Regioselectively substituted cellulose ester based negative birefringent compensation films having improved wavelength dispersion

1 . A film, comprising:

(1) a regioselectively substituted cellulose ester comprising:

(i) a plurality of aromatic-CO— substituents;

(ii) a plurality of a first unsaturated or saturated (C 1-6 )alkyl-CO— substituents; and

(iii) a plurality of hydroxyl substituents;

wherein:

the degree of substitution for the hydroxyl (“DS OH ”) is from 0.2 to 1.1,

the cellulose ester has a C2 degree of substitution for the aromatic-CO— substituent (“C2DS ArCO ”) which is from 0.15 to 0.8,

the cellulose ester has a C3 degree of substitution for the aromatic-CO— substituent (“C3DS ArCO ”) which is from 0.05 to 0.6,

the cellulose ester has a C6 degree of substitution for the aromatic-CO— substituent (“C6DS ArCO ”) which is from 0.05 to 0.6,

the total degree of substitution for the aromatic-CO— substituent (“TotDS ArCO ”) which is from 0.25 to 2.0,

the aromatic-CO— is

(i) an (C 6-20 )aryl-CO—, wherein the aryl is unsubstituted or substituted by 1-5 R 1 ;

(ii) a heteroaryl-CO—, wherein the heteroaryl is a 5- to 10-membered ring having 1- to 4-heteroatoms chosen from N, O, or S, and wherein the heteroaryl is unsubstituted or substituted by 1-5 R 1 ; and

(2) a component A that is

wherein:

ring A is an (C 6-20 )aryl or a 5- to 10-membered heteroaryl containing 1-4 heteroatoms chosen from N, O, or S;

ring B is (C 6-20 )aryl or a 5- to 10-membered heteroaryl containing 1-4 heteroatoms chosen from N, O, or S;

ring C is (C 6-20 )aryl a 5- to 10-membered heteroaryl containing 1-4 heteroatoms chosen from N, O, or S;

R 1 is saturated or unsaturated (C 1-20 )alkyl; saturated or unsaturated halo(C 1-20 )alkyl; (C 6-20 )aryl optionally by 1-5 substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, halo; 5- to 10-membered heteroaryl containing 1-4 heteroatoms chosen from N, O, or S; or —CH 2 C(O)—R 3 ;

R 2 is independently hydrogen, saturated or unsaturated (C 1-20 )alkyl, or saturated or unsaturated halo(C 1-20 )alkyl;

R 3 is saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated halo(C 1-20 )alkyl, (C 6-20 )aryl, or 5- to 10-membered heteroaryl containing 1-4 heteroatoms chosen from N, O, or S, wherein the aryl or heteroaryl are unsubstituted or substituted by 1-5 R 6 ;

R 4 is saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated halo(C 1-20 )alkyl, or saturated or unsaturated (C 1-20 )alkyl-CO—(C 1-20 )alkyl, wherein each of the groups is unsubstituted or substituted by 1-3 hydroxyl, saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated halo(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy, saturated or unsaturated halo(C 1-20 )alkoxy, saturated or unsaturated hydroxy(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy-(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy-hydroxy(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy-(C 1-20 )alkyl-CO—(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkyl-CO, saturated or unsaturated (C 1-20 )alkyl-COO, saturated or unsaturated (C 1-20 )alkyl-O—CO—C (1-20) alkyl, saturated or unsaturated (C 1-20 )alkyl-COO—C (1-20) alkyl, saturated or unsaturated (C 1-20 )alkoxy-(C 1-20 )alkyl-COO—(C 1-20 )alkyl, or (C 1-20 )alkoxy-(C 1-20 )alkyl-O—CO—(C 1-20 )alkyl;

each R 5 is independently hydroxy, cyano, saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated halo(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy, saturated or unsaturated halo(C 1-20 )alkoxy, or halo;

each R 6 is independently hydroxy, cyano, saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated halo(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy, saturated or unsaturated halo(C 1-20 )alkoxy, or halo or (C 6-20 )aryl, wherein the aryl is unsubstituted or substituted by 1-5 R 7 ;

each R 7 is independently hydroxyl, saturated or unsaturated (C 1-6 )alkyl, saturated or unsaturated halo(C 1-6 )alkyl, or saturated or unsaturated (C 1-6 )alkoxyl;

R 8 is saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated halo(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxyl, or saturated or unsaturated halo(C 1-20 )alkoxyl;

each R 9 is R 4 —O—, hydroxy, saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated hetero(C 1-20 )alkyl containing 1-2 heteroatoms chosen from N, O or S, saturated or unsaturated halo(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkyl-CO—(C 1-20 )alkyl-, saturated or unsaturated (C 1-20 )alkyl-COO—(C 1-20 )alkyl-, saturated or unsaturated (C 1-20 )alkyl-COO—, saturated or unsaturated (C 1-20 )alkyl-O—CO—, saturated or unsaturated (C 1-2 )alkyl-CO—, saturated or unsaturated (C 1-20 )alkoxy-(C 1-20 )alkyl-CO— O—(C 1-2 )alkyl, saturated or unsaturated (C 1-2 )alkoxy-(C 1-2 )alkyl-O—CO— (C 1-2 )alkyl, saturated or unsaturated (C 1-2 )alkoxy-(C 1-2 )alkyl-CO— (C 1-20 )alkyl, (C 1-20 )alkoxy-(C 1-20 )alkyl-O—CO—(C 1-20 )alkyl-(C 6-10 )aryl, 5- to 10-membered heteroaryl containing 1-4 heteroatoms chosen from N, O, or S,

wherein each of the groups are unsubstituted or substituted by 1-3 hydroxyl, saturated or unsaturated (C 1-20 )alkyl, saturated or unsaturated halo(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxyl, or saturated or unsaturated halo(C 1-20 )alkoxyl, saturated or unsaturated hydroxy(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy-(C 1-20 )alkyl, saturated or unsaturated (C 1-20 )alkoxy-hydroxy(C 1-20 )alkyl, or saturated or unsaturated (C 1-20 )alkoxy-(C 1-20 )alkyl-CO—(C 1-20 )alkyl-, saturated or unsaturated (C 1-20 )alkyl-CO, saturated or unsaturated (C 1-20 )alkyl-COO, saturated or unsaturated (C 1-20 )alkyl-O—CO—C (1-20) alkyl, saturated or unsaturated (C 1-20 )alkyl-COO—C (1-20) alkyl, saturated or unsaturated (C 1-20 )alkoxy-(C 1-20 )alkyl-COO—(C 1-20 )alkyl, or (C 1-20 )alkoxy-(C 1-20 )alkyl-O—CO—(C 1-20 )alkyl;

each n is 0, 1, 2, 3, 4, or 5;

each m is 0, 1, 2, 3, or 4; and

k is 0, 1, 3, or 4,

wherein:

component A is present at less than 30 wt %, based on the total weight of the film,

the thickness of the film (“d”) (μm) is from 10 μm to 200 μm,

the film exhibits a R e (589 nm) that is less than zero,

the ratio of the R e (589 nm) and d (nm) multiplied by 1000 is from −10 to −0.5,

the ratio of the R th (589 nm) and d (nm) multiplied by 1000 is from −6.0 to 6.0,

the film exhibits a [[—R th (589 nm)/R e (589 nm)]+0.5](“N z ”) is from −3.0 to 3.0,

each R e (589 nm) is the in-plane retardation measured at 589 nm,

each R th (589 nm) is the out-of-plane retardation measured at 589 nm, and the film is stretched.

2 . The film of claim 1 , wherein R e (589 nm) is from −120 to −320 nm and R th (589 nm) is from −60 to 60 nm.

3 . The film of claim 1 , wherein R e (589 nm) is from −120 to −320 nm and R th (589 nm) is from 60 to 220 nm.

4 . The film of claim 1 , wherein the ratio of R e (450 nm) to R e (550 nm) is less than 1.05, wherein R e (450 nm) is the in-plane retardation measured at 450 nm, and R e (550 nm) is the in-plane retardation measured at 550 nm.

5 . The film of claim 4 , wherein the ratio of R e (450 nm) to R e (550 nm) is from 0.75 to 0.85.

6 . The film of claim 1 , wherein the ratio of R e (650 nm) to R e (550 nm) is greater than 0.95, wherein the R e (650 nm) is the in-plane retardation measured at 650 nm and R e (550 nm) is the in-plane retardation measured at 550 nm.

7 . The film of claim 6 , wherein the ratio of R e (650 nm) to R e (550 nm) is from 1.10 to 1.2.

8 . The film of claim 1 , wherein the component A is

9 . The film of claim 1 , wherein the component A is 1,3-diphenyl-1,3-propanedione, avobenzone, (2-hydroxy-4-(octyloxy)phenyl(phenyl)methanone, (2-hydroxy-4-methoxyphenyl)(2-hydroxyphenyl)methanone, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[2-hydroxy-3-(dodecyloxy- and tridecyloxy)propoxy]phenols, isooctyl 2-(4-(4,6-di([1,1′-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-3-hydroxyphenoxy)propanoate, 6,6′-(6-(2,4-dibutoxyphenyl)-1,3,5-triazine-2,4-diyl)bis(3-butoxyphenol), 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(3-((2-ethylhexyl)oxy)-2-hydroxypropoxy)phenol, 7-diethylamino-4-methylcoumarin, or combinations thereof.

10 . The film of claim 1 , wherein the aromatic-CO— is an (C 6-20 )aryl-CO—, wherein the aryl is unsubstituted or substituted by 1-5 R 1 .

11 . The film of claim 1 , wherein the aromatic-CO— is benzoyl or naphthoyl, which is unsubstituted or substituted by 1-5 R 1 .

12 . The film of claim 11 , wherein the aromatic-CO— is benzoyl, unsubstituted or substituted by 1-5 R 1 .

13 . The film of claim 12 , wherein the cellulose ester has a totDS ArCO of from 0.40 to 1.60.

14 . The film of claim 13 , wherein the sum of C2DS ArCO and C3DS ArCO is from 0.30 to 1.25.

15 . The film of claim 11 , wherein the aromatic-CO— is naphthoyl, unsubstituted or substituted by 1-5 R 1 .

16 . The film of claim 15 , wherein cellulose ester has a totDS ArCO of from 0.3 to 0.8.

17 . The film of claim 16 , wherein the sum of C2DS ArCO and C3DS ArCO is from 0.2 to 0.6.

18 . The film of claim 1 , wherein the cellulose ester further comprises a plurality of a second (C 1-20 )alkyl-CO— substituent.

19 . The film of claim 8 , wherein N z is from 0.4 to 0.6.

20 . The film of claim 1 , further comprising 0.1 to 15 wt % of a plasticizer.