WO2011003864A1 - Dispersion de polymères soudable à froid, préparée par polymérisation en émulsion en présence d'un copolymère éthylène/acide (méth) acrylique - Google Patents

Dispersion de polymères soudable à froid, préparée par polymérisation en émulsion en présence d'un copolymère éthylène/acide (méth) acrylique Download PDF

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Publication number
WO2011003864A1
WO2011003864A1 PCT/EP2010/059561 EP2010059561W WO2011003864A1 WO 2011003864 A1 WO2011003864 A1 WO 2011003864A1 EP 2010059561 W EP2010059561 W EP 2010059561W WO 2011003864 A1 WO2011003864 A1 WO 2011003864A1
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ethylene
meth
polymer
composition according
acrylic acid
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PCT/EP2010/059561
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German (de)
English (en)
Inventor
Michael Gross
Oral Aydin
Heiko Diehl
Georg Langhauser
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Basf Se
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Publication of WO2011003864A1 publication Critical patent/WO2011003864A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—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
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or 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
    • 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
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/22—Presence of unspecified polymer
    • C09J2400/228—Presence of unspecified polymer in the pretreated surface to be joined

Definitions

  • the invention relates to a cold-sealable composition in the form of an aqueous polymer dispersion, wherein the aqueous polymer dispersion can be prepared by emulsion polymerization of free-radically polymerizable monomers in the presence of at least one ethylene / (meth) acrylic acid copolymer as protective colloid, the use of the aqueous polymer dispersion for cold sealing, in particular of polymer films , as well as corresponding coated polymer films and their use for the production of packaging.
  • Cold-sealable compositions are adhesives that do not feel sticky on a substrate after application and drying, but which adhere to each other when pressed together at room temperature with pressure. They differ from pressure-sensitive adhesives by their absence at room temperature or at most very low tackiness. They differ from heat-sealable compositions in that they can be pressure bonded together without heat activation. Cold-sealable compositions are known, for example, for sealing bagged packaging, in particular for food or other heat-sensitive goods, in the packaging of which the application of heat is undesirable, e.g. Ice cream or chocolate or when fast packaging speeds and high cycle times are required.
  • substrates coated therewith can be rolled on rolls and stored until use, with no adhesion to the opposite other side of the support substrate, preferably provided with a release coating.
  • a release coating typically, for cold seal adhesives, polymer dispersions based on natural rubber latex are used.
  • the disadvantage here is a comparatively high price volatility, natural quality fluctuations of the natural raw material and, above all, the allergenic potential that these natural products contain.
  • Cold-sealable compositions which are as free as possible of organic solvents, ie aqueous dispersions of polymers which form a cold-sealable coating after drying, are desired.
  • Polymer dispersions which can be prepared by emulsion polymerization generally contain, as a result of the preparation, non-polymeric emulsifiers for stabilizing the dispersions. For some applications, however, emulsifiers are disruptive and undesirable, and emulsifier-free or low-emulsifier systems are desired. It is known that it is also possible to use polymeric protective colloids to stabilize polymer dispersions which can be prepared by emulsion polymerization.
  • WO 2007/085588 describes autoadhesive adhesives which can be prepared by emulsion polymerization, and it is mentioned that protective emulsions can also be used as surface-active compounds in emulsion polymerization, including hydrophilically modified polyolefins, for example acrylic acid. re / ethylene copolymers can act.
  • these polymeric additives may adversely affect the application properties of the dispersions for cold seal applications.
  • a cold-sealable composition in the form of an aqueous polymer dispersion, wherein the aqueous polymer dispersion can be prepared by emulsion polymerization of radically polymerizable monomers in the presence of at least one ethylene / (meth) acrylic acid copolymer having an acid number of 160 to 230 mg KOH / g as a protective colloid.
  • Cold-sealable means that when two coated with a composition according to the invention and dried surfaces when at temperatures below 40 0 C, in particular less than 30 0 C or less 25 0 C, in particular at room temperature (20 0 C) in contact with exerting pressure be brought together, adhere to each other.
  • the adhesion (autoadhesive adhesion) after sealing with 1, 4 bar at 20 ° C is preferably at least 2 N / 15 mm, measured by the method described in the examples for determining the seal strength after storage for one day at room temperature after coating and before sealing and Storage one day after sealing and before measurement (SNF 1 d / 1 d).
  • the cold sealing is expediently carried out at ambient temperature, ie generally at temperatures of 10 to 30 0 C, in particular 15 to 25 0 C and at pressures of a few millibar to several bar above normal pressure (1 bar), eg at 0, 01 to 5 bar, in particular from 0.1 to 3 bar above normal pressure.
  • the sealing time, ie the time during which the pressure is maintained is, for example, 0.1 to 20 seconds, in particular 0.1 to 3 seconds, in particular 0.5 seconds are usual.
  • polymer or "emulsion polymer” is mentioned below, unless expressly stated otherwise, what is meant is the polymerization product formed by emulsion polymerization of the radically polymerizable monomers in the presence of the ethylene / (meth) acrylic acid copolymer.
  • the polymer dispersions according to the invention form a coating which is preferably auto-adhesive and block-resistant to polyamide surfaces.
  • Autoadhesive means that two coated surfaces are cold sealable against each other.
  • Blocking means that the adhesion of a surface coated and dried with a composition according to the invention to a polyamide surface after loading a circular surface with a diameter of 10 cm at 10 tons for one day at 20 ° C. is at most 0.1 N / 25 mm, measured according to the method described in the examples.
  • the polymer dispersions according to the invention are dispersions of polymers in an aqueous medium. This may be e.g. to act completely desalinated water or mixtures of water and a miscible solvent such as methanol, ethanol or tetrahydrofuran. Preferably, no organic solvents are used.
  • the solids contents of the dispersions are preferably from 15 to 75% by weight, preferably from 40 to 60% by weight, in particular greater than 50% by weight. The solids content may e.g. by appropriate adjustment of the amount of water used in the emulsion polymerization and / or the amount of monomers.
  • the average particle size of the polymer particles dispersed in the aqueous dispersion is preferably less than 400 nm, in particular less than 300 nm. More preferably the average particle size is between 140 and 250 nm.
  • average particle size is meant here the dso value of the particle size distribution, i. 50 wt .-% of the total mass of all particles have a smaller particle diameter than the dso value.
  • the particle size distribution can be determined in a known manner with the analytical ultracentrifuge (W. Switzerlandle, Makromolekulare Chemie 185 (1984), page 1025-1039).
  • the pH of the polymer dispersion is preferably adjusted to pH greater than 4, in particular to a pH of between 5 and 9.
  • the composition may consist solely of the water-dispersed polymer and the ethylene / (meth) acrylic acid copolymer for use in the present invention. However, it can also contain other additives, for example fillers, anti-blocking agents, dyes, leveling agents or thickeners.
  • the polymer dispersions according to the invention are preferably emulsifier-poor, ie they contain emulsifiers (non-polymeric, amphiphilic, surface-active substances) in an amount of preferably less than 3 or less than 1% by weight. Particularly preferred are emulsifier-free systems. In one embodiment of the invention, therefore, carried out in the presence of the protective colloid emulsion polymerization emulsifier-free.
  • the ethylene / (meth) acrylic acid copolymer is formed from ethylene as the first monomer and from a second monomer type selected from acrylic acid, methacrylic acid or a mixture thereof.
  • the copolymer may optionally be formed from further, preferably nonionic monomers.
  • the amount of acid monomer is preferably such that the acid value of the copolymer is from 160 to 230 mg KOH / g.
  • the acid number can be determined by acid / base titration. For an ethylene / methacrylic acid copolymer, this corresponds approximately to a content of methacrylic acid of 25-35% by weight. For an ethylene / acrylic acid copolymer, this corresponds approximately to a content of acrylic acid of 20.5-29.5% by weight.
  • the ethylene / (meth) acrylic acid copolymer preferably has a melt viscosity at 120 ° C. in the range of 400-2000 mPa s, for example 800 +/- 100 mPa s.
  • the melt viscosity can be determined with a cone-plate viscometer (ICI Cone & Plate Viscosimeter, Epprecht Instruments + Control AG, measuring body C, 1 1, 72 rpm, stage 2).
  • the ethylene / (meth) acrylic acid copolymer may optionally be formed from further comonomers, apart from ethylene and (meth) acrylic acid. Preferably, no further comonomers are contained. Most preferably, the copolymer consists only of ethylene and methacrylic acid. If comonomers are included, their amount is preferably at most 15% by weight or at most 10% by weight, e.g. 1-10 wt.%, In each case based on the total amount of monomers. Comonomers are, for example, C1-20 alkyl acrylates, C1-20 alkyl methacrylates, vinyl silanes or vinyl phosphonic acid esters.
  • the ethylene / (meth) acrylic acid copolymer is formed from
  • the ethylene / (meth) acrylic acid copolymer is preferably used in amounts of from 0.5 to 60 parts by weight or from 1 to 30 parts by weight, more preferably from 5 to 20 parts by weight (especially when the total solids content of the inventive composition more than 50% by weight), based on 100 parts by weight of the monomers to be polymerized.
  • the active ingredient of the cold-sealable composition acting as a binder is the polymer which can be prepared by emulsion polymerization of free-radically polymerizable monomers.
  • the polymer is preferably at least 60% by weight, preferably at least 80% by weight, e.g. from 80 to 100% by weight, more preferably at least 90% by weight or to 100% by weight of one or more of the main monomers described below.
  • the main monomers are selected from the group consisting of C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of 1 alcohols containing up to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
  • (meth) acrylic acid alkyl ester having a Ci-Cio-alkyl radical such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether.
  • Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds may be mentioned butadiene, isoprene and chloroprene.
  • Preferred main monomers are the C 1 to C 10 -alkyl acrylates and methacrylates, in particular C 1 to C 8 -alkyl acrylates and methacrylates, and vinylaromatics, in particular styrene and mixtures thereof.
  • the polymer may contain other monomers, e.g. Monomers with carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Called z. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Other monomers are z. As well as hydroxyl-containing monomers, in particular Ci-Cio-hydroxyalkyl (meth) acrylates and (meth) acrylamide.
  • Phenyloxyethylglycol mono- (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may also be mentioned as further monomers.
  • Other monomers which may also be mentioned are crosslinking monomers.
  • the polymer may contain hydrophilic groups selected from carboxyl groups, hydroxyl groups, amino groups and carboxamide groups.
  • the content of these hydrophilic groups is in particular 0.001 to 0.5 mol per 100 g of polymer.
  • the content is preferably at least 0.005 mol, particularly preferably at least 0.008 mol and not more than 0.2 mol, in particular not more than 0.1 mol, very particularly preferably not more than 0.05 or 0.03 mol per 100 g / polymer.
  • Particularly preferred are the hydrophilic groups selected from carboxyl groups, hydroxyl groups and carboxamide groups. More preferably, at least 20 mole percent of the total moles of these groups are carboxyl groups.
  • Carboxyl groups are understood as meaning both carboxylic acid groups and their salts. In the case of the salts, these are preferably salts with volatile bases, eg. B. ammonia.
  • the hydrophilic groups can be bound to the polymer by copolymerization of the corresponding monomers.
  • Preferred monomers having hydrophilic groups are the abovementioned monomers having carboxyl groups and hydroxyl groups, in particular z.
  • acrylic acid is preferred.
  • the polymer is at least 60% by weight, more preferably at least 80% by weight, e.g. of from 80 to 100% by weight, and very particularly preferably at least 95% by weight or to 100% by weight, of C 1 to C 20 alkyl (meth) acrylates.
  • the binder is the homopolymer of ethyl acrylate
  • the polymer preferably has a glass transition temperature calculated from Fox of the monomer composition from -50 to + 20 0 C, more preferably from -30 to +10 0 C.
  • the glass transition temperature is according to the Fox equation from the glass transition temperature, the homopolymers of the present in the copolymer Calculated monomers and their weight fraction:
  • Tg calculated glass transition temperature of the copolymer
  • TgA glass transition temperature of the homopolymer of monomer A
  • TgB, TgC Tg corresponding to monomers B, C, etc.
  • the preparation of the polymers can be carried out by emulsion polymerization, it is then an emulsion polymer.
  • emulsion polymerization ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are generally used as surface-active compounds in order to promote the dispersion of the monomers in the aqueous medium.
  • the ethylene / (meth) acrylic acid copolymers having an acid number of 160 to 230 mg KOH / g can be used as the sole protective colloid or as the sole dispersant, i. without additional emulsifiers and without other protective colloids of other types.
  • emulsifiers or of other protective colloids can also be used. If emulsifiers and / or additional protective colloids are used as aids for dispersing the monomers, the total amounts used thereof are, for example, from 0.1 to 5% by weight, based on the monomers. Of course, in the case of the use of mixtures of surfactants, the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests. A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, macromolecular materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 41 1 to 420. Suitable as protective colloids z. B.
  • amphiphilic polymers ie polymers with hydrophobic and hydrophilic groups. They may be natural polymers such as starch or synthetic polymers.
  • Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers. Emulsifiers whose molecular weight, in contrast to the protective colloids, are usually below 2000 g / mol, preferably below 1500 g / mol, are preferred as accompanying surface-active substances, while the number average molecular weight of the protective colloids is above 2000 g / mol, for example 2000 to 100000 g / mol, in particular from 5000 to 50,000 g / mol.
  • emulsifiers are used as additional surface-active substances, they are preferably anionic or nonionic emulsifiers.
  • Suitable emulsifiers are, for example, ethoxylated Cs to C36 or C12 to ds fatty alcohols having a degree of ethoxylation of from 3 to 50 or from 4 to 30, ethoxylated mono-, di- and tri-C 4 - to C 12 or C 4 - C 1 -C 4 -alkylphenols having a degree of ethoxylation of from 3 to 50, alkali metal salts of dialkyl esters of sulfosuccinic acid, alkali metal and ammonium salts of C 2 -C 12 -alkyl sulfates, alkali metal and ammonium salts.
  • Cationic emulsifiers are, for example, compounds having at least one amino or ammonium group and at least one C 8 -C 22 -alkyl group. Further suitable emulsifiers are compounds of the general formula
  • R 5 and R 6 are hydrogen or C 4 - to Cu-alkyl and are not hydrogen at the same time, and X and Y may be alkali metal ions and / or ammonium ions.
  • R 5 , R 6 are linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, wherein R 5 and R 6 are not both simultaneously hydrogen.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred. Particularly advantageous are compounds II in which X and Y are sodium, R 5 is a branched Al kylrest with 12 C atoms and R 6 is hydrogen or R 5 .
  • the emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 90 0 C.
  • the polymerization medium may consist of water only, 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 both as a batch process and in the form of a feed process, including a stepwise or gradient procedure.
  • the feed process in which one submits a portion of the polymerization, heated to the polymerization, polymerized and then the rest of the polymerization, usually over several spatially separate feeds, one or more of which monomers in pure or in emulsified form, continuously or gradually supplied.
  • the emulsion polymerization is carried out in the presence of the ethylene / (meth) acrylic acid copolymers as protective colloid.
  • the ethylene / (meth) acrylic acid Copolymers and optionally further protective colloids are introduced or fed together with monomers to the polymerization vessel. They are preferably initially introduced in the emulsion polymerization, while optionally additionally used emulsifiers together with the monomers can also be supplied in the course of the polymerization.
  • the usual and known adjuvants e.g. water-soluble initiators and regulators are used.
  • Water-soluble initiators for emulsion polymerization are e.g. Ammonium and alkali metal salts of peroxodisulfuric acid, e.g. For example, sodium peroxodisulfate, hydrogen peroxide or organic peroxides, z. B. tert-butyl hydroperoxide.
  • so-called reduction-oxidation (red-ox) initiator systems are so-called reduction-oxidation (red-ox) initiator systems.
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is z. B.
  • the reduction components are, for. B. to alkali metal salts of sulfurous acid, such as. As sodium sulfite, sodium bisulfite, alkali metal salts of the desulfurous acid such as sodium, bisulfite addition compounds aliphatic aldehydes and ketones, such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and salts thereof, or ascorbic acid.
  • the red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states. Usual Red Ox initiator systems are z.
  • the individual components eg. As the reduction component, mixtures may also be z.
  • the compounds mentioned are usually used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question in water.
  • the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1, 0 to 10 wt .-%, based on the solution.
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization. To remove the residual monomers, initiator is usually also added after the end of the actual emulsion polymerization.
  • the polymerization regulators can be used, for. B. in amounts of 0 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be polymerized, whereby the molecular weight is reduced.
  • Suitable z. B. Compounds with a thiol group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethanol, Mercaptopropyltrimethoxysilane or tert-dodecylmercaptan.
  • regulators without thiol group can be used, such as terpinolene.
  • the emulsion polymer prepared by emulsion polymerization is a pure acrylate, i. consists exclusively of alkyl (meth) acrylate monomers, wherein the alkyl group preferably has 1 to 8 C atoms and wherein preferably at least one monomer is ethyl acrylate or which is n-butyl acrylate / methyl methacrylate copolymer which is ethylene / (meth ) acrylic acid copolymer of 65 to 75 wt.% Ethylene and 25 to 35 wt.% Methacrylic acid and the ethylene / methacrylic acid copolymer in an amount of 5 to 20 parts by weight, based on 100 parts by weight of the polymerized Monomers is used.
  • the invention also relates to the use of the above-described aqueous polymer dispersions for cold-sealing, wherein the polymer dispersion after application to a substrate and after drying forms an autoadhesive coating which is block-resistant at room temperature
  • composition according to the invention is suitable for cold sealing of any two substrates, wherein
  • the two substrates are optionally brought under pressure and the temperature in the coated composition is less than 40 0 C (cold sealing, see above).
  • Suitable substrates to be bonded are any, for.
  • substrates of wood, metal, paper or plastic which can be glued together in any combination, wherein preferably at least one substrate is a polymer film.
  • the substrates are coated with the composition according to the invention.
  • the coating can be carried out in a customary manner, for example by printing, in particular by flexographic printing or by gravure printing (gravure printing).
  • Typical layer thicknesses (after drying) are, for example, 1 to 30 g / m 2 , preferably 1 to 10 g / m 2 or 1 to 5 g / m 2 .
  • the composition according to the invention is suitable for the production of packaging. In this case come packaging from any materials, eg. B. of paper or preferably made of plastic. Called z.
  • As packaging of polymer films optionally also metallized polymer films, for. Example of polyethylene, polypropylene, PVC, polyester, polyacetate.
  • a carrier coated on both sides is particularly suitable for the production of packaging, the carrier being provided on one side (hereinafter referred to as front side). characterized) has an outer layer of the composition of the invention and on the other side (hereinafter referred to as the back) having an outer release coating.
  • the carrier may, for. B. from one of the above-mentioned polymer films or metallized polymer films may be mentioned, in particular films of oriented polypropylene, polyethylene, preferably high density polyethylene or polyethylene terephthalate.
  • the polymer films may also be pretreated with corona.
  • the composition according to the invention may be coated directly on the front side of the carrier, but other layers may also be present between the carrier and the composition according to the invention, e.g. B.
  • the release coating may be of any material, it may be a polymeric film, eg, an oriented polypropylene film which is laminated or coextruded, or a liquid paint, e.g. B. a polyamide paint, which is applied and filmed act; It is essential that the adhesive layer applied on the front side of the carrier (in the present case, the composition according to the invention) does not adhere to the release coating (blocking resistance).
  • the carrier is generally rolled up and later processed by the roll. When rolled up, the front and back of the wearer come into direct contact.
  • Adhesive layer composition according to the invention
  • primer layer
  • the carrier coated on both sides is used in particular for the production of packaging, preferably it is adhesively bonded to itself by cold sealing, wherein in each case the front sides coated with the outer composition according to the invention are brought into contact. It is essential that both to be bonded carrier to be bonded, forming the subsequent seal Sites are coated with the composition of the invention.
  • the package is sealed by cold sealing the adhesive layer together once the product to be packaged is filled.
  • the packaging is particularly suitable for food.
  • the invention also relates to a coated polymer film, wherein a polymer support film at least partially, i. at least at the areas forming the subsequent seal seam is coated with a composition according to the invention.
  • the polymer film according to the invention preferably has a first and a second side, wherein the first side as an outer layer is at least partially coated with a composition according to the invention and the second side has a release coating as the outer layer.
  • the polymer support film of the coated polymer film of the invention is polyethylene or oriented polypropylene, and the release coating is formed on the basis of polyamide.
  • the invention also provides the use of the coated polymer film according to the invention for the production of packaging, in particular film packaging for food.
  • the indication of a content refers to the content in aqueous solution or dispersion.
  • Acronal® S 790 aqueous dispersion of a polymer based on acrylate ester
  • Styrene from BASF SE solids content 50%; pH 7.5-9.0
  • Joncryl® 74 acrylate dispersion from BASF SE: solids content 48%;
  • Joncryl® DFC 3025 a polymer resin solution (Styrene Acrylic Resin Solution)
  • Binzil® CC 30 transparent liquid of colloidal silicate from Eka / Akzo Nobel: solids content 29%; pH 8.0
  • Slip dispersion 8645 aqueous, anionic dispersion of montan ester wax of
  • Dynol® 604 and EnviroGem® are wetting agents from Air Products
  • Emulan® EL40 a castor oil ethoxylate from BASF SE
  • Disponil® FES77 sulfated fatty acid ethoxylate from Cognis
  • Poligen® WE3 aqueous dispersion of a polymer based on ethylene-acrylic acid
  • Oppalyte® 33MW247 film recommended for cold seal applications made of surface treated, biaxially oriented polypropylene from Exxon Mobil Corp.
  • Treofan® SHD40 Oriented polypropylene film recommended by Treofan GmbH & Co. KG for cold-seal applications
  • the melt viscosity was measured with a cone and plate viscometer (ICI).
  • the adhesive is applied to the pretreated side of the OPP film Oppalyte® ® 33MW247 and 1 min. At 70 0 C dried.
  • the coated film is covered with a release varnish-coated OPP film.
  • SNF 7d / 7d is the seal seam strength of a coated film which, after coating, was stored for 7 days at room temperature, then sealed against a same, coated film and, after sealing, was stored again for 7 days at room temperature before measuring the seal strength.
  • SNF 1d / 1d is the seal seam strength of a coated film which, after coating, was stored for one day at room temperature, then sealed against a same, coated film and, after sealing, was stored again for one day at room temperature before measurement of the seal seam strength.
  • the coated film is placed against the release varnish-coated side of an OPP-FoNe SHD40, and a 10 cm diameter circular cutout is loaded with 10 tons for 1d. Thereafter, the peel strengths of 25 mm wide strips are determined at a take-off speed of 800 mm / min in N / 25mm.
  • Feed 1 800 g of n-butyl acrylate, 200 g of methyl methacrylate, 2 g of tert-dodecylmercaptan.
  • Feed 2 150 g of a 3.33% strength by weight solution of tert-butyl hydroperoxide in distilled water.
  • Feed 3 100 g of distilled water, 30 g of 10% strength by weight ascorbic acid solution, 10 g of 1% by weight of Dissolvine® E-Fe 13 solution and 1.5 g of 25% strength by weight ammonia.
  • feeds 1, 2, 3 were started in parallel and metered in as indicated.
  • Feed 1 was added within 3 hours.
  • 10% of feed 2 was added in 20 minutes, the remainder of feed 2 in 4 hours.
  • 10% of feed 3 was added in 20 minutes, another 40% in 140 minutes, the remaining 50% were added in 20 minutes.
  • the mixture was stirred for 30 minutes, cooled to room temperature and then filtered through a 125 .mu.m sieve.
  • feed 1 contained 1000 g of ethyl acrylate and 2 g of tert-dodecylmercaptan. Solids content: 59.3%
  • Feed 1 contained 1000 g of ethyl acrylate. Solids content: 59.5%
  • Feed 1 contained 1000 g of ethyl acrylate, 2 g of tert-dodecyl mercaptan and 10 g Dynol ® 604.
  • Feed 2 comprised 150 g of a 3.33 wt.% Solution of tertiary butyl hydroperoxide in distilled water.
  • Feed 3 contained 426 g of distilled water, 30 g of 10% strength by weight ascorbic acid solution, 10 g of 1% by weight Dissolvine® E-Fe 13 solution and 1 l of 25% strength by weight ammonia.
  • Feeds 1, 2, 3 were started in parallel and metered in as indicated. Feed 1 was added within 3 hours. 10% of feed 2 was added in 20 minutes, the remainder of feed 2 in 4 hours. Feed 3 was added within 3 hours. The mixture was stirred for 30 minutes, cooled to room temperature and then filtered through a 125 .mu.m sieve.
  • feed 1 contained 1000 g of ethyl acrylate, 2 g of tert-dodecylmercaptan and 10 g of Envirogem® AD01.
  • feed 1 contained 1000 g of ethyl acrylate, 2 g of tert-dodecylmercaptan and 10 g of Emulan® EL40.
  • Feed 1 contained 1000 g of ethyl acrylate and 2 g of tert-dodecylmercaptan.
  • Feed 2 contained 150 g of a 3.33% by weight solution of tert-butyl hydroperoxide in distilled water.
  • Feed 3 contained 419.5 g of distilled water, 30 g of 10% strength by weight ascorbic acid solution, 10 g of 1% by weight of dissolvine E-Fe 13 solution and 1 1 g of 25% strength by weight ammonia.
  • Feeds 1, 2, 3 were started in parallel and metered in as indicated. Feed 1 was added within 3 hours. 10% of feed 2 was added in 20 minutes, the remainder of feed 2 in 4 hours. Feed 3 was added within 3 hours. It was stirred for 30 minutes, cooled to room temperature and then filtered through a 125 .mu.m sieve.
  • Example 7 an ethylene-2-ethylhexyl acrylate-methacrylic acid terpolymer (30.0 wt.% MAS content, 4.1 wt.% 2-EHA content, 820 mPa s melt viscosity at 120 ° C) was used.
  • Example 7 but an ethylene-2-propylheptyl acrylate-methacrylic terpolymer (30.0 wt.% MAS content, 4.4 wt.% 2-PHA content, 820 mPa s melt viscosity at 120 0 C) was used ,
  • telquel 80 parts by weight (telquel) of the dispersion from Example D3 are mixed with 20 parts by weight (telquel) Binzil® CC 30 (15% strength).
  • telquel 80 parts by weight (telquel) of the dispersion from Example D3 are mixed with 20 parts by weight (telquel) lubricant dispersion 8645 (20% strength).
  • telquel 80 parts by weight (telquel) of the dispersion from Example D3 are mixed with 20 parts by weight (telquel) Acronal ® S790 (50%).
  • Emulsifiers were prepared a polymer dispersion for mixing experiments with nachträgli- sher addition of ethylene / (meth) acrylic acid copolymers.
  • 400 g of distilled water were introduced at 70 0 C and the apparatus for 30 minutes, purged with nitrogen. Subsequently, the following feeds were metered in at 70 ° C.
  • Feed 1 contained an emulsion of 1000 g ethyl acrylate, 2 g of tert-dodecyl mercaptan, 30 wt 66,67g a.% Strength Disponil ® FES77 solution, 11, 11 g of a 45 wt.% Solution of Dowfax ® 2A1 solution and 520g distilled water.
  • Feed 2 contained 160 g of a 5% strength by weight solution of tert-butyl hydroperoxide in distilled water.
  • Feed 3 contained 158 g of a 5.06% strength by weight solution of sodium formaldehyde sulfoxylate (Rongalit®) in distilled water.
  • Feeds 2, 3 were started in parallel and metered in as indicated. In each case 20% of feed 2 and 3 was added in 20 minutes, the remainder in 5 hours. Feed 1 was started 5 minutes after the start of feeds 2 and 3 and metered in within 3 hours. The mixture was stirred for 30 minutes, cooled to room temperature and then filtered through a 125 .mu.m sieve.
  • Example wt V1 (E / MAA copolymer having acid number of 198 as a protective colloid, emulsifier) (in an open 4L reactor equipped with an anchor stirrer was at 70 0 C 668g of a solution of an ethylene-methacrylic acid copolymer 30.4.% MAS content 790 mPa s melt viscosity at 120 0 C) and the apparatus rinsed for 30 minutes with nitrogen.
  • the solution contained 25% by weight of ethylene-methacrylic acid copolymer, the calculated degree of partial neutralization of the carboxyl groups with ammonia was 75%.
  • the preparation of the copolymer solution was carried out analogously to Example D4.
  • Feed 1 contained 333 g of ethyl acrylate and 0.67 g of tert-dodecylmercaptan.
  • Feed 2 contained 53.28 g of a 5 wt .-% solution of tert-butyl hydroperoxide in distilled water.
  • Feed 3 contained 312.6 g of an O, 85% strength by weight solution of sodium formaldehyde sulfoxylate (Rongalit®) in distilled water.
  • feeds 2 and 3 were added within 3 minutes. Subsequently, feed 1 and the residual feeds of 2 and 3 were metered in over the course of 1.5 hours. The mixture was stirred for 1 hour at 70 0 C, then cooled to room temperature and filtered through a 125 .mu.m sieve.
  • Comparative Example C3 E / AS copolymer with acid number 156 as protective colloid, emulsifier-free Equipped with an anchor stirrer, in an open 4L reactor a solution of an ethylene-acrylic acid copolymer (20% AS content wt.) Was added at 70 0 C 334g presented and the apparatus for 30 minutes, purged with nitrogen.
  • the solution contained 25% by weight of ethylene-acrylic acid copolymer, trade name Poligen WE3.
  • the following feeds were metered in at 70 ° C.
  • Feed 1 contained 165.5 g of ethyl acrylate and 0.33 g of tert-dodecylmercaptan.
  • Feed 2 contained 26.64 g of a 5% strength by weight solution of tert-butyl hydroperoxide in distilled water.
  • Feed 3 contained 157.97 g of an O, 85% by weight solution of Rongalit C in distilled water.
  • feed 1 5% of feed 1 were presented at 70 0 C. Subsequently, in each case 30% of the feeds 2 were metered in within 3 minutes. Subsequently, feed 1 and the residual feeds of 2 and 3 were metered in over the course of 1.5 hours. The mixture was stirred for 1 hour at 70 0 C, then cooled to room temperature and filtered through a 125 ⁇ m sieve.
  • Comparative Example C4 E / AS copolymer added subsequently with acid number 156) As Comparative Example C2, but a dispersion of an ethylene-acrylic acid copolymer (20 wt.% AS content, trade name Poligen WE3) was mixed with the acrylate polymer dispersion of Comparative Example C0. An appropriate amount of terminal WE3 was mixed at room temperature with an appropriate amount of the acrylate polymer dispersion of Comparative Example VO and the solids content was adjusted to 35% with distilled water. The content of the ethylene-acrylic acid copolymer in the solid content was 33%.
  • composition V1 according to the invention is distinguished by an unexpected combination of advantageous intrinsic properties in terms of good rheological properties and good applicability despite the freedom of emulsifiers, high seal strength even after prolonged storage, good blocking resistance and freedom from emulsifiers.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention porte sur une composition soudable à froid, sous forme d'une dispersion aqueuse de polymères, la dispersion aqueuse de polymères pouvant être préparée par polymérisation en émulsion de monomères polymérisables par polymérisation radicalaire en présence d'au moins un copolymère éthylène/acide (méth)acrylique, avec un indice d'acide de 160 à 230 mg KOH/g, servant de colloïde protecteur, sur l'utilisation de la dispersion aqueuse de polymères pour le soudage à froid en particulier de feuilles polymères, ainsi que sur des feuilles polymères rendu correspondantes, ainsi que sur son utilisation pour fabriquer des emballages.
PCT/EP2010/059561 2009-07-09 2010-07-05 Dispersion de polymères soudable à froid, préparée par polymérisation en émulsion en présence d'un copolymère éthylène/acide (méth) acrylique WO2011003864A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9062233B2 (en) 2010-06-11 2015-06-23 Basf Se Multistage preparation of aqueous polymer dispersions for producing composite films
JP2017052958A (ja) * 2016-10-13 2017-03-16 ポーラ化成工業株式会社 水溶性コポリマー
US10316342B2 (en) 2017-01-06 2019-06-11 Greenlight Biosciences, Inc. Cell-free production of sugars
US10421953B2 (en) 2013-08-05 2019-09-24 Greenlight Biosciences, Inc. Engineered proteins with a protease cleavage site

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0798357A1 (fr) 1996-03-25 1997-10-01 BASF Aktiengesellschaft Utilisation de dispersions aqueuses comme laque thermosoudable
US5889101A (en) * 1995-02-15 1999-03-30 Basf Aktiengesellschaft Preparation of emulsifier-free aqueous polymer emulsions
US20060052529A1 (en) * 2003-02-07 2006-03-09 Surface Specialties S.A. Aqueous polymer dispersion and process
WO2007085588A1 (fr) 2006-01-30 2007-08-02 Basf Se Matiere auto-adhesive

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US5889101A (en) * 1995-02-15 1999-03-30 Basf Aktiengesellschaft Preparation of emulsifier-free aqueous polymer emulsions
EP0798357A1 (fr) 1996-03-25 1997-10-01 BASF Aktiengesellschaft Utilisation de dispersions aqueuses comme laque thermosoudable
US20060052529A1 (en) * 2003-02-07 2006-03-09 Surface Specialties S.A. Aqueous polymer dispersion and process
WO2007085588A1 (fr) 2006-01-30 2007-08-02 Basf Se Matiere auto-adhesive

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Title
W. MÄCHTLE, MAKROMOLEKULARE CHEMIE, vol. 185, 1984, pages 1025 - 1039

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9062233B2 (en) 2010-06-11 2015-06-23 Basf Se Multistage preparation of aqueous polymer dispersions for producing composite films
US10421953B2 (en) 2013-08-05 2019-09-24 Greenlight Biosciences, Inc. Engineered proteins with a protease cleavage site
JP2017052958A (ja) * 2016-10-13 2017-03-16 ポーラ化成工業株式会社 水溶性コポリマー
US10316342B2 (en) 2017-01-06 2019-06-11 Greenlight Biosciences, Inc. Cell-free production of sugars

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