WO2020053294A1

WO2020053294A1 - Laminates containing a metal layer and a polyester layer

Info

Publication number: WO2020053294A1
Application number: PCT/EP2019/074258
Authority: WO
Inventors: Philippe Desbois; Jasmina SIMON
Original assignee: Basf Se; Thyssenkrupp Steel Europe Ag
Priority date: 2018-09-14
Filing date: 2019-09-11
Publication date: 2020-03-19

Abstract

The present invention relates to a laminate which comprises at least one first layer of at least one first metal and at least one additional layer of a polymer composition (PZ). The present invention further relates to a method for producing the laminate according to the invention.

Description

Laminates containing a metal layer and a polyester layer

description

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.

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. In addition, 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. In addition, 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. In particular, 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,

(B) at least one second polyester,

(C) contains at least one rubber.

It was surprisingly found that the laminates according to the invention have a particularly good peeling behavior and a good modulus of elasticity.

The present invention is explained in more detail below.

Laminate

According to the invention, 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).

In the context of the present invention, “at least one first layer” means exactly one first layer as well as two or more first layers. In the context of the present invention, “at least one first metal” means exactly one first metal as well as a mixture of two or more first metals.

In the context of the present invention, “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). In such a laminate, 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. In other words, 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. In other words, 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. In the context of the present invention, “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.

If 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.

For the at least one second metal of the at least one second layer, 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). In other words, this means that the at least one further layer consists of the polymer composition (PZ).

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.

Polymer composition (PZ)

According to the invention, 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.

In the context of the present invention, “at least one first polyester” means both exactly one first polyester and also a mixture (blend) of two or more first polyesters.

In the context of the present invention, “at least one second polyester” means exactly one second polyester and also a mixture (blend) of two or more second polyesters.

In the context of the present invention, “at least one rubber” means both exactly one rubber and a mixture (blend) of two or more rubbers.

In the context of the present invention, the terms “component (A)” and “at least one first polyester” are used synonymously and therefore have the same meaning. Likewise, in the context of the present invention, the terms “component (B)” and “at least a second polyester” are used synonymously and have the same meaning. The same applies to the terms “component (C)” and “at least one rubber”. These terms are also used synonymously in the context of the present invention and therefore have the same meaning.

It is clear to the person skilled in the art that 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. For example, 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. It is clear to the person skilled in the art that components (A), (B) and (C) are present in the polymer composition (PZ) as a mixture (blend). In the production of the polymer composition (PZ), 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.

In the context of the present invention, “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.

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.

In addition, the polymer composition (PZ) can additionally contain at least one filler.

In the context of the present invention, “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. For example, 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. In the context of the present invention, 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.

In the context of the present invention, “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.

For example, 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.

For example, 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

Polymer composition (PZ).

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

Polymer composition (PZ).

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 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, usually gives 100% by weight.

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. For example, 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,

Antioxidants, light stabilizers, PVC stabilizers, lubricants,

Flame retardants, blowing agents, impact modifiers, adhesion promoters,

Coupling agents and nucleation aids.

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,

Antioxidants, light stabilizers, PVC stabilizers, lubricants,

Flame retardants, blowing agents, impact modifiers, adhesion promoters,

Contains coupling agents and nucleation aids.

These additives are known per se to the person skilled in the art. Coupling agents are also referred to as crosslinking agents. Within the framework of the The present invention understood 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.

In addition, 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.

To determine the melting temperature (T _M <PZ ₎ ) 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.

To determine the enthalpy of fusion DH2 _(RZ) according to ISO 1 1357-4: 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 an enthalpy of fusion DH2 _(RZ) in the range from 10 to 60 J / g.

Component (A)

According to the invention, 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.

All dicarboxylic acids known to the person skilled in the art are suitable as at least one dicarboxylic acid. For example, 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.

In the context of the present 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.

For example, 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).

In the context of the present invention, 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.

Suitable 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. In the context of the present invention, 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).

For example, 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.

In the context of the present invention, 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.

It is clear to the person skilled in the art that the 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).

In dynamic differential calorimetry, the temperature of a sample, in this case a sample of component (A), and the temperature of a reference are changed linearly with time. For this purpose, 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.

If the sample undergoes an endothermic phase change, an additional amount of heat Q must be added in order to keep the sample at the same temperature as the reference. If an exothermic phase change takes place, a quantity of heat Q must be dissipated in order to keep the sample at the same temperature as the reference. 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.

Usually a heating run (H) is carried out during the measurement, i.e. the sample and the reference are heated linearly. During the melting of the sample (phase change solid / liquid), an additional amount of heat Q supplied to keep the sample at the same temperature as the reference. A peak is then observed in the DSC diagram, the so-called melting peak.

Following the heating run (H), 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. During the crystallization or solidification of the sample (phase change liquid / solid), 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.

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.

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 .

The present invention therefore also relates to a laminate in which component (A) contained in the polymer composition (PZ) is a

Enthalpy of fusion DH2 _(A) of <57 J / g.

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)

According to the invention, 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.

In the context of the present invention, 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

(B1) at least one diol,

(B2) terephthalic acid and

(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

(B1) at least one diol,

(B2) terephthalic acid and

(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.

In the context of the present invention, “at least one diol” means both exactly one diol and a mixture of two or more diols.

In the context of the present invention, the terms “component (B1)” and “at least one diol” are used synonymously and therefore have the same meaning. The terms “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.

For 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. In the context of the present invention, “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.

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.

The present invention therefore also relates to a laminate in which the component (B) contained in the polymer composition (PZ) is a

Enthalpy of fusion DH2 _(B) in the range of 57 to 140 J / g.

The present invention furthermore relates to a laminate in which component (A) contained in the polymer composition (PZ) is a

Enthalpy of fusion DH2 _(A) of <57 J / g and / or the component (B) contained in the polymer composition (PZ)

Enthalpy of fusion DH2 _(B) in the range of 57 to 140 J / g.

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).

Component (C)

According to the invention, the polymer composition (PZ) contains at least one rubber as component (C).

In the context of the present invention, 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. In other words, 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 α-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- _| -C ₁₈ alkyl esters of acrylic acid or methacrylic acid,

(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,

(C5) in the range from 0 to 40% by weight of at least one monomer containing epoxy groups,

(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.

It goes without saying that the components (C1), (C2), (C3), (C4), (C5) and (C6) are each different from one another. In particular, 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.

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".

In the context of the present invention, 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 In the context of the present invention, “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.

In other words, 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.

For example, 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.

Further preferred components (C) are, for example, MBS rubbers (methacrylate / butadiene / styrene rubbers) composed of:

65 to 99% by weight of a core obtainable by polymerizing

(C2) in the range from 90 to 100% by weight of at least one diene and 0 to 10% by weight of further crosslinkable monomers and

1 to 35% by weight of a shell obtainable by polymerizing

(C7) in the range from 1 to 30% by weight of styrene or substituted styrenes or mixtures thereof and

(C8) in the range from 70 to 100% by weight of at least one unsaturated nitrile.

Suitable monomers (C7) are styrenes or substituted styrenes of the general formula I and mixtures of these

wherein 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- _| -C ₁₈ - alkyl ester of acrylic acid or methacrylic acid (component (C3)).

Basically, all primary, secondary and tertiary CrCi ₈ alkyl esters of acrylic acid or methacrylic acid are suitable. C- _| are preferred -C ₁₂ alkyl esters, particularly preferred are C ₂ -Ci ₀ alkyl esters. 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 , 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).

Examples of component (C4) are 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.

For example, component (C4) is selected from the group consisting of compounds of the general formulas II and III: R ¹ (R ² OOC) C = C (COOR ³ ) R ⁴ II

in which

R ¹ , R ² , R ³ , R ⁴ independently of one another are hydrogen or alkyl groups having 1 to 6

Represent carbon atoms.

Component (C4) is therefore preferably selected from the group consisting of maleic acid, fumaric acid and maleic anhydride.

For example, component (C5) is selected from the group consisting of compounds of the general formulas IV and V:

, in which

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ independently of one another are hydrogen or alkyl groups with 1 to

6 represent carbon atoms;

m 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).

Particularly preferred as component (C) are olefin polymers obtainable by polymerizing

50 to 98.9% by weight, in particular 55 to 65% by weight, of ethylene,

0.1 to 20% by weight, in particular 0.15 to 10% by weight, of glycidyl acrylate and / or glycidyl methacrylate, acrylic acid and / or maleic anhydride,

1 to 45 wt .-%, in particular 25 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate, and

0 to 10% by weight, in particular 0.1 to 3% by weight, of maleic anhydride or fumaric acid or mixtures thereof, the% by weight being based in each case on the sum of the% by weight of the components used for the polymerization.

As 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).

Also preferred as 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:

1) 20 to 90% by weight of a core which can be obtained from a copolymer by polymerizing an n-alkyl acrylate whose alkyl group has 5 to 12 carbon atoms, preferably 5 to 8 carbon atoms, or a mixture of alkyl acrylates whose alkyl groups have 2 to 12 Have carbon atoms, preferably 4 to 8 carbon atoms; a polyfunctional crosslinking agent with at least one CC double bond, at least one of the CC double bonds being a vinyl group (CH ₂ = C group), and optionally a polyfunctional grafting agent with at least one CC double bond, at least one of the CC double bonds is an allyl group (CH ₂ = CH-CH ₂ group), the core consisting of a molar amount of the polyfunctional crosslinking agent and optionally the polyfunctional grafting agent of 0.05 to 5 mol% and preferably in an amount of 0.5 to 1 , 5 mol% based on the total amount of the core; 2) 80 to 10% by weight of a shell which can be obtained from a copolymer by polymerizing an n-alkyl acrylate whose alkyl group has 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms, or a mixture of alkyl acrylates whose alkyl groups has 2 to 12 carbon atoms , preferably having 4 to 8 carbon atoms; and a polyfunctional grafting agent with at least one CC double bond, at least one of the CC double bonds being an allyl group (CH ₂ = CH-CH ₂ group), the shell of the grafting agent in a molar amount of 0.05 to 2, 5 mol% and preferably in an amount of 0.5 to 1.5 mol% each based on the total amount of the shell, and b) 30 to 10% by weight, preferably 25 to 15% by weight, of one the core-grafted shell, which consists of an alkyl methacrylate polymer, the alkyl group of which has 1 to 4 carbon atoms, or of a random copolymer of an alkyl methacrylate, the alkyl group of 1 to 4

Has carbon atoms, and an alkyl acrylate, the alkyl group has 1 to 8 carbon atoms, the alkyl acrylate in a molar

Amount of 5 to 40 mol% and preferably contained in the range of 10 to 20 mol%, based on the total amount of the random copolymer.

The 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.

Examples of 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. According to the present invention, 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.

If a mixture of alkyl acrylates is used to form copolymers 1) and / or 2), 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.

Examples of 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.

According to the present invention, 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.

Examples of crosslinking agents which can be used are divinylbenzenes, (meth) acrylates of polyalcohols, such as, for example, trimethylolpropane triacrylate,

Trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, diacrylates or methacrylates of alkylene glycols with 2 to 10 carbon atoms in the alkylene chain and in particular ethylene glycol diacrylate, ethylene glycol dimethacrylate, butane-1, 4-diol diacrylate, butane-1, 4-dimethacrylate, hexane, hexane, hexane, hexane -1, 6- dimethacrylate, the diacrylate or dimethacrylate of polyoxyalkylene glycol of the general formula VI are used:

where X is hydrogen or methyl, n is an integer from 2 to 4 and p is an integer from 2 to 20. The diacrylate or dimethacrylate is particularly preferred over polyoxyethylene glycol, in which the polyoxyethylene group has a molecular weight of about 400 (n = 2 and p = 9 in the general formula VI). According to the present invention, 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.

Compounds are preferably used which mainly contain double bonds of the allyl type in their molecules.

Examples of such 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. For example, 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).

In the context of the present invention, “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.

Manufacturing

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

(A) at least one first polyester,

(B) at least one second polyester,

(C) contains at least one rubber, b) heating a first plate made of at least one first metal,

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

(A) at least one first polyester,

(B) at least one second polyester,

(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.

For the polymer composition (PZ) in the process according to the invention, the explanations and preferences described above apply correspondingly to the polymer composition (PZ) of the laminate according to the invention. The above-described explanations and preferences for components (A), (B) and (C) of the laminate also apply accordingly to components (A), (B) and (C).

In 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.

In step b), a first plate made of at least one first metal is heated. The first plate consists of the at least first metal. For the at least one 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). 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).

In 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.

Methods for pressing the heated first plate from step b) with the film provided in step a) in step c) are known per se to the person skilled in the art.

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.

In the laminate obtained, 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).

In the event that the laminate is to contain at least a second layer, an additional step b1) is carried out, in which a second plate made of at least a second metal is heated. For the heating of the second plate in step b1), the explanations and preferences described above for heating the first plate in step b) apply accordingly.

In 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

(A) at least one first polyester,

(B) at least a second polyester and (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 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

(A) at least one first polyester,

(B) at least a second polyester and

(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.

For the at least one second metal of the second plate in the method according to the invention, 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.

For the second plate and the heating of the second plate, the explanations and preferences described above for the first plate and the heating of the first plate apply accordingly.

For step c), in which the second plate is additionally positioned, the explanations and preferences for step c) described above also apply accordingly.

The present invention is explained in more detail below with the aid of examples, without restricting it thereto.

Examples

The following components were used: First polyester

1 P1: polybutylene terephthalate, PBT (Ultradur 6550 from BASF SE)

Second polyester

2P1: polyethylene terephthalate copolymer, PET (Polyclear 1 101 from Invista)

2P2: Polyethylene terephthalate copolymer, PET (Xpure Polyester 7090 from Invista) rubber

K1: Elvaloy AC 34035 (ethylene-butyl acrylate-MSA copolymer with 35% by weight of butyl acrylate based on the total weight of the copolymer)

K2: Lotader AX 8900 (ethylene-acrylic acid ester-glycidyl methacrylate copolymer with 24% by weight acrylic acid ester and 8% glycidyl methacrylate, based on the total weight of the copolymer) first and second metal

steel 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 μm thick. The amounts given in Table 1 are each in% by weight.

DSC measurements were carried out on the granules of the polymer compositions given in Table 1 as described above. The crystallization temperature (T _Kp ) was determined during the first cooling run. The melting temperature (T _M ) and the enthalpy of crystallization (DH2) were each determined in the second heating run. The determination was made in accordance with ISO 1 1357: 2014 with a heating rate and a cooling rate of 20 K / min. Table 1

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.

To produce the laminate, 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. For cooling, the laminate obtained is removed hot from the press and covered with a steel sheet (40x40 mm, 5 mm thick). After cooling, 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.

From the tensile force in Newtons (N) determined from the 100 mm measuring section, the mean value is calculated over the entire measurement and corrected to 40 mm width. The results (T-Peel) for the different laminates can be seen in Table 2.

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.

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.

Claims

Expectations

1. Laminate comprising at least a first layer of at least a first metal and at least one further layer of a polymer composition (PZ), characterized in that the polymer composition (PZ) the components

(A) at least one first polyester,

(B) at least one second polyester,

(C) contains at least one rubber.

2. Laminate according to claim 1, characterized in that the laminate additionally comprises at least one second layer of at least one second metal and that the at least one first layer is connected to the at least one second layer via the at least one further layer.

3. Laminate according to claim 1 or 2, characterized in that the polymer composition (PZ) in the range of 2 to 40 wt .-% of component (C), based on the sum of the weight percentages of components (A), (B) and (C).

4. Laminate according to one of claims 1 to 3, characterized in that 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.

5. Laminate according to one of claims 1 to 4, characterized in that component (B) is a copolymer.

6. Laminate according to one of claims 1 to 5, characterized in that the component (A) contained in the polymer composition (PZ) has a melting enthalpy DH2 _(A) of <57 J / g and / or that contained in the polymer composition (PZ) Component (B) has a melting enthalpy DH2 _(B) in the range from 57 to 140 J / g.

7. Laminate according to one of claims 1 to 6, characterized in that component (A) is selected from the group consisting of polyethylene terephthalate and polybutylene terephthalate.

8. Laminate according to one of claims 1 to 7, characterized in that component (B) at least one copolymer obtainable by polymerizing components (B1) at least one diol,

(B2) terephthalic acid and

(B3) includes isophthalic acid.

9. Laminate according to one of claims 1 to 8, characterized in that the at least one first metal is selected from the group consisting of iron, aluminum, copper, nickel and magnesium and alloys thereof.

10. Laminate according to one of claims 1 to 9, characterized in that the at least one first layer has a thickness in the range from 0.1 mm to 0.6 mm and / or in that the at least one further layer has a thickness in the range from 0 , 02 to 1.5 mm.

11. Laminate according to one of claims 1 to 10, characterized in that component (C) has a glass transition temperature (T _G (C)) which is below 0 ° C.

12. Laminate according to one of claims 1 to 11, characterized in that component (C) is at least one polymer based on olefins.

13. A method for producing a laminate according to any one of claims 1 to 12, comprising the steps a) providing a film made of a polymer composition (PZ) which the

Components

(A) at least one first polyester,

(B) at least one second polyester,

14. The method according to claim 13, characterized in that the first plate in step b) is heated to a temperature in the range of 150 to 350 ° C.

15. The method according to claim 13 or 14, characterized in that the film is provided in step a) by an extrusion process.