Granted Patent B2

US 12,491,704 · App. 17/913,682 · Granted Dec 9, 2025

Inventors: Meng He (South Elgin, IL); Thomas Fauvell (Chicago, IL); Eric Urruti (Elgin, IL)

Assignee: Covestro (Netherlands) B.V.

B32B17/10036B32B17/10559B32B17/1077B32B2250/03B32B2250/40B32B2307/412B32B2307/762B32B2315/08B32B2375/00

Abstract

Claims (84)

1 . A multi-layered optical device comprising:

a polymeric layer disposed between a first optical element layer and a second optical element layer,

wherein each of the polymeric layer, the first optical element layer, and the second optical element layer comprise a first surface and a second surface, wherein the first surface of the polymeric layer is in contact with the first surface of the first optical element layer and the second surface of the polymeric layer is in contact with the first surface of the second optical element layer,

wherein the polymeric layer comprises a product of a composition comprising a self-healing component, wherein said self-healing component consists essentially of molecules comprising self-healing moieties, wherein said composition possesses either:

(a) greater than 30 wt. %, relative to the weight of the entire composition, of the self-healing component; or

(b) greater than 0.015 equivalents of self-healing moieties per 100g of the composition.

2 . The multi-layered optical device of claim 1 , wherein the first optical element layer and/or the second optical element layer are constructed from a material selected from the group consisting of glass, organic materials including polymers and organometallic materials.

3 . The multi-layered optical device of claim 1 , wherein the first optical element layer, the second optical element layer, or both, are coatings from vapor deposition including metals and metal oxides.

4 . The multi-layered optical device of claim 1 , wherein the first surface of the polymeric layer is chemically bonded to the first surface of the first optical element layer, and the second surface of the polymeric layer is chemically bonded to the first surface of the second optical element layer.

5 . The multi-layered optical device of claim 1 , wherein the polymeric layer is configured to possess a light transmittance of greater than or equal to 80%, when tested according to ISO 13468-1:2019.

6 . The multi-layered optical device of claim 1 , wherein the polymeric layer has a thickness of less than or equal to 500 microns.

7 . The multi-layered optical device of claim 1 , wherein the composition possesses a glass transition temperature of less than 150° C.

8 . The multi-layered optical device of claim 1 , wherein the composition is UV-or thermally-curable.

9 . The multi-layered optical device of claim 1 , wherein the composition further comprises:

optionally, a monomer component;

optionally, an oligomer component

an initiator component, wherein the initiator component optionally comprises a photoinitiator; and/or

additives, wherein the additives optionally comprise adhesion promoters, UV absorbers, hindered amine stabilizers, antioxidant, photochromic dyes, thermochromic dyes, liquid crystals, laser dyes, fluorescent dyes, OLED materials, dichroic dyes, or fillers, wherein the fillers optionally comprise thermally- or electrically-conductive fillers; and,

wherein relative to the weight of the entire composition,

the monomer and/or oligomer component is present from 10 wt. % to 65 wt. %;

the self-healing component is present from greater than 30 wt. % to 100 wt. %;

the initiator is present from 0.01 wt. % to 10 wt. %;

and the additives are present from 0 wt. % to 59.99 wt. %;

wherein each of the components adds up to 100 wt. %.

10 . The multi-layered optical device of claim 1 , wherein the self-healing component comprises molecules according to structure (VI):

[A(G) n -D m ]-[A(G) n-1 -D m ] k -Z  (VI);

wherein

A is carbon or nitrogen;

wherein when A is an sp3 carbon, n=3, and when A is an sp2 carbon or a nitrogen, n=2;

m is an integer from 0 to 500;

k is a number from 0-20;

D is, for each occurrence of m, a divalent spacer independently chosen from—O—;

—C(O)—;-Aryl-;—C═C—;—N═N—;—S—;—S(O)—;—S(O) (O)—;

—(CT 2 ) i —; N (T);—Si (T) 2 (CH 2 );—;—(Si (T) 2 O);—;—C(T)—C(T)—;

C (T)—N—;—C(T)=;—N=; or combinations thereof;

wherein

for each instance in D of a single bond, a single bond is connected thereto, and for each instance in D of a double bond, a double bond is connected thereto;

wherein

each T is selected for each occurrence from single valent units including hydrogen, F, Cl, Br, I, C 1 —C 8 alkyl, C 1 —C 8 alkoxy, substituted amino, or substituted aryl;

wherein each T can also be selected from divalent D m and connects to another divalent T that's also selected from D m and form a ring structure; and

i is an integer from 1-40;

wherein each group for each unit of m, n, and k can be the same or different;

Z is chosen from a hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimido group; and

G is, for each occurrence of n, independently selected from hydrogen, Z, or a self-healing moiety according to the following structure (VI-b):

(Z—D m ) j X—D m —  (VI-b);

wherein

X is a multi-hydrogen bonding group, a disulfide group, or a urea group;

j=1 when X is divalent, and j=0 when X is monovalent;

wherein for at least one occurrence of n, G is a self-healing moiety according to structure (VI-b).

11 . The multi-layered optical device of claim 10 , wherein X comprises disulfide groups and/or urea groups, and j=1, and wherein the molecule according to structure (VI) possesses a theoretical molecular weight, MW theo , of between 500 and 100,000 g/mol.

12 . The multi-layered optical device of claim 10 , wherein X is a 2-ureido-4-pyrimidinone (UPy) group, and j=0; wherein the UPy group is the reaction product of 2-amino-4-hydroxy-6-methyl-pyrimidine; and

wherein D comprises a urethane group, wherein the urethane group is the reaction product of a diisocyanate compound.

13 . The multi-layered optical device of claim 1 , wherein the self-healing moieties are self-complementary, wherein a bond dissociation energy between two complementary self-healing moieties is between 9 kcal/mol to 100 kcal/mol, wherein bond dissociation energy is calculated as a direct addition summary of all bonds between complementary self-healing moieties in accordance with Table 1 of The Scientific World JOURNAL (2004) 4, 1074-1082, and references cited therein; and Nature 2002, volume 3, 836-847, and references cited therein.

14 . The multi-layered optical device of claim 1 , wherein the self-healing moieties comprise multi-hydrogen bonding materials, wherein the multi-hydrogen bonding materials optionally comprise 2-ureido-4-pyrimidinone (UPy) groups.

15 . The multi-layered optical device of claim 1 , wherein the self-healing component comprises molecules according to structure (VII):

[UP y -(D m -U-D m ) (2+q) ]-[A(G) (n−1) -D m ] k -Z  (VII);

wherein

UPy represents a UPy group, wherein the UPy group is a 2-ureido-4-pyrimidinone;

U represents-NHC (O) E-or-EC (O) NH—, wherein E is O, NH, N (alkyl), or S;

q is a number greater than or equal to 0 and less than or equal to 10;

k is a number from 0 to 20;

A is selected from carbon and nitrogen;

n is 2 or 3, wherein when A is an sp3 carbon, n=3, and when A is an sp2 carbon or a nitrogen, n=2;

m is an integer from 0 to 500;

D is, for each occurrence of m, a divalent spacer independently chosen from—O—,—C (O)—,-Aryl-,—C═C—,—N═N—,—S—,—S(O)—,—S(O) (O)—,

(CT 2 ) i —,—N(T)—,—Si (T) 2 (CH 2 ) i —,—(Si (T) 2 O ) i —,—C(T)═C (T)—, —C(T)═N—,—C(T)=,—N═, or combinations thereof;

wherein

for each instance in D of a single bond, a single bond is connected thereto, and for each instance in D of a double bond, a double bond is connected thereto;

wherein each T is selected for each occurrence from single valent units including hydrogen, F, Cl, Br, I, C 1 —C 8 alkyl, C 1 —C 8 alkoxy, substituted amino, or substituted aryl;

wherein each T can also be selected from divalent D m and connects to another divalent T that's also selected from D m and form a ring structure; and

i is an integer from 1-40;

Z is chosen from a hydrogen, acryloyloxy, methacryloyloxy, hydroxy, amino, vinyl, alkynyl, azido, silyl, siloxy, silylhydride, thio, isocyanato, protected isocyanato, epoxy, aziridino, carboxylate, hydrogen, F, Cl, Br, I, or maleimido group; and

G is, for each occurrence of n, independently selected from hydrogen,—D m -Z, or a self-healing moiety according to the following structure (VII-b):

(Z—D m ) j X—D m —  (VII-b);

wherein

X is a multi-hydrogen bonding group, a disulfide group, or a urea group;

j=1 when X is divalent, and j=0 when X is monovalent; and

wherein the oligomer possesses greater than 0.022 equivalents of UPy groups per 100 grams of the oligomer.

16 . The multi-layered optical device of claim 1 , wherein the composition possesses from 0.015 to 0.5 equivalents of self-healing groups per 100g of the composition.

17 . The multi-layered optical device of claim 1 , wherein the multi-layered optical device is flat, curved, or cylindrical; and

wherein the multi-layered optical device is an optical fiber, beam splitter, solar panel, antireflection coating, electronic display part, optical lens, optical film, polarizing optics, window, optical filter, lighting device, ophthalmic lens, photochromic lens, microscopy lens, laser mirror, or imaging lens.

18 . The multi-layered optical device of claim 1 , further comprising a third or more optical element layer, wherein at least one optical element layer is in contact with either the second surface of the first optical element layer or the second surface of the second optical element layer.

19 . The multi-layered optical device of claim 1 , wherein the molecules comprising self-healing moieties comprise a reactive urethane oligomer having a backbone derived from a polyether polyol, a polyester polyol, a poly (dimethylsiloxane), a disulfide polyol, or a combination thereof.

20 . The multi-layered optical device of claim 1 , wherein the molecules comprising self-healing moieties have a theoretical molecular weight (MW theo ) of between 500 and 2000 g/mol and further comprise urethane linking groups.

Assignments (1)

Continuity (2)

References Cited (69)