WO2003072654A2 - Agents auto-adhesifs contenant du polyethylene - Google Patents

Agents auto-adhesifs contenant du polyethylene Download PDF

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Publication number
WO2003072654A2
WO2003072654A2 PCT/EP2003/001158 EP0301158W WO03072654A2 WO 2003072654 A2 WO2003072654 A2 WO 2003072654A2 EP 0301158 W EP0301158 W EP 0301158W WO 03072654 A2 WO03072654 A2 WO 03072654A2
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WO
WIPO (PCT)
Prior art keywords
aqueous dispersion
weight
polyethylene
polymer
dispersion according
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PCT/EP2003/001158
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German (de)
English (en)
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WO2003072654A3 (fr
Inventor
Heiko Diehl
Oral Aydin
Gerhard Auchter
Oliver Hartz
Andree Dragon
Original Assignee
Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2003210216A priority Critical patent/AU2003210216A1/en
Publication of WO2003072654A2 publication Critical patent/WO2003072654A2/fr
Publication of WO2003072654A3 publication Critical patent/WO2003072654A3/fr

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Classifications

    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/08—Fastening or securing by means not forming part of the material of the label itself
    • G09F3/10—Fastening or securing by means not forming part of the material of the label itself by an adhesive layer
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • 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
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C

Definitions

  • the invention relates to an aqueous dispersion of a polymer which comprises at least 40% by weight of so-called main monomers selected from Cl to C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms , ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons with 4 to 8 C atoms and two double bonds or mixtures of these monomers, characterized in that the aqueous dispersion continues to contain a Dispersion contains dissolved or dispersed polyethylene which is composed of at least 40% by weight of ethylene.
  • main monomers selected from Cl to C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms , ethylenically unsaturated nitrile
  • the invention further relates to the use of the dispersion as a pressure sensitive adhesive.
  • WO 93/10177 discloses the addition of small amounts of a wax emulsion to improve the cutability of papers coated with pressure-sensitive adhesive and also the ability to be removed.
  • the object of the present invention was to improve the adhesion of the pressure-sensitive adhesives without sacrificing cohesion.
  • Another task was to improve the water resistance of the bonds obtained.
  • these advantageous properties are also to be achieved in the case of bonds on non-polar surfaces.
  • these properties should also be achieved if the PSAs contain wetting agents which adversely affect adhesion and water resistance in general.
  • the polymer dispersed in the aqueous dispersion can be obtained by radical polymerization of ethylenically unsaturated compounds (monomers).
  • the polymer consists of at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, of so-called main monomers.
  • the main monomers are selected from:
  • C ⁇ -C 2 o-alkyl (meth) acrylates vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic Hydrocarbons with 4 to 8 carbon atoms and 2 double bonds or mixtures of these monomers.
  • Examples include (Meth) acrylic acid alkyl ester with a C ⁇ -C ⁇ o-alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are e.g. Vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
  • Suitable vinyl aromatic compounds are vinyl toluene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers examples include vinyl methyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred. Butadiene, isoprene and chloroprene may be mentioned as hydrocarbons with 4 to 8 carbon atoms and two olefinic double bonds.
  • Preferred main monomers are the C 1 -C 4 -alkyl acrylates and methacrylates, in particular C 1 -C 4 -alkyl acrylates and methacrylates and vinyl aromatics, in particular styrene and mixtures thereof.
  • Methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, styrene and mixtures of these monomers are very particularly preferred.
  • the polymer may contain other monomers, e.g. Monomers with carboxylic acid, sulfonic acid or phosphonic acid groups.
  • Carboxylic acid groups are preferred. For example, Acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • monomers are e.g. also monomers containing hydroxyl groups, in particular -CC-hydroxyalkyl (meth) acrylates, (meth) acrylamide.
  • Phenyloxyethyl glycol mono- (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, Arrd.no- (meth-) acrylates such as 2-aminoethyl (meth) acrylate may also be mentioned as further monomers.
  • Crosslinking monomers may also be mentioned as further monomers.
  • the polymers are prepared by emulsion polymerization, so it is an emulsion polymer.
  • the manufacture can e.g. also by solution polymerization and subsequent dispersion in water.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • Suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420.
  • Both anionic, cationic and nonionic emulsifiers Preferably, only accompanying emulsifiers are used as accompanying surface-active substances, the molecular weight of which, in contrast to the protective colloids, is usually below 2000 g / mol lie.
  • the individual components must be compatible with one another, which can be checked with a few preliminary tests if in doubt.
  • Anionic and nonionic emulsifiers are preferably used as surface-active substances.
  • Common accompanying emulsifiers are, for example, ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: Cs to C 36 ), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C to C) 9 ), alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali and ammonium salts of alkyl sulfates (alkyl radical: Cs- to C ⁇ 2 ), of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ⁇ 2 - to C ⁇ 8 ), of ethoxylated alkylphenols (EO grade: 3 to 50, alkyl radical: C to C 9 ), of alkyl sulfonic acids (alkyl radical: C ⁇ 2 - to Ci
  • Suitable emulsifiers are compounds of the general formula II
  • R 5 and R 6 are hydrogen or C - to -CC alkyl and are not simultaneously hydrogen, and X and Y can be alkali metal ions and / or ammonium ions.
  • R 5 , R 6 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms or hydrogen and in particular having 6, 12 and 16 carbon atoms, where R 5 and R 6 are not both hydrogen at the same time.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred.
  • Compounds II in which X and Y are sodium, R 5 is a branched alkyl radical having 12 C atoms and R 6 is hydrogen or R 5 are particularly advantageous.
  • Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (trademark of the Dow Chemical Company).
  • Suitable emulsifiers can also be found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.
  • Trade names of emulsifiers are e.g. Dowfax®2 AI, Emulan® NP 50, Dextrol® OC 50, Emulsifier 825, Emulsifier 825 S, Emulan® OG, Texapon®NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.
  • the surface-active substance is usually used in amounts of 0.1 to 10% by weight, based on the monomers to be polymerized.
  • Water-soluble initiators for emulsion polymerization are e.g. Ammonium and alkali metal salts of peroxidic sulfuric acid, e.g. Sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. tert-butyl hydroperoxide.
  • peroxidic sulfuric acid e.g. Sodium peroxodisulfate
  • hydrogen peroxide or organic peroxides e.g. tert-butyl hydroperoxide.
  • red-ox reduction-oxidation
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is e.g. to the initiators for emulsion polymerization already mentioned above.
  • the reduction components are e.g. alkali metal salts of sulfurous acid, e.g. Sodium sulfite, sodium hydrogen sulfite, alkali metal salts of disulfuric acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones, such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and its salts, or ascorbic acid.
  • the Red-Ox initiator systems can be used with the use of soluble metal compounds, the metallic component of which can occur in several valence levels.
  • Common red-ox initiator systems are e.g. Ascorbic acid / iron (II) sulfate / sodium peroxydisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na hydroxymethanesulfinic acid.
  • the individual components e.g. the reduction component, can also be mixtures e.g. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the compounds mentioned are mostly used in the form of aqueous solutions, the lower concentration being determined by the amount of water which is acceptable in the dispersion and the upper concentration being determined by the solubility of the compound in question in water.
  • the concentration is generally 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1.0 to 10% by weight, based on the solution.
  • the amount of initiators is generally 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the monomers to be polymerized. Several different initiators can also be used in emulsion polymerization.
  • Regulators can be used in the polymerization, e.g. in amounts of 0 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be polymerized, by means of which the molecular weight is reduced. Suitable are e.g. Compounds with a thiol group such as tert. -Butylmercapt n, ethyl thioglycolate, mercaptoethynol, mercaptopropyltrimethoxysilane or tert. -Dodecylmercapant.
  • the emulsion polymerization is usually carried out at 30 to 130, preferably 50 to 90 ° C.
  • the polymerization medium can consist only of water, as well as mixtures of water and thus miscible liquids such as methanol. Preferably only water is used.
  • the emulsion polymerization can be carried out either as a batch process or in the form of a feed process, including a step or gradient procedure.
  • a polymer seed is presented for better adjustment of the particle size.
  • the manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to the person skilled in the art. It can either be completely introduced into the polymerization vessel or used continuously or in stages in the course of the free radical aqueous emulsion polymerization, depending on its consumption. In detail, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. A portion is preferably introduced and the remainder is fed to the polymerization zone in accordance with the consumption. To remove the residual monomers, initiator is usually also added after the end of the actual emulsion polymerization, ie after a conversion of the monomers of at least 95%.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor floor.
  • aqueous dispersions of the polymer are generally obtained with solids contents of from 15 to 75% by weight, preferably from 40 to 75% by weight.
  • dispersions with the highest possible solids content are preferred.
  • solids contents> 60% by weight one should set a bimodal or polymodal particle size, since otherwise the viscosity becomes too high and the dispersion can no longer be handled.
  • a new generation of particles can be generated, for example, by adding seeds (EP 81083), by adding excess amounts of emulsifier or by adding mini-emulsions.
  • Another advantage associated with the low viscosity at high solids content is the improved coating behavior at high solids contents.
  • a new / new generation of particles can be generated at any time. It depends on the particle size distribution desired for a low viscosity.
  • the polymer thus produced is preferably used in the form of its aqueous dispersion.
  • the glass transition temperature of the polymer or of the emulsion polymer is preferably -60 to 0 ° C., particularly preferably -60 to -10 ° C. and very particularly preferably -50 to -20 ° C.
  • the glass transition temperature can be determined by conventional methods such as differential thermal analysis or differentail scanning calorimetry (see e.g. ASTM 3418/82, so-called “midpoint temperature”).
  • the dispersion according to the invention contains a polyethylene in dissolved or preferably dispersed form.
  • Polyethylene is understood to mean a polymer which is composed of at least 40% by weight, in particular at least 60% by weight, of ethylene.
  • the polyethylene can contain other monomers as structural components.
  • Olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 1-decene, or the main monomers or further monomers already mentioned above.
  • the polyethylene is dissolved or dispersed in the aqueous dispersion.
  • the polyethylenes preferably contain polar groups, in particular hydroxyl groups, amino groups, acid groups or salt groups.
  • the polyethylenes preferably contain acid groups, in particular carboxylic acid groups.
  • Polar groups in particular acid groups, can be introduced into the polyethylene by copolymerization with appropriate monomers.
  • Mono- or dicarboxylic acids such as acrylic acid, methacrylic acid or maleic acid are particularly suitable.
  • a content of polar groups, e.g. Carboxylic acid groups in polyethylene can also be obtained by subsequent polymer-analogous reaction, e.g. Oxidation with oxygen can be achieved.
  • the polyethylene preferably has a polar group content (see above), in particular acid groups, particularly preferably carboxylic acid groups, of 0.01 to 1 mol per 100 g of polyethylene; the content is particularly preferably at least 0.2 mol per
  • the polyethylene is preferably a polyethylene wax.
  • the polyethylene preferably has a weight average molecular weight Mw of 1000 to 20,000 g / mol, particularly preferably from 3000 to 18,000 g / mol and very particularly preferably from 5,000 to 15,000 g / mol (determined by gel permeation chromatography).
  • the polyethylenes preferably have a density of 0.8 to 1.0 g / cm 3 , preferably 0.90 to 0.96 g / cm 3 and particularly preferably 0.93 to 0.95 g / cm 3 , measured at 23 ° C.
  • the melt viscosities are preferably in the range from 20 to 20,000 centri Stokes (cSt), preferably in the range from 800 to 2000 cSt, measured at 120 ° C., which corresponds to a molecular weight M w of at most 40,000 g, preferably at most 10,000 g and particularly preferably at most 7500 g.
  • the molecular weight distribution is preferably in the range from 2 to 10.
  • the melting points are preferably in the range from 60 to 125 ° C., preferably 80 to 120 ° C.
  • Polyethylenes are made by polymerizing or copolymerizing ethylene.
  • the production processes can be roughly divided into low-pressure processes, carried out at 20 to 100 bar, and high-pressure processes, carried out at 500 to 4000 bar.
  • the high pressure process is a radical polymerization process that generally does not require a catalyst.
  • one or more organic peroxides are mostly used, for example the Trigonox® or Perkadox® brands from Akzo Nobel, or else air or atmospheric oxygen.
  • the cheapest and therefore the most widespread radical starter is air or atmospheric oxygen.
  • Suitable molecular weight regulators can be used to set the appropriate molecular weight.
  • a frequently used regulator is hydrogen, but when using air or atmospheric oxygen as a radical starter it can lead to the formation of detonating gas and therefore raises concerns for safety reasons.
  • the polyethylenes can first be dissolved or dispersed in water and this solution or dispersion can then be added to the polymer dispersion.
  • the polyethylenes can also be added directly to the polymer dispersion.
  • the weight fraction of the polyethylene is preferably 2 to 20 parts by weight per 100 g parts by weight of the sum of polymer and polyethylene (solid, ie without water, solvent).
  • the proportion by weight of polyethylene is at least 4 parts by weight per 100 parts by weight of polymer + polyethylene.
  • the polyethylene content is preferably less than 15 parts by weight, particularly preferably less than 10 parts by weight, based on 100 parts by weight of polymer + polyethylene.
  • the aqueous dispersion according to the invention is particularly suitable as an adhesive, particularly preferably as a pressure sensitive adhesive.
  • the aqueous polymer dispersion can be used without further additives.
  • the aqueous dispersion can have a tackifier, i.e. a tackifying resin can be added.
  • Tackifiers are e.g. from Adhesive Age, July 1987, pages 19-23 or Polym. Mater. Be. Closely. 61 (1989), pages 588-592.
  • Tackifiers are e.g. Natural resins, such as rosins and their derivatives resulting from disproportionation or isomerization, polymerization, dimerization, hydrogenation. These can be in their salt form (with, for example, mono- or polyvalent counterions (cations) or preferably in their esterified form. Alcohols which are used for the esterification can be mono- or polyvalent. Examples are methanol, ethanediol, diethylene glycol, triethylene glycol , 1,2,3-propanethiol, pentaerythritol.
  • hydrocarbon resins e.g. Coumarone-indene resins, polyterpene resins, hydrocarbon resins based on unsaturated CH compounds, such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene, vinyltoluene.
  • unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene, vinyltoluene.
  • Polyacrylates which have a low molecular weight are also increasingly being used as tackifiers. These polyacrylates preferably have a weight-average molecular weight M w of less than 30,000.
  • the polyacrylates preferably consist of at least 60, in particular at least 80,% by weight of Ci-Cs alkyl (meth) acrylates.
  • Preferred tackifiers are natural or chemically modified rosins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
  • the tackifiers can be added in a simple manner to the polymers according to the invention, preferably to the aqueous dispersions of the polymers.
  • the tackifiers are preferably themselves in the form of an aqueous dispersion.
  • the weight amount of the tackifier is preferably 5 to
  • tackifiers e.g. other additives e.g. Thickeners, preferably associative thickeners, defoamers, plasticizers, pigments, wetting agents or fillers are used when used as a pressure sensitive adhesive.
  • the pressure-sensitive adhesives according to the invention therefore optionally also contain tackifiers and / or the above additives.
  • the pressure sensitive adhesives can in particular wetting aids, e.g. Contain fatty alcohol ethoxylates, alkylphenol ethoxylates, sulfosuccinic acid esters, nonyl phenol ethoxylates, polyoxyethylenes / propylenes or sodium dodecyl sulfonates.
  • the amount is generally 0.05 to 5 parts by weight, in particular 0.1 to 3 parts by weight per 100 parts by weight of polymer (solid).
  • the pressure sensitive adhesives are suitable for the production of self-adhesive articles such as labels, foils or adhesive tapes.
  • the pressure-sensitive adhesive can be applied to substrates, for example paper or polymer films, preferably consisting of polyethylene, polypropylene, which can be biaxially or monoaxially stretched, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyamide or metal by conventional methods, for example by rolling, knife coating, brushing, etc. be applied.
  • supports with non-polar surfaces for example made of polyolefins, in particular polyethylene or polypropylene, are also suitable since the dispersions according to the invention adhere well to them.
  • the water can preferably be removed by drying at 50 to 150 ° C.
  • the carriers can be cut into adhesive tapes, labels or foils before or after applying the adhesive.
  • the side of the substrates coated with pressure sensitive adhesive can be covered with a release paper, for example with a siliconized paper.
  • the self-adhesive articles according to the invention have very good adhesive properties, in particular good adhesion to the substrates and high cohesion (internal strength in the adhesive layer). These good properties are also achieved if the dispersions or pressure-sensitive adhesives contain wetting aids. They also have good adhesion to non-polar surfaces and are therefore particularly suitable for substrates with non-polar surfaces, for example polyolefin surfaces, for example polyethylene (HDPE or LDPE) or polypropylene.
  • the pressure sensitive adhesive also does not tend to rewind, i.e. it remains on the carrier after peeling e.g. of the label.
  • the self-adhesive articles also have a high level of water resistance.
  • Acronal® A 220 aqueous dispersion of a polyacrylate, which is offered as a pressure sensitive adhesive
  • Epotal® DS 2343 aqueous dispersion of a polyethylene with and an acrylic acid content of 20% by weight (commercial product from BASF)
  • Poligen® WE 6 aqueous dispersion of an oxidized polyethylene, dispersed in water using an emulsifier (commercial product from BASF)
  • Lumiten® I-SC wetting agents (sulfosuccinic acid esters)
  • the pressure-sensitive adhesives were coated with an application amount of 20 g / m 2 on polyethylene film and dried at 90 ° C. for 3 minutes.
  • the peel strength (adhesion) and shear strength (cohesion) were then determined.
  • the backing coated with pressure sensitive adhesive was cut into 25 mm wide test strips.
  • To determine the shear strength the test strips with a bonded area of 25 mm 2 were glued to a V2A test sheet, rolled up once with a 1 kg roll, stored for 10 minutes (in standard climate, 50% relative humidity 1 bar, 23 ° C) ) and then suspended with a 1 kg weight (in a normal climate).
  • the measure of the shear strength was the time until the weight dropped; the average of 5 measurements was calculated.
  • a 2.5 cm wide test strip was glued to a test specimen made of polyethylene (HDPE) and rolled up once with a roll weighing 1 kg. It was then clamped with one end in the upper jaws of a tensile strain tester. The adhesive strip was removed from the test surface at 300 mm / min at a 180 ° angle, i.e. the adhesive strip was bent over and pulled off parallel to the test sheet, and the force required was measured. The measure of the peel strength was the force in N / 2.5 cm, which resulted from an average of five measurements.
  • HDPE polyethylene
  • the peel strength was determined 1 minute and 24 hours after the bond. After this time, the adhesive strength has fully developed.
  • the above test strips were glued to commercially available polyethylene shampoo bottles.
  • the bottles were placed in a 5% aqueous shampoo solution for 24 hours. After that, the labels had not peeled off, and no peeling was discernible at the edges either.
  • the labels were peeled off, the adhesive layer remained on the label, there were no adhesive residues on the bottle (no rewinding).
  • A broken adhesion
  • K cohesive break
  • AO rewind
  • f fixed, i.e. without water
  • All pressure-sensitive adhesives contained 1 part by weight of Lumiten ISC, based on 100 parts by weight of polymer (Acronal A 220 without water)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Theoretical Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne des dispersions aqueuses d'un polymère composées d'au moins 40 % en poids de monomères principaux choisis parmi C1- à C20-alkyl(méth)acrylates, vinylesters d'acides carboxyliques contenant jusqu'à 20 atomes de C, vinylaromates contenant jusqu'à 20 atomes de C, nitriles à insaturation éthylénique, vinylhalogénures, vinyléthers d'alcools contenant 1 à 10 atomes de C, hydrocarbures aliphatiques contenant 4 à 8 atomes de C et deux doubles liaisons, ou de mélanges de ces monomères. Ladite dispersion aqueuse est caractérisée en ce qu'elle contient un polyéthylène dissout ou dispersé dans la dispersion, composé d'au moins 40 % en poids d'éthylène.
PCT/EP2003/001158 2002-02-26 2003-02-06 Agents auto-adhesifs contenant du polyethylene WO2003072654A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003210216A AU2003210216A1 (en) 2002-02-26 2003-02-06 Aqueous dispersion containing polyethylene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10208039A DE10208039A1 (de) 2002-02-26 2002-02-26 Haftklebstoffe, enthaltend Polyethylen
DE10208039.9 2002-02-26

Publications (2)

Publication Number Publication Date
WO2003072654A2 true WO2003072654A2 (fr) 2003-09-04
WO2003072654A3 WO2003072654A3 (fr) 2004-03-11

Family

ID=27674950

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/001158 WO2003072654A2 (fr) 2002-02-26 2003-02-06 Agents auto-adhesifs contenant du polyethylene

Country Status (3)

Country Link
AU (1) AU2003210216A1 (fr)
DE (1) DE10208039A1 (fr)
WO (1) WO2003072654A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1862520A1 (fr) * 2006-06-01 2007-12-05 Basf Aktiengesellschaft etiquettes en pellicule
EP2166057A1 (fr) 2008-08-26 2010-03-24 Basf Se Composition de colle pour articles amovibles autocollants à base de polymères adhésifs et de nanoparticules organiques
WO2011062852A1 (fr) * 2009-11-19 2011-05-26 3M Innovative Properties Company Adhésif sensible à la pression comprenant du polyisobutylène fonctionnalisé lié par l'hydrogène à un polymère acrylique
US8530578B2 (en) 2009-11-19 2013-09-10 3M Innovative Properties Company Pressure sensitive adhesive comprising blend of synthetic rubber and functionalized synthetic rubber bonded to an acrylic polymer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755238A (en) * 1970-12-28 1973-08-28 R Wiita High gloss and low block coating composition containing plasticized vinyl resin latex and finely divided polyolefin particles
DE2558916A1 (de) * 1974-12-28 1976-07-01 Copyer Co Ueberzugsmasse
US3969297A (en) * 1975-01-14 1976-07-13 Cosden Technology, Inc. Clear ethylene polymer emulsions having particle size less than 100 angstrom units and polishes containing the same
US4325858A (en) * 1979-06-16 1982-04-20 Kuraray Company, Limited Aqueous dispersion type coating compositions with an improved vibration-damping characteristic
EP0553941A1 (fr) * 1992-01-25 1993-08-04 HANS NESCHEN GmbH & CO. KG Colle thermo-fusible
WO1999054419A1 (fr) * 1998-04-23 1999-10-28 Idemitsu Petrochemical Co., Ltd. Materiau de revetement

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755238A (en) * 1970-12-28 1973-08-28 R Wiita High gloss and low block coating composition containing plasticized vinyl resin latex and finely divided polyolefin particles
DE2558916A1 (de) * 1974-12-28 1976-07-01 Copyer Co Ueberzugsmasse
US3969297A (en) * 1975-01-14 1976-07-13 Cosden Technology, Inc. Clear ethylene polymer emulsions having particle size less than 100 angstrom units and polishes containing the same
US4325858A (en) * 1979-06-16 1982-04-20 Kuraray Company, Limited Aqueous dispersion type coating compositions with an improved vibration-damping characteristic
EP0553941A1 (fr) * 1992-01-25 1993-08-04 HANS NESCHEN GmbH & CO. KG Colle thermo-fusible
WO1999054419A1 (fr) * 1998-04-23 1999-10-28 Idemitsu Petrochemical Co., Ltd. Materiau de revetement

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1862520A1 (fr) * 2006-06-01 2007-12-05 Basf Aktiengesellschaft etiquettes en pellicule
EP2166057A1 (fr) 2008-08-26 2010-03-24 Basf Se Composition de colle pour articles amovibles autocollants à base de polymères adhésifs et de nanoparticules organiques
WO2011062852A1 (fr) * 2009-11-19 2011-05-26 3M Innovative Properties Company Adhésif sensible à la pression comprenant du polyisobutylène fonctionnalisé lié par l'hydrogène à un polymère acrylique
US8530578B2 (en) 2009-11-19 2013-09-10 3M Innovative Properties Company Pressure sensitive adhesive comprising blend of synthetic rubber and functionalized synthetic rubber bonded to an acrylic polymer
US8992720B2 (en) 2009-11-19 2015-03-31 3M Innovative Properties Company Pressure sensitive adhesive comprising functionalized polyisobutylene hydrogen bonded to acylic polymer

Also Published As

Publication number Publication date
AU2003210216A1 (en) 2003-09-09
WO2003072654A3 (fr) 2004-03-11
DE10208039A1 (de) 2003-09-04
AU2003210216A8 (en) 2003-09-09

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