WO2011069950A1 - Adhésif de contact pour films pvc - Google Patents

Adhésif de contact pour films pvc Download PDF

Info

Publication number
WO2011069950A1
WO2011069950A1 PCT/EP2010/068945 EP2010068945W WO2011069950A1 WO 2011069950 A1 WO2011069950 A1 WO 2011069950A1 EP 2010068945 W EP2010068945 W EP 2010068945W WO 2011069950 A1 WO2011069950 A1 WO 2011069950A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
monomers
adhesive
acrylate
polymerization
Prior art date
Application number
PCT/EP2010/068945
Other languages
German (de)
English (en)
Inventor
Carmen-Elena Cimpeanu
Cornelis Petrus Beyers
Andree Dragon
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 US13/514,773 priority Critical patent/US9404023B2/en
Priority to EP10785442.4A priority patent/EP2510067B1/fr
Priority to ES10785442.4T priority patent/ES2438748T3/es
Publication of WO2011069950A1 publication Critical patent/WO2011069950A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • 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
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09J133/18—Homopolymers or copolymers of nitriles
    • C09J133/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]

Definitions

  • the invention relates to an adhesive, in particular for applications on substrates made of soft PVC, comprising a polymer obtainable by free-radical polymerization of ethylenically unsaturated compounds, which is composed of certain amounts of soft acrylate having a glass transition temperature of less than 0 ° C, ethylenically unsaturated nitriles, hard acrylate monomers having a glass transition temperature of at least 60 ° C, ethylenically unsaturated acid monomers and monomers having at least two non-conjugated polymerizable vinyl groups, wherein the polymerization is carried out by step polymerization and at least a portion of the soft acrylate monomers are polymerized in a first polymerization and polymerizing at least a portion of the acrylate hard monomers in a second or later polymerization stage.
  • a PVC film As a carrier material, in particular for so-called graphic arts applications, self-adhesive labels and tapes as well as printed films with flexible PVC are frequently used as carrier material.
  • Soft PVC films contain significant amounts of low molecular weight phthalate based plasticizers or polymeric plasticizers. A problem that arises from the use of these plasticizers is that the plasticizer can migrate from the film into the pressure-sensitive adhesive. As a result, the performance adhesive properties are impaired.
  • Both the cohesion of the adhesive and the adhesion of the adhesive to the surface to which the label or film is adhered are generally significantly reduced by the migration of the plasticizer into the adhesive. This problem occurs increasingly when pre-coated, self-adhesive soft PVC films are stored for a long time before use, especially at higher temperatures.
  • the pressure-sensitive adhesives comprise a polymer obtainable by free-radical polymerization of ethylenically unsaturated compounds, which is composed of at least 60% by weight of main monomers selected from, inter alia, C 1 - to C 20 -alkyl (meth) acrylates and more than 1% by weight of monomers with at least two non-conjugated polymerizable vinyl groups.
  • Adhesives for the production of self-adhesive articles with flexible PVC as support material are also described in EP 1378527, EP 1520898, EP 454426, EP 978551 and WO 93/14161.
  • the further optimization of the three quality requirements with regard to storage stability, blush behavior and shrinkage behavior is not trivial, since an improvement in one criterion is often associated with impairments in at least one of the other criteria.
  • the object of the present invention were therefore adhesives for self-adhesive articles with the lowest possible shrinkage and the best possible water resistance (blushing) and the best possible shelf life, especially at higher temperatures.
  • the adhesives should continue to have good adhesion and cohesion, as well as being easy to process.
  • the invention relates to an adhesive containing a polymer obtainable by free-radical polymerization of ethylenically unsaturated compounds, which is composed of
  • the polymerization is by step polymerization wherein at least a portion of the soft acrylate monomers (a) are polymerized in a first polymerization stage and at least a portion of the hard acrylate monomers (C) are polymerized in a second or later polymerization.
  • the glass transition temperature can be determined by differential scanning calorimetry (ASTM D 3418-08, so-called "midpoint temperature").
  • the adhesive of the invention contains the above-defined polymer.
  • the polymer is obtainable by radical polymerization of ethylenically unsaturated compounds (monomers).
  • the polymer consists of at least 50% by weight, preferably at least 55% by weight, more preferably from 55 to 90% by weight of at least one soft acrylate monomer selected from alkyl acrylates which, when polymerized as a homopolymer, have a glass transition temperature of less than 0 ° C, preferably less than -10 ° C or less than -20 ° C, more preferably less than -30 ° C.
  • Soft acrylate monomers (a) are, for example, alkyl acrylates having a C 2 -C 10 -alkyl radical.
  • Ethylenically unsaturated nitriles (b) are used to at least 1% by weight, preferably from 1 to 15% by weight or from 2 to 10% by weight. Particularly preferred are acrylonitrile, methacrylonitrile and their mixture.
  • the hard acrylate monomers (c) are used to at least 1% by weight, preferably from 1 to 30% by weight.
  • Hard acrylate monomers (c) are e.g. Alkyl acrylates and alkyl methacrylates each having 1 to 10 carbon atoms in the alkyl group, provided that the glass transition temperature of the respective homopolymer is at least 60 ° C, more preferably at least 80 ° C. Preference is given to alkyl methacrylates having 1 to 4 C atoms in the alkyl group.
  • Hard acrylate monomers (c) are e.g. Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate or tert-butyl methacrylate. Particularly preferred is methyl methacrylate.
  • the ethylenically unsaturated acid monomers (d) are used at least 0.1% by weight, preferably from 0.1 to 10% by weight, or from 0.5 to 8% by weight, or from 1 to 6% by weight.
  • Monomers of group (d) are, for example, ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids and vinylphosphonic acid.
  • the ethylenically unsaturated carboxylic acids used are preferably alpha, beta-monoethylenically unsaturated mono- and dicarboxylic acids having from 3 to 6 carbon atoms in the molecule.
  • acrylic acid methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinylacetic acid and vinyllactic acid.
  • Suitable ethylenically unsaturated sulfonic acids are, for example, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, sulfopropyl acrylate and sulfopropyl methacrylate.
  • Preference is given to acrylic acid and methacrylic acid and their mixture, particular preference to acrylic acid.
  • the acid group-containing monomers of group (d) can be used in the form of the free acids as well as in partially or completely neutralized form with suitable bases in the polymerization. In front- It is preferable to use caustic soda, potassium hydroxide or ammonia as a neutralizing agent.
  • the monomers (e) having at least two non-conjugated polymerizable vinyl groups are at least 0.01% by weight, preferably from 0.01 to 0.5% by weight or from 0.05 to 0, 1% by weight used.
  • Preferred vinyl groups are acrylic or methacrylic groups. Called e.g. Divinylbenzene, alkanediol diacrylates, alkanediol dimethacrylates, allyl acrylates and allyl methacrylates. Particular preference is given to alkanediol diacrylates and alkanediol dimethacrylates having in each case 2 to 8, preferably 4 to 6, carbon atoms in the alkanediol group.
  • the polymer contained in the adhesive of the invention may optionally be composed of other monomers (f) other than the monomers (a) to (e).
  • the further monomers (f) may be used in amounts of from 0 to 25% by weight, e.g. from 0.5 to 25% by weight.
  • the polymer is at least 0.5% by weight, in particular from 0.5 to 15% by weight or from 1 to 10% by weight composed of at least one hydroxy monomer (f1) selected from hydroxyalkyl acrylates and hydroxyalkyl methacrylates with in each case 1 to 10 C-atoms in the alkyl groups as well as 0 to 15 Gew.% further, different from the monomers (a) to (f1) further monomers (f2).
  • Preferred hydroxy monomers (f1) are 2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate.
  • a particular embodiment of the invention contains a mixture of 2-hydroxypropyl acrylate and 2-hydroxybutyl acrylate.
  • Other monomers (f2) are for example selected from (a) and (c) different (meth) acrylic acid esters such as methyl acrylate, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, vinyl halides, vinyl ethers of Alcohols containing 1 to 10 C atoms, hydrocarbons having 4 to 8 C atoms and one or two conjugated olefinic double bonds, acrylamide, methacrylamide, phenyloxyethyl glycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate and amino (meth) acrylates such as 2 aminoethyl (meth) acrylate.
  • acrylic acid esters such as methyl acrylate, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, vinyl halides, vinyl ethers of Alcohols containing 1 to 10 C atoms, hydrocarbon
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene, alpha- and para-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • Vinyl ethers are, for example, vinylmethyl ethers or vinylisobutyl ethers.
  • Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • hydrocarbons having 4 to 8 carbon atoms and one or two conjugated olefinic double bonds may be mentioned ethylene, propylene, butadiene, isoprene and chloroprene.
  • Preferred further monomers are vinylaromatics, in particular styrene.
  • the polymer preferably contains hydrophilic groups selected from carboxyl groups, hydroxyl groups, amino groups and carboxamide groups. The content of these hydrophilic groups is in particular 0.001 to 0.5 mol per 100 g of polymer.
  • the content is preferably at least 0.005 mol, particularly preferably at least 0.008 mol and not more than 0.2 mol, in particular not more than 0.1 mol, very particularly preferably not more than 0.05 or 0.03 mol per 100 g / polymer.
  • Particularly preferred are the hydrophilic groups selected from carboxyl groups, hydroxyl groups and carboxamide groups. More preferably, at least 20 mole percent of the total moles of these hydrophilic groups are carboxyl groups. Carboxyl groups are understood as meaning both carboxylic acid groups and their salts. In the case of the salts, these are preferably salts with volatile bases, for example ammonia.
  • the hydrophilic groups can be bound to the polymer by copolymerization of the corresponding monomers.
  • Preferred monomers having hydrophilic groups are the abovementioned monomers having carboxyl groups and hydroxyl groups, in particular, for example, acrylic acid.
  • An embodiment of the invention is characterized in that the soft acrylate monomers (a) are selected from n-butyl acrylate and 2-ethylhexyl acrylate, the monomer (b) is acrylonitrile, the hard acrylate monomer (c) is methyl methacrylate, the acid monomers (d) are selected from acrylic acid and methacrylic acid and the monomers (e) are selected from alkanediol diacrylates, alkanediol dimethacrylates, allyl acrylates and allyl methacrylates.
  • An embodiment of the invention is characterized in that the monomers (a) in amounts of 55 to 90 wt.%, The monomers (b) in amounts of 1 to 15 wt.%, The monomers (c) in amounts of 1 to 30 % By weight, the monomers (d) in amounts of from 0.1 to 10% by weight, the monomers (e) in amounts of from 0.05 to 0.5% by weight and the monomers (f) in amounts of 0, 5 to 25 wt.% Are present.
  • the polymer contained in the adhesive according to the invention is free from vinyl acetate and the adhesive contains, apart from the internal crosslinkers (e), no further crosslinkers, in particular no external crosslinkers.
  • the polymers are produced in a preferred embodiment by emulsion polymerization, which is therefore an emulsion polymer.
  • emulsion polymerization ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • 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.
  • adjuvant surface-active substances exclusively emulsifiers are used whose molecular weight, in contrast to the protective colloids, is usually below 2000 g / mol.
  • emulsifiers are used as surface-active substances.
  • anionic and nonionic emulsifiers are used as surface-active substances.
  • emulsifiers are, for example, ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: Cs to C36), ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ), Alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali and ammonium salts of alkyl sulfates (alkyl group: Cs to C12), ethoxylated alkanols (EO degree: 4 to 30, alkyl group: C12 to Cie), ethoxylated alkylphenols (EO degree : 3 to 50, alkyl radical: C 4 - to C 9), of alkyl sulfonic acids (alkyl radical: C 12 - to Cie) and of alkylaryl sulfonic acids (alkyl radical: C 9 - to ds).
  • emulsifiers are compounds of the general formula I.
  • 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 C atoms and R 6 is hydrogen or R 5 .
  • emulsifiers are 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 ionic emulsifiers or protective colloids are preferred for the present invention.
  • ionic emulsifiers in particular salts and acids, such as carboxylic acids, sulfonic acids and sulfates, sulfonates or carboxylates.
  • the surfactant is usually used in amounts of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the monomers to be polymerized.
  • Water-soluble initiators for the emulsion polymerization are, for example, ammonium and alkali metal salts of peroxodisulfuric acid, for example sodium peroxodisulfate, hydrogen peroxide or organic peroxides, for example tert-butyl hydroperoxide. Also suitable are so-called reduction-oxidation (red-ox) -lititiator systems.
  • the redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is, for example, the above-mentioned initiators for emulsion polymerization.
  • the reduction components are, for example, alkali metal salts of sulfurous acid, such as sodium sulfite, sodium hydrogen sulfite, alkali metal salts of disulfurous acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and its salts, or ascorbic acid.
  • the red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states.
  • Typical redox initiator systems are, for example, ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na-hydroxy-methanesulfinic acid.
  • the individual components for example the reduction component, may also be mixtures, for example a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the compounds mentioned are usually used in the form of aqueous solutions, the lower concentration by in the Dispersible amount of water and the upper concentration is determined 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.
  • 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 may be used, e.g. in amounts of 0 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be polymerized, is reduced by the molecular weight.
  • Suitable are e.g. Compounds with a thiol group such as tert-butyl mercaptan, thioglycolic acid ester, e.g.
  • Suitable regulators are also C6 to C20 hydrocarbons, which when hydrogen abstraction form a pentadienyl radical, e.g. Terpinolene.
  • the emulsion polymerization is generally carried out at 30 to 130, preferably 50 to 90 ° C.
  • the polymerization medium can consist only of water as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the polymerization takes place by step polymerization, wherein at least a portion of the soft acrylate monomers (a) are polymerized in a first polymerization stage and at least a portion of the hard acrylate monomers (c) are polymerized in a second or later polymerization stage.
  • at least 50% by weight i. 50-100 wt.%, In particular 100 wt.% Of the total amount of the soft acrylate monomers (a) polymerized in the first stage and at least 10 wt.%, Preferably 15-60 wt.% Or 20 to 50 wt.% Of the total amount of hard Acrylate monomers (c) in the second or later stage.
  • the individual stages of the emulsion polymerization can be carried out as a batch process or else in the form of a feed process, including gradient cooking.
  • the feed process in which one submits a portion of the polymerization, heated to the polymerization, polymerized and then the remainder of the polymerization of the first stage, usually via a plurality of spatially separate feeds, of which one or more of the monomers in pure or in emulsified form, continuously or with the addition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.
  • the manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. In detail, this depends on the chemical nature of the initiator system as well as on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization. To remove the residual monomers is usually after the end of the actual emulsion polymerization, ie added after a conversion of the monomers of at least 95%, initiator.
  • the individual components can be added to the reactor in the feed process from above, in the side or from below through the reactor bottom.
  • aqueous dispersions of the polymer are generally obtained with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-%.
  • solids contents 15 to 75 wt .-%, preferably from 40 to 75 wt .-%.
  • dispersions having the highest possible solids content are preferred.
  • solids contents> 60% by weight one should set a bimodal or polymodal particle size, since otherwise the viscosity becomes too high and the dispersion can no longer be handled.
  • the generation of a new particle generation can be carried out, for example, by adding seed (EP 81083), by adding excess emulsifier amounts or by adding miniemulsions.
  • Another advantage associated with the low viscosity at high solids content is the improved coating behavior at high solids levels.
  • the generation of a new / new particle generation (s) can take place at any time. It depends on the particle size distribution desired for a low viscosity.
  • the polymer thus prepared is preferably used in the form of its aqueous dispersion.
  • the mean particle size of the polymer particles dispersed in the aqueous dispersion is preferably less than 300 nm, in particular less than 200 nm. More preferably the mean particle size is between 140 and 200 nm.
  • average particle size is meant here the d.sub.50 value of the particle size distribution, i.
  • the particle size distribution can be determined in a known manner with the analytical ultracentrifuge (W. Gonzchtie, Makromolekulare Chemie 185 (1984), page 1025-1039).
  • the pH of the polymer dispersion is preferably adjusted to pH greater than 4.5, in particular to a pH of between 5 and 8.
  • the glass transition temperature of the polymer, or of the polymer is preferably -60 to 0 ° C, more preferably -60 to -10 ° C and most preferably -60 to -20 ° C.
  • the glass transition temperature can be determined by differential scanning calorimetry (ASTM D 3418-08, so-called "midpoint temperature").
  • the adhesives according to the invention are preferably pressure-sensitive adhesives. These may consist solely of the polymer or the aqueous dispersion of the polymer.
  • the adhesive does not require external crosslinkers.
  • a content of external crosslinkers is therefore generally less than 0.5 parts by weight per 100 parts by weight of polymer and in particular less than 0.1 parts by weight. Particular preference is given to external crosslinkers completely omitted.
  • the adhesives and pressure sensitive adhesives may contain other additives fillers,
  • Dyes, leveling agents, thickeners or tackifiers are, for example, natural resins, such as rosin resins and their derivatives resulting from disproportionation or isomerization, polymerization, dimerization, hydrogenation.
  • Alcohols used for esterification may be monovalent or polyvalent, for example, methanol, ethanediol, diethylene glycol, triethylene glycol, 1
  • hydrocarbon resins for example cumarone-indene resins, polyterpene resins, hydrocarbon resins based on unsaturated C-H compounds, such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, are also found Cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene, vinyltoluene are used as tackifiers and polyacrylates which have a low molecular weight are increasingly being used as tackifiers.Preferably these polyacrylates have a weight-average molecular
  • the polyacrylates are preferred to at least 60, in particular at least 80 wt .-% of Ci-Cs alkyl (meth) acrylates
  • Tackifiers are natural or chemically modified rosin resins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
  • 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).
  • the adhesive or pressure-sensitive adhesive is suitable for bonding substrates, characterized in that at least one of the substrate surfaces to be joined is made of soft PVC.
  • the adhesive may be applied to a backing, eg, paper or plastic, and the backing so coated (eg, a label, tape, or foil) may be adhered to a substrate of soft PVC.
  • the adhesives or pressure-sensitive adhesives according to the invention are suitable for the production of self-adhesive articles, such as labels, adhesive tapes or adhesive films, for example protective films.
  • the self-adhesive articles generally consist of a carrier and a one or both sides, preferably one-sidedly applied layer of the adhesive.
  • the carrier material may be, for example, paper, preferably plastic films made of polyolefins or PVC, particularly preferably PVC, very particularly preferably soft PVC.
  • Soft PVC is understood as meaning polyvinyl chloride which has a content of plasticizers and has a reduced softening temperature.
  • Typical plasticizers are, for example, phthalates, epoxides, adipic acid esters.
  • the content of the plasticizer in the soft PVC is generally more than 10, in particular more than 20 wt .-%.
  • plasticizers can migrate into the adhesive layer and significantly impair the adhesive properties.
  • a migration of the plasticizers does not or hardly affects the properties of the adhesive.
  • shrinkage of the substrates by the adhesive according to the invention is avoided or reduced, especially in soft PVC.
  • the present invention therefore also relates to self-adhesive articles with plasticized PVC as a carrier material, in particular in the form of a PVC film, and an adhesive layer of the adhesive according to the invention which is at least partially coated thereon, wherein the PVC film has a plasticizer content of preferably at least 20% by weight. having.
  • the carrier material can be coated in the usual way.
  • the resulting coated substrates are e.g. used as self-adhesive articles, such as labels, adhesive tapes or foils.
  • the self-adhesive articles with soft PVC as a carrier material are particularly suitable for outdoor applications.
  • printed self-adhesive films can be used outdoors and z. B. glued on billboards or vehicles of all kinds.
  • the self-adhesive articles of the invention have good performance properties, in particular a good peel strength (adhesion) and shear strength (cohesion).
  • the properties remain good even with soft PVC as a carrier material and even after prolonged heat storage.
  • a clouding of the adhesive layer by the action of moisture (whitening) is not or hardly observed.
  • the adhesive layer therefore has a high water resistance.
  • a shrinkage of the self-adhesive articles is hardly observed, even if the articles are exposed to high temperatures, eg more than 50 ° C. Examples
  • compositions of the copolymers B1 and B2 according to the invention and of the comparative polymers V1, V2 and V3 are summarized in Table 1.
  • Comparative polymer V1 corresponds to an example of WO 2005/100502.
  • Comparative Example C2 contains crosslinker but no acrylonitrile.
  • Comparative Example C3 contains acrylonitrile, but no crosslinker.
  • the polymers B1 and B2 were prepared by step polymerization (swelling polymerization) by copolymerizing 8 parts by weight (based on 100 parts by weight of all monomers) of methyl methacrylate together with the other monomers in a first polymerization stage and then 4% by weight .-Parts of methyl methacrylate were polymerized in a second polymerization stage.
  • Table 1 Quantities in parts by weight per 100 parts by weight of all monomers
  • PSA compositions were prepared from the aqueous polymer dispersions by thickening with NH 3 and tested for their properties.
  • the pressure-sensitive adhesive compositions were coated on a soft PVC film, available from Renolit, at an application rate of 20 g / m 2 (for all properties except blushing where the application rate was 25 g / m 2 ) and dried at 90 ° C for 3 minutes. Subsequently, the peel strength (adhesion) was determined. The coated one Carrier was cut into 25 mm wide test strips. When determining the peel strength (adhesion), a 2.5 cm wide test strip was glued to a steel test specimen and rolled once with a 1 kg roller. He was clamped with one end in the upper jaws of a tensile-strain test apparatus after 20 minutes.
  • the adhesive strip was peeled off the test surface at 300 mm / min at a 180 ° angle, ie the adhesive strip was bent over and pulled off parallel to the test sheet and the force required for this was measured.
  • the measure of peel strength is the force in N / 2.5 cm, which is the average of five measurements.
  • the test was carried out under standard conditions (50% relative humidity, 1 bar, 23 ° C).
  • the peel strength test was carried out after heat storage.
  • the heat storage of the test composites (3 days, 70 ° C) simulates an accelerated aging of the samples and thus a forced migration of the plasticizer from the PVC carrier into the adhesive layer. The results are shown in Table 2. Blushing (water resistance)
  • test strips were hung at room temperature (about 23 ° C) in a water bath.
  • the haze of the adhesive film was observed over time. The time was determined at which a clear turbidity became apparent. The longer the period, the better the water resistance. The results are shown in Table 2.

Landscapes

  • 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)
  • Adhesive Tapes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un adhésif, en particulier pour des applications sur des matériaux supports à base de PVC souple, qui contient un polymère pouvant être obtenu par polymérisation radicalaire de composés éthyléniquement insaturés, qui comprend d'au moins 50 % en poids de monomères acrylates mous ayant une température de transition vitreuse inférieure à 0°C, au moins 1 % en poids de nitriles éthyléniquement insaturés, au moins 1 % en poids de monomères acrylates durs à une température de transition vitreuse d'au moins 60°C, au moins 0,1 % en poids de monomères acides éthyléniquement insaturés, au moins 0,01 % en poids de monomères ayant au moins deux groupes vinyle non conjugués, polymérisables, la polymérisation ayant lieu par polymérisation par étapes et au moins une partie des monomères acrylates mous étant polymérisés dans une première étape de polymérisation et au moins une partie des monomères acryliques durs étant polymérisés dans une seconde étape de polymérisation ou une étape de polymérisation ultérieure. L'invention concerne également des utilisations de l'adhésif pour assembler des substrats à base de PVC souple ainsi que des articles autoadhésifs muni d'un film PVC comme matériau support et d'un revêtement comprenant l'adhésif selon l'invention.
PCT/EP2010/068945 2009-12-09 2010-12-06 Adhésif de contact pour films pvc WO2011069950A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/514,773 US9404023B2 (en) 2009-12-09 2010-12-06 Pressure-sensitive adhesive for PVC foils
EP10785442.4A EP2510067B1 (fr) 2009-12-09 2010-12-06 Adhésif de contact pour films pvc
ES10785442.4T ES2438748T3 (es) 2009-12-09 2010-12-06 Adhesivo de contacto para películas de PVC

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09178445.4 2009-12-09
EP09178445 2009-12-09

Publications (1)

Publication Number Publication Date
WO2011069950A1 true WO2011069950A1 (fr) 2011-06-16

Family

ID=43431836

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/068945 WO2011069950A1 (fr) 2009-12-09 2010-12-06 Adhésif de contact pour films pvc

Country Status (4)

Country Link
US (1) US9404023B2 (fr)
EP (1) EP2510067B1 (fr)
ES (1) ES2438748T3 (fr)
WO (1) WO2011069950A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9328247B2 (en) 2011-11-10 2016-05-03 Basf Se Paper coating slip additive comprising acid monomer, associative monomer and nonionic monomer
US9950502B2 (en) 2011-12-06 2018-04-24 Basf Se Paper and cardboard packaging with barrier coating
EP3781622B1 (fr) * 2018-04-20 2022-10-12 Basf Se Compositions adhésives à gelcontent de réticulation de groupes céto ou aldéhyde

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107920923A (zh) * 2015-08-31 2018-04-17 3M创新有限公司 包含对湿表面具有增强的粘附性的(甲基)丙烯酸酯压敏粘合剂的负压伤口治疗敷料
DE102015012128A1 (de) * 2015-09-17 2017-03-23 Seca Ag Waage mit Informationsträger
DE102016008257A1 (de) * 2016-07-08 2018-01-11 Carl Freudenberg Kg Hautauflage
CN109776835B (zh) * 2018-12-18 2022-05-17 合肥乐凯科技产业有限公司 一种抗静电保护膜

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0219796A2 (fr) * 1985-10-18 1987-04-29 BASF Aktiengesellschaft Masse d'étanchéité à base de copolymérisats dispersés ayant une adhérence et un plus haut coefficient d'élasticité
EP0454426A2 (fr) 1990-04-24 1991-10-30 Minnesota Mining And Manufacturing Company Film composite à revêtement adhésif susceptible d'adhésion permanente à un substrat plastifié
WO1993014161A1 (fr) 1992-01-10 1993-07-22 Avery Dennison Corporation Autoadhesif a emulsion acrylique separable, resistant a l'eau
EP0978551A1 (fr) 1998-08-04 2000-02-09 Toagosei Co., Ltd. Procédé pour la préparation d'une feuille adhésive sensible à la pression
DE19929561A1 (de) * 1999-06-18 2000-12-21 Hans Neschen Ag Druckempfindliche, reversibel haftende Selbstklebemasse und deren Verwendung zur Herstellung von selbstklebenden, flächigen Substraten
US20030113460A1 (en) * 2001-09-24 2003-06-19 Even Ralph Craig Method for providing improved polymeric composition
EP1378527A1 (fr) 2002-07-02 2004-01-07 Basf Aktiengesellschaft Adhésives sensibles à öle pression pour support en CPV souple
EP1520898A2 (fr) 2003-09-30 2005-04-06 Basf Aktiengesellschaft Composition auto-adhésive contenant une résine de mélamine
WO2005100502A1 (fr) 2004-04-19 2005-10-27 Basf Aktiengesellschaft Colle adhesive pour feuilles de pvc
WO2005100501A1 (fr) 2004-04-15 2005-10-27 Exxonmobil Chemical Patents Inc. Compositions adhesives a base de polyolefines et articles produits a partir de celles-ci

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE622280A (fr) * 1965-08-17
US5302629A (en) * 1992-05-15 1994-04-12 Berejka Anthony J Hydrophilic acrylic pressure sensitive adhesives
US5567773A (en) * 1995-04-04 1996-10-22 Mobil Oil Corporation Cold sealable cohesive polymers
JP3963498B2 (ja) * 1996-04-11 2007-08-22 ローム アンド ハース カンパニー エマルションポリマー組成物
EP0927208B1 (fr) * 1996-09-09 2002-01-02 Basf Aktiengesellschaft Procede de preparation de dispersions aqueuses de polymerisats
US5895801A (en) * 1997-03-31 1999-04-20 Avery Dennison Corporation Pressure-sensitive adhesives for marking films
JP4230080B2 (ja) * 2000-02-18 2009-02-25 リンテック株式会社 ウエハ貼着用粘着シート
US7070051B2 (en) * 2004-03-26 2006-07-04 Atrion Medical Products, Inc. Needle counter device including troughs of cohesive material
EP2016152A1 (fr) * 2006-04-28 2009-01-21 Basf Se Adhésif contenant 2-éthylhexylacrylate et hydroxybutyl(méth)acrylate
US20070276096A1 (en) * 2006-05-25 2007-11-29 Wefer John M Functional polyolefins useful as metal adhesion promoters

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0219796A2 (fr) * 1985-10-18 1987-04-29 BASF Aktiengesellschaft Masse d'étanchéité à base de copolymérisats dispersés ayant une adhérence et un plus haut coefficient d'élasticité
EP0454426A2 (fr) 1990-04-24 1991-10-30 Minnesota Mining And Manufacturing Company Film composite à revêtement adhésif susceptible d'adhésion permanente à un substrat plastifié
WO1993014161A1 (fr) 1992-01-10 1993-07-22 Avery Dennison Corporation Autoadhesif a emulsion acrylique separable, resistant a l'eau
EP0978551A1 (fr) 1998-08-04 2000-02-09 Toagosei Co., Ltd. Procédé pour la préparation d'une feuille adhésive sensible à la pression
DE19929561A1 (de) * 1999-06-18 2000-12-21 Hans Neschen Ag Druckempfindliche, reversibel haftende Selbstklebemasse und deren Verwendung zur Herstellung von selbstklebenden, flächigen Substraten
US20030113460A1 (en) * 2001-09-24 2003-06-19 Even Ralph Craig Method for providing improved polymeric composition
EP1378527A1 (fr) 2002-07-02 2004-01-07 Basf Aktiengesellschaft Adhésives sensibles à öle pression pour support en CPV souple
EP1520898A2 (fr) 2003-09-30 2005-04-06 Basf Aktiengesellschaft Composition auto-adhésive contenant une résine de mélamine
WO2005100501A1 (fr) 2004-04-15 2005-10-27 Exxonmobil Chemical Patents Inc. Compositions adhesives a base de polyolefines et articles produits a partir de celles-ci
WO2005100502A1 (fr) 2004-04-19 2005-10-27 Basf Aktiengesellschaft Colle adhesive pour feuilles de pvc

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Geeignete Emulgatoren finden sich auch in Houben-Weyl, Methoden der organischen Chemie", vol. 14, 1961, GEORG THIEME VERLAG, pages: 192 - 208
W. MÄCHTLE, MAKROMOLEKULARE CHEMIE, vol. 185, 1984, pages 1025 - 1039

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9328247B2 (en) 2011-11-10 2016-05-03 Basf Se Paper coating slip additive comprising acid monomer, associative monomer and nonionic monomer
US9950502B2 (en) 2011-12-06 2018-04-24 Basf Se Paper and cardboard packaging with barrier coating
EP3781622B1 (fr) * 2018-04-20 2022-10-12 Basf Se Compositions adhésives à gelcontent de réticulation de groupes céto ou aldéhyde

Also Published As

Publication number Publication date
ES2438748T3 (es) 2014-01-20
EP2510067B1 (fr) 2013-10-02
US20120244350A1 (en) 2012-09-27
EP2510067A1 (fr) 2012-10-17
US9404023B2 (en) 2016-08-02

Similar Documents

Publication Publication Date Title
EP1378527B1 (fr) Adhésives sensibles à pression pour support en CPV souple
EP2496655B1 (fr) Adhésif polymérique fabriqué de n-butylacrylate, ethylacrylate, vinylacetate et de monomère d'acide
EP1828339B1 (fr) Matiere adhesive reticulable pour supports en pvc mou pouvant etre decolles
EP2697323B1 (fr) Dispersion d'adhésif sensible à la pression, contenant des polymères préparés par polymérisation par étapes lesquels comportent des groupes uréido ou analogues
EP2510067B1 (fr) Adhésif de contact pour films pvc
EP2084240B1 (fr) Adhésif sensible à la pression contenant un acrylate d'alkyle en c10
EP2697324A1 (fr) Dispersion d'adhésif de contact contenant des polymères comportant des groupes uréido ou des groupes analogues uréido et comportant des groupes glycidyle
EP1479744A1 (fr) Adhésifs de contact comprenant des polymères et des composés de silicium
EP1846530B1 (fr) Colle auto-adhesive pour etiquettes en papier a imprimer
EP1740669B1 (fr) Colle adhesive pour feuilles de pvc
WO2007125031A1 (fr) Adhésif contenant n-butylacrylate et hydroxybutyl(méth)acrylate
WO2007125040A1 (fr) Adhésif contenant 2-éthylhexylacrylate et hydroxybutyl(méth)acrylate
EP2016144A1 (fr) Agent auto-adhésif présentant un comportement amélioré au l'application à blanc
EP2547741B1 (fr) Film polymère à morphologie de film multiphase
EP1520898B1 (fr) Utilisation d'une composition auto-adhésive contenant une résine de mélamine pour fabriquer des articles autocollants
EP1685164A1 (fr) Dispersions polymeres contenant du sulfosuccinate
WO2011051206A1 (fr) Adhésif sensible à la pression, contenant un mélange de polymères réalisé par polymérisation par étapes
EP1862520A1 (fr) etiquettes en pellicule
WO2009115473A1 (fr) Procédé pour fabriquer des articles autocollants à base de dispersions polymères contenant des esters d’acide dicarboxylique sulfonés
EP1813660A1 (fr) Adhesive autocollant
WO2007144255A1 (fr) Adhésif sensible à la pression contenant une émulsion polymère comprenant du butyl(méth)acrylate tertiaire
WO2006136574A1 (fr) Procede de production de polymeres en emulsion pour des matieres adhesives
WO2006136575A1 (fr) Procede de production de polymeres en emulsion acides pour des matieres adhesives
WO2005121269A1 (fr) Adhesif contenant de l'ester d'acide adipique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10785442

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010785442

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13514773

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE