Multilayer films for insert mold decoration, methods for making the same, and articles made therefrom
View Patent ↗A multilayer thermoplastic film having polycarbonate layers is disclosed, in which a first layer comprises a first polycarbonate that comprises repeat units derived from one or more of a monoaryl monomer (II) and/or (III), and a diaryl monomer (IV) as defined herein. A second layer, adjacent to the first layer and coextruded therewith, comprises another polycarbonate that is not the same as a polycarbonate in the first layer. The first layer provides improved properties, for example hardness, impact, and/or scratch resistance.
1. A multilayer thermoplastic film comprising:
a first layer comprising a first polycarbonate polymer that comprises repeat units derived from monomers (II), (III), and (IV), wherein
monomer (II) is a first dihydroxy compound of the formula:
wherein n is 0 to 4, and R f1 is a halogen, a C 1-10 hydrocarbon group, or a C 1-10 halogen-substituted hydrocarbon group;
monomer (III) is a second dihydroxy compound not the same as monomer (II) and of the formula:
wherein m is 1 to 4, and R f2 is a halogen, a C 1-10 hydrocarbon group, or a C 1-10 halogen-substituted hydrocarbon group; and
monomer (IV) is a third dihydroxy compound of the formula:
wherein R a and R b are each independently a halogen or C 1-12 alkyl group that is meta to the hydroxy group on the same aromatic ring; R c and R d each independently represent a C 1 -C 12 alkyl group that is ortho to the hydroxy group on the same ring; p and q are each independently integers of 0 to 2; v and w are each independently integers 0 to 2; and X a is a single bond or a bridging group;
wherein
the sum of the mole percent of the repeat units derived from monomers (II) and (III) is greater than or equal to 30 mole percent, based on the total moles of the repeat units derived from monomers (II), (III), and (IV) in the first polycarbonate polymer,
the mole percent of the repeat units derived from monomer (IV) is 5 to 70 mole percent, based on the total moles the repeat units derived from monomers (II), (III), and (IV), and
the total wt. % of the repeat units derived from monomers (II), (III), and (IV) is greater than or equal to 80 wt. % of the first polycarbonate polymer;
an additional polycarbonate polymer that is not the same as the first polycarbonate polymer, wherein the additional polycarbonate polymer comprises
50 to 100 mole percent of repeat units derived from a bisphenol cyclohexane of the formula (VI):
wherein R c1 and R d1 are each independently C 1-12 alkyl, R c2 and R d2 are each independently hydrogen or C 1-12 alkyl, R g is C 1-12 alkyl or halogen, and t is 0 to 10; and
0 to 50 mole percent of repeat units derived from a dihydroxy aromatic compound of formula (VIII):
wherein R e and R f are each independently a halogen or C 1-10 alkyl group; r and s are each independently integers of 0 to 4; X a is a single bond or a bridging group connecting the two hydroxy-substituted aromatic groups; and the dihydroxy aromatic compound of formula (VIII) is not the same as the bisphenol cyclohexylidene of formula (VI); and
0.002 wt. % to 0.07 wt. % of a catalyst for the reaction of the first polycarbonate polymer and the additional polycarbonate polymer, based on the total weight of the polycarbonate polymers; and
a second layer in contact with the first layer, wherein the second layer comprises a second polycarbonate polymer that is not the same as the first polycarbonate polymer in the first layer.
2. The multilayer thermoplastic film of claim 1 , wherein the first layer exhibits at least one of the following properties: a pencil hardness of greater than or equal to 2B, as measured by ASTM D3363-05, and a scratch depth of less than or equal to 0.8 micrometers, measured using a force of 6 N.
3. The multilayer thermoplastic film of claim 1 , wherein the film exhibits a light transmission of greater than or equal to 60% as measured by ASTM D1003-00 for a multilayer film having a thickness of 0.32 mm; a tear initiation strength of greater than or equal to 235 N/mm as measured by ASTM D1004-03; a tear propagation strength of greater than or equal to 8.5 N/mm as measured by ASTM D1938-02; and a tensile modulus of greater than or equal to 2000 MPa as measured by ISO 527.
4. The multilayer thermoplastic film of claim 1 , wherein the film exhibits, to the unaided eye, no cracks when exposed to gasoline for 1 hour at 22° C.
5. The multilayer thermoplastic film of claim 1 , wherein monomer (II) is hydroquinone and monomer (III) methyl hydroquinone.
6. The multilayer thermoplastic film of claim 1 , wherein the monomer (IV) is 1 to 99 mole percent of the bisphenol cyclohexylidene of formula (VI) and 1 to 99 mole percent of a monomer of formula (IV) that is not the same as the bisphenol cyclohexylidene of the formula (VI).
7. The multilayer thermoplastic film of claim 1 , wherein monomer (IV) is 1 to 99 mole percent of dimethyl bisphenol cyclohexane and 1 to 99 mole percent of bisphenol A.
8. The multilayer thermoplastic film of claim 1 , wherein monomer (IV) is 100 mole percent of the bisphenol cyclohexylidene of the formula (VI).
9. The multilayer thermoplastic film of claim 1 , wherein monomer (IV) is 100 mole percent of bisphenol A.
10. The multilayer thermoplastic film of claim 1 , comprising 5 to 95 wt. % of the first polycarbonate polymer and 5 to 95 wt .% of the additional polycarbonate polymer, based on the total weight of first and additional polycarbonate polymers.
11. The multilayer thermoplastic film of claim 1 , comprising 5 to 60 wt. % of the first polycarbonate polymer and 40 to 95 wt. % of the additional polycarbonate polymer, based on the total weight of first and additional polycarbonate polymers.
12. The multilayer thermoplastic film of claim 1 , comprising forming the first layer from a melt-blended composition comprising the first polycarbonate polymer, the additional polycarbonate polymer, and the catalyst, based on a total weight of the polycarbonate polymers in the composition.
13. A molded article comprising the multilayer thermoplastic film of claim 1 , in combination with an injection molded polymeric base to which the film is bonded, wherein the multilayer thermoplastic film has been formed into a non-planar three-dimensional shape matching a three-dimensional shape of the injection molded polymeric base structure, and wherein the film further comprises a printed marking.
14. The multilayer thermoplastic film of claim 1 , wherein the film exhibits a light transmission of greater than or equal to 90%, as measured in accordance with ASTM D1003-00 for a multilayer film having a thickness of 0.32 mm.
15. A multilayer thermoplastic film comprising:
a first layer comprising the reaction product of a first polycarbonate polymer and an additional polycarbonate polymer not the same as the first polycarbonate polymer in the presence of 0.002 wt. % to 0.07 wt. % of a catalyst based on a total weight of the polycarbonate polymers, wherein the first polycarbonate polymer comprises repeat units derived from monomers (II), (III), and (IV), wherein
monomer (II) is a first dihydroxy compound of the formula:
wherein n is 0 to 4, and R f1 is a halogen, a C 1-10 hydrocarbon group, or a C 1-10 halogen-substituted hydrocarbon group;
monomer (III) is a second dihydroxy compound not the same as monomer (II) and of the formula:
wherein m is 1 to 4, and R f2 is a halogen, a C 1-10 hydrocarbon group, or a C 1-10 halogen-substituted hydrocarbon group; and
monomer (IV) is a third dihydroxy compound of the formula:
wherein R a and R b are each independently a halogen or C 1-12 alkyl group that is meta to the hydroxy group on the same aromatic ring; R c and R d each independently represent a C 1 -C 12 alkyl group that is ortho to the hydroxy group on the same ring; p and q are each independently integers of 0 to 2; v and w are each independently integers 0 to 2; and X a is a single bond or a bridging group;
wherein
the sum of the mole percent of the repeat units derived from monomers (II) and (III) is greater than or equal to 30 mole percent, based on the total moles of the repeat units derived from monomers (II), (III), and (IV) in the first polycarbonate polymer,
the mole percent of the repeat units derived from monomer (IV) is 5 to 70 mole percent, based on the total moles the repeat units derived from monomers (II), (III), and (IV), and
the total wt. % of the repeat units derived from monomers (II), (III), and (IV) is greater than or equal to 80 wt. % of the first polycarbonate polymer;
the additional polycarbonate polymer comprises
50 to 100 mole percent of repeat units derived from a bisphenol cyclohexane of the formula (VI):
wherein R c1 and R d1 are each independently C 1-12 alkyl, R c2 and R d2 are each independently hydrogen or C 1-12 alkyl, R g is C 1-12 alkyl or halogen, and t is 0 to 10; and
0 to 50 mole percent of repeat units derived from a dihydroxy aromatic compound of formula (VIII):
wherein R e and R f are each independently a halogen or C 1-10 alkyl group; r and s are each independently integers of 0 to 4; X a is a single bond or a bridging group connecting the two hydroxy-substituted aromatic groups; and the dihydroxy aromatic compound of formula (VIII) is not the same as the bisphenol cyclohexylidene of formula (VI); and
a second layer in contact with the first layer, wherein the second layer comprises a second polycarbonate polymer that is not the same as the first polycarbonate polymer in the first layer.
16. The multilayer thermoplastic film of claim 1 , wherein the additional polycarbonate polymer comprises
50 to 100 mole percent of repeat units derived from a bisphenol cyclohexane of the formula:
wherein R c1 and R d1 are each independently C 1-12 alkyl, R C2 and R d2 are each independently hydrogen or C 1-12 alkyl, R g is C 1-12 alkyl or halogen, and t is 0 to 10; and
0 to 50 mole percent of repeat units derived from a monomer of the formula:
wherein R a and R b are each independently a halogen or C 1-10 alkyl group that is meta to the hydroxy group on the same aromatic ring; p and q are each independently integers of 0 to 2; and X b is a C 1-8 alkylidene bridging group of the formula —C(R j )(R k )—wherein R j and R k are each independently hydrogen or C 1-4 alkyl.
17. The multilayer thermoplastic film of claim 16 , comprising 5 to 95 wt. % of the first polycarbonate polymer and 5 to 95 wt. % of the additional polycarbonate polymer, based on the total weight of first and additional polycarbonate polymers.
18. The multilayer thermoplastic film of claim 16 , comprising 5 to 60 wt. % of the first polycarbonate polymer and 40 to 95 wt. % of the additional polycarbonate polymer, based on the total weight of first and additional polycarbonate polymers.
19. The multilayer thermoplastic film of claim 1 , further comprising a printed marking.
20. A molded article comprising the multilayer thermoplastic film of claim 19 , in combination with an injection molded polymeric base to which the film is bonded.
21. A method of molding an article, comprising placing the multilayer thermoplastic film of claim 1 into a mold, and injecting a base polymer into a mold cavity space behind the multilayer to form a single molded part comprising the multilayer film and the injection molded base resin.
22. The multilayer thermoplastic film of claim 15 , wherein the film exhibits a light transmission of greater than or equal to 90%, as measured in accordance with ASTM D1003-00 for a multilayer film having a thickness of 0.32 mm.
23. The multilayer thermoplastic film of claim 15 , wherein the catalyst is a phase transfer or a transesterification catalyst.