WO2011009800A1 - Stratifié de film sur film, fabriqué à l'aide d'une dispersion aqueuse de polymère comme agent adhésif - Google Patents

Stratifié de film sur film, fabriqué à l'aide d'une dispersion aqueuse de polymère comme agent adhésif Download PDF

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Publication number
WO2011009800A1
WO2011009800A1 PCT/EP2010/060231 EP2010060231W WO2011009800A1 WO 2011009800 A1 WO2011009800 A1 WO 2011009800A1 EP 2010060231 W EP2010060231 W EP 2010060231W WO 2011009800 A1 WO2011009800 A1 WO 2011009800A1
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monomers
weight
film
adhesive
acrylate
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PCT/EP2010/060231
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English (en)
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Karl-Heinz Schumacher
Michael Gross
Steve Kon
Joshua Taylor
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Basf Se
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • 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
    • C09J135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J135/06—Copolymers with vinyl aromatic monomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the present invention relates to film-to-film laminates, to a method of their manufacture and to the use of specific polymer dispersion as film-to-film lamination adhesive agent for forming said laminate.
  • the adhesive agent comprises an adhesive polymer, which is produced from a monomer mixture, comprising main monomers selected from C1- to C12-alkyl (meth)acrylates and styrene; vinyl acetate; hydroxyalkyl (meth)acrylates; and optionally (meth)acrylic acid; and further functional monomers in specific amounts and weight ratios.
  • the present invention is directed to a film-to-film laminate, comprising a first and at least a second sheet of film adhered by an adhesive agent, said adhesive agent comprising an adhesive polymer, said adhesive polymer being produced from a monomer mixture, comprising:
  • main monomers selected from the group consisting of C1- to C12-alkyl acrylates, C1- to C12-alkyl methacrylates, vinyl aromatic monomers and mixtures thereof;
  • hydroxy substituted unsaturated monomers selected from hydroxyalkyl acrylates, hydroxyalkyl methacrylates and mixtures thereof;
  • unsaturated acid monomers selected from acrylic acid, methacrylic acid and mixtures thereof;
  • the present invention is also directed to a flexible food packaging, comprising a lami- nate as described herein.
  • the present invention is also directed to the use of an aqueous polymer dispersion as film-to-film lamination adhesive agent, wherein the aqueous polymer dispersion comprises an adhesive polymer as described herein.
  • the present invention is also directed to a method of forming a laminate, wherein an aqueous polymer dispersion as described herein is coated to at least one side of a first sheet of film, the coating is at least partially dried, a second sheet of film is attached to the coated side of the first sheet of film and the first and second sheet of film are bonded together by application of heat and pressure.
  • the aqueous polymer dispersion comprises an adhesive polymer as described herein.
  • the adhesive agent is a single-component adhesive agent which is applied without one or more external crosslinking agents, i.e. it neither contains a crosslinking second component nor is it mixed with a crosslinking second component prior to use.
  • This is a low-cost, one component, aqueous-based laminating adhesive system with high peel strength and good handling properties for producing film-to-film laminates which does not need a crosslinking second component to provide a film-to-film laminate with sufficiently high peel strength.
  • the adhesive agent according to the invention may nevertheless optionally be formulated as two-component system, for example if specific additional effects are desired such as for example better heat resistance of the laminate and better resistance to chemicals, e.g. to components migrating from packed food into the adhesive between the films.
  • the second component comprises at least one crosslinking agent.
  • Suitable crosslinking agents are water dispersi- ble oligomeric or polymeric isocyanates, aziridines or water dispersible or water soluble silanes. Typical mixing ratios are 100 parts by weight of aqueous adhesive polymer dispersion to 1 to 7 parts by weight of crosslinker.
  • the terms ,,film” and ,,sheet of film as used herein mean materials which may be manufactured in the form of films or foils such as polymeric films or metal foils, including metallized films and surface treated films.
  • the term ,,film-to film laminate means a structure of two or more films which are laminated together by the use of a laminating adhesive.
  • lamination adhesive as used herein means a material that is able to bond together two substrates by application of pressure and heat. Lamination adhe- sives are distinguished from pressure sensitive adhesives by higher peel strength and by lower quick stick.
  • the term ,(meth)acryl and similar terms as used herein mean ,,acryl... or methacryl!.
  • the main monomers a) of the adhesive polymer comprise at least one monomer selected from the group consisting of C1- to C12-alkyl acrylates, C1- to C12-alkyl methacrylates, vinyl aromatic monomers and mixtures thereof.
  • C1- to C12-alkyl acrylates and of C1- to C12-alkyl methacrylates are methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl acry- late, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate and dodecyl acrylate.
  • a combination of n-butyl acrylate and methyl methacrylate is especially pre- ferred.
  • the vinylaromatic compounds preferably have up to 20 carbon atoms. Examples are vinyltoluene, alpha- and p-methylstyrene, alpha-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and, preferably, styrene.
  • the main monomers a) are preferably selected from n-butyl acrylate, methyl methacrylate and styrene.
  • the amount of C1- to C12-alkyl (meth)acrylates is preferably from 60 to 98% by weight and the amount of vinylaromatic monomers is preferably from 0 to 30% or from 1 to 30% by weight, based on the total amount of monomers.
  • the amount of vinyl acetate monomer b) is from 1 to 10% by weight, preferably from 2 to 8% by weight, based on the total amount of monomers.
  • the hydroxy substituted unsaturated monomers c) are hydroxyalkyl (meth)acrylates, i.e. monoesters of acrylic acid or of methacrylic acid with alkanediols. Examples are hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy- propyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. Those hydroxyalkyl (meth)acrylates which exist as different isomers can be used in any of their isomers or in a mixture of two or more isomers. Most preferred are hydroxyethyl acrylate and hydroxypropyl acrylate.
  • the amount of hydroxy substituted unsaturated monomers c) is from 0,2 to 5% by weight, preferably from 0,5 to 4% by weight, based on the total amount of monomers.
  • the weight ratio of the amount of vinyl acetate monomer b) to hydroxy substituted unsaturated monomers c) is from 1 :4 to 40: 1 , preferably from 1 :2 to 10: 1.
  • the unsaturated acid monomers d) are selected from acrylic acid, methacrylic acid and mixtures thereof. Acrylic acid is preferred.
  • the amount of unsaturated acid monomers d) is from 0 to 3% by weight, preferably from 0,5 to 3% by weight, based on the total amount of monomers.
  • the adhesive polymer is preferably composed exclusively of monomers a) to d) but may optionally contain further functional monomers e) in amounts of from 0 up to 5% or from 0,1 to 5% by weight, based on the total amount of monomers.
  • Further monomers d) are for example acetoacetoxyethyl methacrylate (AAEM), vinylsi- lanes, alkanediol diacrylates such as e.g. butanediol diacrylate, hydroxyalkyl
  • (meth)acrylamides such as e.g. hydroxymethyl (meth)acrylamide and similar compounds.
  • the laminates e.g. applications with food contact such as food packaging, it is desired for safety, health or toxicological reasons that no acrylnitril is used for producing the adhesive polymer.
  • the performance properties can be achieved by monomer mixtures according to the invention without the need for acrylnitril, it is one aspect of the invention, that the monomer mixture does not contain acryl- nitril.
  • preferred adhesive polymers are those obtainable by polymerizing the monomer mixture mentioned above in the absence of molecular weight regulators (chain transfer agents).
  • the K value of the adhesive polymer is preferably at least 70, for example 70 to 100 (K value according to Fikentscher, determined in a 1 % by weight solution of the polymer in Tetrahydrofuran).
  • the glass transition temperature Tg of the adhesive polymers of the invention is preferably in the range from -25 to 0 0 C, in particular in the range from -20 to -10 0 C. In this context it proves useful to estimate the glass transition temperature Tg of the dispersed polymer. According to Fox (T.G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1 , 123 [1956] and Ullmanns Enzyklopadie der ischen Chemie, Weinheim (1980), pp. 17, 18), for the glass transition temperature of copolymers at high molecular masses, it holds in good approximation that
  • X1 , X2, . . . , Xn are the mass fractions of the monomers 1 , 2, . . . , n; and Tg1 , Tg2, . . . , Tgn are the glass transition temperatures of the homopolymers of each of the monomers 1 , 2, . . . , n in degrees Kelvin.
  • the latter are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p. 169 or from J. Brandrup, E. H. Immergut, Polymer Handbook 3rd edition, J. Wiley, New York 1989.
  • the adhesive polymer is produced from a monomer mixture, comprising a) from 80 to 98% by weight of main monomers selected from the group consisting of C1- to C10-alkyl acrylates, C1- to C10-alkyl methacrylates, styrene and mixtures thereof;
  • hydroxy substituted unsaturated monomers selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hy- droxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate, including isomers of these monomers;
  • unsaturated acid monomers selected from acrylic acid and methacrylic acid
  • the adhesive agent is in the form of an aqueous dispersion of the adhesive polymer.
  • another embodiment of the invention is a polymer dispersion suit- able as film-to-film lamination adhesive agent for forming laminates as described herein.
  • This aqueous polymer dispersion comprises an adhesive polymer as defined above. It has been found advantageous for the adhesive polymer particles in the polymer dispersions of the invention to have an average particle diameter in the range from 50 to 1000 nm. The particle size can be determined by using an ultracentrifuge or by photon correlation spectroscopy; on particle size determination see W. Machtle,
  • the aqueous polymer dispersions employed in accordance with the invention can be prepared by free-radical aqueous emulsion polymerization of said monomers.
  • the emulsion polymerization is customarily conducted in an aqueous polymerization medium in the presence of at least one free-radical polymerization initiator and, if desired, of a surface-active substance.
  • Suitable free-radical polymerization initiators in principle include both peroxides, such as hydrogen peroxide, organic peroxides such as tert- butyl hydroperoxide, alkali metal and ammoniumperoxodisulfates, for example, and azo compounds.
  • redox initiator systems which are composed of at least one organic reducing agent and at least one peroxide and/or hydroperoxide, an example being tert-butyl hydroperoxide and a sulfur compound, such as the sodium salt of hydroxymethanesulfinic acid, sodium sulfite, sodium disulfite, sodium thiosulfate or acetone bisulfite adduct, or hydrogen peroxide with ascorbic acid.
  • redox initiator systems containing a small amount of a metal compound which is soluble in the polymerization medium and whose metallic component is able to exist in a plurality of valence states, an example being ascorbic acid/iron(ll) sulfate/hydrogen peroxide, in which the ascorbic acid can in many cases also be replaced by the sodium salt of hydroxymethanesulfinic acid, acetone bisulfite adduct, sodium sulfite, sodium hydrogen sulfite or sodium disulfite, and the hydrogen peroxide by organic peroxides, such as tert-butyl hydroperoxide, alkali metal peroxodi- sulfates and/or ammonium peroxodisulfate.
  • organic peroxides such as tert-butyl hydroperoxide, alkali metal peroxodi- sulfates and/or ammonium peroxodisulfate.
  • initiators are peroxodi- sulfates, such as sodium peroxodisulfate or ammonium peroxodisulfate.
  • the amount of free-radical initiator systems employed is from 0.1 to 2% by weight.
  • the initiator can either be all in- eluded in the initial charge to the polymerization vessel or else added continuously or in stages at the rate at which it is consumed in the course of the free-radical aqueous emulsion polymerization. In each individual case it will depend, in a manner known to the skilled worker, both on the chemical nature of the initiator system and on the polymerization temperature.
  • a portion is included in the initial charge and the remainder is supplied to the polymerization vessel at the rate at which it is consumed.
  • Surface-active substances suitable for conducting the emulsion polymerization are the emulsifiers and protective colloids commonly employed for such purposes.
  • the surface-active substances are customarily used in amounts of up to 10% by weight, pref- erably from 0.1 to 5% by weight and, in particular, from 0.5 to 4% by weight, based on the monomers to be polymerized.
  • the surface-active substances can remain in the polymer dispersions and can therefore also be a constituent of the laminating adhe- sives of the invention.
  • suitable protective colloids are polyvinyl alcohols, starch derivatives and cellulose derivatives, or vinylpyrrolidone copolymers.
  • protective colloids can be found in Houben-Weyl, Metho- den der organischen Chemie, Volume XIV/1 , Makromolekulare Stoffe [Macromolecular substances], Georg-Thieme-Verlag, Stuttgart 1961 , pp. 41 1-420. Mixtures of emulsifiers and/or protective colloids can also be used. As surface-active substances it is preferred to employ exclusively emulsifiers, whose relative molecular weights, unlike those of the protective colloids, are usually below 2000. They can be anionic, cationic or else nonionic in nature.
  • the anionic emulsifiers include alkali metal and ammonium salts of alkyl sulfates (alkyl: C8-C12), of dialkyl esters of sulfdsuccinic acid (alkyl: C4-C10), of sulfuric monoesters with ethoxylated alkanols (EO units: 2 to 50, alkyl: C12 to C18) and with ethoxylated alkylphenols (EO units: 3 to 50, alkyl: C4-C10), of alkylsulfonic acids (alkyl: C12-C18) and of alkylarylsulfonic acids (alkyl: C9 to C18).
  • alkyl sulfates alkyl: C8-C12
  • dialkyl esters of sulfdsuccinic acid alkyl: C4-C10
  • sulfuric monoesters with ethoxylated alkanols EO units: 2 to 50, alkyl:
  • the anionic surface- active substances also include mono- and dialkyl derivatives of sulfonylphenoxyben- zenesulfonic salts, especially their sodium, potassium or calcium salts.
  • the alkyl groups in these compounds generally have 6 to 18 and especially 6, 12 or 16 carbon atoms. Use is frequently made of technical mixtures comprising a proportion of from 50 to 90% by weight of the monoalkylated product.
  • These compounds are common knowledge, for example, from U.S. Pat. No.4, 269, 749, and are obtainable commer- cially, for example, as Dowfax(R) 2A1 (trademark of the Dow Chemical Company).
  • Suitable nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, examples being ethoxylated mono-, di- and trialkylphenols (EO units: 3 to 50, alkyl: C4-C9), eth- oxylates of long-chain alcohols (EO units: 3 to 50, alkyl: C8-C36), and also polyethylene oxide/polypropylene oxide block copolymers.
  • ethoxylates of long-chain alkanols alkyl: C10-C22, average degree of ethoxylation: 3 to 50
  • ethoxylates of long-chain alkanols alkyl: C10-C22, average degree of ethoxylation: 3 to 50
  • emulsifiers can be found in Houben-Weyl, Metho- den der organischen Chemie, Volume XIV/1 , Makromolekulare Stoffe [macromolecular substances], Georg-Thieme-Verlag, Stuttgart, 1961 , pp. 192-208.
  • the surface-active substances used to prepare the polymer dispersions of the invention preferably include at least one anionic emulsifier. It has been found advantageous for the stability of the polymer dispersions of the invention, especially to mechanical loads such as shear forces, that the anionic emulsifiers used to prepare the dispersions of the invention can include at least one salt of a dialkyl ester of sulfosuccinic acid (linear or branched C4- C10 and, in particular, C8 alkyl radical), preferably an alkali metal salt and in particular the sodium salt.
  • a dialkyl ester of sulfosuccinic acid linear or branched C4- C10 and, in particular, C8 alkyl radical
  • the emulsion polymerization takes place in general at from 30 to 130, preferably from 50 to 100 0 C.
  • the polymerization medium can consist either of water alone or else of mixtures of water with water-miscible organic liquids such as methanol, ethanol, n- propanol, isopropanol, n-butanol, tert-butanol, tetrahydrofuran, formamide, or dimethyl- formamide, the proportion of said liquids usually being less than 10% by weight based on the polymerization medium. It should be borne in mind here that the presence of alcohols during the polymerization may result in a reduction in molecular weight. Preferably, water alone is used as polymerization medium.
  • the emulsion polymerization can be conducted either as a batch process or in the form of a feed process, including stages or a gradient procedure. Preference is given to the feed process, in which the monomers in pure or emulsified form are supplied to the polymerization zone continuously, in stages or under a concentration gradient, with the polymerization being maintained.
  • the individual components can be added to the reac- tor, in the case of the feed process, from above, from the side or from below, through the reactor floor.
  • a defined polymer particle size can be established by conducting the emulsion polymerization by the seed latex process or in the presence of seed latex prepared in situ.
  • the polymerization is customarily conducted in the presence of from 0.001 to 3% by weight and, in particular, from 0.01 to 1.5% by weight of a seed latex (solids content of the seed latex, based on total monomer amount), preferably with seed latex included in the initial charge (initial charge seed).
  • the latex generally has a weight- average particle size of from 10 to 100 nm and, in particular, from 20 to 50 nm.
  • Exam- pies of its constituent monomers are styrene, methyl methacrylate, n-butyl acrylate and mixtures thereof.
  • the adhesive polymer dispersions of the invention are used in accordance with the invention in aqueous adhesive formulations for producing film-to-film laminates; i.e., in aqueous laminating adhesive formulations for bonding at least two film or foil substrates of large surface area.
  • the present invention therefore also provides a method for producing film-to-film laminates in which an aqueous adhesive formulation is used which comprises at least one of the polymer dispersions of the invention.
  • the aqueous polymer dispersions can be used as they are or after formulation with auxiliary agents.
  • auxiliary agents are wetting agents, thickeners, protective colloids, light stabilizers, biocides, defoamer etc.
  • Typical wetting agents are the anionic surface-active substances mentioned above, e.g. one or more salts of a dialkyl esters of sulfosuccinic acid (linear or branched C4-C10 and, in particular, C8 alkyl radical), preferably an alkali metal salt and in particular the sodium salt.
  • the aqueous adhesive polymer dispersion of the invention or an appropriately formu- lated preparation (formulation), is applied, for example by coating, to at least one side of a first sheet of film.
  • the coating may have a layer thickness of from 0.1 to 20 g/m 2 , preferably from 1 to 7 g/m 2 .
  • the coating is at least partially dried, e.g. by evaporation of the dispersion water for a short time, preferably after from 1 to 60 seconds.
  • the coated first substrate can then be laminated with a second substrate.
  • a second sheet of film is attached to the coated side of the first sheet of film and the first and second sheet of film are bonded together by application of heat and pressure.
  • the temperature can be, for example, from 30 to 200, preferably from 30 to 100 0 C, and the pressure can be, for example, from 100 to 3000, preferably from 300 to 2000 kN/m 2 .
  • the adhesive agent is applied as a one component agent, i.e. without one or more separate crosslinking agents, especially without the use of isocy- anate crosslinking compounds.
  • at least one of a first and second sheet of film can be printed or metallized on its respective side which is coated with the adhesive agent.
  • suitable substrates are polymer films, especially those of polyethylene (PE), oriented polypropylene (OPP), cast polypropylene (CPP), polyamide (PA), poly- ethylene terephtalate (PET), polyacetate, cellophane, metallized films (i.e. polymer films (vapor-)coated with metal, e.g. aluminum) or metal foils, such as those of aluminum.
  • PE polyethylene
  • OPP oriented polypropylene
  • CPP cast polypropylene
  • PA polyamide
  • PET poly- ethylene terephtalate
  • polyacetate cellophane
  • Said foils or films can be bonded to one another, or to a foil or film of a different type, e.g., polymer films to metal foils, different polymer films to one another, etc.
  • Said foils and films can also be printed with printing inks, for example.
  • One embodiment of the invention is a laminate made by using an aqueous adhesive polymer dispersion as described above and wherein the material of a first sheet of film is selected from oriented polypropylene, cast polypropylene, polyethylene, polyethylene terephtalate and polyamide and wherein the material of a second sheet of film is se- lected from oriented polypropylene, cast polypropylene, polyethylene, polyethylene terephtalate, polyamide and metal foils.
  • the first sheet of film and/or the second sheet of film are printed or metallized on their respective side which is coated with the adhesive agent.
  • the thickness of the base films may for example be from 5 to 100 ⁇ m, preferably from 5 to 40 ⁇ m.
  • An advantage of the invention is that substrates of very different kinds can be bonded to one another, i.e., laminated, with the adhesive polymer dispersions of the invention ensuring good adhesion of the adhesive formulation to the substrates and resulting in high strength of the bonded composite.
  • the surface modification of the base films prior to adhesive coating is not required, better results may be obtained if the surface or surfaces of the base films are modified before application of the adhesive agent of the present invention.
  • Conventional surface modification techniques include corona treatment, which is the most common and most preferred procedure for modifying the surface of the polymer base film to enhance coating adhesion.
  • the corona treatment or other surface modification should be sufficient to permit wetting out of the coating. Corona treatment of about 10 watt per square meter per minute is typically sufficient to achieve the desired results.
  • primer or other intermediate layers can optionally be used between the polymer film and the barrier coating.
  • the laminates may include additional functional layers such as barrier layers, printed layers, colored layers or protective layers. The functional layers may be located on the outer surface of the laminates or on the inside, between base substrate and adhesive coating.
  • Disponil® FES 77 32% by weight aqueous solution of sodium salt of fatty alcohol poly- ether sulfate (Cognis)
  • Dowfax® 2A1 45% by weight aqueous solution of dodecylphenoxybenzenedisulfonic acid sodium salt (Dowchemical).
  • Procedures for emulsion polymerization are generally known (see e.g. WO 98/23656).
  • An emulsion was formed in deionized water with monomers according to table 1 , 0,4 pphm NaOH (parts by weight per hundred parts monomers) and 1 pphm Disponil® FES 77.
  • the monomer emulsions of examples D2 to D5 additionally contained 0,2 pphm Dowfax® 2A1.
  • the monomers were polymerized using a total of 0,5% by weight (with respect to the total weight of monomers) of sodium peroxodisulfate, dissolved in deionized water.
  • a polymerization reactor was charged in a nitrogen atmosphere with 250 g of deionized water.
  • the initial charge was heated to 90 0 C and 10% of the total amount of the initiator solution was added to the initial charge. Then addition of the monomer emulsion and addition of the remainder of the initiator solution were added in parallel. The monomer emulsion was added in 3 hours, the remainder of the initiator solution was added in 3,5 hours, beginning simultaneously. The pH can be adjusted by aqueous ammonia. The mixture was subsequently cooled to room temperature and filtered through a 125 ⁇ m sieve.
  • nBA n-butyl acrylate
  • MMA methyl methacrylate
  • S styrene
  • VAc vinyl acetate
  • AA acrylic acid
  • HEA hydroxyethyl acrylate
  • HPA hydroxypropyl acrylate (isomeric mixture of 2-hydroxy-n-propyl acrylate and 2-hydroxy isopropyl acrylate)
  • CE1-3 comparative examples
  • D1-D5 inventive examples
  • the adhesive polymer dispersions were knife-coated in a dry layer thickness of 2 g/m 2
  • OPP oriented polypropylene
  • PE polyethylene
  • PET polyethylene terephtalate
  • film-to-film lamination adhesives D1 to D5 according to the invention show significantly higher peel strength than comparative adhesives C1 to C3.
  • acrylic dispersion D1 , D2, D3, D4 or D5 100 parts by weight of acrylic dispersion D1 , D2, D3, D4 or D5 are mixed with 2 parts by weight of a water dispersible isocyanate crosslinker, e.g. Basonat® F 200 WD (poly- functional aliphatic isocyanate).
  • Basonat® F 200 WD poly- functional aliphatic isocyanate
  • this mixture is processed by coating onto a polymeric film (printed or unprinted OPP or PET).
  • the coated polymer films can be laminated to a second polymeric film (PE or unmetal- lized or metallized PET) in a calender at 70 0 C and under a pressure of 6.5 bar.

Landscapes

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

Abstract

L'invention porte sur un stratifié de film sur film, comprenant des première et seconde feuilles de film collées par un agent adhésif comprenant un polymère adhésif, qui est produit à partir d'un mélange de monomères, comprenant : a) de 80 à 98 % en poids de monomères principaux choisis parmi les (méth)acrylates d'alkyle en C1 à C12 et les monomères vinylaromatiques; b) de 1 à 10 % en poids d'acétate de vinyle; c) de 0,2 à 5 % en poids de (méth)acrylates d'hydroxyalkyle; d) de 0 à 3 % en poids d'acide (méth)acrylique; e) de 0 à 5 % en poids d'autres monomères fonctionnels, le rapport pondéral de l'acétate de vinyle aux monomères insaturés substitués par hydroxy étant de 1:4 à 40:1. L'invention porte également sur un procédé de formation dudit stratifié et sur une dispersion aqueuse de polymère appropriée comme agent adhésif de stratification de film sur film pour la formation dudit stratifié. L'agent adhésif est de préférence un agent adhésif à un seul composant.
PCT/EP2010/060231 2009-07-21 2010-07-15 Stratifié de film sur film, fabriqué à l'aide d'une dispersion aqueuse de polymère comme agent adhésif WO2011009800A1 (fr)

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CN102838952A (zh) * 2012-09-12 2012-12-26 北京高盟新材料股份有限公司 水性烟包镭射转移胶及其制备方法
EP2752472A2 (fr) * 2011-10-05 2014-07-09 LG Hausys, Ltd. Composition adhésive aqueuse variant peu avec le temps
EP3725485A1 (fr) * 2019-04-17 2020-10-21 Basf Se Procédé de recyclage de stratifiés film-sur-film
US10975273B2 (en) 2015-12-08 2021-04-13 Dow Global Technologies Llc Aqueous polymer emulsion and an aqueous adhesive composition formed therefrom
CN113260510A (zh) * 2019-01-11 2021-08-13 巴斯夫欧洲公司 使用凹版辊系统的膜涂覆方法
WO2023010602A1 (fr) * 2021-08-03 2023-02-09 海南赛诺实业有限公司 Film composite haute barrière et procédé de préparation pour celui-ci
US11905353B2 (en) 2017-08-16 2024-02-20 Rohm And Haas Company Pressure sensitive adhesive compositions and methods of making same

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2752472A2 (fr) * 2011-10-05 2014-07-09 LG Hausys, Ltd. Composition adhésive aqueuse variant peu avec le temps
EP2752472A4 (fr) * 2011-10-05 2015-03-25 Lg Hausys Ltd Composition adhésive aqueuse variant peu avec le temps
US9187677B2 (en) 2011-10-05 2015-11-17 Lg Hausys, Ltd. Aqueous adhesive composition that changes little over time
CN102838952A (zh) * 2012-09-12 2012-12-26 北京高盟新材料股份有限公司 水性烟包镭射转移胶及其制备方法
CN102838952B (zh) * 2012-09-12 2013-12-18 北京高盟新材料股份有限公司 水性烟包镭射转移胶及其制备方法
US10975273B2 (en) 2015-12-08 2021-04-13 Dow Global Technologies Llc Aqueous polymer emulsion and an aqueous adhesive composition formed therefrom
US11905353B2 (en) 2017-08-16 2024-02-20 Rohm And Haas Company Pressure sensitive adhesive compositions and methods of making same
CN113260510A (zh) * 2019-01-11 2021-08-13 巴斯夫欧洲公司 使用凹版辊系统的膜涂覆方法
CN113260510B (zh) * 2019-01-11 2023-09-15 巴斯夫欧洲公司 使用凹版辊系统的膜涂覆方法
EP3725485A1 (fr) * 2019-04-17 2020-10-21 Basf Se Procédé de recyclage de stratifiés film-sur-film
WO2023010602A1 (fr) * 2021-08-03 2023-02-09 海南赛诺实业有限公司 Film composite haute barrière et procédé de préparation pour celui-ci

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