WO1996011981A2

WO1996011981A2 - Fluorocarbon additive for use in protective resinous compositions and antigraffiti paints

Info

Publication number: WO1996011981A2
Application number: PCT/US1995/012883
Authority: WO
Inventors: Bruce R. Maier; Michael Van De Mark
Original assignee: A.T.G., Inc.
Priority date: 1994-10-07
Filing date: 1995-10-06
Publication date: 1996-04-25
Also published as: WO1996011981A3; AU3890995A

Abstract

A fluorocarbon additive that may be added to any resinous composition including aqueous and solvent based paints and coatings to improve the soil resistance and stain release characteristics of the composition. The additive is a mixture of discrete non-polymeric oligomers with each oligomer comprising a central core molecule having one or more fluorocarbon chains extending from and bound to the oligomer core by a mainly covalent bond, and having one or more non-fluorinated appendages extending from the core. In a preferred embodiment, the inventive oligomer is comprised of a polyfunctional core molecule having two or more functional groups, wherein a fluorocarbon chain is covalently bound to less than all of the functional groups. Particularly useful polyfunctional core molecules are selected from the group of tri-aziridines, trimers of isocyanates and/or tri-epoxy systems.

Description

FLUOROCARBON ADDITIVE FOR USE IN PROTECTIVE RESINOUS COMPOSITIONS AND ANTIGRAFFITI PAINTS

FIELD OF THE INVENTION

The present invention is generally directed to the field of fluorocarbon technology, and is more specifically directed to a novel fluorocarbon additive that may be used to impart improved soil resistance and stain release characteristics to paints, coatings and other resinous compositions. The unique structure of this additive enables the protective fluorocarbon component to be strongly bound within the resinous composition to which it is added such that the soil resistance and stain release characteristics are maintained even after prolonged periods of time, exposure to the elements and repeated cleaning with solvents.

BACKGROUND OF THE INVENTION

Fluorocarbon compounds have long been known for their ability to convey anti-soiling, non-stick and oil repellency properties to various surfaces and chemical compositions. For this reason, attempts have been made in the past to incorporate fluorocarbon compounds within resinous materials such as moldable plastics, paints and coatings to improve the soil resistance and release characteristics of these compositions. Particularly for those coatings used in industrial facilities that are exposed to excessive amounts of pollutants and/or chemicals, or coatings used on exterior surfaces that ar constantly barraged with graffiti, the ability to resis staining and to be cleaned easily is an importan characteristic. Of course, the coatings must also exhibi other desirable features dependant upon their intended use suc as use having a specific color, opacity or transparency hardness, volume solids content, gloss, adhesion, flow upo application and/or consistency.

Various methods for incorporating fluorocarbons int coatings and other resinous compositions have been utilized i the past. One such method is to add a fluorosurfactan compound to existing coating compositions during or pos production. Although the fluorosurfactants provide a coatin composition that initially exhibits soil resistance, th fluorosurfactant is not bound tightly within the matrix of th coating composition and can be prone to migration. Thus, ove time the fluoro component is worn away from the surface of th coating. This degradation is particularly notable where th coating is frequently soiled requiring repeated cleaning b rubbing and/or the use of solvents. The solvents tend t remove the fluorocarbons and may eventually dela inate a par of the coating itself from the underlying substrate.

In an effort to overcome this problem, some in th art have suggested providing a fluoro-component as an integral part of the coating or other resinous composition, rather than as an additive. For example, U.S. Patent No. 3,398,182, discloses a surface coating comprised of a highly fluorinated oleophobic and hydrophobic terminal portion and a different nonfluorinated oleophilic portion linked together by a urethane radical. In another example, a crosslinkable polymeric fluorosurfactant is suggested for use as a protective coating composition. [See, e.g.. U.S. Patent No. 5,006,624; U.S. Patent No. 4,929,666; U.S. Patent No. 4,764,564; U.S. Patent No. 4,554,325]. While these prior art compositions are relatively soil resistant, they are not suited for addition to existing paints. Since these compositions often times do not exhibit the desired color, gloss, adhesion, bulk or other qualities sought for the specific application, conventional paints and coatings meeting these objectives must also be applied to the substrate surface with the fluoro composition as a separate overcoat or sealant layer. These prior art fluoro containing coatings also may require special application procedures such as applying the coating with heat which can jeopardize the integrity of underlying paint layers.

It is therefore an object of the present invention to provide a fluorocarbon additive for addition to existing paints, coatings and other resinous compositions, wherein the additive imparts water and oil repellency to the resinous composition upon application to a substrate surface.

It is a further object of the present invention to provide a fluorocarbon additive for addition to existing paints, coatings and other resinous compositions which imparts stain and solvent resistance to the resinous composition.

Another object of the invention it to provide a fluorocarbon additive for addition to paints, coatings and other resinous compositions which imparts good stain release characteristics to the resinous composition such that stains and soil can be easily removed from the surface of the coating with wiping or the use of solvent cleaners.

Yet another objective of the invention is to provide a fluorocarbon additive for addition to existing paints, coatings and other resinous compositions to impart stain and oil resistance to the composition, wherein the stain and oil resistance is retained even after prolonged wear, abrasive action and exposure to solvent cleaners. A further object of the invention is to provide a protective soil resistant fluorocarbon additive that may be added to either aqueous or solvent-based paints, coatings and other resinous compositions.

A related objective of the present invention is to provide a protective soil resistant fluorocarbon additive that comprises a mixture of discrete and nonpolymerized molecules which may be easily integrated within paints, coatings or other resinous compositions without destroying or negativel detracting from other physical characteristics of the resinou composition.

Another objective of the present invention is t provide a protective paint, coating or other resinou composition that exhibits good soil, oil, water and stai resistance.

It is also an object of the present invention t provide a protective paint, coating or other resinou composition that exhibits good oil, soil, water and stai resistance, wherein this resistance is retained even afte prolonged wear, abrasive action and repetitive exposure t solvent cleaners.

Another object of the present invention is to provide an anti-graffiti paint or coating which is resistant to staining by graffiti paint and markers.

An additional objective of the present invention is to provide an anti-graffiti paint or coating, wherein the coating has high stain release properties such that graffiti paint or marking can be easily removed from the coating with wiping and/or the use of solvent cleaners.

Another object of the invention is to provide an anti-graffiti paint or coating that retains its resistance to staining and high stain release properties even after prolonged wear, abrasive action and repetitive exposure to solvent cleaners.

Still another objective of the present invention is to provide a method for making and using the above additives and compositions.

SUMMARY OF THE INVENTION

These and other objects of the present invention are achieved by a fluorocarbon additive that may be added to any resinous composition including aqueous and solvent based paints and coatings to improve the soil resistance and stain release characteristics of the composition. The additive is a mixture of discrete non-polymeric oligomers with each oligomer comprising a central core molecule having one or more fluorocarbon chains extending from and bound to the oligomer core by a mainly covalent bond, and having one or more non- fluorinated appendages extending from the core. The fluorocarbon component of the oligomer tends to orient along the surface of the coating when applied to a substrate so as to provide a protective barrier against staining, and the non- fluorinated appendages anchor the oligomer within the matrix of the resinous composition to prevent removal or degradation of the additive over time. To facilitate this anchoring effect, the non-fluorinated appendages need exhibit water tolerance, yet not hydrophilicity, and must be capable of hydrogen bonding and physical entanglement within the resinous matrix.

In a preferred embodiment, the inventive oligomer is comprised of a polyfunctional core molecule having two or more functional groups, wherein a fluorocarbon chain is covalently bound to less than all of the functional groups. Particularly useful polyfunctional core molecules are selected from the group of tri-aziridines, trimers of isocyanates and/or tri- epoxy systems. Chain extenders may, optionally, be bound to the non-fluorinated functional groups to provide extended appendages which anchor the oligomer within the matrix of the resinous composition to which it is added. Suitable chain extenders include glycol, amine and/or carboxylic acid groups. The oligomer additive may be added to any number of different of resinous compositions in amounts up to about 20%, preferably about 12%, of the total composition without altering or negatively effecting other beneficial physical qualities of the composition. Compositions including the additive remain resistant to staining and solvents, and release stains easily even after repetitive solvent cleaning. Graffiti and other forms of soil are easily removed with cleaning, without residual staining or loss of effectiveness over time.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a fluorocarbon additive comprising a mixture of discrete non-polymeric oligomers. Each oligomer comprises a central core having on or more fluorocarbon chains extending from and bound to th core by a mainly covalent bond and one or more non-fluorinate carbon substituted appendages extending from the core. In general, the oligomer of the present invention ma be represented by the general formula:

^R(Y) _m ^(Q)π where R is a central core ring or branching point; is a non-fluorinated carbon substituted branch extending fro the core; Q is a fluorocarbon chain bound to the core; m i equal to 1 to 5, preferably 2 to 4; n is equal to 1 to 4, preferably 1 to 2; and where n + m is equal to or less than 5. The central oligomer core (R) is a central ring or branchin point from which the fluorocarbon chain(s) (Q) and the non fluorinated appendages (Y) extend.

The fluorocarbon chain (Q) bound to the central cor of the oligomer contains a fluoro-aliphatic terminal group an an active hydrogen-containing terminal group, wherein th active hydrogen-containing terminal group forms a mainly covalent bond with the oligomer core. The fluorocarbon chain (Q) is represented by the general formula: R_fV where R_f is a monovalent fluorinated aliphatic radical containing 3 to about 20 carbon atoms, preferably at least !> carbon atoms, and having a perfluoromethyl terminal group. The fluoro-aliphatic terminal group may have a skeletal structure that is straight chained, branch chained or alicyclic. The radical R_f chain may include any number of carbon atom substituents including hydrogen, chlorine, oxygen and nitrogen. V is the active hydrogen-containing terminal reactive group capable of forming a mainly covalent bond with the central core, and may comprise a hydroxyl group (-0H) , amino group (- NHR')_» a carboxyl group (-C00H) , thiol group (-SH) , hydrogen (- H) , carbonamido group (-CONHR') or a sulfonamido group (S0₂NHR') in which R'is hydrogen or an alkyl radical containing 1 to 20 carbon atoms. Examples of suitable fluorocarbon chains for purposes of the present invention are included within Table I below.

TABLE I - FLUOROCARBONS*

CF₃ (CF₂) _aS0₂NCH₃ (CH₂) _bOH

CF₃ (CF₂) _aS0₂NCH₃ (CH₂) _bSH CF₃ ( CF₂ ) _flS0₂NCH₃ ( CH₂ ) _bNH₂

CF₃ (CF₂) _aS0₂NCH₃ (CH₂) _faC0₂H

CF₃ (CF₂) _β- (CH₂) _cOH

CF₃ (CF₂) _fl- (CH₂-CH₂-0 ) _d-H

CF₃ (CF₂) _a- (CH₂) _c-NH₂ CF₃ (CF₂) _a- (CH₂) _c-SH

CF₃ (CF₂) _a- (CH₂) _c-C0₂H

O

II

CF₃ (CF₂) _a- [ CH₂-CH₂0] _dCH₂-C-OH

CF₃ ( CF₂ ) _a- [ CH₂-CH₂-0 ] _e-CH₂-CH₂-NH₂

* a = 4-12 ; b = 2-6 ; c = 1-4 ; ; d = 1-4 ; e = 0 - 12

The fluorocarbon groups utilized in preparing the additive of the present invention may be obtained commercially as a uniform mixture of identical fluorocarbon chains or may comprise a mixture of different fluorocarbon chains each having the prescribed characteristics. One such product that is suitable includes Zonyl BA¹" which is commercially available from DuPont which is a mixture of perfluoro compounds having alcohol terminal groups.

The non-fluorinated appendages (Y) are carbon- substituted straight, branched or cyclic chains capable of hydrogen bonding and entanglement within the matrix of the resinous composition. The non-fluorinated appendages may vary in size, preferably having a molecular weight ranging from 55 to 1000, with a molecular weight in the range of 55 to 165 being preferred. An essential characteristic of the non- fluorinated appendages is that each appendage have at least one and preferably about three hydrogen bonding sites, either donors or acceptors, to enhance hydrogen bonding a entanglement within the resinous matrix. These sites may comprised of oxygen or nitrogen atoms preferably in the form o alcohols, ethers, tertiary amines or amides. In this regard it should be noted that an important characteristic of th additive is that the oligomer constituents remain as discret molecules within the coating composition to which they ar added and are non-polymeric. Cross-linking or polymerizatio among the oligomers could result in preliminary gelling, o gelling within the resinous composition and would not generall be suited for integration into a resinous system. For thi reason, it is essential that the non-fluorinated appendages ar highly stable and relatively inert. On the other hand, th appendages require some hydrogen bond donor or acceptor group to facilitate hydrogen bonding within the resinous matrix. Taking these factors into consideration, the non-fluorinate appendages preferably do not have one or more primary -OH or COOH sites, since these groups are reactive and susceptible t bonding with other oligomer chains during the additiv production. However, it is desirable to include secondary -O groupings within the non-fluorinated appendages of th oligomer. The secondary groups are then available to enhanc hydrogen bonding, yet sufficiently inert to avoid covalent o ionic bonding with other chains of the oligomer mixture. I cross-linking is deemed to be a problem, it is suggested to ad the additive just prior to application of the coating to avoi gelling.

The appendages are characterized by being water an oleo tolerant, yet not hydrophilic nor hydrophobic. In thi manner, the appendages may be integrated within aqueous and/o solvent based paints or coatings and yet provide sufficien hydrogen bonding sites to "lock" the branches into the pain matrix. In order to obtain this characteristic, each non fluorinated appendage preferably comprises at least 2 carbo atoms and at least 2 nitrogen or oxygen atoms. Mos preferably, the carbon to nitrogen/oxygen ratio ranges from 1: to 4:1 carbon to nitrogen/oxygen for each branched appendage In a preferred embodiment, the oligomer additive of the present invention is comprised of a polyfunctional central core molecule having multiple functional group appendages, wherein a fluorocarbon chain is bound to at least one, but less than all, of the functional groups. The polyfunctional core molecule in accordance with this embodiment is represented as follows:

^R(Z)_m with R being a central core ring or branching point; Z being a functional group extending from the core; and m being 1 to 5. The polyfunctional core molecule may include any ring or branched molecule having one or more functional groups capable of forming a mainly covalent bond with a fluorocarbon chain as heretofore described. Thus, a cyclic or branched molecule comprising one or more acids, alcohols, aminos, aziridines, epoxy and/or isocyanate groups or combinations thereof is deemed suitable for these purposes.

Particularly suitable polyfunctional molecules include cyclic and non-cyclic tri-functional groups, such as tri-aziridine, trimers of epoxy and/or trimers of isocyanate groups. For example, a tri-aziridine suitable for these purposes may be represented as follows:

N N

.LA i_Λ

and is commercially available as CX-100 from ICI Resins US out of Wilmington Massachusetts. This molecule comprises a branched core molecule having three aziridine functional groups on separate chains extending from the central core.

A trimer of hexamethylene di-isocyanate molecules suitable for purposes of the present invention may b represented as follows:

O 0=C=N(CH₂)₆ I ^(CH₂)₆N=C=0 N N

N

I (CH₂)₆N=C=0

and is commercially available under the tradename Desmodur N-7 from Miles Laboratories. This trimer constitutes a cyclic cor molecule having three isocyanate groups as the functiona groups.

Another suitable core molecule for purposes of thi invention is a tri-epoxy system represented as follows:

0 0 0

/ \ 1 / \

CH₂ — CH- -CH, C CH,-C — C .H,

\ / \ / 1

N N H

1 1 11

„ C C o' \ / ^vo

CH, 0

\ / \

C — CH.

H

which is commercially available under the tradename Avaldit PT-810 from Ciba Geigy Corporation. Note that each of the tri functional molecules suggested for use includes multipl reactive groups extending generally as appendages from th central core of the molecule, each of these appendage preferably having at least 1 nitrogen or oxygen atom, an preferably 2 carbon to 2 nitrogen or oxygen atoms when th additive is intended for use in aqueous-based coatings.

In this embodiment, a fluorocarbon chain (R_fV) a heretofore described is bound to at least one, but less tha all of the functional groups (Z) of the polyfunctional core. Where the polyfunctional core is a tri-functional molecule, for example, the fluorocarbon group is preferably bound to only one of the functional groups forming an oligomer as represented below: R⁽Z)(_m- 1, Z'V'R_f with R, Z, m and R_f being previously defined; Z' being the remainder of a functional group Z upon bonding with the fluorocarbon chain; and V being the remainder of the fluorocarbon reactive site V previously described. It is essential that the bond formed between the functional group of the polyfunctional core molecule and the fluorocarbon chain is a mainly covalent bond, preferably formed via a ring opening or addition reaction.

With respect to the tri-aziridine, for example, the fluorocarbon chain preferably has an alcohol, acid or thiol hydrogen containing terminal reactive group to covalently bond with an aziridine group of the core molecule. A suitable fluorocarbon for this purpose includes a perfluoro alcohol mixture available under the trade name Zonyl BA from DuPont. In the case of an isocyanate functional group, the fluorocarbon chain preferably comprises an alcohol or amine hydrogen containing terminal group. With respect to an epoxy functional group, the fluorocarbon chain may include an alcohol, acid, amine or thiol hydrogen containing terminal reactive group to form a strong covalent bond with the epoxy. One of the keys to providing a successful and long-lasting fluorocarbon additive is assuring that the bond between the fluorocarbon and the central core is strong and stable. In this fashion, the fluorocarbon cannot be easily removed from the coating by solvents or repeated cleaning over time.

The remaining non-fluorinated functional groups (Z)_(m _1} of the polyfunctional core serve to anchor the oligomer within the matrix of the resinous composition to which the oligomer mixture is added. The non-fluorinated groups preferably have the same characteristics as above specified for the non-fluorinated appendages. The non-fluorinated groups have hydrogen bonding sites and preferably exhibit water tolerance having at least two carbons and two oxygen nitrogen atoms per group. Most preferably, the carbon nitrogen/oxygen ratio ranges from 1:1 to 4:1 carbon nitrogen/oxygen for each non-fluorinated group. This rati assures that the groups are sufficiently water tolerant enable sufficient dispersibility for uniform mixing within th resinous composition to which it is added, yet not hydrophili which would allow water washing or rain to remove the additiv from the surface. Optionally, chain extenders may be bound to the non fluorinated functional groups to increase the number o branching points and to increase hydrogen bonding potential This will improve the ability of the oligomer to anchor itsel within the resinous matrix, and improve the overall stabilit of the oligomer additive. In such cases, the final product ma be represented by the following formula:

R(Z"J)_(m._υZ'V'R_f Z" being the remainder of the Z group previousl defined upon bonding with chain extender J; and J being a chai extender capable of increasing the overall chemical stabilit and/or the hydrogen bonding potential of the non-fluorinate group and increasing entanglement within the resinous matrix

Of course, the choice of chain extender is dependan in part upon the nature of the non-fluorinated functional grou insofar as the bond between the chain extender and functiona group should be relatively stable and preferably of a covalen nature. In addition, it is preferable to incorporate chai extenders which have hydrogen bonding sites to enhance hydroge bonding within the matrix of the resinous composition to whic it is added.

Where the polyfunctional core includes non fluorinated aziridine, isocyanate and/or epoxy groups, fo example, suitable chain extenders may include alcohols, acid and thiols. In a preferred embodiment, the chain extender ha one primary -OH or -COOH to strongly bond to the functiona group of central the core and most preferably, includes on primary and one secondary -OH. The primary -OH group forms strong bond with the functional group while the secondary group enhances hydrogen bonding potential within the resinous matrix. Particularly suitable chain extenders include glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, and polyglycol formulations available from Dow Chemical Company. An oligomer additive in accordance with this invention may be prepared by reacting a pre-determined amount of fluorocarbon with the polyfunctional core molecule so as to provide a molecule having one or more fluorocarbon chains and one or more non-fluorinated appendages. For example, in order to prepare an oligomer additive from the tri-aziridine molecule, equal molar amounts of fluorocarbon and tri-aziridine are combined and mixed with optional shearing to provide a uniform reaction mixture. Equal molar amounts will result in fluorocarbon chain addition to one functional group of the tri- aziridine. The reaction mixture may then be heated, preferably in the range of 70° to 100° C, and most preferably about 80° C, for a period of time ranging from 6 hours to two weeks to form the fluorinated compound. The time period of the reaction is inversely related to the temperature of reaction. Thus, at the preferred temperature of about 80° C, the reaction should be completed within about 9 to 12 hours.

The fluorinated compound may be used in that form as an additive, or optionally, a chain extender may be added to the non-fluorinated groups. If no chain extender is to be added, the reactive aziridine or other non-fluorinated functional groups of the compound may exhibit unwanted reactivity in the coating composition to which it is added. Thus, it is preferable to either delay addition of the additive to the composition until immediately prior to use, or more preferably to render these groups inert by suitable chemical reaction. In addition, the fluorinated oligomer may be combined with a relatively inert solvent such as N-methyl pyrollidone to provide a composition having about 50% solids for actual use as an additive. An emulsifier such as ethylene glycol monobutyl ether may also be added to enhance the stability of the oligomer for storage. The final product may be stored for later use as an additive, or immediately combine with a resinous composition to enhance the overall soi resistance and release properties of the composition.

A chain extender may optionally be added to the non fluorinated functional groups to increase branching an hydrogen bonding potential. The chain extender may be added i excess amounts ranging from 25% to 75% of the total weight o the oligomer mixture, with about 50% by weight of the tota oligomer mixture being preferred. Upon adding the chai extender and mixing, the mixture is then heated in the range o 70° to 100° C, with 80° C preferred, for a period of 6 hours t two weeks. The reaction time is again inversely related to th reaction temperature such that at the preferred temperature o 80° C, the reaction should be completed within 9 to 12 hours The resulting oligomer product may then be diluted with relatively inert solvent such as N-methyl pyrollidone to for an additive comprising about 30 to 70% by weight solids, wit about 50% solids being preferred. The resulting additive i stable for storage for prolonged periods and may be added t any resinous composition such as paints or coating composition to improve the overall soil resistance and stain releas characteristics of the composition.

Fluorocarbon additives prepared in accordance wit the present invention may be included within any aqueous o solvent based resinous composition including conventiona paints and coatings, aqueous urethane dispersions, wate reducible systems, screen printing inks, powder coatings, plural component coatings, emulsions and alkyds. The additive may be included within the resinous composition during initial production of the composition or may be added to an existing paint or coating composition prior to its application and use.

In order to prepare a protective coating composition and/or antigraffi paint in accordance with this invention, the oligomer additive heretofore described is added to the resinous coating or paint in an amount ranging from 2 to 20% by weight of the total composition, with 5 to 12% by weight of the composition being preferred. The mixture is blended with some shearing and/or agitation to form a uniform mixture.

Other additives such as preservatives, surfactants and pigmenting agents commonly used in paint and coating compositions may also be included. Resin cross-linking agents may also be added to the composition provided the cross-linking agent is suited for linking the resinous constituents only and not the oligomer components. Suitable cross-linking agents in most resin based systems include agents commercially available as Zimplex™ from Microchem out of New York; Oxazilene¹" available from Smidit; CX-100™ commercially available from ICI Resins U.S.; and Ucarlink™ available from Union Carbide Chemical Company.

The cross-linking agent tends to create a more compact and webbed resinous matrix so as to enhance entanglement of the non-fluorinated appendages of the oligomer within the matrix. For this reason, a lesser amount of the oligomer ranging from 5 to 7% of the total composition is preferred in compositions additionally including a crosslinking agent; and higher amounts of the oligomer ranging from 10 to 12% are preferred in compositions not including a crosslinker.

The protective coating containing the oligomer additive may then be used and applied to any surface including wood, metal or plastic in any conventional manner generally used and known in the art. No special treatment or means of application such as heating is necessary. The protective coating exhibits water and oil resistance, and high release characteristics such that paints or other soil can be easily removed with rubbing and/or solvent cleaners. The protective coating retains these characteristics even after repetitive contact with solvents and over time.

The following examples are illustrative of the preparation of compositions in accordance with this invention in which all parts and percentages are expressed by weight unless otherwise specified. The examples are illustrative embodiments of the invention and should not be construed as limiting in scope.

While the invention has been described with respect to preferred embodiments thereof, it will be apparent to thos of skill in the art that variations can be made therein withou departing from the spirit and scope of the present invention

EXAMPLE I

Preparation of Fluorocarbon Additive from Tri-Aziridine

An tri-aziridine molecule represented by the formula

N N

L LA commercially available as CX100 from ICI Resins U.S. out o Wilmington, Massachusetts was combined with an equal mola amount of a perfluro alcohol mixture having a general formul represented as follows:

CF₃(CF₂)_nCH₂CH₂OH where n is equal to 3 to 15. This perfluro alcohol i available under the tradename Zonyl BA from DuPont. Th mixture was heated to 80°C for ten hours to form an oligomer i accordance with the present invention which may be represente as follows:

In order to further extend the non-fluorinated aziridine appendages of the oligomer, an excessive amount of propylene glycol equaling about one-half the total weight of the mixture was added to the reaction mixture. The mixture was then heated to 80°C for about ten hours, The resulting oligomer may be represented as follows:

CH₂CH₃(CF₂)nCF₃

CH₃CHCH₂OCH₂CH₂ CH₂CH₂OCH₂CHCH₃

OH OH

The oligomer mixture was then diluted with N- methylpyrollidone to provide a solution of about 50% solids.

EXAMPLE II

Preparation of Additive from Trimer of Isocyanate

A cyclic trimer of hexymethyldiisocyanate represented as follows:

(CH₂)₆N=C=0 and commercially available as DesModur N-75 from Miles Laboratories, is first mixed with an equal amount by weight of N-methyl pyrollidone. A perfluoro alcohol mixture commercially available as Zonyl BA from DuPont is then added in an equal molar amount with that of the trimer in solution to form a reaction mixture. The reaction of fluorocarbon with trimer i accomplished under ambient temperature conditions ranging fro 18°-25°C for a period of about 4 to 10 hours. This reactio may be catalyzed to shorten the overall reaction time t minutes, with the preferred catalysts being di-butyltinlaurat or triethylamine. The resulting fluorinated trimer may b represented as follows:

II c / \ o

CF₃ ( CF₂) CH₂CH₂0 N ( CH₂) ₆ II ( CH₂) ₆N=C=0

/ \ /\/ H N N

I I o* /^o

N

I (CH₂)₆N=C=0

Next is added an excess amount of propylene glyco equaling about one half of the total weight of the mixture This mixture is reacted at 18 to 25° C for 4 to 10 hours t result in oligomer formation. The final oligomer formulatio may be represented as follows:

0

O OH

Additional N-methyl pyrollidone may then be added to provide final product having about 50% solids content. EXAMPLE III

Preparation of Additive from Tri-Epoxy System In this example, an oligomer additive is prepared from a tri-epoxy compound represented as follows: 0

/ \

CH,—CH-

CH, 0

\ / \ C — CH,

I ²

H

which is commercially available under the trade name Araldite PT-810 from Ciba Geigy Corporation.

The tri-epoxy is mixed with an equal molar amount of a perfluoro amine mixture. The mixture is heated to about 20° to 30° C for a period of time ranging from 6 to 12 hours to fluorinate the tri-epoxy. An excessive amount of ethanol amine is then added equaling about one-half of the total mixture, and allowed to react at a temperature of 20° to 30° C for 6 to 12 hours.

The resulting oligomer may be represented as follows: OH 0 OH H

I II I I

CH₂-CH-CH₂ C CH₂-C-CH₂-N-R I \ / \ /

N-H _or CH₃ N N

R' C. C

<? \ / ^So N

I

CH,

I

CHOH I

CH,-N-R' I

^H or ^CH3 With R being CF₃-(CF₂)_a-(CH₂)₃-; R' being H[0-CH₂CH₂ and f=l-4. The oligomer mixture is then diluted with methylpyrollidone to provide a solution of about 50% solids.

EXAMPLE IV

The oligomer produced in Example I was added to aqueous urethane Reichold L-54 composition as a 6% by weig additive. At the time of surface coating the resinous mixtur was charged with 5% CX-100 cross-linking agent, and the painted onto 14 clay quarry tile surfaces. Control surface were painted without the oligomer additive. Six tile surface were challenged by spraying with ACE brand acetone/toluene based paints; and six with a slow-drying, highly penetratin Rustoleum paint. Two control surfaces were identicall challenged. The challenge paint was allowed to totally cur for one week which typically allows encapsulation of the pain and makes removal very difficult.

Contaminated surfaces were tested for removal wit Solvent A [50% water/MEK solution]; and with Solvent B [25 acetone/water with 1% Dawn detergent]. Removal was attempte by spraying the solvents onto test surfaces, waiting 3 seconds, and then applying ten double wipes with a soft cloth

Results were gauged by ratings of "1" = total remova without shadow; "2" = removal with remaining shadows or pain traces; "3" = incomplete removal. Dela ination or film injur to the surface was scored as "4".

TABLE II - SURFACES AND RATINGS OF REMOVAL

Resin Plus Oliσomer Resin Only

ACE RUSTOLEUM ACE RUSTOLEUM

Solvent A 1 1 3 3

Solvent B 1 1 3 3 EXAMPLE V

The contamination and removal cycle of Example IV was repeated 10 times in series on the same surfaces, with the tenth observations reported below. This indicates the permanence of the bond of the oligomer in the structural surface of the resin.

TABLE II - SURFACES AND RATINGS OF REMOVAL

Resin Plus Oliσomer Resin Only

ACE RUSTOLEUM ACE RUSTOLEUM

Solvent A 1 1 3 3

Solvent B 1 1 3 4

EXAMPLE VI

The enhanced solvent resistance of the resinous films prepared in Example IV was tested by spot test in which the solvent was allowed to sit on the surface of the coating for two minutes and then was given five double wipes. The contribution of the oligomer where a cross-linking agent CX-100 was added to the resin and where no cross-linking agent was used is shown.

Results were rated as "na" = no affect; "s" = softening, but film reforms without damage; "df" = film turns white and is damaged; and "dr" = film is damaged and removed.

TABLE VI

100% 100% 50% methylene acetone isopropvl alcohol chloride/water

Resin plus oligomer na s s

Resin only s df dr

Resin plus oligomer plus cross-linker na na na Resin only plus cross-linker s s df EXAMPLE VII The oligomer prepared in Example I was added t Zeneca 9679 urethane resin in an amount of about 6% oligomer Twelve porous bricks were given a basecoat to reduce porosity. The basecoat was a water resin emulsion comprised of 20% resi solids of Zeneca 5045 to which 10% thixotropic thickene Degussa R-972 was added.

Six of the treated bricks were then painted with th urethane containing oligomer coating; and six with the urethan alone, each respectively charged with CX-100 cross-linkin agent. The coating was allowed to cure and was challenged an rated as in Example IV. Removal solvents were Solvent A and in Example IV; and also Westley's Graffiti Remover whic contains N-methyl pyrollidone and MEK as the active solvents

Results were gauged by ratings of "1" = total remova without shadow; "2" = removal with remaining shadows or pain traces; and "3" = incomplete removal. Delamination of th resin film from the surface was scored as "4".

TABLE VII - SURFACES AND RATINGS OF REMOVAL

Resin Plus Oligomer Resin Only ACE RUSTOLEUM ACE RUSTOLEUM

Solvent A 1 1 3 3

Solvent B 1 1 2 3

Westley's 1 1 2 4

EXAMPLE VIII

The composition prepared in Example IV above wa rated for release of Magik Marker. Twenty tiles were prepare as in Example IV and vigorously marked with black Sanfor Sharpie permanent magic marker. The markings were allowed to cure and dry overnight, and then removal was typicall performed by ten double rubs of a cloth wetted with Acetone; _Solvent A from above; and a commercial Westley's Graffiti remover containing N-methyl pyrollidone and MEK.

Results were gauged by ratings of "1" = total removal without shadow; "2" = removal with remaining shadows or paint traces; and "3" with incomplete removal. Delamination of the resin film from the surface was scored as a "4".

TABLE VIII - SURFACES AND RATINGS OF REMOVAL

Resin Plus Oligomer Resin Control

Example 1 Example 2 L-54 9679 Resin Resin Resin Resin

100% Acetone 2 1 3 3

Solvent A 2 1 3 3

Graffiti Remover 2 1 3 3 -------------=---------=-----------=--=-^^

Claims

We claim:

1. An additive for addition to a resinou composition to enhance the soil resistance and soil releas characteristics of said resinous composition, wherein th additive comprises a mixture of discrete non-polymeri oligomers, each said oligomer comprising a central core havin one or more fluorocarbon chains extending from and bound t said core by a mainly covalent bond and one or more non fluorinated appendages extending from said core.

2. An additive according to claim 1, wherein sai fluorocarbon chain comprises a fluoro-aliphatic terminal grou and an active hydrogen-containing terminal group, wherein th active hydrogen-containing terminal group is capable of formin a mainly covalent bond with said central core of the oligomer

3. An additive according to claim 2, wherein sai fluoro-aliphatic terminal group is a monovalent fluorinate aliphatic radical containing 3 to about 20 carbon atoms and perfluoromethyl terminal group.

4. An additive according to claim 3, wherein sai active hydrogen-containing terminal reactive group is selecte from the group consisting of a hydroxyl group (-OH) , an an (C0₂H) , an amino group (-NHR'), a carboxyl group (-COOH) , th-c group (-SH) , hydrogen (H) , carbonamido group (-CONHR') cr sulfonamido group (S0₂NHR') in which R'is hydrogen or an al*) radical containing 1 to 20 carbon atoms.

5. An additive according to claim 1, wherein sai fluorocarbon chain is selected from the group consisting o fluoroalcohols.

6. An additive according to claim 5, wherein sai fluorocarbon chain is selected from the group consisting o CF₃(CF₂)_nCH₂CH₂OH where n ranges from 3 to 20 and mixture thereof.

7. An additive according to claim 1, wherein sai one or more non-fluorinated appendages are capable of hydroge bonding and entanglement within said resinous composition.

8. An additive according to claim 7, wherein eac said non-fluorinated appendage has a molecular weight rangin from 55 to 1000.

9. An additive according to claim 7, wherein each said non-fluorinated appendage is water and oleo tolerant, yet not hydrophilic nor hydrophobic.

10. An additive according to claim 9, wherein each one or more non-fluorinated appendages comprises at least 2 carbon atoms and at least 2 nitrogen or oxygen atoms.

11. An additive according to claim 9, wherein each one or more non-fluorinated appendages has a carbon to nitrogen/oxygen ratio ranging from 1:1 to 4:1 carbon to nitrogen/oxygen.

12. An additive according to claim 1, wherein said resinous composition is selected from the group consisting of aqueous-based resinous compositions, solvent-based resinous compositions and mixtures thereof.

13. An additive according to claim 12, wherein said resinous composition is selected from the group consisting of paints and coatings.

14. An additive according to claim 13, wherein said resinous composition is an aqueous urethane composition.

15. An additive for addition to a resinous composition to enhance the soil resistance and release characteristics of said composition, wherein the additive comprises a mixture of discrete non-polymeric oligomers, each said oligomer comprising a polyfunctional core molecule having multiple functional groups and a fluorocarbon chain bound to less than all of said functional groups by a mainly covalent bond.

16. An additive according to claim 16, wherein said polyfunctional core may be represented as follows:

with R being a central core ring or branching point; Z being a functional group extending from the core; and m being 1 to 5.

17. An additive according to claim 16, wherein said functional groups comprise a chemically reactive group capable of forming a mainly convalent bond with said fluorocarbon chain.

18. An additive according to claim 17, wherein sai functional groups are selected from the group consisting o acid, alcohol, amino, aziridine, epoxy, isocyanate groups an combinations thereof.

19. An additive according to claim 16, wherein sai polyfunctional core molecule is selected from the grou represented as follows:

0 0=C=N(CH₂)₆ II (CH₂)₆N=C=0

(CH₂)₆N=C=0

20. An additive according to claim 16, wherein sai polyfunctional core molecule is selected from the grou represented as follows:

N N

LA -A

21. An additive according to claim 16, wherein said polyfunctional core molecule is selected from the group represented as follows:

0 0 0

_/C c_N o \ / ^No

N I

CH, 0

\ / \ C — CH,

I H

22. An additive according to claim 16, wherein said fluorocarbon chain comprises a fluoro-aliphatic terminal group and an active hydrogen-containing terminal group, wherein the active hydrogen-containing terminal group is capable of forβing a mainly covalent bond with a functional group of said polyfunctional core molecule.

23. An additive according to claim 22, wherein said fluoro-aliphatic terminal group is a monovalent fluorinated aliphatic radical containing 3 to about 20 carbon atoms and a perfluoromethyl terminal group.

24. An additive according to claim 23, wherein said active hydrogen-containing terminal reactive group is selected from the group consisting of a hydroxyl group (-0H) , an acid (C0₂H) , an amino group (-NHR'), a carboxyl group (-C00H) , thiol group (-SH) , hydrogen (-H) , carbonamido group (-C0NHR') or a sulfonamido group (S0₂NHR') in which R'is hydrogen or an alkyl radical containing 1 to 20 carbon atoms.

25. An additive according to claim 19, wherein said fluorocarbon chain is selected from the group consisting of CF₃(CF₂)_nCH₂CH₂OH where n ranges from 3 to 15 and mixtures thereof.

26. An additive according to claim 20, wherein said fluorocarbon chain is selected from the group consisting o CF₃(CF₂)_nCH₂CH₂OH where n ranges from 3 to 15 and mixture thereof.

27. An additive according to claim 21, wherein sai fluorocarbon chain is selected from the group consisting o perfluoro amines and mixtures thereof.

28. An additive according to claim 16, wherein sai fluorocarbon chain is bound to only one of said functiona groups.

29. An additive according to claim 16, wherein chain extender is added to the non-fluorinated functiona groups of said polyfunctional core to provide a non-fluorinate appendage.

30. An additive according to claim 29, wherein sai chain extender is capable of bonding with said non-fluorinate functional group and of increasing the hydrogen bondin potential of said functional group.

31. An additive according to claim 29, wherein sai non-fluorinated appendage has a carbon to nitrogen/oxygen rati ranges from 1:1 to 4:1 carbon to nitrogen/oxygen.

32. An additive for use.in resinous compositions t impart soil resistance and soil release characteristics to th resinous composition, wherein the additive comprises a mixtur of discrete non-polymeric oligomers, each said oligome represented as follows:

O

II

C H OH

/ \ O / I CF₃ (CF₂) CH₂CH₂0 N (CH₂) ₆ II (CH₂) ₆N OCH₂CHCH₃

/ \ /\ / \ / H N N C

I I II o \/^o o N H

I /

(CH₂)₆N

C-0CH,CHCH,

II I O OH

33. An additive for use in resinous compositions to impart soil resistance and soil release characteristics to the resinous composition, wherein the additive comprises a mixture of discrete non-polymeric oligomers, each said oligomer represented as follows: CH₂CH₃(CF₂)nCF₃

NH HN CH₃CHCH₂OCH₂CH₂ ^NCH₂CH₂OCH₂CHCH₃

OH OH

34. An additive for use in resinous compositions to impart soil resistance and soil release characteristics to the resinous composition, wherein the additive comprises a mixture of discrete non-polymeric oligomers, each said oligomer represented as follows:

OH 0 OH H I II I I

CH₂-CH-CH₂ C CH₂-C-CH₂-N-R

\ / \ /

N-H _nr CH, N N

I ^{or 3} I I

CH,

I

CHOH

I

CH,-N-R'

I H _or CH₃ with R being CF₃- (CF₂) _β- (CH₂) ₃- ; R' being H [0-CH₂CH₂] _f and f = 1-4 .