MXPA98007725A - Coating of release, which can be electrorroc - Google Patents

Abstract

The release coating compositions, polymerizable with free radicals containing conductivity enhancers, which can be electrored on a substrate. The compositions comprise (a) about 100 parts by weight of one or more vinyl monomers (s), polymerizable (s) with free radicals, (b) from about 0.05 to about 250 parts by weight of one or more polymer (s) of polydiorganosiloxane, copolymerizable with the vinyl monomer (s), and (c) from about 0.10 to about 10 parts by weight, based on 100 parts by weight of (a) and (b), one or more conductivity (s) of conductivity, non-volatile (s), which are soluble in the monomers (s) and which do not interfere with the polymerization, where the composition can be electro-rounded. The composition may further comprise from about 0.1 to about 5 parts by weight of one or more initiator (s) based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s). Another embodiment of the present invention further comprises at least 0.1 parts by weight, based on 100 parts by weight of the polydiorganosiloxane monomer (s) and polymer (s), of one or more dissociation intersifying agent (s) soluble (s) in the monomer (s)

Description

COATING OF RELEASE, QDE CAN BE ELECTRONICATED Field of the Invention This invention relates to release coating compositions that can be electro-alloyed on a substrate. More particularly, the present invention relates to release coatings, polymerizable with free radicals containing conductivity enhancers, substrates coated with those compositions, and a method for coating the substrates.

Background of the Invention The release of chemicals into the atmosphere, often air pollution, is of substantial interest. 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 emissions of chemical products is to develop solvent-free processes, and requires that chemical products do not evaporate during processing or the final product.

"REF: 028280 Traditionally, release coatings have been thin solvent-borne coatings, ie, dry thicknesses down to about 5 microns.For liquid, continuous coating techniques, the composition has typically been diluted with a large amount of a solvent that is then removed by evaporation, leaving behind the composition in 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 material costs, preparation costs , and higher solvent removal costs In addition, the solvents typically used can be hazardous to the environment Thin coatings, which carry solvents can also be applied by spray processes, although the spray coating can be used to apply a composition to a smooth substrate, this is particularly useful useful as a coating method for a rough or three-dimensional substrate. A problem associated with conventional spray processes is the poor efficiency of the coating where a substantial amount of the coating composition is not deposited on the substrate. However, electrostatic spraying processes provide a more controlled means of spraying, and thus reduce the loss of material. Electro-splicing, a distinct subclass within electrostatic spraying, can be used to apply a thin coating even without a solvent.

Typically, the electrospray can be used to apply a coating with a thickness of about 0.005 microns to about micrometers Although the electro-alloying process is an effective means to apply a thin coating, not every composition can be electro-roored. The composition must meet certain processing requirements. Among the requirements for the electro-spraying are that the composition is essentially a single-phase solution and not a dispersion (solid-in-liquid) or emulsion (liquid-in-liquid), that the composition has sufficient conductivity, and that the composition have a relatively low viscosity. Although a composition with a conductivity between 10"7 siemens per meter (S / m) and 10" 1 S / m can be electrosprayed, for thin coatings, the droplets are preferably relatively small which requires a comity greater than 10" 6 S / m or 1 microsiemens per meter (μS / m), in the same way, because the range of the flow intensities where a solution can be electro-reduced decreases with the increase in conductivity, to obtain the desired flow intensities in production, the conductivity is preferably maintained below about 10"3 S / m (1000 μS /). The compositions can be electrored with c without a solvent, provided that the composition is either a single phase solution or an ionically stabilized emulsion or dispersion. If the composition is not essentially an individual phase solution, the composition can become unstable during the electro-splicing process. In a single phase solution ("true solution") each component is completely soluble. Frequently, a solvent must also be added to the composition in order to obtain the necessary solubility. This added solvent, particularly if it is organic, can present environmental problems if it evaporates during or after processing and is not captured.

When a composition is truly free of solvents, 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 do not meet this definition because the solvents evaporate during processing. For example, although ethanol or methanol can be added to compositions that can be electro-roored to increase solubility and conductivity, they evaporate during processing. For some free radical scavenging systems, such solvents may interfere with the polymerization by serving as chain transfer agents or as inhibitors, and preferably they are removed prior to cure. Water-based compositions, although sometimes called 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-alloyed are organic, and thus tend to be immiscible in water.

During the electrorrociado, the rolling nozzle places a charge in droplets by the principle of electrostatic induction. For the inductive load to work, the conductivity of the spray composition must be within a specific range. A solvent can be added to a composition to increase the conductivity. To achieve the desired conductivity range, in addition to containing a conductivity enhancer, i.e. salt, the compositions often contain a polar solvent typically considered to be an organic, volatile compound (VOC). These organic, volatile compounds can be dangerous to the environment. For the electrorrociado, solvents have been used to increase the conductivity of the solution. For example, EPO Patent Application No. 92.907947.3 (Mazurek et al.) Publishes the addition of methanol in small amounts to increase the conductivity of an electrorrocytically releasable coating. However, the methanol evaporates during processing, otherwise it may adversely interfere with the polymerization with free radicals. US Patent No. 4,059,444 publishes the addition of quaternary ammonium salts, which have inorganic anions with relatively low molecular weights, as conductivity enhancers such as sulfate, borate and iodide, for inking. These conductivity control agents are added at levels of 0.05 to about 1 weight percent to increase the conductivity of the electrostatically applied inks. U.S. Patent No. 5,364,726 publishes a liquid developer or developer comprising a colorant and a curable liquid carrier, solid particles containing an initiator which is substantially insoluble and agents that optionally increase conductivity such as quaternary ammonium compounds as described in U.S. Patent No. 4,059,444. U.S. Patent No. 4,303,924 publishes the addition of an oil soluble salt such as the quaternary salts of mineral acid and organic acid of the Va Group elements, to a curable printing ink containing from 0 to 30% of a solvent polar organic. All examples include a polar organic solvent. For electro-thinning a thin layer having a uniform thickness, each droplet of the fog of the electrorotria preferably has a sufficiently low viscosity to allow moderate dispersion in the substrate. However, for some applications, it may be desirable to cure the individual droplets on the substrate, for example, slip sheets. Many release coatings known in the art contain talee silicones such as polydimethisiloxane for release properties. In general, the viscosity of these compositions tends not to be low enough for the electro-casting. In this way, the solvents have been added to control the viscosity. Alternatively, the reactive diluents have been added to control the viscosity. For example see W095 / 23694 (Kidon et al.) And US Patent No. 4,201,808 (Cully et al.). Regardless of the method of applying a thin, release liner to a substrate, the components of the release liner preferably do not detrimentally interfere with the final function of the product. A component preferably does not evaporate or interfere with the polymerization or become physically trapped in the coating during processing otherwise the component may migrate within the substrate and adversely affect the function of the product. Alternatively, an uncured component can be subsequently evaporated by contaminating the ambient-te, or subsequently can make contact with another surface, remove, and contaminate that surface. Thus, there is a need for a release coating composition that can be electro-roped where substantially all of the components are present in the final product and either copolymerizes with the other components or otherwise becomes a permanent part of the product. coating.

Brief Description of the Invention Release coating compositions that can be electro-alloyed on a substrate have been found, the components of which do not interfere with the polymerization, and when placed on a substrate and polymerized the compositions do not inconveniently degrade the product . By incorporating the conductivity enhancers according to the invention, a composition which was insufficiently conductive for the coating by means of the electro-spraying can be formulated to achieve the desired conductivity. In addition to achieving adequate conductivity, the conductivity enhancers must be soluble in the composition, not adversely affect the viscosity of the composition, preferably either substantially copolymerize or become a permanent part in the final composition, and not inconveniently degrade the final product. The present invention provides release coating compositions, polymerizable with free radicals containing conductivity enhancers which can be electro-alloyed on a substrate. The compositions comprise (a) about 100 parts by weight of one or more vinyl monomer (s), polymerizable with free radicals, (b) from about 0.05 to about 250 parts by weight of one or more polydiorganosiloxane polymer (s), copolymerizable with the vinyl monomer (s), and (c) from about 0.10 to about 10 parts by weight based on 100 parts by weight of (a) and (b) of one or more enhancer (s) of the conductivity, non-volatile, which are soluble in the monomer (s) and which do not interfere with the polymerization, where the composition can be electro-alloy. The composition may further comprise from about 0.1 to about 5 parts by weight of one or more free radical initiator (s) based on 100 parts by weight of the monomer (s) and the polymer (s) of polydiorganosiloxane. Optionally, at least 0.1 part by weight, based on 100 parts by weight of the monomer and the polydiorganosiloxane polymer, of one or more soluble dissociation enhancing agent (s) in the monomers can be added. The compositions of the release coating have viscosities of less than one pascal-second and are suitable for the electrocasting of thin coatings on a substrate and especially on a substrate similar to a rough or three-dimensional sheet. Another embodiment of the present invention is a "solvent-free" release coating composition which can be applied to a substrate by electro-spraying. Another embodiment of the present invention is the release coating for pavement marking tapes applied by the electro-spraying process.

Detailed Description The addition of certain types of salts, such as ampholytic acid-base pairs or complex cation salts of the Group Va, Vía, or Vlla elements, as conductivity enhancers to an organic mixture comprising polymerizable monomers with free radicals significantly increases the conductivity of the mixture without the addition of a solvent. The addition of a conductivity enhancer allows a release coating composition with insufficient conductivity for the electrorrocation to achieve the required conductivity and thus be electro-alloy.

A special class of electrostatic coating, generally referred to as an electro-porous coating, can be used to create coatings that are submicrometer to a few micrometers in thickness. As with most electrostatic coating methods, the electroorbating process requires free ions (ie the ions which physically separate such that they 'behave as uncoordinated ions) in solution to serve as ion conductors. Ionic conductors, known include salts, acids, water and polar solvents containing the dissociated species. Due to the limitations of the process, the compositions that can be electrored are preferably single phase solutions. Water is often not compatible with (ie, miscible with) an organic solution, and thus such a composition could be an emulsion or a dispersion and not a true solution. In addition, the water must be dried, which adds another step of the process and increases the cost of production. Acids are often volatile and corrosive. As discussed above, polar solvents can be used to increase conductivity by acting as an intensifying dissociation agent. However, polar solvents frequently evaporate during processing and can thus be hazardous to the environment. Therefore, to create a solvent-free composition which can be electro-chlorinated, 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 an aqueous solution in solids. Ideally, a solvent-free composition is 100% reactive and does not have or produce any VOCs. As is known in the art, this ideal composition is difficult if not impossible to achieve. In particular, bulk polymerization significantly decreases the speed at the highest conversions, and thus 100% conversion or polymerization is difficult to achieve, even without considering the economic limitations. To account for the non-ideal nature of the compositions, some level of non-reactive components or volatile components is presumed. The North American Environmental Protection Agency (EPA) establishes a test methodology to measure the content of VOCs by radiation curable materials, as found in the American Society for Verification and Materials D 5403-93. (ASTM for its acronym in English). Test method A applies to "radiation curable materials that are essentially 100% reactive but may contain traces (not more than 3%) of volatile materials 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 ASTM standard and thus have a VOC content of no more than 3 weight percent. In addition to satisfying 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 removed 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 polymerized product. final without considering the source of energy used for healing with free radicals. The non-ideal nature of the polymerization is also allowed in less than 2 percent by the requirement of weight loss. To obtain this solvent-free composition, each component is selected such that during processing, polymerization, and in the final product, the composition does not lose material by evaporation or heat extraction to the extent of 2 percent by weight or more. . In addition, the components preferably do not migrate inconveniently within other layers of the final product, otherwise the properties of the product could be altered perjudicially.

Electro-spraying Process The composition to be electro-rounded first becomes a mist or mist of thin, charged droplets having diameters typically less than about 50 micrometers. The mist or mist of the charged droplets is then directed to some form of the substrate, typically a moving fabric, where the droplets contact the substrate and disperse, typically to the point where they eventually merge or fuse to form the thin coating. (Note, however, that in some applications it may be desirable to cure the individual droplets on a substrate, for example, slip sheets.) In the generator of the fog or mist of the electro-dew, this mist with charged droplets is controlled by the design of the spray nozzle and by applying an electrical potential difference inside the spray nozzle. The difference in electrical potential is often called the applied voltage or simply the voltage. The applied voltage causes the free ions of the composition of a charge polarity to move to specific locations along the air-liquid interface of the composition within the spray nozzle. In an electroorbating process, U.S. Patent No. 5,326,598 (Seaver et al.), The forces caused by the excess of those free ions, which were induced to be at selected air-liquid surface locations, cause the liquid in those locations is enlarged in a series of liquid, fine filaments. These liquid filaments, which now contain the free ions of a specific polarity, will in turn be divided into a series of charged droplets that have a diameter in the order of the diameter of the original liquid filament. All the electro-dew generator and many electrostatic spray generators place the charge in the droplets by electrostatic induction. These induction generators require that the composition to be sprayed contains a sufficient amount of free ions for the droplets to become charged. The conductivity of the composition should be in the range of about 10 ~ 7 to about 10-1 S / m, although the preferred conductivity is dependent on the application of the specific coating. For the composition of the release coating of the present invention, the conductivity is preferably from about 10_c to about 10"" S / m (1 to 1000 μS / m), and more preferably from about 10 to about 50 μS. / m. The Rule of alden. { Jordán, P.C., Chemical Kineti cs and Transport, Plenum Press, New York (1980)) conditions that for a given system the product of the ionic conductivity multiplied by the viscosity is approximately a constant. In this way, the ionic conductivity can be increased by decreasing the viscosity. However, the viscosity of the droplet is preferably maintained very low to allow for improved dispersion and flattening of the coating in a short time. Consequently, in an electro-spraying coating, the viscosity of the composition is less than one pascal-second (Pa's), with the preferred lower range of a few tens of millipascal-seconds (mPa's). Typically, viscosity measurements of approximately 10 ~ 3 Pa's to approximately 1 Pa's. Because the viscosity stays down for all generators 'electrostatic, the type of induction, the desired conductivity can not be easily obtained by adjusting the viscosity.

Without the necessary conductivity, a composition can not be electrored. This substantially limits the use of this method of application. However, by adding certain types of salts to those compositions to provide sufficient conductivity, the compositions. which can not be electro-braided, previous can now be applied to substrates by the electro-splicing according to the present invention.

Conductivity Intensifiers Salts, as conductivity enhancers, contain ions that are held together by a coulomb attraction. Simply having ions present does not mean that a saline solution is an adequate ion conductor. The electrostatic attraction joins the ions of opposite charges together in pairs of ions that substantially impede the ionic conductivity. Therefore, to be suitable conductors, the ion pairs must at least partially dissociate and the ions become independent, that is, become free ions (or, less preferably, triplets of ions). Free ions can significantly increase the ionic conductivity of a composition conditional on having sufficient inherent mobility to easily respond to the electric field applied to the composition. The ability of ion pairs to dissociate in a composition depends on several factors such as the dielectric constant of the medium. As with the other components, the ion pairs must be soluble in the mixture to form a true solution so that the composition is potentially electro-decomposable. 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 composition of the release coating of interest is organic, salts with at least one organic ion typically have better solubilities. The solubility of such an organic sai 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 ions of opposite charges, which allows the ion pairs to separate into free ions. In general, dissolved salt ions can be tightly matched (coordinate), and thus be essentially non-conductive, or they can be (as a result of their structure and environment) easily and physically separated such that the ions function as non-ionic ions. coordinated (or free) which are substantially conductive. When the organic compositions become less polar and thus have a lower dielectric constant, the balance between the free ions and the narrow ion pairs changes towards the latter. Therefore, salts that dissolve to form ion pairs which readily dissociate into free ions despite less favorable conditions (ie, low polarity and mixtures of low dielectric constants) are conveniently selected to increase the conductivity. It is believed that the dissociative separation ease of two ions is favorably influenced by the delocalisation of the charge in one or both of the ions and / or by the steric hindrances around the center of the charge which prevents the close coordination of the counterions in an ion pair. Steric hindrance around the site of ion loading can reduce accessibility to counter ion and therefore ions tend to be less closely matched. If the blockage groups spherically do not interfere with the solubility of the salt, the greater steric hindrance will favor the separation of the ion pair in individual ions and tends to increase the conductivity of the composition. However, the increased ion size will eventually reduce the conductivity due to the reduction in ion mobility. Ions can have multiple charges. In general, monovalent ions solubilize and dissociate more readily in 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 favors the aggregation of narrow ions over the larger distances. Polymeric ions, such as from a salt of polyacrylic acid, are severely restricted in mobility, and thus, are limited in conductivity especially in viscous media.

The conductivity enhancers of the invention are not volatile, or their vapor pressures are 1 kPa or less at 25 ° C, preferably less than 0.5 kPa at 25 ° C, and more preferably less than 0.1 kPa at 25 ° C. ° C. Preferably, the conductivity enhancers do not decompose to form volatile products, or become heat removable at any time during processing or the final product. Preferably, the conductivity enhancers should increase the conductivity of the composition when added in relatively low amounts. Typically from about 0.10 parts by weight to about 10 parts by weight, based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s), is added to the conductivity enhancer (s), Preferably, from about 0.5 parts by weight to about 5 parts by weight, based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s), of the enhancer (s) are added. conductivity. In addition, the conductivity enhancer (s) should not interfere with the polymerization of the composition. The conductivity enhancers useful in the present invention include the amfolitic acid-base pairs and complex cation salts of the elements of the groups Va, Via, or Vlla. Preferably, at least a part of the ampholytic acid base pair or a portion of the complex cation salt of the elements of the groups Va, Via, or Vlla of the selected conductivity enhancer is copolymerizable with the rest of the composition. However, if conductivity enhancers are added in a small amount and physically trapped within the cured composition and thus do not migrate to other layers of the substrate, evaporate or become extractable when heated, the conductivity enhancers do not they need to be copolymerized. The migration of the conductivity enhancers can inconveniently interfere with the properties of the final product. Suitable acid / base, ampholytic pairs include N, N-dimethylaminoethyl (meth) acrylate / (meth) acrylic acid; methacrylic acid / diethanolamine; cronic acid / 2-vinylpyridine; itaconic acid / 2-diethylaminoethyl acrylate; methacrylic acid / 2-diethylaminoethyl acrylate; acrylic acid / 2-diethylaminoethyl acrylate; acrylic acid / 2-diethylaminoethyl methacrylate; N-vinylglycine; p-styrenesulfonic acid / 4-vinylpyridine; ethylenesulfonic acid / 4-vinylpyridine; zwitterion of l-vinyl-3- (3-sulfopropyl) imidazolium hydroxide; zwitterion of l-vinyl-2-methyl-3- (3-sulfopropyl) imidazolium hydroxide; zwitterion of 1-vinyl-3- (4-sulfobutyl) imidazolium hydroxide; zwitterion of l-vinyl-2-methyl-3- (4-sulfobutyl) -imidazolium hydroxide; zwitterion of l-vinyl-3- (2-sulfobenzyl) imidazolium hydroxide; zwitterion of 2-vinyl-l- (3-sulfopropyl) pyridinium hydroxide; zwitterion of 2-methyl-5-vinyl-l- (3-sulfopropyl) pyridinium hydroxide; zwitterion of 4-vinyl-1- (3-sulfopropyl) pyridinium hydroxide; zwitterion of dimethyl- (2-methacryloxyethyl) (3-sulfopropyl) ammonium hydroxide; zwitterion of diethyl- (2-methacryloyloxyethoxy-2-ethyl) (3-sulfopropyl) ammonium hydroxide; zwitterion of 4-vinyl-4- (sulfobutyl) pyridinium hydroxide; zwitterion of 2-vinyl-2- (4-sulfobutyl) pyridinium hydroxide; N- (3-sulfopropyl) -N-methacrylamido-propyl-N, N-dimethylammonium betaine; N- (3-carboxypropyl) -N-methacrylamido-ethyl-N, N-dimethylammonium betaine; 4-vinylpiperidinium ethanocarboxy-betaine; 4-vinylpyridinium methanocarboxy-betaine; 4-vinylpyridinium / p-styrenesulfonate; 4-vinyl-N-methylpyridinium / p-styrenesulfonate; 2-methacryloylethyltrimethylammonium / 2-methacryloyloxyethanesulfonate; and the like (see for example Polymer Science and Engineering, vol.11, page 514 under polyamolytes). The complex cation salts which are useful as the conductivity enhancers have the general formula: wherein at least one R is a hydrocarbon having from about 1 to about 18 carbon atoms and each other R is a hydrogen or a hydrocarbon having from about 1 to about 18 carbon atoms, preferably all Rs are hydrocarbon , B is an element of the groups Va, Vía, or Vlla, n is an integer from 2 to 4, and A is an inorganic anion, for example, sulfate, borate, perchlorate, nitrate, thiocyanate, and halogens such as iodide, chloride, and bromide. R may contain ethylenically unsaturated, copolymerizable groups such as acrylate or methacrylate (eg, Ageflex ™ quaternary ammonium acrylates, available from CPC Chemical, Old Bridge, NJ). Preferred complex cation salts include tetraoctylammonium chloride, tetrabutylammonium bromide, tetrabutyl onothiocyanate, tetrabutylphosphonium bromide, and the like. If desired, mixtures of two or more conductivity enhancers may be used.

Dissociation Intensification Agent Dissociation of ion pairs can also be increased by the addition of one or more dissociation enhancing agents. Those dissociation enhancing agents will associate with (ie, "stabilize") one or both of the conductivity enhancer ions. As with each component, the dissociation enhancing agents when added preferentially must comply with the "solvent free" requirements and preferably not interfere with the polymerization. Typically, when present in the composition, at least 0.1 part by weight, based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s) are added, preferably about 0.5 are added to the composition. about 5 parts by weight based on 100 parts by weight of the monomer (s) and the polydiorganosiloxane polymer (s). Preferred dissociation intensifying agents have a dielectric constant of at least 5 at 20 ° C. More preferably, the dielectric constant is at least 10 to 20 ° C and much more preferably at least 20 to 20 ° C. Examples are well known in the art and include materials such as polyethylene glycols, glycerols, propylene carbonates, poly (ethylene oxides), and dialkylureas. Small amounts of co-reactive monomers 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-vinylpyrrolidone, N, N-dimethylacrylamide, methacrylic acid, 2-ethoxyethyl acrylate, Carbowax ™ 750 acrylate (Union Carbide, Danbury, CT), and the like.

Monomers The monomers selected for those compositions are essential and completely miscible with the other components of the mixture. In addition, these monomers have sufficiently low vapor pressures so that a small 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, its vapor pressures are less than 0.5 kPa at 25 ° C, and more preferably less than 0.1 kPa at 25 ° C. Useful monomers include both monofunctional and multifunctional vinyl monomers. Monofunctional monomers, curable with typical radicals, include vinyl monomers which can serve as reactive diluents for the polydiorganosiloxane polymers. Suitable vinyl monomers include, but are not limited to, styrene, butyl acrylate, hexyl acrylate, benzyl acrylate, cyclohexyl acrylate, isobornyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate. , 2-ethylhexyl acrylate, octadecyl acrylate, butyl methacrylate, isobornyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl acrylate, vinyl pivalate, vinyl 2-ethylhexanoate, and mixtures thereof. Such monomers are known in the art, and many are commercially available. Preferred monofunctional vinyl monomer mixtures contain predominantly (i.e., about 50 to about 100 mole percent) of the acrylic monomer due to its rapid cure rate. Most preferred monomers comprise the acrylic monomers selected from the group consisting of acrylic acid esters of non-tertiary alcohols comprising from about six to about twelve carbon atoms, such as those selected from the group consisting of cyclohexyl acrylate, isobornyl, isooctyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and mixtures thereof, due to their good solvation capacity, high "reactivity and low volativility." Polymerizable, free radical polymerizable monomers include, but are not limited to, divinyl benzenes, and acrylates, methacrylates, and beta-acryloxypropionates of alkyl polyols such as 1,6-hexanediol, trimethylolpropane, 1,4-butanediol, tri- and tetraethylene glycol, pentaerythritol, their ethoxylated analogs and propoxylates, and mixtures thereof, such monomers are included in the composition to ensure the speeds fast curing and a tightly reticulated coating. Preferred multifunctional monomers include 1,6-hexanediol acrylates, trimethylolpropane, their ethoxylated and propoxylated analogues and mixtures thereof. Mixtures of one or more suitable monomers can be used if desired.

Initiators The free-radical polymerization of those compositions should be carried out in an oxygen-free environment as possible, for example, in an inert atmosphere such as nitrogen gas. In general, the initiator comprises from about 0.1 to about 5 parts by weight based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s).

Polymerization can also be initiated with irradiation of. high energy, such as a beam of electrons 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 which undergo fragmentation in irradiation, initiators of the type of subtraction of hydrogen, and complexes of donors-receivers. Suitable fctof agmentation 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, 2-hydroxy-2-methyl acetophenone. -l-phenylpropan-1-one, 2, 2, 2-trichloroacetophenone and the like. Suitable initiators of the type of hydrogen subtraction include benzophenone and derivatives thereof, anthraquinone, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone) and the like. Suitable donor-receptor complexes include combinations of donors such as triethanolamine with receptors such as benzophenone. Sensitizers with initiators such as thioxanthone with quinoline sulfonic chloride are also suitable. Thermal energy can also be used to initiate polymerization. The thermal initiators can be selected from conventionally available peroxide or azo type materials. Illustrative examples include benzoyl peroxide, 2,2'-azobis (isobutyronitrile), 1,1'-azo-bis (cyclohexane-1-carbonitrile), dicumylperoxide and the like. Redox initiators, such as amines with peroxides, salts of cobalt carboxylate with peroxides, or persulfate / bisulfide redox pairs, can also be used conditional on the initiators being completely soluble in the monomer mixtures and not prematurely initiating the reaction interfering with the coating process by slowly increasing the viscosity of the solution. If needed, the initiator can be applied first to the substrate by any conventional means.

Polydiorganosiloxane Polymers In general, the silicone release component is a polydiorganosiloxane polymer which is known to have release characteristics. In general, these polymers are themselves crosslinkable and have crosslinkable groups such as ethylene-unsaturated groups, for example, acrylates, methacrylates, acrylamides, methacrylamides, α-methylstyrene, and vinyls. Suitable polydiorganosiloxane polymers include those selected from the group consisting of polymers that fall within the general formula: X-Y-N-R'-Si-O-. { Si-O) n-Si-R'-N-Y-X! I I R R R and mixtures thereof, wherein: X are monovalent portions having an ethylenic unsaturation which may be the same or different; And they are liaison groups, divalent which may be the same or different; D are monovalent portions which may be the same or different selected from the group consisting of hydrogen, an alkyl group of 1 to about 10 carbon atoms, and aryl; each R is a monovalent portion independently selected from alkyl portions preferably having from about 1 to 12 carbon atoms and which may be Replace with, for example, trifluoroalkyl or vinyl groups, cycloalkyl portions having preferably about 6 to 12 carbon atoms and which are Can be substituted with the alkyl, fluoroalkyl and vinyl groups, the aryl portions having preferably from about 6 to 20 carbon atoms and which are can be substituted with, for example, alkyl, cycloalkyl, fluoroalkyl and vinyl groups, preferably at least 50 percent of the portions of R are radicals Methyl with the moiety being monovalent alkyl or substituted alkyl radicals having from 1 to 12 carbon atoms, vinylene radicals, phenyl radicals, or substituted phenyl radicals; R 'are divalent hydrocarbon groups which may be the same or different; and n is an integer from about 25 to about 750. For example, copolymerizable polydimethylsiloxanes, such as ACMAS (acrylamido amido siloxane) and MAUS (methacryloxyurea siloxane) as published in EPO Patent Application No. 92.907947.3 (Mazurek) and collaborators) can be added to the composition to obtain release properties. Other suitable polydiorganosiloxane polymers are disclosed in U.S. Patent No. 4,908,274 (Jachmann et al.) Commercially available from Glodsch idt Chemical Co. , for example as Tego ™ 'RC-706 and Tego ™ RC-726. "US Patent No. 4,908,274 publishes polysiloxanes with (meth) acrylate ester groups bonded to SiC groups which can be obtained by the reaction of the epoxy functional polysiloxanes of the general formula wherein R1 are the same or different lower molecular weight alkyl groups with 1 to 4 carbon atoms or phenyl groups, R2 is the same as R1 or represents the R3 group, 70 to 100% of the R3 groups which are functional groups epoxy and 30 to 0% which are alkyl groups with 2 to 20 carbon atoms or hydrogen, with the proviso that the average molecule contains at least 1.5 epoxy groups, a is an integer having a value from 1 to 1,000 and b is a integer having a value from 0 to 10, with such amounts of an acid mixture, consisting of (a) 10 to 90 mole percent of (meth) acrylic anhydride, and (b) 90 to 10 mole percent of (meth) acrylic acid that the sum of (a) and (b) adds up to 100 mole percent, and that 0.8 to 1.9 equivalents of acid per equivalent of epoxide are present. Other suitable polydiorganosiloxanes include copolymer compositions of polydiorganosiloxane oligourea segments of the general formula wherein each Z is a divalent radical selected from arylene radicals and aralkylene radicals having is preferably from about 6 to 20 carbon atoms, alkylene and cycloalkylene radicals preferably having from about 6 to 20 carbon atoms, preferably Z is 2,6-tolylene, 4,4'-methylene-diphenylene , 2,2'-dimethoxy-4, '-diphenylene, tetramethyl-m-xylylene, 4,4'-methylenedicyclohexylene, 3,5,5- 15 trimethyl-3-methylenecyclohexylene, 1,6-hexamethylene, 1, 4-cyclohexylene, each R is a monovalent portion independently selected from the alkyl portions having Preferably of about 1 to 12 carbon atoms and which can be substituted with, for example, trifluoroalkyl or vinyl groups, the cycloalkyl portions having preferably about 6 to 12 carbon atoms and which can be substituted with the alkyl, fluoroalkyl and vinyl groups, the aryl portions having preferably about 6 to 20 carbon atoms and which can be substituted with, for example, alkyl, cycloalkyl, fluoroalkyl and vinyl groups, Preferred at least 50 percent of the portions of R are methyl radicals with the moiety which are monovalent alkyl radicals or substituted alkyl radicals having from 1 to 12 carbon atoms, vinylene radicals, phenyl radicals, or radicals of substituted phenyl; every Y is a divalent portion independently selected from the alkylene radicals having preferably from 1 to 10 carbon atoms, aralkylene radicals and arylene radicals; each D is a monovalent radical independently selected from the hydrogen, alkyl radicals preferably having from 1 to 10 carbon atoms, aryl or arylalkyl radicals preferably having from about 6 to 20 carbon atoms; and p is a number which is approximately or larger, preferably from about 15 to 2000, more preferably from about 30 to 1500; which is a number which is approximately or larger, preferably from about 15 to 2000, more preferably from about 30 to 1500; t is a number which is from 0 to 20 approximately 8; and each X is independently (a) a portion represented by Ó O II II -Y__ -C-N-Z-N-C-L-K H H where each of Z, Y, and D are as defined above, 10 L is independently -N- K is an end group curable with free radicals such as, for example, acrylate, methacrylate, acrylamido, methacrylamido, α-methyl styrene, and vinyl groups; or (b) a portion represented by _? _ N-C-N- K I I D H wherein D, Y and K are as defined above.

The polydiorganosiloxane polymers preferably do not detrimentally interfere with the conductivity and sprayableness of the monomer mixture. The composition of the release coating of the present invention can be prepared by combining (a) about 100 parts by weight of one or more vinyl monomer (s), and (b) from about 0.05 to about 250 parts by weight, of preferably from about 0.05 to about 200 parts by weight, and more preferably from about 0.05 to about 100 parts by weight, of one or more polydiorganosiloxane polymer (s). From about 0.10 to about 10 parts by weight based on 100 parts by weight of (a) and (b), preferably from about 0.5 parts by weight to about parts by weight, based on 100 parts by weight of (a) and (b), of one or more conductivity intensifier (s). The composition may further comprise from about 0.1 to about 5 parts by weight based on 100 parts by weight of (a) and (b), of one or more free radical initiators, and optionally, at least 0.1 part may be added in Weight based on 100 parts by weight of (a) and (b) of one or more dissociation enhancing agent (s), to provide sufficient conductivity to produce the electro-spraying an application composition. This application composition can be electrored on a substrate and then polymerized. The vinyl monomer (s) can (are) a mixture of both monofunctional and multifunctional vinyl monomers. The monofunctional vinyl monomer (s) typically ranges from about 40 to about 95 parts per 100 parts of the vinyl monomer, preferably from about 50 to about 90 parts, and much more. preferably from about 60 to about 90 parts. The multifunctional vinyl monomer (s) typically varies from about 5 to about 60 parts per 100 parts of the vinyl monomer, preferably from about 10 to about 50 parts, and much more. preferably from about 10 to about 40 parts. Preferred multifunctional vinyl monomers have from 2 to 6 functional groups. The most preferred muitifunctional monomers have from 2 to 3 functional groups. Additives such as opacifying agents, colorants, plasticizers, tackifiers and the like can be used or flow enhancers, non-functional and wetting agents can be added to improve the aesthetics of the coating. These additives must be soluble in solutions that can be sprayed, not be volatile, and preferably not interfere per udicially with the conjunctiveness, the polymerization, c the final properties of the compositions. The composition can be electro-chlorinated on the substrate and then polymerized by exposure to an electron beam, gamma rays, visible light, ultraviolet radiation, or heat. Typically, the substrate has 2 major surfaces, and the composition of the release coating is applied to at least a portion of at least one major surface. One embodiment of the present invention is a substrate comprising a backing having a first and a second side, a layer of adhesive having two sides, a side covered on the first side of the backing, and a release layer on the second side of the backing comprising the polymerized release coating composition. Preferably, the composition of the release coating is electro-generated on the second side of the backrest. When the release liner is used on the pavement marking tapes, and other such rolled substrates, the substrate is wound such that the first side of the backing (if the adhesive has since coated the adhesive layer) makes contact with the substrate. liberation layer. Suitable substrates include, but are not limited to, a sheet, a fiber, or a patterned object. Preferred substrates are those used for the products of pressure sensitive adhesives. The composition can be applied to at least one main surface of 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 (eg, poly (ethylene terephthalate)), polyamide film such as DuPont Kapton ™, cellulose acetate and ethyl cellulose, although any surface that requires release from the adhesives can be selected. The backs can also be constructions with irregular surfaces such as woven fabrics, non-woven fabrics, paper or rough surface. In this manner, the backs may also be woven fabric formed of synthetic yarns or materials such as cotton, nylon, rayon, glass, or ceramic material, or they may be non-woven fabrics such as airlaid fabrics. of natural or synthetic fibers or mixtures thereof, conditioned to the fact that they are not very porous. Due to its high porosity, paper by itself is usually not suitable, unless heavier coatings are applied to counteract impregnation within the paper. However, paper coated or impregnated with plastic is useful. The 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. Unless stated otherwise, the following test methods are used in the examples.

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 heated moderately (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 The Brookfield viscosity (in centipoise (cp), 1 cp = 1 Pa) 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 fí was the height of the meniscus of the solution relative to the background of the bars. When the bars were placed at a solution at a high altitude, and an electric potential was applied through the bars, an electric current was intended to flow between the bars. The solution, air and isolator provided a net resistance R for the flow of electric current. When the bars were placed at the height f 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 approximately 10 ~ 12 S / m or 10"6 μS / m, and the conductivity of the insulators is even lower, in this way for a solution that has a conductivity greater than 0.001 μS / m the resistance -R, within 0.1 percent, was actually 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 = J? s. G depends on the height f as well as other fixed parameters such as the separation-diet 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 using a solution that has a known conductivity s0 that gives a resistance R0 when the bars are placed at some specific height In the eolution, because the geometric factor GO was determined from G0 = R0s0. Knowing Ho r g was determined using g = G0H0 Because g is a constant, g = G0fí0 = GR, and because g is known, G can be determined for any immersion depth of the electrode-bar f. To calibrate the electrode-bar cell, the g cell constant was determined using several saline solutions of known conductivity (Standard Reference Materials (1500, 10000 and 50000 μS / m), available from the National Institute of Standards and Technology (NIST by its initials in English), 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 lejoe of 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 for the height fí. 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) Impedance Analyzer Model 4192A (Hewlett Packard Company, Palo Alto, CA) was connected through the stack and admittance Y and angle D were recorded ep the F frequencies of 100, 300, 500, 700, 900, and 1000 kilohertz (kHz) together with the immersion depth fí of the bars in the eolución. This information was used to calculate the conductivity by the formula s = (gYcosD) / H. For method I, the dielectric constant er of the solution can also be calculated by the formula e- = (gYsinD) / (2pe0FH) where e0 is the permittivity of the 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 tub and the resistance R at a frequency F of 1 kHz measured together with the immersion depth f 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 high altitude in the solution the switch S was momentarily closed and the initial reading Is on the ammeter was recorded. Together with Is, the immersion depth fí of the electrodoes was recorded. In Method III, the battery voltage Vb can be connected through a switch placed in series with an ammeter and a calibration Rc re-calibrator of 1 MO. When this switch was closed, the edited current Ic multiplied by the resistor Rc gave the battery voltage. This information was used to calculate the solution's conductivity using the formula The following materials were used in the Examples: tri (n-octy!) amine (TOA) Aldrich Chemical Company, Milwaukee, Wl Synthesis of 5K MAUS and 5K ACMAS Those polydimethylsiloxanes curable with free radicals (PDMS for its acronym in English) are made according to the procedure summarized in the patent application of EPO No. 92.907947.3 (Mazurek and collaborators). A PDMS of molecular weight a,? -bis (3-aminopropyl) of 5,000 (EPO Patent Application No. 93.924905.8 (Leir et al.)) Was made to react in volume with either 2-isocyanotoethyl methacrylate for produce 5K MAUS, or vinyl dimethylazlactone (prepared as in U.S. Patent No. 4,777,276, Rasmuesen et al.) to produce 5K ACMAS. 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 masterbatch was prepared by mixing quantities of 60 grams of monomer mixtures I0A / 1,6-HDDA 75/25 with the following additives, as detailed in the following table. At rest, sample 11 exhibited phase separation. The Comparative Sample A, that is, the material of the batch maeetro ein additives, had zero conductivity. The conductivity was then measured as described in Method III with the samples at a height H = 5 cm.

Example 2. A composition of the release coating (ie sample I) was prepared by mixing at room temperature 100 parts of a 75/25 monomer mixture of IOA / 1, 6-HDDA, 25 parts of 5K MAUS, 2 parts of Darocur 1173, 0.5 parts of Aliquat 336 and 1 part of NNDMA. A clear, homogeneous solution was obtained. A particular mixing order is not necessary to obtain the conductivity although preferentially the high viscosity components are added in the listed order. Using Method II, a resistance of 326 KO was measured at fí = 4 cm with the LCR meter giving a conductivity of 45.6 μS / m. As a comparison, the composition of the release coating described in sample I was prepared without Aliquat 336 and NNDMA. The current was measured as described in Method III and found to be zero (conductivity also zero). This composition does not meet the conductivity requirements for the electro-dew without a conductivity enhancer and a dissociation agent.

Example 3. A composition of the release coating was prepared by mixing at room temperature 100 partse of the 75/25 mixture of IOA / 1, 6-HDDA, 25 pph Tego RC726, and 2 pph of Darocur 1173. The re-exercise was in excess of the limit of the 10 MO instrument of the LCR meter indicating that the conductivity was less than 1.5 μS / m (measured according to Method II). To make this composition more conductive, 2 pph of NNDMA and 1.5 pph of Aliquat 336 were added. The resulting composition was clear and at a height fí = 4 cm the resistance fell to 606 KO (conductivity of 24.5 μS / m), giving a composition within the most preferred range for the electrorrociado.

Example 4. This Example demonstrates a heat curable composition with increased conductivity in the addition of a complex cation salt and a dissociation enhancing agent. A composition of the release coating was prepared by mixing at room temperature 100 partse of the 75/25 mixture of IOA / 1.6-HDDA, 25 pph of Tego RC726, and 2 pph of VAZO 64 and a conductivity of less than 1.5 was measured. μS / m according to Method II. With the addition of 1.5 pph of Aliquat 336, the resistance at a height fí = 4 cm fell to 3.12 MO (conductivity of 4.8 μS / m). With the addition of 3 pph of NNDMA, the resistance also fell to 731 kO (conductivity of 20.3 μS / m) which was within the most preferred range for the electro-torque.

Example 5. A composition of the release coating was prepared by mixing together the following by simple simple agitation in a jar at room temperature: 100 parts of a 70/30 mixture of IOA / 1, 6-HDDA, 5 pph of 5K ACMAS, 2 pph of Darocur 1173, 1 pph of N-vinyl pyrrolidone, and 0.5 pph of Aliquat 336. The mixture was clear and at a height of fí = 4 cm it had a resistance of 616 kO (conductivity of 24.1 μS / m) measured according to with Method II.

Example 6. The composition described in Example 5, substituting the mixture of IOA / 1, 6-HDDA in a ratio of 60/40. The resistance at a height of 4-cm was 557 kO (conductivity of 26.7 μS / m) measured according to Method II.-Example 7. A composition of the release coating comprising 100 parts of the mixture was prepared. monomers 75/25 of TDA / BDA, 25 pph of 5k MAUS, 2 pph of Darocur 1173, 1 pph of NNDMA, and 0.5 pph of Aliquat 336 when stirring the components in a jar at room temperature. The resistance at a height of 4-cm was 632 kO (conductivity of 23.5 μS / m) measured according to Method II.

Example 8. This Example demonstrates the electro-spraying of the release coating having the acid-base, ampholytic pairs on the tapes for pavement marking. A composition of the release coating was prepared by mixing together the following: 450 g of IOA_ 150 g of 1,6-HDDA 60 g of 5K ACMAS 12 g of Darocur 1173 30 g of N DMA 8.6 g of MAA 12 g of DMAEA The The composition of the release coating was electro-corroded on the pavement marking tapes, indicated, available from Minnesota Mining and Manufacturing Co. (3M), St. Paul, MN, using a process similar to that published in U.S. Patent No. 5,326,598 (Seaver et al.), And U.S. S.N. 08 / 392,108 (Seaver and collaborators). Approximately 0.3 liters of the release coating composition was placed in a small glass jar and a pump was withdrawn (Masterflex® Model 7520-25 drive pump, Micropump ™ Model 07002-26 pumping nozzle both available from Cole -Parmer Instrumenc Co., Chicago, IL) for the rolling nozzle. The coating nozzle of the electrorrociado consisted of two halves of the nozzle, of plastic which when placed together maintained a height of the exit opening of 0.508 mm along the bottom of the nozzle. Inserted into the opening 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 extraction bars were suspended, parallel to the wire in approximately the same horizontal plane. The opening tube had a width of 0.318 m and the end caps of the nozzle added another 0.0127 m, creating a 0.33 m segment of the wet wire 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 layer height, desired at any defined web speed. The wire had a diameter of 1.59 mm and was 0.899 mm from the opening. The extraction rods each tube 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 metal coating drum, grounded (0.508 m in diameter and 0.61 m in width). Lae mueetrae of the pavement marking tapes (each approximately 0.33 by approximately 0.91 m) were attached to the 36-μm thick polyester support fabric (available from 3M) by an available box sealing tape. of 3M. The speed of the fabric remained fixed at the speeds listed below for each corresponding sample and the pump was adjusted to produce the height of the layer or the thickness of the coating, listed. During the coating, the fabric was loaded into 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 wire. diameter attached to a positive energy source (Model PS / G-10P30-DM, available from Glassman High Voltage, Inc., Whitehouse Station, NJ)). The corotron voltage was adjusted to always load the support fabric, polyester at a potential of .1000 volts relative to the coating cylinder, grounded. A 30 kV negative energy source Glassrr-an Model PS / WG-50N6-DM (Glassman Kigh Voltage, Inc.) was connected from the ground to the wire of the spray nozzle. The extractor electrodes were held at ground potential. When a coating flow was introduced and the high voltage was applied, liquid filaments were formed on the wet 0.33m length of the wire below the slot. The instability of the Rayleigh jet caused the filaments to rupture creating a mist or mist of negatively charged droplets which were attracted to the positively charged support fabric. Subsequent to the coating, the samples were cured with UV rays in a UV-ray processor (available from GEO AETEK International, Plainfield, IL) consisting of two UV lights of mercury vapor, medium pressure inside a purge or purification chamber of gas which was inert with nitrogen gas. Each light could be adjusted to an energy setting of 125, 200, 300 and 400 watts per inch (4.92, 7.87, 11.8 and 31.4 k / m). The pavement marking tapes were covered with the release liner at a range of heights (thickness) as described below. As shown, with the addition of a conductivity enhancer, the tapes for marking the pavement, different can be electrocorroced at different coating heights and speeds of the fabric.

Example 9. This Example demonstrates the electro-sputtering of a release coating having a complex cation salt on pavement marking tapes. A composition of the release coating was prepared by mixing together the following: 100 parte of mixture 75/25 IOA / l, 6-HDDA 25 parts of 5K MAUS 0.42 parts of Aliquat 336 1 part of NNDMA 2 parts of Darocur 1173 The release coating was electrocoated onto the following available 3M pavement marking tapes as described in Example 8: Example 10. Pavement marking tapes were electro-cemented with a release liner and measurements of silicone transfer were taken. A composition of the release coating was prepared by mixing the following components at room temperature in a suitable container: 1800 g of IOA_ 600 g of 1, 6-HDDA 24 g of NNDMA 12 g of Aliquat 336 600 g of 5K MAUS 48 g of Darocur 1173 The release liner was applied to the pavement marking tapes subsequently listed by the electro-casting. The electrocoating and UV curing coating assembly used was as described in Example 8 except that the assembly was capable of holding continuous webs of 1.27 m ± 0.05 in width. In order to measure the transfer of silicone, the following procedure was followed: a pressure-sensitive adhesive, based on reein, of polybutadiene was directly recovered on a polyester film recorded by ion spray (4 mil (101.6 μm) available from 3M). A strip of this adhesive-coated polyester was applied to the side with the release coating of each of the samples. The samples were then placed under a 2.27 kg (5 lb) mass for three days in order to facilitate the transfer. A glass panel was placed on top of each sample in order to evenly distribute the weight over an equal area, 102 mm x 152 mm (4-inch x 6-inch). The adhesive was removed from the surfaces just before loading it into the spectrometer (Model 5100, available from Physical Electronics, Eden Prairie, MN). The silicone transfer was measured using an X-ray Photoelectron Spectroscopy (XPS for its acronym in English). The XPS recognition spectra of the adhesive surface indicate that all samples contain silicone. The XPS at angles determined at 45 ° and 90 ° was used to estimate silicone levels on the surface and near the surface regions. The measured atomic concentrations were listed in the following table. Prior to exposure to the electrocorrosed release liner, the adhesive had not been exposed to any of the silicone sources. Therefore, all of the silicone detected on the surface of the adhesive after expo- sure can be attributed to the transfer of the electrospray release coating. For pure polydimethylsiloxane, the atomic percentage of the silicone is approximately , in this way the transfer of silicone from the electrorecorded release liner is minimal.

Example 11. This Example (parts (a) and (b)) demonstrates the effectiveness of a dissociation enhancing agent. A composition was prepared by mixing the following in a suitable container at room temperature: g of 75/25 I0A / 1,6-HDDA with 5% of 5K ACMAS 0.72 g of acrylic acid 1.13 g of DMAEA The conductivity of the composition was determined as described in Method I. The conductivity was 1.2 μS / m. Then the following mueetras were prepared. a) 5 parts of 2-hydroxy ethylacrylate were added to 100 parts of the original composition. The conductivity was measured and found to be 3.5 μS / m b) 5 parts of NNDMA were added to 100 parts of the original composition. The conductivity was measured and found to be 4.0 μS / m. Two parts of Darocur 1173 were added to the sample (b) and the sample was then electro-corroded on a 3M available Stamark ™ pavement marking tape. The composition was electrored as described in Example 8, with a fabric speed of 9.14 m / mir. (30 fpm) and applied to the tape for marking in a range of coatings heights. The composition was then cured with UV rays under an inert atmosphere. Using the silicone transfer test described in Example 10, the atomic concentrations of the silicone were measured at an angle of 45 °. The results are detailed in the following table.

Example 12. The samples were prepared using the release coating composition described in Example 10. The pavement marking tapes (all available from 3M) listed below were then electro-crazed as described in Example 10. Then it was conducted a test of silicone transfer in each sample according to the following procedure. A mueetra was prepared by taking a fabric sample of 0.3 m (one foot) per width (0.33 m) without a support and cutting it into four samples of 0.1 mx 0.15 m (4- inch x 6-inch) through the cloth . Five 0.1m x 0.15m (4-inch x 6-inch) samples of the Stamark ™ 6330 Pavement Marking Tape (available from 3M) were also cut and the liner peeled off 4 of the 5 samples. A stack was formed by alternating the 6330 tape with the electro-coated tape, ending with the sample of the 6330 liner tape at the bottom. The stack placed between pieces of a flat glass of 6.4 cm (0.25 inches) with a mass of 2.27 kg (5-pounds) in the upper center of the stack in an oven heated to 93 ° C (200 ° F) during about one hour. After the stack was cooled to room temperature, the "intermediate" sample 6330 and the liner sample were selected and each was cut into 3 strips of 25.4 mm. The tirae ee applied to stainless steel panels with five steps of a 2.27 kg (5 lb.) roller. Then, the samples were conditioned at room temperature for approximately 5 minutes. Using a Sintech tensile strength instrument (# 6365, available from Sintech, a division of MTS Systeme Corp., Stoughton, MA), a 180 ° adhesion test was performed. The instrument tube had a jaw opening of 0.1 m (4 inches), a crosshead speed of 0.3 m / min (1 ft / min), and a full scale load of 222.5 N (50 lb). With the exception of samples # 3 and # 11, the results of the test were within the desired range of a differential of 17.5 N / 100 mm (one pound) or less of the control. • vO 00 or Example 13. The composition of Example 10 was electro-chlorinated as described in Example 10 in the following tapes for pavement marking at a micrometer liner height. The reflectometry measurements were made using the procedures described in Test Method ASTM D4061-89, "Standard Test Method for Retroreflectance of Horizontal Coatings," using an input angle of 86.5 ° and an observation angle of 0.2 °. . The results are shown in the table below.

Example 14. Electro-sputtered samples were prepared from a master composition containing 100 parts of the 75/25 mixture of IOA / 1, 6-HDDA, 2 parts of Darocur 1173, 0.5 part of Aliquat 336, and 1 part of NNDMA . To prepare each sample, we added 0.1 parts of 5K ACMAS (sample 1), 0.2 parts of 5K A.CMAS (sample 2), 0.3 parts of 5K ACMAS (sample 3), and 10 parts of 5K ACMAS (sample 4). The samples were electro-corrupted as described in Example 8 on a 0.036 mm thick (3M) polyester film at a line speed of 17 meters / min. and cured in line under an inert atmosphere with a medium pressure mercury lamp in a power pack of 200 W / 2.54 cm (approximately 7.9 kW / m). The effectiveness of release release was measured by the release and readherence tests. The immediate release value (in N / 100mm) is a quantitative measurement of the force required to remove a flexible, adhesive strip (# 810 tape available from 3M) of the electrocoated polyester film at an angle and a removal rate specific. Typically, a sample of 19 mm wide tape was laminated to the electrocoated polyester film (1 step at 30 cm / min with a 2 kg rubber covered roller) and the sample was analyzed immediately after the downward movement. using a slip / deep-penetration tester (Model 3M90 from Instrumentors, Inc.) at a speed of 30 cm / min and a 180 ° release angle. The aging release check was conducted in a similar manner with the exception of allowing the adhesive tape / coated polyester film intercalated for 3-day aging at 65 ° C.

Retains (both immediate and aged (three days at 65 ° C)) were measured (reported in N / 100 mm) by adhering the newly extracted tape to a glass plate, clean and measure the adhesion of the film as described before As indicated by the data, the release can be adjusted from firm to smooth by a simple change in the content of the silicone. The constructions release after aging with heat, but the readherence is not affected essentially, thus they show a good cure of the composition.

Example 15. A master batch was prepared by mixing at room temperature 100 g of a 75:25 mixture of IOA / 1, 6-HDDA, 25 g of 5K MAUS, and 2 parts of Darocur 1173. The current was measured using the Method III and it was found to be zero. To this masterbatch 0.5 parts of the iodonium salt GE 9380C was added as a conductivity sensor. The resistance was measured using Method II at a height H = 4 cm, and it was 937 kO (the conductivity is 15.9 μS / m). Then, 1 part of NNDMA was added and the resistance was measured and decreased again to 501 kO (the conductivity is 29.7 μS / m). Both mixtures have conductivities in the most preferred range. 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 modes 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 free radical polymerizable release coating composition, characterized in that it comprises: a) about 100 parts by weight of one or more polymerizable vinyl monomer (s) (e) with free radicalee; b) from about 0.05 to about 250 parts by weight of one or more polydiorganoheiloxane polymer (s), which are copolymerizable with the vinyl monomer (s); and c) from about 0.10 to about 10 parts by weight, based on 100 parts by weight of (a) and (b), of one or more conductive (ee) conductivity, non-volatile (s), where non-volatile is defined as having a vapor pressure of less than or equal to 1 kPa at 25 ° C, which are soluble in the monomer (e) of vinyl and which do not interfere with the polymerization; where the composition can be electro-alloy.

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 polydiorganosiloxane polymer (s) are selected from the group consisting of polymer and included within the general formula: and mixtures thereof, wherein: X are monovalent portions having an ethylenic unsaturation which may be the same or different; And they are divalent linking groups which may be the same or different; D are monovalent portions which may be the same or different, selected from the group that you connected with hydrogen, an alkyl group of 1 to about 10 carbon atoms, and aryl; each R is a monovalent portion selected from the alkyl portions which can be substituted with the trifluoroalkyl or vinyl groups, the cycloalkyl portions which can be substituted with the alkyl, luoroalkyl and vinyl groups, the aryl portions which can be to define the alkyl, cycloalkyl, fluoroalkyl and vinyl groups; R 'are divalent hydrocarbon groups which may be the same or different; and n is an integer from about 25 to about 750.

4. The composition according to claim 1, characterized in that the polydiorganosiloxane polymer (s) are selected from the group consisting of polymers obtained by the epoxy-polysiloxane functional reaction of the general formula wherein R1 has the same or different groups of low molecular weight alkyl with 1 to 4 carbon atoms or phenyl groups, R2 is the same as R1 or represents the group R3, 70 to 100% of the groups R ° which eon epoxy functional groups and 30 10 to 0% which are alkyl groups with 2 to 20 carbon atoms or hydrogen, with the proviso that the average molecule contains at least 1.5 epoxy groups, to ee an integer having a value of 15 the 1,000 and a whole number having a value from 0 to 10, with such amounts of an acid mixture, consisting of (a) 10 to 90 mole percent of (meth) acrylic anhydride, and (b) 90 to 10 mole percent of acid (meth) acrylic that the sum of (a) and (b) adds up to 100 mol percent, and that 0.8 to 1.9 equivalents of acid per equivalent of epoxy are present.

5. The composition according to claim 1, characterized in that the polydiorganosiloxane polymer (s) are selected from the group consisting of segmented copolymer compositions of polydiorganosiloxane oligourea of the general formula wherein each Z is a divalent radical selected from arylene radicals and aralkylene radicals, alkylene and cycloalkylene radicals; each R is a monovalent portion selected from alkyl portions that can be substituted with trifluoroalkyl or vinyl groups, portions 10 of cycloalkyl which can be substituted with alkyl, fluoroalkyl and vinyl groups, aryl portions which can be substituted with alkyl, cycloalkyl, fluoroalkyl and vinyl groups; each Y is a selected divalent moiety of alkylene radicals, aralkylene radicals and arylene radicals; Each D is a monovalent radical selected from hydrogen, alkyl radicals, aryl or arylalkyl radicals; and p is a number which is approximately 25 10 or greater; q is a number which is approximately 10 or greater; t is a number which is 0 to about 8; and 5 each X is (a) a portion represented by O O II II 10 -Y-N-C- -Z-N-C-L-K I I I "D H H where each of Z, Y, and D are as defined above, L is independently -N -._ O -.- S-, 20 D • K is an end group, curable with free radicals; or (b) a portion represented by 25 O II -Y-N-C-N- K I I 30 D H where D, Y and K are as defined above.

6. The composition according to claim 1, characterized in that the conductivity enhancer (s) are selected from the group consisting of acid-base pairs, ampholytics and complex cation salts of the elements in the Va, Via Group, or Vlla.

7. The composition according to claim 6, characterized in that the acid-base, ampholytic pairs are selected from the group consisting of N, N-dimethylaminoethyl- (meth) acrylate / acid (meth) acrylic, methacrylic acid / diethanolamine, acrylic acid / 2-vinylpyridine, itaconic acid / 2-diethylaminoethyl acrylate, methacrylic acid / 2-diethylaminoethyl acrylate, acrylic acid / 2-diethylaminoethyl acrylate, acrylic acid / methacrylate 2 -diethylaminoethyl, N-vinylglycine, p-styrenesulfonic acid / 4-vinylpyridine, ethylenesulfonic acid / 4-vinylpyridine, zwitterion of l-vinyl-3- (3-sulfopropyl) imidazolium hydroxide, zwitterion of l-vinyl-2-hydroxide methyl-3- (3-sulfopropyl) imidazolium, zwitterion of l-vinyl-3- (4-sulfobutyl) imidazolium hydroxide, zwitterion of 1-vinyl-2-methyl-3- (4-sulfobutyl) imidazolium hydroxide, zwitterion of l-vinyl-3- (2-eulfobenzyl) imidazolium hydroxide, zwitterion of 2-vinyl-l- (3-sulfopropyl) pyridinium hydroxide, zwitterion of 2-methyl-5-vinyl-1-hydroxide -epulfopropyl) pyridinium, zwitterion of 4-vinyl-1- (3-sulfopropyl) pyridinium hydroxide, zwitterion of dimethyl- (2-methacryloxy) hydroxide useful) (3-sulfopropyl) ammonium, zwitterion of diethyl- (2-methacryloyloxyethoxy-2-ethyl) (3-sulfopropyl) ammonium hydroxide, zwitterion of 4-vinyl-4- (sulfobutyl) pyridinium hydroxide, zwitterion of hydroxide of 2-vinyl-2- (4-sulfobutyl) pyridinium, N- (3-sulfopropyl) -N-methacrylamido-propyl-N, N-dimethylammonium betaine, N- (3-carboxypropyl) -N-methacrylamido-ethyl-N, N-dimethylammonium betaine, 4-vinylpiperidinium ethanecarboxy-betaine, 4-vinylpyridinium methanocarboxy-betaine, 4-vinylpyridinium / p-styrenesulfonate, 4-vinyl-N-methylpyridinium / p-styrenesulfonate, and 2-methacryloylethyltrimethylammonium / 2-methacryloyloxyethanesulfonate.

8. The composition according to claim 6, characterized in that the complex cation salt is selected from the group consisting of wherein at least one R is a hydrocarbon having from about 1 to about 18 carbon atoms and each other R is a hydrogen or a hydrocarbon having from about 1 to about 18 carbon atoms, B is an element of the Va Group, Via or Vlla, n is an integer from 2 to 4, and A is an inorganic anion.

9. The composition according to claim 8, characterized in that A is selected from the group consisting of sulfate, borate, nitrate, thiocyanate, perchlorate, and halogens such as iodide, chloride, and bromide.

10. The composition according to claim 6, characterized in that the complex cation eal is selected from the group consisting of tetraoctylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium thiocyanate, and tetrabutyl phophonium bromide.

11. The composition according to claim 1, characterized in that at least a portion of the conductivity enhancer is copolymerizable.

12. The composition according to claim 1, characterized in that the polymerizable vinyl monomer (s) with free radicals are selected from the group consisting of divinyl benzenes, and acrylates, methacrylates, and beta-acryloxypropionates of alkyl polyolsethoxylated and propoxylated analogs, styrene, butyl acrylate, hexyl acrylate, benzyl acrylate, cyclohexyl acrylate, isobornyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate , octadecyl acrylate, butyl methacrylate, isobornyl methacrylate, isooctyl methacrylate, tetrahydrofurfuryl acrylate, vinyl pivalate, vinyl 2-ethylhexanoate and mixtures thereof.

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

14. The composition according to claim 13, characterized in that the dissociation enhancing agent (s) are selected from the group consisting of polyethylene glycols, glycerols, propylene carbonates, poly (ethylene oxides), dialkylureas, N , N-dimethyl acrylamide, N-vinylpyrrolidone, methacrylic acid, 2-ethoxyethyl acrylate, and Carbowax "'750 acrylate.

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

16. The composition according to claim 1, further characterized by at least one of the following: (a) the viscosity measurements of the application composition from about 10 ~ 3 Pa's to about 1 Pa's; or (b) the conductivity ranges of the application composition from about 0.1 μS / m to about 100,000 μS / m.

17. A method for applying a release coating composition, characterized in that it comprises one or more polymer (s) of polydiorganosiloxane, one or more monomer (s) of vinyol, poly erizabl (s) with free radicals, and optionally one or more initiator (s) ( es) of polymerization with free radicals that are such that when in the combination they have insufficient conductivity to be electro-rounded, the method comprises the steps of (a) adding one or more conductivity sensor (ee) and optionally one or more agent (e) ) dissociation enhancers to the composition to produce an application composition; (b) applying the application composition to a substrate by means of the electro-dew; and then (c) polymerizing the application composition.

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

19. The method according to claim 17 or 18, characterized in that the sub-stratum 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, natural or synthetic rubber, and ribbons for marking the pavement. SUMMARY OF THE INVENTION The release coating compositions, polymerizable with free radicals containing conductivity enhancers, which can be electrored on a substrate. The compositions comprise (a) about 100 parts by weight of one or more vinyl monomer (e), polymerizable (e) with free radicals, (b) from about 0.05 to about 250 parts by weight of one or more polymer (s) of polydiorganosiloxane, copolymerizable with the vinyl monomer (s), and (c) from about 0.10 to about 10 parts by weight, based on 100 parts by weight of (a) and (b), one or more non-volatile conductivity intensifier (s), which is soluble in the monomer (s) and which does not interfere with the polymerization, where the composition can be electro-rounded. The composition may further comprise from about 0.1 to about 5 parts by weight of one or more initiator (s) based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s). Another embodiment of the present invention further comprises at least 0.1 parts by weight, based on 100 parts by weight of the polydiorganosiloxane monomer (s) and polymer (s), of one or more dissociation enhancing agent (s) soluble (e) in the monomer (s).