MXPA97006202A - Acrylic claddings in emulsion for articles of hule or cau - Google Patents

Abstract

Polymer-coated, powder-free rubber articles are provided, particularly rubber gloves coated with a copolymer in acrylic-based emulsions, formed by the polymerization of at least one monomer with low surface energy, at least one alkyl acrylate, and at least one hard monomer. The copolymers are preferably formed by sequential polymerization. This provides improved properties versus the conventional way of manufacturing rubber gloves which involves immersing a mold in the shape of the article to be formed into a coagulating suspension containing calcium nitrate and calcium carbonate.

Description

ACRYLIC CLADDING IN EMULSION FOR RUBBER OR RUBBER ARTICLES FIELD OF THE INVENTION The invention relates to thin articles with walls, formed of rubber or synthetic or natural rubber, which have on them a polymer coating free of dust that allows or improves the removal and placement of molds or substrate.

BACKGROUND OF THE INVENTION Rubber or rubber articles made of rubber or natural or synthetic rubber include surgical gloves, examination gloves for doctors, gloves for workers, prophylactics, catheters, balloons, tubes, sheets and the like. Some of those articles and particulate gloves require the skill of placement, i.e., the ability of the rubber article to slide to be placed and removed on the surface of the skin (tissue) without causing friction or sticking. Surgical or surgical gloves require wet placement, that is, the ability or ability to slip on wet skin surfaces. Other rubber articles such as catheters and REF: 25462 tubes, require some means to isolate the rubber from body fluids and tissues. Although this invention pertains to polymer coatings for all rubber articles, it will focus on gloves which are the most complex rubber articles in terms of use and manufacture. To obtain acceptable placement properties, the rubber surface of a glove that comes into contact with the skin or fabric has to be modified to reduce friction. Surgery gloves, at present, require that the placement surface be sufficiently hydrophilic in order to absorb moisture that may be present on the surface of the skin or tissue when the article is placed. Hydrogel coatings have been used as described, for example in US Pat. No. 3,813,695, incorporated herein by reference, to achieve this property. The examination and other gloves, in contrast, do not have the requirements of hydrophilicity but still require the ability of the rubber article to slide on the surfaces of the skin (tissue) with minimal drag or friction force.

Traditionally, this has been achieved by applying talc or other powdered materials, such as modified corn starch, on the tissue or skin contact surface. Talc can not be used anymore and other dusts can contaminate the work field. The same applies to gloves worn by workers in dust-free environments such as the manufacture of computer microcircuits and other electronic items. With reference to Figure 1, the conventional way of manufacturing rubber gloves has been to dip a mold in the shape of the article to be formed into a coagulating suspension containing calcium nitrate and calcium carbonate. After drying, the mold is immersed in an emulsion of rubber or rubber (latex) for a sufficient time for the rubber to coagulate and form a coating of desired thickness. The formed coagulated rubber article is cured in an oven, cooled, and then immersed in a starch emulsion. The starch coated surface is dried to provide a powder coating. After cooling, the rubber article is removed from the mold. This causes the glove to turn over. The mold is cleaned and recirculated.

Water washing is usually used as part of the process to remove impurities from the rubber or rubber. Methods and materials for the manufacture of the gloves are also described, for example, in US Patents 3,411,982 and 3,286,011 to Kavalier et. al., both incorporated herein for reference. "Polyurethene Latexes for Coagulation Dipping" Sadowski et. al., Elastomerics. August 1979, pp. 17-20, incorporated herein by reference, and "Dipping with Natural Rubber Latex" Pendle et. al., Natural Rubber Technical Bulletin, also incorporated here as a reference. Halogenation, for example, chlorination and other chemical surface treatments have been used to eliminate the need for a powder coating on the final product to allow dry placement. Although effective, this step is expensive and has the disadvantage that it reduces the shelf life of the rubber article. It would be desirable to provide a rubber article with a dust-free laying surface without resorting to expensive practices that deteriorate the now fashionable item. This could substantially reduce the cost of manufacturing and maximize the shelf life of the rubber article.

U.S. Patent 4,302,852 to Joung, incorporated herein by reference, proposes to covalently bond a silicone coating RTV to the inner surface of a rubber surgical glove after the glove is formed. This is set to reduce but not to eliminate the need for a placement powder. U.S. Patent 4,304,008 also by Joung and incorporated herein by reference, applies a silicone or urethane covalently bonded to the outer surface of the glove and halogen the inner surface. The halogenated interior surface eliminates the need for a placement powder. U.S. Patent 4,310,928 also by Joung and incorporated herein by reference teaches the arrangement of a compound lipo (lipid or lipofilic substances) instead of a powder of mineral origin in combination with a surfactant in a coagulating solution to form a uniform film in a glove mold on which the rubber is coagulated. The compound lipo and the surfactant or surfactant allow the glove formed from its mold to be removed. These and other proposals have not achieved commercial acceptance.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, acrylic-based copolymers are provided which coat and adhere firmly and can, in part, be absorbed onto the surface of a rubber article undergoing deformation therein by coagulation. The copolymers can also be deposited in a preformed rubber article. Copolymers, such as gloves and other rubber articles, are effective in inducing the removal properties of the mold to the formed rubber article and placement without the need for additional chemical treatment. Dry or wet setting properties and removal of the mold can be achieved by depositing the same or a different acrylic-based copolymer on opposite surfaces of the rubber article formed, e.g., gloves. The acrylic-based copolymers are preferably emulsions based on copolymers of at least one low surface energy reactive monomer, preferably a silicone oligomer, at least one alkyl acrylate and at least one reactive hard monomer, the total of hard monomers that they are present in an amount sufficient to form a non-tacky copolymer directly or by mixing copolymers. Preferably the copolymers exhibiting at least one transition temperature peak (Tpi of the dominant glass above 0 ° C and typically at least one peak of dominant glass transition temperature below about 0 ° C. effective glass is generally above about 15 ° C, preferably from about 15 to about 60 ° C. It is preferred in the present that at least the laying surface be formed by sequential polymerization of two monomer systems, one providing the peak of transition temperature of the low, dominant glass, and the other providing the high, dominant glass transition temperature peak.The preferred copolymers present for the release of a mold are the copolymers comprising copolymerizable silicone oligomers, acrylate butyl, methyl acrylate, methacrylic acid, acrylic acid and styrene. Today preferred olimers for dry and wet laying are copolymers comprising an oligomer of silicone, styrene, butyl acrylate, methyl acrylate, acrylic acid, trimethylpropane triacrylate and n-isobutyl acrylamide.

The emulsion copolymers are, for the efficiency of the emulsion polymerization processes, produced as high solids emulsions. The high solids contents are not required for the coating of the product. Accordingly, the emulsions may be diluted to form suspensions of solids containing from about 3 to about 10% by weight, preferably about 6% by weight of the total acrylic-based emulsion copolymer of a solids content typically used for coating the mold and for depositing a coating on the surface of a rubber or rubber article formed. In the alternative, the acrylic-based emulsion copolymer can be recovered from the emulsion and subsequently resuspended. The suspension is used in combination with a multivalent metal salt, soluble in water, which serves as a coagulant for the rubber or rubber emulsion. The coagulant can be deposited in the acrylic-based copolymer or deposited therewith of the suspension. The aim is to provide a surface concentration of coagulating salt that will allow the coagulation of the latex on the deposited copolymer coating at a commercially acceptable time. The preferred coagulant salt is calcium nitrate and is used in a concentration up to about 40, preferably from about 30 to about 40 percent by weight of the suspension. In the manufacture of the article, in particular the manufacture of gloves, the mold having a coated surface of coagulant and polymer is immersed in an emulsion of rubber or latex from which the rubber is deposited and coagulated on the surface of the copolymer forming a coated inner glove surface. The rubber article formed is dried, cured and then immersed in an aqueous suspension thereof or a different acrylic-based copolymer exhibiting good placement characteristics. The submersion forms a polymer coating placed on the outside of the rubber glove. Then the formed coated glove is separated from the mold. This flips the glove by placing the placement lining inside the glove. As is known, cleaning with water can effectively be used for purifying the rubber. In the practice of the invention, the preferred mold is a contoured mold. While molds having a textured surface up to highly polished ceramic or porcelain and molds having a fluorocarbon coating can be employed, it is preferable to employ a mold that is sufficiently textured to produce a matte finish on the deposited laminate formed by deposition of the latex rubber over the copolymer coating. This is achieved by roughening the surface of the mold by spraying with sand or glass beads. The surfaces used have been measured to have a roughness from about 8 to 10 microns from peak to valley. It is preferred to use the same copolymer for the placement and release surfaces of the gloves with the placement side containing corn starch and a small amount of oil, for example, about 0.1% by weight solids. Preferred copolymers have a surface friction that requires an average force of about 0.05 pounds to less than about 0.3 pounds, preferably about 0.2 to about 0.25 pounds to move a drag or weigher weighing 200 grams onto the copolymer coated surface of the rubber article .

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart * of the current rubber glove manufacturing method. Figure 2 is a Differential Scanning Calorimetry (DCE) graph of the heat flux derivative versus temperature, showing the glass transition temperature peaks for the preferred mold release copolymer coating of the invention; and Figure 3 is a graph of Calorimetry of Differential scanning of the derivative of the heat flow as a function of temperature, which shows the glass transition temperature peaks for the preferred placing copolymers of the invention.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, acrylic-based, non-tacky copolymers are provided, which aggressively adhere to the surface of the rubber or other articles to provide flexible copolymer coatings that can be stretched without the separation of a surface. of rubber to which they are united. The copolymers are formed of at least one low surface energy reactive monomer, preferably one or more copolymerizable silicone oligomers, at least one alkyl acrylate and at least one hard monomer. These copolymers provide powder-free coated rubber products that exhibit excellent mold separation and dry placement and provide protective coatings for other articles. By the term "rubber or rubber article" as used herein, it is meant the articles formed of natural and / or synthetic rubber or rubbers. They are typically deposited by coagulation of a latex on a multivalent metal salt. By the term "low surface energy copolymerizable monomer" monomers are indicated which if homopolymerized would require only a low level of stress to release the homopolymer from a surface to which they are applied. In copolymers, copolymerizable monomers of low surface energy reduce the energy to release the copolymers from a surface whether it be a mold, a tissue or the skin. Examples of low surface energy copolymerizable monomers are silicones, fluorocarbons and esters of reactive fatty acids and the like, low surface energy monomers having vinyl, acrylic and / or methacrylic functionalities. Preferred are the copolymerizable silicone oligomers. By the term "copolymerizable silicone oligomer" as used herein, polymeric siloxanes and silicones having acrylate, methacrylate and vinyl functionalities, including but not limited to acrylate polysiloxanes, are indicated. The functionality of acrylate, methacrylate or vinyl is at least 1, preferably from 2 to approximately 3. As an example of the copolymerizable silicone oligomers, Tegro ™ RC 149, 300, 450, 710, 720 and 802 silicone acrylates can be mentioned and ZMR1395 manufactured and sold by Goldschmidt Chemical Corporation of Hopewell, Virginia, which polymers are linear dimethylpolysiloxanes with multiacrylate functionality and a molecular weight between about 1,000 and 20,000 g / mol. They include the reaction product of the dimethylpolysiloxanes with pentaerythritol triacrylate. There may also be mentioned the silicone systems such as GE 6000, a polydimethyl vinyl siloxane and the catalyst concentrate 6010 manufactured and sold by the GE silicones of the General Electric Company. The polysiloxanes substituted with ethoxy can also be used. The copolymerizable monomers of low surface energy and preferably the copolymerizable silicone oligomer are used in concentration from about 0.7 to about 20%, preferably about 1 to about 15% by weight of the monomers which form the acrylic-based copolymer. They work to allow dry and wet placement and facilitate mold release. The balance of the monomers is selected to provide a good bond to the surface of the latex, the placement (dry and wet), a good sense of touch, release of the mold and a non-tacky copolymer having a significant glass transition temperature (Tg) of at least about 15 ° C, preferably from about 15 up to approximately 60 ° C. The monomers are also selected to provide sufficient elongation so that the acrylic-based copolymer coating is stretched or stretched with the rubber with minimal breaking, flaking or peeling. Suitable copolymers have an elongation or elongation of 100 to 500% or more, typically from about 100 to about 300% when self-ligating to a rubber surface. Of the rubber articles that can be manufactured according to the present invention, the surgical articles and articles that have the most critical requirements are the examination and surgical gloves. Due to their complex shape, they must be able to be separated from a mold using commercially acceptable practices and still provide a surface that, when separated from the mold, has a good sense of touch; that is, the ability of a person to pick up items with a good grip. In relation to this, a good sense of touch is against a good separation of the mold. The opposite surface of the glove must allow a good placement (dry or wet), this is the ability to be stretched and slide on the surface of the skin without excessive resistance. The touch and release surface of the mold should be transparent and smooth but is preferably rough and dull as induced by a textured or rough mold. The placement surface usually requires a more directional or irregular surface (no gloss).

With respect to the manufacture of the glove, the copolymers of the present invention provide good mold separation and / or placement properties. In addition to the low surface energy monomers, the following monomers and combinations thereof can be used according to the invention to provide suitable polymers having good placement and / or separation characteristics. One class of the monomers used in the formation of the copolymers are the alkyl acrylate monomers containing from 1 to about 10 carbon atoms in the alkyl group, present in a total amount from about 30 to about 85% by weight of the monomers, preferably from about 40 to about 85% by weight of the monomers that form the acrylic-based copolymers. The alkyl acrylate monomers that may be used include methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate, and the like. Preferred alkyl acrylate monomers herein are butyl acrylate and methyl acrylate.

The balance or equilibrium of the monomer system is comprised of hard monomers. As used herein, "hard monomers" are monomers which, if homopolymerized, would have glass transition temperatures (Tg) greater than about 25 ° C. The content of hard monomers is from about 20 to about 60% by weight of the monomers forming the acrylic-based copolymer. Among such monomers there may be mentioned styrenic monomers such as styrene, alpha methyl styrene and the like; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like; and amides such as an n-isobutoxymethyl acrylamide and the like. One or more unsaturated carboxylic acids containing from 3 to about 5 carbon atoms, such as acrylic acid, methacrylic acid, itaconic acid and the like, may be present and preferably present. They serve to improve cohesive strength or strength and provide adhesion to rubber and other surfaces and are present in a concentration of from about 1 to about 6% by weight, preferably from about 2 to about 6% by weight of the emulsion copolymer.

Other unsaturated vinyl monomers that aggressively copolymerize with the main monomers of the invention and do not create a problem of residual monomer contamination can also be used to modify the properties of the polymers. Such monomers include one or more vinyl esters containing from 2 to about 16 carbon atoms in the alkyl group of the acid. Respresentatives of vinyl esters include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl isobutyrate, vinyl valerate, vinyl versite, and the like. As other useful monomers there may be mentioned the diesters of carboxylic acids and mixtures thereof, in which each ester group of the diester independently contains from about 8 to about 16, preferably from about 8 to about 12 carbon atoms. The preferred diesters are di-2-ethylhexyl maleate (dioctyl maleate), di-2-ethylhexyl fumarate and mixtures thereof. The emulsion copolymers can be prepared according to the present invention by polymerizing the monomers to give a polymer having a suitable average net transition temperature of the glass (Tg) above about 15 ° C, preferably from about 15 ° C. ° C to about 60 ° C, and a solids content ranging from about 40 to about 70% by weight of the emulsion. Catalysts, such as potassium persulfate, tertiary butyl hydroperoxide and the like, and Redox catalysts, such as sodium meta-bisulfite and the like, present in an amount from about 0.15 to about 0.5 parts by weight per 100 parts by weight of monomers that surfactant levels ranging from about 0.5 to about 5% by weight based on the weight of the monomers is preferred. The reaction temperature in general ranges from about 65 to about 85 ° C. "Chain transfer agents" can be included by which organic compounds containing mono- or multi-mercaptan groups, chlorinated groups, hydroxy groups, and the like, are known as are known in the art. Preferred chain transfer agents herein are n-dodecyl ercaptan and t-dodecyl mercaptan provided in a concentration from about 0.01 to about 0.1% by weight of the monomers. In addition, the internal cross-link can be induced by the use of multifunctional acrylates and methacrylates. Although the copolymers prepared according to the present invention can be used for a variety of rubber article applications, including gloves, catheters, tubes, protective covers, prophylactics and the like, the primary focus is their use in the manufacture of free gloves. of dust and other items. Referring again to Figure 1, a mold is coated in a contoured shape with an acrylic-based copolymer of this invention that shows good mold separation properties. The coating of the copolymer is preferably applied from the suspension in combination with a coagulation electrolyte. The steps of coating the copolymer in a mold to be transferred to a latex rubber replaces the step of placing a calcium carbonate slurry on the surface of the mold while depositing the copolymer on a formed article and replacing the article coating with a suspension of starch. The copolymer is applied from the suspension. The article is formed by deposition on a coagulating salt such as calcium nitrate provided in a mold, on a copolymer coating in the mold or co-deposited with the polymer. For gloves, the mold coated with the copolymer provides a surface salt coagulant preferiflemente co-deposited with the copolymer, is immersed in a latex which coagulates rubber on the mold surface shape providing rubber article. It is dried, cured and then immersed in a second suspension of the same or another acrylic-based copolymer which shows excellent placement properties, that is, the ability to slide on a skin surface with minimal friction and blocking. The washing is employed as in the prior art, either before or after curing or before or after providing a coating for placement. Then the formed article is separated from the mold. The mold is cleaned and recycled. The separation causes the glove to turn causing the placing surface to be on the inner side of the glove and the separation surface of the mold to be on the outer side of the glove. For the manufacture of the gloves, it is preferred here to use a rough mold formed by abrasion with sand or glass beads to provide a rough surface which, measured, has a roughness of about 8 to about 10 microns from peak to valley. Other textures can also be used. The emulsion copolymers of the present invention can be used as such or combined with inert granular solids such as calcium carbonate, starch and the like to provide an improvement in placement. The content of inert solids can vary by an amount based on the total weight of solids from about 3 to about 10% by weight solids. It is preferred in the present to employ corn starch in an amount from about 0.3 to about 0.7., more preferably from about 0.3 to about 0.5 parts per part by weight of copolymer. A suitable corn starch is the 400 L-NF corn starch made by Roquetle America Inc., Keokuk, Iowa. The placement coating also preferably contains a small amount, approximately 0.1% by weight of copolymer, of an oil such as octyl sonate or Neobee M-20, a polyol diester of a short cleaned fatty acid, manufactured by Stepan Chemical Co. , Northfield, Illinois. It has been found that for good placement and separation properties, each of the copolymer coatings are preferably formed from at least two polymers. One is a copolymer having a low glass transition temperature, and the other is a copolymer having a high glass transition temperature. The two, in combination, provide a non-tacky copolymer having at least a significant glass transition temperature of about 15 ° C or more and preferably in a range of about 15 to about 60 ° C. Although this can be achieved using a mixture of polymers, it is preferably achieved by a sequential polymerization or "core and shell" of at least two monomer systems, the first forming an acrylic-based copolymer having a glass transition temperature. of less than about 25 ° C, typically from about -50 ° C to about 25 ° C, the other forms an acrylic-based copolymer having a glass transition temperature of from about 25 to about 100 ° C, the first and the second monomer systems do not provide copolymer coating systems. It has been observed that for a copolymer exhibiting good mold release, the copolymer having glass transition temperatures below 0 ° C occupies the volume of the total glass transition temperatures. The opposite may be true for a placement copolymer. In particular, Figure 2 is a graph of the glass transition temperature of a sequential polymerized mixture of copolymers with a higher glass transition temperature peak below 0 ° C and a lower glass transition temperature peak per above 0 ° C to be used as a mold release copolymer coating. Although, not bound by the theory in this "core and shell" approach to a sequential polymerization of two monomer systems, it is believed that a continuous phase of the low glass transition temperature copolymer having dispersed therein is formed or on it, the glass transition high temperature copolymer. Figure 3 is a graph of glass transition temperature for a good placement copolymer coating wherein the relative peak intensities of the glass transition temperature are reversed. For good mold release characteristics, it is preferred that the weight ratio of the low or low glass transition temperature copolymer to the high glass transition temperature copolymer be in the range of about 1: 1 to about 1. : 3, preferably about 1 to 1.5. For good placement characteristics, the weight ratio of low to high glass transition temperature copolymers is in the range of about 3: 1 to about 1: 1, preferably about 1.2 to 1. It has been observed that if too much High Tg copolymer is present, de-scaling will occur. In addition, for a good dry placement, it is desirable that the copolymer forms domains or microparticles. This essentially provides a rough surface which is desirable for good placement and fillers such as calcium chloride can be included in the suspension. If too much low transition temperature copolymer is used, there is a problem of adhesion or blocking. As indicated above, for the process of making the copolymer it is desirable to employ a surfactant system present in the amount of from about 0.5 to about 5 parts by weight to 100 parts by weight of monomers, preferably about 3 parts per 100 parts by weight of monomers It is also desirable that the suspension formed from the emulsion copolymer tolerates the electrolytes typically employed for the coagulation of the latex at the concentration typically used for coagulation of the latex, i.e. in the range of about 3 to about 10% by weight of the suspension. . The preferred surfactant or surfactant system herein is a combination of anionic surfactants. One of the anionic surfactants has the molecular formula C20H37O7NaS and contains 20 moles of ethylene oxide and is used in admixture with anionic surfactants which are salts of sulphonated nonyl phenoxypoly (ethyleneoxy) ethanol and sodium lauryl ether sulfate. The preferred surfactant system herein is one that employs 37.4% by weight of the ammonia salt of nonyl phenoxypoli sulphonated (ethyleneoxy) ethanol, 21.8% by weight of sodium dioctyl sulfoccinate and 40.8% by weight of sodium lauryl ether sulfate. The combination of anionic surfactants allows the formation of a stable suspension of the acrylic-based emulsion copolymers of the invention. The emulsion copolymers of the present invention can be prepared to provide both a high cohesive force and maintain the power to Isa natural or synthetic rubber surfaces as well as the ability to stretch with the rubber surfaces and allow placement. The polymers have an elongation of 100 to 500%, preferably 100 to 300% when they adhere to the rubber and an average coefficient of friction of from about 0.05 to about 0.3 pounds typically from about 0.2 to about 0.25 pounds. The thickness of the copolymer coating is from about 10 to about 25 microns, preferably from about 12 to about 16 microns. The inclusion of the multifunctional monomers such as tetramethylpropane triacrylate and the like, undergoing cross-linking reactions and chain transfer agents as part of the monomer system results in the formation of internally cross-linked emulsion polymers. This differs from the externally crosslinked polymer in that functional groups, such as carboxyl, hydroxyl, and / or amino groups, remain free and available to improve the bond and are available for external crosslinking reactions such as by actinic exposure, radiation by electronic beams and / or through external crosslinking agents. The emulsion copolymers can be used as such or modified by the addition of vinyl-added silicone polymers present in an amount of up to about 30% by weight based on the weight of the emulsion polymer and the silicone system added with vinyl. The vinyl-added silicone systems used are those comprising silicone monomers having vinyl unsaturation which, when mixed with crosslinkers containing silicone hydride, are cured by a Group VIII metal catalyst, preferably a platinum catalyst. . Preferred vinyl-added silicone emulsions herein are mixtures of reactive vinyl silicone polymers of the formulas: CH3 CH3 CH3 CH3 I I 1 1 CHi "CH Si (SiO) m (Si0) n Si - CH - CH - > I I I CH3 CHj CH CH3 II CH-, where m and n are independent integers, and the silicone hydride crosslinking polymers of the formula CHi CH3 CH3 | i "3 | 2. CH Si (SiO) m - (SiO) _ - S - CH3 I \ v | CH3 CH3 H CH3 where m and p are independent integers. Conventional ingredients designed to modify the release properties of the mold may also be included. The vinyl-added silicone systems react by thermally induced addition-cure (hydrosilation) between the polydimethyl-hydrogen siloxane crosslinkers and reactive vinyl functional silicone polymers to provide a cured polymer. Vinyl-functional silicone polymers are polydimethyl siloxanes, where some of the methyl groups have been substituted with vinyl groups or groups containing vinyl unsaturation, that is, the reaction takes place between the vinyl-substituted polydimethyl siloxane and the polydimethylhydrogen siloxane. Complete hydrosilation is catalyzed by the silicone-soluble complex compounds of Group VIII transition metals, particularly platinum. In normal use of vinyl addition silicone systems, a small amount of inhibitor is added to prevent premature reaction between the silicone hydride and the vinyl silicone groups following the mixing of the coating components, before of the deposition on the substrate. The inhibitor is eliminated or rendered ineffective during the thermal curing process. Silicone emulsion systems suitable for the practice of this invention can be obtained from Dow Corning, Rhone-Poulenc and Wacker-Chemic GmbH, for example, the VP 1571E / 1572 system from acker. The emulsion copolymers of the present invention are formed at high solids contents during emulsion polymerization for the efficiency of the emulsion polymerization process. They are usually diluted to form a suspension having less solids content to use coating on a mold for the rubber article to be formed or on the rubber article formed.

As is known in the art the typical solids content is in the range of about 3 to about 10% by weight of the suspension. A coagulating salt is required to cause the rubber to deposit from its emulsion (latex) on a surface of the polymer. The coagulant can be applied after drying the copolymer on the surface of the mold, a considerable saving in time and cost can be obtained by combining a coagulant with the polymeric suspension. It has surprisingly been found that the copolymer suspensions of the present invention can tolerate the high amount of polyvalent metal salts that serve as coagulants if it employs the multi-component anionic surfactant system. Examples of coagulants that can be used are the water soluble salts of calcium, zinc, aluminum and the like. At present calcium nitrate is preferred. A coagulant salt, preferably calcium nitrate, is usually provided in a concentration of up to about 40% by weight of the suspension typically from about 20 to about 40% by weight of the suspension for coating the mold. By combining the coagulant with the emulsion polymers of the present invention, a significant step in the production of the copolymer-coated rubber articles is eliminated. If the copolymer is applied without the coagulant, then the coagulant is applied to the surface of the copolymer after the copolymer has been deposited and dried on the surface of the mold. This adds a step and is, therefore, a more expensive measure. Preferred molds herein are gently contoured molds having a textured surface, or soft ceramic, porcelain or fluorocarbon, which will accept the coating of the copolymer or the copolymer and the coagulant and release the rubber article formed at the completion of the process. The amount of immersion time in the rubber emulsion determines the thickness of the rubber coating formed. A typical thickness is from about 6 to about 10 mils. After the removal, the coagulated rubber articles may be allowed to stand or heat dry in an oven. The formed rubber article is then washed with water. The washed rubber coating is then cured. After curing, the rubber-coated copolymer is allowed to cool to about 60 to 80 ° C and is immersed in a second coagulant-free acrylic-based emulsion copolymer suspension to avoid waste of salt which would require another washing step. The immersion is from approximately 3 hats approximately 6 seconds. The coating is dried at about 100 to 125 ° C for about 2 to 3 minutes. The doubly coated article is then cooled to about 40 ° C and separated from the mold. Because the separation causes the glove to turn over, the second coating becomes the placement coating to contact the fabric or skin while the outer or outer coating that was the separation coating becomes the coating. tactile. While the focus of the discussion has been directed to coatings of copolymers for rubber articles and in particular to gloves, it has been found that the copolymers have other uses, and in particular, for coatings that are known as "rubber" products. soft touch "to be used in the automotive industry. One example is to provide polymeric laminates that have a leather appearance with a touch of fit. The copolymers of the present invention have been successfully evaluated for use in laminates that are formed under vacuum. The construction of the product would consist of a polymer film that acts as a carrier that is removed prior to vacuum formation. The copolymers of the present invention are deposited on the carrier at about 0.25 to about 2 mils in thickness as a pigmented or clear top coat and as the surface is felt by the user. The balance consists of the material deposited to give the appearance of leather, wood grains or the like, as the copolymer layer of the present invention is added or secured the "soft touch". A layer of heat activated adhesive is then added followed by pressure and heat bonding to a 20 mil sheet of polymeric material compatible with the injection molding plastic. The polyester carrier is then removed and the laminate is vacuum formed and inserted by mold to give a contoured plastic part with a desirable and unique soft touch. The copolymers of the present invention could also be used as a spray coating or could be deposited on a backing having a pressure sensitive adhesive on the opposite side. The copolymers provide unusual "soft touch" performance and protection properties. In any application, it is believed that the polymer has unusual exterior performance properties because it contains silicone and acrylic monomers.

EXAMPLE 1 -COPOLIMEROS IN EMULSION FOR SEPARATION OF THE MOLD It was formed in one part by weight based on the first soap solution of 98.2 parts by weight of deionized water, 0.87 parts of tetrasodium pyrophosphate, 10.9 parts by weight of Aerosol ™ NPES 458, a 58% solution of salt of ammonium from nonilpoli Sulphated (ethyleneoxy) ethanol manufactured by Cyanamid, 4. 9 parts of Aerosol ™ Ot 75, a 75% solution of sodium dioctyl sulfonate and 3 parts of Disponil FE S77, a 32.5% solution of sodium lauryl ether sulphate manufactured by Henkel and a second soap solution containing 82.2 parts of deionized water, 0.73 parts of tetrasodium pyrophosphate, 9.1 parts of NPES 450, 4.1 parts of OT 75 and 17.8 parts of surfactants FES 77. Two separate monomer systems were formed. The first monomer system contained 39.6 parts of styrene, 318 parts of butyl acrylate, 50 parts of methyl acrylate, 3.8 parts of methacrylic acid, 3.8 parts of acrylic acid, 71.3 parts of RC 726, a silicone acrylate manufactured and sold by Goldschmidt, 30 parts of silicone GE SL 6000-D1 and 23.5 parts of silicone GE SL-6010-D1. The second monomer system contained 210 parts of styrene, and 102.9 parts of butyl acrylate, 43.9 parts of methyl acrylate, 3 parts of methacrylic acid, 2.7 parts of acrylic acid, and 56 parts of silicone GE SL 6000-D1. A catalyst solution containing 78 parts of deionized water and 2 parts of potassium persulfate was formed separately, and an activating solution containing 78.5 parts by weight of deionized water and 1.5 parts of sodium metabisulfite. An initial reactor charge was formed containing 320 parts of deionized water, 0.08 parts of NPES 458, 4.5 parts of sodium bicarbonate and 3.85 parts of potassium persulfate and 0.15 parts of sodium meta-bisulfate. The mixture of the first monomers and the first soap solution was added slowly to the initial reactor charge, with stirring followed by the incremental addition of the activating solution and then the incremental addition of the catalyst. The temperature of the reactor was maintained between 65 and 73 ° C. Following the completion of the reaction, the second soap solution containing the second loading of monomers was incrementally added. After completion of the reaction, it was treated with aqueous solutions of ammonia and biocide. The emulsion had a pH of 8.7 and the solids content of 57%.

EXAMPLE 2 - COPOLYMER IN EMULSION FOR DRY PLACEMENT Substantially the procedure of Example 1 was repeated except that the monomers for the first charge were in proportion of 95 parts of styrene, 220.7 parts of butyl acrylate, 38.8 parts of methyl acrylate, 9.8 parts of acrylic acid, 15 parts of GE SL 6000-D1, 9 parts of trimethylpropane-triacrylate and 3.3 parts of n-isobutoxymethylacrylamide. For the second charge of monomers, a monomer mixture of 302.3 parts of styrene, 146.2 parts of butyl acrylate, 57.9 parts of methyl acrylate, 17.5 parts of acrylic acid, 40.4 parts of Ge SL 6000-D1, 20 parts was used. of trimethylpropane triacrylate and 4.48 parts of N-isobutoxymethyl acrylamide, the incremental catalyst solution contained 70.5 parts of deionized water, and 2.5 parts of potassium persulfate. The first soap solution contained 6.91 parts of NPES 458, 3.3 parts of OT 75 and 14.7 parts of FES 77 and the first monomers were added to the initial charge of the reactor followed by the incremental addition of the catalyst solution and after completion of the reaction, the second polymer system was added incrementally in a soapy solution containing 4.9 parts of OT-75, 10.29 parts of NPES 458 and 21.89 parts of FES 77. The temperature was maintained at 78 to 85 ° C and after treatment with the solution of biocide and ammonia, the emulsion had a pH of 6.6 and a total solids content of 57.6%.ahs.

EXAMPLE 3 - MANUFACTURE OF GLOVES The copolymer of Example 1 and calcium nitrate as a coagulant were coated on a mold for a scanning glove. The coated mold was immersed in a latex solution and allowed to remain in the solution until a coating of 6 to thousandths of an inch formed on the coating. The coating was then immersed in a solids suspension of the copolymer of Example 2. After the coating of the copolymer of Example 2 was dried, the glove was removed from the mold. The formed glove was left free of fish eyes and had an exterior sheen of post-cure coating of the copolymer of Example 1 and a matte side of the copolymer coating of example 2. The copolymers of examples 1 and 2 were strongly bound to Latex and the glove formed had excellent dry and wet setting properties to be used as an exploration glove. Flaking did not occur when the glove was stretched. Figure 3 shows the DSC profile for the copolymer with main peaks of glass transition temperature at -21.04 ° C, 11.74 ° C +12.45 and + 28.55 ° C. The surface morphology revealed a slightly irregular continuous surface with microcraters and submicron projections, the diameters of the microcraters varied from 0.1 to 1 miera. Figure 4 shows the DSC graphs for this polymer and the various glass transition peaks, the largest of which was -12.51 ° C, 13.57 ° C and 29.76 ° C. The morphology studies revealed a slightly irregular surface with projections of submicras, shallow submicron craters and projections and microcraters of agglomerated particles.

EXAMPLE 4 - COPOLYMER IN EMULSION FOR DRY PLACEMENT A surfactant or surfactant solution comprising, in parts by weight basis, 122.70 parts of deionized water, 1.60 parts of tetrasodium pyrophosphate (0.96 parts dry), 31.27 parts of surfactant was formed. (21.56 dry parts). A monomer mixture containing one part per base by weight was formed separately is 100 parts of styrene, 405.12 parts of butyl acrylate, 37.42 parts of methyl acrylate, 6.5 parts of methacrylic acid, 12.30 parts of acrylic acid, 6.25 parts of RC 705, a silicone acrylate sold by Goldschmidt and 0.08 parts of dodecyl mercaptan. The monomer mixture was added to the surfactant solution in a weight ratio of 4 parts of monomer to 1 part of surfactant or surfactant solution. An incremental catalyst solution of 63 parts by weight of deionized water and 2 parts by weight of potassium persulfate was separately formed as well as a minor amount of surfactant or surfactant. In a stirred, nitrogen-laced reactor, following the charge of 200 parts by weight of deionized water, 3.08 parts by weight of surfactant and 1.5 parts of potassium persulfate, the solution of monomers and surfactants was added incrementally with the catalyst solution. a speed that allowed a reaction to take place with a slight exotherm. The temperature was maintained at 80 + _2 ° C. An emulsion containing a total solids content of about 54.3% was formed. The emulsion was then adjusted to a pH of about 6.5 with a neutralizing biocide / ammonia solution.

EXAMPLE 5 - COPOLYMER IN EMULSION FOR DRY PLACEMENT Example 4 was substantially repeated except that the monomer mixture contained in one part by weight was based on 219.2 parts of methyl methacrylate, 219.2 parts of butyl acrylate, 51.33 parts of methacrylic acid , 13 parts of n-isobutylmethacrylate, 16.66 parts of silicone acrylate (RC 705), and 0.13 parts of n-dodecyl mercaptan and the surfactant or surfactant solution was formed from 27.73 parts of NPES 930 aerosol, 2.7 parts of OT-75 and 24.9 parts of FES-77 and contained 0.66 parts of sodium metabisulfite and 18.81 parts of surfactant in 113.3 parts of deionized water.

EXAMPLE 6 - MANUFACTURE OF GLOVES The emulsion copolymer of Example 5 was evaluated as a 4.8% solids suspension containing 4.5% soap. It was used to coat a washed exploration glove. The deposited coating gave very good dry placement and separation characteristics. No flaking was presented.

EXAMPLE 7 - COPOLYMER OF DRY PLACEMENT AND MANUFACTURE OF THE GLOVES Following the procedure of Example 4, a copolymer was formed containing 46.4% by weight of styrene, 38% by weight of butyl alkylate, 1.3% by weight of methacrylic acid, 3.3% by weight of acrylic acid, 8.5% by weight of silicone acrylate, and 1.9% of isobutoxymethyl acrylamide. The copolymer formed was combined with, by weight of the copolymer; of 0.6% vegetable oil and provided a good copolymer for the placement for the manufacture of the gloves.

EXAMPLE 8 - COPOLYMERS OF DRY PLACEMENT AND MANUFACTURE OF THE GLOVES A mixture of copolymers was formed in a weight ratio of 1: 3 of the copolymer of Example 5 and a copolymer obtained by emulsion polymerization of 48.2% by weight of styrene, 33.1% by weight of butyl acrylate, 6.1 % by weight of acrylate * of methyl, 1.1% by weight of methacrylic acid, 2.1% by weight of acrylic acid, 6.3% by weight of s -licone acrylate, 0.9% by weight of n-isobutoxymethyl acrylamide and 2.3% by weight of trimethylpropane triacrylate. The polymer mixture was deposited in a mold. Calcium nitrate was the coagulant. The procedure of Example 3 was used to form a coating of the latex on the copolymer.

EXAMPLE 9 - COPOLYMER OF DRY PLACEMENT AND MANUFACTURE OF GLOVES An emulsion copolymer was formed of a monomer mixture containing 43% by weight of styrene, 36.5% by weight of butyl acrylate, 8.6% by weight of methyl acrylate. , 1% by weight of methacrylic acid, 1.9% by weight of acrylic acid, 5.2% by weight of silicone acrylate, 0.8% by weight of n-isobutoxymethyl acrylamide and 3% by weight of trimethylpropane triacrylate. A suspension of the copolymer which was coated on molds of large and medium gloves, on which a rubber or rubber layer was formed using the procedure of Example 3.

EXAMPLE 10 - FRICTION MEASUREMENTS In order to determine the surface friction of the copolymer coating, samples of 2.54 cm (1 in.) Of width were prepared, on which a sled of 200 was stretched at a crosshead speed of 15 inches per minute. g that contained three glass balls that had a diameter of 5/8"placed in the corners of an equilateral triangle.A strength of approximately 0.112 pounds of resistance was required to pull the sled onto a powdered surface.The force was 0.07 pounds For a chlorinated surface and a surface with biogel In contrast, the treated surfaces gave a resistance of approximately 0.33 and 0.34 pounds with a tendency to rise from the surface on which they were applied with a considerable tendency towards pulling movement. of Example 7 required a force of approximately 0.22 lb. The polymer blend of Example 8 required a strength of 0.23 pounds, and the composition of Example 9, when deposited from a suspension with 6% solids, required a force of approximately 0.22 pounds. Resistance increased to approximately 0.225 pounds at a solids concentration of 8%. The measurements were made under conditions of humidity at 50% and a temperature of 23 ° C.

EXAMPLE 11 - COPOLYMER IN EMULSION FOR PROTECTIVE COATING Substantially the procedure of Example 1 was repeated except that the monomers for the first charge were in proportion of 150 parts of styrene, 237 parts of butyl acrylate, 22 parts of acrylic acid, 31 parts of RC 726, 9 parts of methacrylic acid-triacrylate and 8.7 parts of N-isobutoxymethylacrylamide. For the second charge of monomers, a monomer mixture of 348 parts of styrene, 136.6 parts of butyl acrylate, 9 parts of methacrylic acid, 248 parts of acrylic acid, 30.8 parts of RC 726, 8.7 parts of N-isobutoxymethyl acrylamide, the incremental catalyst solution was used. it contained 70.5 parts of deionized water, and 2.5 parts of potassium persulfate. The emulsion of the copolymers with a total solids content of 53.3 was formed by sequential emulsion polymerization. The copolymers formed provided aggressive protective coatings for rubber surfaces.

EXAMPLE 12 - PLACEMENT COATING The aqueous solution of the emulsion copolymer of Example 1 was combined with calcium carbonate present in an amount of about 3.3% by weight of the emulsion as formed to which water and a smaller amount of dicaprylate were added. of propylene glycol. The mixture formed an excellent composition to provide a wet and dry placement surface in a glove.

EXAMPLE 13. Example 12 was repeated except that the calcium carbonate was replaced by the starch. Again the coating had excellent dry and wet setting properties.

Claims (47)

1. A composition that provides a polymeric coating on the surface of articles, characterized in that it comprises an aqueous suspension of an emulsion copolymer based on non-tacky acrylic, this copolymer is comprised of the reaction product of about 0.7 to about 20% by weight of at least one low surface energy monomer, copolymerizable, from about 30 to about 85% by weight of at least one alkyl acrylate containing from 1 to about 10 carbon atoms in the alkyl group, the balance of the monomers it comprises hard monomers, said hard monomers, when they are homopolymerized they have a vitreous transition temperature greater than about 25 ° C, and they are present in an amount sufficient to form the emulsion copolymer based on non-tacky acrylic.

2. A composition according to claim 1, characterized in that the copolymerizable low surface energy monomer is a copolymerizable silicone oligomer.

3. A composition according to claim 1 or 2, characterized in that the copolymerizable low surface energy monomer is present in an amount of about 1 to about 15% by weight of the acrylic based copolymer.

4. A composition according to claim 1, 2 or 3, characterized in that the alkyl acrylate is selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof.

5. A composition according to any of claims 1 to 4, characterized in that the hard monomer comprises monomers selected from the group consisting of styrenic monomers, alkyl methacrylates, unsaturated carboxylic acids containing from 3 to about 5 carbon atoms, amides and mixtures thereof.

6. A composition according to any of claims 1 to 5, characterized in that it comprises an aqueous suspension of a non-tacky, acrylic-based emulsion copolymer, ranging from about 0.7 to about 20% by weight of at least one oligomer of copolymerizable silicone, of about 40 to about 80% by weight of an alkyl acrylate selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof, the balance or counterweight of the monomers is selected from the group consisting of styrene, methacrylic acid, acrylic acid, methyl methacrylate, isobutoxymethacrylamide, isobutylmethacrylate, and mixtures thereof.

7. A composition according to any of claims 1 to 6, characterized in that the suspension contains at least two anionic surfactants.

8. A composition according to claim 7, characterized in that the anionic surfactants are selected from the group consisting of dioctyl sodium sulfosuccinate, the ammonium salt of sulfonated nonylphenoxypoly (ethyleneoxy) ethanol and a fatty alcohol polyglycol ester sulfate.

9. A composition according to any of the previous claims, characterized in that it comprises a mixture of emulsion copolymers comprised of a first emulsion copolymer based on acrylic and a second emulsion copolymer based on acrylic, the first and second copolymers formed by the Emulsion polymerization of monomers comprise from about 0.7 to about 20% by weight of at least one copolymerizable, low surface energy monomer, from about 30 to about 85% by weight of at least one alkyl acrylate containing 1 to about 10 carbon atoms in the alkyl group, the balance or counterweight of the monomers comprises hard monomers, which when homopolymerized, have a vitreous transition temperature greater than 25 ° C and are provided in an amount sufficient to form a mixture of first and second acrylic-based emulsion copolymers, which do not are sticky, the first acrylic based emulsion copolymer has a glass transition temperature of about -50 ° C to about 25 ° C, the second acrylic based emulsion copolymer has a glass transition temperature of about 25 ° C a approximately 100 ° C.

10. A composition according to claim 9, characterized in that the low surface energy monomer is a copolymerizable silicone oligomer.

11. A composition according to claim 10 or 11, characterized in that the weight ratio of the first acrylic-based emulsion copolymer to the second acrylic-based emulsion copolymer is in the range of about 1: 1 to about 1: 3.

12. A composition according to claim 10 or 11, characterized in that the ratio or proportion by weight of the first emulsion copolymer based on thermal acrylic to the second copolymer is about 1 to 1.5.

13. A polymer composition according to any of claims 9 to 12, characterized in that the ratio or weight ratio of the first acrylic based emulsion copolymer to the second acrylic based emulsion copolymer is in the range of about 3: 1. a roughly 1: 1.

14. A composition according to any of claims 9 to 13, characterized in that the ratio or weight ratio of the first acrylic based emulsion copolymer to the second acrylic based emulsion copolymer is about 1.2 to 1.

15. A composition according to any of the previous claims, characterized in that it comprises a first emulsion copolymer based on acrylic from which the reaction product of a first monomer system comprises styrene, butyl acrylate, methyl acrylate, methacrylic acid, acid Acrylic and at least one copolymerizable silicone oligomer, the first emulsion copolymer has glass transition temperatures less than about 0 ° C and a second acrylic based emulsion copolymer which is the reaction product of a second monomer system sequentially polymerized in the presence of the first emulsion copolymer, the second monomeric system includes styrene, butyl acrylate, methylacrylate, methacrylic acid, acrylic acid and at least one copolymerizable silicone oligomer, the second copolymer has a glass transition temperature of about 0 ° C to approximately at 100 ° C, the sequentially polymerized mixture of the first and second acrylic-based emulsion copolymers is non-tacky and is formed in the presence of at least two anionic surfactants.

16. An article having a coating deposited on a surface thereof, from an aqueous suspension of at least one emulsion copolymer, the emulsion copolymer comprises from about 0.7 to about 20% by weight of at least one energy monomer low surface, copolymerizable, from about 30 to about 85% by weight of at least one alkyl acrylate containing from about 10 carbon atoms in the alkyl group, the balance or counterbalance of the monomers comprises hard monomers, the monomers When they are homopolymerized, they have a glass transition temperature greater than about 25 ° C and are present in an amount sufficient to provide an emulsion copolymer based on sticky or viscous acrylic.

17. An article having a coating deposited on a surface thereof, of an aqueous suspension comprising an emulsion copolymer, non-tacky or viscous, dust-free, elastic, comprising from about 0.7 to about 20% by weight of at least one low surface energy, copolymerizable monomer, which is a silicone oligomer from about 30 to about 85% by weight of at least one alkyl acrylate containing from 1 to about 10 carbon atoms in the alkyl group , the balance or counterweight of the monomers comprises hard monomers, such hard monomers, when they are homopolymerized they have a glass transition temperature of greater than about 25 ° C and is present in an amount sufficient to provide the emulsion copolymer based on acrylic Sticky or not viscous, the item is rubber or rubber.

18. An article formed by rubber or rubber coagulation from a latex in a mold and having on at least one surface thereof - an elastic, adherent, non-tacky, powder-free polymeric coating, comprised of a base emulsion copolymer acrylic formed by emulsion polymerization of a monomer system comprised of from about 0.7 to about 20% by total weight of at least one low surface energy monomer, copolymerizable, which is a silicone oligomer, and from about 30 to in about 85% by weight form of at least one alkyl acrylate selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate and mixtures thereof, the equilibrium or counterweight of the monomers includes hard monomers which, when they are homopolymerized, they have a glass transition temperature greater than 0 ° C and are provided in an amount sufficient to form the emulsion copolymer Non-sticky emulsion, the emulsion copolymer is deposited from an aqueous suspension of the emulsion copolymer.

19. An article according to any of claims 16 to 18, characterized in that the low surface energy monomer, copolymerizable, is present in an amount of about 1 to 15% by weight of the acrylic-based copolymer.

20. An article according to any of claims 16 to 19, characterized in that the alkyl acrylate is selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof.

21. An article according to any of claims 16 to 20, characterized in that the hard monomer comprises monomers selected from the group consisting of styrenic monomers, alkyl methacrylates, unsaturated carboxylic acids containing from 3 to 5 carbon atoms, amides and mixtures thereof.

22. An article according to any of claims 16 to 21, characterized in that it is in the form of a glove and is formed by coagulating rubber or rubber from a latex.

23. An article according to any of claims 16 to 22, characterized in that the copolymer contains a composite particulate solid, selected from the group consisting of calcium carbonate and starch and deposited in a formed article or a mold in which the article is formed.

24. An article according to claim 22 or 3, characterized in that the finished article is a rubber glove having an internal and external surface, the internal surfaces having therein a placement coating of the first emulsion copolymer based on acrylic and the external surface has a mold release liner on the second acrylic based emulsion copolymer.

25. An article according to claim 24, characterized in that the first and second coatings are the same.

26. An article according to claim 24, characterized in that the first and second coating are different.

27. An article according to any of claims 16 to 26, characterized in that a polymeric coating comprises an adherent acrylic-based copolymer formed of monomers ranging from about 0.7 to about 20% by weight of a copolymerizable silicone oligomer, of about 40 a in an approximate 80 wt% form of at least one alkyl acrylate selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof, and at least one monomer selected from the group consisting of styrene , methacrylic acid, acrylic acid, methyl methacrylate, isobutoxymethacrylamide, isobutylmethacrylate and mixtures thereof, the emulsion copolymer is deposited from an aqueous suspension of the emulsion copolymer.

28. An article according to any of claims 16 to 27, characterized in that the coating comprises a first emulsion copolymer based on acrylic and a second emulsion copolymer based on acrylic, the first and second copolymers formed by emulsion polymerization of monomers ranging from approximately 0.7 to approximately 20% by weight of at least one copolymerizable silicone oligomer, from about 30 to about 85% by weight of at least one alkyl acrylate containing from 1 to about 10 carbon atoms in the alkyl group, the balance or counterweight of the monomers comprises hard monomers, which when homopolymerized, have a glass transition temperature greater than 0 ° C and are supplied in a sufficient amount to form a mixture of an acrylic-based emulsion copolymer which is non-tacky, the first copolymer in acrylic-based emulsion has a glass transition temperature peak greater than about -50 ° At about 25 ° C, the second acrylic-based emulsion copolymer has a peak glass transition temperature greater from about 25 ° C to about 100 ° C.

29. An article according to claim 28, characterized in that the weight ratio of the first acrylic-based emulsion copolymer to the second acrylic-based emulsion copolymer is in the range of about 1: 1 to about 1: 3.

30. An article according to claim 28 or 29, characterized in that the ratio or weight ratio of the first acrylic-based emulsion copolymer to the second acrylic-based copolymer is in the range of about 3: 1 to about 1: 1.

31. An article according to any of claims 28 to 30, characterized in that the mixture comprises a first emulsion copolymer based on non-tacky acrylic, which includes the reaction product of a first monomer system comprising styrene, butyl acrylate , methyl acrylate, methacrylic acid, acrylic acid and at least one copolymerizable silicone oligomer, and a second acrylic based emulsion copolymer which is the reaction product of a second sequentially polymerized monomer system in the presence of the first copolymer in emulsion, the second monomeric system comprises styrene, butyl acrylate, methacrylate, methacrylic acid, acrylic acid and at least one copolymerizable silicone oligomer, the sequentially polymerized mixture of the first and second acrylic-based emulsion copolymers is non-tacky and is formed in the presence of at least two anionic surfactants you.

32. A process for the production of rubber or rubber glove articles by the rubber or rubber coagulation from the latex, the process is characterized in that it comprises: a) forming in a mold for the rubber glove article to be formed, a coating of a first acrylic-based emulsion copolymer capable of being freed from the mold and containing a copolymerized amount of at least one low-energy, copolymerizable surface-active monomer deposited from a suspension and a coagulant salt present in a sufficient concentration for being able to cause the coagulation of the rubber from the latex in the first acrylic-based copolymer; b) immersing the first mold having the coating of the acrylic-based emulsion copolymer and the coagulating salt in a latex containing the rubber for a sufficient time to cause the coagulation of the rubber from the latex on the surface of the coating, for forming a glove having a first surface coated with the acrylic based copolymer; c) immersing the glove article coated with the first acrylic-based copolymer in a second suspension of a laying acrylic base emulsion copolymer containing a copolymerized amount of at least one copolymerizable low surface energy monomer to coat the opposite surface to the first coated surface to provide a second surface coated with acrylic-based copolymer in the rubber glove article; and d) removing a double-sided coated rubber glove from the mold.

33. A process according to claim 32, characterized in that the mold is sufficiently textured to provide a dull coating.

34. A process according to claim 32 or 33, characterized in that an insoluble, inert particulate powder selected from the group consisting of calcium carbonate and corn starch is deposited with the emulsion copolymer based on acrylic placement.

35. A process according to any of claims 32 to 34, characterized in that each emulsion copolymer based on non-tacky acrylic is independently comprised of the reaction product of about 0.7 to about 20% by weight of at least one energy monomer low copolymerizable surface, from about 30 to about 85% by weight of at least one alkyl acrylate containing from 1 to about 10 carbon atoms in the alkyl group, the balance or counterweight of the monomers comprises hard monomers, the monomers When they are homopolymerized, they have a glass transition temperature of greater than about 25 ° C, and are present in an amount sufficient to form a non-tacky, acrylic-based emulsion copolymer.

36. A process according to any of claims 32 to 35, characterized in that the copolymerizable low surface energy monomer is a copolymerizable silicone oligomer.

37. A process according to any of claims 32 to 36, characterized in that the copolymerizable low surface energy monomer is present in an amount of about 1 to about 15% by weight of the acrylic based copolymer.

38. A process according to claims 35, 36 or 37, characterized in that the alkyl acrylate is selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof.

39. A composition according to any of claims 35 to 38, characterized in that the hard monomer comprises monomers selected from the group consisting of styrenic monomers, alkyl methacrylates, unsaturated carboxylic acids containing from 3 to about 5 carbon atoms and mixtures thereof.

40. A process according to any of claims 32 to 39, characterized in that the emulsion copolymer based on acrylic is comprised of about 0.7 to about 20% by weight of at least one copolymerizable silicone oligomer, about 40 a approximately 80% by weight form of an alkyl acrylate selected from the group consisting of methyl acrylate, butyl acrylate, and mixtures thereof, the balance or counterweight of the monomers selected from the group consisting of styrene, methacrylic acid, acrylic acid, methyl methacrylate, isobutoxymethacrylamide, isobutylmethacrylate, and mixtures thereof.

41. A process according to any of claims 32 to 40, characterized in that the suspension contains at least two anionic surfactants selected from the group consisting of dioctyl sodium sulfosuccinate, the ammonium salt of sulphonated nonylphenoxypoly (ethyleneoxy) ethanol and a fatty alcohol polyglycol ether sulfate.

42. A process according to any of claims 32 to 41, characterized in that each of the acrylic-based emulsion copolymers is independently comprised of a mixture of a first emulsion copolymer based on acrylic and a second based emulsion copolymer of acrylic, the first and second copolymers formed by emulsion polymerization of monomers comprise from about 0.7 to about 20% by weight of at least one copolymerizable low surface energy monomer, from about 30 to about 85% by weight of at least one alkyl acrylate containing from 1 to about 10 carbon atoms in the alkyl group, the balance or counterweight of the monomers comprises hard monomers, which when homopolymerized, have a glass transition temperature greater than 25 ° C and are provided in an amount sufficient to form a mixture of the first and second copolymers In acrylic-based emulsion which is not sticky, the first acrylic-based emulsion copolymer has a glass transition temperature of about -50 ° C to about 25 ° C, the second emulsion copolymer based on Acrylic has a glass transition temperature of approximately 25 ° C to approximately 100 ° C.

43. A process according to claim 42, characterized in that the ratio or weight ratio of the first acrylic-based emulsion copolymer to the second acrylic-based emulsion copolymer is in the range of about 1: 1 to about 1: 3.

44. A process according to claim 42 or 43, characterized in that the weight ratio of the first emulsion copolymer based on thermal acrylic to the second copolymer is approximately 1 to 1.5.

45. A process according to any of claims 42 to 44, characterized in that the ratio or weight ratio of the first acrylic-based emulsion copolymer to the second acrylic-based copolymer is in a range of about 3: 1 to roughly 1: 1

46. A process according to any of claims 42 to 45, characterized in that the ratio or weight ratio of the first acrylic-based emulsion copolymer to the second acrylic-based emulsion copolymer is about 1.2 to 1.

47. A process according to any of claims 42 to 46, characterized in that the first emulsion copolymer based on acrylic is comprised of the reaction product of a first monomer system comprising styrene, butyl acrylate, methyl acrylate, methacrylic acid , acrylic acid and at least one copolymerizable silicone oligomer, the first emulsion copolymer has glass transition temperatures less than about 0 ° C and the second acrylic based emulsion copolymer which is the reaction product of a second monomeric system sequentially polymerized in the presence of the first emulsion copolymer, the second monomer or monomer system comprises styrene, butyl acrylate, methylacrylate, methacrylic acid, acrylic acid and at least one copolymerizable silicone oligomer, the second copolymer has a glass transition temperature from about 0 ° C to ap At 100 ° C, the sequentially polymerized mixture of the first and second acrylic-based emulsion copolymers is non-tacky and is formed in the presence of at least two anionic surfactants.