WO2002057383A1 - Pressure sensitive adhesives with a fibrous reinforcing material - Google Patents

Pressure sensitive adhesives with a fibrous reinforcing material Download PDF

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Publication number
WO2002057383A1
WO2002057383A1 PCT/US2001/018500 US0118500W WO02057383A1 WO 2002057383 A1 WO2002057383 A1 WO 2002057383A1 US 0118500 W US0118500 W US 0118500W WO 02057383 A1 WO02057383 A1 WO 02057383A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
pressure sensitive
reinforcing material
adhesive
sensitive adhesive
Prior art date
Application number
PCT/US2001/018500
Other languages
French (fr)
Other versions
WO2002057383A8 (en
Inventor
Zhou Zhiming
Albert I. Everaerts
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to DE60123838T priority Critical patent/DE60123838T2/en
Priority to AU2001266771A priority patent/AU2001266771A1/en
Priority to JP2002558442A priority patent/JP2004525209A/en
Priority to EP01944349A priority patent/EP1354013B1/en
Publication of WO2002057383A1 publication Critical patent/WO2002057383A1/en
Publication of WO2002057383A8 publication Critical patent/WO2002057383A8/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/58Adhesives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00Products made by additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/308Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive tape or sheet losing adhesive strength when being stretched, e.g. stretch adhesive
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1405Capsule or particulate matter containing [e.g., sphere, flake, microballoon, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1452Polymer derived only from ethylenically unsaturated monomer
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1462Polymer derived from material having at least one acrylic or alkacrylic group or the nitrile or amide derivative thereof [e.g., acrylamide, acrylate ester, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1481Dissimilar adhesives
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1486Ornamental, decorative, pattern, or indicia
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer

Definitions

  • the present invention relates to pressure sensitive adhesive compositions.
  • the invention discloses fiber reinforced pressure sensitive adhesives and methods for their preparation and use.
  • Pressure sensitive adhesives are generally characterized by their properties. Pressure sensitive adhesives are well known to one of ordinary skill in the art to possess properties including the following: (1) aggressive and permanent tack, (2) adherence to a substrate 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. Many pressure sensitive adhesives must satisfy these properties under an array of different stress rate conditions. Additives may be included in the pressure sensitive adhesive to optimize the characteristics of the pressure sensitive adhesive. In particular systems, the additive improves the cohesive strength of the pressure sensitive adhesives, yet the tack is reduced.
  • a non-tacky additive may be mixed with a pressure sensitive adhesive, reducing the tack of the mixture (as compared to the tack of the pressure sensitive adhesive without the additive).
  • thermoplastic polymers have been added to styrene block copolymer adhesives to reduce the tack of the resulting pressure sensitive adhesives.
  • care must be taken in choosing an additive.
  • U.S. Patent Number 6,063,838 discloses a pressure sensitive adhesive comprising a blend of at least two components, wherein the first component is at least one pressure sensitive adhesive and the second component is at least one thermoplastic material, wherein the components form a blended composition having more than one domain and, , wherein one domain is substantially continuous (generally, the pressure sensitive adhesive) and the other domain is substantially fibrillous to schistose (generally, the thermoplastic material).
  • the blended pressure sensitive adhesives of the 6,063,838 patent provide adhesives having one or more of the following properties including: (1) a peel adhesion greater than and shear strength similar to that of the pressure sensitive adhesive component if used alone, (2) a shear strength greater than and peel adhesion similar to that of the pressure sensitive adhesive component if used alone, (3) an anisotropic peel adhesion, (4) an anisotropic shear strength, (5) a tensile stress in the down-web direction that is at least two times greater than the tensile stress in the cross-web direction for all elongations up to the break elongation, and (6) a resistance to impact shear that is at least two times greater than that of the pressure sensitive adhesive component if used alone.
  • an adhesive composition that has improved cohesive strength without losing the tackiness indicative of a pressure sensitive adhesive.
  • a stretch removable adhesive composition is desirable.
  • This invention is directed to a fiber reinforced adhesive composition
  • a fiber reinforced adhesive composition comprising a pressure sensitive adhesive matrix and a fibrous reinforcing material within the pressure sensitive adhesive matrix.
  • the fiber reinforced adhesive composition of the invention allows for an improved cohesive strength over the pressure sensitive adhesive alone, yet the tack of the pressure sensitive adhesive remains substantially unreduced.
  • the adhesive composition has a yield strength and a tensile strength.
  • the tensile strength is about 0.7 MPa or greater.
  • the tensile strength is at least about 150% of the yield strength when tested according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).
  • the adhesive composition exhibits at least 50% elongation when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).
  • the fibrous reinforcing material comprises substantially continuous fibers within the pressure sensitive adhesive matrix. Additionally, in preferred embodiments, the fiber reinforced adhesive composition will display stretch removable characteristics and easy removal from a substrate.
  • the invention is directed to a method for making a fiber reinforced adhesive.
  • the method comprises forming a mixture comprising a pressure sensitive adhesive with a reinforcing material capable of forming fibers when subjected to an elongating shear force, and subjecting the mixture to the elongating shear force.
  • “Stretch removable” means that a pressure sensitive adhesive, when pulled and elongated (preferably from a substrate surface at a rate of 30 centimeters/minute and at an angle of no greater than 45°), detaches from a substrate surface without significant damage to the substrate surface (e.g. tearing), and without leaving a significant residue, preferably that which is visible to the unaided human eye on the substrate.
  • “Substantially continuous” means that for an at least 0.5 centimeter length sample of the adhesive composition taken in the machine direction, at least 50% of the fibers present in the sample are continuous (i.e. unbroken).
  • "Tensile strength” is the maximum tensile strength at break when tested according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).
  • the present invention is directed to a fiber reinforced adhesive composition comprising a pressure sensitive adhesive matrix and a reinforcing material within the pressure sensitive adhesive matrix.
  • the fiber reinforced adhesive composition of the present invention has improved cohesive strength, as represented by a higher tensile strength of the fiber reinforced adhesive composition as compared to the pressure sensitive adhesive without the reinforcing material. Additionally, in a preferred embodiment, the adhesive composition is stretch removable.
  • the adhesive composition of the invention has these properties while maintaining substantially unreduced tack properties in many embodiments.
  • the adhesive composition has a yield strength.
  • the yield strength is no less than about 0.1 MPa when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In specific embodiments, the yield strength is no less than about 0.2 MPa when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute) .
  • the adhesive composition has a tensile strength of at least about 150% of the yield strength when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In certain embodiments, the tensile strength is about 0.7 MPa or greater when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In specific embodiments, the tensile strength is about 0.8 MPa or greater when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).
  • the adhesive composition may have a tensile strength of at least about two times greater than the tensile strength of the pressure sensitive adhesive alone when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).
  • the elongation at break for the adhesive composition is at least about 50% when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute), preferably more than about 200%, and may be higher than about 300%. In some embodiments the elongation at break is in excess of about 800%.
  • 35° is less than about 20 Newtons/decimeter. This low removal force permits facile removal of the adhesive composition from a substrate. In certain embodiments, the force necessary to remove the adhesive composition from a substrate at such an angle is as low as about 7 Newtons/decimeter.
  • the pressure sensitive adhesive component can be any material that has pressure sensitive adhesive properties. Furthermore, the pressure sensitive adhesive component can be a single pressure sensitive adhesive or the pressure sensitive adhesive can be a combination of two or more pressure sensitive adhesives.
  • Pressure sensitive adhesives useful in the present invention include, for example, those based on natural rubbers, synthetic rubbers, styrene block copolymers, polyvinyl ethers, poly (meth)acrylates (including both acrylates and methacrylates), polyolefins, and silicones.
  • the pressure sensitive adhesive may be inherently tacky. If desired, tackifiers may be added to a base material to form the pressure sensitive adhesive.
  • Useful tackifiers include, for example, rosin ester resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and terpene resins. Other materials can be added for special purposes, including, for example, oils, plasticizers, antioxidants, ultraviolet ("UN”) stabilizers, hydrogenated butyl rubber, pigments, and curing agents.
  • the pressure sensitive adhesive is based on at least one poly(meth)acrylate (e.g. is a (meth)acrylic pressure sensitive adhesive).
  • Poly(meth)acrylic pressure sensitive adhesives are derived from, for example, at least one alkyl (meth)acrylate ester monomer such as, for example, isooctyl acrylate, isononyl acrylate, 2- methyl-butyl acrylate, 2-ethyl-hexyl acrylate and n-butyl acrylate; and at least one optional co-monomer component such as, for example, (meth)acrylic acid, vinyl acetate, ⁇ -vinyl pyrrolidone, (meth)acrylamide, a vinyl ester, a fumarate, a styrene macromer, or combinations thereof.
  • alkyl (meth)acrylate ester monomer such as, for example, isooctyl acrylate, isononyl acrylate, 2-
  • the poly(meth)acrylic pressure sensitive adhesive is derived from between about 0 and about 20 weight percent of acrylic acid and between about 100 and about 80 weight percent of at least one of isooctyl acrylate, 2-ethyl-hexyl acrylate or n-butyl acrylate composition, preferably isooctyl acrylate.
  • a preferred embodiment for the present invention is derived from between about 2 and about 10 weight percent acrylic acid and between about 90 and about 98 weight percent of at least one of isooctyl acrylate, 2-ethyl-hexyl acrylate or n-butyl acrylate composition.
  • One specific embodiment for the present invention is derived from about 2 weight percent to about 10 weight percent acrylic acid, about 90 weight percent to about 98 weight percent of isooctyl acrylate, and about 2 weight percent to about 6 weight percent styrene macromer. Reinforcing Material
  • the reinforcing material is a polymer.
  • the reinforcing material is elastomeric.
  • the reinforcing material is a semi- crystalline polymer.
  • a semi-crystalline polymer is one having both amorphous and crystalline domains.
  • Many specific embodiments incorporate semi-crystalline polymers, such as polycaprolactone (PCL), polybutene (PB), copolymers derived from ethylene and at least one other alpha-olefin monomer (e.g. poly(ethylene-co-l-alkene) and poly(ethylene-co-l-alkene-co-l-alkene)), ultra low density polyethylene (e.g.
  • polyethylene having a density below 0.915 grams/cubic centimeter, such as ATTANE 4202 commercially available from Dow Chemical Co.
  • linear low density polyethylene e.g. having a density between 0.915 and 0.94 grams/cubic centimeter, such as LL-3003, ECD-125, 377D60, 369G09, 363C32, 361C33, 357C32, 350D65, 350D64, 350D60, LL-3013, and LL-3001 commercially available from ExxonMobil Corp.
  • Preferred reinforcing materials have a measurable yield strength. In certain embodiments, the yield strength of the reinforcing material is less than about 20 MPa.
  • the tensile strength of the reinforcing material is preferably at least about 150% of its yield strength. In specific embodiments, the tensile strength of the reinforcing material is higher than the tensile strength of the pressure sensitive adhesive. These values are measured using ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute) .
  • the reinforcing material preferably has a melting point above the use temperature of the adhesive composition.
  • the reinforcing material preferably has a melting point above the storage temperature of the adhesive composition or any article manufactured with the adhesive composition. Both the use temperature and the storage temperature should not exceed the temperature that the pressure sensitive adhesive decomposes.
  • the reinforcing material has a melting point of at least 70 °C. All temperatures are related as being measurable by differential scanning calorimetry ("DSC") at a scanning rate of 10 °C/minute. It is particularly desirable for the reinforcing material to have a melt viscosity similar to the melt viscosity of the pressure sensitive adhesive at the processing temperature of the method of this invention.
  • the ratio of the reinforcing material melt viscosity to the pressure sensitive adhesive melt viscosity at the processing temperature is less than about 3, preferably less than about 1.5. In particularly preferred embodiments, the ratio is between about 0.5 and about 1.2 depending on specific extrusion parameters (e.g. shear rate, screw speed, temperature). Melt viscosity is measurable as understood by one skilled in the art using a capillary viscometer.
  • the reinforcing material is preferably immiscible (i.e. remains in a separate phase) in the pressure sensitive adhesive during mixing so that the reinforcing material can be substantially uniformly dispersed (i.e. distributed) in the pressure sensitive adhesive.
  • the reinforcing material is in the form of substantially spherical particles having an average diameter less than about 20 micrometers. In certain embodiments, the reinforcing material has an average diameter less than about 10 micrometers.
  • the reinforcing material exists as substantially continuous fibers in the adhesive composition.
  • the fibers are unbroken for at least about 0.5 centimeters in the machine direction of the pressure sensitive adhesive matrix, preferably at least about 2 centimeters.
  • the substantially continuous fibers are continuous for at least about 5 centimeters and most preferably at least about 8 centimeters.
  • the substantially continuous fibers generally have a maximum diameter of about 0.05 to about 5 micrometers, preferably from about 0.1 to about 1 micrometers.
  • the aspect ratio (i.e. the ratio of the length to the diameter) of the substantially continuous fibers is greater than about 1000.
  • the reinforcing material is mixed with the pressure sensitive adhesive before subjecting the mixture to an elongating shear force.
  • Mixing of the reinforcing material and the pressure sensitive adhesive is done by any method that results in a dispersion, preferably a substantially uniform dispersion, of the reinforcing material in the pressure sensitive adhesive.
  • melt blending, solvent blending, or any suitable physical means are able to adequately mix the reinforcing material and the pressure sensitive adhesive.
  • Melt blending devices include those that provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing. Both batch and continuous methods of melt blending can be used. Examples of batch methods include those using a BRABENDER (e.g.
  • BRABENDER PREP CENTER commercially available from C.W. Brabender Instruments, Inc.; Southhackensack, NJ
  • B ANBURY internal mixing and roll milling equipment e.g. equipment available from Farrel Co.; Ansonia, CT.
  • the mixture created may be immediately quenched and stored below melting temperature of the mixture for later processing.
  • Examples of continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding.
  • the continuous methods can include utilizing both distributive elements, such as cavity transfer mixers (e.g. CTM, commercially available from RAPRA Technology, Ltd.; Shrewsbury, England) and pin mixing elements, static mixing elements or dispersive mixing elements (commercially available from e.g., MADDOCK mixing elements or SAXTON mixing elements as described in "Mixing in Single-Screw
  • distributive elements such as cavity transfer mixers (e.g. CTM, commercially available from RAPRA Technology, Ltd.; Shrewsbury, England) and pin mixing elements, static mixing elements or dispersive mixing elements (commercially available from e.g., MADDOCK mixing elements or SAXTON mixing elements as described in "Mixing in Single-Screw
  • the reinforcing material comprises between about 2 and about 70 weight percent of the adhesive composition. In specific embodiments, the reinforcing material comprises between about 5 and about 60 weight percent of the adhesive composition. In preferred embodiments, the reinforcing material comprises between about 5 and about 50 weight percent of the adhesive composition.
  • the pressure sensitive adhesive component comprises between about 30 and about 98 weight percent, preferably between about 40 and about 95 weight percent and more preferably between about 50 and about 95 weight percent of the total adhesive composition. Other additives may also be mixed into the pressure sensitive adhesive composition prior to application thereof, depending on the desired properties of the applied adhesive.
  • the adhesive composition is subjected to an elongating shear force, creating fibers from the reinforcing material in a pressure sensitive adhesive matrix.
  • the adhesive composition is formed by continuous forming methods, including hot melt coating, drawing or extruding, the adhesive composition from the elongating shear force device (e.g. a draw die, a film die, or a rotary rod die) and subsequently contacting the drawn adhesive composition to a moving web (e.g. plastic) or other suitable substrate.
  • a related continuous forming method involves extruding the adhesive composition and a co- extruded backing material from a film die and cooling the layered product to form an adhesive tape.
  • the fibers, thus formed can be solidified by lowering the temperature of the adhesive composition to below the melting point of the reinforcing material. For example, the temperature may be lowered by quenching the adhesive composition using either direct methods (e.g., chill rolls or water baths) or indirect methods (e.g., air or gas impingement). The resulting fiber reinforced adhesive composition is then cooled to ambient temperature.
  • direct methods e.g., chill rolls or water baths
  • indirect methods e.g., air or gas impingement
  • the fiber reinforced adhesive composition can be used for a variety of applications.
  • the fiber reinforced adhesive composition can be applied to sheeting products (e.g., decorative, reflective, and graphical), labelstock, and tape backings to form, for example, first aid dressings, medical drapes, or medical tapes.
  • the fiber reinforced adhesive composition of the present invention can be used in optical fibers and tapes.
  • the substrate can be any suitable type of material depending on the desired application.
  • the fiber reinforced adhesive composition is coated onto at least a portion of a suitable backing.
  • a release material e.g., low adhesion backsize
  • the fiber reinforced adhesive composition is coated, for example by co-extrusion or lamination, onto at least a portion of both sides of the backing. Additionally, the adhesive can be coated on at least one release liner to form a transfer tape.
  • the backing comprises a nonwoven, paper, polypropylene (e.g., biaxially oriented Dolv ⁇ roDvlene CBOPP)). nolvethvlene. nolvester (e.v._ nolvethvlene terephthalate), or a release liner (e.g., siliconized liner).
  • the backing is stretchable so that an article comprising the adhesive composition and the backing would be stretch removable.
  • the adhesive compositions of the present invention are used in tapes that include gauze pads, for example, and are used as first aid dressings (i.e., wound or surgical dressings). They can also be used in a wide variety of other medical articles, such as medical tapes, athletic tapes, surgical drapes, or tapes or tabs used in adhering medical devices such as sensors, electrodes (as disclosed in U.S. Pat. No. 5,215,087 and U.S. Pat. No. 6,171,985, for example), ostomy appliances, or the like.
  • webs made from natural or synthetic fibers or mixtures thereof can be used to form backings, particularly for medical articles.
  • Nonwoven materials can be employed for webs, with nonwoven materials being preferred for most applications. Melt-blown or spunbond techniques can be employed to make such nonwoven webs. Nonwoven webs can also be prepared, for example, on a RANDO WEBBER (Rando Corporation, Ard, NY) air-laying machine or on a carding machine.
  • RANDO WEBBER Radio Corporation, Rochester, NY
  • fibers forming a nonwoven tape backing are intimately entangled with each other in the form of a coherent breathable fibrous nonwoven tape backing.
  • Suitable nonwoven tape backings can be formed as melt blown microfiber webs using the apparatus discussed, for example, in Wente, Van A., "Superfine Thermoplastic Fibers,"
  • microfine fibers are termed melt blown fibers or blown microfibers (BMF) and are generally substantially continuous and form a coherent web between the exit die orifice and a collecting surface by entanglement of the microfibers, due in part to the turbulent airstream in which the fibers are entrained.
  • BMF melt blown fibers or blown microfibers
  • melt spinning type processes such as spunbond processes, where fibers are collected in a web form immediately upon formation, can also be used to form the nonwoven tape backing.
  • the fibers are 100 microns or less in diameter when formed by melt spinning type processes, preferably 50 microns or less.
  • Multicomponent fibers, if formed by the melt blown process can be produced as described in U.S. Pat. Nos. 5,176,952 (Joseph et al); 5,232,770 (Joseph); 5,238,733 (Joseph et al); 5,258,220 (Joseph); or 5,248,455 (Joseph et al).
  • Multicomponent fibers can also be produced by a spunbond process as disclosed in U.S. Pat. Nos. 5,695,868 (McCormach); 5,336,552 (Strack et al); 5,545,464 (Stokes); 5,382,400; 5,512,358
  • materials suitable for the backing of the adhesive article of this invention include polyolefins, such as polyethylene, including high density polyethylene, low density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylene, and polybutylenes; vinyl copolymers, such as poly vinyl chlorides, both plasticized and unplasticized, and poly vinyl acetates; olefinic copolymers, such as ethylene/methacrylate copolymers, ethylene/vinyl acetate copolymers, acrylonitrile-butadiene-styrene copolymers, and ethylene/propylene copolymers; acrylic polymers and copolymers; polycaprolactones; and combinations of the foregoing.
  • polyolefins such as polyethylene, including high density polyethylene, low density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylene, and polybutylenes
  • vinyl copolymers such as poly vinyl chlorides, both plasticized and un
  • any plastic or plastic and elastomeric materials such as polypropylene/polyethylene, polyurethane/polyolefin, polyurethane/polycarbonate, polyurethane/polyester, can also be used. Additionally, any nonstretchable material can be used for the tearable backings or for those with perforations, including paper and even metal.
  • Preferred materials for the backing include polyurethane, polypropylene, ethylene vinyl acetate, or combinations thereof (e.g., blends, mixtures, etc.) in the form of melt blown fibers.
  • Preferred materials for film backings include polycaprolactones and copolymers of ethylene/vinyl acetate and linear low density polyethylene.
  • the backing is formed from coherent multicomponent fibers having at least one pressure sensitive adhesive region or layer and at least one non- pressure sensitive adhesive region or layer as described in U.S. Pat. No. 6,107,219.
  • the backing is a melt blown polypropylene web available from Kimberly Clark Corp.; Irving, TX.
  • the backing is in the form of a laminate
  • additional components could be used, such as absorbent layers (e.g., gauze pads) for adhesive bandage products, or the like. If absorbent layers are used, they are typically thin, coherent, conformable, and able to flex and not interfere with the stretch removable characteristics of the articles, although they can be stretchable or not.
  • absorbent layers are typically thin, coherent, conformable, and able to flex and not interfere with the stretch removable characteristics of the articles, although they can be stretchable or not.
  • a laminate there may be one or more additional layers.
  • the outermost layer of such a laminate is a film that is substantially impervious to fluids, such as could arise from the external environment, yet permits passage of moisture vapor such that the adhesive article is breathable (typically, having a moisture vapor transmission rate (MNTR) of at least about 500 g/m 2 /day).
  • MNTR moisture vapor transmission rate
  • this breathable, liquid impervious film is the outermost (i.e., top) layer.
  • film materials include polyurethanes, polyolefins, metallocene catalyzed polyolefins, polyesters, polyamides, polyetheresters, and A-B-A block copolymers, such as KRATO ⁇ copolymers available from Shell Chemical Ltd.; Houston, TX.
  • This peel adhesion test is similar to the test method described in ASTM D 3330-90, substituting a glass, high density polyethylene or polypropylene substrate for the stainless steel substrate described in the test.
  • the substrate used is noted in each particular example.
  • the substrate panel was either solvent-washed glass, polypropylene (PP), or high density polyethylene (HDPE) using a 2 kilogram roller passed once over the strip.
  • the bonded assembly was allowed to dwell at room temperature for one minute.
  • the assembly was then tested for 180° peel adhesion in the machine direction using an IMASS slip/peel tester (Model 3M90, commercially available from Instrumentors Inc., StrongsviUe, OH) at a crosshead speed of 30 centimeters/minute (12 inches/minute).
  • Adhesive-coated strips which had equilibrated at constant temperature (21°C) and humidity (50% relative humidity) for at least 24 hours, were adhered to a polypropylene (PP) substrate panel using a 2 kilogram roller passed once over the strip.
  • the bonded assemblv was allowed to dwell at room t mn rafnr for one, minute.
  • the assembly was then tested for stretch release by pulling at an angle of between 15 and 35° either "by hand", or "mechanically” using an ASS slip/peel tester (Model 3M90, commercially available from Instrumentors Inc., StrongsviUe, OH) at a crosshead speed of 30 centimeters/minute (12 inches/minute).
  • the data are reported for the by hand samples as “broke” if the sample broke before detachment (i.e. the sample did not stretch release), or “yes” if the sample exhibited stretch release properties.
  • the data is reported as "broke” if the sample broke (i.e. the sample did not stretch release), or, if the sample did exhibit stretch release properties, the maximum stretch release force in Newtons/decimeter is reported.
  • Probe tack measurements were made following the test method described in ASTM D 2979-95 using a TA-XY2 texture tester (commercially available from Stable Microsystems, Surrey, U.K.).
  • the pressure sensitive adhesive matrix was dissolved, leaving behind the fibrous reinforcing material.
  • a strip of the adhesive composition film (approximately 7.5 centimeters long by 2.5 centimeters wide) was cut from the film in the machine direction.
  • the strip was suspended on an open frame by looping the film over the edge of the open frame.
  • the frame and adhesive strip were immersed in a solvent capable of dissolving the pressure sensitive adhesive but not the fibrous reinforcing material. After 24 hours the sample was checked to determine if the pressure sensitive adhesive had completely dissolved and if the fibrous reinforcing material remained on the frame. If fibers were not continuous for at least 5 centimeters, nothing remained on the frame. The samples were rated as "pass” if fibers remained on the frame and "fail” if no fibers remained on the frame.
  • Films of possible fibrous reinforcing material were prepared by hot-press molding each reinforcing material to a thickness of 1 2 micrometers. The films were tested using the Tensile Testing method described above. The results are shown in Table 1. Additionally, the materials are characterized as being elastomeric (rebounds upon deformation) or plastic (deforms permanently).
  • a sample of PSA- 1 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 127 micrometers.
  • the tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 2.
  • a portion of the film was laminated to a PET backing to make a tape.
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a total ultraviolet dose of 300 milliJoules/cm 2 .
  • the tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
  • Comparative Example C2 A mixture of 90 parts PSA- 1, 10 parts ENGAGE 8200 and 0.2 part benzophenone was prepared in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 2. A portion of the film was laminated to a PET backing to make a tape.
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a total ultraviolet dose of 300 milliJoules/cm 2 .
  • the tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
  • Comparative Example C3 A mixture of 90 parts PS A-l , 10 parts of LDPE and 0.2 part benzophenone were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 2.
  • a portion of the film was laminated to a PET backing to make a tape.
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a total ultraviolet dose of 300 milliJoules/cm 2 .
  • the tape was tested for
  • a mixture of 90 parts PSA-1, 10 parts ENGAGE 8490 and 0.2 part benzophenone were mixed in a BRABENDER mixer (commercially available from C.W. Brabender
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm .
  • the tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
  • a mixture of 90 parts PSA-1, 10 parts of ATTANE 4202 and 0.2 part benzophenone were mixed in a BRABENDER mixer (commer ⁇ ially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 127 micrometers.
  • the tensile properties of the film were determined as described in the Tensile Test Method above. The results are shown in Table 2.
  • a portion of the film was laminated to a PET backing to make a tape.
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm 2 .
  • the tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
  • a sample of PSA-1 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape.
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm 2 .
  • the tape was tested for 180° Peel Adhesion from glass in the machine and the cross-web directions. The results are shown in Table 4.
  • a mixture of 90 parts PSA-1 and 10 parts of ATTANE 4202 were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South
  • a sample of PSA-1 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 51 micrometers and was laminated to a PET backing to make a tape.
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm 2 .
  • the tape was tested for 180° Peel Adhesion from glass in the machine and cross-web directions. The results are shown in Table 5.
  • Comparative Example C6 A mixture of 90 parts PSA-1 and 10 parts of LDPE were mixed in a
  • BRABENDER mixer commercially available from C.W. Brabender Instruments, Southhackensack, NJ
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 51 micrometers and was laminated to a PET backing to make a tape.
  • the tape was tested for 180° Peel Adhesion from glass in the machine and cross-web directions. The results are shown in Table 5.
  • Example 4 A mixture of 90 parts PSA-1 and 10 parts of ATTANE 4202 were mixed in a
  • BRABENDER mixer commercially available from C.W. Brabender Instruments, South Hackensack, NJ
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 51 micrometers and was laminated to a PET backing to make a tape.
  • the resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm 2 .
  • the tape was tested for 180° Peel Adhesion from glass in the machine and cross-web directions. The results are shown in Table 5.
  • PSA-2 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape.
  • the tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 6.
  • a mixture of 90 parts PSA-2 and 10 parts of ATTANE 4202 were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape.
  • the tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 6.
  • a sample of PSA-3 was used as obtained and hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape.
  • the tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 7.
  • a mixture of 90 parts PSA-3 and 10 parts of ATTANE 4202 were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape.
  • the tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 7.
  • a sample of PSA-4 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8.
  • a mixture of 85 parts PSA-4 and 15 parts of PS were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, Southhackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8.
  • a mixture of 85 parts PSA-4 and 15 parts HDPE were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, Southhackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8.
  • the mixtures for Examples 9-13 were prepared using PSA-5 with the level of ATTANE 4202 shown in Table 9, were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in
  • Examples 14-16 and Comparative Examples C12-C14 were prepared using PSA-4 with 15 weight % of a polymer as shown in Table 10, and were mixed in a BRABENDER mixer (commercially available form C.W. Brabender instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers.
  • the stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 10.
  • Example 17-22 and Comparative Example C15 were prepared using PSA-4 with the level of ATTANE 4202 shown in Table 11, and were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers.
  • the stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 11.
  • Example 23-25 and Comparative Example C16 were prepared using PSA-6 with the level of ATTANE 4202 shown in Table 12 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers.
  • the stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 12.
  • Examples 26-27 and Comparative Example C17 The mixtures for Examples 26-27 and Comparative Example C17 were prepared using PSA-7 with the level of ATTANE 4202 shown in Table 13 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 127 micrometers. The stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 13. Table 13
  • Example 28-30 and Comparative Example C18 were prepared using PSA-6 with the level of ATTANE 4202 shown in Table 14 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers.
  • the probe tack properties of the films were determined as described in the Probe Tack Test method above. The results are shown in Table 14.
  • Example 31-32 and Comparative Example C19 were prepared using PSA-7 with the level of ATTANE 4202 shown in Table 15 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 or 127 micrometers.
  • the probe tack properties of the films were determined as described in the Probe Tack Test method above. The results are shown in Table 15.
  • Example 33-37 and Comparative Example C20 were prepared using PSA-4 with the level of ATTANE 4202 shown in Table 16 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixtures were hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give films having a thickness of 51 or 127 micrometers.
  • the probe tack properties of the films were determined as described in the Probe Tack Test method above. The results are shown in Table 16. Table 16
  • the mixtures for Examples 38-41 were prepared using PSA-5 with the level of ATTANE 4202 shown in Table 23, and were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the solvent extraction properties of the film were determined as described in the Solvent Extraction Test method above. The results are shown in Table 23.
  • a stretch removable First Aid Dressing (FAD) sample was made by laminating with thumb pressure at room temperature a strip (2.54-cm x 7.6-cm) of a perforated polymer film backing to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20, with the fibers perpendicular to the long axis of the sample.
  • the film backing comprised 60% ethylene/vinyl acetate copolymer, 35% linear low density polyethylene, 5% stabilizers and other additives (PGI Product No.
  • the film had a basis weight of 1.15 oz/yd 2 (27 g/m 2 ), was 5-mils (0.13-mm) thick, and had oval-shaped holes (approximately 0.2-mm width x 0.3-mm length in the greatest dimensions) with the length dimension of the oval holes oriented parallel to the machine direction of the film.
  • the film had about 530 holes/cm 2 arranged in a pattern of staggered lines.
  • the FAD sample was evaluated for ease of removal by adhering the sample with finger pressure to the forearm of a human subject, waiting 60 minutes, and then removing by pulling one end of the sample and stretching the sample at about a 35° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm.
  • a polyurethane backing (melt-blown nonwoven fibrous web comprised of three- layer polymeric fibers having a center layer of blended polyethylene and KratonTM PSA, and outer layers of polyurethane; prepared as described for Backing Sample 16 in U.S. Pat. No. 6,107,219 (Joseph et al.)) was perforated with a metal die to provide parallel rows of holes separated by 3.8 cm. The holes were rectangular in shape (1.75-mm x 0.07 -mm) and the space between holes within a row was 0.7 mm.
  • the polyurethane backing had one side rougher than the other due to the collection technique used during the melt-blown process.
  • a stretch removable FAD sample was made by laminating with thumb pressure at room temperature a strip (2.54-cm x 7.6-cm) of the perforated polyurethane backing to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20, with the fibers perpendicular to the long axis of the sample.
  • the "rough" side of the backing was adjacent the adhesive layer.
  • a 1.8-cm x 2.5-cm gauze pad was attached to the adhesive layer in the center of the sample and the holes had been pre-cut such that the rows began 6 mm from each end of the sample.
  • the FAD sample was evaluated for ease of removal by adhering the sample with finger pressure to the forearm of a human subject, waiting 10 minutes, and then removing by lifting and stretching the gauze pad at about a 90° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm. During stretching and removal, the backing was observed to break and to delaminate from the adhesive layer.
  • a paper backing (Hammermill Laserprint paper (0.11-mm thick), Product No. 00460-4, International Paper, Memphis, TN)) was perforated with a metal die to provide parallel rows of holes separated by 6.35 cm.
  • the holes were rectangular in shape (1.75- mm x 0.07 -mm) with the long sides of the holes oriented in the direction of the rows and the space between holes within a row was 0.7 mm.
  • a FAD sample was made by laminating with thumb pressure at room temperature a strip (2.54-cm x 7.6-cm) of the perforated paper backing to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20, with the fibers perpendicular to the long axis of the sample.
  • a 1.8-cm x 2.5-cm gauze pad was attached to the adhesive layer in the center of the sample and the holes had been pre-cut such that the rows began 6 mm from each end of the sample.
  • the FAD sample was evaluated for ease of removal by adhering the sample with finger pressure to the forearm of a human subject, waiting 10 minutes, and then removing by pulling one end of the sample and stretching the sample at about a 35° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm. During stretching and removal, the backing was observed to break and to delaminate from the adhesive layer.
  • the sheets were oriented such that the adhesive layer, when subsequently stretched for removal, would be stretched in a direction parallel to the machine direction of the adhesive layer. Prior to lamination, the adhesive sheet was covered along one edge with a strip of paper that could serve as a handle for grasping the adhesive layer alone.
  • the resulting laminate was cut into a 2.54-cm x 7.6-cm FAD sample and adhered with thumb pressure onto a mirror-finished steel plate with the paper handle allowed to extend over the end of the plate.
  • the paper handle of the sample was finger-grasped and stretched in the plane of the adhesive-backing interface at a rate of about 150 cm/min. Upon stretching, the adhesive released from between the plate surface and the backing.
  • Example 46 A FAD sample was made by laminating with thumb pressure a room temperature a strip (2.54-cm x 7.6-cm) of a polypropylene backing [melt-blown nonwoven polypropylene (basis weight 20 g/m 2 ), Kimberly-Clark, Irving, TX ] to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20.
  • a 1.3-cm piece of the adhesive/backing laminate was gathered in the middle of the strip in such a way that a fold was made perpendicular to the greatest length of the strip.
  • a 1.8-cm x 2.5-cm gauze pad was attached to the adhesive layer in the center of the sample.
  • the FAD sample was evaluated by adhering the sample with finger pressure to the forearm of a human subject, waiting 10 minutes, and then using the fold in the FAD as a handle, removing by lifting and stretching the gauze pad at about a 90° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm. During stretching and removal, the backing was observed to break and to delaminate from the adhesive layer.
  • Example 47 A FAD sample having a center fold and a gauze pad was made as described in
  • Example 46 except that the polyurethane backing (as described in Example 43) was used in place of the polypropylene backing.
  • the sample was evaluated as described in Example 46. During stretching and removal, the backing was observed to delaminate from the adhesive layer.
  • Example 49 A FAD sample having a center fold and a gauze pad was made as described in Example 46, except that the adhesive described in Example 28 was used as the adhesive. The sample was evaluated and the same results obtained as described in Example 46.
  • Example 49
  • a blend of 80 parts of PSA-7 and 20 parts of ATTANE 4202 were mixed in a BRABENDER mixer (C.W. Brabender Instruments, Southhackensack, NJ) at 140°C to 150°C for 8 to 10 minutes.
  • the resulting mixtures were hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die.
  • the resulting PSA film had a thickness of 127 micrometers and was laminated to a PCL backing of thickness listed in Table 30 (prepared by solvent coating a 20% solids solution of PCL in toluene onto a release liner and drying at 70°C for 10 minutes) to make a tape.
  • the stretch release properties of the tape was determined as described in the Stretch Release Test Method above except that samples were tested not only in the machine direction but also in the cross web direction and at 45° to the machine direction.
  • the results of the laminated samples as well as the PSA film not laminated to a backing are shown in Table 30.

Abstract

This invention is directed to a fiber reinforced adhesive composition comprising a pressure sensitive adhesive matrix and a fibrous reinforcing material within the pressure sensitive adhesive matrix. The adhesive composition has a yield strength and a tensile strength. The tensile strength is at least about 150 % of the yield strength. Generally, the adhesive composition exhibits these properties at least 50 % elongation when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).

Description

PRESSURE SENSITIVE ADHESIVES WITH A FIBROUS REINFORCING
MATERIAL
Field of the Invention
The present invention relates to pressure sensitive adhesive compositions. In particular, the invention discloses fiber reinforced pressure sensitive adhesives and methods for their preparation and use.
Background of the Invention
Pressure sensitive adhesives are generally characterized by their properties. Pressure sensitive adhesives are well known to one of ordinary skill in the art to possess properties including the following: (1) aggressive and permanent tack, (2) adherence to a substrate 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. Many pressure sensitive adhesives must satisfy these properties under an array of different stress rate conditions. Additives may be included in the pressure sensitive adhesive to optimize the characteristics of the pressure sensitive adhesive. In particular systems, the additive improves the cohesive strength of the pressure sensitive adhesives, yet the tack is reduced. For example, a non-tacky additive may be mixed with a pressure sensitive adhesive, reducing the tack of the mixture (as compared to the tack of the pressure sensitive adhesive without the additive). In a specific example, thermoplastic polymers have been added to styrene block copolymer adhesives to reduce the tack of the resulting pressure sensitive adhesives. However, to avoid loss of tack when enhancing the pressure sensitive adhesive 's cohesive strength, care must be taken in choosing an additive.
U.S. Patent Number 6,063,838 discloses a pressure sensitive adhesive comprising a blend of at least two components, wherein the first component is at least one pressure sensitive adhesive and the second component is at least one thermoplastic material, wherein the components form a blended composition having more than one domain and, , wherein one domain is substantially continuous (generally, the pressure sensitive adhesive) and the other domain is substantially fibrillous to schistose (generally, the thermoplastic material). The blended pressure sensitive adhesives of the 6,063,838 patent provide adhesives having one or more of the following properties including: (1) a peel adhesion greater than and shear strength similar to that of the pressure sensitive adhesive component if used alone, (2) a shear strength greater than and peel adhesion similar to that of the pressure sensitive adhesive component if used alone, (3) an anisotropic peel adhesion, (4) an anisotropic shear strength, (5) a tensile stress in the down-web direction that is at least two times greater than the tensile stress in the cross-web direction for all elongations up to the break elongation, and (6) a resistance to impact shear that is at least two times greater than that of the pressure sensitive adhesive component if used alone. What is desired is an adhesive composition that has improved cohesive strength without losing the tackiness indicative of a pressure sensitive adhesive. In conjunction, it is desirable to create an adhesive composition that is removable from a substrate with ease without losing the tackiness indicative of a pressure sensitive adhesive. Additionally, a stretch removable adhesive composition is desirable.
Summary of the Invention
This invention is directed to a fiber reinforced adhesive composition comprising a pressure sensitive adhesive matrix and a fibrous reinforcing material within the pressure sensitive adhesive matrix. The fiber reinforced adhesive composition of the invention allows for an improved cohesive strength over the pressure sensitive adhesive alone, yet the tack of the pressure sensitive adhesive remains substantially unreduced.
The adhesive composition has a yield strength and a tensile strength. In one embodiment, the tensile strength is about 0.7 MPa or greater. In another embodiment, the tensile strength is at least about 150% of the yield strength when tested according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In one embodiment, the adhesive composition exhibits at least 50% elongation when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In certain embodiments, the fibrous reinforcing material comprises substantially continuous fibers within the pressure sensitive adhesive matrix. Additionally, in preferred embodiments, the fiber reinforced adhesive composition will display stretch removable characteristics and easy removal from a substrate. In addition, the invention is directed to a method for making a fiber reinforced adhesive. The method comprises forming a mixture comprising a pressure sensitive adhesive with a reinforcing material capable of forming fibers when subjected to an elongating shear force, and subjecting the mixture to the elongating shear force. In this application, the following terms are defined as follows, unless otherwise stated:
"Stretch removable" means that a pressure sensitive adhesive, when pulled and elongated (preferably from a substrate surface at a rate of 30 centimeters/minute and at an angle of no greater than 45°), detaches from a substrate surface without significant damage to the substrate surface (e.g. tearing), and without leaving a significant residue, preferably that which is visible to the unaided human eye on the substrate.
"Substantially continuous" means that for an at least 0.5 centimeter length sample of the adhesive composition taken in the machine direction, at least 50% of the fibers present in the sample are continuous (i.e. unbroken). "Tensile strength" is the maximum tensile strength at break when tested according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).
Detailed Description of the Invention The present invention is directed to a fiber reinforced adhesive composition comprising a pressure sensitive adhesive matrix and a reinforcing material within the pressure sensitive adhesive matrix. The fiber reinforced adhesive composition of the present invention has improved cohesive strength, as represented by a higher tensile strength of the fiber reinforced adhesive composition as compared to the pressure sensitive adhesive without the reinforcing material. Additionally, in a preferred embodiment, the adhesive composition is stretch removable. The adhesive composition of the invention has these properties while maintaining substantially unreduced tack properties in many embodiments.
In the present invention, the adhesive composition has a yield strength. In certain embodiments, the yield strength is no less than about 0.1 MPa when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In specific embodiments, the yield strength is no less than about 0.2 MPa when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute) .
Additionally, the adhesive composition has a tensile strength of at least about 150% of the yield strength when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In certain embodiments, the tensile strength is about 0.7 MPa or greater when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). In specific embodiments, the tensile strength is about 0.8 MPa or greater when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute). The adhesive composition may have a tensile strength of at least about two times greater than the tensile strength of the pressure sensitive adhesive alone when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute).
For preferred embodiments, the elongation at break for the adhesive composition is at least about 50% when measured according to ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute), preferably more than about 200%, and may be higher than about 300%. In some embodiments the elongation at break is in excess of about 800%.
Additionally, in preferred embodiments, the amount of force required to remove the adhesive composition from a polypropylene substrate at an angle of between 15° and
35° is less than about 20 Newtons/decimeter. This low removal force permits facile removal of the adhesive composition from a substrate. In certain embodiments, the force necessary to remove the adhesive composition from a substrate at such an angle is as low as about 7 Newtons/decimeter.
Pressure Sensitive Adhesive
Any suitable pressure sensitive adhesive composition can be used for this invention. The pressure sensitive adhesive component can be any material that has pressure sensitive adhesive properties. Furthermore, the pressure sensitive adhesive component can be a single pressure sensitive adhesive or the pressure sensitive adhesive can be a combination of two or more pressure sensitive adhesives. Pressure sensitive adhesives useful in the present invention include, for example, those based on natural rubbers, synthetic rubbers, styrene block copolymers, polyvinyl ethers, poly (meth)acrylates (including both acrylates and methacrylates), polyolefins, and silicones. The pressure sensitive adhesive may be inherently tacky. If desired, tackifiers may be added to a base material to form the pressure sensitive adhesive. Useful tackifiers include, for example, rosin ester resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, and terpene resins. Other materials can be added for special purposes, including, for example, oils, plasticizers, antioxidants, ultraviolet ("UN") stabilizers, hydrogenated butyl rubber, pigments, and curing agents.
In a preferred embodiment, the pressure sensitive adhesive is based on at least one poly(meth)acrylate (e.g. is a (meth)acrylic pressure sensitive adhesive). Poly(meth)acrylic pressure sensitive adhesives are derived from, for example, at least one alkyl (meth)acrylate ester monomer such as, for example, isooctyl acrylate, isononyl acrylate, 2- methyl-butyl acrylate, 2-ethyl-hexyl acrylate and n-butyl acrylate; and at least one optional co-monomer component such as, for example, (meth)acrylic acid, vinyl acetate, Ν-vinyl pyrrolidone, (meth)acrylamide, a vinyl ester, a fumarate, a styrene macromer, or combinations thereof. Preferably, the poly(meth)acrylic pressure sensitive adhesive is derived from between about 0 and about 20 weight percent of acrylic acid and between about 100 and about 80 weight percent of at least one of isooctyl acrylate, 2-ethyl-hexyl acrylate or n-butyl acrylate composition, preferably isooctyl acrylate. A preferred embodiment for the present invention is derived from between about 2 and about 10 weight percent acrylic acid and between about 90 and about 98 weight percent of at least one of isooctyl acrylate, 2-ethyl-hexyl acrylate or n-butyl acrylate composition. One specific embodiment for the present invention is derived from about 2 weight percent to about 10 weight percent acrylic acid, about 90 weight percent to about 98 weight percent of isooctyl acrylate, and about 2 weight percent to about 6 weight percent styrene macromer. Reinforcing Material
Various reinforcing materials may be used to practice the present invention. In preferred embodiments, the reinforcing material is a polymer. In specific embodiments, the reinforcing material is elastomeric. Preferably, the reinforcing material is a semi- crystalline polymer. A semi-crystalline polymer is one having both amorphous and crystalline domains. Many specific embodiments incorporate semi-crystalline polymers, such as polycaprolactone (PCL), polybutene (PB), copolymers derived from ethylene and at least one other alpha-olefin monomer (e.g. poly(ethylene-co-l-alkene) and poly(ethylene-co-l-alkene-co-l-alkene)), ultra low density polyethylene (e.g. having a density below 0.915 grams/cubic centimeter, such as ATTANE 4202 commercially available from Dow Chemical Co.), linear low density polyethylene (e.g. having a density between 0.915 and 0.94 grams/cubic centimeter, such as LL-3003, ECD-125, 377D60, 369G09, 363C32, 361C33, 357C32, 350D65, 350D64, 350D60, LL-3013, and LL-3001 commercially available from ExxonMobil Corp.) or combinations thereof. Preferred reinforcing materials have a measurable yield strength. In certain embodiments, the yield strength of the reinforcing material is less than about 20 MPa. The tensile strength of the reinforcing material is preferably at least about 150% of its yield strength. In specific embodiments, the tensile strength of the reinforcing material is higher than the tensile strength of the pressure sensitive adhesive. These values are measured using ASTM D 882-97 at a crosshead speed of 12 inches/minute (30 centimeters/minute) .
The reinforcing material preferably has a melting point above the use temperature of the adhesive composition. Similarly, the reinforcing material preferably has a melting point above the storage temperature of the adhesive composition or any article manufactured with the adhesive composition. Both the use temperature and the storage temperature should not exceed the temperature that the pressure sensitive adhesive decomposes. In certain embodiments, the reinforcing material has a melting point of at least 70 °C. All temperatures are related as being measurable by differential scanning calorimetry ("DSC") at a scanning rate of 10 °C/minute. It is particularly desirable for the reinforcing material to have a melt viscosity similar to the melt viscosity of the pressure sensitive adhesive at the processing temperature of the method of this invention. In specific embodiments, the ratio of the reinforcing material melt viscosity to the pressure sensitive adhesive melt viscosity at the processing temperature is less than about 3, preferably less than about 1.5. In particularly preferred embodiments, the ratio is between about 0.5 and about 1.2 depending on specific extrusion parameters (e.g. shear rate, screw speed, temperature). Melt viscosity is measurable as understood by one skilled in the art using a capillary viscometer.
The reinforcing material is preferably immiscible (i.e. remains in a separate phase) in the pressure sensitive adhesive during mixing so that the reinforcing material can be substantially uniformly dispersed (i.e. distributed) in the pressure sensitive adhesive. In specific embodiments, during mixing, the reinforcing material is in the form of substantially spherical particles having an average diameter less than about 20 micrometers. In certain embodiments, the reinforcing material has an average diameter less than about 10 micrometers.
In preferred embodiments, the reinforcing material exists as substantially continuous fibers in the adhesive composition. Specifically, according to one aspect of the invention, the fibers are unbroken for at least about 0.5 centimeters in the machine direction of the pressure sensitive adhesive matrix, preferably at least about 2 centimeters. In more preferred embodiments, the substantially continuous fibers are continuous for at least about 5 centimeters and most preferably at least about 8 centimeters. According to another aspect of the invention, the substantially continuous fibers generally have a maximum diameter of about 0.05 to about 5 micrometers, preferably from about 0.1 to about 1 micrometers. According to another aspect of the invention, the aspect ratio (i.e. the ratio of the length to the diameter) of the substantially continuous fibers is greater than about 1000.
Mixing
The reinforcing material is mixed with the pressure sensitive adhesive before subjecting the mixture to an elongating shear force. Mixing of the reinforcing material and the pressure sensitive adhesive is done by any method that results in a dispersion, preferably a substantially uniform dispersion, of the reinforcing material in the pressure sensitive adhesive. For example, melt blending, solvent blending, or any suitable physical means are able to adequately mix the reinforcing material and the pressure sensitive adhesive. Melt blending devices include those that provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing. Both batch and continuous methods of melt blending can be used. Examples of batch methods include those using a BRABENDER (e.g. a BRABENDER PREP CENTER, commercially available from C.W. Brabender Instruments, Inc.; South Hackensack, NJ) or B ANBURY internal mixing and roll milling equipment (e.g. equipment available from Farrel Co.; Ansonia, CT). After batch mixing, the mixture created may be immediately quenched and stored below melting temperature of the mixture for later processing.
Examples of continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding. The continuous methods can include utilizing both distributive elements, such as cavity transfer mixers (e.g. CTM, commercially available from RAPRA Technology, Ltd.; Shrewsbury, England) and pin mixing elements, static mixing elements or dispersive mixing elements (commercially available from e.g., MADDOCK mixing elements or SAXTON mixing elements as described in "Mixing in Single-Screw
Extruders," Mixing in Polymer Processing, edited by Chris Rauwendaal (Marcel Dekker Inc.: New York (1991), pp. 129, 176-177, and 185-186).
In certain embodiments, the reinforcing material comprises between about 2 and about 70 weight percent of the adhesive composition. In specific embodiments, the reinforcing material comprises between about 5 and about 60 weight percent of the adhesive composition. In preferred embodiments, the reinforcing material comprises between about 5 and about 50 weight percent of the adhesive composition. Typically, the pressure sensitive adhesive component comprises between about 30 and about 98 weight percent, preferably between about 40 and about 95 weight percent and more preferably between about 50 and about 95 weight percent of the total adhesive composition. Other additives may also be mixed into the pressure sensitive adhesive composition prior to application thereof, depending on the desired properties of the applied adhesive.
Method of Forming the Fiber Reinforced Pressure Sensitive Adhesive The adhesive composition is subjected to an elongating shear force, creating fibers from the reinforcing material in a pressure sensitive adhesive matrix. Preferably, the adhesive composition is formed by continuous forming methods, including hot melt coating, drawing or extruding, the adhesive composition from the elongating shear force device (e.g. a draw die, a film die, or a rotary rod die) and subsequently contacting the drawn adhesive composition to a moving web (e.g. plastic) or other suitable substrate. A related continuous forming method involves extruding the adhesive composition and a co- extruded backing material from a film die and cooling the layered product to form an adhesive tape. Other continuous forming methods involve directly contacting the adhesive composition to a rapidly moving web or other suitable preformed substrate. Using this method, the adhesive composition is applied to the moving preformed web using a die having flexible die lips, such as a rotary rod die. After forming by any of these continuous methods, the fibers, thus formed, can be solidified by lowering the temperature of the adhesive composition to below the melting point of the reinforcing material. For example, the temperature may be lowered by quenching the adhesive composition using either direct methods (e.g., chill rolls or water baths) or indirect methods (e.g., air or gas impingement). The resulting fiber reinforced adhesive composition is then cooled to ambient temperature.
Application of the Fiber Reinforced Adhesive Composition
The fiber reinforced adhesive composition can be used for a variety of applications. For example, the fiber reinforced adhesive composition can be applied to sheeting products (e.g., decorative, reflective, and graphical), labelstock, and tape backings to form, for example, first aid dressings, medical drapes, or medical tapes. Additionally, the fiber reinforced adhesive composition of the present invention can be used in optical fibers and tapes. The substrate can be any suitable type of material depending on the desired application. To form a tape, the fiber reinforced adhesive composition is coated onto at least a portion of a suitable backing. A release material (e.g., low adhesion backsize) can be applied to the opposite side of the backing, if desired. When double-coated tapes are formed, the fiber reinforced adhesive composition is coated, for example by co-extrusion or lamination, onto at least a portion of both sides of the backing. Additionally, the adhesive can be coated on at least one release liner to form a transfer tape.
Typically, the backing comprises a nonwoven, paper, polypropylene (e.g., biaxially oriented DolvϋroDvlene CBOPP)). nolvethvlene. nolvester (e.v._ nolvethvlene terephthalate), or a release liner (e.g., siliconized liner). In specific embodiments, the backing is stretchable so that an article comprising the adhesive composition and the backing would be stretch removable.
In specific embodiments, the adhesive compositions of the present invention are used in tapes that include gauze pads, for example, and are used as first aid dressings (i.e., wound or surgical dressings). They can also be used in a wide variety of other medical articles, such as medical tapes, athletic tapes, surgical drapes, or tapes or tabs used in adhering medical devices such as sensors, electrodes (as disclosed in U.S. Pat. No. 5,215,087 and U.S. Pat. No. 6,171,985, for example), ostomy appliances, or the like. Preferably, webs made from natural or synthetic fibers or mixtures thereof can be used to form backings, particularly for medical articles. Woven or nonwoven materials can be employed for webs, with nonwoven materials being preferred for most applications. Melt-blown or spunbond techniques can be employed to make such nonwoven webs. Nonwoven webs can also be prepared, for example, on a RANDO WEBBER (Rando Corporation, Macedon, NY) air-laying machine or on a carding machine.
Typically, fibers forming a nonwoven tape backing are intimately entangled with each other in the form of a coherent breathable fibrous nonwoven tape backing. Suitable nonwoven tape backings can be formed as melt blown microfiber webs using the apparatus discussed, for example, in Wente, Van A., "Superfine Thermoplastic Fibers,"
Industrial Engineering Chemistry, Vol. 48, pages 1342-1346; Wente, Van A. et al., "Manufacture of Superfine Organic Fibers," Report No. 4364 of the Naval Research Laboratories, published May 25, 1954; and in U.S. Pat Nos. 3,849,241, 3,825,379, and others. These microfine fibers are termed melt blown fibers or blown microfibers (BMF) and are generally substantially continuous and form a coherent web between the exit die orifice and a collecting surface by entanglement of the microfibers, due in part to the turbulent airstream in which the fibers are entrained.
Other conventional melt spinning type processes, such as spunbond processes, where fibers are collected in a web form immediately upon formation, can also be used to form the nonwoven tape backing. Generally, the fibers are 100 microns or less in diameter when formed by melt spinning type processes, preferably 50 microns or less. Multicomponent fibers, if formed by the melt blown process, can be produced as described in U.S. Pat. Nos. 5,176,952 (Joseph et al); 5,232,770 (Joseph); 5,238,733 (Joseph et al); 5,258,220 (Joseph); or 5,248,455 (Joseph et al). Multicomponent fibers can also be produced by a spunbond process as disclosed in U.S. Pat. Nos. 5,695,868 (McCormach); 5,336,552 (Strack et al); 5,545,464 (Stokes); 5,382,400; 5,512,358
(Shawyer et al); or 5,498,463 (McDowall et al).
Representative examples of materials suitable for the backing of the adhesive article of this invention include polyolefins, such as polyethylene, including high density polyethylene, low density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylene, and polybutylenes; vinyl copolymers, such as poly vinyl chlorides, both plasticized and unplasticized, and poly vinyl acetates; olefinic copolymers, such as ethylene/methacrylate copolymers, ethylene/vinyl acetate copolymers, acrylonitrile-butadiene-styrene copolymers, and ethylene/propylene copolymers; acrylic polymers and copolymers; polycaprolactones; and combinations of the foregoing. Mixtures or blends of any plastic or plastic and elastomeric materials such as polypropylene/polyethylene, polyurethane/polyolefin, polyurethane/polycarbonate, polyurethane/polyester, can also be used. Additionally, any nonstretchable material can be used for the tearable backings or for those with perforations, including paper and even metal. Preferred materials for the backing include polyurethane, polypropylene, ethylene vinyl acetate, or combinations thereof (e.g., blends, mixtures, etc.) in the form of melt blown fibers. Preferred materials for film backings include polycaprolactones and copolymers of ethylene/vinyl acetate and linear low density polyethylene.
In a preferred embodiment, the backing is formed from coherent multicomponent fibers having at least one pressure sensitive adhesive region or layer and at least one non- pressure sensitive adhesive region or layer as described in U.S. Pat. No. 6,107,219. In another preferred embodiment, the backing is a melt blown polypropylene web available from Kimberly Clark Corp.; Irving, TX.
If the backing is in the form of a laminate, additional components could be used, such as absorbent layers (e.g., gauze pads) for adhesive bandage products, or the like. If absorbent layers are used, they are typically thin, coherent, conformable, and able to flex and not interfere with the stretch removable characteristics of the articles, although they can be stretchable or not. If a laminate, there may be one or more additional layers. Preferably, the outermost layer of such a laminate is a film that is substantially impervious to fluids, such as could arise from the external environment, yet permits passage of moisture vapor such that the adhesive article is breathable (typically, having a moisture vapor transmission rate (MNTR) of at least about 500 g/m2/day). Typically this breathable, liquid impervious film is the outermost (i.e., top) layer. Examples of such film materials include polyurethanes, polyolefins, metallocene catalyzed polyolefins, polyesters, polyamides, polyetheresters, and A-B-A block copolymers, such as KRATOΝ copolymers available from Shell Chemical Ltd.; Houston, TX.
Examples This invention is further illustrated by the following examples that are not intended to limit the scope of the invention. These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight unless indicated otherwise. All ultraviolet curing of adhesives described in the examples occurred with the adhesive exposed to the ultraviolet radiation source.
Table of Abbreviations
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Test Methods Tensile Testing
Tensile testing was carried out according to ASTM test method D 882-97 "Standard Test Method for Tensile Properties of Thin Plastic Sheeting" using an INSTRON materials tester (commercially available from Instron; Canton, MA) at a crosshead speed of 30 centimeters/minute (12 inches/minute). Using this test, the values for "Yield Strength", "Tensile Strength", and "Percent Elongation at Break" were obtained.
180° Peel Adhesion
This peel adhesion test is similar to the test method described in ASTM D 3330-90, substituting a glass, high density polyethylene or polypropylene substrate for the stainless steel substrate described in the test. The substrate used is noted in each particular example.
Adhesive-coated strips that had equilibrated at constant temperature (21°C) and humidity (50% relative humidity) for at least 24 hours, were adhered to a substrate panel. The substrate panel was either solvent-washed glass, polypropylene (PP), or high density polyethylene (HDPE) using a 2 kilogram roller passed once over the strip. The bonded assembly was allowed to dwell at room temperature for one minute. The assembly was then tested for 180° peel adhesion in the machine direction using an IMASS slip/peel tester (Model 3M90, commercially available from Instrumentors Inc., StrongsviUe, OH) at a crosshead speed of 30 centimeters/minute (12 inches/minute).
Stretch Release Test Method
Adhesive-coated strips, which had equilibrated at constant temperature (21°C) and humidity (50% relative humidity) for at least 24 hours, were adhered to a polypropylene (PP) substrate panel using a 2 kilogram roller passed once over the strip. The bonded assemblv was allowed to dwell at room t mn rafnr for one, minute. The assembly was then tested for stretch release by pulling at an angle of between 15 and 35° either "by hand", or "mechanically" using an ASS slip/peel tester (Model 3M90, commercially available from Instrumentors Inc., StrongsviUe, OH) at a crosshead speed of 30 centimeters/minute (12 inches/minute). The data are reported for the by hand samples as "broke" if the sample broke before detachment (i.e. the sample did not stretch release), or "yes" if the sample exhibited stretch release properties. For the mechanically tested samples, the data is reported as "broke" if the sample broke (i.e. the sample did not stretch release), or, if the sample did exhibit stretch release properties, the maximum stretch release force in Newtons/decimeter is reported.
Probe Tack Test
Probe tack measurements were made following the test method described in ASTM D 2979-95 using a TA-XY2 texture tester (commercially available from Stable Microsystems, Surrey, U.K.).
Solvent Extraction Test
To determine the continuity of the fibrous reinforcing material of the adhesive composition, the pressure sensitive adhesive matrix was dissolved, leaving behind the fibrous reinforcing material. A strip of the adhesive composition film (approximately 7.5 centimeters long by 2.5 centimeters wide) was cut from the film in the machine direction.
The strip was suspended on an open frame by looping the film over the edge of the open frame. The frame and adhesive strip were immersed in a solvent capable of dissolving the pressure sensitive adhesive but not the fibrous reinforcing material. After 24 hours the sample was checked to determine if the pressure sensitive adhesive had completely dissolved and if the fibrous reinforcing material remained on the frame. If fibers were not continuous for at least 5 centimeters, nothing remained on the frame. The samples were rated as "pass" if fibers remained on the frame and "fail" if no fibers remained on the frame.
Tensile Properties of Reinforcing Material
Films of possible fibrous reinforcing material were prepared by hot-press molding each reinforcing material to a thickness of 1 2 micrometers. The films were tested using the Tensile Testing method described above. The results are shown in Table 1. Additionally, the materials are characterized as being elastomeric (rebounds upon deformation) or plastic (deforms permanently).
Table 1
Figure imgf000018_0001
Comparative Example Cl
A sample of PSA- 1 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 2. A portion of the film was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a total ultraviolet dose of 300 milliJoules/cm2. The tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
Comparative Example C2 A mixture of 90 parts PSA- 1, 10 parts ENGAGE 8200 and 0.2 part benzophenone was prepared in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 2. A portion of the film was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a total ultraviolet dose of 300 milliJoules/cm2. The tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
Comparative Example C3 ' A mixture of 90 parts PS A-l , 10 parts of LDPE and 0.2 part benzophenone were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 2. A portion of the film was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a total ultraviolet dose of 300 milliJoules/cm2. The tape was tested for
180° Peel Adhesion from glass. The results are shown in Table 3.
Example 1
A mixture of 90 parts PSA-1, 10 parts ENGAGE 8490 and 0.2 part benzophenone were mixed in a BRABENDER mixer (commercially available from C.W. Brabender
Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 2. A portion of the film was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm . The tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
Example 2
A mixture of 90 parts PSA-1, 10 parts of ATTANE 4202 and 0.2 part benzophenone were mixed in a BRABENDER mixer (commerςially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers. The tensile properties of the film were determined as described in the Tensile Test Method above. The results are shown in Table 2. A portion of the film was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm2. The tape was tested for 180° Peel Adhesion from glass. The results are shown in Table 3.
Table 2
Figure imgf000020_0001
Table 3
Figure imgf000021_0001
Comparative Example C4
A sample of PSA-1 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm2. The tape was tested for 180° Peel Adhesion from glass in the machine and the cross-web directions. The results are shown in Table 4.
Example 3
A mixture of 90 parts PSA-1 and 10 parts of ATTANE 4202 were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South
Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm2. The tape was tested for 180° Peel Adhesion from glass in the machine and the cross-web directions. The results are shown in Table 4. Table 4
Figure imgf000022_0001
Comparative Example C5
A sample of PSA-1 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 51 micrometers and was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm2. The tape was tested for 180° Peel Adhesion from glass in the machine and cross-web directions. The results are shown in Table 5.
Comparative Example C6 A mixture of 90 parts PSA-1 and 10 parts of LDPE were mixed in a
BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 51 micrometers and was laminated to a PET backing to make a tape. The tape was tested for 180° Peel Adhesion from glass in the machine and cross-web directions. The results are shown in Table 5.
Example 4 A mixture of 90 parts PSA-1 and 10 parts of ATTANE 4202 were mixed in a
BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 51 micrometers and was laminated to a PET backing to make a tape. The resulting tape was passed below a Fusion H-bulb lamp (commercially available from Fusion Total Ultraviolet Systems, Inc.; Gaithersburg, MD) at a crosshead speed of 15 meters/minute for a UV dose of 300 milli Joules/cm2. The tape was tested for 180° Peel Adhesion from glass in the machine and cross-web directions. The results are shown in Table 5.
Table 5
Figure imgf000023_0001
Comparative Example C7
A sample of PSA-2 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape. The tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 6.
Example 5
A mixture of 90 parts PSA-2 and 10 parts of ATTANE 4202 were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape. The tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 6. Table 6
Figure imgf000024_0001
Comparative Example C8
A sample of PSA-3 was used as obtained and hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape. The tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 7.
Example 6
A mixture of 90 parts PSA-3 and 10 parts of ATTANE 4202 were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting film had a thickness of 127 micrometers and was laminated to a PET backing to make a tape. The tape was tested for 180° Peel Adhesion on various substrates. The results are shown in Table 7.
Table 7
Figure imgf000024_0002
Comparative Example C9
A sample of PSA-4 was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8.
Comparative Example CIO
A mixture of 85 parts PSA-4 and 15 parts of PS were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8.
Comparative Example Cl 1
A mixture of 85 parts PSA-4 and 15 parts HDPE were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8.
Example 7
A mixture of 85 parts PSA-4 and 15 parts of ATTANE 4202 were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8. Example 8
A mixture of 85 parts PSA-4 and 15 parts PEBH were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The tensile properties of the film were determined as described in the Tensile Testing method above. The results are shown in Table 8.
Table 8
Figure imgf000026_0001
Examples 9-13
The mixtures for Examples 9-13 were prepared using PSA-5 with the level of ATTANE 4202 shown in Table 9, were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in
Table. 9 Table 9
Figure imgf000027_0001
Examples 14-16 and Comparative Examples C12-C14
The mixtures for Examples 14-16 and Comparative Examples C12-C14 were prepared using PSA-4 with 15 weight % of a polymer as shown in Table 10, and were mixed in a BRABENDER mixer (commercially available form C.W. Brabender instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers. The stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 10.
Table 10
Figure imgf000028_0001
Examples 17-22 and Comparative Example C15
The mixtures for Examples 17-22 and Comparative Example C15 were prepared using PSA-4 with the level of ATTANE 4202 shown in Table 11, and were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers. The stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 11.
Table 11
Figure imgf000028_0002
Examples 23-25 and Comparative Example C16
The mixtures for Examples 23-25 and Comparative Example C16 were prepared using PSA-6 with the level of ATTANE 4202 shown in Table 12 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers. The stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 12.
Table 12
Figure imgf000029_0001
Examples 26-27 and Comparative Example C17 The mixtures for Examples 26-27 and Comparative Example C17 were prepared using PSA-7 with the level of ATTANE 4202 shown in Table 13 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 127 micrometers. The stretch release properties of the films were determined as described in the Stretch Release Test Method above. The results are shown in Table 13. Table 13
Figure imgf000030_0001
Examples 28-30 and Comparative Example C18
The mixtures for Examples 28-30 and Comparative Example C18 were prepared using PSA-6 with the level of ATTANE 4202 shown in Table 14 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 micrometers. The probe tack properties of the films were determined as described in the Probe Tack Test method above. The results are shown in Table 14.
Table 14
Figure imgf000030_0002
Examples 31-32 and Comparative Example C19
The mixtures for Examples 31-32 and Comparative Example C19 were prepared using PSA-7 with the level of ATTANE 4202 shown in Table 15 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give a thickness of 51 or 127 micrometers. The probe tack properties of the films were determined as described in the Probe Tack Test method above. The results are shown in Table 15.
Table 15
Figure imgf000031_0001
Examples 33-37 and Comparative Example C20
The mixtures for Examples 33-37 and Comparative Example C20 were prepared using PSA-4 with the level of ATTANE 4202 shown in Table 16 mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixtures were hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die to give films having a thickness of 51 or 127 micrometers. The probe tack properties of the films were determined as described in the Probe Tack Test method above. The results are shown in Table 16. Table 16
Figure imgf000032_0001
Comparative Examples C21-C22
Mixtures of PSA-8 and ELVAX 240 were prepared with the levels of ELVAX 240 shown in Table 17 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 1-17. The tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in Table 17.
Table 17
Figure imgf000032_0002
Comparative Examples C23-C24
Mixtures of PSA-8 and ELVAX 210 were prepared with the levels of ELVAX 210 shown in Table 18 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 1-17. The tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in Table 18.
Table 18
Figure imgf000033_0001
Comparative Examples C25-C26
Mixtures of PSA-9 and ELVAX 240 were prepared with the levels of ELVAX 240 shown in Table 19 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 43-44. The tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in Table 19.
Table 19
Figure imgf000033_0002
Comparative Examples C27-C28
Mixtures of PSA-9 and ELVAX 210 were prepared with the levels of ELVAX 210 shown in Table 20 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 43-44. The tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in Table 20. Table 20
Figure imgf000034_0001
Comparative Examples C29-C30
Mixtures of PSA-8 and ELVAX 450 were prepared with the levels of ELVAX 450 shown in Table 21 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 1-17. The tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in Table 21.
Table 21
Figure imgf000034_0002
Comparative Examples C31-C32
Mixtures of PSA-8 and ELVAX 660 were prepared with the levels of ELVAX 660 shown in Table 22 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 1-17. The tensile properties of the films were determined as described in the Tensile Testing method above. The results are shown in
TΛ T^ _ Table 22
Figure imgf000035_0001
Examples 38-41
The mixtures for Examples 38-41 were prepared using PSA-5 with the level of ATTANE 4202 shown in Table 23, and were mixed in a BRABENDER mixer (commercially available from C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixture was hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The solvent extraction properties of the film were determined as described in the Solvent Extraction Test method above. The results are shown in Table 23.
Table 23
Figure imgf000035_0002
Comparative Examples C33-C34
Mixtures of PSA-8, with ELVAX 210 were prepared with the levels of ELVAX 210 shown in Table 24 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 1-17. The solvent extraction properties of the films were determined as described in the Solvent Extraction Test method above. The results are shown in Table 24.
Table 24
Figure imgf000036_0001
Comparative Examples C35-C36
Mixtures of PSA-8 and ELVAX 240 were prepared with the levels of ELVAX 240 shown in Table 25 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 1-17. The solvent extraction properties of the films were determined as described in the Solvent Extraction Test method above. The results are shown in Table 25.
Table 25
Figure imgf000036_0002
Comparative Examples C37-C38
Mixtures of PSA-9 and ELVAX 210 were prepared with the levels of ELVAX 210 shown in Table 26 and hot melt coated to form films as described in U.S. Patent Number
6,063,838 (Patnode, et al) Examples 43-44. The solvent extraction properties of the films were determined as described in the Solvent Extraction Test method above. The results are shown in Table 26. Table 26
Figure imgf000037_0001
Comparative Examples C39-C40
Mixtures of PSA-9 and ELVAX 240 were prepared with the levels of ELVAX 240 shown in Table 27 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 43-44. The solvent extraction properties of the films were determined as described in the Solvent Extraction Test method above. The results are shown in Table 27.
Table 27
Figure imgf000037_0002
Comparative Examples C41-C42
Mixtures of PSA-8 and ELVAX 450 were prepared with the levels of ELVAX 450 shown in Table 28 and hot melt coated to form films as described in U.S. Patent Number
6,063,838 (Patnode, et al) Examples 1-17. The solvent extraction properties of the films were determined as described in the Solvent Extraction Test method above. The results are shown in Table 28. Table 28
Figure imgf000038_0001
Comparative Examples C43-C44
Mixtures of PSA-8 and ELVAX 660 were prepared with the levels of ELVAX 660 shown in Table 29 and hot melt coated to form films as described in U.S. Patent Number 6,063,838 (Patnode, et al) Examples 1-17. The solvent extraction properties of the films were determined as described in the Solvent Extraction Test method above. The results are shown in Table 29.
Table 29
Figure imgf000038_0002
Example 42
A stretch removable First Aid Dressing (FAD) sample was made by laminating with thumb pressure at room temperature a strip (2.54-cm x 7.6-cm) of a perforated polymer film backing to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20, with the fibers perpendicular to the long axis of the sample. The film backing comprised 60% ethylene/vinyl acetate copolymer, 35% linear low density polyethylene, 5% stabilizers and other additives (PGI Product No. 6012, Polymer Group, Inc., Gainesville, GA); and the film had a basis weight of 1.15 oz/yd2 (27 g/m2), was 5-mils (0.13-mm) thick, and had oval-shaped holes (approximately 0.2-mm width x 0.3-mm length in the greatest dimensions) with the length dimension of the oval holes oriented parallel to the machine direction of the film. The film had about 530 holes/cm2 arranged in a pattern of staggered lines.
The FAD sample was evaluated for ease of removal by adhering the sample with finger pressure to the forearm of a human subject, waiting 60 minutes, and then removing by pulling one end of the sample and stretching the sample at about a 35° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm.
Example 43
A polyurethane backing (melt-blown nonwoven fibrous web comprised of three- layer polymeric fibers having a center layer of blended polyethylene and Kraton™ PSA, and outer layers of polyurethane; prepared as described for Backing Sample 16 in U.S. Pat. No. 6,107,219 (Joseph et al.)) was perforated with a metal die to provide parallel rows of holes separated by 3.8 cm. The holes were rectangular in shape (1.75-mm x 0.07 -mm) and the space between holes within a row was 0.7 mm. The polyurethane backing had one side rougher than the other due to the collection technique used during the melt-blown process.
A stretch removable FAD sample was made by laminating with thumb pressure at room temperature a strip (2.54-cm x 7.6-cm) of the perforated polyurethane backing to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20, with the fibers perpendicular to the long axis of the sample. The "rough" side of the backing was adjacent the adhesive layer. A 1.8-cm x 2.5-cm gauze pad was attached to the adhesive layer in the center of the sample and the holes had been pre-cut such that the rows began 6 mm from each end of the sample.
The FAD sample was evaluated for ease of removal by adhering the sample with finger pressure to the forearm of a human subject, waiting 10 minutes, and then removing by lifting and stretching the gauze pad at about a 90° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm. During stretching and removal, the backing was observed to break and to delaminate from the adhesive layer. Example 44
A paper backing (Hammermill Laserprint paper (0.11-mm thick), Product No. 00460-4, International Paper, Memphis, TN)) was perforated with a metal die to provide parallel rows of holes separated by 6.35 cm. The holes were rectangular in shape (1.75- mm x 0.07 -mm) with the long sides of the holes oriented in the direction of the rows and the space between holes within a row was 0.7 mm.
A FAD sample was made by laminating with thumb pressure at room temperature a strip (2.54-cm x 7.6-cm) of the perforated paper backing to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20, with the fibers perpendicular to the long axis of the sample. A 1.8-cm x 2.5-cm gauze pad was attached to the adhesive layer in the center of the sample and the holes had been pre-cut such that the rows began 6 mm from each end of the sample.
The FAD sample was evaluated for ease of removal by adhering the sample with finger pressure to the forearm of a human subject, waiting 10 minutes, and then removing by pulling one end of the sample and stretching the sample at about a 35° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm. During stretching and removal, the backing was observed to break and to delaminate from the adhesive layer.
Example 45
A stretch removable FAD sample was made by laminating with thumb pressure at room temperature a sheet (10.2-cm square) of a Rayon/Nylon nonwoven backing [thermal spunbond Rayon/Nylon nonwoven fabric, Fiber No. 149-245, basis weight = 25 g/m2, Veratec, Walpole, MA] to a sheet (10.2-cm square) of the adhesive described in Example 20, with the fibers perpendicular to the long axis of the sample. The sheets were oriented such that the adhesive layer, when subsequently stretched for removal, would be stretched in a direction parallel to the machine direction of the adhesive layer. Prior to lamination, the adhesive sheet was covered along one edge with a strip of paper that could serve as a handle for grasping the adhesive layer alone. The resulting laminate was cut into a 2.54-cm x 7.6-cm FAD sample and adhered with thumb pressure onto a mirror-finished steel plate with the paper handle allowed to extend over the end of the plate. The paper handle of the sample was finger-grasped and stretched in the plane of the adhesive-backing interface at a rate of about 150 cm/min. Upon stretching, the adhesive released from between the plate surface and the backing.
Example 46 A FAD sample was made by laminating with thumb pressure a room temperature a strip (2.54-cm x 7.6-cm) of a polypropylene backing [melt-blown nonwoven polypropylene (basis weight 20 g/m2), Kimberly-Clark, Irving, TX ] to a strip (2.54-cm x 7.6-cm) of the adhesive described in Example 20. A 1.3-cm piece of the adhesive/backing laminate was gathered in the middle of the strip in such a way that a fold was made perpendicular to the greatest length of the strip. A 1.8-cm x 2.5-cm gauze pad was attached to the adhesive layer in the center of the sample.
The FAD sample was evaluated by adhering the sample with finger pressure to the forearm of a human subject, waiting 10 minutes, and then using the fold in the FAD as a handle, removing by lifting and stretching the gauze pad at about a 90° angle to the plane of the forearm. Very little force was required to stretch the backing and to remove the sample painlessly from the skin and hair of the forearm. During stretching and removal, the backing was observed to break and to delaminate from the adhesive layer.
Example 47 A FAD sample having a center fold and a gauze pad was made as described in
Example 46, except that the polyurethane backing (as described in Example 43) was used in place of the polypropylene backing. The sample was evaluated as described in Example 46. During stretching and removal, the backing was observed to delaminate from the adhesive layer.
Example 48
A FAD sample having a center fold and a gauze pad was made as described in Example 46, except that the adhesive described in Example 28 was used as the adhesive. The sample was evaluated and the same results obtained as described in Example 46. Example 49
A blend of 80 parts of PSA-7 and 20 parts of ATTANE 4202 were mixed in a BRABENDER mixer (C.W. Brabender Instruments, South Hackensack, NJ) at 140°C to 150°C for 8 to 10 minutes. The resulting mixtures were hot melt coated between two release liners at 150°C using a HAAKE single screw extruder (commercially available from Haake, Inc.; Paramus, NJ) equipped with a draw die. The resulting PSA film had a thickness of 127 micrometers and was laminated to a PCL backing of thickness listed in Table 30 (prepared by solvent coating a 20% solids solution of PCL in toluene onto a release liner and drying at 70°C for 10 minutes) to make a tape. The stretch release properties of the tape was determined as described in the Stretch Release Test Method above except that samples were tested not only in the machine direction but also in the cross web direction and at 45° to the machine direction. The results of the laminated samples as well as the PSA film not laminated to a backing are shown in Table 30.
Table 30
Figure imgf000042_0001
Various modifications and alterations of the present invention will become apparent to those skilled in the art without departing from the spirit and scope of the invention.

Claims

What is Claimed is:
1. An adhesive composition comprising a pressure sensitive adhesive matrix; and a fibrous reinforcing material within the pressure sensitive adhesive matrix; wherein the adhesive composition has a yield strength and a tensile strength, and wherein the tensile strength is about 0.7 MPa or greater, and at least about 150% of the yield strength.
2. The adhesive composition of claim 1 wherein the fibrous reinforcing material comprises substantially continuous fibers.
3. The adhesive composition of claim 1 wherein the adhesive composition has an elongation at break of at least about 50%.
4. The adhesive composition of claim 1 wherein the adhesive composition has an elongation at break of at least about 300%.
5. The adhesive composition of claim 1 wherein the adhesive composition has a tensile strength of about 0.8 MPa or greater.
6. The adhesive composition of claim 1 wherein the adhesive composition has a yield strength of no less than about 0.1 MPa.
7. The adhesive composition of claim 1 wherein the adhesive composition has a yield strength of no less than about 0.2 MPa.
8. The adhesive composition of claim 1 wherein the pressure sensitive adhesive comprises about 60 to about 95 weight % of the adhesive composition and the reinforcing material comprises about 5 to about 40 weight % of the adhesive composition.
9. The adhesive composition of claim 1 wherein the pressure sensitive adhesive comprises about 70 to about 95 weight % of the adhesive composition and the reinforcing material comprises about 5 to about 30 weight % of the adhesive composition.
10. The adhesive composition of claim 1 wherein a ratio of the reinforcing material melt viscosity to the pressure sensitive adhesive melt viscosity is about 0.5 to about 1.2.
11. The adhesive composition of claim 1 wherein the fibrous reinforcing material comprises at least one fiber having a diameter of less than about 5 micrometers.
12. The adhesive composition of claim 1 wherein the fibrous reinforcing material comprises at least one fiber having an aspect ratio of greater than about 1000.
13. The adhesive composition of claim 1 wherein the pressure sensitive adhesive comprises a pressure sensitive adhesive based on at least one of a natural rubber, synthetic rubber, styrene block copolymer, polyvinyl ether, poly(meth)acrylate, polyolefin, silicone or combinations thereof.
14. The adhesive composition of claim 1 wherein the pressure sensitive adhesive comprises a polymer derived from at least one alkyl (meth)acrylate ester monomer selected from isooctyl acrylate, 2-ethyl-hexyl acrylate, and n-butyl acrylate; and at least one co-monomer selected from acrylic acid and acrylamide.
15. The adhesive composition of claim 1 wherein the reinforcing material comprises an elastomer having a yield strength no greater than about 20 MPa and a tensile strength of at least about 150% of the yield strength.
16. The adhesive composition of claim 1 wherein the reinforcing material comprises a semi crystalline polymer.
17. The adhesive composition of claim 1 wherein the reinforcing material has a melting point greater than about 70 °C.
18. A substrate at least partially coated with the adhesive composition of claim 1.
19. The substrate of claim 18 wherein the substrate comprises a release liner.
20. A tape comprising a backing having a first and second side; and the adhesive composition of claim 1 coated on at least a portion of the first side of the backing.
21. A tape comprising a backing having a first and second side; and the adhesive composition of claim 1 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.
22. A stretch removable article comprising the adhesive composition of claim 1.
23. The adhesive composition of claim 1 wherein the adhesive composition is stretch removable from a substrate.
24. An adhesive composition comprising a pressure sensitive adhesive matrix; and a fibrous reinforcing material, having a melting temperature of no less than about 70°C, within the pressure sensitive adhesive matrix; wherein the adhesive composition has a yield strength and a tensile strength, and the tensile strength is at least about 150% of the yield strength.
25. A method for making a fiber reinforced adhesive composition comprising
(a) forming a mixture comprising a pressure sensitive adhesive with a reinforcing material capable of forming fibers when subjected to an elongating shear force; and (b) subjecting the mixture to the elongating shear force to form the adhesive composition of claim 1.
26. The method of claim 25 further comprising quenching the adhesive composition.
27. A medical article comprising the adhesive composition of claim 1.
28. The medical article of claim 27 which is in the form of a wound dressing, surgical dressing, medical tape, athletic tape, or surgical tape.
29. The medical article of claim 27 which is in the form of a sensor, an electrode, or an ostomy appliance.
PCT/US2001/018500 2001-01-17 2001-06-08 Pressure sensitive adhesives with a fibrous reinforcing material WO2002057383A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE60123838T DE60123838T2 (en) 2001-01-17 2001-06-08 ADHESIVE ADHESIVE WITH A FIBER-REINFORCED REINFORCEMENT MATERIAL
AU2001266771A AU2001266771A1 (en) 2001-01-17 2001-06-08 Pressure sensitive adhesives with a fibrous reinforcing material
JP2002558442A JP2004525209A (en) 2001-01-17 2001-06-08 Pressure-sensitive adhesive with fiber reinforcement
EP01944349A EP1354013B1 (en) 2001-01-17 2001-06-08 Pressure sensitive adhesives with a fibrous reinforcing material

Applications Claiming Priority (2)

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US09/764,478 US20020164446A1 (en) 2001-01-17 2001-01-17 Pressure sensitive adhesives with a fibrous reinforcing material
US09/764,478 2001-01-17

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WO2002057383A8 WO2002057383A8 (en) 2003-10-30

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EP (1) EP1354013B1 (en)
JP (1) JP2004525209A (en)
AT (1) ATE342318T1 (en)
AU (1) AU2001266771A1 (en)
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JP2004525209A (en) 2004-08-19
US20020164446A1 (en) 2002-11-07
ATE342318T1 (en) 2006-11-15
WO2002057383A8 (en) 2003-10-30
DE60123838D1 (en) 2006-11-23
EP1354013A1 (en) 2003-10-22
US20020187294A1 (en) 2002-12-12
EP1354013B1 (en) 2006-10-11
DE60123838T2 (en) 2007-05-16
US6756098B2 (en) 2004-06-29
AU2001266771A1 (en) 2002-07-30

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