WO1997009393A1 - Colles thermofusibles autoadhesives, procedes de fabrication et d'utilisation de ces colles - Google Patents

Colles thermofusibles autoadhesives, procedes de fabrication et d'utilisation de ces colles Download PDF

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Publication number
WO1997009393A1
WO1997009393A1 PCT/US1996/014407 US9614407W WO9709393A1 WO 1997009393 A1 WO1997009393 A1 WO 1997009393A1 US 9614407 W US9614407 W US 9614407W WO 9709393 A1 WO9709393 A1 WO 9709393A1
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Prior art keywords
resins
resin
composition
tackifier
comonomers
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PCT/US1996/014407
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English (en)
Inventor
Mun Fu Tse
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Exxon Chemical Patents Inc.
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Publication of WO1997009393A1 publication Critical patent/WO1997009393A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes

Definitions

  • This invention relates to hot melt adhesive compositions, methods for making hot melt adhesive compositions, and articles using hot melt adhesive compositions.
  • a hot melt adhesive is a thermoplastic mixture that is flowable when heated, but cools to a solid after application.
  • HMA is essentially free of water or solvent.
  • low molecular weight additives in a HMA to increase its fluidity at the application temperature or allow a reduction in application temperature resulting in a lower cost process and/or modification of the mechanical properties of the adhesive such as bond strength and low temperature flexibility.
  • Typical HMAs comprise a base polymer and a tackifier.
  • the most widely used hot melt adhesives are based on polyethylene, other polyolefins or mixtures thereof, ethylene-vinyl acetate copolymers (EVA), polyamides, polyesters, and block copolymer rubbers.
  • Typical additives such as tackifiers, waxes, and oils can be used to modify the flow characteristics and odier properties of HMAs.
  • tackifiers such as synthetic hydrocarbon resins or derivatives of natural rosins are added to these ethylene homopolymers and copolymers to give them their adhesive qualities.
  • the strength of the adhesive bond is dependent upon the individual properties and the relative amounts of each the base polymer and the tackifier.
  • an adhesive based on EVA, a polar copolymer, blended with a natural rosin-based tackifier, also a polar composition would be expected to have superior adhesive performance when compared to an EVA blended with a synthetic hydrocarbon-based tackifier, a non-polar compound.
  • U.S. Patent No. 4,973,326 discloses hot melt adhesives comprising resin blends wherein each of the resins is limited only to a maximum glass transition temperature and to content ranges based upon those glass transition temperatures.
  • An object of the invention provides for an HMA having good adhesive performance without requiring an application temperature high enough to damage the substrate.
  • Adhesives using a non-polar hydrocarbon-based tackifier would be essentially acid-free and have less odor and better color stability when compared to adhesives using polar tackifiers. Also, the use of non-polar tackifier resins provides better handling properties when the molten HMA is in contact with metallic surfaces of processing equipment. Therefore, it would be desirable to develop adhesives using hydrocarbon tackifiers that offer bond strength equal to or better than adhesives comprising solar tackifiers.
  • This invention relates to HMA compositions comprising a base polymer and as a tackifier, a blend of at least one solid resin and at least one liquid resin.
  • the base polymer is preferably one or more homopolymers and/or copolymers containing ethylene or propylene.
  • the amounts of the solid and the liquid resins in the blend are preferably such that the tackifier has a composite glass transition temperature of from about 0°C to about 45°C.
  • This invention further relates to methods for producing the novel HMA compositions.
  • sohd resins used in the blends of this invention are hydrocarbon resins or equivalents thereof produced by known methods.
  • Solid resin for the purposes of this patent specification and appended claims is a polymerization product of the monomers and polymerization processes disclosed below that is solid at room temperature ( ⁇ 25°C).
  • a solid resin can be a resin that has been treated to improve its color or that has been blended with stabilizers or other additive packages that do not substantially alter the adhesive properties of the resin.
  • the solid resins have a M w in the range of about 350 to about 2100, preferably about 400 to about 1500, more preferably about 400 to about 1200.
  • the preferred solid resins have a T g in the range of from about 25°C to about 100°C, more preferably from about 35°C to about 85°C, even more preferably from about 40°C to about 70°C.
  • the preferred solid resins are selected from C 5 - Cg aromatic modified aliphatic hydrocarbon resins, C5-C9 aromatic modified aliphatic hydrocarbon/terpene resins, and alicyclic diene monomer containing hydrocarbon resins.
  • the aromatic modified aliphatic hydrocarbon resins, used as the solid resin are prepared by the polymerization of a mixture of a petroleum cracked distillate generally boiling in the range of from about 25 °C to about 80°C and a monovinyl aromatic monomer having 8 or 9 carbon atoms.
  • the polymerization product is characterized as a mixture of components giving a proton distribution such that from about 5 percent to about 30 percent are aromatic protons, from about 0 to about 10 percent are olefinic protons, from about 20 percent to about 50 percent are aliphatic methyl protons, and about 0 to about 30 percent are aromatic methyl protons, as determined by Proton Nuclear Magnetic Resonance spectroscopy (-H NMR).
  • the petroleum cracked distillate typically comprises a mixture of saturated and unsaturated monomers.
  • the unsaturated monomers are monoolefins and/or diolefins, and although the unsaturated materials are predominantly C 5 , some higher and lower materials such as C 6 olefins and diolefins may be present.
  • the distillate may also contain saturated or aromatic materials which can act as a polymerization solvent
  • a preferred monovinyl aromatic monomer is styrene which may have substitution of the hydrogens in the aromatic group.
  • alpha-methyl styrene or vinyl toluene may be used as an aromatic monomer.
  • Preferred aromatic monomers are styrene, all methyl styrene isomers. indene, and all methyl indene isomers. It is, however, preferred for lower and thus improved color to use the pure monomer rather than the commercially available mixtures of vinyl aromatic monomers.
  • Aromatic modified aliphatic hydrocarbon resins are conveniently prepared by Friedel-Crafts catalyzed polymerization in which the mixture of cracked distillate and monovinyl aromatic monomer are treated with from about 0.25 to about 2.5 weight percent of a catalyst.
  • a catalyst for the purpose of U.S. patent practice.
  • Non-limiting examples of such catalysts are aluminum chloride, aluminum bromide, or solutions, slurries or complexes thereof or borontrifluoride.
  • the polymerization mixture may also include but is not limited to from about 10 to 100 weight percent, based on the weight of the feed mixture, of a chain transfer agent such as a diisobutene oligomer to obtain resins having a narrower molecular weight distribution.
  • a chain transfer agent such as a diisobutene oligomer
  • These reactions are generally carried out at temperatures in the range of from 0°C to 120°C, preferably from 0°C to 80°C, more preferably from 20°C to 55°C, the conditions being controlled to yield a resin of the preferred ranges of softening points.
  • Residual catalyst is quenched by suitable methods such as addition of methyl alcohol, ethyl alcohol, isopropyl alcohol, or aqueous solutions of these alcohols, and subsequent filtration followed by water and/or caustic washing.
  • the final solution may then be stripped of unreacted hydrocarbons and low molecular weight oils by vacuum or steam distillation.
  • the most preferred aromatic modified aliphatic hydrocarbon solid resins have ring and ball softening points (ASTM E28-92) in the range of from about 85° C to about 145°C, preferably in the range of from about 90°C to about 130°C, more preferably in the range of from about 90°C to about 115°C, even more preferably in the range of from about 90°C to about 100°C.
  • the preferred aliphatic resins also have a percent aromatic protons in the range of from about 5 to about 30, a percent olefinic protons in the range of from about 0 to about 10, a percent aliphatic methyl protons in the range of about 20 to about 50, and a percent aromatic methyl protons in the range of from about 0 to about 30.
  • aromatic modified aliphatic hydrocarbon solid resins are Escorez® 2000 series (such as but not limited to resins 2101, 2393, 2596) and Escorez® 6000 series (such as but not limited to resin ECR-372B or 6372) available from Exxon Chemical Co., Houston, Texas. Such commercial resins are often sold with antioxidant stabilizers and other additive packages present in small amounts.
  • the alicyclic diene monomer containing hydrocarbon sohd resins to be blended in this invention include those known as cyclopentadiene-dicyclopentadiene (CPD/DCPD) based petroleum resins which can be produced using the Friedel-Crafts polymerization processes discussed above for solid aromatic modified aliphatic petroleum resins.
  • CPD/DCPD resins known thermal polymerization processes are also particularly suitable.
  • any of these resins may be used as is or may be treated with a decolorizing agent or hydrogenated by known memods to remove substantially all the residual ethylenic and aromatic unsaturation, thus improving the color.
  • Typical hydrogenation results in residual ethylenic or aromatic content of less than 10 proton percent, preferably less than 7 proton percent, more preferably less than 5 proton percent, as determined by l NMR.
  • thermoplastic Co, aromatic resin includes but is not limited to those resins produced from pure monomers such as styrene and alkyl-substituted styrenes which are similarly polymerized in Friedel-Crafts catalysts.
  • U.S. Patent Nos. 3,926,878, 4,242,244, 4,276,396, 4,328,090, and 4,629,766, and WO 91/13106 each addressing preparation and/or hydrogenation of alicyclic monomer containing resins are fully inco ⁇ orated herein for purposes of U.S. patent practice.
  • the solid unhydrogenated or substantially hydrogenated alicyclic monomer containing hydrocarbon resins may contain other monomers in addition to the CPD/DCPD.
  • monomers are vinyl aromatic, indene, styrene, C4- C5 acyclic conjugated dienes, CPD codimers with conjugated acyclic dienes, C 9 , substituted C 9 , and other copolymerizable C 4 -C 10 monomers.
  • Preferable alicycHc monomer containing hydrocarbon sohd resins have a ring and ball softening point (ASTM E-28) from about 80°C to about 110°C, a M w of from about 350 to about 900, a z-average molecular weight (M z ) less than about 1600, a Gardner color less than or equal to about 2, and an aliphatic methyl proton percent in the range of about 5 to about 25 percent based on the total number of protons in the resin.
  • ASTM E-28 ring and ball softening point
  • the ring and ball softening point is from about 85°C to about 105 °C
  • the M w is from about 360 to about 700
  • the M z is from about 500 to about 1200
  • the Gardner color is less than about 2, more preferably less than about 1.
  • resins suitable as alicycHc diene monomer containing hydrocarbon tackifiers include the hydrogenated CPD/DCPD Escorez® 5000 series (such as but not Hmited to resins 5300, 5320, and 5380) available from Exxon Chemical Co., Houston, TX; the hydrogenated C5/C9 Eastotac® H100 resin available from Eastman Chemical Products, Inc., Kingsport, TN; and the hydrogenated C 9 /C4 Regalite® R91 and R101 resins available from Hercules, Inc., Wilmington, DE, Arkon® P90 and P100 available from Arakawa Inc., Japan. Such commercial resins are often sold with antioxidant stabilizers and/or other additive packages present in small amounts which do not affect the invention of this specification and appended claims.
  • the Uquid resins used in the blends of this invention are also from the same monomers and by the same methods as disclosed above for the soHd resins.
  • the distinction of Uquid resins from the soHd resins is that the Uquid resins have lower molecular weights (M n and M w ) resulting properties such as lower softening points, glass transition temperatures, and their Uquid consistency at room temperature.
  • Preferred liquid resins have a T g in the range of from about -80°C to about 20°C, preferably from about -60°C to about 0°C, more preferably from about -40°C to about -10°C.
  • a Uquid resin can be a resin that has been treated to improve the color or that has been blended with stabilizers or other additive packages that do not substantially alter the adhesive properties of the resin.
  • the preferred liquid resins have a M w in the range of about 100 to about 2000, preferably about 200 to about 1000, more preferably about 200 to about 800.
  • the preferred Uquid resins to be blended are selected from C5-C9 aromatic modified aliphatic hydrocarbon resins, C5-C 9 aromatic modified aUphatic hydrocarbon/te ⁇ ene resins, and aUcycUc diene monomer containing hydrocarbon resins.
  • the one or more Uquid resins are also compatible with the soHd resins with which they are blended; more preferably they will contain the same or similar type monomers.
  • the most preferred aromatic modified aliphatic hydrocarbon Uquid resins have a percent aromatic protons in the range of from about 5 to about 30, a percent olefinic protons in the range of from about 0 to about 10, a percent aliphatic methyl protons in the range of from about 20 to about 50, and a percent aromatic methyl protons in the range of from about 0 to about 30.
  • Such commercial resins are often sold with antioxidant stabilizers and other additive packages present in smaU amounts.
  • Preferable aUcycHc monomer containing hydrocarbon Uquid resins have a M w of from about 100 to about 2000, a Gardner color less than or equal to about 5, and an aliphatic methyl proton percent in the range of about 5 to about 25 percent based on the total number of protons in the Uquid resin. More preferably, the M w is from about 200 to about 1000, and the Gardner color is less than about 2, more preferably less than about 1.
  • resins suitable as aUcycUc diene monomer containing hydrocarbon tackifiers include the hydrogenated CPD/DCPD Escorez® 5000 series (such as but not Hmited to resin ECR-327 available from Exxon Chemical Co., Houston, TX or Exxon Chemical Belgium, Brussels, Belgium).
  • the Uquid/soUd resin blend of this invention contains one or more Uquid resins and one or more soHd resins.
  • the resins useful as blend components are selected from C5-C9 aromatic modified aliphatic hydrocarbon resins, C5-C9 aromatic modified aliphatic hydrocarbon/te ⁇ ene resins, and aUcycHc diene monomer containing hydrocarbon resins.
  • the Uquid and soHd resins to be blended are preferably selected from similar, thus compatible, types of resins.
  • the soHd and Uquid resins may be blended by any method commonly known to those skiUed in the art.
  • the Uquid and soHd resins can be blended together in the molten state or can be blended directly with the base polymer and other additives, such as wax, during the preparation of the HMA.
  • Liquid resin can also be injected into the polymerizate of the soHd resin as the polymerizate exits the reactor.
  • the soUd and Uquid resin blend can be subsequently recovered and steam stripped.
  • the order of blending of the Uquid resin, soUd resin, and other adhesive components is not critical.
  • the T g of the resin blends can be targeted to a specific desired value since the blends follow the Fox inverse rule:
  • T g / through T gn are the glass transition temperatures of the various blend components
  • T sulfur is the glass transition temperature of the blend.
  • the two liquid resins used in the blends of the examples shown below were Escorez® 2520 and ECR-327, glass transition temperatures of -16°C and -13°C, respectively. All temperatures are converted to degrees Kelvin for this calculation. Therefore, calculation of the T g of 303 °K or 30°C for the tackifier of Example 5 is as follows:
  • the tackifier containing one or more Uquid resins and one or more soUd resins, preferably has a composite T g in the range of about 0°C to about 45°C, more preferably about 10°C to about 40°C, even more preferably about 20°C to about 40°C.
  • the new HMAs contain a base polymer consisting of one or more ethylene-based or propylene-based polymers having a M n greater than 10,000.
  • the base polymer can be polyethylene, a copolymer of ethylene and one or more comonomers, polypropylene, a copolymer of propylene and one or more comonomers, or mixtures thereof.
  • these ethylene and propylene homopolymers and copolymers have a degree of crystaUinity of at least 5 weight percent, more preferably at least 15 weight percent, as measured by DSC.
  • the base polymer comprises ethylene and one or more comonomers.
  • the comonomers may be one or more polar groups such as vinyl acids, vinyl esters, vinyl alcohols, such as ethacryHc acid, crotonic acid, vinyl acetic acid, angelic acid, maleic acid, fumaric acid, ketones, carbon monoxide, 2- hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, and the Hke.
  • Preferred examples of polar comonomers include alkylmethacrylates, alkylacrylates, alkylmethacryUc acids, and alkylacryUc acids.
  • Suitable comonomers include vinyl acetate, acryUc acid, methacryHc acid, methacrylate, ethyl methacrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, and methyl acrylate.
  • Preferred copolymers have a comonomer content of less than 38 weight percent, more preferably in the range of from 10 to 33 weight percent, more preferably from 20 to 30 weight percent based upon the weight of the copolymer. These copolymers are produced by many processes known in the art, such as, but not Hmited to, free radical polymerization, and are available CommerciaUy in many forms.
  • ethylene-vinyl acetate copolymers are produced by high pressure free radical polymerization and are available from Exxon Chemical Company, Houston, TX, under the Escorene® trade name. These Escorene® EVA copolymers have weight percent comonomer in the range of from about 14 to about 33 and a melt index in the range of from about 2.3 to about 2500 dg/min. (ASTM D1238, condition E, 190°C and 2.16 kg).
  • the comonomers may also be a mixture of any of the polar moieties described above and non-polar groups described below.
  • the base polymer is a copolymer of ethylene or propylene, more preferably ethylene.
  • Preferred comonomers for ethylene are one or more higher alpha-olefins, more preferably one or more C3 to C 2 n alpha olefins, preferably one or more C3 to C 8 alpha olefins, more preferably one or more C4 to Cg alpha olefins.
  • Preferred comonomers for propylene are ethylene or one or more higher alpha-olefins, more preferably one or more C 4 to C20 alpha olefins, preferably one or more C4 to Cg alpha olefins, more preferably one or more C4 to C 6 alpha olefins.
  • Ethylene or propylene may also be coplymerized with one or more cycUc olefin monomers, such as norbornene, methyl norbornene, cyclopentene, ethyUdene norbornene, cyclopentadiene, and the like, or mixtures of alpha-olefins and cycUc olefins.
  • Examples include but are not Hmited to copolymers such as ethylene/hexene-1, ethylene/butene-1, ethylene/4-methyl- pentene-1, ethylene/octene-1, ethylene/norbornene, ethylene/butene-l/hexene-1, and the Hke.
  • the comonomers are present at 0.5 to 33 mole percent, preferably 1.5 to 25 mole percent, more preferably 5 to 18 mole percent, based on the total ethylene copolymer.
  • These polymers can be prepared in accordance with weU- known methods, typicaUy by polymerization with Zeigler-Natta catalysts or single site metaUocene catalysts as well as other known catalyst systems.
  • the HMA compositions of this invention comprise a base polymer, a blend of a hydrocarbon soHd and hydrocarbon Uquid resins as a tackifier, and optionaUy other modifiers.
  • the Uquid resin is present in the range of from about 1 part to about 100 parts by weight per 100 parts by weight of the soUd resin, more preferably from about 1 part to about 40 parts, most preferably form about 1 to about 20 parts.
  • Resins to be blended are preferably of a similar, thus more compatible, molecular structure.
  • DCPD-based Uquid resin use of a DCPD-based Uquid resin is preferred when a soUd DCPD resin is used and a soHd aromatic modified aUphatic Uquid resin is preferred when a soUd aromatic modified aliphatic Uquid resin is used.
  • the copolymer may be present in the HMA composition from about 10 to about 90 weight percent, preferably from about 20 to about 80 weight percent, even more preferably from about 30 to about 60 weight percent, most preferably from about 33 to about 50 weight percent, based upon the total weight of the HMA.
  • the resin blend tackifier may be present in the HMA composition from about 10 to about 90 weight percent, preferably from about 20 to about 80 weight percent, even more preferably from about 30 to about 60 weight percent, most preferably from about 33 to about 50 weight percent, based upon the total weight of the HMA.
  • Waxes, antioxidants, and other additives known in the art may be added to the blends of this invention as optional ingredients.
  • additives include but are not Hmited to photostabiUzers, ultraviolet stabiHzers, fiUers, plasticizers, lubricants, coloring agents, and the Hke.
  • additional ingredients are typicaUy present in the adhesive composition at less than or equal to about 35 weight percent, preferably about 1 to about 25 weight percent, even more preferably about 5 to about 15 weight percent, based upon the total weight of the HMA including the additive.
  • the components of the adhesive composition may be blended by ordinary methods known in the art for blending ethylene polymers, tackifiers, and the Hke.
  • an ethylene-vinyl acetate copolymer can be placed in a receptacle, heated, and stirred.
  • Each soUd and Uquid resin can be added to the receptacle so that a uniform dispersion is obtained.
  • the order in which the HMA components are blended is unimportant.
  • the blends may be produced by mixing the components using any suitable mixing device at a temperature above the melting point of the components, e.g. at 130°C to 180°C for a period of time sufficient to form a homogeneous mixture, normaUy 1 to 120 minutes depending on the type of mixing device.
  • Preferred adhesive compositions of the invention have a SAFT of 70°C or higher and show a measurable improvement in T-peel at 25 °C to polymeric substrates such as polyethylene, polypropylene, and MylarTM.
  • Preferred adhesive compositions of the invention also have at least a 50% improvement in T-peel relative to adhesive compositions using only a soHd resin as a tackifier, more preferably greater than a 100% improvement, even more preferably greater than a 200% improvement
  • This T-peel improvement is demonstrated at 25°C, preferably additionaUy as low as 5°C and as high as 45°C, to one or more substrates selected from polypropylene, polyethylene, or MylarTM.
  • Adhesive compositions comprising a tackifier wherein the blended Uquid and soUd resins have the same or similar monomeric constituents also demonstrate improved low temperature performance, such as T-peel at 0°C and higher.
  • preferred tackifiers are blended from one or more Uquid resins and one or more soHd resin wherein aU the resins in a single tackifier are either aromatic-modified aUphatic or DCPD-based.
  • AdditionaUy it is preferred that the T g s of the Uquid and the soUd resins that are blended have individual T g s that differ by 40°C or more.
  • Adhesive compositions based upon EVA as a base polymer show the best performance, especiaUy at a vinyl acetate content of less than 30 weight percent based upon the weight of the EVA.
  • the blends of this invention can then be used as adhesives on substrates such as asphalt, cement, metals (including aluminum), Mylar® (a biaxiaUy-oriented polyethylene terephthalate), polymers (including polyolefins such as rubbers, plastics, thermoplastics), glass, ceramics, wood, paper, rocks, minerals and paint, cardboard, and the Hke.
  • substrates such as asphalt, cement, metals (including aluminum), Mylar® (a biaxiaUy-oriented polyethylene terephthalate), polymers (including polyolefins such as rubbers, plastics, thermoplastics), glass, ceramics, wood, paper, rocks, minerals and paint, cardboard, and the Hke.
  • Preferred examples include polyethylene, polypropylene, and Mylar®.
  • Pressure sensitive adhesives (PSAs), contact adhesives (CAs), and hot melt pressure sensitive adhesives (HMPSAs) may also be improved by use of these novel resin blends.
  • the preferred use is HMA compositions.
  • Such adhesives
  • Proton Nuclear Magnetic Resonance 2 H NMR: data is obtained in a Varian VXR 300 MHz spectrometer equipped with a 10 mm broadband probe. The system is configured so that the decoupler channel can be used to observe the proton signals. Acquisition conditions are as foUows: pulse angle 30°; pulse delay 10 seconds; acquisition 2 seconds; spectral width 10,000 hertz; free induction decays coUected per sample were 200. Samples of whole resins are dissolved in deuterated chloroform at a concentration of 80 mg/ml and run at 50°C. Chemical shifts are given in ppm and are relative to tetramethylsilane which was set to 0 ppm.
  • the different proton types were calculated by integrating the signal area in three spectral regions.
  • the aliphatic region is defined as signals between about 0 and about 3.5 ppm.
  • the olefin region is defined as between about 4.5 and about 6.0 ppm.
  • the aromatic region is defined as about 6.2 to about 7.8 ppm.
  • the percentage of each proton type is calculated by dividing total area into the signal intensity of each region. For aUphatic tackifiers, the unsaturation is expressed in proton percent by ratioing the signal area in the olefinic region to the total proton signal intensity.
  • the aliphatic region is further divided into different proton types. An estimation of the different types present is done by subdividing the aliphatic region into different areas. The region between about 0.2 and about 1.1. ppm is taken to represent the intensity of methyl groups attached to saturated hydrocarbon moieties and the intensity between about 2.0 and about 3.5 ppm represent benzyUc and aUyUc protons. The percent methyl group content or concentration is calculated by ratioing the area of the methyl signal region to aU of the aUphatic intensity and the benzyUc/aUyHc proton concentration was determined by ratioing its area intensity to all of the aUphatic intensity.
  • GPC Gel Permeation Chromatography: Samples are run in tetrahydrofuran (THF) at 30°C on a Waters 410 instrument having a five-column set with nominal porosity ranging from 10 5 to IO 2 angstroms. The flow rate is 2.5 ml/min. and the corresponding plate count is 3500 plates per foot for diis column combination. Filtered solutions of the tackifiers in THF with a concentration of about 0.5 weight to volume ratio at 30°C are used. The molecular weight average for the resins are reported as polystyrene equivalent numbers. It should be noted that the molecular weight values reported from GPC are not absolute because precise caUbration methods are unavailable for tackifiers.
  • T-Peel Strength is defined as the average load per unit width of bond Hne required to produce progressive separation of two bonded adherents. Separation speed is 2 inches (51 mm) per minute. Bonding conditions are described in the examples below.
  • SAFT Shear Adhesion FaUure Temperature
  • One inch square lap shear bonds to kraft paper are prepared. Samples are hung verticaUy in an air circulating oven and a 500 gram weight is suspended from the bottom strip. The oven temperature is raised at the rate of 30°C every 15 minutes.
  • the reported SAFT is the average of three readings. Bonding conditions are described in the examples below.
  • PAFT Peel Adhesion Failure Temperature
  • the reported PAFT is the average of three readings. Bonding conditions are described in the examples below. Stress-Strain Measurements (e.g. tensile strength, strain at break, yield stress, and yield strain) were performed on an Instron model 4505 testing machine.
  • HMA between layers of Teflon-coated aluminum foil for 30 minutes at 150°C to form a molded layer of the HMA 2 mm in thickness.
  • the molded layers were die cut into micro-dumbeU specimens as specified in ASTM D-1708. A crosshead speed of 2 inches (51 mm) per minute was used for each of the examples ' tested. The stress was calculated based on the undeformed cross-sectional area of the tensUe specimens.
  • DMTA Dynamic Mechanical Thermal Analysis
  • Open time is defined to be the maximum time available between the apphcation of the HMA, at 180°C, on a first substrate and the bonding of a second substrate to the first substrate that wiU stiU allow a soUd seal between the two substrates.
  • SoUd seal as defined herein means that when the bond between the two substrates is separated after bonding, the bond is destroyed by failure of the substrate and not failure of the adhesive.
  • a 45 to 55 mg portion of the HMA at 180°C is apphed as a bead of 5 cm over the width of a first substrate.
  • a second substrated is contacted with the first substrate at a pressure of 1.5 bar for a fixed time of 4 seconds. The bond is then separated.
  • the open time is the maximum time interval at which the bond is destroyed by failure of the substrate and not of the adhesive.
  • the substrates used were 50 mm x 62 mm section of Bookbinding Cardboard NR 10, available from L. Coosemans, Dwo ⁇ , Belgium.
  • Set time is defined as the minimum time required to hold together two bonded substrate surfaces mechanicaUy in order to obtain a soHd seal.
  • SoHd seal as defined herein means that when the bond between the two substrates is separated after bonding, the bond is destroyed by faUure of the substrate and not faUure of the adhesive.
  • a 45 to 55 portion of the HMA at 180°C is applied as a 5 cm bead to the width of a first substrate.
  • a second substrate is contacted with the first substrate at a pressure of 1.5 bar for a selected time interval between 0.2 and 30 seconds. The bond is then separated.
  • the set time is the minimum time interval at which the bond is destroyed by faUure of the substrate and not of the adhesive.
  • the substrates used were 50 mm x 62 mm section of Bookbinding Cardboard NR 10, avaUable from L. Coosemans, Dwo ⁇ , Belgium.
  • ECR-327 is a Uquid dicyclopentadiene-based hydrocarbon resin having a M w of approximately 340, a M w /M n of about 3.3, and a T g of about -13°C, and is avaUable from Exxon Chemical Company, Houston, Texas, or Exxon Chemical Europe, Brussels, Belgium.
  • Escorene® UL04533 is an ethylene-vinyl acetate copolymer comprising about 33 weight percent vinyl acetate and having a melt index of about 45 dg/min., and is available from Exxon Chemical Europe, Brussels, Belgium.
  • Escorez® 2393 is a soHd aromatic modified aliphatic hydrocarbon resin having a M w of approximately 1100 and a M ⁇ /M JJ of about 2.4, a Tg of about 47° C, and is avaUable from Exxon Chemical Company, Houston, Texas.
  • Escorez® 2520 is a Uquid aromatic modified aliphatic hydrocarbon resin having a M w of approximately 430 and a M ⁇ /M,, of about 1.5, a Tg of about -16° C, and is avaUable from Exxon Chemical Company, Houston, Texas.
  • Escorez® 5320 is a soUd dicyclopentadiene-based hydrocarbon resin having a M w of approximately 410 and a M ⁇ M n of about 2.6, a Tg of about 66°C, and is available from Exxon Chemical Company, Houston, Texas.
  • Escorez® 5380 is a soUd dicyclopentadiene-based hydrocarbon resin having a M w of approximately 370 and a M w /M n of about 2.3, a Tg of about 36°C, and is available from Exxon Chemical Company, Houston, Texas.
  • Escorez® 6372 is a solid, hydrogenated aromatic modified aUphatic hydrocarbon hydrocarbon resin having a M w of approximately 1250 and a MJM n of about approximately 1.67, a Tg of about 50°C, and is avaUable from Exxon Chemical Europe, Brussels, Belgium.
  • Irganox® 1010 is an oxidation inhibitor and thermal stabilizer avaUable from Ciba-Geigy Co ⁇ ., Ardsley, New York).
  • HMA Blending and Testing A series of HMA blends was made using as a tackifier either a soUd resin alone or a Hquid/soUd resin blend.
  • a series of hot melt adhesives (HMA) based on Escorene® 7750 was formulated using various tackifiers and Aristowax® 165 as a flow modifier. The ratio of components was 45/45/10 respectively by weight in aU cases.
  • HMA formulations were laid out to form a thin film suitable for bonding.
  • the HMA was heated to 150°C in an oven then laid out on release paper using an eight path appUcator to achieve a film that had a nominal thickness of about 0.005" (0.127 mm).
  • the resulting bond was found to be fairly consistent for examples anywhere within the specified range. Molding plates of 1/32" (0.794 mm) aluminum were used to separate the polypropylene film from the platens of the press. After sealing, the bonds were quenched between water cooled platens at a temperature of approximately 25°C using a pressure of approximately 40 p.s.i. (276 kPa). For the p poses of T-peel testing, 0.5" (12.7 mm) strips were cut from the bonded sandwich of polypropylene film and HMA. Test pieces were aUowed to age for a minimum of 24 hours prior to evaluating the strength of the bond.
  • T-peel testing was carried out at room temperature on an Instron 4505 testing frame with an extension rate of 27minute and a sampling rate of 2 points/second.
  • adhesives exhibiting only sHp/stick faUure
  • the T- peel strength was taken as the average of the peaks on the force/displacement plot
  • the T-peel strength was taken as the average of the regions of smooth peel. In cases where both smooth peel and sUp/stick were exhibited by the same sample the average value of the smooth peel is reported.
  • Comparative Example 1 is an adhesive composition comprising only a soHd resin as a tackifier.
  • Examples 2 and 3 are each adhesives comprising, as a tackifier, a blend of a liquid resin and the soUd resin of comparative Example 1.
  • Examples 2 and 3 demonstrate the overall improvement in the balance of adhesive performance when a portion of the soUd resin is replaced with a Uquid resin in accordance with the invention.
  • the T-peel of Examples 2 and 3 are higher than that of comparative Example 1 for aU polymeric substrates (PP, PE, and MylarTM).
  • the rninimum increase in T-peel is 7% as shown in Example 2 using a MylarTM substrate while the maximum increase is 370% as shown in Example 3 using a PE substrate.
  • Examples 2 and 3 demonstrate this increase in T-peel strength at room temperature and at 0°C.
  • Examples 2 and 3 also show improved performance in strain at break and strain at break at low temperature and at room temperature. High temperature performance also improved as demonstrated by the PAFT and SAFT values of Examples 2 and 3 versus comparative Example 1.
  • Tensile strength and yield stress were the only areas where performance was reduced. However, tensUe strength and yield stress are essentiaUy measures of cohesive strength, or the abiUty of a substance resist separation or plastic deformation when subjected to stress.
  • T-peel is a measure of adhesive strength, or the abiUty of two substances to resist separation from each other when subjected to stress.
  • the objective of a HMA is to hold two substrates together. Therefore, the HMA must have both adhesive strength to stay attached to each substrate and cohesive strength to resist separation of the HMA.
  • Comparative Example 4 is an adhesive composition comprising only a sohd resin as a tackifier.
  • Examples 5-7 are each adhesives comprising, as a tackifier, a blend of a liquid resin and the solid resin of comparative Example 4.
  • Examples 5-7 demonstrate the overall improvement in the balance of adhesive performance a portion of the sohd resin is replaced with a Hquid resin in accordance with the invention.
  • the T-peel of Examples 5-7 are higher than that of comparative Example 4 for aU substrates (PP, PE, MylarTM, and aluminum) at 25° C.
  • the minimum increase in T-peel is 111% as shown in Example 6 using an aluminum substrate while the maximum increase is over 2000% as shown in Example 6 using a MylarTM substrate.
  • Examples 5-7 also show equal or improved performance in yield strain and strain at break at low temperature and at room temperature relative to comparative Example 4. SAFT improved for Examples 5-7 over that of comparative Example 4 while PAFT showed a slight drop.
  • T gl is die glass transition temperature of the phase of the HMA rich in the base polymer.
  • T-' is the glass transition temperature of the phase of the HMA rich in tackifier.
  • T j ' is the temperature at which the maximum value of loss tangent occurs, and T gl is the temperature at which the maximum value of tensUe loss module occurs, both as determined by DMTA.
  • T of the HMA comprising the Uquid/soHd resin blend as a tackifier wiU be reduced in the range of from 1°C to 20°C below that of an HMA comprising an equal portion of the same soHd resin as a tackifier, more preferably in the range of from 5°C to 20°C, even more preferably in the range of from 10°C to 20°C.
  • Comparative Example 8 is an adhesive composition comprising only a soUd resin as a tackifier.
  • Example 9 is an adhesive comprismg, as a tackifier, a blend of a Uquid resin and the soHd resin of comparative Example 8.
  • Example 9 demonstrates the overall improvement in the balance of adhesive performance when a portion of the soHd resin is replaced with a Uquid resin in accordance with the invention..
  • Example 9 the T-peel values of Example 9 are higher than that of comparative Example 8 for aU substrates (PP, PE, MylarTM, and alummum) at 25° C and 0°C.
  • the minimum increase in T-peel is 19% using a PP substrate at 0°C while the maximum increase is over 6000% using a MylarTM substrate at 25°C.
  • Example 9 also shows improved performance in yield strain and strain at break at low temperature and at room temperature relative to comparative Example 8. SAFT improved for Example 9 over that of comparative Example 8 whUe PAFT showed a slight drop.
  • Example 9 TensUe strength and yield stress of Example 9 was reduced relative to comparative Example 8. However, as in Examples 2 and 3, since the T-peel tests for Example 9 aU resulted in adhesive failure, the HMAs with blended tackifiers outperformed the comparative even though cohesive performance was reduced somewhat
  • Comparative Example 10 is an adhesive composition comprising only a soHd resin as a tackifier.
  • Example 11 is an adhesive comprising, as a tackifier, a blend of a Hquid resin and the sohd resin of comparative Example 10.
  • Example 11 demonstrated the overall improvement in the balance of adhesive performance when a portion of the soHd resin is replaced with a Hquid resin in accordance with the invention..
  • T-peel values of Example 11 are higher than that of comparative Example 10 for all substrates (PP, PE, MylarTM, and aluminum) at 25° C and 0°C.
  • the mimmum increase in T-peel is 1.4% using a MylarTM substrate at 25°C while the maximum increase was 94% using a PE substrate at 25°C.

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

Abstract

L'invention concerne des compositions de colles thermofusibles autoadhésives présentant des qualités adhésives améliorées. Ces compositions sont produites en mélangeant un polymère de base avec au moins une résine liquide et au moins une résine solide. L'invention traite aussi de procédés pour produire ces compositions.
PCT/US1996/014407 1995-09-07 1996-09-09 Colles thermofusibles autoadhesives, procedes de fabrication et d'utilisation de ces colles WO1997009393A1 (fr)

Applications Claiming Priority (2)

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US52486395A 1995-09-07 1995-09-07
US08/524,863 1995-09-07

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9272795B2 (en) 2012-05-17 2016-03-01 Henkel IP & Holding GmbH Integral hot melt adhesive packaging films and use thereof
US9296930B2 (en) 2011-02-18 2016-03-29 Henkel IP & Holding GmbH Low temperature hot melt adhesives for disposable articles with high creep resistance
US9364985B2 (en) 2012-05-24 2016-06-14 Henkel IP & Holding GmbH Process for preparing flowable amorphous poly-alpha olefin adhesive pellets
US9415532B2 (en) 2012-11-02 2016-08-16 Henkel IP Holding GmbH Molding and overmolding compositions for electronic devices
US9546304B2 (en) 2010-08-26 2017-01-17 Henkel IP & Holding GmbH Low application temperature amorphous poly-a-olefin adhesive
US9695341B2 (en) 2011-08-04 2017-07-04 Henkel IP & Holding GmbH Adhesives and use thereof
US9783703B2 (en) 2010-11-19 2017-10-10 Henkel Ag & Co. Kgaa Adhesive compositions and use thereof
US9914857B2 (en) 2009-08-20 2018-03-13 Henkel IP & Holding GmbH Low application temperature hot melt adhesive
US10266733B2 (en) 2014-08-11 2019-04-23 Henkel IP & Holding GmbH Optically clear hot melt adhesives and uses thereof
US10336920B2 (en) 2013-01-24 2019-07-02 Henkel Ag & Co. Kgaa Foamable hot melt adhesive compositions and use thereof
US10857771B2 (en) 2015-03-02 2020-12-08 Henkel Ag & Co. Kgaa Stretch laminates
US11655400B2 (en) 2014-10-23 2023-05-23 Henkel Ag & Co., Kgaa Hot melt adhesive for polyolefin films
US11970635B2 (en) 2015-04-17 2024-04-30 Henkel Ag & Co. Kgaa Hot melt adhesives and uses thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3577372A (en) * 1968-07-30 1971-05-04 Nat Starch Chem Corp Hot melt adhesive compositions
US4247428A (en) * 1979-08-16 1981-01-27 The Goodyear Tire & Rubber Company Adhesive for polyesters and polyolefins
US4358557A (en) * 1982-03-08 1982-11-09 Eastman Kodak Company Four component hot-melt adhesives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3577372A (en) * 1968-07-30 1971-05-04 Nat Starch Chem Corp Hot melt adhesive compositions
US4247428A (en) * 1979-08-16 1981-01-27 The Goodyear Tire & Rubber Company Adhesive for polyesters and polyolefins
US4358557A (en) * 1982-03-08 1982-11-09 Eastman Kodak Company Four component hot-melt adhesives

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9914857B2 (en) 2009-08-20 2018-03-13 Henkel IP & Holding GmbH Low application temperature hot melt adhesive
US10138398B2 (en) 2009-08-20 2018-11-27 Henkel IP & Holding GmbH Low application temperature hot melt adhesive
US9546304B2 (en) 2010-08-26 2017-01-17 Henkel IP & Holding GmbH Low application temperature amorphous poly-a-olefin adhesive
US10619078B2 (en) 2010-11-19 2020-04-14 Henkel Ag & Co. Kgaa Adhesive compositions and use thereof
US9783703B2 (en) 2010-11-19 2017-10-10 Henkel Ag & Co. Kgaa Adhesive compositions and use thereof
US9296930B2 (en) 2011-02-18 2016-03-29 Henkel IP & Holding GmbH Low temperature hot melt adhesives for disposable articles with high creep resistance
US9695341B2 (en) 2011-08-04 2017-07-04 Henkel IP & Holding GmbH Adhesives and use thereof
US9272795B2 (en) 2012-05-17 2016-03-01 Henkel IP & Holding GmbH Integral hot melt adhesive packaging films and use thereof
US10364079B2 (en) 2012-05-17 2019-07-30 Henkel IP & Holding GmbH Integral hot melt adhesive packaging films and use thereof
US9364985B2 (en) 2012-05-24 2016-06-14 Henkel IP & Holding GmbH Process for preparing flowable amorphous poly-alpha olefin adhesive pellets
US9415532B2 (en) 2012-11-02 2016-08-16 Henkel IP Holding GmbH Molding and overmolding compositions for electronic devices
US10336920B2 (en) 2013-01-24 2019-07-02 Henkel Ag & Co. Kgaa Foamable hot melt adhesive compositions and use thereof
US10266733B2 (en) 2014-08-11 2019-04-23 Henkel IP & Holding GmbH Optically clear hot melt adhesives and uses thereof
US11655400B2 (en) 2014-10-23 2023-05-23 Henkel Ag & Co., Kgaa Hot melt adhesive for polyolefin films
US10857771B2 (en) 2015-03-02 2020-12-08 Henkel Ag & Co. Kgaa Stretch laminates
US11970635B2 (en) 2015-04-17 2024-04-30 Henkel Ag & Co. Kgaa Hot melt adhesives and uses thereof

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