WO2006062504A1 - Films a couches multiples, constructions adhesives et objets les utilisant - Google Patents

Films a couches multiples, constructions adhesives et objets les utilisant Download PDF

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Publication number
WO2006062504A1
WO2006062504A1 PCT/US2004/040767 US2004040767W WO2006062504A1 WO 2006062504 A1 WO2006062504 A1 WO 2006062504A1 US 2004040767 W US2004040767 W US 2004040767W WO 2006062504 A1 WO2006062504 A1 WO 2006062504A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
skin layer
adhesive
base layer
Prior art date
Application number
PCT/US2004/040767
Other languages
English (en)
Inventor
Kevin O. Henderson
Michael David Hilston
Christopher J. Blackwell
Original Assignee
Avery Dennison Corporation
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 Avery Dennison Corporation filed Critical Avery Dennison Corporation
Priority to PCT/US2004/040767 priority Critical patent/WO2006062504A1/fr
Publication of WO2006062504A1 publication Critical patent/WO2006062504A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/15577—Apparatus or processes for manufacturing
    • A61F13/15756—Applying tabs, strips, tapes, loops; Knotting the ends of pads
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/56—Supporting or fastening means
    • A61F13/5622—Supporting or fastening means specially adapted for diapers or the like
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/56—Supporting or fastening means
    • A61F13/62—Mechanical fastening means, ; Fabric strip fastener elements, e.g. hook and loop
    • A61F13/622—Fabric strip fastener elements, e.g. hook and loop
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/06—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions for securing layers together; for attaching the product to another member, e.g. to a support, or to another product, e.g. groove/tongue, interlocking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0228—Vinyl resin particles, e.g. polyvinyl acetate, polyvinyl alcohol polymers or ethylene-vinyl acetate copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/025—Acrylic resin particles, e.g. polymethyl methacrylate or ethylene-acrylate copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0257—Polyolefin particles, e.g. polyethylene or polypropylene homopolymers or ethylene-propylene copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/0278—Polyester particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/746—Slipping, anti-blocking, low friction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2555/00—Personal care
    • B32B2555/02—Diapers or napkins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate

Definitions

  • This invention relates to multilayer films and adhesive constructions such as tapes and tabs for garments, such as diapers, geriatric briefs and the like. This invention also relates to articles using the multilayer film and/or adhesive constructions.
  • an adhesive construction is used on garments, such as disposable diapers, geriatric briefs, and surgical drapes to provide an attachment place for adhesives or closures.
  • garments such as disposable diapers, geriatric briefs, and surgical drapes to provide an attachment place for adhesives or closures.
  • these constructions include tapes and tabs.
  • US Patent 5,057,097 describes a multilayer film to be used as a diaper tape made by a conventional and simple manner, e.g., coextruding or laminating layers characterized in that one or more layers are non-elastic and another layer is elastic, in which the film becomes substantially completely elastic by stretching beyond the yield strength of the non-elastic layer.
  • US Patent 5,700,571 describes a coextruded film having either two or three layers. The film is described as self-supporting or self wound with a release agent on a second olefin-based polymer support film.
  • Production lines that use these adhesive constructions are run at high speeds.
  • the production lines use high-speed knives to cut the constructions to the proper length for fitting on the substrate, such as a diaper.
  • One of the problems associated with these adhesive constructions is shattering of the film of the construction during cutting operations with high-speed knives. Films that are very crystalline in construction will tend to shatter more so than less crystalline films, or films with more amorphous domains. The shattering of the film during processing leads to production stoppage or downtime due to cleanup and restarting of the equipment. Films that did not shatter during this step would lead to more efficiency and continued operation or uptime and would be desirable.
  • One property that the adhesive construction must have is deadfold ability.
  • Deadfold ability is the ability to fold over an edge and not release or lift up from a substrate. When applied, the adhesive construction is often folded overthe edge of the substrate. At high speeds, any lack of deadfold ability can cause production delay or ripping of the garment.
  • Another problem with some polymeric film/adhesive constructions is migration of components of the polymeric film into the adhesive with resultant loss of adhesive properties.
  • the adhesive also contains components that may conversely migrate into the film.
  • Polymeric films often contain additives that may migrate into the adhesive layer and reduce adhesive properties. Additionally, some polymers also have low molecular weight tails, which migrate into the adhesive and reduce the adhesive's properties. Also, low molecular weight material in the adhesive can migrate into the film and cause the adhesive to lose properties.
  • One property that may be reduced is the 180° peel adhesion, as measured by ASTM D1000-61.
  • This invention relates to a multilayer film comprising (a) a base layer having a first and second surface, wherein the base layer is comprised of at least one polyolefin, and (b) a skin layer on the first surface of the base layer, wherein the skin layer comprises at least about 70% by weight propylene homopolymer, and wherein the multilayer film has deadfold in a modulus range from about
  • the films have at least one roughened surface.
  • the films have an adhesive layer on skin layer (b).
  • the adhesive constructions may be used in a tape or tab, such as a diaper tape or tab.
  • the films of the present invention have improved deadfold properties. The films have reduced impact on the properties of adhesives used in conjunction with the films.
  • the invention in another embodiment, relates to a multilayer film, comprising (a) a base layer having a first and second surface and comprising at least one polyolefin and at least one tear resistance improving amount of (i) at least one copolymer of ethylene or propylene and at least one unsaturated carboxylic acid or ester, (ii) at least one ionomer of a copolymer of ethylene and at least one unsaturated carboxylic acid, or (iii) mixtures of two or more thereof,
  • the invention in another embodiment, relates to an adhesive construction comprising a multilayer film having a polyolefin base layer with a first and second surface, (b) a skin layer on the first surface of the base layer, and (d) an adhesive layer on skin layer (b), wherein the skin layer (b) comprises at least greater than 80% by weight propylene homopolymer and wherein the multilayer film has a deadfold in a modulus range from about 45,000 to about 110,000 psi. in the machine direction.
  • the invention in another embodiment, relates to an adhesive construction comprising (a) a multilayer film having a polyolefin base layer with a first and second surface, (b) a skin layer on the first surface of the base layer, (c) a skin layer on the second surface of the base layer, and (d) an adhesive on skin layer (b) wherein the skin layer (b) comprises at least greater than 80% by weight propylene homopolymer and wherein the multilayer film has a deadfold in a modulus range from about 45,000 to about 110,000 psi. in the machine direction.
  • the invention in another embodiment, relates to a multilayer film comprising (a) a base layer having a first and second surface, wherein the base layer is comprised of at least one polyolefin, and (b) a skin layer on the first surface of the base layer, wherein the skin layer comprises at least about 70% by weight a polymer selected from a propylene homopolymer, a polyamide, a polyester, a polystyrene, a polycarbonate, and mixtures of two or more thereof, and wherein the multilayer film has a deadfold in a modulus range from about 45,000 to about 110,000 psi. in the machine direction.
  • Fig. 1 is a cross sectional view of a two layer multilayer film.
  • Fig. 2 is a cross sectional view of a three layer multilayer film.
  • Fig. 3 is a cross sectional view of an adhesive construction formed from a two-layer multilayer film and an adhesive.
  • Fig.4 is a cross sectional view of an adhesive construction formed from a three layer multilayer film and an adhesive.
  • Fig. 5 is a diaper or garment having an adhesive tape and adhesive tabs applied thereto.
  • Fig. 6A is a cross sectional view of an adhesive tab before use of the tab to close the garment.
  • Fig. 6B is a cross sectional view of the adhesive tab once opened and used to close a garment.
  • Fig. 7A is a cross sectional view of an adhesive tab prior to opening the tab to close the garment.
  • Fig. 7B is a cross sectional view of an adhesive tab that has been opened and used to close a garment.
  • Fig. 8A is a cross sectional view of a hook and loop fastener tab prior to opening the tab to close the garment.
  • Fig. 8B is a cross sectional view of a hook or loop fastener tab that has been opened and used to close a garment.
  • Fig. 9 is a cross sectional view of an adhesive construction having a hook or loop fastener laminated thereto.
  • the present invention relates to a multilayer film that has a base layer having a first and second surface and at least one skin layer on the first surface of the base layer.
  • the multilayer films are characterized as having a deadfold in a modulus range from about 45,000 to about 110,000 psi. in the machine direction.
  • a deadfold value is the measure of the ability of the film to be folded around a material and not lift up from the material.
  • the modulus of the film can be measured according to ASTM D882.
  • the deadfold is from about 50,000 to about 100,000, or from about 55,000 to about 90,000 psi. in the machine direction.
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, or time is, for example, from 1 to 90, or from 20 to 80, or from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51 , 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.000 1. 0.00 1 , 0.0 I or 0. 1 as 1 5 appropriate.
  • the multilayer films have improved tear resistance so that the films do not tear during normal handling or application.
  • the Elmendorf Tear is also a means for measuring the amount of crystallization within the structure. A low Elmendorf Tear would correlate to a high amount of crystallization, and thus, a high amount of shattering during the high-speed cutting operation.
  • the multilayer film has a tear resistance from about 100 to about 1800, or from about 110 to about 1600, or from about 120 to about 1200 grams. Tear resistance has also been referred to as Elmendorf Tear resistance. The tear resistance is measured by ASTM D1922- 03.
  • the multilayer films have at least one roughened surface.
  • the roughened surface may have a matte finish.
  • both sides of the multilayer films have a roughened surface.
  • the roughened surfaces improve handling of the film during processing, including adhesive coating.
  • the multilayer film has a surface roughness from about 25 to about 300, or from about 30 to about 250, or from about 35 to about 200, or from about 40 to about 80 Ra.
  • One convenient measure of surface roughness is provided by the "Ra" roughness average or value measured in angstroms with a Dektak 3030 profile measuring system using a 2.5 urn radius stylus. (The Dektak 3030 profile measuring system is manufactured by the Sloan Technology subsidiary of Veeco Instruments Inc.
  • the films generally have a thickness from about 1 mil to about 10 mils, or from about 2 mils to about 8 mils, or from about 3 mils to about 6 mils.
  • the skin layer has thickness sufficient to form a covering over about 80%, or about 90% of the base layer.
  • the skin layer has sufficient thickness to form a continuous covering over the base layer.
  • the skin layer comprises from about 1 % to about 50%, or from 5% to about 50%, or from about 10% to about 45%, or from about 15% to about 40% of the thickness of the multilayer film.
  • the multilayer film is a two layer film wherein the skin layer comprises from about 1 % to about 50%, or from about 5% to about 50%, from about 15% to about 45%, or from about 20% to about 35% of the thickness of the multilayer film.
  • the multilayer film is a three layer multilayer film having base layer and two skin layers.
  • the two skin layers together comprise from about 1 % to about 50%, or from about 5% to 50%, or from about 10% to about 45%, or from about 20% to about 35% of the thickness of the multilayer film.
  • the skin layer or layers independently have a thickness from about 0.5 to about 3, or from about 0.6 to about 2, or from about 0.8 to about 1.5 mil.
  • the base layer has a thickness from about 0.75 to about 9.5, or from about 1 to about 6, or from about 2 to about 5 mils.
  • the multilayer film has a base layer that comprises at least one polyolefin.
  • the polyolefin comprises at least one propylene homopolymer, at least one propylene copolymer, at least one high density polyethylene or mixtures of two or more thereof.
  • the propylene homopolymers include a variety of propylene homopolymers such as those having melt flow rates (MFR) from about 1 to about 30, or from about 4 to about 25, or from about 8 to about 20 as determined by ASTM Test D1238, condition L.
  • Useful propylene homopolymers also may be characterized as having densities in the range of about 0.88 to about 0.92 g/cm 3 .
  • the base layer comprises at least one propylene copolymer.
  • the propylene copolymers comprise copolymers of propylene and up to about 40% by weight of at least one alpha-olefin selected from ethylene, alpha-olefins containing from 4 to about 12, or from 4 to about 8 carbon atoms, and mixtures thereof.
  • alpha-olefins include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene.
  • the copolymers of propylene that are utilized in the present invention comprise copolymers of propylene with ethylene, 1-butene, 1-octene or mixtures thereof.
  • the propylene alpha-olefin copolymers include random as well as block copolymers. Blends of the copolymers as well as blends of the copolymers with propylene homopolymers or high density polyethylene can be utilized as the composition for the base layer.
  • the propylene copolymers are propylene-ethylene copolymers with ethylene contents from about 0.2% to about 10%, or from about 2% to about 10%, or from about 3% to about 6% by weight.
  • 1-butene contents of up to about 15% by weight are useful.
  • the 1-butene content generally may range from about 3% up to about 15%, or from about 5% to about 15% by weight.
  • propylene-1 -octene copolymers useful in the present invention may contain from about 1 % up to about 40% by weight of 1-octene. In one embodiment, the propylene-1 -octene copolymers will contain from about 3% up to about 20% by weight of 1 -octene.
  • the propylene copolymers may be prepared by techniques well known to those skilled in the art, and many such copolymers are available commercially.
  • the copolymers useful in the present invention may be obtained by copolymerization of propylene with an alpha-olefin such as ethylene or 1 -butene using single-site metallocene catalysts.
  • an alpha-olefin such as ethylene or 1 -butene using single-site metallocene catalysts.
  • a list of some useful commercially available propylene copolymers is found in the following Table II.
  • the propylene copolymers useful in the invention have an MFR from about 1 to about 30, or from about 4 to about 20, or from 6 to about 16 g/10 mins.
  • the base layer may comprise a high density polyethylene.
  • polyethylene films having a density above about 0.940 g/cm3 and up to about 0.980 g/cm3.
  • high density polyethylenes include HDPE 12450N (12 MFR); HDPE 17450N (17 MFR); HDPE 25455N (25 MFR); HDPE 30460M (30 MFR) available from Dow Chemical Company and HDPE 53140 (14 MFR) and HDPE 5302 (25 MFR) available from Atofina.
  • the base layer also includes at least one tear resistance additive.
  • the tear resistance additive improves the film's ability to resist tear under normal handling. Under high-speed applications, such as those using high-speed knives, the film is less prone to shattering. Although not wishing to be held to a given theory, in one embodiment, it is believed that the addition of the tear resistance additive lowers the amount of crystallization of the base layer.
  • the tear resistance additive is present in an amount from about 5% to about 60%, or from about 10% to about 50%, or from about 15% to about 40%, or from about 20% to about 30% by weight of the base layer.
  • tear resistance additive comprises (i) at least one polymer of ethylene or propylene and at least one unsaturated carboxylic acid or ester; (ii) at least one ionomer of polymers of ethylene or propylene and at least one unsaturated carboxylic acid; or (iii) mixtures of two or more thereof.
  • the tear resistance additive comprises a polymer of ethylene or propylene and at least one monomer selected from acrylic acid, an acrylic ester, methacrylic acid, a methacrylic ester, vinyl acetate, and mixtures of two or more thereof.
  • the tear resistance additive comprises an ethylene vinyl acetate copolymer.
  • the tear resistance additive comprises at least one polymer derived from ethylene or propylene and at least one functional monomer selected from an alkyl acrylate, acrylic acid, a methacrylate, a methacrylic acid, vinyl acetate and combinations of two or more thereof.
  • the functional monomer(s) component of the copolymer or terpolymer ranges from about 1 to about 15, or from about 1 to about 10 mole percent of the copolymer or terpolymer molecule.
  • the acrylate and methacrylate esters independently have from about 1 to about 12, or from about 2 to about 8, or from about 3 to about 6 carbon atoms in the ester group.
  • the acrylate and methacrylate esters are independently methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyle or dodecyl esters.
  • tear resistance additives include: ethylene/vinyl acetate copolymers; ethylene/methyl acrylate copolymers; ethylene/ethylacrylate copolymers; ethylene/butyl acrylate copolymers; ethylene/methacrylic acid copolymers; ethylene/acrylic acid copolymers; ethylene/methacrylic acid copolymers containing sodium or zinc (also referred to as ionomers); acid-, anhydride- or acrylate-modified ethylene/vinyl acetate copolymers; acid- or anhydride-modified ethylene/acrylate copolymers; and mixtures of two or more thereof.
  • ethylene/vinyl acetate (or EVA) copolymers have a vinyl acetate content from about 2% to about 40%, or from about 4% to about 30%, or from about 6% to about 25% by weight.
  • EVA ethylene/vinyl acetate copolymers
  • Examples of commercially available copolymers and terpolymers that can be used include the ethylene/vinyl acetate copolymers available from DuPont under the tradename Elvax.
  • Elvax 3120 which has a vinyl acetate content of 7.5% by weight
  • Elvax 3124 which has a vinyl acetate content of 9% by weight
  • Elvax 3150 which has a vinyl acetate content of 15% by weight
  • Elvax 3174 which has a vinyl acetate content of 18% by weight
  • Elvax 3177 which has a vinyl acetate content of 20% by weight
  • Elvax 3190 which has a vinyl acetate content of 25% by weight
  • Elvax 3175 which has a vinyl acetate content of 28% by weight
  • Elvax 3180 which has a vinyl acetate content of 28% by weight
  • Elvax 3182 which has a vinyl acetate content of 28% by weight
  • Elvax 3185 which has a vinyl acetate content of 33% by weight
  • Elvax 3190LG which has a vinyl acetate content of 25% by weight.
  • Ethylene vinyl acetate polymers are also available from AT Plastics under the tradename ATEVA ® EVA copolymers. Examples of these include ATEVA 8 1075A, which has a vinyl acetate content of 9% by weight and a melt index of 8; ATEVA ® 1525, which has a vinyl acetate content of 15% by weight and a melt index of 8; ATEVA ® 1820, which has a vinyl acetate content of 18% by weight and a melt index of 3; and ATEVA ® 1821 , which has a vinyl acetate content of 18% by weight and a melt index of 8.
  • the tear resistance additive is at least one ionomer resin.
  • Ionomer resins are available from DuPont under the tradename Surlyn. These are identified as being derived from sodium, lithium or zinc and copolymers of ethylene and methacrylic acid.
  • Ionomer resins include Surlyn 1601 , which is a sodium containing ionomer, Surlyn 1605, which is a sodium containing ionomer, Surlyn 1650, which is a zinc containing ionomer, Surlyn 1652 which is a zinc containing ionomer, Surlyn 1702, which is a zinc containing ionomer, Surlyn 1705-1 , which is a zinc containing ionomer, Surlyn 1707, which is a sodium containing ionomer, Surlyn 1802, which is a sodium containing ionomer, Surlyn 1855, which is a zinc containing ionomer, Surlyn 1857, which is a zinc containing ionomer, and Surlyn 1901
  • the tear resistance additive is an ethylene acid copolymer.
  • the ethylene acid copolymers are copolymers of ethylene and acrylic acid or methacrylic acid.
  • Ethylene acid copolymers available from DuPont under the tradename Nucrel can also be used. These include Nucrel 0407, which has a methacrylic acid content of 4% by weight and Nucrel 0910, which has a methacrylic acid content of 8.7% by weight.
  • the ethylene/acrylic acid copolymers available from Dow Chemical under the tradename Primacor are also useful. These include Primacor 1430, which has an acrylic acid monomer content of 9.5% by weight.
  • EMAC ethylene/methyl acrylate copolymers available from Chevron under the tradename EMAC can be used. These include EMAC 2205, which has a methyl acrylate content of 20% by weight, and EMAC 2268, which has a methyl acrylate content of 24% by weight.
  • nucleating agents and pigments can be incorporated into the films of the present invention.
  • the amount of nucleating agent added should be an amount sufficient to provide the desired modification of the crystal structure while not having an adverse effect on the desired properties of the films. It is generally desired to utilize a nucleating agent to modify the crystal structure and provide a large number of considerably smaller crystals or spherulites to improve the transparency (clarity), and stiffness, and the diecuttability of the film.
  • Nucleating agents which have been used heretofore for polymer films include mineral nucleating agents and organic nucleating agents. Examples of mineral nucleating agents include carbon black, silica, kaolin and talc.
  • organic nucleating agents include salts of aliphatic mono-basic or di-basic acids or aryalkyl acids such as sodium succinate, sodium glutarate, sodium caproate, sodium 4-methylvalerate, aluminum phenyl acetate, and sodium cinnamate.
  • Alkali metal and aluminum salts of aromatic and alicyclic carboxylic acids such as aluminum benzoate, sodium or potassium benzoate, sodium betanaphtholate, lithium benzoate and aluminum tertiary-butyl benzoate also are useful organic nucleating agents.
  • sorbitol derivatives such as bis (benzylidene) and bis (alkylbenzilidine) sorbitols wherein the alkyl groups contain from about 2 to about 18 carbon atoms are useful nucleating agents.
  • sorbitol derivatives such as 1 ,3,2,4-dibenzylidene sorbitol, 1 ,3,2,4-di-para-methylbenzylidene sorbitol, and
  • sorbitol are effective nucleating agents for polypropylenes.
  • Useful nucleating agents are commercially available from a number of sources. Millad 8C-41-10, Millad 3988 and Millad 3905 are sorbitol nucleating agents available from Milliken Chemical Co.
  • the amount of nucleating agent incorporated into the film formulations of the present invention generally range from about 100 to about 6000 ppm of the film. In another embodiment, the amount of nucleating agent in the range of about 1000 to about 5000 ppm.
  • the base layer may contain other additives to modify the properties of the base layer and adhesive construction and/or tape.
  • colorants may be included in the layer such as TiO 2 , CaCO 3 , etc.
  • the presence of small amounts OfTiO 2 results in a white film.
  • the base layer may contain inorganic fillers and other organic or inorganic additives to provide desired properties such as appearance properties (opaque or colored films), durability and processing characteristics.
  • useful materials include metal particles, fibers, flame retardants, antioxidant compounds, heat stabilizers, light stabilizers, ultraviolet light stabilizers, optical brighteners, antiblocking agents, processing aids, acid acceptors, etc.
  • Table III relate to compositions useful as base layers in the multilayer films of the present invention. Unless indicated otherwise, the amounts are in parts by weight.
  • At Plastics 1821 (8 Melt index ethylene-vinyl acetate polymer (18% vinyl acetate))
  • TiO 2 in ethylene methacrylate carrier TiO 2 is present at a 70% loading by weight.
  • Skin layer TiO 2 in ethylene methacrylate carrier, TiO 2 is present at a 70% loading by weight.
  • the base layer (a) has at least one skin layer (b) on its first surface.
  • the base layer has skin layer (b) on its first surface and skin layer (c) on its second surface.
  • the skin layers (b) and (c) may have the same or different compositions. It should be noted that the skin layers may be directly adhered to the base layer or may be adhered through an intermediate tie layer.
  • the skin layer (b) comprises at least 70% by weight propylene homopolymer.
  • the propylene homopolymers include those described above.
  • the propylene homopolymer of the skin layer has a melt flow rate from about 4 to about 30, or from about 6 to about 25, or from about 8 to about 16 g/10 min.
  • the propylene homopolymer comprises greaterthan about 80%, orgreaterthan 85%, or greater than about 90%, or greater than 95% by weight of the skin layer.
  • the skin layer is comprised completely of propylene homopolymer, provided that any polymers used as carriers for additives to the skin layer may be present in the skin layer.
  • the amount of these polymers is less than about 2%, or less than about 1 %, or less than 0.5% by weight.
  • skin layer (b) comprises greater than about 70% by weight of a polymer selected from a propylene homopolymer, a polyamide, a polyester, a polystyrene, a polycarbonate, and mixtures of two or more thereof.
  • a polymer selected from a propylene homopolymer, a polyamide, a polyester, a polystyrene, a polycarbonate, and mixtures of two or more thereof.
  • the propylene homopolymers have been described above.
  • Polyamides are also known to those in the art as Nylon polymers.
  • useful polyamide resins include resins available from EMS American Grilon Inc., Sumter, SC, under the general tradenames GRIVORY ® and GRILON ® , such as CF6S, CR-9, XE3303 and G-21.
  • GRIVORY ® G-21 is an amorphous nylon copolymer having a glass transition temperature of 125°C, a melt flow index (DIN 53735) of 90 ml/10 min and an elongation at break (ASTM D638) of 15.
  • GRIVORY ® CF65 is a nylon 6/12 film grade resin having a melting point of 135°C, a melt flow index of 50 ml/10 min, and an elongation at break in excess of 350%.
  • GRILON ® CR9 is another nylon 6/12 film grade resin having a melting point of 200 0 C, a melt flow index of 200 ml/ 10 min, and an elongation at break at 250%.
  • GRILON ® XE 3303 is a nylon 6.6/6.10 film grade resin having a melting point of 200 0 C, a melt flow index of 60 ml/ 10 min, and an elongation at break of 100%.
  • polyamide resins include those commercially available from, for example, Arizona Chemical Co., Panama City, Florida under the UNI-REZ ® product line, and dimer-based polyamide resins available from Bostik, Emery, Fuller, Henkel (under the VERSAMID ® product line).
  • suitable polyamides include those produced by condensing dimerized vegetable acids with hexamethylene diamine. Examples of polyamides available from Arizona Chemical include UNI-REZ ⁇ 2665; UNI-REZ ® 2620; UNI-REZ 0 2623; and UNI-REZ ® 2695.
  • skin layer (B) comprises a polyester.
  • Polyesters include those prepared from various glycols or polyols and one or more aliphatic or aromatic carboxylic acids.
  • Polyethylene terephthalate (PET) and PETG (PET modified with cyclohexanedimethanol) are useful and available from a variety of commercial sources including Eastman Chemical.
  • Kodar6763 is a PETG available from Eastman Chemical.
  • Selar PT-8307 is polyethylene terephthalate.
  • skin layer (B) comprises a polystyrene.
  • Polystyrenes include homopolymers as well as copolymers of styrene and substituted styrene such as alpha-methyl styrene.
  • styrene copolymers and terpolymers include: acrylonitrile-butene-styrene (ABS); styrene-acrylonitrile copolymers (SAN); styrene butadiene (SB); styrene-maleic anhydride (SMA); and styrene- methyl methacrylate (SMMA); etc.
  • ABS acrylonitrile-butene-styrene
  • SAN styrene-acrylonitrile copolymers
  • SB styrene butadiene
  • SMA styrene-maleic anhydride
  • SMMA styrene- methyl methacrylate
  • KR-10 is believed to be a copolymer of styrene with 1 ,3-butadiene.
  • Another useful polystyrene is a copolymer of styrene and an alkyl acrylate in which the alkyl moiety has 1 to 6 carbon atoms.
  • Butyl acrylate is especially useful as the comonomer of styrene.
  • Styrene/butyl acrylate copolymer dispersions are available under the Trade-mark ACRONAL S312D, S320D and S305D from BASF.
  • the polystyrene is a styrene- acryl copolymer.
  • the acryl may be an acrylic acid or ester, an acrylonitrile or their methacrylic analogs.
  • the these resins include Microgel E-1002, E- 2002, E-5002 (styrene acryl resin emulsion, available from Nippon Paint Co., Ltd.), Voncoat 4001 (acryl emulsion, available from Dainippon Ink & Chemicals, Inc.), Voncoat 5454 (styrene acryl resin emulsion, available from Dainippon Ink & Chemicals, Inc.), SAE 1014 (styrene acryl resin emulsion, available from Nippon Zeon Co., Ltd.), Saivinol SK-200 (acryl resin emulsion, available from Saiden Chemical Industry Co., Ltd.), Nanocryl SBCX-2821 (silicone-modified acryl resin emulsion, available from Toy
  • Nanocryl SBCX-3689 sicone- modified acryl resin emulsion, available from Toyo Ink Mfg. Co., Ltd.
  • #3070 methacrylic acid methyl polymer resin emulsion, available from Mikuni Color Limited
  • SG-60 styrene-acryl resin emulsion, available from Gifu Ceramic Co., Ltd.
  • Grandol PP-1000 Styrene-acryl resin emulsion, available from Dainippon Ink & Chemicals, Inc.
  • the skin layer (B) comprises a polycarbonate.
  • Polycarbonates are available from the Dow Chemical Co. (CALIBRE ® ) G. E. Plastics (LEXAN ® ) and Bayer (MAKROLON 8 ). Most commercial polycarbonates are obtained by the reaction of bisphenol A and carbonyl chloride in an interfacial process. Molecular weights of the typical commercial polycarbonates vary from about 22,000 to about 35,000, and the melt flow rates generally are in the range from 4 to 22 g/10 min.
  • the skin layer (B) is adhered to the base layer (A) through a tie layer. The tie layer may also be used with skin layer (C).
  • tie layers examples include Platamid, available from EIf Atochem, and CXA, Bynel, or Plexar series of tie layers available from DuPont Chemical.
  • a suitable tie coat material is a maleic anhydride functionallzed triblock copolymer consisting of polystyrene end segments and poly(ethvlene/butylene) mid-segments sold under the designation KRATON FG1901X by the Shell Chemical Company.
  • the tear resistance additives, described above may be used as the tie layer.
  • the skin layer includes less than 30%, or less than 20%, or less than 10% by weight of at least one other polyolefin.
  • the polyolefin may be a polyethylene such as a high density polyethylene, low density polyethylene, medium density polyethylene, linear low density polyethylene or the like.
  • the skin layer may also include an ethylene or propylene copolymers such as those described above.
  • the skin layer is free of polyethylene imine octadecyl carbamide.
  • the skin layer is free of long chain fatty carbamide release agents.
  • the skin layer may include an antiblocking agent.
  • antiblocking agents reduces the tendency of the films to block during windup, regulates the slip and anti-static properties of the films and allows a smooth unwinding from the reels.
  • Any of the antiblocking agents described in the prior art as useful additives modifying the properties of polymer films, and in particular, olefin polymer films, can be included in the film formulations of the present invention.
  • Silicas with average particle sizes of about 2 microns or less can be utilized for this purpose, and only small amounts (for example, 1000 to 5000 ppm) of the fine silica are needed.
  • Several antiblocking agents based on synthetic silica are available from A. Schulman, Inc., Akron, Ohio, under the general trade designation Polybatch ® .
  • antiblocking masterbatches comprise free flowing pellets comprising propylene homopolymers or copolymers and the synthetic silica.
  • Polybatch ABPP 05 comprises 5% synthetic silica in a propylene homopolymer
  • ABPP 10 comprises 10% synthetic silica in a propylene homopolymer
  • ABPP 05SC comprises 5% synthetic silica and a random propylene copolymer.
  • the antiblocking agent When the antiblocking agents are to be utilized in the preparation of the multilayer films of the present invention, the antiblocking agent generally is added to the skin layer formulations only.
  • Useful antiblocking agents include Ampacet's Seablock 1 and Seablock 4.
  • Table IV relate to skin layers that contain greater than 70% propylene homopolymer that are useful in the present invention.
  • the amounts are in parts by weight.
  • skin layer (c) is a polyolefin, such as those described herein.
  • skin layer (c) comprises a polymer selected from a propylene homopolymer, a polyamide, a polyester, a polystyrene, a polycarbonate, and mixtures of two or more thereof.
  • skin layer (c) may be a polymer selected from i) at least one homopolymer of ethylene or propylene, (ii) at least one copolymer of propylene and ethylene, (iii) at least one polymer of ethylene or propylene and an alpha olefin having from about 4 to about 18 carbon atoms, or (iv) mixtures thereof.
  • the propylene homopolymers and copolymers are described above.
  • the ethylene polymers may include those described above for the tear resistance additive.
  • skin layer (c) has same composition as described for skin layer (b) above.
  • This multilayer film can be made by coextrusion.
  • the film may be prepared by means known to those in the art. Typically the films are extruded at temperatures between 250 to about 550, or about 300 to about 500 degrees F. A useful procedure for preparing the films is extrusion at 450 degrees F.
  • film 100 has base layer 102 which is bonded to skin layer 104.
  • three layer multilayer film 200 has base layer 202 which has on its surfaces skin layers 204 and 206.
  • the multilayer film has at least one roughened surface.
  • the roughened surface may be prepared by passing the multilayer film against a metal cooling roll with a surface roughness of 60 Ra using a rubber nip pinning method. The surface roughness from the casting roll is imparted to the surface of the multilayer film.
  • skin layer (b) has a roughened surface.
  • skin layers (b) and (c) have a roughened surface.
  • Useful two layer multilayer films are prepared by coextruding each composition of Examples 1-6 as skin layers with each of the base layers A-K described above.
  • the films are coextruded and then cast onto a roughened surface metal cooling roll with a surface roughness of 60 Ra using a rubber nip pinning method.
  • the films are a 3.5 mil multilayer two layer films having a skin layer of 1 mil and a base layer of 2.5 mil.
  • Useful three layer films are prepared by coextruding through a combining adapter feedblock each of the base layer compositions A-K of Table III with skin layers each prepared from Examples 1-6 of Table IV described above.
  • the films are coextruded and then cast onto a roughened surface metal cooling roll with a surface roughness of 60 Ra using a rubber nip pinning method.
  • the films are a 3.5 mil three layer films having two skin layers of 0.5 mil each and a base layer of 2.5 mil.
  • Useful three layer films are prepared by coextruding through a combining adapter feedblock each of the base layer compositions A-K with one skin layer prepared from each of Examples 1-6 described above and another skin layer prepared from Union Carbide SRD4-105 propylene copolymer, having 14% 1-Butene and MFR of 5.
  • the films are coextruded then cast onto a roughened surface metal cooling roll with a surface roughness of 60 Ra using a rubber nip pinning method.
  • the films are a 3.5 mil three layer films having two skin layers of 0.5 mil each and a base layer of 2.5 mil.
  • Useful three layer multilayer films are prepared by coextruding through a combining adapter feedblock each of the base layer compositions A-K with one skin layer prepared from each of Examples 1-6 described above and another skin layer prepared from Dow Chemical DS6D21 , an propylene ethylene copolymer having a MFR of 8.
  • the films are coextruded and then cast onto a roughened surface metal cooling roll with a surface roughness of 60 Ra using a rubber nip pinning method.
  • the films are a 3.5 mil multilayer three layer films having two skin layers of 0.5 mil each and a base layer of 2.5 mil.
  • the multilayer films may be oriented or non-oriented.
  • the films may be stretched and oriented in a single (e.g. uniaxially) or double direction (biaxially).
  • the film is stretched in the machine direction. After stretching, the film is thermally set or annealed. If the film is not sufficiently annealed, polymer stresses can be locked into the film.
  • the means for orienting the film includes but is not limited to cold stretching, hot stretching, compression rolling, hot compression rolling, and a blown extrusion process.
  • the film is uniaxially oriented and/or the material is hot stretched.
  • the multilayer films described above may be used together with an adhesive layer to form an adhesive construction.
  • the adhesive construction is useful as a tape, such as a diaper tape.
  • the diaper tape may be used on the waistband of the diaper as the landing zone for the diaper tab.
  • the adhesive construction may be used as a diaper tab.
  • the adhesive is generally applied to completely or partially cover the multilayer film construction. It should be understood that the adhesive may also be applied in patterns as well as a continuous layer.
  • the adhesive may be applied directly to the multilayer films above by coating the adhesive onto the skin layer as is known to those in the art.
  • the adhesive may be a heat-activated adhesive, a hot melt adhesive, or a pressure sensitive adhesive (PSA).
  • PSA pressure sensitive adhesive
  • Adhesives that are tacky at any temperature up to about 160°C (about 320°F) are particularly useful.
  • PSAs that are tacky at ambient temperatures are particularly useful.
  • a variety of conventional PSAs can be utilized.
  • the adhesives may generally be classified into the following categories: a) random copolymer adhesives such as those based upon acrylate and/or methacrylate copolymers, a-olefin copolymers, silicone copolymers, chloroprene/acrylonitrile copolymers, and the like, b) block copolymer adhesives including those based upon linear block copolymers (i.e., A-B and A-B-A type), branched block copolymers, star block copolymers, grafted or radial block copolymers, and the like, and c) natural and synthetic rubber adhesives.
  • random copolymer adhesives such as those based upon acrylate and/or methacrylate copolymers, a-
  • pressure-sensitive adhesives are useful in the invention. Examples of these adhesives include the hot melt pressure-sensitive adhesives available from H. B. Fuller Company, St. Paul, Minn, as HM-1597, HL-2207-X, HL-2115X, HL-2193-X. Other useful commercially available pressure-sensitive adhesives include those available from Century Adhesives Corporation, Columbus, Ohio.
  • the pressure sensitive adhesive utilized in the present invention comprise rubber based elastomer materials such as linear, branched, graft or radial block copolymers represented by the diblock structures A-B, the triblock A-B-A, the radial or coupled structures (A-B)n, and combinations of these where A represents a hard thermoplastic phase or block which is non-rubbery or glassy or crystalline at room temperature but fluid at higher temperatures, and B represents a soft block which is rubbery or elastomeric at service or room temperature.
  • thermoplastic elastomers may comprise from about 75% to about 95% by weight of rubbery segments and from about 5% to about 25% by weight of non-rubbery segments.
  • the non-rubbery segments or hard blocks comprise polymers of mono- and polycyclic aromatic hydrocarbons, and more particularly vinyl-substituted aromatic hydrocarbons which may be monocyclic or bicyclic in nature.
  • the rubbery blocks or segments are polymer blocks of homopolymers or copolymers of aliphatic conjugated dienes. Rubbery materials such as polyisoprene, polybutadiene, and styrene butadiene rubbers may be used to form the rubbery block or segment.
  • Particularly useful rubbery segments include polydienes and saturated olefin rubbers of ethylene/butylene or ethylene/propylene copolymers. The latter rubbers may be obtained from the corresponding unsaturated polyalkylene moieties such as polybutadiene and polyisoprene by hydrogenation thereof.
  • the block copolymers of vinyl aromatic hydrocarbons and conjugated dienes which may be utilized include any of those which exhibit elastomeric properties.
  • the block copolymers may be diblock, triblock, multiblock, starblock, polyblock or graftblock copolymers. Throughout this specification and claims, the terms diblock, triblock, multiblock, polyblock, and graft or grafted-block with respect to the structural features of block copolymers are to be given their normal meaning as defined in the literature such as in the Encyclopedia of Polymer Science and Engineering, Vol. 2, (1985) John Wiley & Sons, Inc., New York, pp. 325-326, and by J. E. McGrath in Block Copolymers, Science Technology, DaIe J. Meier, Ed., Harwood Academic Publishers, 1979, at pages 1-5.
  • Such block copolymers may contain various ratios of conjugated dienes to vinyl aromatic hydrocarbons including those containing up to about 40% by weight of vinyl aromatic hydrocarbon. Accordingly, multi-block copolymers may be utilized which are linear or radial symmetric or asymmetric and which have structures represented by the formulae A-B, A-B-A, A-B-A-B, B-A-B, (AB)0, 1 ,2...BA, etc., wherein A is a polymer block of a vinyl aromatic hydrocarbon or a conjugated diene/vinyl aromatic hydrocarbon tapered copolymer block, and B is a rubbery polymer block of a conjugated diene.
  • the block copolymers may be prepared by any of the well-known block polymerization or copolymerization procedures including sequential addition of monomer, incremental addition of monomer, or coupling techniques as illustrated in, for example, U.S. Patents 3,251 ,905; 3,390,207; 3,598,887; and 4,219,627.
  • tapered copolymer blocks can be incorporated in the multi-block copolymers by copolymerizing a mixture of conjugated diene and vinyl aromatic hydrocarbon monomers utilizing the difference in their copolymerization reactivity rates.
  • Various patents describe the preparation of multi-block copolymers containing tapered copolymer blocks including U.S. Patents 3,251 ,905; 3,639,521 ; and 4,208,356, the disclosures of which are hereby incorporated by reference.
  • Conjugated dienes which may be utilized to prepare the polymers and copolymers are those containing from 4 to about 10 carbon atoms and more generally, from 4 to 6 carbon atoms. Examples include from 1 ,3-butadiene, 2-methyl-1 ,3-butadiene (isoprene), 2,3-dimethyl-1 ,3-butadiene, chloroprene, 1 ,3-pentadiene, 1 ,3-hexadiene, etc. Mixtures of these conjugated dienes also may be used. The useful conjugated dienes are isoprene and 1 ,3-butadiene.
  • vinyl aromatic hydrocarbons which may be utilized to prepare the copolymers include styrene and the various substituted styrenes such as 0-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1 ,3-dimethylstyrene, alpha-methylstyrene, beta-methylstyrene, p-isopropylstyrene,
  • the useful vinyl aromatic hydrocarbon is styrene.
  • the number average molecular weight of the block copolymers, prior to hydrogenation, is from about 20,000 to about 500,000, or from about 40,000 to about 300,000.
  • the average molecular weights of the individual blocks within the copolymers may vary within certain limits.
  • the vinyl aromatic block will have a number average molecular weight in the order of about 2000 to about 125,000, or between about 4000 and 60,000.
  • the conjugated diene blocks either before or after hydrogenation will have number average molecular weights in the order of about 10,000 to about 450,000, or from about 35,000 to 150,000.
  • the vinyl content of the conjugated diene portion generally is from about 10% to about 80%, and the vinyl content is from about 25% to about 65%, or from about 35% to about 55% when it is desired that the modified block copolymer exhibit rubbery elasticity.
  • the vinyl content of the block copolymer can be measured by means of nuclear magnetic resonance.
  • diblock copolymers include styrene- butadiene (SB), styrene-isoprene (Sl), and the hydrogenated derivatives thereof.
  • triblock polymers include styrene-butadiene-styrene (SBS), styrene -isoprene- styrene (SIS), alpha-methylstyrene-butadiene-alpha-methylstyrene, and alpha-methylstyrene-isoprene alpha-methylstyrene.
  • block copolymers useful as the adhesives in the present invention include those available from Shell Chemical Company under the tradename Kraton.
  • Kraton Rubbers include D1101 (linear SBS); D1107P (linear SIS); D1111 (linear SIS); D1112P (linear SIS); D1113P (linear SIS); D1117P (linear SIS); and D1320X (multi-arm (Sl)n).
  • Vector 4111 is an SIS block copolymer available from Dexco of Houston Texas.
  • a styrene-ethylene-butylene styrene (SEBS) block copolymer Upon hydrogenation of the SBS copolymers comprising a rubbery segment of a mixture of 1 ,4 and 1 ,2 isomers, a styrene-ethylene-butylene styrene (SEBS) block copolymer is obtained. Similarly, hydrogenation of an SIS polymer yields a styrene-ethylene propylene-styrene (SEPS) block copolymer.
  • SEBS styrene-ethylene-butylene styrene
  • the selective hydrogenation of the block copolymers may be carried out by a variety of well known processes including hydrogenation in the presence of such catalysts as Raney nickel, noble metals such as platinum, palladium, etc., and soluble transition metal catalysts.
  • Suitable hydrogenation processes which can be used are those wherein the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst.
  • Such procedures are described in U.S. Patents 3,113,986 and 4,226,952, the disclosures of which are incorporated herein by reference.
  • Such hydrogenation of the block copolymers which is carried out in a manner and to extent as to produce selectively hydrogenated copolymers having a residual unsaturation content in the polydiene block from about 0.5% to about 20% of their original unsaturation content prior to hydrogenation.
  • the conjugated diene portion of the block copolymer is at least 90% saturated and more often at least 95% saturated while the vinyl aromatic portion is not significantly hydrogenated.
  • Particularly useful hydrogenated block copolymers are hydrogenated products of the block copolymers of styrene-isoprene-styrene such as a styrene-(ethylene/propylene)-styrene block polymer.
  • a polystyrene-polybutadiene-polystyrene block copolymer When a polystyrene-polybutadiene-polystyrene block copolymer is hydrogenated, it is desirable that the 1 ,2-polybutadiene to 1 ,4-polybutadiene ratio in the polymer is from about 30:70 to about 70:30.
  • the resulting product resembles a regular copolymer block of ethylene and 1-butene (EB).
  • EB ethylene and 1-butene
  • the conjugated diene employed as isoprene the resulting hydrogenated product resembles a regular copolymer block of ethylene and propylene (EP).
  • Kraton G 1652 is a hydrogenated SBS triblock comprising about 30% by weight of styrene end blocks and a midblock which is a copolymer of ethylene and 1 -butene (EB).
  • EB ethylene and 1 -butene
  • a lower molecular weight version of G 1652 is available from Shell under the designation Kraton G 1650.
  • Kraton G1651 is another SEBS block copolymer which contains about 33% by weight of styrene.
  • Kraton G165 is an SEBS diblock copolymer which contains about 13%w styrene. This styrene content is lower than the styrene content in Kraton G 1650 and Kraton G 1652.
  • the unsaturation of block B is reduced upon hydrogenation to less than 5% of its original value, and the average unsaturation of the hydrogenated block copolymer is reduced to less than 20% of its original value.
  • the block copolymers may also include functionalized polymers such as may be obtained by reacting an alpha, beta-olefinically unsaturated monocarboxylic or dicarboxylic acid reagent onto selectively hydrogenated block copolymers of vinyl aromatic hydrocarbons and conjugated dienes as described above.
  • the reaction between the carboxylic acid reagent in the graft block copolymer can be effected in solutions or by a melt process in the presence of a free radical initiator.
  • the preparation of various selectively hydrogenated block copolymers of conjugated dienes and vinyl aromatic hydrocarbons that have been grafted with a carboxylic acid reagent is described in a number of patents including U.S.
  • Patents 4,578,429; 4,657,970; and 4,795,782 and the disclosures of these patents relating to grafted selectively hydrogenated block copolymers of conjugated dienes and vinyl aromatic compounds, and the preparation of such compounds are hereby incorporated by reference.
  • U.S. Patent 4,795,782 describes and gives examples of the preparation of the grafted block copolymers by the solution process and the melt process.
  • U.S. Patent 4,578,429 contains an example of grafting of Kraton G1652 (SEBS) polymer with maleic anhydride with 2,5-dimethyl-2,5-di(t-butylperoxy) hexane by a melt reaction in a twin screw extruder. (See CoI. 8, lines 40-61.)
  • maleated selectively hydrogenated copolymers of styrene and butadiene examples include Kraton FG1901X, FG1921X, and FG1924X from Shell, often referred to as maleated selectively hydrogenated SEBS copolymers.
  • FG 1901 X contains about 1.7%w bound functionality as succinic anhydride and about 28%w of styrene.
  • FG1921 X contains about 1 %w of bound functionality as succinic anhydride and 29%w of styrene.
  • FG1924X contains about 13% styrene and about 1 % bound functionality as succinic anhydride.
  • Useful block copolymers also are available from Nippon Zeon Co., 2-1 ,
  • the water may be removed in an extruder by using the process described and claimed in U.S. Patent 5,716,669 (LaRose et al).
  • the presence of water or solvents during the coextrusion process can result, and generally does result, in pinholes and bubbles in the coextruded film.
  • the presence of voids in the film due to steam is referred to in the art as "moisture slits.”
  • the adhesive has a coating weight of less than 40, or less than 20 g/m2. In one embodiment, the adhesive layer has a coat weight in the range from about 0.5 to about 20 g/m2. Alternatively, the thickness of the adhesive layer may range from about 0.02 to about 2, or from about 0.02 to about 0.8 mils. It should be understood that the thickness and coat weight of both the polymer film and the adhesive layer may vary depending upon the different types of polymer film material and adhesives that are selected, and the properties desired in the adhesive construction. For example, different polymers and different film thicknesses will result in constructions having different stiffnesses.
  • the adhesive compositions also may contain at least one solid tackifier resin component.
  • a solid tackifier is defined herein as one having a softening point above 80°C.
  • the pressure-sensitive adhesive compositions generally comprise from about 40 to about 80% by weight of a thermoplastic elastomer component and from about 20% to about 60%, or from about 55 to 65% by weight of a solid tackifier resin component.
  • Solid tackifier resins include hydrocarbon resins, rosin, hydrogenated rosin, rosin esters, polyterpene resins, and other resins which exhibit the proper balance of properties.
  • a variety of useful solid tackifier resins are available commercially such as terpene resins which are sold under the trademark Zonatac by Arizona Chemical Company, and petroleum hydrocarbons resins such as the resins sold under the trademark Escorez by Exxon Chemical Company.
  • Escorez 2596 is a C5-C9 (aromatic modified aliphatic) synthetic tackifier having an Mw of 2100 and a dispersity (Mw/Mn) of 2.69.
  • Escorez 131 OLC identified as an aliphatic hydrocarbon resin having an Mw of 1350 and a dispersity of 1.8.
  • Wingtack 95 is a synthetic tackifier resin available from Goodyear, Akron, Ohio consisting predominantly of polymerized structure derived from piperylene and isoprene.
  • the modulus of the adhesive mixtures also may be lowered by the incorporation of liquid rubbers, i.e., liquid at room temperature.
  • the liquid rubbers generally will have an Mw of at least 5,000 and more often at least 20,000.
  • the incorporation of a liquid rubber also produces an adhesive having increased tack and adhesion.
  • Liquid block copolymers such as liquid styrene-isoprene block copolymers are particularly useful.
  • Kraton LVSI-101 available from the Shell Chemical Company, is effective in lowering the modulus of the adhesive, and it has been found, surprisingly, that this liquid styrene-isoprene block copolymer functions as a processing aid, improving the smoothness of the flow of the adhesive from the die.
  • Kraton LVSI-101 has a weight average molecular weight of about 40,000.
  • Another example of a useful liquid rubber is a liquid polyisoprene obtained by depolymerization of high molecular weight polyisoprene.
  • An example of a commercially available depolymerized high molecular weight polyisoprene is lsolene D-400 from Elementis Performance Polymers, Belleville, NJ. , and this liquid rubber has an Mw of about 20,000.
  • Other liquid rubbers which may be incorporated into the adhesive mixture include liquid styrene-butadiene rubbers, liquid butadiene rubbers, ethylene-propylene rubbers, etc.
  • the adhesive compositions also may include other materials such as antioxidants, heat and light stabilizers, ultraviolet light absorbers, fillers, colorants, antiblocking agents, reinforcing agents, processing acids, etc.
  • Hindered phenolic and amine antioxidant compounds may be included in the adhesive compositions, and a wide variety of such antioxidant compounds are known in the art.
  • a variety of antioxidants are available from Ciba-Geigy under the general trade designations "Irganox" and "Irgafos”.
  • the hindered phenolic antioxidant n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenol)- proprionate is available under the general trade designation "Irganox 1076".
  • Irganox 1010 is identified as Tetrakis (methylene 3-(3N,5N-di-tert-butyl-4N-hydroxyphenol) proprionate) methane, lrgafos 168 is another useful antioxidant from Ciba-Geigy.
  • Light stabilizers, heat stabilizers, and UV absorbers also may be included in the adhesive compositions.
  • Ultraviolet absorbers include benzo- triazol derivatives, hydroxy benzyl phenones, esters of benzoic acids, oxalic acid, diamides, etc.
  • Light stabilizers include hindered amine light stabilizers, and the heat stabilizers include dithiocarbamate compositions such as zinc dibutyl dithiocarbamate.
  • Hydroquinone-based antioxidants also may be utilized, and one example of such an antioxidant is 2,5-di-tertiary-amyl-hydroquinone.
  • the adhesive compositions may contain inorganic fillers and other organic and inorganic additives to provide desired properties.
  • useful fillers include calcium carbonate, titanium dioxide, metal particles, fibers, etc.
  • An example of a useful end-block reinforcing agent is Cumar LX509 from Neville Resins.
  • the multilayer films together with an adhesive layer may form adhesive constructions.
  • the adhesive constructions are self wound.
  • the adhesive comes into contact with both sides of the multilayer film.
  • skin layers (b) and (c) comprise at least about 70% by weight propylene homopolymer.
  • skin layers (b) and (c) independently comprise at least about 70% by weight of a polymer selected from a propylene homopolymer, a polyamide, a polyester, a polystyrene, a polycarbonate, and mixtures of two or more thereof.
  • adhesive construction 300 has base layer 302 with the skin layer 304.
  • the skin layer 304 is bonded to adhesive 306.
  • the skin layer 304 has a roughened surface 305 as is described above.
  • the second surface 303 of the base layer 302 has a roughened surface.
  • this construction may also have a release liner on the opposite surface of adhesive film 306. The release liner is not shown. In another embodiment, this adhesive construction may be self wound.
  • adhesive construction 400 has a base layer 402 with skin layers 404 and 408.
  • Skin layer 404 has an adhesive layer 406 bonded to it.
  • skin layer 404 has a roughened surface 405, as described above.
  • skin layers 404 and 408 have roughened surfaces, 405 and 407.
  • This adhesive also may have a release liner on the adhesive layer 406. The release liner is not shown. In another embodiment, this adhesive construction may be self wound.
  • the adhesive constructions may be used as a tape or tab for disposal diapers, geriatric briefs, surgical drapes or other articles requiring a fastener tab or a tape.
  • a disposable diaper 500 has the diaper body 502 which is adhered to a diaper tape 504 and diaper tabs 506a and 506b.
  • Diapertabs 506a and 506b may be any configuration of diapertab known to those in the art, including the Y configuration and Z configuration of diaper tabs.
  • adhesive tab 600 is illustrated having a three layer multilayer film 602 which is composed of a base layer 604 and skin layers 606 and 608 on the surfaces of the base layer. The adhesive tab is folded over on itself and releasably adhered with an adhesive layer 610, such as a pressure sensitive adhesive. The tab is adhered to an adhesive layer 612 which permanently adheres the tab to the diaper extension 614.
  • Fig. 6B illustrates the application of the tab from Fig. 6A where the diaper tab connects two parts of a diaper.
  • Tab 600 is composed of a three layer film 602 having a base layer 604 with skin layers 606 and 608.
  • the multilayer film 602 is permanently adhered to diaper extension 614 with adhesive 612.
  • Adhesive 610 adheres the multilayer film 602 to diaper surface 616.
  • the adhesive layer 610 is releasably adhered to the diaper surface 616.
  • Diaper surface 616 may have a release surface such as those formed by an adhesive tape, like those described herein.
  • Fig. 7 A and B illustrate an adhesive tab which is useful in garments such as diapers.
  • Adhesive tab 700 has a three layer film 702 which is composed of a base layer 704 and two skin layers 706 and 708.
  • the multilayer film 702 is adhered to adhesive layer 710 which permanently adheres to diaper extension 712.
  • Another portion of the multilayer film 702 is releasably adhered to diaper extension 712 through adhesive layer 714 to release layer 716 on diaper extension 712.
  • Fig. 7B illustrates the application of Tab 700 to provide closure of a diaper.
  • the tab 700 is composed of the multilayer film 702 which has base layer 704 with skin layers 706 and 708.
  • Multilayer film 702 is adhered to diaper extension 712 by way of adhesive layer 710.
  • Diaper extension 712 still has a release layer 716 on one of its surfaces.
  • the multilayer film 702 is also adhered through adhesive 714 to a surface of a portion of the diaper 718.
  • the multilayer films and adhesive constructions may be used with hook and loop fasteners which are known to those in the art.
  • Hook and loop fasteners have been described in U.S. Patent 6,524,294, issued in the name of Hilston et al and U.S. Patent 6,419,667 issued in the name of Avalon et al. These patents are hereby incorporated by reference for their disclosure of hook and loop fasteners.
  • the adhesive constructions may contain either the hook or loop portion of the fastener by way of lamination of a substrate containing hook or loop onto the adhesive construction, for instance on a skin layer.
  • the hook and loop fasteners may be used with both the diaper tape or the diaper tab. It is understood that typically the hook or loop would be on the diaper tab or diaper tape.
  • Diaper tab 800 has multilayer film 802 having base layer 804 and skin layers 806 and 808. Skin layer 806 is laminated to a substrate 810 which has hooks 812 projecting therefrom. The hooks are releasably adhered to coating 814. Skin layer 808 is adhered to diaper extension 818 through adhesive layer 816.
  • Fig. 8B illustrates the use of the diaper tab as a closure where tab 800 has been opened and adhered to another portion of the garment which has loops to fasten to the hooks.
  • Multilayer film 802 has base layer 804 with skin layers 806 and 808. Skin layer 806 is laminated to a substrate 810 having hooks 812 protruding therefrom.
  • Hooks 812 attach to loops 822 on a portion of diaper 820.
  • Skin layer 806 still has release coating 814 on its surface.
  • Skin layer 808 is adhered to diaper extension 818 through adhesive 816. It is understood that in the diaper tab, the hook and the loop positions may be interchanged. Additionally, it's understood that only one variety of diaper tab has been illustrated but that the other diaper tabs, including those illustrated in this application, may be used with a hook and loop fastener.
  • the hook or loop portion is attached to a diaper tape.
  • diaper tape 900 has three layer film 902 having a base layer 904 and skin layers 906 and 908. Skin layer 906 is adhered to adhesive layer 910.
  • skin layer 908 is laminated to substrate 912 which has hooks protruding therefrom.
  • skin layer 908 is laminated to substrate 914 which has loops on its exposed surface.

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film à couches multiples (100) comprenant (a) une couche de base (102) ayant une première et une seconde surface, la couche de base (102) étant composée d’au moins une polyoléfine. Ledit film comprend également (b) une couche superficielle (104) sur une surface de la couche de base (102). Ladite couche superficielle (104) comprend au moins environ 70 % en poids d’un homopolymère de propylène et le film à couches multiples (100) a une valeur d’inertie au pli d’environ 45 000 à environ 110 000 psi dans le sens machine.
PCT/US2004/040767 2004-12-06 2004-12-06 Films a couches multiples, constructions adhesives et objets les utilisant WO2006062504A1 (fr)

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PCT/US2004/040767 WO2006062504A1 (fr) 2004-12-06 2004-12-06 Films a couches multiples, constructions adhesives et objets les utilisant

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PCT/US2004/040767 WO2006062504A1 (fr) 2004-12-06 2004-12-06 Films a couches multiples, constructions adhesives et objets les utilisant

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015187646A1 (fr) * 2014-06-02 2015-12-10 Avery Dennison Corporation Films ayant une résistance à l'abrasion, une clarté et une conformabilité améliorées
US9636895B2 (en) 2006-06-20 2017-05-02 Avery Dennison Corporation Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof
US9662867B2 (en) 2006-06-14 2017-05-30 Avery Dennison Corporation Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US9676532B2 (en) 2012-08-15 2017-06-13 Avery Dennison Corporation Packaging reclosure label for high alcohol content products
CN107848048A (zh) * 2015-06-05 2018-03-27 特里迪加胶片制品公司 低微凝胶的表面保护膜
USRE46911E1 (en) 2002-06-26 2018-06-26 Avery Dennison Corporation Machine direction oriented polymeric films and methods of making the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093187A (en) * 1986-11-29 1992-03-03 Beiersdorf Ag Tear strip
US5135800A (en) * 1988-03-14 1992-08-04 Mitsui Petrochemical Industries, Ltd. Obliquely oriented polypropylene cross film and fastening tape for paper diaper comprising said cross film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093187A (en) * 1986-11-29 1992-03-03 Beiersdorf Ag Tear strip
US5135800A (en) * 1988-03-14 1992-08-04 Mitsui Petrochemical Industries, Ltd. Obliquely oriented polypropylene cross film and fastening tape for paper diaper comprising said cross film

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE46911E1 (en) 2002-06-26 2018-06-26 Avery Dennison Corporation Machine direction oriented polymeric films and methods of making the same
US9662867B2 (en) 2006-06-14 2017-05-30 Avery Dennison Corporation Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US9636895B2 (en) 2006-06-20 2017-05-02 Avery Dennison Corporation Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof
US9676532B2 (en) 2012-08-15 2017-06-13 Avery Dennison Corporation Packaging reclosure label for high alcohol content products
WO2015187646A1 (fr) * 2014-06-02 2015-12-10 Avery Dennison Corporation Films ayant une résistance à l'abrasion, une clarté et une conformabilité améliorées
AU2015270854B2 (en) * 2014-06-02 2018-08-02 Avery Dennison Corporation Films with enhanced scuff resistance, clarity, and conformability
US11459488B2 (en) 2014-06-02 2022-10-04 Avery Dennison Corporation Films with enhanced scuff resistance, clarity, and conformability
CN107848048A (zh) * 2015-06-05 2018-03-27 特里迪加胶片制品公司 低微凝胶的表面保护膜

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