EP2016153A1 - CONTACT ADHESIVE CONTAINING n-BUTYLACRYLATE AND HYDROXYBUTYL(METH)ACRYLATE. - Google Patents

CONTACT ADHESIVE CONTAINING n-BUTYLACRYLATE AND HYDROXYBUTYL(METH)ACRYLATE.

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Publication number
EP2016153A1
EP2016153A1 EP07728144A EP07728144A EP2016153A1 EP 2016153 A1 EP2016153 A1 EP 2016153A1 EP 07728144 A EP07728144 A EP 07728144A EP 07728144 A EP07728144 A EP 07728144A EP 2016153 A1 EP2016153 A1 EP 2016153A1
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EP
European Patent Office
Prior art keywords
acrylate
meth
polymer
monomers
weight
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Withdrawn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
EP07728144A
Other languages
German (de)
French (fr)
Inventor
Cornelis Petrus Beyers
Stefan Kirsch
Petra SCHÖCKER
Ines Pietsch
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BASF SE
Original Assignee
BASF SE
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Filing date
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Application filed by BASF SE filed Critical BASF SE
Priority to EP07728144A priority Critical patent/EP2016153A1/en
Publication of EP2016153A1 publication Critical patent/EP2016153A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups

Definitions

  • the invention relates to a pressure-sensitive adhesive which comprises an aqueous polymer dispersion prepared by emulsion polymerization, characterized in that the polymer contains n-butyl (meth) acrylate and hydroxybutyl (meth) acrylate.
  • the invention relates to a process for the preparation of the pressure-sensitive adhesive and the use of the pressure-sensitive adhesive.
  • Adhesive adhesives require both good adhesion to the substrate and sufficient internal strength in the adhesive layer (cohesion). Adhesion and cohesion are opposite performance properties. Measures that improve adhesion generally result in cohesion deterioration and vice versa.
  • Pressure-sensitive adhesives based on aqueous polymer dispersions obtainable by emulsion polymerization have been known for a long time.
  • these are polyacrylates.
  • An improvement in the adhesion and cohesion has been achieved in such emulsion polymers hitherto by selecting suitable comonomers or additives.
  • suitable comonomers or additives By way of example, reference is made to DE-A 103 23 048, according to which positive effects are achieved by adding silicon compounds to the polymer dispersion.
  • EP-A 625 557 discloses pressure-sensitive adhesives which contain hydroxyalkyl acrylates.
  • Self-adhesive articles consist essentially of a carrier and a pressure-sensitive adhesive layer applied thereto.
  • the carrier is transparent to many applications. When water is used, so-called “blushing" often occurs, which is due to cloudiness in the adhesive layer caused by the ingress of water, as the whitening process worsens the performance properties and, of course, cloudiness is impaired especially in the case of transparent film labels the visual appearance.
  • Object of the present invention were therefore a low whitening and good performance properties of the pressure-sensitive adhesive.
  • the pressure-sensitive adhesives should have good adhesion and / or cohesion. Accordingly, the initially defined pressure-sensitive adhesive was found. Also found was a process for its preparation.
  • the pressure-sensitive adhesive according to the invention contains as essential constituent an aqueous polymer dispersion which is prepared by emulsion polymerization;
  • the dispersed polymer is therefore an emulsion polymer.
  • the emulsion polymer is preferably at least 40 wt .-%, preferably at least 50 wt .-%, more preferably at least 60 wt .-% of n-butyl acrylate or n-butyl methacrylate (short n-butyl (meth) acrylate); preferred is n-butyl acrylate.
  • the content of n-butyl (meth) acrylate is not more than 99.9% by weight, in particular not more than 99% by weight.
  • the emulsion polymer can further so-called main monomers selected from C1 to C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides , Vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds or mixtures of these monomers.
  • main monomers selected from C1 to C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides , Vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds or mixtures of these monomers.
  • (meth) acrylic acid alkyl ester having a C 1 -C 10 -alkyl radical such as methyl methacrylate, methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • Suitable hydrocarbons having 2 to 8 C atoms and one or two olefinic double bonds are ethylene, propylene, butadiene, isoprene and chloroprene.
  • Preferred main monomers are the C 1 - to C 10 -alkyl acrylates and -methacrylates, in particular C 1 - to C 8 -alkyl acrylates and -methacrylates and vinylaromatics, in particular styrene and mixtures thereof.
  • Methyl acrylate, methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, styrene and mixtures of these monomers are particularly preferred as further main monomers.
  • the emulsion polymer can, for. B. to 0 to 40, in particular 0 to 30 wt.% Consist of such other major monomers.
  • the polymer in addition to the n-butyl (meth) acrylate, the polymer also necessarily contains hydroxybutyl acrylate or hydroxybutyl methacrylate (hydroxybutyl (meth) acrylate for short).
  • the butyl chain of the hydroxybutyl (meth) acrylate is preferably unbranched, it is an n-butyl chain.
  • the OH group is preferably at the terminal C atom, therefore it is 4-hydroxy-n-butyl (meth) acrylate.
  • the acrylates are particularly preferred over the methacrylates, very particularly preferably 4-hydroxy-n-butyl acrylate
  • the amount of hydroxybutyl (meth) acrylate contained in the polymer is preferably at least 0.1% by weight, more preferably at least 0.3% by weight, very preferably at least 0.5% by weight and in particular at least 1% by weight.
  • the amount of hydroxybutyl (meth) acrylate contained in the polymer is generally not greater than 5% by weight, more preferably not greater than 4.5% by weight and in particular not greater than 3% by weight. All weights are based on the polymer.
  • the polymer may contain so-called auxiliary monomers, e.g. B. monomers with acid groups (acid monomers, see above), for.
  • acid monomers for.
  • carboxylic acid sulfonic acid or phosphonic acid groups.
  • carboxylic acid groups e.g. B. monomers with carboxylic acid, sulfonic acid or phosphonic acid groups.
  • carboxylic acid groups e.g. B. monomers with acid groups (acid monomers, see above), for.
  • carboxylic acid sulfonic acid or phosphonic acid groups.
  • carboxylic acid groups e.g., sulfonic acid or phosphonic acid groups.
  • carboxylic acid groups for.
  • Called z As acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • auxiliary monomers are z.
  • B. also other hydroxyl-containing monomers, in particular C1-C10 hydroxyalkyl (meth) acrylates, or (meth) acrylamide.
  • phenyloxyethylglycol mono- (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may be mentioned as auxiliary monomers.
  • Crosslinking monomers may also be mentioned as auxiliary monomers.
  • the polymer may contain acid monomers, preferably in amounts of from 0.1 to 5, particularly preferably from 0.2 to 4, very particularly preferably from 0.5 to 3,% by weight, based on the polymer.
  • a preferred polymer is z. B. constructed as follows:
  • n-butyl (meth) acrylate (BA) 0.1 to 5% by weight of hydroxybutyl (meth) acrylate (HBA) 1 to 30% by weight of further main monomers (see above) 0 to 5% by weight
  • BA n-butyl (meth) acrylate
  • HBA hydroxybutyl (meth) acrylate
  • further main monomers see above
  • a particularly preferred polymer is z. B. constructed as follows:
  • n-butyl (meth) acrylate (BA) From 50 to 95% by weight of n-butyl (meth) acrylate (BA) from 0.2 to 4% by weight of hydroxybutyl (meth) acrylate (HBA)
  • An especially preferred polymer is z. B. constructed as follows:
  • HBA hydroxybutyl (meth) acrylate
  • the glass transition temperature of the polymer is preferably -60 to 0 ° C, more preferably -60 to -1O 0 C and most preferably -60 to -2O 0 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.
  • 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.
  • protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, pp. 41 1 to 420.
  • Emulsifiers are both anionic, cationic as also 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.
  • Anionic and nonionic emulsifiers are preferably used as surface-active substances. Common accompanying emulsifiers are z.
  • ethoxylated fatty alcohols As 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).
  • emulsifiers are compounds of the general formula II
  • R5 and R6 are hydrogen or C4 to C14 alkyl and are not hydrogen at the same time, and X and Y can be alkali metal ions and / or ammonium ions.
  • R5, R6 are linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, wherein R5 and R6 are not both simultaneously hydrogen.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred.
  • Particularly advantageous are compounds II in which X and Y are sodium, R5 is a branched alkyl radical having 12 C atoms and R6 is hydrogen or R5.
  • technical mixtures are used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax 2A1 (trademark of the Dow Chemical Company).
  • Suitable emulsifiers can also be found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208. Trade names of emulsifiers are z. Dowfax 2 A1, Emulan NP 50, Dextrol OC 50, Emulsifier 825, Emulsifier 825 S, Emulan OG, Texapon NSO, Nekanil 904 S, Lumiten I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL , Emulphor NPS 25.
  • the 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 z.
  • 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.
  • alkali metal salts of sulphurous acid e.g. 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 concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states.
  • Usual Red Ox initiator systems are z.
  • the individual components e.g. the reduction component, can also be mixtures 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, more preferably 0.05 to 0.8 parts by weight and most 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 having a molecular weight of less than 2000, in particular less than 1000 g / mol.
  • the emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 90 ° C.
  • the polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the 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 detail, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.
  • a subset of the monomers may, if desired, be initially charged in the polymerization vessel at the beginning of the polymerization, the remaining monomers, or all monomers, if no monomers are initially charged, are added during the polymerization in the course of 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 with 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 i. preferably at least 70% by weight, particularly preferably at least 80% by weight, very particularly preferably at least 90% by weight are continuously added during the polymerization.
  • no monomers are presented, d. H. the total amount of monomers is added 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.
  • the hydroxybutyl (meth) acrylate is added to the polymerization mixture completely or at least partially only towards the end of the emulsion polymerization.
  • more than 60% by weight of the hydroxybutyl (meth) acrylate (referred to below as residual amount HBA) in the emulsion polymerization is supplied only when the polymerization mixture (present in the polymerization vessel mixture of monomers and already formed polymer) already more than 50 wt. %, more preferably more than 60 wt.%, Very particularly preferably more than 75 wt.% Of the total amount of the monomers.
  • the term "monomer” is intended to include both unpolymerized monomers and monomeric units of the polymer, i. the polymerized monomers understood.
  • the above residual amount of HBA is in particular at least 70% by weight, more preferably at least 80% by weight and most preferably at least 90% by weight. %, or around 100% by weight of the hydroxybutyl (meth) acrylate.
  • the residual amount of HBA is fed at the end of the emulsion polymerization, ie after all the other monomers have already been added to the polymerization mixture.
  • the monomers added to the polymerization mixture are preferably already predominantly polymerized, i. the polymerization mixture is at the beginning of the addition of the residual amount of HBA to at least 40 wt.%, Of already formed polymer.
  • To remove the residual monomers may also after the end of the actual emulsion polymerization, i. after a conversion of all monomers and after copolymerization of the residual amount of HBA, further initiator can be added (chemical deodorization).
  • aqueous dispersions of the polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%.
  • the polymer thus prepared is preferably used in the form of its aqueous dispersion.
  • the polymer is preferably used as or in pressure-sensitive adhesives.
  • the pressure-sensitive adhesive preferably contains the polymer 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 polymer or of the aqueous dispersion of the polymer.
  • the pressure-sensitive adhesive may also contain other additives.
  • a tackifier i. a tackifying resin. 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, monovalent or polyvalent counterions (cations) or preferably in their esterified form.)
  • Alcohols used for the esterification may be monohydric or polyhydric, for example, methanol, ethanediol, diethylene glycol, triethylene glycol , 1,2,3-propanethiol, pentaerythritol.
  • hydrocarbon resins e.g. 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, ⁇ -methylstyrene, vinyltoluene Use.
  • unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene, vinyltoluene Use.
  • tackifiers are increasingly also polyacrylates, which have a low molecular weight used.
  • these polyacrylates have a weight-average molecular weight M w below 30,000.
  • the polyacrylates are preferably at least 60, in particular at least 80 wt .-% of Ci-C8-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 polymers according to the invention, preferably to the aqueous dispersions of the polymers.
  • the tackifiers are preferably themselves in the form of an aqueous dispersion.
  • the amount by weight of the tackifiers is preferably 5 to 100 parts by weight. particularly preferably 10 to 50 parts by weight. based on 100 parts by weight of polymer, (solid / solid).
  • Tackifiern z. B. still further additives z.
  • thickeners preferably associative thickeners, defoamers, plasticizers, pigments, wetting agents or fillers when used as a pressure-sensitive adhesive use.
  • the pressure-sensitive adhesives according to the invention therefore optionally contain, in addition to the aqueous polymer dispersion, tackifiers and / or the above additives.
  • 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 polymer (solid).
  • the pressure-sensitive adhesives are suitable for the production of self-adhesive articles such as labels, films or adhesive tapes.
  • the pressure-sensitive adhesive can be prepared by conventional methods, for. B. by rolling, knife coating, brushing, etc. on carriers, eg. As paper or polymer films, preferably consisting of polyethylene, polypropylene, which may be biaxially or monoaxially stretched, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyamide or metal are applied.
  • supports with non-polar surfaces e.g. from polyolefins, in particular polyethylene or polypropylene, since the dispersions according to the invention adhere well thereto.
  • transparent carrier z.
  • transparent polymer films into consideration.
  • Self-adhesive articles with transparent polymer films are z. B. foil labels.
  • the water may preferably by drying at from 50 to 15O 0 C to be removed.
  • the carriers can be cut into adhesive tapes, labels or foils before or after application of the adhesive.
  • the pressure-sensitive adhesive-coated side of the substrates can be covered with a release paper, for example with a siliconized paper.
  • the self-adhesive articles according to the invention have very good adhesive properties, in particular a good adhesion to the substrates and a high cohesion (internal strength in the adhesive layer). They also have a good adhesion to nonpolar surfaces and are therefore particularly suitable for substrates with nonpolar surfaces, eg. B. Polyolefinober vom, z. As polyethylene (HDPE or LDPE) or polypropylene.
  • the pressure-sensitive adhesives according to the invention are also suitable for transparent carriers, in particular also for film labels, since the so-called “whitening" frequently occurring when water is present does not occur, but is at least reduced , a clouding or other deterioration of the visual appearance is not or hardly observed.
  • Feed 1 was an aqueous emulsion prepared from 271, 84 g of deionized water
  • Disponil FES 77 ethoxylated C12-C14 sodium sulfate
  • Feed 2 was 47.14 g of a 7% strength by weight aqueous solution of sodium peroxodisulfate.
  • feed 3 is started and metered in over 60 minutes.
  • Feed 3 was 12.38 g of either 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate or 4-hydroxybutyl acrylate.
  • feed 4 and feed 5 were started and evenly over 60 min. added.
  • Feed 4 was 5.5 g of a 10 wt% aqueous solution of t-butyl hydroperoxide.
  • Feed 5 was 7.33 g of a 12% by weight aqueous solution of sodium acetone bisulfite.
  • Lumiten To the polymer dispersions was further added Lumiten, so that the amount of Lumiten 1, 2 parts by weight per 100 parts by weight of polymer (solid).
  • the pressure sensitive adhesives were applied at a rate of 19 g / m 2 polyethylene film backing coated (by the transfer method, coating first of silicone paper and transfer to polyethylene) and dried for 3 minutes at 9O 0 C.
  • the pressure-sensitive adhesive coated carrier was cut into 25 mm wide test strips. To determine the shear strength of the test strips were bonded with a bond area of 6.25 cm2 on steel, with a 1 kg roller 1 times rolled, stored for 10 min (under standard conditions, 50% rel. Humidity 1 bar, 23 0 C) and then suspended with a 1 kg weight (in standard climate). The measure of shear strength was the time in hours until the weight dropped; in each case the average of 5 measurements was calculated.
  • a loop was formed from a 17.5 cm long and 2.5 cm wide test strip by clamping both ends in the jaws of a tensile testing machine, which then with a polyethylene surface at a speed of 300 mm / min (lowering the loop on the surface) is brought into contact. After full contact, the loop is after a Contact time of 1 minute withdrawn and determined the determined maximum force in N / 2.5 cm.

Abstract

The invention relates to a contact adhesive containing an aqueous polymer dispersion that is produced by emulsion polymerization. The contact adhesive according to the invention is characterized in that the polymer contains n-butyl(meth)acrylate and hydroxybutyl(meth)acrylate.

Description

Haftklebstoff, enthaltend n-Butylacrylat und Hydroxybutyl(meth)acrylatPressure-sensitive adhesive containing n-butyl acrylate and hydroxybutyl (meth) acrylate
Beschreibungdescription
Die Erfindung betrifft einen Haftklebstoff, der eine durch Emulsionspolymerisation hergestellte wässrige Polymerdispersion enthält, dadurch gekennzeichnet, dass das Polymer n-Butyl(meth)acrylat und Hydroxybutyl(meth)acrylat enthält.The invention relates to a pressure-sensitive adhesive which comprises an aqueous polymer dispersion prepared by emulsion polymerization, characterized in that the polymer contains n-butyl (meth) acrylate and hydroxybutyl (meth) acrylate.
Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung des Haftklebstoffs und die Verwendung des Haftklebstoffs.Furthermore, the invention relates to a process for the preparation of the pressure-sensitive adhesive and the use of the pressure-sensitive adhesive.
Bei Haftklebstoffen ist sowohl eine gute Haftung (Adhäsion) zum Substrat gewünscht als auch eine ausreichende innere Festigkeit in der Klebstoffschicht (Kohäsion). Bei Adhäsion und Kohäsion handelt es sich um entgegengesetzte anwendungstechnische Eigenschaften. Maßnahmen, die eine Verbesserung der Adhäsion bewirken, führen im allgemeinen gleichzeitig zu einer Verschlechterung der Kohäsion und umgekehrt.Adhesive adhesives require both good adhesion to the substrate and sufficient internal strength in the adhesive layer (cohesion). Adhesion and cohesion are opposite performance properties. Measures that improve adhesion generally result in cohesion deterioration and vice versa.
Haftklebstoffe auf Basis von wässrigen Polymerdispersionen, welche durch Emulsionspolymerisation erhältlich sind, sind lange bekannt. Insbesondere handelt es sich dabei um Polyacrylate. Eine Verbesserung der Adhäsion und Kohäsion wurde bei derartigen Emulsionspolymerisaten bisher durch Auswahl geeigneter Comonomere oder Additive erreicht. Exemplarisch sei auf DE-A 103 23 048 verwiesen, wonach durch Zusatz von Siliziumverbindungen zur Polymerdispersion positive Effekte erzielt werden. Aus EP-A 625 557 sind Haftklebstoffe bekannt, die Hydroxyalkylacrylate enthal- ten.Pressure-sensitive adhesives based on aqueous polymer dispersions obtainable by emulsion polymerization have been known for a long time. In particular, these are polyacrylates. An improvement in the adhesion and cohesion has been achieved in such emulsion polymers hitherto by selecting suitable comonomers or additives. By way of example, reference is made to DE-A 103 23 048, according to which positive effects are achieved by adding silicon compounds to the polymer dispersion. EP-A 625 557 discloses pressure-sensitive adhesives which contain hydroxyalkyl acrylates.
Selbstklebende Artikel bestehen im wesentlichen aus einem Träger und einer darauf aufgebrachten Haftklebstoffschicht. Der Träger ist für viele Anwendungen transparent. Bei Einwirkung von Wasser kommt es häufig zum sogenannten „Weißanlaufen" darun- ter ist eine Trübung in der Klebstoffschicht zu verstehen, die durch das Eindringen von Wasser verursacht wird. Durch das Weißanlaufen werden die anwendungstechnischen Eigenschaften verschlechtert; naturgemäß beeinträchtigt die Trübung insbesondere bei transparenten Folienetiketten das optische Erscheinungsbild.Self-adhesive articles consist essentially of a carrier and a pressure-sensitive adhesive layer applied thereto. The carrier is transparent to many applications. When water is used, so-called "blushing" often occurs, which is due to cloudiness in the adhesive layer caused by the ingress of water, as the whitening process worsens the performance properties and, of course, cloudiness is impaired especially in the case of transparent film labels the visual appearance.
Bekannt ist z. B. aus EP-A 1 378 527 oder WO 98/44064, das Weißanlaufen bei wässrigen Polymerdispersionen durch spezielle Aufbaukomponenten des dispergierten Polymeren zu vermindern. Das erreichte Ergebnis ist noch nicht in vollem Umfang zufriedenstellend.It is known z. Example, from EP-A 1 378 527 or WO 98/44064, to reduce the blushing in aqueous polymer dispersions by special structural components of the dispersed polymer. The result achieved is not yet fully satisfactory.
Aufgabe der vorliegenden Erfindung waren daher ein geringes Weißanlaufen und gute anwendungstechnische Eigenschaften des Haftklebstoffs. Insbesondere sollen die Haftklebstoffe eine gute Adhäsion und/oder Kohäsion haben. Demgemäss wurde der eingangs definierte Haftklebstoff gefunden. Gefunden wurde auch ein Verfahren zu seiner Herstellung.Object of the present invention were therefore a low whitening and good performance properties of the pressure-sensitive adhesive. In particular, the pressure-sensitive adhesives should have good adhesion and / or cohesion. Accordingly, the initially defined pressure-sensitive adhesive was found. Also found was a process for its preparation.
Der erfindungsgemäße Haftklebstoff enthält als wesentlichen Bestandteil eine wässrige Polymerdispersion, welche durch Emulsionspolymerisation hergestellt wird; bei dem dispergierten Polymer handelt es sich daher um ein Emulsionspolymerisat.The pressure-sensitive adhesive according to the invention contains as essential constituent an aqueous polymer dispersion which is prepared by emulsion polymerization; The dispersed polymer is therefore an emulsion polymer.
Das Emulsionspolymerisat besteht vorzugsweise zu mindestens 40 Gew.-%, bevorzugt zu mindestens 50 Gew.-%, besonders bevorzugt zu mindestens 60 Gew.-% aus n-Butylacrylat oder n-Butylmethacrylat (kurz n-Butyl(meth)acrylat); bevorzugt ist n-Butylacrylat.The emulsion polymer is preferably at least 40 wt .-%, preferably at least 50 wt .-%, more preferably at least 60 wt .-% of n-butyl acrylate or n-butyl methacrylate (short n-butyl (meth) acrylate); preferred is n-butyl acrylate.
Insbesondere beträgt der Gehalt an n-Butyl(meth)acrylat maximal 99,9 Gew. %, insbesondere maximal 99 Gew. %.In particular, the content of n-butyl (meth) acrylate is not more than 99.9% by weight, in particular not more than 99% by weight.
Neben n-Butyl(meth)acrylat kann das Emulsionspolymerisat weitere sogenannte Hauptmonomere ausgewählt aus C1 bis C20 Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, Vinylethern von 1 bis 10 C Atome enthaltenden Alkoholen, aliphatischen Kohlenwasserstoffen mit 2 bis 8 C Atomen und ein oder zwei Doppelbindungen oder Mischungen dieser Monomeren, enthalten.In addition to n-butyl (meth) acrylate, the emulsion polymer can further so-called main monomers selected from C1 to C20 alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides , Vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds or mixtures of these monomers.
Zu nennen sind z. B. (Meth)acrylsäurealkylester mit einem C1-C10-Alkylrest, wie Me- thyl-methacrylat, Methylacrylat, Ethylacrylat und 2-Ethylhexylacrylat.To name a few are z. B. (meth) acrylic acid alkyl ester having a C 1 -C 10 -alkyl radical, such as methyl methacrylate, methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
Vinylester von Carbonsäuren mit 1 bis 20 C-Atomen sind z. B. Vinyllaurat, -stearat, Vinylpropionat, Versaticsäurevinylester und Vinylacetat.Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
Als vinylaromatische Verbindungen kommen Vinyltoluol, a- und p-Methylstyrol, a-Butyl- styrol, 4-n-Butylstyrol, 4-n-Decylstyrol und vorzugsweise Styrol in Betracht. Beispiele für Nitrile sind Acrylnitril und Methacrylnitril.Suitable vinylaromatic compounds are vinyltoluene, α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.
Die Vinylhalogenide sind mit Chlor, Fluor oder Brom substituierte ethylenisch ungesättigte Verbindungen, bevorzugt Vinylchlorid und Vinylidenchlorid.The vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
Als Vinylether zu nennen sind z. B. Vinylmethylether oder Vinylisobutylether. Bevorzugt wird Vinylether von 1 bis 4 C-Atome enthaltenden Alkoholen.To name as vinyl ethers are, for. As vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
Als Kohlenwasserstoffe mit 2 bis 8 C-Atomen und ein oder zwei olefinischen Doppel- bindungen seien Ethylen, Propylen, Butadien, Isopren und Chloropren genannt. Als Hauptmonomere bevorzugt sind die C1- bis C10-Alkylacrylate und -methacrylate, insbesondere C1- bis C8-Alkylacrylate und -methacrylate und Vinylaromaten, insbesondere Styrol und deren Mischungen.Suitable hydrocarbons having 2 to 8 C atoms and one or two olefinic double bonds are ethylene, propylene, butadiene, isoprene and chloroprene. Preferred main monomers are the C 1 - to C 10 -alkyl acrylates and -methacrylates, in particular C 1 - to C 8 -alkyl acrylates and -methacrylates and vinylaromatics, in particular styrene and mixtures thereof.
Als weitere Hauptmonomere besonders bevorzugt sind Methylacrylat, Methylmethacry- lat, Ethylacrylat, 2-Ethylhexylacrylat, n-Hexylacrylat, Styrol sowie Mischungen dieser Monomere.Methyl acrylate, methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, styrene and mixtures of these monomers are particularly preferred as further main monomers.
Das Emulsionspolymerisat kann z. B. zu 0 bis 40, insbesondere 0 bis 30 Gew. % aus derartigen weiteren Hauptmonomeren bestehen.The emulsion polymer can, for. B. to 0 to 40, in particular 0 to 30 wt.% Consist of such other major monomers.
Erfindungsgemäß enthält das Polymer neben dem n-Butyl(meth)acrylat zwingend auch Hydroxybutylacrylat oder Hydroxybutylmethacrylat (kurz Hydroxybutyl(meth)acrylat). Die Butylkette des Hydroxybutyl(meth)acrylat ist vorzugsweise unverzweigt, es handelt sich um eine n-Butylkette. Die OH - Gruppe steht vorzugsweise am endständigen C- Atom, es handelt sich daher um 4 Hydroxy-n-butyl (meth)acrylat. Besonders bevorzugt sind die Acrylate gegenüber den Methacrylaten, ganz besonders bevorzugt ist das 4 Hydroxy-n-butylacrylatAccording to the invention, in addition to the n-butyl (meth) acrylate, the polymer also necessarily contains hydroxybutyl acrylate or hydroxybutyl methacrylate (hydroxybutyl (meth) acrylate for short). The butyl chain of the hydroxybutyl (meth) acrylate is preferably unbranched, it is an n-butyl chain. The OH group is preferably at the terminal C atom, therefore it is 4-hydroxy-n-butyl (meth) acrylate. The acrylates are particularly preferred over the methacrylates, very particularly preferably 4-hydroxy-n-butyl acrylate
Die Menge des im Polymeren enthaltenen Hydroxybutyl(meth)acrylat beträgt vorzugsweise mindestens 0,1 Gew. %, besonders bevorzugt mindestens 0,3 Gew. %, ganz besonders bevorzugt mindestens 0,5 Gew. % und insbesondere mindestens 1 Gew. %. Die Menge des im Polymeren enthaltenen Hydroxybutyl(meth)acrylat ist im allgemeinen nicht größer als 5 Gew. %, besonders bevorzugt nicht größer als 4,5 Gew. % und insbesondere nicht größer als 3 Gew. %. Alle Gewichtsangaben sind dabei auf das Polymer bezogen.The amount of hydroxybutyl (meth) acrylate contained in the polymer is preferably at least 0.1% by weight, more preferably at least 0.3% by weight, very preferably at least 0.5% by weight and in particular at least 1% by weight. The amount of hydroxybutyl (meth) acrylate contained in the polymer is generally not greater than 5% by weight, more preferably not greater than 4.5% by weight and in particular not greater than 3% by weight. All weights are based on the polymer.
Neben dem n-Butyl(meth)acrylat, dem Hydroxybutyl(meth)acrylat und gegebenenfalls den obigen Hauptmonomeren kann das Polymer sog. Hilfsmonomere enthalten, z. B. Monomere mit Säuregruppen (Säure-Monomere, siehe oben), z. B. Carbonsäure, SuI- fonsäure oder Phosphonsäuregruppen. Bevorzugt sind Carbonsäuregruppen. Genannt seien z. B. Acrylsäure, Methacrylsäure, Itacon-säure, Maleinsäure oder Fumarsäure.In addition to the n-butyl (meth) acrylate, the hydroxybutyl (meth) acrylate and optionally the above main monomers, the polymer may contain so-called auxiliary monomers, e.g. B. monomers with acid groups (acid monomers, see above), for. As carboxylic acid, sulfonic acid or phosphonic acid groups. Preferred are carboxylic acid groups. Called z. As acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
Weitere Hilfsmonomere sind z. B. auch sonstige Hydroxylgruppen enthaltende Mono- mere, insbesondere C1-C10-Hydroxyalkyl(meth)acrylate, oder (Meth)acrylamid.Other auxiliary monomers are z. B. also other hydroxyl-containing monomers, in particular C1-C10 hydroxyalkyl (meth) acrylates, or (meth) acrylamide.
Als Hilfsmonomere seien darüber hinaus Phenyloxyethylglykolmono-(meth-)acrylat, Glycidylacrylat, Glycidylmethacrylat, Amino- (meth-)acrylate wie 2-Aminoethyl-(meth-) acrylat genannt.In addition, phenyloxyethylglycol mono- (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate may be mentioned as auxiliary monomers.
Als Hilfsmonomere seien auch vernetzende Monomere genannt. Insbesondere kann das Polymer Säure-Monomere enthalten, vorzugsweise in Mengen von 0,1 bis 5, besonders bevorzugt 0,2 bis 4, ganz besonders bevorzugt 0,5 bis 3 Gew. %, bezogen auf das Polymer.Crosslinking monomers may also be mentioned as auxiliary monomers. In particular, the polymer may contain acid monomers, preferably in amounts of from 0.1 to 5, particularly preferably from 0.2 to 4, very particularly preferably from 0.5 to 3,% by weight, based on the polymer.
Ein bevorzugtes Polymere ist z. B. wie folgt aufgebaut aus:A preferred polymer is z. B. constructed as follows:
40 bis 98 Gew. % n-Butyl(meth)acrylat (BA) 0,1 bis 5 Gew. % Hydroxybutyl(meth)acrylat (HBA) 1 bis 30 Gew. % weitere Hauptmonomere (siehe oben) 0 bis 5 Gew. % Hilfsmonomere, insbesondere Säure-Monomere40 to 98% by weight of n-butyl (meth) acrylate (BA) 0.1 to 5% by weight of hydroxybutyl (meth) acrylate (HBA) 1 to 30% by weight of further main monomers (see above) 0 to 5% by weight Auxiliary monomers, in particular acid monomers
Ein besonders bevorzugtes Polymere ist z. B. wie folgt aufgebaut aus:A particularly preferred polymer is z. B. constructed as follows:
50 bis 95 Gew. % n-Butyl(meth)acrylat (BA) 0,2 bis 4 Gew. % Hydroxybutyl(meth)acrylat (HBA)From 50 to 95% by weight of n-butyl (meth) acrylate (BA) from 0.2 to 4% by weight of hydroxybutyl (meth) acrylate (HBA)
4 bis 30 Gew. % weitere Hauptmonomere (siehe oben)4 to 30% by weight of other main monomers (see above)
0,2 bis 5 Gew. % Hilfsmonomere, insbesondere Säure-Monomere0.2 to 5 wt.% Auxiliary monomers, in particular acid monomers
Ein ganz besonders bevorzugtes Polymere ist z. B. wie folgt aufgebaut aus:An especially preferred polymer is z. B. constructed as follows:
60 bis 90 Gew. % n-Butyl(meth)acrylat (BA)60 to 90% by weight of n-butyl (meth) acrylate (BA)
0,5 bis 4 Gew. % Hydroxybutyl(meth)acrylat (HBA)0.5 to 4% by weight of hydroxybutyl (meth) acrylate (HBA)
5 bis 30 Gew. % weitere Hauptmonomere (siehe oben)5 to 30% by weight of other main monomers (see above)
0,2 bis 5 Gew. % Hilfsmonomere, insbesondere Säure-Monomere0.2 to 5 wt.% Auxiliary monomers, in particular acid monomers
Die Glasübergangstemperatur des Polymeren beträgt vorzugsweise -60 bis O0C, besonders bevorzugt -60 bis -1O0C und ganz besonders bevorzugt -60 bis -2O0C.The glass transition temperature of the polymer is preferably -60 to 0 ° C, more preferably -60 to -1O 0 C and most preferably -60 to -2O 0 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. 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 anionische, 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 anio- nische 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).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. A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, pp. 41 1 to 420. Emulsifiers are both anionic, cationic as also 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. As 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 IlFurther suitable emulsifiers are compounds of the general formula II
worin R5 und R6 Wasserstoff oder C4- bis C14-Alkyl bedeuten und nicht gleichzeitig Wasserstoff sind, und X und Y Alkalimetallionen und/oder Ammoniumionen sein kön- nen. 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 verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, beispielsweise Dowfax 2A1 (Warenzeichen der Dow Chemical Company).wherein R5 and R6 are hydrogen or C4 to C14 alkyl and are not hydrogen at the same time, and X and Y can be alkali metal ions and / or ammonium ions. Preferably R5, R6 are linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, wherein R5 and R6 are not both simultaneously hydrogen. X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred. Particularly advantageous are compounds II in which X and Y are sodium, R5 is a branched alkyl radical having 12 C atoms and R6 is hydrogen or R5. Frequently, technical mixtures are used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax 2A1 (trademark of the Dow Chemical Company).
Geeignete Emulgatoren finden sich auch in Houben-Weyl, Methoden der organischen Chemie, Band 14/1 , Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961 , Seiten 192 bis 208. Handelsnamen von Emulgatoren sind z. B. Dowfax 2 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, Emulphor NPS 25.Suitable emulsifiers can also be found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular substances, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208. Trade names of emulsifiers are z. Dowfax 2 A1, Emulan NP 50, Dextrol OC 50, Emulsifier 825, Emulsifier 825 S, Emulan OG, Texapon NSO, Nekanil 904 S, Lumiten I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL , Emulphor NPS 25.
Die grenzflächenaktive Substanz wird üblicherweise in Mengen von 0,1 bis 10 Gew.-%, bezogen auf die zu polymerisierenden Monomeren verwendet.The surfactant is usually used in amounts of from 0.1 to 10% by weight, based on the monomers to be polymerized.
Bei der Emusionspolymerisation 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, Wasserstoffperoxid 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, z. 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 schwef- ligen 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 Mitverwendung löslicher Metallverbindungen, deren metallische Komponente in mehreren Wertigkeitsstufen auftreten kann, verwendet werden.The reduction components are, for. For example, alkali metal salts of sulphurous acid, e.g. 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 concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states.
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 Reduktionskompo- nente, können auch Mischungen sein z. B. eine Mischung aus dem Natriumsalz der Hydroxymethansulfinsäure und Natriumdisulfit.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, e.g. the reduction component, can also be mixtures 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, bezogen auf 100 Gew.-Teile der zu polymerisierenden Monomeren betragen. Geeignete Regler sind insbesondere Verbindungen mit einer Mercaptogruppe wie tert.-Butylmercaptan, Thioglycolsäureethylacrylester, Mercaptoethynol, Mercaptopropyltrimethoxysilan oder tert.-Dodecylmercaptan. Bei den Reglern handelt es sich im allgemeinen um niedermolekulare Verbindungen mit einem Molgewicht kleiner 2000, insbesondere kleiner 1000 g/mol.The amount of regulator may in particular 0.05 to 4 parts by weight, more preferably 0.05 to 0.8 parts by weight and most 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 having 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 °C. Das Polymerisationsmedium kann sowohl nur aus Wasser, als auch aus Mischungen aus Wasser und damit mischbaren Flüssigkeiten wie Methanol bestehen. Vorzugsweise wird nur Wasser verwendet. 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 ° C. The polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used. The 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 Durchschnittsfachmann bekannt. Es kann sowohl vollständig in das Polymerisationsgefäß vorgelegt, als auch nach Maßgabe seines Verbrauchs im Verlauf der radikalischen wässrigen Emulsionspolymerisation kontinuierlich oder stufenweise eingesetzt werden. Im einzel- nen 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. Ein 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.The manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In detail, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization. A subset of the monomers may, if desired, be initially charged in the polymerization vessel at the beginning of the polymerization, the remaining monomers, or all monomers, if no monomers are initially charged, are added during the polymerization in the course of 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 mög- liehst 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 Viskosität angestrebten Teilchengrößenverteilung.For a high space / time yield of the reactor, dispersions with 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 Monomeren 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, i. preferably at least 70% by weight, particularly preferably at least 80% by weight, very particularly preferably at least 90% by weight are continuously added during the polymerization. In a particular embodiment, no monomers are presented, d. H. the total amount of monomers is added 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.
In einer bevorzugten Ausführungsform wird das Hydroxybutyl(meth)acrylat dem Polymerisationsgemisch vollständig oder zumindest teilweise erst gegen Ende der Emulsionspolymerisation zugesetzt. Insbesondere werden mehr als 60 Gew. % des Hydroxybutyl(meth)acrylats (im nachfolgenden kurz Restmenge HBA genannt) bei der Emulsionspolymerisation erst dann zugeführt, wenn das Polymerisationsgemisch (im Polymerisationsgefäß vorliegende Mischung aus Monomeren und bereits entstandenem Polymer) bereits mehr als 50 Gew. %, besonders bevorzugt mehr als 60 Gew. %, ganz besonders bevorzugt mehr als 75 Gew. % der Gesamtmenge der Monomeren enthält.In a preferred embodiment, the hydroxybutyl (meth) acrylate is added to the polymerization mixture completely or at least partially only towards the end of the emulsion polymerization. In particular, more than 60% by weight of the hydroxybutyl (meth) acrylate (referred to below as residual amount HBA) in the emulsion polymerization is supplied only when the polymerization mixture (present in the polymerization vessel mixture of monomers and already formed polymer) already more than 50 wt. %, more preferably more than 60 wt.%, Very particularly preferably more than 75 wt.% Of the total amount of the monomers.
Bei allen Angaben, welche auf das Polymerisationsgemisch bezogen sind sollen unter dem Begriff Monomer sowohl noch nicht polymerisierte Monomere als auch Monomer- einheiten des Polymeren, d.h. die einpolymerisierten Monomere, verstanden werden.In the case of all data relating to the polymerization mixture, the term "monomer" is intended to include both unpolymerized monomers and monomeric units of the polymer, i. the polymerized monomers understood.
Bei der vorstehenden Restmenge HBA handelt es sich insbesondere um mindestens 70 Gew. %, besonders bevorzugt um mindestens 80 Gew. % und ganz besonders bevorzugt um mindestens 90Gew. %, bzw. um 100 Gew. % des Hydroxybutyl(meth)a- crylats.The above residual amount of HBA is in particular at least 70% by weight, more preferably at least 80% by weight and most preferably at least 90% by weight. %, or around 100% by weight of the hydroxybutyl (meth) acrylate.
Ganz besonders bevorzugt wird die Restmenge HBA am Ende der Emulsionspolymerisation zugeführt, also nachdem alle anderen Monomeren dem Polymerisationsgemisch bereits zugeführt worden sind.Most preferably, the residual amount of HBA is fed at the end of the emulsion polymerization, ie after all the other monomers have already been added to the polymerization mixture.
Bei Beginn der Zugabe de Restmenge HBA sind die dem Polymerisationsgemisch zugegebenen Monomeren vorzugsweise bereits überwiegend polymerisiert, d.h. das Polymerisationsgemisch besteht bei Beginn der Zugabe der Restmenge HBA zu mindestens 40 Gew. %, aus bereits entstandenem Polymer.At the beginning of the addition of the residual amount of HBA, the monomers added to the polymerization mixture are preferably already predominantly polymerized, i. the polymerization mixture is at the beginning of the addition of the residual amount of HBA to at least 40 wt.%, Of already formed polymer.
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 HBA weiterer Initiator zugesetzt werden (chemische Desodorierung).To remove the residual monomers may also after the end of the actual emulsion polymerization, i. after a conversion of all monomers and after copolymerization of the residual amount of HBA, 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.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 .-%.
Das so hergestellte Polymer wird vorzugsweise in Form seiner wässrigen Dispersion verwendet.The polymer thus prepared is preferably used in the form of its aqueous dispersion.
Das Polymer wird vorzugsweise als oder in Haftklebstoffen verwendet.The polymer is preferably used as or in pressure-sensitive adhesives.
Der Haftklebstoff enthält das Polymer vorzugsweise in Form der wässrigen Polymerdispersion, wie sie durch die Emulsionspolymerisation erhalten wurde oder erhältlich ist. Der Haftklebstoff kann ausschließlich aus dem Polymeren, bzw. der wässrigen Dispersion des Polymeren bestehen.The pressure-sensitive adhesive preferably contains the polymer 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 polymer or of the aqueous dispersion of the polymer.
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. A tackifier, i. 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 Veresterung verwendet werden, können ein- oder mehrwertig sein. Beispiele sind Metha- nol, Ethandiol, Diethylenglykol, Triethylenglykol, 1 ,2,3-Propanthiol, Pentaerythrit.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, monovalent or polyvalent counterions (cations) or preferably in their esterified form.) Alcohols used for the esterification may be monohydric or polyhydric, for example, methanol, ethanediol, diethylene glycol, triethylene glycol , 1,2,3-propanethiol, pentaerythritol.
Des weiteren 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 Verwendung.Furthermore, hydrocarbon resins, e.g. 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, α-methylstyrene, vinyltoluene Use.
Als Tackifier werden zunehmend auch Polyacrylate, welche ein geringes Molgewicht aufweisen, verwendet. Vorzugsweise haben diese Polyacrylate ein gewichtsmittleres Molekulargewicht Mw unter 30 000. Die Polyacrylate bestehen bevorzugt zu mindestens 60, insbesondere mindestens 80 Gew.-% aus Ci-C8-Alkyl(meth)acrylaten.As tackifiers are increasingly also polyacrylates, which have a low molecular weight used. Preferably, these polyacrylates have a weight-average molecular weight M w below 30,000. The polyacrylates are preferably at least 60, in particular at least 80 wt .-% of Ci-C8-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 erfindungsgemäßen Polymerisaten, bevorzugt den wässrigen Dispersionen der Polymerisate zugesetzt werden. Vorzugsweise liegen die Tackifier dabei selber in Form einer wässrigen Dispersion vor.The tackifiers can be added in a simple manner to the polymers according to the invention, preferably to the aqueous dispersions of the polymers. The tackifiers are preferably themselves in the form of an aqueous dispersion.
Die Gewichtsmenge der Tackifier beträgt vorzugsweise 5 bis 100 Gew.-Teile. besonders bevorzugt 10 bis 50 Gew.-Teile. bezogen auf 100 Gew.-Teile Polymerisat, (fest/fest).The amount by weight of the tackifiers is preferably 5 to 100 parts by weight. particularly preferably 10 to 50 parts by weight. based on 100 parts by weight of polymer, (solid / solid).
Neben Tackifiern können z. B. noch weitere Additive z. B. Verdickungsmittel, vorzugsweise Assoziativverdicker, Entschäumer, Weichmacher, Pigmente, Netzmittel oder Füllstoffe bei der Verwendung als Haftklebstoff Verwendung finden. Die erfindungsgemäßen Haftklebstoffe enthalten daher neben der wässrigen Polymerdispersion gegebenenfalls noch Tackifier und/oder die vorstehenden Additive.In addition to Tackifiern z. B. still further additives z. As thickeners, preferably associative thickeners, defoamers, plasticizers, pigments, wetting agents or fillers when used as a pressure-sensitive adhesive use. The pressure-sensitive adhesives according to the invention therefore optionally contain, in addition to the aqueous polymer dispersion, tackifiers and / or the above additives.
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 Polymer (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 polymer (solid).
Die Haftklebstoffe eignen sich zur Herstellung selbstklebender Artikel wie Etiketten, Folien oder Klebebänder. Der Haftklebstoff kann durch übliche Methoden, z. B. durch Rollen, Rakeln, Streichen etc. auf Träger, z. B. Papier oder Polymer-Folien, bevorzugt bestehend aus Polyethylen, Polypropylen, das biaxial oder monoaxial verstreckt sein kann, Polyethylenterephthalat, Polyvinylchlorid, Polystyrol, Polyamid oder Metall auf- gebracht werden. Insbesondere eignen sich auch Träger mit unpolaren Oberflächen, z.B. aus Polyolefinen, insbesondere Polyethylen oder Polypropylen, da die erfindungsgemäßen Dispersionen darauf gut haften.The pressure-sensitive adhesives are suitable for the production of self-adhesive articles such as labels, films or adhesive tapes. The pressure-sensitive adhesive can be prepared by conventional methods, for. B. by rolling, knife coating, brushing, etc. on carriers, eg. As paper or polymer films, preferably consisting of polyethylene, polypropylene, which may be biaxially or monoaxially stretched, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyamide or metal are applied. In particular, supports with non-polar surfaces, e.g. from polyolefins, in particular polyethylene or polypropylene, since the dispersions according to the invention adhere well thereto.
Insbesondere kommen auch transparente Träger, z. B. transparente Polymerfolien, in Betracht. Selbstklebende Artikel mit transparenten Polymerfolien sind z. B. Folienetiketten.In particular, transparent carrier, z. As transparent polymer films, into consideration. Self-adhesive articles with transparent polymer films are z. B. foil labels.
Das Wasser kann bevorzugt durch Trocknung bei 50 bis 15O0C entfernt werden. Die Träger können vor oder nach dem Aufbringen des Klebstoffs zu Klebebändern, Etiket- ten oder Folien geschnitten werden. Zur späteren Verwendung kann die mit Haftklebstoff beschichtete Seite der Substrate, mit einem Releasepapier, z B. mit einem siliko- nisierten Papier, abgedeckt werden.The water may preferably by drying at from 50 to 15O 0 C to be removed. The carriers can be cut into adhesive tapes, labels or foils before or after application of the adhesive. For later use, the pressure-sensitive adhesive-coated side of the substrates can be covered with a release paper, for example with a siliconized paper.
Die erfindungsgemäßen selbstklebenden Artikel haben sehr gute Klebeeigenschaften, insbesondere eine gute Adhäsion zu den Substraten und eine hohe Kohäsion (innere Festigkeit in der Klebstoffschicht). Sie haben auch eine gute Haftung auf unpolaren Oberflächen und eignen sich daher auch besonders für Substrate mit unpolaren Oberflächen, z. B. Polyolefinoberflächen, z. B. Polyethylen (HDPE oder LDPE) oder Polypropylen.The self-adhesive articles according to the invention have very good adhesive properties, in particular a good adhesion to the substrates and a high cohesion (internal strength in the adhesive layer). They also have a good adhesion to nonpolar surfaces and are therefore particularly suitable for substrates with nonpolar surfaces, eg. B. Polyolefinoberflächen, z. As polyethylene (HDPE or LDPE) or polypropylene.
Insbesondere eignen sich die erfindungsgemäßen Haftklebstoffe auch für transparente Träger, insbesondere auch für Folienetiketten, da das bei Einwirkung von Wasser häufig auftretende sog. „Weißanlaufen" nicht auftritt, zumindest aber vermindert ist. Die anwendungstechnischen Eigenschaften bleiben daher auch bei Einwirkung von Was- ser gut, eine Trübung oder sonstige Verschlechterung des optischen Erscheinungsbildes ist nicht oder kaum zu beobachten. BeispieleIn particular, the pressure-sensitive adhesives according to the invention are also suitable for transparent carriers, in particular also for film labels, since the so-called "whitening" frequently occurring when water is present does not occur, but is at least reduced , a clouding or other deterioration of the visual appearance is not or hardly observed. Examples
Herstellung der PolymerdispersionenPreparation of the polymer dispersions
In einem 2-Liter-Polymerisationsreaktor mit Ankerrühren und Heiz-/Kühleinrichtung wurde ein Gemisch aus 102,61 g entionisiertem Wasser und 8,33 g eines 33 gew.- %igen wässrigen Polymerlatex (hergestellt durch radikalisch initiierte Emulsionspolymerisation von Styrol) mit einem gewichtsmittleren Teilchendurchmesser Dw50 von 30 nm unter Stickstoffatmosphäre auf 85°C erhitzt. Dazu wird bei vorgenannter Tempera- tur 4,71 g einer 7 gew.-%igen wässrigen Lösung von Natriumperoxodisulfat gegeben. Nach 2 min wird Zulauf 1 und Zulauf 2 gestartet und werden gleichmäßig über 3 h zudosiert.In a 2-liter anchor stirred and heated / cooled polymerisation reactor, a mixture of 102.61 g of deionized water and 8.33 g of a 33 wt% aqueous polymer latex (prepared by free-radically initiated emulsion polymerization of styrene) with a weight average Particle diameter Dw50 of 30 nm under nitrogen atmosphere at 85 ° C heated. For this purpose, 4.71 g of a 7% strength by weight aqueous solution of sodium peroxodisulfate are added at the aforementioned temperature. After 2 minutes, feed 1 and feed 2 are started and are metered in uniformly over 3 h.
Zulauf 1 war eine wässrige Emulsion hergestellt aus 271 ,84 g entionisiertem WasserFeed 1 was an aqueous emulsion prepared from 271, 84 g of deionized water
18,33 g einer 30 gew.-%igen wässrigen Lösung von Disponil FES 77 (ethoxylier- tes C12-C14 Na-sulfat)18.33 g of a 30% strength by weight aqueous solution of Disponil FES 77 (ethoxylated C12-C14 sodium sulfate)
1 ,9 g einer 58 gew.-%igen wässrigen Lösung von Lumiten I-SC (Bernsteinsäureester) 364,38 g n-Butylacrylat1.9 g of a 58% strength by weight aqueous solution of Lumiten I-SC (succinic acid ester) 364.38 g of n-butyl acrylate
122,38 g Ethylacrylat122.38 g of ethyl acrylate
12,38 g Styrol12.38 g of styrene
27,5 g Methylacrylat.27.5 g of methyl acrylate.
1 1 ,00g Acrylsäure1 1, 00g acrylic acid
Zulauf 2 war 47,14 g einer 7 gew.-%igen wässrigen Lösung von Natriumperoxodisulfat.Feed 2 was 47.14 g of a 7% strength by weight aqueous solution of sodium peroxodisulfate.
Nach 120 Minute wird Zulauf 3 gestartet und über 60 Minute zudosiert.After 120 minutes, feed 3 is started and metered in over 60 minutes.
Zulauf 3 war 12,38g von entweder 2-Hydroxyethylacrylat oder 2-Hydroxypropylacrylat oder 4-Hydroxybutylacrylat.Feed 3 was 12.38 g of either 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate or 4-hydroxybutyl acrylate.
Nach Ende der Zuläufe 1 , 2 und 3 30 min. gerührt. Danach wurde Zulauf 4 und Zulauf 5 gestartet und gleichmäßig über 60 min. zudosiert.After the end of feeds 1, 2 and 3 30 min. touched. Then feed 4 and feed 5 were started and evenly over 60 min. added.
Zulauf 4 war 5,5 g eine 10 gew.-%ige wässrige Lösung von t-Butylhydroperoxid.Feed 4 was 5.5 g of a 10 wt% aqueous solution of t-butyl hydroperoxide.
Zulauf 5 war 7,33 g eine 12 gew.-%ige wässrige Lösung von Natrium-Acetonbisulfit.Feed 5 was 7.33 g of a 12% by weight aqueous solution of sodium acetone bisulfite.
Nach Ende der Zuläufe 5 und 6 wurde die Reaktorinnentemperatur auf 25°C abgesenkt. Die erhaltene wässrige Polymerdispersion wies einen Feststoffgehalt von 53,5 Gew.-% auf. Die mittlere Teilchengröße betrug 200 nm. Tabelle 1 : Zusammensetzung der PolymereAfter the end of feeds 5 and 6, the internal temperature of the reactor was lowered to 25 ° C. The aqueous polymer dispersion obtained had a solids content of 53.5% by weight. The mean particle size was 200 nm. Table 1: Composition of the polymers
Anwendungstechnische PrüfungApplication testing
Zu den Polymerdispersionen wurde noch weiteres Lumiten zugesetzt, so dass die Menge Lumiten 1 ,2 Gew. Teile auf 100 Gew. Teile Polymer (fest) betrug.To the polymer dispersions was further added Lumiten, so that the amount of Lumiten 1, 2 parts by weight per 100 parts by weight of polymer (solid).
Die Haftklebstoffe wurden mit einer Auftragsmenge von 19 g/m2 auf Polyethylenfolie als Träger beschichtet (im Transferverfahren, Beschichtung zunächst von Silikonpapier und Transfer auf Polyethylen) und 3 Minuten bei 9O0C getrocknet.The pressure sensitive adhesives were applied at a rate of 19 g / m 2 polyethylene film backing coated (by the transfer method, coating first of silicone paper and transfer to polyethylene) and dried for 3 minutes at 9O 0 C.
Anschließend wurde der Schiingenwert (loop tack, Adhäsion) und Scherfestigkeit (Ko- häsion) bestimmt.Subsequently, the loop value (adhesion) and shear strength (cohesion) were determined.
Der mit Haftklebstoff beschichtete Träger wurde in 25 mm breite Prüfstreifen geschnitten. Zur Bestimmung der Scherfestigkeit wurden die Prüfstreifen mit einer verklebten Fläche von 6,25 cm2 auf Stahl geklebt, mit einer 1 kg schweren Rolle 1 mal angerollt, 10 min gelagert (im Normklima, 50 % rel. Luftfeuchtigkeit 1 bar, 230C) und anschlie- ßend hängend mit einem 1 kg Gewicht belastet (im Normklima). Das Maß für die Scherfestigkeit war die Zeit in Stunden bis zum Abfallen des Gewichts; es wurde jeweils der Durchschnitt aus 5 Messungen berechnet.The pressure-sensitive adhesive coated carrier was cut into 25 mm wide test strips. To determine the shear strength of the test strips were bonded with a bond area of 6.25 cm2 on steel, with a 1 kg roller 1 times rolled, stored for 10 min (under standard conditions, 50% rel. Humidity 1 bar, 23 0 C) and then suspended with a 1 kg weight (in standard climate). The measure of shear strength was the time in hours until the weight dropped; in each case the average of 5 measurements was calculated.
Bei der Bestimmung des Schiingenwertes wurde aus einem 17,5 cm langen und 2,5 cm breitem Prüfstreifen durch Einspannen beider Enden in die Klemmbacken einer Zugprüfmaschine eine Schlaufe gebildet, die dann mit einer Polyethylenoberfläche mit einer Geschwindigkeit von 300 mm/min (Herabsenken der Schlaufe auf die Oberfläche) in Kontakt gebracht wird. Nach vollflächigem Kontakt wird die Schlaufe nach einer Kontaktzeit von 1 Minute wieder abgezogen und die dabei ermittelte Maximalkraft in N / 2,5 cm bestimmt.When determining the Schiingenwertes a loop was formed from a 17.5 cm long and 2.5 cm wide test strip by clamping both ends in the jaws of a tensile testing machine, which then with a polyethylene surface at a speed of 300 mm / min (lowering the loop on the surface) is brought into contact. After full contact, the loop is after a Contact time of 1 minute withdrawn and determined the determined maximum force in N / 2.5 cm.
Tabelle 2: ErgebnisseTable 2: Results

Claims

Patentansprüche claims
1. Haftklebstoff, enthaltend eine durch Emulsionspolymerisation hergestellte wäss- rige Polymerdispersion, dadurch gekennzeichnet, dass das Polymer n- Butyl(meth)acrylat und Hydroxybutyl(meth)acrylat enthält.1. Pressure-sensitive adhesive, comprising an aqueous polymer dispersion prepared by emulsion polymerization, characterized in that the polymer contains n-butyl (meth) acrylate and hydroxybutyl (meth) acrylate.
2. Haftklebstoff gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Polymer zu mindestens 60 Gew. % aus n-Butyl(meth)acrylat besteht.2. Pressure-sensitive adhesive according to claim 1, characterized in that the polymer consists of at least 60 wt.% Of n-butyl (meth) acrylate.
3. Haftklebstoff gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Polymer insgesamt 0,1 bis 5 Gew. % Hydroxybutyl(meth)acrylat enthält.3. Pressure-sensitive adhesive according to one of claims 1 to 4, characterized in that the polymer contains a total of 0.1 to 5 wt.% Hydroxybutyl (meth) acrylate.
4. Haftklebstoff gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Polymer dadurch erhältlich ist, dass mehr als 60 Gew. % des Hydro- xybutyl(meth)acrylats (im nachfolgenden kurz Restmenge HBA genannt) bei der Emulsionspolymerisation erst dann zugeführt werden, wenn das Polymerisationsgemisch (im Polymerisationsgefäß vorliegende Mischung aus Monomeren und bereits entstandenem Polymer) bereits mehr als 50 Gew. % der Gesamt- menge der Monomeren enthält4. pressure-sensitive adhesive according to one of claims 1 to 3, characterized in that the polymer is obtainable in that more than 60 wt.% Of the hydroxy xylbutyl (meth) acrylate (hereinafter referred to as residual amount HBA) supplied in the emulsion polymerization only then are when the polymerization mixture (present in the polymerization vessel mixture of monomers and already formed polymer) already contains more than 50 wt.% Of the total amount of the monomers
5. Haftklebstoff gemäß Anspruch einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Restmenge HBA erst zugeführt werden, wenn das Polymerisationsgemisch (im Polymerisationsgefäß vorliegende Mischung aus Monome- ren und bereits entstandenem Polymer) bereits mehr als 75 Gew. % der Gesamtmenge der Monomeren enthält5. Pressure-sensitive adhesive according to claim 1, characterized in that the residual amount of HBA is supplied only when the polymerization mixture (present in the polymerization vessel mixture of monomers and already formed polymer) already more than 75 wt.% Of the total amount of Containing monomers
6. Verwendung der Haftklebstoffe gemäß einem der Ansprüche 1 bis 6 zur Herstellung von selbstklebenden Artikeln. 6. Use of the pressure-sensitive adhesives according to one of claims 1 to 6 for the production of self-adhesive articles.
EP07728144A 2006-04-28 2007-04-16 CONTACT ADHESIVE CONTAINING n-BUTYLACRYLATE AND HYDROXYBUTYL(METH)ACRYLATE. Withdrawn EP2016153A1 (en)

Priority Applications (1)

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EP07728144A EP2016153A1 (en) 2006-04-28 2007-04-16 CONTACT ADHESIVE CONTAINING n-BUTYLACRYLATE AND HYDROXYBUTYL(METH)ACRYLATE.

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EP06113276 2006-04-28
EP07728144A EP2016153A1 (en) 2006-04-28 2007-04-16 CONTACT ADHESIVE CONTAINING n-BUTYLACRYLATE AND HYDROXYBUTYL(METH)ACRYLATE.
PCT/EP2007/053679 WO2007125031A1 (en) 2006-04-28 2007-04-16 CONTACT ADHESIVE CONTAINING n-BUTYLACRYLATE AND HYDROXYBUTYL(METH)ACRYLATE.

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CN101657508A (en) * 2007-04-13 2010-02-24 巴斯夫欧洲公司 Form the method for pigment dyestuff
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ES2877611T3 (en) * 2015-01-08 2021-11-17 Basf Se Adhesive protective film
CN110283556B (en) * 2019-06-20 2021-06-25 厦门市豪尔新材料股份有限公司 Aqueous temperature-controlled viscose emulsion, aqueous temperature-controlled viscose prepared from same and preparation method of aqueous temperature-controlled viscose
CN112724885A (en) * 2019-10-29 2021-04-30 襄阳三沃航天薄膜材料有限公司 Medical acrylate pressure-sensitive adhesive and preparation method thereof

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WO1994005713A1 (en) * 1992-09-03 1994-03-17 The Dow Chemical Company Polymer latex composition and coating formulation made therefrom
ID21083A (en) * 1996-09-09 1999-04-15 Basf Ag MAKING WATER POLYMER DISPERSION
US5895801A (en) * 1997-03-31 1999-04-20 Avery Dennison Corporation Pressure-sensitive adhesives for marking films
JP3640921B2 (en) * 2001-12-28 2005-04-20 クラリアントポリマー株式会社 Synthetic resin emulsion, easily water-swellable pressure-sensitive adhesive composition comprising the same, and method for producing synthetic resin emulsion
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WO2007125040A1 (en) * 2006-04-28 2007-11-08 Basf Se Contact adhesive containing 2-ethylhexylacrylate and hydroxybutyl(meth)acrylate

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