Electrochromic mirror with two thin glass elements and a gelled electrochromic medium

• US 6,268,950 B1
• Filed: 04/28/2000
• Issued: 07/31/2001
• Est. Priority Date: 04/02/1997
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Tonar, William L., Bauer, Frederick T., Ash, Kevin L., Roberts, Kathy E.
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): Lucas, Michael A
• Application Number:
  US09/560,849
• Time in Patent Office: 459 Days
• Field of Search: 359/265, 359/266, 359/267, 359/270, 359/273
• US Class Current: 359/265
• CPC Class Codes: B60R 1/088 using a cell of electrically changeable optical characteristic, e.g. liquid-crystal or electrochromic mirrors
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: G02F 1/161 Gaskets; Spacers; Sealing of cells; Filling or closing of cells
• CPC Class Codes: G02F 2001/1502 complementary cell
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

An improved electrochromic rearview mirror for motor vehicles, the mirror incorporating thin front and rear spaced glass elements having a thickness ranging from about 0.5 to about 1.5. A layer of transparent conductive material is placed onto the mirror'"'"'s second surface, and either another layer of transparent conductive material or a combined reflector/electrode is placed onto the mirror'"'"'s third surface. A chamber, defined by the layers on the interior surfaces of the front and rear glass elements and a peripheral sealing member, contains a free-standing gel comprising a solvent and a crosslinked polymer matrix. The chamber further contains at least one electrochromic material in solution with the solvent and interspersed in the crosslinked polymer matrix. The gel cooperatively interacts with the thin glass elements to form a thick, strong unitary member which is resistant to flexing, warping, bowing and/or shattering and further allows the mirror to exhibit reduced vibrational distortion and double imaging.

Claims

1. An electrochromic device, comprising:

front and rear spaced elements, each having front and rear surfaces and each having a thickness ranging from about 0.5 mm to about 1.5 mm;

a layer of transparent conductive material associated with at least one of said front and rear spaced elements;

a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween; and

an electrochromic medium contained within said chamber comprising a free-standing gel, wherein the free-standing gel includes a solvent, a crosslinked polymer matrix, and an electrochromic material.

2. The electrochromic device according to claim 1, wherein said electrochromic material is in solution with said solvent and, as part of said solution, interspersed in said crosslinked polymer matrix.

3. The electrochromic device according of claim 1, wherein said front and rear spaced elements each have a thickness ranging from about 0.8 mm to about 1.2 mm.

4. The electrochromic device according to claim 1, wherein said front and rear spaced elements each have a thickness of about 1.0 mm.

5. The electrochromic device according to claim 1, wherein said polymer matrix results from crosslinking polymer chains and where said polymer chains are formed by polymerizing at least one monomer selected from the group consisting of:

methyl methacrylate;

methyl acrylate;

2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

2-hydroxyethyl methacrylate;

2-hydroxyethyl acrylate;

3-hydroxypropyl methacrylate;

vinyl ether n-butyl methyl methacrylate;

tetraethylene glycol vinyl ether;

glycidyl methacrylate;

4-vinylphenol;

acetoacetoxyethyl methacrylate and acetoacetoxyethyl acrylate.

6. The electrochromic device according to claim 5, wherein said polymer chains are cross-linked by reaction with a compound having a functional group selected from the group consisting of aromatic and aliphatic hydroxyl;

aromatic and aliphatic cyanato;

aromatic and aliphatic isocyanato;

aliphatic and aromatic isothiocyanato, with a functionality of at least 2.

7. The electrochromic device according to claim 5, wherein said polymer chains results from the polymerization of at least two distinct monomers.

8. The electrochromic device according to claim 5, wherein said at least two monomers are selected from the group consisting of:

methyl methacrylate;

methyl acrylate;

2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

2-hydroxyethyl methacrylate;

2-hydroxyethyl acrylate;

3-hydroxypropyl methacrylate;

vinyl ether n-butyl methyl methacrylate;

tetraethylene glycol divinyl ether;

glycidyl methacrylate;

4-vinylphenol;

acetoacetoxyethyl methacrylate and acetoacetoxyethyl acrylate.

9. The electrochromic device according to claim 8, wherein said at least two monomers are selected from the group consisting of:

methyl methacrylate;

2-isocyanatoethyl methacrylate;

2-hydroxyethyl methacrylate; and

glycidyl methacrylate.

10. The electrochromic device according to claim 9, wherein said at least two monomers comprise isocyanatoethyl methacrylate and methyl methacrylate.

11. The electrochromic device according to claim 10, wherein the ratio of isocyanatoethyl methacrylate to methyl methacrylate ranges from about 1:

3 to about 1;

50.

12. The electrochromic device according to claim 11, wherein the ratio of isocyanatoethyl methacrylate to methyl methacrylate is about 1:

20.

13. The electrochromic device according to claim 11, wherein said polymer chains formed from at least isocyanatoethyl methacrylate and methyl methacrylate are crosslinked by a compound having a functional group containing more than one active hydrogen.

14. The electrochromic device according to claim 9, wherein said at least two monomers comprise 2-hydroxyethyl methacrylate and methyl methacrylate.

15. The electrochromic device according to claim 14, wherein the ratio of 2-hydroxyethyl methacrylate to methyl methacrylate is about 1:

10.

16. The electrochromic device according to claim 14, wherein said polymer chains formed from at least 2-hydroxyethyl methacrylate and methyl methacrylate are crosslinked by a compound having more than one functional group that will react with an active hydrogen.

17. The electrochromic device according to claim 1, wherein said polymer matrix is formed from at least two distinct polymer chains, each of said at least two distinct polymer chains comprise at least one monomer selected from the group consisting of methyl methacrylate and methyl acrylate polymerized with at least one monomer selected from the group consisting of 2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

2-hydroxyethyl methacrylate;

2-hydroxyethyl acrylate;

3-hydroxypropyl methacrylate;

glycidyl methacrylate;

4-vinylphenol;

acetoacetoxyethyl methacrylate;

vinyl ether n-butyl methyl methacrylate and acetoacetoxyethyl acrylate, where said first and second polymer chains may be the same or different.

18. The electrochromic device according to claim 17, wherein said first of said at least two polymer chains comprises a copolymer of isocyanatoethyl methacrylate and methyl methacrylate and where said second of said at least two polymer chains comprises a copolymer of 2-hydroxyethyl methacrylate and methyl methacrylate.

19. The electrochromic device according to claim 18, wherein the ratio of isocyanatoethyl methacrylate and methyl methacrylate ranges from about 1:

3 to about 1;

50 and where the ratio of 2-hydroxyethyl methacrylate and methyl methacrylate ranges from about 1;

3 to about 1;

50.

20. The electrochromic device according to claim 1, wherein said cooperative interaction between said free standing gel and said front and rear elements makes said device resistant to bending and breaking.

21. The electrochromic device according to claim 1, wherein comprising polymeric beads disposed within said chamber.

22. The electrochromic device according to claim 21, wherein said beads comprise a material that will dissolve within an electrochromic device at ambient or near-ambient temperatures within about 24 hours.

23. The electrochromic device according to claim 22, wherein said beads comprise a copolymer selected from the group consisting of:

MMA/methacrylic acid, MMA/ethylacrylate, MMA/n-butylacrylate, and poly(propylene carbonate).

24. The electrochromic device according to claim 22, wherein said beads do not impart any refractive imperfections to said device.

25. An electrochromic device, comprising:

non-planar front and rear spaced elements, each having front and rear surfaces;

a layer of transparent conductive material associated with least one of said front and rear spaced elements;

a reflector disposed on one side of said rear element provided that, if said reflector is on said rear surface of said rear element, then said front surface of said rear element contains a layer of a transparent conductive material;

a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween; and

an electrochromic medium contained within said chamber comprising a free-standing gel, wherein the free-standing gel includes a solvent, a crosslinked polymer matrix, and an electrochromic material.

26. The electrochromic device according to claim 25, wherein said electrochromic material is in solution with said solvent and, as part of said solution, interspersed in said crosslinked polymer matrix.

27. The electrochromic device of claim 25, where said front and rear spaced elements each have a thickness ranging from about 0.5 mm to about 1.5 mm.

28. The electrochromic device according of claim 25, wherein said front and rear spaced elements each have a thickness ranging from about 0.8 mm to about 1.2 mm.

29. The electrochromic device according to claim 25, wherein said front and rear spaced elements each have a thickness of about 1.0 mm.

30. The electrochromic device according to claim 25, wherein said polymer matrix results from crosslinking polymer chains and where said polymer chains are formed by polymerizing at least one monomer selected from the group consisting of:

methyl methacrylate;

methyl acrylate;

2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

2-hydroxyethyl methacrylate;

2-hydroxyethyl acrylate;

3-hydroxypropyl methacrylate;

vinyl ether n-butyl methyl methacrylate;

tetraethylene glycol vinyl ether;

glycidyl methacrylate;

4-vinylphenol;

acetoacetoxyethyl methacrylate and acetoacetoxyethyl acrylate.

31. The electrochromic device according to claim 30, wherein said polymer chains are cross-linked by reaction with a compound having a functional group selected from the group consisting of aromatic and aliphatic hydroxyl;

aromatic and aliphatic cyanato;

aromatic and aliphatic isocyanato;

aliphatic and aromatic isothiocyanato, with a functionality of at least 2.

32. The electrochromic device according to claim 30, wherein said polymer chains results from the polymerization of at least two distinct monomers.

33. The electrochromic device according to claim 30, wherein said at least two monomers are selected from the group consisting of:

methyl methacrylate;

methyl acrylate;

2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

2-hydroxyethyl methacrylate;

2-hydroxyethyl acrylate;

3-hydroxypropyl methacrylate;

vinyl ether n-butyl methyl methacrylate;

tetraethylene glycol divinyl ether;

glycidyl methacrylate;

4-vinylphenol;

acetoacetoxyethyl methacrylate and acetoacetoxyethyl acrylate.

34. The electrochromic device according to claim 33, wherein said at least two monomers are selected from the group consisting of:

methyl methacrylate;

2-isocyanatoethyl methacrylate;

2-hydroxyethyl methacrylate; and

glycidyl methacrylate.

35. The electrochromic device according to claim 34, wherein said at least two monomers comprise 2-hydroxyethyl methacrylate and methyl methacrylate.

36. The electrochromic device according to claim 35, wherein the ratio of 2-hydroxyethyl methacrylate to methyl methacrylate is about 1:

10.

37. The electrochromic device according to claim 35, wherein said polymer chains formed from at least 2-hydroxyethyl methacrylate and methyl methacrylate are crosslinked by a compound having more than one functional group that will react with an active hydrogen.

38. The electrochromic device according to claim 34, wherein said at least two monomers comprise isocyanatoethyl methacrylate and methyl methacrylate.

39. The electrochromic device according to claim 38, wherein the ratio of isocyanatoethyl methacrylate to methyl methacrylate ranges from about 1:

3 to about 1;

50.

40. The electrochromic device according to claim 39, wherein the ratio of isocyanatoethyl methacrylate to methyl methacrylate is about 1:

20.

41. The electrochromic device according to claim 39, wherein said polymer chains formed from at least isocyanatoethyl methacrylate and methyl methacrylate are crosslinked by a compound having a functional group containing more than one active hydrogen.

42. The electrochromic device according to claim 30, wherein said polymer matrix is formed from at least two distinct polymer chains, each of said at least two distinct polymer chains comprise at least one monomer selected from the group consisting of methyl methacrylate and methyl acrylate polymerized with at least one monomer selected from the group consisting of 2-isocyanatoethyl methacrylate;

2-isocyanatoethyl acrylate;

2-hydroxyethyl methacrylate;

2-hydroxyethyl acrylate;

3-hydroxypropyl methacrylate;

glycidyl methacrylate;

4-vinylphenol;

acetoacetoxyethyl methacrylate;

vinyl ether n-butyl methyl methacrylate and acetoacetoxyethyl acrylate, where said first and second polymer chains may be the same or different.

43. The electrochromic device according to claim 42, wherein said first of said at least two polymer chains comprises a copolymer of isocyanatoethyl methacrylate and methyl methacrylate and where said second of said at least two polymer chains comprises a copolymer of 2-hydroxyethyl methacrylate and methyl methacrylate.

44. The electrochromic device according to claim 43, wherein the ratio of isocyanatoethyl methacrylate and methyl methacrylate ranges from about 1:

3 to about 1;

50 and where the ratio of 2-hydroxyethyl methacrylate and methyl methacrylate ranges from about 1;

3 to about 1;

50.

45. The electrochromic device according to claim 25, wherein said cooperative interaction between said free standing gel and said front and rear elements makes said device resistant to bending and breaking.

46. The electrochromic device according to claim 25, wherein comprising polymeric beads disposed within said chamber.

47. The electrochromic device according to claim 46, wherein said beads comprise a material that will dissolve within an electrochromic device at ambient or near-ambient temperatures within about 24 hours.

48. The electrochromic device according to claim 47, wherein said beads comprise a copolymer selected from the group consisting of:

MMA/methacrylic acid, MMA/ethylacrylate, MMA/n-butylacrylate, and poly(propylene carbonate).

49. The electrochromic device according to claim 47, wherein said beads do not impart any refractive imperfections to said device.

50. An electrochromic device, comprising:

non-planar front and rear spaced elements, each having front and rear surfaces;

a layer of transparent conductive material associated with at least one of said front and rear spaced elements;

a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween; and

an electrochromic medium contained within said chamber comprising a free-standing gel, wherein the free-standing gel includes a solvent, a crosslinked polymer matrix, and an electrochromic material.

51. An electrochromic device, comprising:

front and rear spaced elements, each having front and rear surfaces;

a layer of transparent conductive material associated with at least one of said front and rear spaced elements;

a perimeter sealing member bonding together said front and rear spaced elements in a spaced-apart relationship to define a chamber therebetween;

an electrochromic medium contained within said chamber comprising a free-standing gel, wherein the free-standing gel includes a solvent, a crosslinked polymer matrix, and an electrochromic material; and

means cooperatively associated with the front and rear spaced elements and the electrochromic medium for increasing pressure point resistance of the electrochromic device greater than approximately 167 pounds.