WO2008085234A1 - Process for forming films and films formed by the process - Google Patents

Abstract

A thin film is formed and cured on a surface with a system comprising (i) a free radical polymerizable monomer, oligomer or polymer, (ii) an organoborane amine complex, (iii) an amine reactive compound, and (iv) oxygen. Ingredients (ii) and (iii) can be distributed between a base and a curing agent. The uncured film formed on the surface is cured by exposure of the base to the curing agent in the presence of ingredient (iv), which may be present as naturally occurring in the air. The process may involve curing to form polymeric and polymer composite films rapidly in ambient air, without heating or irradiation. The system can be applied to inorganic and organic surfaces, and is particularly useful for polymeric surfaces such as low energy plastics.

Description

PROCESS FOR FORMING FILMS AND FILMS FORMED BY THE PROCESS

CROSS REFERENCE

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 60/879,459 filed on 9 January 2007. U.S. Provisional Patent Application Serial No.

60/879,459 is hereby incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] None.

BACKGROUND OF THE INVENTION Technical Field

[0003] A process for forming films employs organoborane amine complexes. Thin films with dielectric properties useful in electronics applications can be prepared on a variety of substrates.

Problem to be Solved [0004] Most current methods for forming thin films employ ultraviolet (UV), electron- beam (e-beam), ion beam, or x-ray irradiation to cure the film. These methods have limitations for curing in depth or in shadowed regions, and also require the presence of the appropriate radiation source and associated process infrastructure, which can be quite costly.

Other non-photochemical methods typically require heat to cure the film. Heating requires ovens, which are costly to install, operate and maintain, and can create problems in curing due to thermal expansion and contraction during heating and cooling steps, respectively.

Further, heat curing processes cannot be used for heat-sensitive articles.

Solution

[0005] This process described herein relates to a new use of organoborane amine based complexes used in a system for generating films of polymers or polymer composites on surfaces at low temperatures including room temperature and below. In this case, the system is defined as the medium or media used to generate a film, and is not limited to thin films.

The system herein contains a base and a curing agent. As used herein, the base, as distinguished from the system, is defined as one or more ingredients of the system that is transferred to the surface in the form of a film. The curing agent is the medium to which the base is exposed to cure the film. The process of curing the film is defined as a process in which the film on the surface undergoes a net increase in number average molecular weight by polymerization and/or crosslinking. The system is reactive and can be rapidly cured in ambient conditions. While the process described herein can be used to form relatively thick films (e.g., greater than 10,000 nanometers to several millimeters) on solid surfaces such as plastics, ceramics, glasses, metals, paper, or wood, it is also useful for creation of thin films (e.g., 10 nm to 10,000 nm) such as those currently created for microelectronics. In addition to being a mild, rapid, and robust ambient process, the process described herein features the key advantage of working with a wide variety of surfaces. Furthermore, the process uses a system that is shelf stable yet allows films to be cured rapidly under ambient conditions. [0006] The process described herein utilizes organoborane chemistry to present a unique, facile, and low cost method of forming films on surfaces including low energy plastics, in ambient conditions, without the need for a heat source or a radiation source such as UV or e- beam. The process allows a wide range of polymers and polymer composites to be created in films on various surfaces, for controlling properties such as surface texture, appearance, adhesion, release, paintability, cell adhesion, friction, protein adsorption, pH response, reactivity, and conductivity for electron, ion, photon, or phonon transport. The process is useful in applications including fabrication of semiconductors, photovoltaic devices, photonic devices, organic electronics and displays such as transistors and light emitting diodes, and fabricating dielectric coatings. BRIEF SUMMARY OF THE INVENTION

[0007] The process relates to forming a cured film. The process is performed by placing an uncured film on a surface and curing to form a cured film. The process uses a system comprising (i) a free radical polymerizable monomer, oligomer or polymer, (ii) an organoborane amine complex, (iii) an amine reactive compound, and (iv) oxygen. According to the process, the ingredients of the system may be distributed in any proportion into a multiple component system such as a base and a separately contained curing agent containing additional ingredients of the system, provided however, that ingredients (ii) and (iii) are stored separately before curing the system. [0008] The process may comprise placing the base onto a surface in the form of an uncured film, and then exposing the base to the curing agent to cure the film at low temperatures, such as below 100 °C, including room temperature and below. Ingredient (iv) oxygen may be present explicitly in the system, or ingredient (iv) may be implicitly present in the environment, such as that naturally present in air. The system can be applied to any surface or combination of surfaces. These and other features of the invention will become apparent from a consideration of the detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0009] As noted above, the process according to the invention utilizes the versatility of organoborane chemistry, and more precisely, that afforded by organoborane amine complexes, which are air stable, yet become extremely powerful free radical polymerization initiators when exposed to an amine reactive compound. This enables virtually instantaneous curing, of a range of unsaturated monomers, oligomers and polymers. By this process, the base may be placed onto a surface by any number of well established methods, including spin coating, roll coating, curtain coating, spray coating, inkjet coating, die coating, dip coating, solvent casting, vapor deposition, or liquid-liquid deposition techniques such as Langmuir- Blodgett film assembly. The resulting uncured film of base may be cured rapidly in ambient conditions on a surface, upon exposure of the base to an appropriate curing agent. The curing agent can be a liquid, a gas, a solid, or a mixture thereof.

[0010] Curing occurs upon mixing of the ingredients of the base with the curing agent. The deposition of the base film onto the surface may be physical, e.g., adsorption, or it may involve the formation of covalent bonds with the surface, e.g., grafting. As opposed to purely physical methods where a dye, pigment, or a fully polymerized polymer is deposited, for example from a solvent which volatilizes to dry the film, the process described herein is a reactive process in which the system during curing undergoes an increase in average molecular weight via free radical polymerization, such as from a monomelic or macromonomeric fluid to a polymer film. In this respect, this process is similar to techniques based upon radiation or heat cure, but this system provides the advantage in that it does not require photoinitiators or a light source or heat source, and this process offers numerous other advantages mentioned herein.

[0011] The system comprises (i) the free radical polymerizable monomer, oligomer, or polymer, (ii) the organoborane amine complex, (iii) the amine reactive compound, and (iv) oxygen. In some cases, the same compound may be used for both (i) and (iii), as long as said compound has both functional groups, as exemplified by acrylic acid and methacrylic acid. Ingredients (i)-(iv) are distributed between the base and the curing agent, such that one of ingredients (ii) and (iii) is in the base and the other of ingredients (ii) and (iii) is in the curing agent, and ingredients (ii) and (iii) are not combined in the presence of ingredient (iv) before curing. Although ingredient (iv) oxygen is inherently present in air, the oxygen may be deliberately excluded from or introduced to the base, the curing agent, or the processing environment.

[0012] For example, the process may be performed by forming the uncured film on the surface with a base comprising (i) a free radical polymerizable monomer, oligomer or polymer, and (ii) an organoborane amine complex, and then exposing the base to a curing agent comprising (iii) an amine reactive compound, in the presence of (iv) oxygen, to cure to form the cured film on the surface.

[0013] Alternatively, the process may be performed by forming the uncured film on the surface with a base comprising (ii) an organoborane amine complex, and then exposing the base to a curing agent comprising (i) a free radical polymerizable monomer, oligomer or polymer and (iii) an amine reactive compound, in the presence of oxygen (iv), to cure to form the cured film on the surface.

[0014] Alternatively, the process may be performed by forming the uncured film on the surface with a base comprising ingredient (iii) the amine reactive compound, then exposing the base to a curing agent comprising ingredients (i) and (ii) to cure to form the cured film on the surface in the presence of oxygen (iv). In this embodiment, the film may be placed on a surface either as base placed post-hoc, placed via a surface functionalization step such as selective priming, UV or corona treatment to create amine-reactive sites on the surface, or placed in-situ via a self assembly process during processing of the substrate in which ingredient (iii) is present in the substrate either inherently or as an additive. [0015] Alternatively, where the system exists in a single package, ingredients (ii) and (iii) may be isolated from one another by being present in separate phases of a multiphase system such as an emulsion, or via encapsulation of at least one of the ingredients (ii) and (iii). Here, because ingredients (ii) and (iii) are in separate phases, it is not necessary to store and process the base in the absence of (iv) oxygen. The base is placed onto the surface of in the form of an uncured film, then cured either by exposure to a curing agent comprising a chemical agent such as a de-emulsifier or solvent, or by exposure to a physical process such shearing, irradiation, heating, cooling, pressurization, or depressurization, to cause ingredients (ii) and (iii) to mix with one another in the presence of (iv) oxygen.

[0016] In any of the embodiments of the invention, except where noted otherwise, ingredients (i) and (iv) may be included with one or more other optional ingredients (v) in either the base, or in the curing agent, or in both. Also, ingredients (i) and (iii) in any embodiment may consist of a single ingredient having both the free-radical polymerizable group and the amine-reactive group.

[0017] The surface on which the system is used to prepare cured films is not limited. Examples include glass surfaces, metal surfaces, quartz surfaces, ceramic surfaces, silicon surfaces, organic surfaces, rigid polymeric surfaces, flexible elastomeric surfaces, or composite surfaces thereof. The surface may also be a frozen liquid, such as ice or dry ice, to create freely standing filmic templates or decals that may be transferred to another surface by allowing the surface to melt after the cured film has been created. The surface may also be a liquid surface, such as water, heptane, silicone oil, or mercury, provided the base retains the desired features of the film until curing is sufficiently progressed to render the film stable or curing is complete. Preferably, the base does not spread or dissolve in the liquid surface when applied to the liquid surface. The resulting properties of the cured film are not particularly limited. For example, the system can be formulated to yield a cured film that may be rigid, flexible, transparent, translucent, opaque, elastomeric, amorphous, semi- crystalline, liquid crystalline, thermoplastic, thermosetting, thermally or electrically insulating, thermally or electrically semi-conductive, or thermally or electrically conductive. [0018] The base may be placed or formed on the surface by any number of well established methods, including brush coating, roll coating, curtain coating, spray coating, inkjet coating, die coating, spin coating, dip coating, solvent casting, vapor deposition, or liquid-liquid deposition techniques such as Langmuir-Blodgett film assembly. The ingredients of the system include (i) a free radical polymerizable monomer, oligomer or polymer; (ii) an organoborane amine complex, (iii) an amine reactive compound, and (iii) oxygen. These ingredients are described in more detail as follows. THE FREE RADICAL POLYMERIZABLE MONOMER, OLIGOMER, OR POLYMER (i) [0019] Ingredient (i) can be an organic compound, or an organometallic compound such as an organosilicon compound. In either case, it can be a single monomer, oligomer, or polymer containing unsaturation and capable of undergoing free radical polymerization. Mixtures of monomers, oligomers, and polymers can also be used. In many cases, it is preferred to use mixtures of monomer, oligomers, and polymers to impart the desired combination of physical properties such as viscosity, volatility, substrate wetting for processability and resolution in the uncured state, glass transition temperature, hardness or solubility, and surface properties such as hydrophilicity or hydrophobicity in the cured state. When ingredient (i) is an organic compound, the selected compound will depend on the use of the cured product. Some suitable organic compounds are described in U.S. Patent 6,762,260 (July 13, 2004), including organic compounds such as 2-ethylhexylacrylate, 2-ethylhexylmethacrylate, methylacrylate, methylmethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, glycidyl acrylate, glycidyl methacrylate, allyl acrylate, allyl methacrylate, stearyl acrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, isobomyl acrylate, isobomyl methacrylate, caprolactone acrylate, perfluorobutyl acrylate, perfluorobutyl methacrylate, IH, IH, 2H, 2H- heptadecafluorodecyl acrylate, IH, IH, 2H, 2H-heptadecafluorodecyl methacrylate, tetrahydroperfluoro acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, bisphenol A acrylate, bisphenol A dimethacrylate, ethoxylated bisphenol A acrylate, ethoxylated bisphenol A methacrylate, hexafluoro bisphenol A diacrylate, hexafluoro bisphenol A dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate), pentaerythritol triacrylate, pentaerythritol trimethacrylate), pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methyl-3-butenoate, allyl methyl carbonate, diallyl pyrocarbonate, allyl acetoacetate, diallyl phthalate, dimethyl itaconate, diallyl carbonate, vinylidene fluoride or combinations thereof. Other useful organic compounds include acrylate tipped polyurethane prepolymers prepared by reacting isocyanate reactive acrylate monomers, oligomers or polymers such as hydroxy acrylates with isocyanate functional prepolymers. [0020] Also useful are a class of conductive monomers, dopants, oligomers, polymers, and macromonomers having an average of at least one free radical polymerizable group per molecule, and the ability to transport electrons, ions, holes, and/or phonons. For example, reference may be had to U.S. Patent 5,929,194 (July 27, 1999) that describes the preparation of various free radical polymerizable hole transporting compounds such as 4,4'4"-tris[N-(3(2-acryloyoxyethyloxy)phenyl)-N-phenylamino]triphenylamine, 4,4'4"-tris[N-(3(benzoyloxyphenyl)-N-phenylamino]triphenylamine, and preparation of electroluminescent devices made there from. It is noted that the acrylic functional group prefixes acryloyl- and acryl- are used interchangeably herein, as are the methacrylic functional group prefixes methacryloyl- and methacryl-. [0021] Also useful are a class of monomers, oligomers, polymer and macromonomers having an average of at least one free radical polymerizable group per molecule, and exhibiting refractive indices over a range useful in optical and photonic applications. Examples include monomers, oligomers, polymer and macromonomers bearing halogenated repeat units such as tetrafluoroethylene, tetrafluoroethylene hexafluoropropylene vinylidene fluoride, ethylene tetrafluoroethylene, pentadecafluorooctyl acrylate, pentadecafluorooctyl methacrylate, nonafluoropentyl acrylate, nonafluoropentylmethacrylate, trifluoroethyl acrylate, trifluoroethylmethacrylate, 1,3,-dichloropropyl methacrylate, p-bromophenyl methacrylate, phenyl alpha-bromoacrylate, and pentabromophenyl methacrylate. Other useful compounds include those having high refractive indices (relative to common polymers) such as acrylate or methacrylate functional macromonomers of polyetheretherketone (PEEK) and polyetherimides

[0022] When an organosilicon compound is used as ingredient (i), again the selected compound depends on the use of the cured product. The organosilicon compound may comprises organosilanes or organopolysiloxanes having on average at least one free radical polymerizable moiety. The organosilicon compound can be monomelic, oligomeric, polymeric, or it can be a mixture of monomers, and/or oligomers, and/or polymers. Higher molecular weight species of such free radical polymerizable compounds are often referred to as macromonomers. The organosilicon compounds can contain mono-functional or multifunctional units in the free radical polymerizable group. This allows for its polymerization to linear polymers, branched polymers of various architecture, copolymers of various architecture, or crosslinked polymeric networks. The monomers and oligomers can be any monomer or oligomer normally used to prepare addition or condensation curable polymers, or they can be monomers or oligomers used in other types of curing reactions, provided they contain at least one free radical polymerizable group.

[0023] Suitable organosilicon monomers include compounds having a structure generally corresponding to the formula R"_nSi(OR"')4-n_> where n has a value ranging from 0 to 4; and where at least one of the R" or R'" groups contains a free radical polymerizable group. The R" and R'" groups can be independently, hydrogen; a halogen atom; or an organic group including alkyl groups, haloalkyl groups, aryl groups, haloaryl groups, alkenyl groups, alkynyl groups, acrylate functional groups, and methacrylate functional groups. The R" and R'" groups may also contain other organic functional groups including glycidyl groups, amine groups, ether groups, cyanate ester groups, isocyano groups, ester groups, carboxylic acid groups, carboxylate salt groups, succinate groups, anhydride groups, mercapto groups, sulfide groups, azide groups, phosphonate groups, phosphine groups, masked isocyano groups, and hydroxyl groups. [0024] Representative examples of free radical polymerizable organosilicon monomers include compounds such as 3-methacryloxypropyltrimethoxysilane,

3-methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxymethyltrimethoxysilane, 3-methacryloxypropyltrimethylsilane, 3-acryloxypropyltriethoxysilane, 3-acryloxylpropyltrimethylsilane, vinyltrimethoxysilane, allyltrimethoxysilane, 1-hexenyltrimethoxysilane, tetra-(allyloxysilane), tetra-(3-butenyl-l-oxy)silane, tri-(3-butenyl-l-oxy)methylsilane, di-(3-butenyl-l-oxy)dimethylsilane, and 3-butenyl-l-oxy trimethylsilane. Other examples include di-alkoxyfunctional analogs of the trialkoxysilanes exemplified above, such as 3-methacryloxypropylmethyldimethoxysilane, mono-alkoxyfunctional analogs of the above, such as 3-methacryloxypropyldimethylmethoxysilane. Also included within this class are halosilane precursors of these monomers, such as 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosilane, and 3-methacryloxypropyldimethylchlorosilane. The preferred free radical polymerizable moieties for these organosilicon compounds are aliphatic unsaturated groups in which the double bond is located at the terminal positions, internal positions, or both positions relative to the functional group. The most preferred free radical polymerizable moiety for the organosilicon compounds are acrylate groups or methacrylate groups.

[0025] When the free radical polymerizable monomer, oligomer, or polymer is an organosilicon component, the component can be an organopolysiloxane having a linear, branched, hyperbranched, or resinous structure. The compound can be homopolymeric or copolymeric. The free radical polymerizable moiety for the organopolysiloxane can be an unsaturated organic group such as an alkenyl group having 2-12 carbon atoms, exemplified by the vinyl group, allyl group, butenyl group, or the hexenyl group. The unsaturated organic group can also comprise alkynyl groups having 2-12 carbon atoms, exemplified by the ethynyl group, propynyl group, or the butynyl group. The unsaturated organic group can bear the free radical polymerizable group on an oligomeric or polymeric polyether moiety such as an allyloxypoly(oxyalkylene) group or a halogen substituted analog thereof. The free radical polymerizable organic group can contain acrylate functional groups or methacrylate functional groups, exemplified by acryloxyalkyl groups such as acryloxymethyl and acryloxypropyl groups, and methacryloxyalkyl groups such as methacryloxymethyl and methacryloxypropyl groups. The unsaturated organic groups can be located at the terminal positions, pendant positions, or both the terminal and pendant positions relative to the polymer backbone. The preferred free radical polymerizable moiety for monomelic, oligomeric, and polymeric organosilicon compounds are acrylate groups and methacrylate groups.

[0026] Any remaining silicon bonded organic groups can be monovalent organic groups free of aliphatic unsaturation. The monovalent organic group can have 1-20 carbon atoms, preferably 1-10 carbon atoms, and is exemplified by alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl; alkyloxypoly(oxyalkylene) groups such as propyloxypoly(oxyethylene), propyloxypoly(oxypropylene), propyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups, halogen substituted analogs thereof; cyanofunctional groups including cyanoalkyl groups such as cyanoethyl and cyanopropyl; carbazole groups such as 3-(N-carbazolyl)propyl; arylamino-functional groups such as 4-(N, N-diphenylamino)phenyl-3-propyl; and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, dichlorophenyl, and 6,6,6,5,5,4 ,4,3,3-nonafluorohexyl.

[0027] The free radical polymerizable organosilicon compound can vary in consistency from a fluid having a viscosity of 0.001 Pa s at 25 °C to a gum. The free radical polymerizable organosilicon compound can also be a solid that becomes flowable at an elevated temperature or by the application of shear.

[0028] Ingredient (i) includes organopolysiloxane fluids having the formulae:

(a) R¹ ₃Si0(R¹ ₂Si0)_a(R¹R²Si0)bSiR¹3,

(b) R³2R⁴SiO(R³ ₂SiO)_c(R³R⁴SiO)_dSiR³ ₂R⁴, or

(c) combinations of such fluids. [0029] In these formulae, subscript a has an average value of zero to 20,000, subscript b has an average value of 1 to 20,000, subscript c has an average value of zero to 20,000, and subscript d has an average value of zero to 20,000. Each R* group is independently a monovalent organic group. The R^ group is independently an unsaturated monovalent organic group. The R³ groups can be the same as the R^ groups. Each R⁴ is independently an unsaturated organic group.

[0030] Suitable Rl groups are monovalent organic groups including acrylic functional groups such as acryloxymethyl, acryloxypropyl, methacryloxymethyl, methacryloxypropyl groups; alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as vinyl, allyl, and butenyl groups; alkynyl groups such as ethynyl and propynyl groups; aromatic groups such as phenyl, tolyl, and xylyl groups; cyanoalkyl groups such as cyanomethyl, cyanoethyl and cyanopropyl groups; halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, dichlorophenyl, and 6,6,6,5,5,4,4,3,3-nonafluorohexyl groups; alkenyloxypoly(oxyalkylene) groups such as allyloxy(polyoxyethylene), allyloxypoly(oxypropylene), and allyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; alkyloxypoly(oxyalkylene) groups such as propyloxy(polyoxyethylene), propyloxypoly(oxypropylene), and propyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; halogen substituted alkyloxypoly(oxyalkylene) groups such as perfluoropropyloxy(polyoxyethylene), perfluoropropyloxypoly(oxypropylene), and perfluoropropyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and ethylhexyloxy groups; aminoalkyl groups such as 3-aminopropyl, 6-aminohexyl, 11-aminoundecyl, 3-(N-allylamino)propyl, N- (2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2- ethylpyridine, and 3-propylpyrrole groups; epoxyalkyl groups such as 3-glycidoxypropyl, 2- (3,4,-epoxycyclohexyl)ethyl, and 5,6-epoxyhexyl groups; ester functional groups such as acetoxymethyl and benzoyloxypropyl groups; hydroxy functional groups such as hydroxy and 2-hydroxyethyl groups; isocyanate and masked isocyanate functional groups such as 3- isocyanatopropyl, tris-3-propylisocyanurate, propyl-t-butylcarbamate, and propylethylcarbamate groups; aldehyde functional groups such as undecanal and butyraldehyde groups; anhydride functional groups such as 3-propyl succinic anhydride and 3-propyl maleic anhydride groups; carboxylic acid functional groups such as 3-carboxypropyl and 2-carboxyethyl groups; carbazole groups such as 3-(N-carbazolyl)propyl; arylamino- functional groups such as 4-(N, N-diphenylamino)phenyl-3-propyl; and metal salts of carboxylic acids such as the zinc, sodium, or potassium salts of 3-carboxypropyl and 2-carboxyethyl.

[0031] The R2 group is exemplified by alkenyl groups such as vinyl, allyl, and butenyl groups; alkynyl groups such as ethynyl and propynyl groups; and acrylic functional groups such as acryloxypropyl and methacryloxypropyl groups. As noted, the R^ groups can be the same as the R^ groups. The R^ group is exemplified by alkenyl groups such as vinyl, allyl, and butenyl groups; alkynyl groups such as ethynyl and propynyl groups; alkenyloxypoly(oxyalkylene) groups such as allyloxy(polyoxyethylene), allyloxypoly(oxypropylene), and allyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; and acrylic functional groups such as acryloxymethyl, acryloxypropyl, methacryloxymethyl, and methacryloxypropyl groups.

[0032] Some representative organopolysiloxane fluids suitable for use as ingredient (i) include α,ω-methacryloxypropyl-dimethylsilyl terminated polydimethylsiloxanes; α,ω-methacryloxymethyl-dimethylsilyl terminated polydimethylsiloxanes; α,ω-acryloxypropyl-dimethylsilyl terminated polydimethylsiloxanes; α,ω-acryloxymethyl-dimethylsilyl terminated polydimethylsiloxanes; pendant acrylate functional polymers and methacrylate functional polymers such as poly(acryloxypropyl-methylsiloxy)-polydimethylsiloxane copolymers and poly(methacryloxypropyl-methylsiloxy)-polydimethylsiloxane copolymers; and telechelic polydimethylsiloxanes having multiple acrylate functional groups or methacrylate functional groups such as compositions formed via Michael addition of multi-acrylate monomers or multi-methacrylate monomers to amine terminated polydimethylsiloxanes. Such functionalizing reactions can be carried out a priori or in-situ.

[0033] It may be desirable to use a mixture of organopolysiloxane fluids differing in their degree of functionality and/or the nature of the free radical polymerizable group. For example, a much faster crosslinking efficiency and a reduced sol content can be obtained by using a tetra-functional telechelic polydimethylsiloxane prepared by the Michael addition reaction of N-(methyl)isobutyl-dimethylsilyl terminated polydimethylsiloxane with two molar equivalents of trimethylolpropane tri-acrylate as ingredient (i) of the composition, relative to di-functional methacryloxypropyl-dimethylsilyl terminated polydimethylsiloxanes having a similar degree of polymerization (DP). However, the latter compositions also produce lower modulus elastomeric films. Hence, combinations of ingredient (i) having differing structures may be quite useful. Methods for preparing such organopolysiloxane fluids are known and include the hydrolysis and condensation of the corresponding organohalosilanes or the equilibration of cyclic polydiorganosiloxanes. [0034] Ingredient (i) can be an organosiloxane resin including MQ resins containing

R^3SiOi/2 units and Siθ4/2 units; TD resins containing R~>SiC>3/2 units and R^2Siθ2/2 units; MT resins containing R^SiO 1/2 units and R^Siθ3/2 units; MTD resins containing

R^3SiOy2 units, R^Siθ3/2 units, and R^SiC^^ units; or combinations thereof. Each R^ group in these organosiloxane resins represents a monovalent organic group. The monovalent organic group R^ can have 1-20 carbon atoms, alternatively 1-10 carbon atoms.

[0035] Some examples of suitable monovalent organic groups representative of the R^ group include acrylate functional groups such as acryloxyalkyl groups; methacrylate functional groups such as methacryloxyalkyl groups; cyanofunctional groups; and monovalent hydrocarbon groups. Monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl groups; cycloalkyl groups such as cyclohexyl groups; alkenyl groups such as vinyl, allyl, butenyl, and hexenyl groups; alkynyl groups such as ethynyl, propynyl, and butynyl groups; aryl groups such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl groups; halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, dichlorophenyl, and 6,6,6,5,5,4,4,3,3-nonafluorohexyl groups; and cyano-functional groups including cyanoalkyl groups such as cyanoethyl and cyanopropyl groups.

[0036] The R^ group can also comprise an alkyloxypoly(oxyalkylene) group such as propyloxy(polyoxyethylene), propyloxypoly(oxypropylene) and propyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; halogen substituted alkyloxypoly(oxyalkylene) groups such as perfluoropropyloxy(polyoxyethylene), perfluoropropyloxypoly(oxypropylene) and perfluoropropyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; alkenyloxypoly(oxyalkylene) groups such as allyloxypoly(oxyethylene), allyloxypoly(oxypropylene) and allyloxy-poly(oxypropylene)-co-poly(oxyethylene) groups; alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and ethylhexyloxy groups; aminoalkyl groups such as 3-aminopropyl, 6-aminohexyl, 11-aminoundecyl, 3-(N-allylamino)propyl, N-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2-ethylpyridine, and 3-propylpyrrole groups; hindered aminoalkyl groups such as tetramethylpiperidinyl oxypropyl groups; epoxyalkyl groups such as 3-glycidoxypropyl, 2-(3,4,-epoxycyclohexyl)ethyl, and 5,6-epoxyhexyl groups; ester functional groups such as acetoxymethyl and benzoyloxypropyl groups; hydroxy functional groups such as hydroxy and 2-hydroxyethyl groups; isocyanate and masked isocyanate functional groups such as 3-isocyanatopropyl, tris-3-propylisocyanurate, propyl-t-butylcarbamate, and propylethylcarbamate groups; aldehyde functional groups such as undecanal and butyraldehyde groups; anhydride functional groups such as 3-propyl succinic anhydride and 3-propyl maleic anhydride groups; carboxylic acid functional groups such as 3-carboxypropyl, 2-carboxyethyl, and 10-carboxydecyl groups; carbazole groups such as 3- (N-carbazolyl)propyl; arylamino-functional groups such as 4-(N, N-diphenylamino)phenyl-3- propyl; and metal salts of carboxylic acids such as zinc, sodium, and potassium salts of 3- carboxypropyl and 2-carboxyethyl. [0037] The organosiloxane resin can contain an average of 1-40 mole percent of free radical polymerizable groups such as unsaturated organic groups. The unsaturated organic groups may be an alkenyl group, alkynyl group, acrylate-functional group, methacrylate- functional group, or a combination of such groups. The mole percent of unsaturated organic groups in the organosiloxane resin is considered herein to be the ratio of (i) the number of moles of unsaturated groups containing siloxane units in the resin, to (ii) the total number of moles of siloxane units in the resin, times a factor of 100. Some specific examples of suitable organosiloxane resins that are useful as ingredient (i) are MMethacryloxymethylQ resins, MMethacryloxypropylQ _resins, MχMethacryloxymethylχ resins, MT^Methacry^loxyP^roPy^]T resins, MDT^Methacryl°xymethyl_TPhenyl_{T resinS;} MDτMethacryloxypropylχPhenyl_τ resins, MViny'TPheny¹ resins, TT^^cry^ymethy¹ resins, TTMethacry'oxypropy¹ resins, jPhenyl^Methacryloxymethyl _resj_ns ^Phenyl^Methacryloxypropyl _resins jjPhenyljMethacryloxymethyl_j-gs^s _ancj ypPhenyljMethacryloxypropyl _resins where M, D, T, and Q have the meanings as defined below. [0038] The symbols M, D, T, and Q used herein represent the functionality of structural units of polyorganosiloxanes including organosilicon fluids, resins, and cured products thereof. The symbols are used in accordance with established understanding in the silicone industry. M represents the monofunctional unit R^SiO 1/2; D represents the difunctional unit

R2SiC"2/2; T represents the trifunctional unit RSiθ3/2; and Q represents the tetrafunctional unit Siθ4/2; where R represents a monovalent atom or group, such as R^ described below. The structural formulae of these units are shown below.

Sii —— OO O — Si — O-

(T) (Q)

[0039] Methods of preparing such organosiloxane resins are known including resins made by treating a resin copolymer produced by a silica hydrosol capping process, with an alkenyl containing endblocking reagent, as described in U.S. Patent 2,676,182 (April 20, 1954). This method involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a mixture thereof, followed by recovery of a copolymer having M and Q units. The copolymer typically contains about 2-5 percent by weight of hydroxyl groups. Organosiloxane resins containing less than 2 percent by weight of silicon bonded hydroxyl groups may then be prepared by reacting the copolymer with an endblocking agent containing unsaturated organic groups, and with an endblocking agent free of aliphatic unsaturation, in an amount sufficient to provide 3-30 mole percent of unsaturated organic groups in the product. Some suitable endblocking agents include silazanes, siloxanes, and silanes; and preferred endblocking agents are described in U.S. Patent 4,584,355 (April 22, 1986), U.S. Patent

4,585,836 (April 29, 1986), and U.S. Patent 4,591,622 (May 22, 1986). A single endblocking agent or a mixture of endblocking agents may be used to prepare such organosiloxane resins. [0040] Another type of organosilicon compound that can be used as ingredient (i) is a composition formed by copolymerizing an organic compound having a polymeric backbone, with an organopolysiloxane, where an average of at least one free radical polymerizable group is incorporated per molecule. Some suitable organic compounds include hydrocarbon based polymers such as polyisobutylene, polybutadienes, and polyisoprenes; polyolefins such as polyethylene, polypropylene and polyethylene polypropylene copolymers; polystyrenes; styrene butadiene; and acrylonitrile butadiene styrene; polyacrylates; polyethers such as polyethylene oxide or polypropylene oxide; polyesters such as polyethylene terephthalate or polybutylene terephthalate; polyamides; polycarbonates; polyimides; polyureas; polymethacrylates; polythiophenes; polypyrroles; polyanilines; polyacetylene; polyphenylene vinylene; polyvinylpyridenes; and partially fluorinated or perfluorinated polymers such as polytetrafluoroethylene; fluorinated rubbers; terminally unsaturated hydrocarbons; olefins; and polyolefins. The organic compound can be a copolymer of any of these polymers, including polymers containing multiple organic functionality, multiple organopolysiloxane functionality, or combinations of organopolysiloxanes and organic compounds. The copolymeric structures can vary in the arrangement of repeating units from random, grafted, to being blocky in nature. [0041] Ingredient (i), in addition to bearing on average at least one free radical polymerizable group, may have a physical transition temperature, bear an organofunctional group with a physical transition temperature, or upon polymerization or crosslinking form particles that have a physical transition temperature, i.e., glass transition or melting transition, such that the composition undergoes changes marked by a softening or non-linear reduction in its viscosity on reaching certain temperatures under the conditions of use. Such materials are particularly useful for encapsulation of actives that are released by the introduction of heat. For example, an organopolysiloxane-based version of ingredient (i) may be an organofunctional silicone wax. The wax can be an uncrosslinked organofunctional silicone wax, a crosslinked organofunctional silicone wax, or a combinations of waxes. Silicone waxes such as these are commercially available and are described in U.S. Patent 6,620,515 (September 16, 2003). When the organofunctional silicone wax bears at least one free radical polymerizable group such as an acrylate or methacrylate group, the wax is useful to impart phase changes when used as ingredient (i). Ingredient (i) can also comprise a mixture of any of the organic compounds, organosilicon compounds, and/or organopolysiloxane compounds described above. [0042] Some representative examples of ingredient (i) include acrylic and methacrylic organic monomers, multifunctional monomers and macromonomers. Also, (meth)acrylic functional siloxane linear polymers, resins, and copolymers may also be included as ingredient (i), and are particularly useful for tuning properties such as surface energy, modulus, thermal stability, moisture resistance, and hydrophobic balance. THE ORGANOBORANE AMINE COMPLEX (U)

[0043] The organoborane amine complex (ii) is a complex formed between an organoborane, and a suitable amine compound that renders the complex stable at ambient conditions. The complex (ii) should be capable of initiating polymerization or crosslinking of ingredient (i) by the introduction of an amine reactive compound and/or by heating in the presence of oxygen. An example is an alkylborane amine complex formed from trialkylboranes and various amine compounds. Examples of trialkylboranes useful for forming ingredient (ii) include trialkylboranes of the formula BR"3 where R" represents linear and branched aliphatic or aromatic hydrocarbon groups containing 1 to 20 carbon atoms. Some examples include triethylborane, tri-n-butylborane, tri-n-octylborane, tri-sec- butylborane, tridodecylborane, and phenyldiethylborane. [0044] Also useful as the organoborane component of the organoborane-amine complexes are a class of organosilicon functional boron compounds described in copending published application WO 2006/073695 on 13 July 2006, entitled Organosilicon Functional Boron Amine Catalyst Complexes and Curable Compositions Made Therefrom", and assigned to the same assignee as the present application. Generally, these compounds consist of a complex having an organosilicon functional organoborane portion containing at least one silicon atom, and the silicon atom is present in the organosilicon functional organoborane portion of the complex as a silicon atom containing group, a siloxane oligomer containing group, or as a siloxane polymer containing group. As set forth in the copending application, the organosilicon functional boron amine catalyst complexes therein are compounds having a formula:

wherein B represents boron; R6, R7, and R8 are groups independently selected from the group consisting of hydrogen; a cycloalkyl group; a linear or branched alkyl group having 1 to 12 carbon atoms on the backbone; an alkylaryl group; an organosilane group; an organosiloxane group; an alkylene group capable of functioning as a covalent bridge to a boron atom; a divalent organosiloxane group capable of functioning as a covalent bridge to a boron atom; and halogen substituted homologues thereof; with the provisos that at least one of the R6, R7, or R8 groups contains one or more silicon atoms, and the silicon-containing group is covalently bonded to boron; R9, RlO, and Rl 1 are a group that yields an amine compound or a polyamine compound capable of complexing boron; and wherein two or more of the R6, R7, or R8 groups, and two or more of the R9, RlO, or Rl 1 groups, are such that they can combine to form heterocyclic structures, provided the sum of the number of atoms from the two combining groups does not exceed 11. Reference may be had to the copending application for additional detail if necessary.

[0045] Some examples of amine compounds useful to form the organoborane amine complex (ii) with the organoborane compounds include organic amine compounds such as 1,3 propane diamine, 1,6-hexanediamine, methoxypropylamine, pyridine, and isophorone diamine. Other examples of amine compounds useful to form organoborane amine complexes are described in U.S. Patent 6,777,512 (August 17, 2004), as well as in U.S.

Patent 6,806,330 (October 19, 2004).

[0046] Silicon containing amine compounds can also be used to form the organoborane amine complex including aminosilanes such as 3-aminomethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminomethyltriethoxysilane,

3-aminopropyltriethoxysilane, 2-(trimethoxysilylethyl)pyridine, aminopropylsilanetriol,

3-(m-aminophenoxy)propyltrimethoxysilane, 3-aminopropyldiisopropylmethoxysilane, aminophenyltrimethoxysilane, 3-aminopropyltris(methoxyethoxethoxy)silane,

N-(2-aminoethyl)-3-aminomethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,

N-(6-aminohexyl)aminomethyltrimethoxysilane,

N-(2-aminoethyl)-l l-aminoundecyltrimethoxysilane,

(aminoethylaminomethyl)phenethyltrimethoxysilane,

N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, and

(3-trimethoxysilylpropyl)diethylene-tri amine.

[0047] Amine functional organopolysiloxanes are also useful for forming the organoborane amine complex (ii) including organosilicon compounds described above in formulae (a) and

(b), and those compounds described previously as organopolysiloxane resins. This is subject to the stipulation that the molecule contain at least one amine functional group, such as

3-aminopropyl, aminomethyl, 2-aminoethyl, 6-aminohexyl, 11-aminoundecyl,

3-(N-allylamino)propyl, N-(2-aminoethyl)-3-aminopropyl,

N-(2-aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2-ethylpyridine, and 3-propylpyrrole.

[0048] Specific examples include terminal and/or pendant amine-functional polydimethylsiloxane oligomers and polymers, terminal and/or pendant amine-functional random, graft and block copolymers and co-oligomers of polydimethylsiloxane and poly(3,3,3 trifluoropropyl-methylsiloxane), terminal and/or pendant amine-functional random, graft and block copolymers and co-oligomers of polydimethylsiloxane and poly(6,6,6,5,5,4,4,3,3-nonfluorohexyl-methylsiloxane), and terminal and/or pendant amine- functional random, graft and block copolymers and co-oligomers of polydimethylsiloxane and polyphenymethylsiloxane. Other examples of useful compounds include resinous amine-functional siloxanes such as the amine-functional compounds described previously as organopolysiloxane resins, as well as amine-functional polysilsequioxanes. [0049] Also useful to form the organoborane amine complex (ii) are other nitrogen containing compounds including N-(3-triethyoxysilylpropyl)-4,5-dihydroimidazole, ureidopropyltriethoxysilane, siloxanes of formulas similar to formulae (a) and (b) noted above, and those compounds described previously as organopolysiloxane resins in which at least one group is an imidazole, amidine, or ureido functional group. When the amine compound is polymeric^the molecular weight is not limited, except that it should be such as to maintain a sufficiently high concentration of boron to permit polymerization of the composition. For example, in a two-part system, the part containing the organoborane initiator may be diluted with the monomer and optionally, the active ingredient to be encapsulated, or it may consist of the initiator complex alone.

[0050] If desired, the system may be stabilized by physically or chemically attaching the organoborane amine complex to solid particles. This provides a way to control reaction times, as well as to stabilize liquid phase organoborane amine complexes against grossly separating from the rest of the composition during storage. For example, chemical attachment can be performed by pretreating solid particles such as ground silica, precipitated silica, calcium carbonate, or barium sulfate, with a condensation reactive compound containing an amine group such as aminopropyltrimethoxysilane. Although it may be desirable to control the particle size and particle size distribution to impart the desired properties, the size of the particles is not inherently limited, and can range from discrete nanoparticles, i.e., nanometer diameter, to agglomerated or fused structures up to millimeter (mm) size. The pretreatment is followed by complexation with an organoborane compound, or by the direct treatment of the solid particles using a preformed organoborane amine complex that is condensation reactive. When the solid particles contain surface functional groups, additives such as surface treating agents or impurities that are inherently amine reactive, require appropriate pre-cautions to avoid premature decomplexation of the organoborane amine complex being attached. Solid particles containing amine reactive substances can be purified or neutralized before attachment of the organoborane amine complex. Alternatively, the attachment of the organoborane amine complex can be performed in an oxygen free environment. [0051] Pre-attachment of ingredient (ii) to monolithic, i.e., continuous rather than particulate, surfaces can be performed where ingredient (ii) is pre-applied to a surface, followed by exposure to ingredient (iii). For example, one may pre-attach an organoborane- amine complex having an alkoxysilyl group such as 3-aminopropyltriethoxysilane, complexed with an equimolar amount of triethylborane, to a surface such as gold or glass, by relying on the strong interaction or reactivity between the surface and the complex. The pre- attachment may be performed selectively in the form of an uncured film covering all or a portion of the surface, e.g., as a general treatment or priming. As described earlier, ingredient (i) can be applied together with either ingredient (ii) or ingredient (iii). To control the film formation and adhesion on the substrate, it may be desirable to use a combination of low and high surface energy alkylborane-amine complexes in the composition. THEAMINE REACTIVE COMPOUND HAVING AMINE REACTIVE GROUPS (Hi) [0052] The polymerizable composition may contain an amine reactive compound (iii) that is capable of initiating cure of the film when mixed with the organoborane amine complex (ii) and exposed to oxygen, e.g., in an oxygenated environment. The amine reactive compound may be delivered as a liquid, gas, or solid. The amine reactive compound may be a small molecule, a monomer, an oligomer, a polymer, or a mixture thereof, may also be diluted or borne by a carrier such as an aqueous or non-aqueous solvent, or by a filler particle. The presence of ingredient (iii) allows cure of the film to occur rapidly at temperatures below the dissociation temperature of the organoborane amine complex (ii), including room temperature and below. To prevent pre-mature cure in the presence of oxygen, ingredients (ii) and (iii) can be physically or chemically isolated, until just prior to the time when it is desirable to cure. For example, the composition may be prepared as two separate solutions, which are applied sequentially to the surface. The remaining ingredients of the system may be distributed in any manner between the two solutions, as long as (ii) and (iii) do not intimately contact each other in the presence of oxygen.

[0053] For example, a first solution, e.g., a base herein, comprising ingredients (i) and (ii), and a second solution, e.g., a curing agent herein, comprising ingredient (iii) are both air stable, but after the base is deposited on a surface in an uncured film, the film cures rapidly when the film is exposed to the second solution in ambient conditions. Alternatively, ingredients (ii) and (iii) or both can be encapsulated, or delivered in separate phases. This can be accomplished by introducing one or both of the ingredients (ii) and (iii) in a solid form, that prevents intimate mixing of ingredients (ii) and (iii). Curing the uncured film can be activated by (a) heating it above the softening temperature of the solid phase component or encapsulant, or (b) by the introduction of a solubilizing agent for the solid phase, that allows mixing of ingredients (ii) and (iii).

[0054] Yet another method includes using a heterophase liquid such as an emulsion, in which ingredients (ii) and (iii) are present in separate liquid phases that comprise the base. The uncured film may then be cured such as by shear or heating to break the emulsion, or chemically by exposing the film to a compound that causes ingredients (ii) and (iii) to contact each other and react.

[0055] Examples of some amine reactive compounds having amine reactive groups (iii) that; can rapidly initiate cure of the base in the presence of oxygen, include mineral acids, Lewis acids, carboxylic acids, carboxylic acid derivatives such as anhydrides and succinates, carboxylic acid metal salts, isocyanates, aldehydes, epoxides, acid chlorides, and sulphonyl chlorides. Some suitable amine reactive compounds include acetic acid, acrylic acid, methacrylic acid, polyacrylic acid, polymethacrylic acid, methacrylic anhydride, undecylenic acid, oleic acid, lauric acid, lauric anhydride, citraconic anhydride, ascorbic acid (Vitamin C), isophorone diisocyanate monomers or oligomers, methacryloylisocyanate, 2- (methacryloyloxy)ethyl acetoacetate, undecylenic aldehyde, and dodecyl succinic anhydride. [0056] The amine reactive compound may be an organosilicon or an organopolysiloxane bearing amine reactive groups. Some examples include organosilanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatomethyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. Other organosilicon compounds bearing amine reactive groups that can be used include triethoxysilylpropyl succinic anhydride; propylsuccinic anhydride functionalized linear, branched, resinous, and hyperbranched organopolysiloxanes; methylsuccinic anhydride functionalized linear, branched, resinous, and hyperbranched organopolysiloxanes; cyclohexenyl anhydride functional linear, resinous, and hyperbranched organopolysiloxanes; carboxylic acid functionalized linear, branched, resinous, and hyperbranched organopolysiloxanes such as carboxydecyl terminated oligomeric or polymeric polydimethylsiloxanes; and aldehyde functionalized linear, branched, resinous, and hyperbranched organopolysiloxanes such as undecylenic aldehyde-terminated oligomeric or polymeric polydimethylsiloxanes.

[0057] U.S. Patent 6,777,512 describes silicon containing compounds that can be used as ingredient (iii) including certain compounds that release an acid when exposed to moisture. U.S. Patent 6,777,512 patent also describes other amine reactive compounds referred to as decomplexation agents that can be used as ingredient (iii).

[0058] Although a notable advantage of this technique is rapid ambient cure without the need for a radiation source, the process may be used to create films using existing radiative processes such as under a UV or e-beam source, to accelerate reaction, enable curing in shadowed regions or in deep sections, or to impart improved adhesion to the substrate. In such cases, it may be useful to include compounds capable of generating amine reactive groups when exposed to ultraviolet radiation such as a photoacid generator. Some examples of such compounds include iodonium salts containing [SbFg ]^~ counterions. In such an embodiment, it may be useful to optionally include a photosensitizing compound such as isopropylthioxanthone.

[0059] In some cases, it may be desirable to attach the amine reactive compound to solid particles. Solid particles may have properties such as electrical conductivity or thermal conductivity, or ferroelectric properties, that can render the resulting film, more useful for subsequent applications. Attachment of the amine-reactive groups can be accomplished by a number of known surface treatments either in-situ or a priori. Some surface treatment methods include, for example, pre-treating solid particles such as ground or precipitated silica, calcium carbonate, carbon black, carbon nanoparticles, silicon nanoparticles, barium sulfate, titanium dioxide, aluminum oxide, boron nitride, silver, gold, platinum, palladium, and alloys thereof; or a base metal such as nickel, aluminum, copper, and steel; with a condensation reactive compound. This is followed by reaction of the pre-treated solid particles with a compound having amine reactive groups, or by the direct treatment of the pre-treated solid particles using amine reactive compounds that have hydrolyzable moieties. In such cases, it is preferred that the particles to which the amine reactive compounds are attached have a similar density to the polymerization medium to facilitate dispersion of the particles in the system. [0060] Some examples of condensation reactive compounds that can be used for attachment, include isocyanatomethyltriethoxysilane, isocyanatopropyltriethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatopropyltrimethoxysilane, triethoxysilylundecanal, glycidoxymethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, 3-(triethoxysilyl)methylsuccinic anhydride, 3-(triethoxysilyl)propylsuccinic anhydride, and 2-(4-chlorosulfonylphenyl) ethyltrimethoxysilane. Attachment of the amine reactive compound to the solid particles can also be accomplished by mixing an acid functional compound with fillers having the appropriate surface functionality, under conditions conducive to formation of an acid base complex, a hydrogen bonded complex, or an acid salt. [0061] Some particulate fillers are commercially available that are pre-treated with surface treating agents referred to as lubricants, or that can be obtained with impurities that contain amine reactive groups, such as carboxylic acid. In this way, ingredient (iii) and an additional ingredient, can be delivered together in the form of a treated filler. In this instance the reaction between the organoborane amine complex and the amine reactive groups on the filler can help remove the lubricant from the surface of the filler particles. The lubricant is necessary for stability of the particle in concentrated form, but it can interfere with the intended function of the filler. The reaction of ingredient (ii) and the amine-reactive lubricant can effectively remove the lubricant from the particle surface, thereby activating the particle. A typical example is a fatty-acid treated silver filler particle, wherein the fatty acid lubricant interferes with particle-to-particle contact, which is needed for establishing electrical conductivity in a final form.

[0062] It may also be advantageous for the sake of stability, to use a combination of fillers containing amine reactive groups, and fillers that are inert with respect to amine compounds. For example, when ingredients (ii) and (iii) are maintained in separate solutions, the filler that is inert with respect to amine compounds, can be combined with ingredients (ii), while the filler bearing amine reactive groups, can be packaged in a separate container from ingredient (ii). In that case, ingredient (i) could be included with any part of the formulation, or with more than one part. Alternatively, the amine reactive compound (iii) can be introduced under conditions that allow it to be delivered in the gas phase to the reaction vessel containing the remainder of the composition. [0063] Pre-attachment of ingredient (iii) to monolithic, i.e., continuous rather than particulate, surfaces can be performed in the embodiment of the invention where ingredient (iii) is pre-applied to a surface, followed by exposure to ingredient (ii). For example, one may pre-attach an amine-reactive compound having an alkoxysilyl group such as 3- isocyanopropyl trimethoxysilane, to a surface such as gold or glass, by relying on the strong interaction or reactivity between the surface and the complex. The pre-attachment may be carried out selectively in the desired film, or as a general treatment or priming, provided at least one of the remaining components of the system is placed in the desired film. As described previously, ingredient (i) can be applied together with either ingredient (ii) or with ingredient (iii), or both in this instance. To control the film formation and adhesion on the substrate, it may be desirable to use a combination of low and high surface energy amine- reactive compounds in the system.

[0064] Some representative and preferred examples of amine reactive groups useful in ingredient (iii) include carboxylic acid, anhydride, isocyanate, aldehydes, and epoxies. Blocked isocyanates may be useful in cases where instead of ambient polymerization, it is desirable to use heat to initiate polymerization rapidly. OXYGEN (iv)

[0065] Oxygen may be present in any diluted, dissolved, or pure form, and may be implicitly present in the form of atmospheric air, or explicitly introduced to the system or processing environment. Although it is not necessary, it may be desirable in some cases to increase, reduce, or eliminate naturally occurring oxygen content in either the base, or in the curing agent, or in ingredients (i), (ii), or (iii) thereof, by controlling pressure and/or quality of the atmosphere in which the ingredients are stored, and in which the process of the invention is performed. Explicit control of the oxygen content may be performed by any known method, including controlling the pressures of various types of gases including oxygen, compressed air, oxygen-enriched air, argon, nitrogen, helium, carbon dioxide and, and/or the inclusion of an oxygen scavenging, oxygen storing, oxygen generating, and/or oxygen releasing substance. Oxygen for purposes herein includes all isotopes of oxygen. Oxygen may be introduced as a gas, a liquid, or a solid, but preferably in introduced in the gas phase. Most preferably, the source of oxygen is air. OPTIONAL INGREDIENTS (v) [0066] One or more optional ingredients can be included in the systems herein such as dyes; pigments; surfactants; water; wetting agents; solvents including common organic aqueous solvents, ionic liquids, and supercritical fluids; diluents; plasticizers; polymers; oligomers; rheology modifiers; adhesion promoters; crosslinking agents; combinations of polymers, crosslinking agents, and catalysts useful for providing a secondary cure of the film; polymers capable of extending, softening, reinforcing, toughening, modifying viscosity, or reducing volatility when mixed into the composition; extending and reinforcing fillers; conductive fillers, spacers; dopants; quantum dots such as nanopaiticles of cadmium selenide; comonomers such as organic acrylates and organic methacrylates; UV stabilizers; aziridine stabilizers; void reducing agents; cure modifiers such as hydroquinone and hindered amines; free radical initiators such as organic peroxides and ozonides; acid acceptors; antioxidants; oxygen scavengers; oxygen sponges; oxygen releasing agents; oxygen generators; heat stabilizers; flame retardants; silylating agents; foam stabilizers; fluxing agents; and desiccants. SURFACES

[0067] The surface of the substrate on which the films are applied is not limited. Although the substrate may be solid or liquid under the conditions of use, in many cases it is desirable to cure films directly on surfaces of solid substrates. Composite articles according to the invention may be curable compositions that can be disposed or applied to a single substrate or between multiple substrates. The substrate or substrates can be organic, thermoplastic, thermosetting, metallic, ceramic, or other suitable inorganic material. The substrates can be multi-layered substrates, such as substrates used in printed circuit boards, in which improved adhesion is desired between the curable film and the substrate or substrates of the composite article. Some specific examples of substrates include silicon, silicon dioxide (and various thermally and physically grown oxide surfaces of silicon), germanium, gallium arsenide, indium, indium nitride, silicon nitride, and other substrates known in the electronics industry as semiconductors or compound semiconductors, silica, alumina, cerium oxide, glass, gold, platinum, palladium, rhodium, silver, steel, stainless steel, anodized steel, aluminum, anodized aluminum, cast aluminum, titanium, nickel, copper, brass, and oxides thereof; building construction materials such as various forms of concrete, brick or stone; circuit boards; polyethylene, polypropylene, polystyrene, syndiotactic-polystyrene, polybutylene terephthalate, polycarbonate, polyphthalamide; polyphenylene sulfide; epoxy resins; bis- maleimide triazine resins; fluoropolymers such as polytetrafluoroethylene, natural rubber, latex rubbers, silicone, fluorosilicone, pressure sensitive tapes and adhesives; and cellulosic polymers such as wood, paper, and natural polymers. [0068] In cases where it is desirable to form freely standing films such as for transfer as decals, the base may be applied onto the surface of substrates that are meltable or sublimable solids such as ice or dry ice, or liquid substrate surfaces such water, oil, or liquid organopolysiloxane, provided the surface does not dissolve the desired film, or otherwise impair cure of the film. In these instances, it may be convenient to introduce ingredient (iii) of the system by imbibing it into the substrate, as exemplified by dissolving of acrylic acid or polyacrylic acid into water or ice. PROCESS

[0069] As discussed previously, the system described above may be assembled in several combinations, and applied in a number of ways to create a polymeric film on a surface. Ingredients (ii) and (iii) are isolated from one another, until after the uncured film has been deposited on the surface. The film is then cured in place upon exposure of ingredients (ii) and (iii) to each other in the presence of (iv) oxygen, without the need for external heating or radiation. The curing agent can be a liquid, vapor or solid, and thus exposure can be effected via a wide range of unit operations amenable to batch, semi-continuous or continuous manufacturing processes. The curing agent may contain an omitted ingredient, and the curing agent may be introduced before or after forming the uncured film e.g., the curing agent may contain ingredient (ii) when the base contains ingredient (iii) but not (ii); alternatively, the curing agent may contain ingredient (iii) when the base contains ingredient (ii) but not (iii). [0070] Alternatively, where the system exists as a single package system, ingredients (ii) and (iii) are isolated from one another by being present in separate phases of a multiphase system such as an emulsion, or via encapsulation of at least one of the ingredients (ii) and (iii). The uncured film is placed onto the surface of interest, then developed by exposure to either a chemical agent such as an de-emulsifier or solvent, or physical processes such as shearing, irradiation, heating, cooling, pressurization, or depressurization, to cause ingredients (ii) and (iii) to come into contact with one another, in the presence of (iv) oxygen. [0071] For example, a base comprising ingredients (i) and (ii) may be deposited in an uncured film onto the surface of interest. The method of deposition may be as simple as brush coating, roll coating, curtain coating, spray coating, inkjet coating, die coating or spin coating, dip coating, solvent casting, vapor deposition, or liquid-liquid deposition techniques such as Langmuir-Blodgett film assembly. The resulting uncured film is then cured by exposing to an environment rich in ingredient (iii), such as by dipping in a curing agent bath comprising ingredient (iii), by passing through a chamber in which the vapor space contains ingredient (iii), by passing through a fluidized bed of solid particles bearing ingredient (iii), or by overcoating the uncured film with a solution comprising ingredient (iii), in the presence of ingredient (iv), or followed by exposure to ingredient (iv). In such multi-package systems, the method of exposing the base to the curing agent may be done in several ways such as via immersion of the entire substrate, by dipping in a bath, exposing to a vapor chamber, or selectively as in over-spraying the film with the curing agent. [0072] More than one layer may be formed on the surface, for example, by a sequential cure where the process comprises 1) forming an uncured film of the base on the surface, and 2) exposing the product of step 1) to the curing agent. This process may be repeated as many time as desired. Alternatively, two or more separate uncured films of the base can be formed on the surface in step 1). In step 2), the resulting multi-layer assembly can be exposed to the curing agent to form the cured film. For purposes of this application, the articles 'a', 'an', and 'the' each refer to one or more.

[0073] Advantages of the process include rapid curing of films at low temperatures including room temperature (e.g., 25 ⁰C) and below without requiring a radiation source or heat source, excellent adhesion to organic substrates, and the versatility to make a variety of cured films ranging from low dielectric constant films to conductive films. This process enables rapid cure of films under ambient conditions, and adhesion to low energy substrates. Another benefit of the process described herein is that it can be used to form relatively thick films (e.g., greater than 10,000 nanometers to several millimeters) on solid surfaces such as plastics, ceramics, glasses, metals, paper, or wood, it is also useful for creation of thin films (e.g., 10 nm to 10,000 nm) such as those currently created for microelectronics. Using monolayer deposition techniques such as Langmuir-Blodgett film assembly, the thickness may be as low as a molecular monolayer. The process described herein can be used to cure elastomeric or rigid organosiloxane materials. Films formed by this process are suitable for a variety of applications, but especially for electronic applications such as semiconductors, displays, transducers, actuators and sensors, industrial coatings for metals, textiles, paper and plastics, and coatings for medical devices and biomaterials. PREPARATION OF THE SYSTEM

[0074] Because the ingredients of the system may be distributed in various manners in the packages described herein, the relative amounts of the ingredients can vary widely. For example, in multiple package systems, the curing agent may contain a large excess of ingredients to allow multiple samples of a film, comprising the remaining ingredients of the system and the surface to be cured by passing through the curing agent in a continuous or semi-continuous process. However, the amount of the curing agent needed to cure just one film may be hundreds of times smaller. In a single package system, the following range of concentrations may be used to cure films.

A. 0.1 to 50 parts by weight of the free radical polymerizable organosilicon monomer, ol i gomer or pol ymer (i ) ;

B. 0.1 to 50 parts by weight of the organoborane amine complex (ii), sufficient to cure the composition, the amount depending on the molecular weight of the complex and the number of boron atoms per molecule;

C. 0.1 to 50 parts by weight of the amine reactive compound (iii); D. 0.0001 to infinite parts by weight of oxygen (iv); and

E. 0 to 50 parts by weight of the optional ingredient (v) or ingredients (v); based on the total weight of the composition. In any case, the system may be scaled to accommodate any convenient mass or volume. The range of ingredients (iv) is essentially unlimited, since oxygen (iv) can be present in any environment such as air. [0075] The cure rate of the system can be controlled by introducing additional amine compounds, to increase the molar ratio of amine groups to boron atoms in the base. The effective amount to be added, depends on the amine:boron ratio of ingredient (ii), and also the amount of any residual acidic impurities that may be introduced with ingredient (i) or any optional ingredients that may be added to the system. It is preferred that the overall amine:boron ratio remain sufficiently low, however, to permit cure to occur. A suitable amine:boron ratio would be less than 10:1, alternatively less than 4:1. When the amine reactive ingredients is already present in the system, e.g., when residual carboxylic acid is present on the filler particles, higher levels of amine compounds may be added to neutralize or partially neutralize the amine reactive groups, to reduce the cure rate. The amine compound may contain monofunctional or multifunctional amine groups, and it can be a primary amine, a secondary amine, and/or a tertiary amine. If desired, the amine compound can contain free radical polymerizable groups, or another functional group such as a hydrolyzable group. The amine compound can be monomelic, oligomeric, or polymeric in nature. Amine groups on the compound may be borne on an organic, organosilicon, or organopolysiloxane compound. USES AND APPLICATIONS

[0076] The ensuing cured film may be used directly, or subjected to post-processing or reaction steps. In particular, the cured films can be used to render a surface selectively receptive to subsequent chemical grafting, binding dyeing, or pigmentation. As an example, the method can be used to selectively prime polyolefins for subsequent reaction over the cured film, in which case it can be carried out by simply dipping a substrate previously subjected to the process described herein into a paint, or by spray painting the entire surface. The cured film may be discrete, continuous, or semi-continuous. The cured film may project from the surface on which the film is applied. In some cases, applied pressure or heat from curing can be used to etch the film below the level of the original surface, as in burning of images into cellulosic substrates in wood burning via the process described herein. EXAMPLES

[0077] The following examples are set forth in order to illustrate the invention to one of ordinary skill in the art. Unless otherwise specified, number average molecular weight (Mn) for organopolysiloxane polymers and resins are values measured by gel permeation chromatography using polystyrene calibration standards. The polydispersity indices for samples analyzed by Gel Permeation Chromatography (GPC) ranged from 1.2-2.2, unless specifically noted otherwise. In all of the following examples, except where it is noted that an argon glove box was used, the level of ingredient (iv) oxygen was not controlled, and it was implicitly present in abundance in the ambient air of the environment in which the examples were conducted, as well as being present to a much lesser extent as naturally dissolved in the ingredients during their storage and handling. Comparative Example 1

[0078] A solution of hydroxy terminated 3-methacryloxypropyl phenyl silsesquioxane _τPh₀₃χMethacryloxypropyl₀₇ resin diluted to 25% solids in l-methoxy-2-propylacetate was spin coated onto a 100 mm diameter clean silicon wafer (Type P<100>, from Exsil, Inc., Providence, R.I., U.S.A.) using a spin coater (EClOl-DT, Headway Research, Inc.) at 1500 rpm for 20 seconds. The freshly coated surface of this film was then placed face down over the top of a 1 pint plastic cup containing 85 g (filling less than 1/5 the total volume of the cup) of acetic acid. The wafer was supported by the 90 mm diameter rim of the cup. After approximately 5 seconds, the wafer was lifted from the cup. The resulting film showed no color change within the area where the film was exposed to the acetic acid vapor in the headspace, relative to the small area on the periphery that was outside the rim of the cup. When part of the film was rinsed with heptane or isopropanol, the film thickness was notably decreased in the exposed area as indicated by a permanent change in the interference color of the film. Example 1

[0079] In a vial, 1.007 g of a hydroxy terminated 3-methacryloxypropyl phenyl silsesquioxane T^ph ₀₃τMethacryloxypropyl_{0 η resin} diluted to 25% solids in l-methoxy-2- propylacetate was combined with 0.070 g of a catalyst comprising triethylborane complexed with an equimolar amount of 1,3 propanediamine. The composition was spin coated onto a 100 mm diameter clean silicon wafer using a spin coater (EClOl-DT, Headway Research, Inc.) at 1500 rpm for 20 seconds. The resulting film appeared somewhat hazy. [0080] A second solution containing 3.8 wt % acrylic acid in octamethyltrisiloxane was then spin coated onto this uncured film at 1500 rpm for 20 seconds. The resulting cured film was hazy and somewhat uneven due to the curing of the film on contact with the puddle of acrylic acid solution; however, the film was well cured, as confirmed by scratching with a spatula and touching with a gloved finger and seeing no transfer of the film to the glove. Adhesion to the substrate was confirmed after 24 hours at room temperature by applying 3M Scotch Magic tape and manually rubbing the tape backing to ensure adequate contact pressure for 5 seconds. The tape was then peeled away by hand at a 90 ° angle at a rate estimated as approximately 100 inches / min, indicating good adhesion to the silicon wafer. Example 2 [0081] In a vial, 1.050 g of a hydroxy terminated 3-methacryloxypropyl phenyl silsesquioxane T^Ph ₀₃T^Methacry^loχyP^roPy¹ ₀1 resin diluted to 25% solids in l-methoxy-2- propylacetate was combined with 0.075 g of a catalyst comprising tri-n-butyl borane complexed with 1.3 molar equivalents of 3-methoxypropyl amine. The composition was spin coated onto a 100 mm diameter clean silicon wafer using a Headway spin coater at 2000 rpm for 20 seconds. The freshly coated surface of this film was then placed face down over the top of a 1 pint plastic cup containing 85 g (filling less than 1/5 the total volume of the cup) of acetic acid. The wafer was supported by the 90 mm diameter rim of the cup. After approximately 5 seconds, the wafer was lifted from the cup. [0082] The resulting film showed a distinct color change within the area where the film was exposed to the acetic acid vapor in the headspace, relative to the small area on the periphery that was outside the rim of the cup. The material on the periphery could be smeared away, but the material inside the rim was well cured into a haze-free film, which was stable to repeated rinsing with heptane. After 24 hours at room temperature, the cured film resisted delamination and showed no color change (which would indicate a change in film thickness) when it was rubbed with 3M Scotch Magic tape for 5 seconds then peeled away by hand at a 90 ° angle at a rate estimated as approximately 100 inches / min, indicating good adhesion to the silicon wafer. Example 3 - Multilayered Film [0083] A multilayered film was created by first spin coating (2500 rpm for 20 s) onto a 100 mm silicon wafer, a solution containing 3.764 g of a hydroxy terminated 3- methacryloxypropyl phenyl silsesquioxane τPⁿo ₃TMethacryloxypropyl₀₇ resin diluted to 25% solids and 0.416 g of a catalyst comprising tri-n-butyl borane complexed with 1.3 molar equivalents of 3-methoxypropyl amine. A drop of deionized water of 8-10 microliters was dispensed onto this film with a fine-tipped micropipette (Samco #235, Samco Scientific

Corp., San Fernando, CA), forming a bead with an obviously positive contact angle that rolls off the film when tilted to an angle. The film was then exposed to a vapor of acrylic acid for 40 s by inverting the wafer over a cup of acrylic acid in a manner similar to that described in Example 2. The resulting film indicated a curing reaction by a color change in the central area that was exposed to the vapors. After exposure, another 8-10 microliter drop of water was dispensed onto the film. This time, the droplet spread on the film surface with a much lower contact angle, confirming presence of polymerized acrylic acid on the surface. A third layer was then deposited by spin coating additional amount of the first solution onto the film under the same conditions. The resulting film surface showed water repellency with similar non-wetting behavior in a water droplet test as observed initially. This example illustrates an embodiment of this process that results in cured multilayer films with alternating layers of hydrophilic and hydrophobic properties, and wherein a hydrophilic layer can be protected from water.

Comparative Example 2 [0084] A solution identical in composition to Comparative Example 1 was spin coated onto a mm silicon wafer having a native surface of silicon dioxide at 2200 rpm for 20s. Comparative Example 3

[0085] In a vial 2.003 g of the solution used in comparative example 1 was mixed with 0.052 g of a catalyst comprising tri-n-butyl borane complexed with 1.3 molar equivalents of 3-methoxypropyl amine. This solution was spin coated onto a 300 mm silicon wafer having a native surface of silicon dioxide at 2200 rpm for 20 s. Example 4

[0086] A film was prepared in an identical manner to Example 3 but was cured by exposing the film to the vapor of glacial acetic acid for 30 s, in the manner described in Example 2. Comparative Example 4 [0087] To a solution comprising 3-methacryloxypropyl phenyl silsesquioxane

resin diluted to 10% solids in toluene was spin coated onto a 300 mm silicon wafer having a native surface of silicon dioxide at 2200 rpm for 20s. Example 5

[0088] In this example, 2.011 g of the solution from Comparative Example 4 were mixed with 0.014 g of a catalyst; tri-n-butyl borane complexed with 1.3 molar equivalents of 3- methoxypropyl amine. A film of the resulting mixture was prepared in an identical manner to Comparative Example 4 but was cured by exposing the film to the vapor of glacial acetic acid for 30 s, in a manner similar to that described in Example 2. Reference Example - Testing of dielectric constant

[0089] Film thicknesses were measured using a J. A. Woollam Co., Inc. M-2000D spectroscopic ellipsometer. A 2-parameter Cauchy model was used to fit the spectra over the wavelength range of 500-1000 nm.

[0090] Dielectric constants were measured at 1 MHz using a parallel plate capacitor stack method, in which the test film lies between the silicon dioxide surface of the wafer and an upper plate which is created by sputter coating a film of aluminum, a Keithley 590 CV impedance gain phase analyzer and a Hewlett Packard HP-4194A impedance / gain phase analyzer connected to a 6 inch wafer sample stage by Signatone Corp.

[0091] The results in this table confirm that the curing of the system according to the process described herein does not introduce a significant change in the refractive index or the dielectric constant of a given resin.

[0092] Other variations may be made in compounds, compositions, and processes described herein without departing from the essential features of the invention. The embodiments of the invention specifically illustrated herein are exemplary only and not intended as limitations on their scope except as defined in the appended claims.

Claims

1. A process of forming a cured film on a surface with a system comprising (i) a free radical polymerizable monomer, oligomer or polymer, (ii) an organoborane amine complex, (iii) an amine reactive compound, and (iv) oxygen, in which the components (i)-(iv) are distributed between a base and a curing agent, such that one of ingredients (ii) and (iii) is in the base and the other of ingredients (ii) and (iii) is in the curing agent, and ingredients (ii) and (iii) are not combined in the presence of ingredient (iv) until a curing step, and wherein the process comprises 1) forming an uncured film of the base on the surface, 2) exposing the product of step 1) to the curing agent, and optionally 3) repeating step 1) using the same or different base before step 2) or repeating both steps 1) and 2) using the same or different base and curing agent.

2. The process of claim 1, where the base comprises ingredients (i) and (ii) and the curing agent comprises ingredients (i) and (iii).

3. The process of claim 1, where the uncured film is formed on the surface by brush coating, roll coating, spray coating, inkjet coating, die coating, spin coating, dip coating, solvent casting, vapor deposition, or liquid-liquid deposition techniques.

4. The process of claim 1, where the curing agent is a liquid.

5. The process of claim 1, where the curing agent is a gas.

6. The process of claim 1, where the curing agent is a gas and the uncured film is formed on the surface by spin coating.

7. The process of claim 1, where the curing agent comprises: (ii) an organoborane amine complex or (iii) an amine reactive compound; and the base comprises:

(iii) an amine reactive compound or (ii) an organoborane amine complex; and wherein (i) a free radical polymerizable monomer, oligomer or polymer and (iv) oxygen, are present in the base component or in the curing agent component, or in both the base component and the curing agent component; and the film is formed on the surface by combining a respective base component with its respective curing agent component.

8. The process of claim 1, where the base comprises (i) a free radical polymerizable monomer, oligomer or polymer; (ii) an organoborane amine complex; and optionally (iv) oxygen; and the curing agent comprises (iii) an amine reactive compound in the absence of oxygen.

9. A process of forming a film on a surface with a one package system comprising (i) a free radical polymerizable monomer, oligomer or polymer, (ii) an organoborane amine complex, and (iii) an amine reactive compound, wherein ingredients (ii) and (iii) are in separate phases, and wherein the process comprises 1) forming an uncured film of the system on the surface, 2) curing the product of step 1) by exposure to a curing agent comprising a chemical agent or a physical process to cause ingredients (ii) and (iii) to combine in the presence of (iv) oxygen, and optionally 3) repeating step 1) with the same or different system before step 2) or repeating both step 1) and step 2) using the same or different system and curing agent.

10. The process of claim 9, where (ii) the organoborane amine complex, (iii) the amine reactive compound, or both, are encapsulated with a capsule or carried by a solid phase, and where the curing agent comprises an ingredient capable of breaking, softening, melting, swelling, or dissolving the capsule or solid phase, to permit ingredients (ii) and (iii) to combine, or the physical process is selected from shearing, irradiation, heating, cooling, pressurization, or depressurization, that causes ingredients (ii) and (iii) to combine in the curing agent.

11. The process of claim 10, where the system comprises an emulsion in which ingredients (ii) and (iii) are in separate phases of the emulsion, and where the curing agent comprises an ingredient capable of disrupting the emulsion to permit ingredients (ii) and (iii) to combine, or the physical process is selected from shearing, irradiation, heating, cooling, pressurization, or depressurization, that disrupts the emulsion and causes ingredients (ii) and (iii) to combine.

12. The process of claim 9, where the uncured film is formed on the surface by brush coating, roll coating, curtain coating, inkjet coating, spin coating, dip coating, solvent casting, vapor deposition or liquid-liquid deposition techniques.

13. The process of claim 1 or claim 9, where the surface is a glass surface, a metal surface, a quartz surface, a ceramic surface, a silicon surface, a silicon dioxide surface, a germanium surface, a gallium arsenide surface, a silicon nitride surface, a semiconductor surface, a compound semiconductor surface, a silica surface, an alumina surface, a cerium oxide surface, a gold surface, a platinum surface, a rhodium surface, a silver surface, an anodized aluminum surface, a cast aluminum surface, a titanium surface, a nickel surface, a copper surface, a brass surface, a building construction material surface, a circuit board surface, a polyethylene surface, a polypropylene surface, a polystyrene surface, a syndiotactic polystyrene surface, a polybutylene terephthalate surface, a polycarbonate surface, a polyphthalamide surface, a polyphenylene sulfide surface, an epoxy resin surface, a bis- maleimide triazine resin surface, a fluoropolymer surface, a natural rubber surface, a latex rubber surface, a silicone surface, a fluorosilicone surface, a pressure sensitive tape surface, a pressure sensitive adhesive surface, a cellulosic polymer surface, an organic surface, a rigid polymeric surface, a flexible elastomeric surface, a liquid, ice, dry ice, or a composite thereof.

14. The process of claim 1 or claim 9, where the organoborane-amine complex (ii) is a complex formed between an organoborane and an amine compound, wherein the organoborane is a boron compound containing organic groups of the formula BR"3 where R" is a linear, branched, aliphatic, or aromatic hydrocarbon group containing 1-20 carbon atoms, or an organosilicon-functional boron compound; and the amine compound is an organic amine compound, or an amine-functional organosilicon compound selected from the group consisting of an aminosilane, an amine-functional organosiloxane, an amine-functional organopolysiloxane, and an amine-functional organopolysilsesquioxane.

15. The process of claim 1 or claim 9, where (iii) the amine reactive compound is selected from the group consisting of mineral acids, Lewis acids, carboxylic acids, carboxylic acid derivatives, carboxylic acid metal salts, isocyanates, aldehydes, epoxides, acid chlorides, and sulphonyl chlorides.

16. The process of claim 1 or claim 9, where ingredient (iii) the amine reactive compound is selected from the group consisting of organosilicon, organosiloxane, and organopolysiloxane compounds bearing amine reactive groups, and ingredient (iii) is present as a neat liquid, solvated liquid, solid, or vapor.

17. The process of claim 1 or claim 9, where the system further comprises one or more additional ingredients selected from the group consisting of dyes; pigments; surfactants; water; wetting agents; organic solvents; aqueous solvents; ionic liquids; supercritical fluids; diluents; plasticizers; polymers; oligomers; rheology modifiers; adhesion promoters; crosslinking agents; combinations of polymers, crosslinking agents, and catalysts; polymers for extending, softening, reinforcing, toughening, modifying viscosity, and reducing volatility; extending fillers; reinforcing fillers; conductive fillers; spacers; dopants; quantum dots; UV stabilizers; aziridine stabilizers; void reducing agents; hydroquinones; hindered amines; free radical initiators; acid acceptors; antioxidants; heat stabilizers; flame retardants; silylating agents; foam stabilizers; fluxing agents; and desiccants.

18. A process according to claim 1 or claim 9, where ingredient (i) is a free radical polymerizable organosilicon monomer, oligomer, or polymer.

19. The process of claim 1 or claim 9, where the uncured film is formed on the surface by spin coating.

20. A cured film formed by the process of any one of claims 1 to 19.

21. A surface containing a cured film formed by the process of any one of claims 1 to 19.