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WO1991018739A1 - Composition d'adhesif en latex autocollant a emulsion acrylique aqueuse - Google Patents

Composition d'adhesif en latex autocollant a emulsion acrylique aqueuse Download PDF

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Publication number
WO1991018739A1
WO1991018739A1 PCT/US1991/003750 US9103750W WO9118739A1 WO 1991018739 A1 WO1991018739 A1 WO 1991018739A1 US 9103750 W US9103750 W US 9103750W WO 9118739 A1 WO9118739 A1 WO 9118739A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
copolymers
monomer
acid
copolymer
Prior art date
Application number
PCT/US1991/003750
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English (en)
Inventor
Michael Jeffrey Skoglund
Original Assignee
Ashland Oil, Inc.
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Publication date
Application filed by Ashland Oil, Inc. filed Critical Ashland Oil, Inc.
Publication of WO1991018739A1 publication Critical patent/WO1991018739A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • the present invention relates to pressure sensitive adhesives and more particularly to a water-based pressure sensitive adhesive suitable for high performance applications.
  • pressure sensitive adhesive tapes are being shifted from organic solvent systems to aqueous latices in order to reduce air pollution and fire hazard, as well as eliminate the rising expense of organic solvents.
  • Pressure sensitive adhesives for high performance application must meet or exceed diverse, often seemingly incompatible, criteria. Initially, the adhesive must coat well on silicone or other release sheets. The adhesive also must exhibit tenacious adherence to film face stock which may serve a masking function or may convey information, e.g. by its imprinting.
  • the adhesive coated film face stock When the adhesive coated film face stock is removed from the release sheet, the adhesive must exhibit initial tack and peel performance when pressure-applied to a substrate.
  • the substrate bearing the adhesively- bound film face stock may be subjected to a variety of manufacturing operations over time. Thermal cycling of the substrate is a condition to which high performance, pressure sensitive adhesives must be designed to confront.
  • removal When the film face stock is removed from the substrate, removal must be clean, i.e. no visible trace of the adhesive should remain on the substrate. Heat aging of the film face stock/substrate laminate, however, tends to cause the adhesive to "build", that is, the necessity to utilize excessive force to remove the film face stock.
  • the adhesive should stick well initially, but no so well that its later removal is difficult. Then too, the adhesive must possess shelf life, viscosity, etc. making it compatible with existing coating and handling techniques utilized in the art.
  • Prior proposals aimed at making pressure sensitive adhesives tapes include, for example, U.S. Pat. No. 3,657,396 which proposes a mixture of polyvinylmethyl ether and an acrylic acid polymer which mixture is dispersed in water.
  • the acrylic polymer is selected from the group consisting of polyacrylic acid, polyacrylamide, N-methylol polyacrylamide and an acrylic copolymer of a monomer selected from the group consisting of acrylic acid, acrylamide, and N- methylol acrylamide in a monomer selected from the group consisting of lower alkyl esters of acrylic acid and methacrylic acid.
  • 24491/84 proposes pressure sensitive adhesives comprising an acrylic copolymer synthesized from 2-ethylhexyl acrylate and n-butyl acrylate, acrylonitrile, acrylic acid, N-methylol acrylamide, and optionally vinyl sulfonic acid; and plasticizer.
  • the present invention is directed to an aqueous emulsion acrylic pressure sensitive adhesive composition that excels in high performance applications.
  • the inventive adhesive composition comprises in water (a) a copolymer of a C 4 -C 18 alkyl (meth)acrylate monomer and between about 0.1% and 5% N-substituted or unsubstituted (poly)acrylamide; (b) a copolymer of a C 4 -C 18 alkyl (meth)acrylate monomer and between about 0.2% and 10% of an ethylenically-unsaturated carboxylic acid; and (c) a surfactant, which preferably comprises between about 0.01% and 10% by dry weight of said copolymers of a phosphate ester surfactant.
  • Said copolymers (a) and (b) are selected from: (i) a blend of copolymers (a) and (b), at least one of which is an emulsion copolymer; (ii) an interpolymer of copolymers (a) and (b) where said alkyl (meth)acrylate monomer of copolymers (a) and (b) are the same; and ( ⁇ i) an interpenetrating polymer network of copolymers (a) and (b).
  • the ratio of acrylamide to unsaturated acid in the copolymer ranges from about 1 :10 to 10:1 by weight.
  • the emulsion copolymer(s) includes up to 25% by weight of styrene or other aromatic monomer (s).
  • the novel adhesive composition is substantially-free of cross-linking monomers, copolymerizable emulsifiers, N- methylol acrylamides and the like, cross-linking additives (i.e. post-polymerization addition yielding a cross- linking reaction or formation of interpolymer bonds, such as, for example, zinc salts, diisocyanates, diglycidyl compounds, etc.), and zwitterionic monomers (i.e. not more than about 15 wt-% of cross-linking ingredient, including monomers and additives). Basification of the copolymer (s) results in a self-thickening adhesive composition and contributes to manufacturing reproduceability of the adhesive composition.
  • cross-linking additives i.e. post-polymerization addition yielding a cross- linking reaction or formation of interpolymer bonds, such as, for example, zinc salts, diisocyanates, diglycidyl compounds, etc.
  • zwitterionic monomers i.e. not more than
  • Advantages of the present invention include a manufacturing process that enables the reproduceable production of the novel adhesive composition. Another advantage is the ability to synthesize an adhesive composition base that is compatible and blendable with other conventional ingredients at all levels. A further advantage is the ability to produce an ultra-removable adhesive composition.
  • the major ingredient in the emulsion copolymer(s) broadly is a C 4 -C 18 alkyl (meth)acrylate monomer and advantageously a C 4 -C 12 alkyl (meth)acrylate monomer.
  • n-Butyl acrylate and 2-ethylhexyl acrylate are two monomers that have proven advantageous in forming the emulsion copolymer(s) of the present invention, though other straight chain, alicyclic, and cyclic alkyl (meth)acrylate monomers may be used as is necessary, desirable, or convenient.
  • the parentheticals used herein designate optional content, i.e.
  • (meth)acrylate means "acrylate” or "methacrylate”, and the same is true for the parenthetical plurals used herein. Also by convention, copolymer and interpolymer both mean a polymer of two or more monomers. The selection of the terms as used herein is for the clarity of understanding and not by way of limitation.
  • a combination of acrylamide and ethylenically unsaturated carboxylic acid form the balance of the emulsion copolymer(s) and their combination is important to the high performance properties realized, whether present in a single interpolymer or present separately in two different copolymers.
  • the proportion of acrylamide ranges from about 0.1 wt-% to about 5 wt-% while the proportion of unsaturated acid ranges from about 0.2 to about 10% by weight.
  • the acrylamide content includes N-alkyl and other substituted acrylamides and polyamides, e.g. diamides.
  • Cross-linking monomers, e.g. N-methylol acrylamides may be present in minor amount (e.g.
  • Latent cross-linking functionality tends to lower tack and initial peel values, thus reducing the strength and suitability of the adhesive composition for some applications.
  • N-methylol substituted acrylamides may be present in the formulation, but they generate formaldehyde when the films are coated which is a health concern in the industry.
  • Latent cross-linking functionality additionally can cause a loss of adhesive properties aged unapplied films and labels.
  • Additive cross linkers cause problems is use with adhesive batch-to-batch consistency, pot life, reactivity, and variation in adhesive perfomance. Fortuitously, latent cross-linking functionality and additive cross-linkers are not required of the novel adhesive composition.
  • Additional acids include, for example, butenic acids, e.g. crotonic acid, isocrotonic acid, and vinyl acetic acid; an acid from the fumaric acid series, e.g. fumaric acid, maleic acid, glutaconic acid, allyl malonic acid, and allyl succinic acid; and dicarboxylic acids, e.g. itaconic acid.
  • Lower alkyl-substituted (e.g. C 1 - C 4 alkyl group) acrylic acid e.g.
  • methacrylic acid additionally can find use in formulating the emulsion copolymer(s) of the present invention.
  • ratio of acrylamide to acrylic acid broadly ranges from about 1:10 to about 10:1 by weight with about 1:2 being optimum for acrylamide to acrylic acid. This ratio is believed to be important in providing removability characteristics with retention of good initial tack and peel values.
  • the emulsion copolymers(s) or interpolymer can contain styrene or another aromatic polymerizable monomer, vinyl chloride, vinylidene chloride, ethylene vinyl acetate, or other hydrophobic monomer.
  • Styrene can be present in an amount up to about 25% by weight and preferably about 5% by weight styrene is included in the monomer mixture that is subjected to emulsion copolymerization in accordance with the precepts of the present invention.
  • interpolymer of alkyl (meth)acrylate, acrylamide content, and unsaturated acid is used in formulating the novel adhesive composition, then such interpolymer is made by emulsion polymerization techniques. If a blend of copolymers with separate acrylamide and unsaturated acid is used in formulating the novel adhesive composition, then at least one of the copolymers is made by emulsion polymerization techniques, while the other copolymer can be made by emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or other technique [see generally, D.H. Solomon, The Chemistry of Organic Film Formers, Robert E. Krieger Publishing Company, Huntington, New York (1977)].
  • the interpenetrating polymer network can be based either on the acrylamide-containing copolymer or on the unsaturated acid-containing copolymer, though synthesis again is by emulsion polymerization. Details on synthesis of interpenetrating polymer network emulsions can be found in U.S. Patent No. 4,616,057 , the disclosure of which is expressly incorporated herein by reference.
  • the emulsion copolymer(s) or interpolymer can be made by a batch, semi batch or continuous process, though preferably a semi-batch process is employed. Despite the ability to meter a constant mixture of the monomers to the reaction vessel, the product emulsion copolymer evidences a two-stage morphology, as will be explored further below.
  • Emulsion polymerization in the aqueous continuous phase is conducted in conventional fashion, such as described by D.H. Solomon in The Chemistry of Organic Film Formers, pp 294-303, supra..
  • a conventional emulsifier e.g. sodium alkylaryl polyethoxy sulfonate or the like, is utilized during the emulsion polymerization reaction.
  • the polymerization preferably is run without a buffer at a pH of about 2-3 as determined by the decomposition of the persulfate catalyst (i.e. sulfonic acid generation). Since the pKa of acrylic acid is about 4, the pH of the emulsion reaction mixture should be very low, e.g. much less than 4, so that the acrylic acid copolymer does not ionize and thicken during the reaction.
  • the copolymer can be basif ⁇ ed (i.e. the pH raised with base above pH of reaction) to a pH of above 3, broadly 3-10, and preferably about 8-9.
  • Basification provides a self-thickening adhesive composition and has been determined to enable manufacturing reproduceability of the adhesive composition.
  • aqueous ammonia can be used to basify the composition, though other bases, e.g. various amines, imines, alkali metal and alkaline earth metal hydroxides, carbonates, etc., can be used as is necessary, desirable, or convenient.
  • the emulsion copolymer(s) or interpolymer need not contain any cross-linking monomers, copolymerizable emulsifiers, N-methylol acrylamides, or zwitterionic monomers.
  • These ingredients generally lower tack and initial peel values, thus reducing the strength and suitability of the adhesive contact, especially in high performance applications.
  • Latent cross-linking functionality additionally, can cause a loss of adhesive properties for aged unapplied films and labels and yellowing or discoloration of the adhesive.
  • such ingredients can be included in the emulsion copolymers(s) or interpolymer in minor amount (e.g. not more than about 15 wt-%), they are not necessary and desirably are avoided.
  • the next ingredient utilized in formulating the novel adhesive composition is a surfactant (preferably a phosphate ester surfactant) that should be present in a proportion of about 0.01% to 10% by dry weight of the emulsion copolymer(s) or interpolymer.
  • a surfactant preferably a phosphate ester surfactant
  • the phosphate ester surfactant serves a dual function in the adhesive composition. One function is to promote the removability of a label or other substrate coated with a cured residue of the adhesive composition. The second function is the ability of the phosphate surfactant to wet-out silicone release sheets which enhances coatability of such release sheets. Too much phosphate, however, tends to promote foaming of the adhesive composition which detracts from its use in commercial settings.
  • phosphate emulsifiers include, for example, ammonium, potassium or sodium salts of alkyl aryl polyethoxy phosphates, alkyl ethoxy phosphates, alkyl phosphates, alkyl polyethoxy phosphates, and the like, and even mixtures thereof.
  • the phosphate coester structure augments the removability and other performance characteristics.
  • Carboxyl and amide-containing acrylate polymers may be expected to contain interpolymer hydrogen bond interactions including COOH/CONH 2 , COOH/COOH, and CONH 2 /CONH 2 . These interpolymer associations are believed to contribute to the removable adhesive properties of the novel adhesive composition. Rapid viscosity increases with neutralization of the copolymer indicate a hydrophilic morphology with carboxylate-amide rich polymer segments occurring in the outer layers of the colloid polymer panicle. This relationship between polymer structure and performance also is supported by the observation that completion of the reaction at lower non-volatile (nv) solids in combination with consuming unreacting monomers results in a different performance profile for the copolymer.
  • nv non-volatile
  • Heat aged performance of different nv solids emulsion copolymerbased adhesive compositions suggest a polymer structure that develops during the polymerization and that this improves adhesive removability. It is believed that polymer hydrophilic morphology develops during the latter states of reaction to create a carboxylate-amide rich latex shell. This structure is best formed only under specific reaction conditions with specific acid-amide functional ratios.
  • Typical phosphate coester surfactants contain hydrophobic groups and a -
  • Phosphate hydrogen bond or electrostatic interaction is possible with carboxyl and amide polymer groups. Phosphate-polymer associations could form a colloid interpolymer network.
  • a postulated colloid polymer structure involves an acrylate polymer core surrounded by a carboxyl/amide rich polymer shell.
  • the surface of the latex is composed of the phosphate ester surfactant and the emulsion copolymer emulsifier.
  • the anionic groups of the surfactant and emulsifier support an electrical charged layer around the particle providing colloid stability. Ionization of polymer bound carboxylic acid at, e.g, pH 3-6, expands the outer layers of the latex particle, resulting in increased latex viscosity. Film formation is affected by the outer layer of structure of the colloid polymer during particle coalescence. The structural changes affect film adhesive properties. Polymer film structure is affected by phosphate coester hydrophobe structure and the extent of ionization of the carboxylic functionality. These interfacial phenomena result in specific structural networks in the coalesced latex adhesive film. This film structure, in turn, yields special performance properties (i.e. low peel build on aging) having pronounced effects on peel and shear values.
  • special performance properties i.e. low peel build on aging
  • surfactants e.g. polyoxyethylenepolyoxypropylene block copolymers, alkanol amides, amine oxides, amines, ethoxylated amines, imidazolines, etc.
  • surfactants e.g. polyoxyethylenepolyoxypropylene block copolymers, alkanol amides, amine oxides, amines, ethoxylated amines, imidazolines, etc.
  • surfactants e.g. polyoxyethylenepolyoxypropylene block copolymers, alkanol amides, amine oxides, amines, ethoxylated amines, imidazolines, etc.
  • the adhesive is removable from a variety of substrates cleanly, i.e. no visible residue, including, for example, metals (e.g., stainless steel, aluminum, etc.) and plastics (e.g., polyethylene, polypropylene, polystyrene, polycarbonate, ABS resin, PVC resin, etc.)
  • metals e.g., stainless steel, aluminum, etc.
  • plastics e.g., polyethylene, polypropylene, polystyrene, polycarbonate, ABS resin, PVC resin, etc.
  • Build on aging generally is less than 100% when the applied adhesive is maintained at 70o C for three weeks and less than 50% when aged at room temperature for three weeks.
  • a viscosity of about 1,000-10,000 centipoises is compatible with existing equipment and handling procedures, and preferably a viscosity of about 2,000-4,000 centipoises is maintained.
  • the adhesive composition may be incorporated into the adhesive composition, including, for example, wetting agents, pigments, opacifying agents, anti-foam agents, and the like and mixtures thereof.
  • the adhesives may be applied to one or both sides of the film face stock in a conventional manner, for example, by spraying, knife coating, roller coating, casting, drum coating, dipping, and the like. Indirect application using a transfer process with silicon release paper also can be used. After the adhesive has been applied, the coated film face stock is dried conventionally.
  • Emulsion polymerizations were conducted in a 3-liter Pyrex brand glass reactor equipped with water bath, mechanical stirrer, N 2 atmosphere, condenser, thermocouple, and pumps for monomer and initiator feeds.
  • a monomer emulsion was prepared with 800 g total monomer (the amount used in all preparations), deionized water (196.3 g), and Triton X-200 emulsifier.
  • the reactor was charged with deionized water (230 g) and the initial monomer emulsion (21.3 g, 2.0%) and warmed to 76° C initiation temperature with stirring. Catalyst #1 and 2 wt-% of catalyst #2 were used to initiate the reaction.
  • the remaining monomer emulsion and potassium persulfate solution were delayed fed at a constant rate over a 3 hour time period while maintaining a reaction temperature of 80° C.
  • the reaction temperature was maintained for an additional 30 minutes after the feed ended.
  • the reaction temperature then was lowered to 50o C and chaser catalysts, tert-butyl hydroperoxide (70%) aqueous solution (0.4 g in 10 ml) and sodium formaldehyde sulfoxylate aqueous solution (0.4 g in 10 ml), were added to reduce residual monomer content.
  • the reaction temperature of 50o C was maintained for 30 minutes and then lowered to 35* C, and a biostat (Kathon LX, 1.5%, 2 g) was added.
  • Emulsion copolymer 4886-155 had a solids content of 61%, a pH of 2.6, and viscosity of 3,040 cps (Brookfield RV spindle #4 at 20 ipm).
  • Polyken Tack Test This test is conducted on a Polyken, Jr. Probe Tack Tester (Polyken is a trademark of the Kendall Company) supplied by Testing Machines, Inc. (Amityville, N.Y.) under the following conditions:
  • Probe 304 SS. 0.5 cm. diameter probe polished to 4/0 emery paper finish.
  • Emulsion copolymers were synthesized by the typical emulsion polymerization procedure detailed above from the following monomer mixtures.
  • the base polymer system composed of butyl acrylate/styrene/acrylic acid (4886-116) displayed tack, shear, and initial peel values in the general range of interest for removable performance. Heat aged peel values, however, show adhesive build to permanent peel levels making an adhesive manufactured from only the emulsion copolymer unsuitable. A lower molecular weight version of the base polymer system (4886-118) was included for comparison and the adhesive made therewith displayed similar characteristics.
  • the remaining polymer systems were generated to vary bulk polymer composition, cross-link density, and internal steric hindrance. For example, when ⁇ -methyl styrene was substituted for styrene (4886-181), an improvement in heat aged peel value was obtained. However, initial tack was depressed below acceptable levels. Divinyl benzene was used in polymer 4886-185 to increase cross- link density; however, a loss of initial tack value also was evidenced. Styrene levels were evaluated at 0-4.5 wt-parts per 100 parts copolymer with the 4.5 wt-part level showing optimum performance characteristics in this series of tests.
  • Triton GR-5M 50% active
  • Silwet 7001 (100% actives), organo silicone surfactant, Union Carbide Corp.
  • D denotes delamination or transfer from Mylar face stock to the stainless steel.
  • Adhesive 4817-193 containing N-methylol a ⁇ ylamide displayed good initial removable performance, though heat aging results showed excessive peel build with values over 3 lbs/in off stainless steel.
  • Emulsion 4886-155, containing a 2:1 acrylic acidracrylamide ratio displayed good initial removable performance.
  • Applied heat aging results showed lower peel build with values under 3 lbs/in off stainless steel.
  • Heat aged free film showed good retention of tack and peel characteristics.
  • the version compounded with Sulfonyl 104-E surfactant offered the best performance profile.
  • Adhesive No. 4886-189 containing a 2.5:1.0 acrylic acidracrylamide ratio, displayed similar characteristics with higher shear and peel values compared to the 2:1 acid/amide version.
  • Adhesives 4924-4 and 4924-6 were synthesized with additional styrene and methyl methacrylate, respectively, in an attempt to further improve applied heat aging characteristics.
  • the Pluronic L-121 surfactant compounded versions of these systems displayed the best heat aged peel characteristics in the series.
  • the methyl methacrylate modification compounded with Pluronic L-121 (4924-6) demonstrated clean removability and meets the high performance profile ideally possessed by the adhesives of the present invention.
  • Adhesives 4886-155 and 189 displayed clean removability.
  • Adhesive 4886- 155 exhibited the highest tack retention values and the best retention of adhesive performance yielding a 50% reduction in peel values for heat aged film stock on 24 hr dwell on stainless steel. No peel build or delamination was observed upon applied heat aging. Overall performance was judged to be the best for these adhesives tested. It should be noted that each of these experimental adhesives conform to FDA, 21 CFR Ch. 1, ⁇ 175.105 making them suitable for indirect contact with food.
  • surfactants generally are reported to be mixtures of mono and coester phosphates prepared from phosphorous pentoxide and various aliphatic and aromatic alcohols and ethoxylates. Commercially, they typically are supplied as free acids or partially neutralized sodium or potassium phosphates.
  • the candidate phosphate surfactants evaluated are detailed below.
  • Example 5 Five of the phosphate surfactants evaluated in Example 5 were selected for further evaluation: Strodex PK-90, Strodex SEK-50, Triton H66, Gafac RD-510, and Emphos CS-141. Each of these surfactants exhibited low adhesion build characteristics in the initial performance screen evaluation. In this example, these surfactants were compounded with four different basification reagents and submitted to testing as described above. The following results were recorded.
  • AMP-95 is 2-amino-2-methylpropanol, Angus Chemical Company.
  • CORCAT P-12 is polyethyleneimine, Virginia Chemical Company. All heat aged films yellowed.
  • Strodex surfactants evaluated in Example 6 were further evaluated with ammonia (14 wt-% concentration) and potassium hydroxide (20 wt-% concentration) basification.
  • adhesive films were dried for different periods in a forced air oven to determine the effect of residual volatile components on adhesive performance.
  • the heat aged data was determined after subjecting the samples to a temperature of 70o C for 72 hours. The following data was recorded.
  • Emulsion polymerizations of n-butyl acrylate/styrene copolymers ranging from 0.0 to 20.0 monomer wt-% acrylamide and/or acrylic acid are summarized in Table 11 below. Polymerizations conducted with 0.0 to 3.0 wt-% acrylamide and 0.0 to 2.0 wt-% acrylic acid were reacted to a nominal 60 wt-% polymer content. Those polymerizations conducted with higher levels of acrylamide and acrylic acid were reacted with abbreviated delayed feeds to a nominal 40 wt-% polymer content to prevent extreme viscosity increases in the later stages of emulsion polymerization.
  • the standard acrylamide/acrylic acid composition of 1.0/2.0 wt-% (4886-155 of Table 1) was prepared at both 60% nv solids (5042-154) and 40% nv solids (5042-158) to determine the effect of lower polymerization solids content on the physical and adhesive characteristics of these emulsion polymer systems and to provide a lower acrylamide/acrylic acid composition reference at 40 wt-% reacted polymer solids.
  • Carboxylic acid-bearing ethylenically-unsaturated monomers were evaluated at equivalent acid stoichiometries in order to determine the effect of carboxylic acid structure on polymer adhesive performance.
  • Copolymerizations of the preferred 4886-155 copolymer were conducted with methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and ⁇ -carboxyethyl acrylate. These emulsion polymerizations are summarized in Table 14 below.
  • Preferred emulsion copolymer 4886-155 is prepared by semi-batch emulsion polymerization with a uniform monomer feed containing n-butyl acrylate/styrene/ acrylic acid/ acrylamide (92.5/4.5/2.0/1.0).
  • the data presented above demonstrates that the acrylic acid and acrylamide polymer content are important structural parameters affecting adhesive performance when the carboxylic acid and and amide functionalities are copolymerized.
  • This example extends the use of carboxylic and amide functional polymers in removable emulsion pressure sensitive adhesives to include polymer architectures other than simple copolymerizations of uniform monomer mixtures.
  • Emulsion polymer physical blend of a carboxylated acrylic latex and an amide functional acrylic latex 1.
  • Interpenetrating emulsion polymers were prepared using equal weights of seed emulsion (5121-8 & 5121-10) dry polymer and interpenetrating second stage monomers. Initial IPN reaction conditions were adjusted to represent the continuous feed reaction (4886-155, 5042-154, APS-1184) at 50% delayed monomer feed reacted.
  • the monomer emulsion was added to the first stage emulsion polymer, mixed for 30 minutes, and reacted in two portions.
  • the emulsions were all compounded with phosphate coester surfactant and basified with aqueous ammonia to afford pressure sensitive adhesives. This compounding is summarized in Table 18 below.
  • Adhesive eveluations were conducted with 1.0 ⁇ 0.1 mil dry adhesive films transfer coated from H.P. Smith 8024 release liner to 2 mil polyester film. All testing was conducted off stainless steel.
  • Peel tests were conducted under PSTC-1 conditions. Heat aging was conducted at 70oC (158oF) in forced air ovens for one week. Data for films heat aged on liner prior to adhesive testing is in parenthesis. All heat aged films and laminates were re-equilibrated to 70oF 50% relative humidity for one day prior to testing.
  • Polymer architecture 1 is the basis for the work reported in the previous examples. Adhesives prepared from this polymer system with copolymerization of 1 wt-% acrylamide and 2 wt-% acrylic acid typically exhibit 0.5 to 1.0 lbs/in of initial peel, building to about 1.5 lbs/in of peel after aging at 70o C. Loop tacks are about 1.0 lbs/in. This is the performance reference for the other polymers.
  • the emulsion polymer blend adhesive exhibited the higher initial peel values of the carboxylated latex and the lower heat-aged peel build of the acrylamide latex. These results indicate higher performing water-borne acrylic emulsion pressure sensitive adhesives can be prepared with latex blends. Also, latex blend ratios may provide specific control over removable adhesive performance. This latter feature would permit greater formulation latitude in developing specialty adhesives.
  • a carboxylated acrylate emulsion copolymer was compounded with a polyacrylamide solution polymer to afford adhesive 5121-17.
  • This adhesive displayed similar initial peel values, but lower peel values after heat aging on liner compared to the carboxylated acrylate emulsion adhesive 5042-184C.
  • An acrylamide acrylate emulsion copolymer was compounded with a polyacrylic acid ammonium salt solution to provide ahesive 5121-16.
  • This adhesive displayed high initial peel values and similar applied heat aged peel values compared to the acrylamide acrylate emulsion copolymer adhesive 5042-184D.
  • the use of the polyacrylic acid solution polymer was found to enhance the peel performance profile of an acylamide acrylate emulsion copolymer adhesive.
  • IPN Interpenetrating Polymer Networks
  • IPN systems Two IPN systems were prepared. An acrylamide-containing IPN was formed in a carboxylated acrylate emulsion polymer (4846-82 and 5121-48A, respectively), and a carboxylated IPN was formed in an acrylamide-containing acrylate emulsion polymer (4846-84 and 5121-48B, respectively). An increase in mean particle size during the IPN reactions, conversion, and performance similarities in alternate IPN first and second stage polymerization arrangements is evidence for actual IPN formation.
  • IPN emulsion adhesives listed in Table 19 displayed very similar adhesive performance, showing good initial peel and tack values, and low peel build upon applied heat aging.
  • Adhesive 4121-48B, an acrylic acid IPN displayed the best peel profile in these comparisons with 30 minutes dwell of 14 oz, 24 hour dwell of 18 oz, one week dwell values of 19 oz, and one week dwell at elevated temperature of 22 oz.
  • Adhesive performance properties recorded are set forth in Table 22.
  • the N-alkyl acrylamides exhibited adhesive peel performance profiles that distinguish N-ethylacrylamide with a superior removable performance.
  • the N- ethylacrylamide copolymer exhibited negligible adhesive peel build at ambient temperature and much less peel build after elevated temperature aging compared to acrylamide and the higher N-alkyl substituted acrylamides, viz, N-octylacrylamide and N-tert -butylacrylamide.
  • N,N-methylenebisacrylamide was employed as an example of a polyfunctional monomer.
  • both amide functionality and multiple polymerization sites for crosslinking reactions are present in the monomer.
  • the resulting copolymer adhesive displayed very low initial peel values and applied aging peel values. This peel profile could have value as an ultra removable pressure sensitive adhesive that remains ultra removable after applied heat-aging cycles.
  • Emulsion polymerization 5042-154 is the standard reaction with 9.0 (phm) Triton X-200 surfactant upon which variations were made.
  • surfactant and nonionic (Igepal CA 897) surfactant.
  • Acrylate esters were varied from ethyl acrylate C 5 monomer to stearyl acrylate C 21 monomer and behenyl methacrylate C 26 monomer.
  • An example of a monomer containing cyclic aliphatic ester also was demonstrated with cyclohexyl methacrylate.
  • Non-acrylate monomers dioctyl maleate, vinylidene chloride, and vinyl versatate also were copolymerized. An emulsion polymerization with n-butyl vinyl ether afforded poor monomer conversion and , therefore, was not evaluated.
  • Adhesive performance results recorded are summarized in Table 26 for the untackified formulations and in Table 27 for the tackified formulations.
  • Adhesive Cohesive
  • D Delamination
  • N Non-adhesive
  • G ghosting
  • Z Zippering
  • Y Yellowed.
  • Adhesive evaluations were conducted with 1.0 ⁇ 0.1 mil dry adhesive films transfer coated from H.P. Smith 8024 release liner to 2 mil polyester film.
  • Adhesive results obtained for the n-butyl acrylate emulsion polymer prepared with the nonionic surfactant (5121-126A) indicate substitution of the anionic surfactant (Triton X-200) with a nonionic surfactant (Igepal CA 897) detracted from the adhesive performance as noted by delamination after applied heat aging.
  • Pressure sensitive adhesives were prepared with acrylate and methacrylate esters ranging from ethyl acrylate C 5 to behenyl methacrylate C 26 . These results are indicative that n-butyl and 2-ethylhexyl acrylate esters exhibit the most utility in the preparation of high performance removable pressure sensitive adhesives.
  • Higher acrylate esters may have use for modification of performance.
  • the stearyl acrylate adhesive (5121-133B) exhibited no peel build upon applied aging in this testing.
  • the vinylidene chloride/n-butyl acrylate copolymer adhesive (5121-126E) displayed an interesting peel profile that could have some utility for a repositionable adhesive. Although the adhesive discolored, it removed cleanly after applied heat aging. EXAMPLE 13
  • Adhesive formulations 4987-77 (copolymer emulsion 4886-155 of Example 1, Strodex SEK-50 surfactant, and aqueous ammonia , see Table 9, Example 6), and 4987-78 (copolymer emulsion 4886-155, Gafac RD-510 surfactant, and aqueous ammonia , see Table 9, Example 6), were coated on super calendered kraft paper release liner at 1.0 and 0.6 mil dry thickness.
  • Label face stocks included unprimed 50 lb semi-gloss litho paper, 2 mil polyester, 3.5 mil vinyl, and a coated thermal paper.
  • coated label stocks were evaluated on a variety of plastic (i.e., polyethylene, polypropylene, polystyrene, polyacrylate, ABS, PVC, and polycarbonate), metal (i.e., aluminum and stainless steel), and glass substrates.
  • plastic i.e., polyethylene, polypropylene, polystyrene, polyacrylate, ABS, PVC, and polycarbonate
  • metal i.e., aluminum and stainless steel
  • the plastic substrates possess different surface energies ranging from relative low values for polyolefins to higher values for engineering plastics such as polyvinyl chloride (PVC) and polycarbonate.
  • High performance removable characteristics for an adhesive are determined, in part, by the ability of the adhesive to anchor well to a low surface energy polyolefin surface and also remove cleanly from high surface energy plastics like polycarbonate.
  • Adhesive 4987-77 displayed clean removability from all surfaces with excellent anchorage to polyester and vinyl film face stocks. Peel values vary from 0.1 lbs/in for polyethylene to over 3 lbs/in for higher surface energy plastics, e.g. PVC.
  • Adhesive 4987-78 displayed lower peel values than did adhesive C4987-77 with values ranging from about 1 oz/in on polyethylene to about 3 lbs/in from higher surface energy plastics. Face stock anchorage was found to be very good with only two delaminations noted from PVC and polycarbonate substrates after applied heat aging cycles.
  • Heat aging of laminated film face stock on liner was conducted in order to compare adhesive aging characteristics and vinyl plasticizer migration effects.
  • Aged vinyl films all showed loss of peel adhesion and Polyken tack compared to aged polyester films samples, which loss is attributed to plasticizer migration.
  • Adhesive 4987-78 demonstrated the best paper face stock performance based on the data in Table 33 as noted by the polypropylene, glass, aluminum, and stainless steel comparisons.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Composition d'adhésif autocollant acrylique à émulsion aqueuse présentant d'excellentes caractéristiques dans des applications à haute performance. La composition d'adhésif de l'invention comprend dans de l'eau (a) un copolymère d'un monomère de C4-C18 alkyle (méth)acrylate et entre environ 0,1 % et 5 % de (poly)acrylamide N substitué ou non substitué; (b) un copolymère d'un monomère de C4-C18 alkyle (méth)acrylate et entre environ 0,2 % et 10 % d'un acide carboxylique à insaturation d'éthylène; et (c) un tensio-actif comprenant de préférence entre environ 0,01 % et 10 % en poids sec desdits copolymères d'un tensio-actif d'ester de phosphate. Lesdits copolymères (a) et (b) sont choisis parmi: (i) un mélange de copolymères (a) et (b), dont au moins un est un copolymère d'émulsion; (ii) un interpolymère de copolymères (a) et (b) où ledit monomère d'alkyle (méth)acrylate de copolymères (a) et (b) sont identiques; et (iii) un réseau polymère interpénétrant de copolymères (a) et (b). De préférence, le rapport entre l'acrylamide et l'acide insaturé dans le copolymère s'établit entre environ 1:10 et 10:1 en poids. Le ou les copolymères d'émulsion comprennent de préférence jusqu'à 25 % en poids de styrène ou d'un ou d'autres monomères aromatiques.
PCT/US1991/003750 1990-05-29 1991-05-24 Composition d'adhesif en latex autocollant a emulsion acrylique aqueuse WO1991018739A1 (fr)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5283092A (en) * 1991-12-31 1994-02-01 Minnesota Mining And Manufacturing Company Imaging manifold
DE4231607A1 (de) * 1992-09-15 1994-03-17 Neschen Hans Gmbh & Co Kg Druckempfindlicher Haftkleber und damit hergestellte, manuell einreißbare Haftklebebänder für die Stickerei- und Textilindustrie
EP0593231A1 (fr) * 1992-10-15 1994-04-20 Rohm And Haas Company Procédé pour améliorer les adhésifs sensibles à la pression
US5552451A (en) * 1991-12-31 1996-09-03 Minnesota Mining And Manufacturing Company Removable, low melt viscosity acrylic pressure sensitive adhesives
US5889118A (en) * 1996-06-03 1999-03-30 Minnesota Mining And Manufacturing Company Thermomorphic "smart" pressure sensitive adhesives
WO2000036039A3 (fr) * 1998-12-15 2000-10-19 Avery Dennison Corp Constructions et adhesifs pour etiquettes presentant une accumulation reduite de residus adhesifs sur des imprimantes
EP1198502A4 (fr) * 1999-04-12 2002-11-06 Ashland Inc Adhesifs sensibles a la pression
US6547887B1 (en) 1998-12-15 2003-04-15 Avery Dennison Corporation Multilayer pressure-sensitive adhesive label constructions
WO2008003758A1 (fr) * 2006-07-07 2008-01-10 Cytec Surface Specialties, S.A. Polymère, composition et procédé
CN102492383A (zh) * 2011-11-18 2012-06-13 合肥工业大学 一种聚烯烃薄膜复合用核壳水性聚氨酯-丙烯酸酯复合乳液胶黏剂的制备方法
CN108203488A (zh) * 2016-12-20 2018-06-26 中国制浆造纸研究院有限公司 纤维密封材料用丙烯酸乳液及其合成方法
WO2018184852A1 (fr) 2017-04-07 2018-10-11 Arkema France Dispersions aqueuses à stabilité élevée pour adhésifs et produits d'étanchéité
CN111171731A (zh) * 2018-11-09 2020-05-19 3M创新有限公司 双网络压敏胶组合物以及包含其的压敏胶制品
EP3974490A1 (fr) * 2020-09-29 2022-03-30 UPM Raflatac Oy Étiquette sans doublure
EP4265699A4 (fr) * 2020-12-15 2024-06-19 Bridgestone Corporation Composition adhésive, composite caoutchouc-câblé de fibres organiques et pneu

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Publication number Priority date Publication date Assignee Title
US4351875A (en) * 1978-09-25 1982-09-28 Rohm And Haas Company Heteropolymer acrylic latices and textiles treated therewith
US4540739A (en) * 1984-04-10 1985-09-10 Polysar Limited Adhesive polymer latex
US4983656A (en) * 1988-03-14 1991-01-08 Japan Synthetic Rubber Co., Ltd. Aqueous pressure-sensitive adhesive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4351875A (en) * 1978-09-25 1982-09-28 Rohm And Haas Company Heteropolymer acrylic latices and textiles treated therewith
US4540739A (en) * 1984-04-10 1985-09-10 Polysar Limited Adhesive polymer latex
US4983656A (en) * 1988-03-14 1991-01-08 Japan Synthetic Rubber Co., Ltd. Aqueous pressure-sensitive adhesive

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5283092A (en) * 1991-12-31 1994-02-01 Minnesota Mining And Manufacturing Company Imaging manifold
US5552451A (en) * 1991-12-31 1996-09-03 Minnesota Mining And Manufacturing Company Removable, low melt viscosity acrylic pressure sensitive adhesives
US5648425A (en) * 1991-12-31 1997-07-15 Minnesota Mining And Manufacturing Company Removeable, low melt viscosity acrylic pressure sensitive adhesives
DE4231607A1 (de) * 1992-09-15 1994-03-17 Neschen Hans Gmbh & Co Kg Druckempfindlicher Haftkleber und damit hergestellte, manuell einreißbare Haftklebebänder für die Stickerei- und Textilindustrie
EP0593231A1 (fr) * 1992-10-15 1994-04-20 Rohm And Haas Company Procédé pour améliorer les adhésifs sensibles à la pression
US5889118A (en) * 1996-06-03 1999-03-30 Minnesota Mining And Manufacturing Company Thermomorphic "smart" pressure sensitive adhesives
US6060159A (en) * 1996-06-03 2000-05-09 Delgado; Joaquin Thermomorphic "smart" pressure sensitive adhesives
US6547887B1 (en) 1998-12-15 2003-04-15 Avery Dennison Corporation Multilayer pressure-sensitive adhesive label constructions
WO2000036039A3 (fr) * 1998-12-15 2000-10-19 Avery Dennison Corp Constructions et adhesifs pour etiquettes presentant une accumulation reduite de residus adhesifs sur des imprimantes
US6423392B1 (en) 1998-12-15 2002-07-23 Avery Dennison Corporation Label adhesives and constructions exhibiting low adhesive residue in printers
EP1198502A4 (fr) * 1999-04-12 2002-11-06 Ashland Inc Adhesifs sensibles a la pression
WO2008003758A1 (fr) * 2006-07-07 2008-01-10 Cytec Surface Specialties, S.A. Polymère, composition et procédé
CN102492383A (zh) * 2011-11-18 2012-06-13 合肥工业大学 一种聚烯烃薄膜复合用核壳水性聚氨酯-丙烯酸酯复合乳液胶黏剂的制备方法
CN108203488B (zh) * 2016-12-20 2020-12-15 中国制浆造纸研究院有限公司 纤维密封材料用丙烯酸乳液及其合成方法
CN108203488A (zh) * 2016-12-20 2018-06-26 中国制浆造纸研究院有限公司 纤维密封材料用丙烯酸乳液及其合成方法
WO2018184852A1 (fr) 2017-04-07 2018-10-11 Arkema France Dispersions aqueuses à stabilité élevée pour adhésifs et produits d'étanchéité
EP3607018B1 (fr) * 2017-04-07 2022-11-09 Arkema France Dispersions aqueuses à stabilité élevée pour adhésifs et matériaux d'étanchéité
CN111171731A (zh) * 2018-11-09 2020-05-19 3M创新有限公司 双网络压敏胶组合物以及包含其的压敏胶制品
CN111171731B (zh) * 2018-11-09 2021-12-03 3M创新有限公司 双网络压敏胶组合物以及包含其的压敏胶制品
EP3974490A1 (fr) * 2020-09-29 2022-03-30 UPM Raflatac Oy Étiquette sans doublure
US12269237B2 (en) 2020-09-29 2025-04-08 Upm Raflatac Oy Linerless label
EP4265699A4 (fr) * 2020-12-15 2024-06-19 Bridgestone Corporation Composition adhésive, composite caoutchouc-câblé de fibres organiques et pneu

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