MXPA97006307A - Film networks deposited from pla - Google Patents

Abstract

The present invention relates to a three-dimensional film network, comprising: a plurality of layers of plasma film of radio frequency discharge, said plasma film layers include a first layer and a second layer covalently linked, at least partially , said first layer, said second layer having a substantially ordered geometric structure, said structure includes a plurality of interstitial spaces dispersed substantially uniformly, said first layer includes a plurality of a first functional group, and said second layer includes a plurality of a second group function

Description

• PLASMA DEPOSITED LICENSE BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to functional film networks and, in particular, to layers of radiofrequency plasma film, deposited in sequence, having an open network structure, thus increasing the interstitial spacing. between the plasma film layers and provides access to the functional groups contained therein. Previous Technique The surfaces of polymeric, metal and ceramic materials are important in many applications. Often, these surfaces must be modified for a specific use. For example, the surfaces of medical devices implanted within the body must be biocompatible. Different methods are generally employed to modify polymer surfaces, as opposed to metal and ceramic surfaces. Several conventional methods of surface modification employ wet chemical processes. More recently developed are the energy methods of surface modification.

Each of these methods for each type of material is discussed below. The modification of wet chemical surfaces of metals and ceramics was achieved either by the formation of compounds, where metals and ceramics are mixed with the matrix resin or by coating these substances with organic coatings. A typical wet chemical approach to surface modifications of polymeric materials uses acids to treat and oxidize the surface. Other approaches employ the swelling of solvents and the penetration of topical coatings within the swollen surfaces. Upon evaporation of the solvent, the coating is incorporated into the top layer of the polymeric article. There are many problems associated with the use of solvents and other wet chemical methods to modify surfaces. For example, the use of wet chemical methods to modify surfaces can take several steps to be carried out. The chemicals used are often disordered, corrosive and toxic to both humans and the environment. There are several methods to modify the surfaces that are achieved in several stages. The chemicals used are often disordered, corrosive and toxic to both humans and the environment. There are often many stages, such as the reaction of application, rinsing and neutralization. It is not easy to change the stages if several chemical products are applied in sequence. Not all surface areas of the material to be modified are accessible to wet chemicals, such as blocked roads and other hidden surfaces. The monomers used must be reactive. The yields are low and the solvents can leave residues on the surfaces that cause contamination of this surface. Additionally, some wet chemical methods can also damage the surface that you are trying to modify. The surface composition of the polymeric materials is commonly modified by the admixture of additives in the polymer by volume, prior to manufacture and allowing surface active agents to migrate to the surface. The end groups of the polymer chain can also be modified with specific functional groups. The changes in polymer volume are thus minimized. The aggregate mobility of the terminal groups relative to the polymer backbone appears to facilitate the self-assembly of the molecular overlays by the surface active end blocks.

A major drawback of this method of surface modification is that there is a limit to the chemical functional density that can be incorporated without significantly altering the basic nature of the material. Energy processes (ie plasma) for surface modification of polymeric materials have also gained acceptance in a number of industries. In the plasma modification, the volume properties of the original polymer are retained, while chemically changing only the top 20 Á of the surface. Polymers, such as polypropylene, polystyrene, polyester, Teflon® and other commercially available polymers, have been modified using this method. For example, a polystyrene material, which normally does not contain nitrogen, can be modified using ionized ammonia gas in a radiofrequency (RF) field. This method commonly employs a vacuum chamber, elements to introduce a reactive gas, such as oxygen, ammonia or nitrous oxide, into the chamber and RF energy, as tools in the modification process. In the modification of the plasma surface, the gas, used to modify the surface of the polymer, is introduced into the vacuum chamber, which contains the surface to be modified. The gas is ionized with the use of RF energy, and this ionized gas interacts with the surface of the material. Ionized gases contain a mixture of highly reactive chemical species, which include free radicals, electrons, ions, and metastable reactive species. These species can easily break the chemical bonds on the surface of the polymeric materials and replace the desired chemical groups on the surface of the material. In this form, functional groups of carbonyl, carboxylic acid, hydroxy and amine have been incorporated within and thus become part of the polymeric surfaces. The design of the reaction chamber, the energy distribution, the excitation frequency and the gas dynamics are critical factors that influence the properties and efficiency of plasma reactions. An extensive work has been published that shows a direct correlation between the frequency of the excitation and the reactivity of the plasma. Unlike polymeric materials, metals and ceramics do not contain bonds that can easily be broken. The deposit of the plasma film offers a resource for modifying the surfaces of such materials. In this process, monomers consisting of polyatomic molecules are typically ionized with the use of RF energy. With the use of plasma polymerization (or the deposition of a plasma film), the functional groups can be incorporated into or deposited on any surface, including polymers, metals, ceramics and composites. The films deposited with the use of plasma polymerization are compositionally very different from the polymers formed in the volume processes of the polymeric materials, which use these same monomers. Materials, such as methane, propane and other saturated hydrocarbons, are commonly used to deposit polymerized plasma films on metals and ceramics. Additionally, the film can be comprised of amines, acids, methacrylates, glycidyls or mixtures, such as methane and amine, or methane and acid. When functional films are deposited on surfaces with the use of the plasma film deposit, the functional density, in most cases, is limited to that achieved by a monolayer. For example, 11% atomic nitrogen in deposited films of diaminocyclohexane on polystyrene is shown in Clinical Ma terials 11 (1992). This concentration is equal to the concentration of 1 nmoles / cm2 of primary amines on the surface or a coating of an amine monolayer on the surface. The difficulty with most single functional density monolayers is that there are a limited number of chemically reactive sites, which are available for interaction with the desired coating material, such as a biomolecule or the matrix resin of a compound. When the number of functional groups available on the surface of a substrate is limited, the benefits that can be achieved are also limited. In the case of compounds, the number of locations where the matrix resin is bound to the reinforcing materials is limited and the final strength of the composite material is also limited. In the case of the union of biomolecules, the lower functional densities decrease the amount of these materials that can be anchored on the surface. Often the binding of more than one biomolecule is desired to facilitate multiple performance attributes. In these cases, the amount of any given material that can be bound decreases and may be below the minimum threshold necessary for the desired performance. Polymerized plasma films have also been deposited with the use of acrylic acid, which produces films with a high density of functional groups.

The density is achieved by the formation of a linear polymer of lic acid on the surface. Additionally, soft plasma or pulse plasma with a variable duty cycle has been used to preserve the functional groups of films during the deposit using plasma polymerization. In addition to leaving only a single layer of monomer deposited, these methods also depend on the formation of long linear chains anchored to the surface, to generate high functional densities, which are convenient. In addition, in the plasma tank, the energy per mole of the monomer determines the number of broken links. At high energy and low concentration of monomers (hard plasma), most bonds are broken and retained less functional character. It is known that the applied energy, the frequency of the pulse, and the work cycle can all be varied to preserve the functional nature of the deposited film. In fact it has been found that with the use of high energy coupled with a lower duty cycle, a larger portion of the functional nature of the deposited film is maintained. A major drawback of these methods is that the deposited films are mechanically weak and can be easily worn and separated. Also, during the deposit of the plasma film, two competing processes occur. One is the deposit of the film and the other is the removal of the film that is deposited. The degree to which a process predominates is a function of both the conditions of the process that is used and the chemical nature of the film that is deposited. In an attempt to form sufficient functional density on the surface with the use of plasma polymerization, there is also an inherent risk that some of the film that is deposited will be worn and separated due to the process conditions that need to be employed. Even if sufficiently long chains of reactive groups can be deposited, the groups in the lower regions of the film are not easily accessible for interactions with the coating materials, as desired. For example, in allylamine deposited films, it has been found that a primary amine concentration on the surface is not as high as would be expected from the surface nitrogen content, as measured by the ESCA device. It has been concluded that perhaps some of these functional groups are buried and not accessible on the surface for reaction with the derivation reagents used in their analysis.

Finally, star polymers have been created using wet chemical methods. For example, the synthesis of the star polymers has been shown after the reaction of multifunctional isocyanates with the glycols. In the patents of E. U. A., Nos. 4,507,466, 4,588,120, 4,568,737, 4,587,329 and 4,694,064, here incorporated by reference, Tomalia et al. , reveals the synthesis of giant star polymers, commonly referred to as "dendrimers". In the mentioned patents, sequential reactions of methlate and ethylenediamine were achieved with the use of methanol as a solvent. Star polymers offer several advantages, that is, an area structure that provides physical strength and the ability to supply high chemical functional densities. There are several problems associated with star polymers. First, the conventional method of forming core molecules produces only small amounts of star polymers and requires several days to complete them. Second, large-scale synthetic methods are yet to be developed. Additionally, in order for star polymers (and dendrimers) to be useful in modifying material surfaces, these star polymers must be anchored to reactive sites on surfaces that use reactive cores as junctions. This type of anchoring has many problems. For example, it is difficult to join the dendrimers to the surface, because the point of anchorage of the nucleus is located in the center of the star. Thus, the anchor can only occur through a reactive group on the periphery of the dendrimer. Even in those cases, the substrate to which the dendrimer joins must be modified by some resource to allow the union. The steric obstruction of the star also limits the amount of dendrimers that can be attached to a surface. Additionally, it is easy to break this simple union. In biomedical applications, for example, with any object placed in the body, medical devices must have a biomédically fixed active agent a and that completely covers the surface. The dendrimers provide space between each joint, leaving areas on the surface of the substrate exposed to body fluids. Most plasma processing techniques employ the deposition of functional groups on the surface as the end point of their process, rather than as an intermediate link in a final structure. Therefore, professionals use conventional materials, such as oxygen, ammonia and other such materials, to deposit the functional groups on the surface. For example, the patent of E. U. A., No. 4,342,693, incorporated herein by reference, a vitreous film is deposited with the use of ionized siloxanes in a plasma. Using the methods of surface modification of the plasma, the ammonia is then used to supply amine functional groups on the surface. Other materials are subsequently linked to this functional group with the use of chemical methods. Accordingly, what is needed is (i) a film network deposited in sequence, comprising several layers of RF plasma and having a strong interface, (ii) a method for supplying networks of high density functional film, with controllable amounts of entanglement for the accessible functional groups; and (iii) resources for supplying large-scale RF plasma deposition, which can be achieved in a relatively short time, without employing wet chemical methods. COMPENDIUM OF THE INVENTION The present invention substantially reduces or overcomes all the problems associated with the prior art. The invention provides a novel functional, three-dimensional film network, and a rapid process for producing the same. The use of the networks of the three-dimensional film with the desired functional groups placed or in the periphery or both in the periphery and in the interstitial spaces of the networks of the invention, offer a resource to significantly increase the superficial functional density in a novel way . The spatial configuration of the network, and thus the access to the internal structure of the network, is controlled by the selection of which functional groups are deposited in sequence. The novel process of the invention uses the deposit in radiofrequency (RF) sequence, thus allowing the synthesis on a larger scale. Additionally, wet chemistry is not used, thus decreasing the production time from days to minutes. The present invention provides a "forest" or a "mushroom" with many functional groups in the periphery. The approach has not been previously achieved with the use of plasma deposit and is not easily obvious or feasible. In the present invention, the deposit in sequence is coupled with an infinite variation in the type and functionality of the monomers used to determine the final structure of the film that is deposited. These variables are used in addition to the variation of the conditions of the process to control the structure of the film. Therefore, it is an object of this invention to provide a functional film network comprising a plurality of RF plasma layers deposited in sequence. It is also an object of this invention to provide high density functional film networks, with controllable amounts of interlacing and interstitial spacing, which provide access for the functional groups therein contained. It is also an object of this invention to provide resources for large-scale deposits that can be achieved in a relatively short time. In accordance with the foregoing objects and others that will be mentioned and will become apparent below, the three-dimensional functional film network, in accordance with this invention, comprises a plurality of layers of radio frequency discharge plasma film. The plasma film layers include a first layer and a second layer, disposed immediately adjacent to the first layer. The first layer includes a plurality of first functional groups and the second layer includes a plurality of second functional groups.

An advantage of this invention is that it provides a film network structure having an increased interstitial spacing, with reactive functional groups disposed within the network structure. These reactive sites can act as ionic binding sites to secure the biomolecules within the networks. DETAILED DESCRIPTION OF THE INVENTION The plasma polymerization technique of the present invention offers a unique method for forming functional network structures. In general, one layer of a class of monomers is alternated with a layer of another class of monomers. The specific monomer selected depends on the type of functional surface that is desired. In some cases, a mixture of gases is used to obtain the desired surface chemistry. The selected monomer class dictates the type and density of the network that is developed. Examples of functional groups that can be incorporated into the network structure of the present invention include, but are not limited to, epoxy (oxiranyl), amino, carboxy, hydroxy, isocyanate, amido and sulfhydryl groups. Sources of monomers of epoxy or oxiranyl functional groups include but are not limited to, allyl glycidyl ether, glycidyl methacrylate, glycidyl isopropyl ether, glycidyl butyrate, 3-glycidoxy-pyrrolimethoxysilane and mixtures thereof. Sources of monomers of alcohol functional groups include, but are not limited to, oxygen; Water; saturated alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol and its isomers, butyl alcohols and their isomers and saturated alcohols and aryl alcohols, such as benzyl alcohol; unsaturated alcohols, such as allyl alcohol, vinyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and other similar compounds; glycols and ethers, such as ethylene glycol, propylene glycol, tetrahydrofuran, diethylene glycol dimethyl ether, tetraethylene glycol dimethacrylate and triethylene glycol dimethyl ether; mixtures of the above compounds; and mixtures of hydrocarbons such as methane or ethylene and the classes of compounds named herein. Sources of isocyanate functional group monomers include, but are not limited to, allyl isocyanate, toluene-2,4-diisocyanate, 1,4-diisocyanatobutane, ethyl isocyanate, hexamethylene diisocyanate, toluene-2,6-diisocyanate and its mixtures Sources of monomers of triazine functional groups include, but are not limited to, acrylonitrile, 2,4-diamino-6-methyl-1,3,5-triazine, 1-trimethylsilyl-2,4,4-triazole and mixtures thereof . Sources of monomers for amine functional groups include, but are not limited to, unsaturated amines, such as allylamine and vinyl-amine; primary amines, such as methylamine, butyl amine, propylamine, hydroxyethyl amine and other alkyl amines; alkane diamines, such as ethylenediamine, 1,3-diaminopropane, 1,4-diamino-butane, 1,5-diamino-pentane, 1,6-diaminohexane, 1,7-diamino-heptane, 1,8 -diamino-octane; polyalkylene polyamines, such as diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylene tetraamine, tripropylenetetraamine, tributylene tetraamine, N, N'-bis (2-aminoethyl) -1,3-propanediamine, bis (3-aminopropyl) amine; aminosilanes, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl-methyldiethoxysilane, 3- (3-aminophenoxy) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, hexamethyldisilazane, and other similar compounds; heterocyclic amines, such as ethylene-amine, piperidines, pyrroles and pyrrolidines; aromatic amines, such as aniline; and various other amines and amino compounds, such as mercaptoethylamine, acrylonitrile, acetonitrile, butyronitrile and 1,4-diaminocyclohexane, mixtures of the above compounds; and mixtures of hydrocarbons such as methane or ethylene and the classes of amino compounds named herein. Sources of monomers for the carboxylic acid functional groups include, but are not limited to, oxygen, carbon dioxide and compounds such as acetic acid, propionic acid, butyric acid, 2-methyl-propionic acid, n-pentanoic acid, 4-methyl-butanoic acid, n-hexanoic acid; unsaturated acids, such as acrylic acid, methacrylic acid, 2-butenoic acid and cinnamic acid; mixtures of the above; and mixtures of a hydrocarbon, such as methane or ethylene and the classes of compounds named herein. Sources of monomers for sulfhydryl groups include, but are not limited to, compounds such as 3-sulfhydryl-propene, hydrogen sulfide, 2-sulfhydrylethylene, and mixtures thereof. Sources of monomers for amido functional groups include compounds such as acrylamide and N, N-dimethylacetylamide. Additionally, the amido groups can be formed by neutralizing the terminal amine with an acid or terminal carboxylic acid function with an amine. Other types of monomers that can be used in building the network structure, regardless of their ability to contribute a functional group within or at the periphery of the network structure include, but are not limited to, compounds such as allyl acetate , allyl methacrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, tertiary butyl acrylate, butyl methacrylate, cyclohexyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate. If multifunctional acrylates are used, such as ethylene glycol dimethacrylate, these monomers will provide additional sources of branching in addition to the amines. Although specific compounds have been named that can be used to form the desired functional groups in the network of the present invention, it will be understood that any material that can be introduced into the RF plasma reaction chamber, or as a vapor or as a aerosol mist, which can be ionized subsequently by the application of RF energy, and which belongs to the family of the compounds named herein, are effective sources of such functional groups. Table 1 lists pairs of reactive monomers that can be employed within the scope of this invention to initiate the extended chains of functional film networks. For example, a plasma film layer having a functional group selected from the first column will form a new layer in the network of the film if it reacts with a layer of plasma film having its functional group pair in the second column . In the reaction No. 1, a previous layer having an amine is reacted with monomers that will deposit ethylene functional groups, producing two network branches in the new layer of the network. TABLE I Reactive Pairs Starting Extended Chains Reaction Terminal Function For Surface or Chain with Produce 1. -NH2 CH2 = CHX CH2CH2X • < CH2CH2X 2. -NH, -, R? O = C < -R, -N = C < R; 3. -COOH NH, R -CONHR 4. -COOH NHR, -CO-NR, R2 5. -COOH NH2 (CH2) nNH2 -CONH (CH2) nNH2 6. -COOR NH2R -CONHR 7. -COOR NHR, - CO-NR, R2 8. -COOR NH2 (CH2) nNH2 -CONH (CH2) pNH2 9. -CHO NH2R -CH = NR 10. -NCO NH3 -NHCONH2 11. -NCO NH2R -NHCONHR 12. -NCO NHR, - NIICO-NR, TABLE I (Continued) Reactive Couples Sue Initiate Extended Chains Reaction Terminal Function For Surface or Chain with Produce 13. ° RNH2 OH -H-- CH2 -CH-CH2NHR 14. NHR,) H - H- -CH2 - H-CHjNR, R?, 2 . ROH OH -di-- CH2 -CH - CH2OR 17. ROH H2 -di- -CH2 -CH-CH2OR 18. -OH-CH2-CHR 19. -OH RSO2Cl -OSO2R 20. -N-a | N 21- -SH where X is -COOH, -COOR, -OH, -NH2, -NH2R, -NCO, and R, Ri and R2 represent aliphatic or aromatic hydrocarbons, which can be introduced into an RF plasma reaction chamber, or as a vapor or an aerosol mist that can subsequently be ionized by the application of RF energy. Additionally, the R, R ^ and R2 groups may contain additional functional groups to allow subsequent branching. The reaction illustrated in line 5 of Table 1 changes a terminal group of -COOH to a terminal group of -NH2, with a variable length (n) of chain extension. Reaction No. 8 changes a terminal group from -COOR to a terminal group of -NH2, with a variable length (n) of chain extension. The reaction of line 19 is used as a wet chemical step before fixing the biomaterial. In reaction No. 20, the source of triazine is acrylonitrile. According to a preferred embodiment of the invention, the construction of the film network occurs as follows: a polymerized initial film layer of plasma is first deposited on the substrate. This initial layer can be selected from the class of compounds, such as ammonia, unsaturated amines, primary amines, aliphatic diamines, polyalkylene polyamines, heterocyclic amines, nitriles, pyrroles, pyrrolidines, aminosilanes and mixtures thereof, so that the functional group of amine is formed on the surface. The initial layer may also comprise oxygen, water, carbon dioxide and mixtures of hydrocarbons and the aforementioned compounds. The second deposited plasma layer is applied using the class of compounds consisting of: (i) saturated carboxylic acids, such as acetic acid, propionic acid, butyric acid, 2-methylpropionic acid, n-pentanoic acid, -methyl-butanoic, n-hexanoic acid, and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid and similar unsaturated acids; or (ii) esters, such as methyl acrylate, methyl methacrylate, glycidyl methacrylate and a similar class of compounds; or (iii) keto-esters, such as carbonyl-bis-3, 3'-methyl propionate; or (iv) oxygen and carbon dioxide; (v) mixtures of hydrocarbons and the class of compounds named in groups (i) to (iv). The second layer can also be constructed using monomers consisting of a mixture of compounds chosen from groups (i) and (ii). Of the three classes of compounds mentioned, it is preferred that the monomer for the second layer be selected from the class of compounds described in groups (i) and (ii). The network of deposited plasma film can also be initiated by depositing a film using the monomers of the class of compounds consisting of: (i) saturated carboxylic acids, such as acetic acid, propionic acid, butyric acid, acid 2-methyl-propionic, n-pentanoic acid, 4-methyl-butanoic acid, n-hexanoic acid and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid and other similar materials; or (ii) esters such as methyl acrylate, methyl methacrylate, glycidyl methacrylate and other similar materials; or (iii) oxygen and carbon dioxide; or (iv) mixtures of hydrocarbons and the class of compounds named in groups (i) to (iii). This first layer can also be formed of a mixture of monomers described in groups (i), (ii) and (iv) or the mixtures described in group (v). The second layer of polymerized plasma film is then deposited from the group consisting of ammonia, unsaturated amines, primary amines, aliphatic diamines, polyalkylene polyamines, heterocyclic amines, nitriles, pyrroles, pyrrolidines, aminosilanes and their mixtures or mixtures of hydrocarbons and the class of amino compounds named herein, as described above. Using a combination of materials, as an example, the following Steps 1-5 illustrate the growth, step by step, of the functional film network over polystyrene, according to the invention. The process also illustrates how the overall structure of the network is achieved. The process of deposit in sequence allows the evaluation of functional character of each stage. The use of difunctional diamines, such as ethylene diamine (see Formula 1) or 1,6-hexanediamine with the allylic or aliphatic acids, such as acrylic acid, will provide a network according to the final Steps 4 and 5. , as illustrated in the following Formulas 7 and 8. The objective of Stage 1 below is to provide a set of reactive sites for branching. Any monomer in the first column of Table 1 can be used in the first stage. In the method shown, an amine having a R group is polymerized from plasma, producing many amine functional groups on the polymeric surface for the next level of branching. The R group of the amine is generally interrupted, leaving the R? _ And R2 groups as part of the functional groups attached to the surface, or leaving unattached in the reaction chamber.

Stage 1 Formula 1 Formula 2 In the next step 2, a matching pair is selected from the second column of Table I. During plasma deposition, the matching partner will now join an amine functional group, previously attached to the surface during Stage 1 In Stage 2 below, an acrylic acid is shown. The two hydrogen bonds in each amine are easily broken. The process can be adjusted so that there is more than one carboxylic acid deposited. For example, if the pulse plasma is used, as illustrated in the next Step 2, two carboxylic acid units will be bound to the nitrogen, creating two branches.

Stage 2 -R, NH2 + 2CH2 = CHCOOH Plasma, Formula 2 Formula 3 Formula 4 The purpose of Stage 3 is to provide another point for branching. For example, as illustrated below, an ethylene diamine plasma is again employed. By the reaction of these amines with carboxylic acid functional groups, deposited in Step 2, amides are supplied. At the other end of each amine is an amine that provides another opportunity to provide two branches.

Stage 3 Plasma Formula 4 Formula 1 Formula 5 Stages 1-3 provide the first generation of the movie network. This first layer has a strong interface with the surface, as opposed to other networks formed of long linear branches and the star polymers join in the nuclei to a surface. The strong interface of the present invention covers the entire surface and is not removed during the additional layer deposits. In addition, there is no problem of steric obstruction when additional functional groups are attached.

When the monomers illustrated in Steps 1-3 are used, the surface layer will have many functional amines. Branching is not achieved when the amines are deposited. However, when the carboxylic acids are deposited on the amine functional groups, branching is possible. As illustrated in the following Steps 4 and 5, the sequence deposit method of the invention is employed to produce a second generation film network. In Step 4, the two hydrogen bonds in each amine are again easily interrupted, as previously shown in Step 3. The process can be adjusted so that more than one carboxylic acid is deposited. For example, if the pulse plasma is used, as illustrated in the following Step 4, two more carboxylic acid units will bind to the nitrogen, providing four branches for each amine functional group attached to the surface. Stage 4 O, R2CNHR, NH2 R.NP + 4CH2 = CHCOOH Plasma R2CNHR, NH2 O Formula 5 Formula 3 Formula 6 Stage 5 + 4NH2RNH, _i Plasma Formula 6 Formula 1 Formula 7 The sequence deposit process can be continued through several iterations until the desired final network structure is achieved. The process is terminated only when the desired thickness of the film network has been deposited on the selection substrate and the density of the target chemical functional group has been incorporated into the network. A structure starting with a trifunctional amine on the surface is illustrated below in Formulas 8-11. Using a tetrafunctional monomer, such as triethylenetetraamine, NH2CH2CH2NHCH2-CH2NHCH2CH2NH2, cleavage of the molecule can occur in a plasma at the location shown by the dotted line. In a manner analogous to the deposit of a diamine, and as shown below, a surface with three attachment points can be obtained, one in the secondary amine and two in the primary amine site.

H j-R.N-R.NH, + 3CH2 = CHCOOH Plasma Formula 8 Formula 3 OH Plasma OR Formula 9 Formula 1 O R2CNHR, NH2 Plasma Formula 10 Formula 3 Formula 11 A structure with the linear amine chain as the starting group is shown in the following Formulas 12-15. When a monomer, such as allylamine, is used as the starting monomer, a pulse plasma can be used to form a linear chain consisting of several amine groups, each of which can act as a branching site. .

NH2 NH2 NH2 Plasma NH2 + 8CH2 = CHCOOH Formula 12 Formula 3 0 Formula 13 Formula 1 m or H When the acrylonitrile is used as the monomer, a triazine structure can also be deposited (not shown). Acrylonitrile offers additional opportunities to form highly branched networks of the present invention, since a trazine structure offers more than two junctions for branching, when this structure is anchored on the surface. By the use of various combinations of functionalities of the monomers employed, the density of the network structure can be controlled. For example, in the process defined by Formulas 1-7, in Step 1, an amine monomer may be employed. In Step 2, an acidic monomer can be used, such as acrylic acid, methacrylic acid, propionic acid and hexanoic acid. Another class of monomers that can be employed within the scope of the invention, as illustrated in Step 2, are acrylates. Monomers of this class include, but are not limited to, methyl acrylate and methyl methacrylate. The hydrocarbon end of the acid or acrylate is replaced by each hydrogen in the amine to form an amide. Applicants have found that monomers with higher carbon numbers in their skeleton will result in a network structure having a loose network, thus increasing the interstitial spacing between the plasma film layers, while those with shorter carbon chains will result in tighter networks. Additionally, applicants have found that when monomers with more than two functional groups are used, a much higher level of branching can be obtained, thus controlling the structure of the network. The following examples, according to the invention, illustrate the use of different functional densities and different skeletal chain lengths to provide a loose type lattice structure, thus increasing the interstitial spacing between the plasma film layers compared to other films, to provide access to the functional groups contained therein. The construction of the film network can, as an example, be initiated with a tank using triethylenetriamine as the monomer. This monomer can then be split into the centrally placed CH2-CH2 bond, shown as a dotted line in the following Formula 16.

NH2CH2CH2NHCH2-CH2NHCH2CH2NH2 Formula 16 The surface of the substrate resulting from a plasma deposit using triethylenetriamine is shown below in Formula 8. Step 1 Plasma + H2NCH2CH2NHCH2CH2NHCH, CH7NH, Formula 16 Formula 8 The next layer is then added in Stage 3, as follows: Stage 2 RNHR, NH2 + 3CH2 = CHCOOH, Plasma, Formula 8 Formula 3 OR R2COH OR R2COH R, N-R, N "R2COH O Formula 9 In this stage, several options are available. Formula 9 can react with Formula 1 to deliver Formula 10, or Formula 9 can react with a trifunctional amine, such as diethylenetriamine, represented by the following Formula 17, to deliver Formula 18.

Plasma Formula 9 Formula 17 Formula 18 The density of the chemical functional group of Formula 18 is very different from that of the chemical functional group of Formula 10, which was also derived from Formula 9. Thus by the mixing and matching of reactive functionality ("monofunctional," "difunctional") , "" trifunctional ", etc.) of the monomer used, plasma deposited film networks with different morphologies and densities can be supplied. Although multifunctional amines and acrylic acid have been employed to illustrate the construction of the deposited plasma film network, it will be apparent to those skilled in the art that the starting film can be constructed of any of the monomers described above and combined with the appropriate reactive pair, shown in the second column of Table I.

For example, glycidyl methacrylate, Formula 19, can be employed in the first stage of depositing the network construction process, to provide a surface with the epoxy reactive group, Formula 20 (often referred to as the oxirane group). This epoxide group can now be reacted with an amine, for example, Formula 1, and as suggested in Table 1, to provide the following Formula 23. The use of a keto-ester, illustrated by Formula 22, is another branching source.

-R-CH-CH2 Formula 19 Formula 20 Formula 20 Formula 1 Formula 21 Plasma Formula 21 Formula 22 Formula 23 R3 and R4 can be any aliphatic or aromatic group, the aliphatic groups are preferred. R3 and R4 can include a reactive chemical functional group and these sites can be used to continue forming the film network. Thus, the construction of the plasma deposited film network can be achieved by using appropriate pairs of reagents, described in Table I, without limitation. When a network that is of the open type (i.e., increased interstitial spacing between the layers of the plasma film) is desired, the monomers can be selected so that the central chain can be represented by the notation (H2) n, where "n" is big enough. As illustrated below, when the value of six (6) is chosen for "n" in the amine, represented by Formula 24, and a value of two (2) is selected for "n" in the allylic acid monomer, Formula 26, allylacetic acid, Formula 29, is produced in Step 2.

Stage 1 Plasma NH2 (CH2) 6NH2 -CH2CH2CH2NH2 Formula 24 Formula 25 Stage 2 CH2CH2CH2NH2 + 2CH2 = CHCH2CH2COOH Plasma, Formula 25 Formula 26 Formula 27 Stage 3 OR 2NH2 (CH2) 6NH2 Formula 27 Formula 24 O Plasma Formula 28 As illustrated by the structure shown in Formula 28, the film network of the present invention has a loose network, thereby increasing the interstitial spacing between the plasma film layers, as compared to the interlacing density and the interstitial spacing obtained when the Ethylene diamine and acrylic acid are reacted using the same three stages illustrated by Formula 29. It will be apparent to those skilled in the art that by the use of monomers with different lengths of the central chain and different reactive functionalities, the morphology and The functionality of the chemical group of the plasma deposited film network can be adjusted in many ways.

Formula 29 In conventional wet chemical methods, used to form the star polymers, the growth of the structure occurs in a geometric manner, as illustrated by the following chemical process: Formula 30 Formula 31 ,, OOH Generally, conventional star polymers can not be manufactured in high volumes by the method shown in the above Formulas 3033. Additionally, the union of these materials to surfaces is a laborious process. However, using the method of the present invention, the surface of any material can have a highly branched film network, covalently bound to the surface within minutes. Additionally, using the plasma film deposition technique of the present invention, the rate of growth of the network can be controlled so that it is somewhat different from the strictly geometric one. For example, if in the second tank stage, previously described in Formulas 3 and 4, and in greater detail in Example 1 below, the process of depositing acrylic acid is adjusted so that only a part of the amines reacts, They achieve two objectives. One is that the network structure having an open network is supplied, thus increasing the interstitial spacing between the layers of the plasma film, as compared to the other films. The other is that some reactive functional groups, within the network structure, they are retained rather than having all the functional groups in the periphery. According to the invention, a method for preventing the reaction of all functional groups uses short deposition times, which only partially cover the previously deposited film. Another method for controlling the interlacing density and the interstitial spacing of the network structure and retaining the functional reactivity within the network is shown in the following formulas 34-37. Here, the process conditions are selected so that not all functional sites will become growth sites. For example, by decreasing the deposit time in the second stage of the process, which, in the example is the deposit of acrylic acid, from the normal process time of 2 minutes to 30 seconds, many of the amine functional groups deposited in The first layer is left unreacted. Another method of reducing the reaction between the amine in the first layer and the acrylic acid that is deposited, is to reduce the flow of the acrylic acid, while maintaining the same process time. As shown in Formula 35 below, if not all functional sites become growth sites, some reactive functional groups remain within the interstices of the network (shown in a circle).

OR Formula 34 Formula 3 Formula 35 NH2RNH, Plasma Formula 35 Formula 1 OR Formula 36 Formula 3 Formula37 Another method to achieve a network of deposited plasma film with chemical functional groups in the interstices of the film, can be illustrated by the following process scheme. In this case, monomers with the epoxy functional group, such as Once the three-membered ring is opened in the second stage, during the deposition of an amine, the epoxy group leaves behind a chemical functional group. For example, as previously shown in Formula 19, glycidyl methacrylate can be employed in the first stage of depositing the network construction process, to provide a surface with the epoxy reactive group, Formula 20 (often referred to as oxirane group). As shown in the following Formulas 20-39, this surface with the epoxy reactive group, Formula 20, can now be reacted with an amine, e.g., Formula 1, and as suggested in Table I, to provide the following Formula 21. As illustrated in Formula 21, a hydroxyl group is left near the surface and an amine is the terminal group. Formula 21 is also reacted with Formula 19, glycidyl methacrylate, to deliver Formula 38, a surface containing two reactive epoxy groups. This can again react with an amine to supply, Formula 39, a surface with a network of deposited plasma film having functional groups within the interstices of the layers of the film.

HR, NH2 Formula 20 Formula 1 Formula 21 Plasma Formula 21 Formula 19 Plasma Formula38 Formula 1 Formula 39 In this way, the hydroxy chemical groups can be incorporated into the interstices of the plasma deposited film network, while the peripheral chemical groups can be of a completely different category, such as an amine, by the selection of the monomer used in the stage of completion of the deposit process » Another method of creating chemical functional groups in the interstices of the plasma deposited film network is shown in the scheme illustrated in the following Formulas 1-41. In this process, the network construction begins with the deposit of an amine, Formula 1, which is then reacted with a ketone, Formula 40, where the ketone group is located, so that the chemical groups on either side of the ketone group They are of different length and are terminated with a chemical functional group. When this ketone is now reacted with another monomer (not shown), the longer arm will react more easily, while the shorter arm may become protected by the steric obstruction, thus remaining intact within the film structure.

Formula 2 Tormula 40 Formula 41 where n2 »n ^ It is clear from these descriptions that, by selecting particular monomer / process stage combinations, appropriate for the particular goal in mind, a vast array of structural morphologies, chemical group densities and chemical functional group locations are can achieve in the plasma deposited film networks described. The following detailed example illustrates a method for depositing a two-dimensional functional film network, according to the invention.

E 1 1 A 4.0-liter plasma reaction chamber was used, with internal electrodes driven by a 200-watt RF generator, operating at 13.56 MHz. The reaction chamber was connected to an Alcatel 2020 CP vacuum pump with a pumping capacity of 453 liters / minute. A manual throttle valve was used to control the pressure of the reaction chamber, independent of monomer flow. Step 1: Plasma polymerization of ethylene diamine. The ethylene diamine was fed to the reaction chamber by evaporation of the ethylene diamine contained in an Erlenmeyer flask, which is maintained at 30 ° C. Plasma polymerization is conducted at a power setting of 90 watts and a reaction chamber pressure of 420 mTorr. The flow and, therefore, the residence time of the monomer within the reaction chamber was controlled by the throttle valve. This valve was adjusted so that the actual pressure inside the reaction chamber was 480 mTorr. The time of the process was 3 minutes. These films were deposited on polystyrene bands of 120 μm. The chemical analysis using the nihydrin test for the primary amines showed a concentration of 1: 1 μmoles / g. The surface area of these strips was 476 cm2 / g. The measured amine concentration is equal to the surface concentration of 4 nmoles / cm2. This surface density is equivalent to a monolayer of functional groups on the surface. Stage 1: Plasma polymerization of acrylic acid. In this step, a polymerized plasma film of acrylic acid was deposited on top of the amine film deposited in Step 1. The acrylic acid was fed to the reactor by bubbling helium through the monomer contained in an Erlenmeyer flask. The power was set at 100 watts, the helium flow rate was 15 cc / min and the pressure was 500 mTorr. The acrylic acid was kept in a water bath, whose temperature was controlled at 45 ° C. The flow and, therefore, the residence time of the monomer in the reaction chamber was controlled by the throttle valve. This valve was adjusted so that the actual pressure in the reaction chamber was 580 mTorr. The plasma was pulsed at 10 Hz and a 10% duty cycle was used. The deposition of the acrylic acid in the untreated polystyrene bands was 180 μm, under these conditions and in a process time of 4 minutes a functional density of 2.1 μmol of acid groups / g resulted. This functional density was transferred to 6.8 nmoles / cm2. Since we already have approximately 2.3 nmoles / cm2 of amines on the surface and each amine group can add two groups of acrylic acid, the processing time for this stage is 3 minutes. It is assumed that the previously determined functional density was retained in Step 2. Since each amine group can accommodate two groups of acrylic acid, Step 2 will incorporate 2.2 μmol / g of acid groups on the surface. Step 3. Plasma polymerization of ethylene diamine. A polymerized plasma film of the ethylenediamine was deposited using the same conditions described in Step 1. Step 3 deposited an amine functional group at each functional acid site deposited in Step 2. This results in a final amine concentration of 2.2 μmol / g of the amine functional group. Chemical analysis using a ninhydrin test for the primary amines showed a concentration of 2.8 μmoles / g of amine functional groups on the surface. While the foregoing detailed description has described various combinations of sequence deposits of particular classes of monomers for a three-dimensional functional film network, in accordance with this invention, it will be understood that the foregoing description is illustrative only and not limitative of the disclosed invention. Particularly, a device and a method according to this invention are included, which produce a loose type functional film network, thus increasing the interstitial spacing between the layers of the plasma film compared to other films. The network, according to the invention, has unique conduction properties, which always allow access to functional groups within the interstices of the network. It will be appreciated that various methods for producing various compounds are within the scope and spirit of this invention.

Claims (68)

1. CLAIMS 1. A three-dimensional film network, which comprises: a plurality of radiofrequency discharge plasma film layers, these plasma film layers include a first layer and a second layer, disposed immediately adjacent to the first layer; this first layer includes a plurality of first functional groups; and the second layer includes a plurality of second functional groups.
2. 2. The three-dimensional film network, according to claim 1, including interstitial spaces, disposed within the network, which provide access to the layers of the film.
3. 3. The three-dimensional film network, according to claim 1, wherein the first and second layers are, at least partially, covalently linked.
4. 4. The three-dimensional film network, according to claim 1, wherein the first functional group comprises an amine functional group.
5. 5. The three-dimensional film network, according to claim 1, wherein the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, isocyanate, hydroxy and sulfhydryl.
6. 6. The three-dimensional film network according to claim 1, wherein the first functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
7. 7. The three-dimensional film network, according to claim 1, wherein the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
8. 8. The three-dimensional film network, according to claim 7, wherein the second functional group is reactive with the first functional group.
9. 9. The three-dimensional film network, according to claim 1, wherein the film network includes a double branched spatial configuration, between adjacent film layers.
10. 10. The three-dimensional film network, according to claim 1, wherein the three-dimensional network includes a triple branched spatial configuration, between the adjacent film layers.
11. 11. The three-dimensional film network, according to claim 1, wherein the three-dimensional film network includes a quadruple branched spatial configuration, between the adjacent film layers.
12. 12. The three-dimensional film network, according to claim 1, wherein the three-dimensional film network includes a heterocyclic ring spatial configuration, between the adjacent film layers.
13. 13. The three-dimensional film network, according to claim 1, wherein the three-dimensional film network includes a spatial configuration of linear chain, between the adjacent film layers.
14. 14. The three-dimensional film network, according to claim 13, wherein the linear chain includes a third functional group, selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
15. 15. A network of three-dimensional film, which comprises: a plurality of radiofrequency discharge plasma film layers, this plurality of plasma film layers include alternative pairs of a first layer and a second layer, disposed immediately adjacent to the first layer; this first layer, which includes a plurality of first functional groups; and the second layer includes a plurality of second functional groups.
16. 16. The three-dimensional film network, according to claim 15, including interstitial spaces disposed within the network, which provide access to the film layers.
17. 17. The three-dimensional film network, according to claim 15, wherein the first and second layers are, at least partially, covalently linked.
18. 18. The three-dimensional film network, according to claim 15, wherein the first functional group comprises an amine functional group.
19. 19. The three-dimensional film network, according to claim 15, wherein the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, isocyanate, hydroxy and sulfhydryl.
20. 20. The three-dimensional film network, according to claim 15, wherein the first functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
21. 21. The three-dimensional film network, according to claim 15, wherein the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
22. 22. The three-dimensional film network, according to claim 21, wherein the second functional group is reactive with the first functional group.
23. 23. The three-dimensional film network, according to claim 15, wherein the film network includes a double branched spatial configuration, between adjacent film layers.
24. 24. The three-dimensional film network, according to claim 15, wherein the three-dimensional network includes a triple branched spatial configuration, between the adjacent film layers.
25. 25. The three-dimensional film network, according to claim 15, wherein the three-dimensional film network includes a quadruple branched spatial configuration, between the adjacent film layers.
26. 26. The three-dimensional film network, according to claim 15, wherein the three-dimensional film network includes a spatial configuration of heterocyclic ring, between the adjacent film layers.
27. 27. The three-dimensional film network, according to claim 15, wherein the three-dimensional film network includes a spatial, linear-chain configuration between the adjacent film layers.
28. 28. The three-dimensional film network, according to claim 27, wherein the linear chain includes a third functional group, selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
29. 29. A substrate structure, which includes: a substrate, which has a surface on it; Y a plurality of radiofrequency discharge plasma film layers, deposited in sequence on the surface of the substrate, these plasma film layers include a first layer and a second layer, disposed immediately adjacent to the first layer, this first layer includes a plurality of first functional groups, and the second layer includes a plurality of second functional groups.
30. 30. The substrate structure, according to claim 29, including interstitial spaces disposed within the film layers.
31. 31. The substrate structure according to claim 29, wherein the first and second layers are, at least partially, covalently bonded.
32. 32. The substrate structure, according to claim 29, wherein the first functional group comprises an amine functional group.
33. 33. The substrate structure according to claim 29 in which the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, isocyanate, hydroxy and sulfhydryl.
34. 34. The substrate structure according to claim 29 in which the first functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
35. 35. The substrate structure according to claim 29 wherein the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
36. 36. The substrate structure, according to claim 35, wherein the second functional group is reactive with the first functional group.
37. 37. The substrate structure, according to claim 29, wherein this substrate structure includes a double branched spatial configuration, between adjacent film layers.
38. 38. The substrate structure, according to claim 29, wherein this substrate structure includes a triple branched spatial configuration, between the adjacent film layers.
39. 39. The substrate structure, according to claim 29, wherein this three-dimensional film network includes a quadruple branched spatial configuration, between the adjacent film layers.
40. 40. The substrate structure, according to claim 29, wherein this three-dimensional film network includes a spatial configuration of heterocyclic ring, between the adjacent film layers.
41. 41. The substrate structure, according to claim 29, wherein this three-dimensional film network includes a spatial configuration of linear chain, between the adjacent film layers.
42. 42. The substrate structure, according to claim 41, wherein the linear chain includes a third functional group, selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
43. 43. A method for sequentially depositing a three-dimensional functional film network on a substrate, which comprises the steps of: placing a substrate, having a surface thereon, on a radiofrequency plasma discharge apparatus; inserting a first plasma medium into the radiofrequency plasma discharge apparatus, this first plasma means comprises a first compound selected from the group consisting of ammonia, unsaturated amine, primary amine, aliphatic diamine, polyalkylene polyamine, aminosilane, heterocyclic amine , nitrile, pyrrole, pyrrolidine, saturated carboxylic acid, unsaturated carboxylic acid, carboxylic ester, keto-ester, and mixtures thereof; subjecting the first plasma medium to a first radiofrequency electric field, whereby a first layer of plasma film is deposited on the surface of the substrate, this first plasma film layer includes a plurality of first functional groups; inserting a second plasma medium into the radiofrequency plasma discharge apparatus, this second plasma means comprises a second compound, selected from the group consisting of ammonia, unsaturated amine, primary amine, aliphatic diamine, polyalkylene polyamine, aminosilane, amine heterocyclic, nitrile, pyrrole, pyrrolidine, saturated carboxylic acid, unsaturated carboxylic acid, carboxylic ester, keto-ester, and mixtures thereof; subjecting the second plasma medium to a second radiofrequency electric field, whereby a second layer of plasma film is deposited on the surface of the substrate, this second plasma film layer includes a plurality of second functional groups.
44. 44. The method according to claim 43, which includes the further step of continuing the sequential deposits of the first and second plasma film layers until a predetermined network of plasma film is deposited on the substrate.
45. 45. The method, according to claim 43, wherein the first plasma means comprises oxygen.
46. 46. The method, according to claim 43, wherein the first plasma means comprises carbon dioxide.
47. 47. The method, according to claim 43, wherein the first plasma means comprises water.
48. 48. The method, according to claim 43, wherein the first plasma means comprises a mixture of a hydrocarbon and the first compound.
49. 49. The method according to claim 43, wherein the second plasma means comprises oxygen.
50. 50. The method, according to claim 43, wherein the second plasma means comprises carbon dioxide.
51. 51. The method according to claim 43, wherein the second plasma means comprises water.
52. 52. The method, according to claim 43, wherein the second plasma means comprises a mixture of a hydrocarbon and the first compound.
53. 53. The method, according to claim 43, wherein the first plasma means comprises a third compound, selected from the group consisting of ammonia, unsaturated amine, primary amine, aliphatic diamine, polyalkylene polyamine, aminosilane, heterocyclic amine, nitrile, pyrrole, pyrrolidine, and their mixtures.
54. 54. The method according to claim 43, wherein the first plasma means comprises a mixture of a hydrocarbon and the third compound.
55. 55. The method, according to claim 53, wherein the first functional group comprises an amine functional group.
56. 56. The method according to claim 55, wherein the second plasma means comprises a fourth group, selected from the group consisting of the saturated carboxylic acid, unsaturated carboxylic acid, carboxylic ester, keto-ester, and mixtures thereof.
57. 57. The method according to claim 56, wherein the second plasma means comprises a mixture of a hydrocarbon and the fourth compound.
58. 58. The method according to claim 55, wherein the second plasma means comprises oxygen.
59. 59. The method according to claim 56, wherein the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, isocyanate, hydroxy and sulfhydryl.
60. 60. The method according to claim 43, wherein the first functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
61. 61. The method according to claim 43, wherein the second functional group is selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.
62. 62. The method, according to claim 43, wherein the second functional group is reactive with the first functional group.
63. 63. The method according to claim 43, wherein the three-dimensional film network includes a double branched spatial configuration between the adjacent film layers.
64. 64. The method according to claim 43, wherein the three-dimensional film network includes a triple branched spatial configuration between the adjacent film layers.
65. 65. The method, according to claim 43, wherein the three-dimensional film network includes a quadruple branched spatial configuration, between the adjacent film layers.
66. 66. The method, according to claim 43, wherein the three-dimensional film network includes a spatial configuration of heterocyclic ring, between adjacent film layers.
67. 67. The method, according to claim 43, wherein the three-dimensional film network includes a spatial configuration of linear chain, between adjacent film layers.
68. 68. The method, according to claim 67, wherein the linear chain includes a plurality of third functional groups, selected from the group consisting of carboxy, carboxylic ester, epoxy, amine, isocyanate, hydroxy and sulfhydryl.