EP2493996A1 - Adhésif sensible à la pression, contenant un mélange de polymères réalisé par polymérisation par étapes - Google Patents

Adhésif sensible à la pression, contenant un mélange de polymères réalisé par polymérisation par étapes

Info

Publication number
EP2493996A1
EP2493996A1 EP10774174A EP10774174A EP2493996A1 EP 2493996 A1 EP2493996 A1 EP 2493996A1 EP 10774174 A EP10774174 A EP 10774174A EP 10774174 A EP10774174 A EP 10774174A EP 2493996 A1 EP2493996 A1 EP 2493996A1
Authority
EP
European Patent Office
Prior art keywords
weight
polymerized
polymer
monomer
stage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10774174A
Other languages
German (de)
English (en)
Inventor
Matthias Gerst
Gerhard Auchter
Cornelis Petrus Beyers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP2493996A1 publication Critical patent/EP2493996A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the invention relates to a pressure-sensitive adhesive comprising a mixture of two polymers P1 and P2, wherein P1 is at least 50% by weight formed from a first main monomer M1, which, when polymerized as a homopolymer, has a glass transition temperature of less than 0 ° C, and wherein P2 is at least 50% by weight, formed of a second main monomer M2 which, when polymerized as a homopolymer, has a glass transition temperature of less than 0 ° C and which is different from M1. P2 is also formed of M1.
  • the polymerization of P2 is carried out by step polymerization, wherein in a first stage, a monomer composition comprising M2 is polymerized and in a second stage, a monomer composition containing M1 is polymerized.
  • the invention also relates to a process for producing a polymer dispersion, to a process for producing self-adhesive articles, and to self-adhesive articles produced by the process, in particular paper labels.
  • Adhesive adhesives require both good adhesion to the substrate and sufficient internal strength in the adhesive layer (cohesion). Adhesion and cohesion are opposite performance properties. Measures that improve adhesion generally result in cohesion deterioration at the same time and vice versa.
  • Pressure-sensitive adhesives based on aqueous polymer dispersions obtainable by emulsion polymerization have been known for a long time.
  • these are polyacrylates.
  • An improvement in the adhesion and cohesion has been achieved in such emulsion polymers hitherto by selecting suitable comonomers or additives.
  • US 2003/0125459 describes aqueous polymer dispersions prepared by polymerization in two stages and their use for producing pressure-sensitive adhesives.
  • WO 00/68335 describes pressure-sensitive adhesives comprising an aromatic emulsifier and a dispersion of a polymer of C 1 -C 12 -alkyl (meth) acrylates, vinylaromatic compound, ethylenically unsaturated hydroxy compound and optionally ethylenically unsaturated acids and further ethylenically unsaturated monomers.
  • US 5886122 describes a process for preparing solvent-based acrylic pressure-sensitive adhesives comprising a copolymer of alkyl (meth) acrylate ester monomers as the main constituent.
  • EP 586966 describes aqueous pressure-sensitive adhesives with high cohesion.
  • the pressure-sensitive adhesives contain copolymers prepared by two-stage emulsion polymerization of low glass transition temperature (less than -20 ° C) in the first stage and high glass transition temperature (greater than + 25 ° C) in the second stage.
  • the object of the present invention was to provide a pressure-sensitive adhesive, in particular for use in the production of paper labels with improved adhesion and / or cohesion, without impairing the respective other property.
  • a pressure sensitive adhesive is a viscoelastic adhesive whose set film remains permanently tacky and tacky at room temperature (20 ° C) when dry. Bonding on substrates takes place immediately by applying slight pressure.
  • the invention relates to a pressure-sensitive adhesive comprising a mixture of at least one first polymer P1 and at least one second polymer P2,
  • P1 and P2 are formed from radically polymerizable monomers, and P1 is at least 50% by weight, based on the sum of all monomers of the first polymer, of a first main monomer M1 which, when polymerized as a homopolymer, has a glass transition temperature of less than 0 ° C,
  • P2 is at least 50% by weight, based on the sum of all monomers of the second polymer, of a second main monomer M2 which, when polymerized as a homopolymer, has a glass transition temperature less than 0 ° C and which is different from M1 is
  • P2 is also formed of M1 and the polymerization of P2 is carried out by step polymerization,
  • a monomer composition containing monomer M2 is polymerized and in a later, second stage a monomer composition containing monomer M1 is polymerized, wherein the total amount of M2 used to form P2 is at least 80% by weight, preferably 90- 100 wt.% Is polymerized in the first stage and the total amount of M1 used to form P2 to at least 80 wt.%, Preferably 90-100 wt.% Is polymerized in the second stage.
  • the polymers P1 and P2 are therefore composed mainly of mutually different, sticky or soft monomers.
  • the main constituent of the polymer P1 is a minor constituent of polymer P2 and copolymerized with the main constituent of P2 by step polymerization in a second step.
  • the monomers M1 and M2 are characterized in that, when polymerized into homopolymers, they each have a glass transition temperature of less than 0 ° C., preferably less than -20 ° C., particularly preferably less than -40 ° C.
  • they are alkyl acrylates. Suitable alkyl acrylates are, for example, alkyl acrylates having 2 to 10 C atoms in the alkyl group.
  • the monomers M1 and M2 are preferably selected from n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethyl hexyl acrylate and propylheptyl acrylate. In a preferred embodiment, monomer M1 is 2-ethylhexyl acrylate and monomer M2 is butyl acrylate.
  • the polymers used according to the invention are obtainable by free-radical polymerization of ethylenically unsaturated compounds (monomers).
  • the polymers may be composed of other ethylenically unsaturated compounds except from the monomers M1 and M2.
  • the polymer P1 is preferably composed of
  • the polymer P2 is preferably composed of
  • Suitable vinylaromatic compounds are vinylaromatics having up to 20 C atoms, in particular vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • Suitable ethylenically unsaturated acids are monomers having carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Examples which may be mentioned are acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. The content of acid monomers in the polymer may, for. B.
  • the acid groups may be in the form of their salts.
  • Other ethylenically unsaturated compounds which may be copolymerized are, for example, of C 1 -C 2 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of from 1 to 10 ° C -Atome-containing alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
  • Examples include (meth) acrylic acid alkyl esters having a C 1 -C 10 -alkyl radical, such as methyl methacrylate and methyl acrylate.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, Versaticklareviny- ester and vinyl acetate.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • Vinyl ethers include, for example, vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds may be mentioned ethylene, propylene, butadiene, isoprene and chloroprene.
  • hydroxyl-containing monomers in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates or (meth) acrylamide.
  • Phenyloxyethyl glycol mono- (meth) acrylate, glycidyl (meth) acrylate, aminoalkyl (meth) acrylates, such as, for example, are also suitable as further monomers.
  • Alkyl groups preferably have from 1 to 20 carbon atoms.
  • Other monomers which may also be mentioned are crosslinking monomers. The other monomers are generally used in minor amounts, their proportion is generally less than 20 wt.%, In particular less than 10 wt.%.
  • the polymer P1 is composed of
  • (V) 0 to 25 wt.%, In particular 0.1 to 20 wt.% Of other ethylenically unsaturated compounds selected from (i) different C1 to C20 alkyl (meth) acrylates, vinyl esters of up to 20 carbon atoms containing carboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds.
  • ethylenically unsaturated compounds selected from (i) different C1 to C20 alkyl (meth) acrylates, vinyl esters of up to 20 carbon atoms containing carboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds.
  • the polymers are preferably prepared by emulsion polymerization, and are therefore preferably a mixture of two emulsion polymers.
  • the pressure-sensitive adhesive is then an aqueous polymer dispersion prepared by emulsion polymerization.
  • emulsion polymerization ethylenically unsaturated compounds (monomers) in water, wherein ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds for stabilizing the monomer droplets and the polymer particles later formed from the monomers.
  • the surface-active substances are usually used in amounts of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the monomers to be polymerized.
  • Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers.
  • Emulsifiers whose molecular weight, unlike the protective colloids, are usually below 2000 g / mol, are preferably used as surface-active substances.
  • Anionic and nonionic emulsifiers are preferably used as surface-active substances.
  • emulsifiers are, for example, ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: Cs to C36), ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9), Alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali metal and ammonium salts of alkyl sulfates (alkyl group: Cs to C12) of ethoxylated alkanols (EO degree: 4 to 30, alkyl group: C12 to Cis) of ethoxylated alkylphenols (EO degree : 3 to 50, alkyl radical: C 4 - to C 9), of alkylsulfonic acids (alkyl radical: C 12 - to Cis) and of alkylarylsulfonic acids (alkyl radical: C 9 - to Cis).
  • emulsifiers are compounds of the general formula
  • R5 and R6 are hydrogen or C4 to C14 alkyl and are not hydrogen at the same time, and X and Y may be alkali metal ions and / or ammonium ions.
  • R5, R6 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 R5 and R6 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, R5 is a branched alkyl radical having 12 C atoms and R6 is hydrogen or R5.
  • emulsifiers include Dowfax ® 2 A1, Emulan® ® NP 50, Dextrol ® OC 50, 825 emulsifier, emulsifier 825 S, Emulan ® OG, Texapon ® NSO, Ne kanil ® 904 S, Lumiten® l-RA, Lumiten E 3065, Disponil ® FES 77, Lutensol ® AT 18, Steinapol VSL, Emulphor NPS 25.
  • ionic emulsifiers or protective colloids are preferred.
  • ionic emulsifiers in particular salts and acids, such as carboxylic acids, sulfonic acids and sulfates, sulfonates or carboxylates.
  • salts and acids such as carboxylic acids, sulfonic acids and sulfates, sulfonates or carboxylates.
  • mixtures of ionic and nonionic emulsifiers may also be used.
  • the emulsion polymerization can be started with water-soluble initiators.
  • Water-soluble initiators are e.g. Ammonium and alkali metal salts of peroxodisulfuric acid, e.g. Sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. tert-butyl hydroperoxide.
  • Also suitable as initiators 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 e.g. to the above-mentioned initiators for emulsion polymerization.
  • the reducing component is e.g.
  • alkali metal salts of sulfurous acid e.g. Sodium sulfite, sodium hydrogen sulfite, alkali metal salts of the desulfurous 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 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.
  • Typical redox initiator systems are e.g.
  • the individual components, e.g. the reducing component may also be mixtures e.g. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the initiators 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 of initiators 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1, 0 to 10 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • molecular weight regulators can be used, for example in amounts of from 0.1 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be polymerized. This can be reduced by a chain termination reaction, the molecular weight of the emulsion polymer.
  • the regulators are bound to the polymer, generally to the chain end.
  • the amount of regulators is particular 0.05 to 4 parts by weight, particularly preferably 0.05 to 0.8 parts by weight and very particularly preferably 0.1 to 0.6 parts by weight, based on 100 parts by weight of the monomers to be polymerized.
  • Suitable regulators are compounds having a thiol group, such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethanol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan.
  • the regulators are generally low molecular weight compounds having a molecular weight of less than 2000, in particular less than 1000 g / mol.
  • the emulsion polymerization is generally carried out at 30 to 130 ° C, preferably at 50 to 90 ° C.
  • the polymerization medium may consist of water only, as well as of 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 , gradually or with the addition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.
  • a polymer seed can be provided.
  • 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 one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In detail, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization. To remove the
  • Residual monomers are usually also after the end of the actual emulsion polymerization, i. added after a conversion of the monomers of at least 95% initiator.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor bottom.
  • aqueous dispersions of the polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%.
  • dispersions having the highest possible solids content are preferred.
  • one should set a bimodal or polymodal particle size since otherwise the viscosity becomes too high and the dispersion can no longer be handled.
  • the generation of a new particle generation for example, by adding seed (EP 81083), by adding excess emulsifier quantities or by adding miniemulsions.
  • Another benefit associated with low viscosity at high solids content is improved coating behavior at high solids levels.
  • the generation of a new / new particle generation (s) can take place at any time. It depends on the particle size distribution desired for a low viscosity.
  • the polymer thus prepared is preferably used in the form of its aqueous dispersion.
  • the size distribution of the dispersion particles may be monomodal, bimodal or multimodal.
  • the average particle size of the polymer particles dispersed in the aqueous dispersion is preferably less than 400 nm, in particular less than 200 nm. Particularly preferably, the average particle size is between 140 and 200 nm.
  • average particle size is meant the d 50 value of the particle size distribution, ie 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.
  • the particle size can be up to 1000 nm.
  • the pH of the polymer dispersion is preferably adjusted to pH greater than 4.5, in particular to a pH of between 5 and 8.
  • the glass transition temperature of the polymers P1 and P2 is preferably -60 to 0 ° C., particularly preferably from -60 to -10 ° ° C and very particularly preferably from -60 to -20 ° ° C.
  • the glass transition temperature can be determined by customary methods such as differential thermal analysis or Differential scanning calorimetry (see eg ASTM 3418/82, so-called "midpoint tempera- ture").
  • the pressure-sensitive adhesive preferably contains the polymers in the form of the aqueous polymer dispersion as obtained or obtainable by the emulsion polymerization.
  • the pressure-sensitive adhesives can consist solely of the polymers or of the aqueous dispersion of the polymers.
  • the pressure-sensitive adhesive may also contain other additives, e.g. Fillers, dyes, leveling agents, thickeners, preferably associative thickeners, defoamers, plasticizers, pigments, wetting agents or tackifiers (tackifying resins). Tackifiers are z. From Adhesive Age, July 1987, pages 19-23 or Polym. Mater. Be. Closely. 61 (1989), pages 588-592.
  • the pressure-sensitive adhesives may in particular comprise wetting aids, eg. As fatty alcohol ethoxylates, alkylphenol ethoxylates, Nonylphenolethoxylate, Polyoxye- thylene / -propylene or sodium dodecylsulfonates.
  • wetting aids eg. As fatty alcohol ethoxylates, alkylphenol ethoxylates, Nonylphenolethoxylate, Polyoxye- thylene / -propylene or sodium dodecylsulfonates.
  • the amount of additives 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).
  • Tackifiers are, for example, natural resins, such as rosin resins and their resulting by disproportionation or isomerization, polymerization, dimerization, hydrogenation Derivatives. These may be in their salt form (with, for example, monovalent or polyvalent counterions (cations) or preferably in their esterified form.) Alcohols used for esterification may be monovalent or polyvalent, for example, methanol, ethanediol, diethylene glycol, triethylene glycol, 1 Furthermore, hydrocarbon resins, eg coumarone-indene resins, polyterpene resins, hydrocarbon resins based on unsaturated C-H compounds, such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, are also found Cyclo- pentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene,
  • the polyacrylates preferably consist of at least 60, in particular at least 80 wt .-% of Ci-Cs alkyl (meth) acrylates
  • Preferred tackifiers are natural or chemically modified rosin resins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
  • the tackifiers can be added in a simple manner to the polymer dispersion.
  • the tackifiers are preferably themselves in the form of an aqueous dispersion.
  • the amount by weight of the tackifiers is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight. based on 100 parts by weight of polymer (solid / solid).
  • the adhesive composition according to the invention can be used for the production of self-adhesive articles.
  • the articles are at least partially coated with the pressure-sensitive adhesive.
  • the self-adhesive articles are removable after the bond.
  • the self-adhesive articles may be e.g. to deal with foils, ribbons or labels.
  • Suitable carrier materials are e.g. Paper, plastic films and metal foils.
  • Self-adhesive tapes according to the invention may be tapes coated on one or both sides from the above substances.
  • Self-adhesive labels according to the invention can be labels made of paper or a thermoplastic film. As the thermoplastic film, e.g.
  • Films of polyolefins e.g., polyethylene, polypropylene
  • polyolefin copolymers films of polyesters (e.g., polyethylene terephthalate) or polyacetate.
  • the surfaces of the thermoplastic polymer films are preferably carbon-treated.
  • the labels are coated on one side with adhesive.
  • Preferred substrates for the self-adhesive articles are paper and polymer films.
  • Preferred self-adhesive articles are paper labels.
  • the articles are at least partially coated on at least one surface with a pressure-sensitive adhesive according to the invention.
  • the adhesive can be applied to the articles by conventional methods such as rolling, knife coating or brushing.
  • the order quantity is preferably 0.1 to 30 g, more preferably 2 to 20 g of solid per m 2 .
  • After application generally followed by a drying step to remove the water or the solvent.
  • the water can be dried by eg 50 to 150 ° C are removed.
  • the resulting coated substrates are used, for example, as self-adhesive articles, such as labels, adhesive tapes or films.
  • the carriers can be cut into adhesive tapes, labels or foils before or after application of the adhesive.
  • the pressure-sensitive adhesive-coated side of the substrates, with a release paper, z. For example, be covered with a siliconized paper.
  • the substrates to which the self-adhesive articles can be advantageously applied it may be e.g. to trade metal, wood, glass, paper or plastic.
  • the self-adhesive articles are particularly suitable for bonding to packaging surfaces, cartons, plastic packaging, books, windows, motor vehicle bodies or body parts.
  • One embodiment of the invention is a self-adhesive paper label.
  • the carrier material is paper and has a first surface and a second surface, wherein the first surface is self-adhesive and at least partially coated with a pressure-sensitive adhesive according to the invention and wherein the second surface may be printed or the second surface or the label at least partially colored can be.
  • the coloration may e.g. be produced by a colored coating with pigments or dyes, by color printing or in thermal papers by the action of heat.
  • the invention also relates to a process for preparing a polymer dispersion comprising a mixture of at least one first polymer P1 prepared by emulsion polymerization and at least one second polymer P2 produced by emulsion polymerization,
  • P1 and P2 are formed from radically polymerizable monomers, and wherein P1 is at least 50% by weight, based on the sum of all monomers of the first polymer, of a first main monomer M1 which, when polymerized as a homopolymer, has a glass transition temperature of less than 0 ° C,
  • P2 is at least 50% by weight, based on the sum of all monomers of the second polymer, of a second main monomer M2 which, when polymerized as a homopolymer, has a glass transition temperature less than 0 ° C and which is different from M1 is
  • P2 is also formed of M1 and the polymerization of P2 is carried out by step polymerization,
  • a monomer composition is polymerized which contains monomer M2 and in a later, second stage a monomer composition is polymerized which contains monomer M1, the total amount of M2 used to form P2 being at least 80% by weight , Preferably 90- 100 wt.% Is polymerized in the first stage and the total for the formation of P2 employed amount of M1 to at least 80 wt.%, Preferably 90-100 wt.% Is polymerized in the second stage.
  • the invention also relates to a process for the production of self-adhesive articles.
  • an above-described, inventive pressure-sensitive adhesive is provided and a carrier is coated with this pressure-sensitive adhesive.
  • the invention also relates to self-adhesive articles obtainable according to this process, in particular self-adhesive paper labels.
  • the self-adhesive articles according to the invention have very good adhesive properties, in particular a good adhesion to the substrates and a high cohesion (internal strength in the adhesive layer).
  • polymer P1 an emulsion polymer is used
  • polymer P2 an emulsion polymer prepared by step polymerization is used.
  • the emulsion polymer is mixed in a weight ratio of 1: 1 (based on solids) with the emulsion polymer P1.
  • the polymer mixture was weighted Ratio 70:30 (based on solids) mixed with the tackifier Snowtack® 932 and it was 0.5 wt% (based on solids) wetting aid Lumiten® I-SC added.
  • Comparative Example C1 Comparative Example C1
  • the polymer P2 used is an emulsion polymer prepared by simultaneous polymerization of:
  • the emulsion polymer is mixed in a weight ratio of 1: 1 (based on solids) with the emulsion polymer P1.
  • the polymer mixture was mixed in a weight ratio of 70:30 (based on solids) with the tackifier Snowtack® 932 and 0.5% by weight (based on solids) wetting aid Lumiten® I-SC was added.
  • the polymer P2 used is an emulsion polymer prepared by simultaneous polymerization of:
  • the emulsion polymer is mixed in a weight ratio of 1: 1 (based on solids) with the emulsion polymer P1.
  • the polymer mixture was mixed in a weight ratio of 70:30 (based on solids) with the tackifier Snowtack® 932 and 0.5% by weight (based on solids) wetting aid Lumiten® I-SC was added.
  • the pressure-sensitive adhesives were coated at a rate of 18 g / m 2 on label paper (Herma, 75 g / m 2 , unprimed) as carrier (by transfer, coating first of silicone paper and transfer to paper) and 3 minutes at 90 ° C. overall dries. Subsequently, the peel strength (adhesion), the shear strength (cohesion) and the Quickstick were determined.
  • the support 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 ⁇ 25 mm were glued onto steel, rolled once with a 1 kg roll, stored for 10 minutes (under standard conditions). 50% rel. Humidity 1 bar, 23 ° C) and then suspended with a 1 kg weight (in standard climate). The measure of shear strength was the time in hours until the weight dropped; in each case the average was calculated from 5 measurements.
  • a 25 mm wide test strip was glued onto a test specimen made of steel or polyethylene and rolled once with a 1 kg roller. It was then clamped at one end into the upper jaws of a tensile-strain tester. The adhesive strip was removed from the test area at 300 mm / min at a 180 ° angle, ie the adhesive strip was bent over and pulled off parallel to the test piece and the force required for this was measured. The measure of the peel strength was the force in N / 25 mm, which resulted as an average of five measurements. The peel strength was determined 24 hours after the bonding. After this time, the adhesive power has fully developed.
  • the test methods essentially correspond to the Finat test methods (FTM) No.
  • the force is determined which opposes an adhesive applied to a carrier material by adhesion without pressure to a substrate at a defined take-off speed from the substrate.
  • the carrier material is label paper 75 g / m 2
  • substrate is polyethylene.
  • a test strip 25 mm wide and 250 mm long is cut from the adhesive-coated carrier and stored for 16 hours under standard conditions (23 ° C., 50% relative humidity). The two ends of the test strip are folded over to about 1 cm in length with the adhesive side inwards. From the adhesive tape, a loop is formed with the adhesive side to the outside, summarized the two ends and clamped in the upper clamp of a tensile tester.
  • test substrate holder is clamped in the lower clamp and the test substrate is inserted.
  • the tape loop is lowered by the tensile testing machine at a speed of 300 mm / minute, so that the adhesive side of the test strip adheres to the substrate without additional pressure.
  • the tensile tester is stopped and immediately raised again when the lower edge of the upper clamp is 40 mm above the substrate.
  • the test result is given in N / 25 mm width. The highest value of the reading is read as a measure of the surface tackiness. From at least 3 individual results an average value is formed. Table 1 Test Results Peel Strength and Shear Strength
  • the inventive example shows an improvement in both the peel strength (adhesion), as well as in the shear strength (cohesion) and the surface tack (Quickstick).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un adhésif sensible à la pression, contenant un mélange de deux polymères P1 et P2 formés à partir de monomères polymérisables par voie radicalaire, au moins 50 % du poids du polymère P1 étant formé à partir d'un premier monomère principal M1, qui, lorsqu'il est polymérisé sous forme d'homopolymère, possède une température de transition vitreuse inférieure à 0°C, et au moins 50 % du poids du polymère P2 étant formé à partir d'un second monomère principal M2, qui, lorsqu'il est polymérisé sous forme d'homopolymère, possède une température de transition vitreuse inférieure à 0°C et qui est différent de M1. P2 est également formé à partir de M1. P2 est polymérisé par polymérisation par étapes, une composition de monomères contenant M2 étant polymérisée au cours d'une première étape et une composition de monomères contenant M1 étant polymérisée au cours d'une seconde étape.
EP10774174A 2009-10-27 2010-10-25 Adhésif sensible à la pression, contenant un mélange de polymères réalisé par polymérisation par étapes Withdrawn EP2493996A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25510809P 2009-10-27 2009-10-27
PCT/EP2010/066024 WO2011051206A1 (fr) 2009-10-27 2010-10-25 Adhésif sensible à la pression, contenant un mélange de polymères réalisé par polymérisation par étapes

Publications (1)

Publication Number Publication Date
EP2493996A1 true EP2493996A1 (fr) 2012-09-05

Family

ID=43098883

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10774174A Withdrawn EP2493996A1 (fr) 2009-10-27 2010-10-25 Adhésif sensible à la pression, contenant un mélange de polymères réalisé par polymérisation par étapes

Country Status (2)

Country Link
EP (1) EP2493996A1 (fr)
WO (1) WO2011051206A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102597150A (zh) 2009-11-05 2012-07-18 巴斯夫欧洲公司 丙烯酸正丁酯、丙烯酸乙酯、乙酸乙烯酯和酸单体的压敏粘合剂聚合物
US9926452B2 (en) * 2012-11-15 2018-03-27 Basf Se Use of aqueous polymer dispersion in coating agents for improving colour retention

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3147008A1 (de) 1981-11-27 1983-06-01 Röhm GmbH, 6100 Darmstadt Verfahren zur herstellung von waessrigen, hochkonzentrierten bimodalen kunststoffdispersionen
EP0586966A3 (en) 1992-09-10 1994-06-15 Nat Starch Chem Invest High cohesion waterborne pressure sensitive adhesives
ATE221899T1 (de) 1995-03-31 2002-08-15 Seikisui Chemical Co Ltd Verfahren zur herstellung von acrylhaltigen druckempfindlichen klebstoffen vom lösungstyp und medizinischer druckempfindlicher klebstoff
DE19920807A1 (de) 1999-05-06 2000-11-09 Basf Ag Haftklebstoffe
US20030125459A1 (en) 2001-12-27 2003-07-03 Basf Akiengesellschaft Aqueous polymer dispersions, their preparation and use
DE10209817A1 (de) * 2002-03-06 2003-09-25 Basf Ag Wässrige Polymerdispersionen, ihre Herstellung und ihre Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011051206A1 *

Also Published As

Publication number Publication date
WO2011051206A1 (fr) 2011-05-05

Similar Documents

Publication Publication Date Title
EP2812407B1 (fr) Dispersion polymère aqueuse pouvant s'utiliser comme agent poisseux pour adhésifs, obtenue par polymérisation en émulsion à base d'acryl(méth)acrylates c1 à c20
EP2496655B1 (fr) Adhésif polymérique fabriqué de n-butylacrylate, ethylacrylate, vinylacetate et de monomère d'acide
EP2697323B1 (fr) Dispersion d'adhésif sensible à la pression, contenant des polymères préparés par polymérisation par étapes lesquels comportent des groupes uréido ou analogues
EP2274349B1 (fr) Dispersions aqueuses de polymère pour colles autoadhésives
EP2619239B1 (fr) Adhésifs sensibles à la pression basés sur des dispersions aqueuses obtenues par procédé en plusieurs étapes
EP3577165B1 (fr) Composition adhésive à un composant a base du gel avec réseautage réversible à base de sels métalliques
EP2697324B1 (fr) Dispersion d'adhésif de contact contenant des polymères comportant des groupes uréido ou des groupes analogues uréido et comportant des groupes glycidyle
EP1479744B1 (fr) Adhésifs de contact comprenant des polymères et des composés de silicium
EP2084240B1 (fr) Adhésif sensible à la pression contenant un acrylate d'alkyle en c10
EP2510067B1 (fr) Adhésif de contact pour films pvc
EP1846530B1 (fr) Colle auto-adhesive pour etiquettes en papier a imprimer
EP2334746B1 (fr) Composition adhésive pour étiquettes autocollantes repositionnables sans plastifiant
WO2016000938A1 (fr) Procédé de collage d'un substrat sur des surfaces froides et humides
WO2007125031A1 (fr) Adhésif contenant n-butylacrylate et hydroxybutyl(méth)acrylate
WO2005100502A1 (fr) Colle adhesive pour feuilles de pvc
WO2007125040A1 (fr) Adhésif contenant 2-éthylhexylacrylate et hydroxybutyl(méth)acrylate
EP2493996A1 (fr) Adhésif sensible à la pression, contenant un mélange de polymères réalisé par polymérisation par étapes
WO2009115473A1 (fr) Procédé pour fabriquer des articles autocollants à base de dispersions polymères contenant des esters d’acide dicarboxylique sulfonés
EP2547741A1 (fr) Film polymère à morphologie de film multiphase
WO2003072654A2 (fr) Agents auto-adhesifs contenant du polyethylene
EP1862520A1 (fr) etiquettes en pellicule
WO2007144255A1 (fr) Adhésif sensible à la pression contenant une émulsion polymère comprenant du butyl(méth)acrylate tertiaire
DE102005029628A1 (de) Verfahren zur Herstellung von Emulsionspolymerisaten für Haftklebstoffe
WO2006136575A1 (fr) Procede de production de polymeres en emulsion acides pour des matieres adhesives

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120529

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130108