MXPA03006051A - Transcripts encoding immunomodulatory. - Google Patents

Abstract

Substantially-isolated polynucleotides encoding human polypeptides having immunomodulatory activity; human homologs of yeast RAD50, Drosophila Septin-2 and rat Acyl-CoA Synthetase compositions and methods; method for detecting the presence of activated T-cells.

Description

ADHESIVE COMPOSITIONS OF REACTIVE HOT FUSION WITH IMPROVED CRUDE RESISTANCE BACKGROUND This invention relates to polymeric urethane compositions, particularly to moisture reactive urethane hot melt polymeric compositions useful as adhesives, to a method for making such compositions and to a method for bonding substrates with such compositions. Some hot melt polymeric compositions reactive to moisture are useful as hot melt reactive adhesives. Some desirable properties of such adhesives are high green strength, high ultimate strength and long exposure time. The raw strength is the bond strength before the reaction is completed with moisture; the final resistance is the adhesive strength after the reaction with moisture is essentially complete; and the exposure time is the period after the hot melt adhesive is applied to one or more substrates, during which subsequent substrates can be contacted with the adhesive, without loss of final strength. The U.S. Patent No. 5021507 describes the modification of reactive hot fusions to polyurethane with acrylic copolymers of specific molecular weight, in which the polymer does not contain monomers with active hydrogen. The U.S. Patent No. 5827926 describes the use of crystalline acrylic polymers that do not contain active hydrogens. The procedures taken in the past that have achieved good resistance in crude have also had undesirably short exposure times. The problem faced by the inventor is the provision of a moisture-reactive hot melt adhesive composition which achieves a desirably long exposure time while maintaining the advantageously high green strength. Surprisingly, the inventor found that the incorporation of certain acrylic polymers having tertiary alkyl amide functionality provide the desired balance of properties. SUMMARY OF THE INVENTION In a first aspect of the present invention, there is provided a moisture-reactive polymeric hot melt composition formed by mixing components comprising at least one polyol, at least one polyisocyanate and at least one acrylic polymer having functionality Tertiary alkyl amide. In a second aspect of the present invention, there is provided a method of making a moisture reactive hot melt composition comprising mixing the components comprising at least one polyol, at least one polyisocyanate and at least one acrylic polymer having functionality tertiary amide. In a third aspect of the present invention, there is provided a method for bonding substrates comprising: (a) making a moisture reactive hot melt composition comprising mixing the components comprising at least one polyol, at least one polyisocyanate and at least one acrylic polymer having tertiary alkyl amide functionality; (b) heating said hot melt composition; (c) applying said heated hot melt composition to a first substrate, - (d) contacting said heated hot melt composition applied with a second substrate; and (e) cooling or allowing to cool said hot melt composition. DETAILED DESCRIPTION The composition of this invention is a hot melt composition reactive to moisture useful as an adhesive. By "moisture reactive" herein is meant that the composition contains isocyanate groups which are capable of desirably reacting with water to effect an increase in the molecular weight of the composition and / or effect the degradation of the composition in order to increase the strength properties of the composition after coming into contact with water. By "hot melt" in the present means that the composition, which may be a solid, semi-solid or viscous mass, may advantageously be heated to provide a fluid adhesive of a viscosity suitable for application and adhesion to substrates. The moisture-reactive hot melt composition of the present invention is formed by mixing the components including at least one polyisocyanate, i.e., an isocyanate bearing at least two isocyanate groups. Polyisocyanates that may be useful include, for example, aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates and combinations thereof. Suitable polyisocyanates include, for example, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 1, cyclohexane diisocyanate, hexahydrotoluene diisocyanate, 1,5-naphthalene diisocyanate, l -methoxy-2, 4-phenylene diisocyanate, 'diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4'-bifenilen diisocyanate, 3, 3'-dimethoxy-4, 4'-biphenyl diisocyanate, 3, 3' -dimethyl-4, 4 '-biphenyl diisocyanate, 3, 3' -dimethyl-4, 4 'diphenylmethane diisocyanate, isophorone diisocyanate,', 4"-triphenylmethane triisocyanate, polymethylene polyphenylene polyisocyanate, 2,4,6-toluene triisocyanate , 4 '-dimethyl-diphenylmethane tetraisocyanate, prepolymers having Mn less than 2000 and bearing at least two isocyanate groups and mixtures thereof are preferred. 4, 4' diphenylmethane diisocyanate (also called 4,4'-MDI), 2, '-diphenylmethane diisocyanate (also called 2,4' -MDI) and mixtures thereof; more preferred is 4,4 '-MDI. The moisture-reactive hot melt composition of the present invention is formed by mixing components that include at least one polyol. A polyol is a compound with two or more functional hydroxyl groups. Suitable polyols include a wide variety of compounds, some of which are described in the Polyurethane Handbook, 2nd edition edited by G. Oertel, Hanser Publishers, 1994. In addition to the hydroxyl functions, suitable polyols may contain other functionalities, such as for example carbonyl, carboxyl, anhydride, unsaturation or other functional groups. Suitable polyols include, for example, polyether polyols, polyester polyols, polyether ester polyols (sometimes called polyether ester polyols and / or polyester ether polyols), fatty polyols and mixtures thereof. The suitable polyol (s) can be independently selected from crystalline, semi-crystalline or amorphous polyols. Polyester polyols suitable for use in the present invention include those formed from diacids or their monoesters, diester or the anhydrous counterparts and diols. The diacids may be saturated C4-C12 aliphatic acids, including branched, unbranched or cyclic materials and / or C8-C15 aromatic acids. Examples of suitable aliphatic acids include, for example, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebasic, 1,12-dodecanedioic, 1,4-cyclohexanedicarboxylic and 2-methylpentanedioic acids. Examples of suitable aromatic acids include, for example, terephthalic, isophthalic, phthalic, 4,4'-benzophenone dicarboxylic, 4'-diphenylamide dicarboxylic acids and mixtures thereof. The diols can be C2-Ci2 branched aliphatic diols, unbranched or cyclic. Examples of suitable diols include, for example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,3-butanediol, hexanediols, 2-methyl-2, 4-pentanediol, cyclohexane-1,4-dimethanol, 1,12-dodecanediol, diethylene glycol and mixtures thereof. Mixtures of the various suitable polyester polyols are also suitable for use in the present invention. Preferred polyester polyols are 1,6-hexanediol adipate; 1,6-hexanediol neopentyl glycol adipate; neopentyl adipate glycol and mixtures thereof. The polyester polyol (s) preferably has an average molecular weight weight ("Mw" as measured by gel permeation chromatography) of from 250 to 8,000, more preferably from 300 to 6,000, even more preferably from 400 to 5,000 and more preferably from 500 to 4,000. Polyester polyols suitable for use in the present invention include polyoxy-C2-C3 alkylene polyols, including branched and unbranched alkylene groups. Examples of suitable polyester polyols include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol or random or block copolymers of those polyethers and mixtures thereof. Mixtures of various suitable polyether polyols are also suitable for use in the present invention. Preferred polyether polyols are polypropylene glycols, also known as polypropylene oxides. The polyether polyol preferably has an average molecular weight weight ("Mw" as measured by gel permeation chromatography) of from 800 to 8,000, more preferably from 900 to 4,000. In some embodiments of the present invention, the components include at least one fatty polyol. "Fatty" herein means any compound that contains one or more fatty acid residues. Fatty acids are well known in the art. They are described, for example, by R.A. Burns in Fundamentáis of Chemistry, (Fundamentals of Chemistry), Third Edition (Prentice Hall, 1999). Fatty acids are long-chain carboxylic acids, with chain lengths of at least 4 carbon atoms. Typical fatty acids have chain lengths of 4 to 18 carbon atoms, although some have longer chains. Linear, branched or cyclic aliphatic groups can join the long chain. The fatty acid residues may be saturated or unsaturated and may contain functional groups, including for example, alkyl groups, epoxide groups, halogens, sulfonate groups or hydroxyl groups, which occur either naturally or have been added. Suitable fatty polyols include, for example, fatty acids, fatty acid esters, fatty acid amides and mixtures thereof, as long as the compound is a polyol. Additional examples of suitable fatty polyols include, for example, dimers, trimers, oligomers or polymers of fatty acids; dimers, trimers, oligomers or polymers of fatty acid esters; dimers, trimers, oligomers or polymers of fatty acid amides; dimers, trimers, oligomers or polymers of fatty acid mixtures; esters of fatty acids and fatty acid amides; or mixtures of such dimers, trimers, oligomers or polymers as long as the compound is a polyol. The hydroxyl functions of a suitable fatty polyol may reside in the fatty acid residue, in other parts of the molecule or both. In the embodiments of the present invention, in which fatty polyols are used, some preferred fatty polyols are castor oil, the hydroxylation products of unsaturated or polyunsaturated natural oils, the hydrogenated products of polyunsaturated or unsaturated polyhydroxyl natural oils, polyhydroxyl esters of alkyl hydroxy fatty acids, polymerized natural oils and alkylhydroxylated fatty acid amides. Castor oil, hydroxylated soybean oil, hydrogenated castor oil, polymerized castor oil, hydroxy ethyl ricinoleate and hydroxy ethyl ricinoleamide are more preferred. More preferred is castor oil. In the practice of the present invention, the preferred polyols are polyether polyols, polyester polyols, fatty polyols and mixtures thereof. More preferred is a mixture containing at least one polyether polyol and at least one polyester polyol. Even more preferred is a mixture containing at least one polyether polyol, at least one polyester polyol and at least one fatty polyol. When both the polyether polyol (s) and the polyester polyol (s) are used, the preferred weight ratio of polyether polyols to polyester polyols is from 0.5: 1 to 12: 1; more 0.6: 1 to 10: 1 is preferred; 0.7: 1 to 8: 1 is further preferred; more preferred is 0.8: 1 to 5: 1. When the fatty polyol (s) is used in addition to other polyols, the preferred weight ratio of fatty polyols to other polyols is from 0.005: 1 to 5: 1; more is preferred 0.008: 1 to 1: 1; more preferred is 0.01: 1 to 0.5: 1 and more preferred 0.02: 1 to 0.1: 1. The moisture-reactive hot melt composition of the present invention is formed by mixing components that include at least one acrylic polymer containing tertiary alkyl amide functionality. Acrylic polymers are polymers formed by the polymerization of one or more (meth) acrylic monomers. These monomers include acrylic acid, methacrylic acid, their esters, amides and derivatives thereof. A polymer made by polymerizing a monomer mixture is said to "include" each of these monomers. In the present "(met) acrylic" will mean "acrylic or methacrylic"; and "(meth) acrylate" will mean "acrylate or methacrylate". Some acrylic monomers suitable for inclusion in the acrylic polymer. of the present invention are, for example, (meth) acrylic acid, alkyl (meth) acrylate esters wherein the ester group consists of a linear, branched or cyclic alkyl group with 1 to 70 carbon atoms. Also suitable are aryl (meth) acrylate esters, esters of halogenated alkyl or aryl (meth) acrylate, other (meth) acrylate esters, N -substituted (meth) acrylamides with two substituents on the nitrogen atom, derivatives of these or mixtures thereof. The acrylic polymers may include monomers other than acrylic monomers such as for example styrene, substituted styrene, vinyl acetate or ethylene. Certain embodiments of the acrylic polymers containing tertiary alkyl amide functionality of the present invention are acrylic polymers that include one or more alkyl methacrylate esters; when the alkyl methacrylate esters are used, esters are preferred wherein the ester group consists of a linear, branched or cyclic alkyl group with 1 to 70 carbon atoms; more than 1 to 10 carbon atoms are preferred and more than 1 to 4 carbon atoms are preferred. Also preferred are acrylic polymers which include one or more acid functional monomers such as for example acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl maleate, monobutyl maleate, maleic anhydride or mixtures thereof; When a functional acidic monomer is used, acrylic acid, methacrylic acid and mixtures thereof are preferred. Acrylic polymers containing little or no hydroxyl functionality are preferred; that is, hydroxyl groups that are not part of the acid groups are considered undesirable as functional groups in the acrylic polymer. The acrylic polymer having tertiary alkyl amide functionality of the present invention is an acrylic polymer having at least one functional group with the following structure attached to the polymer chain: O | c '*' x / NH where R1 has the structure: wherein R2-R10 are, independently, hydrogen or organic groups. The carbon atom of R 1 which binds to the amide nitrogen is a tertiary alkyl carbon atom, so that the functional group is said to have "tertiary alkyl amide functionality". If any of R2-R10 are organic groups, they may independently be alkyl, cycloalkyl, aryl, alkylaryl, unsaturated and / or substituted with one or more halogen, amide, sulphonic, carbonyl or other groups. Any substituent group is suitable, so long as the resulting polymer does not undesirably interfere with the moisture curing reaction of the hot melt composition. Although the present invention is not limited to any particular theory or mechanism, the tertiary alkyl amide functionality is considered desirable because the hydrogen atom attached to the amide nitrogen is considered reactive, but its reactivity is considered to be limited by the Tertiary alkyl group on the amide nitrogen. The tertiary alkyl group is considered to provide steric hindrance, which allows the hydrogen atom in the amide nitrogen to be desirably reactive without being excessively reactive. The acrylic polymer having the tertiary alkyl amide functionality of the present invention can be made by any means known in the art, including for example, making an acrylic copolymer and then performing chemical reactions to add the functionality of the tertiary alkyl amide to the polymer chain. Alternatively or additionally, the acrylic polymer having tertiary alkyl amide functionality of the present invention can be made by polymerizing monomers that include at least one monomer having tertiary alkyl amide functionality. A group of suitable monomers having tertiary alkyl amide functionality is the group of substituted (meth) acrylamides having the following structure: wherein R is hydrogen or methyl and R is as defined above. Preferred monomers having tertiary alkyl amide functionality are 2-acrylamido 2-methylpropane sulfonic acid, diacetone (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-tert-octyl (meth) acrylamide and mixtures thereof; more preferred are N-teart-butyl (meth) acrylamide, N-tert-butyl acrylamide and mixtures thereof; and more N-tert-butyl acrylamide is preferred. When the acrylic polymer having tertiary alkyl amide functionality of the present invention is made by inclusion of tertiary alkyl amide functional monomers, the appropriate amount of such monomers for inclusion in the polymer is from 0.1 to 20% by weight, based on the polymer weight. It is preferred from 1 to 10%; more than 2 to 7% is preferred; and even more than 4 to 6% is preferred. The acrylic polymer having tertiary alkyl amide functionality of the present invention can be made by any method, including for example, bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, as taught by K.J. Sunders in Organic Polymer Chemistry, Chapman and Hall, London, 1973. If water is used in the polymerization (as in, for example, aqueous suspension or emulsion polymerizations), most or all of the water should be removed of the acrylic polymer before the acrylic polymer is included in the moisture reactive composition of the present invention. If the solution polymerization is used, the solvent can be any solvent that has adequate compatibility with the monomer or monomers and with the resulting polymer. Toluene is known to be adequate. If any of the other components of the present invention, such as for example a liquid polyol, have suitable compatibility with the acrylic monomer and the acrylic polymer, that component can be used as the polymerization solvent for the acrylic polymer. The acrylic polymer having tertiary alkyl amide functionality of the present invention can be amorphous, crystalline or a mixture of amorphous and crystalline; amorphous polymers are preferred. Crystalline polymers are those with a measurable melting point and amorphous polymers are those that are not crystalline, as taught by L.H. Sperling in Introduction to Physical Polymer Science, 2nd edition, Wiley, 1992. The amount of acrylic polymer having preferred tertiary alkyl amide functionality for use in the present invention is from 1 to 95% by weight. weight, based on the weight of the hot melt composition; more than 1 to 90% is preferred; even more than 10 to 60% is preferred; more than 20 to 30% is preferred. The preferred molecular weight of the acrylic polymer (average number of molecular weight or n as measured by gel permeation chromatography) is 10,000 to 100,000; More than 15,000 to 80,000 are preferred; even more than 30,000 to 40,000 are preferred. The preferred glass transition temperature of the acrylic polymer (Tg, measured by Dynamic Scanning Calorimetry), is 20 ° C to 120 ° C; more than 30 ° C to 90 ° C is preferred; more preferred is 40 ° C to 80 ° C, more than 50 ° C to 70 ° C is preferred. When the acrylic polymer having tertiary alkyl amide functionality of the present invention is made by solution polymerization in a solvent that is not the component of the present invention, the solvent can be removed, if desired, before the polymer is added to the other components of the present invention. Alternatively, the solution containing the acrylic polymer can be added to one or more components of the present invention and the solvent can be removed from the mixture, if desired, by means known in the art such as for example applying full or partial vacuum and / or by heating. The components of the present invention preferably contain less than 1% water, more preferably less than 0.2% water, still more preferably less than 0.1% by weight based on the total weight of the components. The components can be mixed by conventional or other means, preferably in an inert dry atmosphere. The components can all be mixed together at the same time (in a "one stage" process), alternatively, some components and / or portions of the components can be mixed together in one operation (or "stage") with other components and / or portions. of added components in stage or additional stages. Normally, the components are heated above room temperature. The components can be heated before, during or after the mixing process. If more than one component addition and / or mixing and / or heating step is used, the one-stage mixture may be heated for a time before being added to the next stage. The preferred heating temperature is 50 ° C to 130 ° C. If more than one stage is used, the temperature of each stage can be selected independently. During any of the mixing and / or heating steps, total or partial vacuum may be applied; Nitrogen gas or another dry and / or inert gas can also be used to heat the surface of the mixture. During the mixing and / or heating of the components of the present invention, the acrylic polymer having tertiary alkyl amide functionality can be added to any of the steps. In one embodiment, a solution of the acrylic polymer having tertiary alkyl amide functionality is added to one or more polyether polyols, and the mixture is heated under vacuum; then other components are added in one or more stages. If any material that is added to the reaction mixture is a solid, it is preferably solubilized by heating and mixing with at least one of the components that do not contain isocyanate before being mixed with the polyisocyanate. In addition, a catalyst such as, for example, a tertiary amine or a tin-based catalyst may optionally be mixed with the components, either before, during or after any one or more of the component mixing steps. When such an optional catalyst is used, the level of normal use is less than 0.3% by weight based on the total weight of the mixed components. The adhesive composition of this invention, which is an NCO-functional composition, is stored, preferably under an inert, dry atmosphere until use. The hot melt composition can be formulated by mixing additional conventional ingredients such as fillers, pigments, thickeners, plasticizers, rheology modifiers, thermoplastic acrylic resins, etc., without detracting from the reactivity of the NCO-functional groups, which is maintained desirably In the method of the present invention for bonding substrates, the hot melt composition reactive to moisture is heated in order to achieve a suitable viscosity for transporting the adhesive, such as by pumping or gravity feed to the application equipment. and for the application of the adhesive to a first substrate in the presence of moisture. The temperature should be high enough to achieve a suitable viscosity but low enough to avoid excessive degradation or other undesirable effects on the adhesive. Typical useful temperatures are in the range of 40 ° C to 160 ° C, preferably 50 ° C to 150 ° C and more preferably 100 ° C to 140 ° C. The application of the adhesive can be effected by conventional means, such as, for example, superheated spray applicator, superheated drip applicator, reheated nozzle, and reheated roller coater, to form a continuous or discontinuous adhesive film, as desired. The adhesive can also be applied to the substrate manually, for example, with a portable tool such as, for example, a spatula or other applicator. The adhesive can typically be applied at a level of 50 to 250 g / m2 (4-20 g / ft2) although in cases where one of the substrates is a cloth it can be applied at a level as low as 1-50 g / m2. Then, the applied adhesive is contacted by a second substrate to provide a composite construction. Preferably, the adhesive is contacted by the second substrate while the adhesive has a temperature substantially above room temperature. The construction of the composite thus formed is optionally subjected to applied pressure such as by passing it between rollers to effect increased contact of the substrates with the adhesive and the construction of the composite is then cooled or allowed to cool. In another embodiment, the adhesive can be applied simultaneously or sequentially to two surfaces of the first substrate, the adhesive-coated surfaces of which are simultaneously or sequentially joined to the two additional substrates, which can be the same or different. It is further contemplated that the construction of the compound may subsequently be linked to another substrate (s) b using the same or different adhesives before or after the process described herein. The substrates to be joined in the method of the present invention may be the same or different and include for example, metal, wood, consolidated wood products, paper, elastomers, woven and non-woven fabrics and plastics which may have smooth or structured surfaces and They are provided in the form of rolls, sheets, films, metal sheets, etc. The substrates to be joined in the method of the present invention include, for example, plywood mahogany plywood, impregnated paper, extruded polystyrene foam, expanded polystyrene foam, glass fiber reinforced polyester, polyester cloth, high laminate or low pressure, plywood, aluminum, steel, polyvinyl chloride, synthetic rubber, polymer blends and engineering plastics. It is contemplated that the moisture, ie, the water, which is intended to effect the reaction with the NCO-functional groups thereby increasing the final cohesive strength of the applied adhesive, may be exposed to the hot melt composition reactive to the moisture of the present invention in any of a variety of ways known in the art. For example, after the hot melt composition is applied to a substrate but before it is contacted with a second substrate, the hot melt composition can be exposed to moisture in a variety of ways, including for example, moisture environment, artificially increased or controlled humidified air, a drizzle of water droplets, a spray of liquid water that makes contact with the applied adhesive or combinations thereof. Alternatively or additionally, after the second substrate makes contact with the hot melt composition, the structure of the composite of the substrates and the hot melt composition may be exposed to moisture in any or all of the above forms. The method for exposing the structure of the compound to moisture is especially useful when one or more of the substrates is a material that is permeable to water vapor, such as, for example, wood, paper or textiles. It is further contemplated that the moisture may be increased by other ingredients involved, catalyzing or otherwise facilitating the reactions of the NCO-functional groups with each other. Such an ingredient can be combined with moisture during any or all of the curing process. Examples of such ingredients are certain amines, which are known to bind the NCO-functional groups together through the formation of biuret linkages. Also, some catalysts are known to improve the reactions of the NCO-functional groups with each other. Regardless of the mechanism, the use of such ingredients to increase the moisture curing reaction is contemplated in the present invention. In some embodiments of the present invention, the joining substrates are relatively thin and flat and in such cases the composite article is the so-called laminate or laminated structure. It should be understood that for purposes of the present specification and claims, the range and proportion limits cited herein may be combined. For example, if the ranges of 60 to 120 and 80 to 110 are cited for a particular parameter, it should be understood that the ranges of 60 to 110 and 80 to 120 are also contemplated. In the following Examples, the following test procedures are used. . Resistance in Crude: The adhesive is heated for equilibrium at 120 ° C. It is then applied to a laminated birch plywood of 0.125 inches thick (3.2 mm) to a thickness of 0.004 inches (0.10 mm). A second piece of plywood identical to the first one was laminated, with an overlapped area of 1 inch2 (645 mm2). The laminate was subjected to pressure of 10 psi (69 kPa). After a pause, the rolling resistance was measured with a tension tester, using a tensile rate of 0.05 inch / min (1.3 mm / min), in a coating movement mode. The amount reported is the maximum force divided by the superimposed area. Sufficient laminates are produced so that measurements are made in triplicate at each pause of 5, 10, 30 and 60 minutes. The green strength is desirably at least 0.3 psi (2.1 kPa) at 5 minutes and desirably increases as it is tested at longer pauses. Exposure time The pieces of wood in this procedure are laminated birch plywood, 3 inches X 6 inches X 0.125 inches (76 mm X 152 mm X 3.2 mm). The adhesive is heated to equilibrium at 120 ° C and then applied to a piece of wood to a thickness of 0.004 inches (0.1 mm). Other pieces of wood are laminated to the first at time intervals of 1, 3, 5, 7 and 9 minutes under 10 psi (69 kPa) of pressure. The overlapped area for each piece of wood is 1 inch2 (645 mm2). The laminates are stored at a temperature (25 ° C and room humidity (50% RH) constant for 1 day or 7 days and tested in a tension tester with a tensile rate of 0.05 inch / min (1.3 mm / min) in a coating movement mode The exposure time was arbitrarily selected as the time interval at which less than 75% of contactivity or ripping of the wood was observed after the stress test Adhesion to Surlyn ™ Resins Adhesive heated to equilibrium at 120 ° C and applied to a polycarbonate / ABS base material at 130 g / m2, followed by lamination after a time of exposure of minutes with a second substrate consisting of Surlyn ™ ionomer resin (from E.I. DuPont de Nemours and Company).

The samples were cured for 5 days at 25 ° C and 50% relative humidity. The substrates were then separated by 90 ° by way of detachment in a tension tester a 50 mm / min. The amount reported is the maximum force divided by the amplitude of the sample. Properties of the Film An adhesive film is poured over a silicone release liner at a thickness of 0.006 inches (0.15 mm). The film is cured for 7 days and then tested under tension in a voltage tester. The quantities reported are (1) T100, the force at 100% elongation divided by the cross-sectional area of the sample: (2) Trompimiento, the breaking force divided by the cross-sectional area of the sample; Y (3) Emax, the elongation when breaking.

EXAMPLES Example 1 (comparative) The ingredients were as follows: (1) polypropylene glycol (Mw 2000) 168.58 g (2) Castor oil 9.72 g (3) Polymer Acrylic 155.00 g (Tg 60 ° C, does not include functional monomer tertiary alkyl amide) (4) Methylene bisphenyl diisocyanate 51.63 g (5) 1,6 hexanediol adipate (Mw 3500) 115.07 g (6) 2,2 'dimorpholinoethyl ether 0.30 g Raw materials (1) to (3) were added to a one-liter tank of resin. The acrylic polymer was added as 60% by weight of the solution in toluene. After adjusting the tank with a mechanical agitator and upper part of the reactor, heat was applied to the tank to raise the temperature to 85 ° C. At this point, a vacuum of 20 inches Hg (67 kPa) was applied to the vessel to remove the toluene. After removing the mass of the solvent, the temperature rose slowly to 110 ° C and the vacuum was increased to 27 inches Hg (91 kPa) to remove the residual solvent and moisture. After 30 minutes under these conditions, the temperature was lowered to 100 ° C and the vacuum was removed with dry nitrogen. Then the article (4) was added and the vacuum was replaced. The temperature was allowed to re-equilibrate at 100 ° C, at which temperature the reaction was left standing for 90 minutes. The vacuum was released once more with dry nitrogen, at which point the article was added (5). After re-applying the vacuum, the reaction was continued for 30 minutes at 100 ° C. The article (6) was then added and the mixture allowed to warm for an additional 30 minutes. The reactive hot melt was heated to 115 ° C and emptied into a 1 pint (0.47 liter) plastic container where it was heat-treated with nitrogen and sealed.

Example 2 It is identical to Example 1 except that the acrylic polymer included N-tert-butyl acrylamide, in the amount of 5% by weight based on the weight of the acrylic polymer.

Example 3 (comparative) The ingredients were as follows: (1) polypropylene glycol (w 1000) 106.61 g (2) polypropylene glycol (Mw 2000) 137.62 g (3) Castor oil 15 .74 g (4) Acrylic Polymer (as Example 1) 132 .00 g (5) Methylene bisphenyl diisocyanate 92.03 g (5) 1,6 hexanediol adipate (Mw 2000) 65.99 g (7) 2,2 'dimorpholinoethyl ether 0. 33 g Raw materials (1) to (4) were added to a one liter tank of resin. After adjusting the tank with a mechanical agitator and upper part of the reactor, heat was applied to the tank to achieve the temperature at 85 ° C. At this point, a vacuum of 20 inches Hg (68 kPa) was applied to the vessel to remove the toluene. After removing the mass of the solvent, the temperature rose slowly to 110 ° C and the vacuum was increased to 27 inches Hg (91 kPa) to remove the residual solvent and moisture. After 30 minutes under these conditions, the temperature was lowered to 100 ° C and the vacuum was removed with dry nitrogen. Then article (5) was added and the vacuum was replaced. The temperature was allowed to re-equilibrate at 100 ° C, at which temperature the reaction was left standing for 90 minutes. The vacuum was released once more with dry nitrogen, at which point the article was added (6). After re-applying the vacuum, the reaction was continued for 30 minutes at 100 ° C. Item 7 was then added and the mixture allowed to warm for an additional 30 minutes. The reactive hot melt was heated to 115 ° C and emptied into a 1 pint (0.47 liter) plastic container where it was heat-treated with nitrogen and sealed.

Example 4 It is identical to Example 3, except that the acrylic polymer was the same as that used in Example 2.

Example 5 (comparative) The ingredients were as follows: (1) polypropylene glycol (Mw 2000) 116.90 g (2) Castor Oil 9.65 g (3) Acrylic Polymer (as Example 1) 112.00 g (4) Methylene bisphenyl diisocyanate 49.68 g (5) 1,6 hexane diol neopentyl glycol adipate (Mw 2000) 111.76 g (6) 2,2 'dimorpholinoethyl ether 0.24 g The procedure used to mix and heat the ingredients was the same as in Example 1.

Example 6 It is identical to Example 5, except that the acrylic polymer was the same as that used in Example 2.

Example 7 The results of the green strength and the exposure time tests were as follows: Resistance in Crude psi (kPa) Example 5 min. 10 minutes. 30 min. 60 min. Exposure time (min) 1 (comparative) 77 77 100 103 < 1 (531) (531) (690) (710) 2 3.0 4.7 90 110 6 (21) (32) (617) (758) 3 (comparative) 0.8 1.5 12.7 14.7 < 30 (5.5) (10.3) (87.6) (101) 4 0.4 0.6 0.7 3.5 > 30 (2.8) (4.1) (4.8) (24.1) 5 (comparative) 9.0 14.7 14.6 16.3 < 1 (62) (101) (101) (112) 6 1.5 1.5 2.4 4.4 > 9 (10.3) (10.3) (15.5) (30.3) Each example of the present invention (2, 4 and 6) displays a longer exposure time than its comparative counterpart (1, 3 and 5 respectively) while advantageously showing high green strength.

Example 8 The results of the stress properties tests were as follows: Example T100, psi (Pa) Trompimiento% of Emax psi (Pa) 3 (comparative) 819 (5.65) 2129 (14.7) 602 4 667 (4.60) 2136 (14.7) 642 (comparative) 365 (2.52) 1011 (6.97) 630 6 354 (2.44) 1234 (8.51) 762 Each example of the present invention (Examples 4 and 6) showed tensile properties equivalent to their corresponding comparative example (Examples 3 and 5 respectively).

Example 9 The results of the Adhesion to the Surlyn ™ tests were as follows: Example 4 of the present invention shows better adhesion to Surlyn ™ than Example 3 of the corresponding comparative example.

Claims (9)

1. CLAIMS 1. A hot melt polymeric reactive composition formed by mixing the components comprising at least one polyol, at least one polyisocyanate and at least one acrylic polymer having tertiary alkyl amide functionality. The composition of claim 1, wherein said acrylic polymer is from 1 to 90 percent by weight of said composition, based on the total weight of said composition. The composition of claim 1, wherein said acrylic polymer includes at least one functional tertiary alkyl amide monomer selected from the group consisting of N-tert-butylacrylamide, N-tert-butyl methacrylamide, 2-acrylamido 2-methylpropane acid sulfonic acid, diacetone acrylamide, diacetone methacrylamide, N-tert-octyl acrylamide, N-tert-octyl methacrylamide and mixtures thereof. The composition of claim 1, wherein said polyol comprises at least one polyester polyol and at least one polyether polyol. The composition of claim 1, wherein said acrylic polymer is from 1 to 90 percent by weight of said composition, based on the total weight of said composition; wherein said acrylic polymer includes at least one functional tertiary alkyl amide monomer selected from the group consisting of N-tert-butylacrylamide, N-tert-butyl methacrylamide, 2-acrylamido 2-methylpropane sulfonic acid, diacetone acrylamide, diacetone methacrylamide, N - tert-octyl acrylamide, N-tert-octyl methacrylamide and mixtures thereof; and wherein said polyol comprises at least one polyester polyol and at least one polyether polyol. 6. A method for making a moisture reactive hot melt composition comprising mixing the components comprising at least one polyol, at least one polyisocyanate and at least one acrylic polymer having tertiary alkyl amide functionality. The method of claim 6, wherein said acrylic polymer is from 1 to 90 percent by weight of said composition, based on the total weight of said composition; wherein said acrylic polymer includes at least one functional tertiary alkyl amide monomer selected from the group consisting of N-tert-butylacrylamide, N-tert-butyl methacrylamide, 2-acrylamido 2-methylpropane sulfonic acid, diacetone acrylamide, diacetone methacrylamide, N -tert-octyl acrylamide, N-tert-octyl methacrylamide and mixtures thereof, and wherein said polyol comprises at least one polyester polyol and at least one polyether polyol. 8. A method for joining substrates comprising: (a) making a moisture reactive hot melt composition comprising mixing the components comprising at least one polyol, at least one polyisocyanate and at least one acrylic polymer having tertiary alkyl amide functionality, - (b) heating said composition hot melting; (c) applying said heated hot melt composition to a first substrate; (d) contacting said heated hot melt composition applied with a second substrate; and (e) cooling or allowing to cool said hot melt composition. The method of claim 8, wherein said acrylic polymer is from 1 to 90 percent by weight of said composition, based on the total weight of said composition; wherein said acrylic polymer includes at least one functional tertiary alkyl amide monomer selected from the group consisting of N-tert-butylacrylamide, N-tert-butyl methacrylamide, 2-acrylamido-2-methylpropane sulfonic acid, diacetone acrylamide, diacetone methacrylamide, N - tert-octyl acrylamide, N-tert-octyl methacrylamide and mixtures thereof; and where said * - 36 - SUMMARY A moisture reactive hot melt composition, useful as an adhesive, having an improved balance of exposure time and green strength is provided. In particular, the composition is made from a polyol, a polyisocyanate and an acrylic polymer. Also provided is a method for making such compositions and a method for using such compositions for bonding substrates.