MXPA98007726A - Polymerizable compositions with free radicals, which can be applied through the assistanceelectrostat - Google Patents

Abstract

Compositions that contain conductivity enhancers, which can be coated on a substrate by means of electrostatic assistance. The compositions comprise one or more monomer (s) curable with free radicals and one or more non-volatile conductivity enhancer (s), having cationic or anionic moieties, which are soluble in the monomer (s). s) and which do not interfere with the polymerization of free radicals, wherein the anionic portion is an anion containing carbon, organophilic, uncoordinated. The compositions may further comprise one or more initiator (s), one or more dissociation enhancing agent (s), crosslinking agent (s), cationically polymerizable monomer (s), cationic initiator (s), agent (s) s) leveling, oligomer (s) or polymer (s), preferentially coreactants, and other additives or adjuvants to give specific properties to the coating cure

Description

POLYMERIZABLE COMPOSITIONS WITH FREE RADICALS, WHICH CAN BE APPLIED THROUGH ELECTROSTATIC ASSISTANCE Field of the Invention This invention relates to compositions that can be coated on a substrate by means of electrostatic assistance. More particularly, the present invention relates to polymerizable compositions with free radicals containing conductivity enhancers, substrates coated with these compositions, and methods for coating the substrates.

Background of the Invention The release of chemical substances into the atmosphere, often air pollution, is of substantial importance. In this way, in the chemical industry as new products and processes are developed, a key factor is the environmental effect. A means of reducing chemical emissions is to develop solvent-free processes, and requires that chemicals do not evaporate during processing or the final product. REF: 028282 Traditionally, liquid coatings have been processes based on solvents. The liquid coating is the process of putting the gas, typically air, in contact with a substrate usually a solid surface such as a film or cloth, with a liquid layer. After the deposition of a coating, a liquid can remain, it can be dried if it contains solids dissolved in a volatile liquid, leaving behind a solid and typically an adherent layer, or it can be "cured" (ie, polymerized) or some other solidified form to a functional and typically adherent layer. Volatile solvents have typically been used during the coating processes and then evaporated leaving the desired composition, especially when thin coatings are desired. The coating process is typically selected based on the desired coating height (i.e. the coating thickness). Liquid, continuous coating techniques (such as coating, curtain, grooving, slipping, gravure and the like and combinations thereof) are commonly preferred for applying composition on a smooth substrate at a height of about 5 microns or more. See, in general, Modern Coating and Drying Technology, E. Cohen and E. Gutoff, VCH Publishing, N.Y., 1992. Rough or "three-dimensional" surfaces are preferentially coated by sprinkling processes. Traditionally, thin coatings carrying solvents, i.e., dry thickness down to about 5 microns, have been coated onto substrates for use as a release coating, a primer or an antistatic layer, while thicker coatings have been coated. used for adhesives, or for the manufacture of coated abrasives, etc. Liquid, continuous coating techniques can be used to apply thin coatings; however, the composition has typically been diluted with a large amount of a solvent that is later removed by evaporation, leaving the composition behind to the desired thickness. The uniformity and thickness of the final, dry layer can be difficult to control especially on rough surfaces. The added solvent leads to higher material costs, preparation costs and solvent removal costs. In addition, the solvents typically used can be harmful to the environment. For liquid coating processes, continuous when the line speed of the coating is increased, the process may become unstable allowing entrapment of air to occur in the region where the composition meets the substrate first. This region is usually referred to as the "coating bubble". Fortunately, electrostatic assistance can be used to solve the problem of entrapment of the air that occurs between the bubble of the coating and the substrate. Nevertheless, not all compositions can be applied by electrostatic assistance methods. The composition must have sufficient conductivity such that free ions can move within the composition when an electric field is applied. Then when a high electrical potential difference between the composition and the substrate is applied, an electric field is produced in the composition that induces the ions of a polarity in the composition to move to the surface of the bubble of the coating that is closest to the substrate. In some coaters (eg, gravure) that do not have a bubble of the individual coating, the ions still move to the surfaces of the composition (eg, the surfaces of the composition in the gravure cells) that are closest to the substrate . This "inductive loading" of the composition causes an electrostatic pressure on the surface of the coating bubble that can change the shape of the coating bubble and prevent air from penetrating between the coating bubble and the substrate. In this way, with electrostatic assistance, increased line speeds can be obtained while maintaining uniformity when performing continuous coating. Even with discrete gravure coating methods, electrostatic assistance allows for increased line speeds because the electrostatic pressure "pulls" the composition out of the gravure belts. Thin coatings that carry solvents can also be applied by spraying processes. Although spray coating can also be used to apply a composition to a smooth substrate, it is particularly useful as a method of coating rough or three-dimensional objects and sheet-like fabrics with rough or three-dimensional surfaces. Electrostatic spray processes are commonly preferred for applying a composition having a solvent to a rough surface at a coating height of 5 microns or more. However, a problem associated with the sprinkling processes is the overrun (ie, 50 to 80 weight percent of the composition can not reach the substrate). (Miller, E.P., Chapter 11, Electrostatic Coating; in Electrostatics and Its Applications, Wiley-Interscience (1973) Editor: A. D. Moore). Electrostatic spray processes provide a more controlled means of spraying and thus reduce the loss of material. In the most efficient electrostatic spray processes, the droplets are charged during the formation using inductive load. The inductive load places a charge on the droplets through the electric field within the composition in the sprayer by which the electric field moves the free, positive ions in the opposite direction to the negative free ions. The excess of an ion polarity accumulates in a region along the surface of the composition and creates the electrostatic pressure required to break the composition in a mist of charged droplets. To achieve this inductive load, the composition must have sufficient conductivity to ensure that a reasonable number of free ions are present. The droplets in the electrostatic spray coating typically vary in diameter from about 50 micrometers (μm) to about 200 μm, while conventional (non-electrostatic) spraying processes can have droplets as large as 500 μm. The electro-torque, a distinct subclass within electrostatic spraying, is restricted to low flow rates, which makes it useful for applying the coatings to a thickness of about 0.005 microns to about 10 microns. The electro-color can be used to apply a thin coating without a solvent. In an electrorrocio process, the electrostatic pressure on the surface of the composition in the spray nozzle causes a precisely controlled formation of one or more cones of composition from which a thin filament of liquid emanates. Each filament is divided into a mist of droplets with diameters of the droplets in the order of the diameter of the filament. The diameter of the droplet can be controlled by the conductivity of the coating solution. The diameters of the droplets are typically less than 50 μm, and may be less than 1 μm if the conductivity is sufficiently large. Although the electro-alloy process is an effective means to apply a thin coating, not every composition can be electro-rounded. As is the case with all electrostatic assistance methods, the composition must comply with certain processing requirements. The viscosity and conductivity requirements for the composition to be coated vary with the electrostatic assist method and with the desired coating thickness. For the electro-composition, the composition must be essentially either a single-phase solution or a non-ionically stabilized dispersion or emulsion, otherwise the composition may become unstable during the electro-alloy process. In a single phase solution ("true solution"), each component is completely soluble.

The compositions can be electro-alloyed with or without a solvent, provided that the composition is either a single phase solution or a non-ionically stabilized emulsion or dispersion. Frequently a solvent must also be added to the composition in order to obtain the solubility of the necessary component. This added solvent, particularly if organic, can present environmental problems if it evaporates during or after processing and is not captured. When a composition is truly solvent-free, substantially all of the initial components are present in some form in the final, cured product. There are thin coatings which are solvent waste, but this definition does not fit because the solvent evaporates during processing. For example, although ethanol or methanol can be added to the electro-decomposable compositions to increase solubility and conductivity, they evaporate during processing. For some free radical scavenging systems, such solvents can interfere with polymerization by serving as chain transfer agents or as inhibitors, and preferably they are removed prior to cure. Water-based compositions, although sometimes referred to as "solvent-free", typically require large drying ovens, which occupy a considerable portion of manufacturing space and are added to the cost of the product. In addition, often the compositions to be electro-decomposed are organic, and thus tend to be immiscible with water. A solvent can be added to the composition to increase the conductivity. To achieve the desired conductivity range, the compositions often contain a polar solvent, typically considered to be an organic, volatile compound ("VOC"), in addition to a conductivity enhancer, i.e., salt. These organic, volatile compounds can be hazardous to the environment. For the electrorrocio, solvents have been used to increase the conductivity of the solution. For example, the application of EPO No. 92.907947.3 (Mazurek et al.) Describes the addition of methanol in small amounts to increase the conductivity of a release coating, electro-forcible. However, the methanol evaporates during processing, otherwise it may interfere with free radical polymerization. U.S. Patent No. 4,059,444 describes the addition of quaternary ammonium salts having inorganic anions with relatively low molecular weights as conductivity enhancers, such as sulfate, borate, and iodide, to the ink. These conductivity control agents are added at levels of 0.05 to about 1 weight percent to increase the conductivity of electrostatically applied inks. U.S. Patent No. 5,364,726 discloses a liquid developer or developer comprising a colorant and a curable liquid carrier, solid particles containing an initiator that is substantially insoluble, and optionally conductivity enhancing agents such as quaternary ammonium compounds as described in U.S. Patent No. 4,059,444. U.S. Patent No. 4,097,417 discloses a photocurable, electrically conductive coating having preferably 20 to 50 weight percent of copolymerizable organic salts applied to a substrate by means of any liquid, continuous coating technique such as air knife, reverse roller , photogravure, etc. U.S. Patent No. 4,303,924 discloses the addition of an oil soluble salt, such as mineral acid and quaternary organic acid salts of Group Va elements, to a curable printing ink containing 0 to 30% of an organic solvent polar. All examples include an organic solvent, polar. For electro-thinning a thin layer having a uniform thickness, each droplet of the electro-porous mist must have a sufficiently low viscosity to allow reasonable dispersion on the substrate. However, for some applications, it may be desirable to cure the individual droplets on the substrate, for example slip sheets. "Reactive solvents and diluents have been added to control viscosity, For example, reactive diluents are described in W095 / 23694 (Kidon et al.) And U.S. Patent No. 4,201,808 (Cully et al.). a coating on a substrate, the components preferably do not detrimentally interfere with the final performance of the product.A component preferentially evaporates or does not interfere with the polymerization or becomes physically trapped in the coating during processing, otherwise the component can migrate within the substrate and detrimentally affect the performance of the product, alternatively, it can evaporate later contaminating the environment, or it can have contact with another surface later, remove shine, and contaminate that surface. electrostatic assistance methods offer, compositions must have sufic conductivity. Thus, there is a need for coating compositions that can be applied by electrostatic assistance (i.e., liquid coating, electrostatically assisted continuous (roller, curtain, groove, slip, gravure and the like), electrostatic spray coating or coating electro-alloy) where substantially all of the components are present in the final product and either copolymerize with the other components or otherwise become a permanent part of the coating.

Brief Description of the Invention Compositions have been found that can be applied to a substrate by means of electrostatic assistance, the components of which do not interfere with the polymerization, and when placed on the substrate and substantially polymerized, the compositions do not degrade undesirably the properties of the product. By incorporating the conductivity enhancers according to the invention, a composition can be formulated that was insufficiently conductive for the coating by means of an electrostatic assist to achieve the desired conductivity. In addition to achieving adequate conductivity, the conductivity enhancers must be soluble in the composition, do not adversely affect the viscosity of the composition, preferably either substantially copolymerize or become a permanent part in the final composition, and do not degrade undesirably the final product. Non-volatile salts that have carbon-containing, non-coordinated anions satisfy these requirements. The present invention provides compositions containing conductivity enhancers which are capable of being coated on a substrate by means of electrostatic assistance. The compositions comprise one or more monomer (s) polymerizable with free radicals and one or more non-volatile conductivity enhancer (s) having cationic and anionic moieties which are soluble in the monomer (s) and that do not interfere with free radical polymerization, wherein the anionic portion is a carbon-containing anion, uncoordinated. The compositions may further comprise one or more free radical initiators, one or more agent (s) that increase the dissociation, crosslinking agent (s), cationically polymerizable monomer (s), cationic initiator (s). , leveling agents, oligomer (s) or polymer (s), preferably coreactants, and other additives and adjuvants to give specific properties to the polymerized coating. The viscosity requirements vary with the electrostatic assistance coating method. Another embodiment of the present invention is a "solvent-free" composition that can be applied to a substrate by electrostatic assistance. Another embodiment of the present invention is a composition that can be electrored on a substrate and in particular a rough or three-dimensional substrate.

Detailed Description The addition of certain types of salts as conductivity enhancers to an organic composition comprising monomers polymerizable with free radicals significantly increases the conductivity of the composition without the addition of a solvent. The addition of a conductivity intensifier allows the compositions with sufficient conductivity for the application by electrostatic assistance to achieve the necessary conductivity and thus can be electrostatically coated by liquid coating processes, continuous, electrostatic spray coating, or coating. electro-corruption The conductivity requirement applies only to the application process. Once the composition is applied to a substrate, the conductivity can be significantly reduced or eliminated. Electrostatic assist coating methods that depend on the inductive load require free ions (ie, ions that are physically separated such that they behave as uncoordinated ions) in the solution to serve as ion conductors. Known ionic conductors include salts, acids, water, and polar solvents containing dissociated species. Water is often not compatible with (ie miscible with) an organic solution, and in this way such a composition would be an emulsion or dispersion (typically at least in part ionically stabilized) and not a true solution and thus is not electro-forcible . further, the water must be dried, which can add another process step and increase the production cost. Acids are often volatile and corrosive. As discussed above, polar solvents can be used to increase conductivity by acting as an agent that increases dissociation. However, polar solvents frequently evaporate during processing and can thus be hazardous to the environment. Therefore, to create a solvent-free composition that can be applied by electrostatic assist methods, the salts are useful for increasing conductivity. However, not all salts are useful in organic compositions. An individual definition is not universally used for a solvent-free composition or a high solids solution. Ideally, a solvent-free composition is 100% reactive and has no or no VOC. As is known in the art, this ideal composition is difficult if not impossible to achieve. In particular, volume polymerization decreases speed significantly at higher conversions, and thus 100 percent conversion or polymerization is difficult to achieve, even without considering the economic limitations. To explain the non-ideal nature of the compositions, some level of non-reactive components or volatile components is presumed. The United States Environmental Protection Agency (EPA) has established a testing methodology to measure the content of VOCs for radiation curable materials, as found in the American Society for Analysis and Materials (ASTM). standard D 5403-93. Test method A is applicable to "radiation curable materials that are essentially 100% reactive but may contain very small parts (not more than 3%) of volatile materials such as impurities or introduced by the inclusion of various additives". To determine the presence of volatile materials, the composition is cured and then heated at 100 ± 5 ° C for 60 minutes in a forced draft oven. Weight measurements are taken (all at room temperature) from the substrate, the composition before curing, the composition after curing and the composition cured after heating. In the present invention, the "solvent-free" compositions are those that comply with this standard and thus have a VOC content of not more than 3 weight percent.

In addition to complying with this standard, the solvent-free compositions of the present invention are preferably such that less than 2 weight percent of the total of all original components can be extracted with heat during the application of ASTM D 5403. -93, Test Method A. In this way, preferably at least 98 weight percent of the monomer (s), initiator (s), conductivity enhancer (s) and other additives are present in the product. , polymerized, final without considering the source of energy used for the healing of free radicals. The non-ideal nature of the polymerization is also allowed in the loss requirement of less than 2 weight percent. To achieve this solvent-free composition, each component must be selected such that during processing, polymerization and in the final product, the composition does not lose material by evaporation or "heat extraction" to the degree of 2 percent by weight or more . In addition, the components preferably do not migrate into other layers of the final product, otherwise the properties of the product may be detrimentally altered. The conductivity requirements for the composition vary with the electrostatic coating method (see Table A) and the coating method can be determined by the desired coating height. Walden's rule (Jordan, P.C., Chemi ca l Kineti cs and Transport, Plenum Press, New York (1980)) conditions that for a given system the product of ionic conductivity multiplied by viscosity is approximately a constant. In this way, the ionic conductivity can be increased by decreasing the viscosity. However, in the spray coatings the viscosity of the droplets is preferably kept very low to allow reasonable dispersion and smoothing of the coating in a short time. Consequently, in the electrostatic coating, and in particular in the electro-porous coating, the viscosity of the composition is typically less than 1 pascal-second. Similar restrictions apply to the other methods (See Table A). Because the viscosity is already required to be low for most electrostatic assist methods, the desired conductivity can not be easily obtained by adjusting the viscosity.

Without the necessary conductivity, a composition can not be applied using electrostatic assistance. This substantially limits the use of these application methods. However, by adding certain types of salts to these compositions to provide sufficient conductivity in accordance with the present invention, compositions that can not be electrostatically assisted, can now be applied to substrates by electrostatic assistance methods.

Conductivity Enhancers Salts, as conductivity enhancers, contain ions held together by coulombic attraction. Simply having ions present does not mean that a salt solution is a sufficient ion conductor. The electrostatic attraction joins the oppositely charged ions together in ion pairs that substantially reduce the ionic conductivity. Therefore, to be sufficient conductors, the ion pairs must be at least partially dissociated and the ions become independent, that is, they become free ions (or, less preferably, triplets of ions). Free ions can significantly increase the ionic conductivity of a composition with the condition that they have sufficient inherent mobility to readily respond to the electric field applied to the composition. The ability of the ion pairs to dissociate in a composition depends on several factors such as the dielectric constant of the medium.

As with other additives, ion pairs (ie, the salt) must be soluble to form a true solution so that the composition is potentially electro-forcible. Ions are required for several mixtures of monomers to become conductive, but the solubilities of the salts differ, making some salts more effective than others. Because the compositions of interest are organic, salts with at least one organic ion typically have better solubilities. The solubility of such organic salt can be adjusted by the appropriate selection of the organic group. In general, materials with higher dielectric constants (higher polarity) are better able to stabilize free ions. The polar materials reduce the attraction between the oppositely charged ions, allowing the ion pairs to separate into free ions. In general, the dissolved salt ions can be closely matched (coordinate), and in this way can be essentially non-conductive, or can be (as a result of their structure and environment) easily and physically separated such that the ions behave as Uncoordinated (or free) ions which are substantially conductive. As the organic compositions become less polar and thus have a lower dielectric constant, the equilibrium between free ions and narrow ion pairs changes towards the latter. Therefore, salts that dissolve to form ion pairs that readily dissociate in free ions despite less favorable conditions (i.e., low polarity and low dielectric constant mixtures) are desirably selected to increase conductivity . It is believed that the dissociative separation facility of two ions is favorably influenced by the delocalisation of charges in one or both of the ions and / or by the steric hindrance around the center of the charge which prevents the counterion from being closely coordinated in a pair. ionic. Steric hindrance around the site of ion charge may decrease the accessibility to the counter ion and therefore the ions tend to be less closely spaced. If the sterically hindered groups do not interfere with the solubility of the salt, a greater steric hindrance will favor the separation of the ion pairs in individual ions and will tend to increase the ionic conductivity of the composition. However, the increased ion size will eventually reduce the conductivity due to the reduction in the mobility of the ions. Groups that remove electrons, particularly fluorine or fluorinated groups, generally increase the delocalization of the charge within the anionic portion and thereby increase the conductivity. Ions can have multiple charges. In general, monovalent ions are more easily solubilized and dissociated into free ions with the selected monomer mixtures. Bivalent and trivalent ions can also be used, but unless they "stabilize" well they are generally less preferred because the extra charge promotes narrow aggregation of ions over larger distances. Polymeric ions, such as a salt of polyacrylic acid, are by their size severely restricted in mobility, and thus, limited in conductivity especially in viscous media. The conductivity enhancers are non-volatile, or their vapor pressure is 1 kPa or less at 25 ° C, preferably 0.5 kPa or less at 25 ° C, and more preferably 0.1 kPa or less at 25 ° C. Preferably, the conductivity enhancers do not decompose to form volatile products, or become extractable with heat or water at any time during processing, or the final product. Preferably, the conductivity enhancers increase the conductivity of the composition when they are added in relatively low amounts. Typically, from about 0.001 weight percent to about 10 weight percent is added, preferably from about 0.001 weight percent to about 1 weight percent is added. In addition, conductivity enhancers should not interfere with polymerization. The conductivity enhancers useful in the present invention include salts having an inorganic or organic cation and a carbon containing anion, uncoordinated, organophilic, voluminous to promote the dissolution and ionic dissociation of the salt in organic monomers. Preferably, the anion has a weight of the formula of at least 200 kg / mol.

Preferably, at least a part of the selected conductivity enhancer is copolymerized with the remainder of the composition. However, if the conductivity enhancers are added in a small amount and are physically trapped within the cured composition and thus substantially do not migrate to other layers of the substrate, they evaporate, or become extractable when heated or exposed. to water, the necessary conductivity enhancers are not copolymerized. The migration of the conductivity enhancers may interfere in a desirable way with the properties of the final product. Useful anions include, but are not restricted to, alkyl, cycloalkyl, and aryl sulfonates, fluoroalkylsulfonylimides, fluoroalkylsulfonylmethides, arylborates, carbonate anions, and metallocarborane anions. In certain, boron catecholates are useful. Preferably the anions are substituted with halogen and more preferably halogen is fluorine. The most preferred salts (conductivity enhancers) of this invention comprise fluorinated anions which are (fluoroalkylsulfonyl) imide (I) r (fluoroalkylsulfonyl) metide (II), fluoroalkylsulfonate (III), or fluorinated or fluoroalkylated aryl borate anions (IV) having The respective formulas: i p m iv wherein X is selected from the groups: H, alkyl, alkenyl, aryl, alkaryl, -S02R, -S02Rf, -S02F, C (0) R, and -C (0) Rf, but preferably -S02Rf. R is selected from the group coning of alkyl, cycloalkyl, aralkyl, substituted alkyl, aryl and substituted aryl groups. The substituted aryl may contain halogen or haloalkyl substituents, preferably fluoro or fluoroalkyl substituents. Rf can be an aliphatic, saturated, fluorinated, monovalent radical containing at least one carbon atom. Where the radical contains a plurality of carbon atoms in a skeleton chain, such a chain can be branched or cyclic. The skeleton chain of carbon atoms can be interrupted by heteroporsions, such as divalent oxygen atoms or trivalent nitrogen each of which binds only to carbon atoms, or hexavalent sulfur atoms each of which can be attached to atoms of carbon, fluorine or oxygen, but preferably where such heteroporsions are present, such that the skeleton chain contains no more than one of the heteropor- tional for every two carbon atoms. A hydrogen atom, bromine atom or chlorine atom attached to the occasional carbon may be present. However, where present, they are present preferentially no more than once for every two carbon atoms on average. In this way, the non-skeletal valence bonds are preferably carbon-to-fluorine bonds. That is, Rf is preferably perfluorinated. The total number of carbon atoms in Rf can vary and be, for example, 1 to 12, preferably 1 to 8, and more preferably 1 to 4. Where Rf is or contains a cyclic structure, such structure is preferably it has 5 or 6 ring members, one or two of which may be heteroporrations, for example oxygen and / or nitrogen. Where two or more Rf groups occur in an individual formula, they can be the same or different and can be linked together to form a cycle. Alternatively, Rf may be a fluorinated or fluoroalkylated aromatic group or a fluorine atom. The portion Rf 'in the formula (IV) represents one or more fluorinated substituent (s) per aromatic ring and can be one or more fluorine atoms or Rf groups according to the above description wherein Rf is preferably CF3. Preferably, the total number of carbon atoms without ring per aromatic ring collectively represented by Rf 'is not greater than 4. More preferably, formula (IV) is PFTPB (tetracis [pentafluorophenyl] borate) and TFPB (tetracis [3, 5-bis-trifluoromethylphenyl] orate). A plurality of the portions Rf 'associated with a single borate anion can be the same or different and can be ordered in any combination. R and Rf may additionally contain polymerizable functionality which is reactive with the monomers in which the salt dissolves, thereby providing a mechanism for immobilizing the anion during polymerization. Such immobilization may be necessary in applications where the extraction, filtration or migration of the salt in the cured composition is undesirable. Of the anions represented by the formulas (I) to (IV), the anions of imide, metido, and aryl borate of the formulas (I), (II) and (IV) are more preferred based on solubility and conductivity. Examples of anions useful in the practice of the present invention include, but are not limited to: (C2F5SO2) 2N-) (CASOjfcN-, (C, FpSO2) 3C-, (CF3SO2) 3 < r, (CF3SO2; 2N-, (C4Fs > S02) 3C-, (MC CF.SC SO ^ C? "(CF3SO2) (C4F9S02) N-, (CF3) 2NC2F4S02C- (S02CF3) 2, (3,5- (CF3) 2C6H3) S02N- (S02CF3) (CF3S02) (FS02) IN-, F2C- S02 F2 V F2C- S02 O F N- C2F4S? 2N "S? 2CF3 T - (CF) 4S02N S02CF3 (F-CßH4S? 2) (CF3S02) N-, (H-CF2CF2S? 2) -, C1CF2CF2S02) 2N-, C? SOs ", 3,5- (CF3 C6H3SOf, -N- S? 2 (CF2) 3-S? 3"» (C "H4-p-CF3) 4B-, (C6H4-m-CF3) 4B-, (CfiFJ) 3 (CH3) B-, ( C «Fs) 3 (n-C4H9) B-, (CßH4-p-CH3) 3 (CíF5) B-, (CífeMCßlL.-p-CFjWB-, (CßF5) 3 (n-C18H37?) B-, In general, the bis (perfluoroalkylsulfonyl) imide and cyclic perfluoroalkylenedisulfonylimide salts described above can be prepared as described in U.S.S.N. 08 / 531,598 (Lamanna et al.) And U.S.S.N. 08 / 398,859 (Walddell). These salts are prepared from the reaction of fluoroalkylsulfonyl fluorides, R £ S02F, or perfluoroalkylenedisulfonyl fluoride, FS02Rf3S02F, with anhydrous ammonia. The symmetric imides in which Rfi and R2 are the same, can be prepared in a single step using an organic, weakly basic solvent such as triethylamine as shown in Scheme I, while the non-symmetric imides in which Rfi and Rf2 They are different, they should be prepared in two steps as shown in Scheme II.

Scheme I Et 3 N 2 RfSO 2 F + NH 3 > Et3NH + -N (SO2Rf) + 2 Et3NH + F- Scheme II Ether Rf1SO2F + NH3 > NrV _NH (SO2Rfi) + NH4 + F ~ Et3N Rf1SO2NH2 + Rf2SO2F > Et3NH + -N (SO2Rfi) (SO2Rf2) + Et3NH + F "salts cyclic perfluoroalquilendisulfonilimida can be prepared as described in U.S. Patent No. 4,387,222. Fluorides perfluoroalquilsulfonilo and fluorides perfluoroalquilendisulfonilo used as precursors to salts imide and put this invention can be prepared by a variety of methods known in the art as described, for example, in U.S. Patent Nos. 3,542,864, 5,318,674, 3,423,299, 3,951,762, 3,623,963, 2,732,398, and S. Temple, J. Org. Chem., 33 (1), 344 (US Pat. 1968), DD DesMarteau, Inorg, Chem., 32, 5007 (1993) Fluoroalkylene sulfonyl fluorides having polymerizable functional groups have been described by Gard et al., J. Fluorine Chem. 66, 105 (1994), Gard et al. collaborators, Coordination Chemistry Reviews 112, 47 (1992), Gard et al., J. Fluorine Chem., 4_9 331 (1990), Gard et al., J. Fluorine Chem. 43, 329 (1989), Gard et al., J. Fluori Ne Chem. 67, 27 (1994), Gard et al., J. Fluorine Chem. 55, 313 (1991), Gard et al., J. Fluorine Chem. 3_8_, 3 (1988), Gard et al., Inorg.

Chem., 2_9, 4588 (1990), U.S. Patent No. 5,414,117 (Armand), and U.S. Patent No. 5,463,005 (DesMarteau). Polymers prepared from fluoroalkylene sulfonyl fluorides having functional, polymerizable groups have been described in DesMarteau, Novel Fluorinated Acids for Phosphoric Acid Fuel Cells, Gas Research Institute Report # GRI-92/0385, July 1992, and J. Fluorine Chem ., 72, 203 (1995). In general, the organic perfluorosulfonate salts described above are prepared as generally described in U.S.S.N. 08 / 398,859 (Waddell et al.). These salts are prepared by hydrolysis of the corresponding perfluoroorganosulfonyl fluoride, by means of the reaction with a basic salt having the desired cation (for example, a carbonate, hydroxide or alkoxide salt) in the presence of water and optionally, a solvent polar, additional. The processes useful for the synthesis of fluorochemical imide salts are described in: 1. D.D. Des Marteau et al., Inorg. Chem., 1984, 23, pp. 3720-3723; 2. D.D. Des Marteau et al., Inorg. Chem., 1990, 29, pp. 2982-2985; 3. Canadian Patent 2000142-A; 4. U.S. Patent No. 4,505,997; and U.S. Patent No. 5,072,040. Processes useful for the synthesis of fluorochemical salts and their conjugated acids are described in: 1. U.S. Patent No. 5,273,840; and 2. Turowsky and Seppelt, Inorg. Chem., (1988) 27 pp. 2135-2137. To prepare the perfluoroorganosulfonyl fluoride, the corresponding hydrocarbon sulfonyl fluoride (prepared, for example, according to the techniques described in Hansen, US Pat. No. 3,476,753, is perfluorinated by electrochemical fluorination according to the methods described in Hansen. U.S. Patent No. 3,476,753, Simons, U.S. Patent No. 2,519,983, and Chemistry of Organic Fluorine Compounds, Milos Hudlicky, ed., 2d ed., PTR Prentice Hall (New York), pp. 73-76, followed by purification. In general, the conductivity enhancers of the present invention can be prepared as described in WO95 / 03338 (Lamanna et al.), By anion exchange or metathesis reactions by combining salts containing the desired cation and conventional counterions, such as chlorine, PF5 ~, SbF6 ~, or BF ~, with simple salts, such as alkali metal or alkaline earth metal salts or alkylammonium salts, of non-nucl anions Eophilics of the invention in a suitable solvent. In general, metathesis reactions can be carried out at temperatures ranging from about -80 ° C to about 100 ° C, preferably at room temperature, under conditions in which either the salt of the present invention or the The metathesis byproduct (s) is selectively precipitated, thereby allowing the isolation of the salt of the invention in the form of a solution or a pure solid. Alternatively, ion metathesis can be achieved by passing a salt solution through a column of an insoluble, anion exchange resin containing a non-nucleophilic anion of the invention. The salts of the invention will be formed in itself if the individual components described above are added directly to the composition which can be applied by the electrostatic assistance. However, it is preferred to form the pure salt (conductivity enhancer) in a separate step as a solid or in a suitable solvent before adding it to the composition that can be electrostatically assisted and perform the coating and polymerization process. Suitable metathesis solvents are generally capable of dissolving at least one and preferably all the reactants required for the unreacted metathesis reaction with these reagents. Solvents are generally selected such that the desired salt or metathesis by-products are selectively precipitated, thereby allowing the desired salt to be isolated relatively purely. Normally, the preferred solvent for a particular system is determined empirically. In cases where an anion exchange resin is used, the solvent should not dissolve the resin, but must dissolve the metathesis reagents and the salt of the desired product. Non-limiting examples of suitable solvents include water; chlorocarbons, such as methylene chloride and chloroform; ethers; aromatic hydrocarbons, such as toluene and chlorobenzene; nitriles, such as acetonitrile; alcohols, such as methanol and ethanol; nitrobenzene; nitromethane; ketones, such as acetone and methyl ethyl ketone; and other similar kinds of organic solvents. Solvent mixtures are often desirable to control the solubility of reactants and product salts. The sodium and lithium salts of [3,5- (CF 3) 2 C 6 H 3] B "(TFPB") were prepared following published techniques (H. Kobayashi et al., In Bul l Chem. Soc., Jpn., 57_, 2600 (1984). [Li [B (CSF5)]] 2 (C2H5) 20 was prepared as described in WO95 / 03338 (Lamanna et al.) C6F5LI (70 mmol) was prepared according to the method described by AG Massey. and AH Park, Organometallic Synthesis, 3_, 461 (1986), modified by using a mixture of 200 mL of hexane and 50 mL of diethyl ether as the solvent. 17.5 mL of 1.0 M BC13 in hexane were added dropwise to this mixture at a temperature of -78 ° C. After stirring overnight, the crude product was collected on a Schlenk filter and dried under vacuum. The crude material was purified by extraction of Soxhiet under vacuum with anhydrous methylene chloride to produce a white powder This product was dried under high vacuum to produce a yield of 13 grams (77 percent). 1 H NMR showed that the product contains 2.1 moles of diethyl ether by weight of the formula.As the product was hygroscopic, it was stored under dry nitrogen.The Li [B (n-butyl) (CeF5) 3] was prepared as is described in WO95 / 03338 (Lamanna et al.) To a stirred suspension of 1.17 grams (2.3 mmol) of (C6F5) 3B in 10 mL of hexane, 0.95 mL of a 2.5 M solution of n-butyllithium in hexane was added. A white solid product was precipitated and after 30 minutes it was isolated by filtration and washed with 5 mL of hexane.After vacuum drying, the yield was 0.98 grams X1B NMR (toluene): -7.7 (s) ppm relative to BF3 (OEt2) .The cationic portion of the salts of this invention can be virtually any organic or inorganic cation. For example, the preferred cations are alkali metal, alkaline earth metal or complex cations of the group Va, Via or Vlla such as ammonium, alkylammonium and other cations of nitrogen-onium, phosphonium, arsonium, iodonium and sulfonium. The cations may also preferably contain polymerizable functionality for the immobilization of the salt.

The most preferred salts can be used in concentrations below 1 weight percent and do not require any dissociation enhancing agent. The dissociation enhancing agent (s) may be added or the salts may be used in concentrations greater than 1 weight percent in order to increase the ionic conductivity of relatively non-conductive mixtures.

Increase of Dissociation Agents Dissociation of ion pairs can also be increased by the addition of one or more agent (s) of increased dissociation. These dissociation enhancement agents will associate with (ie "stabilize") one or both of the salt ions. As with each component, the dissociation enhancement agents when added preferentially must comply with the "solvent free" requirements and preferably not interfere with the polymerization. Typically, when the dissociation enhancing agent (s) are part of the composition, at least 0.1 weight percent, preferably about 0.5 to about 5 weight percent, is added. Preferred dissociation increasing agent (s) have a dielectric constant of at least 5 at 20 ° C. More preferably, the dielectric constant is at least 10 at 20 ° C, and much more preferably the dielectric constant is at least 20 at 20 ° C. Examples are well known in the art and include materials such as polyethylene glycols, crown ethers and kryptands and poly (ethylene oxides) which in combination with the alkali salts selectively complex the metal ion of the ion pair thereby inducing dissociation. Small amounts of co-reactive and more polar monomers can also be used to increase dissociation, provided they do not adversely affect the properties of the cured coatings. Examples of such monomers include, but are not limited to, N-vinyl pyrrolidinone, N, N-dimethyl acrylamide, methacrylic acid, 2-ethoxy ethylacrylate, CarboxawMR 750 acrylate (available from Union Carbide, Danbury, CT) and the like.

Monomers The monomers selected for these compositions are essentially and completely miscible with the other components of the mixture.

In addition, these monomers have sufficiently low vapor pressures so that little loss of material occurs during processing. Preferably, the monomers are non-volatile, or are such that their vapor pressures are 1 kPa or less at 25 ° C, more preferably 0.5 kPa or less at 25 ° C and much more preferably 0.1 kPa or less at 25 ° C. The monomers are also selected and at concentrations based on the intended use for the composition. Useful monomers include both monofunctional and multifunctional monomers. Typical monofunctional, curable free radical monomers and comonomers include ethylenically unsaturated compounds, such as vinyl or vinylidene functional materials. Examples of these monomers include, but are not limited to, acrylate and methacrylate monomers, vinyl esters, methacrylamides, acrylamides, fumarates, styrenes, maleimides, and the like. The ethylenically unsaturated group can be attached to an aliphatic or aromatic group with 1 to 26 carbon atoms, more preferably 4 to 20 carbon atoms. Monomers with less than 4 carbon atoms are still sprayable, but are typically volatile, so the composition would not be more solvent-free as defined herein. When the number of carbon atoms exceeds 26, the monomers typically become solid or syrup, and large quantities of reagent of lower viscosity or inert diluents would be required to solvate the solid monomers or decrease the viscosity of the composition so that it becomes stable. I could electro-rot. The structure of the aliphatic or aromatic groups may contain heteroatoms and may be partially or completely fluorinated. Examples of these monomers and co-monomers include, but are not limited to, n-butyl acrylate, 2-methyl-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, 2-ethoxy acrylate, 2-ethoxyethyl methacrylate, lauryl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, styrene, vinyl pyridine, decyl vinyl ether, allyl benzoate, 1,1-dihydro-perfluorooctyl acrylate, glycidyl acrylate, vinyl hexanoate, vinyl pivalate, diethyl fumarate, N-phenyl maleimide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N, N-dimethyl aminoethyl acrylate, N, N-dimethyl aminoethyl methacrylate, 2-acryloxy propyl phosphate, styrene-4-sulfonic acid and salts of the same, N-vinyl pyrrolidinone, N-vinyl-n-methylformamide, acrylic acid, methacrylic acid and the like. Multifunctional, ethylenically unsaturated monomers are sometimes useful. The ethylenically unsaturated group can be a vinyl or vinylidene group. Examples include, but are not limited to, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, its ethoxylated or propoxylated analogs, divinylbenzene, diacrylate. of diethylene glycol, 1,6-hexanediyl (bis-monofumarate), divinyl adipate, diallyl adipate, triallyl cyanurate, 1,6-hexanediyl β-acryloxypropionates, and the like. Drying oils such as linseed oil, cooked linseed oil, or tung or stick oil may also be used. Ethylenically unsaturated monomers can also be used in combination with multifunctional thiol (ie, mercaptan), compounds, or a polyamine. The ethylenically unsaturated monomers can be selected from the broad classes of multifunctional vinylidene or vinyl compounds discussed above, but are preferably selected from non-homopolymerizable olefins easily. The a-mercaptoglicolates and β-mercaptopropionates are particularly useful. Typical examples of multifunctional thiols are tetracis (β-mercaptopropionate) of pentaerythritol, tetracis (α-mercaptoglycolate) of pentaerythritol, functional polydiorganosiloxanes of mercaptoalkyl, 1,4-butanediyl bis (β-mercaptopropionate) and the like. The polyamine reagents for ene-amine compositions can be primary, secondary or tertiary amines, multifunctional, tertiary are preferred. Illustrative examples of tertiary amines are described in EP 0 262 464 and include, but are not limited to, acrylic copolymers containing copolymerizable tertiary amine functional monomers such as corresponding dimethylaminoethyl acrylate or methacrylate, acrylamide or methacrylamides. Also useful are the corresponding diethylamino compounds as well as corresponding monomers in which the aminoethyl group is replaced by aminopropyl or aminobutyl.

Initiators With the possible exception of the ene-thiol and ene-amine compositions, the free-radical polymerization of these compositions should be carried out in an oxygen-free environment as possible, for example, in an inert atmosphere such as nitrogen gas. The ene-thiol and ene-amine compositions can be cured in the presence of oxygen. In general, the initiator comprises from about 0.1 to about 3 weight percent of the total weight of the compositions. See generally, Radiation Curing in Polymer Science and Technology, Vol. 1-4, J.P. Fouassier and J.F. Rabek, Elsevier Applied Science, New York, 1993. Polymerization can also be initiated with high energy irradiation, such as an electron beam or gamma rays. These high energy irradiation systems do not always require initiators. Light (ultraviolet or visible) can be used to initiate polymerization. Photoinitiators include materials that undergo fragmentation with irradiation, initiators of the hydrogen abstraction type, and donor-acceptor complexes. Suitable photofragmentation initiators include, but are not limited to, those selected from the group consisting of benzoin ethers, acetophenone derivatives such as 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl. 1-phenylpropan-1-one, 2, 2, 2-trichloroacetophenone and the like. Suitable initiators of the hydrogen abstraction type include benzophenone and derivatives thereof, anthraquinone, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone) and the like. Suitable donor-acceptor complexes include combinations of donors such as triethanolamine with acceptors such as benzophenone. Also suitable are sensitizers with initiators such as thioxanthone with quinolin sulfonyl chloride. Thermal energy can also be used to initiate polymerization. The thermal initiators may be selected from conventional peroxide or commonly available azo-type materials. Illustrative examples include benzoyl peroxide, 2,2'-azo-bis (isobutyronitrile), 1,1'-azo-bis (cyclohexane-1-carbonitrile), dicumyl peroxide and the like.

Redox initiators, such as amines with peroxides, salts of cobaltous carboxylate with peroxides, persulfate / bisulfite redox pairs, can also be used, provided that the initiators are completely soluble in the monomer mixtures and do not prematurely initiate the reaction by interfering in this way with the coating process by slowly increasing the viscosity of the solution. If necessary, the initiator can first be applied to the substrate by any conventional means.

Crosslinking Agents If desired, the crosslinking agent (s) may be added to the monomer composition. Crosslinking agents, useful are well known in the art. Examples include, but are not limited to, multifunctional acrylates or allyl compounds, photoactive triazines, copolymerizable benzophenone compounds such as 4-acryloxybenzophenone, multifunctional benzophenone crosslinkers, melamines, divinyl benzene, divinyl silane compounds, bis-vinyl ethers, bis-vinyl esters, functional vinyl trialkoxysilanes, functional vinyl ketoximinosilanes, and the like.

Additional Additives The cationically polymerizable monomers, such as vinyl ethers, cyclic ethers, styrenes, vinylidene ethers and the like, can be added to the free radical polymerizable monomers of the present invention to obtain a "hybrid" composition. When the cationically polymerizable monomers are added, a cationic initiator must also be added. Cationic initiators include, but are not limited to, Lewis acids, organic protonic acids, anhydrides, complex cation salts, ferrocenium salts, or salts of organometallic cations. Some initiators can initiate both free radical and cationic polymerization. For example, the complex cation and organometallic salts such as diaryliodonium and triarylsulfonium salts and salts of (cyclopentadienyl) (arene) iron + of the anions PF6 ~ and SbFs ~ may be useful. When two initiators are present, the activation mechanism may be the same or different. When the mechanism is the same (for example, heat or radiation), the initiators can be selected such that the activation energy differential initiates the polymerization at different points in time. In some cases, it may be desirable for cationic and free radical polymerization to occur simultaneously, for example networks of interpenetrating polymers useful for coatings. An example of different activation mechanisms is a UV light initiator for the polymerization of free radicals and a heat activated initiator for cationic polymerization. In order to achieve the specific functionality in the finished coating, the monomers and other components are selected to impart the desired properties. For example, as is well known in the art, the higher alkyl acrylates can function as pressure sensitive adhesive coatings, the "basic" monomers such as N, N-dimethylamino or N, N-dimethyl acrylamide ethyl methacrylate can function as precursors for acidic polymers, and fluorochemical acrylates can function as stain resistant coatings. However, for some applications, it is necessary to include certain co-reactive oligomers to obtain the desired properties. For example, for the low backing of adhesion in pressure sensitive tape applications, copolymerizable polydiorganosiloxanes, such as ACMAS (acrylamidoamido siloxane) and MAUS (methacryloxyurea siloxane) are added as described in the EPO Application. do not. 92.907947.3, Publ. No. 583259 (Mazurek et al.), Goldschmidt Tego ™ RC 706 polydimethylsiloxane functional acrylate (available from Goldschmidt AG, Essen, Germany) and the like, to the composition in varying amounts to obtain various levels of release properties. Similarly, it may be beneficial to use polyethylene glycol diacrylates as part of the composition to give hydrophilicity to the finished coating. Numerous examples can be found in the literature where reactive oligomers such as polyurethanes, polyesters, polyethers, silicones and the like are used to impart resistance to abrasive wear, abrasion resistance, toughness, lubricity, friction and other properties to the finished coating. These reactive oligomers do not detrimentally interfere with the conductivity and sprayableness of the monomer / oligomer mixture. In some cases, the oligomer needs not to be coreactive with the rest of the composition. Additives such as opacifying agents, dyes, pigments, plasticizers or tackifiers and the like can be used or nonfunctional flow intensifiers and wetting agents can be added to improve the aesthetics of the coating. These additives are preferably soluble in the compositions, are non-volatile, and preferably do not interfere detrimentally with the conductivity or curability of the compositions. A composition of the present invention can be prepared to the mixture-together in a suitable container one or more polymerizable monomer (s) with free radicals and optionally one or more free radical initiator (s), such that when in combination they have an insufficient conductivity to be applied by means of electrostatic assistance (ie, liquid, continuous, electrostatically assisted coating, electrostatic spray coating, electro-dew coating). One or more conductivity enhancer (s) and optionally one or more dissociation increasing agent (s) may be added to increase the conductivity by producing an application composition. The composition can then be coated on a substrate using the electrostatic assist method, selected and then polymerized by exposure to the electron beam, gamma rays, visible light, ultraviolet radiation or heat. Typically, the substrate has two major surfaces, and the composition is applied to at least a portion of at least one major surface. One embodiment of the present invention is a release coating composition on a substrate wherein the substrate comprises a backing having a first and a second side, a layer of adhesive having two sides, a side coated on the first side of the backing, and a release layer on the second side of the backing comprising the polymerized composition, formulated as a release coating. Preferably, the release coating composition is electrosprayed on the second side of the backrest. When the release liner is used on pavement marking tapes and others such as rolled substrates, the substrate is wound such that the first side of the backing (if the adhesive has already been coated, the adhesive layer) makes contact with the layer of liberation. Other embodiments include, but are not limited to, primers, thin adhesives, anti-fog coatings, ice release coatings, anti-graffiti coatings, abrasion resistant coatings, durable coatings, light scattering coatings, hard coatings, coatings resistant to stains, abrasion resistant coatings and matt surface coatings. The monomers and additives suitable for each application as well as the selection of the coating thickness can be easily selected by those skilled in the art. Suitable substrates include, but are not limited to, a sheet, a fiber, or a patterned object. The composition can be applied to at least one major surface of the suitable, flexible or inflexible backing materials and then cured. Flexible, useful backing materials include plastic films such as poly (propylene), poly (ethylene), poly (vinyl chloride), poly (tetrafluoroethylene), polyester (e.g., poly (ethylene terephthalate)), polyamide film such as DuPont Kapton R, cellulose acetate and ethyl cellulose. The backs can also be constructions with irregular surfaces such as woven fabrics, non-woven fabrics, paper or rough surfaces. In this way, the backs can also be woven fabric formed of synthetic or natural yarns such as cotton, nylon, rayon, glass, or ceramic material, or they can be non-woven fabrics such as air-laid fabrics. natural or synthetic fibers or mixtures thereof, conditioned to the fact that they are not very porous. Because of its high porosity, paper by itself is usually not suitable, unless heavier coatings of more than one micrometer are applied to counteract impregnation within the paper. However, it is useful to use glass paper, paper coated or impregnated with plastic. Rough surfaces include surfaces in relief or with geometric figures or resins impregnated with particles such as resin (epoxy) covered with abrasive particles and resins covered with glass beads. In addition, suitable substrates can be formed of metal, metallized polymeric film, ceramic laminate, natural or synthetic rubber, or pavement marking tapes.

EXAMPLES The following Examples illustrate several specific features, advantages, and other details of the invention. The particular materials and amounts cited in those Examples, as well as other conditions and details, should not be constructed in a manner that could unduly limit the scope of this invention.

Solubility test The solubility of the conductivity enhancer for each composition was determined by the following method. A sample of the conductivity enhancer was mixed with a monomer solution, clear at room temperature for a maximum of two hours and then verified under agitation for optical clarity. If the conductivity enhancer containing the sample was not completely clear or a "true solution", the sample was moderately heated (such that the sample could be held by the hand) and then allowed to cool to room temperature. A sample which contained visible conductivity enhancer particles was considered to have failed.

Viscosity Measurement Brookfield Viscosity (in centipoise (cp), 1 cp = 1 mPa's) was measured at room temperature with a Brookfield digital viscometer model DV-II available from Brookfield Engineering Laboratories, Inc., Stoughton, MA.

Conductivity Measurements The electrical conductivity of a solution was measured by inserting a simple tub composed of two parallel stainless steel bars that act as electrodes in a glass jar containing the solution. The bars, each approximately 9 cm long and approximately 3 mm in diameter, were separated by a center-to-center spacing of 1 cm and were kept parallel by having both bars embedded at one end inside a piece of insulated material (either a bottle, rubber, normal or a piece of Garolite ™ available from McMaster-Carr, Chicago, IL). The height H 'was the height of the meniscus of the solution relative to the bottom of the bars. When the bars were placed in a solution at a height H, and an electric potential was applied through the bars, an electric current was flowed between the bars. The solution, air and insulator provided a net resistance R for the flow of electric current. When the bars were placed at height H in a solution that was reasonably more conductive than air, then the effective resistance was that of the solution. For example, the air conductivity is about 10 ~ 12 S / m or 10"6 μS / m, and the conductivity of the insulators is even lower, so for a solution that has a conductivity greater than 0.001 μS / m the resistance R, within 0.1 percent, was effectively due only to the solution.The resistance R is directly proportional to a geometric factor G and is inversely proportional to the electrical conductivity s, and in this way G = Rs. ^^ the height H as well as other fixed parameters such as the separation-distance of the bars and the diameter of the bars. If these fixed parameters are defined as a second geometric factor g, then, g = GH where g is a constant defined by the specific geometry of the electrode structure. The value of g was determined Figure 10 using a solution having a known conductivity S0 giving a resistance Rs when the bars are placed at some specific height H0 in the solution. Because s0 was known and Rs was measured, the geometric factor G0 was determined from G0 = R0s0. Knowing Ho r g was determined using g = G0Ho. Since g is a constant, g = GoH0 = GH, and because g is known, G can be determined for any immersion depth of the electrode-bar H. 20 To calibrate the bar of the electrode-bar, the constant of the g cell was determined using several saline solutions of known conductivity (Standard Reference Materials (1500, 10000 and 50000 μS / m), available from National Institute of Standards and Technology (NIST), Gaithersburg, MD). The constant g varied from about 60 cm / m to 1500 μS / m at a value of about 70 cm / m to 50,000 μm. When an impedance analyzer was used to measure the dielectric constant of methanol, isopropyl alcohol (IPA) and methyl ethyl ketone (MEK), g had to be adjusted to obtain the values of the dielectric constant observed in the Chemistry and Physics Handbook (CRC Press, Inc., Boca Raton, FL). When those g values were plotted against the natural logarithm of the measured conductivity for the IPA, the MEK, and the methanol, and the g-values determined using the NIST solutions were also plotted against the natural logarithm of the NIST solution values , all the g values fell in the same straight line. As a result, g = 59.45 cm / m was chosen that gave the exact conductivity at 1000 μS / m. With this value of g, all the conductivity data, reported deviated by approximately 10 percent per decade of conductivity away from 1000 μS / m, being lower for the conductivity below 1000 μS / m and higher for the conductivity above 1000 μS / m. For example, a conductivity reported as 100 μS / m was actually about 10 percent lower, one reported as 10 μS / m is actually about 20 percent lower, etc. Using g = 59.45 cm / m, the conductivity s was determined from the resistance through the tank by the formula s = g / (HR), where R is the resistance of the solution when the tank was inserted into the solution at height H. Three methods were used to determine the resistance R and therefore the conductivity s of the solution. In method I, a Hewlett Packard LF (Low Frequency) Model 4192A Impedance Analyzer (Hewlett Packard Company, Palo Alto, CA) was connected through the stack and admittance Y and angle D were recorded at the F frequencies of 100, 300, 500, 700, 900, and 1000 kilohertz (kHz) together with the immersion depth H of the bars in the solution. This information was used to calculate "the conductivity by the formula s = (gYcosD) / H. For the method I, the dielectric constant er of the solution can also be calculated by the formula er = (gYsinD) / (2pe0FH) where eQ is the permittivity of free space (8.85 x 10-12 farads per meter (F / m)).

In Method II, a BK Precision Model 878 Universal LCR Meter (BK Precision, Maxtec International Corporation, Chicago, IL) was connected through the cell and the resistance R at a frequency F of 1 kHz was measured along with the depth of H dip of the bars in the solution. The conductivity was then calculated by the formula s = g / (HR). In Method III, the tank was connected in series with a resistor Rs of 1 MO, a microammeter A and a switch S. This series circuit was then connected through a battery of the dry, normal 9-turn tank. After the tank was submerged at a height H in the solution, the switch S was closed momentarily and the initial reading Is in the ammeter was recorded. Together with Ia, the immersion depth H of the electrodes was recorded. In Method III, the battery voltage V_ can be connected through a switch placed in series with an ammeter and a calibration resistor Rc of 1 MO. When this switch was closed, the measured current Ic multiplied by the resistor Rc gave the battery voltage. This information was then used to calculate the solution's conductivity using the formula MAIN 5K Synthesis This free radical curable polydimethylsiloxane (PDMS) is prepared according to the procedure outlined in EPO Patent Application No. 92.907947.3 (Mazurek et al.). A PDMS of α, β-bis (3-aminopropyl) of 5,000 molecular weight (EPO Patent Application No. 93.924905.8 (Leir et al.)) Is reacted in volume with either 2-isocyanatoethyl methacrylate to produce the 5K MAUS. The gradual addition of the coating agent to the PDMS with some cooling is desirable to avoid polymerization of the PDMS product curable with free radicals.

Example 1 A release coating composition was prepared by mixing, at room temperature, 100 parts of a 75/25 mixture of IOA / 1,6-HDDA, 25 pph of 5K MAUS, and 2 pph of Darocur 1173. The strength is measured as described in Method II and found to be outside the range of the instrument. Then, 0.1 pph of HQ-115 was added to the composition and at a height of H = 4 cm, the resistance was 293 kO (conductivity 37.4 μS / m). A 0.1 pph of additional HQ-115 was added, which decreased the resistance to 233 kO (conductivity 63.8 μS / m). This example demonstrates that at levels below 1 pph, the salt of HQ-115 increases the conductivity of the UV curable composition to a level within the range required for the electro-vacuum application.

Example 2 The release coating composition of Example 1 was prepared by substituting 2 pph of VAZO 64 for Darocur ™ 1173 as an initiator. When 0.1 pph of HQ-115 was added to the composition, using Method II, at a height of H = 4 cm, the resistance was 331 kO (conductivity of 44.9 μS / m). When 0.1 pph of additional HQ-115 was added, the resistance decreased to 206 kO (conductivity of 72.2 μS / m).

Example 3 The release coating composition of Example 1 was prepared by substituting 0.03 pph of 2-ethyl-4-methyl-imidazole HTFPB for HQ-115 C as the conductivity enhancer. Using Method II, at a height of fí = 4 cm, the resistance measured 378 kO (conductivity of 39.3 μS / m).

Comparative Example A This composition was prepared as described in Example 3 by replacing the imidazolium of HTFPB with a lower cost conductivity enhancer, Aliquat ™ 336, having an organic anion as the counter ion for the complex cation. After the addition of 1.5 pph of Aliquat 336, using Method II at a height of fí = 4 cm, the resistance was approximately 3 MO (conductivity of 5 μS / m). In compositions or applications where only minimal salt levels are tolerable, the use of the conductivity enhancers of this invention offer a benefit over the quaternary ammonium salts with inorganic anions.

Example 4 A UV curable, urethane modified coating was prepared by mixing 50 pph IOA, 30 pph 1,6-HDDA, 20 pph EbecrylMR 230, and 2 pph Darocur 1173 at room temperature. Then, it was added 0.1 pph of HQ-115. The composition was clear and electro-forcible with a height resistance H = 4 cm of 341 kO (conductivity of 43.6 μS / m) as determined by Method II.

Example 5 A mixture of electrochemiable monomers useful as a primer for adhesives containing copolymerized acid was prepared by mixing at room temperature 70 pph of 1,6-HDDA, 30 pph of glycidyl methacrylate, and 0.015 pph of HQ-115. The priming composition was clear and the tube had a Brookfield viscosity of approximately 5 centipoise. Using Method II at a height of fí = 4 cm, the resistance was 342 kO (conductivity of 43.5 μS / m).

Example 6 A composition was prepared as described in Example 4 by changing the ratio of the monomers to 60 pph of 1,6-HDDA and 400 pph of glycidyl methacrylate. The addition of 0.015 pph of HQ-115 resulted in a clear composition containing a Brookfield viscosity of about 7 centipoise. Using Method II at a height of fí = 4 cm, the resistance was 264 kO (conductivity of 56.3 μS / m).

Example 7 This example illustrates that the conductivity of the monomer solutions can be easily adjusted to the desired level for the application of interest. Eighty gram batches were prepared by mixing at room temperature 76.2 g of the monomer mixture 75/25 of IOA / l, 6-HDDA and 3.8 g of 5K MAUS. Then, different levels of HQ-115 were added to each batch of 80 g. The following conductivities were measured using Method I.

Example 8 A sample of Alipal EP-110 was dried in an oven to produce 100% solids material. The dry surfactant was used to decrease the strength of an IOA monomer solution. Using Method II, at fí = 4 cm, a resistance of no more than 10 MO was found for the pure IOA. The addition of 0.75 pph of the surfactant decreased the resistance to 2.0 MO (conductivity of 7.4 μS / m). An additional 0.25 pph of surfactant was added and the resistance dropped to 939 kO (conductivity of 15.8 μS / m). Finally, with a total concentration of 2 pph of surfactant in IOA, the resistance was approximately 81 kO (conductivity of 183 μS / m). This example demonstrates that surfactants can be used to enhance the conductivity of organic solutions.nAN Example 9 A composition was prepared by mixing, at room temperature, 100 pph of a monomer mixture 75/25 of IOA / l, 6-HDDA and 0.02 parts percent of HQ-115. Using Method II, the resistance measurement at a height of H = 4 cm was 4 MO (conductivity 3.7 μS / m). The addition of 0.05 pph of 1, 10-phehroline decreased the resistance to 755 kO (conductivity of 19.2 μS / m). In this way, a polar additive such as 1, 10-phehroline can enhance the dissociation of the lithium salt (conductivity enhancer) by forming a complex with the Li ion.

Example 10 This example demonstrates the use of different conductivity enhancers to otherwise bring essentially non-conductive monomers into a range of conductivity useful for the electro-vacuum application. Some samples also demonstrate the utility of optionally adding dissociation enhancing agents. The samples were prepared by dissolving minimal amounts of the salts in the pure monomer. If the salt did not dissolve at room temperature, the monomer then heated moderately. The samples were then allowed to stand at room temperature for approximately two hours and the solubility was evaluated. Samples that had insoluble materials (particulate materials) were downloaded. Once the salt was determined to be soluble, conductivity was obtained using Method III when measuring the current in microamps (μA). The results are listed in the table below. • • 00 As indicated, the pure monomers are non-conductive, but with the addition of small amounts of the salts of the present invention, the conductivity is increased. For some samples the conductivity was in the range useful for the electro-dew even for the very low concentrations used. More conventional salts, such as NaBF4 or NH4BF4, did not dissolve in these monomers, and therefore, did not increase the ionic conductivity of the acrylate monomer solutions. Some of the salts that were not as effective as conductivity enhancers in a higher concentration can be used or dissociation enhancement agents can be added to increase the concentration of free ions. The monomers of IOA and FOA represent the less polar acrylate monomers. The use of more polar acrylate monomers will probably only enhance the solubility of the salts, and therefore, increase their conductivity enhancing properties. This example also demonstrates that cleavage enhancement agents, such as a polar monomer (e.g., NNDMA) or an alkaline ion forming crown ether complexes, can be used to increase the concentration of free ions and the conductivity of the solutions Example 11 This example demonstrates the use of the salts in the ene-thiol curing polymers. A mixture of master batch monomers was prepared by mixing at room temperature 91.15 g of DMDO and 101.13 g of DVE-3. Using Method III, the measured current was 0.1 μA (conductivity 0.16 μS / m) at a height of fí = 4 cm. (a) To the master batch, 0.044 pph of tetrabutylammonium fluoroborate was added and the current was increased to 4.0 μA (conductivity of 11.2 μS / m). (b) To the master batch, 0.048 pph of LiC (S02CF3) 3 was added and the current was increased to 1.0 μA (conductivity of 1.8 μS / m).

Example 12 An adhesive composition was prepared by mixing at room temperature 80 g of acrylic monomers (made by adding 10% by weight of acrylic acid to a 75/25 monomer mixture of IOA / 1,6-HDDA), 0.16 g of CGI 1700 photoinitiator and 0.12 g of LiN (S02CF3) 2 as a conductivity enhancer.

The composition was electroorbed using a web speed of 9.14 m / minute (30 ft / min) on a sheet of poly (methyl methacrylate) (PMMA) using a process similar to that described in US Pat. No. 5, 326,598 (Seaver et al.) And U.S.S.N. 08 / 392,108 (Seaver et al.). Approximately 0.3 liters of the release coating composition was placed in a small glass jar and extracted by a pump (Masterflex ™ Model 7520-25 booster pump, Micropump ™ Model 07002-26 pump nozzle, both available from Cole-Parmer Instrument Co., Chicago, IL) to the spray nozzle. The electrospray coating spray nozzle consisted of two plastic nozzle halves which, when placed together, maintained a 0.508 mm exit slot along the bottom of the nozzle. Recessed in the slot and compressed to 1.53 mm was a Porex Model X-4920 porous plastic sheet (Porex Technologies, Fairburn, GA) to maintain a reasonable pressure drop and allow a uniform flow. A wire was suspended below the slot and the exhaust bars were suspended parallel to the wire in approximately the same horizontal plane. The slot had a width of 0.318 m and the nozzle caps added another 0.0127 m, creating a 0.33 m segment of the wire wetted by the coating solution. This width of 0.33 m was used in a mass balance equation to calculate the flow velocity required to obtain a desired coating height at any defined speed of the fabric. The wire had a diameter of 1.59 mm and 0.889 mm was placed from the slot. The extractor rods had a diameter of 6.35 mm and were placed on either side of the wire 11.1 mm above the wire and 0.12 m above the grounded metal drum (0.508 m in diameter and 0.61 m in width). The PMMA sheet was joined by a 36 μm thick polyester support fabric (available from 3M) by 3M box sealing tape. The speed of the fabric remained fixed at the speeds listed below for each corresponding sample and the pump was adjusted to produce the listed coating height, or coating thickness. During the coating, the fabric was loaded onto the coating drum using a corotron consisting of a grounded, crescent-shaped conductor made of an ID 72 mm diameter aluminum tube and a 60 micrometer diameter wire coupled to a positive energy source (Model PS / WG-10P30-DM, available from Glassman High Voltage, Inc., hitehouse Station, NJ)). The corotron voltage was adjusted to always charge the polyester carrier fabric at a potential of 1000 volts relative to the grounded coating drum. A negative energy source 30 kV Glassman Model PS / WG-50N6-DM (Glassman High Voltage, Inc.) was connected to the spray nozzle wire. The extractor electrodes were maintained at a ground potential. When a coating flow was present and a high voltage was applied, liquid filaments were formed on the moistened 0.33m length of the wire below the slot. The Rayleigh jet caused a rupture of the filaments creating a mist of negatively charged droplets that were positively attached to the carrier fabric that were attached to the positively charged carrier web. Subsequent to the coating, a second sheet of PMMA was placed on the adhesive coated side of the first sheet and the two-walled "sandwich" was exposed to a high intensity UV light to polymerize. The UV-ray processor (available from GEO AETEK International, Plainfield, IL) consisted of two medium-pressure mercury vapor UV lights inside a gas purge chamber that was inert to the nitrogen gas. These lights were exposed to an energy installation of 4.9 kW / m (125 / pg). The two leaves strongly adhered to each other.

EXAMPLE 13 A composition was prepared by mixing at room temperature 100 g of IOA / AA (ratio of monomers 90/10) containing 12 parts of Ebecryl 230, 0.025 parts of HQ-115 and 2 parts of Darocur 1173, was electro-generated as is described in Example 12, at a coating thickness of 4 micrometers on a polyester protective coating of 38.1 micrometers (1.5 mil). The composition was coated at a speed of 14.1 m / minute (25 ft / m) and cured using a high intensity UV light lamp adjusted to a power of 7.87 kW / m (200 Wats / inch). The total healing energy is approximately 124 mJ / cm2. The cured composition provided a 4 micron thick pressure sensitive adhesive. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention and it should be understood that this invention should not be unduly limited to the illustrative embodiments set forth herein.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following claims is claimed as property.

Claims (19)

1. A polymerizable composition with free radicals, characterized in that it comprises: a) one or more polymerizable monomer (s) with free radicals; b) one or more non-volatile conductivity intensifier (s) having cationic and anionic portions, which are soluble in the monomer (s) and do not interfere with the polymerization wherein the anionic portion is a anion containing carbon, organophilic, uncoordinated; wherein the composition can be coated on a substrate by means of electrostatic assistance.

2. The composition according to claim 1, characterized in that the composition is free of solvents.

3. The composition according to claim 1, characterized in that the monomer (s) is selected from the group consisting of ethylenically unsaturated compounds, ethylenically unsaturated compounds in combination with thiol compounds, multifunctional or polyamines, and mixtures of the same.

4. The composition according to claim 1, characterized in that the carbon-containing, organophilic, non-coordinated anion is further characterized in at least one of the following, the anion: (a) has a formula weight of at least 200 kg / kmol; (b) is selected from the group consisting of alkyl-, cycloalkyl- and arylsulfonates, fluoroalkylsulfonylimides, fluoroalkylsulfonylmethides, arylborates, carboranes, metallocarborans and boron catecholates; or (c) flute.

5. The composition according to claim 1, characterized in that the carbon-containing, organophilic, non-coordinated anion has one of the following formulas: SOzRf p m wherein: X is selected from the groups: H, alkyl, alkenyl, aryl, alkaryl, -S02R-, S02Rf, -S02F, -C (0) R, and -C (0) Rf, R is selected from the groups : alkyl, cycloalkyl, aralkyl, substituted alkyl groups, aryl and substituted aryl; and Rf is an aliphatic, saturated, fluorinated, monovalent radical containing at least one carbon atom.

6. The composition according to claim 5, characterized by at least one of the following: (a) Rf is a perfluoroalkyl or perfluorocycloalkyl group; or (b) X is a group -S02Rf and Rf is a perfluoroalkyl or perfluorocycloalkyl group.

7. The composition according to claim 1, characterized in that the anion containing carbon, organophilic, uncoordinated has the formula IV wherein Rf 'is one or more substituent (s) fluorinated (s) per aromatic ring and is selected from the group consisting of one or more fluorine atoms or aliphatic, saturated, fluorinated, monovalent radicals containing at least one carbon atom .

8. The composition according to claim 1, characterized in that the cationic portion of the conductivity enhancer is selected from the group consisting of alkali metal or alkaline earth cations or complex ions of the group Va, Via or Vlla.

9. The composition according to claim 1, characterized in that it further comprises one or more dissociation enhancing agent (s).

10. The composition according to claim 9, characterized in that the dissociation agent (s) are selected from the group consisting of N, N-dimethyl acrylamide, crown ethers, polyethylene glycol, kryptands, poly (ethylene oxides) , N-vinyl pyrrolidinone, methacrylic acid, 2-ethoxy ethylacrylate, and Carbowax® 750 acrylate.

11. The composition according to claim 1, characterized in that it also comprises one or more free radical initiator (s).

12. The composition according to claim 1, characterized in that it also comprises crosslinking agents.

13. The composition according to claim 1, characterized by at least one of the following: (a) viscosity measurements of about 10 ~ 3 Pa's to about 10 Pa's; (b) conductivity ranges from about 10 ~ 7 S / m to about 10_1 S / m.

14. The composition according to claim 1, characterized in that the composition is applied to a substrate by electro-dew, electrostatic spray or a liquid coating, continuous, electrostatically assisted.

15. A method for applying a composition comprising one or more monomer (s) polymerizable with free radicals and optionally one or more initiator (s), which is such that when they are in combination they have a sufficient conductivity to be applied by methods of electrostatic assistance, the method is characterized in that it comprises the steps of (a) adding one or more conductivity enhancer (s) and optionally one or more dissociation enhancing agent (s) to the composition to produce an application composition; (b) applying the application composition to a substrate by means of electrostatic assistance; and then (c) polymerizing the application composition.

16. A substrate characterized in that it comprises: a) a backing having first and second sides; b) a layer of adhesive having two sides, one side coated on the first side of the backing; and c) a release layer on the second side of the backing comprising a polymerized composition according to claim 1.

17. The substrate according to claim 15 or 16, characterized in that the substrate is selected from the group consisting of poly (propylene), poly (ethylene), poly (vinyl chloride), poly (tetrafluoroethylene), polyester, polyimide film, cellulose acetate, ethyl cellulose, woven fabric, non-woven fabric, paper, cotton, nylon, rayon, glass, metal, metallized polymeric film, ceramic sheet material, abrasive particles, natural or synthetic rubber and ribbons for pavement marking .

18. A substrate having two main surfaces, characterized in that the composition according to claim 1 is electro-corrupted on at least a portion of at least one main surface.

19. The composition according to claim 1, characterized in that the composition is a primer, a thin adhesive, an anti-fog coating, an ice release coating, an anti-graffiti coating, an abrasion resistant coating, a durable coating , a light scattering coating, a stain resistant coating, an abrasive wear resistant coating, or a matt color surface coating.