Title of Invention	CURABLE COATING COMPOSITIONS
Abstract	The present invention relates to curable coating compositions which when cured are substantially transparent and exhibit resistance to markings such as graffiti and scuffing and particulate buildup. In particular, the compositions of the present invenlion when cured provide proteclive coatings to surfaces to prevent absorption and/or wetting of ink compositions. The invention composition may also be used as mold release agents.

Title of Invention

CURABLE COATING COMPOSITIONS

Abstract

The present invention relates to curable coating compositions which when cured are substantially transparent and exhibit resistance to markings such as graffiti and scuffing and particulate buildup. In particular, the compositions of the present invenlion when cured provide proteclive coatings to surfaces to prevent absorption and/or wetting of ink compositions. The invention composition may also be used as mold release agents.

Full Text	CURABLE COATING COMPOSITIONS BACKGROUND OF THE INVENTION Field Of The Invention [0001] The present invention relates to curable coating compositions which when cured are substantially transparent and exhibit resistance to markings such as graffiti and scuffing and particulate buildup. In particular, the compositions of the present invention when cured provide protective coatings to surfaces to prevent absorption and/or wetting of ink compositions. The invention composition may also be used as mold release agents. Brief Description Of Related Technology [0002] Graffiti is understood to mean any unwanted markings on a surface, such as a building structure. Typically, it refers to unwanted paintings, words, and drawings. Such markings usually are applied by paints, such as spray paint, magic markers, or other inks. Paints are the most common source of graffiti, especially oil- based paints, such as enamels, epoxies, lacquers, and urethanes. Unwanted markings, however, may be produced by a variety of other sources, such as grease, crayons, and lipstick, among others. [0003] Graffiti continues to be a problem of significant concern in today's society. Rather than a form of art, graffiti is considered vandalism and is an irritating eyesore in both public and private places. Graffiti decreases the value of private properties and drives customers away from businesses. It often defaces public buildings and institutions, such as schools, trains and buses, as well as their stations, public restrooms, park structures, bridges, and tunnels, among many others. [0004] A number of conventional cleaning techniques have been utilized to deal with the graffiti problem. These techniques typically involve cleaning the surface after it has been defaced by graffiti. Such cleaning techniques include sandblasting, sanding, high pressure power washing, and chemical treatments, among other similar procedures. Examples of cleaning compositions developed for removing graffiti are disclosed in U.S. Patent No. 5,024,780 (Leys). [0005] These cleaning methods, however, are costly and time-consuming. The cleaned or treated surface often is deteriorated by the harsh cleansing or chemicals. As a result, the surface has to be restored and repainted at high costs. Moreover, chemical treatment procedures often involve harsh, environmentally harmful chemicals, which pose dangers to human contact. SUMMARY OF THE INVENTION [0009] The inventive compositions are curable compositions, which when cured impart mark resistant properties to a surface, and which make graffiti removal much easier than known coatings which share substantial transparency. [0010] The inventive compositions also reduce the tendency of particulate buildup on surfaces coated therewith. [0011] In one aspect of the invention, the inventive compositions are curable (such as by exposure to moisture) and include a functionalized siloxane (such as a hydroxy terminated one); at least one agent selected from a multi- functional silane, an amino functional silane, an enoxy functional silane, a silazane, and combinations thereof; and optionally, a carrier. Upon moisture cure at ambient temperature graffiti markings made on a surface coated with such a composition are readily removable. [0012] Another aspect of the present invention is directed to a method for imparting mark-resistant properties to a surface once cured. The method includes the steps of applying a film coating of an inventive composition to a surface to inhibit graffiti markings or other scuff markings thereon, and exposing the film coating to moisture at ambient temperature to cure the composition. [0013] Further aspect of the present invention is directed to a method for imparting particulate buildup- resistant properties to a surface. The method includes the steps of applying a film coating of an inventive composition to a surface to inhibit the buildup of particulate matter thereon once cured, and exposing the film coating to moisture at ambient temperature to cure the composition. [0014] Further aspect of the present invention is directed to a method for using the inventive composition as a mold release agent. The method includes the steps of applying a film coating of an inventive composition to a surface of a mold and exposing the film coating to moisture at ambient temperature to cure the composition. [0015] A still further aspect of the present invention is directed to a method for preparing the inventive composition. This method includes the step of combining with mixing a functionalized siloxane with a crosslinker, optionally in a carrier, thereby forming the inventive composition. [0016] The inventive compositions confer one or more of the following benefits and advantages when cured beyond mark resistance and particulate buildup resistance, high gloss retention and clear or invisible on the substrate surface (that is, substantial transparency when cured). The inventive compositions are also appropriate for use on most smooth surfaces, fast curing at room temperature ( minutes), semi-permanent, UV and weather stable, one- component (no mixing required by the end user) and low surface tension [thus appropriate for use with a wide variety of substrates (even polyolefins, to which are ordinarily difficult to apply a coating)]. BRIEF DESCRIPTION OF THE ACCOMPANING/DRAWINGS [0017] Fig. la is an FTIR spectrum of a cured film coating composition of the present invention. [0018] Fig. 1b is an FTIR spectrum of the coating composition of Fig. la prior to curing. [0019] Fig. 2a is an FTIR spectrum of an uncured film coating composition of the present invention. [0020] Fig. 2b is an FTIR spectrum of the film coating of Fig. 2a after curing. DETAILED DESCRIPTION OF THE INVENTION [0021] The present invention is directed to curable compositions, which upon cure are substantially transparent and are resistant to markings, such as graffiti and scuffing, and repel the collection of dust and dirt thereby preventing buildup thereof on surfaces of substrates to which has been applied the curable compositions. Graffiti or scuff markings made on surfaces coated with these compositions are removable by wiping or with other similar conventional means. [0022] The compositions cure by exposure to moisture at ambient temperature to form a film coating, imparting mark resistant and/or particulate buildup resistant properties to surfaces. The compositions are also useful as a mold release agent. [0023] The term "cure" or "curing," as used herein, refers to a change in state, condition, and/or structure in a material that is usually, but not necessarily, induced by at least one variable, such as time, temperature, moisture, radiation, presence and quantity in such material of a curing catalyst or accelerator, or the like. The terms cover partial as well as complete curing. The mechanisms by which compositions of this invention may cure include, in the context of silicone chemistry, addition cure (such as by way of hydrosilation reactions), condensation cure (in which crosslinking of silanol, silazane, enoxy, alkoxy, acetoxy, and the like groups occur), ring opening cure, UV cure (such as by way of silylene reactions), and of course combinations thereof. [0024] The inventive compositions include broadly a functionalized siloxane and a crosslinker, together with one or more of the following optional components catalyst, carrier, filler, plasticizer, color indicator, and surfactant. [0025] Whether the cure mechanism is by way of a condensation cure, addition cure or UV cure, the base polymer may be a branched or linear siloxane and/or functionalized siloxane within following structure: where the number of repeating units, "n", plays a role in determining the molecular weight and the viscosity of the composition. R1, R2, R3, R4, R5, and R6 may be the same or different and may be siloxane, alkyl, allyl, aryl, alkoxy, amino, hydroxyl, hydrogen, mercapto, halo, and cyano, and n is from 0 to about 100,000. P1 and P2 may be the same or different and may be alkyl, allyl, hydroxyl, hydrogen, amino, acetoxy, alkoxy, enoxy, and oxime. Interruption of the polymer chain by a heteroatom is also within the scope of the present invention. [0026] The crosslinker for condensation cure reactions include functionalized silanes, such as cyclic/linear/branched silicone oligomers that have at least two reactive functionalities. The reactive functionality include silazane, silanol, alkoxy, acetoxy, amino, oximino, amido, and enoxy groups or combinations thereof. For addition cure reactions, the functionality includes allyl, alkyl, hydride groups or combinations thereof. For UV cure reactions, the functionality include allyl, alkyl, mercapto, and (meth)acryloxy groups or combinations thereof. [0027] The compositions of the present invention may also include a catalyst for accelerating or otherwise promoting the cure process, such as with condensation reactions. In such case, the catalyst may be chosen from an organic tin, titanium compound, and strong Lewis bases. Generally, the catalyst is present from about 0% to about 0.5% (w/w). This concentration, however, can be varied depending upon the particular components chosen, the desired cure mechanism and the desired cure rate. [0028] Carriers for the composition may be included, if desired. In such case, the carrier may be chosen from organic solvents (such as aliphatic hydrocarbons containing 8 to 12 carbon atoms and aromatic hydrocarbons containing 8 to 12 carbon atoms), low molecular weight siloxanes (such as siloxanes containing 2 to 6 silicone atoms and cyclic siloxanes containing 3 to 5 silicone atoms), water, aerosol propellants (whether chlorinated fluorocarbons or not, such as propane), and supercritical CO2 fluid. In addition, low VOC solvents may be used to prepare the inventive compositions; low VOC formulations have volatile organic solvents. Carriers may be present in the inventive compositions, for example, in an amount from about 10% to about 90% (w/w). Desirably, carriers are present in an amount from about 60% to about 85%(w/w). [0029] Fillers may be included, such as for the purpose of enhancing the durability of the coating. Suitable fillers include silicas, such as treated silicas, clays, MQ resins (as are known in the art), and titanium oxide. [0030] Plasticizers may also be included to impart a degree of modulus, if desired. Suitable plasticizers include inert oligomeric or polymeric compounds, desirably such compounds are compatible with the cross-linkable base polymers mentioned above. Preferably these plasticizers are less compatible with the crosslinked base polymers; thus, a portion of the plasticizer may be capable of migrating to the surface of the cured coating. These plasticizers include for instance polydialkylsiloxanes, branched polydialkylsiloxanes, polyfluorinated dialkylsiloxanes, and organofunctional polyalkylsiloxanes. [0031] A color indicator such as pigments, dyes, and trace UV dyes may be added where a color is desirable for the composition. [0032] A surfactant may also be desirable where surface wetting and film formation characters should be modified. Surfactants may be chosen from ionic and non-ionic ones, depending of course on the particular set of physical properties sought in the specific application. [0033] A charge dispenser may be useful in some cases to eliminate static charger on a treated surface so less particle matter, such as dust or undesired objects, is attracted to the surface. [0034] For addition cure reactive compositions (sucn as moisture curable compositions), the above optional components may be included, though the catalyst will be organic compounds of platinum, titanium, tin, zirconium and of course combinations thereof. Tetraisopropoxytitanate and tetrabutoxytitanate are particularly desirable. See also U.S. Patent No. 4,111,890, the disclosure of which is expressly incorporated herein by reference. Examples of such organic platinum catalysts include platinum divinyl complex (available commercially from UCT, Pennsylvania and Gelest, Pennsylvania). [0035] For UV cure reactive compositions, the above optional components may include, though the catalyst will be an UV initiator. Examples of such UV initiators include photoinitiators available commercially from Ciba Specialty Chemiclas under the "IRGACURE" and "DAROCUR" tradenames, specifically "IRGACURE" 184 (1-hydroxycyclohexyl phenyl ketone), 907 (2-methyl-l-[4-(methylthio)phenyl]-2- morpholino propan-1-one), 369 (2-benzyl-2-N,N- dimethylamino-1-(4-morpholinophenyl)-1-butanone), 500 (the combination of 1-hydroxy cyclohexyl phenyl ketone and benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (the combination of bis(2,6-dimethoxybenzoyl-2,4,4- trimethyl pentyl) phosphine oxide and 2-hydroxy-2-methyl-l- phenyl~propan-l-one), and 819 [bis(2,4,6-trimethyl benzoyl) phenyl phosphine oxide] and "DAROCUR" 1173 (2-hydroxy-2- methyl-1-phenyl-l-propane) and 4265 (the combination of 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide and 2- hydroxy-2-methyl-1-phenyl-propan-l-one); and the visible light [blue] photoinitiators, dl-camphorquinone and "IRGACURE" 784DC. Of course, combinations of these materials may also be employed herein. [0036] For ring opening cure reactive compositions, the above optional components may be included, though the catalyst will be an acid or a base. Examples of such acid or base catalysts include sulfuric acid and potassium hydroxide, respectively. [0037] The base curable polymer may be formed through a ring opening reaction with chemicals such as silacyclopropane [R1R2Si (CH2CH2) ] or silacyclobutane R1R2Si (CH2CH2CH2), where R1 and R2 can be the same or different and may be selected from H, and alkyl and allyl groups. [0038] The reactive functionality on the crosslinker for ring opening cure include halide (such as chloride), alkoxy (such as methoxy), cyano, silanol or combinations thereof. [0039] Particularly desirable functionalized siloxanes for the base curable component include any conventional hydroxy terminated siloxane, or polysiloxane, which is capable of forming film coating upon combination with an appropriate crosslinker. Such hydroxy terminated polysiloxanes are represented by the following general formula: where R1, R2, R3, R4, R5, and R6 may be the same or different and may desirably be C1-6 alkyl and n is from 1 to about 30,000 amu. Interruption of the polymer chain by a hetero atom other than oxygen is also within the scope of the present invention. [0040] An example of a specific hydroxy terminated polysiloxane that may be used to form structure I is hydroxy terminated polydimethylsiloxane ("PDMS"), as represented by structural formula II: [0041] The number of repeating units, "n", plays a role in determining the molecular weight and the viscosity of the composition. Thus, n is an integer from about 1 to about 30,000 amu. Desirably, PDMSs incorporated into the compositions of the present invention have a molecular weight of 4,000 amu or greater. The molecular weight of PDMS, however, may vary depending upon the desired thickness and/or viscosity of the film coating as applied to a surface. Viscosities of the compositions of the present invention generally are typically less than 2000 cps, and desirably are less than 500 cps. [0042] Functionalized siloxanes, such as PDMSs, may be present in the inventive compositions, for example, in an amount from about 0.001% to about 50% by weight in the final composition (w/w). Desirably, PDMSs are present in an amount from about 0.01% to about 3% (w/w). [0043] The compositions of the present invention also include as noted above a crosslinker to produce crosslinking with the polysiloxane and/or with itself, as well as compositions that interact with a surface material. Crosslinking is the attachment of two or more chains of polymers by, for example, bridges and cross bridges, comprising either an element, a group, or a compound. The crosslinking agent functions as a chemical group that can chemically interact with the functional siloxane as well as the residue functional group on a surface. The interaction of the crosslinking group promotes the chemical bonding of the anti-graffiti coating to the surface so that the coating can last longer in a given environment. The crosslinking reactions will initiate as soon as the inventive composition is exposed to moisture. Certain crosslinking agents unexpectedly have been found to provide curing properties, which in combination with hydroxy terminated polysiloxanes produce compositions having when cured in less than 30 minutes under ambient conditions anti-graffiti or anti-scuffing and/or anti-particulate buildup properties, while retaining substantial transparency yielding high gloss. [0044] Suitable crosslinkers, which when combined with the siloxane have been found to produce mark resistant and/or particulate buildup resistant coatings that are substantially transparent when cured, include certain multi-functional silanes, such as amino functional silanes, hydride functional silanes and enoxy functional silanes, silazanes, and combinations thereof. Upon mixing with appropriate polysiloxanes, these agents provide curing properties and produce compositions that inhibit markings and particulate buildup, as well as provide substantial transparency yielding excellent gloss retention. [0045] Organofunctional silanes, within the class of silicon hydride compounds are known for their ability to assist in the bonding of organic polymers to inorganic substrate materials. The compositions of the present invention may include amino and/or enoxy functional silanes. An example of an amino functional silane that may be used in accordance with the present invention is represented by structural formula III: [0046] Other suitable amino functional silanes include di- or tri-amino functional silanes, such as CH3Si(NHCH3)3. [0047] An example of an enoxy functional silane that may be employed in the compositions of the present invention is represented by structural formula IV: [0048] The incorporation of amino and/or enoxy functional silanes in the compositions of the present invention have been found to provide excellent anti- graffiti, anti-scuffing and anti-particulate buildup properties, when combined with hydroxy terminated polysiloxanes. Certain other functional silanes, particularly ethoxy functional silanes and epoxy functional silanes, do not exhibit as useful anti-graffiti and/or release properties when used alone in the compositions of the present invention. Ethoxy and epoxy functional silanes, however, may be useful when combined into other structures, for example, as a functional group in a ladder structure silazane. [0049] Desirable silazanes for incorporation in the compositions of the present invention include cyclic silazanes and ladder structure silazanes. Silazane compounds contain alternating silicon and nitrogen atoms. Cyclic silazanes contain one or more closed rings. An example of a cyclic silazane is represented by the following general formula V: [0050] One particularly desirable cyclic silazane is tris cyclo silazane, represented by structural formula VI: [0051] Also desirable as silazanes in accordance with the present invention are ladder structure silazanes. Ladder structure silazanes contain linear chains that crosslink in ladder-like formations. Structural formula VII represents a ladder structure silazane suitable for use in the compositions of the present invention. Other similar ladder structure silazanes, however, also may be suitable for use in these compositions. Formula VII is represented by: where each R is independently methyl or ethyl, y ranges from about 20% to about 80% of the compound, z ranges from about 0% to about 40% of the compound, and n is from 1 to about 500. [0052] The ladder structure silazane of formula VII is derived from a linear chain silazane compound, which is represented by structural formula VIII: where each R is independently methyl or ethyl, x ranges from about 20% to about 50% of the compound, y ranges from about 20% to about 80% of the compound, and z ranges from about 0% to about 40% of the compound. [0053] Upon addition of ammonia, the ladder-type structure of formula VII is formed. In particular, ammonium chloride is generated as a by-product of the reaction, which causes in situ formation of the ladder structure. The "x" portion of the structure of formula VIII crosslinks, while the "y" and "z" portions remain in linear chains. Due to their in situ formation, a ladder structure silazane used in the compositions of the present invention is a mixture of the compounds of formula VII and VIII. [0054] Desirable crosslinkers may be present in the inventive compositions, for example, in an amount from about 0.1% to about 50% (w/w). Desirably, crosslinking agents are present in an amount from about 1% to about 15% (w/w). [0055] Any conventional catalyst may be employed provided the desired properties of the inventive compositions are not compromised. Suitable catalysts that may be used include conventional organometallic catalysts, such as organic titanium derivatives, organic tin. [0056] A particularly desirable inventive composition combining these components includes: about 0.01% to about 5% of tris cyclo silazane; about 0.005% to about 1% of hydroxy terminated polysiloxane; and the balance, up to about 99%, of a carrier, is a solvent. [0057] Another desirable inventive composition includes: about 0.5% to about 5% of a ladder structure silazane; about 5% to about 30% of an amino functional silane; about 0.01% to about 5% of a hydroxy terminated polysiloxane; and the balance being a carrier, which includes a solvent. Other desirable compositions are set forth in Table 3. [0058] Upon application to a surface, the inventive compositions moisture cure (desirably in less than 30 minutes at ambient temperature) to form film coatings, which are resistant to markings, such as graffiti or scuffing, as well as particulate buildup, and are substantially transparent and retain their gloss. The application of heat is not necessary to effect curing. [0059] These film coatings desirably have a thickness of less than 2.5 microns as applied to a surface. To enhance the aesthetic effects of the compositions as applied to a surface, the compositions may further include an alkoxy silane prepolymer resin and/or an alkoxy functional prepolymer resin, also referred to as an MQ resin (as such resins are known in the art). Such resins improve the ease of application and/or the surface finish of the film coatings, providing a glossy appearance. The glossier finish may be desirable for a variety of applications, such as for coating the side panels of buses and trains. Generally, concentrations of from about 0% to about 5% (w/w) are sufficient. [0060] The present invention also is directed to methods of imparting to a surface mark-resistant and particulate buildup-resistant properties. According to these methods, a film coating of the inventive composition is applied to a surface to inhibit graffiti markings or other scuff markings thereon, or particulate buildup thereon. [0061] The inventive composition may be applied by wiping or spraying it onto the desired surface, or by any other suitable means, to form a film coating on the surface. A single coat usually will be sufficient, however, additional coats may be applied, as desired. For example, it may be desirable to apply several coats of the inventive composition on rougher surfaces. If multiple coats are applied, curing may desirably be permitted between each application. [0062] Other application methods for the inventive compositions include spraying (such as by aerosol or pump driven), wiping, brushing, dipping, and rolling. [0063] After application to the surface, the inventive composition in film form is exposed to moisture at ambient temperature to cure the composition. Cure ordinarily occurs in less than 30 minutes, and desirably does so. Although heat could be applied, it is not necessary to effect curing sometimes in as short as about 5 to about 20 minutes. The cure time, however, may be even shorter upon addition of certain appropriate catalysts, as described above. Once cured, any graffiti or other scuff markings created on the surface are easily removable by wiping or with other conventional means, and particulate buildup over time is seen to be dramatically less. [0064] The inventive compositions when used as mold release agents desirably cure to a high durability finish that permits a number of releases without contaminating a released part by transfer of the release composition from the mold to the part. In addition, in some embodiments, the coating may desirably cure to a high gloss finish that permits a number of releases without measurable loss of initial gloss value. For example, the compositions of the present invention may cure to a finish having a gloss value of at least 80 as measured by a 60 degree gloss meter. After a number of releases, such as, for example at least five releases, this gloss value remains nearly the same. In addition, the finish remains sufficiently durable after the at least five releases such that the mold release composition has not transferred to the part. [0065] Thus, the invention provides a method of imparting mark-resistant properties to a surface. The steps of this method include: applying a film coating of the inventive composition to a surface to inhibit markings thereon; and exposing the film coating to conditions appropriate to cure the composition. [0066] The invention also provides a method of imparting particulate repellent properties to a surface. The steps of this method include: applying a film coating of the inventive composition to a surface to inhibit particulate buildup thereon; and exposing the film coating to conditions appropriate to cure the composition. [0067] Of course, a mark-resistant film comprising the reaction product of the inventive composition and a particulate buildup film wherein the composition comprising the reaction product of the inventive composition, respectively, are also provided by the invention. [0068] And the invention provides a method of enhancing the gloss value of a part molded in a mold coated with a cured mold release composition to at least 80. The steps of this method include: applying a film coating of a mold release composition to a surface in a mold; and exposing the film coating to conditions appropriate to cure the composition. [0069] End user market opportunities for the inventive compositions include beyond mold release agents, infrastructure (such as application on the surfaces of road signs, school busses, mailboxes, bridges, and tunnels); automotive aftermarket type market applications (such as wheels and wheel wells, front fascia and trims, windshield and side windows and under carriage); construction (such as inside the dwelling like bathrooms, lockers and windows, and the exterior of the dwelling to maintain the appearance of the dwelling); engine compartment; maintenance, repair and operations ("MRO") type market applications (such as paint booths and selective masking); vehicular assembly (such as for all exposed components in the engine compartment for overall cleanliness exciter/toner/ABS rings, sensors, and radiators for cleanliness and heat management and related equipment (such as busses (like school or commuter), trains/subways cars, trucks and trailers, and boats); mold release agents for use with polyesters and epoxy parts and other composites; and additive for paint formulations. [0070] Additional end user automotive after market opportunities include wipe versions, such as for coating wheel rims to protect them from brake dust or for coating the windshield. EXAMPLES Example 1 [0071] This example describes a formulation of components used to make a composition of the present invention. Table 1 depicts the weight percent of each of the following components in the composition: tris cyclo silazane; hydroxy terminated polydimethylsiloxane; and as a solvent, a mixture of aromatic and aliphatic hydrocarbons containing 8 to 12 carbon atoms. [0072] The components were mixed well in the hydrocarbon solvent under nitrogen conditions to prevent the introduction of moisture into the composition. The resulting composition (Sample No. 1) was applied to a surface by either wiping or spraying to form a film coating. The coating was exposed to atmoshereic moisture at ambient temperature for about 5 to 20 minutes to effect curing. [0073] FTIR spectra of both the cured and uncured compositions are depicted in Figs, 1a and 1b respectively. The peak of about 950 cm"1 in Fig. lb shows the presence of a silazane functional group. The FTIR of the cured film (Fig. la peaks at about 800 cm-1, 1020 cm-1, 1100 cm-1, and 1260 cm-1) indicates that all silazane functional groups are consumed. The nature of the cured coating is a crosslinked polysiloxane. [0074] A BYK Gardner 60 degree micro-gloss meter was used to measure part gloss. A clean substrate constructed from polyester gel coat surface has an average gloss value of 91.8. Sample No. 1 demonstrated a glossy finish on the coated surface with an average gloss value of 85.0, which is only a reduction in gloss value of 6.8 units or 7.4%. [0075] Tests referred to as scrape and tape were designed to evaluate graffiti cleanability by mechanical removal. [0076] The scrape and tape tests were conducted by coating a smooth surface with an inventive composition. The two surfaces used in our tests were gray or orange gel coat boards and Imron painted steel panels. One coat of each composition was spray or wiped applied to the smooth surface and allowed to cure. Spray paint was applied over the coating and allowed to dry for more than 12 hours. [0077] In the scrape test, a wooden applicator was used to scrape the painted surfaces and evaluation of graffiti removal was defined by visual inspection. [0078] In the tape test, a scotch brand tape was used on the painted surface. Cleanabilities of both methods were rated on a scale of 1-6. On this scale 1= 0% paint cleaned, 2= ≤5% cleaned, 3= 6-49% cleaned, 4 = 50-94% cleaned, 5= ≥95% cleaned and 6= 100% cleaned. [0079] The anti-graffiti rating was measured to be 5, irrespective of which test was used. Example 2 [0080] This example describes another formulation of components used to make a composition of the present invention. Table 2 depicts the weight percent of each of the following components in the composition: a ladder structure silazane; an amino functional silane; hydroxy terminated polydimethylsiloxane; and a mixture of aromatic hydrocarbons containing 8 and 12 carbon atoms. [0081] The components were mixed well in the solvent under nitrogen conditions to prevent the introduction of moisture into the composition. The resulting composition (Sample No. 2) describes another formulation of components used to make a composition of the present invention. The composition is applied to a surface by either wiping or spraying to form a film coating. The coating is exposed to moisture at ambient temperature for about 5 to 20 minutes to effect curing. [0082] FTIR spectra of both the uncured and cured composition are depicted in Figs. 2a and 2b, respectively. The FTIR spectrum of the uncured composition in film form (Fig. 2a) provides information regarding the presence of the Si-N amino functional group (at about 1109 cm"1) and multiple silazane groups at about 810 and 840 cm"1. Fig. 2b provides information on the presence of polysiloxane. [0083] Sample No. 2 demonstrated a glossy finish. And depending on the particular functional PDMS and solvent selected one can vary the surface gloss retention observed. For example, PDMSs with lower amu lead to higher gloss retention on the surface. The average gloss value for the parts coated with the moisture cured inventive composition was 82.3 and 86.0, which is only a reduction in average gloss value of 9.5 and 5.8 units, respectively, or 10.3% and 6.3%, respectively. [0084] The anti-graffiti rating was measured to be 5, irrespective of which test was used. One can achieve a greater anti-graffiti rating by using PDMSs with higher amu or a blend of PDMSs with different amu. Example 3 Synthesis: A. 1,2,3,4,5,6-hexamethyl-2,4,6-tris(methylamino)- cyclotrisilazane ("tris cyclosilazane"): [0085] Methyl trichloro silane was reacted with methyl amine in a mixed hydrocarbon solvent under nitrogen environment in a pressured reactor. First 0.81 moles of the methyl trichloro silane was blended with 920 ml of a mixture of aromatic solvent in the reactor. Then 4.5 moles of methylamine was added to the batch slowly. The reaction temperature was increased during the amine addition. The addition of amine was completed over a 12 hour period. Slowly the excess amine was purged with dry nitrogen. Next water was added to the reaction, and the resulting suspension stirred overnight. The suspension was filtered under nitrogen, and the solution was collected as the product (in solution) without further purification. This silazane solution was used in Sample No. 3. The concentration of the final product ranged from 8-10% (w/w), as measured in percentage of product fully hydrolyzed with water. B. Tris(methylamino) methyl silane: [0086] Methyl trichloro silane was reacted with methyl amine in a mixed hydrocarbon solvent under nitrogen environment in a pressured reactor. First 0.4 4 moles of the methyl trichlorosilane was blended with 1000 ml of solvent. Then the mixture was cooled to a temperature below 15°C. Methylamine (2.90 moles) was added to the batch, and the reaction temperature controlled at below 20°C until the reaction was completed, which was indicated by a pressure increase inside of the reactor. The suspension which resulted was filtered under nitrogen, and the solution was collected as the product (in solution) without further purification. This silane solution was used in Sample No. 6. The concentration of the final product ranged from 4-6% (w/w) , as measured in percentage of product fully hydrolyzed with water. Formulation: [0087] Sample Nos. 3-10 were formulated using the ranges of the various components identified in Table 3a, and with those components in the amounts specified in Tables 3b and 3c. [0088] The formulations were prepared by combining with mixing the various components in each sample. Example 4 [0089] In Example 4, test method ASTM D 6578-00, was used to evaluate performance of the compositions. In this method, cleanability of graffiti placed on cured coatings of the inventive compositions was evaluated. Here, graffiti resistance was measured based on how a defined set of markings was removed by a defined set of cleaning agents. [0090] As a comparison, the competitive product, TK 1495, available commercially from Sierra, was used. TK 14 95 is reported by the manufacturer to contain among other things a homopolymer of hydroxyl diisocyanate and hexamethylene diisocyanate in solvent. [0091] A general description of the methods follow. The following materials were used for testing: aluminum panels, cellulose sponge, cotton cloth, solvent-based ink markers (such as Sharpie or Marks-A-Lots brand), solvent- based spray paint (such as Krylon brand), mild detergent, citrus-based cleaner, isopropyl alcohol ("IPA") and methyl ethyl ketone ("MEK"). One coat of each sample was applied to aluminum Q-panels, and allowed to cure for 10-20 minutes at room temperature (approximately 72°F) , the precise time depending on humidity conditions. The graffiti marking materials were applied to the coated panels and allowed to dry for more than 12 hours at room temperature. [0092] One panel was used for each level of cleanability testing. Each panel was rubbed with a cotton cloth wrapped cellulose sponge wetted with the defined cleaning agent for 25 back and forth cycles. Evaluation of graffiti removal was done by visual inspection. If the graffiti material was completely removed after 25 cycles, testing was determined to be complete and the coating was rated based on the cleaning agent used. [0093] The cleanability level ratings are as follows: 1= marking completely removed using a clean dry cotton cloth. 2= cleaned with a 1% aqueous solution of mild detergent. 3= cleaned with citrus cleaner (D-limonene from Florida Chemical Co). 4= cleaned with IPA. 5= cleaned with MEK. Not cleanable= MEK did not completely remove the graffiti material from the coated panel. The cleanability data of each of Samples 3-8 was observed to be 3. [0094] This method thus did not distinguish the anti- graffiti properties between the samples above and TK 14 95 though significant anti-graffiti performance differences were observed as noted in the preceding paragraph. [0095] In addition, the samples did not allow the graffiti marking materials to uniformly wet out a Q-panel when first applied; the ASTM designates this as "repellent". In contrast, TK 14 95 caused the graffiti materials to wet out over the panel when first applied; therefore, it is not considered to act as a graffiti repellent. Thus, the methods described above in Example 1 were used. Example 5 [0097] In this example, a composition (Sample No. 7) was packaged in aerosol cans, using propane as a propellant. [0098] The composition was applied in aerosol form to substrates constructed from brick, glass, plastic and various metals for surface appearance observation. Acceptable surface finish on most of these materials was observed. More specifically, the aerosol appearance is listed below in Table 5 as compared with the bulk spray and wiping methods of application. [0099] Ten coats of Sample No. 7 were aerosol spray applied to aluminum Q-panels, allowed to dry 10 minutes after each coat and given a 10-minute final cure. Coating thickness was measured as an average of 32 readings and divided by the number of coatings that had been applied to the Q-panels. Thickness readings were taken using an Elcometer 355 digital coating thickness meter, and are recorded in Table 6. *The average thickness for each entry an average was taken as an average of 4 readings collected from 4 locations of the coated panel, namely the upper part, middle part, lower part, and every corner of the panel, and the overall thickness was calculated to be 0.061, based on the ten coats which were applied Example 6 [00100] In this example, Sample Nos. 3, 6-10 and 11-16 were evaluated as mold release compositions. Apart from Sample No. 12, these samples each demonstrated a gloss value retention on molded parts of at least 80. [00101] More specifically, for instance Sample No. 6 demonstrated a gloss value retention of 86.3 on the molded part. And, Sample No. 3 demonstrated a gloss value retention of 85.0 on the molded part; Sample Nos. 8 and 14 demonstrated a gloss value retention of 91.1 and 87.0, respectively, on the molded part; Sample Nos. 7, 13, 15 and 16 demonstrated a gloss value retention of 85.9, 90.7, 83.2 and 83.0, respectively, on the molded part. The releasability measurements on the molded part were conducted by pouring each sample as a freestanding puddle of about three inches in diameter and allowed to cure over a twelve hour period prior to testing for release properties. Releasability was measured by way of a qualitative scale (1- 6) in which 1= did not release, 2= part broke when forcibly released, 3= flexing of board or heavy pressure required for release, 4= moderate pressure required for release, 5= little pressure required for release, and 6= part fell off board (as a pre-release). Sample Nos. 3 demonstrated a release value of 3; Sample Nos. 8 and 14 demonstrated a release value of 5 and 4, respectively; Sample Nos. 7, 13, 15 and 16 each demonstrated a release value of 5. We Claim : 1. A curable composition, reaction products of which are substantially transparent comprising: a functionalized siloxane such as herin described; and a crosslinker comprising at least one of an amino functional silane, an enoxy functional silane, a silazane, and combinations thereof; wherein when cured under atmospheric conditions in less than 30 minutes reaction products are substantially transparent and markings made on a surface coated with said composition are readily removable. 2. The composition as claimed in Claim 1, wherein said crosslinker is present in amounts of about 0.1% to about 50% by weight of said composition. 3. The composition as claimed in Claim 1, wherein said composition has a viscosity of less than 2000 cps as applied to a surface. 4. The composition as claimed in Claim 1, wherein said functionalized siloxane is a hydroxy terminated poly siloxane. 5. The composition as claimed in Claim 1, wherein said crosslinker is tris cycle silazane. 6. The composition as claimed in Claim 1, wherein said crosslinker is a ladder structure silazane. 7. The composition as claimed in Claim 1, further comprising a carrier selected from the group consisting of an aliphatic hydrocarbon containing 8 to 12 carbon atoms, an aromatic hydrocarbon containing 8 to 12 carbon atoms, a siloxane containing 2 to 6 silicone atoms, a cyclic siloxane containing 3 to 5 silicone atoms, water, and mixtures thereof. 8. The composition as claimed in Claim 1, wherein said functionalized siloxane is present in amounts of about 0.01% to about 50% by weight of said composition. 9. The composition as claimed in Claim 1, further comprising a resin selected from the group consisting of an alkoxy silane prepolymer resin, an alkoxy functional prepolymer resin, and combinations thereof, for improving aesthetic effects of said anti- graffiti composition as applied to a surface. 10. The composition as claimed in Claim 1, further comprising a moisture cure catalyst. 11. The composition as claimed in Claim 1, further comprising a photoinitiator. 12. A mark-resistant film comprising the moisture cure reaction product of a composition comprising a functionalized siloxane and at least one agent selected from the group consisting of an amino functional silane, an enoxy functional silane, a silazane and combinations thereof. 13. A film having improved resistance to particulate buildup, comprising the moisture cure reaction product of a composition comprising a functionalized siloxane and at least one agent selected from the group consisting of an amino functional silane, an enoxy functional silane, a silazane and combinations thereof. 14. A method of imparting mark-resistant properties to a surface, comprising the steps of: applying a film coating of a composition to a surface to inhibit markings thereon; and exposing the film coating to conditions appropriate to cure the composition, wherein the composition comprises a functionalized siloxane, at least one crosslinking agent selected from the group consisting of an amino functional silane, an enoxy functional silane, a silazane, and combinations thereof. 15. The method of Claim 14, wherein the conditions appropriate to cure the composition are exposure to moisture at ambient temperature. 16. A method of imparting particulate repellent properties to a surface, comprising the steps of: applying a film coating of a composition to a surface to inhibit particulate buildup thereon; and exposing the film coating to conditions appropriate to cure the composition, wherein the composition comprises a functionalized siloxane, at least one crosslinking agent selected from the group consisting of an amino functional silane, an enoxy functional silane, a silazane, and combinations thereof. 17. The method of Claim 16, wherein the conditions appropriate to cure the composition are exposure to moisture at ambient temperature. 18. A method of enhancing the gloss value of a part molded in a mold coated with a cured mold release composition to at least 80, comprising the steps of: applying a film coating of a mold release composition to a surface in a mold; and exposing the film coating to conditions appropriate to cure the composition, wherein the composition comprises a functionalized siloxane, at least one crosslinking agent selected from the group consisting of an amino functional silane, an enoxy functional silane, a silazane, and combinations thereof. 19. The method of Claim 18, wherein the conditions appropriate to cure the composition are exposure to moisture at ambient temperature. 20. A method of enhancing release of a molded part from a mold coated with a cured mold release composition, comprising the steps of: applying a film coating of a mold release composition to a surface in a mold; and exposing the film coating to conditions appropriate to cure the composition, the composition comprising a functionalized siloxane; and at least one crosslinking agent selected from the group consisting of a multi-functional silane, an amino functional silane, an enoxy functional silane, a silazane, and combinations thereof; wherein when cured the mold release composition allows a part molded in the mold in which the mold release composition is applied to retain a gloss value of at least 80. The present invention relates to curable coating compositions which when cured are substantially transparent and exhibit resistance to markings such as graffiti and scuffing and particulate buildup. In particular, the compositions of the present invenlion when cured provide proteclive coatings to surfaces to prevent absorption and/or wetting of ink compositions. The invention composition may also be used as mold release agents.

Full Text

CURABLE COATING COMPOSITIONS
BACKGROUND OF THE INVENTION
Field Of The Invention
[0001] The present invention relates to curable coating
compositions which when cured are substantially transparent
and exhibit resistance to markings such as graffiti and
scuffing and particulate buildup. In particular, the
compositions of the present invention when cured provide
protective coatings to surfaces to prevent absorption
and/or wetting of ink compositions. The invention
composition may also be used as mold release agents.
Brief Description Of Related Technology
[0002] Graffiti is understood to mean any unwanted
markings on a surface, such as a building structure.
Typically, it refers to unwanted paintings, words, and

drawings. Such markings usually are applied by paints,
such as spray paint, magic markers, or other inks. Paints
are the most common source of graffiti, especially oil-
based paints, such as enamels, epoxies, lacquers, and
urethanes. Unwanted markings, however, may be produced by
a variety of other sources, such as grease, crayons, and
lipstick, among others.
[0003] Graffiti continues to be a problem of significant
concern in today's society. Rather than a form of art,
graffiti is considered vandalism and is an irritating
eyesore in both public and private places. Graffiti
decreases the value of private properties and drives
customers away from businesses. It often defaces public
buildings and institutions, such as schools, trains and
buses, as well as their stations, public restrooms, park
structures, bridges, and tunnels, among many others.
[0004] A number of conventional cleaning techniques have
been utilized to deal with the graffiti problem. These
techniques typically involve cleaning the surface after it
has been defaced by graffiti. Such cleaning techniques
include sandblasting, sanding, high pressure power washing,
and chemical treatments, among other similar procedures.
Examples of cleaning compositions developed for removing
graffiti are disclosed in U.S. Patent No. 5,024,780 (Leys).
[0005] These cleaning methods, however, are costly and
time-consuming. The cleaned or treated surface often is
deteriorated by the harsh cleansing or chemicals. As a
result, the surface has to be restored and repainted at
high costs. Moreover, chemical treatment procedures often
involve harsh, environmentally harmful chemicals, which
pose dangers to human contact.

SUMMARY OF THE INVENTION
[0009] The inventive compositions are curable
compositions, which when cured impart mark resistant
properties to a surface, and which make graffiti removal
much easier than known coatings which share substantial
transparency.
[0010] The inventive compositions also reduce the
tendency of particulate buildup on surfaces coated
therewith.
[0011] In one aspect of the invention, the inventive
compositions are curable (such as by exposure to moisture)
and include a functionalized siloxane (such as a hydroxy
terminated one); at least one agent selected from a multi-
functional silane, an amino functional silane, an enoxy
functional silane, a silazane, and combinations thereof;
and optionally, a carrier. Upon moisture cure at ambient
temperature graffiti markings made on a surface coated with
such a composition are readily removable.
[0012] Another aspect of the present invention is
directed to a method for imparting mark-resistant
properties to a surface once cured. The method includes
the steps of applying a film coating of an inventive
composition to a surface to inhibit graffiti markings or
other scuff markings thereon, and exposing the film coating
to moisture at ambient temperature to cure the composition.
[0013] Further aspect of the present invention is
directed to a method for imparting particulate buildup-
resistant properties to a surface. The method includes the
steps of applying a film coating of an inventive
composition to a surface to inhibit the buildup of
particulate matter thereon once cured, and exposing the

film coating to moisture at ambient temperature to cure the
composition.
[0014] Further aspect of the present invention is
directed to a method for using the inventive composition as
a mold release agent. The method includes the steps of
applying a film coating of an inventive composition to a
surface of a mold and exposing the film coating to moisture
at ambient temperature to cure the composition.
[0015] A still further aspect of the present invention
is directed to a method for preparing the inventive
composition. This method includes the step of combining
with mixing a functionalized siloxane with a crosslinker,
optionally in a carrier, thereby forming the inventive
composition.
[0016] The inventive compositions confer one or more of
the following benefits and advantages when cured beyond
mark resistance and particulate buildup resistance, high
gloss retention and clear or invisible on the substrate
surface (that is, substantial transparency when cured).
The inventive compositions are also appropriate for use on
most smooth surfaces, fast curing at room temperature ( minutes), semi-permanent, UV and weather stable, one-
component (no mixing required by the end user) and low
surface tension [thus appropriate for use with a wide
variety of substrates (even polyolefins, to which are
ordinarily difficult to apply a coating)].
BRIEF DESCRIPTION OF THE ACCOMPANING/DRAWINGS
[0017] Fig. la is an FTIR spectrum of a cured film
coating composition of the present invention.

[0018] Fig. 1b is an FTIR spectrum of the coating
composition of Fig. la prior to curing.
[0019] Fig. 2a is an FTIR spectrum of an uncured film
coating composition of the present invention.
[0020] Fig. 2b is an FTIR spectrum of the film coating
of Fig. 2a after curing.
DETAILED DESCRIPTION OF THE INVENTION
[0021] The present invention is directed to curable
compositions, which upon cure are substantially transparent
and are resistant to markings, such as graffiti and
scuffing, and repel the collection of dust and dirt thereby
preventing buildup thereof on surfaces of substrates to
which has been applied the curable compositions. Graffiti
or scuff markings made on surfaces coated with these
compositions are removable by wiping or with other similar
conventional means.
[0022] The compositions cure by exposure to moisture at
ambient temperature to form a film coating, imparting mark
resistant and/or particulate buildup resistant properties
to surfaces. The compositions are also useful as a mold
release agent.
[0023] The term "cure" or "curing," as used herein,
refers to a change in state, condition, and/or structure in
a material that is usually, but not necessarily, induced by
at least one variable, such as time, temperature, moisture,
radiation, presence and quantity in such material of a
curing catalyst or accelerator, or the like. The terms
cover partial as well as complete curing. The mechanisms
by which compositions of this invention may cure include,
in the context of silicone chemistry, addition cure (such

as by way of hydrosilation reactions), condensation cure
(in which crosslinking of silanol, silazane, enoxy, alkoxy,
acetoxy, and the like groups occur), ring opening cure, UV
cure (such as by way of silylene reactions), and of course
combinations thereof.
[0024] The inventive compositions include broadly a
functionalized siloxane and a crosslinker, together with
one or more of the following optional components catalyst,
carrier, filler, plasticizer, color indicator, and
surfactant.
[0025] Whether the cure mechanism is by way of a
condensation cure, addition cure or UV cure, the base
polymer may be a branched or linear siloxane and/or
functionalized siloxane within following structure:

where the number of repeating units, "n", plays a role in
determining the molecular weight and the viscosity of the
composition. R1, R2, R3, R4, R5, and R6 may be the same or
different and may be siloxane, alkyl, allyl, aryl, alkoxy,
amino, hydroxyl, hydrogen, mercapto, halo, and cyano, and n
is from 0 to about 100,000. P1 and P2 may be the same or
different and may be alkyl, allyl, hydroxyl, hydrogen,
amino, acetoxy, alkoxy, enoxy, and oxime. Interruption of
the polymer chain by a heteroatom is also within the scope
of the present invention.

[0026] The crosslinker for condensation cure reactions
include functionalized silanes, such as
cyclic/linear/branched silicone oligomers that have at
least two reactive functionalities. The reactive
functionality include silazane, silanol, alkoxy, acetoxy,
amino, oximino, amido, and enoxy groups or combinations
thereof. For addition cure reactions, the functionality
includes allyl, alkyl, hydride groups or combinations
thereof. For UV cure reactions, the functionality include
allyl, alkyl, mercapto, and (meth)acryloxy groups or
combinations thereof.
[0027] The compositions of the present invention may
also include a catalyst for accelerating or otherwise
promoting the cure process, such as with condensation
reactions. In such case, the catalyst may be chosen from
an organic tin, titanium compound, and strong Lewis bases.
Generally, the catalyst is present from about 0% to about
0.5% (w/w). This concentration, however, can be varied
depending upon the particular components chosen, the
desired cure mechanism and the desired cure rate.
[0028] Carriers for the composition may be included, if
desired. In such case, the carrier may be chosen from
organic solvents (such as aliphatic hydrocarbons containing
8 to 12 carbon atoms and aromatic hydrocarbons containing 8
to 12 carbon atoms), low molecular weight siloxanes (such
as siloxanes containing 2 to 6 silicone atoms and cyclic
siloxanes containing 3 to 5 silicone atoms), water, aerosol
propellants (whether chlorinated fluorocarbons or not, such
as propane), and supercritical CO2 fluid. In addition, low
VOC solvents may be used to prepare the inventive
compositions; low VOC formulations have volatile organic solvents. Carriers may be present in the
inventive compositions, for example, in an amount from
about 10% to about 90% (w/w). Desirably, carriers are
present in an amount from about 60% to about 85%(w/w).
[0029] Fillers may be included, such as for the purpose
of enhancing the durability of the coating. Suitable
fillers include silicas, such as treated silicas, clays, MQ
resins (as are known in the art), and titanium oxide.
[0030] Plasticizers may also be included to impart a
degree of modulus, if desired. Suitable plasticizers
include inert oligomeric or polymeric compounds, desirably
such compounds are compatible with the cross-linkable base
polymers mentioned above. Preferably these plasticizers
are less compatible with the crosslinked base polymers;
thus, a portion of the plasticizer may be capable of
migrating to the surface of the cured coating. These
plasticizers include for instance polydialkylsiloxanes,
branched polydialkylsiloxanes, polyfluorinated
dialkylsiloxanes, and organofunctional polyalkylsiloxanes.
[0031] A color indicator such as pigments, dyes, and
trace UV dyes may be added where a color is desirable for
the composition.
[0032] A surfactant may also be desirable where surface
wetting and film formation characters should be modified.
Surfactants may be chosen from ionic and non-ionic ones,
depending of course on the particular set of physical
properties sought in the specific application.
[0033] A charge dispenser may be useful in some cases to
eliminate static charger on a treated surface so less
particle matter, such as dust or undesired objects, is
attracted to the surface.

[0034] For addition cure reactive compositions (sucn as
moisture curable compositions), the above optional
components may be included, though the catalyst will be
organic compounds of platinum, titanium, tin, zirconium and
of course combinations thereof. Tetraisopropoxytitanate
and tetrabutoxytitanate are particularly desirable. See
also U.S. Patent No. 4,111,890, the disclosure of which is
expressly incorporated herein by reference. Examples of
such organic platinum catalysts include platinum divinyl
complex (available commercially from UCT, Pennsylvania and
Gelest, Pennsylvania).
[0035] For UV cure reactive compositions, the above
optional components may include, though the catalyst will
be an UV initiator. Examples of such UV initiators include
photoinitiators available commercially from Ciba Specialty
Chemiclas under the "IRGACURE" and "DAROCUR" tradenames,
specifically "IRGACURE" 184 (1-hydroxycyclohexyl phenyl
ketone), 907 (2-methyl-l-[4-(methylthio)phenyl]-2-
morpholino propan-1-one), 369 (2-benzyl-2-N,N-
dimethylamino-1-(4-morpholinophenyl)-1-butanone), 500 (the
combination of 1-hydroxy cyclohexyl phenyl ketone and
benzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone),
1700 (the combination of bis(2,6-dimethoxybenzoyl-2,4,4-
trimethyl pentyl) phosphine oxide and 2-hydroxy-2-methyl-l-
phenyl~propan-l-one), and 819 [bis(2,4,6-trimethyl benzoyl)
phenyl phosphine oxide] and "DAROCUR" 1173 (2-hydroxy-2-
methyl-1-phenyl-l-propane) and 4265 (the combination of
2,4,6-trimethylbenzoyldiphenyl-phosphine oxide and 2-
hydroxy-2-methyl-1-phenyl-propan-l-one); and the visible
light [blue] photoinitiators, dl-camphorquinone and

"IRGACURE" 784DC. Of course, combinations of these
materials may also be employed herein.
[0036] For ring opening cure reactive compositions, the
above optional components may be included, though the
catalyst will be an acid or a base. Examples of such acid
or base catalysts include sulfuric acid and potassium
hydroxide, respectively.
[0037] The base curable polymer may be formed through a
ring opening reaction with chemicals such as
silacyclopropane [R1R2Si (CH2CH2) ] or silacyclobutane
R1R2Si (CH2CH2CH2), where R1 and R2 can be the same or
different and may be selected from H, and alkyl and allyl
groups.
[0038] The reactive functionality on the crosslinker for
ring opening cure include halide (such as chloride), alkoxy
(such as methoxy), cyano, silanol or combinations thereof.
[0039] Particularly desirable functionalized siloxanes
for the base curable component include any conventional
hydroxy terminated siloxane, or polysiloxane, which is
capable of forming film coating upon combination with an
appropriate crosslinker. Such hydroxy terminated
polysiloxanes are represented by the following general
formula:
where R1, R2, R3, R4, R5, and R6 may be the same or different
and may desirably be C1-6 alkyl and n is from 1 to about
30,000 amu. Interruption of the polymer chain by a hetero

atom other than oxygen is also within the scope of the
present invention.
[0040] An example of a specific hydroxy terminated
polysiloxane that may be used to form structure I is
hydroxy terminated polydimethylsiloxane ("PDMS"), as
represented by structural formula II:

[0041] The number of repeating units, "n", plays a role
in determining the molecular weight and the viscosity of
the composition. Thus, n is an integer from about 1 to
about 30,000 amu. Desirably, PDMSs incorporated into the
compositions of the present invention have a molecular
weight of 4,000 amu or greater. The molecular weight of
PDMS, however, may vary depending upon the desired
thickness and/or viscosity of the film coating as applied
to a surface. Viscosities of the compositions of the
present invention generally are typically less than 2000
cps, and desirably are less than 500 cps.
[0042] Functionalized siloxanes, such as PDMSs, may be
present in the inventive compositions, for example, in an
amount from about 0.001% to about 50% by weight in the
final composition (w/w). Desirably, PDMSs are present in
an amount from about 0.01% to about 3% (w/w).
[0043] The compositions of the present invention also
include as noted above a crosslinker to produce
crosslinking with the polysiloxane and/or with itself, as
well as compositions that interact with a surface material.

Crosslinking is the attachment of two or more chains of
polymers by, for example, bridges and cross bridges,
comprising either an element, a group, or a compound. The
crosslinking agent functions as a chemical group that can
chemically interact with the functional siloxane as well as
the residue functional group on a surface. The interaction
of the crosslinking group promotes the chemical bonding of
the anti-graffiti coating to the surface so that the
coating can last longer in a given environment. The
crosslinking reactions will initiate as soon as the
inventive composition is exposed to moisture. Certain
crosslinking agents unexpectedly have been found to provide
curing properties, which in combination with hydroxy
terminated polysiloxanes produce compositions having when
cured in less than 30 minutes under ambient conditions
anti-graffiti or anti-scuffing and/or anti-particulate
buildup properties, while retaining substantial
transparency yielding high gloss.
[0044] Suitable crosslinkers, which when combined with
the siloxane have been found to produce mark resistant
and/or particulate buildup resistant coatings that are
substantially transparent when cured, include certain
multi-functional silanes, such as amino functional silanes,
hydride functional silanes and enoxy functional silanes,
silazanes, and combinations thereof. Upon mixing with
appropriate polysiloxanes, these agents provide curing
properties and produce compositions that inhibit markings
and particulate buildup, as well as provide substantial
transparency yielding excellent gloss retention.
[0045] Organofunctional silanes, within the class of
silicon hydride compounds are known for their ability to

assist in the bonding of organic polymers to inorganic
substrate materials. The compositions of the present
invention may include amino and/or enoxy functional
silanes. An example of an amino functional silane that may
be used in accordance with the present invention is
represented by structural formula III:

[0046] Other suitable amino functional silanes include
di- or tri-amino functional silanes, such as CH3Si(NHCH3)3.
[0047] An example of an enoxy functional silane that may
be employed in the compositions of the present invention is
represented by structural formula IV:

[0048] The incorporation of amino and/or enoxy
functional silanes in the compositions of the present
invention have been found to provide excellent anti-
graffiti, anti-scuffing and anti-particulate buildup
properties, when combined with hydroxy terminated
polysiloxanes. Certain other functional silanes,
particularly ethoxy functional silanes and epoxy functional
silanes, do not exhibit as useful anti-graffiti and/or
release properties when used alone in the compositions of
the present invention. Ethoxy and epoxy functional
silanes, however, may be useful when combined into other

structures, for example, as a functional group in a ladder
structure silazane.
[0049] Desirable silazanes for incorporation in the
compositions of the present invention include cyclic
silazanes and ladder structure silazanes. Silazane
compounds contain alternating silicon and nitrogen atoms.
Cyclic silazanes contain one or more closed rings. An
example of a cyclic silazane is represented by the
following general formula V:

[0050] One particularly desirable cyclic silazane is
tris cyclo silazane, represented by structural formula VI:

[0051] Also desirable as silazanes in accordance with
the present invention are ladder structure silazanes.
Ladder structure silazanes contain linear chains that
crosslink in ladder-like formations. Structural formula
VII represents a ladder structure silazane suitable for use
in the compositions of the present invention. Other
similar ladder structure silazanes, however, also may be
suitable for use in these compositions. Formula VII is
represented by:

where each R is independently methyl or ethyl, y ranges
from about 20% to about 80% of the compound, z ranges from
about 0% to about 40% of the compound, and n is from 1 to
about 500.
[0052] The ladder structure silazane of formula VII is
derived from a linear chain silazane compound, which is
represented by structural formula VIII:

where each R is independently methyl or ethyl, x ranges
from about 20% to about 50% of the compound, y ranges from
about 20% to about 80% of the compound, and z ranges from
about 0% to about 40% of the compound.
[0053] Upon addition of ammonia, the ladder-type
structure of formula VII is formed. In particular,
ammonium chloride is generated as a by-product of the
reaction, which causes in situ formation of the ladder
structure. The "x" portion of the structure of formula
VIII crosslinks, while the "y" and "z" portions remain in

linear chains. Due to their in situ formation, a ladder
structure silazane used in the compositions of the present
invention is a mixture of the compounds of formula VII and
VIII.
[0054] Desirable crosslinkers may be present in the
inventive compositions, for example, in an amount from
about 0.1% to about 50% (w/w). Desirably, crosslinking
agents are present in an amount from about 1% to about 15%
(w/w).
[0055] Any conventional catalyst may be employed
provided the desired properties of the inventive
compositions are not compromised. Suitable catalysts that
may be used include conventional organometallic catalysts,
such as organic titanium derivatives, organic tin.
[0056] A particularly desirable inventive composition
combining these components includes: about 0.01% to about
5% of tris cyclo silazane; about 0.005% to about 1% of
hydroxy terminated polysiloxane; and the balance, up to
about 99%, of a carrier, is a solvent.
[0057] Another desirable inventive composition includes:
about 0.5% to about 5% of a ladder structure silazane;
about 5% to about 30% of an amino functional silane; about
0.01% to about 5% of a hydroxy terminated polysiloxane; and
the balance being a carrier, which includes a solvent.
Other desirable compositions are set forth in Table 3.
[0058] Upon application to a surface, the inventive
compositions moisture cure (desirably in less than 30
minutes at ambient temperature) to form film coatings,
which are resistant to markings, such as graffiti or
scuffing, as well as particulate buildup, and are

substantially transparent and retain their gloss. The
application of heat is not necessary to effect curing.
[0059] These film coatings desirably have a thickness of
less than 2.5 microns as applied to a surface. To enhance
the aesthetic effects of the compositions as applied to a
surface, the compositions may further include an alkoxy
silane prepolymer resin and/or an alkoxy functional
prepolymer resin, also referred to as an MQ resin (as such
resins are known in the art). Such resins improve the ease
of application and/or the surface finish of the film
coatings, providing a glossy appearance. The glossier
finish may be desirable for a variety of applications, such
as for coating the side panels of buses and trains.
Generally, concentrations of from about 0% to about 5%
(w/w) are sufficient.
[0060] The present invention also is directed to methods
of imparting to a surface mark-resistant and particulate
buildup-resistant properties. According to these methods,
a film coating of the inventive composition is applied to a
surface to inhibit graffiti markings or other scuff
markings thereon, or particulate buildup thereon.
[0061] The inventive composition may be applied by
wiping or spraying it onto the desired surface, or by any
other suitable means, to form a film coating on the
surface. A single coat usually will be sufficient,
however, additional coats may be applied, as desired. For
example, it may be desirable to apply several coats of the
inventive composition on rougher surfaces. If multiple
coats are applied, curing may desirably be permitted
between each application.

[0062] Other application methods for the inventive
compositions include spraying (such as by aerosol or pump
driven), wiping, brushing, dipping, and rolling.
[0063] After application to the surface, the inventive
composition in film form is exposed to moisture at ambient
temperature to cure the composition. Cure ordinarily
occurs in less than 30 minutes, and desirably does so.
Although heat could be applied, it is not necessary to
effect curing sometimes in as short as about 5 to about 20
minutes. The cure time, however, may be even shorter upon
addition of certain appropriate catalysts, as described
above. Once cured, any graffiti or other scuff markings
created on the surface are easily removable by wiping or
with other conventional means, and particulate buildup over
time is seen to be dramatically less.
[0064] The inventive compositions when used as mold
release agents desirably cure to a high durability finish
that permits a number of releases without contaminating a
released part by transfer of the release composition from
the mold to the part. In addition, in some embodiments,
the coating may desirably cure to a high gloss finish that
permits a number of releases without measurable loss of
initial gloss value. For example, the compositions of the
present invention may cure to a finish having a gloss value
of at least 80 as measured by a 60 degree gloss meter.
After a number of releases, such as, for example at least
five releases, this gloss value remains nearly the same.
In addition, the finish remains sufficiently durable after
the at least five releases such that the mold release
composition has not transferred to the part.

[0065] Thus, the invention provides a method of
imparting mark-resistant properties to a surface. The
steps of this method include: applying a film coating of
the inventive composition to a surface to inhibit markings
thereon; and exposing the film coating to conditions
appropriate to cure the composition.
[0066] The invention also provides a method of imparting
particulate repellent properties to a surface. The steps of
this method include: applying a film coating of the
inventive composition to a surface to inhibit particulate
buildup thereon; and exposing the film coating to
conditions appropriate to cure the composition.
[0067] Of course, a mark-resistant film comprising the
reaction product of the inventive composition and a
particulate buildup film wherein the composition comprising
the reaction product of the inventive composition,
respectively, are also provided by the invention.
[0068] And the invention provides a method of enhancing
the gloss value of a part molded in a mold coated with a
cured mold release composition to at least 80. The steps
of this method include: applying a film coating of a mold
release composition to a surface in a mold; and exposing
the film coating to conditions appropriate to cure the
composition.
[0069] End user market opportunities for the inventive
compositions include beyond mold release agents,
infrastructure (such as application on the surfaces of road
signs, school busses, mailboxes, bridges, and tunnels);
automotive aftermarket type market applications (such as
wheels and wheel wells, front fascia and trims, windshield
and side windows and under carriage); construction (such as

inside the dwelling like bathrooms, lockers and windows,
and the exterior of the dwelling to maintain the appearance
of the dwelling); engine compartment; maintenance, repair
and operations ("MRO") type market applications (such as
paint booths and selective masking); vehicular assembly
(such as for all exposed components in the engine
compartment for overall cleanliness exciter/toner/ABS
rings, sensors, and radiators for cleanliness and heat
management and related equipment (such as busses (like
school or commuter), trains/subways cars, trucks and
trailers, and boats); mold release agents for use with
polyesters and epoxy parts and other composites; and
additive for paint formulations.
[0070] Additional end user automotive after market
opportunities include wipe versions, such as for coating
wheel rims to protect them from brake dust or for coating
the windshield.
EXAMPLES
Example 1
[0071] This example describes a formulation of
components used to make a composition of the present
invention. Table 1 depicts the weight percent of each of
the following components in the composition: tris cyclo
silazane; hydroxy terminated polydimethylsiloxane; and as a
solvent, a mixture of aromatic and aliphatic hydrocarbons
containing 8 to 12 carbon atoms.

[0072] The components were mixed well in the hydrocarbon
solvent under nitrogen conditions to prevent the
introduction of moisture into the composition. The
resulting composition (Sample No. 1) was applied to a
surface by either wiping or spraying to form a film
coating. The coating was exposed to atmoshereic moisture
at ambient temperature for about 5 to 20 minutes to effect
curing.
[0073] FTIR spectra of both the cured and uncured
compositions are depicted in Figs, 1a and 1b respectively.
The peak of about 950 cm"1 in Fig. lb shows the presence of
a silazane functional group. The FTIR of the cured film
(Fig. la peaks at about 800 cm-1, 1020 cm-1, 1100 cm-1, and
1260 cm-1) indicates that all silazane functional groups are
consumed. The nature of the cured coating is a crosslinked
polysiloxane.
[0074] A BYK Gardner 60 degree micro-gloss meter was
used to measure part gloss. A clean substrate constructed
from polyester gel coat surface has an average gloss value
of 91.8. Sample No. 1 demonstrated a glossy finish on the
coated surface with an average gloss value of 85.0, which
is only a reduction in gloss value of 6.8 units or 7.4%.
[0075] Tests referred to as scrape and tape were
designed to evaluate graffiti cleanability by mechanical
removal.

[0076] The scrape and tape tests were conducted by
coating a smooth surface with an inventive composition.
The two surfaces used in our tests were gray or orange gel
coat boards and Imron painted steel panels. One coat of
each composition was spray or wiped applied to the smooth
surface and allowed to cure. Spray paint was applied over
the coating and allowed to dry for more than 12 hours.
[0077] In the scrape test, a wooden applicator was used
to scrape the painted surfaces and evaluation of graffiti
removal was defined by visual inspection.
[0078] In the tape test, a scotch brand tape was used on
the painted surface. Cleanabilities of both methods were
rated on a scale of 1-6. On this scale 1= 0% paint
cleaned, 2= ≤5% cleaned, 3= 6-49% cleaned, 4 = 50-94%
cleaned, 5= ≥95% cleaned and 6= 100% cleaned.
[0079] The anti-graffiti rating was measured to be 5,
irrespective of which test was used.
Example 2
[0080] This example describes another formulation of
components used to make a composition of the present
invention. Table 2 depicts the weight percent of each of
the following components in the composition: a ladder
structure silazane; an amino functional silane; hydroxy
terminated polydimethylsiloxane; and a mixture of aromatic
hydrocarbons containing 8 and 12 carbon atoms.

[0081] The components were mixed well in the solvent
under nitrogen conditions to prevent the introduction of
moisture into the composition. The resulting composition
(Sample No. 2) describes another formulation of components
used to make a composition of the present invention. The
composition is applied to a surface by either wiping or
spraying to form a film coating. The coating is exposed to
moisture at ambient temperature for about 5 to 20 minutes
to effect curing.
[0082] FTIR spectra of both the uncured and cured
composition are depicted in Figs. 2a and 2b, respectively.
The FTIR spectrum of the uncured composition in film form
(Fig. 2a) provides information regarding the presence of
the Si-N amino functional group (at about 1109 cm"1) and
multiple silazane groups at about 810 and 840 cm"1. Fig. 2b
provides information on the presence of polysiloxane.
[0083] Sample No. 2 demonstrated a glossy finish. And
depending on the particular functional PDMS and solvent
selected one can vary the surface gloss retention observed.
For example, PDMSs with lower amu lead to higher gloss
retention on the surface. The average gloss value for the
parts coated with the moisture cured inventive composition
was 82.3 and 86.0, which is only a reduction in average

gloss value of 9.5 and 5.8 units, respectively, or 10.3%
and 6.3%, respectively.
[0084] The anti-graffiti rating was measured to be 5,
irrespective of which test was used. One can achieve a
greater anti-graffiti rating by using PDMSs with higher amu
or a blend of PDMSs with different amu.
Example 3
Synthesis:
A. 1,2,3,4,5,6-hexamethyl-2,4,6-tris(methylamino)-
cyclotrisilazane ("tris cyclosilazane"):
[0085] Methyl trichloro silane was reacted with methyl
amine in a mixed hydrocarbon solvent under nitrogen
environment in a pressured reactor. First 0.81 moles of
the methyl trichloro silane was blended with 920 ml of a
mixture of aromatic solvent in the reactor. Then 4.5 moles
of methylamine was added to the batch slowly. The reaction
temperature was increased during the amine addition. The
addition of amine was completed over a 12 hour period.
Slowly the excess amine was purged with dry nitrogen. Next
water was added to the reaction, and the resulting
suspension stirred overnight. The suspension was filtered
under nitrogen, and the solution was collected as the
product (in solution) without further purification. This
silazane solution was used in Sample No. 3. The
concentration of the final product ranged from 8-10% (w/w),
as measured in percentage of product fully hydrolyzed with
water.
B. Tris(methylamino) methyl silane:

[0086] Methyl trichloro silane was reacted with methyl
amine in a mixed hydrocarbon solvent under nitrogen
environment in a pressured reactor. First 0.4 4 moles of
the methyl trichlorosilane was blended with 1000 ml of
solvent. Then the mixture was cooled to a temperature
below 15°C. Methylamine (2.90 moles) was added to the
batch, and the reaction temperature controlled at below
20°C until the reaction was completed, which was indicated
by a pressure increase inside of the reactor. The
suspension which resulted was filtered under nitrogen, and
the solution was collected as the product (in solution)
without further purification. This silane solution was
used in Sample No. 6. The concentration of the final
product ranged from 4-6% (w/w) , as measured in percentage
of product fully hydrolyzed with water.
Formulation:
[0087] Sample Nos. 3-10 were formulated using the ranges
of the various components identified in Table 3a, and with
those components in the amounts specified in Tables 3b and
3c.

[0088] The formulations were prepared by combining with
mixing the various components in each sample.
Example 4
[0089] In Example 4, test method ASTM D 6578-00, was
used to evaluate performance of the compositions. In this
method, cleanability of graffiti placed on cured coatings
of the inventive compositions was evaluated. Here,
graffiti resistance was measured based on how a defined set
of markings was removed by a defined set of cleaning
agents.
[0090] As a comparison, the competitive product, TK
1495, available commercially from Sierra, was used. TK
14 95 is reported by the manufacturer to contain among other
things a homopolymer of hydroxyl diisocyanate and
hexamethylene diisocyanate in solvent.
[0091] A general description of the methods follow. The
following materials were used for testing: aluminum
panels, cellulose sponge, cotton cloth, solvent-based ink
markers (such as Sharpie or Marks-A-Lots brand), solvent-
based spray paint (such as Krylon brand), mild detergent,
citrus-based cleaner, isopropyl alcohol ("IPA") and methyl
ethyl ketone ("MEK"). One coat of each sample was applied
to aluminum Q-panels, and allowed to cure for 10-20 minutes
at room temperature (approximately 72°F) , the precise time
depending on humidity conditions. The graffiti marking
materials were applied to the coated panels and allowed to
dry for more than 12 hours at room temperature.
[0092] One panel was used for each level of cleanability
testing. Each panel was rubbed with a cotton cloth wrapped

cellulose sponge wetted with the defined cleaning agent for
25 back and forth cycles. Evaluation of graffiti removal
was done by visual inspection. If the graffiti material
was completely removed after 25 cycles, testing was
determined to be complete and the coating was rated based
on the cleaning agent used.
[0093] The cleanability level ratings are as follows: 1=
marking completely removed using a clean dry cotton cloth.
2= cleaned with a 1% aqueous solution of mild detergent.
3= cleaned with citrus cleaner (D-limonene from Florida
Chemical Co). 4= cleaned with IPA. 5= cleaned with MEK.
Not cleanable= MEK did not completely remove the graffiti
material from the coated panel. The cleanability data of
each of Samples 3-8 was observed to be 3.
[0094] This method thus did not distinguish the anti-
graffiti properties between the samples above and TK 14 95
though significant anti-graffiti performance differences
were observed as noted in the preceding paragraph.
[0095] In addition, the samples did not allow the
graffiti marking materials to uniformly wet out a Q-panel
when first applied; the ASTM designates this as
"repellent". In contrast, TK 14 95 caused the graffiti
materials to wet out over the panel when first applied;
therefore, it is not considered to act as a graffiti
repellent. Thus, the methods described above in Example 1
were used.
Example 5
[0097] In this example, a composition (Sample No. 7) was
packaged in aerosol cans, using propane as a propellant.

[0098] The composition was applied in aerosol form to
substrates constructed from brick, glass, plastic and
various metals for surface appearance observation.
Acceptable surface finish on most of these materials was
observed. More specifically, the aerosol appearance is
listed below in Table 5 as compared with the bulk spray and
wiping methods of application.

[0099] Ten coats of Sample No. 7 were aerosol spray
applied to aluminum Q-panels, allowed to dry 10 minutes
after each coat and given a 10-minute final cure. Coating
thickness was measured as an average of 32 readings and
divided by the number of coatings that had been applied to
the Q-panels. Thickness readings were taken using an
Elcometer 355 digital coating thickness meter, and are
recorded in Table 6.

*The average thickness for each entry an average was taken as an
average of 4 readings collected from 4 locations of the coated panel,
namely the upper part, middle part, lower part, and every corner of the
panel, and the overall thickness was calculated to be 0.061, based on
the ten coats which were applied
Example 6
[00100] In this example, Sample Nos. 3, 6-10 and 11-16
were evaluated as mold release compositions. Apart from
Sample No. 12, these samples each demonstrated a gloss value
retention on molded parts of at least 80.
[00101] More specifically, for instance Sample No. 6
demonstrated a gloss value retention of 86.3 on the molded
part. And, Sample No. 3 demonstrated a gloss value
retention of 85.0 on the molded part; Sample Nos. 8 and 14
demonstrated a gloss value retention of 91.1 and 87.0,
respectively, on the molded part; Sample Nos. 7, 13, 15 and
16 demonstrated a gloss value retention of 85.9, 90.7, 83.2
and 83.0, respectively, on the molded part. The
releasability measurements on the molded part were conducted
by pouring each sample as a freestanding puddle of about
three inches in diameter and allowed to cure over a twelve
hour period prior to testing for release properties.
Releasability was measured by way of a qualitative scale (1-
6) in which 1= did not release, 2= part broke when forcibly

released, 3= flexing of board or heavy pressure required for
release, 4= moderate pressure required for release, 5=
little pressure required for release, and 6= part fell off
board (as a pre-release). Sample Nos. 3 demonstrated a
release value of 3; Sample Nos. 8 and 14 demonstrated a
release value of 5 and 4, respectively; Sample Nos. 7, 13,
15 and 16 each demonstrated a release value of 5.

We Claim :
1. A curable composition, reaction products
of which are substantially transparent comprising:
a functionalized siloxane such as herin described;
and
a crosslinker comprising at least one of an amino
functional silane, an enoxy functional silane, a
silazane, and combinations thereof;
wherein when cured under atmospheric conditions in
less than 30 minutes reaction products are substantially
transparent and markings made on a surface coated with
said composition are readily removable.
2. The composition as claimed in Claim 1,
wherein said crosslinker is present in amounts of about
0.1% to about 50% by weight of said composition.
3. The composition as claimed in Claim 1,
wherein said composition has a viscosity of less than
2000 cps as applied to a surface.
4. The composition as claimed in Claim 1,
wherein said functionalized siloxane is a hydroxy
terminated poly siloxane.
5. The composition as claimed in Claim 1,
wherein said crosslinker is tris cycle silazane.
6. The composition as claimed in Claim 1,
wherein said crosslinker is a ladder structure silazane.
7. The composition as claimed in Claim 1,
further comprising a carrier selected from the group
consisting of an aliphatic hydrocarbon containing 8 to 12

carbon atoms, an aromatic hydrocarbon containing 8 to 12
carbon atoms, a siloxane containing 2 to 6 silicone
atoms, a cyclic siloxane containing 3 to 5 silicone
atoms, water, and mixtures thereof.
8. The composition as claimed in Claim 1,
wherein said functionalized siloxane is present in
amounts of about 0.01% to about 50% by weight of said
composition.
9. The composition as claimed in Claim 1,
further comprising a resin selected from the group
consisting of an alkoxy silane prepolymer resin, an
alkoxy functional prepolymer resin, and combinations
thereof, for improving aesthetic effects of said anti-
graffiti composition as applied to a surface.
10. The composition as claimed in Claim 1,
further comprising a moisture cure catalyst.
11. The composition as claimed in Claim 1,
further comprising a photoinitiator.
12. A mark-resistant film comprising the
moisture cure reaction product of a composition
comprising a functionalized siloxane and at least one
agent selected from the group consisting of an amino
functional silane, an enoxy functional silane, a silazane
and combinations thereof.
13. A film having improved resistance to
particulate buildup, comprising the moisture cure
reaction product of a composition comprising a
functionalized siloxane and at least one agent selected

from the group consisting of an amino functional silane,
an enoxy functional silane, a silazane and combinations
thereof.
14. A method of imparting mark-resistant
properties to a surface, comprising the steps of:
applying a film coating of a composition to a
surface to inhibit markings thereon; and
exposing the film coating to conditions
appropriate to cure the composition,
wherein the composition comprises a
functionalized siloxane, at least one crosslinking agent
selected from the group consisting of an amino functional
silane, an enoxy functional silane, a silazane, and
combinations thereof.
15. The method of Claim 14, wherein the
conditions appropriate to cure the composition are
exposure to moisture at ambient temperature.
16. A method of imparting particulate
repellent properties to a surface, comprising the steps
of:
applying a film coating of a composition to a
surface to inhibit particulate buildup thereon; and
exposing the film coating to conditions
appropriate to cure the composition,
wherein the composition comprises a
functionalized siloxane, at least one crosslinking agent
selected from the group consisting of an amino functional
silane, an enoxy functional silane, a silazane, and
combinations thereof.

17. The method of Claim 16, wherein the
conditions appropriate to cure the composition are
exposure to moisture at ambient temperature.
18. A method of enhancing the gloss value of a
part molded in a mold coated with a cured mold release
composition to at least 80, comprising the steps of:
applying a film coating of a mold release
composition to a surface in a mold; and
exposing the film coating to conditions
appropriate to cure the composition,
wherein the composition comprises a
functionalized siloxane, at least one crosslinking agent
selected from the group consisting of an amino functional
silane, an enoxy functional silane, a silazane, and
combinations thereof.
19. The method of Claim 18, wherein the
conditions appropriate to cure the composition are
exposure to moisture at ambient temperature.
20. A method of enhancing release of a molded
part from a mold coated with a cured mold release
composition, comprising the steps of:
applying a film coating of a mold release
composition to a surface in a mold; and
exposing the film coating to conditions appropriate
to cure the composition, the composition comprising
a functionalized siloxane; and
at least one crosslinking agent selected from
the group consisting of a multi-functional silane,
an amino functional silane, an enoxy functional
silane, a silazane, and combinations thereof;

wherein when cured the mold release composition allows a
part molded in the mold in which the mold release
composition is applied to retain a gloss value of at
least 80.

The present invention relates to curable coating compositions which when cured are substantially transparent and
exhibit resistance to markings such as graffiti and scuffing and particulate buildup. In particular, the compositions of the present
invenlion when cured provide proteclive coatings to surfaces to prevent absorption and/or wetting of ink compositions. The invention
composition may also be used as mold release agents.

Documents:

1792-kolnp-2005-granted-abstract.pdf

1792-kolnp-2005-granted-assignment.pdf

1792-kolnp-2005-granted-claims.pdf

1792-kolnp-2005-granted-correspondence.pdf

1792-kolnp-2005-granted-description (complete).pdf

1792-kolnp-2005-granted-drawings.pdf

1792-kolnp-2005-granted-examination report.pdf

1792-kolnp-2005-granted-form 1.pdf

1792-kolnp-2005-granted-form 18.pdf

1792-kolnp-2005-granted-form 3.pdf

1792-kolnp-2005-granted-form 5.pdf

1792-kolnp-2005-granted-gpa.pdf

1792-kolnp-2005-granted-reply to examination report.pdf

1792-kolnp-2005-granted-specification.pdf

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Patent Number

231460

Indian Patent Application Number

1792/KOLNP/2005

PG Journal Number

10/2009

Publication Date

06-Mar-2009

Grant Date

04-Mar-2009

Date of Filing

08-Sep-2005

Name of Patentee

HENKEL CORPORATION

Applicant Address

1001 TROUT BROOK CROSSING, ROCKY HILL, CT 06067

Inventors:

#	Inventor's Name	Inventor's Address
1	LU, ZHENG	6 ROBINSON STREET, BRENTWOOD, NH 03833

PCT International Classification Number

C09D 183/06

PCT International Application Number

PCT/US2004/006669

PCT International Filing date

2004-03-04

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/453,023	2003-03-07	U.S.A.