. A substrate treated according to the method of claim 14.