TW200844117A - 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

200844117 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention provides a method for forming a film using an organic rotamamine complex. Films having dielectric properties suitable for electronic applications can be prepared on a variety of substrates. [Prior Art] ^ Problem to be Solved Most current methods for forming thin films use ultraviolet (uv), electron beam, ion beam or x-ray irradiation to cure the film. These methods have limitations in terms of depth in terms of depth or shaded areas, and also require the presence of appropriate radiation sources and associated method infrastructure, which can be quite expensive. Other non-photochemical methods typically require heat to cure the film. Heating requires a phase, which is expensive to install and maintain, and may cause problems in curing due to thermal expansion and shrinkage during the heating and cooling steps, respectively. In addition, the heat curing method cannot be used for heat sensitive articles. solution

Q " This method described herein relates to a new use of an organoborane-based complex in a system which produces a polymer on the surface at a low temperature below temperature. Or poly::::, film. In this case, the system is defined as a medium for producing a film, and is not limited to a film. The system herein contains a binder and a curing agent. As used herein, a binder that is distinct from the system is defined as one or more components of the system that are transferred to the surface in the form of a film. The curing agent is a medium to which the binder is exposed to cure the film. The method of curing the film is defined as being thin on the surface 127115.doc 200844117 The film undergoes a method of net increase in the number average molecular weight by polymerization and/or crosslinking. The system is reactive and can cure rapidly under ambient conditions. Although the methods described herein can be used to form relatively thick films on solid surfaces such as plastic, ceramic, glass, metal, paper or wood (eg, 'greater than! 〇, _ nanometers to a few millimeters), they can also be used In order to produce a film such as that currently made for microelectronics (for example, 1 〇 1 〇, in addition to being a soft, fast and stable surrounding method, the method described herein is also characterized by various The key advantages of using all kinds of surfaces together. In addition, the method uses a left-handed-and-small-sleeve material to stabilize the film while still allowing the film to be rapidly cured under ambient conditions. Chemistry provides a unique, easy, and low-cost method of forming a film on a surface including low energy plastics under ambient conditions without the need for a heat source or source of radiation (such as this method allows for the production of a wide range of polymers on a variety of surfaces) And polymer composite films for controlling such as surface texture, appearance, adhesion, release, paintability, cell adhesion, friction, protein adsorption pH response, reactivity, and conductivity of electron, ion, photon, or phonon transport. The method can be used to fabricate semiconductors, A-electric devices, photonic devices, organic electronic devices, and such as transistors and light-emitting diodes. Displayed in (4) applications, and can be used to make dielectric coatings. SUMMARY OF THE INVENTION The method relates to forming a cured film by placing an uncured film and curing to form a system comprising the following components: (i) from the system. This is carried out by depositing a film on the surface. This method uses a polymerizable monomer, a polymer or a 127115.doc 200844117 polymer, (11) an organoborane amine complex, (iH) amine reactivity. a compound and (iv) oxygen. According to the method, the components of the system can be distributed in any proportion in a multi-component system such as a binder and a separately contained curing agent (containing additional system components), first, and the like: The conditions are that components (ii) and (iii) are stored separately prior to the curing system. The method may comprise placing the substrate on the surface in the form of an uncured film, and then at room temperature and room temperature, The base is exposed to a curing agent to cure the film at a lower temperature (such as below 1 〇〇 C). The component (iv) oxygen may be clearly present in the system, or the component (iv) may be implicitly present in the environment. Such as naturally occurring in the air. The system can be applied to any surface or combination of surfaces. These and other features of the present invention can be clearly understood by reference to the detailed description. ', [Embodiment] As described above, the method according to the present invention Utilizing the versatility of organoborane chemistry, and more precisely, utilizing the versatility provided by organoborane amine complexes, these complexes have air stability and are exposed to amine reactive compounds It is an extremely effective radical polymerization initiator, which enables a range of unsaturated monomers, oligomers and polymers to be virtually instantaneously solidified. By this method, a number of well-established methods can be used. The base material is placed on the surface, and the methods include spin coating, roll coating, curtain coating, spray coating, inkjet coating, die coating, dip coating, solvent washing, vapor deposition, or a film such as Langmuir-Blodgett. assembly Liquid-liquid deposition technology. After the base material is exposed to a suitable curing agent, the resulting base uncured film is rapidly cured on the surface under ambient conditions. The curing agent can be a liquid, a gas, a solid or a mixture of 127115.doc 200844117. Curing occurs after mixing the binder components with the curing agent. The base film may be physically deposited on the surface, such as by adsorption, or it may involve a covalent bond to the surface, such as grafting. In contrast to purely physical methods of, for example, volatilizing a solvent that dries a film to deposit a dye, pigment, or fully polymerized polymer, the methods described herein are via a free radical polymerization (such as from a monomer or macromolecule) during curing. The bulk fluid is polymerized into a polymeric film) and undergoes a reactive method of increasing the average molecular weight. In this regard, this method is similar to radiation or thermal curing based technology, but the advantage provided by this system is that it does not require a photoinitiator or source or heat source, and this method provides many of the other advantages mentioned herein. The system comprises (1) a free-radically polymerizable monomer, a polymer or a polymer, (ii) an organic amine amine complex, (iii) an amine-reactive compound, and (iv) oxygen. In some cases, the same compound can be used for both (1) and (iii) as long as the compound has a functional group exemplified by acrylic acid and methacrylic acid. The components (1) to (iv) are distributed between the binder and the curing agent such that one of the components (Η) and (丨) is in the binder and the other of the components (ii) and (iH) is in the curing agent, and Ingredients (ii) and (iii) are not combined in the presence of component (iv) prior to curing. Although the component (W) oxygen is inherently present in the air, the oxygen may be intentionally excluded from the binder's curing agent or treatment environment or Incorporating into a binder, curing agent or treatment environment. For example, the method can be carried out by using (1) a radical polymerizable monomer, an oligomer or a polymer, and an organic sulfonamide The binder of the complex forms an uncured film on the surface, and then the substrate is exposed to a curing agent containing the (ni) amine-reactive compound to cure on the surface under (iv) oxygen storage 127115.doc 200844117 Forming a cured film. Alternatively, the method can be carried out by the following steps: forming an uncured film on the surface using a base comprising (丨丨) an organoborane amine complex, and then in the presence of oxygen (iv) Exposing the base to contain (1) radical polymerizable monomer The curing agent of the medicinal substance or polymer and (iii) the amine reactive compound forms a cured film on the surface by curing. Alternatively, the method can be carried out by the following steps: using an amine-reactive compound containing a component (Π1) The base material forms an uncured film on the surface, and then the base material is exposed to a curing agent containing the components (1) and (ii) in the presence of oxygen (iv) to cure to form a cured film on the surface. In this embodiment, The film can be placed afterwards, via a functionalization step (such as selective primer, uv or corona treatment to create an amine reactive site on the surface), or processed via a substrate (wherein component (iii) The self-assembly method during the intrinsic or in the presence of the additive in the substrate is placed on the surface by the substrate placed in the original position. Alternatively, in the case where the system is present in a single package, components (ii) and (1)D can be used by Existing in separate phases of a multiphase system such as an emulsion, or isolated from each other, or by at least one of encapsulating components (ii) and (iii). Here, since components (ii) and (iii) are alone Phase, so it is not necessary to store and process the base in the absence of (IV) oxygen. The base is placed on the surface as an uncured film, followed by exposure to contain such as demulsifying agents or a curing agent for the chemical agent of the agent, or by mixing the ingredients (ii) and (iii) in the presence of oxygen at 127115.doc 200844117 by exposure to a physical process such as shearing, irradiation heating, cooling, pressurization or depressurization. And in any embodiment of the present invention, components (1) and (iv) may be included in the binder or included in the curing agent, and/or other optional components (v), unless otherwise stated. In the above, $ is included in both. Also, in any embodiment, the components (1) and (Hi) may be composed of a single component having both a radical polymerizable group and an amine reactive group. The surface on which the system is used to prepare the cured film is not limited. Examples include glass surfaces, metal surfaces, quartz surfaces, ceramic surfaces, tantalum surfaces, organic surfaces, rigid polymer surfaces, flexible elastomer surfaces, or composite surfaces thereof. The surface may also be a chilled liquid (such as ice or dry ice) to produce a free-standing film template or decal, which may be transferred to another surface by allowing the surface to melt after the cured film has been produced. The liquid surface (such as water, heptane, lycopene or mercury) is limited in that the binder maintains the desired film characteristics and the film is stabilized or cured. Preferably, the binder does not expand or dissolve in the liquid surface towel when applied to the surface of the liquid. The properties obtained by curing the film are not particularly limited. For example, the system can be formulated to provide rigidity, flexibility, transparency, translucency, opacity, elastomer, amorphous, semi-crystalline, liquid crystal, thermoplastic, thermal SH1, thermal or electrical insulation, heat or A cured film that is electrically semiconductive or thermally conductive or electrically conductive. The binder can be placed or formed on the surface by a number of well established methods including brushing, roller 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 composition of the system 127115.doc -11 - 200844117 includes (1) free radical polymerizable monomer, shocking characters, ..., g or polymer, (9) organic amine amine complex '(tetra) amine reactive compound And (iv) oxygen. These components are described as follows. The old radical polymerizable monomer, polymer or polymer component (1) may be an organic compound or an organometallic compound such as an organic cerium compound. In any case, it can be a single monomer, polymer or polymer that contains unsaturation and is capable of undergoing free radical polymerization. Mixtures of monomers, vesicles and polymers can also be used. In many cases, it is preferred to use a mixture of monomers, oligomers, and polymers to impart physical properties (such as viscosity, volatility, handleability with respect to uncured state, and substrate wetting, glass transition temperature, Hardness or solubility) is combined with surface characteristics such as hydrophilicity or hydrophobicity of the cure. When component (1) 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-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Acrylic acid, propyl methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimercapto acrylate, glycidyl acrylate, glycidyl methacrylate, acrylic acid acryl Ester, allyl methacrylate, stearyl acrylate, stearyl thioglycolate, tetrahydrofurfuryl methacrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid Caprolactone, perfluorobutyl acrylate, perfluorobutyl methacrylate, 1H, 1H, 2H, 2H-+tl$ ester, methacrylate 111, 111, 211, 211-heptadecafluoroquinone Ester, tetrahydroperfluoroacrylate, phenoxyethyl acrylate, phenoxyethyl acrylate, bisphenol A 127115.doc -12- 200844117 enoate, bisphenol A dimethacrylate, ethoxylate Bisphenol a acrylate, ethoxylated bisphenol A methacrylate, hexafluorobisphenol A dipropylene Acid bismuth, hexafluoro bis-A methacrylic acid, diethylene glycol dipropanoic acid, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol Acrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, trishydroxypropyl propane triacrylate, trimethylol Propane trimethyl propyl & enoate, ethoxylated trimethylolpropane triacrylate, ethoxylated tri-methyl propyl trimethacrylate, pentaerythritol tripropionate, Pentaerythritol trimethacrylate, isoprene tetraol tetraacrylate, isopentaerythritol tetramethacrylate, methyl 3-butenoate, allyl methyl carbonate, mono-propyl propyl carbonate, Allyl acetate, allyl propionate, monomethyl itaconate, diallyl carbonate, vinylidene fluoride or a combination thereof. Other suitable organic compounds include acrylate tip dyed polyurethane preprepared by reacting an isocyanate reactive acrylate monomer such as a hydroxy acrylate, a merging polymer or a polymer with an isocyanate functional prepolymerized Q. Polymer. a class of conductive monomers, dopants, agglomerates, polymers, and macromonomers having an average of at least one free radical polymerizable group per molecule and having the ability to transport electrons, ions, holes, and/or phonons Also applicable. For example, reference is made to U.S. Patent 5,929,194 (July 27, 1999) which describes, for example, 4,4'4''-para [N-(3(2-acryloxyethoxy)) Phenyl)_N•anilino]triphenylamine, 4,4,4"-parade [N_(3(benzylideneoxyphenyl)_N-anilino]triphenylamine of various free radical polymerizable hole transport compounds Preparation, and preparation of electroluminescent devices made therefrom. It should be noted that the acrylic functional group prefix 127115.doc -13· 200844117 acryl fluorenyl- and propylene groups are used interchangeably herein, likewise thiol acrylate functionality The radical methacryl fluorenyl _ is used interchangeably with methacryl yl. A class of monomers having an average of at least one free radical polymerizable group per molecule and exhibiting a refractive index in the range of optical and photonic applications. Oligomers, polymers, and macromonomers are also suitable. (iv) include monomers, oligomers, polymers, and macromonomers having halogenated repeating units such as: tetrafluoroethylene, tetramorphic six Fluoropropene partial ethylene ethylene, ethylene tetrafluoroethylene: fiprotic acid fifteen fluocinolone, methyl propyl acid fifteen Citric vinegar, hexafluoropentaacetic acid acrylic acid, methyl acetoacetic acid ninth vinegar vinegar, triethyl acetal acrylate, methacrylic acid wide a vinegar, methacrylic acid 1>3_dichloropropionate, A Base acrylic acid: benzene vinegar, phenyl acrylate and pentyl bromide methacrylate. Other suitable compounds include compounds with high refractive index (relative to common polymers) such as polyetheretherketone mf IW (PEEK And acrylate or methacrylate functional macromonomer of polyether oxime. When organic cerium compound is used as component (1), the selected compound is also determined depending on the use of the cured product. The invention comprises an average of at least one: an organic decane or an organopolyoxyl which may be a monomer, an oligomeric, polymeric, "may be a mixture of monomers and/or = dipolymers. Equal-radical polymerizable compounds are generally referred to as macromonomers. There are carrageenes," two are: J groups may contain monofunctional or polyfunctional units. This allows for the formation of mounds + n卞/Knife polymer, various racks and spares! = Polymer network. Monomers and oligomers can be Any monomer or oligomer commonly used to prepare addition or condensation, or 127115.doc -14- 200844117 which may be a monomer or oligomer for other types of curing reactions, The restriction is that it contains at least one radical polymerizable group. Suitable organic germanium monomers include compounds having a structure generally corresponding to the formula R"nSi(〇R",) 4 n wherein n has a 〇 to 4 a value within the range; and wherein at least one of the R" or R''' groups contains a free radical polymerizable group. The r" and R''' groups may independently be a hydrogen atom; or an organic group Groups include alkyl, haloalkyl, aryl, haloaryl, dilute, block, acetoacetate functional groups and methacrylate functional groups. R" and R,,, groups may also contain other organic s-b groups, including glycidyl, amine, sulfhydryl, cyanate, isocyano, ester, carboxylic acid, carboxylate , succinate group, anhydride group, sulfhydryl group, thiosyl group, azide group, linonic acid group, (tetra) fluorenyl group and thiol group. Representative examples of the radical polymerizable organic 7 monomer include compounds such as 3-mercaptopropenyloxypropyltrimethoxydecane, 3-methyl acetoxymethyltrimethoxyxanthine, 3-methylpropene oxypropyldiethyl I t-decane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxymercaptotrimethoxydecane, 3·methylpropene oxime Oxypropyl trimethyl sulfonium, 3-propenyl methoxy propyl triethoxy sulphur, 3 propyl methoxy propyl dimethyl decane, vinyl trimethoxy decane, allyl Trimethoxy oxime. Burning, dipyridyl trimethoxy sulphur, 肆 _ (lean propoxyoxy), 肆 _ (3 _ _ _ -1- -1- oxy), _ _ (3_ butene Alkyloxy)methylxanthene, bis(3-butylenyl-p-oxy)dimethylcarbazide and 3·butylphosphonium+oxytrimethylstroxane. Other examples include the above described exemplified bis-oxyalkyl functional analogs (such as 3-methylpropenyloxypropylmethyldimethoxy 127115.doc -15- 200844117) Shixia), an oxo-functional analog such as 3-methylpropenyloxypropyldimethylmethoxynonane. Such also includes halohalogen precursors of such monomers, such as 3-methylpropenyloxypropyltrichloromethane, decyl propylene methoxy propyl methyl dichasite, and 3-methyl Propylene methoxypropyl dimethyl gas smoldering. Preferred radical polymerizable moieties of these organic dream compounds are aliphatic unsaturated groups in which the double bond is located at the terminal position and the internal position i with respect to the functional group. The most preferred radical of the organic hydrazine compound is a acrylate group or a methacrylate group. When the radical polymerizable monomer, oligomer or polymer is an organic oxime component, the component may be an organic polyoxane having a linear, branched, hyperbranched or resinous structure. The compound can be homopolymerized or copolymerized. The organic polyfluorene free radical polymerizable moiety may be an unsaturated organic group such as an alkenyl group having 2 to 12 carbon atoms, which is exemplified by a vinyl group, an allyl group, a butenyl group or a hexenyl group. The unsaturated organic group may also contain an alkynyl group having 2 to 12 carbon atoms as exemplified by an ethynyl group, a propynyl group or a butyl group. The unsaturated organic group may have a radical polymerizable group such as a diloxypropoxyalkylene group or a pharmaceutically acceptable analog thereof on the oligomeric or polymeric polyether moiety. The radical polymerizable organic group may contain an acryloxyalkyl group such as a propylene methoxymethyl group and an acryloxypropyl group, and a methoxymethyl group such as methacryloxymethyl group and methacryloxypropyl group. An acrylate functional group or a methacrylate functional group exemplified by the mercapto acryloxyalkyl group. The unsaturated organic group can be located at the end position, the side position, or both the terminal and the side position relative to the polymer backbone. The preferred free radicals for the monomer, the merging, and the polymeric organic quaternary compound are the acrylic acid s group and the methyl acrylate acid group. 127115.doc -16- 200844117 Any remaining second bonded organic group can be a monovalent organic group free of aliphatic unsaturation. The monovalent organic group may have 20 carbon atoms, preferably 丨_1 〇 one carbon atom, and is exemplified by an alkyl group such as methyl, ethyl, propyl, pentyl, octyl, and ten. a base and an octadecyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a benzyl group and a 2-phenylethyl group; an alkoxy poly(oxyalkylene) group , such as propoxy poly(oxyethyl), propoxy poly(oxypropyl), propoxy-poly(oxypropionyl)-co-poly(oxyethyl) group, a substituted analog; a cyano functional group, including a cyanoalkyl group such as a cyanoethyl group and a cyanopropyl group; a carbazolyl group such as a 3-(N-carbazolyl)propyl group; an arylamino functional group , such as 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. The consistency of the radical polymerizable organic hydrazine compound is self-contained at 25. The fluid with a viscosity of 0.001 Pa.s is changed between the gums and the gel. The radical polymerizable organic hydrazine compound may also be a solid which becomes flowable at a high temperature or by application of shear. Component (1) comprises an organopolyoxane fluid having the formula: (a) R13SiO(R12Si〇)a(R1R2si〇)bsiR13, (b) R32R4SiO(R32Si〇)c(R3R4si〇)dSiR32R4, or (C) a combination of fluids. In this equation, the subscript a has an average value of zero to 2〇5〇〇〇, the subscript b has an average value of 1 to 20,000, the subscript 〇 has an average value of zero to 2〇, and The subscript d has an average value of zero to 20, 〇〇〇. Each group is independently a monovalent organic group. The R2 group is independently an unsaturated monovalent organic group. Han 3 Ji 127115.doc -17- 200844117 The group can be the same as the R1 group. Each R4 is independently an unsaturated organic group. Suitable R1 groups are monovalent organic groups including the following: acrylic functional groups such as propylene methoxymethyl, acryloxypropyl, methacryloxymethyl, methacryloxypropyl Alkyl; such as methyl, ethyl, propyl, and butyl, alkenyl, such as vinyl, allyl and butyryl; alkynyl, such as ethynyl and propynyl; aromatic group, Such as phenyl, tolyl and xylyl; cyanoalkyl, such as cyanomethyl, cyanoethyl and cyanopropyl; halogenated hydrocarbyl, such as 3,3,% trifluoropropyl, 3-chloropropane , dichlorophenyl and 6,6,6,5,5,4,4,3,3-nonafluorohexyl; alkenyloxy poly(oxyalkylene) group, such as allyloxy (polyoxyl) Base ethyl), allyloxy poly(oxypropyl) and allyloxy-poly(oxypropenyl)-co-poly(oxyethyl) groups; alkoxy poly(oxyalkylene) a group such as propoxy (polyoxyethyl), propoxy poly(oxypropyl) and propoxy-poly(oxypropenyl)-co-poly(oxyethyl) Group; _-substituted alkoxy poly Oxyalkylene group, such as perfluoropropoxy (polyoxyethyl), perfluoropropoxy poly(oxypropyl), and perfluoropropoxy-poly(oxypropyl) a poly(oxyethyl) group; an alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and ethylhexyloxy; aminoalkyl, Such as 3-aminopropyl, 6-aminohexyl, fluorenyl-aminoundecyl, 3-(N-allylamino)propyl, N-(2-aminoethyl)-3-amino Propyl, N-(2-aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2-ethylpyridine and 3-propylphosphonyl; epoxyalkyl, such as 3-glycidoxypropyl, 2-(3,4,-epoxy(hexyl)ethyl) and 5,6-3⁄4lacylhexyl; vinegar functional groups such as ethoxylated fluorenyl and phenylhydrazine a methoxyl group; a hydroxy functional group such as a hydroxy group and a 2- to 127115.doc -18- 200844117 ethyl group; an isocyanate and a masking isocyanate functional group such as a 3-isocyanatepropyl group, a para-isocyanate 3 -propyl ester, propyl methacrylate - butyl ester and propyl ethyl carbamate group, aldehyde function Bases such as eleven 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-carboxyl a carbazolyl group such as 3-(N-carbazolyl)propyl; an arylamino functional group such as 4-(N,N-diphenylamino)phenyl-3-yl propyl; Metal salts such as 3-di-propylpropyl and 2-carboxyethyl, rhodium, or y-salt. The R2 group is exemplified by the following groups: alkenyl groups such as vinyl, allyl and butenyl, alkynyl groups such as ethynyl and propynyl; and acrylic functional groups such as acryloxypropyl and a Alkyl methoxypropyl. The Han 3 group can be the same as the R1 group. The R4 group is exemplified by alkenyl groups such as vinyl, allyl and butenyl; alkynyl groups such as ethynyl and propynyl; alkenyloxy poly(oxyalkylene) groups such as alkenyl Propoxy (polyoxyethyl), allyloxy poly(oxypropyl) and allyloxy-poly(oxypropionyl)-co-poly(oxyethyl) groups; and acrylic acid Functional groups such as propylene methoxymethyl, propyloxypropyl, methacryloxymethyl and methacryloxypropyl. Some representative organopolyoxane fluids suitable for use as component (1) include: methacryloxypropyl propyl dimethyl dimethyl alkyl terminated polydimethyl siloxane, methacryloxymethyl methyl _Dimethyl decyl terminated polydimethyl siloxane, α, ω-propylene methoxy propyl dimethyl dimethyl alkyl terminated polydimethyl siloxane, α, ω propylene oxy Methyl-dimethyl decyl terminated polydimethyl siloxane, flanked by acrylate functional polymer and thiol acrylate functional poly 127115.doc -19- 200844117

a compound such as poly(propenyloxypropyl-methyl oxalate alkoxy)-polydimethyl methoxy hydride copolymer and poly(methacryloxypropyl propyl-methyl sulphur oxide a methicone-based oxy-oxygenated copolymer; and a telechelic polydimethyl-enriched gas having a plurality of acrylates/functional or methacrylate functional groups, such as via polyacrylic acid A composition formed by ester monomer or polymethacrylate monomer MichaelM to an amine terminated polydimethyl oxalate. These functionalization reactions can be carried out in advance or in situ.

It is desirable to use a mixture of organopolyoxane fluids that differ in the nature of the functionality and/or free radical polymerizable groups. For example, by using a di-functional methacryloxypropyl-dimethyl decyl-terminated polydimethyl siloxane having a similar degree of polymerization (DP), by using N_(methyl) Tetrafunctional far-polydimethylphenol prepared by the addition reaction of 〃butyl-methyl-methyl-alkyl-terminated polydimethyl siloxane with two molar equivalents of Michael methacrylate As a component of the composition (1), a much faster crosslinking efficiency and a reduced sol content can be obtained. However, the r-functional methacryloyl propyl propyl-dimethyl(tetra)-terminated polydimethyl-osin-oxygenated composition also produces a lower modulus elastomer film. Therefore, a combination of components (1) having different structures may be quite suitable. The methods used to prepare such organic polyoxo-fired fluids are known and include the equilibrium of the corresponding organic digestion and condensation or cyclic polydiorganosiloxane. The component (1) may be an organic oxirane resin comprising the following: an mQ resin containing R 3Si〇i/2 unit and the wrong one and S1〇4/2 early; containing] ^Si〇3/2 single And R52Si〇2/2 unit 3/2 early Fan ^ x know, including R53si〇1/2 unit and R5Si0 early MT resin; contains R mountain. ...sapons, R5si〇3 2 units and 127115.doc • 20- 200844117 R 2Si〇2/2 single ttl MTD resin; or a combination thereof. Each of the R groups in the organic oxime tree sorghum represents a monovalent organic group. The monovalent organic group R5 may have 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Some examples of suitable monovalent organic groups representing the R5 group include: an acrylic acid S-g-energy group, such as an acryloxyalkyl group; a mercapto acrylate functional group, such as a methacryloxyalkyl group; a cyano function a base; and a monovalent hydrocarbon group. The monovalent hydrocarbon group includes: an alkyl group such as methyl, ethyl, propyl, pentyl, octyl, undecyl and octadecyl; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group , butenyl and hexenyl; alkynyl, such as ethynyl, propynyl and butynyl; aryl, such as phenyl, indolyl, diphenyl, benzyl and 2-phenylethyl; Hydrocarbyl groups such as 3,3,3-trifluoropropyl, 3-apropylpropyl, dichlorophenyl and 6,6,6,5,5,4,4,3,3-nonafluorohexyl; Base functional groups including cyanoalkyl groups such as cyanoethyl and cyanopropyl. The R5 group may also comprise: an alkoxy poly(oxyalkylene) group such as propoxy (polyoxyethyl), propoxy poly(oxypropyl) and propoxy-poly (oxy) a propyl-co-poly(oxyethyl) group; a acyl-substituted alkoxy poly(oxyalkylene) group, such as perfluoropropoxy (polyoxyethyl), perfluoro Propoxy poly(oxypropyl) and perfluoropropoxy-poly(oxypropenyl)-co-poly(oxyethyl) groups; alkenyloxy poly(oxyalkylene) groups, Such as allyloxy poly(oxyethyl), allyloxy poly(oxypropyl) and allyloxy-poly(oxypropionyl)-co-poly(oxyethyl) groups; Alkoxy' such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and ethylhexyloxy; aminoalkyl such as 3-aminopropyl, 6 -aminohexyl, 11-aminoundecyl, 3-(N-allylamino)propyl, N-(2-amine 127115.doc -21 - 200844117

Base ethyl)-3-aminopropyl, hydrazine-(2•aminoethyl)-3-aminoisobutyl, p-aminophenyl, 2-ethyl η-pyridine and propyl σ ratio a thiol group; a hindered aminoalkyl group such as tetramethylhexahydropyridyloxypropyl; an epoxyalkyl group such as 3-glycidoxypropyl, 2_(3,4,-epoxy ring) Ethyl)ethyl and 5,6-epoxyhexyl; ester functional groups such as ethoxymethyl and benzyl methoxy propyl; hydroxy functional groups such as hydroxy and 2-hydroxyethyl; isocyanate and masking Isocyanate functional groups, such as 3-isocyanatopropyl, 3-propyl isopropyl isocyanate, propyl methacrylate, and propyl propyl carbamate groups, pendant functional groups, such as Decylaldehyde and butyraldehyde groups; anhydride functional groups such as 3-propyl succinic anhydride and 3-propyl cis-butane phthalic anhydride groups; carboxylic acid functional groups such as 3-carboxypropyl, 2-carboxyethyl and ίο- Carboxyfluorenyl; oxazolyl 'such as 3-(indolylcarbazolyl)propyl; arylamino functional group, such as 4-(indolyl-diphenylamino)phenyl-3-yl propyl; and carboxylic acid Metal salts such as hydroxypropyl and 2-wei The ethyl speech, the sodium and potassium salts. The organodecane resin may contain an average of 1 to 40 mole percent of a radical polymerizable group such as an unsaturated organic group. The unsaturated organic group can be an alkenyl, alkynyl, acrylate functional, methacrylate functional group or a combination of such groups. The molar percentage of the unsaturated organic group in the organodecane resin is herein considered to be (1) the number of moles of the unsaturated group containing a siloxane unit in the resin and (ii) the siloxane unit in the resin. The ratio of the total number of moles is multiplied by a factor of 100. Some specific examples of suitable organic siloxane oxide resins useful as component (1) are Mf*propenyloxymethyl Q resin, (iv) "based Q resin, oxymethyl τ phenyl hydrazine resin, MDTU (tetra) oxybutylene resin, π Rare base rjp stupid base 127115.doc -22- 200844117

Resin, TT, TT, methyl propylene, oxypropyl, phenyl thiophene

Propylene oxymethyl 4 II Η匕rr-i cage A —— Shuyue T, T 'T methyl W ethoxypropyl resin, butyl butyl butyl methyl propyl ethoxymethyl resin and TT Stupid T-methyl intrinsic oxypropyl 此 匕 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 D D D And Q represents the functional group of the structural unit including the organic hydrazine fluid, Shuyue and its solidified product, Pinggu. #人为石夕氧烧. According to the understanding of the construction of ρ途+ > These symbols: Μ represents the car functional unit RdiO"2; d represents - official office __ D a 'yiyi Luyue 匕 early R2Si02/2; τ represents the difunctional unit RSiOh2; and d represents the official one to represent four B The ruthenium is 疋 SiOw; and represents and represents a monovalent atom or group, such as R5 as described below. The structural formula of these units is shown below.

01 cis-irm) R ό I ) -si—R(D) o ο I Is-ο- i ITI ( o Bu) • ο—si—ο-Q)I ( ο ο Preparation of these organic decane resins The method is known, which comprises preparing a resin by treating a resin copolymer produced by a vermiculite hydrosol capping process with an alkenyl-containing capping agent, as in U.S. Patent 2,676,182 (1954) (December 20). This method involves the hydrolysis of Shishishi aquatic glue with a hydrolyzable triorgano 7-burning such as dimethyl benzene, such as hexamethyldioxane under acidic conditions. Or a mixture thereof, followed by recovery of a copolymer having a PCT unit. The copolymer typically contains from about 2 to about 5 weight percent of a hydroxyl group. This can be followed by providing the copolymer with sufficient 3 to 3 〇 127115.doc -23 - 200844117 reacting an unsaturated organic group-containing blocking agent in an amount relative to the unsaturated organic group and reacting with a non-aliphatic unsaturation blocking agent to prepare a less than 2 weight percent ruthenium-bonded hydroxyl group Organic oxirane resins. Some suitable blocking agents include decazane, decane and decane, and are preferred. The capping agent is described in U.S. Patent No. 4,584,355 (April 22, 1986), U.S. Patent No. 4,585,836 (Aug. 29, 1986), and U.S. Patent No. 4,591,622, issued May 22, 1986. Or a mixture of blocking agents to prepare such organodecane resins.

C. Another type of organic ruthenium compound usable as the component (1) is a composition formed by copolymerizing an organic compound having a polymerized main chain with an organopolysiloxane, wherein an average of at least one radical polymerizable group per molecule group. Some suitable organic compounds include: hydrocarbon-based polymers such as polyisobutylene, polybutadiene and polyisoprene; polyolefins such as polyethylene, polypropylene and polyethylene polypropylene copolymers; polystyrene Styrene butadiene; and acrylonitrile butadiene styrene; polyacrylate; polyether, such as polyethylene oxide or polypropylene oxide; polyester, such as polyethylene terephthalate or polyterephthalic acid D: 8; polyamine; polycarbonate; polyimine; polyurea; polymethyl acetoacetate; polyporphyrin ... t polyaniline; polyacetylene; polyphenylene thiophene; Ethylene π ratio biting; and partially fluorinated or perfluorinated polymers such as polytetrafluoroethylene; fluorinated rubber; terminally unsaturated fumes. Olefin, and polyolefin. The organic compound may be a copolymer of such a kind, including a polyorganofunctional group containing a combination of a plurality of == burn-and-organic compounds; the arrangement may be self-regular, the change of grafting is actually = 127115 .doc -24- 200844117. In addition to having an average of at least one radical polymerizable group, the component (1) has / has a physical transfer temperature, has an organic functional group having a physical transfer temperature, or has a physical transfer temperature after self-polymerization or crosslinking (ie, The particles of the glass transfer or melt transfer cause the composition to undergo a change in the mark by the softening or viscosity non-linearity reduction at the specified temperature under the conditions of use. These materials are particularly useful for encapsulating active cattle that are released by the introduction of heat. The composition of the component (1), which is mainly composed of organic polyox, can be an organofunctional polysulfide. The hydrazine may be a combination of an uncrosslinked organofunctional polyoxoquinone, a crosslinked organofunctional polyoxyxide wax or a wax. Polyxime waxes such as such waxes are commercially available and are described in U.S. Patent 6,620,515 (September 16, 2003). The field organic polyfluorene wax has at least one radical polymerizable group such as an acrylate or mercaptopropionate group, and the wax can be used as a phase change when used as the component (1). Component (1) may also comprise a mixture of any of the above-described organic physicochemicals, organic hydrazine compounds and/or organopolyoxyalkylene compounds. Representative examples of the inhibitory injury (1) include acrylic acid and methacrylic acid organic monomer 彳 "b monomer and macromonomer. Also, may include (meth) propylene sulfonium S oxyalkylation linear Polymers, resins and copolymers are used as components ()/, especially for adjusting properties such as surface energy, modulus, thermal stability, moisture resistance and hydrophobic balance. Organoboraneamine complex (ii) Organic boron burning The amine complex (ii) is a complex formed between the organic boron and the suitable amine compound which can make the complex under ambient conditions. The complex 127115.doc -25- 200844117 (ii) should The polymerization or cross-linking of the component (1) can be initiated by introducing an amine-reactive compound and/or by heating in the presence of oxygen. Examples are leucoboramine complexes formed from trialkylboranes and various amine compounds. Examples of the trialkylborane which can be used to form the component (Π) include a trialkylborane of the formula BR", wherein R" represents a linear or branched aliphatic or aromatic group having from 1 to 20 carbon atoms. Hydrocarbyl group. Some examples include triethylborane, tri-n-butylborane, tri-n-octylborane, three Two - butyl borane, tris - dodecyl diethyl borane and phenyl group alone burn.

An organogermanium-functional boron compound of the type disclosed in WO 2006/073695, which is hereby incorporated by reference in its entirety in its entirety, in The title of the case is "Organosilicon Functional Boron Amine Catalyst Complexes and Curable Compositions Made Therefrom-J. ^ m ^ ^ ^ The same assignee of this application. In general, a compound such as & is rented from a complex having a _ functional organic (four) moiety containing: a few dream atoms, and the diarrhea atom is a cleavage atom group, an oxidative polymer group or a milk The form of the polymer group is present in the (4) part of the complex. As stated in the request, the #中==矽B旎boramine catalyst complex is a compound of the formula: R6, R6^BT^N-R10 R8, R11 from the following groups Group B, where B represents a butterfly; R6, R7, and a group selected from the group consisting of 127115.doc -26- 200844117, hydrogen, cycloalkyl, having up to 2 carbon atoms in the main chain = straight A chain or branched chain alkyl group, an alkyl group, an organic group, an organooxo group can act as an alkyl group to a covalent bridge of boron atoms, and can cohere to a covalent bridge of boron atoms. a divalent organic oxoalkyl group and a dentate-substituted homolog thereof, the restriction condition being at least one of the R6, R7 or R8 groups. 纟- or a plurality of shixi atoms, and containing a group Covalent bond to delete; R9,

Rio and Rii are group p groups capable of producing a miscible amine compound or polyamine compound, and wherein two or more of the R6, R7 or R8 groups are combined with two of the R9, (4) or Rl 1 groups. Or two or more such that they can be combined to form a heterocyclic structure, which is limited to a total of no more than 11 atomic numbers of the two combined groups. If necessary, refer to the application in the same towel for additional details. Some examples of amine compounds which can be used to form the organoborane amine complex (ii) with an organoborane compound include organic amine compounds such as 1,3-propylenediamine, 1,6-hexanediamine, methoxypropylamine. , pyridine and isophorone diamine. Other examples of amine compounds which can be used to form organoborane amine complexes are described in U.S. Patent No. 6,777,512 (Aug. 17, 2014) and U.S. Patent No. 6, 806,330 (October 19, 2004). The ceramide compound may also be used to form a force including, for example, the following amine ketone. #机硼胺胺化合物: 3-aminomethyltrimethoxydecane, 3-aminopropyl-methoxy Basear, 3-aminomethyltriethoxydecane, 3-aminopropyltriethoxydecane, 2-(trimethoxydecylalkylethyl)pyridine, aminopropyl aryl triol, 3_(m-aminophenoxy)propyltrimethoxy sylvestre, 3·aminopropyl-isopropylmethoxy decane, aminophenyl trimethoxy decane, and rhodamine 127115.doc -27- 200844117 propyl methoxy(methoxyethoxyethoxy)decane, N-(2-aminoethyl)-3-aminomethyltrimethoxy decane, N-(2-aminoethyl) -3·Aminopropyltrimethoxydecane, N-(6-aminohexyl)aminomercaptotrimethoxydecane, N-(2-aminoethyl)-11-aminoundecyltrimethoxy Base decane, (aminoethylaminomethyl) phenethyltrimethoxydecane, Ν-(2.aminoethyl)-3-aminopropylmethyldimethoxydecane, Ν·(2 -aminoethyl)-3-aminoisobutylmethyldimethoxy zeoxime and (3-trimethoxy oxalate) Diethyl-triamine. The amine functional organopolyoxane can also be used to form organoborane amines comprising the organotelluric compounds described in the above formulas (a) and (b) and their compounds previously described as organopolyoxyalkylene resins. Compound (ii). This is subject to the following regulation: the molecule contains at least one amine functional group such as aminopropyl, aminomethyl, 2-aminoethyl, 6-aminohexyl, 11-aminoundecyl, 3-(N -allylamino)propyl, n-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminoisobutyl, p-amine Phenyl phenyl, 2-ethyl pyridine and 3- propyl σ 嘻. Specific examples include: terminal and/or pendant amine functional polydimethoxy methoxy olefin oligomers and polymers, polydimethyl methoxy oxane and poly(3,3,3-trifluoropropyl-methyl hydrazine Terminal and/or pendant amine functional random, grafted and block copolymers and co-polymers, polydimethyloxane and poly(6,6,6,5,5,4, Terminal and/or pendant amine functional random, grafted and condensed copolymers and co-oligomers of 4,3,3_nonafluorohexyl-methyloxane, and polydimethyloxane Terminal and/or pendant amine functional random, grafted and block copolymers and co-oligomers with polyphenylmethyl oxane. Other examples of suitable compounds include the resinous amine functional oxane (such as the amine functionalization 127115.doc -28-200844117 previously described as an organopolysiloxane resin) and the amine functional polysesquioxane. Other nitrogen-containing compounds which may also be used to form the organoborane amine complex (U) include N-(3-diethoxycalcylpropyl)-4,5-dihydro-u-indole, maimethofol Triethoxy oxime, a compound similar to the above formulas (&) and (b) and the compounds previously described as organopolyoxyalkylene resins (at least one of which The group is an imidazole, hydrazine or ureido functional group). When the amine compound is a polymer, the molecular weight is not limited, but it should be such that a sufficiently high boron concentration is maintained to allow the composition to polymerize. For example, in both systems, the portion containing the organoborane initiator can be diluted with the monomer or, optionally, the active ingredient to be encapsulated, or it can be composed solely of the initiator complex. If necessary, the system can be stabilized by physically attaching the organoborane amine complex to the solid particles chemically. This provides a means to control the reaction time and to stabilize the liquid phase organoborane amine complex against significant separation from the remainder of the composition during storage. For example, chemical attachment can be carried out by pretreating solid particles such as ground vermiculite, precipitated vermiculite, calcium carbonate or barium sulfate with a condensation-reactive compound containing an amine group such as aminopropyl dimethoxydecane. To execute. Although it may be necessary to control particle size and particle size distribution to impart desired properties, particle size is not inherently limited and can range from discrete nanoparticle (ie, nanometer diameter) to coalesced or fused structure to large to millimeters (mm). ) within the size range. The pretreatment is followed by a mismatch with the organoborane compound, or the solid particles are directly treated using a pre-formed organoborane amine complex having condensation reactivity. When the solid particles contain surface functional groups, such as surface treatment agents with inherent amine reactivity or the addition of impurities d, appropriate precautions should be taken to avoid the adhesion of the attached organoborane amines 127115.doc -29- 200844117 Premature resolution. The solid particles containing the amine-reactive substance can be purified before the attachment of the organo-amine complex. Aster, the attachment of the organoborane amine can be carried out in an oxygen-free environment.

Component (u) may be pre-attached to the overall (i.e., continuous rather than particulate) surface by pre-applying component (9) to the surface followed by exposure to component (iv). For example, depending on the strong interaction or reactivity between the surface and the complex, an organoamine complex having an alkoxylated group and a molar amount of a triethylanthene can be mismatched. (such as 3-aminopropyltriethoxylate pre-attached to a surface such as gold or glass. Pre-attachment can cover all or part of the surface in the form of an uncured film (eg, as a general treatment or primer) Alternatively, component (1) can be applied together with component (9) or component (iii) as described above. To control film formation and adhesion on the substrate, it is possible to use low and high surfaces in , and σ. Combination of alkoxyboramine complexes 0 Amine-reactive compound (Ui) having an amine-reactive group The polymerizable composition may contain an amine-reactive compound (iii) which is capable of being mismatched with an organoborane amine (ii) mixing and, for example, initiating film solidification upon exposure to oxygen in an oxidizing environment. The amine reactive compound can be delivered in liquid, gaseous or solid form. The amine reactive compound can be a small molecule, a monomer, a chelating agent, Polymer or The mixture may also be diluted or supported by a carrier such as an aqueous or non-aqueous solvent or by filler particles. The presence of component (iii) allows a temperature below the dissociation temperature of the organoborane amine complex (ii) ( Film curing occurs rapidly at room temperature and below. To prevent premature curing in the presence of oxygen, component (ii) can be physically or chemically isolated from (iii) until 127115.doc •30- 200844117 is required At the time of curing, for example, t, the composition can be prepared as two separate solutions, which are applied successively to the surface. The remaining components of the system can be distributed between the two solutions in any manner as long as (咐 and (iii) ) in fine contact with each other in the presence of oxygen. For example, a first solution comprising components (1) and (ii) (eg, a binder herein) and a second solution comprising component (iii) (eg, herein) The curing agent) is air-stable, but after depositing the binder on the surface in the form of an uncured film, the film is rapidly cured when exposed to the second solution under ambient conditions. Ii) and (iii) or both may be encapsulated or delivered in separate phases. This may be introduced into the components (Π) and (iii) in a solid form by preventing the fine mixing of components (ii) and (iii). Either or both. Curing the uncured film can be initiated by: (heating it to a softening temperature above the solid phase component or encapsulation, or (b) introducing a solid phase solubilizer This allows component (ii) to be mixed with (iii). Another method involves the use of a heterophase liquid such as an emulsion wherein components (H) and (iii) are present in a separate liquid phase comprising the binder. The uncured film is cured by shearing or heating to destroy the emulsion, or chemically by exposing the film to a compound which can bring the components (ii) and (iii) into contact with each other and react. Some examples of the amine-reactive compound (iii) having an amine-reactive group capable of rapidly initiating curing of the binder in the presence of oxygen include: a mineral acid; a Lewis acid; a carboxylic acid; a carboxylic acid derivative such as Anhydrides and succinates; metal carboxylates; isocyanates; aldehydes; epoxides; acid vapors; Some suitable amine-reactive compounds include acetic acid, acrylic acid, 127115.doc-31 - 200844117-based acrylic acid, polyacrylic acid, polymethacrylic acid, methacrylic anhydride, undecylenic acid, oleic acid, lauric acid, and lauric anhydride. , citraconic anhydride, ascorbic acid (vitamin c), isophorone diisocyanate monomer or oligomer, methyl methacrylate isocyanate, 2-(methylpropenyl methoxy) ethyl acetate , undecenal aldehyde and dodecyl succinic anhydride. The amine-reactive compound may be an organic hydrazine or an organic polyoxyalkylene having an amine-reactive group. Some examples include organodecanes such as 3-isocyanatepropyldimethoxydecane, guanidinium isocyanatomethyltrimethoxydecane and 3-glycidoxypropyl 2methoxylate. Other organic compounds of the reactive group of the material (4) include: · triethoxy oxalate propyl hydride; propyl succinic anhydride functionalized linear, branched, resinous and super-branched organic polymerization Shixi oxygen burning; methyl succinic anhydride functionalized linear, branched, resinous and super-branched organopolyoxyalkylene; cyclohexenyl anhydride functional linear, resinous and super-branched organopolyoxyalkylene; Carboxylic acid functionalized linear, branched, resinous, and hyperbranched organopolyoxyalkylenes, such as carboxyl thiol-terminated oligomeric or polymeric polydimethyl hydrazines; and aldehyde functionalized linear, branched, resin Qualitative and hyperbranched organopolyoxy 6' such as undecyl alkenyl terminated oligomeric or polymeric polymethane. & - U.S. Patent 6,777,512 describes certain compounds which can be used as ingredients. U.S. Patent 6,777,5,12 also describes other amine-reactive compounds known as disintegrating agents which can be used as component (m). Although the significant advantage of this technology is fast ambient curing without the need for a light source, this method can also be used (such as using the existing light shot 127115.doc -32-200844117 method to accelerate the reaction, enabling shadows) Curing in a region or deep section, or imparting improved adhesion to the substrate to produce a film. Under such conditions, a compound capable of producing an amine-reactive group upon exposure to ultraviolet radiation such as a photoacid generator may be suitably included. Some examples of such compounds include a lock salt containing [SbFW counterion. In this embodiment, a photosensitizing compound such as isopropylthioxanthone may be suitably included as appropriate. In some cases, an amine reaction may be required. The compound is attached to the solid particles. The solid particles may have properties such as electrical conductivity or thermal conductivity, or the resulting film may be more suitable for subsequent application of ferroelectric properties. Adhesion of amine reactive groups may be handled by many known surfaces. In situ or pre-finished. Some surface treatment methods include, for example, pretreatment of the following substances with solid reactants with condensation-reactive compounds Such as by grinding or slabs, carbonic acid, carbon black, carbon nanoparticles, strontium nanoparticles, barium sulfate, titanium dioxide, aluminum oxide, boron nitride, silver, gold, platinum, palladium and their alloys; or soap a metal such as nickel, aluminum, copper, and steel. Thereafter, the pretreated solid particles are reacted with a compound having an amine reactive i/ group, or the pretreated solid particles are directly treated using an amine reactive compound having a hydrolyzable moiety. Under such conditions, it is preferred that the particles to which the amine-reactive compound is attached have a similar degree of density as the polymerization medium to facilitate dispersion of the particles in the system. • Some examples of condensation-reactive compounds that can be used for attachment include Isocyanatomethyldiethoxydecane, isocyanatopropyltriethoxydecane, isocyanate methyltrimethoxydecane, isocyanatopropyltrimethoxydecane, triethoxydecyl eleven Aldehyde, glycidoxymethyltrimethoxy sulphate, glycidoxypropyltrimethoxy sulphur, 3_(triethoxy xi 127115.doc -33- 200844117 alkyl) methyl sulphate Peric anhydride, 3-(triethoxydecyl)propyl succinic anhydride, and 2-(4-chlorosulfonylphenyl)ethyltrimethoxy decane. The amine reactive compound can also be attached to the solid particles. It is achieved by mixing an acid functional compound with a filler having an appropriate surface S energy group under conditions which facilitate the formation of an acid-base complex, a hydrogen bond complex or an acid salt. It is pretreated by a surface treatment agent called a lubricant, or when it is obtained, it has an impurity containing an amine reactive group (such as a carboxylic acid). In this way, the component (iii) and the additional component can be obtained. It is delivered together in the form of a treated filler. In this case, the reaction between the organic side-burning compound and the amine-reactive group on the filler helps the lubricant to be removed from the surface of the filler particles. The agent is necessary for the stability of the concentrated form of the particles, but it may interfere with the intended function of the filler. The reaction of the component (u) with the amine reactive lubricant effectively removes the lubricant from the particle surface, thereby activating the particles. Typical examples are fatty acid-treated silver filler particles in which the fatty acid lubricant interferes with the contact between the particles, which is required to establish electrical conductivity in the final form. For stability, it may also be advantageous to use A combination of a filler containing an amine-reactive group and a filler inert to the amine compound. For example, when components (ii) and (Hi) are kept in separate solutions, they are present relative to the aminated chemical. An inert filler may be combined with component (8), and a filler having an amine reactive group may be encapsulated in a separate container from component (ii). In this case, component (i) may be combined with any portion of the formulation or Included with more than one moiety, or alternatively, the amine-reactive compound (Hi) can be introduced under conditions which allow it to be passed in the gas phase to the reaction vessel containing the remainder of the composition. 127115.doc -34- 200844117 In an embodiment of the invention, component (iii) may be pre-attached to the overall (i.e., continuous rather than particulate) surface, wherein component (iii) is pre-applied to the surface and subsequently exposed to component (9). For example, an amine reaction port having a silk group (tetra) group (such as 3-isocyanopropyltrimethoxydecane) can be pre-attached to the strong interaction or reactivity between the surface and the complex. For example, the surface of Meng or glass. The pre-adhesion may be carried out in the form of a desired film, or alternatively as a remedy or a primer, with the proviso that the system remains, and, until the evening, placed in the desired film. As described, in this case, the component (1) may be combined with the component (1)) or the component (iii) or both. To control 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. Some representative and preferred examples of the amine-reactive groups which can be used in component (iii) include (iv), anhydrides, isocyanate §|, and epoxides. The blocked isocyanate can be used in situations where heat is required to rapidly initiate polymerization rather than surrounding polymerization. Mouth ί (ίν) Oxygen can be present in any form of dilution, conversion or purity, and can exist in the form of atmospheric air, or in a clear system or treatment environment. Although not necessarily required, it may be necessary to increase, reduce or eliminate the binder or its constituents (1) in the binder or by controlling the pressure and/or quality of the atmosphere of the method of the invention. The naturally occurring oxygen content in (9) or (iii). The explicit control of the oxygen content can be controlled by any known method including controlling the pressure of various types of gases including oxygen, compressed air, oxygen-enriched air, argon, helium, neon and carbon dioxide and / 127115.doc -35- 200844117 Or arbitrage, oxygen storage, oxygen production and / or oxygen release substances. The oxygen used herein includes all oxygen isotopes. Oxygen can be introduced as a gas, a liquid, or preferably, in a gas phase. Optimally, the oxygen source is air. Optional Ingredients The system herein may include one or more optional ingredients such as dyes; pigments; surfactants; water; wetting agents; including common organic aqueous solvents, ionic liquids, and super-reverse, ~. I / melons Lozenge; thinner; plasticizer, polymerizer, oxime modifier; adhesion promoter; crosslinker; polymer, crosslinker and a combination of catalysts that can be used to provide secondary curing of the film; Increment, soften, enhance, diligently, modify viscosity or reduce volatile polymer when mixed into the composition; increase and enhance filler '·conductive filler 四 (4) agent; dopant; quantum dot , such as strontium ore nanoparticles 'copolymer early body' such as organic acrylate and organic methacrylate; chelating agent; aziridine stabilizer; void reducing agent; curing modifier, such as hydrogen S Kun and blocked Amine; free of its 3 丨 如 k _ k again, makeup, mesh by the hair agent, such as organic peroxides and ozonide; acid receptors; antioxidants; oxygen scavengers; oxygen sea, cotton; oxygen release Agent; heat stabilizer; flame retardant'· Xi burnt agent; Bed foam stabilizer; flux; and a desiccant. h Surface The surface of the substrate to which the film is applied is not limited. Although the substrate may be solid or liquid under the conditions of use' in many cases' need to cure directly on the surface of the solid substrate. The composite article according to the present invention may be a curable composition that is placed or applied to a single substrate or between a plurality of substrates. The substrate can be 127115.doc -36 - 200844117 is an organic, thermoplastic, thermosetting, metal, ceramic or other suitable inorganic material substrate can be a base substrate, such as a substrate used in a printed circuit board, wherein in a composite article Improved adhesion is required between the curable film and the substrate. Some specific examples of the substrate include: Shi Xi, dioxide dioxide (and various thermal and physical growth oxide surfaces of Shi Xi), tantalum, gallium arsenide, indium, indium nitride, ratification, and in electronics 1 #巾 is called semiconductor or compound semiconductor /, his substrate Shi Xishi, oxidation | Lu, oxidation _, glass, gold, pin, f

C. Supreme silver steel, stainless steel, anodized steel, Ming, anodized, prayer, Ming Qin* _ 3 copper and its oxides; building materials, such as

Various forms of concrete, holding seven A pieces or stones, circuit boards; polyethylene, polypropylene, polystyrene, fried, present, ethylene, polybutylene terephthalate, polycarbonate , poly(phthalic acid), take - 丄τ I, polyphenylene sulfide; epoxy resin; bis-maleimide triazine resin; fluoropolymer 4^ ^ ^ 弗物, such as poly four gas浠, gluten rubber, latex rubber, _ ^ ^ V yoghurt, murine polyoxyn, pressure sensitive tape and adhesive, and cellulosic polymers, such as the like 'wood, paper and natural polymers. In the case where it is necessary to form a self-supporting thin cavity film (for example, as a decal film for transfer), the base material can be applied to s 7 ^ , and the leaf can be used to melt or sublimate solids (such as , ice or dry ice) on the surface of the substrate J J , or on the surface of a liquid substrate such as water, oil or liquid organic polyoxygenated oxygen, straight yang /, the restriction is that the surface does not dissolve the desired film ' or otherwise Shengbei film curing. In such cases, it is convenient to introduce the components of the system by looking at the composition of the system m (u) and into the substrate (as in the case of acrylic acid or polyacrylic acid dissolved in water or ice). (iii). Methods As previously discussed, a number of combinations can be assembled to assemble the above described system 127115.doc -37.200844117 and applied in a number of ways to produce a polymeric film on the surface. The components (11) and (iii) are isolated from each other until after the uncured film has been deposited on the surface. Subsequent exposure of components (ii) and (iii) to each other in the presence of (IV) oxygen cures the film in place without external heating or radiation. The curing agent can be a liquid, a vapor or a solid, and thus the exposure can be accomplished via a wide range of unit operations that perform batch, semi-continuous or continuous manufacturing methods. The curing agent may contain an omission component, and the curing agent may be introduced before or after the formation of the uncured film, for example, the curing agent may contain the component (11) when the binder contains the component (iii) without (ii); or, the curing agent The component (iii) may be contained when the base contains components containing no (1) hydrazine. Or 'in the case where the system is present as a single package system, components (11) and (111) are isolated from each other by being present in separate phases of a multiphase system such as an emulsion, or via encapsulating components (ii) and (iii) At least one of them is isolated from each other. The uncured film is placed on the surface i of interest, followed by exposure to a chemical such as a deemulsifier or solvent, or a physical process such as shearing, irradiation, heating, cooling, pressurizing or depressurizing at (iv The components (ii) and (iii) are brought into contact with each other in the presence of oxygen to develop. For example, a base comprising components (1) and (ii) can be deposited onto the surface of interest in the form of an uncured film. The deposition method can be as simple as brushing, 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 exposure to an environment rich in component (iii), such as by immersing in a bath of the curing agent comprising component (iii), through a chamber containing component (iii) through the vapor space. Varnishing the uncured film by passing through a fluidized bed having 127115.doc •38- 200844117 solid particles (in) or by a solution containing component (iii) in the presence of component (iv), Or then expose f to component (iv). In such multi-package systems, the method of exposing the base to cure d can be accomplished in several ways, such as by immersing the entire substrate, immersing the substrate in a vapor chamber, or over-spraying with a curing agent. The film is selectively carried out. One or more layers may be formed on the surface, for example, by sequential curing, wherein the method comprises: § 1) forming an uncured film of the substrate on the surface; and 2) exposing the product of V to 1) to the curing agent. This method can be repeated many times as needed. Alternatively, two or more separate uncured films of the binder may be formed on the surface in step 丨). In step 2), the resulting multilayer assembly can be exposed to a curing agent to form a cured film. For the purposes of this application, the terms "a" and "the" refer to one or more. Advantages of the method include: rapid curing of the film at low temperatures including room temperature (for example, 25 Å and below room temperature without the need for a radiation source or heat source; excellent adhesion to an organic substrate; and fabrication of a low dielectric The versatility of a variety of cured films ranging from constant film to conductive film. This method enables the film to cure rapidly under ambient conditions and adhere to low energy substrates. Another benefit of the method described herein is that it can be used Forming a relatively thick film (eg, greater than 1 〇, 〇〇〇 nanometer to a few millimeters) on a solid surface such as plastic, ceramic, glass, metal, paper, or wood, which can also be used to produce, for example, current microelectronics Thin films (eg, 10 nm to 10,000 nm) can be as low in thickness as monolayers by using a single layer deposition technique such as LangmUir_Bi〇dgett film assembly. The method described herein can be 127115.doc -39 - 200844117 Used to cure elastomers or rigid organic siloxane materials. The film formed by this method is suitable for many applications, but is especially suitable for semi-conductive applications. Electronic applications for displays, transducers, actuators and sensors, industrial coatings for metals, fabrics, paper and plastics, and coatings for medical devices and biomaterials. The manner is distributed throughout the package described herein, so the relative amounts of the ingredients can vary widely. For example, in a multi-package system, the curing agent can contain a large excess of ingredients to allow for a continuous or semi-continuous process. The curing agent is used to cure multiple samples of the film (including the remaining components and surface of each system). However, the curing dose required to cure only one film can be hundreds of times smaller. In a single package system, the following concentration ranges can be used to cure the film. A. 0.1 to 50 parts by weight of a radically polymerizable organic fluorene monomer, a merging polymer or a polymer (i); (j 0·1 to 50 parts by weight of an organic boron amide compound (ii), It is sufficient to cure the composition in an amount depending on the molecular weight of the complex and the number of boron atoms per molecule; C·〇·1 to 50 parts by weight of the amine-reactive compound (iii); • · 〇·(9)〇1 to no Large parts by weight of oxygen (iv); and < 0 to 50 parts by weight of optional ingredient (v); the above amounts are based on the total weight of the composition. In any case, the system can be adjusted to accommodate any Suitable mass or volume. The range of component (iv) is essentially unlimited, as oxygen (iv) can be present in any environment such as air. 127115.doc 200844117 (d) rate can be increased by introducing additional amine compounds The molar ratio of the amine-based ruthenium atom in the feed is controlled. The effective amount to be added depends on the amine of the component (8), and can also be introduced as the component (1) or can be added to the system. Depending on the amount of any residual acidic impurities, however, 'Lucky' is the total amine shed. Don't keep it low enough to allow curing to occur. Suitable amine: boron ratio will be less than 丨〇·], alumina ^ ... , ' -1 or less than 4:1. When an amine reactive component is already present in the system, such as when residual tickic acid is present on the filler particles, a higher level of amine compound can be added to neutralize or partially neutralize the amine reactive group to reduce curing. rate. The amine compound may contain a monofunctional or polyfunctional amine group ' and it may be a first amine, a second amine and/or a third amine. The amine compound may contain a radical polymerizable group or an additional-functional group such as a hydrolyzable group, if necessary. The amine compound may be a monomeric, oligomeric or polya-based amine group which may be supported on an organic, organic or organic agglomerated compound. Uses and Applications Subsequent curing of the film can be used directly or after a post-treatment or reaction step. In particular, a cured film can be used to selectively accept subsequent chemical grafting, bond dyeing or coloration. As an example, the method can be used to selectively coat a polyolefin for subsequent reaction on a cured film, in which case it can be simply dipped into the lacquer by a substrate that has previously been subjected to the methods described herein, Or by spraying the entire surface. The cured film can be discrete, continuous or semi-continuous. The cured film can be applied by itself and the surface of the film is protruded. In some cases, the pressure or heat applied by the curing may be used to etch the film below the level of the original surface. The image is burned into the cellulose substrate as described in 127115.doc • 41 - 200844117. EXAMPLES The following examples are set forth to illustrate the invention to the general practitioner. The number average molecular weight (?n) of the organopolyoxyalkylene polymer and the resin is a value measured by gel permeation chromatography using a polystyrene calibration standard unless otherwise impounded. The polydispersity index of the sample analyzed by gel permeation chromatography (GPC) is in the range of 12-2 2 unless otherwise specifically stated. In all of the following examples, the oxygen content of the component (IV) is not controlled except for the case where an argon glove box is to be used, and it is implicitly sufficiently present in the ambient air of the environment in which the examples are carried out, and It exists in a much smaller amount of content which is naturally dissolved in the ingredients during storage and handling. Comparative Example 1 Hydroxylation of 35% solids in 丨-methoxypropyl acetate was carried out using a spin coater (EC101-DT, Headway Research, Inc.) at 150 rpm for 20 seconds. A solution of methacryloxypropyl phenyl sesquiterpene oxide TPh〇.3T methyl propyloxypropyl hydrazine 7 resin was spin-coated onto a 1 mm (mm) diameter clean enamel wafer (Model P<100>, from Exsil, Inc., Providence, RI, USA). The new coated surface of the film was placed face down on top of a 1 pint plastic cup containing 85 g of acetic acid (filled less than 1/5 of the total volume of the cup). The wafer is supported by the outer edge of the 90 mm diameter of the cup. After about 5 seconds, the wafer is lifted from the cup. The resulting film exhibiting film was exposed to a small portion of the area other than the outer edge of the cup relative to the periphery of the acetic acid vapor in the headspace without discoloration. When one portion of the film is washed with heptane or isopropanol 127115.doc -42· 200844117, the thickness of the film in the exposed area is significantly reduced, as indicated by the permanent change in the interference color of the film. Example 1 1.007 g of hydroxy-terminated 3-methylpropenyloxypropylphenyl sesquiterpene oxide diluted to 25 Å/〇 solid in 1-methoxy-2-prop-acetate in a vial The TPh〇3Tu-C (4) resin is combined with a ruthenium-ruthenium catalyst containing triethylboron which is mismatched with a molar amount of ruthenium and 3-propanediamine. The composition was spin coated onto a 100 mm diameter clean enamel wafer using a spin coater (EC101-DT, Headway Research, Inc.) at 1500 rpm for 20 seconds. The resulting film exhibited a slight haze. Next, a second solution containing 3.8 wt% of acrylic acid in octylmethyltrioxane was spin-coated onto the uncured film at 1500 rpm for 20 seconds. The resulting cured film is hazy and slightly uneven due to curing of the film upon contact with the acrylic solution cement; however, the film cures well, such as by scraping with a doctor blade and touching the gloved finger and no film transfer is observed Gloves to confirm. Adhesion to the substrate was confirmed 24 hours after room temperature by applying 3M Scotch Magic tape and manually rubbing the tape substrate to ensure sufficient contact pressure for 5 seconds. The tape was then peeled off by hand at an angle of about 9 〇 at a rate of about 1 〇〇吋/min to indicate good adhesion to the enamel wafer. Example 2 In a vial, it was diluted to 25 Å in 丨-methoxy-2-propyl acetate. Solid 1.050 g hydroxy-terminated 3_mercapto propylene methoxy propyl phenyl sesquiterpene oxy-oxygen TPhG.3Tw propyl... resin with three _ positive _ containing gram of equimolar methoxypropylamine 〇〇75 g catalyst combination of butylborane. 127115.doc -43 · 200844117 The composition was spin coated onto a 100 mm diameter clean enamel wafer using a Headway spin coater at 2000 rpm for 20 seconds. The new coated surface of the film was then placed face down on top of a 1 pint plastic cup containing 85 g (filled less than 1/5 of the total volume of the cup) of acetic acid. The wafer is supported by the outer edge of the 9 mm diameter of the cup. After about 5 seconds, the wafer is lifted from the cup. The resulting film exhibited different discoloration of the film exposed to a small area outside the outer edge of the cup relative to the periphery in the region of the acetic acid vapor in the headspace. The material on the periphery can be applied, but the material inside the outer edge is well cured into a haze-free film which is stable to repeated washing of heptane. After the last 24 hours, the cured film was rubbed with a 3 m Scotch Magic tape for 5 seconds, then peeled off by hand at a rate of about 1 〇〇吋 / min at a 9 〇 angle and resistant to delamination and not shown. Discoloration (this will indicate a change in film thickness) indicating good adhesion to the germanium wafer. Example L Multilayer Film A multilayer film was produced on a 1 〇〇mm 矽 wafer by a first spin coating (2500 rpm for 20 seconds), which is a 3·764 邑 hydroxyl terminated dilution containing 25% solids. 3-methylpropoxypropyl phenyl sesquiterpene oxide TPh〇j methyl propyl oxypropyl m Π — k 0.71⁄43⁄4 and contains 3 methoxy groups with 1.3 molar equivalents The propylamine is mismatched with a solution of one-n-butylborane and 416 g of catalyst. 8-10 microliters of deionized water droplets were applied to the film using a fine pile tip dyeing micropipette (Samco #235, Samco Scientific Corp., San Fernando, CA) to form beads with significant positive contact angles. It rolls off the film when tilted to an angle. The film was then exposed to acrylic acid vapor for 4 seconds by flipping the wafer over the acrylic cup in a manner similar to that described in Example 2. 127115.doc -44- 200844117 The resulting film is indicated by a discoloration exposure to the central region of the vapor. After the exposure, another 8-100 microliter of water droplets are applied to the film. At this time, the small droplets spread over the surface of the film at a much lower contact angle, so that the acrylic polymer was present on the surface. A third layer is then deposited by spin coating the additional first solution onto the film under the same conditions. The surface spread of the resulting film did not have water repellency similar to that originally observed in the water droplet test. This example illustrates an embodiment of this method that produces a cured multilayer film having alternating layers of hydrophilic and hydrophobic properties, and wherein the hydrophilic layer can be protected from water. Comparative Example 2 A solution having the same composition as in Comparative Example 1 was spin-coated at 2200 rpm onto an mm crucible wafer having a native surface of antimony oxide for 2 seconds. Comparative Example 3 In a vial 'Make a comparison example! The 2 〇〇 3 g solution used in the mixture was mixed with 0.052 g of a catalyst containing tri-n-butylborane which was mismatched with 1.3 moles of 3-methoxypropylamine. This solution was spin coated onto a 3 〇〇 mm 矽 wafer having a native surface of ruthenium dioxide at 22 rpm for 2 sec. Example 4 A film was prepared in the same manner as in Example 3 except that the film was exposed to glacial acetic acid vapor for 3 sec. in the manner described in Example 2 to cure the film. Comparative Example 4: Dimethyl propyl methoxy propyl phenyl sesquiterpene oxylate TPh methyl propyl ethoxylated propyl group diluted to 1% by weight in toluene at 2200 rpm

A solution of 〇.85丄 0.1 5 W grease was spin-coated onto a 3 〇〇mm 矽 wafer having a native surface of cerium oxide 127115.doc -45- 200844117 for 20 seconds. Example 5 In this example, 2.011 g of the solution from Comparative Example 4 was subjected to this σ with 0.014 g of a catalyst (three butyl butyl which was mismatched with a molar equivalent of 3-methoxypropylamine). The film of the resulting mixture was prepared in the same manner as in Comparative Example 4, but the film was cured in the same manner as described in Example 2 by exposing the film to glacial acetic acid vapor for 3 sec. Reference Example - Dielectric Constant Test The film thickness was measured using a J.A. W〇〇llam Co., Inc M-2〇〇〇D spectroscopic ellipsometer. The 2_parameter Cauchy model was used to fit the spectrum over a wavelength range of 50 〇 1 〇〇〇 nm. The dielectric constant is measured at i MHz using a parallel plate capacitor stacking method in which the test film is placed between the ceria surface of the wafer and the upper plate produced by sputtering an aluminum film. A Keithley 59 〇 cv impedance gain phase analyzer and a Hewlett Packard HP-4194A impedance/gain phase analyzer were connected to a 6-inch wafer sample station by Signatone Corp. Sample Thickness (A) Comparison of Refractive Index Dielectric Constant Example 2 7900 1.56 ^ ^ 3.38 ±0.17 Comparative Example 3 7995 1.55 ~ 3.56 ±0.18 Example 4 8216 1.55 3.63 ± 0.18 Comparative Example 4 2210 1.56 3.37 ± 0.16 Example 5 2289 1.56 ~ 3.25士 0·16 The results in this table confirm that system curing according to the methods described herein does not introduce significant changes in the refractive index or dielectric constant of a given resin. 127115.doc -46- 200844117 In other instances, other variations can be made in the compositions, compositions, and methods described herein without departing from the essential characteristics of the invention. The embodiments of the invention are specifically described herein, and are not intended to be limiting of the scope of the invention as defined in the appended claims. ’, 127115.doc 47-

Claims (1)

200844117 X. Patent application scope: 1 · A method for forming a cured film on a surface using a system, the system comprising (1) a radical polymerizable monomer, an oligomer or a polymer, (ii) an organoborane amine a complex, (iii) an amine-reactive compound and (iv) oxygen, wherein the components (i) to (iv) are distributed between the binder and the curing agent such that one of the components (1)) and (iii) Present in the binder and the other of components (ii) and (iH) is present in the curing agent, and components (ii) and (iii) are not combined in the presence of component (iv) prior to a curing step And wherein the method comprises: forming an uncured film of the substrate on the k surface, 2) exposing the product of step 1} to the curing agent, and optionally using the same or before step 2) Repeat steps 1) for different binders, or repeat steps 1) and 2) using the same or different binders and curing agents. 2. The method of claim 1, wherein the base comprises components (1) and (Η), and the curing agent comprises components (1) and (iii). 3. The method of claim 1, wherein the uncured film is by brushing, roller coating, spray coating, inkjet coating, die coating, spin coating, dip coating, solvent casting, vapor deposition, or liquid-liquid A deposition technique is formed on the surface. 4. The method of claim 1, wherein the curing agent is a liquid. 5. The method of claim 1, wherein the curing agent is a gas. 6. The method of claim 1, wherein the curing agent is a gas, and the uncured film is formed on the surface by spin coating. 7. The method of claim 1, wherein the curing agent comprises: (11) an organoborane amine complex or (iii) an amine reactive compound; and the binder comprises: 127115.doc 200844117 (in) amine reactivity a compound or (Π) organoborane amine complex; and wherein (1) a radical polymerizable monomer, a polymer or a polymer, and (iv) oxygen are present in the base binder or in the curing agent component Or in both the binder component and the curing agent component; and the film is formed on the surface by combining the respective binder components and their respective curing agent components. 8. The method of claim 1, wherein the binder comprises (1) a radical polymerizable monomer, a voucher or a polymer '(Π) organoborane amine complex, and optionally (iv) oxygen, and The curing agent comprises an amine reactive compound in the absence of oxygen. 9. A method of forming a film on a surface using a single encapsulation system, the system comprising (1) a radical polymerizable monomer, a polymer or a polymer, (π) an organic side amine amine complex, and (iii) An amine-reactive compound in which components (ii) and (111) are present in separate phases, and wherein the process comprises: forming an uncured film of the system on the surface, 2) by exposure to an inclusion chemistry The curing agent or physical process of the agent is to cure the product of step 1) by combining components (ii) and (111) in the presence of (iv) oxygen, and optionally, using the same or different systems prior to step 2). Step 丨), or repeat the steps 丨) and 2) using the same or different systems and curing agents. 10. The method of claim 9, wherein (π) the organoborane amine complex, (iii) the amine reactive compound or both are encapsulated by a capsule or carried by a solid phase and wherein The curing agent comprises a component capable of breaking, softening, melting, swelling or dissolving the capsule or the solid phase to allow the combination of components (ii) and (iii) or the physical process is selected from components (ii) and (iii) Shearing, irradiation, heating, cooling, pressurizing or depressurizing are combined in the curing agent. The method of claim 10, wherein the system comprises an emulsion, wherein the components (π) and (in) are present in separate phases of the emulsion, and wherein the curing agent comprises a component capable of destroying the emulsion The components which allow the combination of the components (1)) and (iii), the physical process is selected from shearing, irradiation, heating, cooling, pressurizing or decompressing which can destroy the emulsion and combine the component (1)) with (丨(1). The method of claim 9, wherein the uncured film is formed by brushing, roll coating, inkjet coating, spin coating, dip coating, solvent washing, vapor deposition, or liquid-liquid deposition techniques. 13. The method of claim 9, wherein the surface is a glass surface, a metal surface, a quartz surface, a ceramic surface, a stone surface, a dioxane: 矽: surface, - germanium surface, - gallium arsenide surface, - tantalum nitride surface, - semiconductor surface, a compound semiconductor surface, a vermiculite surface, an oxidized surface, a niobium oxide surface, a gold surface, a surface, a stack Surface, - silver surface, an anodized surface, a cast Surface, a titanium surface, a recording surface, a copper surface, a brass surface, a surface of a construction material, a Leizheng, a second surface, a surface of a slab, a polyethylene surface, a polypropylene surface, a polystyrene Ethylene surface, a syndiotactic polystyrene table ^ ^ m ^ such as - butyl butyl diester surface, a polycarbonate surface, a polyphthalamide surface, - polyphenylene axis surface, - epoxy resin Surface, surface = imine = resin surface, one gas polymer surface, - natural rubber " rubber surface, polyoxynized surface, - fluoropolyoxygen table - pressure sensitive tape surface, - pressure sensitive adhesive Surface, fiber surface, organic surface 'a rigid polymer surface, - flexible elastomer surface, liquid, ice, dry ice or a composite thereof. 127115.doc 200844117 14. If requested The method of 1 or 9, wherein the organoborane amine complex is a complex formed between an organoborane and an amine compound, wherein the organoborane is a boron compound containing an organic group of the formula BR"r" is a linear, branched, aliphatic group containing 1 20 carbon atoms An aromatic hydrocarbon group, or an organic hydrazine functional boron compound; and the amine compound is an organic amine compound, or is selected from the group consisting of an amino decane, an amine functional organic oxalate, an amine functional organic polyoxy siloxane, and an amine functional organic poly sesqui An amine-functional organic chopping compound of the group consisting of decane. 15. The method of claim 1 or 9 wherein the amine-reactive compound is selected from the group consisting of inorganic acids, Luxian, and tablets. Lewis acid), carboxylic acid, carboxylic acid derivative, carboxylic acid metal ruthenium, sp, ... #鼠酸醋...group of epoxide, acid chloride and %醯. 16·Method of claim 1 or 9 , ······································································································ And the ingredients (out) are present in pure liquid, d-liquid, solid or vapor form. 17. In the case of claim 1 or 9, the system further comprises one or more additional components of the k-free group of surface active _· k: dye; pigment; , water, wetting agent, right sprinkle, hexaqi body; supercritical fluid. aqueous solvent; ionic liquid, diluent; plasticizer; polymer; oligomer; - modifier; adhesion promotion · 'initial catalyst Combination; use # 'polymer, cross-linking agent and degree of volatility to reduce the volatility of the private, sputum, modified adhesive conductive filler. Door A &material; incremental filler; reinforced filler;真充{spacer; dopant; quantum dot; uv stabilizer; 127115.doc 200844117 nitrogen-acrylic bite stabilizer; ^^ 丨 · gas void reducer, 虱醌 · 'hindered amine; hair agent; acid receptor;浐 庐1 8 · As requested in items 1 or 9, Gans, 々\r, 达,,, 中中伤(1) is a free radical double Gt;^右承石夕 monomer, 聚聚土土1 Organic 2 request: r where the uncured thin contact is formed by spin coating on the far surface. C 20· —Cure curing thin, /, fine Formed by the method of any one of claims 1 to 19. 21. A surface, ^ a cured film formed by the method of any one of the items 1 to 19. 127115.doc 200844117 Representative diagram: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) f 127115.doc