MXPA97010254A - Polymeric mixtures containing acryl - Google Patents

Abstract

The present invention relates to a polymer mixture, characterized in that it comprises: a) a modified block copolymer comprising: i) a polystyrene block and ii) a polydiene block or a hydrogenated polydiene block, said polydiene block or block of hydrogenated polydiene is modified to contain an average of one or more carboxyl groups, and b) a polymer comprising a polymerization reaction product, i) at least one acrylic or methacrylic acid ester of a non-tertiary alcohol having from 1 to 14 carbon atoms , inclusive, ii) at least one monomer having a carboxylic acid functional group, which is present in an amount in the range of about 1 to about 15 parts by weight, based on 100 parts by weight of the polymer (b), and iii) a titanate selected from the group consisting of ethanol, the 2,2 ', 2"-nitrilotris-titanium salt of ethanol (4 +), bis (ethyl-3-oxobutanolate-O 1 O 3) bis-2-propanolate titanium; a reaction product of tetraalkyl titanate with a-diketone and an alkanolamine; and tetrabutyl titanate (the salt of 1-butanol, titanium (4 + 1)

Description

POLYMERIC MIXTURES CONTAINING ACRYLATE BACKGROUND OF THE INVENTION Field of the Invention This invention relates to polymer blends useful, for example, as adhesives, binders, inks and paints.

Description of the Previous Technique Low surface energy substrates such as polyethylene, polypropylene, and other polyolefins, are characterized by having critical wetting surface tensions of about 35 dynes / cm or less. Such surfaces are generally not receptive to inks, paints and adhesives, due to their poor wettability. There is a need to improve adhesion to such surfaces, as well as to high energy surfaces.

REF: 26283 BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a mixture comprising (a) a modified block copolymer comprising (i) a polystyrene block and (ii) a polydiene block or a hydrogenated polydiene block, said polydiene block or polydiene block hydrogenated is modified to contain an average of one or more carboxyl groups; (b) a polymer comprising a polymerization reaction product of two or more monoethylenically unsaturated monomers in which (i) at least one of the monomers is an ester of acrylic or methacrylic acid of a non-tertiary alcohol having from 1 to 14 carbon atoms, inclusive, and (ii) at least one of the monomers has the carboxylic acid functional group and is present in an amount in the range of about 1 to about 15 parts by weight, based on 100 parts by weight of the polymer (b); the polymer (b) does not comprise a monomer containing nitrogen. The invention also relates to a method for sizing a substrate, comprising applying to the substrate a mixture containing (a) a modified block copolymer comprising (i) a polystyrene block and (ii) a polydiene block or a hydrogenated polydiene block, said polydiene block or hydrogenated polydiene block is modified to contain an average of one or more carboxylic groups; (b) a polymer comprising a polymerization reaction product of two or more monoethylenically unsaturated monomers in which (i) at least one of the monomers is an ester of acrylic or methacrylic acid of a non-tertiary alcohol having from 1 to 14 carbon atoms inclusive, and (ii) at least one of the monomers has a carboxylic acid functional group and is present in an amount in the range of about 1 to about 15 parts by weight, based on 100 parts by weight of the polymer (b); the polymer (b) does not comprise a monomer containing nitrogen. In particular, the present invention also relates to a method for improving adhesion between a substrate and an adhesive (e.g., a pressure sensitive adhesive, a thermosetting adhesive, a thermoplastic adhesive) comprising the steps of sizing a substrate by the application to the substrate of a mixture containing (a) a modified block copolymer comprising (i) a block of polystyrene and (ii) a polydiene block or a hydrogenated polydiene block, the polydiene block or the hydrogenated polydiene block is modified to contain an average of one or more carboxyl groups; (b) a polymer comprising a polymerization reaction product of two or more monoethylenically unsaturated monomers in which (i) at least one of the monomers is an ester of acrylic or methacrylic acid of a non-tertiary alcohol having from 1 to 14 carbon atoms inclusive, and (ii) at least one of the monomers has a carboxylic acid functional group and is present in an amount in the range of about 1 to about 15 parts by weight, based on 100 parts by weight of the polymer (b); the polymer (b) does not comprise a monomer containing nitrogen; and the application of an adhesive to the prepared substrate. In some preferred modalities, the substrate is a low energy substrate. As used herein, "low energy substrate" refers to a substrate having a critical wetting surface tension no greater than about 35 dynes / cm. Examples include polyolefin polymers such as polyethylene and polypropylene. The invention provides polymer blends that show good adhesion to low energy surfaces (e.g., polyolefins such as polyethylene and polypropylene), as well as to higher energy surfaces (e.g., having surface energies greater than 35 dynes / cm such like metal and glass). The blends are useful as primers (for example, for paints and coatings), adhesives (for example, for use as bonding layers), pressure sensitive adhesives, inks and paints.

DETAILED DESCRIPTION OF THE INVENTION The invention characterizes blends comprising (a) a modified block copolymer and (b) a polymer, as described in the Brief Description of the Invention section. The block copolymer comprises one or more polystyrene blocks. If one or two polystyrene blocks are present, the block copolymer can be designated as an AB block copolymer (containing a polystyrene block) and an ABA block copolymer (containing two polystyrene blocks), "A" designates polystyrene and, "B" designates hydrogenated polydiene or polydiene The examples of a polydiene block or hydrogenated polydiene block include, for example, polybutadiene, polyisoprene, ethylene / butylene, or ethylene / propylene block. Referring to the repeating units of a diene monomer, the hydrogenated polydiene block preferably has a residual unsaturation of less than 10%, more preferably less than 5%, based on the original amount of the ethylenic unsaturation of the polydiene block. Examples of compounds that can be reacted with the polydiene block or with the hydrogenated polydiene block to provide the carboxyl substituent groups, include carboxylic acids and anhydrides (e.g., maleic acid and maleic anhydride). A particularly preferred block copolymer is a maleated styrene-ethylene / butylene-styrene block copolymer. The term "malenate" means that the polydiene or the hydrogenated polydiene block is modified, for example, with maleic acid or maleic anhydride, so that the polydiene or the hydrogenated polydiene block contains an average of one or more carboxyl groups. An example of a preferred copolymer is a styrene-ethylene / butylene-styrene tri-block copolymer containing 2% by weight of succinic anhydride (the source of the carboxyl groups) (commercially available from Shell Chemical Company, Houston, Texas, under the commercial designation "Kraton FG-1901X"). "Kraton FG-1901X" has a tensile strength of approximately 351.53 kg / cm2 (5000 psi), a percentage elongation of approximately 500, a Shore A hardness of approximately 75, a specific gravity of approximately 0.91, and a Brookfield viscosity of approximately 1250 cps at 25 ° C (77 ° F). The block copolymer (a) has a ratio, by weight, of the polystyrene block to the polydiene block or hydrogenated polydiene block, typically in the range of about 5:95 to 95: 5, preferably 10:90 to 50:50. . The polymer (b) comprises a reaction product of polymerization of two or more monoethylenically unsaturated monomers in which (i) at least one of the monomers is an ester of acrylic or methacrylic acid of a non-tertiary alcohol having from 1 to 14 carbon atoms inclusive, and (ii) at least one of the monomers has a carboxylic acid functional group and is present in an amount in the range of about 1 to about 15 parts by weight, based on 100 parts by weight of the polymer (b); and the polymer (b) does not comprise a monomer containing nitrogen. The non-tertiary alcohol preferably includes methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol , 1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol, 3,5,5-trimethyl-1-hexanol, 3-heptanol, 2 -octanol, 1-decanol, or 1-dodecanol. A particularly preferred ester monomer is iso-octyl acrylate. In a preferred embodiment, the homopolymer of the acrylic or methacrylic acid ester has a Tg less than 20 ° C. A polymer portion having a Tg greater than 20 ° C, a weight average molecular weight above 2,000, and capable of associating with one or more of the block copolymer blocks (e.g., a polystyryl portion as described in US Pat. Groves, North American Patent No. 5, 143,972 entitled "Pressure-Sensitive Adhesive Composition" which is incorporated by reference herein) can be polymerized with the ester portions of acrylic or methacrylic acid of the polymer. In this case, it is believed that the association occurs between this polymer portion and the phenyl groups of the styrene blocks. Examples of monomers having a carboxylic functional group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and citraconic acid. This monomer is generally present in an amount in the range of about 1 to about 15 parts, based on 100 parts by weight of the polymer (b), preferably in an amount in the range of 1 to 10. The polymer (b) it may also contain a monomer having a hydroxyl functional group, for example, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. A monomer having a hydroxyl functional group may be present in an amount in the range of about 1 to about 10 parts by weight, based on 100 parts by weight of the polymer (b), preferably 1 to 5. The polymer (b) does not it is crosslinked, and is preferably prepared by photopolymerization initiated by free radicals or thermal polymerization of the base monomers, using conventional polymerization techniques. The block copolymer (a) and the polymer (b), and any optional additives, can be physically mixed together to form a mixture of the present invention. The block copolymer (a) is present in an amount sufficient to allow association with the substrate, particularly if the substrate is a low energy substrate. The polymer (b) is present in an amount sufficient to be associated with the block copolymer (a). The term "association" or "associated" as used herein, with respect to the interaction between a substrate and a block copolymer (a), refers to the bond or contact between the substrate and the block copolymer ( a), such that the substrate, particularly a low energy substrate, is made more receptive to materials, such as inks; paintings; and adhesives. That is, the block copolymer (a), and ultimately the polymer (b), create an energy gradient between the substrate and a higher energy material, for example, an adhesive and / or paint, which has to be be attached to the substrate. The term "association" or "associated" as used herein, with respect to the polymer (b) and the block copolymer (a) refers to the bond or contact between the polymer (b) and the block copolymer ( a), such that each interacts with the other. The proportion of block copolymer (a) to polymer (b) by weight is in the range preferably from about 95: 5 to about 5:95, more preferably from about 75:25 to about 25:75. Examples of the preferred polymer blends include (1) a mixture of the styrene-ethylene / butylene / styrene mallock block copolymer and the iso-octyl acrylate / acrylate / acrylic acid polymer, (2) a block copolymer blend styrene-ethylene / butylene / styrene maleate and the iso-octyl acrylate / methacrylic acid polymer; and (3) a mixture of styrene-ethylene / butylene / styrene mallock block copolymer and iso-octyl acrylate / maleic anhydride polymer. The mixture may be provided in the form of a primer and / or a paint, ink, or adhesive (e.g., a pressure sensitive adhesive) by the use of additives, for example as described below. As a primer, the polymer blend is particularly useful in the case of low energy substrates. As used herein, "low energy substrate" refers to a substrate having a critical wetting surface tension no greater than about 35 dynes / cm. Examples include polyolefin polymers such as polyethylene and polypropylene. The mixtures can be thickened by incorporating a thickening agent, which modifies the structure of the acrylate or methacrylate ester containing polymer, or through a combination of both. Suitable thickeners for the thickening of the mixture include the low molecular weight hydrocarbon resins, and resins based on a- and b-pinene. Many thickeners are commercially available, and the optimum selection thereof can be carried out by one of ordinary skill in the art of adhesive composition. Representative examples of commercially available thickeners, suitable for blends, include the resins available under the trade designations "Regalrez 1018", "Regalrez 1078", and "REZ-D 2084", all of which are available from Hercules Inc., Wilmington, Delaware; "Escorez-143H" and "Escorez 5380", which are available from Exxon Corp., Houston, Texas; and "Wingtack Plus", available from Goodyear Tire and Rubber Company, Akron, Ohio. The thickener amount included in the mixture is preferably in the range of about 20 to about 250 parts per hundred parts of the mixture. In general, lower specifications of thickener are used, where the mixture is in the form of a primer, while higher concentrations are used where the mixture is in the form of a pressure sensitive adhesive. The blends may include an antioxidant to inhibit the oxidation of the thickening agent and the consequent loss of tack as the blends age. Suitable antioxidants are based on (1) a hindered phenol or (2) an organometallic salt containing sulfur. Examples of hindered phenols include the ortho-substituted or 2,5-disubstituted phenols, wherein the substituent group or groups are a branched hydrocarbon radical having from 2 to 30 carbon atoms, for example, tertiary butyl or tertiary amyl radicals. Other hindered phenols useful in the practice of the invention include the para-substituted phenols wherein the substituent groups are OR ', wherein R1 is methyl, ethyl, 3-substituted propionic ester, etc. Examples of commercially available hindered phenols include those available from Ciba-Geigy Corp., Hawthorne, NY., Under the trade designation "Irganox 1076" and those available from American Cyanamid Company, Wayne, NJ, under the trade designation "Cyanox LTDP" . Suitable organometallic sulfur-containing salts are derived from dibutyl diocarbamate nickel. The blends may further include inorganic fillers such as calcium carbonate, clay, talc, silica, and limited amounts of carbon black, as well as organic fillers such as wood flour and starch. Calcium carbonates, clays, and talcs are most commonly used. Mixtures can also be colored by the inclusion of colored pigments or colored concentrates (usually based on polystyrene); the coloration is often desired where the mixtures are in the form of paints or inks. Typical pigments include titanium dioxide and carbon black. Stabilizers such as fungicides and mold removers can also be included. Additives that can be included in the blends of the present invention include titanic acid esters (also known as titanates), silanes, and chlorinated polyolefins ("CPOs"). In addition, resins, such as epoxy resins, can be mixed with the block copolymer (a) and the polymer (b) The amounts of such additives may vary according to the desired mixture. A particularly preferred additive is an ester of titanic acid. Examples of titanic acid esters include ethanol, (2, 2 ', 2"-nitrilotris-titanium (4+)), bis (ethyl-3-bis-2-propanolate titanium salt; tetraalkyl titanate with a β-diketone and an alkanolamine, and tetrabutyl titanate (titanium salt (+4) of 1-butanol.) The titanic acid esters are preferably present in the mixture in amounts ranging from 5 to 50. parts, more preferably from 5 to 30 parts, based on 100 parts by weight of the polymer blend of the present invention.The resistance to ultraviolet light degradation of the mixtures can be improved by incorporating ultraviolet light inhibitors within Typically, 1 part per hundred (phr) load of the ultraviolet light inhibitor having the trade designation "Cyasorb IV 531" (American Cyanamid Company, Wayne, NJ) or a mixture of parts is sufficient to provide this enhancement. equal of inhib Ultraviolet light emitters that have the commercial designations "Tinuvin 328" (Ciba-Geigy Corp., Hawthorne, NY) and "Uvinal 400" (GAF Corp., New York, NY). The improved results can be achieved from a combination of 0.5 phr of one of the three aforementioned ultraviolet light inhibitors, with a nickel chelate having one of the following commercial designations: "Cyasorb UV 1084" (0.5 phr) ( American Cyanamid Company, Wayne, NJ) or "NBC" (0.1 phr) (The Pont du Nemours and Company, Wilmington, Delaware). As used herein, phr is based on the weight of the block copolymer in the mixture, unless stated otherwise.

The above-described blends are particularly useful as precursors for adhesives, for example, pressure sensitive adhesives, thermosetting adhesives, thermoplastic adhesives, and hybrid adhesives. The term "hybrid adhesives" as used herein refers to combinations of two or more different types of adhesives, as well as two or more adhesives suitable for the formation of adhesives. Thermosetting adhesives are generally formed by addition polymerization. Examples of thermosettable adhesives include polysulfides, silicones, polyesters, polyurethanes, epoxies, anaerobic and aerobic acrylics, radiation curable polymers and vulcanization rubbers. The thermosetting additives are typically cured by heat, catalysts, or light or moisture activation. After curing, the thermosetting adhesives are generally insoluble, for example, the adhesive will not dissolve in an organic solvent or in water and is infusible, for example, the adhesive will not flow when heated. Pressure sensitive adhesives in general do not suffer a progressive increase in viscosity after preparation, rather they are permanently in a sticky stage. Pressure sensitive adhesive examples include those derived from polyacrylates, block copolymers as defined herein, and natural or synthetic rubber. Pressure sensitive adhesives typically possess viscoelastic properties and thus exhibit characteristics of a viscous liquid and an elastic solid. Thermoplastic adhesives are soluble and fusible materials. Examples of thermoplastic adhesives include vinyl adhesives, for example, polyvinyl chloride, polyvinyl butyral, polyvinyl alkyl esters and ethers, and vinyl acetate-ethylene copolymer adhesives; acrylic adhesives; hot melt adhesives; cellulosic adhesives; and asphalt adhesives. The thermoplastic adhesives may be in the form of emulsions, solutions, or solids. A pretender of the present invention can be applied using a variety of techniques, including dipping, spraying, brush application, rotogravure, r rod, and blade coating. A particularly useful application technique involves the application of a primer of the present invention to the substrate, and then abrasion. This technique effects chemical reactions induced by mechanical actions such as abrasion, for example, chemical-mechanical. Suitable abrasive products include a lint-free fabric, cloth or sandpaper. When the sandpaper is used, it is preferably wet or dry and 50% of the size of the abrasive grains is preferably in the range of 100 to 2 microns. When the pressure sensitive adhesives are being bonded to a substrate, preferably the size of the abrasive grains is in the range of 8 to 2 microns, more preferably 5.5 to 2.0 microns. When structural adhesives, for example, epoxides and polyurethanes are being bonded to a substrate, preferably the size of the abrasive grains is in the range of 100 to 50 microns. The following non-limiting examples further illustrate the present invention. All percentages are in percentage by weight, unless indicated otherwise.

EXAMPLES TEST METHODS FTL Process for the Chemical Etching of Aluminum Aluminum specimens (typically 152.4 mm x 50.8 mm x 1.6 mm) (commercially available from Vincent Metals, Minneapolis, MN under the designation "2024-T3 Alelad") are treated according to the chemical etching process described in HW Eichner, Forest Products Laboratory; Report No. 1842, April 1, 1954, Madison, Wl, USA. Specifically, the specimens are treated as follows. Each specimen is rinsed with acetone and then allowed to air dry. Next, each specimen is degreased by soaking for 10 minutes in 75 g of Oaktite 163 (alkaline detergent) (commercially available from Oaktite Products, Inc., Berkeley Heights, NJ) per liter of distilled water. Each specimen is then rinsed for 2 minutes in tap water, followed by immersion for 10 minutes at 71 ° C in a chemical etching bath consisting of 1161 g of H2SO4, 156.8 g of Na2Cr2072H20, 1.5 g of 2024-T3 sprinkled with aluminum alloy knots, and enough distilled water to make up 3.5 liters of solution.

After immersion in the chemical etching solution, each specimen is rinsed for 2 minutes with tap water and dried for 10 minutes at 66 ° C.

Static Cutting The shear strength of prepared and unprepared substrates attached to pressure-sensitive, double-coated adhesive foam tapes or pressure-sensitive transfer adhesives is determined according to the following procedure. An aluminum strip 2024-T3 engraved with FPL measuring 50.8 mm x 25.4 mm x 1.6 mm with a hole diameter of 7 mm on the center and 10 mm from one edge of the strip, is prepared from the specimen described above. Likewise, similar strips are prepared from the sizing and unsheathed substrate, each having a thickness that does not flex at the test temperature under the test load. An adhesive tape sensitive to the pressure of 12. 7 mm width carried on a release liner. it is adhered to the solid end of the aluminum strip (for example, the end opposite the hole) and cut to a length of 25.4 mm. The liner or reinforcement is then removed and the solid end of the substrate strip adheres to the exposed adhesive surface. The resulting specimen is placed in a horizontal position and laminated with a 2.4 kg roller to ensure intimate contact between the surfaces. After remaining at room temperature for 24 hours, the specimen is placed in a preheated air circulation oven at 80 ° C. After 15 minutes, a 1 kg weight is hung from the specimen. The specimen is inclined at 2 ° from the vertical, in order to deny any detachment forces. The time it takes to fall to the weight (in minutes) is the "static cut-off value". If the failure does not occur after 6,000 minutes, the test is discontinued.

Adhesion to 90 ° Detachment - Pressure Sensitive Adhesive The adhesions to the detachment (N / 100 mm) of the pressure-sensitive foam strips, doubly coated, to different sized and unprepared substrates, are determined in the following manner. The mesh side of a piece of 114 mm x 15.9 mm x 0.13 mm aluminum sheet (commercially available from Lawrence Fredrick Company, Greenwood, IL, under the trade designation "1145-0-SB") is placed on the unlined side or reinforcement of a sample of foam tape carried on a release liner measuring 101.6 mm x 12.5 mm x 1.1 mm. A steel roller coated with 2.4 kg rubber is then passed back and forth three times on the specimen. Then approximately 50 mm of the liner is cut from the lined side of the sample, and the sample is then placed and centered near one end of a 152.4 mm x 50.8 mm x 5.1 mm plate of the sizing or unprimed substrate. A roll covered with 2.4 kg rubber is again passed back and forth three times on the mounted specimen. The procedure is then repeated to laminate a second construction of aluminum tape, to the other end of the plate. After remaining for the specified length of time at room temperature, the specimen is placed in a 90 ° detachment fitting (commercially available from Consultans INTL, Network, Mentor, OH, under the trade designation "PJ-90") and mounted on an Instron tensile tester (available from Instron Corp., Canton, MA). The adhesion to the 90 ° detachment is measured by the removal of the free end of the foam sheet laminated with aluminum foil, at a speed of 30.5 cm per minute. The reported detachment resistances (in N / 100 mm) are an average of three determinations, except where noted.

Cohesive resistance Cohesive strengths of the commercially available foam strips of Minnesota Mining and Manufacturing Company, St. Paul., MN, under the trade designation of "Scotch Brand", foam tape, were determined according to the adhesion test procedure. 90 ° detachment, except that the tapes were attached to an aluminum panel 2024-T3 engraved with FPL, 152.4 mm x 50.8 mm x 1.6 mm, and left there for 2 hours before the test. The foam tapes used were doubly coated foam tapes, with pressure-sensitive acrylic adhesives (Y-4220, VHB-4205, and VHB-4950), doubly coated with a pressure-sensitive adhesive of styrene-butadiene rubber ( SBR) (VHB-4952); and a 1 mm thick acrylic transfer tape (VHB-4910). All foam tapes failed due to cohesive failure of the foam core. The results shown in Table A are an average of three values for each tape. These values are used as reference points for the semi-quantitative detachment adhesion test, described below.

TABLE A Adherence to Detachment, Semi-quantitative The level of adhesion of prepared and unprepared substrates to pressure sensitive adhesives was determined semiquantitatively, which can not be quantitatively determined (for example, where the substrate is a thin and / or flexible film or a rigid article of dimensions previously adjusted). The sample preparation is carried out according to the 90 ° release adhesion procedure except that two or more foam tapes are used and the aluminum sheet laminate in the form of tape is secured to the substrate, with manual pressure or a roller steel coated with rubber at 2.4 kg. After remaining a specified time (typically 15 minutes), the free end of the aluminum foil sheet laminate is manually pulled out of the substrate. If the cohesive failure of the foam core is not observed, a foam tape having the following lower cohesive strength (determined with reference to the Table) A, previous) is united and then withdrawn. This procedure is repeated with successive foam tapes (with reference to Table A, above) until foam core failure occurs. A semiquantitative level of adhesion of the substrate prepared to the pressure sensitive adhesive of the foam tape is then determined with reference to Table A.

Test Methods of Pressure Sensitive Adhesive The test methods used to evaluate the parameters of the flexible sheet materials coated with the pressure sensitive adhesive compositions according to the invention include standard industrial tests. The standard tests are described in detail in various publications of the American Society for Testing and Materials (ASTM), Philadelphia, PA and the Council of Pressure Sensitive Tapes (PSTC), Glenview, IL. The standard test methods are described in detail below. The reference source of each standard test method is also given.

Cut resistance Reference: ASTM: D3654-78; PSTC-7 The shear strength is a measure of the cohesiveness or internal strength of an adhesive. This is based on the amount of force required to pull an adhesive strip from a standard flat surface, in a direction parallel to the surface to which it has been fixed with a defined pressure. This is measured in terms of the time (in minutes) required to pull a standard area of the sheet material coated with adhesive from a stainless steel test panel under tension of a constant standard load. The tests are conducted on adhesive coated strips, applied to a stainless steel panel such that a 12.5 mm by 12.5 mm portion of each strip is in firm contact with the panel, with an end portion of the tape being free. The panel with the coated strip attached is maintained in a frame or support, such that the panel forms an angle of 178 ° with the extended free end of the tape which is then tensioned by the application of a force of one kilogram, applied as a hanging weight from the free end of the coated strip. 2 degrees less than 180 ° are used to negate any detachment forces, thereby ensuring that only the shear forces are measured in an attempt to determine the most accurate way, the clamping power of the tape being tested. The elapsed time for each tape example to separate from the test panel (in minutes) is recorded as the cut resistance.

Adherence to 180 ° Detachment Reference: ASTM: D3330-78; PSTC-1 (11/76) Peel adhesion is the force required to remove a coated flexible sheet material, from a test panel, measured at a specific angle and speed of removal. In the examples, this shape is expressed in Newtons per 100 mm (N / 100 mm) of coated sheet width. The measurement procedure is as follows. (1) A width of 12.5 mm of coated sheet is applied to the horizontal surface of a clean, test glass plate with at least 12.7 linear cm in firm contact. A hard rubber roller is used to apply the strip. (2) The free end of the coated strip is bent backwards by touching almost itself so that the angle of withdrawal will be 180 °. The free end is coupled to the scale of the adhesion tester. (3) The glass test plate is clamped in the jaws of a tensile test machine, which is capable of moving the plate away from the scale at a constant speed of 2.3 meters per minute. (4) The reading of the scale in Newtons is recorded as the tape is detached from the glass surface. The data is reported as the range of numbers observed during the test.

Cut in Simple Overlap Two substrate plates, each measuring 51 mm x 25.4 mm x 5 mm, are cleaned twice with a soft cloth saturated with heptane, and then rinsed with ethanol. After 15 minutes, the priming solution is applied to one side of each of the plates, using a cotton-tipped applicator and allowed to dry for 30 minutes. Two drops of ethyl cyanoacrylate adhesive (commercially available from Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designation "Pronto CA-40") are then placed on one of the prepared surfaces. Next, the plate of the remaining substrate, remaining, is placed on top of the plate containing cyanoacrylate, to form a 12.7 mm overlap joint. The strong pressure with the finger is maintained on the joint or union for approximately 0.5 minutes. Three test assemblies are prepared for each measurement and left to cure for 72 hours before the test. The strength of the test is measured according to an Instron tensile tester (available from Instron Corp., Canton, MA) at a crosshead speed of 1.47 mm / min.

Adhesions to 90 ° Detachment - Thermosetting Adhesives Adhesions to the release (N / 100 mm) of the polypropylene (PP) and low density polyethylene (LDPE) films bonded with the thermosetting adhesives, are determined in the following manner. A sample of 175 mm x 75 mm x 0.25 mm film was secured to a flat surface using a 0.25 mm acrylic pressure sensitive transfer adhesive (available from Minnesota Mining and Manufacturing Company, St. Paul, MN, under the commercial designation "F9473PC"). The surface of the sample was flooded with an abrading and abrading solution uniformly with a piece of abrasive cloth reinforced, 80 micron grain (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designation). 3M-ITE P220"). After one minute, the surface was flooded again with the priming solution and abraded by an additional minute. The film sample was washed three times each time with xylene and ethanol, and dried under ambient conditions for 24 hours. A 0.5 mm layer of a two-part epoxy adhesive (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designation "Scotch-Weld 2216 B / A") was applied to a 2024 aluminum panel. T3 recorded with FPL of 152.4 mx 101.6 mm x 1.6 mm. The sizing side of the film was bonded to the adhesive using pressure from a roller covered with light rubber. After 72 hours, the film was divided into three 12.5 mm test specimens. The aluminum panel was placed in a 90 ° detachment fitting (available from Consultant INTL Network, Mentor, OH) and mounted on an Instron tensile tester (available from Instron Corp., Canton, MA). The adhesion to the 90 ° release was measured by removing the free end of the film strips at a rate of 30.5 cm per minute. A control sample was prepared in the same manner, except that the sample was not flooded with the priming solution, and the sample was abraded by abrasion in the absence of a priming solution. The reported detachment resistances (N / 100 mm) are an average of three determinations. materials IOA isooctyl acrylate AA "Tyzor TE" acrylic acid a triethanolamine chelate of titanic acid, 80% solids in isopropanol, (ethanol, 2, 2 ', 2"-nitrilotris-titanium (4+) salt) (commercially available from EI DuPont de Nemours &Company, Wilmington, Delaware under the trade designation "Tyzor TE") "Tyzor DC" an ethyl acetoacetate chelate of titanic acid (titanium bis (ethyl-3-oxobutanolate-0X03) bis-2 propanolate) (commercially available from The DuPont de Nemours &Company, Wilmington, Delaware, under the trade designation "Tyzor DC") "Tyzor CLA" a reaction product of tetraalkyl titanate with a β-diketone and an alkanolamine, 77% solids in isopropanol (commercially available from E.l. duPont de Nemours &Company, Wilmington, Delaware, under the trade designation "Tyzor CLA") "Tyzor TBT" tetrabutyl titanate (1-butanol, titanium salt (4+)) (commercially available from The DuPont de Nemours &Company, Wilmington, Delaware, under the trade designation "Tyzor TBT") PSM 2-polystyrethyleth methacrylate (weight average molecular weight of approximately 10,000 g / mol, prepared according to the Patent North American No. 4,554,324; 52% solids in cyclohexane).

Preparation of the Preparation Composition (1) A 25% solution of sizing composition (1) was prepared by dissolving 25.0 g of styrene-ethylene / butylene-styrene elastomer containing 2% bound succinic anhydride (commercially available from Shell Chemical Company, Houston, Texas, under the commercial designation "Kraton FG-1901X ") and 0.25 g of an antioxidant (commercially available from Ciba Geigy Corp., Hawthorne, NY, under the trade designation" Irganox 1076") in 75.0 g of a solvent mixture of cyclohexane, xylene, and ethanol in a Weight ratio of 5.5: 3.5: 1.0.

Preparation of the Preparation Composition (2) A copolymer of iso-octyl acrylate and acrylic acid was prepared as follows in a weight ratio of 95: 5: 47.5 g of IOA, 2.5 g of AA, 0.1 of azobisisobutyronitrile (commercially available from The Du Pont de Nemours and Company, Wilmington , Delaware, under the trade designation "VAZO-64"), 52.5 g of ethyl acetate, 9.0 of methyl isoamyl ketone and 13.5 g of xylene were added to a 237 ml narrow-mouthed bottle. The solution was purged with anhydrous argon for three minutes. The sealed bottle was tumbled in a rotating water bath at 55 ° C for 24 hours. The conversion percentage was determined as greater than 99% by infrared spectrophotometric analysis. The solution contained 39.87% solids and had a viscosity of about 7200 cps and a measured inherent viscosity of about 0.78 dl / g.

Preparation of Entering Solutions The following illustrates the preparation of a typical sizing solution of this invention: a mixture of sizing composition (1) and sizing composition (2) was prepared in a weight ratio of 1: 3 to a total solids concentration of about 3.0%, by dissolving 1.0 g of sizing composition (1) and 1.9 g of sizing composition (2), and 0.25 g of titanate or chelate ester, if present, as indicated below, in approximately 30.4 g of a mixture of solvent of cyclohexane, xylene and ethanol in a weight ratio of 5.5: 3.5: 1.0.

Examples 1-7 A number of finishing solutions of approximately 3.5%, of this invention, were prepared by mixing in a weight ratio of 1: 3 of the sizing composition (1) to the acrylic polymers of the sizing composition (2) as shown right away.

The finishing solutions were applied by brush to plates of 152 mm x 51 mm x 5 mm of low density polyethylene (LDPE), polypropylene (PP) (both available from Precision Punch and Plastics, Minneapolis, MN), and a thermoplastic polyolefin (TPO) (available from Himont USA, Inc., Lansing, MI, under the commercial designation "ETA 3163"). After 10 minutes, samples of pressure sensitive adhesive tape, foamed with aluminum foil (1 mm thick acrylic pressure sensitive adhesive foam tape available from Minnesota Mining and Manufacturing Company, St. Paul , MN, under the trade designation "VHB-4205") were attached to the prepared areas as described in the test method for 90 ° peel adhesion. After one hour, the release values at 90 ° were determined. Each value reported in Table I is an average of three determinations. The control release values were also determined for unresigned plates.

Table 1 Table 1 (continued) foam failure From the results in Table I, it is clear that the surfaces of the low energy polymers can be remarkably changed by treatment with primer solutions of this invention, in order to improve their adhesion to pressure sensitive acrylic adhesives.

Example 8 The sizing composition (1) and the sizing composition (2), IOA / AA of Example 1, were diluted to 3% polymer solids, with a solvent mixture of cyclohexane, xylene, and ethanol in a weight ratio of 5.5: 3.5: 1.0 and applied by brush to PP and LDPE test plates. The release values were determined and compared to Example 1.

Table II The results show that while the individual blend components, when used alone, do not work well as primers, high release adhesions can be obtained when these components are mixed together according to the present invention.

Example 9 The sizing composition (1) and the sizing composition (2) of Example 3 were mixed in weight proportions of 1: 3, 1: 1, and 3: 1, diluted to 3% solids with a cyclohexane solvent mixture. , xylene, and ethanol in a weight ratio of 5.5: 3.5: 1.0 and placed in brushes on TPO test plates. After 10 minutes, the aluminum foamed foam tape (commercially available from the Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designation "VHB-4205") was attached to the prepared samples. After one hour, the release values were determined and shown in Table III.

Table I I I Foam failure The results illustrate that a wide variety of block copolymer / acrylate ester polymer ratios produce compositions effective for low energy surfaces.

Example 10 The primer solutions of Examples 3 and 4 were applied to PP and LDPE test plates with a lint-free cloth (commercially available from Kimberly-Clark Corp., Roswell, GA, under the trade designation "Kimwipe"). After 10 minutes, sized samples, aluminum foil-laminated foam tapes, with 1 mm thick acrylic transfer, pressure sensitive adhesive (commercially available from Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designations "VHB-4205" and VHB-4910". After one hour, the 90 ° release values were evaluated and recorded in Table IV.

TABLE IV TABLE IV (continued) From the results of Table IV, it is apparent that the primer solutions of the present invention improve the adhesion to release of pressure sensitive adhesives from acrylic rubber and styrene-butadiene (SBR) to low energy substrates.

Example 11 Approximately 110 g of the 3.5% sizing solution of Example 3 were modified by the addition of 0.5 g of epoxy resin (commercially available from Shell Chemical Company, Houston, Texas, under the trade designation "Epon 828"), 3.9 g of chlorinated polypropylene (commercially available from Eastman Chemical Company, Kingsport, TN, under the trade designation "CP 3430") and 0.5 g of the silane coupling agent (commercially available from OSi Specialties, Danbury, CT, under the trade designation "Silquest A 186"). Approximately 25 g of this solution were diluted to 1% solids by the addition of 109 g of a solvent mixture of 5.5 parts of cyclohexane, 3.5 parts of xylene and 1.0 parts of ethanol. This priming solution was brushed onto the glass, aluminum and stainless steel test plates. After 10 minutes, the foil tapes laminated with aluminum foil (available from Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designations "VHB-4205", "VHB-4910", and "VHB-4952" ) were attached to the samples prepared. After 72 hours, the release values at 90 ° were determined; the results are recorded in Table V.

Comparative Example 11 The procedure of Example 11 was followed, except that the glass, aluminum and stainless steel test plates were prepared with a chlorinated polypropylene primer (available from Norton Performance Plastics, Granville, NY, under the trade designation "Tite-R-"). Bond-2684").

Table V Table V (continued) foam failure Table V clearly shows that the priming solution of this invention improves the adhesion of acrylic and SBR pressure sensitive adhesives to high surface energy polar substrates, as compared to unprepared substrates and to the sizing solution of Comparative Example 12 Example 12 The finishing solution of Example 11 was applied to LDPE and PP test plates with a lint-free cloth (available from Kimberly-Clark Corp., Roswell, GA under the trade designation "Kimwipe"). After 10 minutes, foamed tapes laminated with aluminum foil (available from Minnesota, Mining and Manufacturing Company, St. Paul, MN under the trade designations "VHB-4205", "VHB-4910", and "VHB-4952") were attached to the samples prepared. After one hour, the release values were determined and the results are recorded in Table VI.

Comparative Example 12 The procedure of Example 12 was followed, except that the LDPE and PP test plates were prepared with a formulated chlorinated polypropylene primer (available from Norton Performance Plastics, Granville, NY, under the trade designation "Tite-R- Bond- 2684").

Table VI Table VI (continued) * Foam failure The results of Table VI demonstrate that a primer solution of the present invention improves the adhesion of the pressure sensitive additives of styrene-butadiene rubber and acrylics to substrates of low surface energy.

Example 13 A 1% primer solution prepared according to Example 11 was brushed onto 125 mm x 75 mm x 0.25 mm specimens of linear low density polyethylene (LLDPE) film (commercially available from Consolidated Thermoplastics Company, Schaumburg, IL. ). After 15 minutes, the foil tape laminated with aluminum foil available from Minnesota, Mining and Manufacturing Company, St. Paul, MN under the trade designations "VHB-4220" and "VHB-4205", were attached to the prepared samples . After one hour, semi-quantitative peel adhesions were measured when manually removing the tapes. Samples of "VHB-4220" could not be removed due to the cohesive failure of the foam core. This indicated that peel adhesion values of at least 425 N / 100 mm had been achieved. Although excellent adhesion of the "VHB-4205" tape was observed, it could be removed from LLDPE prepared without cohesive failure of the foam. After 12 hours, cohesive failure of the foam was observed, indicating that a release value of approximately 1000 N / 100 mm had been achieved.

Comparative Example 13 The procedure of Example 17 was followed, except that it was brushed onto LLDPE specimens on a chlorinated polypropylene primer (commercially available from Norton Performance Plastics, Granville, NY, under the trade designation "Tite-R-Bond-2684") . After 15 minutes, the foam tape "VHB-4220" was attached to the samples. After one hour and twelve hour intervals, the tape could be easily removed manually. The release values were estimated to be only about 90 N / 100 mm or less.

Example 14 A 1% primer solution prepared according to Example 11 was brushed onto two 125 mm x 75 mm x 0.25 mm specimens of LLDPE film following the procedure of Example 13. The sized specimens were then allowed to dry for 15 minutes and 24 hours, respectively. At once, the prepared samples were painted with an enamel for interiors, semi-glossy latex (available from The Glidden Company, Cleveland, OH), a high gloss oil-based enamel for interiors / exteriors (available from Carver Tripp, Parks Corp. Somerset, MA), and a polyurethane lacquer in spray (available from Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation of Part No. -05904). In a similar manner, the unresigned LLDPE film specimens were also painted. After drying under ambient conditions for 24 hours, samples of 125 mm x 75 mm x 0.25 mm filament tape (available from Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation of "Scotch Brand 898") were firmly attached to each painted surface (prepared and unprepared). After 15 minutes, the tape was quickly removed for each specimen. The complete delamination of all paints was observed to the unresigned LLDPE films. No delamination of the paint was observed from any of the LLPDE surfaces prepared.

Comparative Example 14 The procedure of Example 14 was followed, except that it was brushed onto LLDPE specimens, a commercially available chlorinated polypropylene primer (available from Norton Performance Plastics, Granville, NY, under the trade designation "Tite-R-Bond-2684" ). The sized specimens were painted and tested as described in Example 18. Delamination of all the paints was observed for the finished film.

Example 15 To 10 g of a 3% preparation solution prepared according to Example 11, 1 g of titanium dioxide dispersion (available from Hüls America Inc., Piscataway, NY, under the trade designation "GPD 82-0082") was added. . In the same way, 1 g of carbon black dispersion (available from Borden Chemical Company, Cincinnati, OH under the trade designation "Codispersion 31L62") was added to another 10 g of the same preparation solution. After mixing, both pigmented solutions were brushed onto untreated LLDPE film and allowed to dry under ambient conditions for 24 hours. Adhesions to the release of the pigmented coating to the LLDPE film were determined by firmly bonding filamentous tape (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation "Scotch Brand 898") to the coated surfaces, in the manner previously described in Example 18. No delamination of any coating was observed when the tape was quickly removed. This example demonstrates that the compositions according to the invention can be used to prepare coatings, inks, and paints that adhere well to low energy polymeric surfaces.

Example 16 A 1% primer solution prepared according to Example 11 was brushed onto 50.8 mm x 24.4 mm x 5.1 mm thermoplastic olefin (TPO) test plates (commercially available from Himont USA Inc., Lansing, MI, under the commercial designation of "ETA 3163") and were tested for the static cut to aluminum etched with FPL (available from Vincent Metals, Minneapolis, MN, under the designation "2024-T3") at 80 ° under a load of 1.0 kg using foam tape (available from Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation "VHB-4210"). Unrestrained specimens of thermoplastic olefin (TPO) were also tested. The results are reported in Table VIII.

Table VIII The results in Table VIII demonstrate that the primer solutions of the invention improve the high-temperature holding power of an acrylic pressure-sensitive adhesive to substrates of low surface energy.

Example 17 A 3% sizing solution was prepared according to Example 11, by brush on both sides of a specimen of 150 mm x 150 mm x 0.10 mm flexible film, of polyvinyl chloride (PVC) (available from Wiman Plástic Div., St. Cloud, Minnesota) and a 150 mm x 150 mm x 0.35 mm specimen of non-pigmented opaque thermoplastic olefin (TPO) film (available from Himont USA Inc., Lansing, MI under the trade designation "HIFAX CA10A") and it was left to dry for 30 minutes. A 0.25 mm acrylic pressure-sensitive adhesive on a removable liner (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation "F9473 PC") was laminated to one side of each. the films with a hard rubber roller of 2.4 kg. Similarly, 126 mm x 12.5 mm of the same adhesive was laminated to strips of 130 mm x 15.9 mm x 0.13 mm of aluminum foil with a rubber roller of 2.4 kg. The release values of the transfer adhesive to the liners or scrim reinforcement were then determined by laminating a 150 mm x 51 mm sample of each transfer / reinforcement tape construction to 152 mm FPL-etched aluminum plates. x 51 mm x l.6 mm (available from Vincent Metals, Minneapolis, MN, under the trade designation "2024-T3") with a 2.4 kg rubber roller. Approximately 75 mm of the liner were removed from the transfer adhesive samples laminated with aluminum foil, and attached to each of the tape samples on the aluminum plate, in such a way that the two test samples of each tape were prepared. The resulting samples had the following constructions: aluminum plate / transfer adhesive / prepared reinforcement (both sides) / transfer adhesive / aluminum foil. Control samples not prepared were prepared in a similar manner. The values of detachment are reported in Table IX.

Table IX * failure of the adhesive and the film The example illustrates that pressure sensitive adhesive tapes having retention power to the reinforcement, equivalent to the cohesive strength of the adhesive or to the tensile strength or yield strength of the reinforcement, can be prepared.

Example 18 Plates measuring 51 mm x 25.4 mm x 5 mm in polypropylene (PP) and high density polyethylene (HDPE) (available from Precision Punch &Plastics, Minneapolis, MN) were cleaned with heptane and rinsed with ethanol. After 15 minutes a 1% primer solution prepared according to Example 11 was applied to one side of each of the plates, using a cotton-tipped applicator. The prepared plates were then joined together with ethyl cyanoacrylate adhesive, and the strengths of the overlapping bond were determined. The results are reported in Table X.

Table X This example illustrates that the primer solutions of the invention initiate the polymerization of ethyl cyanoacrylate adhesives to give high bond strengths of low surface energy substrates.

Pressure Sensitive Adhesives Example 19 This example illustrates a preferred mixture according to the invention, useful as a pressure sensitive adhesive. The following ingredients were introduced into a one liter container, in the amounts shown.

The vessel was stirred until all the ingredients were dissolved to give a solution containing approximately 45% total solids and a viscosity of approximately 1300 cps (as measured by a Brookfield viscometer, Model HAT, Needle No. 4, Speed 50). rpm). The solution is referred to herein as the "block copolymer". 43.3 g of the block copolymer was introduced into a 118 ml container, together with 26.2 g of an iso-octyl acrylate / 2-polystyrylethyl methacrylate / acrylic acid polymer (IOA / PSM / AA) prepared according to Example 7, except that "Tyzor TE" was not added. The mixture was vigorously stirred until homogeneous. The vessel was capped and heated to 65 ° C for about one hour. The mixture was then vigorously stirred and allowed to stand overnight. The mixture contained 65% by weight of the block copolymer and 35% by weight of the IOA / PSM / AA polymer. After gentle agitation, the mixture was coated on oriented polyethylene terephthalate film, having a thickness of 0.025-mm, by means of a 152 mm blade coater, for laboratory, at a blade setting of approximately 0.25 mm. The coated film was air dried at 95 ° C for 15 minutes, to give an average coating weight of about 6.0 mg / cm2. The samples were prepared according to the test methods previously described, and tested for adhesion to release, to glass, to low density polyethylene (LPDE), to polypropylene (PP), and to stainless steel (SS) and resistance to the cut. The results are shown in Table XI.

Table XI The results of Table XI demonstrate that useful pressure sensitive adhesives can be prepared from mixtures according to the invention.

Example 24 A mixture was prepared by combining 15 g of the block copolymer solution described in Example 1 and 30 g of the acrylate ester polymer described in Example 1. The mixture was combined with 1 g of epoxy resin (available from Shell Chemical Company, Houston, TX, under the trade designation "Epon 828"), 3.0 g of chlorinated polypropylene (available from Eastman Chemical Company, Kingsport, TN, under the trade designation "CP 343-3"), 2.5 g of the silane coupling agent (available from OSi Specialties, Danbury, CT, under the trade designation "Silquest A 186"), 4 g triethanolamine titanate (available from El du Pont de Nemours &Company, Wilmington, DE, under the commercial designation "Tyzor TE"), and 99 g of a solvent mixture of cyclohexane, xylene, and ethanol in a weight ratio of 5.5: 3.5: 1.0 to prepare a solution of about 18%. This solution was emptied onto the non-matte side of three 152.4 mm x 24.5 mm x 1.3 mm aluminum strips (available from Lawrence Fredrick Company, Greenwood, IL). A 0.25 mm thick coating of the solution was dried to form a coating of approximately 0.037 mm thick adhesive on each strip. A 3% primer solution, prepared as described in Example 11, was brushed on three 152.4 mm x 24.5 mm x plates. 2.5 mm thermoplastic olefin (TPO) (available from Himont USA, Inc. Lansing, MI under the trade designation "ETA 3095") and allowed to dry. The adhesive-coated aluminum strips were laminated at approximately 137 mm from the prepared TPO plates, at a temperature of 200 ° C for 30, and 45 seconds, respectively, at low pressure. The values of detachment were determined as of 193 N / 100 mm, and 246 N / 100 mm, respectively. This example illustrates the utility of the compositions of this invention as bonding layers by adhesive for jointly laminating dissimilar materials Example 25 A construction was prepared using a thermosetting adhesive, as described under the 90 ° Peel Adhesion Method - Thermosetting Adhesive Test. A 5% solution was used as described in Table XII. Table XII The surface of the sample was initially flooded with approximately 1.5 ml of the 5% solution and abraded by abrasion, according to the test method described above. A control sample was prepared by abrading the sample in the absence of a priming solution. The results are described in Table XIII.

Table XIII The 90 ° release values were dramatically increased by the use of a solution according to the present invention, as compared to an unprepared substrate.

Example 26 Thermoplastic polyolefin plates, 51 mm x 25.4 mm x 5 mm (available from Himont USA, Inc., Lansing, MI, under the trade designation "ETA 3163"), were cleaned twice with ethanol and allowed to dry. A 5% solution prepared according to Example 25 was brushed on one side of each of the plates and allowed to dry for 24 hours. The sizing plates were bonded with two-part epoxy adhesives (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designation "Scotch-Weld 2216 B / A") to form a 25.4 mm x overlap joint. 12.7 mm The specimens were allowed to cure for 72 hours under a weight of 150 g. A control sample was prepared and run once without using any solution. The bond strengths (N / mm2) were measured in an Instron tensile tester (available from Instron Corp., Canton, MA) at a crosshead speed of 12.7-mm per minute. The values reported in Table XVI are an average of three determinations for Example 26 and a single determination for the control sample.

Table XIV It is noted that in relation to this date, 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, property is claimed as contained in the following:

Claims (10)

1. A polymeric mixture, characterized in that it comprises: (a) a modified block copolymer comprising: (i) a polystyrene block and (ii) a polydiene block or a hydrogenated polydiene block, said polydiene block or hydrogenated polydiene block it is modified to contain an average of one or more carboxyl groups; and (b) a polymer comprising a polymerization reaction product (i) at least one ester of acrylic or methacrylic acid of a non-tertiary alcohol having from 1 to 14 carbon atoms, inclusive, (ii) at least one monomer having a carboxylic acid functional group, which is present in an amount in the range of about 1 to about 15 parts by weight, based on 100 parts by weight of the polymer (b); and (iii) a titanate selected from the group consisting of ethanol, the 2, 2 ', 2"-nitrilotris-titanium salt of ethanol (4+), bis (ethyl-3-oxobutanolate-010pbis-2-titanium propanolate; a reaction product of the tetraalkyl titanate with a β-diketone and an alkanolamine, and tetrabutyl titanate (the salt of 1-butanol, titanium (4+)).

2. A mixture according to claim 1, characterized in that a homopolymer of said ester has a Tg of less than 20 ° C.

3. A mixture according to claim 1, characterized in that the ester comprises iso-octyl acrylate.

4. A mixture according to claim 1, characterized in that the monomer having carboxylic functional group is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, and citraconic acid.

5. A mixture according to claim 1, characterized in that a polymer portion capable of associating with one or more of the blocks of said block copolymer (a) is polymerized with the acrylic or methacrylic acid ester of the polymer (b), having the polymer portion one Tg greater than 20 ° C and a weight average molecular weight greater than 2,000.

6. A mixture according to claim 1, characterized in that the block copolymer (a) is present in an amount sufficient to associate with the substrate.

7. A mixture according to claim 1, characterized in that the polymer (b) is present in an amount sufficient to bind the block copolymer (a).

8. A mixture according to claim 5, characterized in that the titanate (c) is present in an amount in the range of 5 to 50 parts by weight, based on 100 parts by weight of the polymer mixture.

9. A mixture according to claim 1, characterized in that the block copolymer (a) and the polymer (b) are present in a proportion from about 95: 5 to about 5:95.

10. A method for preparing a substrate, characterized in that it comprises applying to the substrate a mixture containing: (a) a modified block copolymer comprising (i) a polystyrene block and (ii) a polydiene block or a polydiene block hydrogenated, the polydiene block or hydrogenated polydiene block is modified to contain an average of one or more carboxyl groups; and (b) a polymer comprising a polymerization reaction product of (i) at least one ester of acrylic or methacrylic acid of a non-tertiary alcohol having from 1 to 14 carbon atoms, inclusive, (ii) at least one monomer having a carboxylic acid functional group which is present in an amount in the range of about 1 to about 15 parts by weight, based on 100 parts by weight of the polymer (b); (iii) a titanate selected from the group consisting of ethanol, salt of 2, 2 ', 2"-nitrilotris-titanium (4+), bis (ethyl-3-oxobutanolate-O1 © 3) bis-2-propanolate titanium a reaction product of tetraalkyl titanate with a β-diketone an alkanolamine, and tetrabutyl titanate, (salt of -butanol, titanium (4+).