MXPA00003030A - Blended pressure-sensitive adhesives - Google Patents

Abstract

A pressure-sensitive adhesive comprising a blend of at least two components, wherein the first component is at least one pressure-sensitive adhesive and the second component is at least one thermoplastic material, wherein the components form a blended composition having more than one domain and, wherein one domain is substantially continuous (generally, the pressure-sensitive adhesive) and the other domain is substantially fibrillous to schistose (generally, the thermoplastic material). The second component can be (a) at least one thermoplastic elastomer, (b) at least one elastomer with a tackifying resin or (c) at least one elastomer.

Description

Pressure Sensitive Mixed Adhesives TECHNICAL FIELD This invention relates to pressure sensitive adhesive compositions, and, more particularly, to pressure sensitive adhesive compositions formed of at least two polymeric materials wherein at least one of which is an adhesive sensitive to the pressure, and the methods of making pressure-sensitive adhesives and for articles with adhesive coating.

Background of the Invention There is a constant need to modify pressure sensitive adhesives to meet the needs of new applications. In general, when additives are incorporated in pressure sensitive adhesives to modify their properties, care must be taken to avoid a loss of surface adhesion or cut resistance. This has prevented the wide use of thermoplastic materials as well as modifiers. The best kinds of pressure sensitive adhesives include sticky natural rubbers; rubbers REF .: 33099 synthetic as butyl rubber; and styrene-blocked, branched and radial, starting, linearly sticky copolymers, such as styrene-butadiene, styrene-ethylene / butylene and styrene-isoprene; polyurethanes; polyvinyl ethers; acrylics, and especially those that have long chain alkyl groups; poly-α-olefins; and silicones. Generally, when additives are used to alter the properties of pressure sensitive adhesives, the additives need to be immiscible with the pressure sensitive adhesive or to form homogeneous mixtures at the molecular level. Some types of pressure sensitive adhesives _ have been modified with sticky thermoplastic elastomers, thermoplastics, and elastomers. For example, thermoplastic materials have been added to hot melt polymerized acrylic pressure sensitive adhesives where the thermoplastic is a packaging material or reinforced tapes that are recycled. In these cases, the type and amount of the thermoplastic material is controlled so that the thermoplastic material can function as a packaging material while avoiding degradation of the adhesive properties of the pressure sensitive adhesive. However, most of the time when a Non-sticky thermoplastic additive is mixed with a pressure sensitive adhesive, the reduction of the overall adhesive properties of the mixture (as compared to the pressure sensitive adhesive) is observed. Thermoplastic polymers have been added to the adhesive styrene block copolymers to reduce the tackiness of the resulting pressure sensitive adhesives for the application of protection sheets for the surfaces of a large area. Pressure sensitive adhesives, modified or not, have been used for more than half a century for a variety of purposes. Pressure sensitive adhesives are generally used in tapes wherein a tape comprises a reinforcement, or substrate, and a pressure sensitive adhesive. Normally, a pressure-sensitive adhesive sticks with only applying pressure with the finger and can stick permanently. In the field of medicine, pressure-sensitive adhesive tapes are used - for different applications in the areas of health and hospitalization. For most applications, the tapes are applied directly to a patient's skin. It is important that the pressure-sensitive adhesive tape be condescending and non-irritating to the skin, as well as adhere to the skin without causing damage to the skin when the tape or adhesive-coated article is removed. A particularly useful medical application for pressure sensitive adhesive articles or tapes is in the field of transdermal patches. The patches are patched to be used as medicament transport membranes or to attach the drug transport membranes to the skin. Although pressure sensitive adhesive items or tapes are used in the medical field, pressure sensitive adhesive articles or tapes are widely used in other areas. For example, transfer tapes can be used to adhere two surfaces together like flexible sheets of packaging material or cloth to a surface, however, transfer tapes generally have a small tensile strength and a solution has added fibers It is also used in the field of labels, which require a wide variety of pressure-sensitive adhesives due to the wide variety of surfaces, however, pressure-sensitive adhesives must they are capable of being easily cut without being joined or detached to allow efficient processing processes Another use for pressure sensitive adhesives is as a means to adhere preformed signaling materials for pavements used as traffic control signals In such applications an adhesive Pressure sensitive is used to adhere on pavements l preformed signage materials of flexible base sheets, resistant to wear in a place for delimited pedestrian steps, containment bars, and lane markers. Pressure sensitive adhesives must resist shear forces associated with tire transit, while maintaining adhesion to the road over a wide range of temperatures. Pressure sensitive adhesives require a delicate balance of viscous and elastic properties resulting in a four-part balance of adhesion, cohesion, stretch and elasticity. Pressure sensitive adhesives generally comprise elastomers that are already inherently tacky, or "thermoplastic" elastomers or elastomers that are sticky with the addition of tackifying resins.

Brief Description of the Invention In one aspect, the present invention provides a pressure sensitive adhesive comprising a mixture of at least two components, wherein the first component is at least one pressure sensitive adhesive and the second component is at least one thermoplastic material, wherein the components form a mixed composition having more than one domain and, wherein one domain is substantially continuous (generally, the pressure sensitive adhesive) and the other domain is substantially fibrilous to schistose (generally , the thermoplastic material). Alternatively, the second component can be (a) at least one thermoplastic elastomer, as described in Series No. 08 / 578,010, filed on December 22, 1995 with a common beneficiary, (b) at least one elastomer with a sticky resin as described in Series No. 08 / 577,603, filed December 22, 1995 with a common beneficiary, or (c) at least one elastomer.

Advantageously, the pressure sensitive blended adhesives of the present invention provide adhesives having one or more of the following properties. These properties are improvements through a previous pressure sensitive adhesive to mix it with a thermoplastic material. These properties include: (1) greater surface adhesion than if it were to be used alone and a shear force similar to that of the pressure sensitive adhesive component, (2) a greater shear force than if it were to be used alone and a surface adhesion similar to the of the pressure-sensitive adhesive component, (3) an anisotropic skin adhesion, (4) an isotropic shearing force, and (5) a tension force in the direction of the low tissue that is at least 2 times greater. that the tensile force in the direction of the transverse tissue for all elongations to the elongation at break. (6) an impact cut resistance that is at least 2 times greater than if it will be used alone to that of the pressure sensitive adhesive component The pressure sensitive adhesive component must be hot melt processable and meet the Dahlquist criteria as described in Manual H of Pressure-sensitive Adhesive Technology, edited by D. Satas, page 172, (1989) at temperatures of use. Typically, the pressure sensitive adhesive component comprises 30-98 weight percent of the composition, preferably 40-95 weight percent, and more preferably 60-95 weight percent. In addition, the pressure sensitive adhesive component may be a single pressure sensitive adhesive or the pressure sensitive adhesive may be a mixture of several pressure sensitive adhesives. The thermoplastic material component is usually a high polymer that can soften when exposed to heat and can return to its solid state when cooled to room temperature. Useful thermoplastic materials are fiber forms and are essentially immiscible in the pressure sensitive adhesive component at use temperature, although the thermoplastic may be miscible in the pressure sensitive adhesive at processing temperatures. Typically, the thermoplastic material component comprises 2-70 weight percent, preferably 5-60 weight percent "and more preferably 5-40 weight percent." Furthermore, the thermoplastic component may be a single component. The thermoplastic material or the thermoplastic material may be a mixture of various thermoplastic materials, In another aspect, a melting process for pressure sensitive blended adhesives is described, both components are melt-blended in a beaker and formed into a composition. of mixed pressure sensitive adhesive The forming step is either (1) the extrusion of the molten mixed components under conditions of extension flow and / or shear stress or (2) the extrusion and extraction of the molten mixture. the formed composition is cooled The articles and tapes coated with the pressure sensitive adhesive are also provided.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of the pressure-stress of the pressure-sensitive adhesive layer of Example 31 in both directions of the low tissue and the transverse tissue.

Figure 2 is a light scattering model for the pressure sensitive adhesive layer of Example 39 which uses the laser light scattering test. Figure 3 is a cross-sectional view of the direction of the tissue below the pressure-sensitive adhesive layer of Example 44 to 4000X using electron microscopy examination (SEM). Figure 4 is a cross-sectional view of the direction of the transverse tissue of the pressure-sensitive adhesive layer of Example 44 to 4000X using the SEM. Figure 5 is the light scattering pattern for the pressure sensitive adhesive layer of Example 44 which uses the light scattering test. Figure 6 is a cross-sectional view of the direction of the tissue under the pressure-sensitive adhesive layer of Comparative Example C8, at 4000X using the SEM. Figure 7 is the light scattering model for the pressure sensitive adhesive layer of Comparative Example C9, using the laser light scattering test. Figure 8 is a cross-sectional view of the direction of the tissue below the pressure-sensitive adhesive layer of Example 46 to 4000X using the SEM. Figure 9 is a cross-sectional view of the direction of the cross-sectional tissue of the pressure-sensitive adhesive layer of Example 46 to 4000X using the SEM. Figure 10 is the light scattering model for the pressure sensitive adhesive layer of Example 46 using the laser light scattering test. Figure 11 is a cross-sectional view of a transdermal matrix device of the present invention. Figure 12 is a cross-sectional view of a transdermal reservoir device of the present invention. Figure 13 is a cross-sectional view of an adhesive device of the transdermal medicament of the present invention. Figure 14 is a cross-sectional view of a transdermal multilamellar device of the present invention. Figure 15 is a cross-sectional view of an alternative embodiment of a transdermal multilamellar device of the present invention. Figure 16 is a graphical representation of the compression of the remaining shear force resulting from Examples 61-64 and Comparative Examples C18-19. Figure 17 is the graphical representation of the shear force compression test that results from Example 65 and Comparative Example 20.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a pressure sensitive adhesive comprising a mixture of at least two components, wherein the first component is at least one pressure sensitive adhesive and the second component is at least one thermoplastic material, wherein the components form a mixed composition that has more than one domain. Alteratively, the second component can be (a) at least one thermoplastic elastomer, as described in Series No. 08 / 578,010, filed on December 22, 1995 with a common beneficiary, (b) at least one elastomer with a sticky resin as described in Series No. 08 / 577,603, filed December 22, 1995 with a common beneficiary, or (c) at least one elastomer. The pressure-sensitive adhesive component may be any material having pressure-sensitive adhesive properties as described in -The Handbook of Pressure-sensitive Adhesives, page 172, paragraph 1, 1989. In addition, the useful pressure-sensitive adhesives are Hot melt processables that meet the Dahlquist criteria at temperatures of use. Typically, the pressure sensitive adhesive component is comprised of 30-98 weight percent, preferably 40-95 weight percent, and more preferably 60-95 weight percent. further, the pressure sensitive adhesive component may be a single pressure sensitive adhesive or the pressure sensitive adhesive may be a mixture of several pressure sensitive adhesives. Useful pressure sensitive adhesives of the present invention include sticky natural rubbers, synthetic rubbers, sticky styrene block copolymers, polyvinyl ethers, acrylates, poly-α-olefins, and silicones. Natural rubber pressure sensitive adhesives generally contain chewed natural rubber, from 25 parts to 300 parts of one or more tackifying resins for 100 parts of natural rubber, and usually 0.5 to 2.0 parts of one or more antioxidants. The natural rubber can be in the range from a light pale green rubber grade to a darkened flanged smoked sheet and including examples such as CV-60, a controlled rubber viscosity grade and SMR-5, a grade of smoked leaf rubber flanged. Sticky resins used with natural rubbers generally include but are not limited to wood rosin and its hydrogenated derivatives; terpene resins of various softening points, and petroleum-based resins, such as, the ESCOREZ 1300 series of resins derived from the C5 aliphatic olefin of Exxon, and polyterpenes, series of PICCOLYTES s, from Hercules, Inc. Antioxidants used to retard the attack of rust on natural rubber, which can result in the loss of the cohesive strength of the natural rubber adhesive. Useful antioxidants include but are not limited to amines, such as N-N 'di-β-naphthyl-1,4-phenylenediamine, available as AgeRite D; phenolic, such as 2,5-di- (t-amyl) hydroquinone, available as SANTOVAR A, available from Monsanto Chemical Co. , tetrakis [methylene 3- (3 ', 5' -di-tert-buty1-4 '-hydroxyphenyl) ropianate] methane, available as IRGANOX 1010 from Ciba-Geigy Corp., and 2-2' -methylenebis (4-methyl) -6-tert butyl phenol), available as an Antioxidant 2246; and dithiocarbamates, such as zinc dithiodibutyl carbamate. Other materials may be added to natural rubber adhesives for special purposes, where the additions may include plasticizers, pigments, and curing agents to partially cure the pressure sensitive adhesive. Another useful class of pressure sensitive adhesives are those comprising synthetic rubber. The adhesives are generally elastic elastomers, which are either self-adhesive or non-sticky and require tackiness. Self-adhesive synthetic pressure-sensitive adhesives including, for example, butyl rubber, a copolymer of isobutylene with at least 3 percent isoprene, polyisobutylene, an isoprene homopolymer, polybutadiene, such as TAKTENE 220 BAYER or rubber of butadiene / styrene. Butyl rubber pressure sensitive adhesives often contain an antioxidant such as zinc dibutyl dithiocarbamate. Polyisobutylene pressure sensitive adhesives usually do not contain antioxidants.

Synthetic pressure sensitive adhesives, which generally require tack, also generally make the melting process easier.They comprise polybutadiene or butadiene / styrene rubber, from 10 parts to 200 parts of an adhesive, and generally from 0.5 to 2.0 parts per 100 parts of an antioxidant rubber such as IRGANOX 1010. An example of a synthetic rubber is AMERIPOL 1011A, a butadiene / styrene rubber available from BF Goodrich.The adhesives that are useful include derivatives of rosins such as FORAL 85, a stabilized rosin ester from Hercules, Inc., the SNO TACK series of rubber rosins from Tenneco, and the AQUATAC series of Sylvachem high oil rosins, and synthetic hydrocarbon resins such as' politerpenes, from the series of PICCOLYTE A, from Hercules, Inc., the ESCOREZ 1300 series of resins derived from aliphatic olefin C5, the ESCOREZ 2000 series of resins derived from aromatic olefin / aliphatic C9, and polyaromatic C9 resins, such as the PICCO 5000 series of aromatic hydrocarbon resins, from Hercules, Inc. Other materials may be added for special purposes, including hydrogenated butyl rubber, pigments, plasticizers, liquid rubbers, such as liquid polyisobutylene rubber. VISTANEX LMMH, available from E.xxon, and curing agents to partially cure the adhesive. The pressure-sensitive adhesives of styrene-blocked copolymers generally comprise elastomers of the type A-B or A-B-A, where A represents a thermoplastic polystyrene block and B represents an elastic block of polyisoprene, polybutadiene, or poly (ethylene / butylene) and resins. Examples of various blocking copolymers useful in pressure-sensitive blocking copolymer adhesives include thinned and linear, radial, styrene-isoprene blocked copolymers, such as KRATON D1107P, available from Shell Chemical Co. , and EUROPRENE SOL TE 9110, available from EniChem Elatómers Americas, Inc .; linear blocked copolymers (ethylene-butylene) styrene such as KRATON G1657, available from Shell Chemical Co.; linear blocked copolymers (ethylene-propylene) styrene such as KRATON G1750X, available from Shell Chemical Co .; radial and linear styrene-butadiene blocked copolymers, radial, such as KRATON D1118X, available from Shell Chemical Co., and EUROPRENE SOL TE 6205, available from EniChem Elastomers Americas, Inc. Polystyrene blocks tend to form domains in the form of spheroids, cylinders, or plates that cause the pressure sensitive adhesives of blocking copolymer that have two structural phases. The resins that are associated with the rubber phase generally develop stickiness in the pressure sensitive adhesive. Examples of the rubber phase that associates resins that include resins derived from aliphatic olefin, such as the ESCOREZ 1300 series and the WINGTACK series, available from Goodyear; esters of colofinia, such as the FORAL series and the STAYBELITE Ester 10, both available from Hercules, Inc .; hydrogenated hydrocarbons, such as the ESCOREZ 5000 series, available from Exxon; polyterpenes, such as the PICCOLYTE A series; and phenolic terpene resins derived from sources of terpentine or petroleum, such as PICCOF? N A100, available from Hercules, Inc. Resins that are associated with the thermoplastic phase tend to stiffen the pressure sensitive adhesive. The thermoplastic phase associating resins includes polyaromatics, such as the PICCO 6000 series of aromatic hydrocarbon resins, available from Hercules, Inc .; coumarone-indene resins, such as the CUMAR series. available from Neville; and other resins of high solubility parameters derived from coal or petroleum pitch having softening points above about 85 ° C, such as the AMOCO 18 series of alphamethylstyrene resins, available from Moco, PICCOVAR 130 alkylaromatic polyindene resin, available from Hercules, Ine, and the PICCOTEX series of the alphamethyl styrene / vinyl toluene resins, available from Hercules. Other materials may be added for special purposes, including plasticizing phase hydrocarbon oil rubber, such as, TUFFLO 6056, available from Lydondell Petrochemical Co. , Chevron Polybutene-8, KAYDOL, available from Witco, and SHELLFLEX 371, available from Shell Chemical Co.; pigments; antioxidants, such as IRGANOX 1010 and IRGANOX 1076, both available from Ciba-Geigy Corp., BUTAZATE, available from Uniroyal Chemical Co. , CYANOX LDTP, available from American Cyamamid, and BUTASAN, available Monsanto Co.; antiozonants, such as NBC, a nickel dibutyldithiocarbamate, available from DuPont. Liquid gums such as polyisobutylene rubber VISTANEX LMMH; and ultraviolet light inhibitors, such as IRGANOX 1010 and TINUVIN P, available from Ciba-Geigy Corp. Polyvinyl ether pressure sensitive adhesives are generally mixtures of vinylmethyl ether, vinylethyl ether or vinyl isobutyl ether homopolymers, or mixtures thereof. homopolymers of vinyl ethers and copolymers of vinyl ethers and acrylates to achieve the desired pressure-sensitive properties. Depending on the degree of polymerization, the homopolymers can be viscous oils, soft sticky resins or rubber-like substances. Polyvinyl ethers that are used as raw materials in polyvinyl ether adhesives include polymers based on: vinyl methyl ether such as LUTANOL 40, available from BASF, and GANTREZ M 574 and GANTREZ M 555, available from ISP Technologies, Inc .; vinyl ethyl ether such as LUTANOL A 25, LUTANOL A 50 and LUTANOL A 100; vinyl isobutyl ether such as LUTANOL I 30, LUTANOL I 60, LUTANOL IC, LUTANOL I 60 D and LUTANOL I 65 D; methacrylate / vinyl isobutyl ether / acrylic acid such as ACRONAL 550 D, available from BASF. Antioxidants useful for stabilizing the pressure sensitive adhesive of polyvinyl ether including, for example, IONOX 30 available from Shell, IRGANOX 1010 available from Ciba-Geigy, and Antioxidant ZKF available from Bayer Leverkusen. Other materials may be added for special purposes as described in the BASF literature including tack, plasticizers and pigments. The acrylic pressure sensitive adhesives generally have a glass transition temperature of about -20 ° C or less and can comprise from 100 to 80 weight percent of an alkyl ester component of 3 to 5 carbon atoms, for example , isooctyl acrylate, 2-ethylhexyl acrylate and n-butyl acrylate and 0 to 20 weight percent of a polar component such as, for example, acrylic acid, methacrylic acid, ethylene vinyl acetate, N-vinylpyrrolidone and styrene macromer. Preferably, the acrylic pressure sensitive adhesives comprise from 0 to 20 weight percent acrylic acid and from 100 to 80 weight percent isooctyl acrylate. Acrylic pressure sensitive adhesives can be self-adhesive or adhesive. Useful adhesives for acrylics are rosin esters such as FORAL 85, available from Hercules, Inc., aromatic resins such as PICCOTEX LC-55WK, aliphatic resins such as PICCOTAC 95, available from Hercules, Inc., and terpene resins as a- pinene and ß-pinene, available as PICCOLYTE A-115, and ZONAREZ B-100 from Atizona Chemical Co. Other materials may be added for special purposes, including hydrogenated butyl rubber, pigments, and curing agents to partially cure the adhesive.

The poly-α-olefin pressure sensitive adhesives, also called poly (1-alkene) pressure sensitive adhesives, generally comprise any substantially non-crosslinked polymer or a non-crosslinked polymer which may have functional activatable radiation groups attached to the same as described in U.S. Patent No. 5,209,971 (Babu, et al.) which is incorporated herein by reference. The poly-α-olefin polymer can be self-tacky and / or include one or more adhesive materials. Without the crosslinking, the inherent viscosity of the polymer is generally between about 0.7 and 5.0 dl / g as measured by ASTM D 2857-93, "Standard Practice for Dilute Solution Viscosity of Polimers". In addition, the polymer is generally predominantly amorphous. Useful poly-α-olefin polymers include, for example, poly (1-alkene) polymers of 3 to 18 carbon atoms, preferably α-olefins of 5 to 12 carbon atoms and copolymers of those with 3 carbon atoms. and more preferably 6 to 8 carbon atoms and copolymers of those with 3 carbon atoms. Sticky materials are usually resins that are immiscible in the poly-α-olefin polymer. The total amount of tackifying resin in the ranges of the poly-α-olefin polymer is between 0 to 150 parts by weight per 100 parts of the poly-α-olefin polymer depending on the specific application. Useful tackifying resins include resins derived by the polymerization of unsaturated hydrocarbon monomers of 5 to 9 carbon atoms, polyterpenes, synthetic polyterpenes and the like. Examples of such commercially available resins based on such a 5-carbon olefin reaction are tackifying resins WINGTACK 95 and WINGTACK 115 available from Goodyear Tire and Rubber Co. Other hydrocarbon resins include REGALREZ 1078 amd REGALREZ 1126 available from Hercules Chemical Co. , and ARKON P115 available from Araka to Chemical Co. Other materials may be added for special purposes, including antioxidants, fillers, pigments, and cross-linked agents with activated radiation. Silicone pressure sensitive adhesives comprise two major components, a polymer or rubber, and a sticky resin. The polymer is usually a higher molecular weight polydimethylsiloxane or polydimethyldiphenylsiloxane, containing residual silanol functionality (SiOH) at the ends of the polymer chain, or a block copolymer comprising soft segments of polydiorganosiloxane and hard segments of urea terminated. The sticky resin is generally a three-dimensional silica structure which is end-capped with trimethylsiloxy groups (OsiMe3) and also contains some residual silanol functionality. Examples of tackifying resins include SR 545, from General Electric Co. , Silicone Resins Division, Waterford, NY, and MQD-32-2 of Shin-Etsu Silicones from American Inc., Torrance, CA. The manufacture of the normal silicone pressure sensitive adhesives is described in U.S. Patent No. 2,736,721 (Dexter). The manufacture of the block-copolymer pressure-sensitive adhesive is described in US Patent No. 5,214,119 (Leir, et al.). Other materials can be added for special purposes, including pigments, plasticizers, and fillers. Fillers are normally used in quantities of 0 parts to 10 parts per 100 parts of the silicone copolymer pressure sensitive adhesive. Examples of fillers can be used including zinc oxide, silica, black carbon, pigments, metal powders and calcium carbonate.

The second component of the pressure-sensitive adhesive composition of the present invention is a thermoplastic material or alternatively as either (a) a thermoplastic elastomeric material, (b) an elastomeric material with a tacky resin, as previously described, or (c) an elastomeric material. The thermoplastic material component is usually a high polymer that can soften when exposed to heat and can return to the solid state when cooled to room temperature. Useful thermoplastic materials are fiber formations and are essentially immiscible in the pressure sensitive adhesive component at the use temperature, although the thermoplastic may be miscible in the pressure sensitive adhesive at melt processing temperatures. Typically, the thermoplastic material component is comprised of 2-70 weight percent in the pressure sensitive adhesive composition, preferably 5-60 weight percent and more preferably 5-40 weight percent. In addition, the thermoplastic material component may be a single thermoplastic material or a mixture of several thermoplastic materials.

The thermoplastic materials useful in the present invention include, for example, polyolefins such as isotactic polypropylene, linear or low density low density polyethylene, medium density polyethylene, high density polyethylene, polybutylene, polyolefin copolymers or terpolymers, such as ethylene copolymer. propylene and mixtures thereof; copolymer of ethylene-vinyl acetate as ELVAX 260, available from DuPont Chemical Co. , copolymers of ethylene acrylic acid, ethylene methacrylic acid copolymers such as SURLYN 1702, available from DuPont Chemical Co, polymethyl methacrylate, polystyrene, ethylene vinyl alcohol, polyester, amorphous polyester, polyamides, fluorinated thermoplastics, polyvinylidene fluoride, polybenzene fluorylene, ethylene copolymers / fluorinated propylene and thermoplastic thermoplastics and fluorinated ethylene / propylene copolymers, such as a chlorinated polyethylene. Any simple thermoplastic can be mixed with at least one pressure sensitive adhesive. Alternatively, a mixture of thermoplastic materials can be used, providing the resulting mixture when the melt mixed with at least one pressure sensitive adhesive in at least two distinct domains at the use temperature. Thermoplastic elastomeric materials are normally material that form at least two phases at 21 ° C, which flow at a temperature greater than 50 ° C and exhibit elastomeric properties. The thermoplastic elastomeric materials that are useful are further described in Series No. 08 / 578,010 filed December 22, 1995 with a common beneficiary. Elastomeric materials are usually materials that form a phase at 21 ° C, have a glass transition temperature less than about 0 ° C and exhibit elastomeric properties. Sticky resins can be added to facilitate mixing of the pressure sensitive component with the elastomeric material component. Useful elastomeric materials include natural rubber, synthetic rubber and those additionally described in Series No. 08 / 577,603, filed December 22, 1995 with a joint beneficiary. Preferably, each of the components has a similar melt viscosity. The ability to form a finely dispersed morphology is related to a viscosity ratio of the shear strength of the components at melt mixing temperatures.The shear viscosity is determined using capillary rheometry at a shear force velocity approaching the extrusion mixing conditions, i.e., 100s_1 and 175 ° C. When a high viscosity component is presented as the minor component, the viscosity ratio of the components from least to greatest is preferably less than about 20: 1, more preferably less than about 10: 1. When a low viscosity material appears as the minor component, the viscosity ratio of the components from least to greatest is preferably greater than about 1:20, more preferably greater than about 1:10. The melting viscosities of the individual components can be altered by the addition of plasticizers, stickiness or solven or varying the temperatures of the mixture. It is also preferable that at least one of the components be easily spread during the coating and melt blending operations to form a finely dispersed morphology with the domains that are fibrillated to schistose, for example, forming sheets, ribbons, fibers, ellipsoids or the like, oriented in the direction of the low tissue in the substantially continuous or co-continuous domain of the other polymeric material. Sufficient interfacial adhesion between the pressure sensitive adhesive component and the thermoplastic material component exists to resist the shear force and extensional deformation present during the forming step and to promote the formation of a continuous film. If none of the polymeric materials can be sufficiently dispersed during the fusion mixture, a pressure sensitive adhesive layer can be produced having coarse and grainy discontinuities in texture. Through the use of suitably selected blending conditions, the melt viscosity ratios, the draw / shear strength conditions during extrusion, the thickness of the fibrillated to schistose domains can be made sufficiently thin where catastrophic delamination of the domain will not occur substantially continuous or co-continuous. Preferably, the thickness of the fibrillary to schistose domains is less than about 20 micrometers, more preferably less than about 10 micrometers, and preferably less than about 1 micrometer.

In the present invention, the components are mixed and coated using the melt extrusion techniques. The mixture can be made by any method that results in a substantially homogeneous distribution of the components. The mixture of components is prepared by the melting mixture of the components in the molten or softened state using devices that provide the dispersive mixture, distributive mixture, or a combination of the dispersive and distributive mixture. Both continuous and batch mixing methods can be used. Examples of batch methods include the internal mix of BRABENDER or BAJSTBURY, and spin milling. Examples of continuous methods include single screw extrusion, double screw extrusion, disk extrusion, reciprocal single screw extrusion, and the extrusion of a single pin barrel screw. The continuous methods may include both distributive elements, plug mixing elements, and static mixing elements, and dispersive elements such as Maddock mixing elements or Saxton mixing elements. After the mixing step, the molten or softened mixture is formed into a layer of a pressure sensitive mixed adhesive having a distinctive morphology. In the present invention, the pressure-sensitive adhesive component forms a substantially continuous domain, while the thermoplastic component forms a discontinuous domain that is fibrilous to schistose-to-nature by the process involving either strain or shear deformations or both Continuous forming methods include extracting the pressure sensitive adhesive composition out of a die film and then connecting a moving plastic fabric or other appropriate substrate. A related continuous method involves extruding the pressure sensitive adhesive composition and a coextruded support material from a film die and followed by cooling to form a pressure sensitive adhesive tape. Other continuous forming methods involve directly contacting the pressure sensitive adhesive mixture to quickly move the plastic fabric or other suitable substrate. In this method, the pressure sensitive adhesive mixture can be applied to the movement of the fabric using a die having flexible die edges such as an inverted hole of the coated die and other contact dies that use rotation rods. After forming, the pressure-sensitive adhesive layers are solidified by cooling using the two direct methods, such as cold rolls or water baths, and indirect methods, such as air or gas impact. Either before or after a pressure sensitive adhesive is covered in a backing, the pressure sensitive adhesive compositions of the invention can be crosslinked by radiation treatment. Suitable sources of radiation include ultraviolet and electron beam. When ultraviolet irradiation is used, photoinitiators are generally added to the adhesive mixture. If the current photoinitiators are those known to experts in the article that are compatible or useful with specific pressure sensitive adhesives. Advantageously, the pressure sensitive blended adhesives of the present invention provide adhesives having one or more of the following properties. These properties have improvements through a pressure sensitive adhesive prior to mixing with a thermoplastic material. These properties include: (1) a higher surface adhesion than if it will be used alone and a shear force similar to that of the pressure sensitive adhesive component, (2) a greater shear force than if it were used alone and a surface adhesion similar to that of the pressure-sensitive adhesive component; (3) an adhesion to the anisotropic skin, (4) an anisotropic shearing force, and (5) a tensile force in the direction of the lower fabric that is at least 2 times greater than the tensile force in the direction of the transverse tissue for all elongations up to the elongation of the fabric. break (6) an impact cut resistance that is at least 2 times greater than if it will be used alone to the pressure sensitive adhesive component. Improved surface adhesions have been observed to be from 20% to 200% greater than those seen with the pressure sensitive adhesive component alone without substantial decrease in shear force. This appears to be due to the additional energy scattering caused by limited interfacial delamination or null formation between domains during detachment. This is observed when the discontinuous domain is the component of thermoplastic material. This will also depend on the type and quantity of the component used. Generally the improved surface adhesions occur over a range of 5% to 20% of the thermoplastic component. For example, if a pressure-sensitive acrylic adhesive is used, the components of thermoplastic material that do not exhibit improved surface adhesion include, for example, polystyrene, polymethylmethacrylate and amorphous polyester. Similarly, thermoplastic materials that exhibit improved adhesion to the surface include, for example, linear low density polyethylene, low density polyethylene, and ethylene vinyl acetate. The shear force, as measured by sustained time, has been found to be 25% to 200% greater than those observed with the pressure sensitive adhesive component alone without a substantial decrease in surface adhesion. This seems to be due to the natural reinforcement of the domains of thermoplastic material and has been observed over a range of thermoplastic material of 5% to 25%. The types of thermoplastic materials do not seem to be a controlling factor.

The anisotropic detachment force is an unusual property where the force necessary for the detachment of the PSA article from a surface to which several adhere when measured along different axes. That is, the PSA article displays a different adhesion when detached from the surface in different directions. When a pressure-sensitive article is made by extruding the adhesive, the preferred orientation of the elastomer will generally be "the direction of the fabric under (or" DW "), ie, parallel to the extrusion coating line. The extrusion coating line generally refers to the "transverse tissue direction" (or "CW"). Generally, the peel force in the parallel direction will be less than 90%, preferably less than 50%, and more preferably less than 10%, of the greater force of detachment (ie, the force of detachment in the perpendicular direction.) This effect is due to the low tissue oriented to the fibrilous to the schematic morphology of the discontinuous phase.When thermoplastic materials have a high tensile strength, ie, polystyrene, polymethyl methacrylate, amorphous polyester, and high density polyethylene, anisotropic detachments are observed when the range of the thermoplastic material is between 5 to 20%. When the thermoplastic material has a low tension force, i.e. linear low density polyethylene, low density polyethylene, and ethylene vinyl acetate, the range is from 20% to 40%. It is believed that the anisotropic adhesion to the surface is due to the hardening of the PSA composition by the thermoplastic material in the direction of the low tissue. The anisotropic shear force is often observed when a pressure sensitive adhesive of the invention exhibits anisotropic adhesion to the surface. In such cases, the direction of the high shear force normally corresponds to the direction of the low surface adhesion. However, the anisotropic shearing force occurs without the occurrence of a corresponding anisotropic surface adhesion. The shearing force in the low cutting direction will be less than 80%, preferably less than 50%, and more preferably less than 10%, of the high shearing force. A tensile force in the direction of the low tissue has been observed to be at least twice as great as the tension force in the direction of the transverse tissue for all elongations up to the elongation of rupture. The tensile force is influenced by the type of materials selected, their concentrations, the length to the ratio of the diameter of the discontinuous domains and the elongation of rupture of the component of thermoplastic material. Tension forces ranging from 0 69 to 20.7 MPa have been observed with structures of the invention. By forming the fiber as schistose similar to discontinuous in situ domains, the finer thermoplastic fibrillary schistose domains (less than 1 μm) can be formed compared to the pressure sensitive adhesive constructions composed of glass fiber placed on the sensitive adhesive. the pressure. Generally, higher tensile strength properties are obtained with more rigid thermoplastic materials, such as polystyrene, polymethyl methacrylate, amorphous polyester and high density polyethylene. The high tensile strengths of the lower fabric and the smaller rupture elongations also allow the pressure sensitive adhesive compositions of the invention to have better dispensing properties when used, for example, as transfer adhesive tapes. Substantial increases in impact cut resistance are observed in the pressure sensitive adhesives containing the second poly phase. When tested using 1 second, the impact force of 163 kg, samples without a second immiscible phase failed (a movement greater than 2.54 cm) within several cycles. Nevertheless, the same pressure sensitive adhesive formulation, with the addition of a second, the immiscible polymer component will require 2 times as many cycles to failure, and will require more frequently the cycle over 500 times without reaching failure. The compositions of the present invention depend on a specific formula, which can be used to make various pressure sensitive articles using the anisotropic properties of some formulas, of pressure-sensitive adhesive tapes, of pressure-sensitive adhesive transfer tapes. , of pressure-sensitive adhesive medical tapes, including for example transdermal drug delivery devices, materials making pressure-sensitive pavement, or pressure-sensitive adhesive layers directly on the desired articles. Alternatively, the various pressure sensitive articles may utilize pressure sensitive adhesive compositions comprising at least one pressure sensitive adhesive component and at least one polymeric component which may be either (a) an elastomeric thermoplastic material, (b) an elastomeric material with a tacky resin, as previously described, or (c) an elastomeric material without a tacky resin. The compositions of the present invention are also useful in medical applications that include transdermal drug delivery devices. The devices generally involve a controlled adhesion to the skin. The adhesion should be sufficient for the application of the initial bonding and not increase the time to a point where the skin can be damaged with removal or decrease in time to a point where the devices can fall off the surface of the skin. Transdermal drug delivery devices are designed to deliver a therapeutically effective amount of medicament through or to a patient's skin. The release of the transdermal drug provides important advantages; a different injection, is non-invasive; "distinct from oral administration, the first hepatic steps to metabolism are avoided, gastrointestinal effects are minimized, and stable blood levels are provided." A variety of transdermal drug delivery devices are known. which the drug is placed inside a non-adhesive polymeric material, the deposition devices where the drug is put in a liquid and released to the skin through a membrane that controls the proportion; which the medicament is put into an adhesive polymer, and more complex multi-laminated devices involving several different layers, i.e., the layers for containing medicament, for containing excipients, for controlling the rate of discharge of the medicament and excipients, and for joining the device to the skin, all the devices incorporate a formula of medication, an adhesive to maintain contact with the patient's skin, a discharge liner that protects the device during storage (and which is removed before applying the device to the skin), and a booster that "protects the device from external contamination while in use. A matrix device is shown in Figure 11. The device 10 comprises a reinforcement 12, a matrix 14 containing the medicament and optionally the excipients, a concentric adhesive layer 16 around the matrix 14, and a release liner 18. A device The reservoir is shown in Figure 12. The device 20 comprises a booster 22, a liquid formula 24 containing the medicament and excipients optionally, a membrane 25 for controlling the proportion at which the medicament and the excipients are released to the skin, an adhesive layer 26, and a release coating 28. The adhesive layer may also be present as a concentric ring as shown in relation to the matrix device (Figure 11). A medicament device in adhesive is shown in Figure 13. The device 30 comprises a backing 32, an adhesive layer 37 containing the medicament and optionally the excipients, and a release liner 38.

A multi-laminated device is shown in Figure 14. The device 40 comprises a reinforcement 42, an adhesive layer 47 containing the medicament and optionally the excipients, a second adhesive layer 43 which controls the ratio at which the medicament and the excipients are released to the skin, and a release liner 48. A second embodiment of a multilamellar device is shown in Figure 15. The device 50 comprises a backing 52, an adhesive layer 57 containing the medicament and optionally the excipients, a membrane 55, a second adhesive layer 56, and a release liner 58. The membrane can be selected to control the rate at which the drug and excipients are released to the skin or to provide physical stability to the device. Adhesion to the skin is a critical requirement of any transdermal drug delivery system. Because the release of the medication is directly proportional to the area of contact with the skin, the device must maintain and establish sufficient adhesion to the skin until it is removed. The adhesives that are used in skin contact layers will preferably exhibit the following properties: good adhesion to the starting skin, i.e., tackiness; Adequate adhesion during a period of use; the clean release of the skin; and skin compatibility; (not irritating and not sensitive). It is important that these properties are maintained when the adhesive is exposed to the medication and particular excipients used in a specific device. Adhesives used in layers that contain any medication and excipients or through which the excipients and medication pass must be compatible with the drug and excipients. Preferably the adhesives will not react chemically with the medicament or excipients. In several cases, it is also preferable that the drug dissolves in the adhesive instead of dispersing therein. It will often be desirable or even necessary to customize the adhesive for a particular drug / excipient combination. The transdermal delivery devices may be made in the form of an article such as a tape, a patch, a sheet, a preparation or any other form known to those skilled in the art.

Generally, the device will be in the form of a patch of an appropriate size to release a preselected amount of the medicament. Suitable release coatings include those listed above in connection with the preparation of PSA tapes. The anisotropic adhesion property to the surface that enables the pressure-sensitive adhesive articles of the invention (e.g., tapes or sheets coated with pressure-sensitive adhesive) is used in graphic arts applications (e.g., a ribbon). pre-coated, pre-spaced tape, graphic art film, die cutting products, or dry transfer labeling, such as graphic arts products described by Satas, supra, Chapter 32). The anisotropic PSA articles of this invention can also be used as a diaper fastening tape, a wall decoration film, or other constructions where a differential release is desirable. As mentioned above, in one embodiment of the pressure sensitive adhesive article of this invention, the type and concentration of the pressure sensitive adhesive and the thermoplastic material components are sufficient to impart the anisotropic release force to the article. An article having an anisotropic detachment force can be used as a graphic application tape (including both pre-spaced and pre-spaced tapes), which is useful in graphic arts work. For example, die cutting graphics often take the form of vinyl decals. Usually, the decal is formed by being cut from a color coated, adhesive sheet vinyl film that has been laminated to a release liner. The loss or residue is immediately removed and then a graphics application tape is applied to the surface of the die-cut decals to lift them off the release liner while keeping them in engraving. The decals are then transferred to the desired designated substrate and the graphics application tape is immediately removed. The graphics application tapes need to be very aggressive to reliably lift all the components of the graphic (ie, the decals in this example) from the release liner, but they should still be removed easily after transferring the graphic to the designated substrate and should not waste nothing of the graphic out of the indicated substrate. This is often a difficult balance to achieve. Using the pressure-sensitive adhesive tape of the present invention as the graphics application tape, one will be able to pull in the high adhesion direction to remove the coating graphic, apply it to the designated substrate, and then remove the graphics application tape. pulling in the direction of low adhesion. Other graphic application tapes do not involve stamped components but will still be an advantage because they have graphical application tapes with a very easy lifting direction because the graphics can be very wide and difficult to pull with conventional adhesives. When a conventional adhesive is formulated to have a low lifting force, the ability to hold the graph is damaged. The anisotropic pressure sensitive adhesive tapes of the present invention may have a high retention capacity but may still consist of a low lifting force. Another application for an anisotropic pressure sensitive adhesive article of this invention is as a wide area graphic or protective film that aggressively adheres to a surface to which it is applied but can be quickly removed. Some uses of this article include, propaganda graphics on the side of a truck, protective films for the finishes of a vehicle during its manufacture, transportation, storage, and a protective film for microreplicated surfaces used in graphic displays on optical screens. Another application in which the release properties of the invention can be used is in the manufacture of the diaper fastening tape. The low detachment force of a tape in the machine finishing direction will allow unwinding a large supply roll of the tape to be placed without the aid of a deliberation material. In the conversion process the supply roll for the individual tapes, the tape may be cut so that the transverse direction of the supply roll, which is the high adhesion direction, reaches the detached direction of the finished diaper product. Yet another application of the pressure sensitive adhesive article will be in films for the decoration of walls. One can produce a graphic decoration for the wall with the anisotropic pressure sensitive adhesive article in such a way that the high adhesion direction is vertical or down the wall to prevent failure due to gravity, while the low adhesion direction is horizontal to provide an easy lifting direction that avoids any damage to the wall. Another use for an anisotropic pressure sensitive adhesive article of the invention is in covering applications that use a cover sheet or mat adhesively attached to a substrate to cover a large area of the substrate. Finishing or covering sheets are used in automotive or finishing paints and in residential or commercial wall paints where a plastic or paper film is secured with tape to the car body part or wall to prevent over-spreading of a layer in the area that is covered. If the cover sheet is relatively long and strong it will induce a constant release force in the direction of the coating which can cause the tape to move away from the substrate. The adhesive can be formulated to be more aggressive and overcome the stress induced by the coating weight, but the tape may then be difficult to completely remove from the substrate after the painting operation is completed. An anisotropic pressure sensitive adhesive tape of the present invention showing low peel strength in the machine finish direction and high peel force in the transverse direction is useful in the coating applications. The tape can be made to have a greater resistance of detachment or holding capacity in the transverse direction to overcome the force of detachment induced by the weight of the coating, but it has only a very low lifting force or detachment in the direction along Remove the tape without damaging the substrate. The impact cut resistance allows the pressure sensitive adhesive articles of the invention to be advantageously used in pavement signal applications, (for example, wear resistance, flexible base sheets of signaling materials in preformed pavements adhered to the place for bounded footpaths, containment bars, and lane markers used to facilitate traffic control.) As mentioned above, the improved impact cut resistance can be used to substantially improve the performance of pavement marking materials. Signals on pavements such as pedestrian crossing signs, grab bars, and lane markers are subject to high shear forces, short periods of acceleration and stoppage, and rolling of vehicles. To provide adhesives to resist these forces, U.S. Patent No. 5,453,320 (Harper et al.) Teaches the use of a high adhesive load, US Patent No. 3,902,939.

(Eigenmann) shows the use of a non-stick adhesive activated by heat, the American Patent No.4, 146, 635 (Eigemmann) shows the use of an inextensible, stress-resistant intermediate layer, and US Patent No. 2,956,904 (Hendricks) shows the use of a high-energy electron beam bombardment of sensitive adhesives to the pressure of the rubber resin type to increase the cohesive properties of the adhesive. All of the aforementioned methods of increasing the strength of the shear force of the pressure sensitive adhesives adversely affects the bonding ability of the pressure sensitive adhesive. The technique teaches the use of the former to improve the bonding of the shear-resistant adhesive to the road surface. The use of a second, immile polymer phase within a pressure-sensitive adhesive to be used as a pavement marking material is allowed for articles that can withstand the impact of shear forces associated with acceleration and stopping, and traffic bearing, without adversely affecting bonding capacity of the adhesive. The pressure sensitive adhesive articles are made by applying the pressure sensitive adhesive by the well known hot melt coating process. Any suitable substrate can be used, including, but not limited to, for example, glass fiber cloth and fabric, metallized films and films, polymeric films, polymer coated paper and paper, non-woven fabrics, and foam reinforcements. Polymeric films include, but are not limited to, polyolefins such as polypropylene, polyethylene, low density polyethylene, linear low density polyethylene, and high density polyethylene; polyesters such as polyethylene terephthalate; polycarbonates; cellulose acetates; polyimides like KAPTON. Non-woven fabrics, generally made from randomly oriented fibers, include, but are not limited to, nylon, polypropylene, ethylene vinyl acetate copolymer, polyurethane, rayon and the like. Foam reinforcements include, but are not limited to, acrylic, silicone, polyurethane, polyethylene, neoprene rubber, and polypropylene, and may be full or unfilled. Reinforcements that are covered, such as polyethylene aluminum membrane composites, are also appropriate. In the case of pressure sensitive tapes, these materials are normally applied by making a first tape construction comprising a layer of the pressure sensitive adhesive material coated in a reinforcement. The exposed surface of the PSA coating can subsequently be applied to the surface from which they can be subsequently released or directly to the desired substrate. A transfer adhesive tape can be made by coating the composition between two coatings which are covered with a release coating. The release coatings often comprise a transparent polymeric material such as a polyolefin or polyester that is transparent to ultraviolet radiation. Preferably, each release coating is first coated with a release material for the pressure sensitive adhesive used in the invention. This invention is further illustrated by the following examples which are not intended to limit the scope of the invention. The following test methods were used to evaluate and characterize the film surfaces produced in the examples.

Examples This invention is further illustrated by the following examples which are not intended to limit the scope of the invention. In the examples, all parts, proportions and percentages are by weight unless otherwise indicated. The following test methods were used to characterize the pressure sensitive adhesive compositions in the following examples: Test Methods Cutting Viscosity Cutting viscosity was determined using a high pressure capillary rheometer (RHEOGRAPH 2001, available from Gottfert Co.) operated with a capillary die 30 mm long and 1 mm in diameter at a temperature of 175 ° C. C unless otherwise indicated. At a cut-off ratio of 100s_1, the apparent viscosity was calculated from the Poiseuille equation and converted to an actual viscosity using the Weissenberg-Rabinovitch correction. 180 ° Surface Adhesion Test Samples of 1.25 cm wide and 15 cm long pressure sensitive adhesive tape were tested for 180 ° of surface adhesion to steel, final surface 63. Samples were adhered to Test surfaces rolling the tapes with a 2.1 kg roller using 4 steps. After maturing at controlled temperature and humidity conditions (approximately 22 ° C, 40% relative humidity) for approximately 1 hour, the tapes were tested using a Model 3M90 surface / error tester, available from Instrumentors, Inc., of 180 ° of geometry in 30.5 cm / min of surface proportion, unless otherwise indicated. 180 ° Surface Adhesion Test to Steel Samples of pressure sensitive adhesive tape of 1.25 cm wide and 15 cm long for 180 ° surface adhesion to steel, final surface 63. Samples were adhered to the rolling test surfaces the tapes with a 2.1 kg roller using 4 steps. After maturing at controlled temperature and humidity conditions (approximately 22 ° C, 40% relative humidity) for approximately 1 hour, the tapes were tested using an INSTRON Model 122 tension tester, available from Instron Corp, at 180 ° C. geometry in 25.4 cm / min of surface ratio.

Shear Strength Test The shear force, as determined by the holding time, was measured in the samples of pressure-sensitive adhesive tape at controlled temperature and humidity conditions (approximately 22 ° C, 40% relative humidity) . A 25.4 mm x 25.4 mm section of the tape was adhered to an unstained steel sheet with a 2.1 kg roller using 4 steps. A weight of 1000 grams was suspended from the sample. The amount of time for which the weight will be dropped was recorded. The test stopped at 10,000 minutes.

Test of shear force at 50 ° C. The shear force at an elevated temperature, as determined by the retention time, was measured in the samples of pressure-sensitive adhesive tape at controlled temperature and humidity conditions (approximately 50 ° C, 5% relative humidity). A 12.7 mm x 12.7 mm section of the tape was adhered to an unstained steel sheet with a 2 kg roller using 4 steps. A weight of 500 grams was suspended from the sample. The amount of time for which the weight will be dropped will be recorded. The test was stopped at 10, 000 minutes.

Laser Light Scattering Test Samples of pressure-sensitive adhesive tape were tested for their light scattering characteristics. A helium neon laser operating at 632 nm wavelength and 3 mm in dot size of mm went normal to the plane of the adhesive tape. A shutter controlled the exposure time of the beam in the sample and the resulting light scattering image was captured in the Polaroid # 55 film that was 120 mm behind the tape sample. The presence of the fibrinous domains to schistosomes produced in - a fatty substance of the intensity of light scattered in a broad or fine line oriented at 90 degrees of fiber or direction of the low tissue in the plane of the film. The absence of the dispersed domain or the presence of a spherically formed dispersed domain produced an isotropic or spherical light scattering model.

Stress Testing The stress test was used to obtain stress force data for various mixed pressure-sensitive adhesive coatings, the 2.54 cm wide samples having thicknesses of 51 to 127 microns were tested using an INSTRON Model. 1122 equipped with a set of INSTRON Series 9 programs at a crosshead speed of 102 cm / min.The samples were tested in both DW and CW directions.

Skin Adhesion Test The skin adhesion test was carried out by placing the tape samples 2.5 cm wide by 5 cm long on the back of a human object. Each tape is rolled down with one step forward and one reverse step using a 2 kg roller moved at a speed of approximately 30 cm / min. Adhesion to the skin was measured as the detachment force required to remove the tape at an angle of 180 ° at a speed of 15 cm / min of lifting. Adhesion was immediately measured after initial application (T0) and after 48 hours (T48). The preferred skin adhesive generally exhibits a T0 of between about 50 to 100 grams (1.9 to 3.8 N / dm) and a T48 of between approximately 150 to 300 grams (5.8 to 11.5 N / dm). The results of 14 tests were averaged.

Skin Adhesion Lifting Test When the skin adhesion test for 48 hours was performed, the tape sample was examined by the amount of area that was lifted (released) from the skin prior to removal of the tape. and valuations were given as: 0 non-visible survey 1 survey only at the edges of the belt 2 survey above 1% to 25% of the test area 3 survey above 25% to 50% of the test area 4 survey above 50% to 75% of the test area 5 rising above 75% to 100% of the test area The results of 14 tests were averaged. Surface adhesives generally show a test average below about 2.5.

Residual Skin Adhesive Test When the skin adhesion test was performed for 48 hours, the skin under the tape sample was examined visually to determine the amount of adhesive residue on the surface of the skin and evaluated as: 0 no visible residue 1 residue only on the edges of the tape 2 cover of the waste 1% to 25% of the test area 3 cover of the waste 25% to 50% of the test area 4 cover of the residue 50% to 75% of the test area 5 residue cover 75% to 100% of the test area The results of the 14 tests were averaged. Preferred surface adhesives generally show a test average below about 2.5.

Surface Test at 4 o C for Concrete Samples of pressure-sensitive adhesive tape 2.54 cm wide and 25.4 cm long were tested for surface adhesion at 90 ° C to the concrete. The adhesive samples, laminated to 0.05 mm of a polyester film, were allowed to equilibrate, together with the concrete block, at 4 ° C. The samples were then adhered to the concrete surfaces by rolling the tapes with a 2.1 kg roller using 4 steps. After 15 minutes, the peak force required to remove the tapes at a 90 ° angle was recorded using "an ACCUFORCE CADETE, 0-501b DIGITAL FORCÉ GAGE, available from AMETEK.

Simulation Test that Uses a Vehicle This test is used to simulate the cut associated with a rotating tire. The simulator has a test area consisting of a horizontal annular ring approximately 1.8 meters in diameter and meters in width that has an unprimed concrete surface. The adhesive samples were laminated to the pavement marking material, STAMARK 5760, available from 3M Company, and cut into rectangles of 5 cm and 15 cm. The laminate is mounted on an annular ring with the long axis of the laminate being aligned with the radial axis of the ring. The laminate is rotated by hand with a 2-kg rubber roller to provide good contact with the surface of the concrete without priming and the initial position is noted. Two tires, from B.F. Goodrich P165 / 80R13 radial rims with steel belts with an inflation pressure of 2.1 x 105 Pascals were positioned vertically on the test area at opposite ends of a rigid junction frame. Downward pressure is applied to the frame pneumatically to provide a load of "between 190 to 200 kg on each tire." The frame is rotated, driving the tires on the surface of the test area at 5 revolutions per minute, which simulates a diameter of .3 meters rotating at approximately 1.6 kilometers per hour.The lateral movement of the laminate is recorded after a specified number of wheel crashes.

Cutting / Compression Testing The cut / compression test is used to simulate conditions in hot climates where pavement marking materials undergo a combination of compression and shear forces. A single layer of adhesive is subjected to a cyclic load between 0 and 74 kg (0 and 163 Ib), applied and removed at a displacement speed of 2.54 cm / min. The load is applied at an angle of 26 ° (2 wedges with its hypotenuse deflect horizontally to 26 °) resulting in a compressive tension of 2.8 x 105 Pascal and a cutting force of 1.4 x 105 Pascal (to simulate the forces applied to a pavement marking in a curve).

This test is performed at 3.3 ° C being less resistant to cutting in these conditions. A Materials Test System (MTS) model 810, available from MTS Systems Corporation, has its test chamber balanced at 3.3 ° C. The axial displacement speed is set at 2.54 cm / min, the peak axial force is set at 163 kg, the inclined angle is set at 26 °, the remaining time between cycles is indicated at 1 second. Samples of 5 cm x 10 cm of the adhesive to be tested are placed between two steel panels, with a surface finish of 63 and allowed to equilibrate at 37.8 ° C. The cut offset is plotted against the cycle number.

Examples 1-17 and Comparative Example Cl In Examples 1 and 2, a pressure sensitive adhesive, the acrylic component (95 weight percent isooctyl acrylate / 5 weight percent acrylic acid, water polymerized emulsion , cutting viscosity - 150 Pascals, prepared according to US Patent No. 24,906, (Ulrich) which is incorporated herein by reference, and dried), and one component of thermoplastic material, ELVAX 210 (copolymer of ethylene vinyl acetate, cutting viscosity of 10 Pascals, available from Dupont), were melt blended in a co-rotating twin-screw extruder that meshes totally 34 mm in diameter (LEISTRITZ Model LSM34GL, available from Leistritz, Inc.). The thermoplastic material component was introduced into the feed throat of the extruder and the pressure sensitive adhesive component was introduced into zone 4. The temperature increased progressively from 38 ° C to 177 ° C from zone 1 to zone 4 The temperature of the remaining zones was maintained from 177 ° C to 191 ° C. In Examples 1 and 2, the feed rate was adjusted to provide a ratio of the pressure sensitive adhesive component to the thermoplastic material component of 95: 5 and 85:15, respectively. The twin screw extruder was continuously discharged at a pressure of at least about 0.69 MPa of 25.4 cm width from a film die (ULTRAFLEX 40 die, Model 89-12939, available from Extrusion Dies, Inc.). The die was maintained from 177 ° C to 191 ° C and the die opening was 0.5 to 0.8 mm). The blended adhesive composition was fed between a film of biaxially oriented polyethylene terephthalate with a thickness of 51 μm and a release coated paper fabric at a speed of 6.4 kg / hr. The film and the fabric were fed at a rate of 13.7 m / min between cold rolls held at a temperature of 21 ° C to form a pressure-sensitive adhesive tape with a layer of pressure-sensitive adhesive composition of a thickness of about 64 microwaves Alternatively, some blended adhesive composition was fed between two release coated paper tissues to further test the adhesive layer or subsequently transfer the adhesive layer to a different substrate. Examples 3, 4 and 5 were prepared in the same manner as Example 1 except that a different thermoplastic material component, ELVAX 240 (ethylene vinyl acetate copolymer, cut viscosity - 210 Pascal), was added to the adhesive component sensitive to the pressure at proportions of the pressure-sensitive adhesive component to 95: 5 thermoplastic component, 85:15 and 70:30. respectively. Examples 6, 7 and 8 were prepared in the same manner as Examples 3, 4 and 5, respectively, except that a different thermoplastic material component, ELVAX 450 (ethylene vinyl acetate copolymer, cut viscosity - 470 Pa) was added. -s), to the adhesive component sensitive to pressure. Examples 9, 10, 11 and 12 were prepared in the same manner as Example 1 except that a different thermoplastic material component was added, ELVAX 260 (ethylene vinyl acetate copolymer, cutting viscosity - 600 Pa-s), pressure sensitive adhesive component at proportions of the pressure sensitive adhesive component to the thermoplastic material component of 95: 5, 85:15, 70:30 and 40:60, respectively. Examples 13, 14 and 15 were prepared in the same manner as Examples 3, 4 and 5, respectively, except that a different thermoplastic material component was added, ELVAX 660 (ethylene vinyl acetate copolymer, cut viscosity - 730 Pa) -s) to the adhesive component sensitive to pressure. Examples 16 and 17 were prepared in the same manner as Examples 3 and 4, respectively, except that a different thermoplastic material component, SURLYN 1702 (ethylene copolymer of methacrylic acid, available from DuPont) was added to the adhesive component sensitive to the pressure. Comparative Example Cl was prepared as in Example 1 except that only the pressure sensitive adhesive component, with the component of non-thermoplastic material, was used to prepare the pressure-sensitive adhesive tape. The viscosity ratio of the discontinuous to the substantially continuous component and the thickness of the adhesive in the samples of each pressure-sensitive adhesive tape were determined and the 180 ° surface adhesion test on glass, the 180 ° surface adhesion test on biaxially oriented polypropylene (BOPP) and the shear force was carried out in the two directions of the low tissue (DW) and the transverse tissue (CW) .The results are indicated in Table 1.

Table 1 Table 1 (Continued) Examples Cl through '17 show the fibrilous to schistose morphology as determined by the laser light scattering test. As the data in Table 1 can be seen, the addition of the thermoplastic material components (ethylene vinyl acetate copolymers and ethylene methacrylic acid copolymers) to the acrylic pressure sensitive adhesive component increases the surface adhesion to the glass and / or the biaxially oriented polypropylene, and the shear force of the control adhesive (Cl) for Examples 1-4, 8, 9, 12 and 16. A simultaneous increase in surface adhesion and shear is unusual since most of the adhesives Pressure sensitive rubber / resin have a free exchange between these two properties. Improved properties begin to be present around 5% of the concentration of the thermoplastic material component. The improvement of the surface adhesion is the most pronounced for the examples containing ethylene vinyl acetate copolymers. The shear force was most pronounced for the examples containing ethylene copolymers of methacrylic acid. Examples 5-7, 10-11 and 13-15 demonstrate that a significant anisotropic surface adhesion can be obtained with a transverse tissue surface adhesion significantly greater than with the low tissue surface adhesion.

Examples 18-22 Examples 18 and 19 and 20 were made according to Examples 3 and 4 and 5, respectively, only that a component of different thermoplastic material, TENITE 1550P (a low density polyethylene, cutting viscosity - was added) 675 Pa-s, available from Eastman Kodak) to the pressure-sensitive adhesive component. Examples 21 and 22 were made according to Examples 1 and 2, respectively, except that a different thermoplastic material component was added, DOWLEX 2517 (a linear low density polyethylene, cutting viscosity - 280 Pa-s, available from Dow Chemical) to the pressure sensitive adhesive component. The viscosity ratio of the discontinuous or substantially continuous component and the thickness of the adhesive in the samples of each pressure-sensitive adhesive tape was determined and the surface adhesion test at 180 ° C in the glass, the 180 ° surface adhesion test C in biaxially oriented polypropylene (BOPP) and shear force were carried out in the two directions of the low tissue (DW) and the transverse tissue (CW). The results are indicated in Table 2 together with those of Comparative Example Cl.

Table 2 Examples 18-22 show the fibrilous morphology as determined by the light scattering test. As can be seen from the data in Table 2, the addition of the linear low density low density polyethylene thermoplastic material component to the acrylic pressure sensitive adhesive increases the surface adhesion to biaxially oriented glass and / or polypropylene and / or the shear force of the control adhesive (Cl) for Examples 19, 21 and 22. Examples 20-21 show an anisotropic behavior for all three properties.

Examples 23-29 and Comparative Examples C2 Examples 23-29 were made according to Example 1 except that one thickness of the pressure sensitive adhesive layer is different, the different thermoplastic material components and various proportions of the adhesive component were used. Pressure sensitive to the thermoplastic material component. In Examples 23-29 and Comparative Example C2, the thickness of the pressure sensitive adhesive layer was about 90 μm. In Examples 23 and 24, the FINA 3374X thermoplastic material component (a polypropylene, viscosity cut of 700 Pa-s, available from Fina Oil and Chemical) was added to the pressure sensitive adhesive component at the 90:10 proportions. and 85:15, respectively. Examples 25 and 26 were made according to Examples 23 and 24, respectively, except that the thermoplastic material component was ESCOPENE 3860 (a polypropylene, available from EXXON). Example 27 used DURAFLEX 0200 (one polybutylene, cutting viscosity - 682 Pa-s, available from Shell Chemical) and the ratio was 85:15. Examples 28 and 29 used the ethylene acrylic ester copolymer of PRIMACORE 1430, cut viscosity - 630 Pa-s, available from Dow Chemical) and the ratios were 92: 8 and 87:13, respectively. Comparative Example C2 was made with only the pressure sensitive adhesive component in the layer of the pressure sensitive adhesive composition. The viscosity ratio of the discontinuous to substantially continuous component of each pressure-sensitive adhesive tape was determined and the 180 ° surface adhesion test on glass, the 180 ° surface adhesion test on biaxially oriented polypropylene (BOPP) and strength Cutting was carried out in the two directions of the low tissue (DW) and the transverse tissue (CW). The results are indicated in Table 3 along with those of Comparative Example C2.

Table 3 Examples 23-29 show the fibrilous morphology as determined by the light scattering test. As can be seen from the data in Table 3, the addition of various components of polypropylene thermoplastic material to the acrylic pressure sensitive adhesive increased the surface adhesion to the glass and / or the biaxially oriented polypropylene and / or the shear strength of the adhesive control (C2) for Examples 23-29. Examples 23-27 and 29 show anisotropic behavior "for one or more of the three properties.

Examples 30-33 Examples 30-33 were prepared according to Example 1 Except that the temperature of zone 4 was 204 ° C, the different thermoplastic material components were used and the ratio of the pressure sensitive adhesive component to the thermoplastic material component was 85:15. In Examples 30 and 31, the thermoplastic component was Kodar 6763 (an amorphous polyester, cutting viscosity - 3150 Pa-s, available from Eastman Chemical Products) and Styron 615 (one polystyrene, cutting viscosity - 650 Pa-s, available from Dow Chemical), respectively. In Examples 32 and 33, the thermoplastic material component was Plexiglas VM 100 (a polymethyl methacrylate, cutting viscosity - 1900 Pa-s, available from Ato Haas) and PETROTHENE 3150B (a high density polyethylene, cutting viscosity - 340 Pa -s, available from Quamtum Chemical), respectively. The thickness of the pressure-sensitive adhesive layer was 64 μm.

The proportion of * viscosity of discontinuous component to substantially continuous surface adhesion test at 180 ° in glass, the test of surface adhesion in biaxially oriented polypropylene (BOPP) and the cutting force were carried out in the directions of the low tissue (DW) and transverse tissue (CW). The results are indicated in Table 4 together with those of Comparative Example Cl.

Table 4 Examples 30-33 show the fibrilous morphology as determined by the light scattering test. As can be seen from the data in Table 4, the addition of various other acrylic pressure-sensitive thermoplastic adhesive material components resulting in anisotropic surface adhesion to glass and / or biaxially oriented polypropylene and / or anisotropic shear force. The pressure sensitive adhesive layers of Examples 30-33 and Comparative Example Cl were also tested for tension and elongation properties using the stress and elongation test. Figure 1 depicts the tension staining curve for the directions of the lower fabric (DW) and the transverse fabric (CW) of Example 31. The performance stresses correspondingly for the direction of the low fabric of Examples 30-33 were 3.5 Mpa, 20.7 Mpa, 2.2 Mpa and 6.3 Mpa, respectively. The direction of the transverse tissue of Examples 30-33 did not have a yield stress but was natural elastomeric The elongation at break for Comparative Example Cl and Examples 30-33 in the low tissue direction was 1143%, 1125 %, 650%, 962% and 911%, respectively The elongation at break for Comparative Example Cl and Examples 30-33 in the cross-fabric direction was 845%, 1638%, 1775%, 1970% and 1797% , respectively.

When the hard or thick thermoplastic polymers were added to the acrylic pressure sensitive adhesive, the directional tension of the low tissue increases substantially, the elongation rupture of the lower fabric direction decreased while the elongation rupture of the transverse tissue direction increase. This leads to a clear break of the pressure sensitive adhesive when it is only used as a transfer adhesive tape.

Examples 34-35 and Comparative Examples C3-C4 Examples 34-35 were made according to Example 33 except that a different pressure sensitive adhesive component and a different thermoplastic material component were used. In Example 34 the pressure sensitive adhesive was similar to this in Example 33 except 0.3 part of acryloxybenzophenone, and the thermoplastic material was ELVAX 260. In Example 35, the pressure sensitive adhesive was HRJ 4326 (2-ethylhexyl acrylate, 10 Pa-s cut viscosity, available from Schenectedy International) and the thermoplastic material was ELVAX 240 The pressure sensitive adhesive tapes of Comparative Examples C3 and C4 were made as in Examples 34 and 35, except that they do not have a thermoplastic material component. The viscosity ratio of the discontinuous to the substantially continuous component of each pressure sensitive adhesive tape was determined and the 180 ° surface adhesion test on glass, the 180 ° surface adhesion test on biaxially oriented polypropylene (BOPP) and the Cutting force were carried out in both directions of the low tissue (DW) and the transverse tissue (CW). The results are indicated in Table 5.

Table 5 Examples 34-35 show the fibrilous morphology as determined by the light scattering test. As can be seen from the data in Table 5, the addition of thermoplastic material components to the acrylic pressure sensitive adhesives resulting in the anisotropic surface adhesion to the glass for Example 35 and the improved release of the glass for Example 34.

Examples 36-42 and Comparative Examples C5-C6 Examples 36-42 were made according to Example 1 except that a different pressure sensitive adhesive and a different thermoplastic material component are used at various proportions of the adhesive component sensitive to the pressure to the thermoplastic material component, and the thickness of the pressure sensitive adhesive composition varied. In addition, the pressure sensitive adhesive of any of the Examples contains a sticky material. The pressure sensitive adhesive used in Examples 36-2 and Comparative Examples C5-C6 was a pressure-sensitive adhesive suspension of polymerized acrylic in place of the polymerized adhesive of the water emulsion used in Example 1. The adhesive suspension pressure sensitive polymerized acrylic was prepared in accordance with US Patent No. 4,833,179 (Young et al.) as follows: A double-helix reactor equipped with a condenser, thermowell, nitrogen inlet, agitator driven by stainless steel motor, and a heat mantle with temperature control was charged with 750 g of deionized water, which was added to 2.5 g of zinc oxide and 0.75 g of hydrophilic silica (CAB-O-SIL EH-5, available from Cabot Corp.) and heated to 55 ° C while purging with nitrogen until the zinc oxide and silica have completely dispersed. At this point, a charge of 480 g of isooctyl acrylate, 20 g of methacrylic acid, 2.5 g of the initiator (VAZO 64, available from DuPont Co.) and 0.5 g of an isooctyl thioglycolate chain transfer agent are mixed. together. The resulting solution with the initiator and the chain transfer agent are then added to the initial aqueous mixture while maintaining a vigorous stirring (700 rpm) to obtain a good suspension. The reaction was continued with nitrogen purification for at least 6 hours, during which the reaction time was monitored to maintain a reaction temperature of less than 70 ° C. The resulting pressure sensitive adhesive was collected and dried to at least 90% solids by weight. In Examples 36-39, the "thermoplastic material component was Styron 615 and the ratio of the pressure sensitive adhesive to the thermoplastic material was 95: 5, 90:10, 90:10 and 80:20, respectively. pressure sensitive adhesive tapes of Examples 40-42 according to Example 36, respectively, except that the pressure sensitive adhesive further contained an aliphatic / aromatic C9 sticky material, ESCOREZ 2393 (available from EXXON) in an adhesive ratio pressure sensitive paxa a sticky material or 76:19, 76:19 and 64:16, respectively, and the thickness of the pressure-sensitive adhesive composition was approximately 46 μm, 30 μm and 33 μm, respectively. Comparative Examples C5 and C6 according to Example 36 except with only the pressure-sensitive adhesive component in the pressure-sensitive adhesive composition The thickness of the adhesive in the samples of each adhesive tape sensitive to pressure. the pressure, the 180 ° surface adhesion test on glass, the 180 ° surface adhesion test on biaxially oriented polypropylene (BOPP) and the shear force were carried out in the two directions of the low tissue (DW) and the tissue transverse (CW) The results are indicated in Table 6.

Table 6 Examples 36-42 show the fibrilous morphology as determined by the laser light scattering test. As can be seen from the data in Table 6, the addition of the thermoplastic material components to the different acrylic pressure sensitive adhesives resulted in the anisotropic surface adhesion to the glass and / or the biaxially oriented polypropylene and the anisotropic shear force. The properties of the pressure sensitive adhesive are not significantly dependent on the thickness over the test range as seen by Comparative Examples C5 and C6. The addition of a sticky material to the pressure sensitive adhesive component changes the higher surface adhesion values and decreased the anisotropic behavior.Examples 43-46 and Comparative Examples C7-C9 A mixing and coating apparatus for making pressure sensitive adhesives of natural and synthetic rubber is described in US Patent No. 5,539,033 which is incorporated herein by reference. In Examples 43-44, a synthetic rubber, NATSYN 2210 (synthetic polyisoprene, cutting viscosity - 1500 Pa-s, available from Goodyear), a tack, EXCOREZ 1310LC a plasticizer, mineral oil, and a component of thermoplastic material, STYPON 615 were melt blended in a co-rotating twin-screw extruder which meshes totally 30 mm in diameter - (Model ZSK 30, available from Werner-Pfleiderer, having a length at the diameter ratio of 47: 1). The two polymers elastomeric and thermoplastic were fed into zone 1 (barrel 1) of the extruder. The adhesive was fed into the slit in zone 2 (6-10% barrel) and zone 3 (8-90% barrel). The plasticizers were fed into the barrel 10. The temperature progressively increased from 60 ° C to 204 ° C from zone 1 to zone 5. The temperature of the remaining zones was maintained at 170 ° C. The screw speed was 200 revolutions per minute. The feed rates were adjusted to provide a pressure sensitive adhesive component with a ratio of synthetic rubber to tack for the plasticizer of 61: 32: 7 and a pressure sensitive adhesive composition with a proportion of the adhesive component sensitive to pressure to the thermoplastic component of 90:10 and 80:20 for Examples 43 and 44, respectively. The mixture was extruded on a 51 μm thick biaxially oriented terephthalate polyethylene film using a contact die with a rotating rod to form a pressure-sensitive adhesive tape having a thickness of the pressure-sensitive adhesive layer of 38 μm. μm. The film moves at 9 m / min. Examples 45-46 were made according to Examples 43-44, respectively, except that a natural rubber, (CV-60) was used instead of synthetic rubber. Comparative Examples C7-C9 were made according to Examples 43 and 45, respectively, except that no component of thermoplastic material was added. ~ Comparative Example C8 is Example 44 dissolved in toluene and coated on a 51 μM PET film. The thickness of the adhesive in the samples of each pressure-sensitive adhesive tape was determined, and the test of surface adhesion to 180 ° in glass, the test of surface adhesion to 180 ° in biaxially oriented polypropylene (BOPP) and the shear force were carried out in the two directions of the low tissue (DW) and the transverse tissue (CW). The results are indicated in Table 7.

Table 7 The examples 43-46 show the fibrilous morphology as determined by the laser light scattering test and is described in Figures 5 and 10 for Example 44 and Example 46, respectively. This was also confirmed by an SEM cryogenic fracture analysis of samples stained with osmium tetroxide and is described in Figures 3-4, and 8-9 for Example 44 and Example 46, respectively. As can be seen from the data in Table 7, the addition of thermoplastic material components to either synthetic or natural rubber pressure sensitive adhesives resulting in anisotropic surface adhesion to glass and biaxially oriented polypropylene. In addition, the anisotropic shear force was also observed. Figures 6 and 7 describe the spherical morphology for Comparative Example C8. This spherical morphology shows a low isotropic shear strength and surface adhesion as compared to the compositions of the invention.

Examples 47-50 and Comparative Examples ClO-Cll Examples 47-50 and Comparative Examples ClO-Cll were made according to Examples 43-46 and Comparative Examples C7 and C9, respectively, except that those were subsequently exposed to electron beam radiation. Samples of each tape were subjected to electron beam radiation using an ELECTROCURTAIN Model CB-175 (available from Energy Ciences Incorporated, Wilmington, MA) at an acceleration voltage of 125 kV. Irradiation was carried out in an inert nitrogen atmosphere at a calculated dose of 4.0 Mrads. The 180 ° surface adhesion test on glass, the 180 ° surface adhesion test on biaxially oriented polypropylene (BOPP) and the shear force were carried out in the two directions of the low tissue (DW) and the transverse tissue (CW) ). The results are indicated in Table 8.

Table 8 Examples 47-50 still show the fibrilous morphology as determined by the laser light scattering test. This was also confirmed by the SEM cryogenic fracture analysis of the samples stained with osmium tetroxide. As can be seen from the data in Table 8, the shear forces generally lift the subsequent crosslinking and decrease the surface adhesions but do not significantly change the anisotropic properties.

Example 51 and Comparative Example C12 In Example 51 and Comparative Example C12, the pressure sensitive adhesive tapes were prepared as in Example 37 and Comparative Example C5, except that the thickness of the pressure-sensitive adhesive layer was 58 μm and a different substrate was used. The substrate was a non-occlusive, ie breathable, support fabric having a 180 x 48 plain weave acetate taffeta fabric, 75 fiber diner in the warp direction and 150 fiber diner in the direction of the plot, available from Milliken and Co. , Spartamburg, GA. The pressure-sensitive adhesive tapes were tested in both directions of the DW and the CW for adhesion to the skin immediately after application, T0, and after 48 hours, T48, the removal of adhesion to the skin after 48 hours and the residue of adhesion to the skin after 48 hours. The results are indicated in Table 9.

Table 9 As can be seen from the data in Table 9, the pressure sensitive adhesive tapes of Example 51 have an anisotropic skin release performance for TQ: 48 adhesion and have been controlled by an appropriate blend of the acrylic adhesive component and the thermoplastic component. Thus the tape is easily removed from the skin when it is pulled in one direction but has a good holding power.

Examples 52-57 and Comparative Examples C13-C14 The adhesives of the invention can control the rate of drug release of a multilayer transdermal drug delivery device as demonstrated by the method described below. The adhesive control rate used in these test patches of Examples 52-57 and Comparative Examples C13-C14 were made according to Examples 30, 32, 33, 34, 37 and 42 and Comparative Examples C13-C14, respectively, except that each adhesive was applied to a release paper. Each test patch consists of 4 layers: a reinforcement, a first layer of adhesive containing medicine, a second adhesive layer to provide a proportion control, and a release liner. The acrylate adhesive copolymer (57.5 / 39 / 3.5 p / p / p isooctyl acrylate / acrylate 2-hydroxyethyl / ELVACITE (ICI Acrylics) 1020 polymethylmethacrylate macromonomer 50% solids in ethyl acetate) and phenobarbitol was combined after mixing to provide a homogeneous coating formulation. The formulation was covered over a reinforcement (1109 SCOTCHPAK tanner, laminated polyester film, available from 3M Company) then dried at 43 ° C for 15"minutes.The resulting coating contained 5 weight percent phenobarbital and had a thickness 127 μm The exposed surface was laminated to a layer of the proportion control adhesive of the invention carried in a release coating.The test patches (above, 5 cm 2) are die cut from the resulting laminate. the release of the drug from the periphery of the patch, each test patch was concentrically aligned with an adhesive cover.An adhesive cover (about 25 cm3, a layer of 25 μm polyisobutylene coated with a reinforcement) was laminated the patch reinforcement of test such that the patch and cover were aligned concentrically.The release liner was removed from the test patch.A ring-shaped cover (25 cm2 , with an inside diameter of 22 mm, a 25 μm layer of polyisobutylene coated with a reinforcement) was centered on the laminated test pad / cover, then the adhesive surfaces were laminated together to provide a seal around the periphery of the test patch. The release liner was placed behind the test patch, then the entire assembly was die cut "(about 12.5 cm" -) so that the test patch is centered. The assembly is sealed by heating in a laminated bag and allowing equilibration for 8 days. The assembly is then removed from the bag and attached to one end of a glass plate with a double coated tape, so that the reinforcement of the assembly comes into direct contact with the double coated tape. The release liner is removed from the test patch. The slide of the glass is suspended in a 120 ml high-form glass bottle equipped with a magnetic stirrer. A release solution was prepared by combining 6 1 MPLC of water grades; 2.2835 g of sodium phosphate, monobasic monohydrate; 9.7538 g of sodium phosphate, dibasic heptahydrate; and 46.4502 g of sodium chloride. A 100 ml portion of a 32 ° C release solution was added to the bottle. The test patch is completely submerged in the release solution. The bottle was covered, then placed in a temperature controlled chamber at 32 ° C. The release solution was stirred throughout the experiment. At specified time points (1 hr, 6.5 hr, 24 hr, 72 hr, 168 hr, and 336 hr), the cover was removed and a sample of "1.0 ml of the release solution was removed and placed in a vial of HPLC sample The phenobarbitol content of the sample was quantified using liquid chromatography performing a high reverse phase (LC1 Plus Module water; column: 15 cm X 4.6 mm inner diameter Supelcosil LC-ALZ, 5 particle size 5 μm; mobile phase: 75% / 25 mM of potassium phosphate monobasic buffer / 25% acetonitrile v / v, flow rate: 2.0 ml / min, detector: uv, 254 nm to 0.005 AUFS, execution time: 10 minutes; injection volume 20 μl.) The percentage of release was obtained using the following equation: where: [C (100 - (/ - l)] +? Ca_I] R, = at x 100_ (TC x S .A.) Where: Ri = percentage of phenobarbitol released from the sample a time point "i" i = number sequential time point (values: 1, 2, 3 ... n) Ci = sample concentration (μg / ml) HPLC analysis at time point J Co = 0 TC = theoretical phenobarbitol content in μg / cm2 SA = surface area of the test patch in cm2 The table below shows the thickness of the ratio control adhesive and the cumulative percentage released for each time point, each value being the average of the determinations for four separate test patches.

Table 10 The diffusion rate of a medicament can be varied by the addition of another thermoplastic component substantially immiscible to a pressure sensitive adhesive where the minor component forms the discrete domains having a fibrilous to schistose morphology. This increases the differential adsorption and desorption effects of the two polymeric domains with a tortuous path caused during the formation of the proportion controlling the adhesive layer.

Example 58 and Comparative Examples C15-C17 The adhesives of the invention containing thermoplastic elastomeric components that can control the release rate of the medicament of a multi-layer transdermal drug delivery device as the method shown below. In Example 58, the pressure sensitive adhesive component of polymerized acrylic suspension of water described in Example 36 was melt blended with a thermoplastic elastomeric adhesive component (prepared by mixing 50 part of the KRATON thermoplastic elastomeric block copolymer D1107P , 1 part of IRGANOX 1010 antioxidant and 50 parts "of ESCOREZ 1310LC sticky resin) in a co-rotating twin-screw extruder, Model ZSK 30, having 30 mm barrel diameter and a length to diameter ratio of 37: 1 with the acrylic adhesive for the thermoplastic elastomeric adhesive ratio which is 50:50, respectively.The thermoplastic elastomeric block copolymers are fed in zone 1, the sticky resin in zone 2 and the acrylic pressure sensitive adhesive in zone 3. Temperatures between 249 ° C and 165 ° C were maintained. The resulting pressure-sensitive adhesive composition was applied to the Berar the papers such that the adhesive layer was 51 μm thick. In Comparative Example C15, the pressure sensitive adhesive was prepared using only the acrylic adhesive of Example 58. In Comparative Example C16, the pressure sensitive adhesive was prepared as follows. The acrylate adhesive in example 36 was dissolved in a 90/10 heptane / isopropyl alcohol mixture at 20% solids. The KRATON 1107 thermoplastic elastomer and the ESCOREZ 1310LC adhesive were dissolved in a 50/50 mixture in toluene at 50% solids.

The 50/50 ratio of the acrylate / sticky thermoplastic elastomer was prepared by combining the appropriate amounts of acrylate adhesive and the Kraton adhesive mixture.The pressure sensitive composition in solvent was knife coated and dried. dry coating was 51 μm Drying conditions were 5 minutes at 43 ° C, 2 minutes at 85 ° C and 2 minutes at 107 ° C. In Comparative Example C17, the pressure sensitive adhesive was prepared using only the sticky thermoplastic elastomer component of Example 58. Each test patch consisted of 4 layers: a reinforcement, a first adhesive layer containing medicament, a second adhesive layer to provide proportion control, and a release coating. acrylate (59/39/2 p / p / p isooctyl acrylate / 2-hydroxyethyl acrylate / ELVACITE (Acrylics ICI) polymethylmethacrylate macromonomer 1020 51.9% solids in 95/5 ace ethyl acetate / isopropanol) and phenobarbital were then combined to mix to provide a homogeneous coating formulation. The formulation was coated with a reinforcement (1109 SCOTCHPAK tanning agent, laminated polyester film, available from 3M Company) then dried at 43 ° C for 15 minutes. The resulting coating contains 8 percent by weight of phenobarbital and has a thickness of 15 millimeters (382 μm). The exposed surface was laminated to a 2 millimeter (51 μm) layer of a proportion control adhesive carried in a release coating. The test patches (about, 5 cm2) were die-cut from the resulting laminate. To prevent drug release from the edge of the patch, each test patch was fitted with an adhesive cover. An adhesive cover (about 25 cm 2, a 1 mm (25 μm) layer of polyisobutylene coated with a reinforcement) was laminated to the test patch reinforcement such that the patch and covers were concentrically aligned. The release liner was removed from the test patch. A ring-shaped cover (25 cm2, with an inner diameter of 22 mm, a 25 μm layer of polyisobutylene coated with a reinforcement) was centered on the test pad / laminated cover, then the adhesive surfaces were laminated together to provide a seal around the periphery of the test patch. The release liner was placed behind the test patch, then the entire assembly was die cut (about 12.5 cpr) so that the test patch was centered. The assembly was heat sealed in a laminated bag and allowing equilibration for 8 days. The assembly is then removed from the bag and fixed to one end of a glass plate with a double coated tape, so that the reinforcement of the assembly is in direct contact with the double coated tape. The release liner is removed from the test patch. The sliding glass was suspended in a 120 ml high-form glass flask equipped with a magnetic stirrer. A release solution was prepared by combining 6 1 HPLC of water grades; 2.2835 g of sodium phosphate, monobasic monohydrate; 9.7538 g of sodium phosphate, dibasic heptahydrate; and 46.4502 g of sodium chloride. A 100 ml portion of a 32 ° C release solution was added to the bottle. The test patch was completed by immersing it in the release solution. The bottle was covered, then placed in a temperature controlled chamber at 32 ° C. The release solution was stirred throughout the experiment.

At the specified time points (1 hr, 4 hr, 8 hr, 24 hr, 97.5 hr, 168 hr, 264 hr and 336 hr), the cover is removed and the 1.0 ml sample of the release solution is removed and was placed in an HPLC sample vial. The phenobarbital content of the sample is quantified using reverse phase liquid chromatography (LC1 Plus Module water: column: 15 cm X 4.6 mm inner diameter of Supelcosil LC-ABZ, particle size 5 μm, mobile phase: 75% / 25 M potassium phosphate monobasic buffer / 25% acetonitrile v / v, flow rate: 2.0 ml / min, detector: uv, 254 nm to 0.005 AUFS: execution time: 10 minutes, injection volume 20 μl) . The percentage released was obtained using the following equation: R, = a = lx 100 (TC X SA) where: Ri = percentage of phenobarbitol released from the sample a time point "i" i = sequential number of the time point (values: 1, 2, 3 ... n ) Ci = concentration "of sample (μg / ml) HPLC analysis at the time point J Co = 0 TC = theoretical phenobarbitol content in_ μg / cm2 SA = surface area of the test patch in cm2 The following table shows the identity of the adhesive used in the proportion control layer and the cumulative percentage released for each time point, each value is the average of the determinations for four separate test patches.

Table 11 The diffusion rate of a medicament can be varied by the addition of another thermoplastic component substantially immiscible to a pressure sensitive adhesive where the minor component forms the discrete domains having a fibrilous to schistose morphology. As observed by comparing Example 58 to Comparative Example C16, the fibrilous to schistose morphology enhances the differential adsorption and desorption effects of two polymeric domains with a tortuous path caused during the formation of the proportion controlling the adhesive layer.

EXAMPLE 60 In Example 60, a pressure sensitive adhesive component as described in Example 36 was melt blended in a co-rotating twin screw extruder which meshes totally 30 mm in diameter (Model ZSK-30, available from Werner &Pfleiderer Corp., Ramsey, NJ, which has a length for the diameter ratio of 36: 1) with a similar process that is described in Example 19 of U.S. Patent No. 5,539,033. The configuration of the screw used was the same as shown in Figure 4 of the North American Patent No. 5,539,033. The elastomeric polymer, NATSYN 2210 is added in zone 1. The acrylic pressure sensitive adhesive was added in zone 9. The elastomer for the acrylic pressure-sensitive adhesive ratio was 50:50. The screw speed was 475 rpm. Air was injected into zone 3 and the temperature was maintained at 133 ° C to reduce the molecular weight of the elastomer to make it more processable to hot melt. The temperature of the die was 15 ° C. The pressure sensitive adhesive was applied as a 42 μm thick layer on a 30 μm thick polyethylene terephthalate film moving at 9.1 m / min. The pressure-sensitive adhesive layer was essentially non-granular, sticky to the touch, and exhibits fibrilous morphology as determined by the light scattering test.

Examples 61-64 and Comparative Examples C18-C19 Examples 61-64 and Comparative Examples C18-C19 were prepared according to Examples 43-46, and Comparative Examples C7-C9. In Examples 61, a synthetic rubber, TAKTENE 220 (synthetic polybutadiene, available from Bayer), an adhesive, PICCOLYTE A135, (available from Hereules) and a thermoplastic component, ELVAX 220, (available from DuPont) were mixed to give a rubber final for the resin to the thermoplastic ratio of 10: 11.5: 1.5. Example 62 was prepared according to Example 61, except that the thermoplastic component was ELVAX 660, (available from DuPont) to provide a final rubber for the resin at the thermoplastic ratio of 10: 11.5: 2. Example 63 was prepared according to Example 61, except that the thermoplastic component was replaced with an elastomer, a natural rubber (available as SIR 3 CV60 from Goodyear) to give a final gum for the resin at the elastomer ratio of 10. : 11.5: 1.5. Comparative Example C18, was prepared according to Example 61, except that no additional component was added, to give a final rubber at the resin ratio of 10: 11.5. Example 64 was prepared according to Example 61, except that the PICCO 5120 adhesive (available from Hercules), and the thermoplastic was replaced with a thermoplastic elastomer, KRATON 1107 (available from Shell) to provide a final rubber for the resin at the thermoplastic ratio 10: 11.5: 1. Comparative Example C19, was prepared according to Example 64, except that no additional component was added, to give a final rubber for the resin ratio of 10: 11.5. Each adhesive was coated to a thickness of 0.076 mm and subjected to electron beam radiation using an ELECTROCURTAIN Model CB-175 (available from Energy Sciences Incorporated, Wilmington, MA) at an acceleration voltage of 175 kV. Irradiation was carried out in an inert nitrogen atmosphere at a calculated dose of 6.5 Mrads. The 0.076 mm thick adhesive samples were laminated to a 0.05 mm thick polyester film and tested for the surface adhesion test at 180 ° C to the steel, shear strength test at 50 ° C, and the surface test at 4 ° C for concrete. The results are outlined in Table 12.

Table 12 The 0.076 mm thick adhesive samples were laminated to a thickness of 0.152 mm and tested by shear compression tests. The results are outlined graphically in Figure 16. As the data in Table 12 and Figure 16 show, the addition of a second, immiscible polymer in the pressure sensitive adhesive system that can substantially improve the strength of the adhesive system pressure sensitive for the types of impact cutting seen by pavement marking materials. This is done in most cases with small effects on adhesion properties.

Example 65 and Comparative Example C20 Example 65 and Comparative Example C20 were prepared according to Examples 43-46, and Comparative Examples C7-C9. In Example 65, natural rubber, (available as SIR 3 CV60 from Goodyear) an adhesive, PICCOLYTE S115, (available from Hercules) and a thermoplastic component, ELVAX 220, (available from DuPont) were mixed to give a final rubber to the resin at the thermoplastic ratio of 10: 11.5: 2. Comparative Example C20, was prepared according to Example 65, except that no additional component was added, to give a final rubber at the resin ratio of 10: 11.5. Each adhesive was coated with a thickness of 0.21 mm.

The 0.21 mm adhesive samples were laminated to 0.05 mm film thickness of the polyester film and tested by the 180 ° surface adhesion test to the steel, the shear strength test at 50 ° C, and the surface test at 4 ° C for concrete. The results are outlined in Table 13.

Table 13 Adhesive samples 0.21 mm thick were tested by the compression compression tests. The results are outlined graphically in Figure 17.

As the data in "Table 13 and Figure 17 show, the addition of a second, immiscible polymer in the pressure-sensitive adhesive system that can substantially improve the strength of the pressure-sensitive adhesive system for types of impact cut observed by pavement marking materials Even when surface adhesion drops at 4 ° C, surface adhesion to steel and shear forces at 50 ° C improve.

Examples 66-68 and Comparative Examples C21-C22 Examples 66-68 and Comparative Examples C21 -C22 were prepared according to Examples 43-46, and Comparative Examples C7-C9. In Example 66, a synthetic rubber, TAEXTENE 220 (synthetic polybutadiene, available from Bayer), an adhesive, PICCOLYTE A135, (available from Hercules) and a thermoplastic component, ELVAX 220, (available from DuPont) were blended to give a final rubber for the resin at a thermoplastic ratio of 10: 11.5: 1. Example 67 was prepared according to Example 61, except that the thermoplastic component was replaced with an elastomer, natural rubber (available from SIR 3 CV60 from Goodyear) to give a final rubber for the resin at an elastomeric ratio of 10: 11.5: 3. Comparative Example C21, was prepared according to Example 66, except that no additional component was added, to give a final rubber at the resin ratio of 10: 11.5. Example 68 was prepared according to Example 66, except that the adhesive was PICCO 5120 (available from Hercules), and the thermoplastic was replaced with a thermoplastic elastomer, KRATON 1107 (available from Shell) to give a final rubber for the resin to the thermoplastic ratio of 10: 11.5: 1. Comparative Example C22, was prepared according to Example 64, except that no additional component was added, to give a final rubber at the resin ratio of 10: 11.5. Each adhesive was coated to .076 mm thick "and subjected to electron beam radiation using an ELECTROCURTAIN CB-175 (available from Energy Sciences Incorporated, Wilmington, MA) at an acceleration voltage of 175 kV. performed in an inert nitrogen atmosphere at a calculated dose of 3 Mrads.

The 0.076 mm thick adhesive samples were laminated to a thickness of 0.23 mm in STAMARK 5760 of the pavement marking tape (available from 3M) and tested by the simulation test used by a vehicle. The results are outlined in Table 14.

Table 14 Table 14 demonstrates the dramatic improvement in adhesive compositions containing a second, immiscible polymer, to improve the performance of signage applications for the pavement.

The various modifications and alterations of this invention will be clear to those skilled in the art without departing from the scope and spirit of this invention and this invention should not be restricted as indicated therein for illustrative purposes only.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers. Having described the invention as above, property is claimed as contained in the following:

Claims (3)

1. A pavement marking article characterized in that it comprises a mixture of at least one pressure sensitive adhesive component and at least one component of thermoplastic material which is immiscible with the pressure sensitive adhesive component at a temperature of use, composition includes (1) at least 40 weight percent of the pressure sensitive adhesive component and at least 5 weight percent of the thermoplastic material component and (2) a morphology comprising at least two distinct domains, a first domain is substantially continuous and a second domain is fibrilous to schistose, which has, if used alone, an impact cut resistance that is at least twice as high as that of the pressure sensitive adhesive component and has at least a pressure-sensitive adhesive property of the group consisting of (a) a higher surface adhesion if it will be used alone and a similar shear force of the pressure-sensitive adhesive component, (b) a higher shear force than if it were used alone and a surface adhesion similar to that of the pressure-sensitive adhesive component, (c) an anisotropic surface adhesion, (d) a force anisotropic shear, and (e) a tensile force in the direction of the low tissue that is at least 2 times greater than the tensile force in the direction of the transverse tissue for all elongations up to the elongation at break.

2. A flagging article characterized in that it comprises a mixture of at least one pressure-sensitive adhesive component and at least one component of thermoplastic, elastomeric material that is immiscible with the pressure-sensitive adhesive component at a temperature of use, the composition 'includes (1) at least 40 weight percent of the pressure sensitive adhesive component and at least 5 weight percent of the thermoplastic, elastomeric material component and (2) a morphology comprising at least two distinct domains, a first domain is substantially continuous and a second domain is fibrilous to schistose, which has, if used alone, an impact cut resistance that is at least two times greater than that of the adhesive component sensitive to pressure and has at least one adhesive property sensitive to the pressure of the group consisting of (a) a higher surface adhesion than if sun will be used oy a shear force similar to that of the pressure sensitive adhesive component, (b) a greater shear force than if it were to be used alone and a surface adhesion similar to that of the pressure sensitive adhesive component, (c) an anisotropic surface adhesion, ( d) an anisotropic shear force, and (e) a tension force in the direction of the tissue below which is at least 2 times greater than the tensile force in the direction of the transverse tissue for all elongations up to the elongation at break.

3. A pavement marking article characterized in that it comprises a mixture of at least one pressure-sensitive adhesive component and at least one component of elastomeric material that is immiscible with the pressure-sensitive adhesive component at a temperature of use, The composition includes (1) at least 40 weight percent of the pressure sensitive adhesive component and at least 5 weight percent of the thermoplastic material component and (2) a morphology comprising at least "two distinct domains. , a first domain is substantially continuous and a second domain is fibrilous to schistose, which has, if used alone, an impact cut resistance that is at least two times greater than that of the pressure sensitive adhesive component and has less a pressure-sensitive adhesive property of the group consisting of (a) a higher surface adhesion than if it were used alone and a similar shear force to the pressure sensitive adhesive component, (b) a greater shear force than if it will be used alone and a surface adhesion similar to that of the pressure sensitive adhesive component, (c) an anisotropic surface adhesion, (d) an anisotropic shear force, and (e) a force of tension in the direction of the low tissue which is at least 2 times greater than the tensile force in the direction of the transverse tissue for all elongations up to the elongation at break. Pressure Sensitive Mixed Adhesives SUMMARY OF THE INVENTION A pressure sensitive adhesive comprising a mixture of at least two components, wherein the first component is at least one pressure sensitive adhesive and the second component is at least one thermoplastic material, wherein the components form compositions which has more than one domain and, wherein one domain is substantially continuous (generally it is the pressure sensitive adhesive) and the other domain is substantially fibrilous to schistose (generally, the thermoplastic material). The second component can be (a) at least one thermoplastic elastomer, (b) at least one elastomer with at least one tackifying resin or (c) at least one elastomer.