WO2001062817A1 - Polyurethane-based pressure-sensitive adhesives, systems for such adhesives, articles therefrom, and methods of making - Google Patents

Polyurethane-based pressure-sensitive adhesives, systems for such adhesives, articles therefrom, and methods of making Download PDF

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Publication number
WO2001062817A1
WO2001062817A1 PCT/US2000/015448 US0015448W WO0162817A1 WO 2001062817 A1 WO2001062817 A1 WO 2001062817A1 US 0015448 W US0015448 W US 0015448W WO 0162817 A1 WO0162817 A1 WO 0162817A1
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Prior art keywords
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polyurethane
parts
polyol
sensitive adhesive
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French (fr)
Inventor
Lawrence M. Clemens
Richard G. Hansen
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to DE60033059T priority Critical patent/DE60033059T2/de
Priority to AU2000255961A priority patent/AU2000255961A1/en
Priority to EP00941224A priority patent/EP1257590B1/en
Priority to JP2001562596A priority patent/JP2003524041A/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/40—Compositions for pressure-sensitive adhesives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/905—Polymer prepared from isocyanate reactant has adhesive property
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer

Definitions

  • the present invention relates generally to polyurethane-based pressure-sensitive adhesives, systems (e.g., 100% solids, waterborne, and solventborne) for such adhesives, articles therefrom, and methods of their preparation.
  • systems e.g., 100% solids, waterborne, and solventborne
  • polyurethane-based adhesives A wide variety of polyurethane-based adhesives are known. For example, see U.S. Patent Number 5,910,536 (Kydonieus et al.), which describes a particular type of polyurethane-based adhesive - a pressure-sensitive poly[urethane-(meth)acrylate]-based adhesive.
  • the adhesives therein are prepared from 100% solids (i.e., essentially solvent- free and water-free) systems.
  • polyurethane-based adhesives in both solventborne (i.e., those using mostly organic solvents as a solvating medium) and waterborne (i.e., those using mostly water as a dispersing medium) systems. These adhesive systems are applied to a substrate in the form of a solution or dispersion, respectively. Generally, whether the adhesive system is solventborne or waterborne, it must be coated onto a desired substrate and dried to remove solvating or dispersing medium (i.e., organic solvent or water, respectively) in order to form an adhesive coating.
  • solventborne i.e., those using mostly organic solvents as a solvating medium
  • waterborne i.e., those using mostly water as a dispersing medium
  • Reactive polyurethane-based adhesive systems have been described in the literature, but coatable mixtures prepared from such systems generally have a limited useful life.
  • Examples of reactive polyurethane-based adhesive systems include those described in U.S. Patent Numbers 3,246,049 (Webber); 3,437,622 (Dahl); 3,718,712 (Tushaus); 3,879,248 (Kest); 3,925,283 (Dahl); 4,087,392 (Hart ann); 5,102,714 (Mobley et al.); 5,486,570 (St. Clair); 5,591,820 (Kydonieus); and 5,714,543 (Shah). Further descriptions include those in GB 1,113,925 (Weller); GB 1,216,672 (Grindley); and PCT Publication Number WO 97/22,642 (Chang).
  • the parts of a reactive polyurethane-based adhesive system include an isocyanate-containing part (i.e., an isocyanate-terminated polyurethane prepolymer) and a chain extending part. Due to the presence of isocyanate-functional groups on the polyurethane prepolymer, storage of that part must be carefully controlled so that moisture does not react with the isocyanate-functional groups, rendering the composition non-reactive and, thus, unusable. Sensitivity to moisture can also lead to variations in properties of these coated adhesives due to, for example, local variations in ambient temperature and humidity when the adhesive is coated. Furthermore, special handling procedures may be required for the multi-part system, especially by those that are sensitive to isocyanate chemicals.
  • non-reactive systems are preferable over reactive systems from at least a storage stability standpoint and ease of use standpoint. Premixing of components and special storage considerations for the components are not required in non-reactive systems.
  • non-reactive, solventborne or waterborne system When using a non-reactive, solventborne or waterborne system, to form an adhesive coating on a substrate, one merely applies the composition, which contains a fully reacted polymer in the form of a solution or dispersion, to the substrate and then dries the solvating or dispersing medium to form the adhesive coating.
  • non-reactive systems may require the addition of external emulsifiers or cationic stabilization agents to maintain stability of the solution or dispersion prior to coating to form the adhesive.
  • PSA compositions are a unique subset of adhesives well known to those of ordinary skill in the art to possess properties including the following: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength to be removed cleanly from the adherend.
  • Materials that have been found to function well as PSAs are polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power.
  • PCT Publication Number WO 98/31,760 (Dow Chemical Company) describes a polyurethane PSA-forming latex composition comprising a polyurethane PSA-forming material, wherein a polyurethane PSA is obtained by dehydrating the PSA-forming latex composition.
  • the process for preparing the polyurethane PSA includes emulsifying a polyurethane prepolymer in water, chemically reacting the prepolymer to react substantially all unreacted functional groups, and dehydrating the aqueous dispersion.
  • the polyurethane prepolymer is formed from reactants including polyisocyanates and active hydrogen compounds, such as polyols. It is stated that polyols can be employed individually or in mixtures as di-, or a combination thereof, polyoxyalkylene polyols. Suitable active hydrogen compounds are polyols having a molecular weight less than 6,000.
  • polyurethane-based chemistries for preparing PSAs are desirable. It would be particularly desirable to provide polyurethane-based PSAs that can be tailored to have a wide range of peel adhesion and shear strength properties.
  • Polyurethane-based pressure-sensitive adhesives (PSAs) of the invention comprise the reaction product of: a polyol component comprising at least one diol having a weight average molecular weight of at least about 2,000, wherein the at least one diol comprises less than about 8 weight % monols; an isocyanate-functional component an optional reactive emulsifying compound; and an optional chain extending aaggeenntt.
  • PSAs can be prepared from 100% solids, waterborne or solventborne systems.
  • the PSAs can be prepared from poly(urethane-urea) dispersions.
  • a polyurethane-based PSA dispersion of the invention comprises the reaction product of: a polyol component comprising at least one diol having a weight average molecular weight of at least about 2,000, wherein the at least one diol comprises less than about 8 weight % monols; an isocyanate-functional component; an optional reactive emulsifying compound; and an optional chain extending agent, wherein the reaction product is dispersed in a dispersing medium.
  • a polyurethane- based PSA solution of the invention comprises the reaction product of: a polyol component comprising at least one diol having a weight average molecular weight of at least about 2,000, wherein the at least one diol comprises less than about 8 weight % monols; an isocyanate-functional component; an optional reactive emulsifying compound; and an optional chain extending agent, wherein the reaction product is solvated in a solvating medium.
  • the polyol component comprises at least one polyoxyalkylene polyol.
  • each polyol in the polyol component is a diol.
  • the at least one diol comprises a diol having a ratio of diol molecular weight to weight % monol of at least about 800, or still further, at least about 1,000, or even further, at least about 1,500.
  • the polyol component comprises a first polyol having a weight average molecular weight of less than 2,000 and a second polyol having a weight average molecular weight of 2,000 or more.
  • the first polyol has a weight average molecular weight of less than about 1,800.
  • the first polyol has a weight average molecular weight of less than about 1,000.
  • the second polyol has a weight average molecular weight of greater than about 2,500. In even further embodiments, the second polyol has a weight average molecular weight of greater than about 6,000.
  • the weight average molecular weights of the first and second polyols differ by at least about 500. In even further embodiments, the weight average molecular weights of the first and second isocyanate-reactive materials differ by at least about 2,500.
  • the second polyol comprises a majority of the polyol component based on total weight of the polyol component.
  • the first polyol comprises about 1 to about 40 percent by weight of the polyol component and the second polyol comprises about 60 to about 99 percent by weight of the polyol component.
  • the first polyol comprises about 5 to about 25 percent by weight of the polyol component and the second polyol comprises about 75 to about 95 percent by weight of the polyol component.
  • the isocyanate-functional component comprises a diisocyanate.
  • the reactive emulsifying compound comprises at least about 0.5% by weight of the total reactants.
  • the polyurethane- based PSA further comprises the reaction product of a chain extending agent.
  • PSAs of the invention may be at least partially coated on a substrate.
  • PSAs of the invention are useful in tapes.
  • the tapes comprise a backing having a first and second side and the PSA coated on at least a portion of the first side of the backing and, optionally, on at least a portion of the second side of the backing.
  • a method of preparing the polyurethane-based PSAs of the invention comprises the, not necessarily sequential, steps of: providing a polyol component comprising at least one diol having a weight average molecular weight of at least about 2,000 wherein the at least one diol comprises less than about 8 weight % monols; providing an isocyanate-functional component; optionally providing a reactive emulsifying compound; allowing the polyol component, the isocyanate-functional component, and the optional reactive emulsifying compound to react to form a polyurethane prepolymer; and chain extending the polyurethane prepolymer.
  • the method can further comprise the step of dispersing the polyurethane prepolymer in a dispersing medium.
  • the method can further comprise the step of drying the dispersing medium to form a coating of the polyurethane-based PSA.
  • PSAs Pressure-sensitive adhesives of the invention are polyurethane-based.
  • polyurethane as used herein includes polymers containing urethane (also known as carbamate) linkages, urea linkages, or combinations thereof (i.e., in the case of poly(urethane-urea)s).
  • polyurethane-based PSAs of the invention contain at least urethane linkages and, optionally, urea linkages.
  • PSAs of the invention are based on polymers where the backbone has at least 80% urethane and/or urea repeat linkages formed during the polymerization process, such as the polymerization processes described below.
  • the polyurethane-based polymers are formed from prepolymers that are preferably terminated by isocyanate groups. Then, further reactants used to form the PSAs from the prepolymers are selected such that no more than about 20%, preferably no more than about 10%, more preferably no more than about 5%, and preferably none of the repeat linkages between polymeric segments formed in the polymeric backbone during polymerization are other than urethane and urea linkages.
  • PSAs of the invention are preferably prepared from systems that are essentially non-reactive.
  • polyurethane-based PSA systems of the invention are preferably storage-stable.
  • Storage-stable PSA systems are those compositions that can be coated on a substrate to form a continuous film at any time after the composition is formed up until the shelf life of the material has expired.
  • the shelf life of the material is at least three days, more preferably at least about one month, even more preferably at least about six months, and most preferably at least about one year.
  • PSAs of the present invention may be derived from 100% solids, solventborne or waterborne systems.
  • Environmental and regulatory demands are prompting manufacturers of adhesives to move more rapidly from solventborne systems to waterborne systems.
  • water is less costly and more environmental friendly.
  • flammability and combustibility of waterborne systems is reduced as compared to solventborne systems.
  • the polyurethane-based PSAs of the invention are derived from waterborne systems, using essentially only water as the dispersing medium.
  • Dispersions of the invention are prepared by reacting components, including at least one isocyanate-reactive (e.g., hydroxy-functional, such as polyol) component, at least one isocyanate-functional (e.g., polyisocyanate) component, and, optionally, at least one reactive emulsifying compound, to form an isocyanate-terminated polyurethane prepolymer.
  • the polyurethane prepolymer is then dispersed, and chain-extended, in a dispersing medium to form polyurethane-based dispersions of the invention.
  • hydrocarbon groups may include one or more heteroatoms (e.g., oxygen, nitrogen, sulfur, or halogen atoms), as well as functional groups (e.g., oxime, ester, carbonate, amide, ether, urethane, urea, carbonyl groups, or mixtures thereof).
  • aliphatic group means a saturated or unsaturated, linear, branched, or cyclic hydrocarbon group. This term is used to encompass alkylene (e.g., oxyalkylene), aralkylene, and cycloalkylene groups, for example.
  • alkylene group means a saturated, linear or branched, divalent hydrocarbon group. Particularly preferred alkylene groups are oxyalkylene groups.
  • oxyalkylene group means a saturated, linear or branched, divalent hydrocarbon group with a terminal oxygen atom.
  • aralkylene group means a saturated, linear or branched, divalent hydrocarbon group containing at least one aromatic group.
  • cycloalkylene group means a saturated, linear or branched, divalent hydrocarbon group containing at least one cyclic group.
  • oxycycloalkylene group means a saturated, linear or branched, > divalent hydrocarbon group containing at least one cyclic group and a terminal oxygen atom.
  • aromatic group means a mononuclear aromatic hydrocarbon group or polynuclear aromatic hydrocarbon group.
  • aromatic group includes arylene groups.
  • arylene group means a divalent aromatic group.
  • the isocyanate-reactive component contains at least one isocyanate-reactive material or mixtures thereof.
  • an isocyanate-reactive material includes at least one active hydrogen.
  • amines, thiols, and polyols are isocyanate-reactive materials.
  • the isocyanate-reactive material be a hydroxy- functional material.
  • Polyols are the preferred hydroxy-functional material used in the present invention.
  • Polyols of the invention can be of any molecular weight, including relatively low molecular weight polyols (i.e., having a weight average molecular weight of less than about 250) commonly referred to as "chain extenders” or “chain extending agents,” as well as those polyols having higher molecular weights.
  • Chain extenders or chain extending agents
  • Polyols provide urethane linkages when reacted with an isocyanate-functional component, such as a polyisocyanate.
  • Polyols as opposed to monols, have at least two hydroxy-functional groups.
  • diols are used in the present invention. Diols contribute to formation of relatively high molecular weight polymers without requiring crosslinking, such as is conventionally introduced by polyols having greater than two hydroxy- functional groups.
  • PSAs prepared from such diols generally have increased shear strength, peel adhesion, and/or a balance thereof, to provide PSA properties that may be desired for certain applications.
  • polymers having a relatively large amount of crosslinking may not be suitable for many PSA applications and/or materials therefrom may not be readily processable.
  • polyols useful in the present invention include, but are not limited to, polyester polyols (e.g., lactone polyols) and the alkylene oxide (e.g., ethylene oxide; 1,2- epoxypropane; 1,2-epoxybutane; 2,3-epoxybutane; isobutylene oxide; and epichlorohydrin) adducts thereof, polyether polyols (e.g., polyoxyalkylene polyols, such as polypropylene oxide polyols, polyethylene oxide polyols, polypropylene oxide polyethylene oxide copolymer polyols, and polyoxytetramethylene polyols; polyoxycycloalkylene polyols; polythioethers; and alkylene oxide adducts thereof), polyalkylene polyols, mixtures thereof, and copolymers therefrom. Polyoxyalkylene polyols are preferred.
  • polyester polyols e.g., lactone polyols
  • chemically similar repeating units may be randomly distributed throughout the copolymer or in the form of blocks in the copolymer.
  • chemically similar repeating units may be arranged in any suitable order within the copolymer.
  • oxyalkylene repeating units may be internal or terminal units within a copolymer.
  • the oxyalkylene repeating units may be randomly distributed or in the form of blocks within a copolymer.
  • One preferred example of a copolymer containing oxyalkylene repeating units is a polyoxyalkylene-capped polyoxyalkylene polyol (e.g., a polyoxyethylene-capped polyoxypropylene).
  • PSAs having fewer residuals i.e., reactive components, such as monomers, that remain unreacted in the reaction product
  • Such applications include, for example, electronics applications and medical applications.
  • the presence of residuals in PSAs used for these applications may be problematic.
  • the presence of residuals in PSAs used for electronics applications may contaminate other components in the electronic component, for example, by acting as a plasticizer.
  • Plasticization of magnetic media in a hard disk drive could result in a shortened useful life for the hard disk drive.
  • the presence of residuals in PSAs used for medical applications may cause irritation, sensitization, or skin trauma if the residuals migrate from the PSA to the surface in contact with skin, for example.
  • the polyol component be "highly pure" (i.e., the polyol approaches its theoretical functionality - e.g., 2.0 for diols, 3.0 for triols, etc.).
  • These highly pure polyols preferably have a ratio of polyol molecular weight to weight % monol of at least about 800, preferably at least about 1,000, and more preferably at least about 1,500.
  • the highly pure polyol contains about 8% by weight monol or less.
  • polyols having molecular weights of about 3,000 or less preferably contain less than about 1% by weight of monols.
  • Polyols having molecular weights of greater than about 3,000 to about 4,000 preferably contain less than about 3% by weight of monols.
  • Polyols having molecular weights of greater than about 4,000 to about 8,000 preferably contain less than about 6% by weight of monols.
  • Polyols having molecular weights of greater than about 8,000 to about 12,000 preferably contain less than about 8% by weight of monols.
  • highly pure polyols examples include those available from Lyondell Chemical Company of Houston, Texas, under the trade designation, ACCLAIM, and certain of those under the trade designation, ARCOL.
  • NMR Nuclear Magnetic Resonance
  • preferred diols useful in the present invention can be represented by Formula I:
  • R represents an aliphatic group, aromatic group, mixtures thereof, polymers thereof, or copolymers thereof.
  • R is a polyalkylene group, polyoxyalkylene group, or mixtures thereof.
  • polyols containing more than two hydroxy-functional groups are generally less preferred than diols, certain higher functional polyols may also be used in the present invention. These higher functional polyols may be used alone, or in combination with other isocyanate-reactive materials, for the isocyanate-reactive component.
  • these higher functional polyols are converted to diols prior to their use in the isocyanate-reactive component. After conversion, the reaction products are considered diols according to the present invention.
  • one preferred class of higher functional polyols that can be used in the present invention includes polyoxyalkylene triols, which can be reacted with a carboxylic acid cyclic anhydride or a sulfocarboxylic acid cyclic anhydride to reduce the functionality thereof.
  • the polyoxyalkylene triol is preferably polyoxypropylene or, more preferably, a polyoxypropylene polyoxyethylene copolymer.
  • the cyclic carboxylic anhydride is preferably selected from anhydrides such as succinic; glutaric; cyclohexanedicarboxylic; methylsuccinic; hexahydro-4-methylphthalic; phthalic; 1,2,4-benzenetricarboxylic; maleic; fumaric; itaconic; 3,4,5,6-tetrahydrophthalic; 1-dodecen-l-yl succinic; cis- aconitic; and mixtures thereof.
  • the sulfocarboxylic cyclic anhydride is preferably 2- sulfobenzoic acid cyclic anhydride.
  • the ester-acid reaction products are preferably used in combination with another isocyanate- reactive material.
  • the use of such lower molecular weight triols in combination with another isocyanate-reactive material may even obviate the need for the reactive emulsifying compound, which is described below, when preparing polyurethane-based dispersions of the invention.
  • the ester-acid reaction product is generally suitable for use without other isocyanate-reactive materials and may also obviate the need for the later described reactive emulsifying compound when preparing polyurethane-based dispersions of the invention.
  • At least two isocyanate-reactive materials such as polyols, may be used for the isocyanate-reactive component. It has been found that using at least one material having a relatively low weight average molecular weight in combination with at least one material having a relatively high weight average molecular weight results in PSAs having significantly greater shear strength (i.e., holding power), but comparable, or still adequate, peel adhesion, as compared to those PSAs derived from isocyanate-reactive components containing a single isocyanate-reactive material. Thus, this aspect of the present invention provides PSAs that can be used in applications where higher holding power is desired, but ease of removability from the adherend is also desired.
  • the ratio and types of materials in the isocyanate-reactive component mixture can be adjusted to obtain a wide range of shear strengths and peel adhesions in PSAs prepared therefrom.
  • the use of a mixture of materials for the isocyanate-reactive component also allows for improved cost-effectiveness, where desired. For example, more expensive isocyanate-reactive materials may be mixed with less expensive isocyanate-reactive materials for the isocyanate-reactive component. This may be the case, for example, when highly pure relatively high molecular weight polyols are mixed with relatively high molecular weight polyols that are less pure or with lower molecular weight polyols.
  • the mixture of isocyanate-reactive materials for the isocyanate- reactive component includes at least two diols, most preferably all polyols in the mixture are diols.
  • diols are preferred over other polyols due to their tendency to contribute to higher molecular weight polymers without crosslinking.
  • polyols other than diols comprise less than about 10% by weight, more preferably less than about 5% by weight, of the polyol component.
  • the weight average molecular weights of the two polyols differ by at least about 500, more preferably at least about 1,000, even more preferably at least about 1,500, even more preferably at least about 2,000, and most preferably at least about 2,500.
  • relatively low weight average molecular weight polyols are those having a weight average molecular weight of less than 2,000.
  • relatively high weight average molecular weight polyols are those having a weight average molecular weight of 2,000 or more.
  • the relatively low weight average molecular weight polyol has a weight average molecular weight of less than about 1,800, more preferably less than about 1,600, and most preferably less than about 1,000.
  • the relatively high weight average molecular weight polyol has a weight average molecular weight of greater than about 2,500, more preferably greater than about 3,000, and most preferably greater than about 3,500. In one embodiment of the invention, the relatively high weight average molecular weight polyol has a weight average molecular weight of greater than about 6,000.
  • the proportion of the two polyols in such a combination can vary widely.
  • a majority of the polyol component comprises a relatively high molecular weight polyol.
  • the relatively low molecular weight polyol comprises about 1 to about 40 percent by weight of the polyol component.
  • the relatively low molecular weight polyol comprises about 5 to about 25 percent by weight of the polyol component.
  • the relatively high molecular weight polyol comprises about 60 to about 99 percent by weight of the polyol component.
  • the relatively high molecular weight polyol comprises about 75 to about 95 percent by weight of the polyol component.
  • the isocyanate-reactive component is reacted with an isocyanate-functional component during formation of the polyurethane-based PSAs of the invention.
  • the isocyanate-functional component may contain one isocyanate-functional material or mixtures thereof.
  • Polyisocyanates including derivatives thereof (e.g., ureas, biurets, allophanates, dimers and trimers of polyisocyanates, and mixtures thereof), (hereinafter collectively referred to as "polyisocyanates”) are the preferred isocyanate-functional materials for the isocyanate-functional component.
  • Polyisocyanates have at least two isocyanate-functional groups and provide urethane linkages when reacted with the preferred hydroxy-functional isocyanate-reactive components.
  • diisocyanates are the preferred polyisocyanates.
  • Particularly preferred diisocyanates useful in the present invention can be generally represented by Formula H:
  • Z represents any suitable polyvalent radical, which may be, for example, polymeric or oligomeric.
  • Z can be based on arylene (e.g., phenylene), aralkylene, alkylene, cycloalkylene, polysiloxane (e.g., polydimethyl siloxane), or polyoxyalkylene (e.g., polyoxyethylene, polyoxypropylene, and polyoxytetramethylene) segments and mixtures thereof.
  • arylene e.g., phenylene
  • aralkylene alkylene
  • cycloalkylene e.g., polysiloxane (e.g., polydimethyl siloxane)
  • polyoxyalkylene e.g., polyoxyethylene, polyoxypropylene, and polyoxytetramethylene segments and mixtures thereof.
  • Z has about 1 to about 20 carbon atoms, and more preferably about 6 to about 20 carbon atoms.
  • Z can be selected from 2,6-tolylene; 2,4-tolylene; 4,4'- methylenediphenylene; 3 ,3 -dimethoxy-4,4'-biphenylene; tetramethyl-/w-xylylene; 4,4'-methylenedicyclohexylene; 3 , 5 , 5-trimethyl-3 -methylenecyclohexylene; 1,6-hexamethylene; 1,4-cyclohexylene; 2,2,4-trimethylhexylene; or polymeric or oligomeric alkylene, aralkylene, or oxyalkylene radicals and mixtures thereof.
  • Z is a polymeric or oligomeric material it may include, for example, urethane linkages.
  • the type of polyisocyanate used for the isocyanate-functional material may affect the properties of the PSA. For example, when symmetrical polyisocyanates are used, an increase in shear strength may be observed, as compared to using the same amount of a nonsymmetrical polyisocyanate.
  • any diisocyanate that can react with the isocyanate-reactive material can be used in the present invention.
  • diisocyanates include, but are not limited to, aromatic diisocyanates (e.g., 2,6-tolyene diisocyanate; 2,5-tolyene diisocyanate;
  • cycloaliphatic diisocyanates e.g., methylenedicyclohexylene-4,4'-diisocyanate
  • 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate isophorone diisocyanate); 2,2,4-trimethylhexyl diisocyanate; and cyclohexyl ene-l,4-diisocyanate), and other compounds terminated by two isocyanate-functional groups (e.g., the diurethane of tolyene-2,4-diisocyanate-terminated polypropylene oxide polyol).
  • diisocyanates include: 2,6-tolyene diisocyanate; 2,4-tolyene diisocyanate; tetramethyl-w-xylylene diisocyanate; methylenedicyclohexylene-4,4'- diisocyanate; 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate); 1,6-diisocyanatohexane; 2,2,4-trimethylhexyl diisocyanate; cyclohexylene- 1 ,4-diisocyanate; methylenedicyclohexylene-4,4'-diisocyanate; and mixtures thereof.
  • 2,6-tolyene diisocyanate 2,4-tolyene diisocyanate
  • tetramethyl-/w-xylylene diisocyanate 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate); methylenedicyclohexylene-4,4'-diisocyanate; and mixtures thereof.
  • Triisocyanates include, but are not limited to, polyfunctional isocyanates, such as those produced from biurets, isocyanurates, adducts, and the like.
  • Some commercially available polyisocyanates include portions of the DESMODUR and MONDUR series from Bayer Corporation; Pittsburgh, Pennsylvania, and the PAPI series from Dow Plastics, a business group of the Dow Chemical Company; Midland, Michigan.
  • Preferred triisocyanates include those available from Bayer Corporation under the trade designations DESMODUR N-3300 and MONDUR 489.
  • the isocyanate- reactive and isocyanate-functional components may optionally be reacted with at least one reactive emulsifying compound according to one embodiment of the invention.
  • the reactive emulsifying compound contains at least one anionic-functional group, cationic- functional group, group that is capable of forming an anionic-functional group or cationic-functional group, or mixtures thereof. This compound acts as an internal emulsifier because it contains at least one ionizable group. Thus, these compounds will hereinafter be referred to as "reactive emulsifying compounds.”
  • Reactive emulsifying compounds are capable of reacting with at least one of the isocyanate-reactive and isocyanate-functional components to become incorporated into the polyurethane prepolymers.
  • the reactive emulsifying compound contains at least one, preferably at least two, isocyanate- or active hydrogen-reactive (e.g., hydroxy- reactive) groups.
  • Isocyanate- and hydroxy-reactive groups include, for example, isocyanate, hydroxyl, mercapto, and amine groups.
  • the reactive emulsifying compound contains at least one anionic- functional group or group that is capable of forming such a group (i.e., an anion-forming group) when reacted with the isocyanate-reactive (e.g., polyol) and isocyanate-functional (e.g., polyisocyanate) components.
  • the anionic-functional or anion-forming groups of the reactive emulsifying compound can be any suitable groups that contribute to ionization of the reactive emulsifying compound.
  • suitable groups include carboxylate, sulfate, sulfonate, phosphate, and similar groups.
  • a reactive emulsifying compound in the polyurethane prepolymer increases water dispersibility of the polyurethane prepolymer.
  • dispersions prepared from such polyurethane prepolymers have improved dispersion stability as compared to many conventional dispersions.
  • such dispersions may not require external emulsifiers, such as surfactants, for stability.
  • a sufficient amount of reactive emulsifying compound is reacted such that an external emulsifier is not necessary for preparing a storage-stable dispersion.
  • the polyurethane prepolymers derived therefrom are also able to be dispersed into finer particles using less shear force than what has previously been possible with many conventional dispersions.
  • a sufficient amount is generally such that the resulting polyurethane-based polymer comprises about 0.5 to about 5 weight percent, more preferably about 0.75 to about 3 weight percent, of segments derived from the reactive emulsifying compound.
  • polyurethanes produced therefrom may be difficult to disperse, and dispersions produced therefrom may be unstable (i.e., subject to de-emulsification and/or coagulation at temperatures above room temperature, or at temperatures greater than about 20° C).
  • the amount of reactive emulsifying compound used in this preferred embodiment may be less to form a stable dispersion.
  • employing more reactive emulsifying compound in the reaction may produce an unstable dispersion or a resulting PSA that is too sensitive to moisture (i.e., such that physical properties of the PSA are affected to the degree that they are no longer consistently useful for their desired application).
  • X, Y, R, and R l may be the same or different.
  • X, Y, R, and R 1 are independently selected from aliphatic organic radicals free of reactive functional groups (e.g., alkylene groups that are free of reactive functional groups), preferably having from about 1 to about 20 carbon atoms, and combinations thereof, with the provisos that: (i.) R can be hydrogen; and (ii.)
  • R 1 is not required if Q is COO " .
  • dimethylolpropionic acid is a useful reactive emulsifying compound for this embodiment of the invention.
  • 2,2- dimethylolbutyric acid, dihydroxymaleic acid, and sulfopolyester diol are other useful reactive emulsifying compounds.
  • Those of ordinary skill in the art will recognize that a wide variety of reactive emulsifying compounds are useful in the present invention.
  • the isocyanate-reactive and isocyanate-functional components are allowed to react, forming an isocyanate-terminated polyurethane prepolymer (i.e., a polymer having a weight average molecular weight of less than about 50,000).
  • an isocyanate-terminated polyurethane prepolymer i.e., a polymer having a weight average molecular weight of less than about 50,000.
  • the isocyanate-functional group to isocyanate-reactive group ratio of the reactants is preferably about 1.1 to about 2.5, most typically about ⁇ .5. If the isocyanate-functional group to isocyanate-reactive group ratio is lower than in this preferred range, prepolymer viscosity may be too high to be useful for forming dispersions according to one aspect of the invention.
  • the isocyanate-terminated polyurethane prepolymer is then chain extended with a chain extending agent (e.g., water (including ambient moisture), a polyamine, a relatively low molecular weight polyol (i.e., a polyol having a weight average molecular weight of less than about 250) and combinations thereof) to increase its molecular weight.
  • a chain extending agent e.g., water (including ambient moisture)
  • a polyamine e.g., a polyamine, a relatively low molecular weight polyol (i.e., a polyol having a weight average molecular weight of less than about 250) and combinations thereof) to increase its molecular weight.
  • a chain extending agent e.g., water (including ambient moisture)
  • a polyamine e.g., a polyamine, a relatively low molecular weight polyol (i.e., a polyol having a weight average molecular weight of less than about 250) and
  • the polyurethane prepolymer is first introduced into a dispersing or solvating medium (e.g., water or an organic solvent such as N-methylpyrolidone, acetone, methyl ethyl ketone (MEK), or combinations thereof).
  • a dispersing or solvating medium e.g., water or an organic solvent such as N-methylpyrolidone, acetone, methyl ethyl ketone (MEK), or combinations thereof.
  • a dispersing or solvating medium e.g., water or an organic solvent such as N-methylpyrolidone, acetone, methyl ethyl ketone (MEK), or combinations thereof.
  • organic solvents in a waterborne system may also help in reducing the viscosity of the prepolymer, which facilitates formation of the dispersion.
  • a neutralizing agent is also added to the polyurethane prepolymer to more easily disperse the polyurethane prepolymer in the dispersing medium.
  • a base such as a tertiary amine or alkali metal salt
  • a neutralizing agent can be used as a neutralizing agent to neutralize any anion-forming groups in the polymeric chain and more easily disperse the polyurethane prepolymer in the dispersing medium.
  • a tertiary amine is used for the neutralizing agent.
  • a tertiary amine, an alkali metal salt, or a combination thereof is used as the neutralizing agent.
  • the polyurethane prepolymer is then chain extended through the reaction of the isocyanate-functional groups in combination with water, at least one polyamine, or mixtures thereof.
  • Isocyanate-functional groups react with water to form an unstable carbamic acid.
  • the carbamic acid then converts to a primary amine and carbon dioxide.
  • the primary amine forms a urea linkage with any remaining isocyanate-functional groups of the polyurethane prepolymer.
  • the chain extending agent comprises a polyamine
  • the polyamine forms urea linkages with the isocyanate- functional groups of the polyurethane prepolymer.
  • the resulting polyurethane- based polymer contains both urethane and urea linkages therein.
  • the polyurethane prepolymer may alternatively be chain extended using other suitable chain extenders, which may be selected according to whether the polymer is formed using a 100% solids, solventborne, or waterborne system.
  • the chain extending agent comprises a polyamine
  • any suitable compound having at least two amine functional groups can be used for the polyamine.
  • the compound may be a diamine, triamine, etc. Mixtures of polyamines may also be used for the chain extending agent.
  • the isocyanate-functional group to amine- functional group ratio of the reactants is preferably about 0.1 to about 1.5, most typically about 1.
  • polyamines useful in the present invention include, but are not limited to, polyoxyalkylene polyamines, alkylene polyamines, and polysiloxane polyamines.
  • the polyamine is a diamine.
  • the polyoxyalkylene polyamine may be, for example, a polyoxyethylene polyamine, polyoxypropylene polyamine, polyoxytetramethylene polyamine, or mixtures thereof.
  • Polyoxyethylene polyamine may be especially useful when preparing the PSA for medical applications, for example, where a high vapor transfer medium and/or water absorbency may be desirable.
  • polyoxyalkylene polyamines are commercially available.
  • polyoxyalkylene diamines are available under, trade designations such as D-230, D-400, D-2000, D-4000, DU-700, ED-2001 and EDR-148 (available from Huntsman Corporation; Houston, Texas, under the family trade designation JEFFAMINE).
  • Polyoxyalkylene triamines are available under trade designations such as T-3000 and T- 5000 (available from Huntsman Corporation; Houston, Texas).
  • Alkylene polyamines include, for example, ethylene diamine; diethylene triamine; triethylene tetramine; propylene diamine; butylene diamine; hexamethylene diamine; cyclohexylene diamine; piperazine; 2-methyl piperazine; phenylene diamine; tolylene diamine; xylylene diamine; tris(2-aminoethyl) amine; 3,3'-dinitrobenzidine; 4,4'-methylenebis(2-chloroaniIine); 3,3'-dichloro-4,4'-biphenyl diamine; 2,6- diaminopyridine; 4,4'-diaminodiphenylmethane; menthane diamine; m-xylene diamine; isophorone diamine; and dipiperidyl propane. Many alkylene polyamines are also commercially available. For example, alkylene diamines are available under trade designations such as DYTEK A and DYTEK EP (available from
  • PSAs of the present invention may contain various additives and other property modifiers.
  • fillers such as filmed silica, fibers (e.g., glass, metal, inorganic, or organic fibers), carbon black, glass or ceramic beads/bubbles, particles (e.g., metal, inorganic, or organic particles), polyaramids (e.g., those available from DuPont Chemical Company; Wilmington, DE under the trade designation, KEVLAR), and the like can be added, generally in amounts up to about 50 parts per hundred parts by weight of the polyurethane-based polymer, provided that such additives are not detrimental to the properties desired in the final PSA composition.
  • filmed silica fibers (e.g., glass, metal, inorganic, or organic fibers), carbon black, glass or ceramic beads/bubbles, particles (e.g., metal, inorganic, or organic particles), polyaramids (e.g., those available from DuPont Chemical Company; Wilmington, DE under the trade designation, KEVLAR), and the like can be added, generally in amounts up to about 50 parts per hundred parts by weight of the polyurethan
  • additives such as dyes, inert fluids (e.g., hydrocarbon oils), plasticizers, tackifiers, pigments, flame retardants, stabilizers, antioxidants, compatibilizers, antimicrobial agents (e.g., zinc oxide), electrical conductors, thermal conductors (e.g., aluminum oxide, boron nitride, aluminum nitride, and nickel particles), and the like can be blended into these compositions, generally in amounts of from about 1 to about 50 percent by total volume of the composition. It should be noted that, although tackifiers and plasticizers may be added, such additives are not necessary for obtaining PSA properties in polyurethane-based adhesives of the invention.
  • the polyurethane-based PSA is prepared from a solventborne or waterborne system, once the solution or dispersion is formed, it is easily applied to a substrate and then dried to form a PSA coating. Drying can be carried out either at room temperature (i.e., about 20°C) or at elevated temperatures (e.g., about 25 °C to about 150°C). Drying can optionally include using forced air or a vacuum. This includes the drying of static- coated substrates in ovens, such as forced air and vacuum ovens, or drying of coated substrates that are continuously conveyed through chambers heated by forced air, high- intensity lamps, and the like. Drying may also be performed at reduced (i.e., less than ambient) pressure.
  • a PSA coating can be formed on a wide variety of substrates.
  • the PSA can be applied to sheeting products (e.g., decorative, reflective, and graphical), labelstock, and tape backings.
  • the substrate can be any suitable type of material depending on the desired application.
  • the substrate comprises a nonwoven, paper, polymeric film (e.g., polypropylene (e.g., biaxially oriented polypropylene (BOPP)), polyethylene, polyurea, polyurethane, or polyester (e.g., polyethylene terephthalate)), or release liner (e.g., siliconized liner).
  • polypropylene e.g., biaxially oriented polypropylene (BOPP)
  • polyethylene polyurea
  • polyurethane polyurethane
  • polyester e.g., polyethylene terephthalate
  • release liner e.g., siliconized liner
  • PSAs according to the present invention can be utilized to form tape, for example.
  • a PSA coating is formed on at least a portion of a suitable backing.
  • a release material e.g., low adhesion backsize
  • a PSA coating is formed on at least a portion of both sides of the backing.
  • PSAs of the invention may also be prepared from 100% solids and solventborne systems. PSAs prepared from 100% solids and solventborne systems also benefit from the use of chemistries described herein.
  • the polyurethane-urea dispersion to be tested was cast onto a polyethylene terephthalate backing at a dry thickness of approximately 25 micrometers using a MEYER rod or a knife coater depending on the viscosity of the dispersion.
  • the coating was allowed to dry at room temperature followed by further drying for 10 minutes in a 70°C oven.
  • the samples were placed in a constant temperature and humidity room (22°C and 50% relative humidity) overnight prior to testing.
  • This peel adhesion test is similar to the test method described in ASTM D 3330- 90, substituting a glass substrate for the stainless steel substrate described in the test (for the present purpose, also referred to as "glass substrate peel adhesion test").
  • PSA tapes prepared as described above, were cut into 1.27-centimeter by 15-centimeter strips. Each strip was then adhered to a 10 centimeter by 20 centimeter clean, solvent-washed glass coupon by passing a 2-kilogram roller once over the strip. The bonded assembly dwelled at room temperature for about one minute.
  • Each sample so prepared was tested for 180° peel adhesion using an IMASS slip/peel tester (Model 3M90, commercially available from Instrumentors Inc.; Stropgsville, OH) at a rate of 2.3 meters/minute (90 inches/minute) using a five second data collection time. Two samples of each composition were tested. The reported peel adhesion value is an average of the peel adhesion value from each of the two samples.
  • This shear strength test is similar to the test method described in ASTM D 3654- 88.
  • PSA tapes prepared as described above, were cut into 1.27-centimeter by 15- centimeter strips. Each strip was then adhered to a stainless steel panel such that a 1.27- centimeter by 1.27-centimeter portion of each strip was in firm contact with the panel and one end portion of the strip hung free.
  • the panel with the attached strip was placed in a rack such that the panel formed an angle of 178° with the extended free end of the strip.
  • the strip was tensioned by application of a force of one kilogram applied as a hanging weight from the free end of the strip. The 2° less than 180° was used to negate any peel forces, thus ensuring that only shear strength forces were measured, in an attempt to more accurately determine the holding power of the tape being tested.
  • the measured weight % of monol for certain of the higher molecular weight polyols was determined using proton-NMR spectroscopy.
  • the weight % monol measured was the proportion of allyl protons with respect to the total number of protons in the polymer backbone of the polyol.
  • the dispersion prepared in Part II was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 3. Additionally, the test results for Example 2 are reported in Table 24 for comparison purposes.
  • Example 1 The same procedure described in Example 1, Part I was followed, except using the reagents and amounts shown in Table 1.
  • Example 2 The same procedure described in Example 1, Part II was followed, except using the reagents and amounts shown in Table 2.
  • the dispersions prepared in Part II were used to prepare tape samples as described above.
  • the 180° Peel Adhesion and Shear Strength of each tape sample were tested as described above and are reported in Table 3.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C-100°C overnight and cooled to room temperature prior to use.
  • a glass reaction vessel 126.86 parts by weight of ACCLAIM 3201 and 50.30 parts by weight anhydrous MEK were combined and mixed until homogeneous (about five minutes).
  • a separate vessel 2.75 parts by weight DMPA and 14.00 parts by weight NMP were combined and mixed until the DMPA was dissolved (about fifteen minutes).
  • the DMPA/NMP solution was combined with the polyol/MEK solution. The resulting mixture was mixed until homogeneous (about five minutes).
  • Example 1 The same procedure described in Example 1, Part II was followed, except using 209.19 parts by weight of the prepolymer prepared in Part I, 3.81 parts by weight of TEA, and a premix containing 1.80 parts by weight of EDA and 278 parts by weight of distilled water.
  • the dispersion prepared in Part ⁇ was used to prepare a tape sample as described above.
  • the peel and shear properties of the tape sample were tested as described above and are reported in Table 3. Additionally, the test results for Example 4 are reported in Table 24 for comparison purposes.
  • a premix of 0.91 parts by weight of TEA, 1.08 parts by weight of EDA, and 301 parts by weight of distilled water was prepared. Then, 225.00 parts by weight of the prepolymer prepared in Part I was dispersed in the water/TEA/EDA premix in a MICROFLUIDICS HOMOGENIZER Model # HC-5000 (commercially available from Microfluidics Corp.; Newton, MA) at a line air pressure of 0.621 MPa. Examples 6-7
  • the dispersions prepared in Part II were used to prepare tape samples as described above.
  • the 180° Peel Adhesion and Shear Strength of each tape sample were tested as described above and are reported in Table 6. Additionally, the test results for Example 5 are reported in Table 24 and the test results for Examples 6 and 7 are reported in Table 13 for comparison purposes.
  • the polyols Prior to use, the polyols, ACCLAIM 12200 and ARCOL PPG-425, were dehydrated in-vacuo at 90 C -100°C overnight and cooled to room temperature.
  • a glass reaction vessel 96.32 parts by weight of ACCLAIM 12200, 24.08 parts by weight of ARCOL PPG-425, and 52.85 parts by weight of MEK were combined and mixed until homogeneous (about five minutes).
  • a separate vessel 2.26 parts by weight of DMPA and 11.34 parts by weight of NMP were combined and mixed until the DMPA was dissolved (about fifteen minutes).
  • the DMPA NMP solution was combined with the polyol/MEK v solution and mixed until homogeneous (about five minutes).
  • Example 1 The same procedure described in Example 1, Part II was followed, except using 193.50 parts by weight of the prepolymer prepared in Part L 1.55 parts by weight of TEA, and a premix containing 2.23 parts by weight of EDA and 262 parts by weight of distilled water.
  • the dispersion prepared in Part JJ was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 7.
  • the polyol, ACCLAIM 12200 was dehydrated in-vacuo at 90°C-100°C overnight and cooled to room temperature prior to use.
  • a glass reaction vessel 144.48 parts by weight of ACCLAIM 12200, 67.30 parts by weight of MEK, 2.36 parts by weight of DMPA, and 10.38 parts by weight of IPDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80°C for 48 hours followed by being placed in a 70 C oven for four hours.
  • Part II The same procedure described in Example 1, Part II was followed, except using 201.00 parts by weight of the prepolymer prepared in Part I, 0.80 gram of TEA, and a premix containing 0.83 gram of EDA and 269 parts by weight of distilled water.
  • Part UI Tape Preparation
  • the dispersion prepared in Part II was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 7.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C-100°C overnight and cooled to room temperature before use.
  • a.glass reaction vessel 130.00 parts by weight of ACCLAIM 3201, 0.66 gram of 1,5-PDO, 1.43 parts by weight of DMPA, 65.10 parts by weight of anhydrous acetone, 19.91 parts by weight of IPDI, and 0.14 gram of FASCAT 4224 were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for sixteen hours followed by being placed in a
  • Part II The same procedure described in Example 1, Part II was followed, except using 210.00 parts by weight of the prepolymer prepared in Part I, 1.05 parts by weight of TEA, and a premix containing 1.73 parts by weight of EDA and 283 parts by weight of distilled water.
  • Part UI Tape Preparation
  • the dispersion prepared in Part II was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 10.
  • the dispersions prepared in Part II were used to prepare tape samples as described above.
  • the 180° Peel Adhesion and Shear Strength of each tape sample were tested as described above and are reported in Table 10.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C-100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 130.00 parts by weight of ACCLAIM 3201, 1.32 parts by weight of 1,5-PDO, 2.88 parts by weight of DMPA, 68.40 parts by weight of anhydrous acetone and 25.42 parts by weight of IPDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for 48 hours followed by being placed in a 70 C oven for one hour.
  • ACCLAIM 3201 comprised 99% by weight of the polyol.
  • the other 1% by weight of the polyol comprised a short chain diol, as indicated in Table 11.
  • the dispersion prepared in Part JI was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 11.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 130.00 parts by weight of ACCLAIM 3201, 1.32 parts by weight of 1,4-BDO, 2.89 parts by weight of DMPA, 68.60 parts by weight of anhydrous acetone and 26.11 parts by weight of IPDI were combined.
  • the reaction vessel was rotated in a thermostated" temperature bath at 80°C for 46 hours followed by being placed in a 70 C oven for one hour.
  • ACCLAIM 3201 comprised 99% by weight of the polyol.
  • the other 1% by weight of the polyol comprised a short chain diol, as indicated in Table 11.
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 11.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 130.00 parts by weight of ACCLAIM 3201, 1.32 parts by weight of 2-M-l,3-PDO, 2.89 parts by weight of DMPA, 68.60 parts by weight of anhydrous acetone, and 26.11 parts by weight of IPDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for 46 hours followed by being placed in a 70°C oven for one hour.
  • ACCLAIM 3201 comprised 99% by weight of the polyol.
  • the other 1% by weight of the polyol comprised a short chain diol, as indicated in Table 11.
  • the dispersion prepared in Part ⁇ was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 11.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 130.00 parts by weight of ACCLAIM 3201, 1.32 parts by weight of DEG, 2.88 parts by weight of DMPA, 68.30 parts by weight of anhydrous acetone, and 25.34 parts by weight of IPDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at
  • ACCLAIM 3201 comprised 99% by weight of the polyol.
  • the other 1% by weight of the polyol comprised a short chain diol, as indicated in Table 11.
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 11.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 130.00 parts by weight of ACCLAIM 3201, 1.32 parts by weight of DPG, 2.87 parts by weight of DMPA, 67.90 parts by weight of anhydrous acetone, and 24.45 parts by weight of IPDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for 46 hours followed by being placed in a 70 C oven for one hour.
  • ACCLAIM 3201 comprised 99% by weight of the polyol.
  • the other 1% by weight of the polyol comprised a short chain diol, as indicated in Table 11.
  • Part H Tape Preparation
  • the dispersions prepared in Part ⁇ were used to prepare tape samples as described above.
  • the 180° Peel Adhesion and Shear Strength of each tape sample were tested as described above and are reported in Table 13.
  • Example 1 The same procedure described in Example 1, Part II was followed, except that 220.00 parts by weight of the prepolymer prepared in Part I, 2.00 parts by weight of TEA, 1.73 parts by weight of EDA, and 295 parts by weight of water were used.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 139.55 parts by weight of ACCLAIM 3201, 2.95 parts by weight of DMPA, 68.55 parts by weight of anhydrous acetone, and 17.55 parts by weight of TDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for seventeen hours followed by being placed in an 80 C oven for sixteen hours.
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 14. Additionally, the test results for Example 22 are reported in Table 24 for comparative purposes.
  • the dispersions prepared in Part II were used to prepare tape samples as described above.
  • the 180° Peel Adhesion and Shear Strength of each tape sample were tested as described above and are reported in Table 16. Additionally, the results of Example 25 are reported in Table 18 for comparative purposes.
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 18.
  • Example 19 The same procedure described in Example 1, Part I was followed, except using the reagents shown in Table 19 with the modification that ACCLAIM 3205 was used in place of ACCLAIM 3201. Furthermore, HFTC was also added to the reaction mixture for Example 27, as noted in Table 19. Table 19
  • the dispersions prepared in Part II were used to prepare tape samples as described above.
  • the 180° Peel Adhesion and Shear Strength of each tape sample were tested as described above and are reported in Table 21.
  • the polyols, ACCLAIM 3201 and SPD were dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature prior to use.
  • a glass reaction vessel 90.00 parts by weight of ACCLAIM 3201, 90.00 parts by weight of SPD, 66.20 parts by weight of anhydrous acetone, and 20.00 parts by weight of NMP were combined and mixed until homogeneous (about five minutes).
  • a separate vessel 2.09 parts by weight of DMPA and 10.40 parts by weight of NMP were combined and mixed until the DMPA was dissolved (about fifteen minutes).
  • the DMPA/NMP solution was combined with the polyol/acetone solution and mixed until homogeneous (about five minutes).
  • reaction mixture vessel was placed in an 80 C oven for six hours and agitated intermittently.
  • the dispersion prepared in Part ⁇ was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 22.
  • the polyols, ARCOL R-2585 and ACCLAIM 6320 were dehydrated in-vacuo at 90 C -100 C overnight and cooled to room temperature prior to use.
  • a glass reaction vessel 171.68 parts by weight of ARCOL R-2585, 9.04 parts by weight of ACCLAIM 6320, and 61.74 parts by weight of anhydrous acetone were combined and mixed until homogeneous (about five minutes).
  • a separate vessel 5.67 parts by weight of DMPA and 27.90 parts by weight of NMP were combined and mixed until the DMPA was dissolved (about fifteen minutes).
  • the DMPA/NMP solution was combined with the polyol/acetone solution and mixed until homogeneous (about five minutes).
  • reaction mixture vessel was placed in an 80 C oven for six hours and agitated intermittently.
  • Example 1 The same procedure described in Example 1, Part II was followed, except using 224.20 parts by weight of the prepolymer prepared in Part I, 1.61 parts by weight of TEA, and a premix containing 1.02 parts by weight of EDA and 299 parts by weight of distilled water.
  • the dispersion prepared in Part ⁇ was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 23,
  • the polyol, ARCOL R-2585 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature prior to use.
  • a glass reaction vessel 188.25 parts by weight of ARCOL R-2585 and 74.00 parts by weight of anhydrous acetone were combined and mixed until homogeneous (about five minutes).
  • a separate vessel 3.35 parts by weight of DMPA and 16.77 parts by weight of NMP were combined and mixed until the DMPA was dissolved (about fifteen minutes).
  • the DMPA/NMP solution was combined with the polyol/acetone solution and mixed until homogeneous (about five minutes).
  • To this mixture was added, sequentially, 20.04 parts by weight of DES-W and 0.19 gram of HFTC. After each addition, the resulting mixture was mixed until homogeneous (about five minutes).
  • the reaction mixture vessel was placed in an 80 C oven for six hours and agitated intermittently.
  • the polyols, ACCLAIM 3201 and ARCOL PPG-425 were dehydrated in-vacuo at 90 C -100 C overnight and cooled to room temperature before use.
  • a glass reaction vessel 120.46 parts by weight of ACCLAIM 3201, 6.34 parts by weight of ARCOL PPG-425, 2.68 parts by weight of DMPA, 63.70 parts by weight of anhydrous acetone, and 19.27 parts by weight of TDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for forty hours.
  • a premix solution of 1.91 parts by weight of TEA and 264 parts by weight of distilled water was prepared. Then, 200.00 parts by weight of the prepolymer prepared above was dispersed in the water/TEA mixture using a MICROFLUIDICS HOMOGENIZER Model # HC-5000 (commercially available from Microfluidics Corp.; Newton, Massachusetts) at an airline pressure of 0.621 MPa. The reaction mixture was stirred overnight at ambient temperature with a magnetic stir bar.
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 24.
  • Part II The same procedure described in Example 32, Part II was followed, except using 2.89 parts by weight of TEA, 287 parts by weight of distilled water, and 218.00 parts by weight of the prepolymer prepared in Part I.
  • Part HI Tape Preparation
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 25.
  • the polyols, ARCOL PPG-4025 and ARCOL PPG-425 were dehydrated in-vacuo at 90 C -100 C overnight and cooled to room temperature before use.
  • a glass reaction vessel 128.35 parts by weight of ARCOL PPG-4025, 6.76 parts by weight of ARCOL PPG-425, 3.98 parts by weight of DMPA, 68.10 parts by weight of anhydrous acetone, and 19.98 parts by weight of TDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for forty hours.
  • the dispersion prepared in Part ⁇ was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 25.
  • the polyols, ACCLAIM 4200 and ARCOL PPG-425 were dehydrated in-vacuo at 90 C -100 C overnight and cooled to room temperature before use.
  • a glass reaction vessel 91.68 parts by weight of ACCLAIM 4200, 22.92 parts by weight of ARCOL PPG-425, 2.64 parts by weight of DMPA, 61.10 parts by weight of anhydrous acetone, and 25.34 parts by weight of TDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for 45 hours.
  • the dispersion prepared in Part ⁇ was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 26.
  • the polyols, ARCOL PPG-4025 and ARCOL PPG-425 were dehydrated in-vacuo at 90 C -100 C overnight and cooled to room temperature before use.
  • a glass reaction vessel 91.68 parts by weight of ARCOL PPG-4025, 22.92 parts by weight of ARCOL PPG-425, 2.63 parts by weight of DMPA, 60.90 parts by weight of anhydrous acetone, and 24.89 parts by weight of TDI were combined.
  • the reaction vessel was placed in a LAUNDER-OMETER Model LEF (commercially available from Atlas Electric Devices
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 26.
  • the solution prepared in Part II was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape were tested as described above and are reported in Table 27.
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 139.55 parts by weight of ACCLAIM 3201, 4.99 parts by weight of DMPA, 71.10 parts by weight of anhydrous acetone, and 21.52 parts by weight of TDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for forty hours.
  • a premix solution of 3.50 parts by weight of TEA and 289 parts by weight distilled water was prepared. Then, 220.00 parts by weight of the prepolymer prepared above was dispersed in the water/TEA mixture using a MICROFLUIDICS HOMOGENIZER Model # HC-5000 (commercially available from Microfluidics Corp.; Newton, Massachussetts) at an airline pressure of 0.621 MPa. The reaction mixture was stirred overnight at ambient temperature with a magnetic stir bar.
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 28. Table 28
  • the polyol, ACCLAIM 3201 was dehydrated in-vacuo at 90°C-100° C overnight and cooled to room temperature prior to use.
  • a glass reaction vessel 348.02 parts by weight of ACCLAIM 3201 and 111.32 parts by weight anhydrous acetone were combined and mixed until homogeneous (about five minutes).
  • a separate vessel 15.73 parts by weight DMPA and 78.69 parts by weight NMP were combined and mixed until the DMPA was dissolved (about fifteen minutes).
  • the DMPA/NMP solution was combined with polyol/MEK solution and the resulting mixture was mixed until homogeneous (about five minutes).
  • the dispersions prepared in Part II were used to prepare tape samples as described above.
  • the 180° Peel Adhesion and Shear Strength of each tape sample were tested as described above and are reported in Table 30.
  • the polyol, ACCLAIM 4200 was dehydrated in-vacuo at 90°C -100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 130.98 parts by weight of ACCLAIM 4200, 2.73 parts by weight of DMPA, 63.30 parts by weight of anhydrous acetone, and 14.19 parts by weight of TDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for 44 hours.
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape sample were tested as described above and are reported in Table 31.
  • the polyol, ARCOL PPG-4025 was dehydrated in-vacuo at 90°C-100°C overnight and cooled to room temperature before use.
  • a glass reaction vessel 130.98 parts by weight of ARCOL PPG-4025, 2.72 parts by weight of DMPA, 63.10 parts by weight of anhydrous acetone, and 13.56 parts by weight of TDI were combined.
  • the reaction vessel was rotated in a thermostated temperature bath at 80 C for 44 hours.
  • Part H Prepolymer Preparation and Dispersion
  • a glass reaction vessel 145.33 parts by weight of the diol prepared in Part I and 8.73 parts by weight of TDI were placed. The mixture was stirred and heated at 90°C for three hours. Then, the mixture was cooled to 60°C and a 25.00 part by weight aliquot was removed. To the aliquot, 0.34 part by weight of an amine (TEA) was added and the prepolymer mixture was immediately dispersed in 75.0 parts by weight of deionized water using an OMNI Mixer Homogenizer (commercially available from OMNI International;resston, VA). The dispersion was stirred overnight.
  • OMNI Mixer Homogenizer commercially available from OMNI International; Randton, VA
  • Example 43 Part I
  • 18% fewer equivalents of S A was used (i.e. 0.1323 OH equivalents (from ACCLAIM 6320) and 0.03744 anhydride equivalents (from SA)).
  • Part H Prepolymer Preparation and Dispersion
  • Example 44 Part JJ, The same procedure used in Example 43, Part JJ, except using the reagents and amounts shown in Table 32 for each of three samples - Examples 44-1, 44-2, and 44-3.
  • a catalyst (T-12) was added along with the diisocyanate in Examples 44-2 and 44-3.
  • a 15.00 part by weight aliquot was obtained and the prepolymer was dispersed in 53.0 parts by weight deionized water for each sample.
  • the second amine, JEFFAMINE D-2000 was then added to the initial dispersion.
  • Part H Prepolymer Preparation and Dispersion
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape were tested as described above and are reported in Table 33.
  • Example 43 Part ⁇ was followed, except using the reagents and amounts as described below for each of three samples - Examples 46-1, 46- 2, and 46-3.
  • 125.00 parts by weight of the diol from Part I and 9.57 parts by weight TDI were used to form a prepolymer.
  • Example 46-1 and 46-2 a 35.00 part by weight aliquot of each sample was obtained and neutralized with 0.59 part by weight of TEA. Then, the aliquot was dispersed in 105.0 parts by. weight of deionized water using an OMNI Mixer Homogenizer (commercially available from OMNI International; Randton, VA). Furthermore, for Example 46-2, 0.22 part by weight EDA was further dispersed into the dispersion. Each dispersion was stirred overnight.
  • Example 46-3 the resulting prepolymer was heated to 95°C and 22% by weight of a terpene resin tackifier (prepared as described in U. S . Patent Number 3,718,712 (Tushaus), Example 1) was added. A 35.00 part by weight aliquot of the sample was obtained and neutralized with 0.59 part by weight of TEA. Then, the aliquot was dispersed in 105.0 parts by weight of deionized water using an OMNI Mixer Homogenizer (commercially available from OMNI International; Randton, VA). The dispersion was stirred overnight.
  • OMNI Mixer Homogenizer commercially available from OMNI International; Randton, VA
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape were tested as described above and are reported in Table 33.
  • Part H Prepolymer Preparation and Dispersion
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape were tested as described above and are reported in Table 33.
  • Part H Prepolymer Preparation and Dispersion
  • the dispersion prepared in Part H was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape were tested as described above and are reported in Table 33.
  • Part H Prepolymer Preparation and Dispersion
  • Part H Prepolymer Preparation and Dispersion
  • the solution prepared in Part II was used to prepare a tape sample as described above.
  • the 180° Peel Adhesion and Shear Strength of the tape were tested as described above and are reported in Table 34.

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DE60033059T DE60033059T2 (de) 2000-02-25 2000-06-05 Haftklebstoff auf basis von polyurethan, systeme für solche klebstoffe, daraus hergestellte gegenstände und verfahren zur herstellung solcher klebstoffe
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3353258A4 (en) * 2015-09-21 2019-05-01 3M Innovative Properties Company CHEMICAL-RESISTANT POLYURETHANE ADHESIVE
US10611873B2 (en) 2014-12-16 2020-04-07 3M Innovative Properties Company Polyurethane pressure-sensitive adhesives

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6642304B1 (en) * 2000-02-25 2003-11-04 3M Innovative Properties Company Polyurethane-based adhesives, systems for such adhesives, articles therefrom, and methods of making
EP1361236B1 (en) * 2002-04-25 2004-12-29 Sicpa Holding S.A. A polyurethane resin derived from hard ketonic resins
DE10317791A1 (de) * 2003-04-16 2004-12-02 Tesa Ag Haftklebstoff aus Polyurethan für empfindliche Oberflächen
RU2230765C1 (ru) * 2003-05-07 2004-06-20 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" Клеевая композиция
US20050137375A1 (en) * 2003-12-19 2005-06-23 3M Innovative Properties Company Polyurethane-based pressure sensitive adhesives and methods of manufacture
WO2005105857A1 (en) * 2004-04-27 2005-11-10 Ashland Inc. Polyester-polyether hybrid urethane acrylate oligomer for uv curing pressure sensitive adhesives
US7816472B2 (en) * 2004-08-19 2010-10-19 3M Innovative Properties Company Polydiacetylene polymer compositions and methods of manufacture
US7371511B2 (en) * 2004-08-19 2008-05-13 3M Innovative Properties Company Polydiacetylene polymer blends
JP5008046B2 (ja) * 2005-06-14 2012-08-22 ローム株式会社 半導体デバイス
WO2007048145A2 (en) * 2005-10-21 2007-04-26 Entrotech, Inc. Protective sheets, articles, and methods
US8545960B2 (en) * 2006-10-23 2013-10-01 Entrotech, Inc. Articles comprising protective sheets and related methods
US20090030146A1 (en) * 2007-07-24 2009-01-29 Yuliya Berezkin Polyurethane dispersions for sealants
EP2193024A4 (en) 2007-09-25 2013-11-06 Entrotech Inc PAINT SHEET FILMS, COMPOUNDS THEREOF AND RELATED METHODS
KR101503561B1 (ko) * 2007-12-27 2015-03-17 쓰리엠 이노베이티브 프로퍼티즈 컴파니 우레아계 감압성 접착제
US10981371B2 (en) * 2008-01-19 2021-04-20 Entrotech, Inc. Protected graphics and related methods
US20090078590A1 (en) 2008-01-21 2009-03-26 Smith Dennis R Ultrasecure card package
WO2010132176A2 (en) 2009-05-15 2010-11-18 3M Innovative Properties Company Urethane-based pressure sensitive adhesives
JP5767235B2 (ja) 2009-11-09 2015-08-19 スリーエム イノベイティブ プロパティズ カンパニー 医療用物品及び不混和性材料を用いる製造方法
WO2011057175A1 (en) 2009-11-09 2011-05-12 3M Innovative Properties Company Medical articles and methods of making using miscible composition
CN102058895A (zh) * 2009-11-17 2011-05-18 上海普天欣生物技术有限公司 一种消毒活性贴膜及其制备方法和用途
US9089624B2 (en) * 2010-08-23 2015-07-28 Basf Se Ultrathin fluid-absorbent cores comprising adhesive and having very low dry SAP loss
WO2012158483A2 (en) 2011-05-16 2012-11-22 Avery Dennison Corporation Adhesive containing microparticles
US9818499B2 (en) * 2011-10-13 2017-11-14 Flexcon Company, Inc. Electrically conductive materials formed by electrophoresis
US9427945B2 (en) * 2011-12-30 2016-08-30 Liberman Distributing And Manufacturing Co. Extendable self-supporting material composites and manufacture thereof
WO2013148506A1 (en) 2012-03-30 2013-10-03 3M Innovative Properties Company Urea-based and urethane-based pressure sensitive adhesive blends
JP5961474B2 (ja) * 2012-07-31 2016-08-02 日東電工株式会社 表面保護フィルム
CN105567115B (zh) 2013-02-07 2018-09-07 艾利丹尼森公司 具有改进性质的抗微生物粘合剂
EP2968014B1 (en) 2013-03-15 2019-04-24 Avery Dennison Corporation Transparent cover dressing application system and inclusion of label strip
EP3013294B1 (en) 2013-06-28 2019-09-25 3M Innovative Properties Company Fibrin-coated wound dressing
ES2978949T3 (es) * 2014-05-13 2024-09-23 Basf Se Preparación con bajo contenido de fenol a base de poliuretano termoplástico
ES2755097T3 (es) * 2014-05-16 2020-04-21 Henkel Ag & Co Kgaa Adhesivo de fusión en caliente de poliuretano termoplástico
EP2944662B1 (en) * 2014-05-16 2018-07-18 Henkel AG & Co. KGaA Thermoplastic polyurethane hot melt adhesive
EP3151813B1 (en) 2014-06-05 2020-12-09 Avery Dennison Corporation Articles with active agent concentrated at the substrate contacting surface and related methods
WO2018057379A1 (en) 2016-09-20 2018-03-29 Aero Advanced Paint Technology, Inc. Paint film appliques with reduced defects, articles, and methods
US11453777B2 (en) 2016-12-16 2022-09-27 Oregon State University Pressure sensitive adhesives from plant oil-based polyols

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4985491A (en) * 1989-10-05 1991-01-15 Olin Corporation Polyurethane sealants made using high molecular weight polyols prepared with double metal cyanide catalysts
EP0573206A1 (en) * 1992-06-05 1993-12-08 ARCO Chemical Technology, L.P. Isocyanate-terminated prepolymers derived from polyether polyol mixtures having low monol content and their use in polyurethanes
WO1999038900A1 (en) * 1998-01-28 1999-08-05 Bristol-Myers Squibb Company Methods of preparing polyurethane adhesives, adhesives produced thereby and medical devices employing the same

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3246049A (en) 1963-08-30 1966-04-12 Norton Co Pressure sensitive adhesive comprising an isocyanate cross-linked polyester of castor oil and diglycolic acid, and tape coated with said adhesive
US3360599A (en) 1963-11-06 1967-12-26 Shell Oil Co Preparation of coherent block copolymer films of high tensile strength and extensibility
GB1113925A (en) 1964-09-18 1968-05-15 Dunlop Co Ltd Polyurethane pressure-sensitive adhesives
US3437622A (en) 1965-12-06 1969-04-08 Anchor Continental Inc Polyurethane-based pressure-sensitive adhesives
US3503917A (en) 1967-03-09 1970-03-31 Burke Oliver W Jun Aqueous latices of high polymer compositions and processes for producing same
GB1216672A (en) 1967-05-16 1970-12-23 Dunlop Co Ltd Polyurethane pressure-sensitive adhesives
US3925283A (en) 1970-06-29 1975-12-09 Continental Tapes Inc Polyurethane pressure-sensitive adhesive products and processes
US3796678A (en) 1970-08-17 1974-03-12 Minnesota Mining & Mfg Highly branched,capped polyurethanes for pressure sensitive adhesives
US3767040A (en) 1971-03-01 1973-10-23 Minnesota Mining & Mfg Pressure-sensitive polyurethane adhesives
US3718712A (en) 1971-03-01 1973-02-27 Minnesota Mining & Mfg Pressure-sensitive adhesives based on cyclic terpene urethane resin
US3743617A (en) 1971-05-17 1973-07-03 D Kest Urethane base pressure sensitive adhesive
DE2436873A1 (de) 1974-07-31 1976-02-19 Basf Ag Verfahren zur herstellung von haftklebern
US4123403A (en) 1977-06-27 1978-10-31 The Dow Chemical Company Continuous process for preparing aqueous polymer microsuspensions
JPS5552369A (en) 1978-10-13 1980-04-16 Toyo Tire & Rubber Co Ltd Water-dispersed pressure-sensitive adhesive composition
JPS62270613A (ja) * 1986-05-19 1987-11-25 Dainippon Ink & Chem Inc 接着力のすぐれたポリウレタン水性分散液の製造方法
US5102714A (en) 1988-12-20 1992-04-07 The Dow Chemical Company Removable polyurethane adhesive
US5037864A (en) 1989-07-11 1991-08-06 The Dow Chemical Company Semi-continuous process for the preparation of polyurethane-urea aqueous dispersions
US5532058A (en) 1990-12-10 1996-07-02 H. B. Fuller Licensing & Financing, Inc. Dry-bonded film laminate employing polyurethane dispersion adhesives with improved crosslinkers
EP0552420A3 (en) 1992-01-24 1993-09-15 H.B. Fuller Licensing & Financing, Inc. Water dispersed polyurethane polymer for improved coatings and adhesives
NZ248977A (en) 1992-11-09 1995-06-27 Squibb & Sons Inc Pressure-sensitive adhesive comprising a polyurethane having excess hydroxyl functionality; medical articles comprising a layer of such adhesive
US5354808A (en) 1992-12-08 1994-10-11 Minnesota Mining And Manufacturing Company Polyurethanes including pendant hindered amines and compositions incorporating same
DE4242687B8 (de) 1992-12-17 2006-01-12 Henkel Kgaa Hydrophile Polyurethane
US5442028A (en) 1993-08-20 1995-08-15 Morton International, Inc. Curatives for aqueous adhesives
US5554686A (en) 1993-08-20 1996-09-10 Minnesota Mining And Manufacturing Company Room temperature curable silane-terminated polyurethane dispersions
US5608000A (en) 1993-09-24 1997-03-04 H. B. Fuller Licensing & Financing, Inc. Aqueous polyurethane dispersion adhesive compositions with improved heat resistance
US5703158A (en) 1993-09-24 1997-12-30 H.B. Fuller Licensing & Financing, Inc. Aqueous anionic poly (urethane/urea) dispersions
JPH07102233A (ja) 1993-10-01 1995-04-18 Sekisui Chem Co Ltd 水性接着剤組成物
US5714543A (en) 1994-01-13 1998-02-03 Bristol-Myers Squibb Company Water soluble polymer additives for polyurethane-based pressure sensitive adhesives
US5486570A (en) 1994-09-29 1996-01-23 Shell Oil Company Polyurethane sealants and adhesives containing saturated hydrocarbon polyols
AU722654B2 (en) 1995-12-19 2000-08-10 Bristol-Myers Squibb Company Polyurethane pressure-sensitive adhesives
US5952422A (en) 1995-12-20 1999-09-14 Bristol-Myers Squibb Company Polyurethane pressure-sensitive adhesives
KR0173522B1 (ko) 1995-12-20 1999-04-01 최근배 폴리우레탄 프리폴리머의 제조방법, 상기 프리폴리머로부터 제조되는 수용성 폴리우레탄 분산체의 제조방법 및 그의 용도
US5576382A (en) * 1996-05-05 1996-11-19 Arco Chemical Technology, L.P. Aqueous polyurethane dispersions based on polyether polyols of low monol content
US5807919A (en) 1996-08-13 1998-09-15 H.B. Fuller Licensing & Financing, Inc. Water-based sulfonated polymer compositions
US5880250A (en) 1996-08-16 1999-03-09 Inolex Investment Corporation Polymeric acid functional polyols, polyurethanes and methods for making same
US5985317A (en) 1996-09-06 1999-11-16 Theratech, Inc. Pressure sensitive adhesive matrix patches for transdermal delivery of salts of pharmaceutical agents
US6130309A (en) * 1996-09-20 2000-10-10 Tyndale Plains-Hunter, Ltd. Hydrophilic polyether polyurethanes containing carboxylic acid
ES2190583T3 (es) 1997-01-16 2003-08-01 Dow Global Technologies Inc Adhesivo de latex de poliuretano sensible a la presion y procedimiento para fabricarlo.
DE19725297A1 (de) 1997-06-14 1998-12-17 Basf Ag Wässrige Polyurethandispersionen aus Polypropylenglykol mit geringem Harnstoffgehalt
BR9812514A (pt) 1997-09-24 2000-07-25 Henkel Kgaa Adesivo de poliuretana
US6162863A (en) * 1997-12-04 2000-12-19 Henkel Kommanditgesellschaft Auf Aktien Waterborne polyurethanes with urea-urethane linkages

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4985491A (en) * 1989-10-05 1991-01-15 Olin Corporation Polyurethane sealants made using high molecular weight polyols prepared with double metal cyanide catalysts
EP0573206A1 (en) * 1992-06-05 1993-12-08 ARCO Chemical Technology, L.P. Isocyanate-terminated prepolymers derived from polyether polyol mixtures having low monol content and their use in polyurethanes
WO1999038900A1 (en) * 1998-01-28 1999-08-05 Bristol-Myers Squibb Company Methods of preparing polyurethane adhesives, adhesives produced thereby and medical devices employing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10611873B2 (en) 2014-12-16 2020-04-07 3M Innovative Properties Company Polyurethane pressure-sensitive adhesives
EP3353258A4 (en) * 2015-09-21 2019-05-01 3M Innovative Properties Company CHEMICAL-RESISTANT POLYURETHANE ADHESIVE
EP3792325A1 (en) * 2015-09-21 2021-03-17 3M Innovative Properties Company Chemical resistant polyurethane adhesive

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DE60033059D1 (de) 2007-03-08
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EP1257590A1 (en) 2002-11-20
DE60033059T2 (de) 2007-11-08
AU2000255961A1 (en) 2001-09-03
JP2003524041A (ja) 2003-08-12

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