EP3390473A1 - Dispersions polymères aqueuses pauvres en émulsifiant pour la préparation de feuilles composites - Google Patents

Dispersions polymères aqueuses pauvres en émulsifiant pour la préparation de feuilles composites

Info

Publication number
EP3390473A1
EP3390473A1 EP16809753.3A EP16809753A EP3390473A1 EP 3390473 A1 EP3390473 A1 EP 3390473A1 EP 16809753 A EP16809753 A EP 16809753A EP 3390473 A1 EP3390473 A1 EP 3390473A1
Authority
EP
European Patent Office
Prior art keywords
monomers
acid
group
weight
monomer
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Withdrawn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
EP16809753.3A
Other languages
German (de)
English (en)
Inventor
Christine TONHAUSER
Karl-Heinz Schumacher
Georg Langhauser
Sindy SCHUSTER
Christoph Kiener
Matthias ZORN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3390473A1 publication Critical patent/EP3390473A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B32B15/082—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 comprising vinyl resins; comprising acrylic resins
    • 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
    • B32B15/085—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 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
    • 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
    • B32B15/088—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 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
    • 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
    • B32B15/09—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 comprising polyesters
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/042—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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
    • B32B27/06—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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • 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
    • 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
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • 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
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • 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
    • B32B2255/06—Coating on the layer surface on metal 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
    • B32B2255/10—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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/02—Synthetic macromolecular particles
    • B32B2264/0214—Particles made of materials belonging to B32B27/00
    • B32B2264/025—Acrylic resin particles, e.g. polymethyl methacrylate or ethylene-acrylate copolymers
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/732—Dimensional 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
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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

Definitions

  • the invention relates to certain emulsifier-poor aqueous polymer dispersions, to a process for their preparation and to their use as adhesives, in particular for the production of composite films.
  • Adhesive systems based on organic solvents are widely used in this application. Water-based adhesive systems represent an alternative for reducing organic solvent emissions.
  • Acrylate ester polymer dispersions also known as acrylate latex, are of particular importance.
  • Acrylate ester based adhesives are e.g. described in WO 98/23656 and in WO 00/50480. The use of polymer dispersions prepared by emulsion polymerization using emulsifiers may lead to undesirable foaming in the machine film coating.
  • Typical protective colloids are acid group-containing polymers which are water-soluble upon neutralization of the acid groups at elevated pHs.
  • the protective colloids can act as foam stabilizers, which in turn can lead to undesirable foaming in the machine film coating.
  • a reduction in the content of emulsifiers and protective colloids is not readily possible since the polymer dispersions are then generally not sufficiently stable, e.g. are not shear stable and can coagulate, especially in their large scale production on a ton scale.
  • WO 201/154920 describes a two-stage preparation of aqueous polymer dispersions for producing composite films.
  • the polymer produced in the first stage acts during the second stage polymerization as a protective colloid. Due to the content of protective colloid, undesired foaming or undesirable foam stabilization may occur when applied by machine to films.
  • WO 00/50480 describes aqueous acrylate copolymer dispersions for use as laminating adhesives. Relatively high amounts of emulsifier are used and no neutralization takes place during the polymerization.
  • GB 2070037 describes pressure-sensitive adhesive dispersions, in which case the polymerization is initially carried out with low emulsifier or emulsifier-free and then substantial amounts of emulsifier are added and the neutralizing agent is already present at the beginning of the polymerization. Uses as laminating adhesives for the production of composite films are not described.
  • the object was to provide aqueous polymer dispersions which are suitable as adhesives, in particular for the production of composite films, wherein the polymer dispersions do not foam or only as little as possible when applied by machine application to polymer films and at the same time despite only a very small or missing content of emulsifiers or protective colloids are as stable as possible, in particular shear-stable, do not coagulate and have good adhesive values, for example with regard to peel strength and heat resistance.
  • the invention relates to an aqueous polymer dispersion containing water-dispersed polymer particles
  • polymer particles having a mean particle diameter of greater than 200 nm, preferably greater than 250 nm, wherein the polymer particles have a monomodal particle size distribution and
  • the feed of the monomer mixture takes place during the polymerization with a first and at least one second feed rates, wherein the first feed rate is preferably slower than the second feed rate and wherein the acid groups of the monomers b) during the emulsion polymerization wholly or partly by the addition of a base be neutralized, wherein the feed of the base during the emulsion polymerization begins after at least 5 wt.%, Preferably 10 to 70 wt.% Of the total monomer mixture in the reaction vessel under polymerization.
  • the invention also relates to a corresponding process for the preparation of the aqueous polymer dispersions.
  • the principle of the method according to the invention is based on the seed-controlled formation of uniform, large polymer particles in aqueous dispersion with largely avoiding the formation of water-soluble oligomers and polymers.
  • the invention also provides a two-component adhesive comprising a polymer dispersion according to the invention in a first component and at least one crosslinker reactive with the first component in a second component.
  • the invention also relates to the use of the aqueous polymer dispersion according to the invention as an adhesive, in particular as a laminating adhesive, e.g. for the production of composite films.
  • the invention also provides a composite film which has a first and at least one second film which are glued together using an adhesive comprising an aqueous polymer dispersion of the invention or a two-component adhesive according to the invention.
  • the invention also provides a process for producing composite films, wherein an aqueous polymer dispersion according to the invention is provided and at least two films are bonded together using the aqueous polymer dispersion.
  • the glass transition temperature is determined by differential scanning calorimetry (ASTM D 3418-08, so-called "midpoint temperature”).
  • the glass transition temperature of the polymer of the polymer dispersion is the glass transition temperature obtained on evaluation of the second heating curve (heating rate 20 ° C./min).
  • the polymer particles have a uniform glass transition temperature. This means that only a single glass transition temperature is measured when measuring the glass transition temperature.
  • the polymer dispersions prepared according to the invention are obtainable by free-radical emulsion polymerization of ethylenically unsaturated compounds (monomers).
  • the polymerization takes place here emulsifier-free or emulsifier poor in the sense that less than 0.8, preferably less than or equal to 0.5 parts by weight of emulsifier, based on 100 parts by weight of monomers are added to stabilize the polymer dispersion of the invention.
  • Emulsifiers are added to the polymerization mixture before, after or after the polymerization. polymeric, amphiphilic, surfactants. Small amounts of emulsifiers, which are caused, for example, by the use of emulsifier-stabilized polymer seed, are harmless in this case.
  • a total of less than 0.3 parts by weight or less than 0.2 parts by weight of emulsifier for example from 0.05 to 0.8 parts by weight, or from 0.05 to 0.5 parts by weight. Parts, or from 0.05 to 0.3 parts by weight, based on 100 parts by weight of monomers or no emulsifier used.
  • protective colloids are polymeric compounds which upon solvation bind large quantities of water and are capable of stabilizing dispersions of water-insoluble polymers. In contrast to emulsifiers, they usually do not lower the interfacial tension between polymer particles and water.
  • the number average molecular weight of protective colloids is e.g. above 1000 g / mol.
  • the monomer mixture consists of at least 60% by weight, preferably at least 80% by weight, for example from 80 to 99.9% by weight, more preferably at least 90% by weight, based on the total amount of monomers, of at least one monomer a) selected from the group consisting of C 1 - to C 20 -alkyl acrylates, C 1 - to C 20 -alkyl methacrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, vinyl halides, vinyl ethers of 1 to 10 C atoms containing alcohols, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds and mixtures of these monomers.
  • Suitable monomers a) are, for example, (meth) acrylic acid alkyl esters having a Ci-Cio-alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate and behenyl (meth) acrylate, isobutyl acrylate, tert-butyl (meth) acrylate and cyclohexyl (meth) acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for.
  • vinyl laurate vinyl stearate, vinyl propionate, versatic acid vinyl ester 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. As vinyl methyl ether or vinyl isobutyl ether. Vinyl ether is preferably from 1 to 4 C-containing alcohols.
  • Suitable hydrocarbons having 4 to 8 C atoms and two olefinic double bonds are butadiene, isoprene and chloroprene.
  • Preferred monomers a) are the C 1 -C 10 -alkyl acrylates and methacrylates, especially C 1 -C -alkyl acrylates and methacrylates, and also styrene and mixtures thereof.
  • methyl acrylate methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, 2-propylheptyl acrylate, styrene and mixtures of these monomers.
  • the monomer mixture consists of at least 0.1% by weight, in particular from 0.1 to 5% by weight or from 0.5 to 3% by weight, based on the total amount of monomers, of at least one ethylenically unsaturated monomer having at least one Acid group (acid monomer).
  • the acid monomers b) include both monomers containing at least one acidic groups, as well as their anhydrides and their salts.
  • the monomers b) include alpha, beta-monoethylenically unsaturated mono- and dicarboxylic acids, half esters of alpha, beta-monoethylenically unsaturated dicarboxylic acids, the anhydrides of the aforementioned alpha, beta-monoethylenically unsaturated carboxylic acids and ethylenically unsaturated sulfonic acids, phosphonic acids or dihydrogen phosphates and their water-soluble salts, eg their alkali metal salts.
  • these are 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.
  • Preferred monomers b) are alpha, beta-monoethylenically unsaturated C3-C8 carboxylic acids and C4-C8 dicarboxylic acids, e.g. Itaconic acid, crotonic acid, vinylacetic acid, acrylamidoglycolic acid, acrylic acid and methacrylic acid, and their anhydrides.
  • Particularly preferred monomers b) are itaconic acid, acrylic acid and methacrylic acid.
  • the acid groups of the monomer b) are not yet neutralized at the beginning of the polymerization. They are neutralized during the emulsion polymerization wholly or partly by the addition of a base, wherein the feed of the base during the emulsion polymerization (ie after the start of the polymerization) begins after at least 5 wt.%, Preferably 10 to 70 wt.% Of the total monomer in the Reaction vessel under Polymerisati- ons claim present.
  • Suitable bases are e.g.
  • the monomer mixture may optionally contain at least one further monomer c) other than the monomers a) and b).
  • the monomers c) may e.g. from 0 to 10% by weight or from 0 to 5% by weight, in particular from 0.1 to 10% by weight, or from 0.1 to 5% by weight or from 0.2 to 3% by weight, based on the total amount of monomers are used.
  • Monomers c) are, for example, neutral or nonionic monomers with increased water solubility, e.g.
  • the amides or the N-alkylolamides of the abovementioned carboxylic acids for example acrylamide, methacrylamide, N-methylolacrylamide and N-methylolmethacrylamide or phenyloxyethylglycol mono (meth) acrylate.
  • Further monomers c) are, for example, also hydroxyl-containing monomers, in particular the hydroxyalkyl esters of the aforementioned alpha, beta-monoethylenically unsaturated carboxylic acids. preferably C 1 -C 10 -hydroxyalkyl (meth) acrylates such as, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate and 4-hydroxybutyl acrylate.
  • Other monomers c) are e.g. also amino-containing monomers, in particular the aminoalkyl esters of the aforementioned alpha, beta-monoethylenically unsaturated carboxylic acids, preferably Ci-Cio-aminoalkyl (meth) acrylates such. 2-aminoethyl (meth) acrylate or tert-butylaminoethyl methacrylate.
  • monomers c) are the nitriles of alpha, beta-monoethylenically unsaturated C3-C8-carboxylic acids, such as. Acrylonitrile or methacrylonitrile into consideration.
  • Suitable monomers c) are also bifunctional monomers which, in addition to an ethylenically unsaturated double bond, have at least one glycidyl group, oxazoline group, ureido group, urido-analogous group or carbonyl group.
  • monomers having glycidyl group are ethylenically unsaturated glycidyl ethers and glycidyl esters, e.g. Vinyl, allyl and methylallylglycidyl ethers, glycidyl (meth) acrylate.
  • Examples of monomers having a carbonyl group are the diacetonylamides of the above-mentioned ethylenically unsaturated carboxylic acids, e.g. Diacetone (meth) acrylamide and the esters of acetylacetic acid with the abovementioned hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, e.g. Acetylacetoxyethyl (meth) acrylate.
  • Examples of monomers c) with oxazoline group are those of the formula:
  • R is a C2-2o alkenyl radical comprising at least one ethylenically unsaturated group
  • R 3 , R 4 , R 5 , R 6 are independently selected from H, halogen, Ci-20-alkyl,
  • the oxazoline monomers are at least one monomer selected from the group consisting of 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl- 2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline, 2-vinyl-5,5-dimethyl-2-oxazoline, 2-vinyl-4, 4,5,5-teramethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-4 ethyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline, 2-isopropenyl
  • 2-vinyl-2-oxazoline and / or 2-isopropenyl-2-oxazoline in particular preferred is 2-isopropenyl-2-oxazoline (iPOx).
  • monomers c) having ureido group or ureido-analogous group are, for example, those of the formula
  • X is CH 2 , O, NH or NR 1 and R 1 is a C1 to C4 alkyl group, R is hydrogen or methyl and A is a divalent linking group, preferably a C1 to C10 alkyl group or a C2 to C4 alkyl group.
  • Ureidoalkyl (meth) acrylates having 1 to 10 C atoms, preferably 2 to 4 C atoms in the alkyl group, in particular ureidoethyl methacrylate (UMA), are particularly preferred.
  • Examples of monomers c) are also crosslinking monomers which have more than one free-radically polymerizable group, in particular two or more (meth) acrylate groups, for example butanediol di (meth) acrylate or allyl methacrylate.
  • Preferred monomers c) are those which enable the post-crosslinking of the polymer, for example with polyfunctional amines, hydrazides, isocyanates or alcohols.
  • Crosslinking is also possible by metal salt crosslinking of the carboxyl groups using polyvalent metal cations, e.g. Zn or AI.
  • Suitable crosslinking may e.g. in that the polymer contains keto or aldehyde groups (preferably 0.0001 to 1 mol, or 0.0002 to 0.10 mol, or 0.0006 to 0.03 mol) and the polymer dispersion additionally contains a compound with at least 2 functional groups, in particular 2 to 5 functional groups, which undergo a crosslinking reaction with the keto or aldehyde groups.
  • the keto or aldehyde groups can be bound to the polymer by copolymerization of suitable monomers c).
  • suitable monomers c) are e.g.
  • N-oxoalkyl (meth) acrylamides are also suitable. Particularly preferred are acetoacetyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate and especially diacetone acrylamide.
  • Compounds which can undergo a crosslinking reaction with the keto or aldehyde groups are, for example, compounds with hydrazide, hydroxylamine, oxime ether or amino groups.
  • Suitable compounds having hydrazide groups are, for example, polycarboxylic acid hydrazides having a molecular weight of up to 500 g / mol.
  • Preferred hydrazide compounds are dicarboxylic acid dihydrazides having preferably 2 to 10 C atoms.
  • oxalic acid dihydrazide malonic acid dihydrazide, succinic dihydrazide, glutaric acid dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and / or isophthalic dihydrazide.
  • adipic dihydrazide sebacic dihydrazide and isophthalic dihydrazide.
  • Suitable as compounds with amino groups for example, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimines, partially hydrolyzed polyvinylformamides, ethylene oxide and propylene oxide adducts such as the "Jeffamine", cyclohexanediamine and xylylenediamine.
  • the compound with the functional groups can be added to the composition or the dispersion of the polymer at any time. In the aqueous dispersion, no crosslinking with the keto or aldehyde groups occurs. Only on drying does crosslinking occur on the coated substrate.
  • the amount of the compound having the functional groups is preferably such that the molar ratio of the functional groups to the keto and / or aldehyde groups of the polymer is from 1:10 to 10: 1, in particular from 1: 5 to 5: 1, particularly preferably 1: 2 to 2: 1 and most preferably 1: 1, 3 to 1, 3: 1.
  • equimolar amounts of the functional groups and the keto and / or aldehyde groups are preferred.
  • the monomers of the polymerization are selected so that the calculated glass transition temperature is in the range of -40 ° C to +15 ° C, especially from -35 ° C to +10 ° C.
  • the actual, measured glass transition temperature of the polymer of the polymer dispersion of the invention is preferably in the range of -40 ° C to +15 ° C, in particular from -35 ° C to +10 ° C.
  • x 1 , x 2 , .... x n are the mass fractions of the monomers 1, 2, .... n and T g 1 , T g 2 , .... T g n the glass transition temperatures of each of only one of Monomers 1, 2, .... n constructed polymers in degrees Kelvin.
  • the T g values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, page 169, VCH Weinheim, 1992; further sources of glass transition temperatures of homopolymers form, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 st ed., J. Wiley, New York 1966, 2 nd Ed. J.
  • At least one molecular weight regulator is used in the polymerization. This can be reduced by a chain termination reaction, the molecular weight of the emulsion polymer.
  • the regulators are bound to the polymer, generally to the chain end.
  • the amount of regulator is in particular 0.05 to 4 parts by weight, particularly preferably 0.05 to 0.8 parts by weight and very particularly preferably 0, 1 to 0.6 parts by weight, based on 100 wt. Parts of the monomers to be polymerized.
  • Suitable regulators are, for example, compounds having a thiol group, such as tert-butyl mercaptan, thioglycol acid ethylacrylic ester, mercaptoethanol, mercaptopropyltrimethoxysilane or part. -Dodecylmer- captan.
  • the regulators are generally low molecular weight compounds having a molecular weight of less than 2000, in particular less than 1000 g / mol. Preference is given to 2-ethylhexyl thioglycolate (EHTG), isooctyl-3-mercaptopropionate (IOMPA) and tert-dodecylmercaptan (tDMK).
  • EHTG 2-ethylhexyl thioglycolate
  • IOMPA isooctyl-3-mercaptopropionate
  • tDMK tert-dodecylmercaptan
  • seed latex is an aqueous dispersion of finely divided polymer particles having an average particle diameter of preferably 20 to 40 nm. Seed latex is used in an amount of preferably 0.01 to 0.5 parts by weight, particularly preferably 0.03 to 0.3 wt ., Or from 0.03 to less than or equal to 0.1 parts by weight based on 100 parts by weight of monomers. It is suitable, e.g. a latex based on polystyrene or based on polymethylmethacrylate. A preferred seed latex is polystyrene seed.
  • the preparation of the polymer dispersion according to the invention is carried out by emulsion polymerization.
  • ethylenically unsaturated compounds are polymerized in water, ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers usually being used as surface-active compounds for stabilizing the monomer droplets and the polymer particles later formed from the monomers , According to the invention, however, the polymerization takes place emulsifier poor and without addition or formation of protective colloids.
  • the stabilization of the resulting polymer dispersion is carried out by the special driving style. This is due to a slow initial monomer feed in the presence of very little amount of polymer seed (seed control) followed by neutralization of the acid monomers used in the course of the polymerization.
  • the neutralization of acid groups of the polymer is carried out by feeding a neutralizing agent during the polymerization, wherein the acid groups are completely or partially neutralized by the addition of a base, wherein the feed of the base during the emulsion polymerization begins after at least 5 wt.%, Preferably 10-70 % By weight of the total monomer mixture in the reaction vessel under polymerization conditions.
  • the neutralizing agent may e.g. be added in a separate feed parallel to the inlet of the monomer mixture. After all monomers have been fed in, the amount of neutralizing agent required to neutralize at least 10%, preferably 10 to 100% or 25 to 90% acid equivalents, is preferably contained in the polymerization vessel.
  • the addition of the monomer mixture takes place after the start of the polymerization reaction by feeding the monomer mixture with a first and at least one second feed rate, wherein the first feed rate may be slower than the second feed rate.
  • the first feed rate is slower than the second feed rate.
  • the (average) feed rate changes increases the factor 2 to 10 after 3 to 30 wt.%, Preferably 5 to 20 wt.% Of the total monomer mixture was added.
  • the increase in the feed rate can be carried out in one or more stages or continuously.
  • the emulsion polymerization can be started with water-soluble initiators.
  • Water-soluble initiators 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.
  • redox 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, for example, the above-mentioned initiators for emulsion polymerization.
  • the reduction components are, for example, alkali metal salts of sulfurous acid, such as, for example, 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-hydroxymethanesulfinic 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 initiators mentioned are usually used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question in water.
  • concentration of initiators 0.1 to 30 wt .-%, preferably 0.5 to 20% by weight, particularly preferably 1, 0 to 10 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • the emulsion polymerization is generally carried out at 30 to 130 ° C, preferably at 50 to 90 ° C.
  • the polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • a polymer seed is introduced for better adjustment of the particle size.
  • 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 and, depending on its consumption, in the course of the free radical aqueous emulsion polymerization. be used gradually or in stages. 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, it is customary to add initiator even after the end of the actual emulsion polymerization, ie after a conversion of the monomers of at least 95%.
  • 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 from 15 to 75% by weight, preferably from 40 to 60% by weight, particularly preferably greater than or equal to 50% by weight.
  • the polymer thus prepared is preferably used in the form of its aqueous dispersion.
  • the size distribution of the dispersion particles is monomodal.
  • the average particle diameter of the polymer particles dispersed in the aqueous dispersion is greater than 200 nm, preferably greater than 250 nm, for example from 200 nm to 400 nm or from 250 nm to 350 nm.
  • the measurement of mean particle diameters x PC s and particle size distribution is carried out by Photon correlation spectroscopy (ISO standard 13321: 1996).
  • a monomodal size distribution of the dispersion particles is present when there is only a single maximum in the measurement of the particle size distribution.
  • the pH of the polymer dispersion is preferably adjusted to pH greater than 5, in particular to a pH of between 5.5 and 8.
  • the polymer dispersions of the invention can be used in aqueous adhesive formulations, e.g. for the production of laminates, i. in aqueous Kaschierklebstoffzurungen for bonding large-area substrates, in particular for the production of composite films.
  • the present invention thus also relates to a process for producing composite films in which an aqueous adhesive preparation is used which comprises at least one inventive polymer dispersion or a two-component adhesive according to the invention.
  • the aqueous polymer dispersions can be used as such or after packaging with conventional excipients.
  • auxiliaries are, for example, crosslinkers, wetting agents, thickeners, light stabilizers, biocides, defoamers, etc.
  • the adhesive formulations according to the invention do not necessarily require the addition of defoamers, since their particular advantage consists in particularly low foaming when applied to substrates.
  • the polymer dispersion according to the invention or a correspondingly prepared preparation is preferably applied to the large-area substrates to be bonded with a layer thickness of 0.1 to 20 g / m 2 , more preferably 1 to 7 g / m 2 z. B. by doctoring, brushing, etc. applied.
  • Conventional coating methods can be used, such as roll coating, reverse roll coating, gravure roll coating, countergraduate roll coating, brush coating, bar brushing, spray coating, airbrush coating, meniscus coating, curtain coating or dip coating.
  • the coated substrate can then be laminated with a second substrate, wherein the temperature, for example 20 to 200 ° C, preferably 20 to 100 ° C and the pressure z. B. 100 to 3000 kN / m 2 , preferably 300 to 2000 kN / m 2 may be.
  • the polymer dispersion of the invention can be used as a one-component agent, i. without additional crosslinking agents, especially without Isocyanatvernetzer.
  • the polymer dispersion of the present invention may also be used as a two-part adhesive in which a crosslinking component, such as e.g. a water-emulsifiable isocyanate is added.
  • a crosslinking component such as e.g. a water-emulsifiable isocyanate is added.
  • At least one of the films may be printed or metallized on the adhesive coated side. Suitable substrates are z.
  • polymer films in particular polyethylene (PE), oriented polypropylene (OPP), unstretched polypropylene (CPP), polyamide (PA), polyethylene terephthalate (PET), polyacetate, cellophane, with metal, z.
  • coated (steamed) polymer films in short: metallized films
  • metal foils for. B. aluminum.
  • the films mentioned can each other or with a film of another type, for.
  • polymer films with metal foils various polymer films are bonded together, etc.
  • the films mentioned can also be printed with printing inks, for example.
  • One embodiment of the invention is a composite film produced using one of the aqueous polymer dispersions according to the invention described above, wherein the material of a first film is selected from OPP, CPP, PE, PET and PA and wherein the material of a second film is selected from OPP, CPP , PE, PET, PA and metal foil.
  • the thickness of the substrate films may, for example, be from 5 to 100 ⁇ m, preferably from 5 to 40 ⁇ m.
  • a surface treatment of the film substrates is not absolutely necessary before coating with a polymer dispersion according to the invention. However, better results can be obtained by modifying the surface of the film substrates prior to coating.
  • conventional surface treatments can be used, for example corona treatment to enhance the adhesion.
  • the corona treatment or other surface treatments are performed to the extent necessary for sufficient wettability with the coating composition. Usually, a corona treatment of about 10 watts per square meter per minute is sufficient for this purpose.
  • primers or intermediate layers between the film substrate and the adhesive coating it is optionally also possible to use primers or intermediate layers between the film substrate and the adhesive coating.
  • the composite films further, have additional functional layers, eg Barnere füren, printing layers, dye or lacquer layers or protective layers.
  • the functional layers may be located outside, ie on the side of the film substrate facing away from the adhesive-coated side, or inside, between the film substrate and the adhesive layer.
  • Basonat® Basonat® HW 100 water-dispersible polyisocyanate based on isocyanurated hexamethylene diisocyanate
  • the polymer dispersion is diluted to 0.01% solids content and the light transmission is measured in comparison to pure water.
  • Tg Glass transition temperature, calculated according to the Fox equation from the glass transition temperature, the homopolymers of the monomers present in the copolymer and their weight fraction:
  • TgA glass transition temperature of the homopolymer of monomer A
  • TgB, TgC Tg corresponding to monomers B, C, etc.
  • Tg from DSC glass transition temperature measured by DSC measurement
  • TG from HDC average particle diameter measured by photon correlation spectroscopy (ISO 13321: 1996)
  • a mixture of 136.38 g of water and 1.82 g of a 33% Polystyrolfeinsaat (in water) is heated to 85 ° C and stirred for 5 min. Thereafter, 8.57 g of a 7% sodium peroxodisulfate solution are added and stirred again for 5 minutes. Subsequently, the dosage of 91, 15 g of the monomer mixture in 1 h and then 820.4 g of the monomer mixture are metered in 2 h. In parallel, the dosage of 34.29 g of sodium peroxodisulfate (7% solution in water) in 3h. As soon as the second part of the monomers is metered, the dosage of 19.15 g of a 3.1% ammonia solution in 2 hours takes place in parallel.
  • Example 1 b-d the monomer composition is varied while the polymerization process remains the same.
  • Example 1 d an addition of 32.48 g of a 4.62% adipic dihydrazide solution is additionally carried out at the end.
  • Example Dispersion 1 e
  • examples 2a and 2b is added in two stages and the monomer composition as well as the driving style compared to the examples 1 a-1 e varies. Furthermore, in Examples 2a and 2b little or no emulsifier is used.
  • the regulations are based on dispersions according to WO201 1/154920.
  • a mixture of 136.38 g of water and 5.45 g of a 33% Polystyrolfeinsaat (in water) is heated to 80 ° C and stirred for 5 min. Then 42.86 g of a 7% sodium peroxodisulfate solution are added and stirred again for 5 minutes. Subsequently, the dosage of 20 g of the monomer mixture 2a1 takes place in 10 minutes and then 265.27 g of the monomer mixture 2a1 in 50 min. The temperature is raised to 85 ° C.
  • a mixture of 462 g of water and 5.45 g of a 33% Polystyrolfeinsaat (in water) is heated to 80 ° C and stirred for 5 min. Then 42.86 g of a 7% strength sodium peroxodisulphate solution are added and stirred again for 5 minutes. Subsequently, the dosage of 20 g of the monomer mixture 2b1 in 10 min and then 109.48 g of the monomer mixture 2b1 in 30 min. Thereafter, the dosage of 40 g of the monomer mixture 2b2 in 15 min and then done 441, 26 g of the monomer mixture 2b2 in 2h 45min. The temperature is increased to 95 ° C in 3h.
  • a mixture of 136.38 g of water and 0.91 g of a 33% Polystyrolfeinsaat (in water) is heated to 85 ° C and stirred for 5 min. Thereafter, 4.29 g of a 7% sodium peroxodisulfate solution are added and stirred again for 5 min. Subsequently, the dosage of 20 g of the monomer mixture in 10 min and then 963.27 g of the monomer mixture in 2h 50min. In parallel, the dosage of 38.57 g of sodium peroxodisulfate (7% solution in water) takes place in 3 hours.
  • Table 1 Wet Sample Values of Adhesive Dispersions.
  • 3b 1 IS, 9.5 MA, 12 S, 77.5 0.6% Dowfax®-25.1 46.7 43 -27 312.1 nBA 2A1, 0.24% Lu- miten® I-SC
  • Polyethylene film 50 ⁇ thick, corona pretreated, surface tension> 38 mN / m;
  • the base film is fixed on the laboratory coating table with the pretreated side up and the adhesive to be tested is coated directly onto the film by means of a doctor blade.
  • the adhesive is dried for 2 minutes with a hot air blower and then the laminating film with a hand roller and pressed in the roll laminating at 70 ° C, with a roller speed of 5 m / minute and a laminating pressure of 6.5 bar.
  • the laminate is cut by means of a cutting template in 15-millimeter-wide strips and subjected to various storage cycles.
  • the laminate strip is pulled apart on the tensile testing machine and the required force is recorded.
  • the test is carried out on a tensile testing machine at an angle of 90 degrees with a take-off speed of 300 mm / min.
  • the test strip is separated on one side, one of the now loose ends in the upper clamp, the other clamped in the lower jaw of the tensile tester and started the test.
  • the mean value of the force is given from 3 single measurements in N
  • the samples can be tested according to different storage conditions:
  • the base film is fixed on the laboratory coating table with the pretreated side up and the adhesive to be tested is coated directly onto the film by means of a doctor blade.
  • the adhesive is dried for 2 minutes with a hot-air blower and then the laminating film is placed in a hand roll and pressed in the roll laminating station at 70 ° C., with a roll speed of 5 m / minute and a laminating pressure of 6.5 bar. Thereafter, the laminate is cut by means of the cutting template in 15 mm wide strips and min. Stored 24 hours at 23 ° C / 50% relative humidity. After storage, the laminate strip on the tensile testing machine with climate chamber is pulled apart at a temperature of 90 ° C and the required force is held.
  • the test is carried out on a tensile testing machine with climatic chamber with a take-off speed of 300 mm / min.
  • the test strip is separated on one side, one of the now loose ends in the upper clamp, the other clamped in the lower jaw of the tensile tester and started the test.
  • the measurement starts after 1 minute waiting time to condition the test strip.
  • the mean value of the force is given from 3 single measurements in N / 15 millimeters.
  • A100 adhesive layer remains completely on the base film (adhesion break)
  • A0 adhesive layer separates from the base film and passes over to the laminating film (rewinding)
  • A0 / R adhesive layer is transferred to the laminating film, but punctate residues on the base film.
  • K separation in the adhesive layer without detachment from a material (cohesive failure)
  • K * separation in the adhesive layer without detachment from a material (cohesive failure), the adhesive has no residual tackiness
  • Adhesive layer remains completely on the base film, but punctate residues on the laminating film
  • Table 3 Adhesive values of selected adhesive dispersions, with and without crosslinking with varying substrate surfaces.
  • the dispersion to be tested is filled to the mark (about 6.5 cm corresponds to 50 ml of dispersion) in a glass tube at the lower end of which is a glass frit.
  • This tube is located on a glass bulb with air supply.
  • the air is passed through the glass flask by means of a flow meter (1 bar, 1 l / h) and through the glass frit from below into the

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des dispersions polymères aqueuses et un procédé pour leur préparation. Les dispersions polymères contiennent des particules polymères présentant un diamètre moyen de particule supérieur à 200 nm, une répartition monomodale des grosseurs de particule et une température de transition vitreuse uniforme et sont préparées par polymérisation radicalaire en émulsion d'un mélange de monomères contenant des monomères éthyléniquement insaturés, polymérisables par voie radicalaire, tout en utilisant un germe de polymère, moins de 0,8 % en poids d'émulsifiants et sans utiliser de colloïde de protection. Le mélange de monomères est constitué par a) au moins 60 % en poids d'au moins un monomère choisi dans le groupe constitué par les acrylates de C1-C20-alkyle, les méthacrylates de C1-C20-alkyle, les esters vinyliques d'acides carboxyliques contenant jusqu'à 20 atomes de carbone, des aromatiques de vinyle comprenant jusqu'à 20 atomes de carbone, les nitriles éthyléniquement insaturés, les halogénures de vinyle, les vinyléthers d'alcools contenant 1 à 10 atomes de carbone, les hydrocarbures aliphatiques comprenant 2 à 8 atomes de carbone et une ou deux doubles liaisons et les mélanges de ces monomères ; b) au moins 0,1 % en poids d'au moins un monomère présentant au moins un groupe acide ; et c) éventuellement d'autres monomères, les groupes acides des monomères b) étant partiellement ou totalement neutralisés pendant la polymérisation en émulsion. Les dispersions polymères aqueuses peuvent être utilisées comme adhésif, en particulier pour la fabrication de feuilles composites.
EP16809753.3A 2015-12-17 2016-12-07 Dispersions polymères aqueuses pauvres en émulsifiant pour la préparation de feuilles composites Withdrawn EP3390473A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15200689 2015-12-17
PCT/EP2016/080061 WO2017102497A1 (fr) 2015-12-17 2016-12-07 Dispersions polymères aqueuses pauvres en émulsifiant pour la préparation de feuilles composites

Publications (1)

Publication Number Publication Date
EP3390473A1 true EP3390473A1 (fr) 2018-10-24

Family

ID=55173731

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16809753.3A Withdrawn EP3390473A1 (fr) 2015-12-17 2016-12-07 Dispersions polymères aqueuses pauvres en émulsifiant pour la préparation de feuilles composites

Country Status (6)

Country Link
US (1) US20190002743A1 (fr)
EP (1) EP3390473A1 (fr)
JP (1) JP2019506467A (fr)
CN (1) CN108431058A (fr)
BR (1) BR112018012149A2 (fr)
WO (1) WO2017102497A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019162206A2 (fr) 2018-02-21 2019-08-29 Basf Se Procédé de production d'articles revêtus d'adhésif
CN112004878A (zh) * 2018-04-20 2020-11-27 巴斯夫欧洲公司 具有基于通过酮基或醛基的交联的凝胶含量的粘合剂组合物
EP3908461B1 (fr) * 2019-01-11 2024-08-14 Basf Se Procédé de revêtement par une feuille au moyen d'un système de cylindre de gravure
WO2021023568A1 (fr) * 2019-08-05 2021-02-11 Basf Se Procédé d'amélioration de la stabilité au cisaillement de compositions polymères adhésives aqueuses hautement concentrées
JP2023507478A (ja) * 2019-12-20 2023-02-22 ベーアーエスエフ・エスエー シード樹脂で安定化された高固形分エマルジョンポリマー

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4316830A (en) 1980-02-19 1982-02-23 Union Carbide Corporation Surfactant free process for production of pressure sensitive adhesive latexes
US4997877A (en) * 1986-07-11 1991-03-05 Hercules Incorporated Polyacrylate dispersions prepared with a water-soluble conjugated unsaturated monomer in the absence of a protective colloid
AU8024794A (en) * 1993-12-09 1995-06-15 Nalco Chemical Company An improved process for the preparation of water soluble polymer dispersion
DE19649383A1 (de) 1996-11-29 1998-06-04 Basf Ag Kaschierklebstoffe
DE19908183A1 (de) 1999-02-25 2000-08-31 Basf Ag Wässrige Polymerdispersionen
ES2602049T3 (es) 2010-06-11 2017-02-17 Basf Se Preparación multi-etapa de dispersiones acuosas de polímeros para producir películas compuestas
US9062233B2 (en) * 2010-06-11 2015-06-23 Basf Se Multistage preparation of aqueous polymer dispersions for producing composite films
WO2012028202A1 (fr) * 2010-09-03 2012-03-08 Henkel Ag & Co. Kgaa Film multicouche scellable pour matériaux d'emballage
WO2014053410A1 (fr) * 2012-10-05 2014-04-10 Basf Se Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères

Also Published As

Publication number Publication date
WO2017102497A1 (fr) 2017-06-22
BR112018012149A2 (pt) 2018-11-27
US20190002743A1 (en) 2019-01-03
JP2019506467A (ja) 2019-03-07
CN108431058A (zh) 2018-08-21

Similar Documents

Publication Publication Date Title
EP3390473A1 (fr) Dispersions polymères aqueuses pauvres en émulsifiant pour la préparation de feuilles composites
EP3405540B1 (fr) Utilisation d'un adhésif de stratification monocomposant pour le contrecollage de films composites
EP2619239B1 (fr) Adhésifs sensibles à la pression basés sur des dispersions aqueuses obtenues par procédé en plusieurs étapes
EP2496655B1 (fr) Adhésif polymérique fabriqué de n-butylacrylate, ethylacrylate, vinylacetate et de monomère d'acide
EP2580254B1 (fr) Préparation en plusieurs étapes de dispersions aqueuses de polymères pour la production de films composites
EP2697324B1 (fr) Dispersion d'adhésif de contact contenant des polymères comportant des groupes uréido ou des groupes analogues uréido et comportant des groupes glycidyle
CH708031B1 (de) Chloroprenkautschukbasierte Polymerlatexzusammensetzung.
EP2978818A1 (fr) Utilisation d'une dispersion polymère pour sceller à froid
EP3286235B1 (fr) Dispersions aqueuses de polymères pour le contrecollage de films composites
EP3202795B1 (fr) Utilisation d'une dispersion d'adhésif pour le laminage brillant de films
EP3271409B1 (fr) Dispersions aqueuses de polymères contenant de l'oxazoline pour le contrecollage de films composites
EP2904018A1 (fr) Fabrication de dispersions polymères aqueuses présentant des colloïdes protecteurs, au cours d'un procédé d'apport en masse de monomères
EP3781622B1 (fr) Compositions adhésives à gelcontent de réticulation de groupes céto ou aldéhyde
EP2719532B1 (fr) Utilisation d'une dispersion d'adhésif pour le laminage de films
EP1979430B1 (fr) Matiere auto-adhesive
WO2007141198A1 (fr) Adhésif pour revêtements pour le sol
EP2038358B1 (fr) Film adhésif avec au moins deux phases continues
DE102005012813B4 (de) Verwendung einer Zusammensetzung enthaltend ein vernetzbares Polymer als Kaschierklebstoff
EP3755753B1 (fr) Procédé de production d'articles enduits d'adhésifs
WO2019201695A1 (fr) Composition d'additifs pour dispersions aqueuses de polymères hydrophobes
EP1420055B1 (fr) Adhesifs à contrecoller réticulables aux UV
WO2006136574A1 (fr) Procede de production de polymeres en emulsion pour des matieres adhesives
DE69402754T2 (de) Verbesserte Adhäsiv-Zusammensetzungen für Laminate
WO2006136575A1 (fr) Procede de production de polymeres en emulsion acides pour des matieres adhesives

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20180717

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20190807

STAA Information on the status of an ep patent application or granted ep patent

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

18D Application deemed to be withdrawn

Effective date: 20191218