WO2003072654A2 - Aqueous dispersion containing polyethylene - Google Patents

Aqueous dispersion containing 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
Prior art date
Application number
PCT/EP2003/001158
Other languages
German (de)
French (fr)
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WO2003072654A3 (en
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/en
Publication of WO2003072654A3 publication Critical patent/WO2003072654A3/en

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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)

Abstract

The invention relates to an aqueous dispersion of a polymer which contains at least 40 wt. % of so-called main monomers selected from C1 - C20 alkyl (meth) acrylates, vinylesters having up to 20 C-atoms containing carboxilic acids, vinyl aromatics having up to 20 C-atoms, ethylenically unsaturated nitriles, vinylhalogenides, vinylethers having from 1 - 10 C atoms containing alcohols, aliphatic hydrocarbons having 4 - 8 C atoms and two double-bonds or mixtures of said monomers. The invention is characterised in that the aqueous dispersion also contains a polyethylene dispersed or dissolved in the dispersion, containing at least 40 wt. % ethylene.

Description

Haftklebstoffe, enthaltend PolyethylenPressure sensitive adhesives containing polyethylene
Beschreibungdescription
Die Erfindung betrifft eine wässrige Dispersion eines Polymeren, welches zu mindestens 40 Gew. % aus sogenannten Hauptmonomeren, ausgewählt aus Cl bis C20 Alkyl (meth) acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinyl- halogeniden, Vinylethern von 1 bis 10 C Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 4 bis 8 C Atomen und zwei Doppelbindungen oder Mischungen dieser Monomeren aufgebaut ist, dadurch gekennzeichnet, dass die wässrige Dispersion weiter- hin ein in der Dispersion gelöstes oder dispergiertes Polyethylen, welches zu mindestens 40 Gew. % aus Ethylen aufgebaut ist, enthält.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.
Des weiteren betrifft die Erfindung die Verwendung der Dispersion als Haftklebstoff.The invention further relates to the use of the dispersion as a pressure sensitive adhesive.
Bei Haftklebstoffen ist sowohl eine hohe Klebrigkeit (Tack, Adhäsion) als auch eine hohe Kohäsion, d.h. ein hoher innerer Zusammenhalt in der Klebstoffschient, gewünscht.With pressure sensitive adhesives, there is both a high level of tack (tack, adhesion) and a high level of cohesion, i.e. a high level of internal cohesion in the adhesive splint, desired.
Es ist bekannt, zur Verbesserung der Adhäsion polymere Bindemittel zu verwenden, welche einen Gehalt an Monomeren mit langen Seitenketten haben. Auch werden sogenannte Tackifier zur Verbesserung der Adhäsion zugemischt.It is known to use polymeric binders which contain monomers with long side chains to improve the adhesion. So-called tackifiers are also mixed in to improve the adhesion.
Derartige Maßnahmen verschlechtern jedoch im allgemeinen die Kohäsion.However, such measures generally worsen cohesion.
Aus WO 93/10177 ist der Zusatz von geringen Mengen einer Wachs- Emulsion zur Verbesserung der Schneidbarkeit von mit Haftklebstoff beschichteten Papieren und auch der Wiederabziehbarkeit bekannt .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.
Aufgabe der vorliegenden Erfindung waren demgegenüber die Verbes- serung der Adhäsion der Haftklebstoffe ohne Einbuße bei der Kohäsion. Weiterhin war Aufgabe die Verbesserung der Wasserfestigkeit der erhaltenen Verklebungen. Insbesondere sollen diese vorteilhaften Eigenschaften auch bei Verklebungen auf unpolaren Oberflächen erreicht werden. Insbesondere sollen diese Eigenschaften auch erreicht werden, wenn die Haftklebstoffe Netzmittel enthal- ten, welche die Adhäsion und Wasserfestigkeit im allgemeinen stark beeinträchtigen.In contrast, 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. In particular, these advantageous properties are also to be achieved in the case of bonds on non-polar surfaces. In particular, these properties should also be achieved if the PSAs contain wetting agents which adversely affect adhesion and water resistance in general.
Demgemäß wurde die eingangs definierte Dispersion und ihre Verwendung als Haftklebstoff gefunden.Accordingly, the dispersion defined at the outset and its use as a pressure-sensitive adhesive have been found.
Das in der wäßrigen Dispersion dispergierte Polymer ist durch radikalische Polymerisation von ethylenisch ungesättigten Verbindungen (Monomere) erhältlich.The polymer dispersed in the aqueous dispersion can be obtained by radical polymerization of ethylenically unsaturated compounds (monomers).
Das Polymer besteht zu mindestens 40 Gew.-%, bevorzugt zu mindestens 60 Gew.-%, besonders bevorzugt zu mindestens 80 Gew.-% aus sogenannten Hauptmonomeren.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.
Die Hauptmonomeren sind ausgewählt ausThe main monomers are selected from
Cχ-C2o-Alkyl (meth) acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, Vinylethern von 1 bis 10 C-Atome enthaltenden Alkoholen, aliphatischen Koh- lenwasserstoffen mit 4 bis 8 C-Atomen und 2 Doppelbindungen oder Mischungen dieser Monomeren.Cχ-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.
Zu nennen sind z.B. (Meth) acrylsäurealkylester mit einem Cι-Cιo-Alkylrest, wie Methylmethacrylat, Methylacrylat, n-Butyla- crylat, Ethylacrylat und 2-Ethylhexylacrylat .Examples include (Meth) acrylic acid alkyl ester with a Cι-Cιo-alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
Insbesondere sind auch Mischungen der (Meth) acrylsäurealkylester geeignet .Mixtures of the (meth) acrylic acid alkyl esters are also particularly suitable.
Vinylester von Carbonsäuren mit 1 bis 20 C-Atomen sind z.B. Vinyllaurat, -stearat, Vinylpropionat, Versaticsäurevinylester und Vinylacetat.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.
Als vinylaromatische Verbindungen kommen Vinyltoluol, a- und p- Methylstyrol, a-Butylstyrol, 4-n-Butylstyrol, 4-n-Decylstyrol und vorzugsweise Styrol in Betracht. Beispiele für Nitrile sind Acrylnitril und Methacrylnitril .Suitable vinyl aromatic compounds are vinyl toluene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.
Die Vinylhalogenide sind mit Chlor, Fluor oder Brom substituierte ethylenisch ungesättigte Verbindungen, bevorzugt Vinylchlorid und Vinylidenchlorid.The vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
Als Vinylether zu nennen sind z.B. Vinylmethylether oder Vinyl- isobutylether. Bevorzugt wird Vinylether von 1 bis 4 C-Atome ent- haltenden Alkoholen. Als Kohlenwasserstoffe mit 4 bis 8 C-Atomen und zwei olefinischen Doppelbindungen seien Butadien, Isopren und Chloropren genannt.Examples of vinyl ethers are 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.
Als Hauptmonomere bevorzugt sind die C-χ- bis Cio-Alkylacrylate und -methacrylate, insbesondere Cι~ bis Cs-Alkylacrylate und -meth- acrylate und Vinylaromaten, insbesondere Styrol und deren Mischungen.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.
Ganz besonders bevorzugt sind Methylacrylat, Methylmethacrylat, Ethylacrylat , n-Butylacrylat, n-Hexylacrylat, Octylacrylat und 2-Etyhlhexylacrylat, Styrol sowie Mischungen dieser Monomere.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.
Neben den Hauptmonomeren kann das Polymer weitere Monomere enthalten, z.B. Monomere mit Carbonsäure, Sulfonsäure oder Phosphon- säuregruppen. Bevorzugt sind Carbonsäuregruppen. Genannt seien z.B. Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure oder Fumarsäure .In addition to the main monomers, 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.
Weitere Monomere sind z.B. auch Hydroxylgruppen enthaltende Monomere, insbesondere Cι-Cιo-Hydroxyalkyl (meth) acrylate, (Meth) acrylamid.Other monomers are e.g. also monomers containing hydroxyl groups, in particular -CC-hydroxyalkyl (meth) acrylates, (meth) acrylamide.
Als weitere Monomere seien darüberhinaus Phenyloxyethylglykol- mono- (meth-) acrylat, Glycidylacrylat, Glycidylmethacrylat, Arrd.no- (meth-) acrylate wie 2-Aminoethyl- (meth-) acrylat genannt.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.
Als weitere Monomere seien auch vernetzende Monomere genannt.Crosslinking monomers may also be mentioned as further monomers.
Die Herstellung der Polymere erfolgt in einer bevorzugten Aus- führungsform durch Emulsionspolymerisation, es handelt sich daher um ein Emulsionspolymerisat.In a preferred embodiment, the polymers are prepared by emulsion polymerization, so it is an emulsion polymer.
Die Herstellung kann jedoch z.B. auch durch Lösungspolymerisation und anschließende Dispergierung in Wasser erfolgen.However, the manufacture can e.g. also by solution polymerization and subsequent dispersion in water.
Bei der Emulsionspolymerisation werden ionische und/oder nichtionische Emulgatoren und/oder Schutzkolloide bzw. Stabilisatoren als grenzflächenaktive Verbindungen verwendet.In emulsion polymerization, ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
Eine ausführliche Beschreibung geeigneter Schutzkolloide findet sich in Houben-Weyl, Methoden der organischen Chemie, Band XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, S. 411 bis 420. Als Emulgatoren kommen sowohl anionische, kationische als auch nichtionische Emulgatoren in Betracht. Vorzugs- weise werden als begleitende grenzflächenaktive Substanzen ausschließlich Emulgatoren eingesetzt, deren Molekulargewicht im Unterschied zu den Schutzkolloiden üblicherweise unter 2000 g/mol liegen. Selbstverständlich müssen im Falle der Verwendung von Gemischen grenzflächenaktiver Substanzen die Einzelkomponenten miteinander verträglich sein, was im Zweifelsfall an Hand weniger Vorversuche überprüft werden kann. Vorzugsweise werden anionische und nichtionische Emulgatoren als grenzflächenaktive Substanzen verwendet. Gebräuchliche begleitende Emulgatoren sind z.B. ethoxylierte Fettalkohole (EO-Grad: 3 bis 50, Alkylrest: Cs- bis C36) , ethoxylierte Mono-, Di- und Tri-Alkylphenole (EO-Grad: 3 bis 50, Alkylrest: C- bis C9) , Alkalimetallsalze von Dialkylestern der Sulfobernsteinsäure sowie Alkali- und Ammoniumsalze von Alkylsulfaten (Alkylrest: Cs- bis Cχ2) , von ethoxylierten Alkanolen (EO-Grad: 4 bis 30, Alkylrest: Cχ2- bis Cι8) , von ethoxylierten Alkylphenolen (EO-Grad: 3 bis 50, Alkylrest: C- bis C9) , von Alkylsulfonsäuren (Alkylrest: Cι2- bis Cis) und von Alkylarylsulfonsäuren (Alkylrest: C9- bis Cis) •A detailed description of 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. Of course, if mixtures of surface-active substances are used, 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 Cχ 2 ), of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: Cχ 2 - to Cι 8 ), of ethoxylated alkylphenols (EO grade: 3 to 50, alkyl radical: C to C 9 ), of alkyl sulfonic acids (alkyl radical: Cι 2 - to Cis) and of alkylarylsulfonic acids (alkyl radical: C 9 to Cis) •
Weitere geeignete Emulgatoren sind Verbindungen der allgemeinen Formel IIOther suitable emulsifiers are compounds of the general formula II
Figure imgf000005_0001
worin R5 und R6 Wasserstoff oder C - bis Cι -Alkyl bedeuten und nicht gleichzeitig Wasserstoff sind, und X und Y Alkalimetallionen und/oder Ammoniumionen sein können. Vorzugsweise bedeuten R5, R6 lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen oder Wasserstoff und insbesondere mit 6, 12 und 16 C-Atomen, wobei R5 und R6 nicht beide gleichzeitig Wasserstoff sind. X und Y sind bevorzugt Natrium, Kalium oder Ammoniumionen, wobei Natrium besonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen II in denen X und Y Natrium, R5 ein verzweigter Alkylrest mit 12 C-Atomen und R6 Wasserstoff oder R5 ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, beispielsweise Dowfax® 2A1 (Warenzeichen der Dow Chemical Company) .
Figure imgf000005_0001
wherein 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).
Geeignete Emulgatoren finden sich auch in Houben-Weyl, Methoden der organischen Chemie, Band 14/1, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, Seiten 192 bis 208. Handelsnamen von Emulgatoren sind z.B. Dowfax®2 AI, Emulan® NP 50, Dextrol® OC 50, Emulgator 825, Emulgator 825 S, Emulan® OG, Texapon®NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Dis- ponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.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.
Die grenzflächenaktive Substanz wird üblicherweise in Mengen von 0,1 bis 10 Gew.-%, bezogen auf die zu polymerisierenden Monomeren verwendet .The surface-active substance is usually used in amounts of 0.1 to 10% by weight, based on the monomers to be polymerized.
Wasserlösliche Initiatoren für die Emulsionspolymerisation sind z.B. Ammonium- und Alkalimetallsalze der Peroxidischwefelsäure, z.B. Natriumperoxodisulfat, Wasserstoffperoxid oder organische Peroxide, z.B. tert-Butylhydroperoxid.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.
Geeignet sind auch sogenannte Reduktions-Oxidations (Red-Ox) -Initiator Systeme.So-called reduction-oxidation (red-ox) initiator systems are also suitable.
Die Red-Ox-Initiator-Systeme bestehen aus mindestens einem meist anorganischen Reduktionsmittel und einem anorganischen oder orga- nischen Oxidationsmittel .The redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
Bei der Oxidationskomponente handelt es sich z.B. um die bereits vorstehend genannten Initiatoren für die Emulsionspolymerisation.The oxidation component is e.g. to the initiators for emulsion polymerization already mentioned above.
Bei der Reduktionskomponenten handelt es sich z.B. um Alkalimetallsalze der schwefligen Säure, wie z.B. Natriumsulfit, Natriumhydrogensulfit, Alkalisalze der Dischwefligen Säure wie Natriumdisulfit, Bisulfitadditionsverbindungen aliphatischer Aldehyde und Ketone, wie Acetonbisulfit oder Reduktionsmittel wie Hydroxymethansulfinsäure und deren Salze, oder Ascorbinsäure . Die Red-Ox-Initiator-Systeme können unter Mitverwendung löslicher Metallverbindungen, deren metallische Komponente in mehreren Wertigkeitsstufen auftreten kann, verwendet werden.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.
Übliche Red-Ox-Initiator-Systeme sind z.B. Ascorbinsäure/Ei- sen(II) sulfat/Natriumperoxidisulfat, tert-Butylhydroperoxid/Na- triumdisulfit, tert-Butylhydroperoxid/Na-Hydroxymethansulfin- säure. Die einzelnen Komponenten, z.B. die Reduktionskomponente, können auch Mischungen sein z.B. eine Mischung aus dem Natrium- salz der Hydroxymethansulfinsäure und Natriumdisulfit .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.
Die genannten Verbindungen werden meist in Form wäßriger Lösungen eingesetzt, wobei die untere Konzentration durch die in der Dispersion vertretbare Wassermenge und die obere Konzentration durch die Löslichkeit der betreffenden Verbindung in Wasser bestimmt ist. Im allgemeinen beträgt die Konzentration 0,1 bis 30 Gew.-%, bevorzugt 0,5 bis 20 Gew.-%, besonders bevorzugt 1,0 bis 10 Gew.-%, bezogen auf die Lösung.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.
Die Menge der Initiatoren beträgt im allgemeinen 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, bezogen auf die zu polyme- risierenden Monomeren. Es können auch mehrere, verschiedene Initiatoren bei der Emulsionspolymerisation Verwendung finden.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.
Bei der Polymerisation können Regler eingesetzt werden, z.B. in Mengen von 0 bis 0,8 Gew. -Teile, bezogen auf 100 Gew. -Teile der zu polymerisierenden Monomeren, durch die die Molmasse verringert wird. Geeignet sind z.B. Verbindungen mit einer Thiolgruppe wie tert . -Butylmercapt n, Thioglycolsäureethylacrylester, Mercaptoe- thynol, Mercaptopropyltrimethoxysilan oder tert. -Dodecylmercap- tan.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.
Die Emulsionspolymerisation erfolgt in der Regel bei 30 bis 130, vorzugsweise 50 bis 90°C. Das Polymerisationsmedium kann sowohl nur aus Wasser, als auch aus Mischungen aus Wasser und damit mischbaren Flüssigkeiten wie Methanol bestehen. Vorzugsweise wird nur Wasser verwendet. Die Emulsionspolymerisation kann sowohl als Batchprozeß als auch in Form eines ZulaufVerfahrens, einschließlich Stufen- oder Gradientenfahrweise, durchgeführt werden. Bevorzugt ist das Zulaufverfahren, bei dem man einen Teil des Po- lymerisationsansatzes vorlegt, auf die Polymerisationstemperatur erhitzt, anpolymerisiert und anschließend den Rest des Polymerisationsansatzes, üblicherweise über mehrere räumlich getrennte Zuläufe, von denen einer oder mehrere die Monomeren in reiner oder in emulgierter Form enthalten, kontinuierlich, stufenweise oder unter Überlagerung eines Konzentrationsgefälles unter Aufrechterhaitung der Polymerisation der Polymerisationszone zuführt. Bei der Polymerisation kann auch z.B. zur besseren Einstellung der Teilchengröße eine Polymersaat vorgelegt werden.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. Preference is given to the feed process, in which part of the polymerization batch is initially charged, heated to the polymerization temperature, polymerized and then the rest of the polymerization batch, usually via a plurality of spatially separate feeds, one or more of which contain the monomers in pure or in emulsified form , continuously, stepwise or with a concentration gradient superimposed while maintaining the polymerization of the polymerization zone. In the polymerization, e.g. a polymer seed is presented for better adjustment of the particle size.
Die Art und Weise, in der der Initiator im Verlauf der radikalischen wäßrigen Emulsionspolymerisation dem Polymerisationsgefäß zugegeben wird, ist dem Durchschnittsfachmann bekannt. Es kann sowohl vollständig in das Polymerisationsgefäß vorgelegt, als auch nach Maßgabe seines Verbrauchs im Verlauf der radikalischen wäßrigen Emulsionspolymerisation kontinuierlich oder stufenweise eingesetzt werden. Im einzelnen hängt dies von der chemischen Natur des Initiatorsystems als auch von der Polymersiationstempera- tur ab. Vorzugsweise wird ein Teil vorgelegt und der Rest nach Maßgabe des Verbrauchs der Polymerisationszone zugeführt. Zur Entfernung der Restmonomeren wird üblicherweise auch nach dem Ende der eigentlichen Emulsionspolymerisation, d.h. nach einem Umsatz der Monomeren von mindestens 95 %, Initiator zugesetzt.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%.
Die einzelnen Komponenten können dem Reaktor beim Zulaufverfahren von oben, in der Seite oder von unten durch den Reaktorboden zugegeben werden.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.
Bei der Emulsionspolymerisation werden wäßrige Dispersionen des Polymeren in der Regel mit Feststoffgehalten von 15 bis 75 Gew.-%, bevorzugt von 40 bis 75 Gew.-% erhalten.In emulsion polymerization, 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.
Für eine hohe Raum/Zeitausbeute des Reaktors sind Dispersionen mit einem möglichst hohen Feststoffgehalt bevorzugt. Um Fest- stoffgehalte > 60 Gew.-% erreichen zu können, sollte man eine bi- oder polymodale Teilchengröße einstellen, da sonst die Viskosität zu hoch wird, und die Dispersion nicht mehr handhabbar ist. Die Erzeugung einer neuen Teilchengeneration kann beispielsweise durch Zusatz von Saat (EP 81083) , durch Zugabe überschüssiger Emulgatormengen oder durch Zugabe von Miniemulsionen erfolgen. Ein weiterer Vorteil, der mit der niedrigen Viskosität bei hohem Feststoffgehalt einhergeht, ist das verbesserte Beschichtungsver- halten bei hohen Feststoffgehalten. Die Erzeugung einer neuen/ neuer Teilchengeneration/en kann zu einem beliebigen Zeitpunkt erfolgen. Er richtet sich nach den für eine niedrige Viskosität angestrebten Teilchengrößenverteilung.For a high space / time yield of the reactor, dispersions with the highest possible solids content are preferred. In order to be able to reach 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.
Das so hergestellte Polymer wird vorzugsweise in Form seiner wäßrigen Dispersion verwendet.The polymer thus produced is preferably used in the form of its aqueous dispersion.
Die Glasübergangstemperatur des Polymeren, bzw. des Emulsionspo- lymerisats beträgt vorzugsweise -60 bis 0°C, besonders bevorzugt -60 bis -10°C und ganz besonders bevorzugt -50 bis -20°C.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.
Die Glasübergangstemperatur läßt sich nach üblichen Methoden wie Differentialthermoanalyse oder Differentail Scanning Calorimetrie (s. z.B. ASTM 3418/82, sog. "midpoint temperature") bestimmen.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").
Die erfindungsgemäße Dispersion enthält neben dem obigen Polye- ren ein Polyethylen in gelöster oder vorzugsweise dispergierter Form.In addition to the above polymer, the dispersion according to the invention contains a polyethylene in dissolved or preferably dispersed form.
Unter Polyethylen wird ein Polymer verstanden, welches zu mindestens 40 Gew.-%, insbesondere zu mindestens 60 Gew.-% aus Ethylen aufgebaut ist. Das Polyethylen kann neben Ethylen weitere Monomere als Aufbaukomponenten enthalten.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. In addition to ethylene, the polyethylene can contain other monomers as structural components.
Genannt seien z.B. Olefine wie Propylen, 1-Buten, 1-Penten, 1-He- xen, 1-Octen oder 1-Decen, oder die bereits oben genannten Hauptmonomeren oder weiteren Monomeren.For example, 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.
Das Polyethylen ist in der wäßrigen Dispersion gelöst oder dis- pergiert .The polyethylene is dissolved or dispersed in the aqueous dispersion.
Dazu haben die Polyethylene vorzugsweise einen Gehalt an polaren Gruppen, insbesondere Hydroxylgruppen, Aminogruppen, Säuregruppen oder Salzgruppen.For this purpose, the polyethylenes preferably contain polar groups, in particular hydroxyl groups, amino groups, acid groups or salt groups.
Vorzugsweise enthalten die Polyethylene Säuregruppen, insbesondere Carbonsäuregruppen.The polyethylenes preferably contain acid groups, in particular carboxylic acid groups.
Polare Gruppen, insbesondere Säuregruppen, können durch Copoly- merisation mit entsprechenden Monomeren in das Polyethylen einge- führt werden.Polar groups, in particular acid groups, can be introduced into the polyethylene by copolymerization with appropriate monomers.
In Betracht kommen insbesondere Mono- oder Dicarbonsäuren wie Acrylsäure, Methacrylsäure oder Maleinsäure.Mono- or dicarboxylic acids such as acrylic acid, methacrylic acid or maleic acid are particularly suitable.
Ein Gehalt an polaren Gruppen, z.B. Carbonsäuregruppen, im Polyethylen kann aber auch durch nachträgliche polymer-analoge Umsetzung, z.B. Oxidation mit Sauerstoff, erreicht werden.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.
Vorzugsweise hat das Polyethylen einen Gehalt an polaren Gruppen (siehe oben) , insbesondere von Säuregruppen besonders bevorzugt von Carbonsäuregruppen von 0,01 bis 1 Mol pro 100 g Polyethylen; der Gehalt beträgt besonders bevorzugt mindestens 0,2 Mol proThe 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
100 g Polyethylen. Der Gehalt übersteigt im allgemeinen nicht100 g polyethylene. The content generally does not exceed
0,8 Mol, bzw. 0,6 Mol pro 100 g.0.8 moles, or 0.6 moles per 100 g.
Beim Polyethylen handelt es sich bevorzugt um ein Polyethylen- wachs .The polyethylene is preferably a polyethylene wax.
Das Polyethylen hat vorzugsweise ein gewichtsmittleres Molekular- gewicht Mw von 1000 bis 20.000 g/Mol, besonders bevorzugt von 3000 bis 18.000 g/Mol und ganz besonders bevorzugt von 5.000 bis 15.000 g/Mol (bestimmt durch Gelppermeationschromatographie) .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).
Bevorzugt haben die Polyethylene eine Dichte von 0,8 bis 1,0 g/cm3, bevorzugt von 0,90 bis 0,96 g/cm3 und besonders bevorzugt von 0,93 bis 0,95 g/cm3, gemessen bei 23°C. Die Schmelzviskositäten liegen bevorzugt im Bereich von 20 bis 20000 centri Stokes (cSt) , bevorzugt im Bereich von 800 bis 2000 cSt, gemessen bei 120°C, das entspricht einem Molekulargewicht Mw von maximal 40000 g, bevorzugt maximal 10000 g und besonders bevorzugt maximal 7500 g. Die Molekulargewichtsverteilung liegt bevorzugt im Bereich von 2 bis 10. Die Schmelzpunkte liegen bevorzugt im Bereich von 60 bis 125°C, bevorzugt 80 bis 120°C.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.
Polyethylene werden durch Polymerisation oder Copolymerisation von Ethylen hergestellt.Polyethylenes are made by polymerizing or copolymerizing ethylene.
Die Verfahren zur Herstellung lassen sich grob in Niederdruckverfahren, durchgeführt bei 20 bis 100 bar, und Hochdruckverfahren, durchgeführt bei 500 bis 4000 bar, einteilen. Das Hochdruckverfahren ist ein radikalisches Polymerisationsverfahren, das im Allgemeinen ohne Katalysator auskommt. Zum Starten der radikalischen Kettenreaktion verwendet man meistens ein oder mehrere organische Peroxide, beispielsweise die Trigonox® oder Perka- dox®-Marken der Akzo Nobel, oder aber Luft bzw. Luftsauerstoff. Der billigste und deshalb am weitesten verbreitete RadikalStarter ist Luft bzw. Luftsauerstoff.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. To start the radical chain reaction, 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.
Zur Einstellung des geeigneten Molekulargewichts kann man geeignete Molekulargewichtsregler verwenden.Suitable molecular weight regulators can be used to set the appropriate molecular weight.
Ein häufig verwendeter Regler ist Wasserstoff, der aber bei der Verwendung von Luft oder Luftsauerstoff als RadikalStarter zur Bildung von Knallgas führen kann und deshalb aus sicherheitstechnischen Gründen Bedenken hervorruft.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.
Weitere häufig verwendete Regler sind Kohlenmonoxid CO und Alkane wie beispielsweise Ethan oder Propan. Kohlenmonoxid ist stark giftig, so dass bei der Verwendung aufwendige Sicherheitsmaßnahmen erforderlich sind. Gasförmige Regler wie Ethan und Propan erfordern ebenfalls strenge Sicherheitsregeln.Other commonly used regulators are carbon monoxide CO and alkanes such as ethane or propane. Carbon monoxide is highly toxic, so that extensive safety measures are required when using it. Gaseous regulators such as ethane and propane also require strict safety rules.
Die Polyethylene können zunächst in Wasser gelöst oder disper- giert werden und diese Lösung bzw. Dispersion kann dann der Polymerdispersion zugesetzt werden.The polyethylenes can first be dissolved or dispersed in water and this solution or dispersion can then be added to the polymer dispersion.
Die Polyethylene können auch direkt in die Polymerdispersion gegeben werden.The polyethylenes can also be added directly to the polymer dispersion.
Soweit der Gehalt an polaren Gruppen nicht ausreichend ist, das Polyethylen zu dispergieren, können dazu auch Emulgatoren und Schutzkolloide verwendet werden. In Betracht kommen z.B. die oben erwähnten Emulgatoren und Schutzkolloide. Der Gewichtsanteil des Polyethylen beträgt vorzugsweise 2 bis 20 Gew. -Teile auf 100 g Gew. -Teile der Summe aus Polymer und Polyethylen (fest, d.h. ohne Wasser, Lösemittel) .If the polar group content is not sufficient to disperse the polyethylene, emulsifiers and protective colloids can also be used. For example, the emulsifiers and protective colloids mentioned above come into consideration. 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).
Insbesondere beträgt der Gewichtsanteil des Polyethylen mindestens 4 Gew. -Teile auf 100 Gew. -Teile Polymer + Polyethylen.In particular, the proportion by weight of polyethylene is at least 4 parts by weight per 100 parts by weight of polymer + polyethylene.
Vorzugsweise ist der Gehalt des Polyethylens kleiner 15 Gew.- Teile, besonders bevorzugt kleiner 10 Gew. -Teile, bezogen auf 100 Gew. -Teile Polymer + Polyethylen.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.
Insbesondere eignet sich die erfindungsgemäße wäßrige Dispersion als Klebstoff, besonders bevorzugt als Haftklebstoff.The aqueous dispersion according to the invention is particularly suitable as an adhesive, particularly preferably as a pressure sensitive adhesive.
Die wäßrige Polymerdispersion kann dazu ohne weitere Zusatzstoffe Verwendung finden.The aqueous polymer dispersion can be used without further additives.
Bei der Verwendung als Haftklebstoff kann der wäßrigen Dispersion ein Tackifier, d.h. ein klebrigmachendes Harz zugesetzt werden. Tackifier sind z.B. aus Adhesive Age, Juli 1987, Seite 19-23 oder Polym. Mater. Sei. Eng. 61 (1989), Seite 588-592 bekannt.When used as a pressure sensitive adhesive, 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.
Tackifier sind z.B. Naturharze, wie Kolophoniumharze und deren durch Disproportionierung oder Isomerisierung, Polymerisation, Dimerisation, Hydrierung entstehenden Derivate. Diese können in ihrer Salzform (mit z.B. ein- oder mehrwertigen Gegenionen (Kationen) oder bevorzugt in ihrer veresterten Form vorliegen. Alkohole, die zur Veresterung verwendet werden, können ein- oder mehrwertig sein. Beispiele sind Methanol, Ethandiol, Diethylen- glykol, Triethylenglykol, 1,2, 3-Propanthiol, Pentaerythrit .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.
Des weiteren finden auch Kohlenwasserstoffharze, z.B. Cumaron- Inden-Harze, Polyterpen-Harze, Kohlenwasserstoffharze auf Basis ungesättigter CH-Verbindungen, wie Butadien, Penten, Methylbuten, Isopren, Piperylen, Divinylmethan, Pentadien, Cyclopenten, Cyclo- pentadien, Cyclohexadien, Styrol, α-Methylstyrol, Vinyltoluol Verwendung.Furthermore, 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, α-methylstyrene, vinyltoluene.
Als Tackifier werden zunehmend auch Polyacrylate, welche ein geringes Molgewicht aufweisen, verwendet. Vorzugsweise haben diese Polyacrylate ein gewichtsmittleres Molekulargewicht Mw unter 30 000. Die Polyacrylate bestehen bevorzugt zu mindestens 60, insbesondere mindestens 80 Gew.-% aus Ci-Cs Alkyl (meth) acrylaten. Bevorzugte Tackifier sind natürliche oder chemisch modifizierte Kolophoniumharze. Kolophoniumharze bestehen zum überwiegenden Teil aus Abietinsäure oder Abietinsäurederivaten.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.
Die Tackifier können in einfacher Weise den erfindungsgemäßen Polymerisaten, bevorzugt den wäßrigen Dispersionen der Polymerisate zugesetzt werden. Vorzugsweise liegen die Tackifier dabei selber in Form einer wäßrigen Dispersion vor.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.
Die Gewichtsmenge der Tackifier beträgt vorzugsweise 5 bisThe weight amount of the tackifier is preferably 5 to
100 Gew. -Teile, besonders bevorzugt 10 bis 50 Gew. -Teile, bezogen auf 100 Gew. -Teile Polymerisat, (fest/fest) .100 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of polymer, (solid / solid).
Neben Tackifiern können z.B. noch weitere Additive z.B. Verdik- kungsmittel, vorzugsweise Assoziatiwerdicker, Entschäumer, Weichmacher, Pigmente, Netzmittel oder Füllstoffe bei der Verwendung als Haftklebstoff Verwendung finden. Die erfindungsgemäßen Haftklebstoffe enthalten daher neben der wäßrigen Polymerdispersion gegebenenfalls noch Tackifier und/oder die vor- stehenden Additive.In addition 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. In addition to the aqueous polymer dispersion, the pressure-sensitive adhesives according to the invention therefore optionally also contain tackifiers and / or the above additives.
Für eine bessere Benetzung von Oberflächen können die Haftklebstoffe insbesondere Benetzungshilfsmittel, z.B. Fettalkoholetho- xylate, Alkylphenolethoxylate, Sulfobernsteinsäureester, Nonyl- phenolethoxylate, Polyoxyethylene/-propylene oder Natriumdodecyl- sulfonate enthalten. Die Menge beträgt im allgemeinen 0,05 bis 5 Gew. -Teile, insbesondere 0,1 bis 3 Gew. -Teile auf 100 Gew.- Teile Polymer (fest) .For better wetting of surfaces, 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).
Die Haftklebstoffe eignen sich zur Herstellung selbstklebender Artikel wie Etiketten, Folien oder Klebebänder. Der Haftklebstoff kann durch übliche Methoden, z.B. durch Rollen, Rakeln, Streichen etc. auf Träger, z.B. Papier oder Polymer-Folien, bevorzugt bestehend aus Polyethylen, Polypropylen, das biaxial oder monoaxial verstreckt sein kann, Polyethylenterephthalat, Polyvinylchlorid, Polystyrol, Polyamid oder Metall aufgebracht werden. Insbesondere eignen sich auch Träger mit unpolaren Oberflächen, z.B. aus Poly- olefinen, insbesondere Polyethylen oder Polypropylen, da die erfindungsgemäßen Dispersionen darauf gut haften. Das Wasser kann bevorzugt durch Trocknung bei 50 bis 150°C entfernt werden. Die Träger können vor oder nach dem Aufbringen des Klebstoffs zu Klebebändern, Etiketten oder Folien geschnitten werden. Zur späteren Verwendung kann die mit Haftklebstoff beschichtete Seite der Substrate, mit einem Releasepapier, z.B. mit einem silikonisierten Papier, abgedeckt werden. Die erfindungsgemäßen selbstklebenden Artikel haben sehr gute Klebeeigenschaften, insbesondere eine gute Adhäsion zu den Substraten und eine hohe Kohäsion (innere Festigkeit in der KlebstoffSchicht) . Diese guten Eigenschaften werden auch erreicht, wenn die Dispersionen, bzw. Haftklebstoffe Benetzungshilfsmittel enthalten. Sie haben auch eine gute Haftung auf unpolaren Oberflächen und eignen sich daher auch besonders für Substrate mit unpolaren Oberflächen, z.B. Polyolefinoberflachen, z.B. Polyethylen (HDPE oder LDPE) oder Polypropylen.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. In particular, 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. For later use, 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.
Der Haftklebstoff neigt auch nicht zum Umspulen, d.h. er verbleibt auf dem Träger nach Abziehen z.B. des Etiketts.The pressure sensitive adhesive also does not tend to rewind, i.e. it remains on the carrier after peeling e.g. of the label.
Die selbstklebenden Artikel haben auch eine hohe Wasserfestig- keit.The self-adhesive articles also have a high level of water resistance.
Beispielexample
Acronal® A 220: wäßrige Dispersion eines Polyacrylats , welches als Haftklebstoff angeboten wirdAcronal® A 220: aqueous dispersion of a polyacrylate, which is offered as a pressure sensitive adhesive
(BASF)(BASF)
Epotal® DS 2343 : wäßrige Dispersion eines Polyethylen mit und einem AcrylSäuregehalt von 20 Gew. -% (Handelsprodukt der BASF)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: wäßrige Dispersion eines oxidierten Polyethylen, dispergiert in Wasser mit Hilfe eines Emulgators (Handelsprodukt der BASF)Poligen® WE 6: aqueous dispersion of an oxidized polyethylene, dispersed in water using an emulsifier (commercial product from BASF)
Lumiten® I-SC: Benetzungshilfsmittel (Sulfobernsteinsäure- ester)Lumiten® I-SC: wetting agents (sulfosuccinic acid esters)
Aus diesen Ausgangsstoffen wurden die in der Tabelle angegebenen Haftklebstoffe gemischt und die anwendungstechnischen Prüfungen mit den Haftklebstoffen durchgeführt.The PSAs listed in the table were mixed from these starting materials and the application tests were carried out with the PSAs.
Anwendungstechnische PrüfungApplication test
Die Haftklebstoffe wurden mit einer Auftragsmenge von 20 g/m2 auf Polyethylenfolie beschichtet und 3 Minuten bei 90°C getrocknet.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.
Anschließend wurde die Schälfestigkeit (Adhäsion) und Scherfestigkeit (Kohäsion) bestimmt. Der mit Haftklebstoff beschichtete Träger wurde in 25 mm breite Prüfstreifen geschnitten. Zur Bestimmung der Scherfestigkeit wurden die Prüfstreifen mit einer verklebten Fläche von 25 mm2 auf ein V2A-Prüfblech geklebt, mit einer 1 kg schweren Rolle 1 mal angerollt, 10 min gelagert (im Normklima, 50 % rel. Luftfeuchtigkeit 1 bar, 23°C) und anschließend hängend mit einem 1 kg Gewicht belastet (im Normklima) . Das Maß für die Scherfestigkeit war die Zeit bis zum Abfallen des Gewichts; es wurde jeweils der Durchschnitt aus 5 Messungen berechnet.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.
Bei der Bestimmung der Schälfestigkeit (Adhäsion) wurde jeweils ein 2,5 cm breiter Prüfstreifen auf einen Prüfkörper aus Polyethylen (HDPE) geklebt und mit einer 1 kg schweren Rolle 1 mal angerollt. Er wurde dann mit einem Ende in die oberen Backen einer Zug-Dehnungs-Prüfapparatur eingespannt. Der Klebestreifen wurde mit 300 mm/min unter einem 180° Winkel von der Prüffläche abgezogen d.h. der Klebestreifen wurde umgebogen und parallel zum Prüfblech abgezogen und der dazu benötigte Kraftaufwand gemessen. Das Maß für die Schälfestigkeit war die Kraft in N/2, 5 cm, die sich als Durchschnittswert aus fünf Messungen ergab.When determining the peel strength (adhesion), 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.
Die Schälfestigkeit wurde 1 Minute und 24 Stunden nach der Verklebung bestimmt. Nach dieser Zeit hat sich die Klebekraft voll ausgebildet .The peel strength was determined 1 minute and 24 hours after the bond. After this time, the adhesive strength has fully developed.
Wasserfestigkeitwater resistance
Zur Bestimmung der Wasserfestigkeit wurden die obigen Prüfstreifen auf handelsübliche Shampoo-Flaschen aus Polyethylen geklebt. Die Flaschen wurden 24 Stunden in eine 5 %ige wäßrige Shampoo-Lösung gelegt. Danach hatten sich die Etiketten nicht abgelöst, auch an den Rändern war keine Ablösung erkennbar. Die Etiketten wurden abgezogen, die Klebstoffschicht blieb dabei auf dem Etikett, auf der Flasche blieben keine Klebstoffrückstände (kein Umspulen) . To determine the water resistance, 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).
Tabelletable
Figure imgf000015_0001
Figure imgf000015_0001
A: Adhäsionsbruch; K: Kohäsionsbruch; AO: Umspulen; f: fest, d.h. ohne WasserA: broken adhesion; K: cohesive break; AO: rewind; f: fixed, i.e. without water
Alle Haftklebstoffe enthielten 1 Gew. -Teil Lumiten ISC, bezogen auf 100 Gew. -Teile Polymer (Acronal A 220 ohne Wasser) 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)

Claims

Patentansprüche claims
1. Wässrige Dispersion eines Polymeren, welches zu mindestens 40 Gew. % aus sogenannten Hauptmonomeren, ausgewählt aus Cl bis C20 Alkyl (meth) acrylaten, Vinylestern von bis zu 20 C- Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinyl- halogeniden, Vinylethern von 1 bis 10 C Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 4 bis 8 C- Atomen und zwei Doppelbindungen oder Mischungen dieser Monomeren aufgebaut ist, dadurch gekennzeichnet, dass die wässrige Dispersion weiterhin ein in der Dispersion gelöstes oder dispergiertes Polyethylen, welches zu mindestens 40 Gew. % aus Ethylen aufgebaut ist, enthält.1. Aqueous dispersion of a polymer which comprises at least 40% by weight of so-called main monomers, selected from C1 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 carbon atoms, aliphatic hydrocarbons with 4 to 8 carbon atoms and two double bonds or mixtures of these monomers, characterized in that the aqueous dispersion is also a solution in or dissolved in the dispersion dispersed polyethylene, which is composed of at least 40% by weight of ethylene.
2. Wässrige Dispersion gemäß Anspruch 1, dadurch gekennzeichnet, dass das Polymer zu mindestens 40 Gew. % aus Cl bis C20 Alkyl (meth) acrylaten besteht .2. Aqueous dispersion according to claim 1, characterized in that the polymer consists of at least 40% by weight of Cl to C20 alkyl (meth) acrylates.
3. Wässrige Dispersion gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei dem Polymeren um ein Emulsionspolymerisat handelt.3. Aqueous dispersion according to claim 1 or 2, characterized in that the polymer is an emulsion polymer.
4. Wässrige Dispersion gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Glasübergangstemperatur des Polymeren -60 bis 0°C beträgt.4. Aqueous dispersion according to one of claims 1 to 3, characterized in that the glass transition temperature of the polymer is -60 to 0 ° C.
5. Wässrige Dispersion gemäß einem der Ansprüche 1 bis 4, da- durch gekennzeichnet, dass das Polyethylen im Wasser disper- giert ist.5. Aqueous dispersion according to one of claims 1 to 4, characterized in that the polyethylene is dispersed in the water.
6. Wässrige Dispersion gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Polyethylen einen Gehalt von 0,01 bis 1 Mol Carbonsäuregruppen (berechnet als COOH) pro 100 g Polyethylen aufweist.6. Aqueous dispersion according to one of claims 1 to 5, characterized in that the polyethylene has a content of 0.01 to 1 mol of carboxylic acid groups (calculated as COOH) per 100 g of polyethylene.
7. Wässrige Dispersion gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Polyethylen ein gewichts- mittleres Molgewicht von 5000 bis 15000 g/mol hat.7. Aqueous dispersion according to one of claims 1 to 6, characterized in that the polyethylene has a weight-average molecular weight of 5000 to 15000 g / mol.
8. Wässrige Dispersion gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Menge des Polyethylen 2 bis 20 Gew. Teile, bezogen auf 100 Gew. Teile der Gewichtssumme des Polymeren und des Polyethylen beträgt. 8. Aqueous dispersion according to one of claims 1 to 7, characterized in that the amount of polyethylene is 2 to 20 parts by weight, based on 100 parts by weight of the total weight of the polymer and of the polyethylene.
9. Verwendung der wässrigen Dispersion gemäß einem der Ansprüche 1 bis 8 als Haftklebstoff.9. Use of the aqueous dispersion according to one of claims 1 to 8 as a pressure sensitive adhesive.
10. Selbstklebende Artikel, insbesondere Etiketten, Klebebänder oder Folien, erhältlich unter Verwendung einer wässrigen Dispersion gemäß einem der Ansprüche 1 bis 9 als Haftklebstoff.10. Self-adhesive articles, in particular labels, adhesive tapes or foils, obtainable using an aqueous dispersion according to one of claims 1 to 9 as a pressure sensitive adhesive.
11. Verwendung der selbstklebenden Artikel gemäß Anspruch 10 auf unpolaren Oberflächen. 11. Use of the self-adhesive article according to claim 10 on non-polar surfaces.
PCT/EP2003/001158 2002-02-26 2003-02-06 Aqueous dispersion containing polyethylene WO2003072654A2 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1862520A1 (en) * 2006-06-01 2007-12-05 Basf Aktiengesellschaft film labels
EP2166057A1 (en) 2008-08-26 2010-03-24 Basf Se Adhesive compound for self-adhesive, detachable item on the basis of adhesive polymers and organic nanoparticles
WO2011062852A1 (en) * 2009-11-19 2011-05-26 3M Innovative Properties Company Pressure sensitive adhesive comprising functionalized polyisobutylene hydrogen bonded to acylic polymer
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

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DE2558916A1 (en) * 1974-12-28 1976-07-01 Copyer Co Aq. alkaline coating compsn for electrostatic recording sheets - contg. ethylene-(meth)acrylic acid and (meth)acrylic acid copolymers
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 (en) * 1992-01-25 1993-08-04 HANS NESCHEN GmbH & CO. KG Hot-melt adhesive
WO1999054419A1 (en) * 1998-04-23 1999-10-28 Idemitsu Petrochemical Co., Ltd. Coating material

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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 (en) * 1974-12-28 1976-07-01 Copyer Co Aq. alkaline coating compsn for electrostatic recording sheets - contg. ethylene-(meth)acrylic acid and (meth)acrylic acid copolymers
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 (en) * 1992-01-25 1993-08-04 HANS NESCHEN GmbH & CO. KG Hot-melt adhesive
WO1999054419A1 (en) * 1998-04-23 1999-10-28 Idemitsu Petrochemical Co., Ltd. Coating material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1862520A1 (en) * 2006-06-01 2007-12-05 Basf Aktiengesellschaft film labels
EP2166057A1 (en) 2008-08-26 2010-03-24 Basf Se Adhesive compound for self-adhesive, detachable item on the basis of adhesive polymers and organic nanoparticles
WO2011062852A1 (en) * 2009-11-19 2011-05-26 3M Innovative Properties Company Pressure sensitive adhesive comprising functionalized polyisobutylene hydrogen bonded to acylic polymer
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

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DE10208039A1 (en) 2003-09-04
WO2003072654A3 (en) 2004-03-11
AU2003210216A1 (en) 2003-09-09

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