Release coating material applicable by electrospray

专利摘要:
PURPOSE: It is preferable that conventional release coating material do not affect the final ability of product and that components do not prevent polymerization reaction or are evaporated or captured in coating during the process. Otherwise the coating material moves to a substrate and thus affects the ability of the product harmfully. And unhardened components may contaminate environment by being evaporated afterward, or may abrade and contaminate other surfaces by contacting with the surfaces. CONSTITUTION: Free radical polymeric release coating material contains a conductivity enhancing agent and which can be electrosprayed. The composition can be electrosprayed by using 1 or more non-volatile conductivity enhancing agent being soluble and not preventing the polymerization reaction to the vinyl polymer, to 1 or more free radical polymeric vinyl monomer and 1 or more polydiorganosiloxane polymer which can copolymerize with the vinyl monomer.
公开号:KR20000004982A
申请号:KR1019980707593
申请日:1996-07-09
公开日:2000-01-25
发明作者:알버트 아이. 에버래츠；미치슬로 에이치. 마주렉；알버트 이. 시버
申请人:스프레이그 로버트 월터；미네소타 마이닝 앤드 매뉴팩춰링 캄파니；
IPC主号:

专利说明:

Release coatings that can be applied by electrospray
The release of chemicals into the atmosphere and polluting the air is a serious problem. Thus, in the chemical industry, new materials and new methods are being developed that focus on environmental impact. One way to reduce the release of chemicals is to develop a solvent-free process and it is not necessary for the chemicals to evaporate during processing or from the final product.
Traditionally, solvent-based thin coatings, ie thin films with a dry thickness of less than about 5 μm, have been used as release coatings. In the continuous liquid coating technique, the composition is mostly diluted with a large amount of solvent, which solvent is subsequently removed by evaporation leaving a composition having a predetermined thickness. The uniformity and thickness of the dried final layer can be difficult to control, especially on rough surfaces. The added solvent raises material costs, manufacturing costs, and solvent removal costs. In addition, conventional solvents used may be harmful to the environment.
Solvent-based thin films can also be applied by a spraying process. Although spray coating can be used to apply the composition to smooth substrates, it is particularly useful as a method of coating on rough or three-dimensional substrates. However, a problem associated with conventional spraying processes is that the coverage is poor, and a significant amount of coating composition does not settle on the substrate. However, the electrostatic spray method provides controlled spray means to prevent material loss. Electrospray, a unique subclass of electrostatic spraying, can be used to apply thin films without solvents. Typically, electrospray can be usefully used to apply a coating having a thickness of about 0.005 to about 10 μm.
Although the electrospray process is an efficient way to apply thin films, not all compositions can be electrosprayed. The composition must meet certain processing requirements. For the requirements of electrospray, the composition must be a substantially single phase solution, not a dispersion (liquid in solids) or an emulsion (liquid in liquids), the composition must have sufficient conductivity and a relatively low viscosity.
Compositions having a conductivity of 10 ⁻⁷ Siemens / meter (S / m) to 10 ⁻¹ S / m may also be electrosprayed, but relatively small droplets are desirable for thin films, with a conductivity of 10 ⁻⁶ S / m Or 1 microsiemens / meter (μS / m) or more. Similarly, the range of flow rates at which the solution can be electrosprayed decreases as the conductivity increases, and it is desirable to keep the conductivity below about 10 ⁻³ S / m (1000 μS / m) in order to obtain the desired flow rate.
The composition may be electrosprayed with or without solvent, provided the composition is a single phase solution or a nonionic stabilized emulsion or dispersion. If the composition is not substantially a single phase solution, the composition may become unstable during the electrospray process. In the case of a single phase solution ("gin solution"), each component is completely soluble. It is often necessary to add a solvent to the composition in order to obtain the required solubility. Added solvents, especially organic solvents, can cause environmental problems if they are not evaporated and trapped during or after the process treatment.
If the composition is truly solvent free, then almost all initial components will be present in some form in the final cured product. Thin films exist as solvent molds but do not meet this definition because solvents are removed during processing. For example, ethanol or methanol may be added to the electrosprayable composition to increase solubility and conductivity, but they will evaporate during processing. In some free radical cure systems, these solvents may act as chain extenders or initiators and interfere with the polymerization reaction, so it is desirable to remove them before curing.
Although the aqueous composition is sometimes referred to as "solvent-free", a large amount of drying ovens are required, which increases the manufacturing space and increases the cost of the product. In addition, the compositions to be electrosprayed are organic and therefore often incompatible with water.
During electrospray, the spray head places charge on the droplets by the principle of electrostatic induction. In inductive charging operations, the conductivity of the spray composition must fall within a certain range.
Solvents may be added to the composition to increase conductivity. In order to achieve the desired conductivity range, the composition mainly comprises a polar solvent, in addition to the conductivity enhancer, i.e., a salt, which is commonly regarded as a volatile organic compound ("VOC"). Such volatile compounds can be harmful to the environment.
In electrospray, solvents have been used to improve the conductivity of the solution. For example, EP 92.907947.3 (Mazurek et al.) Describes a method for increasing the conductivity of an electrospray release coating by adding a small amount of methanol. However, methanol is evaporated during the treatment process, otherwise it adversely affects the free radical polymerization reaction.
U.S. Patent No. 4,059,444 discloses the addition of quaternary ammonium salts having relatively low molecular weight inorganic anions, such as sulfates, borates, and iodides, to the ink as conductivity enhancers. Such conductivity modifiers may be added at a concentration of 0.05 to about 1 weight percent to improve the conductivity of the electrostatically applied ink.
U.S. Patent No. 5,364,726 discloses liquid developers containing colorants and curable liquid carriers, solid particles containing substantially insoluble initiators and optionally conductivity enhancers (e.g., quaternary ammonium compounds disclosed in U.S. Patent No. 4,059,444). It is described.
U.S. Patent No. 4,303,924 discloses the addition of oil soluble salts such as inorganic and organic acid quaternary salts of Group Va elements to curable print inks comprising 0-30% of polar organic solvents. All examples include polar organic solvents.
In order to electrospray the thin film layer to a uniform thickness, each droplet from the electrospray mist must have a sufficiently low viscosity and be properly dispersed and applied to the substrate. However, for some applications, it may be appropriate to cure individual droplets on a substrate such as a slip sheet.
Most release coatings known in the art include silicones such as polydimethylsiloxane to achieve release properties. In general, the viscosity of these compositions tends not to be low enough to electrospray. Therefore, the viscosity has been adjusted by adding a solvent. Alternatively, the viscosity was adjusted using a reactive diluent. For example, International Patent Application No. 95/23694 (Kidon et al.) And US Patent No. 4,201,808 (Cully et al.).
Despite the method of applying a thin release coating to the substrate, the release coating component preferably does not adversely affect the final performance of the product. The components are preferably evaporated or do not interfere with the polymerization reaction or are physically trapped in the coating during processing, otherwise they are transferred to the substrate and adversely affect the performance of the product. Or the uncured component may later evaporate to contaminate the environment or may subsequently contact, wear and contaminate another surface. Thus, there has been a need for a release coating composition that substantially all of the components are present in the final product, copolymerized with other components or otherwise electrosprayed to be a permanent part of the coating.
The present invention relates to a release coating composition capable of electrospraying a substrate. More specifically, the present invention relates to a free radically polymerizable release coating comprising a conductivity enhancer, a substrate coated with such a composition and a method of coating the substrate.
Summary of the Invention
Applicants have found a release coating composition that can be electrosprayed onto a substrate and found that these components do not interfere with the polymerization reaction and, when applied to the substrate and nearly polymerized, the composition does not improperly degrade the product.
By incorporating the conductivity enhancer according to the invention it is possible to formulate a composition having a conductivity which is insufficient for coating by electrospray to have a desired conductivity. In addition to obtaining an appropriate conductivity, the conductivity enhancer must be soluble in the composition, must not adversely affect the viscosity of the composition, preferably should be nearly copolymerized or be a permanent part of the final composition, and unfairly degrade the final product. It should not be done.
The present invention provides a free radically polymerizable release coating composition comprising a conductivity enhancer, which composition can be electrosprayed onto a substrate. The composition comprises (a) about 100 parts by weight of one or more free radically polymerizable vinyl monomer (s), (b) about 0.05 one or more polydiorganosiloxane polymer (s) copolymerizable with the vinyl monomer (s). To about 250 parts by weight, and (c) based on 100 parts by weight of (a) and (b) one or more nonvolatile conductivity enhancer (s) that are soluble in the vinyl monomer (s) and do not interfere with the polymerization reaction. About 0.10 to about 10 parts by weight, wherein the composition may be electrosprayed.
The composition may further comprise 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 polydiorganosiloxane polymer (s) and monomer (s).
Based on the polydiorganosiloxane polymer and 100 parts by weight of the monomer, about 0.1 part by weight of one or more dissociation enhancer (s) soluble in the monomer may be optionally added. The viscosity of this release coating composition is 1 Pascal · sec or less, which is suitable for electrospraying a thin film onto a substrate, especially a rough or three-dimensional sheet type substrate.
Another embodiment of the present invention relates to a "solvent free" release coating composition that can be applied to a substrate by electrospray.
Another embodiment of the invention relates to a release coating for a pavement marking tape that can be applied by an electrospray process.
details
As conductivity enhancers, certain types of salts, such as amphoteric acid-base pairs or onium salts of Group Va, Group VIa or Group VIIa elements, are added to the organic mixture containing free radically polymerizable monomers to improve the conductivity of the composition without adding solvent. It can greatly improve. The addition of a conductivity enhancer makes it possible to electrospray by providing the necessary conductivity to a release coating composition having insufficient conductivity to electrospray.
Certain classes of electrostatic coating, generally electrospray coating, can be used to produce submicrometer coatings of several micrometers in thickness. Like most electrostatic coating methods, electrospray processes require free ions (i.e., ions that are physically separated to act as non-coordinated ions) in a solution that will act as an ionic conductor. Examples of known ionic conductors include salts, acids, water and polar solvents including decomposing species. Due to process limitations, the electrosprayable composition is preferably a single phase solution. Since water is not compatible (ie miscible) with organic solutions, the composition is an emulsion or dispersion and not a gin solution. In addition, since water must be dried out, another process step is added which increases production costs. Acids are mainly volatile and corrosive. As mentioned above, the conductivity can be improved by using a polar solvent to act as a dissociation enhancer. However, polar solvents can be primarily evaporated during the process and are harmful to the environment. Thus, salts are useful for improving conductivity to produce solvent-free compositions that can be electrosprayed. However, not all salts are useful in organic compositions.
Single definitions for solvent-free compositions or high-solids solutions are not universally used. Ideally, the solventless composition is 100% reactive, which does not contain or produce any VOCs. As is known in the art, ideal compositions are difficult, if not impossible, to obtain. In particular, the bulk polymerization proceeds very slowly at high conversions, so that 100% conversion or polymerization is difficult to obtain without considering economical limitations. In view of the non-ideal nature of such compositions, one can assume certain concentrations of non-reactive or volatile components. The US Environmental Protection Agency (EPA) has created a test method to measure the VOC content of radiation curable materials, as can be seen in American Society for Testing and Materials (ASTM) Standard D 5403-93. Test Method A can be applied to "radiation curable materials which have almost 100% reactivity but may contain traces (up to 3%) of volatiles as impurities or impurities introduced by incorporating various additives." To determine the amount of non-volatile material present, the composition is cured and then heated to 100 ± 5 ° C. in a strong draft oven for 60 minutes. The weight of the substrate, the composition before curing, the composition after curing and the cured composition after heating are all measured at room temperature. In the present invention, a "solvent-free" composition is one that meets this standard and has a VOC content of 3% by weight or less.
In addition to meeting these standards, it is preferred that the solvent-free compositions of the present invention be less than 2% by weight of the total initial component heat extractable during application of ASTM D 5403-93, Test Method A. Thus, irrespective of the energy source used for free radical curing, preferably at least 98% by weight of monomer (s), initiator (s), conductivity enhancer (s) and other additives are present in the final polymerization product. The nature of the non-ideal polymerization reaction is such that the loss requirement is less than 2% by weight.
In order to obtain such a solvent-free composition, each component must be selected so that the composition does not evaporate to about 2% by weight or more in the processing, polymerization reaction and final product or loses material by "heat extraction".
It is also desirable that the components do not migrate to other layers of the final product, or the properties of the product may be poorly modified.
Electrospraying
The composition to be electrosprayed first turns into a fine mist of charged droplets, usually up to about 50 micrometers in diameter. The mists of the charged droplets are then guided and diffused into some form of substrate, usually a moving web, in contact with the droplets, and usually they coalesce to ultimately form a thin film. (Note, however, that in some applications it is desirable to cure individual droplets on a substrate, such as a slip sheet). In an electrospray mist generator, this charged droplet mist is controlled by the design of the spray head and the application of an electrical potential difference in the spray head. The electrical potential difference is usually called an applied voltage or simply a voltage. The applied voltage generates one charged polar composition free ion that moves to a specific position along the liquid-air interface of the composition in the head spray. In one electrospray process, the process described in US Pat. No. 5,326,598 (Seaver et al.), The forces generated by such excess free ions can be induced at selected air-liquid surface locations, where a series of fine liquid filaments Is elongated. Liquid filaments containing such one specific polarity of free ions are pulverized into charged droplets about the diameter of the original liquid filament. All electrospray generators and most electrostatic spray generators generate charge on the droplets by electrostatic induction. Such induction generators need to contain a sufficient amount of free ions for the sprayed composition to charge the droplets. Preferred conductivity depends on the specific coating application, but the conductivity of the composition should be about 10 ⁻⁷ to about 10 ⁻¹ S / m. In the release coating composition of the present invention, the conductivity is preferably about 10 ⁻⁶ to about 10 ⁻³ S / m (1 to 1000 μS / m), most preferably about 10 to about 50 μS / m.
Walden's law (Jordan, P., Chemical Kinetics and Transport, Plenum Press, New York, USA (1980)) states that the product's ion conductivity x viscosity is usually constant for a given system. okay. Thus, ionic conductivity can be increased by decreasing the viscosity. However, it is preferable that the viscosity of the droplets is very low to enable proper application and smoothing of the coating in a short time. As a result, in the case of electrospray coating, the viscosity of the composition is usually less than 1 Pa · s, and the preferred range is tens of millipascal-seconds (mPa · s) or less. Usually, the viscosity is measured from about 10 ⁻³ Pa · s to about 1 Pa · s. Since all the induction electrostatic generators are required to have low viscosity, a predetermined conductivity cannot be easily obtained by adjusting the viscosity.
If the conductivity of the composition is not included in the essential requirements, the composition cannot be applied by electrospray. However, by adding certain types of salts to such compositions to provide sufficient conductivity, compositions that were previously impossible for electrospray can be applied to the substrate by the electrospray method according to the present invention.
Conductivity enhancer
As conductivity enhancers, salts contain ions held together by Coulomb's attraction. Simply including ions present does not mean that the salt solution is a sufficient ionic conductor. Electrostatic attraction is the pairing of oppositely charged ions to substantially reduce the ionic conductivity. Therefore, to be a sufficient conductor, the ion pair must be at least partially dissociated so that the ions are independent, ie, free ions (or less preferably three ion pairs). Free ions can significantly increase the ionic conductivity of the composition, provided they have an inherent flow that readily responds to the electric field applied to the composition. The ability of an ion pair to dissociate in a composition is determined by several factors, such as dielectric constant.
Using other components, the ion pairs must be soluble in the mixture to form a thick solution such that the composition is potentially electrosprayable. Ions are needed for the various monomer mixtures to be conductive, but the solubility of the salts is different, making some salts much more efficient than others. Since the release coating composition used is organic, salts containing at least one organic ion usually have better solubility. The solubility of such organic salts can be adjusted by appropriate choice of organic groups.
In general, materials with high dielectric constants (large polarities) can better stabilize free ions. Polar materials, on the other hand, reduce the attractive force between the charged ions, thereby separating the ion pairs into free ions. In general, dissolved salt ions can be strongly paired (form coordination bonds) and thus become nearly non-conductive or physically separated to act as substantially conductive non-coordinating (or free) ions. do. As the polarity of the organic composition decreases, the dielectric constant becomes lower, so that the equilibrium between free ions and strong ion pairs shifts toward the latter. Thus, even if the less desirable conditions (ie, a mixture of low polarity and low dielectric constant) are properly selected to improve conductivity, the dissolved salts form ion pairs and readily dissociate into free ions.
The ease of dissociation separation of two ions is advantageously influenced by charge delocalization at one or both sides of the ions and / or by steric hindrance around the center of charge which prevents the counter ions from strongly coordinating to the ion pair. The steric hindrance around the charged site of the ions can reduce access to the counter ions so that the ions pair less strongly. If the steric hindrance does not interfere with salt solubility, the greater the steric hindrance, the easier the ion pair separation into individual ions, and the easier the ionic conductivity of the composition is. However, as the ion size increases, the conductivity decreases because eventually the ion flow rate decreases.
Ions can be multiple charged. In general, monovalent ions are solubilized easily and dissociate into free ions with the selected monomer mixture. Divalent and trivalent ions can be used, but if not sufficiently "stabilized", the extra charge becomes less desirable because of the strong aggregation of ions at larger distances. Polymer ions, for example salts of polyacrylic acid, are greatly limited in their fluidity due to their size, so that the conductivity is greatly limited in the viscous medium.
The conductivity enhancers are nonvolatile, i.e., their vapor pressure is 1 kPa or less at 25 占 폚, preferably 0.5 kPa or less at 25 占 폚, more preferably 0.1 kPa or less at 25 占 폚. The conductivity enhancer preferably forms volatiles without degradation or becomes heat or water extractable during processing or from the final product at any time. It is desirable to increase the conductivity of the composition when the conductivity enhancer is added in a relatively small amount. Usually the conductivity enhancer is added from about 0.10 to about 10 parts by weight, preferably from about 0.5 to about 5 parts by weight, based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s). In addition, the conductivity enhancer (s) should not interfere with the polymerization reaction of the composition. Conductivity enhancers useful in the present invention include amphoteric acid-base pairs and onium salts of Group Va, Group VIa or Group VIIa elements. It is preferred that at least a portion of the positive acid-base pair and selected onium salts of Group Va, Group VIa or Group VIIa elements of the selected conductivity enhancer can be copolymerized with the rest of the composition. However, when the conductivity enhancer is added in small amounts so that it is physically entrapped in the cured composition and thus not extractable when moved to another layer of the substrate, or when evaporated or exposed to heating or water, the conductivity enhancer There is no need to copolymerize. Movement of the conductivity enhancer has an undesirable effect on the properties of the final product.
Suitable amphoteric acid / base pairs include N, N-dimethyl aminoethyl (meth) acrylate / (meth) acrylic acid, methacrylic acid / diethanolamine, acrylic acid / 2-vinylpyrrolidine, itaconic acid / 2-diethyl Aminoethyl acrylate, methacrylic acid / 2-diethylaminoethyl acrylate, acrylic acid / 2-diethylaminoethyl acrylate, acrylic acid / 2-diethylaminoethyl methacrylate, N-vinylglycine, p-styrenesul Phonic acid / 4-vinylpyridine, ethylenesulfonic acid / 4-vinylpyridine, 1-vinyl-3- (3-sulfopropyl) imidazolium hydroxide intramolecular salt, 1-vinyl-2-methyl-3- (3 -Sulfopropyl) imidazolium hydroxide intramolecular salt, 1-vinyl-3- (4-sulfobutyl) imidazolium hydroxide intramolecular salt, 1-vinyl-2-methyl-3- (4-sulfo Butyl) imidazolium hydroxide intramolecular salt, 1-vinyl-3- (2-sulfobenzyl) imidazolium hydroxide intramolecular salt, 2-vinyl-1- (3-sulfopropyl) pyridinium hydroxide between Intra-molecular salt, 2-methyl-5-vinyl-1- (3-sulfopropyl) pyridinium hydroxide intramolecular salt, 4-vinyl-1- (3-sulfopropyl) pyridinium hydroxide intramolecular salt , Dimethyl- (2-methacryloxyethyl) (3-sulfopropyl) ammonium hydroxide intramolecular salt, diethyl- (2-methacrylyloxyethoxy-2-ethyl) (3-sulfopropyl) ammonium Hydroxide intramolecular salt, 4-vinyl-4- (sulfobutyl) pyridinium hydroxide intramolecular salt, 2-vinyl-4- (sulfobutyl) pyridinium hydroxide intramolecular salt, 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 methanecarboxy-betaine, 4-vinylpyridinium / p-styrenesulfonate, 4-vinyl-N-methylpyridinium / p-styrenesulfonate, 2-methacrylylethyltrimethylammonium / 2-methac Ryllocyloxyethanesulfonate and the like (see Polymer Science and Engineering, Vol. 11, p. 514, polyampolitis).
Onium salts useful as conductivity enhancers are represented by the following formulae.
Wherein at least one of R is a hydrocarbon having 1 to 18 carbon atoms, the other R is hydrogen or a hydrocarbon having 1 to about 18 carbon atoms, preferably R is all hydrocarbons, B is Group Va, An element of group VIa or VIIa, n is an integer from 2 to 4, and A is an inorganic anion such as sulfate, borate, perchlorate, nitrate, thiocyanate and iodide, chloride and bromide. R may include copolymerizable ethylenically unsaturated groups such as acrylates and methacrylates (eg, Ageflex ™ quaternary ammonium acrylates available from CPC Chemical, Old Bridge, NJ).
Preferred onium salts include tetraoctylammonium chloride, tetrabutylammonium bromide, tetrabutyl ammonium thiocyanate, tetrabutylphosphonium bromide and the like.
If desired, mixtures of two or more suitable conductivity enhancers can be used.
Dissociation enhancer
Dissociation of ion pairs can be enhanced by adding one or more dissociation enhancer (s). These dissociation neutralizers bind (ie, "stabilize") one or both of the ions of the salt. If each of these components is used to add dissociation enhancers, the "solvent free" requirement must be met and preferably should not interfere with the polymerization reaction. When present in the composition, the dissociation enhancer (s) is usually added at least 0.1 parts by weight, preferably from about 0.5 to about 5 parts by weight, based on 100 parts by weight of the monomer (s) and the polydiorganosiloxane polymer (s). Preferred dissociation enhancer (s) have a dielectric constant of at least 5 at 20 ° C. The dielectric constant is more preferably 10 or more at 20 ° C, most preferably 20 or more at 20 ° C. Examples well known in the art include polyethylene glycol, glycerol, propylene carbonate, poly (ethylene oxide) and dialkyl ureas. Small amounts of simultaneous reactivity and high polar monomers can be used to enhance dissociation, but they should not adversely affect the properties of the cured coating. Examples of such monomers include N-vinyl pyrrolidinone, N, N-dimethyl acrylamide, methacrylic acid, 2-ethoxyethyl acrylate, Carbowax ™ 750 acrylate (Enduri, Connecticut, USA). Union Carbide), but is not limited to these.
Monomer
The monomers selected for the compositions of the present invention are almost completely miscible with the other components of the mixture. In addition, these monomers have sufficiently low vapor pressures that little material is lost during processing. The monomer is preferably nonvolatile, ie, its vapor pressure is 1 kPa at 25 ° C, more preferably 0.5 kPa at 25 ° C, and most preferably 0.1 kPa at 25 ° C. Examples of useful monomers include monofunctional vinyl monomers and multifunctional vinyl monomers.
Representative free radical curable monofunctional monomers include vinyl monomers that can act as reactive diluents for polydiorganosiloxane polymers. Examples of suitable vinyl monomers include 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, but are not limited to these. Such monomers are known in the art and most are commercially available.
Preferred monofunctional vinyl monomer mixtures comprise predominantly (ie about 50 to about 100 mole%) acrylic monomers because of their fast cure rate. Most preferred monomers are acrylic monomers selected from the group consisting of acrylic acid esters of non-tertiary alcohols containing from about 6 to about 12 carbon atoms, such as cyclohexyl acrylate, isobornyl acrylate, isooctyl acrylate, 2 It is selected from the group consisting of ethylhexyl acrylate, lauryl acrylate and mixtures thereof, because of their excellent solvation performance, high reactivity, and low volatility.
Multifunctional free radically polymerizable vinyl monomers include divinyl benzene, divinyl acrylate, divinyl methacrylate, 1,6-hexanediol, trimethylolpropane, 1,4-butanediol, triethylene glycol, tetraethylene glycol, penta Beta acryloxypropionates of alkyl polyols such as erythritol, ethoxylated analogs and propoxylated analogs thereof, and mixtures thereof, but are not limited to these. Such monomers are included in the composition to ensure fast cure rates and a robust crosslinking coating. Preferred multifunctional monomers include acrylates of 1,6-hexanediol, acrylates of trimethylolpropane, ethoxylated and propoxylated analogs thereof and mixtures thereof.
If desired, mixtures of one or more suitable monomers may be used.
Initiator
The free radical polymerization reaction of the composition should be carried out in an oxygen free environment, for example inert atmosphere, such as nitrogen gas, if possible. Generally, the initiator is included from about 0.1 to about 5 parts by weight based on 100 parts by weight of the monomer (s) and polydiorganosiloxane polymer (s). The polymerization reaction can also be initiated by irradiation of high energy, such as electron beams or gamma rays. Such high energy irradiation systems do not always require an initiator.
Light (ultraviolet or visible) may be used to initiate the polymerization reaction. Photoinitiators include substances that cleave upon irradiation, hydrogen extraction initiators, and donor-receptor complexes. Examples of suitable photoinitiators include 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, but is not limited thereto. Examples of suitable hydrogen extraction initiators include benzophenone and its derivatives, anthraquinones, 4,4'-bis (dimethylamino) benzophenones (Micler Ketones), and the like. Suitable donor-receptor complexes include combinations of donors such as triethanolamine with receptors such as benzophenone. Also suitable are photosensitizers for the initiator, such as thioxanthones for quinoline sulfonylchloride.
Thermal energy can also be used to initiate the polymerization reaction. The thermal initiator may be selected from conventional peroxides or commercially available azoform materials. Examples thereof include benzoyl peroxide, 2,2'-azo-bis (isobutyronitrile), 1,1'-azo-bis (cyclohexane-1-carbonitrile), dicumylperoxite and the like. Redox initiators such as amines with peroxides, cobalt carboxylate salts with peroxides or persulfide / hydrosulfite salt redox pairs can also be used as initiators, provided the initiator is completely dissolved in the monomer mixture, solution Gradually increasing the viscosity of does not pre-initiate a reaction that interferes with the coating process. If desired, the initiator may be first applied to the substrate using conventional means.
Polydiorganosiloxane polymer
In general, the silicone release component is a polydiorganosiloxane polymer known to have release properties. Typically, these polymers crosslink themselves and have ethylenically unsaturated groups such as crosslinkable groups such as acrylate, methacrylate, acrylamide, methacrylamide, α-methyl styrene and vinyl.
Suitable polydiorganosiloxane polymers are selected from the group consisting of polymers belonging to the formulas and mixtures thereof.

Where
X is a monovalent moiety having the same or different ethylenically unsaturated moieties,
Y is the same or different divalent linking group,
D is the same or different monovalent moiety selected from the group consisting of hydrogen, alkyl groups having 1 to about 10 carbon atoms and aryl,
Each R is an alkyl moiety (preferably about 1 to 12 carbon atoms, such as may be substituted with a trifluoroalkyl or vinyl group), a cycloalkyl moiety (preferably about 6 to 12 carbon atoms, an alkyl group, Monovalent moieties selected from fluoroalkyl groups and vinyl groups), aryl moieties (preferably about 6 to 20 carbon atoms, and may be substituted by alkyl groups, cycloalkyl, fluoroalkyl groups and vinyl groups); , Preferably at least 50% of the R moiety is a monovalent alkyl or substituted alkyl radical having 1 to 12 carbon atoms, a methyl radical that is balanced with a substituted alkyl radical, a vinylene radical, a phenyl radical or a substituted phenyl radical,
R 'is the same or different divalent hydrocarbon group,
n is an integer from about 25 to about 750.
For example, copolymerizable polydimethylsiloxanes disclosed in European Patent No. 92.907947.3 (Mazurek et al.), Such as ACMAS (acrylamidoamido siloxane) and MAUS (methacryloxyurea siloxane), are added to the composition to provide release properties. You can get it.
Other suitable polydiorganosiloxane polymers include the compounds described in US Pat. No. 4,908,274 (Jachmann et al.), Tego ™ RC-706 and Tego ™ RC-726 available from Goldstmid Chemical Company. U.S. Patent No. 4,908,274 discloses polysiloxanes having a (meth) acrylate ester group bonded to a SiC group, which represents an epoxy functional polysiloxane of the formula
(a) 10 to 90 mol% of (meth) acrylic anhydride,
(b) 90 to 10 mol% of (meth) acrylic acid having a total of (a) and (b) up to 100 mol% and present at 0.8 to 1.9 acid equivalents per epoxide equivalent
Obtained by reaction with an acid mixture consisting of:

Where
R ^{1 is} the same or different low molecular weight alkyl or phenyl group having 1 to 4 carbon atoms,
R ² represents a same or R ³ and R ^1, 70 to 100% of the R ³ groups is an epoxy functional group, 30 to 0% of the number of carbon atoms from 1 to 20 alkyl group, or are susoyi, but the average molecule at least 1.5 epoxy groups Has,
a is an integer from 1 to 1,000,
b is an integer of 0-10.
Other suitable polydiorganosiloxanes include polydiorganosiloxane oligourea segmented copolymer compositions of the formula:

Where
Z is a divalent selected from an arylene radical and an aralkylene radical (preferably about 6 to 20 carbon atoms), an alkylene radical and a cycloalkylene radical (preferably about 6 to 20 carbon atoms) Radical, preferably Z is 2,6-tolylene, 4,4'-methylenediphenylene, 2,2'-dimethoxy-4,4'-diphenylene, tetramethyl-m-xylylene , 4,4'-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylenecyclohexylene, 1,6-hexamethylene, 1,4-cyclohexylene,
Each R is an alkyl moiety (preferably about 1 to 12 carbon atoms, such as may be substituted with a trifluoroalkyl or vinyl group), a cycloalkyl moiety (preferably about 6 to 12 carbon atoms, an alkyl group, Monovalent moieties selected from fluoroalkyl groups and vinyl groups), aryl moieties (preferably about 6 to 20 carbon atoms, and may be substituted by alkyl groups, cycloalkyl, fluoroalkyl groups and vinyl groups); , Preferably at least 50% of the R moiety is a monovalent alkyl or substituted alkyl radical having 1 to 12 carbon atoms, a methyl radical that is balanced with a substituted alkyl radical, a vinylene radical, a phenyl radical or a substituted phenyl radical,
Each Y is a divalent moiety selected from an alkylene radical (preferably having from 1 to 10 carbon atoms), an aralkylene radical and an arylene radical,
D is a monovalent radical selected from hydrogen, an alkyl radical (preferably having 1 to 10 carbon atoms), an aryl radical or an arylalkyl radical (preferably having 6 to 20 carbon atoms),
p is a number of about 10 or more, preferably about 15 to 2000, more preferably about 30 to 1500,
q is about 10 or more, preferably about 15 to 2000, more preferably about 30 to 1500,
t is from 0 to about 8,
X is each (a)

Wherein Z, Y and D are as defined above,
L is , ,
K is a free radical curable end group), or
(b)
(Where D, Y and K are as defined above).
It is preferred that the polydiorganosiloxane polymer does not have the effect of poor conductivity and sprayability of the monomer mixture.
The release coating composition of the present invention comprises (a) about 100 parts by weight of one or more vinyl monomer (s), and (b) about 0.05 to about 250 parts by weight of one or more polydiorganosiloxane polymer (s), preferably about 0.05 to about 200 parts by weight, more preferably from about 0.05 to about 100 parts by weight can be prepared by combining. The conductivity enhancer is used in about 0.10 to about 10 parts by weight, preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of (a) and (b). The composition further comprises about 0.1 to about 5 parts by weight of one or more free radical initiators based on 100 parts by weight of (a) and (b), optionally including one or more dissociation enhancer (s) (a) and (b). It may comprise at least 0.1 parts by weight based on 100 parts by weight), provided that the conductivity provided is sufficient to electrospray the resulting coating composition.
The vinyl monomer (s) can be a mixture of both monofunctional and multifunctional vinyl monomers. The monofunctional vinyl monomer (s) is usually about 40 to about 95 parts, preferably about 50 to about 90 parts, most preferably about 60 to about 90 parts per 100 parts of vinyl monomer. The polyfunctional vinyl monomer (s) is usually about 5 to about 60 parts, preferably about 10 to about 50 parts, and most preferably about 10 to about 40 parts per 100 parts of vinyl monomer. Preferred multifunctional vinyl monomers have 2 to 6 functional groups. Most preferred multifunctional monomers have 2 to 3 functional groups.
Additives, such as deglossants, dyes, plasticizers or viscosifiers, may be used or non-functional flow improvers and hydrating agents may be added to improve the appearance of the coating. Such additives are preferably soluble in the composition and must be nonvolatile and do not adversely affect the conductivity, polymerization reaction or final properties of the composition.
The composition can be polymerized by electrospraying the substrate and then exposing it to electron beams, gamma rays, visible light, ultraviolet radiation or heat. Typically, the substrate has two major surfaces to which a release coating composition is applied to at least a portion of one or more major surfaces.
In one embodiment of the invention, the substrate comprises a backing having a first side and a second side, a second side of the backing comprising a double sided adhesive layer coated on one side of the backing and a release coating composition polymerized as a release coating. And a planar release layer. The release coating composition is preferably electrosprayed to the second side of the backing. When a release coating is used for a road marking tape and a rolled substrate in the form of a roll, the substrate is rolled into a roll so that the first side of the backing (the adhesive layer, if already covered with an adhesive) is in contact with the release layer.
Examples of suitable substrates include, but are not limited to, sheets, fibers, or shaped articles. Preferred substrates are those used for pressure sensitive adhesive products. The composition may be applied to at least one major surface of a suitable flexible or non-flexible backing material and then cured. Although any surface requiring release properties for the adhesive is selected, examples of useful flexible backing materials include plastic films such as poly (propylene), poly (ethylene), poly (vinyl chloride), poly (tetrafluoroethylene) , Polyesters (eg poly (ethylene terephthalate)), polyimide films such as DuPont tradename Kapton, cellulose acetate and ethyl cellulose. In addition, the backing may be a structure having an irregular surface, such as a woven fabric, a nonwoven fabric, papermaking, or a rough surface. Thus, the backing may be a woven fabric made of yarn of synthetic or natural materials, such as cotton, nylon, rayon, glass or ceramic materials or they may be airlays of natural or synthetic fibers or hybrids thereof unless they are too porous. It may be a nonwoven fabric such as a web. Because of their large porosity, the paper itself is usually unsuitable when the film thickness is not less than 1 μm and is not applied to the paper by offset immersion. However, plastic coated or impregnated papers are useful. Examples of rough surfaces include embossed or patterned surfaces or resins impregnated with particles such as abrasive particle coated (epoxy) resins and resins coated with glass beads. In addition, suitable substrates may be formed of metals, metallized polymer films, ceramic sheet materials, natural rubber, synthetic rubber or road marking tape.
The following examples illustrate various specific features, advantages, and other details of the invention. The specific materials and contents recited in these examples, as well as other conditions and details, should not be construed as unduly limiting the scope of the invention.
Solubility test
The solubility of the conductivity enhancer in each composition was measured by the following method. Samples of the conductivity enhancer were mixed with the clear monomer solution at room temperature for up to 2 hours and then checked for optical clarity under stirring. The sample containing the conductivity enhancer is not completely transparent or is not a "dust solution" and the sample is moderately heated (so that the sample can be picked up by hand) and then cooled to room temperature. Samples containing visible conductivity enhancer particles were considered defective.
Viscosity measurement
Brookfield Viscosity at Centrifuge (cp), 1 at Brookfield Engineering Laboratories, Inc., Stoftton, Mass., Using the Brookfield Digital Viscometer Model DV-II, commercially available. cp = 1 mPa * s] was measured.
Conductivity measurement
A simple cell consisting of two balanced stainless steel rods acting as electrodes was inserted into a glass container containing the solution to measure the electrical conductivity of the solution. The bars, each about 9 cm in length and about 3 mm in diameter, are separated from the center to the center at intervals of 1 cm each, and one end of each rod is a component of insulation (McMaster-Car, Chicago, Illinois, USA). Two rods embedded in standard rubber bottle caps or under the trade name Garolite sold by the company are in equilibrium. The height Η is the height of the solution asperities relative to the bottom of the rod. When the rod is placed in solution at a height ƒ, an electrical potential is applied to the rod, and current flows between the rods. The solution, air and insulator provide a net resistance R to the current. When the rod was placed in the solution at a height Η, the solution showed a higher conductivity than air, and the effective resistance was taken as the resistance of the solution. For example, the conductivity of air is about 10 ^-12 S / m or 10 ^-6 μS / m, and the conductivity of the insulator is much lower, so the resistance R for a solution with a conductivity of 0.001 μS / m or more is 0.1% for the solution only. Are affected within. Since the resistance R is directly proportional to the geometric factor G and inversely proportional to the electrical conductivity σ, G = Rσ to be. G depends not only on the height Η, but also on other fixed variables such as the separation interval of the rod and the diameter of the rod. If these fixed variables are defined as the second geometric factor g, g = GH Where g is a constant defined by the particular geometry of the electrode structure. The value of g was measured using a solution having a known conductivity σ ₀ which gives the resistance R ₀ when the rod is located at some specific height H ₀ in the solution. σ ₀ Since we know and measured R ₀ , the geometric factor G ₀ is G ₀ = R ₀ σ ₀ Was measured. Since we know H ₀ , g is g = G ₀ H ₀ Determined using. g is a constant g = G ₀ H ₀ = GH Since g is known, G can be determined for any bar electrode immersion depth H.
To calibrate the rod electrode cell, the cell constant g is the standard reference material (1500, 10000, and 50000 μS available from several salt solutions with known conductivity [National Institute of Standards and Technologies (NIST), Gettersburg, Maryland, USA). / m)]. The constant g was about 60 cm / m at 1500 μS / m to about 70 cm / m at 50,000 μm. When measuring the dielectric constants of methanol, isopropyl alcohol (IPA) and methyl ethyl ketone (MEK) using an impedance analyzer, Handbook of Chemistry and Physics, CAL Press, Incorporated, Boca Leton, FL, USA G] was adjusted to obtain a dielectric constant value. When these g values are plotted against the natural log of conductivity measurements for IPA, MEK and methanol, and the g value measured using the NIST solution, and also plotted against the natural log value of the NIST solution, all g values are the same. Located on a straight line. As a result, g = 59.45 cm / m was chosen to provide exactly 1000 μS / m conductivity. With respect to the g value, all recorded conductivity data has a deviation of about 10% per conductivity, in 10-fold increments from 1000 μS / m, lower when the conductivity is less than 1000 μS / m, and the conductivity is 1000 μS / m. If greater, it is higher. For example, a conductivity of 100 μS / m is actually about 10% less, while a 10 μS / m recorded is actually about 20% lower. Using the g value = 59.45 cm / m, the conductivity σ is σ = g / (HR) Was measured from the resistance across the cell at. Where R is the resistance of the solution when the cell is inserted at a height H into the solution.
Three methods were used to measure the resistance R and thus the conductivity σ of the solution.
In Method I, the Hewlett Packard LF (Low Frequency) Inductance Analyzer Model 4192A (Hewlett Packard Company, Palo Alto, Calif.) Was connected across the cell, and the admittance Y and angle D were 100, 300, 500, Recordings were made according to the immersion depth H of the rod in solution at frequencies F of 700, 900 and 1000 Hz. Expression using this information σ = (gYcosD) / H The conductivity was calculated by. In method I, the dielectric constant ε _{r of the} solution is also expressed ε _r = (gYsinD) / (2πε ₀ FH) Here, ε ₀ can be calculated as free space permittivity (8.85 × 10 ^-12 farads / meter (F / m)).
In Method II, a BK Precision Model 878 Universal LCR Meter (BK Precision, Maxtec International Corporation, Chicago, Ill.) Was connected to both ends of the cell, and a resistance R at a frequency F of 1 Hz was applied to the rod immersion depth H in solution. Measured according to. Then, the conductivity is σ = g / (HR) Calculated using.
In Method III, the cell was connected in series with a 1 kW resistor R _S , a micro ammeter A and a switch S. This series circuit was connected to both ends of a standard 9 volt dry cell battery. After the cell was immersed in the solution at height H, the switch S was closed briefly and the initial value I _S of the ammeter was recorded. With I _S , the immersion depth H of the electrode was recorded. In Method III, the battery voltage V _b was connected across a switch located in series with an ammeter and a 1 kW correction resistor. When closing the switch, the voltage of the battery was obtained from the measured current I _c x resistance R _c . Then, using this information, the conductivity of the solution was calculated by the following equation.
The materials shown in the table below were used in the examples.
ingredientSupply source 2,2'-azobis (isobutyronitrile) (VAZO ™ 64)Dupont, Wilmington, Delaware 1,4-butanediol diacrylate (BDA)SR 213, Satomer Company, West Chester, PA 1,6-hexanediol diacrylate (1,6-HDDA)SR 238, Satomer Company, West Chester, PA. 2-hydroxyethyl acrylateDow Chemical, Midland, Miami 2-sulfoethyl methacrylate (SEMA)Eastman Chemital, Kingsport, TN α, ω-acrylamidoamido siloxane (5K ACMAS)European Patent No. 92.907947.3 (Mazurek et al.) Acrylic acidBASF Corporation, Chalotte, NC Darocur ™ 1173Shiva Gaigi Corporation, Adsley, NY GE 9380GE Silicon, Waterford, NY Isooctyl acrylate (IOA)SR 440, Satomer Company, West Chester, PA
ingredientSupply source Methacrylic acid (MAA)BASF Corporation, Chalotte, NC α, ω-methacryloxyurea siloxane (5K MAUS)European Patent No. 92.907947.3 (Mazurek et al.) Methyl (trialkyl (C ₈ ~ C ₁₀ ) ammonium bromide (Adogen ™ 464)Aldrich Chemical Company, Milwaukee, WI Methyl (tricaprylyl) ammonium bromide (Aliquat ™ 336)Henkel Corporation, Kankaki, Illinois N, N-dimethyl acrylamide (NNDMA)Zachem Industries, Inc., Newark, NJ N, N-dimethylamino ethylacrylate (DMAEA)CPS Chemical Company, Old Bridge, NJ N, N-dimethylamino ethylmethacrylate (DMAEMA)CPS Chemical Company, Old Bridge, NJ N-vinyl pyrrolidoneBASF Corporation, Chalotte, NC Tego RC726 (100% solid polydiorganosiloxane)Goldsmiths AG, located in Essen, Germany Tetrahydrofurfuryl acrylate (THFA)SR 285, Satomer Company, West Chester, PA Tridecyl acrylate (TDA)SR 489, Satomer Company, West Chester, PA Tri (n-octyl) amine (TOA)Aldrich Chemical Company, Milwaukee, WI
Synthesis of 5K MAUS and 5K ACMAS
These free radical curable polydimethylsiloxanes (PDMS) were prepared according to the method outlined in EP 92.907947.3 (Mazurek et al.).
Mass reaction of α, ω-bis (3-aminopropyl) PDMS [European Patent No. 93.924905.8, (Leir et al.)] With 2-isocyanotoethyl methacrylate to obtain 5K MAUS or vinyl Dimethylazlactone (US Pat. No. 4,777,276, Rasmussen et al.) Gave 5K ACMAS. It is desirable to add the capping agent stepwise to the PDMS cooled to some extent to avoid polymerization of the free radical curable PDMS product.
Example 1
A main batch was prepared by mixing 60 g of a 75/25 IOA / 1,6-HDDA monomer mixture with the additives shown in Table 2 below. After standing, Sample 11 showed phase separation. Comparative Sample A, the main batch without additives, had a conductivity of zero. The conductivity of the sample was then measured as described in Method III at height H = 5 cm.
sampleAdditive (g)Current (μAmp)Conductivity (μS / m) OneAdogen 464-0.25THFA-1.501.672.60 2MAA-1.62DMAEA-2.40NNDMA-3.01.281.90 3MAA-1.0TOA-4.11NNDMA-3.01.362.04 4MAA-2.0TOA-8.22NNDMA-3.02.454.26 5Adogen 464-0.25NNDMA-0.65K ACMAS-9.0 Dark Locker 1173-1.27.862.8 6Aliquot 336-0.25 NNDMA-0.65K ACMAS-9.0 Multi Locker 1173-1.26.629.3 7Adogen 464-0.52.384.09 8Adogen 464-0.5NNDMA-3.06.426.4
sampleAdditive (g)Current (μAmp)Conductivity (μS / m) 9Adogen 464-0.25NNDMA-1.53.46.68 10Adogen 464-0.25NNDMA-3.05.416.5 11DMAEMA- 1.0SEMA-2.25NNDMA-3.08.290.7 Aradish00
Example 2
A release coating composition (i.e., sample I) was prepared by mixing 100 parts of IOA / 1,6-HDDA at 75/25, 25 parts of 5K MAUS, 2 parts of Daroker 1173, 0.5 parts of Aliquet 336 and 1 part of NNDMA. . A clear homogeneous solution was obtained. It is preferable to add the highly viscous components in the order recorded first, but no specific mixing order is necessary.
Using Method II, the resistance was 326 kΩ as measured at H = 4 cm of an LCR instrument providing a conductivity of 45.6 μS / m.
For comparison, the release coating compositions described in Sample I were prepared without Aliquot 336 and NNDMA. The current was measured as described in Method III, which resulted in 0 (the conductivity was also zero). This composition did not meet the conductivity required for electrospray without conductivity enhancers and separators.
Example 3
A release coating composition was prepared by mixing 100 parts of IOA / 1,6-HDDA at 75/25, 25 pph of Tego RC726S and 2 pph of Darocer 1173 at room temperature. The resistance was 10 MΩ above the limit of the LCR instrument, which means that the conductivity is 1.5 μS / m or less (measured according to Method II). To further improve the conductivity of this composition, 2 pph of NNDMA and 1.5 pph of Aliquet 336 were added. The resulting composition was transparent and at height H = 4 cm the resistance dropped to 606 kΩ (conductivity 24.5 μS / m), which is in the most preferred range for electrospray.
Example 4
This example demonstrates that adding onium salts and dissociation enhancers improves the conductivity of the thermosetting composition.
A release coating composition was prepared by mixing 100 parts of IOA / 1,6-HDDA at 75/25, 25 pph of Tego RC726 and 2 pph of VAZO 64 at room temperature. The conductivity measured in accordance with Method II was 1.5 μS / m or less. Adding 1.5 pph of Aliquet 336, the resistance dropped to 3.12 MΩ (conductivity of 4.8 μS / m) at H = 4 cm. When NNDMA 3 pph is added, the resistance is further lowered to 731 kΩ (conductivity of 20.3 μS / m), which is in the most preferable range for electrospray.
Example 5
In a container at room temperature, 100 parts of 70/30 IOA / 1,6-HDDA, 5K ACMAS 5pph, Darocer 1173 2 pph, 1 pph N-vinyl pyrrolidone and 0.5 pph Aliquot 336 were mixed together and then simply stirred A release coating composition was prepared. This mixture was clear and the resistance measured at H = 4 cm according to Method II was 616 kΩ (conductivity 24.1 μS / m).
Example 6
The composition described in Example 5 was prepared, with the ratio of IOA / 1,6-HDDA replaced by 60/40. The 4 cm height resistance, measured according to Method II, was 557 kΩ (conductivity 26.7 μS / m).
Example 7
A release coating composition containing the above ingredients was prepared by mixing together 100 parts of 75/25 TDA / BDA monomer mixture, 5K MAUS 25pph, Darocer 1173 2 pph, NNDMA 1 pph and Aliquet 336 0.5 pph together in a container at room temperature. . The 4 cm height resistance measured according to Method II was 632 kΩ (conductivity 23.5 μS / m).
Example 8
This embodiment describes electrospraying a release film having a positive acid-base pair on a pavement marking tape.
The release coating composition was prepared by mixing the following components together.
IOA 450 g
1,6-HDDA 150 g
5K ACMAS 60 g
Darlock 1173 12 g
NNDMA 30 g
MAA 8.6 g
DMAEA 12 g
Using a method similar to that described in U.S. Patent No. 5,326,598 (Sieber et al.) And U.S. Patent No. 08 / 392,108 (Sieber et al.), The release coating composition was manufactured in Minnesota Mining and Manufacturing Com. It was electrosprayed on a pavement marking tape sold by Pany.
Approximately 0.3 liters of the release coating composition is placed in a small glass container and the pump (Masterflex ™ pump drive models 7520-25, Micropump ™ model 07002, available from Cole Farmer Instrument Company, Chicago, Illinois, USA Pump head) to the spray head
The electrospray coated head die has two bisected plastic heads that hold 0.508 mm each other out of the slot height along the bottom of the die. The recessed and compressed slots to 1.53 mm are Porex Model X-4920 porous plastic sheets (Forex Technologies, Fairborn, GA), which maintains a moderate pressure drop and allows uniform flow rates. . The wire is suspended under the slot, and the extraction rod is suspended parallel to the wire in approximately the same horizontal plane. The width of the slot was 0.318 m and 0.0127 m of die end cap was added, resulting in 0.33 m of wet wire segment in the coating liquid. A width of 0.33 m was used in the mass balance equation to calculate the flow rate required to achieve the desired coat height at any web speed. The diameter of this wire was 1.59 mm and placed 0.889 mm from the slot. The diameter of each of the extraction rods was 6.35 mm and was placed at 11.2 mm above the wire and 0.12 m above ground-ground metal clad drum (0.508 m diameter, 0.61 m width).
A sample of the pavement marking tape (about 0.33 m × about 0.91 m) was attached to a polyester carrier web (available at 3M) with a thickness of 36 μm with a box sealing tape sold at 3M. The web speed was set at the speed shown below for each corresponding sample and the pump was adjusted to obtain film height or film thickness.
During encapsulation, the web is attached to an ID aluminum pipe with a diameter of 72 mm and an anode power supply (model PS / WG-10P30-DM, Glassman High Voltage, Inc., Whitehouse, NJ, USA). A coated drum using a corotron made of a half moon-shaped conductor grounded to a ground made of 60 micrometers in diameter. The corotron voltage was adjusted to charge the polyester carrier web at a 1000 volt potential relative to the grounded coated drum.
A negative 30 kV Glassman power supply model PS / WG-50N6-DM (Glassman High Voltage, Inc.) was connected from the ground to the spray head wire. The extraction electrode was kept at ground potential.
When the coating flow was present and high voltage was applied, a liquid filament formed over the wetted wire length 0.33 m below the slot. The back of the filament induced by Rayleigh jet instability creates a haze of droplets charged with the cathode, which is attached to the carrier web filled with the anode.
After coating, the samples were UV cured in a UV treater (available from GEO AETEK International, Plainfield, Ill.). The UV processor is equipped with two medium pressure mercury vapor UV light and the like in a gas cleaning chamber deactivated with nitrogen gas. Each lamp can set power to 125, 200, 300 and 400 watts per inch (4.92, 7.87, 11.8 and 31.4 kW / m).
The pavement marking tape was released in the height (thickness) range shown below. As can be seen, by adding conductivity enhancers, different pavement marking tapes can be electrosprayed at the above-described film height and web speed.
samplePavement marking tapeWeb speed (fpm)UV power (W / in)Film height (㎛) One380 Starmark ™30 (9.14 m / min)200 (7.87 kW / m)1,2,4 2420 Starmark ™25 (7.62 m / min)200 (7.87 kW / m)1,2,4 3331 Starmark ™50 (15.24 m / min)200 (7.87 kW / m)1,2,4 4620 Scotch Lane ™90 (27.43 m / min)400 (15.74 kW / m)1,2,2.8
Example 9
This embodiment describes the electrospray of a release coating with onium salt onto a pavement marking tape.
The release coating composition was prepared by mixing the following components together.
100 parts of 75/25 IOA / 1,6-HDDA
5K MAUS Part 25
Aliquot 336 Part 0.42
NNDMA Part 1
Darloc 1173 Part 2
The release coating was electrosprayed onto the following pavement marking tape commercially available at 3M as described in Example 8.
samplePavement marking tapeWeb speed (fpm)Film height (㎛) One380 starmark30 (9.14 m / min)1,2,4 2420 starmark25 (7.62 m / min)1,2,4 3331 Starmark90 (27.43 m / min)One 45730 starmark90 (27.43 m / min)1,2,2.8
Example 10
The pavement marking tape was electrosprayed with a release coating and measurements of silicon transfer were obtained.
The release coating composition was prepared by mixing the following components in a suitable container at room temperature.
IOA 1800 g
1,6-HDDA 600 g
NNDMA 24 g
Aliquot 336 12 g
5K MAUS 600 g
Dark locker 1173 48 g
The release coating was applied by electrospray onto the pavement marking tape shown below. The electrospray coating and UV curing assembly used were as described in Example 8 except that the assembly could handle continuous webs having a width of 1.27 m ± 0.05 m.
In order to measure the silicon transcription, the following procedure was used. Polybutadiene resin-based pressure sensitive adhesives were directly coated onto sputter eroded polyester [4 mil (101.6 μm) film, commercially available at 3M]. This strip of adhesive coated polyester was applied to each release coated side of the sample. The sample was then placed under 5 pounds (2.27 kg) for 3 days to facilitate transfer. A glass plate was placed on top of each sample to distribute the weight evenly over the same area 4 inches by 6 inches (102 mm by 152 mm). Immediately after detaching the adhesive from the surface, it was mounted on a spectrometer (Model 5100, available from Physical Electronics, Eden Prairie, Minn.). Silicon transfer was measured by X-ray photoelectron spectroscopy (XPS).
XPS irradiation spectra on the adhesive surface showed that all of the samples contained silicon. Angular resolution XPS at 45 ° and 90 ° was used to measure silicon concentration near the surface and surface area. The atomic concentrations measured are shown in the table below. Prior to exposure to the electrospray release coating, the adhesive was not exposed to any silicon source. Thus, all of the silicon detected on the surface of the adhesive after exposure may be transferred from an electrospray release coating.
sampleAnglePavement marking tapeSilicon concentration (atomic%) One45420 tapes coated with 1 micron release coating4.490 3.3 245621 tapes coated with 0.25 micron release coating1.390 1.0 345380 tapes anodized with 1 micron release coating6.790 5.7 445331 tapes coated with 1 micron release coating2.190 1.6 545620 tapes coated with 0.25 micron release coating2.590 1.7
For pure polydimethylsiloxanes, the% silicon atom is about 25, so the silicon transfer in the electrospray release coating is minimal.
Example 11
The following examples [arts (a) and (b)] illustrate the effect of dissociation enhancers.
The composition was prepared by mixing the following ingredients in a suitable container at room temperature.
20 g of 75/25 IOA / 1,6-HDDA and 5% by weight 5K ACMAS
0.72 g acrylic acid
DMAEA 1.13 g
The conductivity of the composition was measured according to the method I below. The conductivity was 1.2 μS / m.
Then, the following sample was 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 was added to 100 parts of the original composition. The conductivity was measured and found to be 4.0 μS / m.
Two parts of Daroker 1173 was added to sample (b), and the sample was then electrosprayed onto a commercially available 380 Starmark ™ pavement marking tape at 3M.
The composition was electrosprayed at a web speed of 30 fpm (9.14 m / min) as described in Example 8 and applied to the indicator tape in the range of film heights.
The composition was then UV cured under inert atmosphere. Using the silicon transfer test method shown in Example 10, the atomic concentration of silicon was measured at a 45 ° angle. The results are shown in Table 6 below.
sampleFilm height (㎛)UV power (W / inch)Silicon concentration (atomic%) OneOne200 (7.87 kW / m)2.8 22125 (4.92 kW / m)3.1 32200 (7.87 kW / m)3.7 42200 (7.87 kW / m)4.2 52300 (11.8 kW / m)3.5 64200 (7.87 kW / m)3.4
Example 12
Samples were prepared using the release coating compositions shown in Example 10. The pavement marking tapes (all sold at 3M) shown below were electrosprayed as described in Example 10. A silicon transfer test was then performed on each sample according to the following procedure. Samples were made from 1 foot (0.3 m) x web width (0.33 m) samples without carrier, and the web was cut into four 4 inch x 6 inch (0.1 m x 0.15 m) samples. Five 4 inch by 6 inch (0.1 m by 0.15 m) samples of the 6330 Starmark ™ Pavement Marking Tape (commercially available at 3M) were cut and the liner was peeled off in four of the five samples. The laminate was made by alternately laminating the 6330 tape and the electrospray coated tape and finished with a 6300 tape sample with a liner at the bottom.
The laminate is placed between two pieces of 0.25 inch (6.4 mm) glass plates, a 5 pound (2.27 kg) mass is placed on top of the center of the laminate and heated in an oven heated to 200 ° F. (93 ° C.) for 1 hour. I was. After the laminate was cooled to room temperature, a “medium” 6330 sample and a sample with a liner were selected, each cut into three 25.4 mm strips. This strip was applied to a stainless steel panel and passed through a 5 pound (2.27 kg) roller five times. The sample was then conditioned for 5 minutes at room temperature. The 180 ° peel test was performed using a Syntech tensile strength instrument (# 6365, commercially available from Division of MTS Systems, Inc. Stowton, Mass.). The instrument had jaw spacing of 4 inches (0.1 m), crosshead speed of 1 foot / minute (0.3 m / min), and a total measured load of 50 pounds (222.5 N).
Except for Samples # 3 and # 11, the test results were within a predetermined range of differences of 1 pound (17.5 N / 100 mm) or less than the control.
samplePavement marking tapeWeb speed (fpm)Film height (㎛)UV power (W / in)180 ° peeling sample (lb)180 ° peeling control (lb) One38030 (9.14 m / min)One200 (7.87 kW / m)6.40 (112 N / 100 mm)6.3 (110 N / 100 mm) 238030 (9.14 m / min)One200 (7.87 kW / m)6.40 (112 N / 100 mm)6.3 (110 N / 100 mm) 338030 (9.14 m / min)2125 (4.92 kW / m)4.5 (79 N / 100 mm)6.3 (110 N / 100 mm) 438030 (9.14 m / min)2200 (7.87 kW / m)6.10 (107 N / 100 mm)6.3 (110 N / 100 mm) 538030 (9.14 m / min)2200 (7.87 kW / m)7.10 (124 N / 100 mm)6.3 (110 N / 100 mm) 638030 (9.14 m / min)2300 (11.8 kW / m)5.90 (103 N / 100 mm)6.3 (110 N / 100 mm) 738030 (9.14 m / min)4200 (7.87 kW / m)6.60 (116 N / 100 mm)6.3 (110 N / 100 mm) 838030 (9.14 m / min)4200 (7.87 kW / m)6.90 (121 N / 100 mm)6.3 (110 N / 100 mm) 942030 (9.14 m / min)2125 (4.92 kW / m)5.30 (93 N / 100 mm)6.3 (110 N / 100 mm) 1042030 (9.14 m / min)2200 (7.87 kW / m)6.10 (107 N / 100 mm)6.3 (110 N / 100 mm) 1142030 (9.14 m / min)2200 (7.87 kW / m)7.40 (130 N / 100 mm)6.3 (110 N / 100 mm) 1242030 (9.14 m / min)2300 (11.8 kW / m)5.50 (96 N / 100 mm)6.3 (110 N / 100 mm)
Example 13
The composition of Example 10 was electrosprayed to a film height of 1 μm on the pavement marking tape shown below as shown in Example 10.
Reflectometer measurements were performed using an incident angle of 86.5 ° and an observation angle of 0.2 ° according to the procedure described in ASTM Test Method D4061-89, “Standard Test Method for Reflectivity of Horizontal Films”. The results are shown in Table 8 below.
samplePavement marking tapeWeb speed (fpm)Reflectance (mcd / m ² / lux)Allowable value (mcd / m ² / lux) One573090-120 (27.43-36.58 m / min)983≥550 238030 (9.14 m / min)2131≥1100 342025 (7.62 m / min)1150≥700 433080 (24.38 m / min)1202≥1092 533180 (24.38 m / min)835≥819 662080-100 (24.38-30.48 m / min)3130≥1770 762180-100 (24.38-30.48 m / min)1423≥1310
Example 14
The electrospray sample was prepared with a master composition containing 100 parts of IOA / 1,6-HDDA of 75/25, 2 parts of Darocer 1173, 0.5 parts of Aliquet 336 and 1 part of NNDMA. To prepare each sample, 0.1 part 5K ACMAS (Sample 1), 0.2 part 5K ACMAS (Sample 2), 0.3 part 5K ACMAS (Sample 3), and 10 parts 5K ACMAS (Sample 4) were added. These samples were electrosprayed onto a 0.036 mm thick polyester film (3M) as shown in Example 8 at a linear speed of 17 meters / minute. Subsequently, it was cured in-line on a medium pressure mercury lamp whose power under inert atmosphere was set to 200 W / 2.54 cm (about 7.9 kW / m).
The effectiveness of the release coating was measured through the release test and the reattachment test. The immediate release value (in N / 100 mm) is the force required to remove the flexible adhesive tape (# 810 tape, commercially available from 3M) from the electrospray coated polyester film at a specific removal angle and removal rate. Is a quantitative measure of. A sample of tape, usually 19 mm wide, was laminated to an electrospray coated polyester film (one pass at 30 cm / min with a roller covered with 2 kg of rubber) and a slip / peel tester immediately after rolling the sample. (Model 3M90, available from Instruments, Inc.) was tested at a speed of 30 cm / min and a peel angle of 180 °.
The aged release test was performed in the same manner except that the adhesive tape / coated polyester film sandwich was aged at 65 ° C. for 3 days.
Re-adhesion (both immediate and after aging (3 days at 65 ° C.)) was measured by re-adhesion of freshly squeezed tape to a clean glass plate (unit is N / 100 mm) and the peel adhesion was measured as mentioned previously. .
sampleSilicone (part)Immediate release (N / 100 mm)Aging release (N / 100 mm)Instant re-adhesion (N / 100 mm)Aging re-adhesion (N / 100 mm) One0.102.59.82325 20.201.63.92529 30.300.291.62531 41000.582331
The data presented indicate that the release can be difficult or easily controlled by changing the silicon content of the sample. After thermal aging, the release was increased, but the re-adhesive force was substantially unaffected, thus demonstrating good curing of the composition.
Example 15
A master batch was prepared by mixing 100 g of a mixture of IOA / 1,6-HDDA 75/25, 25 g of 5K MAUS and 2 parts of Darokker 1173 at room temperature. The current was measured using Method III and found to be zero. To this master batch 0.5 parts of GE 9380C iodium salt was added as a conductivity enhancer. The resistance was measured at height H = 4 cm using Method II, resulting in 937 kΩ (conductivity is 15.9 μS / m). Subsequently, 1 part of NNDMA was added, and the resistance was measured again, and as a result, it fell to 501 k All of these mixtures had the most preferred range of conductivity.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention, and the invention is not unduly limited to the above-described exemplary embodiments.

权利要求:
Claims (19)
[1" claim-type="Currently amended] a) about 100 parts by weight of one or more free radically polymerizable vinyl monomer (s),
b) about 0.05 to about 250 parts by weight of one or more polydiorganosiloxane polymer (s) copolymerizable with the vinyl monomer (s), and
c) about 0.10 to about 10 parts by weight of one or more nonvolatile conductivity enhancer (s) soluble in the vinyl monomer (s) and not interfering with the polymerization reaction, based on 100 parts by weight of a) and b)
A free radically polymerizable release coating composition comprising a; and capable of electrospraying.
[2" claim-type="Currently amended] The free radical polymerizable release coating composition according to claim 1, wherein the composition is free of solvent.
[3" claim-type="Currently amended] The free radically polymerizable release coating composition according to claim 1, wherein the polydiorganosiloxane polymer (s) is selected from the group consisting of polymers belonging to the general formula and mixtures thereof.

Where
X is a monovalent moiety having the same or different ethylenically unsaturated moieties,
Y is the same or different divalent linking group,
D is the same or different monovalent moiety selected from the group consisting of hydrogen, alkyl groups having 1 to about 10 carbon atoms and aryl,
R is each an alkyl moiety (which may be substituted with a trifluoroalkyl or vinyl group), a cycloalkyl moiety (which may be substituted with an alkyl group, a fluoroalkyl group and a vinyl group), an aryl moiety (an alkyl group, a cycloalkyl group, a fluoroalkyl group and a vinyl) Monovalent moiety), and a monovalent moiety selected from
R 'is the same or different divalent hydrocarbon group,
n is an integer from about 25 to about 750.
[4" claim-type="Currently amended] The process of claim 1 wherein the polydiorganosiloxane polymer (s) comprises an epoxy functional polysiloxane of formula
(a) 10 to 90 mol% of (meth) acrylic anhydride,
(b) the total of (a) and (b) is a maximum of 100 mol% and is obtained by reacting with an acid mixture consisting of 90 to 10 mol% of (meth) acrylic acid present at 0.8 to 1.9 acid equivalents per epoxide equivalent A free radically polymerizable release coating composition selected from the group consisting of polymers.

Where
R ^{1 is} the same or different low molecular weight alkyl or phenyl group having 1 to 4 carbon atoms,
R ² represents a same or R ³ and R ^1, 70 to 100% of the R ³ groups is an epoxy functional group, 30 to 0% is 2 to 20 carbon atoms an alkyl group or hydrogen, but the average molecule at least 1.5 epoxy groups Has,
a is an integer from 1 to 1,000,
b is an integer of 0-10.
[5" claim-type="Currently amended] The free radical polymerizable release coating composition according to claim 1, wherein the polydiorganosiloxane polymer (s) is selected from the group consisting of polydiorganosiloxane oligourea segmented copolymer compositions of the formula:

Where
Z is a divalent radical selected from arylene radicals and aralkylene radicals, alkylene radicals and cycloalkylene radicals,
R is each an alkyl moiety (which may be substituted with a trifluoroalkyl or vinyl group), a cycloalkyl moiety (which may be substituted with an alkyl group, a fluoroalkyl group and a vinyl group), an aryl moiety (an alkyl group, a cycloalkyl group, a fluoroalkyl group and a vinyl) Monovalent moiety), and a monovalent moiety selected from
Y is a divalent moiety selected from an alkylene radical, an aralkylene radical and an arylene radical, respectively,
D is a monovalent radical selected from hydrogen, alkyl radicals, aryl radicals or arylalkyl radicals, respectively
p is a number of about 10 or more,
q is a number of about 10 or more,
t is from 0 to about 8,
X is each (a)
Wherein Z, Y and D are as defined above,
L is , ,
K is a free radical curable end group), or
(b)
(Where D, Y and K are as defined above).
[6" claim-type="Currently amended] The free radical polymerizable release coating composition according to claim 1, wherein the conductivity enhancer (s) is selected from the group consisting of an amphoteric acid-base pair and an onium salt of elements of group Va, group VIa or group VIIa.
[7" claim-type="Currently amended] The positive acid-base pair according to claim 6, wherein the amphoteric acid-base pair is N, N-dimethyl aminoethyl (meth) acrylate / (meth) acrylic acid, methacrylic acid / diethanolamine, acrylic acid / 2-vinylpyrrolidine, 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, 1-vinyl-3- (3-sulfopropyl) imidazolium hydroxide intramolecular salt, 1-vinyl-2-methyl-3 -(3-sulfopropyl) imidazolium hydroxide intramolecular salt, 1-vinyl-3- (4-sulfobutyl) imidazolium hydroxide intramolecular salt, 1-vinyl-2-methyl-3- ( 4-sulfobutyl) imidazolium hydroxide intramolecular salt, 1-vinyl-3- (2-sulfobenzyl) imidazolium hydroxide intramolecular salt, 2-vinyl-1- (3-sulfopropyl) pyri Dinium Hydrolock Intra-molecular salt, 2-methyl-5-vinyl-1- (3-sulfopropyl) pyridinium hydroxide intramolecular salt, 4-vinyl-1- (3-sulfopropyl) pyridinium hydroxide intramolecular salt , Dimethyl- (2-methacryloxyethyl) (3-sulfopropyl) ammonium hydroxide intramolecular salt, diethyl- (2-methacrylyloxyethoxy-2-ethyl) (3-sulfopropyl) ammonium Hydroxide intramolecular salt, 4-vinyl-4- (sulfobutyl) pyridinium hydroxide intramolecular salt, 2-vinyl-4- (sulfobutyl) pyridinium hydroxide intramolecular salt, 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 methanecarboxy-betaine, 4-vinylpyridinium / p-styrenesulfonate, 4-vinyl-N-methylpyridinium / p-styrenesulfonate and 2-methacrylylethyltrimethylammonium / 2- A free radically polymerizable release coating composition selected from the group consisting of methacrylyloxyethane sulfonate.
[8" claim-type="Currently amended] The free radically polymerizable release coating composition according to claim 6, wherein the onium salt is selected from the group consisting of compounds represented by the following formulas.

Wherein at least one of R is a hydrocarbon having 1 to 18 carbon atoms, the other R is hydrogen or a hydrocarbon having 1 to about 18 carbon atoms, B is an element of group Va, group VIa or group VIIa, n is an integer of 2-4, A is an inorganic anion.
[9" claim-type="Currently amended] The free radical polymerizable release coating composition according to claim 8, wherein A is selected from the group consisting of sulfates, borates, nitrates, thiocyanates, perchlorates and halogens such as iodide, chloride and bromide.
[10" claim-type="Currently amended] 7. The free radically polymerizable release coating composition according to claim 6, wherein the onium salt is selected from the group consisting of tetraoctylammonium chloride, tetrabutylammonium bromide, tetrabutyl ammonium thiocyanate and tetrabutylphosphonium bromide.
[11" claim-type="Currently amended] The free radical polymerizable release coating composition according to claim 1, wherein at least a part of the conductivity enhancer is copolymerizable.
[12" claim-type="Currently amended] The method of claim 1, wherein the free radically polymerizable vinyl monomer (s) is beta-acryloxypropionate of divinyl benzene, divinyl acrylate, divinyl methacrylate and alkyl polyols, ethoxylated analogs and pros Foxylation analogues, 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 their A free radically polymerizable release coating composition selected from the group consisting of mixtures.
[13" claim-type="Currently amended] The free radically polymerizable release coating composition of claim 1 further comprising at least one dissociation enhancer (s).
[14" claim-type="Currently amended] The method of claim 13, wherein the dissociation enhancer (s) is polyethylene glycol, glycerol, propylene carbonate, poly (ethylene oxide), dialkyl urea, N, N-dimethyl acrylamide, N-vinyl pyrrolidone, methacryl A free radically polymerizable release coating composition selected from the group consisting of acid, 2-ethoxyethyl acrylate and Carbowax ™ 750 acrylate.
[15" claim-type="Currently amended] The free radical polymerizable release coating composition of claim 1 further comprising at least one free radical initiator (s).
[16" claim-type="Currently amended] The free radical polymerizable release coating composition according to claim 1, further comprising at least one of the following features (a) or (b):
(a) the viscosity of the coating composition is from about 10 ⁻³ Pa · s to about 1 Pa · s
(b) the conductivity of the coating composition is about 0.1 to about 100,000 μS / m.
[17" claim-type="Currently amended] One or more polydiorganosiloxane polymer (s), one or more free radical polymerizable vinyl monomer (s) and optionally one or more free radical polymerization reaction initiator (s), which are insufficient to be blended together and electrosprayed As a method of applying a release coating composition exhibiting a conductivity,
(a) adding at least one conductivity enhancer (s) and optionally at least one dissociation enhancer (s) to the composition to prepare a coating composition,
(b) applying the coating composition to the substrate by electrospray, and
(c) polymerizing the coating composition
Method of applying the release coating composition comprising a.
[18" claim-type="Currently amended] A substrate having two major surfaces, wherein the composition according to claim 1 is electrosprayed on at least a portion of at least one major surface.
[19" claim-type="Currently amended] 19. The method of claim 17 or 18, wherein 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, non-woven, paper, cotton, nylon, rayon, glass, metal, metallized polymeric film, ceramic sheet material, abrasive, natural rubber or synthetic rubber, and pavement marking tape.

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同族专利:

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公开号 | 公开日

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AT192476T|2000-05-15|

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EP0889940A1|1999-01-13|

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DE69608138D1|2000-06-08|

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DE69608138T2|2000-09-21|

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CN1215423A|1999-04-28|

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EP0889940B1|2000-05-03|

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US5858545A|1999-01-12|

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CA2248312A1|1997-10-02|

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AU6456196A|1997-10-17|

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JP2000507300A|2000-06-13|

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WO1997035941A1|1997-10-02|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1996-03-26|Priority to US08/622,075

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1996-03-26|Priority to US08/622,075

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1996-07-09|Application filed by 스프레이그 로버트 월터, 미네소타 마이닝 앤드 매뉴팩춰링 캄파니

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2000-01-25|Publication of KR20000004982A

优先权:

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申请号 | 申请日 | 专利标题

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US08/622,075|US5858545A|1996-03-26|1996-03-26|Electrosprayable release coating|

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US08/622,075|1996-03-26|