MXPA97008137A - Segmented segmented polidiorganosiloxan-poliurea copolymer, adhesives, and process for your manufacture - Google Patents

Abstract

An adhesive composition comprising (a) a segmented polydiorganosiloxane polyurea copolymer comprising the reaction product of (i) at least one polyamine, wherein the polyamine comprises at least one polydiorganosiloxane diamine, or a mixture of at least one polydiorganosiloxane diamine and at least one organic polyamine, and (ii) at least one polyisocyanate, wherein the molar ratio of isocyanate to amine is between 0.9.1 and 0.95: 1 or between 1.05: 1 and approximately 1.3: 1, and ( b) silicate resins. Adhesive compositions are useful as pressure sensitive adhesives, particularly for foamed backing tapes, medical tapes and the like, hot melt adhesives, vibration dampers, anticorrosive materials.

Description

COPOLYMERS OF SEGMENTED POLIDIORGANOSILOXAN-POLYUREA, ADHESIVES AND PROCESS FOR ITS MANUFACTURE * TECHNICAL FIELD 5 This invention relates to segmented polydiorganosiloxane polyurea copolymers and a process for their manufacture.

BACKGROUND OF THE INVENTION Pressure-sensitive adhesive tapes have been used for more than half a century for a variety of marking, fastening, protection, sealing and masking. Pressure sensitive adhesive tapes comprise a backing, or substrate, and a pressure sensitive adhesive. Pressure sensitive adhesives are materials which adhere with no more pressure than the finger and are aggressively and permanently adhesive. The pressure sensitive adhesives do not require activation, exert a strong retention force and tend to be removable from a smooth surface without leaving residues. In some applications, the pressure sensitive adhesives of interest are silicone-based adhesives REP: 25863 Traditionally, polydiorganosiloxane pressure-sensitive adhesives have been made in solution. Conventional solvent based polydisorganosiloxane pressure sensitive adhesives are generally mixtures of high molecular weight silanol functional polydiorganosiloxanes, ie, polydiorganosiloxane rubbers, and silanol copolymerics functional silicate resin, ie, MQ resins, which they comprise units R3SiO? / 2 and units Si0 / 2. In order to obtain the desired adhesive properties, it has been necessary to react the copolymer silicate resin with the polydiorganosiloxane. Improvements in such properties of pressure sensitive adhesives are achieved when the copolymer polydiorganosiloxane resin and the polydiorganosiloxane are intercondensed, providing intra and intercondensation within the adhesive. The condensation step requires 1) the addition of a catalyst, 2) reacting the copolymer polydiorganosiloxane resin and the polydiorganosiloxane in solution, and 3) allowing the reaction to take place over a period of time at an elevated temperature. Solutions of pressure-sensitive adhesives of intercondensed polydiorganosiloxane are generally applied to a support, heated to move the solvent, and cross-linked, if necessary to improve physical properties. If reticular is necessary, peroxide catalysts are commonly used. Disadvantages of the applied pressure sensitive adhesive solution of polydiorganosiloxane include the need to make drying ovens to remove the solvent, and crosslinking if required, ovens that operate at temperatures above 140 ° C are required to initiate catalyzed crosslinking per diaryl peroxide. Such high temperature furnaces limit the usefulness of the substrate? in the manufacture of pressure sensitive adhesive tapes' to those that can withstand high temperatures. In the medical field, pressure sensitive adhesive tapes are used for many different applications in the hospital and health areas, but basically perform one of two functions. They are used to restrict movement, such as in various restraint applications, or are used to hold something in place, such as a healing or wound dressing. It is important in each function that the pressure-sensitive adhesive tape is docile with and does not irritate the skin and adhere well to the skin without causing damage to the skin upon removal. In recent years, pressure sensitive adhesives have been used in applications of transdermal patches such as drug transport membranes or to attach the drug transport membranes to the skin. Although there is a continuous development of new drugs and the need for different transport speeds of the * Existing drugs, pressure sensitive adhesives are still needed that can carry such drugs at various speeds. In addition, there is a continuing need to adhere 5 new drug transport membranes to the skin during a treatment period. In the automotive industry, there are applications that have not yet been addressed by the current m-tape products. One such application is related to the automotive paints and finishes that are formulated for environmental conservation, recyclability, improved appearance * improved durability, as well as resistance to sources of environmental contamination. The painted substrates that use these new formulations are difficult to adhere to the products of current tape. Another application involves mounting side frames to the automotive body of thermoplastic polyolefin. Similarly, the first electrical tapes were black abrasive tapes, and the adhesive was soft and often separated when unrolled. Current electrical tapes have a layer of pressure sensitive adhesive applied to a plasticized polyvinyl chloride support or a polyethylene support or rubber film. The electrical tape is used to isolate, retain, reinforce and protect electrical wires. Other uses include providing a matrix for varnish impregnation,? identify wires in electrical circuits, and protect terminals during the manufacture of electrical circuit boards. The electrical tape must be flexible, conformable and satisfy the requirements of anti-flammability. The corrosion protection materials must be distributed in a conformable form for their W optimum performance. The capacity of adhesives pressure sensitive to instantly bond to exposed surfaces is very useful for applying protective constructions and for the convenient repair of broken protective coatings associated with steel pipes and related structures subjected to corrosion. In those related applications, the material should not flow easily or wear easily. It is known that some of the properties of commercially available silicones provide some degree of protection against corrosion. For many thermal shrinkage applications, it is A single article capable of withstanding high temperatures and simultaneously providing an environmental seal is desirable. It is preferred that the adhesive be transparent, to allow to see the divided or protected region. The tubes that are thermally double-walled are usually tubes Co-extruded polyolefins (shrinkable sleeves) and EVA (for hot melt sealing) .The use of these products is limited by the rheology of the hot melt.The tubes that are thermally shrunk at high temperatures are generally They make fluorinated materials.

The hot melts used in materials are thermally double-walled can be from a wide range of materials, as described in US Pat. No. 4,509,820. However, no adhesives have been identified W ~ hot melt with satisfactory flow and stability of temperature for use in pipes at high shrinkage temperature. Preformed pavement marking materials "include pavement marking sheet materials and raised pavement markers that are used as road markers and passed pedestrians. They are often reflective and strategically oriented to increase reflective efficiency when illuminated by the headlights of a vehicle at night. Marking materials must adhere to a variety of surfaces such as concrete or asphalt, which can be cold, hot, oily, moist, rough or smooth. Current pavement marking adhesives generally have inadequate initial bonding or inadequate permanent bonding to surface surfaces. roads, which is illustrated in five problem areas: (1) adhesive bonding limited to cold temperatures giving as Y ^ resulted in a narrow application window, (2) reduced durability under cut or impact making the removal of temporary marks difficult, (3) low molecular weight fractions in the adhesives on the removable marks that have the concrete surfaces with a clear color, (4) delimited ductility allowing the marks to rise sometimes when breaking after the impact with the tires of - a vehicle and (5) insufficient elasticity for fill the10 spaces between the marks and rough road surfaces, thus leading to a premature detachment of the road surface marking. Hot melt adhesives are compositions that can be used to join non-hot surfaces adhesive in one composition. During application to a substrate, hot melt adhesives should be sufficiently fluid to wet the surface completely and not leave gaps, even if the surface is rough. Consequently, the adhesive must be low viscosity at the time of application. However, the bonded adhesive generally solidifies to develop sufficient cohesive strength to remain adhered to the substrate under high stress conditions. For hot melt adhesives,.

Fluid to solid transition can be achieved in several ways. First, the hot melt adhesive can cause the thermoplastic to soften and melt when heated and harden again when cooled. Such heating results in a sufficiently high fluidity for achieve a successful humidification. Alternatively, the hot melt adhesive can be dissolved in a solvent or carrier that lowers the viscosity of the adhesive sufficiently to allow satisfactory wetting and increases the adhesive viscosity when the solvent or carrier be removed. Such adhesive can be thermally activated, if necessary. Damping is the dissipation of mechanical energy as heat by a material in contact with the source of such energy. The temperature range and the range of The frequency at which damping occurs can be very broad, depending on the particular application. For example, to cushion tall buildings that experience oscillations due to weather or seismic vibrations, the frequency range may be as low as approximately 0.1 Hertz (Hz) up to about 10 Hz. The higher frequency damping applications can be those such as for computer disk drives (of the order of 1000 Hz) or higher frequency applications (io, 000 Hz) • In addition , outdoor damping applications expose the damping treatment to a wide range of temperature and humidity. Although the operation of a surface layer damping treatment depends to a large extent on the dynamic properties of the material, it also depends on other parameters. The geometry, rigidity, mass, and form of combination of the cushioning material and the structure to which it is applied will affect the performance of the cushion Jtt material. The viscoelastic materials hitherto known consist of a single component or polymer blends. Since the single-component viscoelastic materials known hitherto operate on very narrow temperature ranges, conventional solutions at wide temperature variations incorporate multiple layers of viscaelastic material, with each of the layers being optimized for a different temperature range. .

BRfeVfe DESCRIPTION OF THE. INVENTION The present invention provides compositions comprising (a) oleate compositions of segmented polydiorganosiloxane polyurea comprising the product of the reaction of (i) at least one polyamine, Wherein the polyamine comprises at least one polydiorganosiloxane diamine, or a mixture of at least one polydiorganosiloxane diamine and at least one organic amine, and (11) at least one polyisocyanate, wherein the molar ratio of isocyanate to amine is between 0.9: 1 and 0.95: 1 and between 1.05: 1 and 5 about 1: 3: 1, and (b) silicate resins. The composition may optionally contain the product of the addition reaction of at least one polydiorganosiloxane monoamine and at least one polyisocyanate and optionally fm polydiorganosiloxane diamine. The compositions can also Optionally contain additives such as fillers, pigments, stabilizers, plasticizers, organic adhesives, antioxidants, compatibilizers and the like. The composition can also have vibration dampers, PSA, hot melt, and characteristics of protection against corrosion. The present invention further provides a segmented polydiorganosiloxane polyurea copolymer composition, adhesive comprising (a) a polydiorganosiloxane polyurea copolymers segmented with units of soft polydiorganosiloxane and alternating hard polyisocyanate residue units, (wherein the polyisocyanate residue is the polyisocyanate minus the -NCO groups), and optionally, soft and / or hard organic polyamine units, so that the residues of the units of amine e isocyanate are connected by urea bonds. The compositions of the present invention typically have inherent viscosities of at least 0.8 dL / g, or are essentially insoluble in common organic solvents, such as, for example, chloroform, tetrahydrofuran, 5-dimethyl formamide, toluene, isopropyl alcohol, and combinations thereof, and (b) silicate resin. The composition may optionally contain the addition product of at least one polydiorganosiloxane monaamine and at least one polyisocyanate and optionally polydiorganosilaxan diamine. The composition may also have characteristics of vibration damping, PSA, hot melt, and corrosion protection. The compositions of the present invention are particularly useful as pressure sensitive adhesives And in one aspect of the present invention, pressure sensitive adhesives (PSA) can be used to make PSA articles, wherein the PSA articles comprise a flexible substrate and a PSA layer prepared according to the present invention. In addition, the substrate can be any The substrate may be known to those skilled in the art, may be pre-made or co-extruded with the PSA, and may further be coated or treated to provide a low energy release surface, such as a coating with a low adhesion size, a similar removable coating. In addition, the substrate can be made of a low surface energy material, such as, TEFLON "11 and polyolefins Particularly useful items include medical tapes, transdermal drug delivery systems, corrosion protection tapes and pavement markers. In another aspect of the present invention, hot melt residues such as bars, sheets, prepared granules and the like can be used which can be subsequently applied in a molten state or thermally activated to produce an adhesive bond between different substrates. may be known to those skilled in the art and the invention could be especially useful for adhering low surface energy materials and electronic components.The segmented polydiorganosiloxane polyurea copolymer pressure sensitive adhesives of this invention provide superior corrosion protection to substrates. metallic coughs and ease of application. They also offer the right combination of viscosity, thermal stability and transparency for thermal shrinkage applications. The present invention also provides a vibration dampening composition comprising at least one substrate and at least one layer of the composition of the present invention. The substrate may be flexible, hard, or rigid. In addition, the substrate can be any substrate that W may be known to those skilled in the art and may additionally be coated or treated to provide a low energy release surface, such as a coating with a low adhesion size, a release liner and the like. Such compositions can be a constrained layer construction, wherein the construction comprises at least one substrate that has a sufficient stiffness to cause the É resonance within the substrate in response to a force applied internally or externally and at least one layer of the composition of the present invention. The restricted layer construction preferably has a factor, so S greater than or equal to 0.40 in the temperature range of between about -80 and 150 ° C and in the frequency range fifteen - . 15 - from 0.01 to 100,000 Hz as evaluated by a Mark II Thermal Analyzer from Polymer Laboratories Dynamic Mechanical in the cutting mode. The useful temperature range depends both on the frequency and on the characteristics of the buffer composition. In another aspect, the construction of the composite article may be such as to provide a constrained layer construction that dampens bidirectional vibration, comprising at least two annular members, and at least one layer of the composition of the present invention. By way of Generally, each annular member has a stiffness that exceeds that of a 0.25 cm steel plate. Preferably, the composition which dampens the vibration has a tan d greater than or equal to 0.4 in the temperature range of -80 ° C and 150 ° C and in the frequency range of 0.1 to 10 Hz, of 5 to that evaluated by a Mark II Thermal Analyzer from Polymer Laboratories Dynamic Mechanical in the cutting mode. Advantageously, articles formed can be produced, for example, by techniques such as molding by * compression, injection molding, casting, calendering and extrusion. The compositions of the present invention have the excellent physical properties typically associated with polydiorganosiloxane polymers such as moderate thermal and oxidative stabilities, resistance to UV, low surface energy and hydrophobicity, resistance to k- degradation of exposure to heat and water, good dielectric properties, good adhesion to substrates of low surface energy, low refractive index, and flexibility at low temperatures. In addition, the compositions exhibit a combination of unexpected properties including, for example, excellent mechanical strength after cooling, which allow subsequent operations to contact the surface directly after the compositions have been applied, excellent Shock-absorbing operation of a wide temperature range, and ability to resist such elongation, excellent adhesion to a variety of substrates when formulated for adhesives, and handling characteristics that allow to easily obtain the desired thicknesses and shapes. The compositions of the invention have good resistance to environmental conditions and good performance over a wide range of frequency and flf temperature. The compositions that dampen the vibration of The present invention has wide utility for minimizing adverse vibration in layer-restricted damping treatments as well as for minimizing the minimum oscillation due to wind and adverse seismic influences in buildings subjected to large distances. variations of temperature and humidity. The polyurea functionality of the polydiorganosiloxane-based compositions allows the formulation to take advantage of the thermally dissociable crosslinks that are formed via the hydrogen bonds of the functional groups urea in the polymeric skeleton. These crosslinks are thermally dissociated during the hot melt process to allow the coating and can be reformed after cooling to restore the original mechanical properties without the need for agents additional crosslinkers.

The present invention further provides a method for manufacturing a bondable processable composition comprising the steps of mixing a polyamine with a polyisocyanate in a hot container, until both react to make the segmented polydiorganosiloxane urea copolymer and add a silicate adhesive resin. The process is preferably carried out under substantially solvent-free conditions. The V silicate adhesive resin can be added at any point in the process, from preferably before or during the reaction step, and more preferably before the reaction step. Optionally, the silicate adhesive resin can be added later to the polydiorganosiloxane polyurea segmented copolymer which reacted eh solution.

P The substantial elimination of the solvent in the process of the present invention has many advantages which involve the environment, economy and safety. This process without solvent is environmentally advantageous since it is not evaporate solvents from the final composition. The continuous nature of this process has several other inherent advantages over the conventional solution polymerization process. The ratio of isocyanate to amine can be varied downwards and, most notably, upwards of 1: 1 to optimize the properties obtaining still strong, extrudable materials. Another advantage of this process is the ability to use high molecular weight segmented polydiorganosiloxane polyurea copolymers which can not be obtained using the solution polymerization processes due to the insolubility of the polymer formed in the solvent medium or the excessively high viscosities in the solvent. practical solution concentrations. Another advantage of this continuous process, substantially without solvent, is the ability to add or mixing, in-line, the silicate resin, as well as various fillers, and other property modifiers in the polydiorganosiloxane polyurea copolymer segmented before, during, or after the formation of the copolymers. Optionally, non-reactive additives such as fillers, plasticizers, pigments, stabilizers, antioxidants, flame retardants, co-catalysts can be added and similarly they can be added at any point in each of the above processes.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a perspective view of a bidirectional vibration damper of the present invention.

Figure 2 is a cross-sectional view of an i? transdermal matrix device of the present invention. Figure 3 is a cross-sectional view of a transdermal reservoir device of the present invention. Figure 4 is a cross-sectional view of a transdermal drug adhesive device of the present invention. mf Figure 5 is a cross-sectional view of up multi-layered, transdermal device of the present invention. Figure 6 is a cross-sectional view of an alternative embodiment of the transdermal multiple-layered device of the present invention. 15 DESCRIPTION OF THE PREFERRED MODALITIES * The segmented polydiorganosiloxane polyurea copolymers of the invention can be represented by the repeated unit: (D wherein each R is a portion that is independently an alkyl portion, which preferably has from about 1 to 12 carbon atoms and can be substituted with, for example, trifluoroalkyl or vinyl groups, a vinyl radical or a higher alkenyl radical preferably represented by the formula -R2 (CH2) aCH = CH2 wherein R2 is - (CH2) b- or - (CH2) CCH = CH- is already 1, 2 or 3; b is 0, 3 m or 6; and c is 3, 4 or 5; a cycloalkyl portion that has approximately 6 to 12 carbon atoms and can be substituted with alkyl, fluoroalkyl and vinyl groups, or an aryl portion which preferably has from about 6 to 20 carbon atoms and which can be substituted with, for example, alkyl groups, cycloalkyl, Fluoroalkyl and vinyl or R is a perfluoroalkyl group as described in US Patent No. 5,028,679, wherein such a description is incorporated herein by reference, a group containing fluorine, as described in US Patent No. 5,236,997, in US Pat. where such description is incorporated herein by reference, or a group containing perfluoroether, as described in U.S. Patent Nos. 4,900,474 and 5,118,775, wherein such descriptions are incorporated herein by reference; preferably at least 50% of the portions are radicals Methyl, the rest being monovalent substituted alkyl or alkyl radicals having from 1 to 12 carbon atoms.

"Wmpw carbon, alkenylene radicals, phenyl radicals or substituted phenyl radicals; each Z is a polyvalent radical that is a -aralkylene radical or an aralkylene radical which preferably have from about 6 to 20 carbon atoms, an alkylene or cycloalkylene radical which preferably have from about 6 to 20 carbon atoms.

Wf carbon, preferably Z is 2,6-tolylene, 4,4'-methylenediphenylene, 3,3'-dimethoxy-4,4'-biphenylene, tetramethyl-m-xylylene, 4,4-methylenedicyclohexylene, , 5, 5-trimethyl-3-methylenecyclohexylene, 1,6-hexamethylenes, 1, -cyclohexylene, 2, 2, 4-trimethylhexylene, and mixtures thereof; each Y is a polyvalent radical which is independently an alkylene radical of 1 to 10 carbon atoms, an aralkylene radical or an arylep radical, which preferably have from 6 to 20 carbon atoms; each D is selected from the group consisting of hydrogen, an alkyl radical of 1 to 10 carbon atoms, phenyl, and a radical that completes an annular structure including B or Y to form a heterocycle; B is a polyvalent radical selected from the group consisting of alkylene, aralkylene, cycloalkylene, phenylene, polyalkylene oxide, including for example, polyethylene oxide, polypropylene oxide, ^ polytetramethylenes, and copolymers and mixtures thereof; m is a number that is 0 to about 1000; n is a number that is equal to or greater than 1; and 5 p is a number that is about 10 or greater, preferably from about 15 to 2000, more preferably from about 30 to 1500. In the use of polyisocyanates (Z is a radical that flr * has a higher functionality than 2) and the polyamines (B is a The radical having a functionality greater than 2), the structure of Formula I will be modified to reflect L branching in the polymer backbone. The polydiorganosiloxane dismines useful in the process of the present invention can be represented by the formula wherein each of R, Y, D, and p are as defined above. Generally, the number average molecular weight of the polydiorgansysxan diaxamines useful in the present invention is greater than about 700.

The polydiorganosiloxane diamines (also known as silicone diamines) useful in the present invention are any that fall within the above Formula II and include those which have molecular weights in the range of about 700 to 150,000. Polydiorganosiloxane diamines are described, for example, in U.S. Patent No. 3,890,269, U.S. Patent No. 4,661,577, U.S. Patent No. 5,026,890, U.S. Patent No. 5,276,122, each of which is incorporated herein by reference. incorporated herein by reference, and International Patent Publication No. WO 95/03354. Polydiorganosiloxane diamines are commercially available from, for example, Shin Etsu Silicones of America, Inc., Torrance, CA and Hüls America, Inc. Polydiorganosiloxane are preferred. substantially pure diamines prepared as described in US Patent No. 5,214,199 which is incorporated herein by reference. Polydiorganosiloxane diamines having such high purity are prepared from the reaction of cyclic organosilanes and bis (aminoalkyl) disiloxans using an anhydrous amino alkyl functional silanolats catalyst such as tetramethylammonium-3-aminopropyldimethyl silanolate, preferably in an amount less than 0.15 percent by weight based on the total weight of the total amount of the cyclic organosilane with the reaction carried out in two stages.

Particularly preferred polydiorganosiloxane diamines are prepared using cesium and rubidium catalysts. The preparation of the polydiorganosiloxane diamine includes combining under the reaction conditions (1) a functional end block of amine represented by the formula 10 (ni) where each R, D and Y are as defined above and 15 x is an integer of approximately 1 to 150; (2) sufficient cyclic siloxane to obtain a polydiorganosiloxane diamine having a numerical average molecular weight greater than the molecular weight of the blocker end; and (3) a catalytically effective amount of cesium hydroxide, rubidium hydroxide, cesium silanolate, rubidium silanolate, cesium polysiloxane, rubidium polysiloxane, and mixtures thereof. The reaction was continued until substantially all of the functional end-blocker of the amine was consumed. The reaction is then terminated by adding a volatile organic acid to form a mixture of a polydiorganosiloxane diamine which usually has more than about 0.01 weight percent of silanol impurities and one or more of the following: a cesium salt of the organic acid, a salt Rubidium of organic acid, or # both there is a small molar excess of organic acid in relation to the catalyst. The silanol groups of the reaction product were condensed under reaction conditions to form the polydiorganosiloxane diamine having less than or equal to about 0.01 per cent by weight of silanol impurities while the unreacted cyclic siloxane is separated. Optionally, the salt is removed by subsequent filtration. Examples of polydiorganosiloxane diamines useful in the present invention include but are not limited to polydimethylsiloxane diamine, polydiphenylsiloxane diamine, polytrifluoropropylmethylsiloxane diamine, polyphenylmethylsiloxane diamine, polydiethylsiloxane diamine, polydivinylsiloxane diammine, polyvinylmethylsiloxane diamine, poly (5-hexenyl) methylsiloxane diamine, and copolymers and mixtures thereof.

Examples of organic polyamines useful in the present invention include but are not limited to polyoxyalkylene diamines, such as D-230, D-400, D-2000, D-4000, DU-700, ED-2001 and EDR-148, available of Huntsman, polyoxyalkylene triamines, such as T-3000 and T-5000 available from Huntsman, polyalkylenes, such as Dytek A and Dytek EP, available from DuPont. The different polyisocyanates in the reaction will modify the properties of the segmented polydiorganosiloxane polyurea copolymer. For example, if a polycarbodiimide-modified diphenylmethane diisocyanate is used, such as ISONATE 143L, available from Dow Chemical Co., the resultant segmented polydiorganosiloxane polyurea copolymer has greater resistance to solvents when compared to the prepared copolymers with other diisocyanates. If using tetramethyl-rp-xylylene diisocyanate, the resulting segmented copolymer has a very low melt viscosity which makes it particularly useful for injection molding. The diisocyanates useful in the process of the present invention can be represented by the formula OCN-Z-NCO (IV) Any diisocyanate that can react with a polyamine, and in particular with a polydiorganosiloxane diamine of Formula II can be used in the present invention. Examples of such diisocyanates include, but are not limited to, aromatic diisocyanates, such as 2,6-toluene diisocyanates, 2,5-toluene diisocyanate, 2,4-toluene diisocyanate, m-phenylene diisocyanate, diisocyanate. of p-phenylene, methylene bis (o-chlorophenyl diisocyanate), methylene diphenylene-4, -diisocyanate, polycarbodiimide-modified methylene diphenylene diisocyanate, (4, 3-diisocyanate 3, 3 ', 5, 5'-tetraethyl. . -df-phenylmethane, 4,4'-diisocyanate-3, 3'-dimethoxyphenyl (o-dianisidine diisocyanate), 5-chloro-2,4-toluene diisocyanate, l-chloromethyl-2,4-diisocyanate benzene, aromatic-aliphatic diisocyanates such as m-xylylene diisocyanate, tetramethyl-m-xylylene diisocyanate, aliphatic diisocyanates, such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,12-diisocyanatododecane, 2-methyl -1, 5-diisocyanatopentane, and cyclic-aliphatic diisocyanates such as methylenedicyclohexylene-4,4'-diisocyanate, 3-isocyanate diisocyanate Natomethyl-3, 5, 5-trimethylcyclohexyl (isophorone diisocyanate), 2,2,4-trimethylhexyl diisocyanate, and cyclohexylene-1,4-diisocyanate and mixtures thereof. • - "- Preferred diisocyanates include "2,6-toluene diisocyanate, methylenediphenylene-4,4'-diisocyanate, polycarbodiimide-modified methylenediphenyl diisocyanate, 4,4'-diisocyanate-3, 3'-dimethoxybiphenyl- (o-dianisidine diisocyanate), diisocyanate tetramethyl-m-xylylene, methylenedicyclohexylene-4,4'-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,6-diisocyanatohexane, 2,2,4-trimethylhexyl diisocyanate, and cyclohexylene-1,4-diisocyanate Particularly preferred is tetramethyl-m-xylylene diisocyanate Segmented polydiorganosiloxane polyurea copolymers produced using tetramethyl-m-xylylene diissatinate generally have lower melt-like viscosities than the similar copolymers produced using other diisocyanates, -k and a larger modulus. Any triisocyanate that can react with a polyamine, and in particular with the polydiorganosiloxane diamine of Formula II in the present invention. The examples of such triisocyanates include, but are not limited to, polyfunctional isocyanates, such as those produced from biurets, isocyanurates, adducts and the like. Some commercially available polyisocyanates include portions of the Bayer series DESMODUR ^ and MONDUR ^ and the PAPI1 ^ series from Dow Plastics.

Preferred triisocyanates include DESMODUR * ® * N-3300 and MONDUR "11 489. When the reaction of the polyamine and the polyisocyanate is carried out under solvent-free conditions to prepare the segmented polydiorganosiloxane polyurea copolymers, the relative amounts of amine and isocyanate can be varied over a much broader range than those produced by the above methods The isocyanate to amine molar ratios provided continuously to the reactor are preferably from about 0.9: 1 to 1.3: 1, more preferably from 1: 1 to 1.2: 1. Once the reaction of the polyisocyanate with the polyamine has occurred, the active hydrogens in the The urea link may still be available to react with the excess isocyanate. By increasing the ratio of isocyanate to amine, the formation of biuret portions can be facilitated, especially at high temperatures, resulting in a cross-linked branched polymer. The Formation of low to moderate amounts of biuret can be advantageous for the cutting properties and resistance to solvents. The polydiorganosiloxane polyamine component used to prepare the polydiorganosiloxane copolymers The segmented polyurea of this invention provides a means for adjusting the modulus of the resulting copolymer. In general, high molecular weight polydiorganosiloxane polyamines provide lower modulus copolymers, while low molecular weight polydiorganosiloxane polyamines provide high modulus segmented polydiorganosiloxane polyurea copolymers. When the segmented polydiorganosiloxane polyurea copolymer compositions contain an optional organic polyamine, this optional component provides yet another means for modifying the modulus of the copolymers of the invention. The concentration of the organic polyamide as well as the type and molecular weight of the organic polyamine determine how the modulus of polydiorganosiloxane polyurea copolymers containing this component is influenced. The silicate resin plays an important role in determining the physical properties of the compositions of the present invention. For example, when the silicate resin content is increased from a low to high concentration a vitreous transition occurs at higher temperatures. In this way, by varying the concentration of silicate resins in vibration damping applications, the maximum damping area is moved to the desired temperature range. I Of course the ratio of M to Q, and the content of D and T, and the molecular weight of the resin can have a # Significant influence on the relative "hardness" of the resin and can be considered when selecting the resin type and concentration. In addition, a single silicate resin need not be limited to 5 as it may be beneficial to employ a combination of resins in a single composition to achieve the desired performance. The silicate resins in the present invention include those resins composed of the following structural units M, D, T, and Q, and combinations thereof. For example, MQ silicate resins, MQD silicate resins, and MQT silicate resins which may also be preferred as copolymer silicate resins and which preferably have an average molecular weight.

Numbering from about 100 to about 50,000, more preferably from about 500 to about 10,000, and generally has methyl substituents. Silicate resins include both non-functional and functional resins, resins Functional 2Qs have one or more functionalities including, for example, hydrogen bonded to silicone, alkenyl bonded to silicone, and silanol. MQ silicate resins are copolymer silicate resins having R3SiO? / 2 units and Si04 / 2 units. Such resins are described in, for example, Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley & Sons; New York, (1989), pp 265-270, and US Patent No. 2,676,182, US Patent No. 3,627,851, US Patent No. 3,772,247, and US Patent No. 5,248 ^, 739, wherein such descriptions are incorporated herein by reference . MQ silicate resins having functional groups are described in U.S. Patent No. 4,774,310 having silyl hydride groups, U.S. Patent No. 5,262.55 having vinyl and trifluoropropyl groups, and U.S. Patent No. 4,707,531 having silyl hydrides. and vinyl groups, wherein the description of each of the references is incorporated herein by reference. The resins described above are generally prepared in solvent. MQ silicate resins dry, or solvent-free, can be prepared, as described in U.S. Patent No. 5,319,040, U.S. Patent No. 5,302,685, and U.S. Patent No. 4,935,484, wherein such descriptions are incorporated herein by reference. MQD silicate resins are terpolymers having R'3SiO? / 2 units, Si04 / 2 units, and R'2Si02 / 2 units, such as those taught in U.S. Patent No. 2,736,721 where such a description is incorporated herein as reference. MQT silicate resins are terpolymers having R'3SiO? / 2 units, Si042 units, and RrSi03 / 2 units, such as those taught in U.S. Patent No. 5,110,890 where such a description is incorporated herein by reference and the Japanese Patent Kokai HE 2-36234. Commercially available silicate resins include SR-545, MQ resin in toluene, available from General Electric Co., Silicon Resins Division, Waterford, NY; MQOH resins, which are MQ resins available from PCR, Inc. Gainesville, FL; MQR-32-1, MQR-32-2, and MQR-32-3 which are MQD resins in toluene, available from Shin-Etsu Silicones of America, Inc., Torrance, CA, and PC-403 a functional MQ resin of hydride in toluene available from Rhone-Poulenc, Latex and Specialty Polymers, Rock Hill, SC. Such resins are generally distributed in organic solvent and can be used in the compositions of the present invention as received. However, these organic silicate resin solutions can also be dried by any number of techniques known in the art, such as spray drying, oven drying and the like, or separation, to provide a silicate resin having a content of non-volatile of substantially 100% for use in the compositions of the present invention. Also useful in the compositions of the present invention are mixtures of two or more silicate resins. The component of the segmented polydiorganosiloxane oligourea copolymerThe optional of this invention provides another means for varying the modulus of polymeric compositions containing this component. Similar to the function of the polydiorganosiloxane polyamine, the optional segmented polydiorganosiloxane oligourea copolymer can serve either to increase or decrease the modulus of the resulting copolymer, depending on the particular polydiorganosiloxane mono and diamine used in the preparation of the segmented polydiorganosilyxane oligourea copolymer. The composition preferably contains from about 20 to 80 parts by weight of segmented polydiorganosiloxane polyurea copolymer, more preferably from about 25 to 75 parts by weight, more preferably from about 30 to 70 parts by weight. The composition preferably contains from about 20 to 80 parts by weight of silicate resin, more preferably from about 25 to 72 parts by weight, more preferably from about 30 to 70 parts by weight. The total weight parts of the segmented polydiorganosiloxane polyurea copolymer and the silicate resin is equal to 100. The composition may optionally contain segmented polydiorganosiloxane oligourea copolymer, when present, it is preferably present in an amount of about 5 to 50 parts per 100. Total parts of polydiorganosiloxane polyurea copolymer * Segmented and silicate resin. The optional segmented polydiorganosiloxane oligourea copolymers can be represented by Formula V, as follows: (V) where: Z, Y, R and D are as described above; each X is a monovalent portion, which does not react under wet or free radical cure conditions and which is independently a portion Alkyl which preferably have from about 1 to 12 carbon atoms and which can be substituted with, for example, trifluoroalkyl or vinyl groups, or an aryl portion which preferably have from about 6 to 20 carbon atoms and which can to be substituted with, for example, alkyl, cycloalkyl, fluoroalkyl and vinyl groups; And q is 5 to 2Q00 or greater; r is 1 to 2000 or greater; and t is O or l a d or greater. The optional semisolid polydiorganosiloxane urea oligomer components of Formula V can be made either by a solvent process or a solventless process similar to that used to make the segmented polydiorganosiloxane urea polymer except that the input materials comprise: (A) at least a diisocyanate represented by Formula IV; (B) at least one polydiorganosiloxane monoamine represented by Formula VI as follows: wherein R, Y, D, X, and q are as defined above; and (C) optionally, at least one polydiorganosiloxane diamine represented by Formula II except that p is an integer greater than 0.

In general about one mole of (A) is used for every two moles of (B) and about one additional mole of (A) is used for each mole of (C) that is used. In the process for making segmented polydiorganosiloxane oligourea copolymers, the optional polydiorganosiloxane monoamines, isocyanates and polydiorganosiloxane diamines are mixed in a reaction vessel and allowed to react to form the segmented polydiorganosiloxane oligourea copolymer, which can then be removed from the reaction vessel . The composition of the present invention may also optionally contain several fillers and other property modifiers. Fillers such as fuming silica, carbon fibers, carbon black, glass beads, glass bubbles, glass fibers, mineral fibers, clay particles, organic fibers, for example, nylon, KEVLAR, metal particles and the like can be added. amounts of up to about 50 parts per 100 parts of segmented polydiorganosiloxane urea polymer and silicate resin, provided that if and when incorporated, such additives are not detrimental to the function and functionality of the final polymer product. Other additives such as dyes, pigments, flame retardants, stabilizers, anti-oxidants, compatibilizers, antimicrobial agents such as zinc oxide, electrical conductors, thermal conductors can be mixed. • such as aluminum oxide, boron nitride, aluminum nitride, and nickel particles and the like in such systems in amounts of about 1 to 50 volume percent of the composition. The compositions and constructions of the invention can be made by solvent processes known in the art, by a continuous solvent process or by a combination of the two. The examples of solvent processes by which the segmented polydiorganosiloxane polyurea copolymer useful in the present invention can be prepared include: Tyagi et al., "Segmented Organosiloxane Copolymers: 2. Thermal and Mechanical Properties of the Siloxane-Urea Copolymers", Polymer, vol.

December 25, 1984 and North American Patent No. 5,214,119 (Leir et al.), Which are incorporated herein by reference for that purpose. The silicate resin can then be added to the solvent solution of the segmented polydiorganosiloxane polyurea polymer to form the composition useful in the constructions and joining methods, protection against corrosion, or vibrational damping article of the present invention. In the process of the present invention, the reagents, including at least one polyamine, wherein The polyamine is at least one polydiorganosiloxane diamine or a mixture of at least one polydiorganosiloxane diamine and at least one organic polyamine and at least one polyisocyanate diamine are mixed in a reactor and allowed to react to form the polydiorganosiloxane polyurea segmented copolymer which can then be removed from the reaction vessel. In the process of the invention, the following reaction occurs: The properties of the compositions of the present invention result from the molecular weight and architecture of the copolymer. The flexibility of the process of the present invention leads to interesting materials, some of which, although they may not be completely soluble in solvents by inherent viscosity or molecular weight determinations, may nonetheless be very useful materials in terms of physical properties, ^ and they can be even extrudable. One skilled in the art can expect the optimum material for a particular application to be a function of the ratio of isocyanate to amine, architecture of the polyisocyanate and polyamine, order of addition of the reactants, mixing speed, temperature, reactor performance, configuration and reactor size, residence time, residence time distribution, and if any fillers, additives or property modifiers were added. This process will allow to freely vary w molecular weight and architecture over a wide range, thus allowing one to design the properties to the extent of a variety of applications. Any reactor that can provide intimate mixing of the polyamine and polyisocyanate and the reaction products herein is suitable for use in the invention. The reaction can be carried out as a discrete process using, for example, a flask equipped with a mechanical stirrer, provided that the reaction product has a sufficiently low viscosity at the processing temperature to allow mixing, or as a process continuous using, for example, a single screw, or twin screw extruder. Preferably, the reactor is an extruder with two co-rotating or counter-rotating screws with a clean surface. The temperature in the reactor should be sufficient for the reaction between the polyisocyanate and the polyamine The temperature should also be sufficient to allow the transport of materials through the reactor, and any subsequent processing equipment such as, for example, feed blocks and dies or dies. For transportation of the reacted material, the temperature should preferably be in the range of about 140 to 250 ° C, more preferably in the range of about 160 to 220 ° C. The residence time in the reactor typically ranges from about 5 seconds to 8 minutes, more typically from about 15 seconds to 3 minutes. The reference time depends on several parameters, including, for example, the ratio of length to diameter of the reactor, mixing speeds, total flow rates, reactants, and the need to mix additional materials. For materials involving reaction with a minimal or non-reactive non-reactive component, the reaction can easily take place in units of length to diameter as small as 5: 1 of a twin-screw extruder. When a clean surface reactor is used, it preferably has relatively narrow spaces between the landing zones of the screws and the drum, with this value typically being between 0.1 to about 2 mm. The screws used are preferably completely or partially meshed or completely or partially cleaned in the areas where a substantial portion of the reaction takes place. Because a rapid reaction occurs between the polyamide and the polyisocyanate, both reactants are preferably fed into an extruder at non-variable speeds, particularly when high molecular weight polyamines are used, that is, with molecular weights of about 50,000 and greater. Such feeding generally reduces the undesirable variability of the final product. One method to ensure continuous feeding in the extruder when a very low flow polyisocyanate stream is used is to allow the polyisocyanate feed line to be very close to touching the threads of the passing screws. Another method could be to use a continuous spray injection device that produces a continuous stream of fine drops of. the polyisocyanates in the reactor. Typically, in the formulation of polydiorganosiloxane polyurea block copolymers segmented with additives such as adhesive resins, inorganic fillers or other materials essentially unreactive with the segmented polydiorganosiloxane polyurea copolymer reagents, the additives to be mixed are further added downstream in the reactor after that * A substantial portion of the reaction of the polyamide and polyisocyanate has taken place. The silicate resin that is mixed with the segmented polydisorganosiloxane polyurea block copolymer and the optional organic fillers, or other materials that are essentially unreactive with the polydiorganosiloxane polyurea copolymer reagents * segmented, additional current can also be added down in the reactor after a substantial portion of the reaction of the polyamine and polyisocyanate has taken place. Another suitable order of addition is the introduction of the polyamine in the first place, the silicate resin and the other materials in the second place, and the polyisocyanate in the third place. place, with the polyisocyanate fed in a continuous form. If the silicate resin and the other additives can be transported in the reactor, they can be added in the reactor first with the polyamine and polyisocyanate followed separately in the final stages of the process.

Several streams can also be mixed before addition, such as mixing small amounts of fuming silica with the polyamine. However, different reagents and additives can be added in any order provided that the addition of an additive does not interfere with the reaction of the reagents. An additive that is particularly reactive with a polyisocyanate reagent could typically be added until after the reaction of the polyisocyanate with a polyamine reagent. In addition, the reagents can be added simultaneously or sequentially in the reactor and in any sequential order, for example, the polyisocyanate stream can be the first component added to the reactor in a manner as mentioned above. Polyamine can * then be added downstream in the reactor. By way of Alternatively, the polyisocyanate stream can also be added after the polyamine has been introduced into the reactor. The process of the present invention has several advantages over solution polymerization processes Conventional methods for making segmented polydiorganosiloxane polyurea copolymers such as (1) the ability to vary the ratio of isocyanate to amine to obtain materials with properties superior to that of polymerized materials in solution, (2) the capacity of polymerize high molecular weight compositions that can not be easily produced using solution polymerization, (3) the ability to directly produce shaped articles with reduced thermal histories, (4) the ability to directly mix fillers, resins adhesives, plasticizers, and other property modifiers; and (5) solvent removal. The flexibility of altering the isocyanate to amine ratio in the continuous process is a distinct advantage. This relationship can be varied above and below the theoretical value of 1: 1 very easily. In solution, ratios much higher than about 1.05: 1 and lower than 0.95: 1 produce lower molecular weight copolymers. In the process of the present invention, they can produced polydiorganosiloxane-segmented polyurethane copolymers with ratios as high as 1.3: 1, depending on the numerical average molecular weight of the polydiorganosiloxane diamine. Such polymers have inherent viscosities much higher than those of made with conventional solution processes but can still be processed by melting. These polymers can also have superior mechanical properties when compared to polymerized copolymers in solution. In some relationships, the resulting polymers may become insolubles, preventing the possibility of the determination of the inherent viscosity, but the material can be processible melted and can also possess a high strength. The ability to manufacture high weight compositions Molecules that can not be produced by solution polymerization due to the insolubility of the polymer formed in the solvent medium, lead to useful, unique compositions. When the chain extension of the polyamide is carried out in solution with certain polyisocyanates such as the polycarbodiimide-modified diphenylmethane diisocyanate, available, for example, from Dow Chemical Co. as IS0NATE 143L, the newly formed polymer can precipitate from the solution , thus not allowing the formation of the high molecular weight copolymer. When this composition is prepared using the solvent-free method of the present invention, materials with high solvent resistance are formed. In a similar manner, materials made from a mixture of two polyamines of very different molecular weights polymerized with polyisocyanate using the solvent-free process of the present invention can be made with high inherent viscosities. In general, prolonged exposure to heat degrades segmented polydiorganosiloxane polyurea copolymers and leads to a degradation of physical properties. The degradation experienced by many of the segmented polydiorganosiloxane polyurea copolymers polymerized in solution after drying and subsequent hot melt extrusion is also overcome by the continuous process of the present invention because the extruded polyurethane-polyurea copolymers of extruded polyurethane. Reactive manner can be extruded = directly from the polymerization zone through a matrix to form shaped articles such as pipes and 5 films without the additional thermal history associated with the removal of the solvent and the subsequent reheating of the polymer. The ability to eliminate the presence of the solvent during the reaction of polyamine and polyisocyanate produces a much more efficient reaction. The average residence time using the process of the present invention is typically 10 to 1000 times shorter than that required in the solution polymerization. A small amount of non-reactive solvent can be added, if necessary, for example, from about 0.5% to about 5% of the total composition, in this process either as a carrier to inject materials under other solid circumstances or to increase the stability of a low flow rate stream in others circumstances of material in the reaction chamber. Although the process without continuous solvent to produce the compositions of the materials has many advantages over the process with solvent, there may be some situations where the process is preferred with Solvent or where a combination of the two is preferred.

In the latter case, the segmented polydiorganosiloxane urea copolymer could be made by the continuous process and subsequently mixed in solvent with the silicate resin, the optional polydiorganosiloxane urea oligomer, and the optional filler components. The compositions of the present invention, depending on the specific formulation can be used to make pressure-sensitive adhesive tapes, adhesive or pressure sensitive adhesive tapes, adhesives. pressure-sensitive sprays, pressure sensitive adhesive medical tapes, including for example transdermal drug delivery device, or pressure sensitive adhesives that are coated directly on the desired articles. 15 Pressure-sensitive adhesive articles are made by applying the pressure-sensitive adhesive by the hot melt coating process or with a well-known solvent. Any suitable substrate can be used, including, but not limited to, for example, fabric and "fiberglass fabric, metallized films and foils, polymeric films, non-woven fabrics, paper and polymer coated paper, and foamed backings." Polymeric films include, but are not limited to, polyolefins such as polypropylene, polyethylene ,, low polyethylene density, linear low density polyethylene and high density polyethylene; polyesters such as terephthalate # - polyethylene; polycarbonates; cellulose acetates; polyimides such as KAPTON "11. Non-woven fabrics, generally made of randomly oriented fibers, include, but are not limited to, nylon, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, rayon, and the like. , but are not limited to acrylic, silicone, polyurethane, polyethylene, neoprene rubber, and • polypropylene, and can be filled or not .. The supports laminates, such as polyethylene-aluminum membrane compositions, are also suitable. In the case of pressure sensitive tapes, those materials are typically applied by first making a tape construction, which comprises a layer of material pressure sensitive adhesive coated on a support. The exposed surface containing PSA can then be applied to a surface from which it could be released later or directly to the desired substrate. A transfer tape can be made coating the composition between two coatings both of which are coated with a release liner. Peelable coatings often comprise a clear polymeric material such as a polyolefin or polyester that is transparent to radiation ultraviolet. Preferably, each release liner is first coated with a release material for the pressure sensitive adhesive used in the invention. The compositions of the present invention are also useful in medical applications including transdermal drug delivery devices. Transdermal drug delivery devices are designed to deliver a therapeutically effective amount ^ of a drug through or to the skin of a patient. The The release of transdermal drugs provides significant advantages; unlike the injection, it is not invasive; unlike oral administration, it avoids the first hepatic step of metabolism, minimizes gastrointestinal effects, and provides stable blood levels.

A variety of transdermal drug delivery devices have been described. Devices known in the art include matrix devices in which the drug is placed within a non-adhesive polymeric material; reservoir devices in the Wherein the drug is placed in a liquid and is released to the skin through a membrane that controls the speed; drug devices in the adhesive in which the drug is placed inside an adhesive polymer; and more complex multi-layered devices that involve several different layers, for example, layers containing the drug, which contain the excipients, for F control the rate of release of the drug and the excipients, and to attach the device to the skin. All devices incorporate a drug formulation, an adhesive to maintain contact with the patient's skin, a removable liner that protects the device during storage and is removed prior to application of the device to the skin, and a support that protects the device. the device of external factors while using.

Figure 2 shows a matrix device. The device 10 comprises a support 12, a matrix 14 containing the drug and optionally excipients, a concentric adhesive layer 16 surrounding the matrix 14, and a release liner 18. 15 A reservoir device is shown in Figure 3. The device 20 comprises a support 22, a liquid formulation 24 containing the drug and optionally excipients, a membrane 25 for controlling the rate at which the drug and the excipients are released to the skin, an adhesive layer 26, and a release liner 28. The adhesive layer may also be present as a concentric ring as described in relation to the matrix device (Figure 2). In the "Figure 4 a device with drug in the adhesive. The device 30 comprises a support 32, an adhesive layer 37 containing drug and * optionally excipients, and a removable liner 38. A reed device is shown in Figure 5. multiple. The device 40 comprises a support 42, an adhesive layer 47 containing drug and optionally excipients, a second adhesive layer 43 which controls the rate at which the drug and the excipients are released towards the skin, and a release liner 48.

In Figure 6 a second embodiment of a multi-lamella device is shown. The device 50 comprises a support 52, an adhesive layer 57 containing drug and optionally 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 the excipients are released to the skin 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 drug is directly proportional to the skin contact path, the device must establish and maintain sufficient adhesion to the skin until it is removed. Adhesives that are used in skin contact layers should preferably exhibit the following properties: good adhesion to the initial skin, ie adhesion; adequate adhesion during the period of use; clean detachment of the skin; and compatibility with the skin (non-irritant and non-sensitizing). It is important that these properties are maintained when the adhesive is exposed to the drug and particular excipients that are used in a given device. The adhesives used in the layers that are in contact with the drug and the excipients or through the? which the drug and the excipients should also be compatible with the drug and the excipients. Preferably, the adhesives should not react chemically with the drug or excipients. In many cases, it is also preferable that the drug dissolves in the adhesive instead of dispersing therein. Often it will be desirable or even It is necessary to customize the adhesive for a particular drug / excipient combination. The transdermal delivery devices can be made in the form of an article such as a tape, a patch, a sheet, a dressing or cure or any other known to those skilled in the art. Generally, the device should be in the form of an appropriately sized patch to release a preselected amount of the drug. Suitable peelable coatings include those listed above in connection with the preparation of PSA tapes.

The compositions of the present invention are also useful for adhering pavement marking sheet materials and pavement markers for pavement surfaces such as concrete and asphalt. Pavement marking materials generally comprise an upper layer, a composite layer, and an adhesive layer or layers to adhere to the pavement. The materials for the top layer and the adhesive should be selected so that the joint between them is strong enough to resist. delamination under conditions in which the pavement marker is exposed. The top layer is typically a flexible polymeric layer which is preferably durable and resistant to wear. Illustrative examples of materials from which the layers can be made The upper ones include but are not limited to polyvinyls, polyurethanes, epoxy resins, polyamines, polyureas, and polyesters. Mixtures of such materials can also be used. Suitable polymeric materials can also be either thermoplastic or thermoset polymers.

In general, the upper layer also comprises a plurality of retroreflective particles and / or skid resistant particles embedded in the upper layer with some particles projecting from the upper surface. Optionally, you can apply a sheet base to the lower surface of the top layer to impart the desired conformability and strength. The base sheet may contain particulate fillers to reduce costs and modify properties such as hardness or surface flexibility. Optionally, 5 pigments can be added to the upper layer or to the base sheet to impart the desired coloration. The pavement marking sheet material generally has a layer of adhesive rubber resin applied to the bottom surface to adhere to the pavement In the present invention, the pressure sensitive adhesive based on segmented polydiorganosilaxap polyurea copolymer can be applied directly to the lower surface of the top layer if a base layer is not present or can be applied to the bottom surface of the base layer, if present. In addition, the adhesive can be advantageously applied to the lower surface of the rubber resin pressure sensitive adhesive. The polydiorganosiloxane polyurea copolymer The segmented material is preferably applied as a hot melt coatable composition with 100% solids and can be applied by various methods including knife coating or extrusion coating. Alternatively, the pressure sensitive adhesive of the present The invention is formed as an adhesive layer ent, r§.

Removable coated coatings, i.e., a transfer tape, a removable coated coating is removed and the adhesive adheres to the top layer, the base layer or the rubber resin pressure sensitive adhesive of the pavement marking material according to the invention. be appropriate The other release liner, now on the lower surface of the pavement marking material can then be removed before application to a pavement surface. The pavement marking sheet materials of the present invention possess excellent adhesion to various pavement surfaces, stable peel strength values over time, and excellent performance over a wide range of temperature and low high humidity conditions. The compositions of the present invention can also be used in pressure sensitive adhesives that readily bond to prepared and unprepared surfaces, especially metals, providing a high coating in continuous, highly conformable interfacial silicone, which prevents the entry of environmental pollutants that attack corrosively the unprotected surfaces. The invention solves the market need for a protective coating that can be applied outside of, the conditions of laboratory or factory controlled. The coating should adhere to cold, wet or oxidized metal as well as to existing protective coatings such as epoxy, polyethylene and polypropylene over oil and gas pipelines. A non-exhaustive list of applications includes: permanent repair of defects due to coating gaps; coating ends of tubes that have been cut to be joined; protection of parts which must be discovered before being mounted in the field; removable media to prevent instantaneous oxidation of bare metal before further processing; and as a protective adhesive between adjacent coated or uncoated steel parts, as in bare mesh. A pressure-sensitive adhesive patch typically consists of a protective silicone pressure sensitive adhesive and optionally a barrier or barrier adhesive with edge, layers of conformable barrier or support materials, or combinations of those materials. For some applications it is preferable that the support does not cover the protected electric field, making a more open structure support for solid films of, for example, polyethylene or PVC. A beveled or adhesive adhesive layer. Shaped to better fit the topology of the surface may be preferred when patching some surfaces.

The composition of the present invention can also be used as a pressure sensitive adhesive or hot melt adhesive for heat shrink tubing. These constructions provide a single article that can withstand the high temperatures experienced during the thermal contraction operation and provide an environmental seal after cooling. The rheology, thermal stability, adhesion, and clarity of these materials make them especially suitable for this application. The compositions of the invention also be coated on different release coatings; that is, a release liner having a first release coating on one side of the liner and a second release liner coated on the opposite side. The two release coatings preferably have different release values. For example, a release liner can have a release value of 5 grams / cm (i.e., 5 grams of force is required to remove a strip of material 1 cm in width from coating), while the second release liner can have a release value of 15 grams / cm. The material can be coated on the coating of the release liner which has the highest release value. The resulting tape can be wound on a roll. When the tape is unrolled, the pressure sensitive adhesive adheres to the release liner with a higher release value. After the tape is applied to a substrate, the release liner can be removed 5 to expose an adhesive surface for further use. Useful peelable coatings that can be used in the above constructions include those that are suitable for use with silicone adhesives. An example is the coating coated with polyfluoropolyether described in European Patent Publication No. 433070. Other useful release liner removable coating compositions are described in European Patent Publication No. 378420, US Patent No. 4,889,753, and Publication of European Patent No. 311662. Commercially available coatings and compositions include SYL-OFF * ®1 fluorsilicon removable coating Q2-7785 from Down Corning, available from Dow Corning Corp., Midland, MI, removable coatings' dß fluorosilicon X-70-029NS available from Shin-Etsu Silicones of America, Inc., Torrance, CA; S TAKE OFF fluro silicone release liner "1 * 2402 from Reléase International, Bédford Park, IL and the like. compositions that can be used to bond non-stick surfaces together in a composition. During application to a substrate, hot melt adhesives should be sufficiently fluid to wet the surface completely and not leave gaps, even if the surface is rough. Consequently, the adhesive must be of low viscosity at the time of application. However, the bonded adhesive generally becomes a solid to develop sufficient cohesive strength to remain -WP adhesive to the substrate under high stress conditions. 10 For hot melt adhesives, the transition from fluid to solid can be made in several ways. First, the hot melt adhesive can be a thermoplastic that softens and melts when heated and hardens again when it is cooled. Such heating gives as a result a high enough fluidity to achieve successful wetting. Alternatively, the hot melt adhesive can be dissolved in a solvent or carrier that lowers the viscosity of the adhesive sufficiently to allow satisfactory wetting and Increase the viscosity of the adhesive when the solvent or carrier is removed. Such adhesive can be thermally activated, if necessary. The compositions of the present invention can also be used as materials to dampen vibrations alone, i.e., free-layer treatment, or in conjunction with a rigid layer, i.e., as part of a restricted layer treatment. Vibration damping materials are used more efficiently if they are sandwiched between the structure / device to be damped and a relatively rigid layer 5, such as a thin metal sheet. This forces the viscoelastic material to deform in the cut when the panel vibrates, dissipating substantially more energy than when the material deforms in extension and? compression, as in a free-layer treatment. From Preferably, the constrained layer construction consists of a sheet of one or more rigid layers and one or more layers of the vibration damping material. Restricted layer constructions can be prepared by several processes. In a process, a layer of The vibration damping material is coated on a release liner by conventional f-solution coating or other hot melt coating techniques known in the art. The resulting viscoelastic material layer is transferred to a rigid support and adheres to it, thereby providing a constrained layer construction. In another process, a layer of vibration damping material is coated directly on a rigid support by means of the conventional solution coating or, the techniques oe hot melt coating known in the art.

In each case, the construction of restricted layers is then fixed to the structure that needs to be damped. The construction can be joined in any form provided that the restricted layer is fixed only to the vibrating structure via the interface of the viscoelastic material, ie free of mechanical bonding. When the structure subsequently vibrates under the influence of a force applied internally or externally, the vibration is damped. -A Another application of the buffer materials of vibrations of the present invention is a bidirectional damping unit as described in Neilsen, E. J. et al, "General View of Viscoelastic Damping for Seismic and Wind Applications", Structural Engineering Association of California, Tahoc, Olympiad, October, 1994. Bidirectional damping, or longitudinal displacement, is the transfer of subsonic oscillations of a structure, such as a building, into the shear deformation of a viscoelastic material for the purpose of dampening the oscillations of the structure. In In this application, the materials having vibration damping capacity preferably have a shear storage modulus, G ', of between about 6.9 x 103 Pa to 3.45 x 107 Pa, more preferably 3.45 x 104 Pa to 1.4 x 107 Pa. , more preferably 3.45 x 105 ^ Pa to 6.9 x 106 Pa, a the temperature of use, and have as high a d as possible during the temperature and frequency range of use. The materials also preferably have a strain elongation of at least 100 percent or a shear deformation capacity of at least 5 100 percent_ within their range of temperature and frequency of use. When the vibration damping material has pressure-sensitive adhesive properties, the material can usually be adhered to a rigid layer without the use of an additional bonding agent. However, it is sometimes necessary to use a thin layer, for example, 20-50 μm thick, of a high strength adhesive, such as, for example, an acrylic adhesive, an epoxy adhesive, or an adhesive. silicone, all of which are fine known to those skilled in the art, for attaching the vibration-damping composition of the invention to a structure. For most applications, the layer of vibration dampening material has a thickness of At least 0.01 mm to about 100 mm, more preferably 0.05 to 100 mm. The damping material can be applied by any of the techniques known in the art such as by spraying, immersion, blade, or curtain coating, or molding, rolling, casting, extrusion.

As mentioned earlier, a rigid layer is »An essential part of the constrained layer vibration dampening constructions of the present invention. A material suitable for a rigid layer preferably has a stiffness of at least about 100 times the stiffness, i.e., the storage modulus, of the vibration damping material, the stiffness of the rigid layer is measured in extension. The desired stiffness of the rigid layer can be varied by adjusting the thickness of this cap, by example, from about 25 micrometers to 5 centimeters, depending on the modulus of the rigid layer. Examples of rigid materials suitable for use in a constrained layer construction include, for example, metals such as iron, steel, nickel, aluminum, chromium, cobalt, and copper, and alloys thereof and rigid polymeric materials such as polystyrene; polyester; polyvinyl chloride; polyurethane; polycarbonate; polyimide; And polyepoxide; fiber reinforced plastics such as fiberglass reinforced polyester, reinforced with ceramic fiber, and reinforced with metallic fibers; glasses; and ceramics. The vibration damping compositions of the present invention are useful in a variety of applications that require effective damping over a wide range of temperature and frequency, with the additional requirement that the minimum and / or maximum module requirements must also be satisfied, over a specified n '^ r temperature range. It is often desirable that the maximum buffer region, ie the point at which the loss factor approaches a maximum occurs in the center of the desired temperature and damping frequency range. The design of the optimal cushioning material for a specific application requires understanding the effect of the polydiorganosiloxane copolymer -W segmented polyurea, the silicate resin, the copolymer of Optional polydiorganosiloxane oligourea segmented and filler, and the concentration of each have on the buffering operation. The compositions of the invention, depending on the specific formulation used, may be pressure sensitive adhesives, thermally activated adhesive vibration damping materials, and non-adhesive materials. In order to employ non-adhesive vibration damping materials, the use of a binding agent is required, ie a material for fixing the damping material to either a restricted layer and / or a resonant structure depending on the particular use geometry desired. . In the case of vibration damping materials that provide "sensitive adhesive properties to the pressure, those materials are typically applied by first making a construction the tape which comprises a layer m? t ^ of the vibration damping material coated between two coatings at least one of which is coated with a release material. A transfer tape can is made by coating the composition of the coatings both of which are coated with a release coating. Removable coatings typically comprise a polymeric material such as polyester, "f-polyethylene, polyolefin and the like, or coated paper removable or paper coated with polyethylene. Preferably, each of the release liner is coated or printed first with a release material for the vibration damping materials used in the invention. The vibration damping materials of the invention have pressure sensitive adhesive qualities which adhere well to polyesters, polycarbonates, polyolefins such as polyethylene and polypropylene, and TEFLON "11 of which the last two classes of materials are known traditionally for being difficult materials to be united. The present invention is best illustrated with the following examples which are not intended to limit the scope of the invention. In the examples all parts and percentages are by weight unless otherwise indicated CQ.sa.

All the molecular weights reported are the weights Molecular average numerical Hr in g / mol.

Titration of Polydiorganosiloxane and Organic Paliamines The actual numerical average molecular weight of the polydiorganosiloxane or organic polyamines was determined by the following acid titration. Suffnt diamine was dissolved to give approximately 1 milliequivalent amine in tetrahydrofuran / 50/50 isopropyl alcohol to form a 10% solution. This solution was titrated with 0.1 N hydrochloric acid with bromophenyl blue as an indicator to determine the numerical average molecular weight. However, when the diamines were In the case of polydiorganosiloxane diamines, the molecular weights of these diamines depended on the exact ratio of the reagents used in the synthesis of the diamine and the degree of separation of cyclic s loxanes. The resulting cyclics are diluent that increase the apparent molecular weight of the polydiorganosiloxane diamine.

PREPARATION OF THE POLIDIORGANOSILOXAN DIAMINES Políd ± mßtxlsiloxan Diamine A A mixture of 4.32 parts of bis (3-aminopropyl) tetramethyl disiloxane and 95.68 parts of octamethylcyclotetrasiloxane was placed in a batch reactor and purged with nitrogen for 20 minutes. The mixture was then heated in the reactor to 150 ° C. The catalyst was added, 100 ppm of 50% aqueous cesium hydroxide, and heating was continued for 6 hours until it was consumed. bis (3-aminopropyl) tetramethyl disiloxane. The reaction mixture was cooled to 90 ° C, neutralized with an excess of acetic acid in the presence of some triethylamine, and heated in a high vacuum to remove the cyclic silscans for a period of at least five hours. The material was cooled to room temperature, filtered to remove any cesium acetate that had formed, and was titrated with 1.0N hydrochloric acid to determine the average numerical molecular weight. HE. they prepared four lots. The molecular weights of Polydimethylsiloxane Diamine A were Lot 1: 5280, Lot 2: 5330, Lot 3: 5570, Lot 4: 5260.

Polidi me ti lsi loxan Diamine B The polydi ethylsiloxane diamine was prepared as described for the Polydimethylsiloxane Diamine A except that 2.16 parts of bis (3-aminopropyl) tetramethyl disiloxane and 97.84 parts of octamethylcyclotetrasiloxane were used. Two batches were prepared. The molecular weights of the Polydimethylsiloxane Diamine B were Lot 1: 10,700 and Lot 2: 10,700.

Polldi Methylsiloxane Diamine C A mixture of 21.75 parts of Polydimethylsiloxane Diamine A and 78.25 parts of octamethylcyclotetrasiloxane was placed in a batch reactor, purged with nitrogen during minutes and then heated in the reactor to 150 ° C. The catalyst, 100 ppm 50% aqueous cesium hydroxide was added, and heating was continued for 3 hours until the equilibrium concentration of the cyclic siloxanes was observed by gas chromatography. The mixture of The reaction was cooled to 90 ° C, neutralized with an excess of acetic acid in the presence of some triethylamine, and heated under high vacuum to remove the cyclic siloxanes for a period of at least 5 hours. The material was cooled to room temperature, filtered, and titrated with acid. hydrochloric 1.0N to determine the numerical average molecular weight. Three batches were prepared. The molecular weights of \ L The Polydimethylsiloxane Diamine C were Lot 1: 22,300, Lot 2: 22,000, and Lot 3: 19,000.

Polymethylsiloxane Diamine D The polydimethylsiloxane diamine was prepared as or described for the polydimethylsiloxane diamine C except that 1 used 12.43 parts of Polydiorganosiloxane Diamine A and 87.57 parts of octamethylcyclotetrasiloxane. Three batches were prepared. Molecular weights of Polydimethylsiloxane Diamine D were: Lot 1: 37,800, Lot 2: 35,700, and Lot 3: 34,800.

Polydimethyl Siloxane Diamine E The polydimethylsiloxane diamine was prepared as described for the Polydimethylsiloxane Diamine C except that 8.7 parts of Polydimethylsiloxane Diamine A and 91.3 parts of octamethylcyclotetrasiloxane were used. Three 20 batches were prepared. The molecular weights of the Polydimethylsiloxane Diamine E were: Lot 1: 58,700,. Lot 2: 52,900, and Lot 50,200.

Polydimethylsiloxane Diamine F The polydimethylsiloxane diamine was prepared as described for the Polydimethylsiloxane Diamine C except that 5.8 parts of Polydimethylsiloxane Diamine A and 94.2 parts of octamethylcyclotetrasiloxane were used. The molecular weight of this Polydimethylsiloxane Diamipa F was 71,000.

Polydimethylsiloxane Diamine G The polydimethylsiloxane diamine was prepared as described for the Polydimethylsiloxane Diamine C except that 4.35 parts of Polydimethylsiloxane Diamine A and 95.65 parts of octamethylcyclotetrasiloxane were used. The molecular weight of this Polydimethylsiloxane Diamine G was 105,000.

Polydimethyl siloxane Diamine H The polydimethylsiloxane diamine was prepared by placing in a batch reactor under nitrogen purge, and with stirring 1.98 parts of bis (3-aminopropyl) tetra-methyldisiloxane and 9.88 parts of octamethylcyclotetrasiloxane.

The mixture was heated to 91 ° C and traces were added (about 0.15 parts) of silanolate catalyst of 3-aminopropyldimethyltetramethylammonis. The resulting mixture is added dropwise over a period of 5 hours to 88.0 parts * of octamethylcyclotetrasiloxane. The reaction mixture was maintained at 91 ° C for an additional 7 hours and then heated at 149 ° C for 30 minutes to decompose the catalyst. The product was then separated at 91 ° C and 2700 N / m2 (2700 Pa) for approximately 120 minutes to remove volatile materials. The molecular weight of the resulting Polydimethylsiloxane Diamine H was 9970. ft. 10 Polydifonyldim &tils ± laxan Diamine I To a 3-neck spherical bottom flask equipped with metal stirrer, static nitrogen atmosphere, oil heating bath, thermometer and condenser After refluxing, 75.1 parts of octamethylcyclotetrasiloxane, 22.43 parts of octaphenylcyclotetrasiloxane, and w 2.48 parts of bis (3-aminopropyl) tetramethyldisiloxane were added. Under the atmosphere of static nitrogen, the reactants were heated to 150 ° C and degassed under suction by vacuum for 30 seconds before restoring the static nitrogen * atmosphere. A charge of 0.02 parts of sodium hydroxide solution (50% aqueous) was added to the flask and heating was continued for 16 hours at 150 ° C. The flask was cooled to room temperature and then 2 were added. mL of triethylamine and 0.38 mL of acetic acid. With good agitation the flask was placed under a vacuum of 100 N / m2 (100 fe Pa), dried heated to 150 ° C, and maintained at 150 ° C for 5 hours to remove volatile materials. 5 hours later the heat was removed and the contents cooled to room temperature - environment. The molecular weight of Polydiphenyldimethyl siloxane Diamine I was 9620.

Polydiphenyldim &tyl siloxane Diamine J F 10 The polydimethylsiloxane diamine was prepared by placing in a batch reactor under a nitrogen purge, and with stirring 4.42 parts of bis (3-aminopropyl) tetramethydrylsiloxane and 22.25 parts of octamethylcyclotetrasiloxane. The mixture was heated to 91 ° C and added traces (approximately 0.03 parts) of silanolate catalyst of 3-aminopropyldimethyltetramethylammonia. The resulting mixture was added dropwise over a period of 5 hours to 73.30 parts of octamethylcyclotetrasiloxane. The reaction mixture was maintained at 91 ° C for 7 hours Additional 20 and then heated at 149 ° C for 30 minutes to decompose the catalyst. The product was then separated at 91 ° C and 2700 N / m2 (2660 Pa) for approximately 120 minutes to remove volatile materials. The molecular weight of Polydimethylsiloxane Diamine I was 4930.

PREPARATION OF COPOLYMERS OF POLIDIORGANOSILOXAN POLIUREA ft SEGMENTADOS The following polydiorganosiloxane copolymers segmented polyurea were prepared either by a solvent-based process or by a solvent-free process as described below. All polyisocyanates were used as received and the polyisocyanate: polyamine ratios were calculated using the weight The molecular weight of the polyisocyanate reported by the polyisocyanate distributor and the molecular weight of the polydiorganosilicon diamine was determined by acid titration.

Copolymer of Polymethylsiloxane Polyurea Segmented A Methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 1.20 g / min (0.0045 mol / min) in the sixth zone of a 18 mm twin-screw extruder from Leistritz under a nitrogen atmosphere and the Polydimethylsiloxane Diamine X-22-rl61A, Lot 112052 (from Shin-Etsu Silicones of America, Inc., Torrance, California), molecular weight 1620, was injected at a rate of 7.7 g / min. (0.00475 mol / min) in the seventh. The line of --- feeding Methylenedicyclohexylene-4,4'-diisocyanate was placed sufficiently close to the screws, so that each of the threads of the passing screws each take a small amount of diisocyanate into the screw, resulting in complete wetting of the screw forward of this point of addition and dry threads behind this point. The extruder was used in cogiratory mode with fully geared double-start screws through the entire length of the drum, rotating at 150 revolutions per minute. The profile of temperature fc for each of the zones of 90 mm in length was: zones 1 to 5 - 40 ° C; zone 6 - 60 ° C; zone 7 - 100 ° C; zone 8 - 154 ° C; and area or final part - 170 ° C. The resulting segmented polydimethylsiloxane polyurea copolymer, which had an inherent viscosity of 0.19 dL / g, was extruded into a strand, cooled in air and collected. 15 Copolymer of Polydimethylsiloxane Polyurea Segmented B Polydimethylsiloxane Diamine C, 'Lot 1, molecular weight of 22,300, at a rate of 25.9 g / min was injected (0.00118 mol / min) in the fifth zone of a two screw, co-rotating, 8-zone extruder of 34 mm diameter from Leistritz and methylenedicyclohexylene-4,4'-diisocyanate was added at a speed of 0.335 g / min ( 0.00128 mol / min) in the sixth zone with the feed line brushing the screws.

The screws were fully engaged screws turning at 47 revolutions per minute. The temperature profile of each zone of 120 mm in length was: zone 1 to 4 - 25 ° C; zone 5 - 50 ° C; zone 6 - 75 ° C; zone 7 - 120 ° C; zone 8 - 150 ° C, and area or final part - 180 ° C. The resultant segmented polydimethylsiloxane polyurea copolymer was extruded into a strand, cooled in air and collected.

Copolymer d? Polydimethylsiloxane Polyurea Segmented CF 10 Polydimethylsiloxane Diamine D, Lot 1, molecular weight of 37,800, at a speed of 22.5 g / min (0.000595 mol / min) was injected into the second zone of a twin screw extruder, counter-rotating, 34 mm in diameter, from Leistritz and methylenedicyclohexylene-4,4r-diisocyanate was fed at a rate of 0.206 g / min (0.000786 mol / min) in the eighth zone of the extruder. The screws were elements with 12 mm separation fully engaged, rotating at 50 revolutions per minute. The temperature profile of each one of the zones of 120 mm in length was: zone I - 30ßC; zone 2 - 50 ° C; zone 3 - 80 ° C; zone 4 - 130 ° C; zone 5 - 160 ° C; zone 6 - 170 ° C; and zone 6 to 10 and area or final part - 180 ° C. The resulting segmented polydimethylsiloxane polyurea copolymers were extruded into a strand, cooled in air and collected, Pollio Polymethylsiloxane Polyurea Segmented D Copolymer Copolymer of Polydimethylsiloxane Polyurea Segmented D was prepared as the Copolymer of Polydimethylsiloxane Segmented B Polyurea, except that it was used Polydimethylsilyxane Diamine G, molecular weight of 105,000, instead of Polydimethylsiloxane Diamine C and fed at a rate of 13.6 g / min (0.000130 mol / min), methylene dicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.033 g / min (0.000126 mol / min), and the screw speed was 25 revolutions per minute. The resultant segmented polydi ethylsiloxane polyurea copolymers which had an inherent viscosity of 2.52 dL / g was extruded into a strand, cooled in air and collected. 15 Elastomer of Polydylethylsilaxan Polyurea Segmented E Isocyanate of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl was fed at a rate of 0.338 g / min (0.00152 mol / min) in the first zone of a Leistritz 18 mm diameter twin screw extruder under a nitrogen atmosphere with the feed line brushing the screws and injected with Polydimethylsiloxane Diamine A, Lot 2, molecular weight of 5330 , at a speed of -8.0 g / min (0.00150 mol / min) in the second zone. The extruder was used in the cogratory modp with two fully engaged screws, of? Fc double start to the whole length of the drum, ring at 100 revolutions per minute. Sections of 20 mm length of linker blocks were placed in zone 3, 4, and 5. temperature profile for each of the 90 mm long zones was: zone 1 - 30 ° C; zone 2 - 75 ° C; zone 3 - 120 ° C; zone 4 - 130 ° C; zone 5 - 140 ° C; zone 6 - 150 ° C; zone 7 - 155 ° C; zone 8 - 170 ° C; and area or final part - 170 ° C. The fc copolymer of segmented polydimethylsiloxane polyurea The resulting extrudate, which had an inherent viscosity of 1.89 dL / g, was extruded into a strand, cooled in air and collected.

Copolymer of Polydi methylsiloxane Segmented Polyurea 15 Injected Polydimethylsiloxane Diamine A, Lot 1, molecular weight of 5280, at a rate of 227 g / min (0.0430 mol / min) in the seventh zone of a twin-screw extruder, co-guiding, 40 mm in diameter, from Berstorff and fed methylenedicyclohexylene-4,4'-diisocyanate at a rate of 11.26 g / min (0.0430 mol / min) in the eighth zone. Fully geared, double-start screws were used all the way around the drum, ring at 20 revolutions per minute. The temperature profile for each one of the 160 mm long zones was: zone 1 - 20 ° C; zone 2 to 6 - 50 ° C; zone 7 and 8 - 55 ° C; zone 9 - 115 ° C; ft zone 10 - 152 ° C; zone or final part and fusion pump - 180 ° C. The resultant segmented polydimethylsiloxane polyurea copolymer was extruded into a strand, cooled in a water bath, granulated and collected.

Copolymer of Polydi metilsiloxan Segmented Polyurea G ft Polydimethylsiloxane diamine A, Lot 2, was injected molecular weight of 5330, at a rate of 76.1 g / min (0.0143 mol / min) in zone two of a twin-screw, co-ring, 40 mm diameter, Berstorff extruder and tetramethyl-m-diisocyanate was fed xylylene at a rate of 3.97 g / min (0.0163 mol / min) in zone 8 with the power line by brushing the screws. Fully geared, double-start screws were used all the way around the drum, ring at 100 revolutions per minute. The temperature profile for each of the 160 mm long zones was: zone 1 - 27 ° C; zone 2 to 8 - 60 ° ^; zone 9 twenty - . 20-120 ° C; zone 10 - 175 ° C; and area or final part - 180 ° C. The resultant segmented polydimethylsiloxane polyurea copolymer which had an inherent viscosity of 0.46 dL / g was extruded into a strand, cooled in a water bath, granulated, and collected. - 25 Lime Coating of Polidime tílsiloxan Segmented Polyurea H ft The Polydimethylsiloxane Segmented Polyurea Copolymer H was prepared as the Copolymer of Segmented Polydiorganosiloxane Polyurea E, except that a mixture of 50 parts by weight of methylenedicyclohexylene-4, 4-diisocyanate and 50 parts by weight of tetramethyl-m-xylylene diisocyanate was replaced by isocyanate of 3-fc isocyanatomethyl-3,5,5-trimethylcyclohexyl and was fed to a speed of 0.425 g / min (0.00168 mol / min) in the sixth zone, the Polydimethylsiloxane Diamine J, molecular weight of 4930, was replaced by the Polydimethylsiloxane Diamine A and fed at a speed of 7.8 g / min (0.00158 mol / min) in the seventh zone, kneading blocks were placed in zones 3, 4, and 5, and the temperature profile for each of the 90 mm long zones was: zones 1 to 5 - uncontrolled temperatures; zone 6 - 55 ° C; zone 7 - 85 ° C; zone 8 - 150aC; and area or final part - 180 ° C. The resultant segmented polydimethylsiloxane polyurea copolymer, which had an inherent viscosity of 0.51 dL / g was extruded into a strand, cooled in air and collected.

Copolymer of Polydimethylsiloxane Segmented Polyurea I A mixture of 450 parts of Polydimethylsiloxane Diamine A, Lot 1, molecular weight of 5280, 511 parts of Polydimethylsiloxane Diamine B, Lot 1, molecular weight of 10,700, 450 parts of Polydimethylsxloxan Diamine C, Lot 2, molecular weight of 22,000, 450 parts of Polydimethylsiloxane Diamine D, Lot 2, molecular weight of 35,700, 450 parts of fc Polydimethylsiloxane Diamine E , Lot 1, molecular weight of 58,700, 462 parts of Polydimethylsiloxane Diamine F, molecular weight "" * - 71,000, and 454 parts of Polydimethylsiloxen Diamine G, molecular weight of 105,000, with a calculated average molecular weight of 17,500 was fed at a rate of 7.93 g / min (0.000453 mol / min) in the back of the The third zone (open hole) of a Leistritz 18mm diameter two-screw extruder was fed and methylene-cyclohexylene-4,4'-diisocyanate was fed at a rate of 0.118 g / min (0.000450 mol / min) at the front portion of the the third zone. The extruder was used in the cogiratory mode with screws completely geared, double start, all the way out of the drum, turning at 50 revolutions per minute. The temperature profile for each of the 90 mm zones was: zones 1 to 3 - 30 ° C; zone 4 - 45 ° C; zone 5 - 95 ° C; zone 6 - 120 ° C; zone 7 - 160 ° C; and zone 8 and ^ zone or final part -. 25 - 180 ° C. The copolymer of polydimethylsiloxane polyurea segmented, which had an inherent viscosity Ü of 1.26 dL / g was extruded into a strand, cooled in air and collected.

Copolymer of Polydimethylsiloxane Polyurea Segmented J To a 3-neck spherical bottom flask equipped with static nitrogen atmosphere and metal stirrer was added 30 parts of Polydi ethylsiloxane Diamine D, Lot 1, molecular weight of 37,800. The contents of the flask were heated with a heating barrel at 65-70 ° C and placed under a vacuum aspirator for 2 minutes to be degassed. The vacuum was released and the flask was cooled to room temperature under a static nitrogen atmosphere. At temperature At room temperature, 170 parts of toluene were added with stirring followed by 0.212 parts of methylenedicyclohexylene-4,4'-diisocyanate. The flask was continued stirring for 3 days to complete the preparation. This provided a solution of polydimethylsiloxane polyurea copolymer segmented with about 15 weight percent solids.

Copolymer of Polydi etidiphenylsiloxane Segmented Polyurea K - To a 3-neck spherical bottom flask equipped with an oil-heating bath, static nitrogen atmosphere, metal stirring thermometer was added 50 parts ft of Polydiphenyldimethylsiloxane Diamine I, with a molecular weight of 9620 and 154.3 parts of isopropanol. At room temperature, 1.42 parts of ethylenedicyclohexylene-4,4'-diisocyanate were added to the flask with stirring and allowed to react for 20 minutes before the flask was heated to 70 ° C and maintained at that temperature for 2 hours to allow the reaction to complete. This Wf provided a viscous clear, segmented polydifenyldimethylsiloxane polyurea copolymer solution at about 25 weight percent solids. - Preparation of Polidlorganosxloxan Monoamines The following polydiorganosiloxane monoamines are 1 prepared for several examples according to the procedures of US Patent No. 5,091,483, which is incorporated herein by reference. The terminal agent used in the preparation of the monoamines was prepared from according to Example 6 of U.S. Patent No. 5,091,483. The actual numerical average molecular weight of the different batches was determined using the acid titration as described with respect to polydiorganosiloxane and organic polyamines. 25 Terminal Agent of Aminopropyldimethyl Fluorosilane To a 3 L 3-neck spherical bottom flask were added 279.6 g of 1,3-bis (3-amino-5-propyl) -tetramethyldisiloxane, 177.6 g of ammonium fluoride, and about 2 L of cyclohexane. This mixture was made azeotropic with water until it became clear and. then it was separated under vacuum. While heating under reflux, the water was removed using a Dean-Stark trap.

The clear, colorless solution was transferred while heating to a 1-neck, 1-neck, round bottom flask. The solvent was stirred in a rotary evaporator to provide 990 grams of white solid. The solid was dissolved in 2 L of methylene chloride, 193.2 were added grams of hexamethyl disiloxane, and the mixture was stirred and heated under reflux for 16 hours. The solvent was removed f under a vacuum aspirator. The product was distilled (70 ° C boiling point) under a vacuum aspirator to provide 3-aminopropyldimethyl fluorosilane as an oil clear, colorless. The yield was 293.0 g (100%), whose purity was determined by vapor phase chromatography. The structure was confirmed by NMR spectroscopy, Polyd ± methylsiloxane Monoamine ^ A To 1.6 parts by weight of 2.5 M n-butyl lithium were added 7.4 parts by weight of 5-octamethylcyclotetrasiloxane, which had been purged with argon and the mixture was then stirred for 30 minutes; 500 parts of 50% hexamethylcyclotrisiloxane in dry tetrahydrofuran was added and the reaction mixture was stirred at -fc. room temperature for 18 hours until the polymerization was complete. To the resulting viscous syrup were added 3.4 parts by weight (1 mole part) of terminal agent 3-aminopropyldimethyl fluorosilane. The viscosity decreased rapidly. After stirring for 2 hours, the solvent was distilled using a rotary evaporator. He The product was filtered to remove the lithium fluoride and give the polydimethylsiloxane monoamine as a clear, colorless oil. Titration with 1.0 N HCl gave a number average molecular weight of 9830.

Polydimethylsiloxane Monoamine B To 1.6 parts by weight of 2.5 M n-butyl lithium were added 7.4 parts by weight of octamethylcyclotetrasiloxane, which had been purged with argon and. the mixture was stirred then for 30 minutes; 750 ppm of 50% hexamethylcyclotrisiloxane in dry tetrahydrofuran was added and the reaction mixture was stirred at room temperature during 18 hours until the polymerization was complete. To the resulting viscous syrup were added 3.4 parts by weight (1 mole part) of 3-aminopropyldimethyl fluorosilane terminal agent.

The viscosity decreased rapidly. After stirring for 2 hours, the solvent was distilled in a rotary evaporator. The product was filtered to remove the lithium fluoride and give the polydimethylsiloxane monoamine as a clear, colorless oil. Titration with 1.0 N HCl gave a numerical average molecular weight was 14,760. -i, PREPARATION OF POLLIDORGANOSILOXAN OLIGOUREA SEGMENTADOS COPOLYMERS The following segmented polydiorganosiloxane oligourea copolymers were prepared as described below.

Copolymer of Polydimethyloxan Oligourea Segmented A To a 250 mL spherical bottom flask equipped with a mechanical stirrer and static nitrogen atmosphere was added 25 g of Polydimethylsiloxane -Monoamine A, molecular weight of 9830. While stirring, the contents of the flask were heated under a vacuum aspirator to 65.degree. -70 ° C, and Tft after degassing for 2 minutes was cooled to ambient conditions under a static nitrogen atmosphere before adding 50 mL of toluene and stirring until a uniform mixture was obtained. A solution that contained 0. 33 g of methylenedicyclohexylene-4,4'-diisocyanate and 20 L of toluene were added dropwise over a period of 1 minute to the flask with stirring and stirring was continued for 24 hours. fc The solution of the polydimethylsiloxane copolymer oligourea segmented that contained approximately 30% solids was packed in a glass bottle.

Copolymer of Polydi Methylsiloxane Oligourea Segmented B To a 250 mL spherical bottom flask equipped with a mechanical stirrer and static nitrogen atmosphere was added 25 g of Polydimethylsiloxane Monoamine B, molecular weight of 14,760. While stirring, the contents of the flask were • heated under a vacuum aspirator at 65'-70 ° C, and After degassing for 2 minutes, it was cooled to ambient conditions under a static nitrogen atmosphere before adding 35 mL of toluene and stirring until a uniform mixture was obtained. A solution containing 0.22 g of methylenedicyclohexylene-4,4'-diisoeianate and 10 mL of Toluene was added dropwise over a period of 1 minute to the flask with stirring. Stirring was continued for 24 hours. The solution of the segmented polydimethylsiloxane oligourea copolymer containing about 40% solids was packed in a glass bottle.

Polydimethylsiloxan Oligourea Segmented C Copolymer A 250 ml round bottom flask equipped with mechanical stirrer and static nitrogen atmosphere was added 16.7 g of Polydimethylsiloxane Monoamine A, molecular weight of 9830 and 8.3 g of Polydimethylsiloxane Diamine, Lot 2, molecular weight of 10,700. With mechanical agitation the contents of the flask were heated under a vacuum aspirator at 65-70 ° C, and after degassing for 2 minutes it was It was cooled to ambient conditions under a static nitrogen atmosphere before adding 50 mL of toluene and continuing stirring until a uniform mixture was obtained. A solution containing 0.44 g of methylenedicyclohexylene-4,4'-diisocyanate and 20 mL of toluene was added dropwise during A period of 1 minute was added to the flask with stirring and stirring was continued for 24 hours before the solution of the segmented polydimethylsiloxane oligourea copolymer containing about 30% solids was packed in a glass bottle. 25 METHODS OF TESTING « The following test methods were used to characterize the segmented polydiorganosiloxane polyurea copolymer based compositions produced in the following examples.

Adhesion Test at 18CP ft 10 Pressure-sensitive adhesive coatings based on polydiorganosiloxane polyurea copolymer-based segmented over polyester films were coated with a removable coating and cut into 12.7 mm (0.5 inch) strips per 15 cm (6 inches) ). The coating removable was removed and the strip adhered to a clean, solvent-washed 10 cm (4 inch) by 20 cm (8 inch) glass container, using a 2 kg (4-1 / 2 pound) roller last twice on the strip. The bound assembly was maintained at room temperature for approximately twenty minutes the 180 ° adhesion test was performed using an I-Mass adhesion test device at a separation rate of 30.5 cm / minute (12 inches / minute) for a data collection time of 10 seconds. HE. they tested two uestrajt / -e-h value of addition reported is an average for the two samples. Preferably, the pressure sensitive adhesive tapes have a 180 ° adhesion of at least about 5.5 N / dm (ounces / inch) more preferably of at least 21.8 N / dm (20 ounces / inch).

Cut resistance Adhesive coatings sensitive to pressure based of polydiorganosiloxane polyurea copolymer segmented onto polyester film were covered with a release liner and cut into strips of 12.7 mm (0.5 inches) by 15 cm (6 inches). The release liner was removed and the strip adhered to a stainless steel panel so that a 12.7 mm by 12.7 mm portion of each strip was in firm contact with the panel and an end portion of the tape was free. The panel with the attached coated strip was held on a support so that the panel formed an angle of 178 ° with the free end of the extended tape, which was stressed by applying a force of one kilogram applied as a weight hanging from the free end of the coated strip. 2 ° less than 180 ° were used to negate any detachment forces, thus ensuring that only the shear forces were measured, in an attempt to more accurately determine the holding power of the tape being tested. The elapsed time to separate each example of tape from the test panel was recorded as the cut resistance. Unless otherwise noted, all of the cutting failures reported here were cohesive adhesive failures.

Deformation by Accelerated Shear Effort The samples were prepared as for the Shear Strength Test except that a weight of 500 grams and aluminum panels was used, the contact area was 12.7 mm by 25.4 mm, and the support was placed in a forced air oven 70 °. If the sample was still attached to the aluminum panel 10,000 minutes later, the distance the sample slid over the aluminum plate was measured and recorded as the shear strain.

Gel Permeation Chromatography The number average molecular weight of each segmented polydimethylsiloxane polyurea copolymer was determined via gel permeation chromatography with an HP 1090 Chromatograph, an HP Refractive Index Detector 1047A, and an HP Ultraviolet Detector Diode Array placed 254 nanometers before the Addition of the adhesive resin. The copolymer was dissolved in 0.5% tetrahydrofuran, filtered with a fi injection 50 microliters in Mixed Bed of Jordi Association and a Waters 100A. The elution speed was 1.0 ml. The molecular weight given was based on the polystyrene standards obtained from Pressure Chemical Company ^ Pittsburgh, PA.

Inherent Viscosity The inherent viscosities were measured at 3G ° C using a Canon-Fenske viscometer (Model No. 50 P296 ..). Edn chloroform solutions at 30 ° C at concentrations between 0. 18 and 0.26 g / dL. It was found that the inherent viscosities of the materials of the invention were essentially independent of the concentration in the range of 0.1 to 0. 4 g / dL.

Speed d? Humid steam transport (9TR? The Humid Steam Transmission Rate - Upwards (MT u- was measured in samples using a modified ASTK E-96-80.) A laminated sample assembly was first made-a sample of thirty-five millimeters in diameter from a film of 0.025 cm thickness of the adhesive to a 0.0275 cm polyurethane fabric that had an MVTRup of 2000 to 2400 g / m2 / 24 hours measured at 40 ° C and a differential relative humidity * 80 percent. Next, the laminated sample was sandwiched between the adhesive surfaces of two axially aligned sheet adhesive rings having 2.54 cm diameter holes. The sample was pulled to secure a flat sheet, free of wrinkles and gap-free / sample / sheet. Next, a four-ounce container (0.14 liters) was filled with distilled water. The container was equipped with a screw cap that had a hole of 3.8 cm in diameter concentrically aligned with a rubber stopper having an external diameter of 4,445 cm and an internal diameter of 2.84 cm. The sheet / sample / sheet sheet was placed concentrically on the rubber stopper and the sub-assembly containing the sample was screwed loosely onto the container. The sample was then tested in the assembly. The assembly was balanced by placing it in a chamber maintained at a temperature of 40 ° C and a relative humidity of 20 percent. After four hours, the assembly was removed from the camera and weighed to an accuracy of 0.01 grams (Wi), the lid was screwed tightly on the jar without buckling the sample, and the assembly was immediately returned to the chamber for 18 more hours. The assembly was then removed and weighed to an accuracy of 0.01 grams (W2).

The MVTRUp of the laminated sample (measured in grams of water transmitted per square meter of sample area over a twenty-four hour period) was then calculated according to the formula set out below: 5 MVTRup = (Wx - W2) (4.74 x 10) / t where: i is the initial weight of the assembly (grams), W2 is the final weight of the assembly (grams), and • ?? t is the period of time between i and W2 (hours). 10 Three samples of each adhesive were tested and se. reported the average of the three samples. . "The Wet Vapor Transmission Rate" - Inverted (MVTRinvt) was measured in the same way as the MVTRup except that the assembly was reversed inside the chamber one time the layer was tightly screwed onto the container, so that the Water came directly in contact with the foil sheet / sample / sheet while the assembly was inside the chamber.

Skin Adhesion Test The skin adhesion test was carried out by placing tape samples 2.5 cm wide by 5 cm long on the back of a human subject. Each tape is placed a 2 Kg roller moving forward and backward at a speed of approximately 30 cm / min. The adhesion to the skin was measured as the detachment force required to remove the tape at an angle of 180 ° at a removal rate of 15 cm / min. Adhesion was measured 5 directly after the initial application (T0) and 24 hours after (T24). Preferred skin adhesives generally exhibit a T0 of about 50 to 100 grams (1.9 to 3.8 N / dm) and T2 of between about 150 to fcr 300 grams (5.8 to 11.5 N / dm). The results were averaged out of 9 tests to give the reported value. F Skin Adhesion Lifting Test When the skin adhesion test for 24 hours was done, the samples of tape were examined for ML determine the amount of the area that was lifted (peeled) off the skin before removal of the tape and the following qualifications were given as: 0 non-visible lifting 20 1 lifting only at the edges of the belt 2 lifting about 1% at 25% of the test area 3 survey over 25% to 50% of the test area 4 survey over 50% to 75% of the test area 5 survey over 75% to 100% of the test area 25 The results of 9 tests were averaged to give * the reported value. Preferred skin adhesives generally exhibit an average rating of less than about 2.5. 5 Test of Residuals of Adhesiro for the Skin When the skin adhesion test was performed for 24 hours, the skin under the test sample was visually inspected to determine the amount of adhesive residue on the surface of the skin and scored as: 0 non-visible residues 1 waste only at the edges of the belt 15 2 residues covering 1% to 25% of the test area 3 residues covering 25% to 50% of the test area 4 residues covering 50% to 75% of the test area 20 5 waste covering 75% to 100% of the test area.

The results of 9 tests were averaged to give the reported value. Preferred skin adhesives will generally exhibit an average rating of less than about 2.5.

Crash Properties (Storage Module and Loss Factor) Thickness samples of approximately 750 μm were prepared using one of the following methods; 1) coating a solution of vibration damping material, using a knife coating device with an orifice positioned between about 250 to 380 μm, on a removable 50 μm polyethylene terephthalate facing and drying for 1 minute at 70 ° C followed by 10 minutes at 175 ° C and laminating in several pieces of the resulting vibration buffer layer together under pressure through a pressure roller to obtain samples of the appropriate thickness. 2} by pouring a solution of the vibration dampening material directly onto the release liner at the bottom of a shallow reservoir and allowing it to dry for about 2 days on condition that ambient conditions are obtained to obtain a sample of the proper thickness, or 50 μm, at 160 ° C to obtain a sample of the appropriate thickness. The storage module, G ', and the loss factor, tan d, were determined using a Dynamic Mechanical Analyzer from Polymer Laboratories (DMTA) Mark II and a multiplexing frequency technique during a thermal scan, ie Properties were measured when both the "frequency and the temperature changed." Temperatures varied from -100 ° C to 200 ° C at a rate of 2 ° C / minute continuous at a fixed effort of 1. Measurements were reported at a frequency of 1.0 Hz and were taken at intervals of approximately 3 ° C to 5 ° C and interpalated to obtain measurements at 10 ° C intervals for reporting purposes., the utility window of the storage module, G ', refers to the temperature range over which the storage module is between 3.45xl0 Pa and 6.9x106 Pa. The utility window of the loss factor, tan d, refers to to the temperature range over which the loss factor is greater than 0.4"The useful temperature range refers to the temperature range over which the storage modulus, G ', is between 3.45 x 105 Pa and 6.9 x 106 Pa and the loss factor, tan d, is greater than 0.4.Where indicated, the flow to molten mass means that the sample exhibited flow in the form of a melt at high temperature * The flow in the form of melt It is generally undesirable for damping applications, so that materials that exhibit flow in the form of a melt should be used below the flow temperature in the form of a melt.; - Thermally Activated Adhesive Bonding Test The segmented polydiorganosiloxane polyurea copolymers were tested as thermally activated adhesives by creating cut specimens superimposed, between two steel members, which had an overlap area of approximately 1.61 cm2 and pulling the cut sample overlaid on a Sintech test machine of the frame type E a head speed of 50.8 cm / min to evaluate adhesion. The samples were prepared for the test as follows. Steel members measuring 0.32 cm x 1.27 cm x 5.08 cm were cleaned with a sand blast. The 30-milimeter-thick layer of the segmented polydiorganosilaxan polyurea copolymer measuring about 1.3 cm per side, prepared using the methods described in the "Shock-absorbing Properties" section, was placed on one end of a steel member and cut. to create a joint area measuring 1.27 cm on each side, the adhered thickness was controlled by placing two parallel strands of copper wire 12 mils in diameter, oriented in a transverse direction with respect to the longitudinal dimension of the steel, on the polydiorganosiloxane polyurea copolymer segmented to approximately 0.2 cm from the edges of the adhesive The joint was covered with a second piece of steel and held in place with a small spring-loaded sidewalk fastener The overlaid Jfc 1a sample was placed in place. in a forced air oven for 10 minutes at 180 °, it was stirred, -was allowed to cool to ambient air conditions. and, and it was shown as described above. The maximum stress at breakage was reported in MN / mm2.

Measurements of Iapedancy spectroscopy, E & ametropy (E1S) The EIS measurements gave information on the level of corrosion protection provided by the coatings on metal, providing a convenient method for studying pressure sensitive adhesives in one aspect of the invention. Detailed information for this type of impedance measurement exists in an article by M. Kendig and J. Scully ("Corrosion", vol 46, No. 1, pages 22-29 (1990)). The measurements were made according to ASTM-G 106 with 3% NaCl in a deionized water solution.

Dry Adhesion Test and Protection Against Corrosion L03 cold rolled steel panels were cleaned by abrading with steel sand followed by removal of excess sand. A pressure sensitive adhesive tape was made by extruding 0.2 mm of pressure sensitive adhesive over a 0.1 mm thick polyester film. Then strips of 30 x 1.9 cm of this construction were placed against the steel, and a uniform application was made on the strip to the steel by passing a 2 kg roller. The sheet was then left at conditions of one hour at room temperature. The adhesion test was carried out at an angle of 180 ° and a speed of 30.5 cm / min.

Wet Adhesion Test and Protection Against Corrosion After abrasion with steel sand, as described under the Dry Adhesion and Corrosion Protection Test, the steel test panel was subjected to three alternate immersion cycles, then the steel was dried to develop oxidation on the test surface. The pressure-sensitive adhesive tape was then applied to the surface of the plate through tap water, followed by two hours of conditioning, and finally the adhesion or release test.

Static Cutting Test for Corrosion Protection Were static cuts made according to AS? D3654-78, PSTC-7. Pressure-sensitive adhesive coatings were coated in solution at 25 a 38μm In the following examples, all of the polyisocyanates and organic polyamines were used as received and the isocyanate to amine ratios were calculated using the polyisocyanate molecular weight reported by the polyisocyanate distributor and the molecular weights of the polydiorganosiloxane and organic polyamine, wherein the Molecular weights were determined by acid titration and / or were reported by the distributor.

Examples Ej saplos 1 - 7 In Example 1, the dry MQ adhesive resin containing 1.3% toluene, obtained from GE Silicone Products Division, Waterford, NY, as experimental material # 1170-002, was fed into the first zone of a two-screw extruder of 18 mpt of diameter of Leistritz at a speed ^ ^ - of 6.33 g / min. Polydi-ethylsiloxan Diamine-A, Lot 1, molecular weight of 5280, was fed to the rear of the fourth zone of the extruder at a rate of 6.22 g / min (0.001188 mol / min). Methylenedicyclohexylene-4, -diisocyanate was fed to the front portion of the fourth zone at a rate of 0.321 g / min (0.00123 mol / min). The diisocyanate feed line was placed sufficiently close to the screws so that each pass of the screw threads touched a small amount of the diisocyanate on the screw. The extruder was used in cogiratory mode with fully geared, double-start screws rotating at 75 revolutions per minute. The temperature profile for each of the zones of 9-0 mm in length - was: zone 1 - 30 ° C; zone 2 - 34 ° C; zone 3 - 43 ° C; zone 4 - 66 ° C; zone 5 - 120 ° C; zones 6 and 7 - 150 ° C - zone 8 - 180 ° C; and area or final part - 19O ° C. The resulting pressure sensitive adhesive was extruded into a strand, cooled in air, and collected. The pressure sensitive adhesive was later dissolved in toluene / isopropyl alcohol (50/50) at 30 percent solids, coated on a polyethylene terephthalate film of 38 μm (1.5 mils) in thickness with a knife coating device, and dried in the air. In Example 2, a pressure sensitive adhesive based on polydiorganosiloxane polyurea was prepared as in Example 1, except that Polydimethylsiloxane Diamine B, Lot 1, molecular weight of 10,700, was replaced with Polydimethylsiloxane Diamine A and fed at a rate of 6.22 g / min (0.000581 mol / min), methylenedicyclohexylene-4, 4 ' - diisocinato was fed at a speed of 0.170 g / min (0.000649 mol / min), and the temperature profile was zone 1 - 30 ° C; zone 2 - 32 ° C; zone 3 - 38 ° C; zone 4 - 56 ° C; zone 5 - -F- 100 ° C; zone 6 - 140 ° C, and 7 - 150 ° C; zone 8 - 180 ° C; and area or final part - 190 ° C. The resulting adhesive was collected and the solution was coated as described in Example 1. In Example 3, a pressure sensitive adhesive based on polydiorganosiloxane polyurea was prepared as in Example 2, except that Polydimethylsiloxane Diamine C was used. , Lot 1, molecular weight of 22,300 and fed at a speed of .6.22 g / min (0.000279-- mol / min), and the Methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.0850 g / min (0.000324 mol / min). The adhesive ~ mmM. Sensitive to the resulting pressure was collected and the solution was coated as described in Example 1. In Example 4, the 18 mm extruder used was used. in Example 1 in the counter-rotating mode. He fed Polydimethylsiloxane Diamine F, molecular weight of 71,000, in the first zone of the extruder at a speed of 6.40 g / min (0.0000901 mol / min.) Dry MQ adhesive resin was fed, will dry to approximately 1% toluene by evaporation of toluene in SR-545 at room temperature for four days, then further drying under vacuum at 55tc for lh hours, in the second zone of the extruder at 6.4 g / min. Methylenedicyclohexylene-4,4'-diisocyanate was fed into zone 6 of the extruder at 0.0225 g / mip (0.0Q00859 mol / min).

The rotation of the screw was 120 revolutions per minute. The temperature profile for each of the 90 mm long zones was: zone 1 - 30 ° C; zones 2 - 5 - 50 ° C; zone 6 - 70 ° C; zones 7 - 8 and area or final part - 145 ° C. The extrudate was cooled in air and collected. The adhesive sensitive to The resultant polydiorganosiloxane polyurea pressure was collected and the solution was coated as described in Example 1. In Example 5, dry, spray-dried MQ adhesive resin was fed to 1% toluene of SR-545 under nitrogen, at a speed of 77.2 g / min in the first zone of a co-rotating two-screw extruder, of 1600 mm * Length, 40 mm diameter, Berstorff, 10 zones, equipped with double start screws, with full self-cleaning. Polydimethylsiloxane diamine H, molecular weight of 9970, was injected at a rate of 75.5 g / min (0.00757 mol / min) in the second zone. Tetramethyl-m-xylylene diisocyanate was fed into zone 8 of that extruder at a rate of 2.01 g / min (0.00824 mol / min) with the feed line brushing the screws. The speed of # 10 screw extruder was 100 revolutions per minute and the temperature profile for each of the areas of 160 mpt was: zone 1 - 27 ° C; zones 2 to 8 - 60 ° C; zone 9 - 120 ° C; zone 10 - 175 ° C; and area or final part - 180 ° C. • The inherent viscosity of the polydimethylsiloxane copolymer portion segmented oligourea of the pressure sensitive adhesive, harvested before the MQ resin added to the extruder, was 0.83 dL / g. The resulting pressure sensitive adhesive was collected and the solution was coated as described in Example 1. In Example 6, tetramethyl-m-xylylene diisocyanate was fed at a rate of 0.079 g / min (0.000324 mol / min. ) in the first zone of a 1200 mm long, 34 mm diameter counter-rotating extruder from Leistritz with. the line dß feeding brushing slightly screw threads. HE} , extruder was equipped with double starter screws, * ^ P fully engaged, rotating at 125 revolutions per minute. Polydi ethylsiloxan Diaraine E, Lot 2, molecular weight of 52,900 was injected into the second zone of the extruder at a rate of 17.0 g / min (0.000321 mol / min). Queen MQ was fed, dried as in Example 5, at a rate of 16.9 g / min in the fifth zone of the extruder. The temperature profile was: zone 1 - 20 ° C; zones 2 - 50 ° C; zone 3 - 80 ° C; zone 4 - 130 ° C zone 5 - 170 ° C; zones 6 up to 10 and zone or final part - 180 ° C. The extrudate was cooled in aitβ and collected. The resulting pressure sensitive adhesive. Sft- was collected and coated in solution as described in Example 1. In Example 7, dried, dried MQ resin was fed. as in Example 4 and Polydimethylsiloxane Diamine C, Lot 2, molecular weight of 22,000, at a rate of 14.7 g / min (0.000668 mol / min) in the first zone of a screw extruder, cogiratory, 1200 mm long, 34 mm in diameter, from Leistritz. Isocyanate of 3- 20 isocyanato-methyl-3,5,5-trimethylcyclohexyl was fed at a rate of 0.182 g / min (0.000820 mol / min) in the fifth zone of the extruder with the feed line away from the screw threads. The fully engaged, double-start screws rotated at 30 revolutions per minute. He temperature profile for each of the 120 mm zones. it was: zone 1 - 30 ° C; zone 2 to 5 - 50 ° C; zone 6 - 100 ° C; zones 7 and 8 - 150 ° C; zones 9 and 10 - 160 ° C; and area or final part - 180 ° C. Vacuum was drawn in zone 8. The resulting pressure sensitive adhesive was collected and coated in solution as described in Example 1. Each of the pressure sensitive adhesive tapes of Examples 1-7 had a thickness of approximately 0.025 mm (1 thousandth of an inch). Each tape was tested to determine adhesion at 180 ° and * 10 resistance to cutting. The results are shown in Table 1.

Table 1 fifteen twenty As can be seen from the data in the Table Tft 1, the increase in molecular weight of the diamine in Examples 1-4 from 5280 to 10,000 to 22,300 to 71,000, respectively, and the use of methylenedicyclohexylene-4, '-diisocyanate caused an increase in the peel strength at 180 °. and some reduction in cut resistance. Examples 2 and 5 show that for diamines with similar molecular weight, the substitution of tetramethyl-m-xylylene diisocyanate with methylenedicyclohexylene-4,4'-diisocyanate caused an increase in the peel strength at 180 °. The increase in molecular weight of the diamine in Example 5 and 6 from 9970 to 52,900 and the use of tetramethyl-m-xylylene diisocyanate decreased the release values and the resistance to cut was reduced. Examples 3 and 7 show that for diamines of similar molecular weight, the substitution of the isocyanate of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl by methylenedicyclohexylene-4,4'-diisocyanate causes an increase in the peel strength at 180.degree. °. 20 Examples 8-12 In Example 8, the SR-545 MQ is dried as in the Example 5, and se. fed into the first zone- of an extruder two screws, co-rotating, 30 mm in diameter, 1350 mm in length, from Werner-Pfleiderer at a speed of 39.4 g / min. Polydimethylsiloxane Diamine D, Lot 2, molecular weight of 35,700 was injected into the third zone of the extruder at a rate of 38.8 g / min (0.00109 mol / min). 5 Methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.290 g / min (0.00111 mol / min) with the diisocyanate feed line by lightly brushing the screw threads. All the screws were double fc drag screws fully engaged, and the rotation speed was 200 revolutions per minute. The temperature profile of each of the 90 mm zones was: zones 1 to 3 ** 50 ° C; zones 4 to 6 - 60 ° C; zones 7 and 8 - 115 ° C; zones ^ up to 13 - 170 ° C; zone 14 - 180 ° C; and zone 15 - 151 ° C. Vacuum was drawn in zone 13. The adhesive sensitive to The resulting pressure was extruded into a 3 mm diameter strand, placed in a water bath and collected. The pressure-sensitive adhesive was subsequently hot melt coated with a 1.9 cm (3/4 inch) diameter single screw extruder (Haake) rotating to 40 revolutions per minute. The temperature profile of the extruder was: zone 1 - uncontrolled; zone 2 - 163 ° C; zone 3 - 188 ° C. The temperature of the nozzle and the die (12.7 cm wide) were 210 ° C. The extrudate was emptied between pressure rollers with a film. "Of polyethylene terephthalate of 35.6 μm (1.4 mils) on one roller and one removable coating on the other. In Example 9, dried SR-545 MQ resin, dried as in Example 5, in a manner similar to Example 7 was fed at a rate of 13.0 g / min in the first zone of a counter-rotating extruder, 1200 mm in length, 34 mm in diameter, from Leistritz, equipped with double start screws, fully engaged, - rotating at 250 revolutions per minute. Polydimethylsiloxane was injected. ft 10 Diamine F, molecular weight of 71,000 in the second zone of the extruder at a rate of 13.2 g / mip (0.000186 mol / min) Methylenedicyclohexylene * -4, '-diisocyanate was fed at a rate of 0.0550 g / min (0.000210 mol / min) in the eighth zone of the extruder with the feeding line brushing slightly screw threads. The temperature profile was: zone 1 - 60 ° C; zone 2 - 50 ° C; zones 3 to 7 - 60 ° C; zone 8 - 95 ° C; zone 9 - 120 ° C; zone 10 - 160 ° C; and area or final part - 19 ° C. The resulting adhesive was collected and hot melt coated as described in Example 8. In Example 10, a pressure sensitive adhesive based on polydiorganosiloxane polyurea was prepared as in Example 9, except that the pulverized SR-545 MQ was fed at a rate of 16.1 g / min.

In Example 11, a pressure sensitive adhesive based on polydiorganosiloxane polyurea was prepared as in Example 10, except that the dried SR-545 MQ resin was added at a rate of 14.4 g / min, Polydimethylsiloxan was injected Diamine G, molecular weight of 105,000, at a rate of 14.1 g / min (0.000134 mol / min), methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.044 C g / min (0.000168 mol / min), and the temperature profile was: zone 1 -j? 40 ° C; zone 2 - 59 ° C; zone 3 - 53 ° C; zone 4 - 61 ° C; zone 5- - 57 ° C; zone 6 - 54 ° C; zone 7 - 66aC; zone 8 - 95 ° C; zone 9 - 120 ° C; zone 10 - 160 ° C; and area or final part - 190 ° C. The inherent viscosity of the co-polymer portion of the segmented polydimethylsiloxane oligurose from the pressure sensitive adhesive, collected before the MQ was added. to the extruder was 1.82 dL / g. In Example 12, a homogeneous mixture of 25 percent Polydimethylsiloxane Diamine A, Lot 1, molecular weight of 5.280, and 75 weight percent of Polydimethylsiloxane Diamine E, Lot 1, molecular weight of 58,700. This diamine mixture was fed at a speed of 16.0 g / min (0.000962 mol / min) into the first zone of a 1224 mm long, 34 mm diameter co-rotating extruder, from Leistritz, equipped with fully geared double start screws. spinning at 50 revolutions per minute. MQ-dried SR-545 resin was added in a similar manner to Example 4 in the second extrusion zone at a speed of 15.7 g / min. Methylenedicyclohexylene-4,4'-diisocyanate was fed into the sixth zone of the extruder at a rate of 0.270 g / min (0.00103 mol / min) with the line of feed by lightly brushing the screw threads. The extruder temperatures were: zone 1 - 20 ° C; zone 2 - 35 ° C; zone 3 - 35sC; zone 4 - 50aC; zone 5 - 50 ° C; zone 6 - 86 ° C; zone 7 - 150 ° C; zone 8 - 170 ° C; zone 9 - ^ 180 ° C; zone 10 - 18Q ° C; and area or final part - 170 ° C. He The resulting adhesive was collected and hot melt coated as described in Example 8. Each of the hot-melt pressure sensitive adhesive tapes of Examples 8-12 was tested for 180 ° adhesion. and 15 resistance to cutting. The adhesive thickness of the tapes was approximately 38 μm (1.5 mils) for Examples 8, 10 and 12, and approximately 50 μm (2 mils) for Examples 9 and 11. The results are set forth in Table 2 Table 2 As can be seen from the data in Table 2, the molecular weight increase of the diamine from 35,700 in Example 8 to 105,000 in Example 11, using mixtures of two diamines with different molecular weights in Example 12, or making varying the concentration of adhesive resin in Examples 9 and 10 all resulted in a satisfactory 180 ° peel strength and cut resistance.

Examples 23-17 In Example 13, a pressure sensitive adhesive based on polydiorganosiloxane pbliurea was prepared as in Example 3, except that Polydimethylsiloxane Diamine E, Lot 1, molecular weight 58,700, was replaced by Diamine Ca at a rate of 14.7 g / min (0.000250 mol / min) and resin the resin SR-545, dried as in Example 4, at a speed of 14.8 g / min, were fed into the first zone of the extruder. A solution of 18.0 parts of methylenedicyclohexylene-4,4'-diisocyanate, 72.9 parts of octamethylcyclo-tetrasiloxane; and 9.1 Parts of tetrahydrofuran in the seventh zone of the extruder so that the flow rate of methylenedicyclohexylene-4,4'-diisocyanate was 0.063 g / min (0.00024 mol / min). The screw speed was 60 revolutions per minute, and the temperature profile was: zone 1 - 30 ° C; zones 2 to 7 - 150 ° C; zones 8 and 9 - 160 ° C; and zone 10 and area or final part - 180 ° C. No vacuum was drawn in this sample. The resulting adhesive was collected and the solvent was coated as described in Example 1. In Example 14, the pressure sensitive adhesive based on polydiorganosiloxane polyurea was prepared as in Example 13, except that a solution containing 18.5 parts of isocyanate of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl, 74.1 parts of octamethylcyclotetrasiloxane and 7.4 parts of tetrahydrofuran by the solution of methylenedicyclohexylene-4,4'-diisocyanate and was fed in zone 7 at a rate of 0.054 grams of diisocyanate / min (0.00024 mol / min) and the MQ resin was fed into the first zone, (the MQ adhesive resin containing less than 0.1% toluene, was obtained from GE Silicone Products Division, Waterford, NY), and the temperature of zone 10 and the area or final part was 180 ° C. The resulting adhesive was collected and the solvent was coated as described in Example 1. In Example 15, the pressure sensitive adhesive based on polydiorganosiloxane polyurea was prepared as in Example 14, except that the resin SR-545, dried as in Example 4, it was fed at a rate of 17.4 g / min. The resulting elastomer was collected and the solvent was coated as described in Example 1. In Example 16, the pressure-sensitive adhesive based on polydiarganosilyxane polyurea prepared in the Example 15 was dissolved, under vacuum, and dried following the procedure of Example 1 and subsequently exposed to electron beam irradiation (0.75 MRad). In Example 17, a pressure sensitive adhesive based on polydiorganosiloxane polyurea was prepared as in Example 13, except that a solution containing 18.5 parts isocyanate of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl, 74.1 was replaced. parts of octamethylcyclotetrasiloxane and 7.4 parts of tetrahydrofuran by the solution of methylenedicyclohexylene-4,4'-diisocyanate and was used at a rate of 0.054 grams of diisocyanate / min (0.00024 mol / min) and the temperature profile in zone 10 and zone g final part was 160 ° C. The resulting adhesive was collected and solvent coated as described in Example 1. Each pressure-sensitive adhesive tape had an adhesive thickness of approximately 25 μm (1 mil) and was tested for the 180 ° adhesion test. ° Cut resistance. The results are shown in Table 3.

Table 3 As can be seen from the data in Table 3, Examples 13-15 demonstrate that diluents can be used. Example 16 demonstrates that the crosslinking of the adhesive using electron beam radiation affects only slightly the adhesion at 180 ° C while the resistance ft to the cut is improved.

Examples 18-21 5 In Example 18, methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.59 g / min (0.0023 mol / min) into the back of the first zone of a two screw extruder. , cogiratory, of 1200 mm of ft 10 length, 34 mm of diameter, of Leistritz and Polydimethylsiloxane Diamine A, Lot 4, molecular weight of 5,260, is added in the front portion of the zone 1 of the extruder at a speed of 10.9 g / min (0.00207 mol / min). The screws were elements with a separation of 12 mm, double start fully engaged, rotating at 150 revolutions per minute. The temperature profile for each of the 120 mm zones was: zone 1 - 30 ° C; zone 2 - 150 ° C; zone 3 - 160 ° C; zones 4 to 10 and area or final part - 170 ° C. The product of the polydimethylsiloxane polyurea copolymer The resulting 20 segmented was cooled and collected. Subsequently, 6.0 g of segmented polydimethylsiloxane urea copolymer, a solution of 14.7 g of SR-545 resin, 4.8 g of toluene, and. 4.5 g of 2-propanol were introduced into a glass vessel, stirred slowly to dissolve the copolymer and obtain a uniform composition, and then coated on a polyethylene terephthalate film of F 50 μm (2 mils) thick using a knife coating device and allowed to dry at ambient conditions for 15 minutes followed by 15 minutes at 70 ° C in a forced air oven, to provide a coating thickness of pressure sensitive adhesive 50 μm (2 mils). The adhesion at 180 ° was 30 N / dm. In Example 19, an elastomer of polydimethylsiloxane polyurea segmented as in Example 18, except that methylenedicyclohexylene-4,4 * -diisocyanate was fed at a rate of 0.26 g / min (0.Q0099 mol / min), Polydimethylsiloxane Diamine C, Lot 3, molecular weight was fed of 19,000, at a speed of 18.1 g / min (0.000953 mol / min), the screw speed was 100 revolutions per minute, and the temperature profile was: zone 1- 30 ° C; zone 2 - 155 ° C; zone 3 - 175 ° C; zones 4 to 8 - 200 ° C; zone 9 - 220 ° C; and zone 10 and zone or final part - 200 ° C. The pressure sensitive adhesive solution was prepared as in in Example 18, except that the viscosity of the solution was adjusted by adding 7.5 g of toluene / 2-propanol mixture 70/30 (by weight) to obtain a coatable viscosity. The solution was coated to produce the same dry coating thickness as in Example 18. The "180" adhesion was 58 N / dm.

In Example 20, methylenedicyclohexylene-4,4'-diisocyanate was fed at 0.0715 g / min (0.000273 msl / min) and Polydimethylsiloxane Diamine D, Lot 1, molecular weight 37.800, at 7.96 g / min (0.000211 mol / min), in the first zone of 5 a 18 mm twin screw extruder from Leistritz. The extruder was used in the cogiratory mode with fully geared, double-start screws all the way through the drum, rotating at 100 revolutions per minute. The temperature ife profile for each of the 90 mm zones was: 1-30 ° C; zone 2 - 77sC; zone 3 - 120 ° C; zones 4 - 130 ° C; zone 5 - 140 ° C; zone 6 - 155 ° C; zone 7 - 165 ° C; zone 8 - 175 ° C; zone or final part - 180 ° C. The pressure sensitive adhesive solution was prepared as in Example 18, except that an additional 45 g of toluene / 2-propanol mixture was added. 70/30 (by weight) to obtain a coatable viscosity. The solution was coated to produce the same dry coating thickness as in Example 18. The 180 ° adhesion was 72 N / dm. In Example 21, dß copolymer was prepared polydimethylsiloxane polyurea segmented as in Example 18, except that methylenedicyclohexylene-4'-diisocyanate was fed at a rate of 0.060 g / min (0.00023 mol / min), Polydimethylsiloxane Diamine E, Lot 1, molecular weight of 58,700 was fed , at a speed of 13.1 g / min (0.000223 mol / min), the screw speed was 50 revolutions per minute. 66.7 g of a pressure sensitive adhesive solution composed of 150 parts of segmented polydimethylsiloxane urea copolymer and 600 parts of toluene / 2-propanol 70/30 (by weight) and 32.5 g of resin solution SR-545 MQ were introduced. in an 8-ounce glass container and stirred slowly to dissolve the copolymer and obtain a uniform composition. A coating was prepared as in Example 18. The 180 ° adhesion was 97 N / dm. The pressure-sensitive adhesive tapes prepared in Examples 18-21 illustrate, that the copolymers? of polydimethylsiloxane polyurea segmented extruded in a reactive manner polydimethylsiloxane derivatives of a variety of molecular weights ranging from about 5,000 to 60,000 provide pressure sensitive adhesives when they become adhesives with MQ resins in solution. When the molecular weight of the diamine used increases, the 180 ° adhesion also increases.

Example 22 In Example 22, methylenedicicla-henylene-4,4'-diisocyanate was fed into the first zone of a 18-mm, co-rotating, two-screw extruder, of Leistritz at a rate of 0.190 g / min (0.000725 mol / min) under a nitrogen atmosphere and a homogeneous mixture of 25.0 weight percent Diamine A, Lot 3, molecular weight of 5.570, and 75.0 weight percent Diamine E, Lot 3, 5 molecular weight of 50,200, mixed was injected. day before the reaction and having a calculated numerical average molecular weight of 16,700, in the second zone at a rate of 11.3 g / min (0.000677 mol / min). The extruder had screws f fully geared, double start, all the length of the drum, rotating at 100 revolutions per minute. The temperature profile of each of the 90 mm zones was: zone «l - 30 ° C; zone 2 - 75 ° C; zone 3 - 120 ° C; zone 4 - 130 ° C; zone 5 - 140 ° C; zone 6 - 150 ° C; zone 7 - 155 ° C; zone 8 - 170 ° C; and area or final part - 170 ° C. Sixteen were introduced grams of segmented polydimethylsiloxane polyurea copolymer, 25.9 g of SR-545 MQ resin solution, and 33 g of toluene / 2-propanol 70/30 in a glass vessel and stirred slowly overnight to dissolve the copolymer and provide a uniform solution. A preparation was prepared coating as in Example 1. The adhesion at 180 ° was 97 N / dm. The composition prepared in this example illustrates that reactive extruded segmented polydimethylsiloxane polyurea copolymers derived from a mixture of polydimethylsilaxane diamines of two different molecular weights provide a pressure sensitive adhesive when making MQ resin adhesives in solution.

Examples 23-29 In Example 23, Polydimethylsiloxane Diamine D, Lot 1, molecular weight of 37,800 was fed at a rate of 22.5 g / min (0.000595 mol / min) into zone 2 of an extruder, cogiratory, 1224 mm long, 34 mm diameter *. ™ from Leistritz and methylenedicyclohexylene-4, 4 * -diisocyanate was added at a rate of 0.206 g / mip (0.000786 mol / min) in the area eight with the line dß power brushing lightly the screws. The extruder was equipped with double-start screws, fully engaged, rotating at 50 revolutions per minute. The temperature profile was: zone 1 - 30 ° C; zone 2 - 50 ° C; zone 3 - 80 ° C; zone 4 - 130 ° C; zone 5 - 160 aC; zone 6 - 170 ° C; and zones 7 to 10 and zone or final part - 180 ° C. The product of the segmented polydimethylsilyxane polyurea copolymer was cooled and collected. Then they waved 150 g of the segmented polydimethylsiloxane urea copolymer and 600 g of toluene / 2-propanol (70/30 by weight) slowly in a vessel to form a copolymer solution of. segmented polydimethylsiloxane polyurea. Then 81.3 g of copolymer solution, 14.2 g of SR-545 MQ resin solution, and 4.6 g of toluene / 2-propanol (70/30 by weight) were mixed to obtain a homogeneous solution. The coatings were made as in Example 18. The results of accelerated adhesion and deformation due to cutting are shown in Table 4. In Example 24, a pressure-sensitive adhesive was made based on polydimethylsiloxane polyurea copolymer segmented as in Example 23, except that 75.0 g of the co-polymer solution of Example 23 was added to 16.2 g of SR-545 solution and 8.2 g of toluene / 2-propanol. The The sample was coated as in Example 23. The results are set forth in Table 4. In Example 25, a pressure-sensitive adhesive based on segmented polydimethylsiloxane polyurea copolymer was made as in Example 23, except that they were added. 68.7 g of the copolymer solution of Example 23 to 18.2 g of SR-545 solution and 13.0 g of toluene / 2-propanol. The sample was coated as in Example 23. The results are set forth in Table 4. In Example 26, an adhesive sensitive to the pressure based polydimethylsiloxane polyurea copolymer segmented as in Example 23, except that 62.5 g of the copolymer solution of Example 23 was added to 20.2 g of SR-545 solution and 17.3 g of toluene / 2-propanol. The sample was coated as in Example 23 .. The results were are shown in Table 4.

In Example 27, an adhesive sensitive to the W 'pressure based on polydimethylsiloxane polyurea copolymer segmented as in Example 23, except that they were added 56. 3 g of the copolymer solution of Example 23 at 22.3 g of solution of SR-545 and 21.5 g of toluene / 2-propanol. The sample was coated as in Example 23. The results are set forth in Table 4. In Example 28, a pressure sensitive adhesive based on polydimethylsiloxane polyurea copolymer was made. segmented as in Example 23, except that they were added 50. 0 g of the copolymer solution of Example 23 to 24.3 g of SR-545 solution and 25.7 g of toluene / 2-propansl. The sample was coated as in Example 23. The results are set forth in Table 4. In Example 29, a pressure-sensitive adhesive based on segmented polydimethylsiloxane polyurea copolymer was made as in Example 23, except that they added 43. 8 g of the copolymer solution of Example 23 to 26.3 g of SR-545 solution and 30.0 g of toluene / 2-propanol. The The sample was coated as in Example 23. The results are set forth in Table 4.

Table 4 The compositions prepared in Examples 23-29 illustrate that a wide range of MQ resin concentrations effectively render adhesives of segmented polydimethylsiloxane polyurea copolymer reactive extruded to provide pressure sensitive adhesives based on segmented polydimethylsiloxane polyurea copolymer. When the amount of MQ adhesive resin was increased to 55 percent by weight, the values of 180 ° detachment were increased. The deformation due to the cut was increased by increasing the quantities of resin MQ -.- Examples 30-31 ft. In Example 30, Polydimethylsiloxap Diamine C, Lot 1, molecular weight of 22,300, was injected at a speed of 25.9 g / min. 0.00116 mol / min) in zone 5 of a fully-geared, fully rotating two-screw extruder, 8-zone 34 mm from Leistritz, and methylenedicyclohexylene-4, 4 * -diisocyanate was added in zone 6 open at a rate of 0.335 g / min (0.00128 mol / min) with the power line 10 brushing the screws. The ß temperature profile of each of the 160 mpi longi areas are: zone 4 - 25 ° C; zone 5 - 50 ° C; zone 6 - 75 ° C; zone 7 - 120 ° C; zone 8 - 150 ° C; and area or final part - 180 ° C. The screw speed was 45 revolutions per minute. HE introduced 50.0 g of segmented polydimethylsiloxane polyurea copolymer, 79.0 g of SR-545 solution, and 193.5 g of toluene / 2-propanol (70/30 by weight) in a glass vessel and stirred slowly to obtain a solution homogeneous A coating was prepared as in Example 18.

The adhesion at 180 ° was 41 N / dm. In Example 31, a segmented polydimethylsiloxane polyurea copolymer was prepared as in Example 30, except that the Polydimethylsiloxane Diamine C, Lot 1, molecular weight of 22,300, was fed at a rate of. 25.4 g / min (0.00114 mol / min), and the tetramethyl-m-xylylene diisocyanate was fed at a rate of 0.306 g / min (0.00125 mol / min). Then 48.0 g of segmented polydimethylsiloxane polyurea copolymer, 78.2 g of SR-545 solution, 186.3 g of toluene / 2-propanol (70/30 by weight) were added to a glass vessel and slowly stirred to obtain a homogeneous solution. A coating was prepared as in Example 18. The 180 ° adhesion was 45 N / dm. The compositions of Examples 30 and 31 fc demonstrate that a variety of diisocyanates can be employed to prepare the polydimethylsiloxane polyurea copolymers segmented via reactive extrusion for use in pressure sensitive adhesive compositions based on segmented polydimethylsiloxane polyurea copolymer. Also the MQ resin can be added to the copolymer of polydimethylsiloxane polyurea segmented after the polymerization of the copolymer.

Examples 32-34 In Example 32, a segmented polydimethylsiloxane polyurea copolymer solution of Example 20 was mixed with 26.7 g MQR-32-1 (an MQD adhesive resin having 2 weight percent dimethylsiloxane units distributed at 70 weight percent of solids in toluene, available from Shin-Etsu Silicones of America, Inc., Torrance CA) to form a homogeneous solution. This solution is coated as in Example 18 to form a pressure sensitive adhesive tape with 55% MQD resin. The adhesion at 180 ° was 79 N / dm. In Example 33, a pressure sensitive adhesive was prepared as in Example 32, except that 26.1 g of MQR-32-2 (an MQD adhesive resin having 5 weight percent of di-ethylsiloxane units distributed) was replaced. to 70 weight percent solids in toluene, available from 10 Shin-Etsu Silicones of America, Inc., Torrance CA) by MQR-32-1 to form a homogeneous solution. This solution was coated as in Example 18 to form a pressure-sensitive adhesive tape * with 55% MQD resin. The adhesion at 180 ° was 74 N / dm. In Example 34, a pressure sensitive adhesive was prepared as in Example 32, except that 26.1 g of MQR-32-3 (an MQD adhesive resin having 8 weight percent of dimethylsiloxane units distributed to 70 percent by weight solids in toluene, available from Shin-Etsu Silicones of America, Inc., Torrance CA) by the MQR-32-1 to form a homogeneous solution. This solution was coated as in Example 18 to form a pressure sensitive adhesive tape with 55% MQD resin. The adhesion at 180 ° was 61 N / dm.

Examples 32-34 illustrate the segmented extruded polydimethylsiloxane polyurea copolymers reactively extruded with various MQD resins provide pressure sensitive adhesives based on segmented polydimethylsiloxane polyurea copolymer. The increase in the amounts of dimethylsiloxane units in the MQD resin reduced the adhesion at 180 ° C, although each of the adhesives of Examples 32-34 exhibited good adhesion at 180 °. ft 10 Examples 35-37 In Example 35, 40.5 g of MQ SR-545 adhesive resin solution and 36.4 g of MQD MQR-32-1 adhesive resin solution were mixed to form a solution of resin. Next, 33.3 g of this resin solution and 58.3 g of segmented polydimethylsiloxane polyurea copolymer solution of Example 20 were mixed to form a homogeneous solution. The pressure sensitive adhesive solution was coated as in Example 18 to form a pressure sensitive adhesive tape that was applied to a polypropylene coupon, 3 mu thick, 5.1 cm wide and 12.7 long, which had been washed 3 times with 2-propanol as in Example 18. The samples they were tested to determine 180 °, 20 minutes after drying. The adhesion to 180 ° of polypropylene was 104 N / dm.

In Example 36, 80.9 g of MF SR-545 adhesive resin solution? F and 71.2 g of MQD-32-2 MQD adhesive resin solution were mixed to form a resin solution. 33.3 g of this resin solution and 58.3 were mixed g of segmented polydimethylsiloxane polyurea copolymer solution of Example 20 was coated, and tested as in Example 35. The adhesion to 180 ° of polypropylene was 100 N / dm * In Example 37, 65.3 g of solution were mixed of SR-545 MQ adhesive resin and 55.6 g of adhesive resin MQR- » 32-3 MQD to form a resin solution. It will mix » 32. 1 g of this resin solution and 58.3 g of polydimethylsiloxane polyurea copolymer solution segmented from the Example 20, was coated and tested as in Example 35. The adhesion to polypropylene was 84 N / dm. The compositions prepared in Examples 35-37 I illustrate that reactive extruded segmented polydimethylsiloxane polyurea copolymers can be rendered adhesive with mixtures of MQ and MQD resins to provide pressure sensitive adhesives based on polydimethylailoxane polyurea copolymers. As in Examples 32 34, compositions prepared with MQD resins with small amounts of dimethylsiloxane units had higher 180 ° adhesion. 25 Ejesaplos 38-39 In Example 38, methylenedicyclohexylene-4,4'-diisocyanate was fed into the first zone of an extruder, with two Leistritz screws of 18 mm, which had a length: diameter ratio of 40: 1 at a speed of 0.0590 g / min (0.000225 mol / min) with purge of nitrogen atmosphere. Polydi-ethylsiloxane Diamine D, Lot 1, molecular weight of 37,800 was injected into the second zone at a rate of 8.0 g / min (0.000212 mol / min). The extruder had fully geared, double-start screws = across the entire length of the drum, rotating at 10O revolutions per minute. The temperature profile for each of the 90 mm long zones are: zone 1 - 30 ° C; zone 2 - 75 ° C; zone 3 - 120 ° C; zone 4 - 130 ° C; zone 5 - 140 ° C; zone 6 - 150 ° C; zone 7 - 155 ° C; zone 8 - 170 ° C; and area or final part - 170 ° C. 20 parts by weight of segmented polydimethylsiloxane polyurea copolymer and 80 parts by weight of toluene / 2-propanol (70/30 by weight) were mixed to form a homogeneous solution. Then 50 g of copolymer solution of this copolymer solution, 15.9 g of SR-545 MQ resin solution, and 34.1 g of toluene / 2-propanol (70/30 by weight) were mixed, and was tested as in Example 35 to obtain a pressure sensitive adhesive.

In Example 39, a pressure sensitive adhesive based on segmented polydimethylsiloxane polyurea copolymer was prepared and tested as in Example 38 except that the methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.700 g / min. (0.000267 mol / min). The molecular weight of the copolymer and the inherent viscosity, adhesion at 180 ° to the polypropylene and shear strength were determined. The results are shown in Table 5.

Table 5 As can be seen from the data of the Table 5, the use of adhesives containing the copolymer having high molecular weight (Example 39) provided a much higher shear strength than the adhesives prepared with the lower molecular weight copolymer (Example 38).

LAYERS OF COMPOSITE SHEETS TO MARK PAVEMENT Layers of composite pavement marking sheets were prepared from polydiorganosiloxane polyurea copolymers segmented as follows.

Composite Sheet Layer A The granules of an ultra low density polyethylene filled with calcium carbonate, Spectrum Colo 1080906 EUV, available from Reed Spectrum Sandez Division? Chemicals Corporation, Minneapolis, Minnesota, were dried and extruded using a Killion single screw extruder equipped with a film matrix on a polyester cloth carrier fabric, BAYEX XP 482 available from BAYEX Division of Bay Mills Limited, St. Catharines, Ontario, Canada, to form sheets of 10.5 thousandths of an inch (267 micrometers) thick of conformable sheet material composed on a cambay carrier fabric. The granules of ethylene-methacrylic acid copolymer (EMAA) Nucrel 699 available from Dupont and from a pigment concentrate (50% by weight of titanium dioxide in ethylene-acrylic acid copolymer (EAA), Spectratech IM 88947, available from USI Division of the Quantum Chemical Company, Clinton, Massachusetts), were stirred in a drum to provide a uniformly distributed mixture of granules with a titanium dioxide content of 20%, an EAA content of 20% and an EMAA content of 60%. %. This mixture was extruded through a matrix to form films on a composite sheet material web to provide a pigmented top layer for the conformable score sheet. This conformable marking sheet fabric composed or transported on the surface of a hot cam heated to a temperature of 210 ° C (for example, is sufficiently hot to bring the material from the pigmented top layer to a soft condition, cas-i fused , but not so hot that the carrier fabric could not melt, although in contact with the hot cam at high temperature, the microbeads (with a size of 200 to 600 micrometers, refractive index of 1.9, surface treated with gamma-aminopropyl) -trietoxy silane brand UNION CARBIDE "1 A-1100) and small particles of aluminum oxide sand (30 Grit) were spread on the hot surface of the top layer.The upper layer pigmented with particles on its surface was maintained at high temperature rolling it around the hot cam with the cloth moving at a speed of 0.02 m / sec (4 fpm) so that the particles could partially dissipate the surface of the polymer. and that the polymer could wet the surface of the particles while in the nearly molten state. The fabric was then passed over a cooling roller to resolidify the film containing the reflective elements and anti-skid particles on the upper surface. The carrier fabric was separated from the lower surface of the composite sheet and the sheet was wound on a transformable sheet-shaped sheet roller.

Composite Sheet Layer 3 A composite layer of saturation #r adhesive was prepared and subsequently coated with a fibrous cloth, 1.6 ounces / yard2 (57 g / m2) of Typa Spun Polypropylene available from Reemay, Inc., Old Hickory, Tennessee, with a pressure sensitive adhesive. of rubber resin as described in U.S. Patent No. 4,299,874 which is incorporated herein by reference. The . adhesive layer dß adhesive with a thickness of 16 thousandths of an inch (400 micrometers). The composite layer of rubber resin pressure sensitive adhesive was laminated to the lower surface of the Composite Sheet Layer A to provide composite sheet sheet with a bottom surface coated with adhesive.

Layer of Composite Sheets C A composite sheet was prepared with Example 8 of U.S. Patent No. 5,194,113 which is incorporated herein by reference.

Composite Sheet Layer D A composite sheet was prepared as in Example ft 10 5 of U.S. Patent No. 5,194,113. • # Composite Sheet Layer E A composite layer of the adhesive was prepared by saturation 15 and subsequently coating a fibrous fabric, 2.4 oz / yd2 (86 g / m2) of REEMAY * non-woven polyester available from Reemay, Inc. Old Hickory, TN, with an adhesive sensitive to the rubber resin pressure as described in U.S. Patent No. 4,299,874. The composite layer of adhesive has a thickness of 15 thousandths of inch (375 μm). The composite layer of rubber resin pressure sensitive adhesive was laminated to the lower surface of a pavement marking support sheet as described in Table I of US Patent No. 4,490,432, incorporated herein by reference, which has a rubber layer ~ 'with a thickness of 18 25 thousandths of an inch (450 μm) and a top layer of vinyl with a thickness of 2 to 3 mils (50 to 75 μm), > to provide a sheet of composite sheets with a bottom surface coated with adhesive.

Examples 40 to 47 In Example 40, Polydimethylsiloxane was fed Diamine E, Lot 2, molecular weight of 52,900, at a rate fc of 15.5 g / min (0.000293 mol / min) in the first zone of a two-screw extruder, cogiratory, 1200 mm long, 34 mm in diameter, from Leistritz. SR-545 resin MQ was fed, dried as in Example 7, in zone two at a rate of 15.4 g / min. Methylenedicyclohexylene-4,4'-di-isocyanate was fed at a rate of 0.075 g / min (0.00029 mol / min) in zone six of the extruder with the feed line lightly brushing the screws. The extruder was equipped with fully meshed screws through, rotating at 50 revolutions per minute. The temperature profile of each one of the zones of 120 mm in length was: zones 1 and 2 - 30 ° C; zone 3 - 35 ° C; zones 4 and 5 - 50 ° C; zone 6 - 100 ° C; zone 7 - 170 ° C; zones 8 to 10 - 180 ° C; and area or final part - 140 ° C. The extrudate was cooled in air and collected to provide a pressure-sensitive adhesive based on segmented polydi-ethylsiloxane polyurea copolymer which was hot melt coated to 100% solids. This pressure-sensitive adhesive based on segmented polydimethylsiloxane polyurea copolymer is coated as in Example 8 on the side coated with rubber resin pressure sensitive adhesive of the Composite Sheet Layer with a thickness of 50 μm (2 mils) to provide a pavement marking sheet fc having a lower layer of pressure sensitive adhesive. based on segmented polydimethylsiloxane polyurea copolymer. A removable, light polyester coating of 50 μm (2 mils) thick was laminated, available as S TAKE-OFE * ® 2402 available from Résele International, Bedford Park, Illinois, to the surface of Pressure sensitive adhesive based on segmented polydimethylsiloxane polyurea copolymer. In Example 41, a pavement marking sheet was prepared as in Example 40 except that pressure sensitive adhesive based on polydimethylsiloxane polyurea copolymer was applied to the bottom surface coated with adhesive of the Composite Laminate Layer 'B. In Example 42, a pavement marking sheet was prepared as in Example 40, except that it was coated pressure sensitive adhesive based on polydimethylsiloxane polyurea copolymer segmenon the aluminum foil side of the Composite Laminate Layer:! D at a thickness of 125 μm (5 mils). In Example 43, a sheet was prepared to mark pavement prepared as in Example 40, except that pressure sensitive adhesive based on polydimethylsiloxane polyurea copolymer base was coaon the lower surface of the Composite Laminate-A to a thickness of 125 μm (5 mils) In Example 44, a pavement marking sheet was prepared as in Example 40, except that the pressure sensitive adhesive based on segmenpolydimethylsiloxane polyurea copolymer was prepared with the following modifications. The MQ resin was fed at a rate of 18.4 g / min and the methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.072 g / min. (0.00027 mol / min). In Example 45, a pavement marking sheet was prepared as in Example 41, except that the pressure sensitive adhesive 20 based on the polydimethylsiloxane polyurea copolymer base of Example 44 was replaced by that of Example 40. In the Example 46, a pavement marking sheet was prepared as in Example 42, except that the pressure sensitive adhesive based on the segmenpolydimethylsiloxane polyurea copolymer of Example 44 was replaced by that of Example 40. In Example 47 , a pavement marking sheet was prepared as in Example 43, except that the pressure sensitive adhesive based on segmenpolydimethylsiloxane polyurea copolymers of Example 44 was replaced by that of Example 40. The release coatings were removed from samples with dimensions of 304 cm by 10 cm (10 feet by 4 inches) of score sheets of Examples 40-47 and those * samples were applied to a concrete pavement surface that had a temperature of approximately 1 * (34 ° F). The samples were stamped against the surface using a 3M Roller Tamper Cart (model RTC-2 available from 3M Company, St. Paul, Minnesota) with a load of 90 Kg (200 pounds). The adhesion of the sheets to mark the Examples 40 to 47 to the dry pavement was excellent. The pressure sensitive adhesives of Example 40 to 47 exhibisurprisingly good adhesiveness and easy attachment to the concrete pavement surface at a low temperature of 1 ° C (34 ° F), Examples 48-59 In Example 48, the pressure sensitive adhesive based on the segmenpolydimethylsiloxane polyurea copolymer of Example 17 was coaas in Example 8 on the removable coaside of the removable S TAKE-OFF coating "2402 at a thickness of 125 μm (5 mils) A second release liner, SCOTCHPAK "1022 3M Relay Liner, available from 3M Company, St. Paul, Minnesota, was laminaat the point of contact between the rollers to the adhesive surface? sensitive to pressure. A Composite Laminate was prepared by laminating joints, manually, at light pressure, four layers of an 875 μm (35 mils) thick foamed acrylic pressure sensitive adhesive, 3M Acrylic Foam Tape Y4253 Type 3 available from 3M Company, St. Paul, Minnesota, to produce a layer of 3.5 mm (140 thousandths of an inch) thick. The Composite Laminate Layer was manually laminato the lower surface of the marker body of an embossed pavement marker 280 Mark 3M, available from 3M Company, St. Paul, Minnesota. The S TAKE-OFF "* 2402 release liner was peeled from the surface of the pressure sensitive adhesive based on segmenpolydimethylsiloxane polyurea copolymer and the pressure sensitive adhesive was laminated on the lower surface of the Laminate Composite layer Jft attached to the body of the marker to produce a pavement marker having a lower layer of pressure sensitive adhesive based on segmenpolydimethylsiloxane polyurea copolymer. The 3M ™ SCOTCHPAK? 1111022 release liner was removed from the underside of the pavement marker and replaced with an additional release sheet S TAKE-OFF141 * 2402. In Example 49, a sensitive adhesive was coa IQ at the copolymer-based pressure of > polydimethylsiloxane polyurea segmented onto a release coating as in Example 48 and a second release liner was laminated at the point of contact between the rollers to the surface of the pressure sensitive adhesive as in Example 48. The removable S TAKE-OFF coating "2402 was peeled from the surface of the pressure-sensitive adhesive and the pressure-sensitive adhesive was laminated to the lower surface coated with rubber resin adhesive of the label. pavement Series 620 SCOTCHL NE "* available from the 3M Company, St. Paul, Minnesota, to provide a pavement marking sheet Removed SCOTCHPAKM" 1022 3M ™ removable liner from bottom surface of pavement marking sheet and pavement marking tape from Composite Sheet was applied to a pavement surface with asphalt traffic and stampeded in place as in Examples 40-47, except that the air temperature was about 22 ° C and the surface temperature of the pavement was about 28 ° C. Six days later, the marking sheet was peeled from the pavement surface at a 90 ° peel angle at a constant speed of 48.5 cm / min (18.7 inches / min) and the peel force was measured. The peel force was 1.3-1.4 N / cm wide (3-3.25 pounds / 4 inches-wide) and the pavement surface under the marking sheet was dried by removing the mark. i In Example 50, SR 545 MC / resin, dried as in Example 1, was fed at a rate of 9.35 g / min in zone 1 of a co-rotating two-screw extruder, 737.5 mm in length, 25 mm of diameter of Berstorff. The polydimethylsiloxane diamine G, molecular weight of 105,000, was injected into zone 2 at a rate of 9.35 g / min (0.0000890 mol / min). Methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.0403 g / min (0.000154 mol / min) into zone 6 of the extruder with the feed line lightly brushing the screws. The extruder was removed with double start screws, fully engaged, through, rotating at 125 revolutions per minute. The temperature profile of each zone of ".125 n__ of length (except for zone 1 of 112.5 mm) was: zone 1 - 27 ° C; zones 2 and 3 - 32 ° C; zone 4 - 50 ° C; zone 5 - 100 ° C; zone 6 - 160 ° C; and area or final part - 170 ° C. The extrudate was cooled in air and collected to provide a pressure sensitive adhesive based on segmented polydimethylsiloxane polyurea copolymer which could be hot melt coated at 100% solids. This pressure sensitive adhesive based on segmented polydimethylsiloxane polyurea copolymer was used to make a pavement marking sheet as in Example 40, was coated to a thickness dß 76-μ (3 ft 10 mils) on the bottom surface coated with adhesive of the Composite Laminate Layer E. * In Example 51, a pavement marking sheet was prepared as in Example 50, except that the pressure-sensitive adhesive based on the copolymer Segmented polydimethylsiloxane polyurea was coated to a thickness of 32 μm (1.25 mils). In Example 52, a pavement marking sheet was prepared as in Example 51 except that the pressure sensitive adhesive based on the copolymer of Segmented polydimethylsiloxane polyurea was coated on the bottom surface of the cover with STAMARK pavement sheet adhesive "11 Series 5730 available from 3M Company, St. Paul, Minn. In Example 53, a marking sheet was prepared. pavement as in Example 50 except that the adhesive Pressure sensitive material based on segmented polydimethylsiloxane polyurea copolymer was prepared with an MQ resin with a flow rate of 11.4 g / min. In Example 54, a pavement marking sheet was prepared as in Example 53except that the pressure sensitive adhesive was coated to a thickness of 32 μm (1.25 mils). In Example 55, the release liner was peeled from the surface of the pavement marking sheet of Example 50. The surface of pressure sensitive adhesive was exposed to electron beam radiation. The source of electrons was an Electrocurtain of 300 KeV. available from Energy Sciences, Incorporated, Woburn, Massachusetts with a fixed voltage of 200 KV, a linear velocity of 7.6 m / min (25 fpm) and the current was adjusted to provide an electron beam dose of 3 Mrad to crosslink the sensitive adhesive to the pressure. After irradiation, a release liner, S TAKE-OFF "2402, was laminated to the surface of pressure sensitive adhesive of the sheet-to mark pavement In Examples 56-59, the pavement marking sheets of Examples 51 -54, respectively, were subjected to electron beam radiation as in Example 55. - Sheet samples were applied to mark 152 cm by 10 cm (5 feet by 4 inches) of Examples 50-59 to an asphalt pavement surface. The air temperature was approximately 32 ° C (90 ° F) and the pavement temperature was approximately 38 ° C (100 ° F). The samples were stamped as in Examples 40-47.- Approximately one hour after application to the pavement surface, 30 cm (12 inches) of length was removed from each sheet to mark the pavement surface at an angle of detachment of 90 degrees at a speed-; Yes- constant of 47.5 cm / min (18.7 inches / min) and it was measured * Ja- strength of detachment. Two weeks later, was it repeated? the detachment test. The results of the initial release force measurements and at two weeks are shown in Table 6.

Table 6 Continuation of Table 6 The data in Table 6 show that the Marking Sheets of Examples 50-59 have very stable peel strength values over the two week period. The surfaces of two 2 cm by 30 cm (12 inch by 12 inch), 5 cm (2 inch) thick concrete patio blocks were cleaned by sandblasting to expose a new concrete surface and added.

Both blocks were dried at an ambient temperature of about 21 ° C (70 ° F). Parts of 30 cm, (12 inches) in length and 5 cm (2 inches) in width were applied pavement marking tapes of Examples 51 and 56 to the top surface of each of the two concrete patio blocks and were stamped in place using a 3M Roller Ta per Cart Model RTC-2 loaded with 200 pounds (90 Kg) . One of the blocks was completely submerged in a water tube. The second block was placed in a water tube with the water level so that the 5 cm (two inch) thick block would remain submerged in the water, ie, the water depth was about 2.5 cm. (1 inch) to allow water to percolate through and saturate the block, but not cover the top surface - of the block to which the mark will be made. After about two hours both blocks appeared to be saturated with water. At that time, the adhesion of the marks to the blocks was evaluated qualitatively by manually detaching the marks of the blocks. Each of the pavement marking sheets of Examples 51 and 56 adhered to the surface of each block and exhibited some resistance to being peeled off.

Ex & 6Q ~ 7G In Examples 60-67, pavement marking sheets were prepared by coating various pressure sensitive adhesives based on polydimethylsiloxane polyurea copolymers segmented applied to the lower surfaces coated with adhesive of various pavement marking sheet materials available from 3M Company, St. Paul, Minnesota, using the procedure of Example 40. Pavement marking sheet materials, pressure sensitive adhesive and The thickness of the adhesive is shown in Table 7.

Table 7 In Examples 68-70, samples of sheet materials for pavement markings of Examples 60, 62 and 63, respectively, were subjected to electron beam irradiation as in Example 55. Samples of 152 cm by 10 cm were applied ( 5 feet by 4 inches) of marking sheets of Examples 50-70, to the area of the edge line on an asphalt road pavement surface at the end of autumn. The air and pavement temperatures were approximately * 0 (45 * FH The samples were adhered to the asphalt using the procedures as in Example 4Q-> 47. ' After: * 5 months of exposure through the winter in Minnesota, -posing sheets of Examples 50-70 were placed and adhered well to the road surface.

Example 71 In Example 71, pulverized MQ resin containing less than 1% toluene (GE Silicones, material 1170-002 batch EF002) was fed at a rate of 30.1 g / min in the rear »portion of zone 1 of an extruder of two screws, cogitative, 1600 mm long, 40 mm diameter, from Berstorff and Polydi ethylsiloxan Diamine D, Lot 3, molecular weight of 34 * J800 were fed at a rate of 29.9 g / min (0.000859 mol / min) in the front portion of zone 1. A mixture of 10 parts by weight of DESMODUR N-330O (polyisocyanate with an equivalent weight of NCO of 195, Bayer, Pittsburgh, PA 15205) and 90 parts by weight of methylenedicyclohexylene-4,4'-diisocyanate was fed. at a speed of 5 0.233 g / min (0.00172 equivalents of NCO / min) in zone 8 to provide an NC0: 'NH2 ratio of 1.00: 1.00, The isocyanate feed line was placed close to the screw threads as in Example 1. Fully geared, double-start screws were used, ^ - 9 -. 9-120 ° C; zone 10 - 180 ° C; zone or final part and fusion pump - 180 ° C. The resulting pressure sensitive adhesive 15 was collected and coated in solution as described in Example 1. Peel strength Example 72 In Example 72, a pressure sensitive adhesive based on polydimethylsiloxane urea as in Example 71 was prepared, except that a mixture of 10 parts by weight of MONDUR 489 (polyisocyanate with an equivalent weight of 25 NCO of 137 was fed. , Bayer, Pittsburgh, PA 15205) and 90 parts by weight of methylenedicyclohexylene-4,4'-diisocyanate at a rate of 0.226 g / min (0.00172 equivalents of NCO / min) to provide an NC0 / NH2 ratio of 1.00: 1.00. The resultant pressure sensitive adhesive was collected and coated in solution as described in Example 1. The peel strength was 44 N / dm.

Example 73 ft * In Example 73, was a sensitive adhesive prepared? at "pressure based on polydimethylsiloxane polyurea, relleaad *. as in Example 71. Powdered MQ resin i was fed at a rate of 21.6 g / min Three parts by weight of Polydimethylsiloxane Diamine D, Lot 3, molecular weight of 15 34.800, with 4 parts by weight of A1203 were mixed. It was pulverized and fed at a rate of 56.6 g / min (0.000697 mol diamine / min). ^ Methylenedicyclohexylene-4,4'-d-soctanate was fed at a rate of 0.183 g / min (0.00699 mol / l). min) in zone 8 to provide an NC0: NH2 ratio of 1.00: 1.00 The resulting pressure sensitive adhesive was collected by hot melt coating as described in Example 8. The peel strength was of 4.1 N / dm The thermal conductivity, measured by the ASTM C518 method, was 0.16 W / m ° K. An elastomer, similar without filler or MQ had a conductivity of 0.10 W / m ° K.

Examples 74-78 f In Example 74, the pressure sensitive adhesive based on polydi ethylsiloxane polyurea of Example 40 was coated as in Example 8 to a thickness of 38 μm (1.5 mils) on a release liner, and laminated to a woven rayon fiber backing to form a pressure sensitive adhesive tape. The support was first formed by passing 2.5 to 5 cm in length, fibers cuts of 1.5 denier viscose rayon through a two-cylinder truck (available from Spinnbau GmbH, Bremen, Germany) to form a plush fiber fabric with a fiber weight between 41 g / m2 and 54 g / m2 . The plush fiber fabric was compacted to a similar condition of the fabric and was prepared by being fed through the point of contact between a pair of horizontal compression rollers, the lower one of which was immersed in an aqueous bath of rubber acrylate sizing latex to join the fiber (RH0PLEX B-15 , available from Rohm and Hass Co.), diluted with water to provide a size weight approximately equal to the weight of the fiber) and then dried. In Example 75, a pressure sensitive adhesive tape was made as in Example-74 with the polydimethylsiloxane polyurea ft pressure sensitive adhesive of Example 44. In Example 76, an adhesive tape was made sensitive to the pressure as in Example 74 with a pressure sensitive adhesive 5 based on polydimethylsiloxane polyurea prepared as in Example 40 with the following modifications. Polydimethylsiloxane diamine F, molecular weight of 71,000 was injected at a rate of 15.9 g / min (0.000224 fc mol / min). Powdered MQ resin was fed at a speed of 15.7 g / min. Methylenedicyclohexylene-4, - diisocyanate was fed at a rate of 0.054 g / min (0.000206 mol / min). The temperatures in zones 7 and 8 were 170 ° C and in zones 9 and 10 they were 1 0 ° c. In Example 77, an adhesive tape was made pressure sensitive as in Example 74 with a pressure sensitive adhesive based on polydimethylsiloxane polyurea prepared as in Example 50, but with the following modifications. The pulverized MQ resin was fed at a rate of 18.9 g / min. Polydi etilsiloxan was injected Diamine E, Lot 2, molecular weight of 52,900 at a rate of 18-9 g / min (0.000357 mol / min). Methylenedicyclohexylene-4,4-diisocyanate was fed at a rate of 0.114 g / min (0.000435 mol / min). In Example 78, a tape sensitive to the Pressure as in Example 74 with the pressure sensitive adhesive based on polydi ethylsiloxane polyurea of Example 50. The pressure sensitive adhesive tapes were tested for the upward and inverted MVTR, adhesion to the skin immediately after application. application, T0, and 24 hours later, T24, skin adhesion lift after 24 hours, T24 lift, adhesion residues on the skin after 24 hours, T24 residue and adhesion of the skin to a wet surface immediately after of the application, wet T0. The results are shown in Table 8.

Table 8 The data in Table 8 for Examples 74-78 ft present the results of the adhesion tests, wet steam transmission rate, residues, and lifting tests for medical pressure sensitive adhesives of the present invention. All the Examples present the minimum lifting desired and without leaving residues on the skin after the removal of the tape. The upward and inverted MVTR of the tested samples change in a controlled manner the values in opposite directions. The adhesion after aging against the skin for 24 hours is almost double, and it can be formulated that it is within the optimum range for medical applications.

Examples 79 and 80 and Comparative Examples Cl and C2 In Example 79, Polydimethylsiloxane Diamine F, molecular weight of 71,000, was fed at a rate of 32.1 g / min (0.000452 mol / min) with dry, dried MQ adhesive resin. per 1% toluene spray of SR-545 under nitrogen, at a rate of 32.0 g / min, in zone 1 of a co-rotating, 1600 mm long, 40 mm diameter twin screw extruder, from Berstorff . Methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.lL 5 g / min (0.000401) NCO equivalents / min) in zone 4 to provide an NC0íNH2 ratio of 0.89: 1.00. the diisocyanate feed line was placed near the screw threads as in Example 1. Fully geared, double-start screws were used, rotating at 100 revolutions for 5 minutes the entire length of the drum. Vacuum was drawn in zone 8. The temperature profile for each of the 160 mm zones was: zone 1 - 20 ° C; zones 2 and 3 - 50 ° C; zone 4 60 ° C; zone 5 - 100 ° C; zone 6 - 130 ° C; zone 7 - 160 ° C; zone 8 F - 180 ° C; zone 9 - 160 ° C; zone 10 - 160 ° C; zone or final part 10 and fusion pump - 160 ° C. The pressure sensitive adhesive based on polydimethylsiloxane polyurea was collected and coated onto a nonwoven rayon fiber backing at 41 μm (1.6 mils) thick as in Example 74. In Example 80, the adhesive sensitive to the pressure based on polydimethylsiloxane polyurea of Example 79 was coated on a support prepared as described in Example 74 in a continuous pattern at a coating weight of 0.6 g / dm 2 as described in Example 1 and in the North American patent application. entitled "A Material of Adhesive Sheet Suitable for Use on Wet Surfaces ", US Patent Serial No. 08 / 317,854, filed October 4, 1994. In Comparative Examples Cl and C2, the pressure-sensitive adhesive tapes of block copolymer adhesive with a continuous and discontinuous adhesive coating, respectively, were prepared as described * in Example 1 of the US Patent Serial No. 98 / 317,854, filed on October 4, 1994. Pressure sensitive adhesive tapes were tested to terminate adhesion to the skin immediately after application, T0 - Day , and adhesion of the skin to a wet surface immediately after application, T0-Wet, and the percent of adhesion was calculated f wet to dry adhesion. The results are exposed in Table 9. fifteen twenty The data in Table 9 demonstrate that the coated pressure-sensitive adhesive pattern of the present invention performs exceptionally well under moist skin adhesion conditions, doubling the bonding%. in Wet / Dry, while the comparative example increased only slightly.

Example 81 In Example 81, a segmented polydimethylsiloxane polyurea copolymer was prepared in an 18 mm Leistritz as in Example 1 with the following modifications. The temperature profile for each of the 90 mm zones was: zones 1 to 3 - 30 ° C; zone 4 - 50 ° C; zone 5 - 80 ° C; zone 6 - 150 ° C; zone 7 - 180 ° C; zone 8 - 190 ° C; and area or final part - 195 ° C. A 1: 1 molar mixture of Polydimethylsiloxane Diamine E, Lot 3, molecular weight of 50,200 and Dytek 1"® (2-methyl-1,5-pentanediamine obtained from DuPont) was fed at a rate of 6.16 g / min (0.000242). mol / min) in zone 1 of the extruder The speed of rotation of the screw was 75 revolutions per minute Methylenedicyclohexylene-4,4'-diisocyanate was fed in zone 4 at a rate of 0.0635 g / min (0.000242 mol / min) The resultant segmented polydimethylsiloxane polyurea copolymer was extruded into a 3 mm diameter strand, cooled in air, and collected.This psiurea was very soluble in 50/50 iopanol / toluene, partially dissolved, mixed with MQ adhesive resin in 50 parts of polydimethylsiloxane polyurea copolymer segmented to 50 parts of MQ resin, coarsely filtered, then coated to produce a pressure sensitive adhesive tape as in Example 18, except that the thickness of the final adhesive was about 3 thousandths of an inch. The peel test was performed at a rate of 90 inches / min after the tape was fixed on a glass plate for about one minute. ifc Examples 82-84 10 In Example 82, the two-screw extruder of Example 50 was used with the following modifications. The screw, operating at 100 revolutions per minute was built with fully double-geared screws Start in combination with partially engaged screws. A set of kneading blocks of 25 mm in length was located at the beginning of zone 4 and three games were located at the end of zone 5. The temperature profile for each of the zones was: zone 1 - 30sC; zone 2 - 75 ° C; zone 3 - 100 ° C; zone 4 - 125 ° C; zone 5 - 150 ° C; zone 6 - 175 ° C, zone or final part and fusion pump - 175 ° C and nozzle - 190 ° C. The fed reagents were kept under a nitrogen atmosphere. Polydimethylsiloxane Diamine A, Lot 1, molecular weight of 5280._a was fed at a rate of 4.84 g / min (0.000917 mol / min) in the first part of zone 1 and tetramethyl-m-xylylene diisocyanate was fed (obtained * from Cytec) at a speed of 3.19 g / min (0.0131 mol / min) in the second part of zone 1. Jeffamine polyoxypropylenediamine "11 D-4000, (obtained from Huntsman Corporation, graded molecular weight of 4660 g / mol for Lot # 513-1-0393-0594) at 29.09 g / min (0.00624 mol / min) in zone 3. Dytek 1"* * (2-met? ll, 5- pentanediamine obtained from DuPont, was injected, molecular weight titrated from fc 117 g / mol for Lot # SC94030211) in zone 4 to a speed of 0.687 g / min (0.00587 mol / min). The segmented polydi ethylsiloxane polyurea copolymer was collected, mixed and coated as in Example 81, with the exception that 7 parts of copolymer and 3 parts of MQ resin were used to produce an adhesive tape sensitive to the pressure. The numerical average molecular weight of the product was determined via gel permeation chromatography with an HP 1090 Chromatograph equipped with a HP 1037A Refractive Index Detector, a Waters 590 pump, an injector automatic Waters Wisp, and a column kiln Kariba, R. T. The copolymer was dissolved in DMF, LiBr 0.05% w / v at 15 mg / 5 mL, filtered with a 0.2 micron nylon filter, and 100 microliters were injected into a column of Mixed Bed Jordl * - La speed of The elution was 0.5 mL / min in DMF + LiBr at 0.05% in weight / volume. The calibration was based on standards of Polystyrene from Chemical Company, Pittsburg, PA, in this way the reported molecular weights are of polystyrene equivalents. The numerical average molecular weight was 5.9xl04. In Example 83, a pressure sensitive adhesive was produced as in Example 82, except that the FORAL ™ 85 adhesive, available from Hercules Inc., to 50 parts of 50 part adhesive of segmented copolymer of polydimethylsiloxane polyurea and the sample required heating to dissolve the adhesive. In Example 84, a pressure sensitive adhesive was produced as in Example 82, except that 25 parts of FORAL "11 85, available from Hercules Inc., and 25 parts of the mixture were mixed. parts of MQ resin with 50 parts of segmented polydimethylsiloxane polyurea copolymer and the sample required heating to dissolve the adhesive. The pressure sensitive adhesive tapes in Examples 81-84 were tested and the adhesion results were are shown in Table 10. Table 10 The adhesion data found in Table 10 for Examples 81-84 show that the pressure sensitive adhesive of Example 81 was based on a segmented copolymer of polydimethylsiloxane polyurea derived from an equimolar mixture of polydimethylsiloxane diamine with an approximate molecular weight of 50,000 and Dytek A, available from Dupont, a short chain hydrocarbon diamine, which when made adhesive with MQ resin produces a pressure sensitive adhesive. The adhesion data for Examples 82-84 show that the pressure sensitive adhesives of the present invention based on the polydimethylsiloxane segmented polyurea copolymers derived from a polydimethylsiloxane diamine of molecular weight of about 5300 and two organic diamines; Jeffamine "1 * D-4000, a polypropylene oxide diamine with a molecular weight of about 4,500 and Dytek A" 1 *, a short chain hydrocarbon diamine having a molecular weight of about 100, wherein the propylene oxide it constitutes approximately 77 weight percent of the copolymer, when it is made adhesive with an MQ silicate resin, an organic adhesive resin, or a combination of MQ resins and organic resin provides useful pressure sensitive adhesives.

Examples 85-88 In Examples 84-88, vibration damping materials were prepared by blending various segmented polydi ethylsiloxane polyurea copolymers, SR-545 (MQ silicate resin, 60 weight percent in toluene, available from General Electric Silicone Products Division, Waterford, NY ), toluene and isopropanol in the amounts shown in the Table F 11.

Table 11 fifteen ft twenty In Example 85, the solution was emptied into a reservoir coated with a release liner and dried to form a vibration damping material. In In Examples 86-88, the solutions were coated on a release liner and dried! The storage modulus, G ', and the loss factor, tan d, were determined and reported in Table 12. As can be seen from the data in Table 12, with the molecular weight of the diamine used to produce the segmented polydimethylsiloxane polyurea copolymer was increased from 1620 to 105,000 the utility window for G 'decreased from 92 to 181 ° C.

Table 12 As can be seen from the data in Table 12, with the molecular weight of the diamine used to produce the segmented polydimethylsiloxane polyurea copolymer was increased from 1620 to 105,000 the utility window for G 'decreased from 92 to 181 ° C.

Table 12 As can be seen from the data in Table 12, with the molecular weight of the diamine used to produce the segmented polydimethylsiloxane polyurea copolymer increased from 1620 to 105,000 the utility window for G 'decreased from 92 to 181 ° C, for him. Example 85. 55 to 114 ° C for Example 86, 22 to 74 ° C for Example 87, and 25 to 73 ° C for Example 88. At so S > 0.4, Examples 85-88 had utility windows of tan d from 83 to 118 ° C, 36 ° C for melt flow, 4 ° C for melt flow and 2 ° C for melt flow, respectively. Thus, a temperature range of 92 to 118 ° C can be observed for Example 85, and was the same as that of the utility window G 'for Examples 86-88 since those values were narrower than the ranges. of temperature for tan d.

Examples 89-92 In Examples 89-92, vibration damping materials were prepared as in Examples 85-88 using the amounts of various segmented polydimethylsiloxane polyurea copolymers, silicate resin, toluene and isopropanol as set forth in Table 13.

Table 13 In Examples 89 and 92, the solutions were coated on a release liner and dried to form vibration damping material. In Examples 90 and 91, the solutions were emptied into a reservoir coated with a release liner and dried for form a vibration damping material. Each sample was evaluated to determine the storage modulus, G ', and ft the loss factor, so d at 1 Hz. The results are shown in Table 14. twenty Table 14 The data in Table 14 demonstrate that the vibration damping materials of Examples 89-92, which were prepared using the copolymers of pslidimethylsiloxane psiurea segmented from polydimethylsiloxane diamines of molecular weight of about 5300 and various diisocyanates, had useful temperature ranges of 17 to 78 ° C, 16 to 65 ° C, 23 to 79 ° C and 9 to 73 ° C, respectively. Examples 91 and 92 were also evaluated as thermally activated adhesives T produced breaking stress values of 0.99 MN / m2 and 0.93 MN / m2, respectively.

Examples 93-98 In Examples 93-98, Polydiphenyldimethylsiloxan Polyurea Segmented K Copolymer was mixed with SR-545 MQ silicate resin solution or dry SR-545 MQ silicate resin obtained by drying the resin in a forced oven at 150 ° C until the The toluene content was less than 1%, under slow stirring until a homogeneous mixture was obtained in the amount shown in Table 15.

Table 15 Continuation of Table 15 Each solution was coated on a release liner and dried to form a vibration damping material. The storage modulus, G ', and the loss factor i, tan d, were determined for each sample at 1 Hz. The results are shown in Table 16.

Table 16 As can be seen from the data in Table 16, the increase in the amounts of silicate resin in Examples 93 to 98, ie, 20, 30, 40, 50, 60, and 70 percent in Weight, respectively, caused the useful temperature ranges to increase and expand from -64 to -52 ° C in Example 93 to 49 to 91 ° C in Example 98, Examples 93 and 98 were also evaluated as thermally activated adhesives. and they gave values of effort to the break of 1.00 MN / m2 and 1.47 MN / m2, respectively. 10 Examples 99-100 In Example 99 a homogeneous mixture of 25 parts of Polydimethylsiloxane Diamine E, Lot l weight was fed molecular weight of 58,700, and 75 parts of Polydimethylsiloxane Diamine A, batch 1, molecular weight of 5,280, at a ft speed of 15.9 g / min (0.00233 mol / min) in the first zone of a two-screw extruder, counter-rotating, of 34 mm in diameter, dís Leistritz. The Sr-545 MQ silicate resin dried, prepared from SR-545 MQ silicate resin which was dried to about 13 percent toluene by evaporation of the toluene from the SR-545 resin solution for 4 days, further dried under vacuum at 55 ° C. ° C for 16 hours, was fed at a speed of 15.7 g / min in the second zone of the extruder. Methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.65 g / min (0.00248 mol / min) in the sixth zone of the extruder. The extruder was equipped with fully meshed screws through, and the screws rotated at 50 revolutions for 5 minutes. The temperature profile for each of the 120 mm long zones was: zone 1 - 25 ° C; zones 2 and 3 - 35 ° C; zones 4 and 5 - 5Q ° C; zone 6 - 86 ° C; zone 7 - 150 ° C; zone 8 - 170 ° C; zones 9 and 10 - 180 ° C; and area or final part - 170 ° C. The vibration damping material * 10 was collected and cooled. Subsequently, the vibration damping material based on segmented polydimethylsiloxane polyurea copolymer was hot pressed between parallel aluminum plates of 1/8 inch thickness, coated with a coating removable, at 160 ° C to form the vibration damping material. # - In Example 100, 25 parts of the vibration damping material based on segmented polydimethylsiloxane polyurea copolymer of Example 99 and 25 parts of toluene: isopropanol 70:30 were stirred slowly in a glass vessel until a homogeneous mixture was obtained. The solution was coated on a release liner and dried to form the vibration damping material. 25 The storage module / G ', and the factor of an d, measured at 1Hz are shown in Table 17. Table 17 Table 17 shows that the vibration damping compositions of the present invention used directly from an extruder, or resolvated and emptied from the solvent provide equally wide useful temperature ranges, i.e., -10 to 94 ° C for Example 99 and - 2 to 104 ° C for Example 100.

Example 101 F 10 In Example 101, 25.0 parts of Polydimethylsiloxane Polyurea Segmented I Copolymer, 39.7 parts of SR-545 MQ solution, and 35.3 parts of toluene: isopropanol 70:30 were slowly stirred in a glass vessel to obtain a homogeneous mixture. The solution is coated on a release liner and dried to form a vibration damping material. The storage modulus, G ', and the loss factor, tan d, measured at 1Hz for Example 101 are shown in Table 18. 20 Examples 102-104 In Example 102, 8 parts of Polydimethylsiloxane Polyurea Segmented C Copolymer were slowly stirred, 12 parts of dried SR-545 MQ resin, dried as in Example 96-98, and 80 parts of toluene: isopropanol 70:30 in a glass container until a homogeneous mixture is obtained. Then 1.6 parts of hydrophilic silica (CAB-O-SIL "1 * M-5, available from Cabot Corp., Boston, MA) was added and the The solution was stirred with an air stirrer for 4 hours. In Example 103, a solution was prepared as in Example 102, except that the amounts of Copolymer C and MQ resin were twice those of Example 102 and 7.1 parts of hydrophobic silica were replaced (AEROSIL "1 *, available from Degussa Corp., Teterboro, NJ) by the hydrophilic silica. In Example 104, a solution as in Example 102 was prepared except that 8.6 parts of powdered calcium carbonate (CAMEL-KOTE ", available from Jenstar Stone Products C, Hunt Valley, MD) was replaced by the hydrophilic silica. The solution was coated on a release liner and dried to form a vibration damping material The storage modulus and loss factor for each sample were determined The results are set forth in Table 19 together with those of Example 87, a similar composition that does not have filler.

Table 19 fifteen ft twenty The data in Table 19 demonstrate that filler addition 25 increases the upper limit of the useful temperature range from 22 to 74 ° C for Example 87 without filler, 31 to 107 ° C with hydrophilic silica, 40 to 109 ° C with hydrophobic silica and 24 to 93 with calcium carbonate. It could be expected that the addition of these fillers would reduce the cost of these vibration damping materials. Example 103 was also evaluated as a thermally activated adhesive and gave a breaking stress value of 0.97 MN / m2.

Example 105 In Example 105, 66.7 parts of Polyidimethylsiloxane Polyurea Segmented J Copolymer solution prepared by using solvent polymerization, 23.8 parts of SR-545 silicate resin solution, and 9.5 parts of toluene: isopropapol 70:30 were stirred slowly in a glass container until a homogeneous mixture is obtained. The solution was coated on a release liner and dried to form a vibration damping material. The storage module and the loss factor measured at 1 Hz for Example 105 are shown in Table 20.

Table 20 ft 10 fifteen ft twenty The data in Table 20 demonstrate that a vibration damping composition of the present The present invention, formulated using segmented polydimethylsiloxane polyurea copolymer prepared by a solvent process, provides a composition having a useful temperature range of 23 to 71 ° C.

Examples 106-109 In Example 106, 12.6 parts of vibration damping material based on F - segmented polydimethylsiloxane polyurea copolymer of the Example 99, 7.6 parts of silicate SR-545 MQ resin solution, 9.0 parts of Polydimethylsiloxan Oligourea Segmented A Copolymer, and 70.8 parts of toluene: isopropanol 70:30 in a glass vessel until a homogeneous mixture is obtained. The solution was coated on a coating removable and dried. In Example 107, a solution was prepared as in Example 106 except that 6.8 parts of Polydimethylsiloxane Oligourea Segmented B Copolymer were replaced by the parts of the Polydimethylsiloxane Oligourea Segmented A Copolymer and used 73.0 parts of toluene: isopropanol. In Example 108, a solution as in Example 106 was prepared, except that 9.0 parts of Polydimethylsiloxane Oligourea Segmented C Copolymer was replaced by the Polydimethylsiloxane Oligourea Segmented Copolymer. n Example 109, A solution was prepared as in Example 106, except that segmented polydimethylsiloxane oligourea copolymer was not added. Each solution was coated on a peelable and dried coating to form a vibration damping material. The storage modulus, G ', and the loss factor, measured at 1 Hz, were determined for each material. The results are shown in Table 21.

Table 21 10 fifteen # twenty Table 21 (continued) The data in Table 21 demonstrate that the addition of segmented polydimethylsiloxane oligourea copolymers to compositions containing d-copolymers Segmented polydimethylsiloxane polyurea, silicate resin, toluene and isopropanol, provides vibration damping compositions having similar useful temperature ranges of 8 to 79 ° C, 16 to 85 ° C, 13 to 87 ° C and 12 to 91 ° C, respectively, for Examples 106-109. He Example 106 was also evaluated as a thermally activated adhesive and gave an effort value to the breakage of # 0.95 MN / m2.

Example 110 In Example 110, methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.0065 g / min (0.000025 mol / min) and Polydimethylsiloxane Diamine E, Lot 1, molecular weight 58,700, at a rate of 2.0 g / min (0.000034 mol / min) in the first zone of a Leistritz 18 mm diameter two-screw extruder. MQD silicate resin (MQR-32-3, 70 weight percent in toluene, available from Shin-Etsu Silicones of America, In., Torrance, CA) was fed, the toluene from the solution had been previously evaporated, a 7.7 g / min in the second zone of the extruder. The extruder was used in the cogiratory mode with fully geared, double-start screws, all the way around the drum, rotating at 75 revolutions per minute. The Jpl temperature profile for each of the 90 mm zones length was: zones 1 and 2 - 22 ° C; zone 3 - 50 ° C; zone 4 -. 100 ° C; zone 5 - 140 ° C zones 6 and 7 - 180 ° C; zone 8 and zone fo final part - 200 ° C. The extrudate was cooled in air "and it was collected, then the vibration-absorbing material based on polydimethylsiloxane copolymer segmented polyurea was pressed by fusion between aluminum plates 3.2 mm (1/8 inch) thick, parallel, ¥ Coated with a removable coating. At 160 ° C. The data 'of the storage module and loss factor measured at 1 Hz are shown in Table 22. 20 Table 22 The data in Table 22 demonstrate that the vibration dampening composition formulated using 80 weight percent of an MQD silicate resin provides a vibration damping composition having a useful temperature range of 55 to 89 ° C.

Example 111 In Example 111, 95 parts by weight of Polydimethylsiloxane Diamine A, Lot 1, molecular weight 5 of 5,280, were mixed well with 5 parts by weight of fumed silica AEROSIL "1 * R-972. The bubbles already incorporated were allowed to degas during The MQ resin containing approximately 0.1% toluene, obtained from GE Sili.cones, Inc. as experimental material 1170-002, and further dried at vacuum 10 ft for 16 hours at 55 ° C, was dried in an oven under vacuum at night at 50 ° C to decrease the toluene content to less than 0.1% This dry MQ resin was fed, at a rate of 93.6 g / min in the first zone of a two screw extruder, co-rotary 1600 mm in length, 40 mm diameter, from Berstorff. The fuming polydimethylsiloxane diamine / fumed silica mixture was injected into zone two at a rate of 59.5 g / min (0.0107 mol diamine / min). Dicyclohexylmethane-4,4'-diisocyanate was fed at a rate of 2.95 g / min (0.0113 mol / min) in zone five for Provide an NCO: NH2 ratio of 1.06: 1. Fully geared, double-start screws were used all the way around the drum, rotating at 225 revolutions per minute. The temperature profile for each of the 160 mm long zones was: zone 1 - 30 ° C; zone 2 - 53 ° C; zone 3 - 57 ° C; zone 4 - 58 ° C; zone 5 - 74 ° C; zone 6 - 125 ° C; zone 7 - 168 ° C; zones 8, 9, 10, zone or final part, and fusion pump -200 ° C. Vacuum was drawn in zone 8. The vibration dampening material thus prepared that exited the extruder was collected in a square aluminum frame, measuring approximately * 5 330 mm per side and having a depth of approximately 19 mm, coated with removable coating based on 50.8 μm polyethylene terephthalate, coated with fluorosilicon, and allowed to cool to room temperature. "Fa A vibration damper was built bidirectional using this composition. The peelable coatings were removed and the plates were cut into 4 pieces of 165 mm x 165 mm. The pieces were stacked one on top of the other, between pieces of the polyethylene terephthalate-based release liner described above, and were pressed in a hot plate press with a fixed gap of 19 mm for 10 minutes at 127 ° C. The sample was removed from the press, allowed to cool to room temperature, and placed in a vacuum oven at 80 ° C at a pressure of 0.25 mmHg for 16 hours to degas the sample. Immediately after degassing, the release liners were removed from the sample, replaced with two new release liners, the sample was again placed on the plate press with a fixed spacing of 13.4 mm for 60 minutes at 127 ° C, and a then removed from the press. The coatings The removables were removed again and replaced with new release liners, and the sample was pressed an additional 3 hours at 127 ° C with a separation of 13.4 mm. The flat, bubble-free plate was removed from the press and allowed to cool to room temperature. The peelable coatings were removed from the plate and the wide faces of the plate abraded with a SCOTCHBRITE fiber "1 * # 7447 Hand Pad, available from 3M Company, St. Paul, MN, to roughen the surface of the plate. They cut two square sections of vibration dampening material measuring 38.1 mm per side and had a thickness of 12.7 mm from this plate, a bidirectional damper was built, similar in appearance to that of Figure 1, joining the vibration damping material 1 of Figure 1, using epoxy adhesive, to a 4.7 mm thick laminated steel plate 2 and to members 3a and 3b of Figure 1 , which had been cleaned before assembly by a sand blast and defatted with solvent. The epoxy bonded bi-directional damper assembly was set 24 hours at room temperature to maintain parallelism between the steel members and the vibration dampening material during epoxy curing. The damper assembly was rigidly mounted on a hydraulically operated closed loop feedback control test machine number 312.21 model MTS equipped with a temperature controlled chamber. The viscoelastic material was equilibrated at 24 ° C and cyclically conditioned by deforming the viscoelastic material a total of 3 cycles at a voltage of 50% and a frequency of 0.1 Hz. The three mechanical dynamic test cycles were then carried out at temperatures of 0, 10, 21, and 36 ° C and voltages of 50% and 100% at each temperature. The storage modulus, G ', and the loss factor, d, were determined at 1 Hz and were reported in Table 23.

Table 23 The results in Table 23 demonstrate that the storage modulus and the loss factor of this composition are high and relatively insensitive to changes in temperature. These are particularly desirable characteristics of the vibration damping materials used in bidirectional damping constructions.

Examples 112 and 113 In Examples 112 and 113, the segmented polydimethylsiloxane polyurea copolymers of Examples 71 and 72 were respectively tested to determine the vibration damping properties. The materials of Examples 112 and 113 were pressed molten between parallel aluminum plates as described in Example 99, except that the temperature of the press was 127 ° C. HE % 10 determined the storage modulus, G *, and the loss factor, so d, measured at 1 Hz and reported in Table 24. Example 112 was also evaluated as a thermally activated adhesive and gave an effort value to breaking of 0.45 MN / m2. 15 Table 24 twenty Table 24 continued The data in Table 24 demonstrate that the vibration damping materials of Examples 112 and 113, formulated using a mixture of diisocyanate and triisocyanate, provided useful temperature ranges of -20 to -11 ° C and -38 to 8 ° C respectively .

Example 114 In Example 114, the segmented polydimethylsiloxane polyurea copolymer of Example 73 was tested to test the vibration damping properties. The material was pressed molten between parallel aluminum plates as described ei. Example 112. The storage modulus, G ', and the loss factor, d, were determined as measured at 1 Hz and reported in Table 25.

Table 25 The data in Table 25 demonstrate that the vibration damping material of Example 114, formulated with 41% by weight aluminum oxide, provides a useful temperature range of -42 to 2 ° C.

Example 115-118 * In Examples 115-118 vibration damping compositions were prepared by blending the segmented polydimethylsiloxane polyurea copolymers of Examples 81-84, dry MQ resin and / or organic adhesive resin FORALMR 85, available from Hercules Inc., toluene, and isopropanol as shown in Table 26. The samples were slowly stirred until dissolved. Examples 117 and 118, which ft 10 contained organic adhesive resin, FORALTM 85, required heating to dissolve the adhesive resin.

Table 26 fifteen The samples were then coated on a removable liner, dried for 15 minutes at a temperature of 70 ° C, and laminated to form a vibration damping material. The storage modulus, G ', and the loss factor, d, were determined, measured at 1 Hz and reported in Table 27. 25 Table 27 The data in 'Table 27 show that the Example 115, based on the segmented polydimethylsiloxane polyurea copolymer derived from equimolar amounts of a polydimethylsiloxane diamine of molecular weight of about 50,000 and Dytek Am, a short chain hydrocarbon diamine, provide a vibration damping material with a useful temperature range of - 25 to 35 ° C when adhesive is made with MQ resin. The data in Table 27 for Examples 116, 117, and 118 show that the polydimethylsiloxane polyurea segmented copolymer derived from a polydimethylsiloxane diamine of molecular weight of about 5300 and two organic diamines, Jeffamine "1 * D-4000, a diamine of propylene oxide having a molecular weight of about 4,500, and Dytek A "1 * a short chain hydrocarbon diamine. having a molecular weight of about 100, wherein the propylene oxide constitutes approximately 77% by weight of the copolymer, is made adhesive with an MQ silicate resin, an organic adhesive resin, or a combination of MQ resin and organic adhesive provide materials vibration dampers with useful temperature ranges from 21 to 52 ° C, -5 to 5 ° C, and -24 to 13 ° C. Examples 115, 116 and 118 were also evaluated as thermally activated adhesives and gave stress values at break of 0.30 MN / m2, 0.84 MN / m2 and 0.15 MN / m2, respectively.

Example 119 In Example 119, powdered MQ resin containing less than 1%, of toluene G $, Silicones, material 1170-002) was fed at a rate of 42.8 g / min into zone 1 of a screw extruder, co-rotator, from 1600 m in length, 40 mm in diameter, from Berstsrff. Polydimethylsiloxane Diamine C, Lot 2, molecular weight of 22,000, was injected at a rate of 38.1 g / min (0.00173 mol / min) in zone 2. Methylenedicyclohexylene-4,4'-diisocyanate was fed at a rate of 0.585 g / kg. min (0.00223 mol / min) in zone 5 to provide a ratio of NC0: NH2 of 1. 29: 1.00. The diisocyanate feed line was placed near the screw threads as in Example 1. Fully geared, double-start screws were used, rotating at 100 revolutions per minute, throughout the length of the drum. The fixed temperatures for each of the 160 mm zones were: zone - 25 °; zones 2 to 4 - 40 ° C; zone 5 - 60 ° C; zone 6 - 120 ° C; zone 7 - 160 ° C; and zones 8 to 10, zone or final part, and fusion pump - 180 ° C. Vacuum was drawn in zone 8. The pressure sensitive adhesive of segmented polydimethylsiloxane polyurea copolymer was collected and cooled in air.

Example 120 In Example 120, pressure sensitive adhesive of segmented polydiorganosiloxane polyurea copolymer was produced as in Example 119, with the following changes. The flow rate of the MQ resin was 55.8 g / min, the polydimethylsiloxane diamine was Polydimethylsiloxane • Diamine F, molecular weight of 71,000, injected at 37.0 g / min 0.000521 mol / min), and the diisocyanate was fed at Q.143 g / min (0.000546 mol / min). The fixed temperature points were: zone 4-60 ° C; zone 5 - 120 ° C; zone 6 - 160 ° C; and zone 7 - 180 ° C.

Example 121 * 10 In Example 121, pressure sensitive adhesive of segmented polydiorganosiloxane polyurea copolymer was produced as in Example 120, except that the flow rate of the MQ resin was 30.4 g / min.

Comparative Example C3 The silicone pressure sensitive adhesive from Dow Corning 280A was finally coated and cured according to the manufacturer's specifications. Examples 110-121 and Comparative Example Cl were tested to determine the dry release against steel, wet rust release, protection against initial corrosion via EIS, and protection against corrosion 3 weeks after aging in electrolyte solution. , The results are shown in Table 27.

Table 27 Table 27 'shows that the three representative segmented polydiorganosiloxane polyurea copolymer formulations can be optimized for wet adhesion, shear strength and corrosion. Comparative Example C3 is a commercial silicone PSA that offers no corrosion resistance.

Example 122 In Example 122, pressure sensitive adhesive of segmented polydiorganosiloxane polyurea copolymer was produced as in Example 119, with the following changes. The flow velocity of the res to MQ was 31.4 g / min, the polydimethylsiloxane diamine was Polydimethylsiloxane ? Diamine G, molecular weight of 105,000, injected at 29X0 g / min (0.000276 mol / min) in zone 3, and the diisocyanate was fed at 0.0803 g / min (0.000307 mol / min). The screw speed was 250 revolutions per minute. Zone 1 was set at 15 ° C. In Examples 123-126, sß produced pressure sensitive adhesives of polydiorganosiloxane polyurea copolymer in a similar manner to that of Example 122, but with * Different flow rates of MQ and isocyanate, co or '10 listed in Table 28. The pressure sensitive adhesives of the segmented polydiorganosiloxane polyurea copolymer of Examples 122-126 were coated to 0.2 mm on a polyester backing, applied to sandblasting steel, and dipped into deionized water at 50 ° C for 3 15 months. Table 28 lists those pressure sensitive adhesive formulations in decreasing order of protection, as determined by visual inspection.

Table 28 20 Example 127 In Example 127, a pressure sensitive adhesive of segmented polydiorganosiloxane polyurea copolymer was produced as in Example 119- with the following changes. The flow rate of the MQ resin was 21.6 g / min, the polydimethylsiloxane diamine was Poidymethylsiloxane Diamine D, Lot 1, molecular weight 37.800, injected at 21-5 g / min (0.000569 mol / min), and the isocyanate, ISONATE "1 * 243L from Dow, was fed at 0.168 g / min (0.000568 mol / min) .The fixed temperature points were: zone 1 - 30 ° C, zones 2 to 4 - 5G ° C, zone 5 - 60 ° C; zone 6 - 100 ° C, zone 7 - 160 ° C, and zones 8 ~ -10, zone or final part, and fusion pump - 180 ° C. A pressure-sensitive adhesive tape was produced via solvent coating , as in Example 1, to produce a 0.4 mm thick pressure sensitive adhesive layer This tape was applied on a preexisting oxide stain on a steel plate This construction was placed in an electrolyte at room temperature, aerated (3% NaCl in deionized water) for seven days.The corrosion of the unprotected metal occurred rapidly, while the appearance of the surface under the tape did not change.

Example 128 * The pressure sensitive adhesive of segmented polydiorganosiloxane polyurea copolymer of Example 125 was extruded, as in Example 8, as a 0.2 mm thick film on release liners. Strips of adhesive were cut from the film, wrapped around a braided connection between two copper wires, and inserted into an expanded THVMR thermal shrink tube. (3M Co.). A thermal contraction oven was used to contract the outer tube, which caused the adhesive to flow around the wires and seal the connection. The test piece was immersed in 5% by weight salt water and connected to a 50 volt power supply, as specified in the Initial Current Leakage Test (ICLT) "Military Specification 23053. After 24 hours of exposure, the current leakage remained below 25 μA, satisfying the test specification. The test sequence was repeated in six more sealed samples with adhesive strips plus 20 small ones, producing identical results. The pressure sensitive adhesives of segmented polydiorganosiloxane polyurea copolymers possess a rheology at sufficiently high thermal shrinkage temperature so that the pressure sensitive adhesive does not flow out of the ^ Desired configuration, and it is still appropriate to conform around the desired geometry. The different modifications and alterations of this invention will be evident to those experts in the is not departing from the scope and principles of this invention, and it should be understood that this invention can not be unduly limited by the illustrative embodiments set forth hereinbefore. All publications and * f patents are incorporated here as rence in the same degree that if each of the publications or individual patents were specifically and individually indicated here incorporated as rence-.

It is noted that in relation to this date, the The best method known to the applicant to carry out the aforementioned invention is that which is clear from the # present description of the invention. Having described the invention as above, the content in the following is claimed as the property:

Claims (18)

1. An adhesive composition, characterized in that it comprises (a) a segmented polydiorganosiloxane polyurea copolymer, comprising the product of the reaction of (i) at least one polyane, wherein the polyamine comprises at least one polydiorganosiloxane diamine, or a mixture of at least one polydiorganosiloxane diamine and at least one ^ organic polyamine, and (ii) at least one polyisocyanate., in 10 where the molar ratio of isocyanate to amine is between 0.9: 1 and 0.95: 1 or between 1.05: 1 and approximately 1.3: 1, and (b) silicate resins.

2. An adhesive composition, characterized in that it comprises (a) a polydiorganosiloxane segmented polyurea polypeptide, comprising the product of the reaction of (i) F at least one polyamine, wherein the polyamine comprises at least one polydiorganosiloxane diamine, or a mixture of at least one polydiorganosiloxane diamine, and at least one organic amine, and (ii) at least one polyisocyanate, wherein the composition has viscosities of at least 0.8 dL / g, or is essentially insoluble in common organic solvents.

3. The adhesive composition according to claim 1, characterized in that the segmented polydiorganosiloxane polyurea copolymer is represented by the repeated unit: wherein: each R is a portion that is independently an alkyl portion having about 1 to 12 carbon atoms and can be substituted with trifluoroalkyl or vinyl groups, a vinyl radical or higher alkenyl radical represented by the formula -R2 (CH2 ) tJCH = CH2 where R2 is ~ (CH2) b- or - (CH2) CCH = CH- is already 1, 2, or 3; b is 0, 3 or 6; and c is 3, 4, or 5, a cycloalkyl portion having from about 6 to 12 carbon atoms and can be substituted with alkyl, fluoroalkyl, and vinyl groups, or an aryl portion that preferably has from about 6 to 20 carbon atoms and can be substituted with alkyl, cycloalkyl, fluoroalkyl and vinyl groups or R is a perfluoroalkyl group, a fluorine-containing group, or a group that. contains perfluoroether; each Z is a polyvalent radical that is a radical * arylene or an aralkylene radical having from 6 to 20 carbon atoms, an alkylene or cycloalkylene radical having from about 6 to 20 carbon atoms; Each Y is a polyvalent radical which is independently an alkylene radical of 1 to 10 carbon atoms, an aralkylene radical or an arylene radical having from 6 to 20 carbon atoms; mf each D is selected from the group consisting of Hydrogen, an alkyl radical of 1 to 10 carbon atoms, phenyl, and a radical that completes an annular structure including B or Y to form a heterocycle; B is a polyvalent radical selected from the group consisting of alkylene, aralkylene, cycloalkylene, phenylene, polyalkylene oxide, including copolymers and mixtures thereof; r i is a number that is 0 to approximately 1000; n is a number that is equal to or greater than 1; and p is a number that is approximately 10 or greater.

4. The adhesive composition according to claim 3, characterized in that R is at least 50% of the R portions being methyl radicals with "the moiety," being monovalent alkyl or substituted alkyl radicals of 1 to 12 carbon atoms, alkenylene radicals, phenyl radicals, or substituted phenyl radicals.

5. The adhesive composition according to claim 3, characterized in that Z is 2,6-tolylene, 4,4t-methylenediphenylene, 3,3'-dimethoxy-4,4'-biphenylene, tetramethyl-m-xylylene, 4,4'-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylenecyclohexylene, 1,6 -hexamethylene, 1,4- • SP cyclohexylene, 2,2,4-trimethylhexylene and mixtures thereof 10 same.

Adhesive composition according to claim 1, characterized in that the silicate resin is an MQ resin having triorganosilaxy units and 15 units of Si0 / 2, an MQD resin having units R3Si0? / 2, units Si04 / 2 and units R2Si02 / 2 where R is a mixture of f alkyl radicals having from 1 to 4 carbon atoms or an MQT resin which has units R3SiO? / 2, units Si04 / 2, and units RSi03 where R is a mixture of alkyl radicals 20 having 1 to 4 carbon atoms.

7. A vibration-absorbing, constrained layer construction characterized by at least one substrate having a stiffness and at least one 25 layer comprising an adhesive composition in accordance with claim 1 or claim 2, wherein the * Adhesive composition is fixed to the substrate.

8. A vibration damping composition, characterized in that it comprises a flexible substrate coated with a composition according to claim 1 or claim 2. f

9. A restricted layer construction 10 bidirectional vibration damper, characterized X because it comprises at least two rigid members, each rigid membrane has a surface close to a broad surface of another rigid member and closely spaced from it and an adhesive composition in accordance with claim 1 or claim 2, wherein the adhesive composition is contained between the rigid members closely spaced and adhered to the members.

10. OR? article coated with an adhesive 20 pressure sensitive, characterized in that it comprises a flexible substrate and coated on an adhesive composition according to claim 1 or claim 2.

11. A pavement marker, characterized in that it comprises a base layer having an upper surface useful as a pavement marking indicator and a lower surface of an adhesive composition in accordance with claim 1 or claim 2.

12. A construction that protects against corrosion, characterized in that it comprises an adhesive composition according to claim 1 or claim 2, so that the construction prevents corrosion of the metal surface, wherein the construction to protect against corrosion has a film surface resistivity of 1 MO / cm2, measured by Electrochemical Impedance Spectroscopy after exposure to a corrosive environment 3 weeks later in an aqueous solution of 3% NaCl.

13. Coated articles, characterized in that they comprise a segmented polydiorganosiloxane polyurea copolymer, adhesive, according to claim 1 or claim 2, which prevents corrosion of the metal surface, wherein the coated articles have a film surface resistivity of 1. . MO / cm2, measured by Electrochemical Impedance Spectroscopy after exposure to a corrosive environment for 3 weeks in an aqueous solution of 3% NaCl.

14. A tube that is thermally contracted, characterized in that it comprises the segmented polydiorganosiloxane polyurea copolymer adhesive, according to claim 1 or claim 2.

15. A construction of medical tape, ". -T-characterized in that it comprises a substrate and a layer of adhesive segregated polydiorganosiloxane polyurea copolymer, according to claim 1 or claim 2.

16. The medical tape construction according to claim 15, characterized in that the construction is a transdermal drug delivery device.

17. A hot-melt adhesive, characterized in that it comprises the segmented polydiorganosiloxane polyurea copolymer adhesive, according to claim 1 or claim 2.

18. A process for producing a segmented adhesive polydiorganosiloxane polyurea copolymer, characterized in that it comprises the steps of: (a) continuously providing reagents wherein the reagents include at least one polyisocyanate, at least one polyamine, wherein the polyamine comprises at least one polydiorganosiloxane diamine, or a mixture of at least one polydiorganosiloxane diamine and at least one organic amine and at least one silicate resin to up reactor; (b) mixing the reactants under substantially solvent-free conditions; k (c) allowing the reactants to react to form a segmented polydiorganosiloxane polyurea co-polymer, and (d) transporting the copolymer from the reactor. An adhesive composition comprising (a) a segmented polydiorganosiloxane polyurea copolymer comprising the product of the reaction of (i) at least one polyamine, wherein the paliamine comprises at least one polydiorganosiloxane diamine, or a mixture of at least one polydiorganosiloxane diamine and at least one organic polyamine, and (ii) at least one polyisocyanate, wherein the molar ratio of isocyanate to amine is between 0.9 [mu] l and

0. 95: 1 or between 1.05: 1 and approximately 1.3: 1, and silicate resins. Adhesive compositions are useful as pressure sensitive adhesives, particularly for foamed backing tapes, medical tapes and the like, hot melt adhesives, vibration dampers, anticorrosive materials.