MXPA97010263A - Polymeric mixtures containing acrylate and methods for use - Google Patents

Abstract

The present invention relates to a method for preparing a substrate, characterized in that it comprises applying to the substrate a mixture comprising: a) a block copolymer comprising: i) a block of polystyrene and ii) a block of polydiene or a block of hydrogenated polydiene, the block copolymer (a) being unmated, and b) a polymer comprising a polymerization reaction product of i) at least one acrylic or methacrylic acid ester of a non-tertiary alcohol having 1 to 14 carbon atoms, inclusive, ii) at least one nitrogen-containing monomer selected from the group consisting of an N-vinyl lactam and an N, N-dialkylacrylamide, and iii) 1-10 parts, based on 100 parts of the polymer (b), of a monomer having at least one functional carboxylic acid group, a hydroxy functional group or an epo functional group

Description

POLYMERIC MIXTURES CONTAINING ACRILATE AND METHODS FOR USE Background of the Invention Field of the Invention This invention relates to polymer blends useful, for example, as adhesives, printers, inks, and paints.

Description of the prior art U.S. Patent No. US-A-5, 143, 972 discloses a composition comprising a mixture consisting essentially of: (1) an adhesive composition comprising a sticky, sticky, or pressure sensitive adhesive; Y (2) a pressure-sensitive, usually sticky adhesive composition comprising a polymer having at least a major weight portion of monomeric, polymerized acrylic or methacrylic acid ester in its backbone and grafted to the spinal column , polymeric portions that have a REP: 26282 Tg greater than 20 ° C, and a weight average molecular weight greater than 2,000, the adhesive of the adhesive composition has portions that associate with the polymer portions grafted to the backbone of the polymer of the adhesive composition (2). Low surface energy substrates such as polyethylene, polypropylene, and other polyolefins are characterized by having critical wetting surface tensions at about 35 mN / m or less. Such surfaces are generally not receptive to inks, paints, and adhesives, due to their poor wetting capacity. There is a need to improve the adhesion of such surfaces, as well as high energy surfaces.

Brief Description of the Invention In a first aspect, the invention features a method for preparing a substrate, comprising applying to the substrate a mixture comprising (a) a block copolymer comprising (i) a polystyrene block and (ii) a block of polydiene or a hydrogenated polydiene block, the block copolymer (a) is unadulterated; and (b) a non-crosslinked copolymer which comprises 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 is a nitrogen-containing monomer. In a second aspect, the invention features a polymer blend comprising (a) a block copolymer comprising (i) a polystyrene block and (ii) a polydiene block or a hydrogenated polydiene block, said block copolymer (a) is unadulterated; and (b) a non-crosslinked polymer comprising a polymerization reaction product of (i) at least one monoethylenically unsaturated acrylic or methacrylic acid ester of a non-tertiary alcohol having from 1 to 14 carbon atoms, inclusive; (ii) at least one monomer containing nitrogen, monoethylenically unsaturated; and (iii) from 1 to 10 parts by weight, based on 100 parts of polymer, of a monomer having at least one carboxylic acid functional group, a hydroxyl functional group, and an epoxy functional group. The invention further characterizes a method for preparing the polymer blends above described, by physically mixing the block copolymer (a) and the polymer (b) together. 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 mN / M such like metal and glass). The blends are useful as primers (eg, before the application of paints, adhesives and coatings) as well as adhesives (eg, for use as bonding layers and pressure sensitive adhesive), inks, and paints. Mixtures can be used for more than one function, for example, the mixture can be a primer and a paint or a primer and an adhesive.

Detailed description of the invention The invention features blends having a block copolymer (a) and a polymer containing acrylate or methacrylate ester (b) as described in the Brief Description of the Invention section.

The block copolymer (a) comprises one or more blocks of polystyrene and one or more blocks of polydiene or hydrogenated polydiene. If one or two polystyrene blocks and a polydiene or hydrogenated polydiene block are present, the block copolymer can be designated as AB block copolymer (containing a polystyrene block and a hydrogenated polydiene or polydiene block) or a copolymer in block ABA (containing two blocks of polystyrene and a block of polydiene or hydrogenated polydiene) "A" designates polystyrene and "B" designates polydiene or hydrogenated polydiene. Examples of a polydiene block or hydrogenated polydiene block include, for example, polybutadiene, polyisoprene, ethylene / butylene, or ethylene / propylene block. The term "polydiene" refers 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. At least one of the block copolymer blocks (a) is preferably a block of butadiene, isoprene, ethylene / butylene or ethylene / propylene. A block copolymer (a), particularly preferred, is a styrene-ethylene / butylene-styrene block copolymer. Examples of suitable block copolymers include styrene-butadiene-styrene, styrene-isoprene-styrene (for example, commercially available from Shell Chemical Company, Houston Texas, under the trademark designation "Kraton D-1107"), styrene-ethylene / butylene-styrene (e.g., commercially available from Shell Chemical Company, Houston, Texas, under the designation "Kraton G-1657), styrene-ethylene / butylene-styrene and styrene-butadiene (e.g., commercially available from Fina Chemical Company , Dallas, Texas, under the designation "Finaprene 1205" and "Finaprene 411P".) For illustration, "Kraton G-1657" has a tensile strength of 23.45 MPa, (3400 psi), a percentage elongation of approximately 750, a Shore A hardness of about 65, and a specific gravity of about 0.90, a Brookfield viscosity (20 wt.% toluene) of about 1.1 Pa.s (1100 cps) at 25 ° C (77 ° F), and a Weight ratio of styrene to rubber from 14 to 86. The block copolymer (a) preferably has a proportion, by weight, of the polystyrene block to the polydiene block or the block of hydrogenated polydiene, which is in the range of 5:95 to 95: 5, more preferably 10:90 to 50:50. The block copolymer (a) is not malleable. The term "malenate" as used herein means modified to contain an average of one or more carboxyl groups. 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 is a monomer containing nitrogen. In addition, polymer (b) may also comprise component (iii), for example, a monomer having at least one of a carboxylic acid functional group, a hydroxyl functional group, and an epoxy functional group, or combinations of these monomers. Examples of the monomer (iii) include acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. Acrylic and methacrylic acid are preferred. The amount of component (iii) when present, is preferably 1 to 10 parts by weight, more preferably from 1 to 5 parts by weight, based on 100 parts by weight of the polymer (b). In any case, the polymer (b) comprising the components (i) and (ii), or (y), (ii) and (iii), is not crosslinked. 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-l-pentanol, 2-methyl-l-pentanol, 3-methyl-l-pentanol, 2-ethyl-l-butanol, 3,5,5-trimethyl-1-hexanol, 3-heptanol, 2- octanol, 1-decanol, or 1-dodecanol. A particularly preferred ester monomer is isooctyl acrylate. The nitrogen-containing monomer comprises an N-vinyl lactam (for example N-vinylpyrrolidone or N-vinylcaprolactam), acrylamide, an N-alkyl acrylamide (for example N-methylacrylamide) or N, N-dialkylacrylamide (for example, N, -dimethylacrylamide) or combinations thereof. The amount of monomer containing nitrogen depends on the monomer selected. Typically, the amount of the nitrogen-containing monomer is at least 2 parts by weight, preferably 5 parts to 40 parts by weight, based on the weight of the polymer (b), more preferably 15 to 30 parts by weight based on 100 parts of the polymer. For example, 5 to 30 parts by weight is preferred when using N- vinyl lactams and N, N-dimethylacrylamides individually. In addition, at least 5 parts by weight of acrylamide is typical when used alone; however, if N-vinyl lactam and acrylamide are used together, the amount of acrylamide used may be less than 5 parts by weight, for example, 1 to 4 parts by weight. The nitrogen-containing monomer of the present invention does not contain ester groups of acrylic and methacrylic acid, as is the case of N-vinyl lactams, but may contain acrylic or methacrylic acid or derivatives thereof, as in the case of acrylamide, N-alkylacrylamide, or N, N-dialkylacrylamide. It is believed that the nitrogen-containing monomer improves the compatibility of the mixture through association with the phenyl groups of the styrene blocks, resulting in improved properties. In a preferred embodiment, the homopolymer of the ester of acrylic or methacrylic acid has a Tg of less than 20 ° C. A polymer portion having a Tg greater than 20 ° C, a weight average molecular weight greater than 2,000, and capable of associating with one or more of the blocks of the block copolymer (e.g., a polystyryl portion as described in US Pat. Groves, Patent No. 5,143,972 entitled "Pressure Sensitive Adhesive Composition" may be polymerized with the acrylic or methacrylic acid ester portions of the polymer (b). In this case, it is believed that the additional association occurs between this polymer portion and the phenyl groups of the styrene blocks. The polymer (b) is preferably prepared by polymerization initiated by free radicals or thermal polymerization of the base monomers, using conventional polymerization techniques, and is then physically mixed with the block copolymer (a). 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 bonding 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, paints; and adhesives. 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 one interacts with the other. The proportion, by weight, of block copolymer (a) to polymer (b) is preferably in the range of 95: 5 to 5:95, more preferably 75:25 to 25:75. Examples of preferred mixtures include: (1) a mixture of styrene-ethylene / butylene-styrene block copolymer and isooctyl acrylate polymer / N-vinylcaprolactam / acrylic acid; (2) a mixture of styrene-ethylene / butylene-styrene block copolymer and isooctyl acrylate / N-vinylcaprolactam polymer; (3) a mixture of styrene-ethylene / butylene-styrene block copolymer and isooctyl acrylate macromer polymer / N-vinylpyrrolidone / acrylic acid / acrylamide / polystyrene; (4) a mixture of styrene-ethylene / butylene-styrene block copolymer and isooctyl acrylate / acrylamide polymer; (5) a mixture of styrene-ethylene / butylene-styrene block copolymer and isooctyl acrylate / N, N-dimethylacrylamide polymer. The mixture can be provided in the form of a primer and / or 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 not greater than about 35 mN / m. Examples include olefin polymers such as polyethylene and polypropylene. The mixtures may be thickened by incorporating a thickening agent, modifying the structure of the acrylate ester or methacrylate ester polymer, or through a combination of both. Thickeners suitable for thickening the mixtures include low molecular weight hydrocarbon resins, and resins based on α- and β-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, DE;" Escorez-143H "and" Escorez 5380, "which are available from Exxon Corp., Houston, Texas; "Wingtack Plus", available from Goodyear Tire and Rubber Co., Akron, OH The amount of thickener included in the mixture is preferably in the range of 20 to 250 parts per hundred parts of the mixture. of the thickener are used where the mixture is in the form of a primer, while the highest concentrations are used where the mixture is in the form of a pressure sensitive adhesive.The mixtures may include an antioxidant to inhibit oxidation and consistent loss of tack as mixtures age The suitable antioxidants are based either on (1) a hindered phenol or (2) an organometallic salt containing sulfur Examples of hindered phenols include ortho-substituted phenols or 2, 5 -gave substituted, wherein the substituent group (s) is / are branched hydrocarbon radicals having from 2 to 30 carbon atoms, for example, tertiary butyl or tertiary amyl radicals, and para-substituted phenols, wherein the substituent groups are ORÍ, where R1 is methyl, ethyl, or 3-substituted propionic ester. Examples of hindered phenols commercially available include those available from Ciba-Geigy Corp., Hawthorne, NY, under the trade designation "Irganox 1076", and those available from American Cyanamid Co. Wayne, NJ, under the trade designation "Cyanox LTDP". Suitable organometallic sulfur-containing salts are the dibutyl dithiocarbamate nickel derivatives. 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. The mixtures can also be colored by the inclusion of anhydrous pigments or colored concentrates (usually based on polystyrenes); 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 are also included. Other additives that can be included in the mixtures are chlorinated silanes, titanates and polyolefins ("CPOs"). In addition, resins such as epoxy resins can be mixed with the polymer mixture comprising the block copolymer (a) and the polymer (b). Resistance to degradation by ultraviolet light of mixtures, it can be improved by incorporating UV inhibitors into the mixtures. Typically, one part per hundred (phr) of ultraviolet light inhibitor filler having the trade designation "Cyasorb IV 531" (available from American Cyanamid Company, Wayne, NJ) or a mixture of equal parts of ultraviolet light inhibitors that have the commercial designations "Tinuvin 328" (available from Ciba-Geigy Corp., Hawthorne, NY) and "Uvinal 400" (GAF Corp., New York, NY) is sufficient to provide this improvement. 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) (available from American Cyanamid Company, Wayne, NJ) or "NBC" (0.1 phr) (available from EI du Pont de Nemours and Company, Wilmington, DE). As used herein, phr is based on the weight of the copolymer in block in the mix, unless otherwise stated. The mixtures described above 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 polymers suitable for the formation of adhesives. Thermosetting adhesives are generally formed by addition polymerization. Examples of thermosetting adhesives include polysulfides, silicones, polyesters, polyurethanes, epoxies, anaerobic and aerobic acrylics, radiation curable polymers, and vulcanization rubbers. Thermosetting adhesives typically cure by heat, catalysts or activation by light or moisture. After curing, the thermosettable adhesives are generally insoluble, for example, the adhesive will not dissolve in an organic solvent or in water, and will be non-fusible, for example, the adhesive will not flow when heated. Pressure sensitive adhesives in general do not suffer a progressive increase in viscosity after the preparation, rather they are permanently in an adherent or sticky state. Examples of pressure sensitive adhesives 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 can be in the form of emulsions, solutions or solids. A primer of the present invention can be applied, using a variety of techniques including dip, spray, brush application, rotogravure, Meier rod and blade coating. A particularly useful application technique involves the application of an apretter of the present invention to the substrate and then the 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 μm. When the pressure sensitive adhesives are being bonded to a substrate, preferably the size of the abrasive grain is in the range of 8 to 2 μm, more preferably 5.5 to 2.0 μm. When the structural adhesives, for example, epoxides and polyurethanes, are being bonded to a substrate, preferably the size of the abrasive grain is in the range of 100 to 50 μm. The following non-limiting examples further illustrate the present invention.

EXAMPLES TEST METHODS FPL Process for 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 trade designation "2024-T3 Alelad"), are treated according to the chemical etching process described in H.W. Eichner, Forest Products Laboratory; Report No. 1842, April 1, 1954, Madison, WI, USA. Specifically, the specimens are treated as follows. Each specimen is rinsed in acetone and then allowed to air dry. Next, each specimen is degreased by rinsing for 10 minutes in 75 g of Oakite 164 (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 etch bath consisting of 1161 g of H2SO4, 156.8 g of Na2Cr2? 72H20, 1.5 g of chopped of bare aluminum alloy 2024-T3, and enough distilled water to make 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, bonded to double-coated, pressure-sensitive adhesive foam tapes or pressure-sensitive transfer adhesives, is determined according to the following procedure. An aluminum strip engraved with FPL (commercially available from Vincent Metals, Minneapolis, MN under the trade designation "2024-T3 Alelad") measuring 50.8 mm x 25.4 mm x 1.6 mm with a hole diameter of 7 mm in the center, and 10 mm from one edge of the strip, is prepared from the previously described specimen. Similarly, similar strips are prepared from the prepared and unsheathered substrate, each having a thickness that does not deform at the test temperature under the test load. A 12.7 mm wide pressure sensitive adhesive tape worn on a release liner is adhered to the solid end of the aluminum strip (for example, the end opposite the end with hole) and cut to a length of 25.4 mm. The liner is then removed and the solid end of the substrate strip adhered to the exposed fiber 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 weight of 1 kg of the specimen is hung. 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 Detachment at 9 ° C - Adhesive Sensitive to The adhesions to the release (N / 100 mm) of doubly coated pressure-sensitive foam strips, to various prepared and unprepared substrates, are determined in the following manner.

The matte 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 covered with hard rubber, 2.4 kg, is then passed back and forth 3 times on the specimen. Next, about 50 mm of the liner or reinforcement 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 primed or untapped substrate. . A roller covered with 2.4 kg hard rubber is passed again, back and forth three times on the mounted specimen. The procedure is then repeated to laminate a second construction of foam-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 ° C detachment fitting (commercially available from Consultants INTL, Network, Mentor, OH, under the trade designation "PJ-90") and mounted on an Instron voltage tester (available from Instron, Corp., Canton, MA). Adherence to peel at 90 ° C is measured by removing the free end of the laminated foamed aluminum foil tape at a rate of 30.5 cm per minute. The reported detachment resistances (in N / 100 mm) are an average of three determinations, except where specified.

Cohesive resistance The cohesive resistances of the foam tapes were determined according to the procedure of the adhesion test to the 90 ° detachment, except that the tapes were joined to an aluminum panel recorded with FPL, of 152.4 mm x 50.8 mm x 1.6 mm (available from Vincent Metals, Minneapolis, MN under the trade designation "2024-T3") and allowed to stand for 2 hours before the test. The foam tapes used were commercially available from Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation of "Scoth Brand" in conjunction with the designations "Y-4220", VHB-4205", and VHB-4950" (double coated with pressure sensitive adhesive, acrylic); "VHB-4952" (double coated with a styrene-butadiene rubber (SBR), adhesive pressure sensitive); and "VHB-4910" (a 1 mm thick acrylic transfer tape). 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 marks for the detachment adhesion test, semiquantitative described below TABLE A Adherence to Detachment, Semi-quantitative The level of adhesion of prepared and unprepared substrates to pressure-sensitive adhesives, which can not be determined quantitatively (eg, where the substrate is a thin and / or flexible film or a rigid article) pre-dimensioned), is determined semiquantitatively. Sample preparation is carried out according to the 90 ° release adhesion procedure, except that two or more foam tapes are used, and the tape / foil laminate is secured to the substrate with manual pressure or a roller steel coated with 2.4 kg rubber. After remaining for a specified time (typically 15 minutes), the free end of the aluminum foil laminate / tape is manually pulled from the substrate. If no cohesive failure of the foam core is observed, a foam tape having the following lower cohesive strength (determined with reference to Table A above) is attached and then removed. This procedure is repeated with successive foam tapes (with reference to Table A above) until cohesive failure occurs in the foam core. A semiquantitative level of adhesion of the substrate primed to the pressure sensitive adhesive of the foam tape is then determined with reference to Table A.

Cut in Simple Overlap Two substrate plates, each measuring 51 mm x 25.4 mm x 5 mm, are cleaned twice with one 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 remnant substrate plate 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 for approximately 0.5 minutes. Three test mounts are prepared for each measurement, and allowed to cure 72 hours before the test. The bond strength is measured in an Instron tensile or tensile tester (Commercially available from Instron Corp. Canton, MA) at a crosshead speed of 1.47 m / min.

Adherence to 90 ° Detachment - Adhesive Thermosetting The adhesions to the release (N / 100 mm) of the films of polypropylene (PP) and of the low density polyethylene (LDPE) joined with the binder 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 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 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 was applied (available from Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designation "Scotch-Weld 2216 B / A") to an aluminum panel 2024-T3 engraved with FPL of 152.4 x 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.

EXAMPLE 1 This example illustrates a preferred mixture according to the invention, useful as a primer.

Preparation of Block Copolymer Solution A 25% solution of block copolymer was prepared by dissolving 25.0 g of styrene-ethylene / butylene-styrene tri-block copolymer commercially available from Shell Chemical Company, Houston, Tx, under the trade designation "Kraton G-1657") and 0.25 g of antioxidant (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 composition of 5.5: 3.5: 1.0.

Preparation of Acrylate Ether Polymer A terpolymer consisting of isooctyl acrylate / vinyl caprolactam / acrylic acid (IOA / NVC / AA) (78/20/2) was prepared in the following manner. 39 g of IOA, 10 g of NVC, 1 g of AA, 0.1 g of azobisisobutyronitrile (commercially available from EI du Pont de Nemours &Company, Wilmington, DE, under the trade designation "VAZO-64"), 52.5 were added. g of ethyl acetate 9.0 g of methyl isoamyl ketone, and 13-5 g of ethylene to a narrow-mouthed bottle of 237 ml. The resulting solution was purged with anhydrous argon for three minutes and sealed. The sealed bottle was rotated in a rotating water bath at 55 ° C for 24 hours. The conversion percentage was determined with 99.1% by infrared spectrophotometric analysis. The solution contained 40% solids and had a viscosity of approximately 7.5 P.as. The inherent viscosity was determined as about 0.72 dl / g.

Preparation of the mixture A mixture of the block copolymer and the acrylate ester polymer was prepared in a weight ratio of 1: 3 at a total solids concentration of 3.0%, by dissolving 1.0 g of the block copolymer solution prepared as described above. described above, and 1.9 g of the acrylate ester polymer solution prepared as described above, in 30.4 g of a solvent mixture of cyclohexane, xylene and ethanol, in a weight ratio of 5.5: 3.5: 1.0.

EXAMPLES 2 to 9 In a similar manner, the block copolymer blends prepared as described in Example 1, and various acrylate ester polymers, were prepared in a weight ratio of 1: 3. The identities of the acrylate ester polymers are described in Table 1, below.

TABLE I 1 ACM is acrylamide. 2 NVP is N-vinylpyrrolidone. PSM is 2-polystyrethylethyl methacrylate (weight average molecular weight of about 10,000 g / mol, prepared according to U.S. Patent No. 4,554,324, 52% solids in cyclohexane. 3 DMACM is N, N-dimethylacrylamide.

The mixtures prepared according to Examples 1-9, were applied by brush to 152 mm x 51 mm x 5 mm plates of low density polyethylene (LDPE), polypropylene (PP) (available from Precision Punch and Plastics, Minneapolis, MN), and a thermoplastic polyolefin (TPO) available from Hi ont USA, Inc., Lansing, MI, under the trade designation "ETA 3163"). After 10 minutes, the foam pressure-sensitive adhesive tape samples laminated with aluminum foil (pressure-sensitive adhesive tapes, acrylic 1 mm thick, 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 adhesion to detachment to 90 °. After one hour the release values at 90 ° were determined; the values are reported in Table II as an average of three measurements. Control release values were also determined for unrestricted plates. The results are shown in Table II.

COMPARATIVE EXAMPLE A A mixture was prepared according to Example 1, except that the IOA / AA copolymer (95/5) was replaced by the IOA / NVC / AA copolymer. The release values at 90 ° were determined as described above; the results are reported in Table II under the designation "Ex. Comp. A".

TABLE II TABLE II (continued) The results in Table II demonstrate that the use of blends according to the invention for sizing low energy surfaces improves the adhesion of pressure sensitive adhesives to surfaces.

EXAMPLE 10 The block copolymer solution prepared according to Example 1, and the acrylate ester polymer prepared according to Example 8, were each diluted to 3% polymer solids, using a solvent mixture of cyclohexane, xylene, and ethanol , in a weight ratio of 5.5: 3.5: 1.0, and applied by brush to polypropylene (PP) test plates and Low density polyethylene (LPDE) as described above. The release values were determined as described above, and compared to the values for the block copolymer / acrylate ester polymer mixture prepared according to Example 8, and reported in Table II. The results are shown in Table III.

TABLE III The results in Table III show that while the individual components of the mixture, when used alone, do not work well as primers, high adhesions to the release are obtained when these are mixed together.

EXAMPLE 11 The block copolymer containing blends prepared as in Example 1 and the acrylate ester polymer of Example 8 were prepared in weight proportions of 1: 3, 1: 1, and 3: 1, diluted to 3% solids polymeric, and applied by brush on the thermoplastic olefin (TPO) test plates as described above. The release values were determined using the VHB-4205 tape, as described in example 1; the results are shown in Table IV.

TABLE IV The results in Table IV demonstrate that a wide variety of block copolymer / acrylate ester polymer ratios produce effective primer compositions for low energy surfaces.

EXAMPLE 12 The mixture prepared according to Example 8 was applied to polypropylene (PP) and low density polyethylene (LDPE) test plates using a lint-free cloth. After 10 minutes, foam sheets laminated with aluminum foil were bonded to the prepared substrates. The foam tapes used were pressure sensitive adhesive tape, acrylic, doubly coated (available from the Minnesota Mining and Manufacturing Company, St, Paul, MN, under the trade designation "VHB-4205"), adhesive tape sensitive to the pressure, transfer, acrylic, 1 mm thick (available from Minnesota Mining and Manufacturing Company, St, Paul, MN under the trade designation "VHB-4910"), and pressure sensitive foam tape from styrene rubber / butadiene, doubly coated (available from Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation "VHB-4952"). After one hour, the release values at 90 ° were determined; the values for unrestricted substrates were also determined. The results are reported in Table V.

TABLE V The results in Table V demonstrate that the use of a mixture according to the invention as a primer improves the adhesion to release of acrylic adhesives and pressure sensitive adhesives of styrene-butadiene rubber (SBR) to the surfaces of low energy.

EXAMPLE 13 Approximately 109 g of a 3% preparation solution, prepared according to the Example 8, was modified by the addition of 0.5 g epoxy resin (available from Shell Chemical Company, Houston, Tx, under the trade designation "Epon 828"), 3.0 g chlorinated polypropylene (available from Eastman Chemical Company, Kingsport, TN, under the trade designation "CP 343-3") 0.5 g of silane coupling agent (available from OSi Specialties, Inc., Danbury, CT, under the trade designation "Silquest A 186") and 0.8 g triethanolamine titanate (available of EI du Pont de Nemours &Company, Wilmington DE, under commercial designation "Tyzor TE"). About 25 of this solution was diluted to 1% solids, by the addition of 109 g of a solvent mixture of cyclohexane, xylene, and ethanol, in a weight ratio of 5.5: 3.5: 1.0. The priming solution was applied by brush on the glass, aluminum (Al), and stainless steel (Ac. Inox.) Test plates. After 10 minutes, the foils laminated with aluminum foil ("VHB-4205", "VHB-4910", and "VHB-4952") were attached to the prepared samples. After 72 hours, the adhesion values at 90 ° were determined; the results are recorded in Table VI.

COMPARATIVE EXAMPLE B The procedure of Example 13 was followed, except that the glass, aluminum and stainless steel test plates were prepared with a chlorinated polypropylene primer (commercially available from Norton Performance Plastics, Granville, NY, under the trade designation "Tite-R-"). Bond-2684"). The results are shown in Table VI.

TABLE VI TABLE VI (continued) Table VI demonstrates that the primer solution of this invention improves the adhesion of acrylic adhesives and pressure sensitive adhesives of styrene-butadiene rubber (SBR) to high surface energy substrates (e.g., glass, stainless steel and aluminum).

EXAMPLE 14 A 1% primer solution prepared according to Example 13 was applied to test panels of low density polyethylene (LDPE) and polypropylene (PP) with a lint-free cloth (available from Kimberly-Clark, Corp., Roswell, GA, under the commercial designation "Kimwipe"). After 10 minutes, the tapes Foam laminates with foil (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designations "VHB-4205", "VHB-4910, and" VHB-4952") were attached to the prepared samples. After one hour, the release values were determined.The values are reported in Table VII.

COMPARATIVE EXAMPLE C The procedure of Example 14 was followed, except that the LDPE and PP test plates were primed with a formulated chlorinated polypropylene primer. The results are reported in Table VII.

TABLE VII TABLE VII (continued) The results in Table VII demonstrate that the dressing of Example 14 results in higher release values with pressure sensitive adhesives, acrylic and SBR, to low surface energy substrates compared to the chlorinated polyolefin dressing of Example Comparative C.

EXAMPLE 15 A 1% primer solution prepared according to Example 13 was applied by brush over specimens of 75 mm x 125 mm x 0.25 of linear low density polyethylene film (LLDPE) (available from Consolidated Thermoplastics Company, Schaumburg, IL). After 15 minutes, the aluminum foil laminated samples of the "VHB-4220" tape were attached to the prepared samples. After one hour, the tape "VHB-4220" could not be removed due to the cohesive failure of the foam core. This indicated that release values of at least 425 N / 100 mm had been achieved.

COMPARATIVE EXAMPLE D The procedure of Example 15 was followed, except that a chlorinated polypropylene primer, formulated (available from Norton Performance Plastics, Granville, NY, under the trade designation "Tite-R-Bond 2684") was applied with a brush over the LLDPE specimens. After 15 minutes, the "VHB-4220" tape was attached to the samples. After one hour and after twelve hours, the tape could be easily removed by hand. The detachment values were estimated to be of the order of 90 N / 100 mm or less.

EXAMPLE 16 A 1% sizing solution prepared according to Example 13 was applied by brush onto two specimens of 125 mm x 75 mm x 0.25 linear low density polyethylene film (LLDPE) (available from Consolidated Thermoplastics Company, Schaumburg, IL) . The specimens ready were then left to dry for 15 minutes and 24 hours, respectively. Next, the prepared samples were painted with a latex semi-gloss interior glaze (available from The Glidden Company, Cleveland, OH), a high-gloss oil-based enamel, for indoor / outdoor (available from Carver Tripp, Parks Corp Somerset, MA) and a polyurethane spray lacquer (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation "Part NO-05904"). In a similar way, the untempered specimens of the LLDPE film were also painted. After drying under ambient conditions for 24 hours, filament tape samples of 125 mm x 75 mm x 0.25 mm (available from Minnesota Mining and Manufacturing Company, St. Paul, MN under the trade designation "Scoth Brand 898") were firmly bonded to each painted surface (prepared and unprimed). After After 15 minutes, the tape was quickly removed from each specimen. The complete delamination of all the paints to the untested films of LLDPE was observed. No delamination of the paint was observed from any of the LLDPE surfaces prepared.

COMPARATIVE EXAMPLE E The procedure of Example 16 was followed, except that the commercially available chlorinated polypropylene preparer (available from Norton Performance Plastics, Granville, NY, under the trade designation "Tite-R-Bond 2684"), was brushed onto LLDPE specimens. . The sized specimens were painted and tested as described in Example 16. The complete delamination of all the paints was observed for the finished film.

EXAMPLE 17 To 10 g of a 3% sizing solution prepared according to Example 13, one gram of titanium dioxide dispersion (available from Hüls America Inc, Piscataway, NJ, low designation) was added. commercial "GPD 82-0082"). Similarly, to another 10 g of the same sizing solution, one gram of carbon black dispersion (available from Borden Chemical Company Cincinnati, OH under the trade designation "Codispersion 31L62") was added. After mixing, both pigmented solutions were applied by brush on untreated LLDPE film, and allowed to dry under ambient conditions for 24 hours. Adhesions to the release of pigmented coatings to the LLDPE film, was determined by firmly bonding the filamentous tape (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN under the designation "Scotch Brand 898") to the coated surfaces. , in the manner described in Example 16. 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 18 A 1% primer solution prepared according to Example 13, was applied by brush on 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 trade designation "ETA 3163") and tested for the static cut to aluminum 2024-T3 engraved with FPL, at 80 ° C 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"). The unprimed thermoplastic olefin specimens (TPO) were also tested. The results are reported in Table VIII.

TABLE VIII The results in Table VIII demonstrate that the primers of the invention improve the high temperature holding power of an adhesive Pressure sensitive, acrylic, to low energy substrates.

EXAMPLE 19 A 3% primer solution prepared according to Example 13, was applied by brush on both sides of a specimen of 150 mm x 150 mm x 0.10 mm of flexible, clear polyvinyl chloride (PVC) film available from Wiman Plástic Div. St. Cloud, Minnesota, MN) and a 150 mm x 150 mm x 0.35 mm film of opaque thermoplastic olefin (TPO) not pigmented (available from Himont USA, Inc. Lansing, MI, under the trade designation "HIFAX CA10A") and allowed to dry for 30 minutes. A 0.25 mm acrylic pressure sensitive transfer adhesive was then laminated onto a removable liner (available from the Minnesota Mining and Manufacturing Company, St. Paul, MN, under the trade designation "F 9473 PC") on one side of each of 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 hard rubber roller of 2.4 kg.

The release values of the transfer adhesive, reinforcements or sizing tape liners were then determined by laminating a 150 mm x 51 mm sample of each transfer / reinforcement tape construction to aluminum plates etched with FPL of 152 mm x 51 mm x 1.6 mm (available from Vincent Metals, Minneapolis, MN under the trade designation "2024-T3") with a 2.4 kg rubber roller. Approximately 75 mm of liner was removed from the laminated transfer adhesive samples, with aluminum foil, and attached to each of the ribbon samples on the aluminum plate, in such a way that two test samples for each tape were prepared. The resulting samples had the following construction: 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 * adhesive and film failure.

This example illustrates that pressure sensitive adhesive tapes having retention power to the reinforcement, equivalent to the cohesive strength of the adhesive, or the tensile strength or resistance to reinforcement be prepared.

EXAMPLE 20 Plates measuring 51 mm x 25.4 mm x 5 mm of 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% preparation solution prepared according to the Example 13, on one side of each of the plates using a cotton tipped agitator. The prepared plates were then joined together (for example, HDPE plates were attached to the HDPE plates and the PP plates were attached to PP plates) with an ethyl cyanoacrylate adhesive and the overlapping bond strengths 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 or resistances between low surface energy substrates.

Example 21 Example 21 involved a construction using a thermosetting adhesive, and was prepared as described under the Adhesive test method Adherence to the Release 90 'Thermosetting The solution used is described in Table XI: Table XI The surface of the sample was initially flooded with approximately 1.5 ml of the 5% solution, and weathered according to the test method described above. The control mixture was prepared by abrasion of the sample in the absence of a priming solution. The results are described in Table XII.

Table XII 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 22 They were cleaned twice with ethanol, 51 mm x 25.4 mm x 5 mm thermoplastic polyolefin plates (available from Himont USA, Inc., Lansing, MI, under the trademark designation "ETA 3163") and allowed to dry. A 5% solution prepared according to Example 21 was brushed onto 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 designation of the "Scotch-Weld 2216 / B / A" brand) to form an overlap joint of 25.4 mm x 12.7 mm. The samples were allowed to cure for 72 hours under a weight of 150 g. Additionally, control samples were run three times without using any preparation solution. The bond strengths (N / mm3) 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 XIII are an average of three determinations.

TABLE XII 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 (9)

1. A method for preparing a substrate, characterized in that it comprises applying to the substrate a mixture comprising: (a) a block copolymer comprising (i) a block of polystyrene and (ii) a block of polydiene or a block of hydrogenated polydiene, the block copolymer (a) is unadulterated; and (b) a non-crosslinked 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, and (ii) at least one nitrogen-containing monomer selected from the group consisting of an N-vinyl lactam and an N, N-dialkylacrylamide, and optionally (iii) from 1 to 10 parts, based on 100 parts of polymer (b) ), of a monomer having at least one carboxylic acid functional group, hydroxyl functional group, and epoxy functional group.

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

3. The method according to claim 1, characterized in that the monomer (iii) is selected from the group consisting of acrylic acid, methacrylic acid, or itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, and glycidyl methacrylate.

4. A polymer blend characterized in that it comprises: (a) a block copolymer, comprising (i) a polystyrene block; and (ii) a polydiene block or a hydrogenated polydiene block, the block copolymer (a) is unmapped, and (b) a non-crosslinked polymer comprising a polymerization reaction product of (i) at least one monoethylenically unsaturated acrylic or methacrylic acid ester, of a non-tertiary alcohol having from 1 to 14 carbon atoms, inclusive; (ii) at least one monomer containing nitrogen, monoethylenically unsaturated, selected from the group consisting of an N-vinyl lactam and N, N-dialkylacrylamide; and optionally (iii) from 1 to 10 parts, based on 100 parts of the polymer (b), of a monomer having at least one of a carboxylic acid functional group, hydroxyl functional group, and epoxy functional group.

5. The mixture according to claim 4, characterized in that the monomer (iii) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, and methacrylate. of glycidyl.

6. The mixture according to claim 4, characterized in that the mixture comprises styrene-ethylene / butylene-styrene block copolymer and isooctyl acrylate / N-vinylcaprolactam / acrylic acid polymer.

7. The mixture according to claim 4, characterized in that the mixture comprises styrene-block copolymer. ethylene / butylene-styrene and isooctyl acrylate / acrylamide polymer / acrylic acid.

8. The mixture according to claim 4, characterized in that the mixture comprises styrene-ethylene / butylene-styrene block copolymer and isooctyl acrylate / N, N-dimethylacrylamide / acrylic acid copolymer.

9. The mixture according to claim 4, characterized in that the polymer comprises 15 to 30 parts by weight of the nitrogen-containing monomer based on 100 parts of polymer.