IP Library Granted Patent US 11,752,743
Granted Patent B2
US 11,752,743 · App. 17/595,840 · Granted Sep 12, 2023

Multilayer polypropylene film

Inventors: Jingbo Wang (Linz, AT); Markus Gahleitner (Linz, AT); Klaus Bernreitner (Linz, AT); Pauli Leskinen (Porvoo, FI); Manfred Gruenberger (Linz, AT)
Assignee: BOREALIS AG
B32B27/08B32B27/32C08F4/64C08L23/142B32B2250/246B32B2270/00B32B2274/00B32B2307/30B32B2307/412B32B2439/80C08L2207/02
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Quick Facts
Patent No.
US 11,752,743
App. No.
17/595,840
Granted
Sep 12, 2023
Kind
B2
Abstract

Multilayer film comprising at least a skin layer, a core layer and an inner layer, whereby the inner layer comprises a single site catalyst derived (SSC) random propylene ethylene copolymer having—a melting temperature (Tm) from 120° C. to 144° C., —a content of units derived from ethylene in an amount of 1.5 to 6.0 wt.-%, —the melting temperature (Tm) fulfilling the following equation Tm<156° C.−[5.2×C2 content in wt.-%]° C. wherein C2 content stands for the content of units derived from ethylene; and —a xylene cold soluble content (ISO 16152, 1st ED, 2005 Jul. 1; 25° C.) of preferably below 30 wt.-% wherein the multilayer film is free of phthalic acid esters as well as decomposition products thereof.

Claims (73)

1. A multilayer film comprising at least a skin layer, a core layer and an inner layer,

the skin layer comprising a homo polypropylene or a random propylene ethylene copolymer including up to 2.5 wt.-% units derived from ethylene, the homo polypropylene or the random propylene ethylene copolymer having a MFR 2 (ISO1133, 230° C.) of 2.0 to 20 g/10 min and a melting temperature (Tm) of 145 to 170° C.;

the core layer comprising a mixture obtainable by melt blending 20 to 80 wt.-% of a random heterophasic copolymer and 20 to 80 wt.-% of styrene based thermoplastic elastomer (TPE),

wherein the random heterophasic copolymer comprises

a matrix phase and dispersed therein an elastomer phase, whereby the matrix phase is formed by a random propylene ethylene copolymer and

wherein the random heterophasic copolymer has

a melting temperature (Tm) of 130° C.-145° C.

a flexural modulus of 250 to 850 MPa when measured on injection molded specimens (23° C., 50% humidity, ISO 178) and

wherein the random heterophasic copolymer includes an ethylene propylene copolymer rubber; and

wherein the styrene based thermoplastic elastomer (TPE) has a styrene content of from 5 to 20 wt.-%, and

the inner layer comprising a single site catalyst derived (SSC) random propylene ethylene copolymer having

a melting temperature (Tm) from 120° C. to 144° C.,

a content of units derived from ethylene in an amount of 1.5 to 6.0 wt.-%,

the melting temperature (Tm) fulfilling the following equation

Tm<156° C.−[5.2×C2 content in wt.-%]° C.

wherein C2 content stands for the content of units derived from ethylene; and

a xylene cold soluble content (ISO 16152, 1st ED, 2005 Jul. 1; 25° C.) of preferably below 30 wt.-%

wherein the multilayer film is free of phthalic acid esters as well as decomposition products thereof.

2. The multilayer film according to claim 1 , wherein xylene cold soluble fraction (XCS) of the random heterophasic copolymer contributing to the core layer has an intrinsic viscosity of 1.0 to 2.0 dl/g (DIN ISO 1628/1, 10/1999; Decalin, 135° C.).

3. The multilayer film according to claim 1 having a total thickness of 50 to 250 micrometer.

4. The multilayer film according to claim 1 , wherein the core layer has a thickness of 50 to 85% with respect to the thickness of the multilayer film.

5. The multilayer film according to claim 1 , wherein the thicknesses of the skin layer is 10 to 25% with respect to the total thickness of the multilayer film and/or

wherein the thicknesses of the inner layer is 10 to 25% with respect to the total thickness of the multilayer film.

6. The multilayer film according to claim 1 , wherein the skin layer consists of the homo polypropylene or random propylene ethylene copolymer; and/or

the core layer consists of the mixture obtainable by melt blending 20 to 80 wt.-% of a random heterophasic copolymer and 20 to 80 wt.-% of styrene based thermoplastic elastomer (TPE); and/or

the inner layer consists of the single site catalyst derived (SSC) random propylene ethylene copolymer, or

the inner layer consists of a mixture obtainable by blending the single site catalyst derived (SSC) random propylene ethylene copolymer and a propylene ethylene elastomer having an ethylene content of less than 20 wt.-%; or

the inner layer consists of a mixture obtainable by blending the single site catalyst derived (SSC) random propylene ethylene copolymer and a styrene ethylene butylene styrene copolymer (SEBS).

7. The multilayer film according to claim 1 , wherein the propylene homopolymer of the skin layer has an MFR (230° C., 2.16 kg, ISO1133) of 4.0 to 13 g/10 min and/or

a melting temperature of above 154° C. up to 170° C. and/or

a flexural modulus of above 1300 MPa when measured on injection molded specimens (23° C., 50% humidity, ISO 178) or

the random propylene ethylene copolymer of the skin layer has an MFR (230° C., 2.16 kg, ISO1133) of 4.0 to 13 g/10 min, an ethylene content of 0.5 to 2.2 wt.-% and/or a melting temperature of 145 to 155° C. and/or

a flexural modulus of above 975 MPa when measured on injection molded specimens (23° C., 50% humidity, ISO 178).

8. The multilayer film according to according to claim 1 , wherein the random heterophasic copolymer having a melting temperature (Tm) of 130 to 145° C. contributing to the core layer has a MFR 2 of 3.0 to 7.0 g/10 min (ISO 1133, 230° C., 2.16 kg) and/or

a total ethylene content of 7.0 to 14.0 wt.-% and/or

an amount of the xylene cold soluble fraction (XCS) in the range of 18.0 to 25.0 wt.-% and/or

an intrinsic viscosity of 1.0 to 1.6 dl/g (DIN ISO 1628/1, 10/1999; Decalin, 135° C.) of the xylene cold soluble fraction (XCS).

9. The multilayer film according to claim 1 , wherein the single site catalyst derived (SSC) random propylene ethylene copolymer of the inner layer has a the melting temperature (Tm) fulfilling the following equation

Tm<154° C.−[5.2×C2 content in wt.-%]° C.

wherein C2 content stands for the content of units derived from ethylene; and/or

has an ethylene content of 1.5 to 6.0 wt.-%, preferably 1.6 to 4.0 and/or has an melt flow rate of 3.0 to 20 preferably 3.0 to 9.0 g/10 min (230° C., 2.16 kg, ISO1133), and/or

a flexural modulus of from 600 to 900 MPa when measured on injection molded specimens (23° C., 50% humidity, ISO 178).

10. The multilayer film according to claim 1 , wherein the core layer comprises a mixture obtainable by melt blending 40 to 60 wt.-% of a random heterophasic copolymer and 60 to 40 wt.-% of styrene based thermoplastic elastomer (TPE).

11. The multilayer film according to claim 1 , wherein the core layer comprises a mixture obtainable by melt blending 60 to 80 wt.-% of a random heterophasic copolymer and 40 to 20 wt.-% of styrene based thermoplastic elastomer (TPE).

12. A pouch made from the multilayer film of claim 1 .

13. A process for preparing a film according to claim 1 , wherein the components forming the skin layer, the core layer and the inner layer are extruded on a multi layer cast film line.

14. A process for preparing a film according to claim 1 , wherein the single site catalyst derived (SSC) random propylene ethylene copolymer is obtained in the presences of a single site catalysts comprising

(i) a complex of formula (I):

wherein

M is zirconium or hafnium;

each X is a sigma ligand;

L is a divalent bridge selected from —R′2C—, —R′2C—CR′2-, —R′2Si—, —R′2Si— SiR′2-, —R′2Ge—,

wherein each R′ is independently a hydrogen atom, C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl;

R2 and R2′ are each independently a C1-C20 hydrocarbyl radical optionally containing one or more heteroatoms from groups 14-16;

R5′ is a C1-20 hydrocarbyl group containing one or more heteroatoms from groups 14-16 optionally substituted by one or more halo atoms;

R6 and R6′ are each independently hydrogen or a C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16; wherein R6′ is preferably a tertiary alkyl group

R7 is hydrogen or C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16;

R7′ is hydrogen;

Ar is independently an aryl or heteroaryl group having up to 20 carbon atoms optionally substituted by one or more groups R1;

Ar′ is independently an aryl or heteroaryl group having up to 20 carbon atoms Optionally substituted by one or more groups R1;

each R1 is a C1-20 hydrocarbyl group or two R1 groups on adjacent carbon atoms taken together can form a fused 5 or 6 membered non aromatic ring with the Ar group, said ring being itself optionally substituted with one or more groups R4; each R4 is a C1-20 hydrocarbyl group; and

(ii) a cocatalyst comprising at least one or two compounds of a group 13 metal, such as Al and/or boron compound.

15. A process for preparing a film according to claim 1 , comprising at least a skin layer, a core layer and an inner layer, wherein the skin layer comprises a homo polypropylene or a random propylene ethylene copolymer including up to 2.5 wt.-% units derived from ethylene, the homopolypropylene or the random propylene ethylene copolymer having a MFR 2 (ISO1133, 230° C.) of 2.0 to 20 g/10 min and a melting temperature (Tm) of 145 to 170° C., wherein the homo polypropylene or the random propylene ethylene copolymer is obtainable by polymerization in the presence of a Ziegler-Natta catalyst (ZN-C) comprising compounds (TC) of a transition metal of Group 4 to 6 of IUPAC, a Group 2 metal compound (MC) and an internal donor (ID), wherein said internal donor (ID) is a selected from

optionally substituted malonates,

maleates,

succinates,

glutarates,

cyclohexene-1,2-dicarboxylates,

benzoates and derivatives and/or mixtures thereof,

citraconate; or

the combination of two internal donors (IDs) being 1,3-diethers and succinates

optionally a co-catalyst (Co), and

optionally an external donor (ED).

Assignments (2)
CHANGE OF ADDRESS Recorded Feb 23, 2022
From: BOREALIS AG
To: BOREALIS AG
Reel/Frame 059219/0949 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 22, 2022
From: WANG, JINGBO; GAHLEITNER, MARKUS; BERNREITNER, KLAUS; LESKINEN, PAULI; GRUENBERGER, MANFRED
To: BOREALIS AG
Reel/Frame 059067/0452 →