WO2020053294A1 - Stratifiés contenant une couche de métal et une couche de polyester - Google Patents

Stratifiés contenant une couche de métal et une couche de polyester Download PDF

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Publication number
WO2020053294A1
WO2020053294A1 PCT/EP2019/074258 EP2019074258W WO2020053294A1 WO 2020053294 A1 WO2020053294 A1 WO 2020053294A1 EP 2019074258 W EP2019074258 W EP 2019074258W WO 2020053294 A1 WO2020053294 A1 WO 2020053294A1
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WO
WIPO (PCT)
Prior art keywords
component
range
polymer composition
layer
laminate
Prior art date
Application number
PCT/EP2019/074258
Other languages
German (de)
English (en)
Inventor
Philippe Desbois
Jasmina SIMON
Original Assignee
Basf Se
Thyssenkrupp Steel Europe Ag
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, Thyssenkrupp Steel Europe Ag filed Critical Basf Se
Publication of WO2020053294A1 publication Critical patent/WO2020053294A1/fr

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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
    • 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
    • B32B15/06—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 natural rubber or synthetic rubber
    • 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/026—Knitted fabric
    • 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
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B32B2262/065—Lignocellulosic fibres, e.g. jute, sisal, hemp, flax, bamboo
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B32B2262/067—Wood fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/103—Metal fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/105—Ceramic fibres
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2605/00—Vehicles
    • B32B2605/12—Ships
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft

Definitions

  • Laminates containing a metal layer and a polyester layer Laminates containing a metal layer and a polyester layer
  • the present invention relates to a laminate comprising at least a first layer of at least one first metal and at least one further layer of a polymer composition (PZ) and a method for producing the laminate according to the invention.
  • PZ polymer composition
  • a task that is frequently asked today is the provision of new materials, in particular for aircraft construction, automobile construction and boat construction, which are lighter than the materials previously used. At the same time, these new materials should have the same mechanical properties, in particular strength, rigidity and stability as the known materials, or even be superior to them.
  • the new materials should also be able to be formed using known methods, such as deep drawing, rolling, bending, embossing or folding.
  • WO 2005/014278 describes laminates which contain an adhesive polymer layer between two outer metal layers.
  • This polymer layer contains a polyamide 6, polyamide 6.6, polyamide 11, polyamide 12, polyamide 4.6, polyamide 6.10 or polyamide 6.12 and a copolymer of ethylene and an unsaturated carboxylic acid and / or a carboxylic acid derivative and a reactive copolymer.
  • the copolymer of ethylene and an unsaturated carboxylic acid and / or a carboxylic acid derivative can be grafted with polar groups.
  • a disadvantage of the laminates described in WO 2005/014278 is that they only have poor tensile strength, especially after storage in a moist environment.
  • the polymer layer often exhibits fluctuating moisture absorption and, as a result, fluctuating adhesion properties.
  • US 2011/0200816 describes laminates which comprise two metal layers and an intermediate polymer layer.
  • the polymer layer contains, for example, a polyamide 6/66 copolymer.
  • various other thermoplastic polymers such as polyolefins and polyimides are described.
  • the laminates described in US 2011/0200816 also have poor tensile strengths, especially after storage in a moist environment, or are even destroyed by air humidity to the point of being unusable.
  • DE 10 201 1 084519 describes sealing layers for solar cells, which comprise a first outer layer, a middle layer and a second outer layer.
  • the Layers can contain polyamides such as polyamide 6 or polyamide 66.
  • the object on which the present invention is based is therefore to provide a laminate and a method for its production which do not have the disadvantages of the laminates described in the prior art or only have them to a reduced extent.
  • the laminate should still have a high tensile strength even after prolonged storage at higher atmospheric humidity.
  • This object was achieved by a laminate comprising at least one first layer of at least one first metal and at least one further layer of a polymer composition (PZ), characterized in that the polymer composition (PZ) comprises the components (A) at least one first polyester,
  • (C) contains at least one rubber.
  • the laminates according to the invention have a particularly good peeling behavior and a good modulus of elasticity.
  • the laminate comprises at least one first layer of at least one first metal and at least one further layer of a polymer composition (PZ).
  • PZ polymer composition
  • At least one first layer means exactly one first layer as well as two or more first layers.
  • at least one first metal means exactly one first metal as well as a mixture of two or more first metals.
  • “at least one further layer” means exactly one further layer as well as two or more further layers.
  • the laminate preferably additionally comprises at least one second layer of at least one second metal, the at least one first layer of at least one first metal being connected to the at least one second layer of at least one second metal via the at least one further layer of the polymer composition (PZ).
  • PZ polymer composition
  • the at least one first layer is followed by at least one further layer and in turn at least one second layer.
  • Such a laminate which comprises at least one first layer, at least one further layer and at least one second layer, is also referred to as sandwich material.
  • the present invention therefore also relates to a laminate in which the laminate additionally comprises at least one second layer of at least one second metal and in which the at least one first layer is connected to the at least one second layer via the at least one further layer.
  • the at least one first metal of the at least one first layer can be the same or different from the at least one second metal of the at least one second layer.
  • the at least one first metal of the at least one first layer is preferably equal to the at least one second metal of the at least one second layer.
  • the laminate comprises at least a first layer of at least one first metal.
  • the laminate comprises at least a first layer, which consists of at least a first metal.
  • the at least one first layer of at least one first metal has, for example, a thickness in the range from 0.1 to 0.6 mm, preferably in the range from 0.15 to 0.4 mm and particularly preferably in the range from 0.18 to 0.3 mm on.
  • the present invention therefore also relates to a laminate in which the at least one first layer has a thickness in the range from 0.1 to 0.6 mm.
  • the laminate preferably additionally comprises at least one second layer of at least one second metal.
  • the laminate preferably additionally comprises at least one second layer, which consists of at least one second metal.
  • the at least one second layer of at least one second metal has, for example, a thickness in the range from 0.1 to 0.6 mm, preferably in the range from 0.15 to 0.4 mm and particularly preferably in the range from 0.18 to 0.3 mm on.
  • the present invention therefore also relates to a laminate in which the laminate additionally comprises at least one second layer of at least one second metal, the at least one second layer having a thickness in the range from 0.1 to 0.6 mm.
  • the thickness of the at least one second layer can be the same or different from the thickness of the at least one first layer.
  • the thickness of the at least one second layer is preferably equal to the thickness of the at least one first layer.
  • Suitable as the at least one first metal of the at least one first layer are all metals and metal alloys known to the person skilled in the art which are solid at the production temperatures and the use temperatures of the laminate.
  • the at least one first metal of the at least one first layer is preferably selected from the group consisting of iron, aluminum, copper, nickel and magnesium and alloys thereof.
  • the at least one first metal is particularly preferably an alloy of iron, particularly preferably the at least one first metal is steel.
  • the present invention therefore also relates to a laminate in which the at least one first metal of the at least one first layer is selected from the group consisting of iron, aluminum, copper, nickel and magnesium and alloys thereof.
  • the present invention therefore also relates to a laminate in which the at least one first metal is selected from the group consisting of iron, aluminum, copper, nickel and magnesium and alloys thereof.
  • steel is known to the person skilled in the art.
  • steel means alloys which contain iron as the main constituent. This corresponds to the definition of steel according to DIN EN 10020: 2000-07.
  • the at least one first metal can be coated or uncoated.
  • the at least one first metal is preferably coated. Suitable coatings for the at least one first metal are known per se to the person skilled in the art and are, for example, adhesion promoter layers, corrosion protection layers, paint, zinc or magnesium coatings.
  • the at least one first metal is preferably galvanized. “Galvanized” means that the at least one first metal is coated with a further metal, in particular with zinc or alloys of zinc.
  • the at least one first metal is therefore particularly preferably galvanized steel.
  • the at least one first metal can be galvanized by methods known to the person skilled in the art, for example by hot-dip galvanizing or by galvanizing.
  • the at least one first metal is galvanized, it can also have further coatings, such as, for example, adhesion promoter layers and / or paint. This is known to the person skilled in the art.
  • the at least one first metal can be coated by all methods known to the person skilled in the art, for example the coating can be carried out from an aqueous solution or a dispersion.
  • the explanations and preferences described above apply accordingly for the at least one first metal of the at least one first layer.
  • the present invention therefore also relates to a laminate in which the laminate additionally comprises at least one second layer of at least one second metal, the at least one second metal of the at least one second layer being selected from the group consisting of iron, aluminum, copper, nickel and magnesium and alloys made from them.
  • the laminate comprises at least one further layer of a polymer composition (PZ).
  • PZ polymer composition
  • the at least one further layer of a polymer composition (PZ) has, for example, a thickness in the range from 0.02 to 1.5 mm, preferably in the range from 0.05 to 1 mm and particularly preferably in the range from 0.1 to 0.5 mm on.
  • the present invention therefore also relates to a laminate in which the at least one further layer has a thickness in the range from 0.02 to 1.5 mm.
  • the present invention therefore also relates to a laminate in which the at least one first layer has a thickness in the range from 0.1 mm to 0.6 mm and / or in which the at least one further layer has a thickness in the range from 0.02 to 1.5 mm.
  • the polymer composition (PZ) contains the components (A) at least one first polyester, (B) at least one second polyester and (C) at least one rubber.
  • “at least one first polyester” means both exactly one first polyester and also a mixture (blend) of two or more first polyesters.
  • At least one second polyester means exactly one second polyester and also a mixture (blend) of two or more second polyesters.
  • At least one rubber means both exactly one rubber and a mixture (blend) of two or more rubbers.
  • component (A) and “at least one first polyester” are used synonymously and therefore have the same meaning.
  • component (B) and “at least a second polyester” are used synonymously and have the same meaning.
  • component (C) and “at least one rubber”.
  • the at least one first polyester differs from the at least one second polyester.
  • Component (A) is therefore different from component (B).
  • the present invention therefore also relates to a laminate in which component (A) contained in the polymer composition (PZ) is different from component (B) contained in the polymer composition (PZ).
  • the polymer composition (PZ) can be produced by all methods known to the person skilled in the art.
  • the components (A), (B) and (C) contained in the polymer composition (PZ) are compounded in an extruder and the polymer composition (PZ) is thus obtained.
  • components (A), (B) and (C) are present in the polymer composition (PZ) as a mixture (blend).
  • the components (A), (B) and (C) contained in the polymer composition (PZ) can react at least partially with one another. This is known to the person skilled in the art.
  • the polymer composition (PZ) can additionally contain at least one further polymer.
  • At least one further polymer means exactly one further polymer as well as a mixture (blend) of two or more further polymers. All further polymers known to the person skilled in the art are suitable as at least one further polymer. It goes without saying that the at least one further polymer is different from components (A), (B) and (C).
  • the at least one further polymer is preferably selected from the group consisting of polyethylene and copolymers of at least two monomers, selected from the group consisting of ethylene, acrylic acid, maleic anhydride, isobutylene, butene, propylene, octene, alkyl acrylate and alkyl methacrylate.
  • the present invention therefore also relates to a laminate in which the polymer composition (PZ) additionally comprises at least one further polymer selected from the group consisting of polyethylene and copolymers of at least two monomers selected from the group consisting of ethylene, isobutylene, butene, propylene, Contains octene, alkyl acrylate, alkyl methacrylate, acrylic acid and maleic anhydride.
  • PZ polymer composition
  • Alkyl acrylates are known to the person skilled in the art and are also referred to as alkyl acrylates. Alkyl acrylates form when acrylic acid is reacted with an alkyl alcohol. According to the invention, n-butyl acrylate is preferred as the alkyl acrylate.
  • Alkyl methacrylates are also known to the person skilled in the art and are also referred to as alkyl methacrylates. Alkyl methacrylates can be obtained, for example, by reacting methacrylic acid with an alkyl alcohol. Alkyl methacrylates can also be substituted, for example. An example of substituted alkyl methacrylates is 2,3-epoxypropyl methacrylate.
  • 2,3-epoxypropyl methacrylate is also known as glycidyl methacrylate.
  • Alkyl methacrylate is preferred according to the invention selected from the group consisting of methyl methacrylate and 2,3-epoxypropyl methacrylate.
  • the polymer composition (PZ) can additionally contain at least one filler.
  • At least one filler means both exactly one filler and a mixture of two or more fillers.
  • Suitable fillers are all fillers known to the person skilled in the art which can be mixed with components (A), (B) and (C) and, if appropriate, with the at least one further polymer in the polymer composition (PZ).
  • the at least one filler is preferably selected from the group consisting of inorganic fillers, organic fillers and natural fillers.
  • the at least one filler is usually particulate.
  • the at least one filler can be a fiber material or, for example, be in the form of spheres.
  • the at least one filler has, for example, an aspect ratio in the range from 1 to 15, preferably in the range from 1 to 10 and particularly preferably in the range from 1 to 5.
  • the “aspect ratio” is understood to mean the ratio of the largest dimension of a particle of the at least one filler to the smallest dimension of a particle of the at least one filler.
  • fiber materials are understood to mean all materials which have fibers, such as, for example, individual fibers, fiber bundles (rovings), nonwovens, scrims, fabrics or knitted fabrics.
  • the at least one filler is therefore selected from the group consisting of wollastonite, talc, boron fiber materials, glass fiber materials, carbon fiber materials, silicic acid fiber materials, ceramic fiber materials, basalt fiber materials, metal fiber materials, aramid fiber materials, poly (p-phenylene-2,6) -benzas fiber material ,
  • Nylon fiber materials polyethylene fiber materials, wood fiber materials,
  • Flax fiber materials hemp fiber materials, coconut fiber materials and sisal fiber materials.
  • the at least one filler is particularly preferably selected from the group consisting of glass fiber materials, carbon fiber materials,
  • Aramid fiber materials poly (p-phenylene-2,6-benzobisoxazole) fiber materials, Boron fiber materials, metal fiber materials and potassium titanate fiber materials.
  • the at least one filler is particularly preferably a glass fiber material.
  • the polymer composition (PZ) preferably contains no filler.
  • the polymer composition (PZ) contains in the range from 10 to 90% by weight of component (A), preferably in the range from 30 to 80% by weight and particularly preferably in the range from 40 to 70% by weight of component ( A), based in each case on the sum of the% by weight of components (A), (B) and (C), if appropriate of the at least one further polymer and if appropriate of the at least one filler, preferably based on the total weight of the polymer composition (PZ) .
  • the polymer composition (PZ) contains, for example, in the range from 5 to 80% by weight of component (B), preferably in the range from 10 to 60% by weight and particularly preferably in the range from 20 to 40% by weight of component ( B), based in each case on the sum of the% by weight of components (A), (B) and (C), if appropriate of the at least one further polymer and if appropriate of the at least one filler, preferably based on the total weight of the
  • the polymer composition (PZ) contains, for example, in the range from 2 to 40% by weight of component (C), preferably in the range from 5 to 30% by weight and particularly preferably in the range from 10 to 20% by weight of component ( C), based in each case on the sum of the% by weight of components (A), (B) and (C), if appropriate of the at least one further polymer and if appropriate of the at least one filler, preferably based on the total weight of the
  • the present invention therefore also relates to a laminate in which the polymer composition (PZ) contains in the range from 2 to 40% by weight of component (C), based on the sum of the percentages by weight of components (A), (B) and (C).
  • the polymer composition (PZ) contains, for example, in the range from 0 to 50% by weight, preferably in the range from 5 to 50% by weight and particularly preferably in the range from 10 to 30% by weight, of the at least one further polymer, in each case based to the sum of the% by weight of components (A), (B) and (C), the at least one further polymer and optionally the at least one filler, preferably based on the total weight of the polymer composition (PZ).
  • the polymer composition (PZ) contains, for example, in the range from 0.1 to 70% by weight of the at least one filler, preferably in the range from 0.5 to 60% by weight and particularly preferably in the range from 1 to 50% by weight of the at least one filler, in each case based on the sum of the% by weight of components (A), (B) and (C), of the at least one filler and optionally of the at least one further polymer, preferably based on the total weight of the polymer composition (PZ ).
  • the molar ratio of component (A) to component (B) in the polymer composition (PZ) is, for example, in the range from 90 to 10 to 30 to 70, preferably in the range from 80 to 20 to 35 to 65 and particularly preferably in the range from 60 to 40 to 40 to 60.
  • the present invention therefore also relates to a laminate in which the molar ratio of component (A) to component (B) in the polymer composition (PZ) is in the range from 90 to 10 to 30 to 70.
  • the polymer composition (PZ) can also contain additives known to those skilled in the art.
  • additives that can be contained in the polymer composition (PZ) are selected from the group consisting of stabilizers, dyes, antistatic agents, filler oils, surface improvers, desiccants, mold release agents, release agents,
  • the present invention therefore also relates to a laminate in which the polymer composition (PZ) additionally comprises at least one additive selected from the group consisting of stabilizers, dyes, antistatic agents, filler oils, surface improvers, siccatives, mold release agents, release agents,
  • additives are known per se to the person skilled in the art.
  • Coupling agents are also referred to as crosslinking agents.
  • additives which further improve the adhesion of the polymer composition (PZ) of the at least one further layer to the at least one first layer and, if appropriate, to the at least one second layer.
  • the polymer composition (PZ) usually has a melting temperature (T M ( PZ ) ).
  • the melting temperature (T M ( PZ ) ) of the polymer composition (PZ) is, for example, in the range from 180 to 260 ° C, preferably in the range from 190 to 240 ° C and particularly preferably in the range from 195 to 225 ° C, determined according to ISO 1 1357-3: 2014.
  • the polymer composition (PZ) is usually used as granules.
  • the granules of the polymer composition (PZ) then usually have a size in the range from 1 mm to 10 mm.
  • the present invention therefore also relates to a laminate in which the polymer composition (PZ) has a melting temperature (T M ⁇ PZ ) ) which is in the range from 180 to 260 ° C.
  • the polymer composition (PZ) preferably has a melting enthalpy DH2 (RZ) in the range from 10 to 60 J / g, more preferably in the range from 15 to 50 J / g and particularly preferably in the range from 20 to 40 J / g, determined by means of dynamic differential calorimetry (DSC) according to ISO 1 1357-4: 2014.
  • RZ melting enthalpy DH2
  • the polymer composition (PZ) is usually used as granules.
  • the granules of the polymer composition (PZ) then usually have a size in the range from 1 mm to 10 mm.
  • the present invention therefore also relates to a laminate in which the polymer composition (PZ) has an enthalpy of fusion DH2 (RZ) in the range from 10 to 60 J / g.
  • component (A) contained in the polymer composition (PZ) is at least one first polyester.
  • Polyesters are known per se to those skilled in the art.
  • Component (A) is preferably obtainable by reacting at least one diol with at least one dicarboxylic acid and / or at least one dicarboxylic acid derivative. This implementation is known per se to the person skilled in the art.
  • dicarboxylic acids known to the person skilled in the art are suitable as at least one dicarboxylic acid.
  • the at least one dicarboxylic acid is selected from the group consisting of aliphatic C 2 -C 18 dicarboxylic acids and aromatic C 6 -C 14 dicarboxylic acids.
  • Aromatic C 6 -C 14 dicarboxylic acids are preferred according to the invention.
  • aliphatic C 2 -C 18 dicarboxylic acids are understood to mean aliphatic compounds which are saturated or unsaturated with 2 to 18 carbon atoms and two carboxy groups (-COOH groups).
  • the 2 to 18 carbon atoms can be arranged in the main chain or in side chains, so the aliphatic C 2 -C 18 dicarboxylic acids can be branched or unbranched or cycloaliphatic.
  • aliphatic C 2 -C 18 dicarboxylic acids are selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, brassylic acid and subaric acid (suberic acid).
  • aromatic C 6 -C 14 dicarboxylic acids mean aromatic compounds which are saturated or unsaturated and have 6 to 14 carbon atoms and two carboxy groups (-COOH groups).
  • Suitable aromatic C 6 -Ci dicarboxylic acids are selected, for example, from the group consisting of naphthalenedicarboxylic acid and terephthalic acid. Terephthalic acid is particularly preferred.
  • Dicarboxylic acid derivatives are known per se to those skilled in the art.
  • Dicarboxylic acid derivatives are, for example, dicarboxylic acid esters from the dicarboxylic acids and CrC alcohols described above or dicarboxylic acid halides.
  • At least one aliphatic diol is preferred as at least one diol.
  • a diol is understood to mean a dihydroxy compound.
  • the terms “diol” and “dihydroxy compound” are therefore used synonymously in the context of the present invention and therefore have the same meaning.
  • the at least one aliphatic diol is preferably selected from the group consisting of C 2 -C 6 alkanediols and C 5 -C 7 cycloalkanediols.
  • C 2 -C 6 alkanediols are understood to mean aliphatic compounds which are saturated or unsaturated, preferably saturated, having 2 to 6 carbon atoms and two hydroxyl groups (—OH groups).
  • C 5 -C 7 cycloalkanediols are understood to mean cycloaliphatic compounds which are saturated or unsaturated, preferably saturated, have 5 to 7 carbon atoms in the ring and two hydroxyl groups (—OH groups).
  • the at least one diol is selected from the group consisting of 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol and 1,4-cyclohexanediol.
  • Aromatic polyesters are preferred as at least one first polyester.
  • Polyalkylene terephthalates of C 2 -C 6 alkanediols are preferred.
  • the at least one first polyester is particularly preferably selected from the group consisting of polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) and copolymers thereof.
  • the at least one first polyester is particularly preferably selected from the group consisting of polybutylene terephthalate and polyethylene terephthalate, and copolymers thereof.
  • the present invention therefore also relates to a laminate in which component (A) is selected from the group consisting of polyethylene terephthalate and polybutylene terephthalate.
  • the at least one first polyester is preferably a homopolymer.
  • the present invention therefore also relates to laminate in which component (A) is a homopolymer.
  • a “homopolymer” is understood to mean a polymer which is derived from exactly one monomer. This monomer can also be a hypothetical monomer. A homopolymer therefore has exactly one type of repeating unit.
  • Component (A) usually has a melting temperature (T M ( A>).
  • the melting temperature (T M (A) ) of component (A) is, for example, in the range from 200 to 240 ° C, preferably in the range from 205 to 235 ° C and particularly preferably in the range from 210 to 230 ° C, determined according to ISO 11357-3: 2014.
  • the present invention therefore also relates to a laminate in which component (A) contained in the polymer composition (PZ) has a melting temperature (T M ⁇ A)) which is in the range from 200 to 240 ° C.
  • Component (A) usually has a crystallization temperature (T kP (A)).
  • the crystallization temperature (T kP (A)) of component (A) is usually in the range from> 175 to 210 ° C, preferably in the range from 180 to 205 ° C and particularly preferably in the range from 185 to 200 ° C, determined by means of dynamic Differential scanning calorimetry (DDK) as described below.
  • DDK dynamic Differential scanning calorimetry
  • crystallization temperature (T kP (A)) of component (A) is usually below the melting temperature (T M ⁇ A) ) of component (A).
  • the present invention therefore also relates to a laminate in which the crystallization temperature (T kP (A)) of component (A) is below the melting temperature (T M ( A ) ⁇ of component (A).
  • the temperature of a sample in this case a sample of component (A), and the temperature of a reference are changed linearly with time.
  • heat is supplied to and removed from the sample and the reference.
  • the amount of heat Q that is necessary to keep the sample at the same temperature as the reference is determined.
  • the quantity of heat Q R supplied or removed from the reference serves as the reference value.
  • the measurement provides a DSC diagram in which the quantity of heat Q which is supplied to or removed from the sample is plotted as a function of the temperature T.
  • a heating run H is carried out during the measurement, i.e. the sample and the reference are heated linearly.
  • an additional amount of heat Q supplied to keep the sample at the same temperature as the reference is then observed in the DSC diagram, the so-called melting peak.
  • a cooling run (K) is usually measured.
  • the sample and the reference are cooled linearly, so heat is removed from the sample and the reference.
  • a larger amount of heat Q must be dissipated in order to keep the sample at the same temperature as the reference, since heat is released during the crystallization or solidification.
  • a peak, the so-called crystallization peak is then observed in the DSC diagram of the cooling run (K) in the opposite direction to the melting peak. If necessary, a second heating run (H2) is measured in analogy to the heating run (H) after the cooling run (K).
  • Such a DSC diagram with a heating run (H) and a cooling run (K) is shown as an example in FIG. 1.
  • the melting temperature (T M ⁇ A)) and the crystallization temperature (T kP (A)) can be determined on the basis of the DSC diagram.
  • T M ⁇ A To determine the melting temperature (T M ⁇ A)), a tangent is applied to the baseline of the heating run (H), which runs at the temperatures below the melting peak. A second tangent is applied to the first inflection point of the melting peak, which lies at temperatures below the temperature at the maximum of the melting peak. The two tangents are extrapolated to such an extent that they intersect. The vertical extrapolation of the point of intersection onto the temperature axis gives the melting temperature (T M ⁇ A)).
  • the melting temperature (T M (A>) is usually measured during the second heating run (H2). For the sake of clarity, however, only the first heating run (H) is shown in FIG. 1 and the determination of the melting temperature (T M (A>) during this.
  • the crystallization temperature (T kP (A)) corresponds to the temperature at the crystallization peak.
  • Component (A) is preferably partially crystalline. It is therefore preferred that component (A) is at least a partially crystalline polyester.
  • the present invention therefore also relates to a laminate in which component (A) is at least one partially crystalline polyester.
  • Partially crystalline in the context of the present invention means that component (A) has a melting enthalpy DH2 (A) of greater than 20 J / g and preferred of greater than 25 J / g, each measured by means of differential scanning calorimetry (DSC) according to ISO 1 1357- 4: 2014.
  • DSC differential scanning calorimetry
  • Component (A) according to the invention usually has a melting enthalpy DH2 (A) of ⁇ 57 J / g and preferably of ⁇ 55 J / g, in each case measured by means of dynamic differential calorimetry (Differential Scanning Calorimetry; DSC) according to ISO 1 1357-4: 2014 .
  • DSC dynamic differential calorimetry
  • the present invention therefore also relates to a laminate in which component (A) contained in the polymer composition (PZ) is a
  • the melting enthalpy DH2 (A) is a measure of the crystallinity. A crystallinity of 100% corresponds to a melting enthalpy DH2 (A) of 140 J / g, determined by means of differential scanning calorimetry (DSC) according to ISO 1 1357-4: 2014.
  • component (B) contained in the polymer composition (PZ) is at least a second polyester.
  • the at least one second polyester is different from the at least one first polyester.
  • the at least one second polyester is preferably a copolymer.
  • Component (B) is therefore preferably a copolymer.
  • the present invention therefore also relates to a laminate in which component (B) is a copolymer.
  • a “copolymer” is understood to mean a polymer which contains two or more different repeating units.
  • Component (B) is preferably at least one copolymer, obtainable by polymerizing the components
  • (B3) isophthalic acid.
  • the present invention therefore also relates to a laminate in which component (B) at least one copolymer can be obtained by polymerizing the components
  • (B3) includes isophthalic acid.
  • a copolymer obtainable by polymerizing components (B1), (B2) and (B3) is also referred to as a copolyester.
  • Component (B) is therefore preferably a copolyester.
  • At least one diol means both exactly one diol and a mixture of two or more diols.
  • component (B1) and “at least one diol” are used synonymously and therefore have the same meaning.
  • component (B2) and “terephthalic acid” are also used synonymously, as are the terms “component (B3)” and “isophthalic acid”. They therefore also have the same meaning in each case.
  • component (B1) the explanations and preferences described above apply correspondingly to the diol used for the production of component (A).
  • Component (B1) is therefore preferably selected from the group consisting of 1,2-ethanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol and 1,4-cyclohexanediol.
  • Component (B1) is particularly preferably selected from the group consisting of 1,2-ethanediol and 1,4-butanediol.
  • Component (B) is therefore particularly preferably a copolymer of 1,2-ethanediol, terephthalic acid and isophthalic acid and / or of 1,4-butanediol, terephthalic acid and isophthalic acid.
  • Component (B) is usually amorphous or partially crystalline.
  • “amorphous” is understood to mean that component (B) has no melting point in dynamic differential calorimetry (differential scanning calorimetry; DSC), measured in accordance with ISO 11357-4: 2014.
  • No melting point means that the enthalpy of fusion DH2 (B) of component (B) is less than 10 J / g, preferably less than 8 J / g and particularly preferably less than 5 J / g, each measured by means of dynamic differential calorimetry (differential Scanning Calorimetry; DSC) according to ISO 11357-4: 2014.
  • Component (B) according to the invention is preferably partially crystalline.
  • the present invention therefore also relates to a laminate in which the component (B) contained in the polymer composition (PZ) is partially crystalline.
  • Partially crystalline in the context of the present invention means that component (B) has a melting enthalpy DH2 (B) of greater than 20 J / g and preferably greater than 25 J / g, in each case measured by means of dynamic differential calorimetry (differential scanning calorimetry; DSC) according to ISO 1 1357- 4: 2014.
  • DSC dynamic differential calorimetry
  • Component (B) according to the invention usually has a melting enthalpy DH2 (B) in the range from 57 to 140 J / g and preferably in the range from 58 to 100 J / g, in each case measured by means of dynamic differential calorimetry (DSC) in accordance with ISO 1 1357-4: 2014.
  • DSC dynamic differential calorimetry
  • the present invention therefore also relates to a laminate in which the component (B) contained in the polymer composition (PZ) is a
  • the present invention furthermore relates to a laminate in which component (A) contained in the polymer composition (PZ) is a
  • Component (B) usually has a melting temperature (T M ⁇ B) ).
  • the melting temperature (T M (B) ) of component (B) is, for example, in the range from> 240 to 300 ° C, preferably in the range from 245 to 290 ° C and particularly preferably in the range from 250 to 280 ° C, determined according to ISO 11357-3: 2014.
  • the present invention therefore also relates to a laminate in which the component (B) contained in the polymer composition (PZ) has a melting temperature (T M ⁇ B)) which is in the range from> 240 to 300 ° C.
  • Component (B) usually has a crystallization temperature (T kP (B)).
  • the crystallization temperature (T kP (B)) of component (B) is, for example, in the range from 0 to 175 ° C., preferably in the range from 50 to 170 ° C. and particularly preferably in the range from 100 to 165 ° C., determined by means of dynamic differential calorimetry (DDK; differential scanning calorimetry, DSC) as described above for the crystallization temperature (T kP (A)) of component (A).
  • DDK dynamic differential calorimetry
  • the polymer composition (PZ) contains at least one rubber as component (C).
  • a “rubber” is also referred to as an “impact-modified polymer” or as a “rubber-elastic polymer” or as an “elastomer”. These terms are therefore used synonymously in the context of the present invention and therefore have the same meaning.
  • Component (C) is preferably at least one polymer based on olefins.
  • the present invention therefore also relates to a laminate in which component (C) is at least one polymer based on olefins.
  • Component (C) is furthermore preferably not an olefin homopolymer.
  • component (C) is preferably at least one polymer based on two or more olefins. “Based on two or more olefins” means in the context of the present invention that the polymer can be obtained by polymerizing two or more several olefins.
  • the present invention therefore also relates to a laminate in which component (C) is at least one polymer based on two or more olefins.
  • Preferred rubbers are polymers based on olefins, which can be obtained by polymerizing the following components:
  • (C1) in the range from 40 to 100% by weight, preferably in the range from 55 to 79.5% by weight, of at least one ⁇ -olefin having 2 to 8 C atoms, (C2) in the range from 0 to 90% by weight of at least one diene,
  • (C3) in the range from 0 to 45% by weight, preferably in the range from 20 to 40% by weight, of at least one C-
  • (C4) in the range from 0 to 40% by weight, preferably in the range from 0.5 to 20% by weight, of at least one ethylenically unsaturated monocarboxylic acid and / or an ethylenically unsaturated dicarboxylic acid or a derivative of at least one ethylenically unsaturated monocarboxylic acid and / or an ethylenically unsaturated dicarboxylic acid,
  • component (C6) in the range from 0 to 5% by weight of other radically polymerizable monomers, with the proviso that component (C) is not an olefin homopolymer, the% by weight in each case being based on the sum of the% by weight of the Components (C1), (C2), (C3), (C4), (C5) and (C6).
  • The% by weight of components (C1), (C2), (C3), (C4), (C5) and (C6) relate to the% by weight of components (C1), (C2), (C3 ), (C4), (C5) and (C6) before they reacted with each other. It goes without saying that during the reaction of the components (C1), (C2), (C3), (C4), (C5) and (C6) with one another, the% by weight may change.
  • components (C1), (C2), (C3), (C4), (C5) and (C6) are each different from one another.
  • component (C3) is different from component (C4).
  • Rubbers obtainable by polymerizing components (C1), (C2), (C3), (C4), (C5) and (C6) are also referred to in the context of the present invention as olefin polymers.
  • EPM rubbers So-called ethylene-propylene rubbers (EPM rubbers) and ethylene-propylene-diene rubbers (EPDM rubbers) are preferred as rubbers, each preferably having a ratio of units derived from ethylene to units derived from propylene in the range from 40:60 up to 90:10.
  • EPM rubbers generally have essentially no more double bonds in the polymer chain, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms in the polymer chain.
  • EPDM rubbers can be obtained, for example, by polymerizing components (C1) and (C2).
  • Component (C1) is at least one a-olefin with 2 to 8 carbon atoms. "At least one a-olefin with 2 to 8 carbon atoms” is also used in the context of the present invention as “C 2 -C 8 alkene” or referred to as “C 2 -C 8 alpha olefin”.
  • a C 2 -C 8 -a olefin is understood to mean an unsubstituted or at least monosubstituted hydrocarbon having 2 to 8 carbon atoms and at least one carbon-carbon double bond (CC double bond), at least one carbon-carbon
  • “at least one carbon-carbon double bond” means exactly one carbon-carbon double bond as well as two or more carbon-carbon double bonds. Exactly one carbon-carbon double bond is preferred.
  • C 2 -C 8 a olefin means that the hydrocarbons having 2 to 8 carbon atoms are unsaturated.
  • the hydrocarbons can be branched or unbranched.
  • Examples of C 2 -C 8 -a-olefins with exactly one CC double bond are ethene, propene, 1-butene, 2-methylpropene (isobutylene), 1-pentene, 2-methyl-1-butene, 3-methyl-1 -Butene, 1-hexene and 4-methyl-1-pentene.
  • component (C1) is selected from the group consisting of ethene, propene, 1-butene, 2-methylpropene (isobutylene), 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1- Hexene and 4-methyl-1-pentene.
  • Component (C1) is preferably selected from the group consisting of ethene, propene, 1-butene and 2-methylpropene (isobutylene) and most preferably component (C1) is selected from ethene and propene.
  • Component (C2) is selected, for example, from the group consisting of conjugated dienes, non-conjugated dienes having 5 to 25 carbon atoms, cyclic dienes, alkenylnorbornenes and tricyclodienes.
  • Suitable conjugated dienes are, for example, isoprene or butadiene.
  • Suitable non-conjugated dienes with 5 to 25 carbon atoms are, for example, penta-1,4-diene, hexa-1,4-diene, hexa-1,5-diene, 2,5-dimethylhexa-1,5- dien and octa-1, 4-diene.
  • Suitable cyclic dienes are, for example, cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene.
  • Suitable alkenyl norbornenes are, for example, 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene.
  • Suitable tricyclodienes are, for example, 3-methyl-tricyclo (5.2.1 0.2.6) -3,8-decadiene
  • Component (C2) is preferably selected from the group consisting of hexa- 1, 5-diene, 5-ethylidene-norbornene and dicyclopentadiene.
  • the diene content of the EPDM rubbers is preferably 0.5 to 50% by weight, in particular 2 to 20% by weight and particularly preferably 3 to 15% by weight, based on the total weight of component (C).
  • EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives. Suitable reactive carboxylic acids are, for example, acrylic acid, methacrylic acid and their derivatives and maleic anhydride.
  • MBS rubbers methacrylate / butadiene / styrene rubbers
  • (C7) in the range from 1 to 30% by weight of styrene or substituted styrenes or mixtures thereof and
  • Suitable monomers (C7) are styrenes or substituted styrenes of the general formula I and mixtures of these
  • R is a C to C 8 alkyl radical, preferably methyl or ethyl, or hydrogen and R 1 is a C to C 8 alkyl radical, preferably methyl or ethyl, and n has the value 1, 2 or 3.
  • Another group of preferred olefin polymers are copolymers of a-olefins having 2 to 8 C-atoms, in particular of ethylene with at least one C-
  • Examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, i-butyl methacrylate, i-butyl methacrylate, i-butyl methacrylate, i-butyl methacrylate, i-butyl methacrylate, i-butyl methacrylate , Octyl methacrylates, decyl methacrylates.
  • Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and decyl acrylate are preferred.
  • N-Butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • the proportion of methacrylic acid esters and acrylic acid esters (C3) in the olefin polymers is, for example, in the range from 0 to 60% by weight, preferably in the range from 10 to 50% by weight and particularly preferably in the range from 30 to 45% by weight, in each case based on the sum of the% by weight of components (C1) to (C6).
  • component (C4) examples include dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids and their monoesters.
  • Component (C4) is preferably a latent acid-functional monomer.
  • Latent acid-functional monomers are to be understood as compounds which form free acid groups during the polymerization and / or when component (C) is incorporated into the polymer composition (PZ). Examples of this are anhydrides of dicarboxylic acids with up to 20 carbon atoms, in particular maleic anhydride.
  • R 1 , R 2 , R 3 , R 4 independently of one another are hydrogen or alkyl groups having 1 to 6
  • Component (C4) is therefore preferably selected from the group consisting of maleic acid, fumaric acid and maleic anhydride.
  • component (C5) is selected from the group consisting of compounds of the general formulas IV and V:
  • R 5 , R 6 , R 7 , R 8 , R 9 independently of one another are hydrogen or alkyl groups with 1 to
  • n is an integer from 0 to 20 and
  • n is an integer from 0 to 10.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently hydrogen, m 0 or 1 and n 1.
  • Preferred compounds of the formulas IV and V are epoxy group-containing esters of acrylic acid and / or methacrylic acid, glycidyl acrylate and glycidyl methacrylate being particularly preferred.
  • Component (C5) is preferably selected from the group consisting of alkenyl glycidyl ether and vinyl glycidyl ether.
  • the proportion of components (C4) or (C5) is in each case preferably 0.07 to 40% by weight, in particular 0.1 to 20% by weight and particularly preferably 0.15 to 15% by weight, based on the total weight of components (C1) to (C6).
  • component (C) are olefin polymers obtainable by polymerizing
  • component (C6) for example vinyl esters and vinyl ethers come into consideration.
  • the olefin polymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.
  • the melt index of the olefin polymers is generally in the range from 1 to 80 g / 10 min (measured at 190 ° C. and 2.16 kg load).
  • component (C) are acrylate rubbers composed of: a) 70 to 90% by weight and preferably 75 to 85% by weight of a crosslinked elastomeric core, which is composed of:
  • the alkyl group has 1 to 8 carbon atoms, the alkyl acrylate in a molar
  • n-alkyl acrylates which can be used to form copolymers 1) and / or 2) can be the same or different.
  • Suitable n-alkyl acrylates for forming the copolymer 1) are, for example, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate and n-octyl acrylate. n-Octyl acrylate is preferred.
  • n-alkyl acrylates which can be used according to the invention to form the copolymer 2) are, for example, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate and n-octyl acrylate.
  • n-Octyl acrylate is preferred.
  • n-alkyl acrylates and in particular n-octyl acrylate are preferably used for the production of copolymers 1) and 2).
  • Suitable mixtures of alkyl acrylates contain, for example, at least two compounds selected from the group consisting of ethyl acrylate, n-propyl acrylate, n-butyl acrylate, amyl acrylate, 2-methylbutyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-dyl acrylate and 3,5,5-trimethylhexyl acrylate.
  • n alkyl acrylate is used, for example, in a proportion by weight of at least 10% by weight of the mixture of alkyl acrylates, this amount preferably being in the range from 20 to 80% by weight .-% lies. If a mixture of alkyl acrylates is used to form copolymers 1) and / or 2), 20 to 80% by weight of n-octyl acrylate and preferably 80 to 20% by weight of n-butyl acrylate are preferably used.
  • alkyl methacrylates which can be used to form the shell grafted onto the crosslinked elastomeric core according to the present invention are, for example, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate; n-butyl methacrylate, isobutyl acrylate and methyl methacrylate. Methyl methacrylate is particularly preferred.
  • the crosslinking agent used to form the copolymer 1) can in particular be selected from the derivatives which have at least two vinyl-type double bonds or one or more vinyl-type double bonds and at least one allyl-type double bond.
  • Compounds are preferably used which mainly contain double bonds of the vinyl type in their molecules.
  • crosslinking agents which can be used are divinylbenzenes, (meth) acrylates of polyalcohols, such as, for example, trimethylolpropane triacrylate,
  • the grafting agent used to prepare the copolymer 2) can be selected in particular from the derivatives which contain at least two double bonds of the allyl type or one or more double bonds of the allyl type and at least one double bond of the vinyl type.
  • grafting agents are, for example, diallyl maleate, diallyl itaconate, allyl acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate and triallyl trimesate.
  • Component (C) usually has a glass transition temperature (T G (C)) which is below 0 ° C.
  • T G (C) glass transition temperature
  • the glass transition temperature (T G (C)) of component (C) is in the range from -150 to 0 ° C and preferably in the range from -60 to -30 ° C, determined in accordance with ISO 1 1357-2: 2014.
  • the present invention therefore also relates to a laminate in which component (C) has a glass transition temperature (T G (C)) which is below 0 ° C.
  • the glass transition temperature (T G (C)) of the component (C) refers according to the ISO 11357-2: 2014 in the context of the present invention to the glass transition temperature (T G (C)) of the dry component (C).
  • dry means that component (C) contains less than 1% by weight, preferably less than 0.5% by weight and particularly preferably less than 0.1% by weight, of water on the total weight of component (C). More preferably, “dry” means that component (C) does not contain water, and most preferably that component (C) contains no solvent.
  • the laminate according to the invention can be produced by all methods known to the person skilled in the art.
  • the laminate is preferably produced in a continuous process.
  • the laminate according to the invention is preferably produced in a process comprising the following steps: a) Providing a film of a polymer composition (PZ), the components
  • (C) contains at least one rubber, b) heating a first plate made of at least one first metal,
  • step c) pressing the heated first plate from step b) with the film provided in step a) to obtain the laminate.
  • the present invention therefore also relates to a method for producing a laminate according to the invention, comprising the steps a) providing a film made of a polymer composition (PZ) which contains the components
  • (C) contains at least one rubber, b) heating a first plate made of at least a first metal, c) pressing the heated first plate from step b) with the film provided in step a) to obtain the laminate.
  • step a) a film made of the polymer composition (PZ) is provided.
  • the film provided in step a) consists of the polymer composition (PZ).
  • Methods for providing a film from a polymer composition (PZ) are known per se to those skilled in the art.
  • the film is preferably provided in step a) by an extrusion process.
  • the present invention therefore also relates to a process in which the film in step a) is provided by an extrusion process.
  • Suitable extrusion processes for providing the film from the polymer composition (PZ) are known to the person skilled in the art and for example casting processes, calendering processes, blowing processes or multi-blowing processes.
  • the film made of the polymer composition (PZ) provided in step a) can have any thickness.
  • the film made of the polymer composition (PC) provided in step a) usually has a thickness in the range from 1 to 20% greater than the at least one further layer of the laminate to be produced, preferably in the range from 2 to 15% greater than the at least one further layer of the laminate to be produced and particularly preferably in the range from 4 to 10% larger than the at least one further layer of the laminate to be produced.
  • a first plate made of at least one first metal is heated.
  • the first plate consists of the at least first metal.
  • the explanations and preferences described above apply correspondingly for the first metal contained in the laminate.
  • the first plate can be heated by all methods known to the person skilled in the art, preferably the first plate is inductively heated in step b).
  • the present invention therefore also relates to a method in which the first plate is heated inductively in step b).
  • the first plate can be heated to any temperature in step b).
  • the first plate is preferably heated to a temperature which is above the melting temperature (T M ⁇ PZ)) and below the decomposition temperature of the polymer composition (PZ).
  • the first plate is preferably heated in step b) to a temperature in the range from 150 to 350 ° C., particularly preferably in the range from 210 to 280 ° C. and particularly preferably in the range from 220 to 250 ° C.
  • the present invention therefore also relates to a process in which the first plate is heated to a temperature in the range from 150 to 350 ° C. in step b).
  • step c) the heated first plate from step b) is pressed with the film provided in step a) to obtain the laminate.
  • the film connects to the first plate.
  • the thickness of the film can decrease.
  • Steps b) and c) can be carried out simultaneously or in succession. Steps b) and c) are preferably carried out simultaneously. The first plate is then heated while it is pressed with the film provided in step a).
  • the laminate obtained in step c) is usually cooled.
  • the cooling can be carried out by all methods known to the person skilled in the art, for example by blowing compressed air onto the laminate.
  • the laminate is preferably cooled while the pressure of the pressing is maintained.
  • the heated first plate is the at least one first layer of at least one first metal and the film is the at least one further layer of the polymer composition (PZ).
  • an additional step b1) is carried out, in which a second plate made of at least a second metal is heated.
  • a second plate made of at least a second metal is heated.
  • step c) the heated first plate is then pressed with the heated second plate from step b1), while the film provided in step a) is between the two plates.
  • the method for producing the laminate according to the invention then usually comprises the following steps: a) providing a film made of a polymer composition (PZ) which contains the components
  • the present invention therefore also relates to a method for producing a laminate according to the invention, which additionally comprises at least one second layer of at least one second metal and in which the at least one first layer is connected to the at least one second layer via the at least one further layer the steps: a) providing a film of a polymer composition (PZ), the components
  • (C) contains at least one rubber, b) heating a first plate made of at least a first metal, b1) heating a second plate made of at least a second metal, c) positioning the film provided in step a) between the first heated in step b) Plate and the second plate heated in step b1), and pressing the first plate heated in step b) and the second plate heated in step b1) with the film provided in step a) to obtain the laminate.
  • the statements and preferences described above apply to the optionally at least one second metal contained in the laminate corresponds to the at least one second layer.
  • step c) in which the second plate is additionally positioned, the explanations and preferences for step c) described above also apply accordingly.
  • P1 polybutylene terephthalate, PBT (Ultradur 6550 from BASF SE)
  • 2P1 polyethylene terephthalate copolymer
  • PET Polyclear 1 101 from Invista
  • 2P2 Polyethylene terephthalate copolymer, PET (Xpure Polyester 7090 from Invista) rubber
  • the polymers listed in Table 1 were compounded in the amounts shown in Table 1 using a Haake PolyLab QC with extruder CTW 100 at 280 ° C. and extruded through a slot film die with a width of 100 mm.
  • the strand obtained was processed and wound up on a water-cooled 20 cm wide roller to form a film at least 5 mm wide and 420 ⁇ m thick.
  • the amounts given in Table 1 are each in% by weight.
  • the films of the polymer composition (PZ) and the first plate and the second plate of the steel were dried for 7 days at 80 ° C. and a pressure of ⁇ 5 mbar before the production of the laminates.
  • a first plate of the steel and a second plate of the steel were placed in a device.
  • a film of the polymer composition was placed between the first plate and the second plate.
  • the plates are pressed with a hydraulic press for 60 seconds at 250 ° C and 30 bar.
  • the laminate obtained is removed hot from the press and covered with a steel sheet (40x40 mm, 5 mm thick).
  • the laminates are stored in air with ⁇ 1% relative humidity.
  • the test specimens are measured in a lasting machine (Zwicki BT1-FR 5.0 TN with pneumatic jaws) in accordance with DIN 11339, the measuring speed being 200 mm / min and the thickness of the test specimens being 0.75-0.95 mm.
  • the modulus of elasticity was determined according to ISO 527-1: 2012. The results are shown in Table 2.
  • the tensile strength was determined according to ISO 527-1: 2012. The results are shown in Table 2.
  • the laminates according to the invention have an improved peel value compared to laminates which contain only one polyester or a mixture of two polyesters and no rubber in the polymer composition.
  • the laminates according to the invention also have a particularly low modulus of elasticity and good tensile strength.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un stratifié comprenant au moins une première couche d'au moins un premier métal et au moins une autre couche d'une composition polymère (PZ), ainsi qu'un procédé de fabrication du stratifié selon l'invention.
PCT/EP2019/074258 2018-09-14 2019-09-11 Stratifiés contenant une couche de métal et une couche de polyester WO2020053294A1 (fr)

Applications Claiming Priority (2)

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EP18194534 2018-09-14
EP18194534.6 2018-09-14

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WO2020053294A1 true WO2020053294A1 (fr) 2020-03-19

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19929301A1 (de) * 1999-06-25 2000-12-28 Basf Ag Aus mit Epoxypolymeren vorbehandelten glasfaserverstärkten Formteilen geschweißte Verbunde
WO2005014278A1 (fr) 2003-08-07 2005-02-17 Usinor Stratifie metal-polyamide/polyethylene-metal
US20110200816A1 (en) 2010-02-15 2011-08-18 Productive Research Llc Formable light weight composite material systems and methods
DE102011084519A1 (de) 2011-10-14 2013-04-18 Evonik Industries Ag Verwendung einer Mehrschichtfolie für die Herstellung photovoltaischer Module

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19929301A1 (de) * 1999-06-25 2000-12-28 Basf Ag Aus mit Epoxypolymeren vorbehandelten glasfaserverstärkten Formteilen geschweißte Verbunde
WO2005014278A1 (fr) 2003-08-07 2005-02-17 Usinor Stratifie metal-polyamide/polyethylene-metal
US20110200816A1 (en) 2010-02-15 2011-08-18 Productive Research Llc Formable light weight composite material systems and methods
DE102011084519A1 (de) 2011-10-14 2013-04-18 Evonik Industries Ag Verwendung einer Mehrschichtfolie für die Herstellung photovoltaischer Module

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