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EP0000558A1 - Stratifiés dont les couches sont liées au moyen d'une couche adhésive - Google Patents

Stratifiés dont les couches sont liées au moyen d'une couche adhésive 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
Authority
EP
European Patent Office
Prior art keywords
layer
ethylene
copolymer
alkyl acrylate
adhesion
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Withdrawn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
EP78100462A
Other languages
German (de)
English (en)
Inventor
Ulrich Dr. Koenig
Wolfgang Dr. Druschke
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 EP0000558A1 publication Critical patent/EP0000558A1/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Withdrawn legal-status Critical Current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
    • 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)
EP78100462A 1977-07-29 1978-07-21 Stratifiés dont les couches sont liées au moyen d'une couche adhésive Withdrawn EP0000558A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2734294 1977-07-29
DE19772734294 DE2734294A1 (de) 1977-07-29 1977-07-29 Schichtstoffe

Publications (1)

Publication Number Publication Date
EP0000558A1 true EP0000558A1 (fr) 1979-02-07

Family

ID=6015176

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100462A Withdrawn EP0000558A1 (fr) 1977-07-29 1978-07-21 Stratifiés dont les couches sont liées au moyen d'une couche adhésive

Country Status (2)

Country Link
EP (1) EP0000558A1 (fr)
DE (1) DE2734294A1 (fr)

Cited By (8)

* 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
EP0192075A3 (fr) * 1985-01-23 1988-03-16 Rockwell International Corporation Procédé pour réparer des articles en matière plastique transparente
EP0240886A3 (en) * 1986-04-11 1988-11-09 Wolff Walsrode Aktiengesellschaft Sealable, stretched composite films
EP0272412A3 (fr) * 1986-12-04 1989-12-06 General Electric Company Articles de carbonate aromatique liés par une composition acrylique photoréticulée
DE4219325A1 (de) * 1991-06-17 1992-12-24 Mitsubishi Chem Ind Klebharzzusammensetzungen und polystyrollaminate unter verwendung der zusammensetzung fuer eine klebstoffschicht
EP0595550A1 (fr) * 1992-10-26 1994-05-04 Rohm And Haas Company Substrats en polyoléfine ayant des propriétés s'adhésion améliorées
DE19529402A1 (de) * 1995-08-10 1997-02-13 Basf Ag Mehrschichtlaminat
US6640495B1 (en) * 1999-01-21 2003-11-04 Syracuse Castings Sales Corp. Safety hatch for preventing fall-through and unauthorized entry

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3573559D1 (en) * 1984-07-13 1989-11-16 Gen Electric Laminate comprising an outer layer of polycarbonate
DE3921677A1 (de) * 1989-07-01 1991-01-10 Basf Ag Siegelfaehige kunststoff-folie
WO1992012008A1 (fr) * 1991-01-02 1992-07-23 Eastman Kodak Company Feuilles multicouches ayant un excellent pouvoir adhesif

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6412768A (fr) * 1963-11-15 1965-05-17
FR1428109A (fr) * 1965-02-12 1966-02-11 Hitachi Wire And Cable Ltd Procédé pour souder des matériaux à base de polyéthylène
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
US3758431A (en) * 1971-06-03 1973-09-11 D Taft Hot melt compositions
DE2329035A1 (de) * 1973-06-07 1975-01-16 Basf Ag Haftkleber
US3926878A (en) * 1972-01-24 1975-12-16 Arakawa Rinsan Kagaku Kogyo Hot-melt compositions comprising E/VA copolymer and hydrogenated petroleum resin
GB1471464A (en) * 1973-06-02 1977-04-27 Sumitomo Chemical Co Method of bonding with adhesives

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6412768A (fr) * 1963-11-15 1965-05-17
FR1428109A (fr) * 1965-02-12 1966-02-11 Hitachi Wire And Cable Ltd Procédé pour souder des matériaux à base de polyéthylène
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
US3758431A (en) * 1971-06-03 1973-09-11 D Taft Hot melt compositions
US3926878A (en) * 1972-01-24 1975-12-16 Arakawa Rinsan Kagaku Kogyo Hot-melt compositions comprising E/VA copolymer and hydrogenated petroleum resin
GB1471464A (en) * 1973-06-02 1977-04-27 Sumitomo Chemical Co Method of bonding with adhesives
DE2329035A1 (de) * 1973-06-07 1975-01-16 Basf Ag Haftkleber

Cited By (9)

* 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
EP0192075A3 (fr) * 1985-01-23 1988-03-16 Rockwell International Corporation Procédé pour réparer des articles en matière plastique transparente
EP0240886A3 (en) * 1986-04-11 1988-11-09 Wolff Walsrode Aktiengesellschaft Sealable, stretched composite films
EP0272412A3 (fr) * 1986-12-04 1989-12-06 General Electric Company Articles de carbonate aromatique liés par une composition acrylique photoréticulée
DE4219325A1 (de) * 1991-06-17 1992-12-24 Mitsubishi Chem Ind Klebharzzusammensetzungen und polystyrollaminate unter verwendung der zusammensetzung fuer eine klebstoffschicht
EP0595550A1 (fr) * 1992-10-26 1994-05-04 Rohm And Haas Company Substrats en polyoléfine ayant des propriétés s'adhésion améliorées
DE19529402A1 (de) * 1995-08-10 1997-02-13 Basf Ag Mehrschichtlaminat
DE19529402C2 (de) * 1995-08-10 2001-11-29 Basf Ag Mehrschichtlaminat
US6640495B1 (en) * 1999-01-21 2003-11-04 Syracuse Castings Sales Corp. Safety hatch for preventing fall-through and unauthorized entry

Also Published As

Publication number Publication date
DE2734294A1 (de) 1979-02-08

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Inventor name: DRUSCHKE, WOLFGANG, DR.

Inventor name: KOENIG, ULRICH, DR.