EP2121782A1 - Pressure-sensitive adhesive for paper labels - Google Patents

Pressure-sensitive adhesive for paper labels

Info

Publication number
EP2121782A1
EP2121782A1 EP08701460A EP08701460A EP2121782A1 EP 2121782 A1 EP2121782 A1 EP 2121782A1 EP 08701460 A EP08701460 A EP 08701460A EP 08701460 A EP08701460 A EP 08701460A EP 2121782 A1 EP2121782 A1 EP 2121782A1
Authority
EP
European Patent Office
Prior art keywords
weight
acrylate
meth
acid
monomers
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Withdrawn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
EP08701460A
Other languages
German (de)
French (fr)
Inventor
Petra SCHÖCKER
Karl-Heinz Schumacher
Heiko Diehl
Udo Spuhler
Erich Ettel
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
Priority to EP08701460A priority Critical patent/EP2121782A1/en
Publication of EP2121782A1 publication Critical patent/EP2121782A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F2/18—Suspension polymerisation
    • 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
    • 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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer

Definitions

  • the invention relates to pressure-sensitive adhesive coated paper labels, wherein
  • the pressure-sensitive adhesive contains no vinyl acetate in free or copolymerized form
  • - contains as binder an emulsion polymer, which is composed of
  • Labels are pressure-sensitive adhesive coated self-adhesive articles.
  • the labels should stick as well as possible on different substrates.
  • the substrates may be z. B. to deal with packaging or containers made of different materials.
  • substrates eg. As packaged foods that are stored permanently at reduced temperature. Odor-intensive pressure-sensitive adhesives are not suitable for such uses.
  • paper as a carrier material for labels, there are special requirements due to the porosity and the associated permeability. Compared to films as a carrier material, the odor caused by volatile components is particularly noticeable.
  • Suitable pressure-sensitive adhesives require both good adhesion and sufficient internal strength in the adhesive layer (cohesion) even at low temperatures. Both properties are generally opposite, d. H. An improvement of one property leads to the deterioration of the other.
  • Pressure-sensitive adhesives are known from EP-A 625 557 which, in addition to vinylaromatics, hydroxyalkyl acrylates and methyl methacrylate, necessarily contain at least 5% by weight of methyl acrylate.
  • EP-A-1342762 describes pressure-sensitive adhesives which imperatively contain hydroxyalkyl acrylates, vinyl aromatics and optionally vinyl acetate.
  • the subject of WO 00/68335 are pressure-sensitive adhesives which are prepared with an aromatic emulsifier; the pressure-sensitive adhesives contain various alkyl (meth) acrylates, eg. As well as ethylhexyl acrylate and methyl methacrylate, in addition to vinyl aromatics, hydroxy compounds and ethylenically unsaturated acids.
  • the non-prepublished patent application PF 58054 describes pressure sensitive adhesives containing hydroxy monomers and tertiary butyl (meth) acrylate.
  • Object of the present invention were paper labels with good application properties, especially good adhesive properties even at low temperatures; the cohesion should still be sufficient, in particular, the coated carrier should be processed by cutting or punching to paper labels.
  • the paper labels are coated with a pressure sensitive adhesive.
  • the pressure-sensitive adhesive contains no vinyl acetate, either in free form or in polymerized form.
  • the pressure-sensitive adhesive contains as binder an emulsion polymer.
  • the emulsion polymer is composed of:
  • C 6 -C 10 alkyl (meth) acrylates are n-butyl acrylate and 2-ethylhexyl acrylate or mixtures thereof. Particularly preferred is 2-ethylhexyl acrylate.
  • the content of C6-C10 alkyl (meth) acrylates in the emulsion polymer is preferably 75 to 95% by weight, more preferably 78 to 90% by weight and most preferably 80 to 90% by weight.
  • the content of methyl methacrylate (MMA) in the emulsion polymer is preferably from 3 to 15% by weight, more preferably from 4 to 12% by weight and most preferably from 4 to 8% by weight.
  • Preferred vinylaromatic monomer c) is styrene.
  • the content of the vinylaromatic monomer in the emulsion polymer is preferably 1 to 8, more preferably 1 to 5 wt .-% and most preferably 2 to 5 wt .-%.
  • Preferred hydroxyalkyl (meth) acrylates are the C 2 to C 12 hydroxyalkyl (meth) acrylates and in particular the C 2 to C 6 hydroxyalkyl (meth) acrylates. Very particular preference is given to hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate or hydroxybutyl methacrylate.
  • the content of the hydroxyalkyl (meth) acrylates in the emulsion polymer is preferably 0.5 to 8, more preferably 1 to 5 wt .-% and most preferably 1, 5 to 4 wt .-%.
  • Preferred monomers having at least one acid or acid anhydride group (e) are z.
  • the content of these monomers in the emulsion polymer is preferably 0.5 to 4, more preferably 0.6 to 3.5 wt .-% and most preferably 0.8 to 3 wt .-%.
  • the emulsion polymer optionally contains tertiary butyl acrylate or tertiary butyl (meth) acrylate (abbreviated tertiary butyl (meth) acrylate).
  • the emulsion polymer necessarily contains tertiary butyl (meth) acrylate.
  • the content of the tertiary butyl (meth) acrylate in the emulsion polymer is preferably 0.2 to 10, particularly preferably 0.5 to 5 wt.% And most preferably 0.8 to 5 wt.%.
  • the emulsion polymer may also contain further monomers (g).
  • the emulsion polymer necessarily contains not more than 3% by weight, preferably not more than 2% by weight, of methyl acrylate. In a particular embodiment, the emulsion polymer contains less than 0.5% by weight of methyl acrylate and in particular less than 0.1% by weight of methyl acrylate. Most preferably, the emulsion polymer does not contain methyl acrylate.
  • ethylenically unsaturated nitriles ethylenically unsaturated amides
  • the content of the further monomers in the emulsion polymer may preferably be 0 to 10, more preferably 0 to 8 wt .-% and most preferably 0 to 5 wt .-%. be. In a particular embodiment, other monomers are not included.
  • the emulsion polymer is preferably composed of
  • the emulsion polymer is composed of:
  • the emulsion polymer is composed of:
  • the glass transition temperature of the emulsion polymer is preferably -70 to 0 ° C, and more preferably -70 to -10 ° C; most preferably -60 to -30 ° C.
  • the glass transition temperature can be determined by customary methods such as differential thermal analysis or differential scanning calorimetry (see, for example, ASTM 3418/82, so-called “mid-point temperature”).
  • the polymers are prepared by emulsion polymerization, which is therefore an emulsion polymer.
  • ethylenically unsaturated compounds are polymerized in water using ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers as surface-active compounds for stabilizing the monomer droplets and the polymer particles later formed from the monomers.
  • Suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg Thieme Verlag, Stuttgart, 1961, p. 41 1 to 420.
  • Suitable emulsifiers are anionic, cationic and nonionic emulsifiers into consideration.
  • Emulsifiers whose molecular weight, unlike the protective colloids, are usually below 2000 g / mol, are preferably used as surface-active substances.
  • the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests.
  • Anionic and nonionic emulsifiers are preferably used as surface-active substances. Common accompanying emulsifiers are z.
  • ethoxylated fatty alcohols EO degree: 3 to 50, alkyl: Cs to C36
  • ethoxylated mono-, di- and tri-alkylphenols EO degree: 3 to 50, alkyl: C 4 - to Cg
  • alkali metal salts of dialkyl esters of sulfosuccinic acid and of alkali metal and ammonium salts of alkyl sulfates alkyl radical: Cs to C12
  • ethoxylated alkylphenols EO degree: 3 to 50, alkyl radical: C 4 to Cg
  • alkylsulfonic acids alkyl radical: C 12 to Cis
  • alkylarylsulfonic acids alkylarylsulfonic acids
  • emulsifiers are compounds of the general formula I.
  • R 5 and R 6 is hydrogen or C 4 - to C 4 represent alkyl and are not simultaneously hydrogen
  • X and Y can 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 alkyl radical having 12 carbon atoms and R 6 is hydrogen or R. 5 Industrial mixtures verwen- det which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of 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.
  • emulsifiers are z. B. Dowfax ® 2 A1, Emulan ® NP 50, Dextrol ® OC 50, 825 emulsifier, emulsifier 825 S, Emulan ® OG, Texapon ® NSO, Nekanil ® 904 S, Lumiten ® I-RA, Lumiten E 3065, Disponil FES 77 , Lutensol AT 18, Steinapol VSL, E-mulphor NPS 25.
  • the preparation of the emulsion polymer is particularly preferably carried out using emulsifiers, as described in WO 00/68335.
  • emulsifiers of the above formula I particularly preferred are mixtures of emulsifiers of the formula I with alkoxylated fatty acid sulfates of the formula (II)
  • R 8 C 1 -C 18 alkyl, preferably C 6 to C 16 alkyl
  • n an integer of 1 to 40, preferably 2 to 30
  • K a cation, preferably an alkali cation or ammonium ion
  • the surfactant is usually used in amounts of from 0.1 to 10% by weight, based on the monomers to be polymerized.
  • water-soluble initiators are usually used for the radical polymerization of the monomers.
  • Water-soluble initiators for the emulsion polymerization are z.
  • ammonium and alkali metal salts of peroxodisulfuric z.
  • sodium peroxodisulfate, hydrogen peroxide or organic peroxides eg. B. 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 z. B. to the above-mentioned initiators for emulsion polymerization.
  • the reduction components are, for. B. to alkali metal salts of sulfurous acid, such as.
  • alkali metal salts of sulfurous acid such as.
  • sodium sulfite, sodium hydrogen sulfite, alkali metal salts of Dischwef- ligen acid such as sodium disulfite
  • 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 use of soluble metal compounds whose metallic component can occur in multiple valence states. Usual Red Ox initiator systems are 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.
  • regulators can be used. Regulators cause a chain termination reaction and thus reduce the molecular weight of the polymer.
  • the regulators are bound to the polymer, generally to the chain end.
  • the amount of regulator may in 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, in particular, compounds having a mercapto group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan.
  • the regulators are generally low molecular weight compounds with 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, 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 feed process can be carried out in a stepwise or gradient mode. Preferably, 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. In the polymerization can also z. B. be presented for better adjustment of the particle size of a polymer seed.
  • 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 particular, 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.
  • a subset of the monomers may, if desired, be initially charged in the polymerization vessel at the beginning of the polymerization, the other monomers, or all monomers, if no monomers are introduced, are added in the feed process during the polymerization.
  • the regulator can be partially submitted, be added in whole or in part during the polymerization or towards the end of the polymerization.
  • dispersions having the highest possible solids content are preferred.
  • solids contents> 60 wt .-% you should set a bimodal or polymodal particle size, otherwise the viscosity is too high, and the dispersion is no longer manageable.
  • the generation of a new particle generation can be carried out, for example, by adding seed (EP 81 083), by adding excess amounts of emulsifier 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 monomers are added continuously at least partially during the polymerization. In some cases, monomers can also be initially charged in the polymerization vessel before the beginning of the polymerization.
  • a maximum of 30% by weight of the total amount of the monomers is initially charged in the polymerization vessel.
  • the remaining monomers ie preferably at least 70% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight, are continuously added during the polymerization.
  • no mono meren, ie the total amount of monomers is fed during the polymerization.
  • 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 .-%. Particular preference is given to aqueous dispersions of the emulsion polymer having a content of the emulsion polymer of greater than 60% by weight, based on the total polymer dispersion.
  • the emulsion polymer thus prepared is preferably used in the form of its aqueous dispersion.
  • the emulsion polymer is used as or in pressure-sensitive adhesives.
  • the pressure-sensitive adhesive preferably contains the emulsion polymer initially in the form of the aqueous polymer dispersion as obtained or obtainable by the emulsion polymerization.
  • the pressure-sensitive adhesive can consist exclusively of the emulsion polymer or its aqueous dispersion.
  • the pressure-sensitive adhesive may also contain other additives.
  • Tackifiers are z. From Adhesive Age, July 1987, pages 19-23 or Polym. Mater. Be. Closely. 61 (1989), pages 588-592.
  • Tackifiers are z.
  • natural resins such as rosins and their by disproportionation or isomerization, polymerization, dimerization, hydrogenation resulting derivatives. These may 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 may be mono- or polyvalent Examples are methanol, ethanediol, Diethylene glycol, triethylene glycol, 1, 2,3-propanethiol, pentaerythritol.
  • hydrocarbon resins eg.
  • polyester terpene resins hydrocarbon resins based on unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, a-methylstyrene , Vinyltoluene Use fertil.
  • unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, a-methylstyrene , Vinyltoluene Use fertil.
  • tackifiers are increasingly also polyacrylates, which have a low molecular weight used. These polyacrylates preferably have a weight-average molecular weight M w of less than 30,000.
  • the polyacrylates preferably contain at least 60, in particular at least 80% by weight of C 1 -C 8 -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 emulsion polymers, preferably to the aqueous dispersions of the polymers.
  • the tackifiers are preferably themselves in the form of an aqueous dispersion.
  • Pressure-sensitive adhesive preferably contains tackifiers.
  • the pressure-sensitive adhesive preferably contains from 50 to 95% by weight of emulsion polymer and from 5 to 50% by weight of tackifying resin, based on the solid of the pressure-sensitive adhesive, that is to say the pressure-sensitive adhesive. H. without water.
  • thickening agents preferably associative thickeners, defoamers, plasticizers, pigments, wetting agents or fillers when used as a pressure-sensitive adhesive use and are added to the pressure-sensitive adhesive.
  • the pressure-sensitive adhesives for a better wetting of surfaces, the pressure-sensitive adhesives, in particular wetting aids, z.
  • wetting aids As fatty alcohol ethoxylates, Alkylphenolethoxylate, sulfosuccinic, Nonylphenolethoxylate, polyoxyethylene / -propylenes or sodium dodecylsulfonate included.
  • 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 emulsion polymer (solid).
  • the pressure-sensitive adhesives are used according to the invention for the production of paper labels.
  • Paper labels are self-adhesive articles with paper backing.
  • the paper is coated on at least one side, preferably on one side, with the pressure-sensitive adhesive.
  • the liquid adhesive based on the water content can be applied directly or indirectly (by transfer) to paper by conventional means. coating method are coated.
  • the water may preferably be removed by drying at 50 to 150 ° C.
  • the coated carriers can be cut into the format required for labels before or after application of the adhesive.
  • the paper labels according to the invention have very good performance properties. In the production of paper labels (cutting, punching), there is little or no edge leakage of the pressure-sensitive adhesive due to the good cohesion.
  • the pressure-sensitive adhesive adheres well to the support (paper), has a very good adhesion to the substrates and a high cohesion (internal strength in the adhesive layer).
  • the pressure-sensitive adhesive and thus also the paper labels are odorless.
  • the paper labels adhere well to a wide variety of substrates, including substrates with non-polar surfaces.
  • the substrates may be z. B. to deal with packaging or containers made of different materials.
  • substrates eg. As packaged foods that are stored permanently at reduced temperature.
  • the paper labels are therefore also suitable for substrates which have a temperature in the range of -5 to 10 0 C, in particular -5 to 5 0 C, that is stored at these temperatures.
  • the dispersions were mixed with 20 parts each of a tackifier dispersion based on a partially hydrogenated abietic acid ester. After a maturation time of 24 hours, the adhesives were applied to a label paper (80 g / m 2 ) in a thickness of 20 ⁇ m. To determine the peel strength according to Finat Test Method 01, the coated papers were stuck to the test surface (above, polyethylene or cardboard) and subjected to the peel test after 1 min in a tractor.
  • the Quickstick measurements were also carried out in a tractor according to the Finat Test Method 09; During this test, a loop is formed from the coated label pier, the coated side is brought into contact with the test surface and the force required for redrawing (N / 25 mm) is determined.

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

Abstract

Paper labels, coated with a pressure-sensitive adhesive, characterized in that the pressure-sensitive adhesive does not contain any vinyl acetate in free or copolymerized form and, as binder, contains an emulsion polymer which is built up from a) 70 to 95% by weight of a C6 to C10 alkyl (meth)acrylate, b) 1 to 20% by weight of a methyl methacrylate, c) 0.5 to 10% by weight of a vinylaromatic monomer, d) 0.5 to 10% by weight of a hydroxyalkyl (meth)acrylate, e) 0.5 to 5% by weight of a monomer with at least one acid or acid anhydride group, f) 0 to 10% by weight of a tertiary butyl (meth)acrylate, and g) 0 to 20% by weight of additional monomers, wherein the additional monomers contain a maximum of 3% by weight of methyl acrylate.

Description

Haftklebstoff für Papieretiketten Pressure-sensitive adhesive for paper labels
Beschreibungdescription
Die Erfindung betrifft mit Haftklebstoff beschichtete Papieretiketten, wobeiThe invention relates to pressure-sensitive adhesive coated paper labels, wherein
- der Haftklebstoff kein Vinylacetat in freier oder einpolymerisierter Form enthält undthe pressure-sensitive adhesive contains no vinyl acetate in free or copolymerized form, and
- als Bindemittel ein Emulsionspolymerisat enthält, welches aufgebaut ist aus- contains as binder an emulsion polymer, which is composed of
a) 70 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 1 bis 20 Gew.-% Methylmethacrylat c) 0,5 bis 10 Gew.-% eines vinylaromatischen Monomern d) 0,5 bis 10 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0 bis 10 Gew.-% tertiär-Butyl(meth)acrylat und g) 0 bis 20 Gew.-% weiteren Monomeren, wobei die weiteren Monomeren maximal 3 Gew.-% Methylacrylat enthaltena) from 70 to 95% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 1 to 20% by weight of methyl methacrylate c) from 0.5 to 10% by weight of a vinylaromatic monomer d) from 0.5 to 10% by weight % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0 to 10% by weight of tertiary butyl (meth) acrylate and g) 0 to 20 wt .-% of further monomers, wherein the further monomers contain a maximum of 3 wt .-% methyl acrylate
Etiketten sind mit Haftklebstoff beschichtete selbstklebende Artikel. Die Etiketten sollen auf unterschiedlichsten Substraten möglichst gut kleben. Bei den Substraten kann es sich z. B. um Verpackungen oder Behälter aus unterschiedlichen Materialien handeln. Insbesondere handelt es sich im Verpackungsbereich oft um Substrate, z. B. verpackte Lebensmittel, die bei erniedrigter Temperatur dauerhaft gelagert werden. Geruchsintensive Haftklebstoffe kommen für derartige Verwendungen nicht in Betracht. Bei Pa- pier als Trägermaterial für Etiketten bestehen aufgrund der Porosität und damit verbundenen Durchlässigkeit besondere Anforderungen. Gegenüber Folien als Trägermaterial ist der von flüchtigen Bestandteilen ausgelöste Geruch besonders gut wahrnehmbar.Labels are pressure-sensitive adhesive coated self-adhesive articles. The labels should stick as well as possible on different substrates. The substrates may be z. B. to deal with packaging or containers made of different materials. In particular, in the packaging sector are often substrates, eg. As packaged foods that are stored permanently at reduced temperature. Odor-intensive pressure-sensitive adhesives are not suitable for such uses. With paper as a carrier material for labels, there are special requirements due to the porosity and the associated permeability. Compared to films as a carrier material, the odor caused by volatile components is particularly noticeable.
Geeignete Haftklebstoffe benötigen sowohl eine gute Haftung (Adhäsion) als auch eine ausreichende innere Festigkeit in der Klebstoffschicht (Kohäsion) auch bei niedrigen Temperaturen. Beide Eigenschaften sind im allgemeinen gegenläufig, d. h. eine Verbesserung der einen Eigenschaft führt zur Verschlechterung der anderen.Suitable pressure-sensitive adhesives require both good adhesion and sufficient internal strength in the adhesive layer (cohesion) even at low temperatures. Both properties are generally opposite, d. H. An improvement of one property leads to the deterioration of the other.
Aus EP-A 625 557 sind Haftklebstoffe bekannt, die neben Vinylaromaten, Hydroxyalky- lacrylaten und Methylmethacrylat zwingend mindestens 5 Gew.-% Methylacrylat enthalten.Pressure-sensitive adhesives are known from EP-A 625 557 which, in addition to vinylaromatics, hydroxyalkyl acrylates and methyl methacrylate, necessarily contain at least 5% by weight of methyl acrylate.
EP-A-1342762 beschreibt Haftklebstoffe, die zwingend Hydroxyalkylacrylate, Vinyl- aromaten und gegebenenfalls Vinylacetat enthalten. Gegenstand von WO 00/68335 sind Haftklebstoffe, die mit einem aromatischen Emul- gator hergestellt werden; die Haftklebstoffe enthalten verschiedene Al- kyl(meth)acrylate, z. B. auch Ethyhexylacrylat und Methylmethacrylat, neben Vinylaro- maten , Hydroxyverbindungen und ethylenisch ungesättigte Säuren.EP-A-1342762 describes pressure-sensitive adhesives which imperatively contain hydroxyalkyl acrylates, vinyl aromatics and optionally vinyl acetate. The subject of WO 00/68335 are pressure-sensitive adhesives which are prepared with an aromatic emulsifier; the pressure-sensitive adhesives contain various alkyl (meth) acrylates, eg. As well as ethylhexyl acrylate and methyl methacrylate, in addition to vinyl aromatics, hydroxy compounds and ethylenically unsaturated acids.
Die nicht vorveröffentlichte Patentanmeldung PF 58054 beschreibt Haftklebstoffe, welche Hydroxy-Monomere und tertiär-Butyl(meth)acrylat enthalten.The non-prepublished patent application PF 58054 describes pressure sensitive adhesives containing hydroxy monomers and tertiary butyl (meth) acrylate.
Aufgabe der vorliegenden Erfindung waren Papieretiketten mit guten anwendungs- technischen Eigenschaften, insbesondere guten Klebeeigenschaften auch bei tiefen Temperaturen; die Kohäsion sollte trotzdem ausreichend sein, insbesondere sollen die beschichteten Träger durch Schneiden oder Stanzen zu Papieretiketten verarbeitbar sein.Object of the present invention were paper labels with good application properties, especially good adhesive properties even at low temperatures; the cohesion should still be sufficient, in particular, the coated carrier should be processed by cutting or punching to paper labels.
Demgemäß wurden die eingangs definierten Papieretiketten gefunden.Accordingly, the paper labels defined above were found.
Die Papieretiketten sind mit einem Haftklebstoff beschichtet. Der Haftklebstoff enthält kein Vinylacetat, weder in freier Form, noch in einpolymerisierter Form.The paper labels are coated with a pressure sensitive adhesive. The pressure-sensitive adhesive contains no vinyl acetate, either in free form or in polymerized form.
Der Haftklebstoff enthält als Bindemittel ein Emulsionspolymerisat. Das Emulsionspolymerisat ist aufgebaut aus:The pressure-sensitive adhesive contains as binder an emulsion polymer. The emulsion polymer is composed of:
a) 70 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 1 bis 20 Gew.-% Methylmethacrylat c) 0,5 bis 10 Gew.-% eines vinylaromatischen Monomern d) 0,5 bis 10 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mit mindestens einer Säure- oder Säureanhydridgruppe f) 0 bis 10 Gew.-% tertiär-Butyl(meth)acrylat und g) 0 bis 20 Gew.-% weiteren Monomeren, wobei die weiteren Monomeren maximal 3 Gew.-% Methylacrylat enthaltena) from 70 to 95% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 1 to 20% by weight of methyl methacrylate c) from 0.5 to 10% by weight of a vinylaromatic monomer d) from 0.5 to 10% by weight .-% of a hydroxyalkyl (meth) acrylate e) 0.5 to 5 wt .-% of a monomer having at least one acid or acid anhydride group f) 0 to 10 wt .-% tertiary butyl (meth) acrylate and g) 0 to 20 wt .-% of further monomers, wherein the further monomers contain a maximum of 3 wt .-% methyl acrylate
Bevorzugte C6 - C10 Alkyl(meth)acrylate sind n-Butylacrylat und 2-Ethylhexylacrylat oder deren Mischungen. Besonders bevorzugt ist 2-Ethylhexylacrylat. Der Gehalt der C6 - C10 Alkyl(meth)acrylate im Emulsionspolymerisat beträgt vorzugsweise 75 bis 95 Gew.-%, besonders bevorzugt 78 bis 90 Gew.-% und ganz besonders bevorzugt 80 bis 90 Gew.-%.Preferred C 6 -C 10 alkyl (meth) acrylates are n-butyl acrylate and 2-ethylhexyl acrylate or mixtures thereof. Particularly preferred is 2-ethylhexyl acrylate. The content of C6-C10 alkyl (meth) acrylates in the emulsion polymer is preferably 75 to 95% by weight, more preferably 78 to 90% by weight and most preferably 80 to 90% by weight.
Der Gehalt des Methylmethacrylats (MMA) im Emulsionspolymerisat beträgt vorzugs- weise 3 bis 15 Gew.-%, besonders bevorzugt 4 bis 12 Gew.-% und ganz besonders bevorzugt 4 bis 8 Gew.-%. Bevorzugtes vinylaromatisches Monomer c) ist Styrol.The content of methyl methacrylate (MMA) in the emulsion polymer is preferably from 3 to 15% by weight, more preferably from 4 to 12% by weight and most preferably from 4 to 8% by weight. Preferred vinylaromatic monomer c) is styrene.
Der Gehalt des vinylaromatischen Monomeren im Emulsionspolymerisat beträgt vorzugsweise 1 bis 8, besonders bevorzugt 1 bis 5 Gew.-% und ganz besonders bevorzugt 2 bis 5 Gew.-%.The content of the vinylaromatic monomer in the emulsion polymer is preferably 1 to 8, more preferably 1 to 5 wt .-% and most preferably 2 to 5 wt .-%.
Bevorzugte Hydroxyalkyl(meth)acrylate sind die C2 bis C12 Hydroxyal- kyl(meth)acrylate und insbesondere die C2 bis C6 Hydroxyalkyl(meth)acrylate. Ganz besonders bevorzugt sind Hydroxyethylacrylat, Hydroxyethylmethacrylat, Hydroxypro- pylacrylat, Hydroxypropylmethacrylat, Hydroxybutylacrylat oder Hydroxybutylmethacry- lat.Preferred hydroxyalkyl (meth) acrylates are the C 2 to C 12 hydroxyalkyl (meth) acrylates and in particular the C 2 to C 6 hydroxyalkyl (meth) acrylates. Very particular preference is given to hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate or hydroxybutyl methacrylate.
Der Gehalt der Hydroxyalkyl(meth)acrylate im Emulsionspolymerisat beträgt vorzugsweise 0,5 bis 8, besonders bevorzugt 1 bis 5 Gew.-% und ganz besonders bevorzugt 1 ,5 bis 4 Gew.-%.The content of the hydroxyalkyl (meth) acrylates in the emulsion polymer is preferably 0.5 to 8, more preferably 1 to 5 wt .-% and most preferably 1, 5 to 4 wt .-%.
Bevorzugte Monomere mit mindestens einer Säure- oder Säureanhydridgruppe (e) sind z. B. Monomere mit mindestens einer, vorzugsweise ein oder zwei, Carbonsäure, Sulfonsäure oder Phosphonsäuregruppen. Bevorzugt sind Carbonsäuregruppen. Genannt seien z. B. Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure oder Fumar- säure. Besonders bevorzugt ist Acrylsäure oder Methacrylsäure. Der Gehalt dieser Monomeren im Emulsionspolymerisat beträgt vorzugsweise 0,5 bis 4, besonders bevorzugt 0,6 bis 3,5 Gew.-% und ganz besonders bevorzugt 0,8 bis 3 Gew.-%.Preferred monomers having at least one acid or acid anhydride group (e) are z. B. monomers having at least one, preferably one or two, 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. Particularly preferred is acrylic acid or methacrylic acid. The content of these monomers in the emulsion polymer is preferably 0.5 to 4, more preferably 0.6 to 3.5 wt .-% and most preferably 0.8 to 3 wt .-%.
Das Emulsionspolymerisat enthält gegebenenfalls tertiär-Butylacrylat oder tertiär- Butyl(meth)acrylat (kurz tertiär-Butyl(meth)acrylat). In einer besonderen Ausführungsform enthält das Emusionspolymerisat zwingend tertiär-Butyl(meth)acrylat. Der Gehalt des tertiär-Butyl(meth)acrylats im Emulsionspolymerisat beträgt vorzugsweise 0,2 bis 10, besonders bevorzugt 0,5 bis 5 Gew. % und ganz besonders bevorzugt 0,8 bis 5 Gew. %.The emulsion polymer optionally contains tertiary butyl acrylate or tertiary butyl (meth) acrylate (abbreviated tertiary butyl (meth) acrylate). In a particular embodiment, the emulsion polymer necessarily contains tertiary butyl (meth) acrylate. The content of the tertiary butyl (meth) acrylate in the emulsion polymer is preferably 0.2 to 10, particularly preferably 0.5 to 5 wt.% And most preferably 0.8 to 5 wt.%.
Das Emulsionspolymerisat kann gegebenenfalls auch noch weitere Monomere (g) enthalten.If appropriate, the emulsion polymer may also contain further monomers (g).
Das Emulsionspolymerisat enthält jedoch zwingend maximal 3 Gew.%, vorzugsweise maximal 2 Gew. % Methylacrylat. In einer besonderen Ausführungsform enthält das Emulsionspolymerisat weniger als 0,5 Gew. % Methylacrylat und insbesondere weniger als 0,1 Gew. % Methylacrylat. Ganz besonders bevorzugt enthält das Emulsionspolymerisat kein Methylacrylat.However, the emulsion polymer necessarily contains not more than 3% by weight, preferably not more than 2% by weight, of methyl acrylate. In a particular embodiment, the emulsion polymer contains less than 0.5% by weight of methyl acrylate and in particular less than 0.1% by weight of methyl acrylate. Most preferably, the emulsion polymer does not contain methyl acrylate.
Im übrigen können weitere Monomere, z. B. sonstige C1 bis C20 Alkyl(meth)acrylaten (die nicht Monomeren a) bis f) entsprechen), ethylenisch ungesättigte Nitrile, ethyle- nisch ungesättigte Amide mitverwendet werden. Der Gehalt der weiteren Monomere im Emulsionspolymerisat kann vorzugsweise 0 bis 10, besonders bevorzugt 0 bis 8 Gew.-% und ganz besonders bevorzugt 0 bis 5 Gew.- %. betragen. In einer besonderen Ausführungsform werden weitere Monomere nicht mitverwendet.Incidentally, other monomers, for. B. other C1 to C20 alkyl (meth) acrylates (which do not correspond to monomers a) to f)), ethylenically unsaturated nitriles, ethylenically unsaturated amides are also used. The content of the further monomers in the emulsion polymer may preferably be 0 to 10, more preferably 0 to 8 wt .-% and most preferably 0 to 5 wt .-%. be. In a particular embodiment, other monomers are not included.
Das Emulsionspolymerisat ist insgesamt vorzugsweise aufgebaut ausOverall, the emulsion polymer is preferably composed of
a) 70 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 1 bis 20 Gew.-% Methylmethacrylat c) 0,5 bis 10 Gew.-% eines vinylaromatischen Monomern d) 0,5 bis 10 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0 bis 10 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 20 Gew.-% weiteren Monomeren, wobei Methylacrylat ausgeschlossen ista) from 70 to 95% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 1 to 20% by weight of methyl methacrylate c) from 0.5 to 10% by weight of a vinylaromatic monomer d) from 0.5 to 10% by weight % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0 to 10% by weight of tertiary butyl (meth) acrylate g) 0 to 20 Wt .-% of other monomers, with methyl acrylate is excluded
Besonders bevorzugt ist es aufgebaut ausIt is particularly preferably composed of
a) 70 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 1 bis 20 Gew.-% Methylmethacrylat c) 0,5 bis 10 Gew.-% eines vinylaromatischen Monomern d) 0,5 bis 10 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mit mindestens einer Säure- oder Säureanhydridgruppe f) 0,2 bis 10 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 20 Gew.-% weiteren Monomeren, wobei Methylacrylat ausgeschlossen ista) from 70 to 95% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 1 to 20% by weight of methyl methacrylate c) from 0.5 to 10% by weight of a vinylaromatic monomer d) from 0.5 to 10% by weight .-% of a hydroxyalkyl (meth) acrylate e) 0.5 to 5 wt .-% of a monomer having at least one acid or acid anhydride group f) 0.2 to 10 wt .-% tertiary-butyl (meth) acrylate g) 0 to 20 wt .-% of other monomers, with methyl acrylate is excluded
Ganz besonders bevorzugt ist es aufgebaut ausMost preferably, it is composed of
a) 75 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 3 bis 15 Gew.-% Methylmethacrylat c) 1 bis 8 Gew.-% eines vinylaromatischen Monomeren d) 0,5 bis 8 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säu- reanhydridgruppe f) 0,5 bis 5 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 10 Gew.-% weiteren Monomeren, wobei Methylacrylat ausgeschlossen ist.a) from 75 to 95% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 3 to 15% by weight of methyl methacrylate c) from 1 to 8% by weight of a vinylaromatic monomer d) from 0.5 to 8% by weight % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0.5 to 5% by weight of tertiary butyl (meth) acrylate g) 0 to 10 wt .-% of other monomers, with methyl acrylate is excluded.
In ganz besonderen Ausführungsform ist das Emusionspolymerisat aufgebaut aus:In a very particular embodiment, the emulsion polymer is composed of:
a) 78 bis 90 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 4 bis 12 Gew.-% Methylmethacrylat c) 1 bis 5 Gew.-% eines vinylaromatischen Monomeren d) 1 bis 5 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 4 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0,8 bis 5 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 10 Gew.-% weiteren Monomeren, wobei Methylacrylat ausgeschlossen ist.a) 78 to 90 wt .-% of a C6 to C10 alkyl (meth) acrylate b) 4 to 12 wt .-% of methyl methacrylate c) 1 to 5% by weight of a vinylaromatic monomer d) 1 to 5% by weight of a hydroxyalkyl (meth) acrylate e) 0.5 to 4% by weight of a monomer having at least one acid or acid anhydride group f) 0 , 8 to 5 wt .-% tertiary-butyl (meth) acrylate g) 0 to 10 wt .-% of other monomers, with methyl acrylate is excluded.
In weiteren ganz besonderen Ausführungsform ist das Emusionspolymerisat aufgebaut aus:In a further very particular embodiment, the emulsion polymer is composed of:
a) 80 bis 90 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 4 bis 8 Gew.-% Methylmethacrylat c) 2 bis 5 Gew.-% eines vinylaromatischen Monomeren d) 1 ,5 bis 4 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,6 bis 3,5 insbesondere 0,8 bis 3 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0,8 bis 5 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 5 Gew.-% weiteren Monomeren, wobei Methylacrylat ausgeschlossen ist.a) from 80 to 90% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 4 to 8% by weight of methyl methacrylate c) from 2 to 5% by weight of a vinylaromatic monomer d) from 1 to 5% by weight % of a hydroxyalkyl (meth) acrylate e) from 0.6 to 3.5, in particular from 0.8 to 3,% by weight of a monomer having at least one acid or acid anhydride group f) from 0.8 to 5% by weight tertiary butyl ( Meth) acrylate g) 0 to 5 wt .-% of further monomers, with methyl acrylate is excluded.
Die Glasübergangstemperatur des Emulsionspolymerisats beträgt vorzugsweise -70 bis 0 °C und besonders bevorzugt -70 bis -10 °C; ganz besonders bevorzugt -60 bis - 30 °C.The glass transition temperature of the emulsion polymer is preferably -70 to 0 ° C, and more preferably -70 to -10 ° C; most preferably -60 to -30 ° C.
Die Glasübergangstemperatur lässt sich nach üblichen Methoden wie Differentialther- moanalyse oder Differentail Scanning Calorimetrie (s. z. B. ASTM 3418/82, sog. "mid- point temperature") bestimmen.The glass transition temperature can be determined by customary methods such as differential thermal analysis or differential scanning calorimetry (see, for example, ASTM 3418/82, so-called "mid-point temperature").
Die Herstellung der Polymere erfolgt durch Emulsionspolymerisation, es handelt sich daher um ein Emulsionspolymerisat.The polymers are prepared by emulsion polymerization, which is therefore an emulsion polymer.
Bei der Emulsionspolymerisation werden ethylenisch ungesättigte Verbindungen (Monomere) in Wasser polymerisiert, wobei ionische und/oder nicht -ionische Emulgatoren und/oder Schutzkolloide bzw. Stabilisatoren als grenzflächenaktive Verbindungen zur Stabilisierung der Momer-tröpfchen und der später aus den Monomeren gebildeten Polymerteilchen verwendet werden.In the emulsion polymerization, ethylenically unsaturated compounds (monomers) are polymerized in water using ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers as surface-active compounds for stabilizing the monomer droplets and the polymer particles later formed from the monomers.
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. 41 1 bis 420. Als Emulgatoren kommen sowohl ani- onische, kationische als auch nichtionische Emulgatoren in Betracht. Vorzugsweise werden als grenzflächenaktive Substanzen 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 grenz-flächenaktive 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: C4- bis Cg), Alkalimetallsalze von Dialkylestern der Sulfobernstein- säure sowie Alkali- und Ammoniumsalze von Alkylsulfaten (Alkylrest: Cs- bis C12), von ethoxylierten Alkanolen (EO-Grad: 4 bis 30, Alkylrest: C12- bis Cis), von ethoxylierten Alkylphenolen (EO-Grad: 3 bis 50, Alkylrest: C4- bis Cg), von Alkylsulfonsäuren (Alkylrest: C12- bis Cis) und von Alkylarylsulfonsäuren (Alkylrest: Cg- 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, p. 41 1 to 420. Suitable emulsifiers are anionic, cationic and nonionic emulsifiers into consideration. Emulsifiers whose molecular weight, unlike the protective colloids, are usually below 2000 g / mol, are preferably used as surface-active substances. 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. Anionic and nonionic emulsifiers are preferably used as surface-active substances. Common accompanying emulsifiers are z. Example, ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl: Cs to C36), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl: C 4 - to Cg), alkali metal salts of dialkyl esters of sulfosuccinic acid and of alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C12 to Cis), of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to Cg), of alkylsulfonic acids (alkyl radical: C 12 to Cis) and of alkylarylsulfonic acids (alkyl radical: Cg to Cis).
Weitere geeignete Emulgatoren sind Verbindungen der allgemeinen Formel IFurther suitable emulsifiers are compounds of the general formula I.
worin R5 und R6 Wasserstoff oder C4- bis Ci4-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 Il in denen X und Y Natrium, R5 ein verzweigter Alkylrest mit 12 C- Atomen und R6 Wasserstoff oder R5 ist. Häufig werden technische Gemische verwen- det, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, beispielsweise Dowfax® 2A1 (Warenzeichen der Dow Chemical Company).wherein R 5 and R 6 is hydrogen or C 4 - to C 4 represent alkyl and are not simultaneously hydrogen, and X and Y can be alkali metal ions and / or ammonium ions. Preferably 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 alkyl radical having 12 carbon atoms and R 6 is hydrogen or R. 5 Industrial mixtures verwen- det which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of 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.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.
Handelsnamen von Emulgatoren sind z. B. Dowfax®2 A1 , Emulan® NP 50, Dextrol® OC 50, Emulgator 825, Emulgator 825 S, Emulan® OG, Texapon® NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL, E- mulphor NPS 25.Trade names of emulsifiers are z. B. Dowfax ® 2 A1, Emulan ® NP 50, Dextrol ® OC 50, 825 emulsifier, emulsifier 825 S, Emulan ® OG, Texapon ® NSO, Nekanil ® 904 S, Lumiten ® I-RA, Lumiten E 3065, Disponil FES 77 , Lutensol AT 18, Steinapol VSL, E-mulphor NPS 25.
Besonders bevorzugt erfolgt die Herstellung des Emusionspolymerisats unter Verwendung von Emulgatoren, wie sie in WO 00/68335 beschrieben sind. Besonders bevorzugt sind Emulgatoren der obigen Formel I, ganz besonders bevorzugt sind Gemische von Emulgatoren der Formel I mit alkoxylierten Fettsäuresulfaten der Formel (II)The preparation of the emulsion polymer is particularly preferably carried out using emulsifiers, as described in WO 00/68335. Particularly preferred are emulsifiers of the above formula I, very particularly preferred are mixtures of emulsifiers of the formula I with alkoxylated fatty acid sulfates of the formula (II)
R8— O — (Z-O) n SO3. K +R 8 - O - (ZO) n SO 3. K +
Worin die Variablen folgende Bedeutung haben:Where the variables have the following meaning:
R8: C1-C18 Alkyl, vorzugsweise C6 bis C16 AlkylR 8 : C 1 -C 18 alkyl, preferably C 6 to C 16 alkyl
Z: CH2-CH2 oder CH (CH3)-CH2, vorzugsweise CH2-CH2Z: CH 2 -CH 2 or CH (CH 3) -CH 2, preferably CH 2 -CH 2
n: eine ganze Zahl von 1 bis 40, vorzugsweise 2 bis 30n: an integer of 1 to 40, preferably 2 to 30
K: ein Kation, vorzugsweise ein Alkalikation oder AmmoniumionK: a cation, preferably an alkali cation or ammonium ion
Die grenzflächenaktive Substanz wird üblicherweise in Mengen von 0,1 bis 10 Gew.-%, bezogen auf die zu polymerisierenden Monomeren verwendet.The surfactant is usually used in amounts of from 0.1 to 10% by weight, based on the monomers to be polymerized.
Bei der Emulsionspolymerisation werden üblicherweise wasserlösliche Initiatoren für die radikalische Polymerisation der Monomere verwendet.In the emulsion polymerization, water-soluble initiators are usually used for the radical polymerization of the monomers.
Wasserlösliche Initiatoren für die Emulsionspolymerisation sind z. B. Ammonium- und Alkalimetallsalze der Peroxidischwefelsäure, z. B. Natriumperoxodisulfat, Wasserstoff- peroxid oder organische Peroxide, z. B. tert-Butylhydroperoxid.Water-soluble initiators for the emulsion polymerization are z. For example, ammonium and alkali metal salts of peroxodisulfuric, z. For example, sodium peroxodisulfate, hydrogen peroxide or organic peroxides, eg. B. tert-butyl hydroperoxide.
Geeignet sind auch sogenannte Reduktions-Oxidations(Red-Ox)-lnitiator Systeme.Also suitable are so-called reduction-oxidation (red-ox) -lititiator systems.
Die Red-Ox-Initiator-Systeme bestehen aus mindestens einem meist anorganischen Reduktionsmittel und einem anorganischen oder organischen 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 z. B. to the above-mentioned initiators for emulsion polymerization.
Bei der Reduktionskomponenten handelt es sich z. B. um Alkalimetallsalze der schwefligen Säure, wie z. B. Natriumsulfit, Natriumhydrogensulfit, Alkalisalze der Dischwef- ligen 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 Mit- Verwendung löslicher Metallverbindungen, deren metallische Komponente in mehreren Wertigkeitsstufen auftreten kann, verwendet werden. Übliche Red-Ox-Initiator-Systeme sind z. B. Ascorbinsäure/Eisen(ll)sulfat/Natrium- peroxidisulfat, tert-Butylhydroperoxid/Natriumdisulfit, tert-Butylhydroperoxid/Na- Hydroxymethansulfinsäure. Die einzelnen Komponenten, z. B. die Reduktionskomponente, können auch Mischungen sein z. B. eine Mischung aus dem Natriumsalz der Hydroxymethansulfinsäure und Natriumdisulfit.The reduction components are, for. B. to alkali metal salts of sulfurous acid, such as. For example, sodium sulfite, sodium hydrogen sulfite, alkali metal salts of Dischwef- ligen acid such as sodium disulfite, 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 use of soluble metal compounds whose metallic component can occur in multiple valence states. Usual Red Ox initiator systems are z. As ascorbic acid / iron (II) sulfate / sodium peroxydisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na hydroxymethanesulfinic. The individual components, eg. As the reduction component, mixtures may also be z. B. 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 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. In general, 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.
Die Menge der Initiatoren beträgt im allgemeinen 0,1 bis 10 Gew.-%, bevorzugt 0,5 bis 5 Gew.-%, bezogen auf die zu polymerisierenden Monomeren. Es können auch mehrere, verschiedene Initiatoren bei der Emulsionspolymerisation Verwendung finden.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.
Bei der Polymerisation können auch Polymerisationsregler, kurz Regler, eingesetzt werden. Regler bewirken eine Kettenabbruchsreaktion und verringern somit das MoI- gewicht des Polymeren. Die Regler werden dabei an das Polymer gebunden, im allgemeinen an das Kettenende.In the polymerization and polymerization, regulators can be used. Regulators cause a chain termination reaction and thus reduce the molecular weight of the polymer. The regulators are bound to the polymer, generally to the chain end.
Die Menge der Regler kann insbesondere 0,05 bis 4 Gew.-Teile, besonders bevorzugt 0,05 bis 0,8 Gew.-Teile und ganz besonders bevorzugt 0,1 bis 0,6 Gew.-Teile, bezo- gen auf 100 Gew.-Teile der zu polymerisierenden Monomeren betragen. Geeignete Regler sind insbesondere Verbindungen mit einer Mercaptogruppe wie tert- Butylmercaptan, Thioglycolsäureethylacrylester, Mercaptoethynol, Mercaptopropyltri- methoxysilan oder tert.-Dodecylmercaptan. Bei den Reglern handelt es sich im allgemeinen um niedermolekulare Verbindungen mit einem Molgewicht kleiner 2000, insbe- sondere kleiner 1000 g/mol.The amount of regulator may in 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, in particular, compounds having a mercapto group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethynol, mercaptopropyltrimethoxysilane or tert-dodecylmercaptan. The regulators are generally low molecular weight compounds with a molecular weight of less than 2000, in particular less than 1000 g / mol.
Die Emulsionspolymerisation erfolgt in der Regel bei 30 bis 130, vorzugsweise 50 bis 90 0C. 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. Das Zulaufverfahren kann in Stufen- oder Gradientenfahrweise, durchgeführt werden. Bevorzugt ist das Zulaufverfahren, bei dem man einen Teil des Polymerisationsansatzes 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 Aufrechterhaltung 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 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 feed process can be carried out in a stepwise or gradient mode. Preferably, 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. In the polymerization can also z. B. be presented for better adjustment of the particle size of a polymer seed.
Die Art und Weise, in der der Initiator im Verlauf der radikalischen wässrigen Emulsionspolymerisation dem Polymerisationsgefäß zugegeben wird, ist dem Durchschnitts- fachmann 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 Polymerisationstemperatur ab. Vorzugsweise wird ein Teil vorgelegt und der Rest nach Maßgabe des Verbrauchs der Polymerisationszone zugeführt.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 particular, 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.
Eine Teilmenge der Monomere kann, wenn gewünscht, zu Beginn der Polymerisation im Polymerisationsgefäß vorgelegt werden, die übrigen Monomere, bzw. alle Monomere, wenn keine Monomere vorgelegt werden, werden beim Zulaufverfahren im Laufe der Polymerisation zugegeben.A subset of the monomers may, if desired, be initially charged in the polymerization vessel at the beginning of the polymerization, the other monomers, or all monomers, if no monomers are introduced, are added in the feed process during the polymerization.
Auch der Regler kann zum Teil vorgelegt werden, ganz oder teilweise während der Polymerisation oder gegen Ende der Polymerisation zugegeben werden.Also, the regulator can be partially submitted, be added in whole or in part during the polymerization or towards the end of the polymerization.
Für eine hohe Raum/Zeitausbeute des Reaktors sind Dispersionen mit einem möglichst hohen Feststoffgehalt bevorzugt. Um Feststoffgehalte > 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 81 083), 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 Beschichtungsverhalten bei hohen Feststoffgehalten. Die Erzeugung einer neuen/neuer Teilchengeneration/en kann zu einem beliebigen Zeitpunkt erfolgen. Er richtet sich nach den für eine niedrige Viskosi- tat angestrebten Teilchengrößenverteilung.For a high space / time yield of the reactor, dispersions having the highest possible solids content are preferred. In order to achieve solids contents> 60 wt .-%, you should set a bimodal or polymodal particle size, otherwise the viscosity is too high, and the dispersion is no longer manageable. The generation of a new particle generation can be carried out, for example, by adding seed (EP 81 083), by adding excess amounts of emulsifier 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.
Die Monomeren werden zumindest teilweise während der Polymerisation kontinuierlich zugegeben. Zum Teil können Monomere auch im Polymerisationsgefäß vor Beginn der Polymerisation vorgelegt werden.The monomers are added continuously at least partially during the polymerization. In some cases, monomers can also be initially charged in the polymerization vessel before the beginning of the polymerization.
Vorzugsweise wird maximal 30 Gew.-% der Gesamtmenge der Monomeren, besonders bevorzugt maximal 20 Gew.-%, ganz besonders bevorzugt maximal 10 Gew.-% der Monomeren im Polymerisationsgefäß vorgelegt. Die übrigen Monomeren, d. h. vorzugsweise mindestens 70 Gew.-%, besonders bevorzugt mindestens 80 Gew.-%, ganz besonders bevorzugt mindestens 90 Gew.-% werden während der Polymerisation kontinuierlich zugegeben. In einer besonderen Ausführungsform werden keine Mono- meren vorgelegt, d. h. die Gesamtmenge der Monomere wird während der Polymerisation zugefahren.Preferably, a maximum of 30% by weight of the total amount of the monomers, particularly preferably not more than 20% by weight, very particularly preferably not more than 10% by weight, of the monomers is initially charged in the polymerization vessel. The remaining monomers, ie preferably at least 70% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight, are continuously added during the polymerization. In a particular embodiment, no mono meren, ie the total amount of monomers is fed during the polymerization.
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 bottom.
Zur Entfernung der Restmonomeren kann auch nach dem Ende der eigentlichen Emulsionspolymerisation, d. h. nach einem Umsatz aller Monomeren und nach Einpolymeri- sieren der Restmenge tBA weiterer Initiator zugesetzt werden (chemische Desodorie- rung).To remove the residual monomers, even after the end of the actual emulsion polymerization, d. H. after a conversion of all monomers and after incorporation of the residual amount tBA, further initiator can be added (chemical deodorization).
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. Besonders bevorzugt sind wässrige Dispersionen des Emulsionspolymerisats mit einem Gehalt des Emulsionspolymerisats größer 60 Gew., % bezogen auf die gesamte Polymerdispersion.In the emulsion polymerization, aqueous dispersions of the polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%. Particular preference is given to aqueous dispersions of the emulsion polymer having a content of the emulsion polymer of greater than 60% by weight, based on the total polymer dispersion.
Das so hergestellte Emusionspolymerisat wird vorzugsweise in Form seiner wässrigen Dispersion verwendet.The emulsion polymer thus prepared is preferably used in the form of its aqueous dispersion.
Das Emulsionspolymerisat wird als oder in Haftklebstoffen verwendet.The emulsion polymer is used as or in pressure-sensitive adhesives.
Der Haftklebstoff enthält das Emulsionspolymerisat vorzugsweise zunächst in Form der wässrigen Polymerdispersion, wie sie durch die Emulsionspolymerisation erhalten wurde oder erhältlich ist.The pressure-sensitive adhesive preferably contains the emulsion polymer initially in the form of the aqueous polymer dispersion as obtained or obtainable by the emulsion polymerization.
Der Haftklebstoff kann ausschließlich aus dem Emulsionspolymerisat, bzw. dessen wässriger Dispersion bestehen.The pressure-sensitive adhesive can consist exclusively of the emulsion polymer or its aqueous dispersion.
Der Haftklebstoff kann jedoch auch noch weitere Zusatzstoffe enthalten.However, the pressure-sensitive adhesive may also contain other additives.
In Betracht kommt z. B. ein Tackifier, d. h. ein klebrigmachendes Harz. Tackifier sind z. B. aus Adhesive Age, Juli 1987, Seite 19-23 oder Polym. Mater. Sei. Eng. 61 (1989), Seite 588-592 bekannt.In consideration comes z. B. a tackifier, d. H. a tackifying resin. Tackifiers are z. 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 Disproportio- nierung 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 Ve- resterung verwendet werden, können ein- oder mehrwertig sein. Beispiele sind Methanol, Ethandiol, Diethylenglykol, Triethylenglykol, 1 ,2,3-Propanthiol, Pentaerythrit. Desweiteren finden auch Kohlenwasserstoffharze, z. B. Cumaron-Inden-Harze, PoIy- terpen-Harze, Kohlenwasserstoffharze auf Basis ungesättigter CH-Verbindungen, wie Butadien, Penten, Methylbuten, Isopren, Piperylen, Divinylmethan, Pentadien, Cyclo- penten, Cyclopentadien, Cyclohexadien, Styrol, a-Methylstyrol, Vinyltoluol Verwen- düng.Tackifiers are z. As natural resins such as rosins and their by disproportionation or isomerization, polymerization, dimerization, hydrogenation resulting derivatives. These may 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 may be mono- or polyvalent Examples are methanol, ethanediol, Diethylene glycol, triethylene glycol, 1, 2,3-propanethiol, pentaerythritol. Furthermore, find hydrocarbon resins, eg. As coumarone-indene resins, polyester terpene resins, hydrocarbon resins based on unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, a-methylstyrene , Vinyltoluene Use fertil.
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 mindes- tens 60, insbesondere mindestens 80 Gew.-% aus Ci-C8-Alkyl(meth)acrylaten.As tackifiers are increasingly also polyacrylates, which have a low molecular weight used. These polyacrylates preferably have a weight-average molecular weight M w of less than 30,000. The polyacrylates preferably contain at least 60, in particular at least 80% by weight of C 1 -C 8 -alkyl (meth) acrylates.
Bevorzugte Tackifier sind natürliche oder chemisch modifizierte Kolophoniumharze. Kolophoniumharze bestehen zum überwiegenden Teil aus Abietinsäure oder Abietin- säurederivaten.Preferred tackifiers are natural or chemically modified rosin resins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
Die Tackifier können in einfacher Weise den Emulsionspolymerisaten, 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 emulsion polymers, preferably to the aqueous dispersions of the polymers. The tackifiers are preferably themselves in the form of an aqueous dispersion.
Haftklebstoff enthält vorzugsweise Tackifier. In diesem Fall enthält der Haftklebstoff vorzugsweise 50 bis 95 Gew.-% Emulsionspolymerisat und 5 bis 50 Gew.-% klebrigmachendes Harzes (Tackifier), bezogen auf den Feststoff des Haftklebstoffs, d. h. ohne Wasser.Pressure-sensitive adhesive preferably contains tackifiers. In this case, the pressure-sensitive adhesive preferably contains from 50 to 95% by weight of emulsion polymer and from 5 to 50% by weight of tackifying resin, based on the solid of the pressure-sensitive adhesive, that is to say the pressure-sensitive adhesive. H. without water.
Neben Tackifiern können auch noch weitere Additive z. B. Verdickungsmittel, vorzugsweise Assoziativverdicker, Entschäumer, Weichmacher, Pigmente, Netzmittel oder Füllstoffe bei der Verwendung als Haftklebstoff Verwendung finden und dem Haftklebstoff zugesetzt werden.In addition to Tackifiern also other additives z. As thickening agents, preferably associative thickeners, defoamers, plasticizers, pigments, wetting agents or fillers when used as a pressure-sensitive adhesive use and are added to the pressure-sensitive adhesive.
Für eine bessere Benetzung von Oberflächen können die Haftklebstoffe insbesondere Benetzungshilfsmittel, z. B. Fettalkoholethoxylate, Alkylphenolethoxylate, Sulfobern- steinsäureester, Nonylphenolethoxylate, Polyoxyethylene/-propylene oder Natriumdo- decylsulfonate enthalten. Die Menge beträgt im allgemeinen 0,05 bis 5 Gew.-Teile, insbesondere 0,1 bis 3 Gew.-Teile auf 100 Gew.-Teile Emulsionspolymerisat (fest).For a better wetting of surfaces, the pressure-sensitive adhesives, in particular wetting aids, z. As fatty alcohol ethoxylates, Alkylphenolethoxylate, sulfosuccinic, Nonylphenolethoxylate, polyoxyethylene / -propylenes or sodium dodecylsulfonate included. 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 emulsion polymer (solid).
Die Haftklebstoffe werden erfindungsgemäß zur Herstellung von Papieretiketten verwendet. Papieretiketten sind selbstklebende Artikel mit Papier als Trägermaterial. Das Papier ist zumindest auf einer Seite, vorzugsweise auf einer Seite, mit dem Haftklebstoff beschichtet.The pressure-sensitive adhesives are used according to the invention for the production of paper labels. Paper labels are self-adhesive articles with paper backing. The paper is coated on at least one side, preferably on one side, with the pressure-sensitive adhesive.
Zur Herstellung der Papieretiketten kann der aufgrund des Wassergehalts flüsssige Haftklebstoff direkt oder indirekt (im Transferverfahren) auf Papier durch gängige Auf- tragsverfahren beschichtet werden. Das Wasser kann bevorzugt durch Trocknung bei 50 bis 150 C entfernt werden. Die beschichteten Träger können vor oder nach dem Aufbringen des Klebstoffs in das für Etiketten notwendige Format geschnitten werden. Zur späteren Verwendung kann die mit Haftklebstoff beschichtete Seite der Substrate, mit einem Releasepapier, z. B. mit einem silikonisierten Papier, abgedeckt werden.For the production of the paper labels, the liquid adhesive based on the water content can be applied directly or indirectly (by transfer) to paper by conventional means. coating method are coated. The water may preferably be removed by drying at 50 to 150 ° C. The coated carriers can be cut into the format required for labels before or after application of the adhesive. For later use, the pressure-sensitive adhesive-coated side of the substrates, with a release paper, z. B. with a siliconized paper, covered.
Die erfindungsgemäßen Papieretiketten haben sehr gute anwendungstechnische Eigenschaften. Bei der Herstellung der Papieretiketten (Schneiden, Stanzen) kommt es aufgrund der guten Kohäsion nicht oder kaum zu Kantenaustritt des Haftklebstoffs. Der Haftklebstoff haftet gut auf dem Träger (Papier), hat eine sehr gute Adhäsion zu den Substraten und eine hohe Kohäsion (innere Festigkeit in der Klebstoffschicht). Der Haftklebstoff und somit auch die Papieretiketten sind geruchsfrei.The paper labels according to the invention have very good performance properties. In the production of paper labels (cutting, punching), there is little or no edge leakage of the pressure-sensitive adhesive due to the good cohesion. The pressure-sensitive adhesive adheres well to the support (paper), has a very good adhesion to the substrates and a high cohesion (internal strength in the adhesive layer). The pressure-sensitive adhesive and thus also the paper labels are odorless.
Die Papieretiketten haften gut auf unterschiedlichsten Substraten, auch auf Substraten mit unpolaren Oberflächen. Bei den Substraten kann es sich z. B. um Verpackungen oder Behälter aus unterschiedlichen Materialien handeln. Insbesondere handelt es sich im Verpackungsbereich oft um Substrate, z. B. verpackte Lebensmittel, die bei erniedrigter Temperatur dauerhaft gelagert werden.The paper labels adhere well to a wide variety of substrates, including substrates with non-polar surfaces. The substrates may be z. B. to deal with packaging or containers made of different materials. In particular, in the packaging sector are often substrates, eg. As packaged foods that are stored permanently at reduced temperature.
Die Papieretiketten eignen sich daher auch für Substrate, welche eine Temperatur im Bereich von -5 bis 10 0C, insbesondere -5 bis 5 0C haben, d. h. bei diesen Temperaturen gelagert werden.The paper labels are therefore also suitable for substrates which have a temperature in the range of -5 to 10 0 C, in particular -5 to 5 0 C, that is stored at these temperatures.
BeispieleExamples
In einem 2-Liter-Polymerisationsreaktor mit Anker Rührer und Heiz-/Kühleinrichtung wurde ein Gemisch aus 200 g Wasser und 0.75 g Ascorbinsäure unter Stickstoffatmosphäre auf 90 0C erhitzt. Dazu wird bei vorgenannter Temperatur 23.5 g einer 7 gewichtsprozentigen wässrigen Lösung von Natriumperoxodisulfat gegeben. Nach 5 Mi- nuten wird Zulauf 1 und innerhalb von 5 Stunden zudosiert. Zulauf 1 wird innerhalb von 45 Minuten auf die 4.5-fache Geschwindigkeit gesteigert. Zeitgleich mit Zulauf 1 wird mit der Zugabe von 126,5 g einer 7 gewichtsprozentigen Lösung von Natriumperoxodisulfat gestartet und mit konstanter Geschwindigkeit 300 Minuten zudosiert. Anschließend wird mittels 3 g Natronlauge in 58 g Wasser teilneutralisiert und schließ- lieh 30 g einer 10%igen Lösung von tert.-Butylperoxid in Wasser sowie 36 g einer Ace- tonbisulfitlösung in Wasser zeitgleich unter Rühren zudosiert. Letztlich werden bei 90 0C in 15 Minuten 15 g einer wässrigen Lösung (50%ig) eines Sulfobernsteinsäurediok- tylesters zugegeben. Der Feststoffgehalt wird auf 66-70 % eingestellt. Zulauf 1 : 175 g WasserIn a 2-liter polymerization reactor with anchor stirrer and heating / cooling device, a mixture of 200 g of water and 0.75 g of ascorbic acid was heated to 90 0 C under a nitrogen atmosphere. For this purpose, 23.5 g of a 7 weight percent aqueous solution of sodium peroxodisulfate is added at the aforementioned temperature. After 5 minutes, feed 1 is metered in and within 5 hours. Feed 1 is increased to 4.5 times the speed within 45 minutes. Concurrently with feed 1 is started with the addition of 126.5 g of a 7 weight percent solution of sodium peroxodisulfate and added at a constant rate for 300 minutes. Subsequently, it is partially neutralized by means of 3 g of sodium hydroxide solution in 58 g of water and finally 30 g of a 10% solution of tert-butyl peroxide in water and 36 g of an acetone bisulfite solution in water are added simultaneously with stirring. Finally, 15 g of an aqueous solution (50% strength) of a Sulfobernsteinsäurediok- tylesters be added at 90 0 C in 15 minutes. The solids content is adjusted to 66-70%. Feed 1: 175 g of water
46.9 g einer 32%igen wässrigen Lösung des Natriumsalzes des Schwefelsäurehalbesters von mit 30 Ethylenoxideinheiten ethoxyliertem Dodecanaol (Disponil FES 77) 6.7 g einer 45%igen Lösung des Natriumsalzes des mit einem C12-C14-Alkylrest und mit zwei Sulfonylresten derivatisierten Diphenylethers (Dowfax 2A1 ) 18 g einer 25%igen wässrigen Lösung von Natronlauge 15 g Acrylsäure (1 %)46.9 g of a 32% aqueous solution of the sodium salt of the sulfuric monoester of ethoxylated dodecanol (Disponil FES 77) containing 6.7 g of a 45% solution of the sodium salt of the diphenyl ether derivatized with a C 12 -C 14 -alkyl radical and two sulfonyl radicals (Dowfax 2A1) 18 g of a 25% aqueous solution of sodium hydroxide solution 15 g of acrylic acid (1%)
1320 g 2-Ethyl-hexylacrylat (88%)1320 g of 2-ethylhexyl acrylate (88%)
30 g 2-Hydroxypropylacrylat(2%) 90 g Methylmethacrylat (6%)30 g of 2-hydroxypropyl acrylate (2%) 90 g of methyl methacrylate (6%)
45 g Styrol (3%)45 g of styrene (3%)
Bei den anderen Beispielen wurde wie bei E1 verfahren, mit dem Unterschied, dass in Zulauf 1 die in nachfolgender Tabelle angegebenen Monomermengen verwendet wurden.In the other examples, the procedure was the same as for E1, with the difference that in feed 1 the monomer amounts indicated in the table below were used.
Klebewerte:Adhesive values:
Prüfungen: Exams:
Für die Prüfungen wurden die Dispersionen mit jeweils 20 Teilen einer Tackifier- Dispersion auf Basis eines teilhydrierten Abietinsäureesters abgemischt. Nach einer Reifezeit von 24 h wurden die Klebstoffe in einer Auftragsstärke von 20 μm auf ein Etikettenpapier (80 g/m2) aufgetragen. Zur Ermittlung der Schälfestigkeit nach Finat Test Method 01 wurden die beschichteten Papiere auf die Prüfoberfläche (oben angegeben, Polyethylen oder Karton) geklebt und nach 1 min in einer Zugmaschine der Schälprüfung unterzogen. Die Quickstick-messungen erfolgten nach der Finat Test Method 09 ebenfalls in einer Zugmaschine; bei dieser Prüfung wird aus dem beschichteten Etikettenpier eine Schlaufe gebildet, die beschichtete Seite mit der Prüfoberfläche in Kontakt gebracht und die zum Wiederabziehen nötige Kraft (N/25 mm) bestimmt. For the tests, the dispersions were mixed with 20 parts each of a tackifier dispersion based on a partially hydrogenated abietic acid ester. After a maturation time of 24 hours, the adhesives were applied to a label paper (80 g / m 2 ) in a thickness of 20 μm. To determine the peel strength according to Finat Test Method 01, the coated papers were stuck to the test surface (above, polyethylene or cardboard) and subjected to the peel test after 1 min in a tractor. The Quickstick measurements were also carried out in a tractor according to the Finat Test Method 09; During this test, a loop is formed from the coated label pier, the coated side is brought into contact with the test surface and the force required for redrawing (N / 25 mm) is determined.

Claims

Patentansprüche claims
1. Mit einem Haftklebstoff beschichtete Papieretiketten, dadurch gekennzeichnet, dass - der Haftklebstoff kein Vinylacetat in freier oder einpolymerisierter Form enthält und - als Bindemittel ein Emulsionspolymerisat enthält, welches aufgebaut ist aus1. With a pressure-sensitive adhesive coated paper labels, characterized in that - the pressure-sensitive adhesive contains no vinyl acetate in free or copolymerized form and - contains as binder an emulsion polymer, which is composed of
a) 70 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 1 bis 20 Gew.-% Methylmethacrylat c) 0,5 bis 10 Gew.-% eines vinylaromatischen Monomeren d) 0,5 bis 10 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0 bis 10 Gew.-% tertiär-Butyl(meth)acrylat und g) 0 bis 20 Gew.-% weiteren Monomeren, wobei die weiteren Monomeren maximal 3 Gew.-% Methylacrylat enthaltena) 70 to 95 wt .-% of a C6 to C10 alkyl (meth) acrylate b) 1 to 20 wt .-% of methyl methacrylate c) 0.5 to 10 wt .-% of a vinyl aromatic monomer d) 0.5 to 10 wt % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0 to 10% by weight of tertiary butyl (meth) acrylate and g) 0 to 20 wt .-% of further monomers, wherein the further monomers contain a maximum of 3 wt .-% methyl acrylate
2. Papieretiketten gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Emulsi- onspolymerisat aufgebaut ist aus2. paper labels according to claim 1, characterized in that the emulsion onspolymerisat is constructed from
a) 70 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 1 bis 20 Gew.-% Methylmethacrylat c) 0,5 bis 10 Gew.-% eines vinylaromatischen Monomeren d) 0,5 bis 10 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0 bis 10 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 20 Gew.-% weiteren Monomeren, wobei Methylacrylat ausge- schlössen ista) 70 to 95 wt .-% of a C6 to C10 alkyl (meth) acrylate b) 1 to 20 wt .-% of methyl methacrylate c) 0.5 to 10 wt .-% of a vinyl aromatic monomer d) 0.5 to 10 wt % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0 to 10% by weight of tertiary butyl (meth) acrylate g) 0 to 20 Wt .-% of other monomers, with methyl acrylate is excluded
3. Papieretiketten gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Emulsionspolymerisat aufgebaut ist aus3. Paper labels according to claim 1 or 2, characterized in that the emulsion polymer is constructed from
a) 70 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 1 bis 20 Gew.-% Methylmethacrylat c) 0,5 bis 10 Gew.-% eines vinylaromatischen Monomeren d) 0,5 bis 10 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mit mindestens einer Säure- oder Säureanhydridgruppe f) 0,2 bis 10 Gew. % tertiär-Butyl(meth)acrylat g) 0 bis 20 Gew.-% weiteren Monomeren, wobei Methylacrylat ausgeschlossen ista) 70 to 95 wt .-% of a C6 to C10 alkyl (meth) acrylate b) 1 to 20 wt .-% of methyl methacrylate c) 0.5 to 10 wt .-% of a vinyl aromatic monomer d) 0.5 to 10 wt % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0.2 to 10% by weight of tertiary butyl (meth) acrylate g) 0 to 20 wt .-% of other monomers, with methyl acrylate is excluded
4. Papieretiketten gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Emulsionspolymerisat aufgebaut ist aus4. Paper labels according to one of claims 1 to 3, characterized in that the emulsion polymer is constructed from
a) 75 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 3 bis 15 Gew.-% Methylmethacrylat c) 1 bis 8 Gew.-% eines vinylaromatischen Monomern d) 0,5 bis 8 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0,5 bis 5 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 10 Gew.-% weiteren Monomeren, wobei Methylacrylat ausge- schlössen ista) from 75 to 95% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 3 to 15% by weight of methyl methacrylate c) from 1 to 8% by weight of a vinylaromatic monomer d) from 0.5 to 8% by weight % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0.5 to 5% by weight of tertiary butyl (meth) acrylate g) 0 to 10 Wt .-% of other monomers, with methyl acrylate is excluded
5. Papieretiketten gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Haftklebstoff 50 bis 95 Gew.-% Emulsionspolymerisat und 5 bis 50 Gew.-% klebrigmachendes Harzes (Tackifier) enthält (bezogen auf den Fest- stoff des Haftklebstoffs, d. h. ohne Wasser)5. Paper labels according to one of claims 1 to 4, characterized in that the pressure-sensitive adhesive 50 to 95 wt .-% emulsion polymer and 5 to 50 wt .-% tackifying resin (tackifier) contains (based on the solid of the pressure-sensitive adhesive, ie without water)
6. Verwendung der Papieretiketten gemäß einem der Ansprüche 1 bis 5 für Substrate, welche eine Temperatur im Bereich von -5 bis 10 0C haben.6. Use of the paper labels according to any one of claims 1 to 5 for substrates which have a temperature in the range of -5 to 10 0 C.
7. Wässrige Polymerdispersion, enthaltend ein Emulsionspolymerisat aufgebaut aus7. Aqueous polymer dispersion containing an emulsion polymer composed of
a) 75 bis 95 Gew.-% eines C6 bis C10 Alkyl(meth)acrylats b) 3 bis 15 Gew.-% Methylmethacrylat c) 1 bis 8 Gew.-% eines vinylaromatischen Monomern d) 0,5 bis 8 Gew.-% eines Hydroxyalkyl(meth)acrylats e) 0,5 bis 5 Gew.-% eines Monomeren mir mindestens einer Säure- oder Säureanhydridgruppe f) 0,5 bis 5 Gew.-% tertiär-Butyl(meth)acrylat g) 0 bis 10 Gew.-% weiteren Monomeren, wobei Methylacrylat ausgeschlossen ist a) from 75 to 95% by weight of a C 6 to C 10 alkyl (meth) acrylate b) from 3 to 15% by weight of methyl methacrylate c) from 1 to 8% by weight of a vinylaromatic monomer d) from 0.5 to 8% by weight % of a hydroxyalkyl (meth) acrylate e) 0.5 to 5% by weight of a monomer having at least one acid or acid anhydride group f) 0.5 to 5% by weight of tertiary butyl (meth) acrylate g) 0 to 10 Wt .-% of other monomers, with methyl acrylate is excluded
EP08701460A 2007-01-15 2008-01-14 Pressure-sensitive adhesive for paper labels Withdrawn EP2121782A1 (en)

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EP07100550 2007-01-15
EP08701460A EP2121782A1 (en) 2007-01-15 2008-01-14 Pressure-sensitive adhesive for paper labels
PCT/EP2008/050339 WO2008087113A1 (en) 2007-01-15 2008-01-14 Pressure-sensitive adhesive for paper labels

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CN104099044A (en) * 2013-04-02 2014-10-15 联冠(开平)胶粘制品有限公司 Label adhesive for sticking on oil stain surface and preparation method thereof
KR102032016B1 (en) * 2013-06-19 2019-10-14 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 Pressure-sensitive adhesive composition for polarization plates, pressure-sensitive adhesive sheet for polarization plates, polarization plate with pressure-sensitive adhesive layer, laminate body and flat panel display
EP3164431B1 (en) * 2014-07-02 2020-02-12 Basf Se Method for adhering substrates on cold and moist surfaces
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CN111116848B (en) * 2019-12-31 2020-12-22 河南省科学院高新技术研究中心 Malathion ester modified acrylate emulsion and preparation method thereof
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