HK1134296B - Fluoroalkyl phosphate compositions - Google Patents

Description

Fluoroalkyl phosphate compositions

Technical Field

The present invention relates to the field of polyfluorinated compounds comprising a vinylidene fluoride telomer linkage in the polyfluorinated chain, in particular to such fluorophosphates, and to their use as surfactants, coating additives or treatment agents to impart water, oil and grease repellency to substrates such as paper, wood, ceramic, masonry, cement or stone.

Background

The polyfluorinated compositions are useful in the preparation of a variety of surface treatment materials. These polyfluorinated compositions are typically made from perfluorinated carbon chains attached, directly or indirectly, to non-fluorinated functional groups capable of further reaction (e.g., hydroxyl groups, carboxylic acid groups, halide groups, and other groups). A variety of materials made from perfluorinated compositions are known to be useful as surfactants or treating agents to provide surface effects to substrates. Surface effects include repellency to moisture, dirt and stains, and other effects that are particularly useful for fibrous substrates and other substrates such as hard surfaces. Many such surfactants and treatments are fluorinated polymers or copolymers.

Most commercially available fluorinated polymers that can be used as treating agents to impart surface effects to substrates contain mostly eight or more carbons in the perfluoroalkyl chain to provide the desired properties. Honda et al in "Macromolecules", 2005, 38, 5699-_fThe orientation of the perfluoroalkyl groups of the groups remains in a parallel configuration, whereas for such chains having less than 6 carbons, reorientation occurs. This reorientation will weaken the surface properties, such as contact angle. Thus, polymers containing shorter chain perfluoroalkyl groups have not been successfully used for commercial applications.

EP 1238004 (Longoria et al) discloses mixtures of fluoroalkyl phosphate and fluoroacrylate polymers for use in providing stain resistance to stone, masonry and other hard surfaces.

It is desirable to improve specific surface effects and increase fluorine efficiency; that is, the efficiency or performance of the treating agent is increased such that the same level of performance can be achieved using only a smaller amount of the expensive fluorinated composition, or such that better performance can be achieved using the same level of fluorine. It is desirable to shorten the chain length of the perfluoroalkyl group to reduce the fluorine content while still achieving the same or superior surface effects.

There remains a need for compositions that can significantly improve the repellency and stain resistance of fluorinated treating agents for substrates when lower levels of fluorine are used. There also remains a need for compositions that can be used as additives to coatings (e.g., paints, stains, or clearcoats) to provide block resistance and extended open time. The present invention provides such compositions.

Summary of The Invention

One embodiment of the present invention is a composition comprising one or more compounds of formula (I) or (II):

wherein

r and q are independently integers from 1 to 3;

R_fis a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms;

j is an integer of 0 or 1, or a mixture thereof,

x is 1 or 2, and the compound is,

z is-O-or-S-,

x is hydrogen or M, and

m is an ammonium ion, an alkali metal ion, or an alkanolammonium ion.

Another aspect of the present invention is a method of providing water repellency, oil repellency, and stain resistance to a substrate comprising contacting the substrate with a composition comprising one or more compounds of formula (I) or (II).

Another aspect of the present invention is a method of providing block resistance, open time extension, and oil repellency to a substrate having a coating composition deposited thereon, said method comprising adding to the coating composition a composition comprising one or more compounds of formula (I) or (I I) prior to deposition of the coating composition onto the substrate.

Another embodiment of the invention is a substrate to which is applied a composition comprising one or more compounds of formula (I) or (II).

Detailed Description

The trademarks below are designated by capital letters.

The present invention includes fluorinated aqueous compositions. The fluorinated aqueous compositions provide improved oil repellency, water repellency, and stain resistance when applied to a substrate surface, and include methods of treating such substrates with the compositions of the present invention. The compositions of the present invention may also be used as additives to coating compositions to impart certain surface characteristics to substrates coated with such compositions. Other embodiments of the present invention include substrates having improved surface characteristics such as oil repellency and stain resistance.

The fluorinated compounds of formulae (I) and (II) above that are useful in various embodiments of the present invention may be obtained by synthesis according to the following scheme:

telomerization of vinylidene fluoride (VDF) with linear or branched perfluoroalkyl iodides is well known and can be used to prepare R_f(CH₂CF₂)_pA compound of structure I wherein p is 1 to 3 or greater, and R_fIs a C1-C6 perfluoroalkyl group. See, for example, Balague et al, "Synthesis of fluorinated tetramers, Part 1, oligomerization of vinylidenefluoride with perfluorinated ethylene oxides", J.Flourchem. (1995), 70(2), 215-23. The particular telomer iodides (V) are isolated by fractional distillation. Telomer iodides (V) can be treated with ethylene by the procedure described in U.S. Pat. No. 3,979,469(Ciba-Geigy, 1976) to provide telomer ethylene iodides (VI) wherein q is 1 to 3 or greater. Telomer ethylene iodides (VI) can be treated with oleum and hydrolyzed to provide the corresponding telomer alcohols (VII) according to the procedure disclosed in WO 95/11877(Elf Atochem s.a.). The higher homologues of telomer ethylene iodide (VI) (q ═ 2, 3) can be obtained using excess ethylene under high pressure. Telomer ethylene iodides (VI) can be treated with various reagents to provide the corresponding thiols according to the procedure described in "J. fluorine Chemistry", 104, 2173-. One example is the reaction of telomer ethylene iodides (VI) with sodium thioacetate, followed by hydrolysis.

Specific fluorinated telomer alcohols derived from telomerization of vinylidene fluoride with ethylene and useful in the present invention are listed in table 1A.

TABLE 1A

Numbering structure for compounds

1. C₂F₅CH₂CF₂CH₂CH₂OH，

2. C₂F₅(CH₂CF₂)₂CH₂CH₂OH，

3. C₂F₅(CH₂CF₂)₃CH₂CH₂OH，

4. C₂F₅CH₂CF₂(CH₂CH₂)₂OH，

5. C₂F₅(CH₂CF₂)₂(CH₂CH₂)₂OH，

6. C₄F₉CH₂CF₂CH₂CH₂OH，

7. C₄F₉(CH₂CF₂)₂CH₂CH₂OH，

8. C₄F₉(CH₂CF₂)₃CH₂CH₂OH，

9. C₄F₉CH₂CF₂(CH₂CH₂)₂OH，

10. C₄F₉(CH₂CF₂)₂(CH₂CH₂)₂OH，

11. C₆F₁₃CH₂CF₂CH₂CH₂OH，

12. C₆F₁₃(CH₂CF₂)₂CH₂CH₂OH，

13. C₆F₁₃(CH₂CF₂)₃CH₂CH₂OH，

14. C₆F₁₃CH₂CF₂(CH₂CH₂)₂OH，

15. C₆F₁₃(CH₂CF₂)₂(CH₂CH₂)₂OH。

Specific fluoroether thiols useful in forming the compounds of the present invention include those listed in Table 1B.

TABLE 1B

Numbering structure for compounds

21. C₂F₅CH₂CF₂CH₂CH₂SH，

22. C₂F₅(CH₂CF₂)₂CH₂CH₂SH，

23. C₂F₅(CH₂CF₂)₃CH₂CH₂SH，

24. C₄F₉CH₂CF₂CH₂CH₂SH，

25. C₄F₉(CH₂CF₂)₂CH₂CH₂SH，

26. C₄F₉(CH₂CF₂)₃CH₂CH₂SH，

27. C₆F₁₃CH₂CF₂CH₂CH₂SH，

28. C₆F₁₃(CH₂CF₂)₂CH₂CH₂SH，

29. C₆F₁₃(CH₂CF₂)₃CH₂CH₂SH。

Fluoroalkyl phosphates of formula (I) and (II) were prepared according to the methods described by Longoria et al in U.S. Pat. No. 6,271,289, and Brace and Mackenzie in U.S. Pat. No. 3,083,224, both incorporated herein by reference. Typically, phosphorus pentoxide (P)₂O₅) Or phosphorus oxychloride (POCl)₃) With fluoroalkyl alcohols or fluoroalkyl thiols to give mixtures of mono-or bis- (fluoroalkyl) phosphoric acids. Neutralization is carried out using a common base such as ammonium hydroxide or sodium hydroxide, or an alkanolamine such as Diethanolamine (DEA) to provide the corresponding phosphate ester. Excess fluoroalkyl alcohol or fluoroalkyl thiol with P₂O₅Reaction, followed by neutralization, provides a mixture of mono (fluoroalkyl) phosphate and bis (fluoroalkyl) phosphate. Higher ratios of bis (fluoroalkyl) phosphate to mono (fluoroalkyl) phosphate can be obtained by using the method of Hayashi and Kawakami in us 4,145,382. Phosphite and phosphinate compositions were prepared in a similar manner.

The resulting composition is then diluted with water, a mixture of water and solvent, or further dispersed or dissolved in a solvent selected from simple alcohols and ketones suitable for use as the solvent for the final application of the substrate (hereinafter referred to as the "application solvent"). Alternatively, aqueous dispersions made by conventional methods using surfactants are prepared by removing the solvent by evaporation and using emulsification or homogenization procedures known to those skilled in the art. Such solventless emulsions may be preferred to minimize concerns over flammability and Volatile Organic Compounds (VOCs). The final product applied to the substrate may be a dispersion (if water-based), or a solution.

It will be apparent to those skilled in the art that many variations of any or all of the procedures described above may also be used to optimize reaction conditions to achieve maximum yield, productivity or product quality.

The present invention includes fluorinated aqueous mixtures comprising mixtures of anionic fluoroalkyl phosphate, fluoroalkyl phosphite or fluoroalkyl phosphinate acid aqueous solutions neutralized with a base, preferably an amine, such as a dialkanolamine base. The composition is neutralized to a pH of about 5 to about 10, preferably to a pH of about 6 to about 9, and most preferably to a pH of about 6 to about 8.

Various molar ratios of fluoroalcohol or fluorothiol, acid and base can be represented by the format (a: 1: b). Thus, the (2: 1) salt is, for example, a bis (fluoroalkyl) phosphate amine salt, the (1: 2) salt is, for example, a fluoroalkyl phosphate bis (amine salt), and the (1: 1) salt is, for example, a fluoroalkyl phosphate amine salt. Preferably, the (2: 1) salt is bis (fluoroalkyl) phosphate diethanolamine salt, the (1: 2) salt is fluoroalkyl phosphate bis (diethanolamine salt), and the (1: 1) salt is fluoroalkyl phosphate diethanolamine salt.

A preferred embodiment of the present invention is a composition of formula (I) or (II) wherein R is_fHaving 4 to 6 carbon atoms and r, q and j are each 1. Other preferred embodiments are compositions wherein M is an ammonium ion or an alkanolammonium ion. According to the inventionOther preferred compositions include: about 15 to 80 mole percent of a mono (fluoroalkyl) phosphate of formula (I) wherein x is 1, and about 20 to about 85 mole percent of a bis (fluoroalkyl) phosphate of formula (I) wherein x is 2. These preferred compositions are useful and preferred for all other embodiments of the present invention, including the application methods and treated substrates described herein.

The salts of fluoroalkyl phosphates are preferred over the corresponding acids depicted in us patent 3,083,224 because of their increased water solubility.

The present invention also includes a method of providing water repellency, oil repellency, and stain resistance to a substrate comprising contacting the substrate with a composition of formula (I) or (II) as defined above, or a mixture thereof. The compositions of the present invention are typically applied by contacting the substrate with the composition using conventional methods including, but not limited to, brushes, sprayers, rollers, doctor blades, swabbing, dipping techniques, foaming, liquid injection, and casting. Optionally, more than one coating may be used, especially on porous surfaces.

The compositions of the present invention may be used as additives in the preparation of substrates. They may be added at any suitable point in the preparation process. For example, in the case of paper, it may be added to the pulp at the time of sizing. Preferably, from about 0.3% to about 0.5% by weight of the composition of the present invention, based on dry solids of the composition and dry paper fibers, is added to the pulp.

When used as a surface treatment for paper, the compositions of the present invention are typically diluted with water to give an application solution containing from about 0.01% to about 20%, preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5% by weight of the solids-based composition. The coverage of the application solution applied to the paper was about 10g/m²To about 200g/m²And preferably about 10g/m²To about 100g/m²The solution is applied. Preferably, the application will be such that about 0.1g/m²To about 5.0g/m²Is applied to the paper.

When used on stone, masonry and other hard surfaces, the compositions of the present invention are typically diluted with water to give an application solution containing from about 0.1% to about 20%, preferably from about 1.0% to about 10%, and most preferably from about 2.0% to about 5.0% by weight of the solids-based composition. The amount of coverage of the application solution applied to the substrate is about 100 grams per square meter (g/m) for a semi-porous substrate such as limestone²) The solution was applied at 200g/m for a porous substrate such as Saltillo blanket (Saltillo)²The solution is applied. Preferably, the application will be such that about 0.1g/m²To about 2.0g/m²Is applied to the surface.

The compositions of the present invention are applied to or contacted with a substrate in the manner described above, or applied in combination with one or more other finishes or surface treatments. The compositions of the present invention optionally further comprise additional components such as treating agents or finishes to achieve additional surface effects, or additives commonly used with such agents or finishes. Such additional components include compounds or compositions that provide surface effects such as stain resistance, stain release, soil resistance, soil release, water repellency, oil repellency, antimicrobial protection, and the like. One or more such treating agents or finishes may be mixed with the compositions of the present invention and applied to a substrate.

Other additives commonly used with such treatments or finishes may also be present, such as surfactants, pH adjusters, leveling agents, wetting agents, and other additives known to those skilled in the art. Examples of such finishes or agents include processing aids, foaming agents, lubricants, soil repellents, and the like. The composition may be applied at the manufacturing facility, at the retail location, or prior to installation and use, or at the consumer location.

The present invention also includes a method of providing block resistance, extended open time, and oil repellency to a substrate having a coating composition deposited thereon, said method comprising adding to the coating composition a composition of formula (I) or (II) above, or a mixture thereof, prior to deposition of the coating composition onto the substrate. Suitable coating compositions, termed "coating binders" herein, include compositions (typically liquid formulations) of: alkyd paints, type I polyurethane paints, unsaturated polyester paints or water-dispersed paints, and are applied to a substrate for the purpose of creating a durable film on the substrate surface. These are conventional paint, stain and similar coating compositions.

As used herein, the term "alkyd coating" refers to a conventional liquid coating based on alkyd resins, typically a paint, a clear coat or a stain. Alkyd resins are complex branched and crosslinked polyesters containing unsaturated fatty acid residues. Conventional alkyd coatings, like the binder or film-forming component, utilize a cured or drying alkyd resin. Alkyd resin coatings comprise unsaturated fatty acid residues derived from drying oils. These resins spontaneously polymerize in the presence of oxygen or air to form a solid protective film. The polymerization reaction is referred to as "drying" or "curing" and proceeds as a result of the natural oxidation of unsaturated carbon-carbon bonds in the fatty acid component of the oil with atmospheric oxygen. When applied to a surface as a thin liquid layer of a formulated alkyd coating, the resulting cured film is relatively hard, non-melting, and substantially insoluble in many organic solvents, which act as solvents or diluents for the unoxidized alkyd resin or drying oil. Such drying oils have been used as raw materials for oily coatings and are described in the literature.

As used hereinafter, the term "polyurethane coating" refers to conventional liquid coatings based on type I polyurethane resins, typically coatings, clearcoats, or stains. Polyurethane coatings typically comprise the reaction product of a polyisocyanate (typically toluene diisocyanate) and a polyol ester of a drying oleic acid. ASTM D-1 classifies polyurethane coatings into five categories. The type I polyurethane Coatings comprise pre-reacted autoxidisable binders as described in the previously cited "Surface Coatings" volume I. They are also known as polyurethane alkyds (uralkyds), polyurethane modified alkyds, oil modified polyurethanes, polyurethane oils or polyurethane alkyds, are the largest class of polyurethane coatings and include coatings, clear coatings or stains. The cured coating is formed by air oxidation and polymerization of unsaturated drying oil residues in the binder.

As used hereinafter, the term "unsaturated polyester coating" refers to a conventional liquid coating, typically a coating, clear coating or gel coat formulation, based on an unsaturated polyester resin and dissolved in monomers and containing initiators and catalysts as required. The unsaturated polyester resin, like the unsaturated prepolymer, contains a product resulting from the polycondensation reaction of a diol (e.g., 1, 2-propanediol or 1, 3-butanediol) with an unsaturated acid, such as maleic acid (or maleic acid with an unsaturated acid, such as phthalic acid), in the form of an anhydride. Unsaturated prepolymers are linear polymers containing unsaturated bonds in the chain. It is dissolved in a suitable monomer such as styrene to prepare the final resin. The linear polymer and monomer copolymerize by a free radical mechanism to form a film. The free radicals may be generated by heating or, more commonly, by the addition of a peroxide, such as benzoyl peroxide, which is packaged separately and added prior to use. Such coating compositions are often referred to as "gel coat" finishes. In order for curing to occur at room temperature, peroxides are catalytically decomposed by certain metal ions (usually cobalt) into free radicals. The solutions of peroxide and cobalt compound were added separately to the mixture and stirred well before application. Unsaturated polyester resins that cure by a free radical mechanism are also suitable for radiation curing using, for example, ultraviolet light. This cured form does not generate heat and is particularly suitable for use as a film on wood or wood panels. Other radiation sources, such as electron beam curing, may also be used.

As used herein, the term "water-dispersed coating" refers to a coating that is used to decorate or protect a substrate and that is composed of water as an essential dispersed 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 describing many formulations and includes members of the above classification as well as members of other classifications. Water-dispersed coatings typically contain other common coating ingredients. Examples of water-dispersed coatings include, but are not limited to: colored coatings, such as latex coatings; pigment-free coatings, such as wood sealants, stains, and finishes; coatings for masonry and cement; and an aqueous asphalt emulsion. The water-dispersed coating optionally contains surfactants, protective colloids and thickeners, pigments and filler pigments, preservatives, fungicides, freeze-thaw stabilizers, defoamers, pH control agents, coalescing aids, and other ingredients. For latex paints, the film-forming material is a latex polymer of acrylate-acrylic, ethylene, or mixtures thereof. Martens in "emulsions and Water-solvent 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 has dried, set, or cured. Such a final film can be obtained by the following non-limiting examples: curing, coalescing, polymerizing, interpenetrating, radiation curing, uv curing, or evaporating. The final film can also be applied in a dry final state, such as a dry paint.

Blocking is the undesirable sticking to one another when two coated surfaces are pressed together or left in contact with one another for an extended period of time. When blocking occurs, the release surface can cause damage to the coating on one or both sides. Thus, improved blocking resistance is beneficial for many situations where two coated surfaces need to be brought into contact, for example on window frames.

As used herein, the term "open time extension" refers to the time during which one layer of liquid coating composition can be mixed into an adjacent layer of liquid coating composition without exhibiting wrinkles, brush marks, or other marks of application. Which is also referred to as wet edge time. Latex coatings containing low boiling point Volatile Organic Compounds (VOCs) have less than ideal open times because they do not contain high boiling point temperature VOC solvents. Insufficient extension of the open time will result in surface defects such as overlapping brush marks or other marks. A longer open time is beneficial when the appearance of the coated surface is important, as it allows the application of the coating without leaving an overlap, brush mark or other application mark in the overlap area between one coating layer and an adjacent coating layer.

When used as an additive, the compositions of the present invention can be effectively incorporated into a coating base or other composition by thorough stirring at room or ambient temperature. More thorough mixing may be employed, for example using a mechanical shaker or heat or other methods. Such methods are not necessary and do not significantly improve the final composition. When used as an additive to latex paints, the compositions of the present invention are typically added to the wet paint in an amount of from about 0.001% to about 5% by weight, based on the dry weight of the composition of the present invention. Preferably about 0.01 wt% to about 1 wt%, and more preferably 0.1 wt% to about 0.5 wt% is used.

The invention also includes substrates that have been treated with the compositions of the invention. Suitable substrates include fibers and hard surface substrates. Fibrous substrates include wood, paper, and leather. Hard surface substrates include porous and non-porous mineral surfaces such as glass, stone, masonry, concrete, unglazed brick, porous clay, and a variety of other substrates having a porous surface. Specific examples of such substrates include: glazed concrete, bricks, tiles, stone (including granite, limestone and marble), grout, stucco, statues, monuments, wood, composite materials (such as terrazzo), and wall and ceiling panels (including those made with gypsum board). They can be used in the construction of buildings, pavements, parking ramps, driveways, floors, fireplaces, fireplace hearths, countertops for kitchens and for other decorative purposes in interior and exterior applications.

The compositions of the present invention are useful for providing one or more of excellent water repellency, oil repellency, and stain resistance to treated substrates. They may also be used to provide blocking resistance, open time extension and oil repellency to substrates coated with a coating composition to which the compositions of the present invention are added. These properties are achieved using lower fluorine concentrations than conventional perfluorocarbon surface treating agents, thereby providing improved "fluorine efficiency" in the protection of the treated surface. The compositions of the present invention are effective at fluorine concentrations of about one-half to one-third of the fluorine concentration of conventional fluorochemical surface protectors. The compositions of the present invention also allow the use of lower fluoroalkyl groups containing 6 or less fluorinated carbon atoms, which would typically show poor oil and water repellency properties for conventional commercially available surface treatment products if the fluoroalkyl group contains less than 8 carbon atoms.

Materials and test methods

The following materials and test methods were used in the examples herein. Groups C mentioned in tables 1A and 1B and in the examples herein, in the list of specific alcohols and thiols₃F₇、C₄F₉And C₆F₁₃All refer to linear perfluoroalkyl groups unless otherwise specifically indicated. Compound numbers refer to the list of alcohols in table 1A.

Compound 6

Ethylene (25g) was added to the charge C₄F₉CH₂CF₂I (217g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated to 240 ℃ and maintained for 12 hours. The product is separated by vacuum distillation to give C₄F₉CH₂CF₂CH₂CH₂I。

To 50g C₄F₉CH₂CF₂CH₂CH₂Fuming sulfuric acid (70mL) was added slowly to I, and the mixture was stirred at 60 ℃ for 1.5 hours. Using ice-cold 1.5 wt% Na₂SO₃The reaction was stopped with the aqueous solution and heated to 95 ℃ for 0.5 hour. The bottom layer was separated and washed with 10 wt% aqueous sodium acetate and distilled to give compound 6: boiling point at 2mmHg (267 Pa) 54 to 57 ℃.

Compound 7Ethylene (18g) was added to the charge C₄F₉(CH₂CF₂)₂I (181g) and d- (+) -limonene (1g) in an autoclave and the reactor was heated to 240 ℃ and maintained for 12 hours. Distilling the product to obtain C₄F₉(CH₂CF₂)₂CH₂CH₂I。

C is to be₄F₉(CH₂CF₂)₂CH₂CH₂I (10g) was heated with N-methylformamide (8.9mL) to 150 ℃ for 26 hours. The reaction was then cooled to 100 ℃ followed by addition of water to isolate the crude ester. To the crude ester were added ethanol (3mL) and p-toluenesulfonic acid (0.09g), and the reaction was stirred at 70 ℃ for 15 minutes. Then ethyl formate and ethanol were distilled off to obtain a crude product. The crude alcohol was dissolved in ether, washed with aqueous sodium sulfite, water and brine in that order, and then dried over magnesium sulfate. Distillation of the product affords compound 7: boiling point at 2mmHg (257 Pa) of 90 to 94 ℃.

Compound 11

Ethylene (15g) was added to the charge C₆F₁₃CH₂CF₂I (170g) and d- (+) -limonene (1g) in an autoclave, then the reactor was heated to 240 ℃ and maintained for 12 hours. The product is separated by vacuum distillation to give C₆F₁₃CH₂CF₂CH₂CH₂I。

To C₆F₁₃CH₂CF₂CH₂CH₂To I (112g) was added oleum (129mL) slowly. The mixture was stirred at 60 ℃ for 1.5 hours. Then, ice-cold 1.5 wt% Na was used₂SO₃The reaction was stopped with the aqueous solution and heated to 95 ℃ for 0.5 hour. The bottom layer was separated and washed with 10% aqueous sodium acetate and distilled to give compound 11: melting point 38 ℃.

Compound 12

Ethylene (56g) was added to the charge C₆F₁₃(CH₂CF₂)₂I (714g) and d- (+) -limonene (3.2g) in an autoclave and the reactor was heated to 240 ℃ and maintained for 12 hours. Separating the product by vacuum distillation to obtain C₆F₁₃(CH₂CF₂)₂CH₂CH₂I. C is to be₆F₁₃(CH₂CF₂)₂CH₂CH₂I (111g) was heated with N-methylformamide (81mL) to 150 ℃ for 26 hours. The reaction was then cooled to 100 ℃ followed by addition of water to isolate the crude ester. To the crude ester were added ethanol (21mL) and p-toluenesulfonic acid (0.7g), and the reaction was stirred at 70 ℃ for 15 minutes. Ethyl formate and ethanol were then distilled off to give the crude alcohol. The crude alcohol was dissolved in ether, washed with aqueous sodium sulfite, water and brine in that order, and then dried over magnesium sulfate. The product was distilled under vacuum to afford compound 12: melting Point 42 ℃.

Test method 1Paper oil repellency

The paper was tested for oil repellency using the American Association of textile dyeing workers (AATCC) kit test procedure (118-. Each test piece was placed on a clean flat surface with the test side up and carefully handled without touching the area to be tested. A drop of test solution from an intermediate Kit Number (intercede Kit Number) test bottle was added drop-wise to the test area from a height of about one inch (2.5 cm). A stopwatch was used to start the timing from the time the droplet was applied. After exactly 15 seconds, a piece of clean cotton tissue was used to remove excess fluid, and the wetted area was immediately examined. The marked darkening of the sample by penetration under the action of the drop, even in small areas, proved to be unacceptable. The procedure was repeated as necessary to ensure that the droplets from other cartridge-numbered bottles fell in the untouched areas. The results were recorded on a kit rating (KitRating) as the highest numbered solution that was left on the sample for 15 seconds without causing failure. The average kit grade value for the five samples was recorded by rounding.

TABLE 2A

Composition of American Association of textile dyeing workers' Kit (AATCC Kit) Test Solution (Tappi Kit Test Solution)

Grade numbering	Composition results
		0	Test sample failed Kaydola
1	By Kaydol
		2	By 65: 35(v/v) Kaydol n-hexadecane
3	By the reaction of n-hexadecane
		4	By n-tetradecane
5	By means of n-dodecane
		6	By n-decane
7	By n-octane
		8	By passing n-heptane

^aKaydol (CAS # 8020-83-5) is available from Pfaltz&Light mineral oil of Bauer, Waterbury, CT, USA.

Test method 2Blocking resistance of the architectural latex coating

The test method described herein is a modification of the ASTM D4946-89 standard test method for block resistance testing of architectural coatings and is hereby specifically incorporated by reference.

The face-to-face blocking resistance of the coatings to be tested was evaluated in this test. For the purposes of this test, blocking is defined as unwanted adhesion to one another when two paint surfaces are pressed together, or placed in contact with one another for an extended period of time.

The paint to be tested was cast onto a polyester test panel using a paint scraper. All paint templates should be free of grease, oil, fingerprints, dust, etc.; surface contamination can affect the blocking resistance results. Typically, the test results began 24 hours after casting the dope. The panel was conditioned for the duration of time required for treatment in the air conditioned room specified by the test method, and six squares (3.8cm by 3.8cm) were cut from the paint test panel. The cut pieces (three pairs) were placed with the paint surfaces of each paint to be tested facing each other. The cut pieces (three pairs) were placed with the paint surfaces of each paint to be tested facing each other. The samples facing each other were placed on marble trays in an oven at 50 ℃. A No. 8 plug was placed on top with the smaller diameter end in contact with the sample, and then a 1000g weight was placed on top of the plug. This will generate a pressure of 1.8psi (12,400 Pa) on the sample. One weight and plug were used for each sample to be tested. After exactly 30 minutes, the test sample was removed from the oven and the stopper and weight were removed and the block resistance was determined after cooling in an air conditioned room for 30 minutes.

After cooling, the sample was separated by peeling with a slow and steady force. The blocking resistance is rated from 0 to 10 according to a subjective tack assessment (sound generated when paint samples are separated) or sealing (complete adhesion of two paint surfaces) determined by the operator of the process. The samples were brought close to the ear to truly hear the degree of tackiness. The rating system is described in table 2B. The degree of sealing was evaluated based on the appearance of the sample and the adhered paint surface portion. Paint barely torn off the test panel backing was an indication of sealing. Higher numbers indicate better blocking resistance.

Table 2B: blocking resistance value rating

Blocking resistance value rating	Description of the separation	Description of Performance
			10	Tack free property	Perfection
9	Very weak adhesiveness	Is excellent in
			8	Very weak adhesion	Is very good
7	Weak adhesiveness	Good/very good
			6	Moderate to weak tack	Good taste
5	Moderate tack	Medium and high grade
			4	Strong tack-no seal	Poor to moderate
3	5 to 25% sealing	Difference (D)
			2	25 to 50% sealing	Difference (D)
1	50 to 75% sealing	Very poor
			0	75 to 100% sealing	Very poor

Test method 3Surface tension measurement

Surface tension was measured using a Kruess tensiometer according to the equipment instructions K11 version 2.501. The Wilhelmy plate method was used. A vertical plate of known perimeter was attached to a balance and the force due to wetting was measured. 10 replicate samples of each dilution were tested and the following machine settings were used:

the method comprises the following steps: surface tension test by plate method

Spacing: 1.0s

Wet length: 40.2mm

Reading limit value: 10

Minimum standard deviation: 2 dyne/cm

Acceleration of gravity (gr.acc): 9.80665m/s 2

Test method 4Contact angle measurement

Contact angles were measured using The sessile drop method, described by A.W. Adamson in "The physical chemistry of Surfaces", fifth edition, Wiley & Sons, New York, NY, 1990. Additional information on the equipment and procedures used to measure contact angles is provided by r.h. dettre et al in "wettabilitity", ed.by j.c. berg, Marcel Dekker, New York, NY, 1993.

In the sessile drop method, a Rame [ Hart ] optical bench (available from Rame [ Hart Inc.; 43Bloomfield Ave., Mountain Lakes, NJ) is used to hold the substrate in a horizontal position. The contact angle was measured at the specified temperature using a telescopic goniometer from the same manufacturer. A drop of the test liquid was dropped onto a polyester frosted test coupon (Leneta P-121 dark black type or equivalent, Leneta Company, Mahwah, NJ) to precisely determine the tangent line at the point of contact between the drop and the surface. The advance angle is determined by increasing the size of the droplets and the retreat angle is determined by decreasing the size of the droplets. Data are typically expressed as advancing and receding contact angles.

The relationship between water and organic liquid contact angles, as well as the degree of dust removal and dust deposition on the surface, are described in a.w. adamson, cited above. Generally, a higher hexadecane contact angle indicates a surface with higher dirt and dirt repellency, and easier surface dusting.

The water and hexadecane advance angles of the dry coating compositions comprising the compositions of the present invention (as additives) were measured on coatings cast onto Leneta panels available from Leneta Company, Mahwah, NJ. The control was the same coating composition without the addition of the composition of the invention.

Test method 5Prolongation of open time

Open time is the time during which a layer to which the liquid coating composition is applied can be mixed into the liquid coating composition of an adjacent layer without exhibiting wrinkles, brush marks or other marks of application. Also known as wet edge time. Low VOC latex coatings have less than ideal open times because they do not contain high boiling temperature VOC solvents. Insufficient open time will result in overlapping brush marks or other marks. Open time testing is performed by accepted industry practice, referred to as finger pressure as described herein. Double-band tensile panels of the control sample and the sample containing 0.1% of the active ingredient of the sample to be tested were used. The coating composition to be tested and the control were the same coating composition, wherein the control contained no additive to be tested and the sample to be tested contained the composition of the present invention as an additive. The panels were prepared using a 7cm doctor blade at 20-25 ℃ and 40-60% relative humidity. The thumb is then pressed against each sample side by side with equal pressure every 1-2 minutes. Endpoint when no coating residue on the thumb was observed. The time from stretch formation to endpoint was recorded as the open time. The percent difference between the control and the sample containing the additive was recorded as percent open time extension. The compositions of the present invention were tested in semi-gloss latex paints.

Test method 6Determination of Water and oil repellency

The test method describes a procedure for testing water repellency on hard surface substrates comprising limestone and granite. Mixing limestone (Euro Beige) and granite (White Cashmere) at 12 square inches (30.5cm)²) The tiles were cut into 4 inch (10.2cm) by 12 inch (30.5cm) samples. After cutting, the sample is rinsed to remove any dust or dirt and allowed to dry thoroughly, typically for at least 24 hours. The composition of the present invention was mixed with deionized water to prepare a permeate solution to provide a fluorine concentration of 0.8 wt% fluorine. The solution was applied to a sample of each substrate surface using an 1/2 inch (1.3cm) paint brush. The surface was then dried for 15 minutes. If necessary, the surface is wiped with a cloth soaked in the treatment solution to remove any excess solution. After the treated substrates were dried overnight, three drops of deionized water and three drops of canola oil were dropped onto each substrate and allowed to stand for five minutes. Water and oil repellency were determined using visual contact angle measurements. The following rating chart using ratings from 0 to 5 was used to determine the contact angle as follows:

repellency rating 5 (excellent): the contact angle is 100-120 degrees.

Repellency rating 4 (very good): the contact angle is 75-90 degrees.

Repellency grade 3 (good): the contact angle is 45-75 degrees.

Repellency rating 2 (general): the contact angle is 25-45 degrees.

Rejection rating 1 (poor): the contact angle is 10-25 degrees.

Repellency rating 0 (penetration): the contact angle is less than 10 degrees. Higher numbers indicate higher repellency, with grades 2 to 5 being acceptable. Data are recorded in tables as water beading (water beading) and oil beading (oil beading).

Test method 7Determination of soiling resistance

Stain resistance was measured on limestone and granite substrates using this method. 12 square inches (30.5cm) of limestone (EuroBeige) and granite (White Cashmere) samples were prepared²) The tiles were cut into 4 inch (10.2cm) by 12 inch (30.5cm) samples. After cutting, the sample is rinsed to remove any dust or dirt and allowed to dry thoroughly, typically for at least 24 hours. The composition of the present invention was mixed with deionized water to prepare a permeate solution to provide a fluorine concentration of 0.8 wt% fluorine. The solution was applied to a sample of each substrate surface using an 1/2 inch (1.3cm) paint brush. The surface was then dried for 15 minutes. If necessary, the surface is wiped with a cloth soaked in the treatment solution to remove any excess solution. After the treated substrate was dried overnight, the following food stains were applied to the substrate surface at intervals: 1) hot bacon grease, 2) cola, 3) black coffee, 4) grape juice, 5) italian salad dressing, 6) tomato sauce, 7) lemon juice, 8) mustard, 9) canola oil, and 10) motor oil. After 24 hours, the food stain was blotted dry or gently scraped off the substrate surface. The substrate surface was rinsed with water and 1% soap solution and the surface was brushed back and forth for 10 cycles using a rigid brush. The substrate was rinsed with additional water and dried for 24 hours before rating.

Stains remaining on the tile surface after cleaning were visually rated according to the following ratings 0 to 4: 0 is no stain; 1 ═ trace stain; 2 ═ a small amount of stain; 3 medium amount of stain; and 4 ═ high amounts of soil. The ratings for each type of substrate for each stain were aggregated to give a rating for each type of composition. The maximum total score for each type of substrate is: the maximum score 4 for 10 stains was 40. A lower score indicates better stain resistance, a score of 20 or less is acceptable, and zero indicates optimal protection from the presence of no stain.

Examples

Example 1

Phosphorus pentoxide (1.44g, 0.0102mol) was added to compound 6(10g, 0.03mol, Table 1A) at 85 deg.C and the mixture was heated to 100 deg.C and maintained for 16 hours. Then to the reaction mixture was added isopropanol (17.05mL) at 85 ℃ and stirred for 0.5 hour, then addedIonic (DI) water (21.66 mL). After 1.5 hours, diethanolamine (DEA, 3.0mL, 0.031mol) was added and the reaction was stirred at 65 ℃ for 2 hours to give phosphate 1 represented by formula (I) wherein R, q and j are 1, R_f＝-C₄F₉And X⁺＝⁺NH₂(CH₂CH₂OH)₂。

Examples 2 to 4

Compounds 11, 7 and 12 (table 1A) were treated in a similar manner as described in example 1 to give phosphate 2(R, q and j ═ 1, R, respectively_f＝-C₆F₁₃) Phosphate 3(R ═ 2, q and j ═ 1, R_f＝-C₄F₉) And phosphate 4(R ═ 2, q and j ═ 1, R_f＝-C₆F₁₃) Wherein each X⁺＝⁺NH₂(CH₂CH₂OH)₂。

Comparative example A

The procedure of example 1 was followed, but using the same equivalents of formula F (CF)₂)_aCH₂CH₂A perfluoroalkylethanol mixture of OH having an average molecular weight of 471, wherein a is from 6 to 14, and predominantly 6, 8 and 10. A typical mixture is as follows: 27% to 37% of a ═ 6; 28% to 32% of a ═ 8; 14% to 20% of a ═ 10; 8% to 13% of a ═ 12; and 3% to 6% of a ═ 14.

Examples testing

The products of examples 1 to 4 and comparative example a were diluted to contain equal weight percent solids and applied to paper through a filler paper sample. After drying, the paper samples were tested for oil repellency using test method 1. The paper used in this test was white paper (bleached No. 50 paper). The results are shown in Table 3.

Table 3: oil repellency tested on paper

Examples	Phosphate ester g/m2	Fluorine g/m2	Oil repellency
				Untreated control	0	0	0
1	0.2929	0.138	3
				2	0.2929	0.151	5
3	0.2929	0.141	3
				4	0.2929	0.158	4
Comparative example A	0.2929	0.154	4
				1	0.5859	0.275	5
2	0.5859	0.303	6
				3	0.5859	0.281	5
4	0.5859	0.316	6
				Comparative example A	0.5859	0.308	5

The results demonstrate that the above examples provide excellent oil repellency when applied to paper substrates and are comparable or in some cases superior to comparative examples having perfluoroalkyl groups containing 6 to 8 carbon atoms, without vinylidene fluoride telomer linkages.

The product of example 4 was applied to limestone and granite and tested for water and oil repellency using test method 6 and stain resistance using test method 7. The results are shown in tables 4 and 5.

Table 4: soil, water and oil repellency of limestone ^a

Food stains	Example 4	Control substance
			Cola	1	2
Mustard	1	4
			Tomato sauce	0	2
Grape juice	2	4
			Italian sauce	1	4
Coffee	2	3
			Lemon juice	4	4
Motor oil	0	4
			Canola oil	0	4
Fat and oil of bacon	0	4
			Total of	11	35
			Beading of water	4	1
Oil beading	4	1

^aSolution% F0.8%; the application amount is 0.37g/m²

Table 5: stain resistance, water repellency and oil repellency of granite ^a

	Example 4	Control substance
			Food stains
Cola	0	2
			Mustard	0	3
Tomato sauce	0	1
			Grape juice	3	4
Italian sauce	0	4
			Coffee	2	3
Lemon juice	0	2
			Motor oil	0	4
Canola oil	0	4
			Fat and oil of bacon	0	4
Total of	5	31
Beading of water	2	1
			Oil beading	3	1

^aSolution% F0.8%; the application amount is 0.36g/m²

The data in table 4 shows that limestone treated with the composition of example 4 exhibits improvements in stain resistance, oil repellency, and water repellency, demonstrating its efficacy with a hard porous surface protective seal layer. The data in table 5 shows that granite treated with the composition of example 4 also shows improvements in stain resistance, oil repellency and water repellency, demonstrating its efficacy with a hard porous surface protection seal layer.

The surface tension of examples 1 to 4 was also tested according to test method 3. The results are shown in Table 6. Examples 1 to 4 were added to a semi-gloss latex paint in an amount of 0.03% based on the dry weight of the examples in the wet coating, and the contact angle was measured using test method 4 and the blocking resistance was measured using test method 2. The results are shown in tables 7 and 8. Examples 3 and 4 were added to a semi-gloss latex paint in an amount of 0.01% based on the dry weight of the examples in the wet coating, and the open time extension was measured using test method 5. The results are shown in Table 9.

Example 5

Phosphorus pentoxide (0.99g, 0.007mol) was added to compound 6(5g, 0.016mol) at 85 deg.C and the mixture was heated to 100 deg.C for 14 hours. Isopropanol (5.31mL) was then added to the reaction mixture at 65 deg.C, stirred at 50 deg.C for 1 hour, and then deionized water was addedWater (6.72 mL). After 5 minutes, ammonia (1.05mL, 30% aqueous solution, 0.027mol) was added and the reaction was stirred at 32 ℃ for 1 hour to give phosphate 5(R, q and j ═ 1, R_f＝-C₄F₉) Wherein⁺X is⁺NH₄. Of the product³¹P nmr showed 46.3 mol% bis (fluoroalkyl) phosphate (x ═ 2) and 31.8 mol% fluoroalkyl phosphate (x ═ 1). The resulting products were tested for surface tension, contact angle, blocking resistance and open time extension as described below, and the results are shown in tables 6 to 9.

Examples 6 to 8

Compounds 11, 7 and 12 (table 1A) were treated in a similar manner as described in example 5 to give phosphate 6(R, q and j ═ 1, R, respectively_f＝-C₆F₁₃) Phosphate 7(R ═ 2, q and j ═ 1, R_f＝-C₄F₉) And phosphate 8(R ═ 2, q and j ═ 1, R_f＝-C₆F₁₃) Wherein each of⁺X are all⁺NH₄. Of phosphoric acid ester 6³¹P nmr showed 43.1 mol% bis (fluoroalkyl) phosphate (x ═ 2) and 28.9 mol% fluoroalkyl phosphate (x ═ 1). Of phosphoric acid ester 7³¹P nmr showed 54.1 mol% bis (fluoroalkyl) phosphate (x ═ 2) and 25.9 mol% fluoroalkyl phosphate (x ═ 1). The resulting products were tested for surface tension, contact angle, blocking resistance and open time extension as described below, and the results are shown in tables 6 to 9.

Example 9

Phosphorus pentoxide (0.96g, 0.0068mol) was added to compound 6(5g, 0.015mol) at 85 ℃ and the mixture was heated to 105 ℃ and maintained for 14 hours. Ethylene glycol (12.5g, EG) was added to the reaction mixture at 95 deg.C, stirred for 25 minutes, then TERGITOL 15-S-9 surfactant (1.16g) from Sigma Aldrich, St. Louis, Mo was added at 86 deg.C. After 10 min, ammonia (0.95mL, 0.0153mol, 30%) was added and the reaction stirred at 70 ℃ for 10 min. Adding water (3)0mL) and the reaction stirred at 70 ℃ for 1 hour, then ammonia (1.6mL, 30%) was added to adjust the pH to 9.8 to give phosphate 9(R, q and j ═ 1, R)_f＝-C₄F₉) Wherein⁺X is⁺NH₄. The resulting products were tested for surface tension, contact angle, blocking resistance and open time extension as described below, and the results are shown in tables 6 to 9.

Examples 10 to 12

Compounds 11, 7 and 12 were treated in a similar manner as described in example 9 to give phosphate 10(R, q and j ═ 1, R_f＝-C₆F₁₃) Phosphate 11(R ═ 2, q and j ═ 1, R_f＝-C₄F₉) And phosphate 12(R ═ 2, q and j ═ 1, R_f＝-C₆F₁₃) Wherein each of⁺X are all⁺NH₄. The resulting products were tested for surface tension, contact angle, blocking resistance and open time extension as described below, and the results are shown in tables 6 to 9.

Examples testing

The products of examples 1-12 were added to deionized water at a solids content (wt.%), and the surface tension was measured according to test method 3. The results obtained are shown in Table 6.

The products of examples 1-12 were added to a semi-gloss latex paint in an amount of 0.03 wt% based on the dry weight of the inventive composition in the wet paint. The contact angle was measured using test method 4 and the resulting data are shown in table 7. Blocking resistance was measured according to test method 2 and the results are shown in table 8.

The products of examples 1-12 were added to a semi-gloss latex paint in an amount of 0.10% by weight based on the dry weight of the inventive composition in the wet paint. The open time extension was measured using test method 5 and the resulting data are shown in table 9.

Table 6: surface tension data ^a (dyne/cm)

Example numbering	0.000％	0.001％	0.005％	0.010％	0.050％	0.100％	0.200％	0.500％
									1	74.6	58.5	45.1	35.3	35.7	30.9	32.0	31.5
2	73.7	58.1	43.8	38.1	19.7	16.1	15.7	15.7
									3	71.7	39.0	24.8	18.7	15.8	15.4	15.2	15.0
4	72.1	65.6	55.4	53.5	41.4	36.5	32.6	29.6
									5	72.1	45.5	43.5	37.5	20.2	17.6	16.9	16.1
6	72.3	56.7	50.7	47.8	37.5	29.6	29.9	25.1
									7	73.8	45.5	28.0	22.3	19.2	18.6	18.0	16.4
8	74.1	62.9	54.7	49.7	42.1	37.2	33.9	26.8
									9	72.5	42.0	31.4	27.9	18.4	17.5	17.2	17.0
10	71.0	43.4	31.9	29.1	24.0	22.2	20.8	19.5
									11	72.4	38.0	21.9	18.8	17.7	17.5	17.3	17.2
12	72.3	51.4	39.9	35.6	26.8	24.4	22.7	21.8

^aThe average of 10 replicates was recorded. Standard deviation < 1 dyne/cm.

The normal surface tension of deionized water is about 72 dynes/cm (shown in the graph as 0% additive). From these test results, excellent surface tension reduction can be found from all examples of the present invention.

Table 7: advancing contact angle of semi-gloss latex paint ^a

Examples	Hexadecane (Hexadecane)
		Control substance	28.1
1	76.8
		2	68.4
3	56.8
		4	67.5
5	74.2
		6	73.2
7	57.4
		8	63.7
9	74.0
		10	62.0
11	64.2
		12	53.6

^aAverage of 3 replicates of 7 mil tensile samples.

Advancing contact angle of hexadecane correlates with oil repellency. It can be seen from the hexadecane (oil) contact angle data that the products of examples 1-12 exhibit excellent oil repellency.

Comparative example B

The procedure of example 5 was followed, but using formula F (CF)₂)_aCH₂CH₂Mixtures of perfluoroalkyl alcohols of OH, wherein a is 6 to 14, and predominantly 6, 8 and 10. A typical mixture is as follows: 27% to 37% of a ═ 6; 28% to 32% of a ═ 8; 14% to 20% of a ═ 10; 8% to 13%a is 12; and 3% to 6% of a ═ 14. The resulting product was tested for blocking resistance and open time extension as described below. The results are shown in 8 and 9.

Comparative example C

The procedure of example 9 was followed, but using the formula F (CF)₂)_bCH₂CH₂A mixture of perfluoroalkyl alcohols of OH, wherein b is 6 to 14, and is predominantly 6, 8 and 10. A typical mixture is as follows: 27% to 37% of b ═ 6; 28% to 32% of b-8; 14% to 20% of b ═ 10; 8% to 13% of b ═ 12; and 3% to 6% of b-14. The resulting product was tested for blocking resistance and open time extension as described below. The results are shown in 8 and 9.

Examples testing

Examples 1 to 12 and comparative examples B and C were added to a semi-gloss latex paint in an amount of 0.03 wt% based on the dry weight of the composition in the wet coating and tested for blocking resistance using test method 2. The data obtained are shown in Table 8. Examples 1 to 12 and comparative examples B and C were added to a semi-gloss latex paint in an amount of 0.10 wt% based on the dry weight of the composition in the wet coating, and the open time extension was measured using test method 5. The data obtained are shown in Table 9.

Table 8: blocking resistance in semi-gloss latex paints ^a

Examples	Grade of blocking Properties
		Untreated control	2.7
1	8.7
		2	8.3
3	7.7
		4	8.7
5	8.0
		6	8.3
7	5.0
		8	8.0
9	9.0
		10	8.7
11	6.3
		12	6.0
Comparative exampleExample B	6.3
		Comparative example C	6.3

^aThe average of 3 replicates was recorded.

According to the results in Table 8, excellent blocking resistance was observed for the products of examples 1-12, and the performance of the various examples was superior to comparative examples B and C.

Table 9: open time extension in semi-gloss latex paints

Examples	Extended open time (minutes)	Percentage elongation (%)
			3	3	12.0
4	6	26.1
			5	7	25.9
6	6	23.1
			7	4	14.8
8	7	25.9
			9	5	18.5
10	4	12.5
			11	4	11.4
12	4	13.3

According to the results in table 9, significantly increased open time extension values were observed for coatings comprising the products of examples 3-12.

Claims (10)

1. A composition comprising a compound of formula (I) or (II):

wherein

r and q are independently integers from 1 to 3;

R_fis a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms;

j is an integer of 0 or 1,

x is 1 or 2, and the compound is,

z is-O-or-S-,

x is hydrogen or M, and

m is an ammonium ion, an alkali metal ion, or an alkanolammonium ion.

2. The composition of claim 1, wherein R_fHaving 4 to 6 carbon atoms; r, q and j are each 1; and M is ammonium or alkanolammonium.

3. The composition of claim 1 comprising 15 to 80 mole percent of a mono (fluoroalkyl) phosphate of formula (I) wherein x is 1; and 20 to 85 mole% of a bis (fluoroalkyl) phosphate of formula (I) wherein x is 2.

4. The composition of claim 1, further comprising

a) An agent providing at least one surface effect selected from the group consisting of stain repellency, stain release, soil resistance, soil release, water repellency, oil repellency, and antimicrobial protection,

b) surfactants, pH regulators, wetting agents, leveling agents or

c) Mixtures thereof.

5. A method of providing water repellency, oil repellency, and stain resistance to a substrate comprising contacting the substrate with the composition of claim 1.

6. A method of providing block resistance, extended open time, and oil repellency to a substrate having a coating composition deposited thereon, said method comprising adding to said coating composition the composition of claim 1 prior to deposition of said coating composition onto said substrate.

7. The method of claim 6, wherein the coating composition is a water-dispersed coating, an alkyd coating, a type I polyurethane coating, or an unsaturated polyester coating.

8. The method of claim 5 or 6, wherein R_fHaving 4 to 6 carbon atoms; r, q and j are each 1; and M is ammonium or alkanolammonium.

9. A substrate treated according to the method of claim 5 or 6.

10. A substrate to which has been applied a composition according to claim 1.