EP0000558A1 - Multilayered products, the layers of which are bonded together by means of an adhesive layer - Google Patents

Multilayered products, the layers of which are bonded together by means of an adhesive layer Download PDF

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Publication number
EP0000558A1
EP0000558A1 EP78100462A EP78100462A EP0000558A1 EP 0000558 A1 EP0000558 A1 EP 0000558A1 EP 78100462 A EP78100462 A EP 78100462A EP 78100462 A EP78100462 A EP 78100462A EP 0000558 A1 EP0000558 A1 EP 0000558A1
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EP
European Patent Office
Prior art keywords
layer
ethylene
copolymer
alkyl acrylate
adhesion
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EP78100462A
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German (de)
French (fr)
Inventor
Ulrich Dr. Koenig
Wolfgang Dr. Druschke
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BASF SE
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BASF SE
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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
    • 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
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • 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
    • B32B2479/00—Furniture
    • 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
    • B32B2509/00—Household appliances
    • B32B2509/10—Refrigerators or refrigerating equipment

Definitions

  • the invention relates to the use of ethylene-alkyl acrylate copolymers as adhesion promoters for the production of laminates from thermoplastic materials.
  • DT-OS 2 329 035 describes a pressure-sensitive adhesive mixture based on an ethylene-methyl acrylate copolymer.
  • This pressure-sensitive adhesive mixture which contains a tackifying resin as a further essential component in addition to the ethylene copolymer, already has a high surface tack at room temperature and is therefore suitable for producing self-adhesive materials.
  • PSAs can be combined with various substances such as wood, metal, rubber, plastics, etc., using pressure alone. Using these pressure-sensitive adhesive mixtures, any composite systems can be easily and quickly manufactured. However, the adhesive strength of these composite systems is relatively low compared to the use of fixed adhesives.
  • US Pat. No. 3,926,878 discloses melt adhesive mixtures of an ethylene-acrylate copolymer and a hydrogenated one aromatic hydrocarbon resin described.
  • These hotmelt adhesives which develop their adhesive properties only in the molten state, can be used to produce coatings or composite systems with various substrates such as metal, paper, wood or plastics.
  • the copolymers in these hot-melt adhesive mixtures must have a relatively low molecular weight and / or be mixed with waxes or thermoplastic resins to improve the adhesive properties.
  • the production of thermoplastic laminates using the hot melt adhesive based on ethylene-acrylate copolymers at processing temperatures. made under the processing temperatures of the thermoplastics to be joined. This limits the choice of processing methods when using the hot-melt adhesive, so that, for example, when using the hot-melt adhesive, no co-extrusion processes can be used to produce the composite systems.
  • Coextrusion processes for the production of thermoplastic laminates can only be carried out with substances as adhesion-promoting components whose processing temperature is of the same order of magnitude as the processing temperatures of the plastics to be joined and which have a rheological behavior similar to this.
  • adhesion promoters Such substances are generally referred to as adhesion promoters.
  • the present invention thus relates to laminates composed of at least two different layers A and C made of thermoplastic materials which are bonded to one another by an adhesion promoter layer B, characterized in that the adhesion promoter layer B consists essentially of an ethylene-alkyl acrylate copolymer which consists of 15 to Contains 80% by weight of an alkyl acrylate having 1 to 4 carbon atoms polymerized in the alkyl radical and which has a melt index at 190 ° C.
  • the layers A and C are composed of an olefin polymer, an optionally impact-modified styrene polymer or styrene copolymer, a chlorine-containing polymer, a polyamide, polycarbonate, polyvinyl alcohol and / or polyurethane.
  • the adhesion promoter layer B of the laminates according to the invention essentially consists of an ethylene-alkyl acrylate copolymer which is derived from alkyl acrylates having 1 to 4 carbon atoms in the alkyl radical.
  • Suitable alkyl acrylates for the preparation of these copolymers are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate and isobutyl acrylate.
  • the copolymers are prepared in a customary and known manner by copolymerizing ethylene and the alkyl acrylates at pressures above 500 atmospheres and temperatures between 150 and 400 ° C. in the presence of free-radical polymerization initiators.
  • the ethylene-alkyl acrylate copolymers to be used as adhesion promoters according to the invention should contain 15 to 80% by weight, preferably 30 to 70% by weight, of the alkyl acrylates in copolymerized form.
  • Suitable copolymers generally have a melt index of 1 to 40 g / 10 min at 190 ° C. and 2.16 kp (DIN 53 735).
  • Their softening point should be adapted to the softening point of the thermoplastic to be joined and is generally in the range from 125 to 140 ° C (DIN 1995, ring and ball).
  • the most favorable range for the alkyl acrylate content of the copolymers and for their melt index can vary and depends on the one hand on the alkyl acrylate used and on the other hand on the thermoplastic materials to be bonded.
  • the ethylene-alkyl acrylate copolymers which contain a straight-chain alkyl group in the acrylate building block that the optimum content of alkyl acrylate in the copolymer increases with the number of carbon atoms in the alkyl radical.
  • the ethylene-alkyl acrylate copolymer contains as high a proportion of ethylene as possible in copolymerized form in the adhesion promoter layer B.
  • the most favorable ranges for the composition of the copolymer and its melt index can be determined for a given application by a few simple tests.
  • the ethylene-methyl acrylate copolymers have proven to be particularly favorable for the use according to the invention, particularly those with a methyl acrylate content in the range from 30 to 50% by weight and a melt index in the range from 5 to 40 g / 10 min.
  • the layers A and C of the new laminates are different from one another, that is to say they are composed of different thermoplastic materials of the type mentioned. Mixtures of the thermoplastic materials mentioned can also be used for the production of layers A and C, provided that these plastics are compatible with one another and give homogeneous mixtures.
  • Composites are preferred in which layer A consists of a styrene polymer, in particular polystyrene, with impact-modified polystyrene, ABS, ASA or AES polymers with a diene rubber.
  • Layer C then advantageously consists of another styrene polymer, a chlorine-containing polymer, in particular a vinyl chloride polymer, or an olefin polymer, such as polyethylene or polypropylene.
  • layer A consists of an olefin polymer, in particular polyethylene
  • layer C consists of a chlorine-containing polymer, in particular polyvinyl chloride.'
  • an ethylene / alkyl acrylate copolymer as an adhesion promoter it can be expedient to influence its thermoplastic flow behavior in a targeted and sustainable manner by mixing with additives.
  • lubricants such as Butyl stearate or paraffin oil in the order of about 1 to 10% by weight to increase the melt index.
  • the melt index decreases when e.g. inorganic fillers, e.g. Talc or limestone powder, or if you add less flowing, partially partially cross-linked elastomers, e.g. based on polybutadiene, polyacrylates or styrene-butadiene-styrene block polymers.
  • additives are useful up to concentrations of approximately 40 to 45% by weight, based on the adhesion promoter layer.
  • the ethylene-alkyl acrylate copolymer serving as an adhesion promoter contains small amounts of a polyhydric alcohol, for example neopentyl glycol, to reduce the flow behavior.
  • the amount of alcohol added is generally in the range from 0.1 to 1.5% by weight, based on the ethylene-alkyl acrylate copolymer.
  • the adhesion promoter layer B can also be composed of up to 30% by weight of other plastics which are compatible with this copolymer.
  • thermoplastic materials used for the production of layers A and C can also contain such additives as dyes, pigments, stabilizers, UV absorbers, antistatic agents, flame retardants, etc., generally in amounts of up to 30% by weight, based on layer A and layer C, respectively.
  • the waste produced in the course of production and processing is preferably added to layer B, but should generally not make up more than about 15% by weight of layer B.
  • ethylene-alkyl acrylate copolymers By means of the high molecular weight ethylene-alkyl acrylate copolymers to be used for the purpose of the invention, composites with very good adhesive strengths can be produced between the thermoplastic materials mentioned.
  • ethylene-methyl acrylate copolymers as adhesion promoters and styrene polymers, chlorine-containing polymers and / or polyolefins for layers A and C, practically inseparable composites can be obtained. This was surprising since, as described and generally known in US Pat. No. 3,926,878, the adhesive properties of adhesion promoters with higher molecular weights are generally inadequate and the higher the molecular weight, the worse the higher the molecular weight.
  • the laminates according to the invention can be produced in various ways in a manner which is customary and known per se, for example by briefly heating and pressing the individual layers.
  • the laminates are preferably produced at melt temperatures between 15C and 250 ° C by the known coextrusion processes either in multi-layer dies - i.e. in blocks in which several slot dies are arranged one above the other; the highly plastic laminate usually leaves the block through a common die gap - or in adapter coextrusion systems - i.e. Plants in which several plastic melts are layered in a laminar flow on top of one another in the feed channel to a slot die and spread together in the slot die - or in ring die coextrusion systems which e.g. can consist of concentrically arranged ring nozzles.
  • the strips or hoses obtained are then expediently pressed together in the plastic state, for example with the aid of a pair of rollers or by the action of compressed air.
  • the thickness of the individual layers can be varied by varying the number of extruders.
  • the layer thickness essentially depends on the field of application. In the case of films, layer thicknesses of 0.1 to 20 mm are generally suitable.
  • the laminates produced according to the invention can be used in various fields and can be used in the form of foils, for example as cladding, covers, wall elements, decorative panels, etc. In particular, they can be used under usual temperature and pressure conditions L Process and form into various types of molded parts by deep drawing. Such molded parts can be designed as trough-shaped or shell-shaped bodies with different contours and dimensions. However, they can also be provided as a roll or sheet with a recurring profile, such as ribs, beads, grids, cups or other stiffening elements. Areas of application for molded parts are machine covers, housing parts, components, containers, drip trays, caps and more. The shaped laminates can be used, for example, in the packaging sector, in the refrigerator and furniture industry.
  • a granulated ethylene methacrylate polymer with about 40% methyl acrylate, the melt index of 25 g / 10 min at 190 ° C and 2.16 kp and a softening point of 137 ° C was at 200 ° C in a steam-heated plate press to a press plate with the dimensions 1 x 200 x 2,000 mm.
  • This plate was placed between a 1 mm thick plate made of impact-resistant polystyrene with a heat resistance according to Vicat / B of 90 ° C (DIN 53 460) and polyethylene with a density of 0.929 / cm 3 .
  • Vicat / B of 90 ° C
  • polyethylene with a density of 0.929 / cm 3
  • An ethylene-ethyl acrylate polymer with approx. 35% ethyl acrylate, a softening point of approx. 132 ° C (DIN 1995, J Ring and ball) and the melt index 12 g / 10 min, measured at 190 ° C and 2.16 kp (DIN 53 735) was with 40% of a styrene-butadiene-styrene block polymer containing 32% styrene copolymerized with the help of a counter-rotating, steam-heated pair of rollers mixed in the melt at 190 ° C.
  • the mixture had a melt index of 1.3 g / 10 min, at 190 ° C. and 2.16 kp, and was processed in a multilayer coextrusion plant to form a three-layer material made of impact-resistant polystyrene (layer A), adhesion promoter layer and polybutylene terephthalate (layer C).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The multilayered products essentially contain, as adhesion- promoting layer, an ethylene-alkyl acrylate copolymer which contains, in copolymerised form, from 15 to 80% by weight of an alkyl acrylate having 1 to 4 carbon atoms in the alkyl radical. The copolymer may optionally contain additives up to a concentration of 45% by weight, based on the adhesion-promotion layer. The copolymer has a melt flow index at 190 DEG C and 2.16 kp (DIN 53 735) of from 1 to 40 g/10 min. The softening point of the adhesion-promoting layer is in the range from 125 to 140 DEG C (DIN 1995, ring and ball), and is matched to the softening point of the thermoplastics to be bonded, such as olefins, styrene homopolymers or copolymers, or optionally impact-modified representatives, and other thermoplastics, such as PVC, polyamide, polycarbonate, polyvinyl alcohol and/or polyurethanes.

Description

Die Erfindung betrifft den Einsatz von Äthylen-Alkylacrylat-Copolymerisaten als Haftvermittler für die Herstellung von Schichtstoffen aus thermoplastischen Kunststoffen.The invention relates to the use of ethylene-alkyl acrylate copolymers as adhesion promoters for the production of laminates from thermoplastic materials.

Es ist bekannt, Äthylen-Alkylacrylat-Copolymerisate zur Herstellung von Verbundsystemen einzusetzen. So wird beispielsweise in der DT-OS 2 329 035 eine Haftkleber-Mischung auf Basis eines Äthylen-Methylacrylat-Copolymerisates beschrieben. Diese Haftklebermischung, die neben dem Äthylencopolymerisat als weitere wesentliche Komponente ein klebrigmachendes Harz enthält, besitzt bereits bei Raumtemperatur eine hohe Oberflächenklebrigkeit und eignet sich daher zur Herstellung selbstklebender Materialien. Derartige Haftklebemassen lassen sich allein unter Anwendung von Druck mit diversen Stoffen, wie Holz, Metall, Gummi, Kunststoffe etc., verbindungen. Mittels dieser Haftkleber-Mischungen lassen sich daher leicht und schnell beliebige Verbundsysteme herstellen. Die Haftfestigkeit dieser Verbundsysteme ist jedoch im Vergleich zum Einsatz von Festklebern relativ gering.It is known to use ethylene-alkyl acrylate copolymers for the production of composite systems. For example, DT-OS 2 329 035 describes a pressure-sensitive adhesive mixture based on an ethylene-methyl acrylate copolymer. This pressure-sensitive adhesive mixture, which contains a tackifying resin as a further essential component in addition to the ethylene copolymer, already has a high surface tack at room temperature and is therefore suitable for producing self-adhesive materials. Such PSAs can be combined with various substances such as wood, metal, rubber, plastics, etc., using pressure alone. Using these pressure-sensitive adhesive mixtures, any composite systems can be easily and quickly manufactured. However, the adhesive strength of these composite systems is relatively low compared to the use of fixed adhesives.

In der US-PS 3 926 878 werden Schmelskleber-Mischungen aus einem Äthylen-Acrylat-Copolymerisat und einem hydrierten aromatischen Kohlenwasserstoffharz beschrieben. Diese Schmelzkleber, die ihre Hafteigenschaften erst im aufgeschmolzenen Zustand entwickeln, können zur Herstellung von Überzügen oder Verbundsystemen mit verschiedenen Substraten, wie Metall, Papier, Holz oder Kunststoffen, eingesetzt werden. Damit eine gute Haftfestigkeit erzielt wird, müssen die Copolymerisate in diesen Schmelzkleber-Mischungen ein relativ niedriges Molekulargewicht besitzen und/oder zur Verbesserung der Hafteigenschaften mit Wachsen oder thermoplastischen Harzen abgemischt werden. Weiterhin wird die Herstellung von thermoplastischen Schichtstoffen unter Einsatz der Schmelzkleber auf Basis von Äthylen-Acrylat-Copolymerisaten bei Verarbeitungstempera-. turen vorgenommen, die unterhalb der Verarbeitungstemperaturen der zu verbindenden Thermoplaste liegt. Man ist dadurch bei der Verwendung der Schmelzkleber in der Wahl der Verarbeitungsverfahren eingeschränkt, so daß man beispielsweise bei Einsatz der Schmelzkleber keine Koextrusionsverfahren zur Herstellung der Verbundsysteme einsetzen kann.US Pat. No. 3,926,878 discloses melt adhesive mixtures of an ethylene-acrylate copolymer and a hydrogenated one aromatic hydrocarbon resin described. These hotmelt adhesives, which develop their adhesive properties only in the molten state, can be used to produce coatings or composite systems with various substrates such as metal, paper, wood or plastics. In order to achieve good adhesive strength, the copolymers in these hot-melt adhesive mixtures must have a relatively low molecular weight and / or be mixed with waxes or thermoplastic resins to improve the adhesive properties. Furthermore, the production of thermoplastic laminates using the hot melt adhesive based on ethylene-acrylate copolymers at processing temperatures. made under the processing temperatures of the thermoplastics to be joined. This limits the choice of processing methods when using the hot-melt adhesive, so that, for example, when using the hot-melt adhesive, no co-extrusion processes can be used to produce the composite systems.

Koextrusionsverfahren zur Herstellung von thermoplastischen Schichtstoffen lassen sich nur mit solchen Substanzen als haftvermittelnder Komponente durchführen, deren Verarbeitungstemperatur in der gleichen Größenordnung wie die Verarbeitungstemperaturen der zu verbindenden Kunststoffe liegt und die ein ähnliches rheologisches Verhalten wie diese aufweisen. Solche Substanzen werden im allgemeinen als Haftvermittler bezeichnet.Coextrusion processes for the production of thermoplastic laminates can only be carried out with substances as adhesion-promoting components whose processing temperature is of the same order of magnitude as the processing temperatures of the plastics to be joined and which have a rheological behavior similar to this. Such substances are generally referred to as adhesion promoters.

Es wurde nun gefunden, daß bestimmte Äthylen-Acrylat-Copolymerisate mit hohem Molekulargewicht auch ohne den Zusatz der sonst üblichen und notwendigen Modifizierungsmittel, wie Wachse und/oder Harze, als Haftvermittler für die Herstellung von Schichtstoffen aus bestimmten thermoplastischen Kunststoffen eingesetzt werden können.It has now been found that certain ethylene-acrylate copolymers with a high molecular weight can also be used as adhesion promoters for the production of laminates from certain thermoplastics without the addition of the otherwise customary and necessary modifiers, such as waxes and / or resins.

Gegenstand der vorliegenden Erfindung sind somit Schichtstoffe aus mindestens zwei voneinander verschiedenen Schichten A und C aus thermoplastischen Kunststoffen, die durch eine Haftvermittlerschicht B miteinander verbunden sind, dadurch gekennzeichnet, daß die Haftvermittlerschicht B im wesentlichen aus einem Äthylen-Alkylacrylat-Copolymerisat besteht, welches 15 bis 80 Gew.% eines Alkylacrylats mit 1 bis 4 Kohlenstoffatomen im Alkylrest einpolymerisiert enthält.und welches einen Schmelzindex bei 190°C und 2,16 kp im Bereich von 1 bis 40 g/10 min (DIN 53 735)besitzt, und die Schichten A und C aus einem Olefinpolymerisat, einem gegebenenfalls schlagzäh modifizierten Styrolpolymerisat oder Styrolcopolymerisat, einem chlorhaltigen Polymeren, einem Polyamid, Polycarbonat, Polyvinylalkohol und/oder Polyurethan aufgebaut sind.The present invention thus relates to laminates composed of at least two different layers A and C made of thermoplastic materials which are bonded to one another by an adhesion promoter layer B, characterized in that the adhesion promoter layer B consists essentially of an ethylene-alkyl acrylate copolymer which consists of 15 to Contains 80% by weight of an alkyl acrylate having 1 to 4 carbon atoms polymerized in the alkyl radical and which has a melt index at 190 ° C. and 2.16 kp in the range from 1 to 40 g / 10 min (DIN 53 735), and the layers A and C are composed of an olefin polymer, an optionally impact-modified styrene polymer or styrene copolymer, a chlorine-containing polymer, a polyamide, polycarbonate, polyvinyl alcohol and / or polyurethane.

Die Haftvermittlerschicht B der erfindungsgemäßen Schichtstoffe besteht im wesentlichen aus einem Äthylen-Alkylacrylat-Copolymerisat, welches sich von Alkylacrylaten mit 1 bis 4 Kohlenstoffatomen im Alkylrest ableitet. Geeignete Alkylacrylate für die Herstellung dieser Copolymerisate sind Methylacrylat, Äthylacrylat, Propylacrylat, n-Butylacrylat und iso-Butylacrylat. Die Copolymerisate werden in üblicher und bekannter Weise durch Copolymerisieren von Äthylen und den-Alkylacrylaten bei Drücken oberhalb 500 Atmosphären und Temperaturen zwischen 150 und 400°C in Gegenwart radikalischer Polymerisationsinitiatoren hergestellt. Die erfindungsgemäß als Haftvermittler einzusetzenden Äthylen-Alkylacrylat-Copolymerisate sollen dabei 15 bis 80 Gew.%, vorzugsweise 30 bis 70 Gew.%, der Alkylacrylate einpolymerisiert enthalten. Geeignete Copolymerisate haben im allgemeinen einen Schmelzindex von 1 bis 40 g/10 min bei 190°C und 2,16 kp (DIN 53 735). Ihr Erweichungspunkt soll dem Erweichungspunkt der zu verbindenden thermoplastischen Kunststoffe angepaßt sein und liegt im allgemeinen im Bereich von 125 bis 140°C (DIN 1995, Ring und Kugel). Der günstigste Bereich für den Alkylacrylatgehalt der Copolymerisate und für ihren Schmelzindex kann variieren und richtet sich zum einen nach dem eingesetzten Alkylacrylat und zum anderen nach den zu verbindenden thermoplastischen Kunststoffen. Beispielsweise hat sich für die Äthylen-Alkylacrylat-Copolymerisate, die eine geradkettige Alkylgruppe im Acrylat-Baustein enthalten, gezeigt, daß der optimale Gehalt an Alkylacrylat im Copolymerisat mit der Zahl der Kohlenstoffatome'im Alkylrest steigt. Für Schichtstoffe, bei denen die Schicht A oder die Schicht C aus einem Polyolefin besteht, ist es vorteilhaft, wenn das Äthylen-Alkylacrylat-Copolymerisat in der Haftvermittlerschicht B einen möglichst hohen Anteil an Äthylen einpolymerisiert enthält. Die günstigsten Bereiche für die Zusammensetzung des Copolymerisats und seinen Schmelzindex lassen sich für eine gegebene Anwendung durch wenige einfache Versuche ermitteln. Als besonders günstig für den erfindungsgemäßen Einsatz als Haftvermittler haben sich die Äthylen-Methylacrylat-Copolymerisate erwiesen, insbesondere solche mit einem Methylacrylat-Gehalt im Bereich von 30 bis 50 Gew.% und einem Schmelzindex im Bereich von 5 bis 40 g/10 min.The adhesion promoter layer B of the laminates according to the invention essentially consists of an ethylene-alkyl acrylate copolymer which is derived from alkyl acrylates having 1 to 4 carbon atoms in the alkyl radical. Suitable alkyl acrylates for the preparation of these copolymers are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate and isobutyl acrylate. The copolymers are prepared in a customary and known manner by copolymerizing ethylene and the alkyl acrylates at pressures above 500 atmospheres and temperatures between 150 and 400 ° C. in the presence of free-radical polymerization initiators. The ethylene-alkyl acrylate copolymers to be used as adhesion promoters according to the invention should contain 15 to 80% by weight, preferably 30 to 70% by weight, of the alkyl acrylates in copolymerized form. Suitable copolymers generally have a melt index of 1 to 40 g / 10 min at 190 ° C. and 2.16 kp (DIN 53 735). Their softening point should be adapted to the softening point of the thermoplastic to be joined and is generally in the range from 125 to 140 ° C (DIN 1995, ring and ball). The most favorable range for the alkyl acrylate content of the copolymers and for their melt index can vary and depends on the one hand on the alkyl acrylate used and on the other hand on the thermoplastic materials to be bonded. For example, it has been shown for the ethylene-alkyl acrylate copolymers which contain a straight-chain alkyl group in the acrylate building block that the optimum content of alkyl acrylate in the copolymer increases with the number of carbon atoms in the alkyl radical. For laminates in which layer A or layer C consists of a polyolefin, it is advantageous if the ethylene-alkyl acrylate copolymer contains as high a proportion of ethylene as possible in copolymerized form in the adhesion promoter layer B. The most favorable ranges for the composition of the copolymer and its melt index can be determined for a given application by a few simple tests. The ethylene-methyl acrylate copolymers have proven to be particularly favorable for the use according to the invention, particularly those with a methyl acrylate content in the range from 30 to 50% by weight and a melt index in the range from 5 to 40 g / 10 min.

Für den Aufbau der Schicht A und der Schicht C der neuen Schichtstoffe können folgende thermoplastische Kunststoffe eingesetzt werden:

  • Olefinpolymerisate, wie Polyäthylen, Polypropylen, Polybuten oder Copolymerisate der Olefine untereinander;
  • Styrolpolymerisate, die gegebenenfalls mit einen Kautschuk schlagfest modifiziert sein können, insbesondere Polystyrol, mit Polybutadien oder Styrol-Butadien-Blockpolymerisaten schlagfest modifiziertes Polystyrol, Copolymerisate des Styrols mit Acrylnitril, deren Gehalt an einpolymerisiertem rAcrylnitril im Bereich von 10 bis 80 Gew.% liegt, Copolyme-' risate des Styrols mit d-Methylstyrolj die sogenannten ABS-, ASA- und AES-Polymerisate, bei denen Styrol/Acrylnitril-Copolymerisate mit Dien-Kautschuken, kautschukartigen vorzugsweise vernetzten Acrylat-Polymerisaten bzw. mit kautschukartigen Äthylen-Propylen-Polymerisaten schlagfest modifiziert wurden;
  • chlorhaltige Polymere, wie Polyvinylchlorid, Polyvinylidenchlorid, Copolymerisate des Vinylchlorids oder des Vinylidenchlorids, chlorierte Polyolefine oder nachchloriertes Polyvinylchlorid;
  • Polyvinylalkohol oder Äthylen-Vinylalkohol-Polymerisate;
  • ferner auch Polyurethane, Polycarbonate oder Polyamide.
The following thermoplastic materials can be used to build up layer A and layer C of the new laminates:
  • Olefin polymers, such as polyethylene, polypropylene, polybutene or copolymers of the olefins with one another;
  • Styrene polymers, which can optionally be impact-modified with a rubber, in particular polystyrene, impact-modified polystyrene with polybutadiene or styrene-butadiene block polymers, copolymers of styrene with acrylonitrile, the content of which is copolymerized r acrylonitrile is in the range from 10 to 80% by weight, copolymers of styrene with d-methylstyrene, the so-called ABS, ASA and AES polymers, in which styrene / acrylonitrile copolymers with diene rubbers, preferably rubber-like crosslinkers Acrylate polymers or with rubber-like ethylene-propylene polymers were modified impact-resistant;
  • chlorine-containing polymers, such as polyvinyl chloride, polyvinylidene chloride, copolymers of vinyl chloride or vinylidene chloride, chlorinated polyolefins or post-chlorinated polyvinyl chloride;
  • Polyvinyl alcohol or ethylene-vinyl alcohol polymers;
  • also also polyurethanes, polycarbonates or polyamides.

Die Schichten A und C der neuen Schichtstoffe sind dabei voneinander verschieden, d.h. sind aus unterschiedlichen thermoplastischen Kunststoffen der genannten Art aufgebaut. Für die Herstellung der Schichten A und C können auch Mischungen der genannten thermoplastischen Kunststoffe verwendet werden, sofern diese Kunststoffe miteinander verträglich sind und homogene Mischungen geben. Bevorzugt sind Verbunde, bei denen die Schicht A aus einem Styrolpolymerisate, insbesondere Polystyrol, mit einem Dienkautschuk schlagfest modifizierten Polystyrol, ABS-, ASA- oder AES-Polymerisaten besteht. Die Schicht C besteht dann vorteilhafterweise aus einem anderen Styrolpolymerisat, einem chlorhaltigen Polymeren, insbesondere einemVinylchloridpolymerisat, oder einem Olefinpolymerisat, wie Polyäthylen oder Polypropylen. Bei anderen, ebenfalls interessanten Verbundsystemen, besteht die Schicht A aus einem Olefinpolymerisat, insbesondere Polyäthylen, und die Schicht C aus einem chlorhaltigen Polymerisat, insbesondere Polyvinyl- chlorid.'The layers A and C of the new laminates are different from one another, that is to say they are composed of different thermoplastic materials of the type mentioned. Mixtures of the thermoplastic materials mentioned can also be used for the production of layers A and C, provided that these plastics are compatible with one another and give homogeneous mixtures. Composites are preferred in which layer A consists of a styrene polymer, in particular polystyrene, with impact-modified polystyrene, ABS, ASA or AES polymers with a diene rubber. Layer C then advantageously consists of another styrene polymer, a chlorine-containing polymer, in particular a vinyl chloride polymer, or an olefin polymer, such as polyethylene or polypropylene. In other, also interesting composite systems, layer A consists of an olefin polymer, in particular polyethylene, and layer C consists of a chlorine-containing polymer, in particular polyvinyl chloride.'

Um mit einem Äthylen-Alkylacrylat-Copolymerisat als Haftvermittler gemäß der vorliegenden Erfindung eine hohe Anwendungsbreite zu erreichen, kann es sinnvoll sein, dessen thermoplastisches Fließverhalten gezielt und nachhaltig durch Vermischen mit Zusätzen zu beeinflussen. So kann man durch Zugabe von Schmiermitteln, wie z.B. Butylstearat oder Paraffinöl in der Größenordnung von ca. 1 bis 10 Gew.% den Schmelzindex zu erhöhen. Der Schmelzindex nimmt ab, wenn man z.B. anorganische Füllstoffe, wie z.B. Talk oder Kalksteinmehl, zumischt oder wenn man schwerer fließende, gegebenenfalls teilweise vernetzte Elastomere zugibt, z.B. auf Basis von Polybutadien, Polyacrylaten oder von Styrol-Butadien-Styrol-Blockpolymerisaten. Solche Zusätze sind bis zu Konzentrationen von ca. 40 bis 45 Gew.%, bezogen auf die Haftvermittlerschicht, sinnvoll.In order to achieve a wide range of applications with an ethylene / alkyl acrylate copolymer as an adhesion promoter according to the present invention, it can be expedient to influence its thermoplastic flow behavior in a targeted and sustainable manner by mixing with additives. So you can by adding lubricants such as Butyl stearate or paraffin oil in the order of about 1 to 10% by weight to increase the melt index. The melt index decreases when e.g. inorganic fillers, e.g. Talc or limestone powder, or if you add less flowing, partially partially cross-linked elastomers, e.g. based on polybutadiene, polyacrylates or styrene-butadiene-styrene block polymers. Such additives are useful up to concentrations of approximately 40 to 45% by weight, based on the adhesion promoter layer.

Als besonders günstig, gegebenenfalls in Kombination mit den letzgenannten Elastomeren, hat es sich erwiesen, wenn das als Haftvermittler dienende Äthylen-Alkylacrylat-Copolymerisat geringe Mengen eines mehrwertigen Alkohols, beispielsweise Neopentylglykol, zur Verringerung des Fließverhaltens, zugemischt enthält. Die Menge an zugemischtem Alkohol liegt im allgemeinen im Bereich von 0,1 bis 1,5 Gew.%, bezogen auf das Äthylen-Alkylacrylat-Copolymerisat. Die Haftvermittlerschicht B kann neben dem Äthylen-Alkylacrylat-Copolymerisat als wesentlichem Bestandteil auch noch aus bis zu 30 Gew.% an anderen, mit diesem Copolymerisat verträglichen Kunststoffen aufgebaut sein. So wurde gefunden, daß durch den Zusatz von Styrol-Butadien-Blockpolymerisaten mit einem Styrolgehalt von 5 bis 45 Gew.% zu dem Äthylen-Alkylacrylat-Copolymerisat in der Schicht B die haftvermittelnden Eigenschaften verbessert werden können. Als besonders vorteilhaft haben sich dabei insbesondere J styrol-Butadien-Blockpolymerisate des Typs A-B, A-B-A und ' A-B-A-B (A = Polystyrol-Block, B = Dienpolymerisat-Block) erwiesen. Die thermoplastischen Kunststoffe, die für die Herstellung der Schichten A und C eingesetzt werden, können auch solche Zusatzstoffe wie Farbstoffe, Pigmente, Stabilisatoren, UV-Absorber, Antistatika, Flammschutzmittel etc., im allgemeinen in Mengen bis zu 30 Gew.%, bezogen auf die Schicht A bzw. die Schicht C, enthalten.It has proven to be particularly favorable, optionally in combination with the latter elastomers, if the ethylene-alkyl acrylate copolymer serving as an adhesion promoter contains small amounts of a polyhydric alcohol, for example neopentyl glycol, to reduce the flow behavior. The amount of alcohol added is generally in the range from 0.1 to 1.5% by weight, based on the ethylene-alkyl acrylate copolymer. In addition to the ethylene-alkyl acrylate copolymer as an essential constituent, the adhesion promoter layer B can also be composed of up to 30% by weight of other plastics which are compatible with this copolymer. It has been found that by adding styrene-butadiene block polymers with a styrene content of 5 to 45% by weight to the ethylene-alkyl acrylate copolymer in layer B, the adhesion-promoting properties can be improved. In particular, J Styrene-butadiene block polymers of the types AB, ABA and 'ABAB (A = polystyrene block, B = diene polymer block) have been proven. The thermoplastic materials used for the production of layers A and C can also contain such additives as dyes, pigments, stabilizers, UV absorbers, antistatic agents, flame retardants, etc., generally in amounts of up to 30% by weight, based on layer A and layer C, respectively.

Weiterhin ist es möglich, den beim Herstellen und Verarbeiten der neuen Schichtstoffe auftretenden Abfall dadurch wieder zu verwenden, daß man ihn einer oder mehreren Schichten der neuen Schichtstoffe wieder zusetzt. Vorzugsweise wird der bei der Herstellung und Verarbeitung anfallende Abfall der Schicht B zugesetzt, soll dabei jedoch im allgemeinen nicht mehr als ca. 15 Gew.% der Schicht B ausmachen.Furthermore, it is possible to reuse the waste occurring in the production and processing of the new laminates by adding it to one or more layers of the new laminates. The waste produced in the course of production and processing is preferably added to layer B, but should generally not make up more than about 15% by weight of layer B.

Mittels der zum Zwecke der Erfindung einzusetzenden hochmolekularen Äthylen-Alkylacrylat-Copolymerisate lassen sich zwischen den genannten thermoplastischen Kunststoffen Verbunde mit sehr guten Haftfestigkeiten herstellen. Bei Einsatz von Äthylen-Methylacrylat-Copolymerisaten als Haftvermittler und Styrolpolymerisaten, chlorhaltigen Polymeren und/oder Polyolefinen für die Schichten A und C lassen sich praktisch untrennbare Verbunde erhalten. Dies war überraschend, da, wie in der US-PS 3 926 878 beschrieben und allgemein bekannt ist, die Hafteigenschaften bei Haftvermittlern mit höheren Molekulargewichten im allgemeinen ungenügend sind und um so schlechter liegen je höher das Molekulargewicht ist. Gute Hafteigenschaften mit hochmolekularen Äthylencopolymerisaten ließen sich bislang nur durch Zumischen von Wachsen oder thermoplastischen Harzen erzielen. Beim Einsatz der beschriebenen Äthylen-Alkylacrylat-Copolymerisate als Haftvermittler für die genannten 'thermoplastischen Kunststoffe kann nun auf den Zusatz dieser haftverbessernden Zusätze verzichtet werden, und es werden dennoch sehr gute Haftfestigkeiten erzielt.By means of the high molecular weight ethylene-alkyl acrylate copolymers to be used for the purpose of the invention, composites with very good adhesive strengths can be produced between the thermoplastic materials mentioned. When using ethylene-methyl acrylate copolymers as adhesion promoters and styrene polymers, chlorine-containing polymers and / or polyolefins for layers A and C, practically inseparable composites can be obtained. This was surprising since, as described and generally known in US Pat. No. 3,926,878, the adhesive properties of adhesion promoters with higher molecular weights are generally inadequate and the higher the molecular weight, the worse the higher the molecular weight. Until now, good adhesive properties with high molecular weight ethylene copolymers could only be achieved by adding waxes or thermoplastic resins. When using the described ethylene-alkyl acrylate copolymers as adhesion promoters for the above 'Thermoplastic materials can now be dispensed with the addition of these adhesion-enhancing additives, and very good adhesive strengths are nevertheless achieved.

Die Herstellung der erfindungsgemäßen Schichtstoffe kann auf verschiedene Arten in an und für sich üblicher und bekannter Weise beispielsweise durch kurzzeitiges Erhitzen und Verpressen der Einzelschichten, erfolgen. Vorzugsweise werden die Schichtstoffe bei Massetemperaturen zwischen 15C und 250°C nach den bekannten Koextrusions-Verfahren hergestellt entweder in Mehrschichtdüsen - d.h. in Blöcken, in denen mehrere Breitschlitzdüsen übereinander angeordnet sind; der hochplastische Schichtstoff verläßt meist durch einen gemeinsamen Düsenspalt den Block - oder in Adapter-Koextrusionsanlagen - d.h. Anlagen, in denen im Zulaufkanal zu einer Breitschlitzdüse mehrere Kunststoffschmelzen laminar fließend übereinander geschichtet und in der Breitschlitzdüse gemeinsam breitgelegt werden - oder in Ringdüsen-Koextrusionsanlagen, die z.B. aus konzentrisch ineinander angeordneten Ringdüsen bestehen können.The laminates according to the invention can be produced in various ways in a manner which is customary and known per se, for example by briefly heating and pressing the individual layers. The laminates are preferably produced at melt temperatures between 15C and 250 ° C by the known coextrusion processes either in multi-layer dies - i.e. in blocks in which several slot dies are arranged one above the other; the highly plastic laminate usually leaves the block through a common die gap - or in adapter coextrusion systems - i.e. Plants in which several plastic melts are layered in a laminar flow on top of one another in the feed channel to a slot die and spread together in the slot die - or in ring die coextrusion systems which e.g. can consist of concentrically arranged ring nozzles.

Die erhaltenen Bänder bzw. Schläuche werden dann zweckmäßigerweise noch im plastischen Zustand, beispielsweise mit Hilfe eines Walzenpaares oder durch Einwirkung von Druckluft, zusammengepreßt. Durch Variation der Extruderzahl kann die Dicke der einzelnen Schichten variiert werden. Die Schichtdicke hängt im wesentlichen vom Anwendungsgebiet ab. Bei Folien kommen im allgemeinen Schichtdicken von 0,1 bis 20 mm in Frage.The strips or hoses obtained are then expediently pressed together in the plastic state, for example with the aid of a pair of rollers or by the action of compressed air. The thickness of the individual layers can be varied by varying the number of extruders. The layer thickness essentially depends on the field of application. In the case of films, layer thicknesses of 0.1 to 20 mm are generally suitable.

Die nach der Erfindung hergestellten Schichtstoffe sind auf verschiedenen Gebieten verwendbar und lassen sich in Form von Folien, beispielsweise als Verkleidungen, Abdeckungen, Wandelemente, Dekorplatten usw. anwenden. Insbesondere lassen sie sich unter üblichen Temperatur- und Druckbedingungen L durch Tiefziehen zu verschiedenartigen Formteilen verarbeiten und umformen. Solche Formteile können als mulden- oder schalenförmige Körper mit unterschiedlichen Konturen und Abmessungen ausgebildet sein. Sie können jedoch auch als Rollen- oder Bahnenware mit einem wiederkehrenden Profil, wie z.B. Rippen, Sicken, Rastern, Napfen oder anderen Versteifungselementen versehen sein. Anwendungsgebiete für Formteile sind Maschinenabdeckungen, Gehäuseteile, Bauelemente, Behälter, Auffangschalen, Verschlußkappen und anderes mehr. Die geformten Schichtstoffe können beispielsweise auf dem Verpackungssektor, in der Kühlschrank- und Möbelindustrie eingesetzt werden.The laminates produced according to the invention can be used in various fields and can be used in the form of foils, for example as cladding, covers, wall elements, decorative panels, etc. In particular, they can be used under usual temperature and pressure conditions L Process and form into various types of molded parts by deep drawing. Such molded parts can be designed as trough-shaped or shell-shaped bodies with different contours and dimensions. However, they can also be provided as a roll or sheet with a recurring profile, such as ribs, beads, grids, cups or other stiffening elements. Areas of application for molded parts are machine covers, housing parts, components, containers, drip trays, caps and more. The shaped laminates can be used, for example, in the packaging sector, in the refrigerator and furniture industry.

Die in den Beispielen angegebenen Teile und Prozente beziehen sich auf das Gewicht.The parts and percentages given in the examples relate to the weight.

Beispiel 1example 1

Ein granuliertes Äthylen-Methacrylat-Polymerisat mit ca. 40 % Methylacrylat, dem Schmelzindex von 25 g/10 min bei 190°C und 2,16 kp und einem Erweichungspunkt von 137°C (DIN 1995, Ring und Kugel) wurde bei 200°C in einer dampfbeheizten Plattenpresse zu einer Preßplatte mit den Abmessungen 1 x 200 x 2 000 mm verpreßt. Diese Platte wurde zwischen je eine 1 mm dicke Platte aus schlagfestem Polystyrol mit eine Wärmeformbeständigkeit nach Vicat/B von 90°C (DIN 53 460) und Polyäthylen der Dichte 0,929/cm3 gelegt. Bei 220°C wurde in der gleichen Plattenpresse ein praktisch untrennbarer Dreischichtstoff hergestellt.A granulated ethylene methacrylate polymer with about 40% methyl acrylate, the melt index of 25 g / 10 min at 190 ° C and 2.16 kp and a softening point of 137 ° C (DIN 1995, ring and ball) was at 200 ° C in a steam-heated plate press to a press plate with the dimensions 1 x 200 x 2,000 mm. This plate was placed between a 1 mm thick plate made of impact-resistant polystyrene with a heat resistance according to Vicat / B of 90 ° C (DIN 53 460) and polyethylene with a density of 0.929 / cm 3 . At 220 ° C, a practically inseparable three-layer material was produced in the same plate press.

Beispiel 2Example 2

Ein Äthylen-Äthylacrylat-Polymerisat mit ca. 35 % Äthylacrylat, einem Erweichungspunkt von ca 132°C (DIN 1995, J Ring und Kugel) und dem Schmelzindex 12 g/10 min, gemessen bei 190°C und 2,16 kp (DIN 53 735) wurde mit 40 % eines Styrol-Butadien-Styrol-Blockpolymerisates, welches 32 % Styrol einpolymerisiert enthielt, mit Hilfe eines gegenläufig rotierenden, dampfbeheizten Walzenpaares bei 190°C in der Schmelze gemischt. Die Mischung hatte den Schmelzindex 1,3 g/10 min, bei 190°C und 2,16 kp, und wurde in einer Mehrschicht-Koextrusionsanlage zu einem Dreischichtstoff aus schlagfestem Polystyrol (Schicht A), Haftvermittlerschicht und Polybutylenterephthalat (Schicht C) verarbeitet.An ethylene-ethyl acrylate polymer with approx. 35% ethyl acrylate, a softening point of approx. 132 ° C (DIN 1995, J Ring and ball) and the melt index 12 g / 10 min, measured at 190 ° C and 2.16 kp (DIN 53 735) was with 40% of a styrene-butadiene-styrene block polymer containing 32% styrene copolymerized with the help of a counter-rotating, steam-heated pair of rollers mixed in the melt at 190 ° C. The mixture had a melt index of 1.3 g / 10 min, at 190 ° C. and 2.16 kp, and was processed in a multilayer coextrusion plant to form a three-layer material made of impact-resistant polystyrene (layer A), adhesion promoter layer and polybutylene terephthalate (layer C).

Claims (1)

Schichtstoffe aus mindestens zwei voneinander verschiedenen Schichten A und C aus thermoplastischen Kunststoffen, die durch eine Haftvermittlerschicht B miteinander verbunden sind, dadurch gekennzeichnet, daß die Haftvermittlerschicht B im wesentlichen aus einem Äthylen-Alkylacrylat-Copolyrerisat besteht, welches 15 bis 80 Gew.% eines AlkylacryLats mit 1 bis 4 Kohlenstoffatomen im Alkylrest einpolymerisiert enthält und einem Schmelzindex bei 190°C und 2,16 kp im Bereich von 1 bis 40 g/10 min besitzt, und die Schicht A und die Schicht C aus einem Olefinpolymerisat, einem gegebenenfalls schlagzäh modifizierten Styrolpolymerisat oder Styrolcopolymerisat, einem chlorhaltigen Polymeren, einem Polyamid, Polycarbonat, Polyvinylalkohol und/oder Polyurethan aufgebaut sind.Laminates of at least two mutually different layers A and C made of thermoplastic materials which are bonded to one another by an adhesion promoter layer B, characterized in that the adhesion promoter layer B essentially consists of an ethylene-alkyl acrylate copolymer which contains 15 to 80% by weight of an alkyl acrylate contains copolymerized with 1 to 4 carbon atoms in the alkyl radical and has a melt index at 190 ° C and 2.16 kp in the range from 1 to 40 g / 10 min, and layer A and layer C from an olefin polymer, an optionally impact-modified styrene polymer or styrene copolymer, a chlorine-containing polymer, a polyamide, polycarbonate, polyvinyl alcohol and / or polyurethane.
EP78100462A 1977-07-29 1978-07-21 Multilayered products, the layers of which are bonded together by means of an adhesive layer Withdrawn EP0000558A1 (en)

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Cited By (8)

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EP0161035A2 (en) * 1984-05-02 1985-11-13 Shell Internationale Researchmaatschappij B.V. Laminated sheet
EP0192075A2 (en) * 1985-01-23 1986-08-27 Rockwell International Corporation Method of repairing plastic transparencies
EP0240886A2 (en) * 1986-04-11 1987-10-14 Wolff Walsrode Aktiengesellschaft Sealable, stretched composite films
EP0272412A2 (en) * 1986-12-04 1988-06-29 General Electric Company Aromatic carbonate articles bonded by a photocured acrylic composition
DE4219325A1 (en) * 1991-06-17 1992-12-24 Mitsubishi Chem Ind Adhesive compsns. for polystyrene laminated mfr. - contg. graft polymer of unsatd. carboxylic acid or deriv. mixed with ethylene@]-acrylate] copolymer and polystyrene
EP0595550A1 (en) * 1992-10-26 1994-05-04 Rohm And Haas Company Polyolefin substrates with improved adhesion properties
DE19529402A1 (en) * 1995-08-10 1997-02-13 Basf Ag Clear, stiff, tough multilayer laminate useful for bottles of carbonated drinks and food packaging film - has layers of styrene-butadiene block copolymer and has low gas permeability, high transparency and good toughness and stiffness
US6640495B1 (en) * 1999-01-21 2003-11-04 Syracuse Castings Sales Corp. Safety hatch for preventing fall-through and unauthorized entry

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DE3573559D1 (en) * 1984-07-13 1989-11-16 Gen Electric Laminate comprising an outer layer of polycarbonate
DE3921677A1 (en) * 1989-07-01 1991-01-10 Basf Ag SEALABLE PLASTIC FILM
WO1992012008A1 (en) * 1991-01-02 1992-07-23 Eastman Kodak Company Multilayered sheets having excellent adhesion

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FR1428109A (en) * 1965-02-12 1966-02-11 Hitachi Wire And Cable Ltd Process for welding polyethylene-based materials
US3519531A (en) * 1966-12-30 1970-07-07 Hercules Inc Coated polypropylene film and laminates formed therefrom
GB1309011A (en) * 1969-03-10 1973-03-07 Dow Chemical Co Multilayer laminated sheet
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0161035A3 (en) * 1984-05-02 1986-07-23 Shell Internationale Research Maatschappij B.V. Laminated sheet
EP0161035A2 (en) * 1984-05-02 1985-11-13 Shell Internationale Researchmaatschappij B.V. Laminated sheet
EP0192075A3 (en) * 1985-01-23 1988-03-16 Rockwell International Corporation Method of repairing plastic transparencies
EP0192075A2 (en) * 1985-01-23 1986-08-27 Rockwell International Corporation Method of repairing plastic transparencies
EP0240886A3 (en) * 1986-04-11 1988-11-09 Wolff Walsrode Aktiengesellschaft Sealable, stretched composite films
EP0240886A2 (en) * 1986-04-11 1987-10-14 Wolff Walsrode Aktiengesellschaft Sealable, stretched composite films
EP0272412A2 (en) * 1986-12-04 1988-06-29 General Electric Company Aromatic carbonate articles bonded by a photocured acrylic composition
EP0272412A3 (en) * 1986-12-04 1989-12-06 General Electric Company Aromatic carbonate articles bonded by a photocured acrylic composition
DE4219325A1 (en) * 1991-06-17 1992-12-24 Mitsubishi Chem Ind Adhesive compsns. for polystyrene laminated mfr. - contg. graft polymer of unsatd. carboxylic acid or deriv. mixed with ethylene@]-acrylate] copolymer and polystyrene
EP0595550A1 (en) * 1992-10-26 1994-05-04 Rohm And Haas Company Polyolefin substrates with improved adhesion properties
DE19529402A1 (en) * 1995-08-10 1997-02-13 Basf Ag Clear, stiff, tough multilayer laminate useful for bottles of carbonated drinks and food packaging film - has layers of styrene-butadiene block copolymer and has low gas permeability, high transparency and good toughness and stiffness
DE19529402C2 (en) * 1995-08-10 2001-11-29 Basf Ag Multilayer laminate
US6640495B1 (en) * 1999-01-21 2003-11-04 Syracuse Castings Sales Corp. Safety hatch for preventing fall-through and unauthorized entry

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