WO2023110961A1

WO2023110961A1 - At least partially biobased layered structure with good favourable properties

Info

Publication number: WO2023110961A1
Application number: PCT/EP2022/085751
Authority: WO
Inventors: Theivanayagam Deivaraj; Norbert HERMANNS; Roland Kuenzel; Dirk Pophusen; Holger SCHMEER; Heinz Pudleiner; Wieland Hovestadt
Original assignee: Covestro Deutschland Ag
Priority date: 2021-12-17
Filing date: 2022-12-14
Publication date: 2023-06-22

Abstract

The invention is related to a layered structure (S), providing a first surface (S1) and a second surface (S2) opposite to the first surface (S1), the layered structure (S) comprising: (a) at least one first polymer (a), preferably a poly-condensate or a co-poly-condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (a) comprises a diol component (D) which comprises isosorbide in an amount of at least 48 wt.-%, preferably in a range of from 48 to 80 wt.-%, based on the total weight of the diol component (D); (b) at least one second polymer (b), preferably a poly-condensate or a co-poly-condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (b) comprises a diol component (D1) which comprises isosorbide in an amount of ≤ 30 wt.-%, more preferably ≤ 10 wt.-%, especially preferably ≤ 5 wt.-%, based on the total weight of the diol component (D1); wherein polymer (a) builds at least 80 %, preferably 90 %, more preferably 100 % of the first surface (S1), based on the total surface of the first surface (S1), and polymer (b) builds at least 80 %, preferably 90 %, more preferably 100 % of the second surface (S1), based on the total surface of the first surface (S1) as well as the production process of such layered structure (S) and its uses.

Description

At least partially biobased layered structure with good favourable properties

The invention is related to a layered structure (S), providing a first surface (SI) and a second surface (S2) opposite to the first surface (SI), the layered structure (S) comprising at least one first polymer (a), preferably a poly-condensate or a co-poly-condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (a) comprises a diol component (D) which comprises isosorbide in an amount of at least 48 wt.-%, preferably in a range of from 48 to 80 wt.-%, based on the total weight of the diol component (D); at least one second polymer (b), preferably a poly-condensate or a co-poly- condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (b) comprises a diol component (DI) which comprises isosorbide in an amount of < 30 wt.-%, more preferably < 10 wt.-%, especially preferably < 5 wt.-%, based on the total weight of the diol component (DI); wherein polymer (a) builds at least 80 %, preferably 90 %, more preferably 100 % of the first surface (SI), based on the total surface of the first surface (SI), and polymer (b) builds at least 80 %, preferably 90 %, more preferably 100 % of the second surface (SI), based on the total surface of the first surface (SI). Also, the production process and the use of the layered structure (S) according to the invention is related to the invention.

Polymeric layered structures are used in many application fields. As sustainability combined with good chemical resistance of polymeric materials becomes more and more a prerequisite for their applicability, there exists a need for polymeric structures which are not petro-based but are not less chemically resistant. However, known biobased materials, for example those described in US2010/0190953A1, often fail the requirement of different applications of polymers for example if they are applied in automobiles, where there are high requirements for high chemical and crack resistance, high toughness and compatibility with other materials. Therefore, it exists a need of biobased materials that provide these requirements.

One object of the invention was to diminish at least one disadvantage of the prior art at least partially. A further object of the invention was to provide polymeric layered structures which are at least partly based on biobased material, but have a good crack resistance, toughness and can be processed easily with a variety of other materials.

A first aspect of the invention refers to a layered structure (S), providing a first surface (SI) and a second surface (S2) opposite to the first surface (SI), the layered structure (S) comprising:

(a) at least one first polymer (a), preferably a poly-condensate or a co-poly-condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (a) comprises a diol component (D) which comprises isosorbide in an amount of at least 48 wt.-%, preferably in a range of from 48 to 80 wt.-%, based on the total weight of the diol component (D); (b) at least one second polymer (b), preferably a poly-condensate or a co-poly-condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (b) comprises a diol component (DI) which comprises isosorbide in an amount of < 30 wt.-%, more preferably < 10 wt.-%, especially preferably < 5 wt.-%, based on the total weight of the diol component (DI); wherein polymer (a) builds at least 80 %, preferably 90 %, more preferably 100 % of the first surface (SI), based on the total surface of the first surface (S 1), and polymer (b) builds at least 80 %, preferably 90 %, more preferably 100 % of the second surface (SI), based on the total surface of the first surface (SI).

The layered structure (S) is preferably a flat structure, preferably having a length in a range of from 10 mm to 2000 m, more preferably of from 50 mm to 500 m, even more preferably of from 100 mm to 100 m, especially preferably of from 0.3 m to 1.5 m and a width in a range of from 10 mm to 10 m, more preferably of from 50 mm to 5 m, most preferably of from 100 mm to 2 m. The layered structure (S) preferably has an aspect ratio of length or width to thickness in a range of from 1000: 1 to 1000000: 1, more preferably from 2000: 1 to 500000: 1, even more preferably from 5000: 1 to 100000: 1.

According to the invention, flat structure means that its extension in the plane is many times greater than its thickness. The surface of the layered structure may be even or textured. A textured surface will also be called flat structure if not specified differently.

The dimension of the first surface (SI) is preferably defined as the area composed of its respective selected width, respective selected length and a thickness of 50 pm, preferably 40 pm, more preferably 30 pm.

The dimension of the second surface (S2) is preferably defined as the area composed of its respective selected width, respective selected length and a thickness of 50 pm, preferably 40 pm, more preferably 30 pm.

The surfaces (SI) and (S2) preferably have the same shape and size. Preferably, the layered structure (S) has a flat shape where both surfaces (SI) and (S2) have nearly the same dimension.

The first surface (SI) or the first layer (A) is preferably flat, preferably having a length in a range of from 10 mm to 2000 m, more preferably of from 50 mm to 500 m, even more preferably of from 100 mm to 100 m, especially preferably of from 0.3 m to 1.5 m and a width in a range of from 10 mm to 10 m, more preferably of from 50 mm to 5 m, most preferably of from 100 mm to 2 m. The first surface (S 1 ) or the first layer (A) preferably has an aspect ratio of length or width to thickness in a range of from 1000: 1 to 1000000: 1, more preferably from 2000: 1 to 500000: 1, even more preferably from 5000: 1 to 100000: 1. The second surface (S2) or the second layer (B) is preferably flat, preferably having a length in a range of from 10 mm to 2000 m, more preferably of from 50 mm to 500 m, even more preferably of from 100 mm to 100 m, especially preferably of from 0.3 m to 1.5 m and a width in a range of from 10 mm to 10 m, more preferably of from 50 mm to 5 m, most preferably of from 100 mm to 2 m. The second surface (S2) or the second layer (B) preferably has an aspect ratio of length or width to thickness in a range of from 1000: 1 to 1000000: 1, more preferably from 2000: 1 to 500000: 1, even more preferably from 5000: 1 to 100000: 1.

Preferably, the surfaces (SI) and (S2) or the layers (A) and (B) have a dimension in the range of from 1 cm² to 100 m², more preferably of from 2 cm² to 50 m², even more preferably of from 5 cm² to 10 m². The difference of the sizes of the two surfaces (SI) and (S2) is preferably no more than ± 10 %, more preferably no more than ± 5 %, based on the size of surface (SI).

The total amount of isosorbide in the first surface (S 1) or first layer (A) is preferably in a range of from 40 to 80 wt.-%, more preferably 45 to 75 wt.-%, most preferably 48 to 72 wt.-%, based on the total weight of the first surface (SI) or the first layer (A).

The total amount of isosorbide in the second surface (S2) or second layer (B) is preferably in a range of from 0 to 40 wt.-%, more preferably 0 to 20 wt.-%, most preferably 0 to 10 wt.-%, based on the total weight of the second surface (S2) or the second layer (B).

To evaluate the isosorbide content of the surfaces (SI) and/or (S2) polymer matrix is taken from the respective surface (SI) or (S2) extending up to 50 pm, preferably up to 40 pm, more preferably up to 30 pm, most preferably up to 20 pm into the layer structure (S) perpendicular to the respective surface.

The diol component (D) further comprises diols which are different from isosorbide. Preferably, the diol component (D) further comprises cyclohexane- l,4-diyl)dimethanol. The ratio of isosorbide to cyclohexane- l,4-diyl)dimethanol of the diol component (D) preferably lies in a range of from 80:20 to 60:40, more preferably from 70:30 to 50:50, especially if no further diols are used. Preferably the diol component (D) comprises cyclohexane- l,4-diyl)dimethanol in an amount of from 20 to 52 wt.-%, more preferably of from 25 to 50 wt.-%, especially preferably from 30 to 40 wt.-%, based on the total weight of the diol component (D).

Furthermore, aliphatic, cycloaliphatic or araliphatic diols with 2 to 16 C atoms are preferably used as the diol component (D) of the poly- or copolycondensate in addition to the isosorbide, such as ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3 -propanediol, neopentyl glycol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, p-xylenediol and mixtures of at least two of the above compounds, preferably etyleneglycol, diethyleneglycol, 1,4-butanediol and mixtures of at least two of the above compounds. Preferably the diol component (D) comprises one of the aforementioned additional diols in an amount of from 0 to 20 wt.-%, more preferably of from 2 to 10 wt.-%, especially preferably from 3 to 8 wt.-%, based on the total weight of the diol component (D).

The diol component (D) may still contain up to 10 mol% of other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 21 C atoms, such as 2-ethylpropanediol-l,3, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-l, 3 and 2-ethylhexanediol-l,6, 2,2- diethylpropanediol-1,3, hexanediol-2,5, l,4-di-([beta]-hydroxyethoxy)-benzene, 2,2-bis-(4- hydroxycyclohexyl)-propane, 2,4-dihydroxy-l,l,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-[beta]- hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (cf. DE 25 07 674, DE 25 07 776, DE 27 15 932), l,4:3,6-dianhydro-D-sorbitol (isosorbide), and 2,4,8, 10-tetra- oxaspiro[5.5]undecane-3,9-diethanol as well as mixtures of at least two of the above compounds.

The diol component (DI) comprises isosorbide preferably in a range of from 0 to 30 wt.-%, more preferably in a range of from 0 to 20 wt.-%, even more preferably in a range of from 0.1 to 10 wt.-%, based on the total weight of the diol component (DI).

The diol component (DI) further comprises diols which are different from isosorbide. Preferably, the diol component (DI) further comprises cyclohexane- l,4-diyl)dimethanol. The ratio of isosorbide to cyclohexane- l,4-diyl)dimethanol of the diol component (DI) preferably lies in a range of from 20:80 to 40:60, more preferably from 30:70 to 50:50, especially if no further diols are used. Preferably the diol component (DI) comprises cyclohexane- l,4-diyl)dimethanol in an amount of from 40 to 100 wt.-%, more preferably of from 50 to 90 wt.-%, especially preferably from 60 to 80 wt.-%, based on the total weight of the diol component (DI). Additionally or alternatively aliphatic, cycloaliphatic or araliphatic diols with 2 to 16 C atoms are preferably used as the diol component (DI) of the poly- or copoly condensate, such as ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol, p-xylenediol and mixtures of at least two of the above compounds, preferably etyleneglycol, diethyleneglycol, 1,4-butanediol and mixtures of at least two of the above compounds. Preferably the diol component (DI) comprises one of the aforementioned additional diols in an amount of from 1 to 20 wt.-%, more preferably of from 2 to 10 wt.- %, especially preferably from 3 to 8 wt.-%, based on the total weight of the diol component (DI).

The diol component (DI) may still contain up to 10 mol% of other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 21 C atoms, such as 2-ethylpropanediol-l,3, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-l, 3 and 2-ethylhexanediol-l,6, 2,2- diethylpropanediol-1,3, hexanediol-2,5, l,4-di-([beta]-hydroxyethoxy)-benzene, 2,2-bis-(4- hydroxycyclohexyl)-propane, 2,4-dihydroxy-l,l,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-[beta]- hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (cf. DE 25 07 674, DE 25 07 776, DE 27 15 932), l,4:3,6-dianhydro-D-sorbitol (isosorbide), and 2,4,8, 10-tetra- oxaspiro[5.5]undecane-3,9-diethanol as well as mixtures of at least two of the above compounds. The layered structure (S) may have any shape the person skilled would select for providing a layered structure (S), especially for use in an injection moulding process. Preferably, the layered structure (S) is flat. Preferably, the aspect ratio of the thickness to the plain lies in a region of from 1 : 100 to 1 : 10000000, more preferably in a region of from 1 : 1000 to 1 : 1000000.

Preferably the first layer (A) provides at least one, preferably at least two, more preferably at least three, especially preferably at least four, most preferably all of the following properties:

(Al) a thickness in a range of 20 to 500 pm, preferably in a range of 30 to 3750 pm; more preferably in a range of 40 to 250 pm, measured according to DIN ISO 4593-2019-06;

(A2) a roughness R3z in a range of 0 to 30 pm, measured according to ISO 4287: 1997;

(A3) a gloss value of 10 to 99, measured according to ISO 2813:2014;

(A4) a heat deflection temperature in a range of from 82 to 102°C (1.8 MPa, ISO75 - 1 / - 2);

(A5) Co-efficient of thermal expansion 6.9 x 10'⁵ to 7.3 x 10'⁵ according to ISO 11359 -2:2021.

Preferably, the first layer (A) provides one property or one property combination selected from the group consisting of (Al); (A2); (A3); (A4); (A5); (Al) and (A2); (Al) and (A3); (Al) and (A4); (Al) and (A5); (A2) and (A3); (A2) and (A4); (A2) and (A5); (A3) and (A4); (A3) and (A5); (A4) and (A5); (Al) and (A2) and (A3); (Al) and (A2) and (A4); (Al) and (A2) and (A5); (Al) and (A3) and (A4); (Al) and (A3) and (A5); (Al) and (A4) and (A5); (A2) and (A3) and (A4); (A2) and (A3) and (A5); (A2) and (A4) and (A5); (A3) and (A4) and (A5); (Al) and (A2) and (A3) and (A4); (Al) and (A2) and (A3) and (A5); (Al) and (A2) and (A4) and (A5); (Al) and (A3) and (A4) and (A5); (A2) and (A3) and (A4) and (A5); (Al) and (A2) and (A3) and (A4) and (A5); most preferably Al) and (A2) and (A3) and (A4) and (A5).

The diol component (D) of the polymer (a) or the diol component (DI) of the polymer (b) is a diol that has been reacted with a diol reactive component (R). Preferably, the polymer (a) or the polymer (b) is a poly condensate or co-poly condensate.

The polycondensate or co-polycondensate of polymer (a) comprises the reaction product of the diol component (D) and the reaction product of a diol reactive component (R). The diol reactive component (R) is preferably selected from the group consisting of carbonate groups, acid groups, acid esters, amine groups, acylhalogenide, anhydride or mixtures of at least two thereof. The polycondensate or copolycondensate is preferably selected from the group consisting of an acid ester.

The polycondensate or co-polycondensate of the second layer (B) comprises the reaction product of the diol component (DI) and the reaction product of a diol reactive component (Rl). The diol reactive component (Rl) is preferably selected from the group consisting of acid groups, amine groups. The polycondensate or copolycondensate is preferably selected from the group consisting of carbonate groups, acid groups, acid esters, amine groups acylhalogenide, anhydride or mixtures of at least two thereof. The polycondensate or copolycondensate is preferably selected from the group consisting of an acid ester.

Preferably, the reactive component (R) is the same as the reactive component (Rl).

Preferably, the polymer (a) comprises the reactive component (R) in an amount in a range of from 30 to 70 wt.-%, more preferably in a range of from 35 to 65 wt.-%, even more preferably in a range of from 40 to 60 wt.-%, based on the total amount of the polymer (a).

Preferably, the polymer (b) comprises the reactive component (Rl) in an amount in a range of from 30 to 70 wt.-%, more preferably in a range of from 35 to 65 wt.-%, even more preferably in a range of from 40 to 60 wt.-%, based on the total amount of the polymer (b).

In a preferred embodiment of the layered structure (S), the first surface (SI) is at least part of the first layer (A) comprising the polymer (a) and the second surface (S2) is at least part of the second layer (B) comprising the polymer (b). Preferably, the first surface (SI) builds the whole first layer (A) comprising the polymer (a). Preferably, the second surface (S2) builds the second layer (B) comprising the polymer (b).

Preferably, the first layer (A) covers the whole first surface (SI) of the layered structure (S). Preferably, the second layer (B) covers the whole second surface (S2) of the layered structure (S).

In a preferred embodiment of the layered structure (S), the layered structure (S) comprises furthermore:

(C) optionally at least one third layer (C), comprising a polymer (c),

(E) a further layer (E), especially in from of a printing layer, wherein the further layer (E) is in direct contact with second layer (B).

Preferably, the further layer (E) has a thickness in a range of from 5 to 500 pm, more preferably in a range of from 10 to 100 pm. The further layer (E) may comprise any polymer which the person skilled in the art would select for the purpose, e.g. as printing layer. Examples of inks for the further layer (E) are AquaPress®, NoriAmid®, NoriAmid® APM, Noricryl®, CoriCure® IMS, NoriPET®, NoriPress SMK®, NORIPHAN® XWR, NORIPHAN® PCI N, NORIPHAN® N2K, NORIPHAN® HTRN, all of Proll GmbH (Germany).

Preferably, the second layer (B) provides at least one, more preferably at least two, even more preferably at least three, especially all of the following properties:

(Bl) a roughness R3z in a range of 0.1 to 30 pm, measured according to ISO 4287: 1997;

(B2) a gloss value of 10 to 99, measured according to ISO 2813:2014;

(B3) a heat deflection temperature in a range of from 110 to 130°C (1.8 MPa, ISO75 - 1 / - 2); (B4) Co-efficient of thermal expansion 6.5 x 10'⁵ to 6.9 x 10'⁵ according to ISO 11359 -2:2021. Preferably, the second layer (B) provides one property or one property combination selected from the group consisting of (Bl); (B2); (B3); (B4); (Bl) and (B2); (Bl) and (B3); (Bl) and (B4); (B2) and (B3); (B2) and (B4); (B3) and (B4); (Bl) and (B2) and (B3); (Bl) and (B2) and (B4); (Bl) and (B3) and (B4); (B2) and (B3) and (B4); (Bl) and (B2) and (B3) and (B4).

In a preferred embodiment of the layered structure (S) the thickness of the first surface (SI) or the first layer (A) is > 10 pm, preferably > 20 pm, more preferably > 30 pm preferably, most preferably > 50 pm. Preferably, the first surface (SI) is formed by the first layer (A) and therefore is identical to the first layer (A).

Preferably, the thickness of the first surface (SI) or the first layer (A) is in a range of 10 to 500 pm, preferably in a range of from 15 to 400 pm, preferably in a range of from 20 to 300 pm, even more preferably in a range of from 25 to 200 pm, especially preferably in a range of from 30 to 150 pm, even more preferably of from 50 to 100 pm.

Preferably, the thickness of the layered structure (S) is in a range of from 60 to 900 pm, more preferably in a range of from 80 to 800 pm, even more preferably in a range of from 100 to 700 pm, even more preferably of from 150 to 500 pm.

In a preferred embodiment of the layered structure (S) the ratio of the thickness of the first surface (SI) or the first layer (A) to the thickness of the second surface (S2) or the second layer (B) is in a range of 1: 10 to 10: 1, preferably 1:5 to 5: 1, more preferably 2:5 to 5:2, especially preferably in a range of 1 : 10 to 1: 1.

In a preferred embodiment of the layered structure (S) the diol component (D) of polymer (a), especially the isosorbide and optionally the diol component (DI) of polymer (b) comprises a constitutional unit derived from a dihydroxy compound represented by formula (1) and a constitutional unit derived from an alicyclic dihydroxy compound.

Preferably, the isosorbide is a diol, wherein the Abbe number is 50 or more and the 5% thermal reduction temperature is 340°C or more, wherein the ratio of the dihydroxy compound represented by formula (1) and the alicyclic dihydroxy compound to all dihydroxy compounds constituting the polycarbonate copolymer is 90 mol% or more, wherein the alicyclic dihydroxy compound is at least one compound selected from the group consisting of cyclohexanedimethanol, tricyclodecanedimethanol, adamantanediol and pentacyclopentadecanedimethanol

( 1

In a preferred embodiment of the layered structure (S) the second surface (S2) or the second layer (B) comprises a further polymer (b ), wherein the further polymer (b ) is a polycarbonate or a copolycarbonate and the further polymer (b ) provides constituents according to formula (2)

(2).

Particularly, aromatic polycarbonates or co-polycarbonates are suitable as poly or co-polycarbonates in preferred embodiments.

Polycarbonates or co-polycarbonates in the well-known way can be linear or split.

These polycarbonates can be produced in the well-known way from diphenols, carbonic acid derivatives, possibly chain breaking agents and possibly splitters. Details of the production of polycarbonates have been given in many patent specifications for approximately 40 years. By way of example, reference is made here to “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, P.R. Muller, H. Nouvertne', BAYER AG, “Polycarbonates” in Encyclopedia of Polymer Science and Engineering, Volume 11, Second edition, 1988, pages 648-718 and finally to Dres. U. Grigo, K. Kirchner and P.R. Muller “Polycarbonate” in Becker/Braun, Plastics Manual, volume 3/1, Polycarbonates, Polyacetals, Polyesters, Cellulose Esters, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299.

Suitable diphenols for example can be dihydroxyaryl compounds with the general formula (I),

HO-Z-OH (I) where Z is an aromatic residue with 6 to 34 C-atoms, which can contain one or several possibly substituted aromatic cores and aliphatic or cycloaliphatic residues and/or alkyl aryls or hetero atoms as bridge members.

Examples of suitable dihydroxyaryl compounds are: dihydroxy benzenes, dihydroxy diphenyls, bis- (hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-aryls, bis- (hydroxyphenyl)-ether, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfides, bis- (hydroxyphenyl)-sulfones, bis-(hydroxyphenyl)-sulfoxides, 1 , 1 '-bis-(hydroxyphenyl)-diisopropyl benzenes, as well as their ring-alkylated and ring-halogenated compounds.

This and further suitable other dihydroxyaryl compounds are described for example in DE-A 3 832 396, FR-A 1 561 518, in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, pages 28 ff; pages 102 ff. and in D.G. Legrand, J.T. Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, page 72 ff.

Preferred dihydroxyaryl compounds are for example Resorcin, 4,4'-dihydroxydiphenyl, bis-(4- hydroxyphenyl)-methane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, bis-(4-hydroxyphenyl)- diphenyl-methan, 1,1 -bis (4-hydroxyphenyl)-l -phenyl -ethane, 1,1 -bis (4-hydroxyphenyl)-l (1- naphthyl)-ethane, 1,1 -bis (4-hydroxyphenyl)-l-(2-naphthyl)-ethane, 2,2-bis (4-hydroxyphenyl)- propane, 2,2-bis (3-methyl-4-hydroxyphenyl)-propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl)- propane, 2,2-bis (4-hydroxyphenyl)-l -phenyl -propane, 2,2-bis (4-hydroxyphenyl)-hexadecimal fluorine propane, 2,4-bis (4-hydroxyphenyl)-2 -methyl -butane, 2,4-bis (3, 5 -dimethyl -4-hydroxyphenyl)- 2-methyl butane, 1,1-bis (4-hydroxyphenyl)-cyclohexane, 1,1-bis (3, 5 -dimethyl -4-hydroxyphenyl)- cylohexane, 1,1-bis (4-hydroxyphenyl)-4-methyl-cylohexane, 1,3-bis [2 (4-hydroxyphenyl)-2 -propyl] - benzene, 1, 1'-bis (4-hydroxyphenyl)-3-diisopropyl-benzene, 1, 1'-bis (4-hydroxyphenyl)-4-diisopropyl- benzene, 1,3-bis [2 (3,5-dimethyl-4-hydroxyphenyl)-2-propyl]-benzene, bis (4-hydroxyphenyl)-ether, bis (4-hydroxyphenyl)-sulfide, bis (4-hydroxyphenyl)-sulfone, bis (3, 5 -dimethyl -4-hydroxyphenyl) - sulfone and 2,2', 3,3'-tetrahydro-3,3,3', 3 '-tetramethyl- l,l'-spirobi [lH-indene]-5,5'-diol or dihydroxydiphenyl cycloalkane of the formula (la)

where

R¹ and R² independent from one another mean hydrogen, halogen, preferably chlorine or bromine, Ci-Cs- alkyl, Cs-Ce cycloalkyl, Ce-Cio- aryl, preferably phenyl, and C7-C12- aralkyl, preferably phenyl Ci - C4- alkyl, in particular benzyl, m means a whole number from 4 to 7, preferably 4 or 5,

R³ and R⁴ for each X individually selectable, independent from one another, mean hydrogen or Ci-C e- alkyl and

X means carbon, provided that, on at least one atom X, R³ and R⁴ simultaneously mean alkyl. Preferably, R³ and R⁴ are simultaneously alkyl on one or two atom(s) X, in particular only on one atom X in the formula (la).

Preferred alkyl residue for the residues of R³ and R⁴ in formula (la) is methyl. The X-atoms in alpha - position to the diphenyl-substituted C-atom (C-l) are preferably not dialkyl-substituted, on the other hand the alkyl disubstitution in beta position to C-l is preferred.

Particularly preferred dihydroxydiphenyl cycloalkanes of the formula (la) are those with 5 and 6 ring C atoms X in the cycloaliphatic residue (m = 4 or 5 in the formula (la)), for example the diphenols of the formulae (la-1) to (la-3),

(Ia-2)

(la-3)

A particularly preferred dihydroxydiphenyl cycloalkane of the formula (la) is 1,1 -bis (4- hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (formula (la-1) with R¹ and R² equal to H).

Such polycarbonates can be produced in accordance with EP-A 359 953 from dihydroxydiphenyl cycloalkanes of the formula (la).

Particularly preferred dihydroxyaryl compounds is Resorcin, 4,4'-dihydroxydiphenyl, bis (4- hydroxyphenyl)-diphenyl -methane, 1,1 -bis (4-hydroxyphenyl)-l -phenyl -ethane, bis (4- hydroxyphenyl)-l (l-naphthyl)-ethane, bis (4-hydroxyphenyl)-l (2-naphthyl)-ethane, 2,2-bis (4- hydroxyphenyl)-propane, 2,2-bis (3, 5 -dimethyl -4-hydroxyphenyl)-propane, 1,1 -bis (4-hydroxyphenyl)- cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, 1,1-bis (4-hydroxyphenyl)-3,3,5- trimethyl-cyclohexane, l,l'-bis (4-hydroxyphenyl)-3-diisopropyl-benzene and l,l'-bis-(4- hydroxyphenyl)-4-diisopropyl-benzene.

Particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4- hydroxyphenyl)-propane .

Both a dihydroxyaryl compound under formation of homopolycabonates and different dihydroxyaryl compounds under formation of co-polycabonates can be used. Both a dihydroxyaryl compound of the formula (I) or (la) under formation of homopolycarbonates and several dihydroxyaryl compounds of the formula (I) and/or (la) under formation of co-polycarbonates can be used. The different dihydroxyaryl compounds can be linked together both statistically and block-by-block. In the case of co-polycabonates made from dihydroxyaryl compounds of the formulae (I) and (la), the molecular ratio of dihydroxyaryl compounds of the formula (la) to that of the other dihydroxyaryl compounds of the formula (I) possibly to be used is preferably between 99 mol % (la) to 1 mol % (I) and 2 mol % (la) to 98 mol % (I), preferably between 99 mol % (la) to 1 mol % (I) and 10 mol % (la) to 90 mol % (I) and in particular between 99 mol % (la) to 1 mol % (I) and 30 mol % (la) to 70 mol % (I).

A particularly preferred co-polycarbonate can be produced using 1,1-bis (4-hydroxyphenyl)-3,3,5- trimethyl-cyclohexane and 2,2-bis (4-hydroxyphenyl)-propane dihydroxyaryl compounds of the formulae (la) and (I). Suitable carbonic acid derivatives for example can be diaryl carbonates of the general formula (II),

where

R, R' and R" independently directly or differently stand for hydrogen, linear or split Ci-C34-alkyl, C7- C34-alkylaryl or Ce-C34-aryl, R can also mean - COO-R", whereby R" stands for hydrogen, linear or split Ci-C34-alkyl, Cy-C -alk lar l or Ce-C34-aryl.

Preferred diaryl carbonates are for example diphenyl carbonate, methylphenyl phenyl carbonates and di (methylphenyl) - carbonates, 4-ethylphenyl-phenyl-carbonate, di (4-ethylphenyl) - carbonate, 4-n- propylphenyl-phenyl-carbonate, di (4-n-propylphenyl) - carbonate, 4-iso-propylphenyl-phenyl- carbonate, di (4-iso-propylphenyl) - carbonate, 4-n-butylphenyl-phenyl-carbonate, di (4-n-butylphenyl) - carbonate, 4-iso-butylphenyl-phenyl-carbonate, di (4-iso-butylphenyl) - carbonate, 4-tert-butylphenyl- phenyl-carbonate, di (4-tert-butylphenyl) - carbonate, 4-n-pentylphenyl-phenyl-carbonate, di (4-n- pentylphenyl) - carbonate, 4-n-hexylphenyl-phenyl-carbonate, di (4-n-hexylphenyl) - carbonate, 4-iso- octylphenyl-phenyl-carbonate, di (4-iso-octylphenyl) - carbonate, 4-n-nonylphenyl-phenyl-carbonate, di (4-n-nonylphenyl) - carbonate, 4-cyclohexylphenyl-phenyl-carbonate, di (4-cyclohexylphenyl) - carbonate, 4 (1 -methyl- 1 -phenylethyl) - phenyl phenyl carbonate, di [4 (1 -methyl- 1 -phenylethyl) - phenyl] - carbonate, biphenyl -4-yl -phenyl -carbonate, di (biphenyl -4-yl) - carbonate, 4 (1 -naphthyl) - phenyl phenyl carbonate, 4 (2 -naphthyl) - phenyl phenyl carbonate, di [4 (1 -naphthyl) - phenyl] - carbonate, di [4 (2-naphthyl) phenyl] - carbonate, 4-phenoxyphenyl-phenyl-carbonate, di (4- phenoxyphenyl) - carbonate, 3-pentadecylphenyl-phenyl-carbonate, di (3 -pentadecylphenyl) - carbonate, 4-tritylphenyl-phenyl-carbonate, di (4-tritylphenyl) - carbonate, methyl salicylate phenyl carbonate, di (methyl salicylate) - carbonate, ethyl salicylate phenyl carbonate, di (ethyl salicylate) - carbonate, n-propyl salicylate-phenyl-carbonate, di (n-propyl salicylate) - carbonate, iso propyl salicylate phenyl carbonate, di (iso propyl salicylate) -carbonate, n-butyl salicylate-phenyl-carbonate, di (n-butyl salicylate) - carbonate, iso butyl salicylate phenyl carbonate, di (iso butyl salicylate) - carbonate, tert butyl salicylate phenyl carbonate, di (tert butyl salicylate) - carbonate, di (phenylsalicylat) - carbonate and di (benzylsalicylat) - carbonate. Particularly preferred diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di (4-tert-butylphenyl) - carbonate, biphenyl -4-yl -phenyl -carbonate, di (biphenyl -4-yl) - carbonate, 4 (1- methyl-1 -phenylethyl) - phenyl phenyl carbonate, di [4 (1 -methyl- 1 -phenylethyl) - phenyl] - carbonate and di (methyl salicylate) - carbonate.

Diphenyl carbonate is particularly preferred.

Both a diaryl carbonate and different diaryl carbonates can be used.

To control and/or change the final groups additionally for example one or several monohydroxyaryl compound(s) can be used as chain breaking agents, which were not used to produce the diarylcarbonate(s) employed. It can concern those of the general formula (III),

where

R^A stands for linear or split Ci-C34-alkyl, CT-C’s -alkylaryl. Ce-C34-aryl or for - COO-R^D, whereby R^D stands for hydrogen, linear or split Ci-C34-alkyl, C?-C34-alkylaryl or Ce-C34-aryl, and

R^B, R^C, independently directly or differently, stand for hydrogen, linear or split Ci-C34-alkyl, C7-C34- alkylaryl or Ce-C34-aryl.

Such monohydroxyaryl compounds are for example 1, 2 - or 3 -methyl phenol, 2,4-dimethylphenol 4- ethyl phenol, 4-n-propylphenol, 4-iso-propylphenol, 4-n-butylphenol, 4-isobutylphenol, 4-tert- butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-iso-octylphenol, 4-n-nonylphenol, 3- pentadecylphenol, 4-cyclohexyl phenol, 4 (1 -methyl- 1 -phenylethyl) - phenol, 4-Phenylphenol, 4- phenoxyphenol, 4 (1 -naphthyl) - phenol, 4 (2 -naphthyl) - phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso propyl salicylate, n-butyl salicylate, iso butyl salicylate, tert butyl salicylate, phenyl salicylate and benzyl salicylate, where 4-tert-butylphenol, 4-iso-octylphenol and 3- pentadecylphenol are especially preferred.

Suitable splitters are compounds with three and more functional groups, preferably such with three or more hydroxyl groups.

Suitable compounds with three or more phenolic hydroxyl groups are for example Phloroglucin, 4,6- dimethyl-2,4,6-tri (4-hydroxyphenyl) - heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) - heptane, 1,3,5-tri (4-hydroxyphenyl) - benzene, 1,1,1-tri (4-hydroxyphenyl) - ethane, tri (4-hydroxyphenyl) - phenyl methane, 2,2-bis (4,4-bis (4-hydroxyphenyl) - cyclohexyl] - propane, 2,4-bis (4-hydroxyphenyl- iso propyl) - phenol and tetra (4-hydroxyphenyl) - methane. Other suitable compounds with three and more functional groups are for example 2,4-dihydroxybenzoic acid, trimesic acid (tri chloride), cyanuric acid trichloride and 3,3-bis (3 -methyl -4-hydroxyphenyl) 2- oxo-2, 3 -dihydroindole .

Preferred splitters are 3,3-bis (3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1-tri (4- hydroxyphenyl)-ethane .

In the case where the first surface (SI) or the first layer (A) comprises less than 100 wt.-% of polymer (a), the first surface (SI) or the first layer (A) preferably comprises in addition to polymer (a) a polycarbonate or copolycarbonate selected from those described in connection with the polymer (b ) of the second layer (B).

Further to the diols mentioned in the connection with polymer (b ), the diol component (D) may be any diol component the person skilled in the art would select. Aliphatic, cycloaliphatic or araliphatic diols with 2 to 16 C atoms are preferably used as the diol component (D) of the poly- or copolycondensate, such as ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4- butanediol, 1,5 -pentanediol, 1,6-hexanediol, p-xylenediol and mixtures of at least two of the above compounds, preferably etyleneglycol, diethyleneglycol, 1,4-butanediol and mixtures of at least two of the above compounds.

The diol component (D) may still contain up to 10 mol% of other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 21 C atoms, such as 2-ethylpropanediol-l,3, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-l, 3 and 2-ethylhexanediol-l,6, 2,2-diethyl- propanediol-1,3, hexanediol-2,5, l,4-di-([beta]-hydroxyethoxy)-benzene, 2,2-bis-(4- hydroxycyclohexyl)-propane, 2,4-dihydroxy-l,l,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-[beta]- hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (cf. DE 25 07 674, DE 25 07 776, DE 27 15 932), l,4:3,6-dianhydro-D-sorbitol (isosorbide), and 2,4,8, 10-tetra- oxaspiro[5.5]undecane-3,9-diethanol as well as mixtures of at least two of the above compounds.

Preferably, the first surface (SI) or the first layer (A) comprises polymer (b') in an amount in a range of from 0.1 to 52 wt.-%, more preferably in a range of from 0.2 to 40 wt.-%, even more preferably in a range of from 0.5 to 20 wt.-%, based on the total weight of the first surface (SI) or first layer (A).

In a preferred embodiment of the layered structure (S) the layered structure (S) comprises a third layer (C). Preferably, the third layer comprises a third polymer (c). Preferably, the composition and properties of the third polymer (c) are the same as those of polymer (b). Preferably, the composition and properties of the third layer (C) are the same as those of second layer (B). Preferably, the third layer (C) is placed on the surface of the first layer (A) which is opposite to layer (B). Preferably, the third polymer (c) comprises the same polymeric composition as layer (B) or solely polymer (b ).

In a preferred embodiment of the layered structure (S) the layered structure provides at least one of the following properties

(51) a thickness in a range of 75 to 500 pm, more preferably of 80 to 400 pm;

(52) gloss level in a range of 10 to 100 GU, more preferably of 20 to 80 GU;

(53) %LT in a range of 3 to 95 %, more preferably of 5 to 90 %.

The methods used for achieving the values of features (SI, (S2) or (S3) are described in the method section below.

Preferably, the layered structure (S) provides one property or one property combination selected from the group consisting of (SI); (S2); (S3); (SI) and (S2); (SI) and (S3); (S2) and (S3); (SI) and (S2) and (S3); especially preferably (SI) and (S2) and (S3).

In a preferred embodiment of the layered structure (S) the second surface (S2) or the second layer (B) has a thickness in the range 10 to 500 pm. Preferably, the second surface (S2) is formed by the second layer (B) and therefore is identical to the second layer (B).

Preferably, the thickness of the second layer (B), the third layer (C) or the further (E) is independently at least 50 pm, preferably in a range of from 50 to 500 pm, more preferably in a range of from 70 to 300 pm, most preferably in a range of from 100 to 200 pm.

In a preferred embodiment of the layered structure (S) the layered structure, especially the first layer (A) further comprises an additive. However, also layer (C) or further layer (E) may comprise an additive. Preferably the additive is selected from the group consisting of an UV-absorber, dyes, pigments, inorganic fillers, organic fillers, both fillers as micron, submicron or nanosized particles or mixtures of at least two thereof. Various additives can have been admixed with the polymer a) or the polymer b), which might be described just as polymer. If only polymer is used, both polymers, polymer a) and/or polymer b) are meant.

Addition of additives serves to prolong service life or to increase colourfastness (stabilizers), to simplify processing (e.g. mould-release agents, flow aids, antistatic agents), or for adaptation of the properties of the polymer to particular stresses (impact modifiers, such as rubbers; flame retardants, colourants, glass fibres).

These additives can be added individually or in any desired mixture or in a plurality of different mixtures to the polymer, especially to the polymer melt, and specifically directly during isolation of the polymer or else after melting of pellets in what is known as a compounding step. The form in which the additives here, or a mixture of these, can be added to the polymer melt can be that of solid, of powder, or of melt. Another metering method uses masterbatches or a mixture of masterbatches of the additives, or an additive mixture.

Suitable additives are described by way of example in ’’Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999”, in ’’Plastics Additives Handbook, Hans Zweifel, Hanser, Mtinchen 2001”. Examples of suitable antioxidants or heat stabilizers are: alkylated monophenols, alylthiomethylphenols, hydroquinones, alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, O-, N- and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxy compounds, triazine compounds, acylaminophenols, esters of P-(3,5-di-tert-butyl-4- hydroxyphenyl)propionic acid, esters of f>-(5 -tert-butyl -4-hydroxy-3-methylphenyepropionic acid, esters of P-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, esters of 3, 5 -di -tert-butyl -4- hydroxyphenylacetic acid, amides of P-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, suitable thiosynergists, secondary antioxidants, phosphites and phosphonites, benzofuranones and indolinones.

Preference is given to organic phosphites, phosphonates and phosphanes, and mostly to those in which the organic moieties are composed entirely or to some extent of optionally substituted aromatic moieties.

Suitable complexing agents for heavy metals and for the neutralization of traces of alkali are o/m- phosphoric acids, or fully or partially esterified phosphates or phosphites.

Suitable light stabilizers (UV absorbers) are: 2-(2'-hydroxyphenyl)benzotriazoles, 2- hydroxybenzophenones, esters of substituted and unsubstituted benzoic acids, acrylates, sterically hindered amines, oxamides, 2.8.2-(2-hydroxyphenyl)-l,3,5-triazines. Preference is given to substituted benzotriazoles.

Polypropylene glycols can be used alone or in combination with, for example, sulphones or sulphonamides, as stabilizers to inhibit damage by gamma radiation

These and other stabilizers can be used individually or in combination and can be in any of the forms mentioned when they are added to the polymer, especially to polymer a) or polymer b).

Suitable flame-retardant additives are phosphate esters, i.e. triphenyl phosphate, resorcinol diphosphate, bromine-containing compounds, such as brominated phosphoric esters, brominated oligocarbonates and polycarbonates, and also preferably salts of fluorinated organic sulphonic acids.

Suitable impact modifiers are butadiene rubber with grafted-on styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers with grafted-on maleic anhydride, ethyl and butyl acrylate rubbers with grafted-on methyl methacrylate or styrene -acrylonitrile, and interpenetrating siloxane and acrylate networks with grafted-on methyl methacrylate or styrene-acrylonitrile.

Colourants can also be added, examples being organic dyes or pigments or inorganic pigments, or IR absorbers, individually, in a mixture, or else in a combination with stabilizers, with glass fibres, with (hollow) glass beads, or with inorganic fillers. It is also possible to use carbon black as additive.

Various layer-specific functions of the layers themselves can be achieved via various types of additives.

As exterior layer, the layer (A) comprising polymer a) and/or the layer (B) comprising polymer b), preferably comprises a laser-sensitive additive. A suitable additive is carbon black or a dye that absorbs infrared light. These laser sensitive additives are useful to mark the layered structure. The marking can be done in black or any colour, depending on the chosen additive and the light source or light intensity.

When standard lasers are used, specifically the widely used Nd-YAG solid-state lasers with wavelength 1.06 pm, a colour change or a colour transition takes place at the point of impact of the laser on the surface of the material, and high-clarity, high-contrast inscriptions and markings are obtained.

Particularly suitable additives are colour pigments and metal salts, copper hydroxide phosphate iriodin, a pearl-lustre pigment obtainable commercially from Merck, and especially carbon black. The amount of these additives admixed with the polymer (a) or polymer (b), preferably the polycarbonate of the invention is in particular of the order of magnitude of from a few parts per 1000 to at most 10 wt.-%, based on the total weight of polymer (a) or polymer (b) .

The polymer (a) or polymer (b), preferably the polycarbonate can also comprise further inorganic fillers. Examples of suitable inorganic fillers for achieving an opaque or translucent polycarbonate layer are conventional inorganic pigments, in particular metals or metal oxides, such as aluminum oxides, silica, titanites, and also alkali-metal salts, e.g. carbonates or sulphates of calcium or barium. Suitable particulate fillers can be homogeneous and are mainly composed of a material such as titanium dioxide or barium sulphate alone. As an alternative, at least a proportion of the filler can be heterogeneous. By way of example, there can also be a modifier admixed with the actual filler. By way of example, the actual filler can also have been provided with a surface modifier, e.g. with a pigment, with a processing aid, with a surfactant or with any other modifier, in order to improve or alter compatibility with the polycarbonate. Preferably, the polymer (a) or polymer (b), preferably the polycarbonate comprises titanium dioxide.

The amount of the said inorganic fillers in the polymer (a) or polymer (b), preferably the polycarbonate is preferably from 2 to 50 wt.-%, particularly preferably from 3 to 30 wt.-%, based on the total weight of polymer (a) or polymer (b). Preferably, the additive is positioned in at least one of the outer layers of the layered structure (S). In the case layer (A) and/or layer (B) is one of the outer layers, the first layer (A) and/or the second layer (B) preferably comprises the additive, especially the UV-absorber in an amount of 0.1 to 10 wt.-%, more preferably of 0.5 to 7 wt.-%, most preferably of 1 to 5 wt.-%, based on the total weight of the respective layer. In the case layer (C) and/or layer (E) is one of the outer layers, the third layer (C) and/or the further layer (E) preferably comprises the additive, especially the UV-absorber in an amount of 0.1 to 10 wt.- %, more preferably of 0.5 to 7 wt.-%, most preferably of 1 to 5 wt.-%, based on the total weight of the respective layer.

A further aspect of the invention relates to a process for producing a layered structure (S), comprising at least the following steps:

I) heating a first polymer (a) or a mixture of polymer (a) and polymer (b ) by an extruder,

II) heating a second polymer (b) or a mixture of polymer (b) and polymer (b ) by an extruder,

III) optionally heating a third polymer (c) by an extruder,

IV) co-extruding the first polymer (a) or the mixture of polymer (a) and polymer (b ) together with the second polymer (b) or the mixture of polymer (b) and polymer (b ) and optionally the third polymer (c) through a dye to form a first layer (A) consisting of polymer (a) or the mixture of polymer (a) and polymer (b ), a second layer B) consisting of the second polymer (b) or the mixture of polymer (b) and polymer (b ) and optionally a third layer (C) consisting of polymer (c) to result in the layered structure (S),

V) cooling the layered structure (S) to room temperature and optionally pressing the layered structure (S) through two rolls,

VI) optionally further processing, preferably decorating and/or back injection molding of the layered structure (S) of step V), preferably by a further printed layer (E) in a FIM process.

The extruder utilized in step I) or step II) and optionally III) could be any extruder the person skilled in the art would select for extruding polymer (a), (b), (b') or (c).

The co-extruding in step IV) is performed via a die where the melts of step I) to III) are combined. The cooling in step V) could be established by any means the person skilled in the art would select for cooling a layered structure (S). Preferably, the cooling in step V) is selected from the group consisting of cooling at room temperature (25°C), cooling via cool air (10 to 15°C), cooling in a tempered room (30 to 50°C). Preferably the cooling in step V) is established at room temperature. The layered structure (S) is preferably pressed through two rolls while cooling in step V). Preferably, the rolls are rollers having metal or rubber surfaces which are polished or textured. If the layered structure (S) should be clear and transparent two polished rollers are used. By using one polished and one textured roller a matt surface may be achieved. If two textured rollers are applied, the layered structure (S) may be formed to a less transparent structure.

The polymers (a), (b) and (b') are preferably those described in the context of the first layer (A), second layer (B) and third layer (C) to form the layered structure according to the invention above. Also, the compositions, properties of polymers A), B) and C) are selected in a way to form the compositions as described in the context of the first layer (A), second layer (B) and third layer (C) to form the layered structure according to the invention above.

The layered structure (S) formed according to the afore mentioned process comprises the preferred properties as mentioned for the layered structure (S) according to the invention as mentioned above.

In an optional step VI) of the process a further processing of the layered structure (S) is performed. The further processing is preferably selected from the group consisting of providing a decorative and/or chemically resistant layer onto the layered structure (S), printing onto the layered structure (S), forming the layered structure (S), trimming of the edges of the layered structure (S), back injection mold the layered structure (S) or a combination of at least two thereof. The providing a decorative and/or chemically resistant layer is preferably performed by applying a further layer onto the layered structure (S) of step V) via a FIM process or a lamination process. FIM stands for Film Insert Molding (FIM) which is an advanced form of In Mold Decorating (IMD) and known to the person skilled in the art.

The FIM process is preferably established in a mold made of a metal alloy. The mold preferably has a shape selected from the group consisting of angled polygons, round, oval or a combination of at least two thereof. Preferably, the angled polygon provides curvature radii in a range of from 0.1 to 0.5 mm, more preferably from 0.2 to 0.4 mm. The FIM process is preferably performed at a pressure of 20 to 300 bars. The material which is back injection molded to the layered structure (S) via the FIM process preferably is selected from the group consisting of polycarbonate, blends of polycarbonate or combinations of at least two thereof and form layer (E).

The printing onto the layered structure (S) can be performed by any printing process the person skilled in the art would use. Preferably, the printing is selected from the group consisting of screen printing, ink-jet printing, pad printing, laser printing, stamp printing, embossing, non-impact printing, such as direct thermal printing, thermal transfer printing, 3D printing, dye-sublimation printing, laser marking or a combination of at least two thereof.

The forming of the layered structure (S) can be performed by any forming process the person skilled in the art would use. Preferably, the forming is a welding, a thermoforming, a cutting of the layered structure (S) or a combination of at least two thereof. The trimming of the edges of the layered structure (S) can be performed by any trimming process the person skilled in the art would use. Preferably, the trimming is a cutting, grinding or melding of the material at the edges of the layered structure (S).

The back injection molding of the layered structure (S) can be performed by any back injection molding process the person skilled in the art would use.

In a preferred embodiment of the process the first polymer (a) has a higher content of isosorbide than the second polymer (b). Preferably, the content of isosorbide of the first polymer (a) is 1 to 100 fold higher than in the second polymer (b), more preferably 2 to 80 fold higher than in the second polymer (b), more preferably 5 to 50 fold higher than in the second polymer (b).

A further aspect of the invention relates to a layered structure (S) obtained by a process according to the invention. The layered structure (S) as well as each of its layers, the first layer (A), the second layer (B) and optionally the third layer (C) or any further layer (E) provide the same properties as described in the context of the first layer (A), second layer (B), third layer (C) and any further layer (E) to form the layered structure (S) according to the invention above.

A further aspect of the invention relates to the use of a layered structure (S) according to the invention or produced by a process according to the invention for insert molding, especially of parts made by film insert molding, especially of decorative parts in cars. Film Insert Moulding (FIM) is an advanced form of In Mold Decorating (IMD). It allows for labeling and graphics to be applied to plastic parts during the moulding process. FIM also enables components to be integrated into a single unit. FIM creates products with scratch resistant hard coats that are extremely durable. It can be used in multiple applications, but film insert moulding is most commonly associated with automotive interiors and handheld electronic devices. As a type of in-mold decoration, FIM eliminates the need for separate steps, such as coating or painting, that would otherwise be required to decorate or functionalize plastic components, even where these items are complex in shape. This offers manufacturers extensive flexibility in design and manufacturing - as well as considerable savings in costs, time and machine investment.

The decorated film used in FIM can create a huge variety of visual effects - be they monochromatic, multicolored, or metallic. The process also allows for integrated symbols, transmitted light design, surface impression (glossy, textured, or matte) and high gloss, which can be set selectively. Few other methods allow the decoration of parts to be changed as quickly without interrupting production, i.e. decoration can be changed by simply inserting different printed films from shot to shot. Additional properties, such as media and UV resistance, scratch and abrasion resistance, electrical conductivity or a soft-touch finish, can be achieved through the use of special composite or coated films. Key elements of the FIM process include printing, forming, trimming, and back injection as already mentioned in the context of the inventive layered structure (S) above. Each aspect has its own unique technological considerations. The most established printing technique for the FIM method is screen printing. Printing inks used in the process are preferably highly flexible and adhere well to the fdm due to the rigors of forming.

A further aspect of the invention relates to a printed polymeric article obtainable using a layered structure (S) according to the invention or produced according to the invention.

The most established printing technique for the FIM method is screen printing. Printing inks used in the process need to be highly flexible and adhere well to the fdm due to the rigors of forming. Furthermore, the inks must be able to withstand the thermal load and shear forces of the injection molding melt. These requirements are met by Noriphan® HTR N screen printing ink from Prbll GmbH, polycarbonate fdms like Makrofol® or Bayfol®. Apart from screen printing, the layered structure can also be decorated by means of digital and offset printing.

Film insert molding (in-mold decoration) is a widely used surface finishing process. In this process, a decorated film is shaped, trimmed and then positioned in an injection mold and a molten molding composition is then injected in the mold on the back of the film. In the case of films decorated on their backside, while the decoration is indeed protected by an external transparent film, when such films are insert molded the decoration is exposed to elevated temperatures and shear stresses which result in washing out in the area of the gates. In order to avoid washing out, it is known to cover the decorative layer with a protective layer such that the melt does not come directly into contact with the decorative layer. Such a protective layer consists, for example, of polycarbonate (PC), acrylonitrile/butadiene/styrene (ABS), polymethyl methacrylate (PMMA), acrylonitrile/styrene/acrylate (ASA). Said layer is either applied directly during production of a component by coextrusion or is subsequently laminated with the assistance of coupling agents. This process is described, for example, in P. Enewoldsen, H. Braun, Folienhinterspritzen - Dekorieren in der SpritzgieBmaschine, KU Kunststoffe 89 (1999) 9, pages 102-104. More details of the film insert molding are described in US 2004/183229 Al.

Methods:

1. Thickness

The thickness has been measured according to DIN ISO 4593-2019-06;

2. Roughness

The roughness R3z is measured according to ISO 4287: 1997; 3. Heat deflection temperature

The heat resistance measured according to DIN EN ISO 75-1-2013-08 (1.80MPa);

4. Co-efficient of thermal expansion

The co-efficient of thermal expansion has been measured according to ISO 11359-2:2021;

5. Gloss value

The gloss value has been measured according to ISO 2813:2014;

6. Transparency [%LT]

The transparency has been measured according to ASTM DI 003.

Materials used:

Polymer al) for forming first layer (A) or surface (SI):

In Example lathe material for the first layer (A) was Durabio™ 7340 of Mitsubishi, Japan

Polymer a2) for forming first layer (A) or surface (SI):

For the examples lb and 3 the material for the first layer (A) was Durabio™ 5380 of Mitsubishi, Japan

Polymer bl) for forming second layer (B):

For the examples 2 and 4 the material for the second layer (B) was

Makrolon® 3108: Very viscous amorphous, thermoplastic bisphenol A-polycarbonate with an MVR of 6 cm³/10min according to ISO 1133-1:2012-03 at 300°C and 1.2 kg supplied by Covestro Deutschland AG, Germany

Polymer b2) for forming second layer (B):

For the example 3 the material for the second layer (B) was

Makrolon® LED2245: Very viscous amorphous, thermoplastic bisphenol A-polycarbonate with an MVR of 34 cm³/10min according to ISO 1133:2012-03 at 300°C and 1.2 kg supplied by Covestro Deutschland AG, Germany.

The production of the layered structures (S) was established by extruders of the company Breyer (Germany) for heating and melting of polymer A) and heating and melting of polymer B) to form the comparative and inventive examples la, lb and 2 to 4. The temperature selected in the different phases of the extrusion are listed in table 1. The results of all examples la, lb and 2 to 4 are listed in table 2. Examples

Example 1

General production standard for extrusion and co-extrusion films

The plant used consists of

■ an extruder A with a screw of 105 mm in diameter (D) and a length of 41xD for applying polymer A) to form first layer (A). The screw has a degassing zone;

■ a coextruder B with a screw of the length 25 D and a diameter of 35 mm for applying polymer B) to form second layer (B)

■ a reversing head;

■ a special coextrusion nozzle 1500 mm in width;

■ a triple roller polishing calendar with horizontal roller arrangement, whereby the third roller is tiltable by +/- 45° relative to the horizontal;

■ a roller race;

■ a machine for reciprocal application of a protective plastic film (C) made of polypropylene;

■ a take-off machine;

■ a spooling station.

Granulates of the polymer A) were fed to the main extrusion hopper. Granulates of the polymer B) were fed to the coextrusion hopper. Melting and conveying of the respective material took place in the respective cylinder/screw plastifier system. Both material melts came together in the coextrusion nozzle. The melt arrived at the polishing calendar from the nozzle. Final shaping and cooling of the material took place on the polishing calendar. The temperatures of the polishing calenders are listed in table 2. One rubber roller and one polished chrome or steek rollers were used for structuring the film surfaces. Subsequently the film was transported by a take-off machine, the protective plastic film applied on both sides, and afterwards the film was spooled.

Table 1 : results of film insert molding 1 to 4 according to method 1

The results in table 1 show that layered structures which comprise a combination of at least one first layer (A) and at least one second layer (B) show stable film insert molding parts, in contrast to those which only comprise a layer formed solely of material comprising more than 48 wt.-% of isosorbide as diol component, here mentioned as comparative example la and lb. By passing the standard of a reproducible FIM process, under conditions described below, which results in a homogenous surface the examples 2 to 4 have achieved the same results as a FIM process with a standard polycarbonate film of 375 pm, for example made of material (bl) or (b2).

A fail in the test would mean that the part made by the FIM process has defects due to delamination caused by total or partial adhesion loss between the ink layer in form of layer (E) and the film comprising layer (A) and (B), wherein layer (B) is in contact with layer (E). This has initially been proven by visual inspection. Visual inspection was conducted using a LED lamp of the type “LED lamp MAULvisio” of company Jakob Maul GmbH, Germany, with a magnifying factor of 1,75. The LED lamp is preferably of 2000 lux illuminance and examination is performed by ensuring a 30 - 40 cm distance between the sample and the magnifying element. If a failure in form of a partial or complete delamination was visually recognized no further examination was necessary. If the visual inspection was passed the adhesion was examined using a standard cross-hatch test according to ISO 2409:2007. The failure can manifest itself directly after the FIM process or after a climate chamber test (storage in an oven at 90 °C & 96 % RH for 72 h.). To pass the test the adhesion after the climate chamber test had to be 0 according to ISO 2409:2007.

The temperatures T1 when the polymers exit the extruder and T2 when the polymers exit the dye are listed in table 2.

Figures The figures show in:

Figure 1: a schematic illustration of a layered structure (S) according to the invention;

Figure 2: a scheme of the inventive process;

Figure 3: a photo of a comparative layered structure according to example la;

Figure 4: a photo of a comparative layered structure according to example lb;

Figure 5: a photo of an inventive layered structure according to example 2.

In figure 1 a layered structure (S) 50 according to the invention is shown comprising a first layer (A) 10 coextruded with a second layer (B) 20 with the materials and under the conditions as described in the process of Example 4. After coextruding the inventive layered structure (S) 50 the layered structure 50 was formed and printed by Noriphan® HTR N screen printing ink from Prbll GmbH and formed in a FIM process under a pressure of 100 bar with a cycle time of 20 seconds and then back injection molded by a polycarbonate (Makrolon® 3108) forming the layer 30 as layer (E) in contact with layer (B) 20.

Cold or hot forming processes can be applied to shape films into their preferred 3 dimensional shape. High pressure forming (HPF) process can be used to shape at temperatures around the softening temperature using compressed air. Another alternative shaping technique is thermoforming. In this process, the film is heated to significantly above its softening temperature and then formed.

Back-injection can be either a one-component (IK) or a two-component (2K) process. Injection compression molding is very effective in the FIM process. Typically, clear or tinted polycarbonate (Makrolon® ) or polycarbonate blend (Bayblend® ) will be used for back injection.

In figure 2 a scheme of a process according to the invention is shown. In step I) 100 the heating of the first polymer a) is established in the extruder. In parallel or after step I) 100, the second polymer b) is heated in step II) 200, and optionally in parallel the second polymer c) is heated in step III) 300, each in a separate extruder. In step IV) 400 the heated polymers a), b) and optionally c) are co-extruded via a dye. The kind of material and the conditions are described in example 1 and in the tables 1 and 2. The thickness of the layered structure (S) lies in a range of from 150 to 1000 pm. The built layered structure (S) might optionally be pressed through two rolls to receive a flat structure (S). In step V) 600 the layered structure (S) was formed and printed via a FIM process under a pressure of 200 bars with a cycle time of 20 seconds.

In figure 3 a layered structure 60 according to a comparative example, exactly according to example la is shown after a printing layer consisting of polycarbonate Makrolon® 3108 has been applied to the foil consisting of (al) via insert molding in a FIM process. It can be seen that the layered structure is delaminating from the surface to which it was insert molded to. Especially in the edges or comers where the layer structure is exposed to particular stress, one can observe the detachments as indicated by the red circles. These parts could not be used and are counted among the failed parts. The results of the FIM results are listed in table 1.

In figure 4 a layered structure (60) according to a comparative example, exactly according to example lb is shown. It can be seen that the layered structure (S) 60 is delaminating 40 from the surface to which it was insert molded to. In these three examples manufactured according to example lb at least a part of the surface is delaminated 40 after the insert molding process. The results of the FIM results are listed in table 1.

In figure 5 a layered structure (S) 50 according to an inventive example, exactly according to example 2 is shown. It can be seen that the layered structure (S) 60 is totally intact and no delaminating from the surface to which it was insert molded to can be seen or measured. The results of the FIM results are listed in table 1 also for this example.

Claims

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Claims

1. A layered structure (S) providing a first surface (S 1) and a second surface (S2) opposite to the first surface (SI), the layered structure (S) comprising:

(a) at least one first polymer (a), preferably a poly-condensate or a co-poly-condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (a) comprises a diol component (D) which comprises isosorbide in an amount of at least 48 wt.-%, preferably in a range of from 48 to 80 wt.-%, based on the total weight of the diol component (D);

(b) at least one second polymer (b); preferably a poly-condensate or a co-poly-condensate, especially preferably a polycarbonate or a copolycarbonate, wherein the polymer (b) comprises a diol component (DI) which comprises isosorbide in an amount of < 30 wt.-%, more preferably < 10 wt.-%, especially preferably < 5 wt.-%, based on the total weight of the diol component (DI). wherein polymer (a) builds at least 80 %, preferably 90 %, more preferably 100 % of the first surface (SI), based on the total surface of the first surface (SI), and polymer (b) builds at least 80 %, preferably 90 %, more preferably 100 % of the second surface (S2), based on the total surface of the second surface (S2).

2. The layered structure (S) according to claim 1, wherein the first surface (SI) is at least part of a first layer (A) comprising the polymer (a) and the second surface (S2) is at least part of a second layer (B) comprising the polymer (b) wherein the first layer (A) builds one outside surface of the layered structure (S) and preferably the first polymer (a) forms > 80 wt.-%, preferably > 90 wt.-%, more preferably > 95 wt.-%, based on the total weight of the first layer (A).

3. The layered structure (S) according to any of the preceding claims, wherein the layered structure (S) comprises furthermore:

(C) optionally at least one third layer (C), comprising a polymer (c),

(E) a further layer (E), especially in form of a printing layer, wherein the further layer (E) is in direct contact with second layer (B).

4. The layered structure according to any of the preceding claims, wherein the thickness of the first surface (SI) or the first layer (A) is > 10 pm, preferably > 20 pm, more preferably > 30 pm preferably, most preferably > 50 pm.

5. The layered structure according to any of the preceding claims, wherein the ratio of the thickness of the first surface (S 1) or the first layer (A) to the thickness of the second surface (S2) or the second layer (B) is in a range of 1: 10 to 10: 1, preferably 1:5 to 5: 1, more preferably 2:5 to 5:2. The layered structure (S) according to any of the preceding claims, wherein the layered structure (S) provides at least one of the following properties

(51) a thickness in a range of 75 to 500 pm, according to DIN ISO 4593-2019-06;

(52) a gloss level in a range of 10 to 100 GU, according to ISO 2813:2014;

(53) %LT in a range of from 3 to 95%, according to ASTM D1003. The layered structure (S) according to any of the preceding claims, wherein the second surface (S2) or the second layer (B) has a thickness in the range 10 to 500 pm. The layered structure (S) according to any of the preceding claims, wherein the layered structure (S), especially the first layer (A) further comprises an additive, preferably selected from the group consisting of an UV-absorber, dyes, pigments, inorganic fillers or a mixture of at least two thereof. The layered structure (S) according to any of claims 3 to 8 formed in a FIM process, whereby layer (B) is in contact with layer (E). A process for producing a layered structure (S), comprising at least the following steps:

III) optionally heating a third polymer (c) by an extruder,

IV) co-extruding the first polymer (a) or the mixture of polymer (a) and polymer (b ) together with the second polymer (b) or the mixture of polymer (b) and polymer (b ) and optionally the third polymer (c) through a dye to form a first layer (A) consisting of polymer (a) or the mixture of polymer (a) and polymer (b ), a second layer (B) consisting of the second polymer (b) or the mixture of polymer (b) and polymer (b ) and optionally a third layer (C) consisting of polymer (c) to result in the layered structure (S),

VI) optionally further processing, preferably decorating and/or back injection molding of the layered structure (S) of step V), preferably by a further printed layer (E) in a FIM process. The process according to claim 11, wherein the first polymer (a) has a higher content of isosorbide than the second polymer (b). A layered structure (S) obtained by a process according to claims 11 or 12. Use of a layered structure (S) according to any of claims 1 to 9 or 12 or produced by a process according to claim 10 or 11 for fdm insert molding, especially for fdm insert molding of decorative parts, like the layered structure (S), preferably in cars, The use of the layered structure (S) according to claim 13, wherein layer (B) is on one outside of the decorative part. A printed polymeric article obtainable using a layered structure (S) according to any of claims 1 to 9 or 12 or produced according to claim 10 or 11.