CN117480050A - Ultra-thin layered structure with specific properties - Google Patents

Ultra-thin layered structure with specific properties Download PDF

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Publication number
CN117480050A
CN117480050A CN202280040589.0A CN202280040589A CN117480050A CN 117480050 A CN117480050 A CN 117480050A CN 202280040589 A CN202280040589 A CN 202280040589A CN 117480050 A CN117480050 A CN 117480050A
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range
layer
polymer
layered structure
din
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H·普德莱纳
T·戴瓦拉吉
J·罗纳
S·詹克
N·赫尔曼斯
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Covestro Deutschland AG
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Covestro Deutschland AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings

Abstract

The invention relates to a layered structure S comprising: A. at least one first layer a having a first outer surface A1 and a second surface A2 comprising at least a polymer (a), wherein layer a has a thickness in the range of 10 to 50 μm, preferably in the range of 10 to 30 μm, and b. at least one additional layer B comprising at least a polymer (B), wherein layer a of the layered structure s. Provides at least one, preferably two, more preferably all of the following properties: s1 an adhesion between the at least one first layer A and the at least one additional layer B, measured according to ASTM D903-1998 at a traction angle of 180 DEG, is in the range of 0.001 to 0.05N/cm; s2, according to DIN EN ISO 868-2003-10, the hardness is more than or equal to 85D, preferably more than or equal to 87D, more preferably more than or equal to 90D; s3, the melting temperature is more than or equal to 200 ℃; preferably in the range of 210 to 350 ℃, more preferably in the range of 230 to 330 DEG CAn inner part; most preferably in the range of 250 to 320 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein T g Defined as midpoint temperature (tangent); s4, the glass transition temperature Tg is more than or equal to 70 ℃; preferably in the range of 80 to 250 ℃, more preferably in the range of 80 to 240 ℃; most preferably in the range of 80 to 200 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein T g Defined as midpoint temperature (tangent); s5 melt volume Rate (MVR; measured according to DIN ISO 1133-1-2012-03; 300 ℃,2.16 kg) > 3cm 3 Preferably ≡3.5 cm/10 min 3 /10min, still more preferably 4cm or more 3 10min; s6. The additives are in the range of 0.01 to 0.5% by weight.

Description

Ultra-thin layered structure with specific properties
The invention relates to a layered structure s comprising at least two layers, namely at least one layer a and at least one layer b, to a method for the production thereof and to the use thereof as a coating for internal and external applications.
The production of very thin layers has limitations because many parameters must be controlled during the production, transportation and use of the thin layers. To date, it has not been easy to produce films with continuously good quality in a wide variety of ways for a variety of applications.
Accordingly, there is a need to develop a layered structure that includes at least one thin layer that can be easily separated to provide a thin film. Furthermore, it is necessary to develop a layered structure comprising at least one thin layer with high quality standards, especially in terms of constant thickness, which can be used for different applications, such as internal and external applications.
Solutions to such a hierarchy are described in claim 1 and the dependent claims related to the hierarchy S.
A first aspect of the invention relates to a hierarchical structure s, comprising:
A. at least one first layer a having a first outer surface A1 and a second surface A2 comprising at least a polymer (a), wherein the first layer a has a thickness in the range of 10 to 50 μm, preferably in the range of 10 to 30 μm, and
B. at least one additional layer B comprising at least a polymer (B),
wherein layer a of the layered structure s. Provides at least one, preferably two, more preferably three, most preferably all of the following properties:
s1 an adhesion between the at least one first layer A and the at least one additional layer B, measured according to ASTM D903-1998 at a traction angle of 180 DEG, is in the range of 0.001 to 0.05N/cm, preferably in the range of 0.005 to 0.04N/cm, more preferably in the range of 0.01 to 0.02N/cm;
s2, according to DIN EN ISO 868-2003-10, the hardness is more than or equal to 85D, preferably more than or equal to 87D, more preferably more than or equal to 90D;
s3, the melting temperature is more than or equal to 200 ℃; preferably in the range of 210 to 350 ℃, more preferably in the range of 230 to 330 ℃; most preferably in the range of 250 to 320 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein T g Defined as midpoint temperature (tangent);
s4, the glass transition temperature Tg is more than or equal to 70 ℃; preferably in the range of 80 to 250 ℃, more preferably in the range of 80 to 240 ℃; most preferably in the range of 80 to 200 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein T g Defined as the midpoint temperature (tangential method), or Vicat softening temperature B/50. Gtoreq.70℃as determined according to ISO 306-2014-03 (50N; 50 °/h); preferably in the range of 75 to 230 ℃, more preferably in the range of 80 to 230 ℃; optimum for the production of a productSelected in the range of 85 to 225 ℃;
s5 melt volume Rate (MVR; measured according to DIN ISO 1133-1-2012-03; 300 ℃,2.16 kg) > 3cm 3 Preferably ≡3.5 cm/10 min 3 /10min, still more preferably 4cm or more 3 /10min；
The s6. Additives are in the range of 0.01 to 0.5 wt%, preferably in the range of 0.02 to 0.3 wt%, more preferably in the range of 0.05 to 0.1 wt%.
Preferably, the layered structure s. Provides a property or a combination of properties selected from the group consisting of: s1; s2; s3; s4; s5; s6; s1, and s 2; s1, and s 3; s1, and s 4; s1, and s 5; s1, and s 6; s2, and s 3; s2, and s 4; s2, and s 5; s2, and s 6; s3, and s 4; s3, and s 5; s3, and s 6; s4, and s 5; s4, and s 6; s5, and s 6; s1, S2, S3; s1, S2, S4; s1, S2, S5; s1, S2, S6; s1, S3, S4; s1, S3, S5; s1, S3, S6; s1, S4, S5; s1, S4 and S6; s1, S5, S6; s2, S3, S4; s2, S3, S5; s2, S3, S6; s2, S4, S5; s2, S4 and S6; s2, S5 and S6; s3, S4, S5; s3, S4, S6; s3, S5, S6; s4, S5 and S6; s1, S2, S3 and S4; s1, S2, S3 and S5; s1, S2, S3 and S6; s1, S2, S4 and S5; s1, S2, S4 and S6; s1, S2, S5 and S6; s1, S3, S4 and S5; s1, S3, S4 and S6; s1, S3, S5 and S6; s1, S4, S5 and S6; s2, S3, S4 and S5; s2, S3, S4 and S6; s2, S3, S5 and S6; s1, S2, S3, S4 and S5; s1, S2, S3, S4 and S6; s1, S2, S3, S5 and S6; s1, S2, S4, S5 and S6; s1, S3, S4, S5 and S6; s2, S3, S4, S5 and S6; s1 and s2 and s3 and s4 and s5 and s6.
Preferably, the adhesion between the at least one first layer a. And the at least one additional layer b. Measured at a pull angle of 180 ° according to ASTM D903-1998 is in the range of 0.001 to 0.05N/cm, preferably in the range of 0.005 to 0.04N/cm, more preferably in the range of 0.01 to 0.02N/cm.
In a preferred embodiment of the layered structure s., preferably layer a, provides at least one, preferably two, more preferably all of the following properties:
s7. a thickness in the range of 15 to 250 μm, preferably in the range of 20 to 200 μm, most preferably in the range of 30 to 100 μm;
s8. thickness deviation over an area of 20 x 20cm, preferably 50 x 50cm, more preferably 100 x 100cm is in the range of 0.01 to 5 μm, preferably 0.02 to 2 μm, more preferably 0.03 to 1 μm, most preferably 0.05 to 0.5 μm;
s9 the tensile strength measured according to DIN EN ISO 527-1:2012-06 is in the range of 10 to 150MPa, preferably 20 to 100 MPa;
s10. an elongation at break in the range of 20 to 500%, preferably 50 to 400%, measured according to DIN N ISO 527-1:2012-06;
s11. water absorption (ISO 62:2008; 24 hours at 23 ℃) is in the range of 0.01 to 0.5 wt%, more preferably in the range of 0.05 to 0.4 wt% (saturation value).
Preferably, the layered structure s. Provides a property or a combination of properties selected from the group consisting of: s7; s8; s9; s10; s11; s7, and s 8; s7, and s 9; s7, and s 10; s7, and s 11; s8, and s 9; s8, and s 10; s8, and s 11; s9, and s 10; s9, and s 11; s10, and s 11; s7, S8, S9; s7, S8, S10; s7, S8, S11; s7, S9, S10; s7, S9, S11; s8, S9, S10; s8, S9, S11; s8, S10, S11; s9, S10, S11; s7, S8, S9 and S10; s7, S8, S9, and S11; s7, S8, S10 and S11; s7, S9, S10 and S11; s8, S9, S10 and S11; s7, S8, S9, S10, and S11.
Preferably, the layered structure s. In addition to any of properties s1, to s6, and combinations thereof mentioned, any of the combinations of properties listed above for s7, to s11.
Preferably, the adhesion is chosen within a range where the two layers a, b can be easily separated by manual force, but not by itself without any force input. The adhesion between the layers a, b enables the layered structure s to be transported without risk of cracking in the thin layer a, but the layer a is easily separated for further processing by separating the layer b by hand only or with a machine using small forces. The separation of layer a from layer B is preferably provided without any detectable polymer (B) residue on layer a.
Preferably, the regulation of the adhesion between layer a and layer b is not supported by any additives in layer a or layer b. Due to the layered structure s. Possibly for specific applications where additives are not desired, the content of additives such as plasticizers, defoamers, pigments and any other organic or inorganic components is preferably low. According to the invention, additives are molecules having a molecular mass of 1000g/mol or less, more preferably 500g/mol or less, still more preferably 300g/mol or less.
In a preferred embodiment of the layered structure s, layer a provides at least one, preferably at least two, more preferably all of the following properties:
a1. the gloss at 60℃angle measured according to DIN EN ISO 2813-2015-02 is in the range from 10 to 110;
a2. the surface roughness of at least the first surface A1 measured according to DIN EN ISO 4287:2010-07/DIN EN ISO 4288:1998-04 is in the range of 0.1 to 5.50 μm;
a3. a birefringence measured by a polarizing microscope in the range of 1 to 100 nm;
a4. transparency measured according to ASTM D1003-13 is in the range of 5 to 95%;
a5. a density in the range of 1 to 1.35g/l measured according to DIN EN ISO 1183-1:2019-09;
a6. tensile strength measured according to DIN EN ISO 527-1:2012-06 is in the range of 10 to 150MPa, preferably 20 to 100 MPa;
a7. An elongation at break measured according to DIN N ISO 527-1:2012-06 in the range of 20 to 500%, preferably 50 to 400%;
a8. the thickness is in the range of 5 to 50 μm, preferably in the range of 10 to 25 μm, most preferably in the range of 10 to 20 μm;
a9. the thickness deviation is in the range of 0.001 to 0.1 μm, preferably 0.002 to 0.05 μm, more preferably 0.003 to 0.03 μm, most preferably 0.005 to 0.01 μm.
Preferably, the first layer a. Of the layered structure s. Provides a property or combination of properties selected from the group consisting of: a1.; a2; a3.; a4.; a5.; a6.; a7.; a8.; a9.; a1. and a 2; a1. and a3.; a1. and a4.; a1. and a5.; a1. and a6.; a1. and a7.; a1. and a8.; a1. and a9.; a2. and a3.; a2. and a4.; a2. and a5.; a2. and a6.; a2. and a7.; a2. and a8.; a2. and a9.; a3. and a4.; a3. and a5.; a3. and a6.; a3. and a7.; a3. and a8.; a3. and a9.; a4. and a5.; a4. and a6.; a4. and a7.; a4. and a8.; a4. and a9.; a5. and a6.; a5. and a7.; a5. and a8.; a5. and a9.; a6. and a7.; a6. and a8.; a6. and a9.; a7. and a8.; a7. and a9.; a8. and a9.; a1. a2, and a3.; a1. a2, and a4.; a1. a2, and a5.; a1. a2, and a6.; a1. a2, and a7.; a1. a2, and a8.; a1. a2, and a9.; a1. and a3. and a4.; a1. and a3. and a5.; a1. and a3. and a6.; a1. and a3. and a7.; a1. and a3. and a8.; a1. and a3. and a9.; a1. and a4. and a5.; a1. and a4. and a6.; a1. and a4. and a7.; a1. and a4. and a8.; a1. and a4. and a9.; a1. and a5. and a6.; a1. and a5. and a7.; a1. and a5. and a8.; a1. and a5. and a9.; a1. and a6. and a7.; a1. and a6. and a8.; a1. and a6. and a9.; a1. and a7. and a8.; a1. and a7. and a9.; a1. and a8. and a9.; a2. and a3. and a4.; a2. and a3. and a5.; a2. and a3. and a6.; a2. and a3. and a7.; a2. and a3. and a8.; a2. and a3. and a9.; a2. and a4. and a5.; a2. and a4. and a6.; a2. and a4. and a7.; a2. and a4. and a8.; a2. and a4. and a9.; a2. and a5. and a6.; a2. and a5. and a7.; a2. and a5. and a8.; a2. and a5. and a9.; a2. and a6. and a7.; a2. and a6. and a8.; a2. and a6. and a9.; a2. and a7. and a8.; a2. and a7. and a9.; a2. and a8. and a9.; a3. and a4. and a5.; a3. and a4. and a6.; a3. and a4. and a7.; a3. and a4. and a8.; a3. and a4. and a9.; a3. and a5. and a6.; a3. and a5. and a7.; a3. and a5. and a8.; a3. and a5. and a9.; a3. and a6. and a7.; a3. and a6. and a8.; a3. and a6. and a9.; a3. and a7. and a8.; a3. and a7. and a9.; a3. and a8. and a9.; a4. and a5. and a6.; a4. and a5. and a7.; a4. and a5. and a8.; a4. and a5. and a9.; a4. and a6. and a7.; a4. and a6. and a8.; a4. and a6. and a9.; a4. and a7. and a8.; a4. and a7. and a9.; a4. and a8. and a9.; a5. and a6. and a7.; a5. and a6. and a8.; a5. and a6. and a9.; a5. and a7. and a8.; a5. and a7. and a9.; a5. and a8. and a9.; a6. and a7. and a8.; a6. and a7. and a9.; a6. and a8. and a9.; a7. and a8. and a9.; a1. a2, and a3. and a4.; a1. a2, and a3. and a5.; a1. a2, and a3. and a6.; a1. a2, and a3. and a7.; a1. a2, and a3. and a8.; a1. a2, and a3. and a9.; a1. a2, and a4. and a5.; a1. a2, and a4. and a6.; a1. a2, and a4. and a7.; a1. a2, and a4. and a8.; a1. a2, and a4. and a9.; a1. a2, and a5. and a6.; a1. a2, and a5. and a7.; a1. a2, and a5. and a8.; a1. a2, and a5. and a9.; a1. a2, and a6. and a7.; a1. a2, and a6. and a8.; a1. a2, and a6. and a9.; a1. a2, and a7. and a8.; a1. a2, and a7. and a9.; a1. a2, and a8. and a9.; a1. and a3. and a4. and a5.; a1. and a3. and a4. and a6.; a1. and a3. and a4. and a7.; a1. and a3. and a4. and a8.; a1. and a3. and a4. and a9.; a1. and a3. and a5. and a6.; a1. and a3. and a5. and a7.; a1. and a3. and a5. and a8.; a1. and a3. and a5. and a9.; a1. and a3. and a6. and a7.; a1. and a3. and a6. and a8.; a1. and a3. and a6. and a9.; a1. and a3. and a7. and a8.; a1. and a3. and a7. and a9.; a1. and a3. and a8. and a9.; a1. and a4. and a5. and a6.; a1. and a4. and a5. and a7.; a1. and a4. and a5. and a8.; a1. and a4. and a5. and a9.; a1. and a4. and a6. and a7.; a1. and a4. and a6. and a8.; a1. and a4. and a6. and a9.; a1. and a4. and a7. and a8.; a1. and a4. and a7. and a9.; a1. and a4. and a8. and a9.; a1. and a5. and a6. and a7.; a1. and a5. and a6. and a8.; a1. and a5. and a6. and a9.; a1. and a5. and a7. and a8.; a1. and a5. and a7. and a9.; a1. and a5. and a8. and a9.; a1. and a6. and a7. and a8.; a1. and a6. and a7. and a9.; a1. and a6. and a8. and a9.; a1. and a7. and a8. and a9.; a2. and a3. and a4. and a5.; a2. and a3. and a4. and a6.; a2. and a3. and a4. and a7.; a2. and a3. and a4. and a8.; a2. and a3. and a4. and a9.; a2. and a3. and a5. and a6.; a2. and a3. and a5. and a7.; a2. and a3. and a5. and a8.; a2. and a3. and a5. and a9.; a2. and a3. and a6. and a7.; a2. and a3. and a6. and a8.; a2. and a3. and a6. and a9.; a2. and a3. and a7. and a8.; a2. and a3. and a7. and a9.; a2. and a3. and a8. and a9.; a2. and a4. and a5. and a6.; a2. and a4. and a5. and a7.; a2. and a4. and a5. and a8.; a2. and a4. and a5. and a9.; a2. and a4. and a6. and a7.; a2. and a4. and a6. and a8.; a2. and a4. and a6. and a9.; a2. and a4. and a7. and a8.; a2. and a4. and a7. and a9.; a2. and a4. and a8. and a9.; a2. and a5. and a6. and a7.; a2. and a5. and a6. and a8.; a2. and a5. and a6. and a9.; a2. and a5. and a7. and a8.; a2. and a5. and a7. and a9.; a2. and a5. and a8. and a9.; a2. and a6. and a7. and a8.; a2. and a6. and a7. and a9.; a2. and a6. and a8. and a9.; a2. and a7. and a8. and a9.; a3. and a4. and a5. and a6.; a3. and a4. and a5. and a7.; a3. and a4. and a5. and a8.; a3. and a4. and a5. and a9.; a3. and a4. and a6. and a7.; a3. and a4. and a6. and a8.; a3. and a4. and a6. and a9.; a3. and a4. and a7. and a8.; a3. and a4. and a7. and a9.; a3. and a4. and a8. and a9.; a3. and a5. and a6. and a7.; a3. and a5. and a6. and a8.; a3. and a5. and a6. and a9.; a3. and a5. and a7. and a8.; a3. and a5. and a7. and a9.; a3. and a5. and a8. and a9.; a3. and a6. and a7. and a8.; a3. and a6. and a7. and a9.; a3. and a6. and a8. and a9.; a3. and a7. and a8. and a9.; a4. and a5. and a6. and a7.; a4. and a5. and a6. and a8.; a4. and a5. and a6. and a9.; a4. and a5. and a7. and a8.; a4. and a5. and a7. and a9.; a4. and a5. and a8. and a9.; a5. and a6. and a7. and a8.; a5. and a6. and a7. and a9.; a5. and a6. and a8. and a9.; a6. and a7. and a8. and a9.; a1. a2, and a3., and a4., and a5.; a1. a2, and a3., and a4., and a6.; a1. a2, and a3., and a4., and a7.; a1. a2, and a3., and a4., and a8.; a1. a2, and a3., and a4., and a9.; a1. a2, and a4., and a5., and a6.; a1. a2, and a4., and a5., and a7.; a1. a2, and a4., and a5., and a8.; a1. a2, and a4., and a5., and a9.; a1. a2, and a4., and a6., and a7.; a1. a2, and a4., and a6., and a8.; a1. a2, and a4., and a6., and a9.; a1. a2, and a4., and a7., and a8.; a1. a2, and a4., and a7., and a9.; a1. a2, and a4., and a8., and a9.; a1. a2, and a5., and a6., and a7.; a1. a2, and a5., and a6., and a8.; a1. a2, and a5., and a6., and a9.; a1. a2, and a5., and a7., and a8.; a1. a2, and a5., and a7., and a9.; a1. a2, and a5., and a8., and a9.; a1. a2, and a6., and a7., and a8.; a1. a2, and a6., and a7., and a9.; a1. a2, and a6., and a8., and a9.; a1. a2, and a7., and a8., and a9.; a1. and a3. and a4. and a5. and a6.; a1. and a3. and a4. and a5. and a7.; a1. and a3. and a4. and a5. and a8.; a1. and a3. and a4. and a5. and a9.; a1. and a3. and a4. and a6. and a7.; a1. and a3. and a4. and a6. and a8.; a1. and a3. and a4. and a6. and a9.; a1. and a3. and a4. and a7. and a8.; a1. and a3. and a4. and a7. and a9.; a1. and a3. and a4. and a8. and a9.; a1. and a3. and a5. and a6. and a7.; a1. and a3. and a5. and a6. and a8.; a1. and a3. and a5. and a6. and a9.; a1. and a3. and a5. and a7. and a8.; a1. and a3. and a5. and a7. and a9.; a1. and a3. and a5. and a8. and a9.; a1. and a3. and a6. and a7. and a8.; a1. and a3. and a6. and a7. and a9.; a1. and a3. and a6. and a8. and a9.; a1. and a3. and a7. and a8. and a9.; a1. and a4. and a5. and a6. and a7.; a1. and a4. and a5. and a6. and a8.; a1. and a4. and a5. and a6. and a9.; a1. and a4. and a5. and a7. and a8.; a1. and a4. and a5. and a7. and a9.; a1. and a4. and a5. and a8. and a9.; a1. and a4. and a6. and a7. and a8.; a1. and a4. and a6. and a7. and a9.; a1. and a4. and a6. and a8. and a9.; a1. and a4. and a7. and a8. and a9.; a1. and a5. and a6. and a7. and a8.; a1. and a5. and a6. and a7. and a9.; a1. and a5. and a6. and a8. and a9.; a1. and a5. and a7. and a8. and a9.; a1. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6.; a2. and a3. and a4. and a5. and a7.; a2. and a3. and a4. and a5. and a8.; a2. and a3. and a4. and a5. and a9.; a2. and a3. and a4. and a6. and a7.; a2. and a3. and a4. and a6. and a8.; a2. and a3. and a4. and a6. and a9.; a2. and a3. and a4. and a7. and a8.; a2. and a3. and a4. and a7. and a9.; a2. and a3. and a4. and a8. and a9.; a2. and a3. and a5. and a6. and a7.; a2. and a3. and a5. and a6. and a8.; a2. and a3. and a5. and a6. and a9.; a2. and a3. and a5. and a7. and a8.; a2. and a3. and a5. and a7. and a9.; a2. and a3. and a5. and a8. and a9.; a2. and a3. and a6. and a7. and a8.; a2. and a3. and a6. and a7. and a9.; a2. and a3. and a6. and a8. and a9.; a2. and a3. and a7. and a8. and a9.; a2. and a4. and a5. and a6. and a7.; a2. and a4. and a5. and a6. and a8.; a2. and a4. and a5. and a6. and a9.; a2. and a4. and a5. and a7. and a8.; a2. and a4. and a5. and a7. and a9.; a2. and a4. and a5. and a8. and a9.; a2. and a4. and a6. and a7. and a8.; a2. and a4. and a6. and a7. and a9.; a2. and a4. and a6. and a8. and a9.; a2. and a4. and a7. and a8. and a9.; a2. and a5. and a6. and a7. and a8.; a2. and a5. and a6. and a7. and a9.; a2. and a5. and a6. and a8. and a9.; a2. and a5. and a7. and a8. and a9.; a2. and a6. and a7. and a8. and a9.; a3. and a4. and a5. and a6. and a7.; a3. and a4. and a5. and a6. and a8.; a3. and a4. and a5. and a6. and a9.; a3. and a4. and a5. and a7. and a8.; a3. and a4. and a5. and a7. and a9.; a3. and a4. and a5. and a8. and a9.; a3. and a4. and a6. and a7. and a8.; a3. and a4. and a6. and a7. and a9.; a3. and a4. and a6. and a8. and a9.; a3. and a4. and a7. and a8. and a9.; a3. and a5. and a6. and a7. and a8.; a3. and a5. and a6. and a7. and a9.; a3. and a5. and a6. and a8. and a9.; a3. and a5. and a7. and a8. and a9.; a3. and a6. and a7. and a8. and a9.; a4. and a5. and a6. and a7. and a8.; a4. and a5. and a6. and a7. and a9.; a4. and a5. and a6. and a8. and a9.; a4. and a5. and a7. and a8. and a9.; a4. and a6. and a7. and a8. and a9.; a5. and a6. and a7. and a8. and a9.; a1. a2, and a3. and a4., and a5. and a6.; a1. a2, and a3. and a4., and a5. and a7.; a1. a2, and a3. and a4., and a5. and a8.; a1. a2, and a3. and a4., and a5. and a9.; a1. a2, and a3. and a4., and a6. and a7.; a1. a2, and a3. and a4., and a6. and a8.; a1. a2, and a3. and a4., and a6. and a9.; a1. a2, and a3. and a4., and a7. and a8.; a1. a2, and a3. and a4., and a7. and a9.; a1. a2, and a3. and a4., and a8. and a9.; a1. a2, and a3. and a5., and a6. and a7.; a1. a2, and a3. and a5., and a6. and a8.; a1. a2, and a3. and a5., and a6. and a9.; a1. a2, and a3. and a5., and a7. and a8.; a1. a2, and a3. and a5., and a7. and a9.; a1. a2, and a3. and a5., and a8. and a9.; a1. a2, and a3. and a6., and a7. and a8.; a1. a2, and a3. and a6., and a7. and a9.; a1. a2, and a3. and a6., and a8. and a9.; a1. a2, and a3. and a7., and a8. and a9.; a1. a2, and a4. and a5., and a6. and a7.; a1. a2, and a4. and a5., and a6. and a8.; a1. a2, and a4. and a5., and a6. and a9.; a1. a2, and a4. and a5., and a7. and a8.; a1. a2, and a4. and a5., and a7. and a9.; a1. a2, and a4. and a5., and a8. and a9.; a1. a2, and a4. and a6., and a7. and a8.; a1. a2, and a4. and a6., and a7. and a9.; a1. a2, and a4. and a6., and a8. and a9.; a1. a2, and a4. and a7., and a8. and a9.; a1. a2, and a5. and a6., and a7. and a8.; a1. a2, and a5. and a6., and a7. and a9.; a1. a2, and a5. and a6., and a8. and a9.; a1. a2, and a5. and a7., and a8. and a9.; a1. a2, and a6. and a7., and a8. and a9.; a1. and a3. and a4. and a5. and a6. and a7.; a1. and a3. and a4. and a5. and a6. and a8.; a1. and a3. and a4. and a5. and a6. and a9.; a1. and a3. and a4. and a5. and a7. and a8.; a1. and a3. and a4. and a5. and a7. and a9.; a1. and a3. and a4. and a5. and a8. and a9.; a1. and a3. and a4. and a6. and a7. and a8.; a1. and a3. and a4. and a6. and a7. and a9.; a1. and a3. and a4. and a6. and a8. and a9.; a1. and a3. and a4. and a7. and a8. and a9.; a1. and a3. and a5. and a6. and a7. and a8.; a1. and a3. and a5. and a6. and a7. and a9.; a1. and a3. and a5. and a6. and a8. and a9.; a1. and a3. and a5. and a7. and a8. and a9.; a1. and a3. and a6. and a7. and a8. and a9.; a1. and a4. and a5. and a6. and a7. and a8.; a1. and a4. and a5. and a6. and a7. and a9.; a1. and a4. and a5. and a6. and a8. and a9.; a1. and a4. and a5. and a7. and a8. and a9.; a1. and a4. and a6. and a7. and a8. and a9.; a1. and a5. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6. and a7.; a2. and a3. and a4. and a5. and a6. and a8.; a2. and a3. and a4. and a5. and a6. and a9.; a2. and a3. and a4. and a5. and a7. and a8.; a2. and a3. and a4. and a5. and a7. and a9.; a2. and a3. and a4. and a5. and a8. and a9.; a2. and a3. and a4. and a6. and a7. and a8.; a2. and a3. and a4. and a6. and a7. and a9.; a2. and a3. and a4. and a6. and a8. and a9.; a2. and a3. and a4. and a7. and a8. and a9.; a2. and a3. and a5. and a6. and a7. and a8.; a2. and a3. and a5. and a6. and a7. and a9.; a2. and a3. and a5. and a6. and a8. and a9.; a2. and a3. and a5. and a7. and a8. and a9.; a2. and a3. and a6. and a7. and a8. and a9.; a2. and a4. and a5. and a6. and a7. and a8.; a2. and a4. and a5. and a6. and a7. and a9.; a2. and a4. and a5. and a6. and a8. and a9.; a2. and a4. and a5. and a7. and a8. and a9.; a2. and a4. and a6. and a7. and a8. and a9.; a2. and a5. and a6. and a7. and a8. and a9.; a3. and a4. and a5. and a6. and a7. and a8.; a3. and a4. and a5. and a6. and a7. and a9.; a3. and a4. and a5. and a6. and a8. and a9.; a3. and a4. and a5. and a7. and a8. and a9.; a3. and a4. and a6. and a7. and a8. and a9.; a3. and a5. and a6. and a7. and a8. and a9.; a4. and a5. and a6. and a7. and a8. and a9.; a1. a2, and a3. and a4., and a5. and a6. and a7.; a1. a2, and a3. and a4., and a5. and a6. and a8.; a1. a2, and a3. and a4., and a5. and a6. and a9.; a1. a2, and a3. and a4., and a5. and a7. and a8.; a1. a2, and a3. and a4., and a5. and a7. and a9.; a1. a2, and a3. and a4., and a5. and a8. and a9.; a1. a2, and a3. and a4., and a6. and a7. and a8.; a1. a2, and a3. and a4., and a6. and a7. and a9.; a1. a2, and a3. and a4., and a6. and a8. and a9.; a1. a2, and a3. and a4., and a7. and a8. and a9.; a1. a2, and a3. and a5., and a6. and a7. and a8.; a1. a2, and a3. and a5., and a6. and a7. and a9.; a1. a2, and a3. and a5., and a6. and a8. and a9.; a1. a2, and a3. and a5., and a7. and a8. and a9.; a1. a2, and a3. and a6., and a7. and a8. and a9.; a1. a2, and a4. and a5., and a6. and a7. and a8.; a1. a2, and a4. and a5., and a6. and a7. and a9.; a1. a2, and a4. and a5., and a6. and a8. and a9.; a1. a2, and a4. and a5., and a7. and a8. and a9.; a1. a2, and a4. and a6., and a7. and a8. and a9.; a1. a2, and a5. and a6., and a7. and a8. and a9.; a1. and a3. and a4. and a5. and a6. and a7. and a8.; a1. and a3. and a4. and a5. and a6. and a7. and a9.; a1. and a3. and a4. and a5. and a6. and a8. and a9.; a1. and a3. and a4. and a5. and a7. and a8. and a9.; a1. and a3. and a4. and a6. and a7. and a8. and a9.; a1. and a3. and a5. and a6. and a7. and a8. and a9.; a1. and a4. and a5. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6. and a7. and a8.; a2. and a3. and a4. and a5. and a6. and a7. and a9.; a2. and a3. and a4. and a5. and a6. and a8. and a9.; a2. and a3. and a4. and a5. and a7. and a8. and a9.; a2. and a3. and a4. and a6. and a7. and a8. and a9.; a2. and a3. and a5. and a6. and a7. and a8. and a9.; a2. and a4. and a5. and a6. and a7. and a8. and a9.; a3. and a4. and a5. and a6. and a7. and a8. and a9.; a1. a2, and a3. and a4., and a5. and a6. and a7. and a8.; a1. a2, and a3. and a4., and a5. and a6. and a7. and a9.; a1. a2, and a3. and a4., and a5. and a6. and a8. and a9.; a1. a2, and a3. and a4., and a5. and a7. and a8. and a9.; a1. a2, and a3. and a4., and a6. and a7. and a8. and a9.; a1. a2, and a3. and a5., and a6. and a7. and a8. and a9.; a1. a2, and a4. and a5., and a6. and a7. and a8. and a9.; a1. and a3. and a4. and a5. and a6. and a7. and a8. and a9.; a2. and a3. and a4. and a5. and a6. and a7. and a8. and a9.; a1. a2, a3., a4., a5., a6., a7., a8., a9..
Preferably, layer a. Differs from layer b. In at least one, preferably at least two, even more preferably all of the following properties:
pr1. The thickness difference is in the range of 0.01 to 50 μm, preferably 0.02 to 30 μm, more preferably 0.03 to 10 μm, most preferably 0.05 to 1 μm;
pr2. The tensile strength difference measured according to DIN EN ISO 527-1:2012-06 is in the range of 50 to 500kPa, preferably 60 to 400 kPa;
pr3 the difference in elongation at break measured according to DIN N ISO 527-1:2012-06 is in the range of 10 to 100%, preferably 20 to 80%;
pr4. the difference in refractive index n is not more than 0.5, preferably not more than 0.3, more preferably not more than 0.1;
pr5. the difference in birefringence is 10nm or less, preferably 5 or less, more preferably 2 or less.
The polymer (a) may be any polymer chosen by the person skilled in the art for establishing a layer a in the layered structure s. Preferably, the polymer (a) provides a Tg in the range of 100 to 180 ℃, more preferably in the range of 120 to 160 ℃, most preferably in the range of 130 to 150 ℃, as determined by Differential Scanning Calorimetry (DSC) at a heating rate of 20K/min according to standard DIN EN 61006:2004, wherein Tg is defined as midpoint temperature (tangential method).
The polymer (B) may be any polymer chosen by the person skilled in the art for establishing a layer B in the layered structure s. Preferably, polymer (B) provides a Tg in the range of 10 to 80 ℃, more preferably in the range of 20 to 60 ℃, most preferably in the range of 30 to 50 ℃, as determined by Differential Scanning Calorimetry (DSC) at a heating rate of 20K/min according to standard DIN EN 61006:2004, wherein Tg is defined as the midpoint temperature (tangential method).
Particularly suitable polymers (A) or (B) are one or more polycarbonates or copolycarbonates based on diphenols, one or more polyacrylates or copolyacrylates and one or more polymethacrylates or copolymethacrylates, for example and preferably polymethyl methacrylate or poly (meth) acrylate (PMMA), one or more styrene-containing polymers or copolymers, for example and preferably Polystyrene (PS), acrylonitrile-butadiene-styrene (ABS) or polystyrene-acrylonitrile (SAN), one or more thermoplastic polyurethanes and one or more polyolefins, for example and preferably polypropylene type or cycloolefin (COC) based polyolefins, for example Hoechst (now TOPAS Advanced Polymers)One or more polycondensates or copolycondensates of terephthalic acid, for example and preferably polyethylene terephthalate or copolyethylene terephthalate (PET or CoPET), glycol-modified PET (PETG), glycol-modified poly-or copolycyclohexanedimethanol terephthalate (PCTG), or polybutylene terephthalate or copolybutylene terephthalate (PBT or CoPBT), polyamide (PA), one or more polycondensates or copolypolycondensates of naphthalene dicarboxylic acid, for example and preferably polyethylene naphthalate (PEN), one or more polycondensates or copolycondensates of at least one cycloalkyl dicarboxylic acid Copolycondensates, such as and preferably polycyclohexanedimethanol cyclohexane dicarboxylic acid (PCCD), polysulphone (PSU), mixtures of at least two of the abovementioned or blends thereof.
Particularly preferred polymers (A) or (B) are one or more polycarbonates or copolycarbonates based on diphenols or blends comprising at least one polycarbonate or copolycarbonate. Very particular preference is given to blends comprising at least one polycarbonate or copolycarbonate and at least one polycondensate or copolycondensate of terephthalic acid, naphthalenedicarboxylic acid or cycloalkyldicarboxylic acid, preferably cyclohexanedicarboxylic acid. Very particular preference is given to polycarbonates or copolycarbonates, in particular having an average molecular weight Mw of from 500 to 100000, preferably from 10000 to 80000, particularly preferably from 15000 to 40000, or to blends thereof with at least one polycondensate or copolycondensate of terephthalic acid having an average molecular weight Mw of from 10000 to 200000, preferably from 21000 to 120000.
Suitable polycondensates or copolycondensates of terephthalic acid are polyalkylene terephthalates in a preferred embodiment of the invention. Suitable polyalkylene terephthalates are, for example, the reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g.dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols, and mixtures of these reaction products.
Preferred polyalkylene terephthalates may be prepared from terephthalic acid (or reactive derivatives thereof) and aliphatic or cycloaliphatic diols having from 2 to 10C atoms by known methods (Kunststoff-Handbuch, vol. VIII, p. 695 and thereafter Karl-Hanser-Verlag, munich 1973).
Preferred polyalkylene terephthalates contain at least 80 mole%, preferably 90 mole%, of terephthalic acid radicals, based on the dicarboxylic acid component, and at least 80 mole%, preferably at least 90 mole%, based on the diol component, of ethylene glycol and/or butane-1, 4-diol and/or cyclohexane-1, 4-dimethanol radicals.
Preferred polyalkylene terephthalates may contain up to 20 mole%, in addition to terephthalic acid radicals, of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, for example radicals of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4' -diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
Preferred polyalkylene terephthalates may contain, in addition to ethylene glycol and/or butane-1, 4-diol groups, up to 80 mol% of radicals of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, such as propane-1, 3-diol, 2-ethylpropane-1, 3-diol, neopentyl glycol, penta-1, 5-diol, hexane-1, 6-diol, cyclohexane-1, 4-dimethanol, 3-methylpentan-2, 4-diol, 2, 4-trimethylpenta-1, 3-diol and 2-ethylhexyl-1, 6-diol, 2-diethylpropane-1, 3-diol the radicals of hexane-2, 5-diol, 1, 4-di (. Beta. -hydroxyethoxy) benzene, 2-bis (4-hydroxycyclohexyl) propane, 2, 4-dihydroxy-1, 3-tetramethylcyclobutane, 2-bis (3 (. Beta. -hydroxyethoxyphenyl) propane and 2, 2-bis (4-hydroxypropyloxyphenyl) propane (see DE-OS2407674, 2407776, 2715932).
The polyalkylene terephthalates may be branched by incorporating relatively small amounts of tri-or tetraols or tri-or tetracarboxylic acids as described, for example, in DE-OS1900270 and U.S. Pat. No. 3,92744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
In a preferred embodiment of the layered structure s, the polymer (a) and/or the polymer (B) are independently selected from the group consisting of polycarbonate, copolycarbonate, blends of polycarbonates, blends of copolycarbonates, polyamide, cyclic Olefin Copolymer (COC), polyethylene or a mixture or blend of at least two thereof.
Preferably, the polymer (a) is selected from polycarbonates or poly-carbonates, polyamides, PET or mixtures or blends of at least two thereof, especially those as described above.
Preferably, the polymer (B) is selected from Cyclic Olefin Copolymers (COC) and polyamides, polyethylenes or mixtures thereof.
Preferably, polymer (a) is selected from polycarbonates or poly-carbonates, polyamides, PET or mixtures or blends of at least two thereof, especially those described above, and polymer (B) is selected from Cyclic Olefin Copolymers (COC) and polyamides, polyethylene or mixtures thereof.
Preferably, layer a. Comprises 80 to 100 wt% of a polymer (a) selected from the group consisting of polycarbonate or poly-carbonate, polyamide, PET or a mixture or blend of at least two thereof, especially those as described above, based on the total weight of layer b.
Preferably, layer B comprises 80 to 100 wt% of a polymer (B) selected from Cyclic Olefin Copolymers (COC) and polyamides, polyethylenes or mixtures thereof, based on the total weight of layer B.
In a preferred embodiment of the layered structure s, layer a is comprised in the range of 50 to 100 wt%; preferably in the range of from 70 to 99% by weight, more preferably in the range of from 80 to 97% by weight, most preferably in the range of from 90 to 95% by weight. Layer a. May comprise at least one additional additive. The additive is preferably selected from pigments, dyes, surfactants, ultraviolet absorbers and colorants or a combination of at least two thereof. Preferably, the layer a. Comprises additives or the sum of all additives in an amount in the range of 0.1 to 10 wt. -%, more preferably in the range of 0.2 to 7 wt. -%, most preferably in the range of 0.5 to 5 wt. -%, based on the total weight of the layer a.
In a preferred embodiment of the layered structure s, layer B comprises polymer (B) in an amount in the range of 50 to 100 wt%, preferably in the range of 70 to 99 wt%, more preferably in the range of 80 to 97 wt%, most preferably in the range of 90 to 95 wt%. Layer b. May comprise at least one additional additive. The additive is preferably selected from pigments, dyes, surfactants, ultraviolet absorbers and colorants or a combination of at least two thereof. Preferably, the layer b. Comprises additives or the sum of all additives in an amount in the range of 0.1 to 10 wt. -%, more preferably in the range of 0.2 to 7 wt. -%, most preferably in the range of 0.5 to 5 wt. -%, based on the total weight of the layer b.
Preferably, the first layer a. Comprises polymer (a) or a polymer combination comprising polymer (a), wherein polymer (a) or polymer combination comprising polymer (a) provides a Tg in the range of 100 to 180 ℃, more preferably in the range of 120 to 160 ℃, most preferably in the range of 130 to 150 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein Tg is defined as midpoint temperature (tangential method).
Preferably, the second layer B comprises polymer (B) or a polymer combination comprising polymer (B), wherein polymer (B) or polymer combination comprising polymer (B) provides a Tg in the range of 10 to 80 ℃, more preferably in the range of 20 to 60 ℃, most preferably in the range of 30 to 50 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein Tg is defined as midpoint temperature (tangential method).
Preferably, the layered structure s comprises a first layer a and a second layer B, wherein the first layer a of the layered structure s comprises at least one polymer (a) providing a Tg in the range of 100 to 180 ℃, more preferably in the range of 120 to 160 ℃, most preferably in the range of 130 to 150 ℃, and the second layer B comprises at least one polymer (B) providing a Tg in the range of 10 to 80 ℃, more preferably in the range of 20 to 60 ℃, most preferably in the range of 30 to 50 ℃, as determined by Differential Scanning Calorimetry (DSC) at a heating rate of 20K/min according to standard DIN EN 61006:2004, wherein Tg is defined as midpoint temperature (tangential method).
In a preferred embodiment of the layered structure s. The first layer a. Comprises at least one polymer (a) in an amount in the range of 80 to 100 wt. -%, wherein the at least one polymer (a) provides a Tg in the range of 100 to 180 ℃, more preferably in the range of 120 to 160 ℃, most preferably in the range of 130 to 150 ℃, and the second layer B. Comprises a polymer (B) in an amount in the range of 80 to 100 wt. -%, wherein the polymer (B) provides a Tg in the range of 10 to 80 ℃, more preferably in the range of 20 to 60 ℃, most preferably in the range of 30 to 50 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein Tg is defined as midpoint temperature (tangential).
In a preferred embodiment of the layered structure s, the layered structure s further comprises at least one layer C comprising the polymer (C). The polymer (C) may be any polymer chosen by the person skilled in the art for establishing a layer C in the layered structure s.
In a preferred embodiment of the layered structure s, the polymer (C) is different from the polymer (a) and/or the polymer (B). Preferably, polymer (C) is different from polymer (a) and polymer (B). Preferably, the polymer (C) is selected from the group consisting of polycarbonates, copolycarbonates, blends of polycarbonates, blends of copolycarbonates, polyamides, cyclic Olefin Copolymers (COC), polyethylene or mixtures or blends of at least two thereof. Examples of preferred polycarbonates are mentioned above in relation to polymer (A), which are also preferred for polymer (C). Preferably, polymer (C) is polyethylene.
Layer c. May comprise at least one additional additive. The additive is preferably selected from pigments, dyes, surfactants, defoamers, plasticizers, ultraviolet absorbers and colorants or a combination of at least two thereof. Preferably, the layer c comprises a total amount of the additive or additives in the range of 0.01 to 0.5 wt. -%, more preferably in the range of 0.05 to 0.4 wt. -%, most preferably in the range of 0.1 to 0.3 wt. -%, based on the total weight of the layer c.
In a preferred embodiment of the layered structure s, at least an additional layer b is arranged between the two layers a. Preferably, at least one layer c is arranged on top of each layer a. In an alternative embodiment of the layered structure s, the at least one layer a is arranged between at least one additional layer b and at least one layer c.
Preferably, the layered structure s is assembled in a layer combination selected from:
-layer a and layer b;
layer a, layer b, layer a;
layer c, layer a, and layer B;
layer c, layer a, layer b, layer a,
layer C, layer a, layer b, layer a, layer C.
Another aspect of the invention relates to a method for manufacturing a layered structure s, wherein the layered structure s comprises at least one first layer a having a thickness in the range of 10 to 50 μm, preferably 10 to 30 μm, the method comprising at least the following steps
P1. providing a pellet a comprising polymer (a);
p2. providing a pellet B comprising polymer (B);
p3. optionally, providing pellets C comprising polymer (C);
p4. heating the pellets a and B and optionally the pellets C to a temperature T which is at least 80 ℃, preferably at least 100 ℃ higher than the softening point or glass transition temperature of the respective polymers (a), (B) and optionally (C) to obtain melts (a), (B) and optionally (C);
p5. the melts of at least melt (a) and melt (B) and optionally melt (C) are combined to obtain a co-extrudate of at least one layer a from melt (a) and a layer B from melt (B) and optionally at least one layer C from melt (C) with a thickness in the range of 10 to 50 μm to obtain a layered structure s.
P6. cooling the layered structure s to a temperature in the range of 20 to 40 ℃;
p7. optionally, winding the layered structure s. Onto a roll;
p8. optionally, post-processing the layered structure s, wherein the post-processing is preferably selected from printing on at least one surface, shaping, laser marking or a combination of at least two thereof;
p9. optionally, delamination of layers a, b, and optionally c, by unwinding and rewinding processes.
The provision of the pellets a. Comprising polymer (a) in step p1 may be achieved by any means chosen by the person skilled in the art for the process. The provision of the pellets B comprising polymer (B) in step p2 may be achieved by any means chosen by the person skilled in the art for the process. The provision of pellets C comprising polymer (C) in step p2 may be achieved by any means chosen by the person skilled in the art for the process. Preferably, the provision in step p1, or step p2, or step p3 is achieved using an extruder.
The heating of the pellets a and B, and optionally the pellets C, in step p4 to a temperature T at least 10 ℃ above the softening point or glass transition temperature of the respective polymers (a), (B) and optionally (C) to obtain the melt (a), (B) and optionally (C) can be achieved by any means chosen by the person skilled in the art. If an extruder is used in steps p 1-p 3, the extruder comprises heating means.
Combining at least the melts of melt (a) and melt (B) and optionally melt (C) in step P5. to obtain at least one layer a. From melt (a) and at least one layer B. From melt (B) and optionally at least one layer C. From melt (C) having a thickness in the range of 10 to 50 μm to obtain a layered structure s. Can be performed by any means selected by the person skilled in the art for combining melts. Preferably, the melts (a) and (B) and optionally (C) are combined in or before the slot die and a coextrudate is obtained. Preferably, the layered structure s comprises a layer selected from the group consisting of layers a-B-; -a.—b.—a; C. -a.—b.—a.—c.
Cooling of the layered structure s to a temperature in the range of 20 to 40 ℃ in step p6 may be achieved by any means selected by the person skilled in the art for cooling the layer. Preferably, the cooling is achieved by storing the layered structure s. at room temperature, preferably in the temperature range of 20 to 30 ℃, more preferably in the range of 22 to 27 ℃. If the cooling should be accelerated, a cooling medium, such as cold air or cold fluid in the form of cold water, may be led onto the layer. The cold fluid in air or water form preferably has a temperature in the range of 1 ℃ to 20 ℃.
Winding the layered structure s onto a roll in step p7 may be achieved by any means chosen by the person skilled in the art for winding the layer. Preferably, the winding is established by means of a conventional winder.
The post-processing of the layered structure s in step p8 may be selected from any processing that one skilled in the art would select for the post-processing of the layer. The post-processing is preferably selected from printing, shaping, laser marking, or a combination of at least two thereof on at least one surface.
The layers a, b, and optionally c may optionally be delaminated in step p9 by an unwinding and rewinding process. Delamination may be achieved by a method selected from any process that one skilled in the art would select for post-processing of the layer. If delamination is not performed manually, a conventional delamination machine may be used.
In a preferred embodiment of the method, polymer (a), polymer (B) and/or polymer (C) are independently selected from the group consisting of polycarbonate, copolycarbonate, blends of polycarbonates, blends of copolycarbonates, polyamide, cyclic Olefin Copolymer (COC), polyethylene or a mixture or blend of at least two thereof. Preferably, polymer (C) is polyethylene. Preferably, polymer (B) is COC.
In a preferred embodiment of the process, the polymer (a) is selected from the group consisting of polycarbonates, copolycarbonates, blends of polycarbonates, blends of copolycarbonates, polyamides, cyclic Olefin Copolymers (COC) or mixtures or blends of at least two thereof, but is different from the polymer (B), preferably from the polymer (C). Preferably, the polymer (A) is a polycarbonate or copolycarbonate.
Another aspect of the invention relates to a foil with a thickness in the range of 10 to 100 μm, preferably in the range of 20 to 80 μm, produced by the method according to the invention.
Another aspect of the invention relates to the use of a layered structure s according to the invention or a layered structure s made by a method according to the invention or a foil according to the invention as a surface covering. Uses of the layered structure s. Include methods of using the layered structure s. Or foil as a surface covering. The surface may be any surface chosen to be covered by a person skilled in the art. The surface is preferably selected from the group consisting of a display, a screen, glass, a surface of an automobile interior. The covering is preferably a protective covering of a surface.
Drawings
Examples of layered structure S. Are shown in
FIG. 1 is a schematic view of a layered structure S according to the invention having layers A and B
FIG. 2 is a schematic view of a layered structure S according to the invention with layers A, B and C
FIG. 3 is a schematic illustration of a process according to the invention
In fig. 1 a schematic diagram of a layered structure s.50 according to the invention is shown. The layered structure s.50 comprises a first layer a.10 comprising polymer (a) and a second layer b.20 comprising polymer (B). Polymer (A) is COC, preferably TOPAS from Hoechst (now TOPAS Advanced Polymers), and polymer (B) is Covesro AG3108. The thickness of layer a. Is about 30 μm and the thickness of layer b. Is about 100 μm. Optionally, an additional layer may be disposed on layer a on the side of the second layer b. opposite to the side of layer a. or on the side of layer a. opposite to the side of layer b. Preferably, two layers of layer a. Are arranged on both sides of layer B, which form part of the layered structure s. In fig. 2.
In fig. 2 a schematic diagram of a layered structure s.50 according to the invention is shown, comprising 5 layers, namely two first layers a.10 comprising polymer (a), a second layer b.20 comprising polymer (B) and two third layers c.30 comprising polymer (C). The materials of layers a, and b are the same as described for layered structure s of fig. 1. The polymer (C) is polyethylene. Optionally, additional layers may be disposed on both sides of the layered structure s.50.
In fig. 3, the main steps of the method of manufacturing a structure s.50 according to the invention are shown. In step P1.100, the provision of pellets a. Comprising polymer (a) as described in fig. 1 is achieved by pouring pellets a. Into an extruder. In step P2.200, the provision of pellets b. comprising polymer (B) as described in fig. 1 is achieved by pouring the pellets b. into a second extruder. In optional step P3.300, the provision of pellets C comprising polymer (C) as described in fig. 1 is achieved by pouring the pellets C into a third extruder. In step P4.400, heating of the pellets (a), (B) and optionally (C) is effected in an extruder. The extruder may be any commercially available extruder capable of extruding the polymers as described for layers a, b and c. The extruder heats the respective pellets to a temperature T which is at least 80 ℃, preferably at least 100 ℃, above the softening point or glass transition temperature of the respective polymers (a), (B) and optionally (C) to obtain the melts (a), (B) and optionally (C). In step P5.500, the melts of at least melt (a) and melt (B) and optionally melt (C) are combined to obtain a layer a from melt (a) having a thickness of about 10 to 30 μm on one or both sides of one layer B from melt (B), and optionally at least one layer C from melt (C) on one of the layers a to obtain a layered structure s.50 as shown in fig. 2. The layered structure s.50 was cooled at room temperature for several hours in step P6.600. This cooling process can be accelerated by providing a cooling medium, such as cold air or water, at a temperature in the range of 1 to 20 ℃. After cooling the layered structure s.50 to room temperature of about 23 ℃, the layered structure s.50 is wound onto a roll by a winder in optional step P7.700. The hierarchical structure s.50 may be post-processed in step P8.800. In step P9.900, the layered structure s.50 is delaminated between layer a. And layer b. To obtain one or two thin layers a.
Experimental part:
masterbatch for layer a:
the production of the masterbatch for producing layer a. Of the coextruded film is carried out with a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures of from 250 ℃ to 330 ℃ conventionally used for polycarbonates.
Compounding and then granulating a masterbatch having the following composition:
masterbatch 1:100 wt.%3108, or
Masterbatch 2:100 wt% Durabio TM 7340,Mitsubishi Chemical Performance Polymers, japan
Master batch for layer b:
the production of the masterbatch for producing layer b. Of the co-extruded film is carried out with a conventional twin-screw compounding extruder (ZSK 32) at a processing temperature of 210 ℃ to 240 ℃ conventionally used for COC.
Compounding and then granulating a masterbatch having the following composition:
masterbatch 3:100 wt.%(Mitsui, japan), or
Masterbatch 4:100 wt.%TR90 (EMS Chemie, switzerland), or +.>
Masterbatch 5 TPU9365D (Covestro Deutschland AG, germany), or
Masterbatch 6 TPU9385D (Covestro Deutschland AG, germany); or (b)
Masterbatch 7:786E (polycarbonate type TPU) (Covestro Deutschland AG, germany); or (b)
Masterbatch 8 TPU3660D (Covestro Deutschland AG, germany).
Production of co-extruded films comprising layer A and layer B
The apparatus used for producing the co-extruded film comprises:
an extruder for melting the polymer (A) and extruding the melt (A) to form a layer A comprising at least one polycarbonate, having a screw with a diameter (D) of 60mm and a length of 33D.
The screw has a degassing zone;
an extruder for extruding the molten polymer (B) and extruding the melt (B) to form a layer B;
melt pump;
crosshead;
a slot die having a width of 450 mm;
a three-roll smoothing calender with horizontal roll orientation, wherein the third roll can rotate +/-45 ° relative to horizontal;
roller conveyor;
thickness measuring means;
a tool for double-sided application of a protective film;
traction means (haul-off);
winding station.
One or more pellets of the masterbatch are transferred from the dryer to a hopper of an extruder. The material is melted and conveyed in the barrel/screw plasticizing system of the extruder. The melt is transferred from the slot die to a smoothing calender. The final shaping and cooling of the film was carried out on a smoothing calender (consisting of three rolls). The surface was embossed using a textured steel roller (No. 6 surface) and a textured silicone rubber roller (No. 2 surface). In US-4368240 from Nauta Roll Corporation a rubber roller for texturing the surface of a film is disclosed. The film is then transported past a pulling tool and then wound up.
In table 1, examples of the invention of layered structure s. Are listed together with the adhesion between the different materials of layer a. And layer b. The cited materials are formed from a masterbatch as described above. The layers a, b can be delaminated by hand without deforming one of the layers a, b and without any residue of the material of the respective other layer or the polymer of the other layer on the layers a, b.
TABLE 1 values of adhesion between different materials of layer A. And layer B ]
* Measured by delamination according to ASTM D903-1998 at a pull angle of 180 DEG
In table 2, comparative examples of adhesion between different layered structures comprising two layers (layer a. And layer b.) are listed. The two layers a, and b cannot be manually delaminated from each other. If more force is applied to delaminate layers a, b, the layers may be broken or at least tearing may be visible in at least one of layers a, b.
TABLE 2 comparison of the values of the adhesion between the different materials of the layers A. And B. Of the layered structure
* As measured by delamination at a pull angle of 180 deg. according to ASTM D903-1998.

Claims (15)

1. Hierarchical structure s., comprising:
A. at least one first layer a having a first outer surface A1 and a second surface A2 comprising at least a polymer (a), wherein the first layer a has a thickness in the range of 10 to 50 μm, preferably in the range of 10 to 30 μm, and
B. at least one additional layer B comprising at least a polymer (B),
wherein layer a of the layered structure s. Provides at least one, preferably two, more preferably all of the following properties:
s1 an adhesion between the at least one first layer A and the at least one additional layer B, measured according to ASTM D903-1998 at a traction angle of 180 DEG, is in the range of 0.001 to 0.05N/cm;
S2, the hardness measured according to DIN EN ISO 868-2003-10 is more than or equal to 85D;
s3, the melting temperature is more than or equal to 200 ℃; preferably in the range of 210 to 350 ℃, more preferably in the range of 230 to 330 ℃; most preferably in the range of 250 to 320 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein T g Defined as midpoint temperature (tangent);
s4, the glass transition temperature Tg is more than or equal to 70 ℃; preferably in the range of 80 to 250 ℃, more preferably in the range of 80 to 240 ℃; most preferably in the range of 80 to 200 ℃, as determined by Differential Scanning Calorimetry (DSC) according to standard DIN EN 61006:2004 at a heating rate of 20K/min, wherein T g Defined as the midpoint temperature (tangential method), or Vicat softening temperature B/50. Gtoreq.70℃as determined according to ISO 306-2014-03 (50N; 50 °/h); preferably in the range of 75 to 230 ℃, more preferably in the range of 80 to 230 ℃; most preferably at 85 to 225 DEG CWithin the range;
s5 melt volume Rate (MVR; measured according to DIN ISO 1133-1-2012-03; 300 ℃,2.16 kg) > 3cm 3 Preferably ≡3.5 cm/10 min 3 /10min, still more preferably 4cm or more 3 /10min；
S6. The additives are in the range of 0.01 to 0.5% by weight.
2. The layered structure s, preferably layer a, according to claim 1, wherein the layered structure s, preferably layer a, provides at least one, preferably two, more preferably all of the following properties:
s7. a thickness in the range of 15 to 250 μm, preferably in the range of 20 to 200 μm, most preferably in the range of 30 to 100 μm;
s8. thickness deviation over an area of 20 x 20cm is in the range of 0.01 to 1 μm, preferably 0.02 to 0.5 μm, more preferably 0.03 to 0.3 μm, most preferably 0.05 to 0.1 μm;
s9 the tensile strength measured according to DIN EN ISO 527-1:2012-06 is in the range of 10 to 150MPa, preferably 20 to 100 MPa;
s10. an elongation at break in the range of 20 to 500%, preferably 50 to 400%, measured according to DIN N ISO 527-1:2012-06;
s11. water absorption (ISO 62:2008; 24 hours at 23 ℃) is in the range of 0.01 to 0.5 wt%, more preferably in the range of 0.05 to 0.4 wt% (saturation value).
3. The layered structure s according to any one of the preceding claims, wherein layer a provides at least one, preferably at least two, more preferably all of the following properties:
a1. the gloss at 60℃angle measured according to DIN EN ISO 2813-2015-02 is in the range from 10 to 110;
a2. the surface roughness of at least the first surface A1 measured according to DIN EN ISO 4287:2010-07/DIN EN ISO 4288:1998-04 is in the range of 0.1 to 5.50 μm;
a3. A birefringence measured by a polarizing microscope in the range of 1 to 100 nm;
a4. transparency measured according to ASTM D1003-13 is in the range of 5 to 95%;
a5. a density in the range of 1 to 1.35g/l measured according to ISO 1183-1:2019-09;
a6. tensile strength measured according to DIN EN ISO 527-1:2012-06 is in the range of 10 to 150MPa, preferably 20 to 100 MPa;
a7. an elongation at break measured according to DIN N ISO 527-1:2012-06 in the range of 20 to 500%, preferably 50 to 400%;
a8. the thickness is in the range of 5 to 50 μm, preferably in the range of 10 to 25 μm, most preferably in the range of 10 to 20 μm;
a9. the thickness deviation is in the range of 0.01 to 1 μm, preferably 0.02 to 0.5 μm, more preferably 0.03 to 0.3 μm, most preferably 0.05 to 0.1 μm.
4. The layered structure s according to any one of the preceding claims, wherein polymer (a) and/or polymer (B) are independently selected from the group consisting of polycarbonate, copolycarbonate, blends of polycarbonates, blends of copolycarbonates, polyamide, cyclic Olefin Copolymer (COC), polyethylene or a mixture or blend of at least two thereof.
5. The layered structure s according to any one of the preceding claims, wherein layer a. Is comprised in the range of 50 to 100 wt%; preferably in the range of from 70 to 99% by weight, more preferably in the range of from 80 to 97% by weight, most preferably in the range of from 90 to 95% by weight.
6. The layered structure s according to any one of the preceding claims, wherein layer B comprises polymer (B) in an amount in the range of 50 to 100 wt. -%, preferably in the range of 70 to 99 wt. -%, more preferably in the range of 80 to 97 wt. -%, most preferably in the range of 90 to 95 wt. -%.
7. The layered structure s according to any one of the preceding claims, wherein the first layer a. Of the layered structure s. Comprises at least one polymer (a) in an amount in the range of 80 to 100 wt. -%, wherein the at least one polymer (a) provides in the range of 100 to 100A Tg in the range of 180 ℃, more preferably in the range of 120 to 160 ℃, most preferably in the range of 130 to 150 ℃ and the second layer B. Comprises at least one polymer (B) in an amount in the range of 80 to 100 wt%, wherein the at least one polymer (B) provides a Tg in the range of 10 to 80 ℃, more preferably in the range of 20 to 60 ℃, most preferably in the range of 30 to 50 ℃, as determined by Differential Scanning Calorimetry (DSC) at a heating rate of 20K/min according to standard DIN EN 61006:2004, wherein T g Defined as the midpoint temperature (tangent method).
8. The layered structure s according to any one of the preceding claims, wherein the layered structure s further comprises at least one layer C comprising polymer (C).
9. The layered structure s according to any one of the preceding claims, wherein the polymer (C) is different from polymer (a) and/or polymer (B).
10. The layered structure s according to the preceding claim, wherein at least an additional layer b is arranged between two layers a.
11. A method of manufacturing a layered structure s, wherein the layered structure s comprises at least one first layer a having a thickness in the range of 10 to 50 μm, preferably 10 to 30 μm, the method comprising at least the following steps
P1. providing a pellet a comprising polymer (a);
p2. providing a pellet B comprising polymer (B);
p3. optionally, providing pellets C comprising polymer (C);
p4. heating the pellets a and B and optionally the pellets C to a temperature T which is at least 80 ℃, preferably at least 100 ℃ higher than the softening point or glass transition temperature of the respective polymers (a), (B) and optionally (C) to obtain melts (a), (B) and optionally (C);
p5. the melts of at least melt (a) and melt (B) and optionally melt (C) are combined to obtain a co-extrudate of at least one layer a from melt (a) and a layer B from melt (B) and optionally at least one layer C from melt (C) with a thickness in the range of 10 to 50 μm to obtain a layered structure s.
P6. cooling the layered structure s to a temperature in the range of 20 to 40 ℃;
p7. optionally, winding the layered structure s. Onto a roll;
p8. optionally, post-processing the layered structure s, wherein the post-processing is preferably selected from printing on at least one surface, shaping, laser marking or a combination of at least two thereof;
p9. optionally, delamination of layers a, b, and optionally c, by unwinding and rewinding processes.
12. The method according to claim 11, wherein polymer (a), polymer (B) and/or polymer (C) are independently selected from the group consisting of polycarbonate, copolycarbonate, blends of polycarbonates, blends of copolycarbonates, polyamides, cyclic Olefin Copolymers (COC) or mixtures or blends of at least two thereof.
13. The method according to any one of claims 11 or 12, wherein polymer (a) is selected from the group consisting of polycarbonate, copolycarbonate, blends of polycarbonates, blends of copolycarbonates, polyamides, cyclic Olefin Copolymers (COC) or mixtures or blends of at least two thereof, but is different from polymer (B).
14. Foil having a thickness in the range of 10 to 100 μm made by a method according to any one of claims 11 to 13.
15. Use of a layered structure s according to any one of claims 1 to 10, or a layered structure s made by a method according to any one of claims 11 to 13, or a foil according to claim 14 as a surface covering.
CN202280040589.0A 2021-06-07 2022-06-03 Ultra-thin layered structure with specific properties Pending CN117480050A (en)

Applications Claiming Priority (3)

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EP21178017.6 2021-06-07
EP21178017 2021-06-07
PCT/EP2022/065157 WO2022258506A1 (en) 2021-06-07 2022-06-03 Ultrathin layered structure with specific properties

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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1580834A (en) 1968-01-04 1969-09-12
US4368240A (en) 1981-07-27 1983-01-11 Nauta Roll Corporation High gloss rubber roll
JP2002103410A (en) * 2000-09-29 2002-04-09 Toray Ind Inc Method for manufacturing polymeric sheet, and polymeric sheet
US20060159888A1 (en) * 2004-10-29 2006-07-20 Hebrink Timothy J Optical films incorporating cyclic olefin copolymers
US11344386B2 (en) * 2019-01-30 2022-05-31 Usi Corporation Multilayer sheet structure for dental appliance

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