Seal for electrochromic devices

• US 6,157,480 A
• Filed: 09/21/1998
• Issued: 12/05/2000
• Est. Priority Date: 09/21/1998
• Status: Expired due to Term

• Current Assignee: Gentex Corporation
• Original Assignee: Gentex Corporation
• Inventors: Tonar, William L., Guarr, Thomas F., Anderson, John S., Ash, Kevin L.
• Primary Examiner(s): Epps, Georgia
• Assistant Examiner(s): Lester, Evelyn A.
• Application Number:
  US09/158,423
• Time in Patent Office: 806 Days
• Field of Search: 359/265-275
• US Class Current: 359/267
• CPC Class Codes: G02F 1/161 Gaskets; Spacers; Sealing of cells; Filling or closing of cells

Abstract

An improved seal member is provided as a part of an electrochromic device to bond two glass elements together in a spaced-apart relationship. In one embodiment the seal member provides improved adhesion to a reflector/electrode on the third surface of an electrochromic mirror, or to a layer of metal on the second or third surface for an electrochromic light filter. This seal member comprises a mixture of an organic resin sealing system and an adhesion promoter, where the adhesion promotor comprises a first and a second region, where the first region interacts with the reflector/electrode or the metal layer, and a second region that interacts with the organic resin sealing system, and may even chemically react with the organic resin sealing system. In another embodiment the seal member is provided with a coefficient of thermal expansion that is closer to glass than a standard epoxy sealing system.

Claims

1. An electrochromic mirror, comprising front and rear spaced elements, each having front and rear surfaces, said rear surface of said front element having a layer of transparent conductive material disposed thereon, at least a major portion of said front surface of said rear element having a reflector/electrode disposed thereon, said mirror further comprising a seal member bonding said front and rear spaced elements together in a spaced-apart relationship to define a chamber containing an electrochromic medium, said seal member comprising a sealing system and an adhesion promoter, said adhesion promoter comprising a first region that is a phosphorous- or sulfur-containing organic moiety, where said reflector/electrode is effective to reflect light through said medium and said front element when said light reaches said reflector/electrode after passing through said front element and said electrochromic medium.

2. The electrochromic mirror of claim 1, where said first region is a moiety selected from the group comprising phosphines, thiols, dithiols, thioacids, thioamides, thioesters, sulfides, disulfides and tetrasulfides.

3. The electrochromic mirror of claim 2, where said adhesion promoter further comprises a second region that interacts with said seal member.

4. The electrochromic mirror of claim 1, where said first region interacts with said reflector/electrode through chemisorption or complexation.

5. The electrochromic mirror of claim 1, where said adhesion promoter further comprises a second region that interacts with said seal member.

6. The electrochromic mirror of claim 5, where said second region interacts with said seal member through a chemical reaction.

7. The electrochromic mirror of claim 1, where said adhesion promoter further comprises a second region that is compatible with said seal member.

8. The electrochromic mirror of claim 7, where said adhesion promoter is selected from the group comprising:

##STR7## where n is an integer of 1 to 4, m is an integer of 1 or 2, and R₁ and R₂ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted alkyl-, aryl-, aralkyl- or alkoxy-silane having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted alkyl-, aryl-, aralkyl- or alkoxy-phosphine having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted straight or branched alkyl chains having 1-20 carbons, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted aryl, or aralkyl having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof; and

where if R₁ and R₂ can form a substituted or unsubstituted cyclic alkyl of 2-20 carbons, as well as alkyl-, alkenyl, amido and primary, secondary and tertiary amino derivatives thereof; and

if R₁ and R₂ are substituted, they are substituted with a member of the group comprising;

acetals, acetoacetates, nitriles, alkynes, acid anhydrides, acyl halides, alcohols, aldehydes, alkyl halides, alkyl hydroperoxides, amides, primary, secondary and tertiary amines, 2-aminothiols, aryl dichloroarsines, carbamyl chloride, carboxylic acids, cyanates, cyanoacetates, epoxides, ethylene imines, halohydrins, ketones, malonates, metal alkoxides, phenols, phosphines, alkyl phosphonic acids, phthalimides, alkyl silicon halides, siloxanes, thiocyanates, thioacids, thiols and thionyl chlorides.

9. The electrochromic minor of claim 8, where said adhesion promoter is selected from the group comprising:

##STR8## where R₃, R₄ and R₅ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted straight or branched alkyl, aralkyl or alkoxyalkyl having 1-10 carbons;

substituted and unsubstituted cyclic, polycyclic or heterocyclic, alkyl having 1-10 carbons;

R₆ is selected from the group comprising substituted and unsubstituted straight or branched alkyl or aralkyl having 1-14 carbons;

or substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, or alkoxy-alkyl having 1-14 carbons;

space="preserve" listing-type="equation">H.sub.2 N--R.sub.7 --(S--).sub.m --R.sub.8 --NH.sub.2

where m is an integer from 1 to 4, R₇ and R₈ are the same or different and are selected from the group comprising substituted and unsubstituted alkyl, aryl or aralkyl having a chain of 1-14 carbons which may be branched or straight;

or substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having 1-14 carbons which may be branched or straight;

if R₇ and R₈ are substituted then they are substituted with a member of the group comprising;

acetals, acetoacetates, nitrites, alkynes, acid anhydrides, acyl halides, alcohols, aldehydes, alkyl halides, alkyl hydroperoxides, amides, primary, secondary and tertiary amines, 2-aminothiols, aryl dichloroarsines, carbamyl chloride, carboxylic acids, cyanates, cyanoacetates, epoxides, ethylene imines, halohydrins, ketones, malonates, metal alkoxides, phenols, phosphines, alkyl phosphonic acids, phthalimides, alkyl silicon halides, siloxanes, thiocyanates, thioacids, thiols and thionyl chloride;

##STR9## where R₉ and R₁₀ are the same or different and are selected from the group comprising hydrogen;

straight or branched alkyl, aryl and aralkyl having 1-14 carbons;

or cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having 1-14 carbons; and

where R₉ and R₁₀ also form a cyclic alkyl of 4-12 carbons or a aryl of 6 to 10 carbons;

##STR10## where m is an integer from 1-4, R₁₁, R₁₂, R₁₃, R₁₆, R₁₇ and R₁₈ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted straight or branched alkyl, aralkyl or alkoxyalkyl having 1-10 carbons;

substituted and unsubstituted cyclic, polycyclic or heterocyclic alkyl having 1-10 carbons, and R₁₄ and R₁₅ is selected from the group comprising substituted and unsubstituted straight or branched alkyl or aralkyl having 1-14 carbons;

or substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, or alkoxy-alkyl having 1-14 carbons; and

##STR11## where R₁₉, R₂₀, R₂₁, and R₂₂ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted straight or branched alkyl, aryl or aralkyl having 1-14 carbons, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having 1-14 carbons, as well as amido and primary, secondary and tertiary amino derivatives thereof.

10. The electrochromic mirror of claim 9, where said adhesion promoter is selected from the group comprising:

##STR12##

11. The electrochromic mirror of claim 1, where said reflector/electrode comprises one or more layers, each of which is selected from the group comprising:

chromium, rhodium, molybdenum, platinum, gold, aluminum, silver, and silver alloys.

12. The electrochromic mirror of claim 1, where said layer of transparent conductive material is selected from the group comprising:

fluorine-doped tin oxide, tin-doped indium oxide, gold, aluminum, silver, silver alloys, zinc indium oxide, and IMI.

13. The electrochromic mirror of claim 1, where said layer of transparent conductive material is selected from the group comprising gold, aluminum, silver, and silver alloys and where the layer is disposed in a pattern.

14. The electrochromic mirror of claim 13, where said layer of transparent conductive material covers less than 50 percent of the geometric area of said rear surface of said front element.

15. The electrochromic mirror of claim 1, where said adhesion promoter is uniformly dispersed throughout said seal member.

16. The electrochromic mirror of claim 15, where said adhesion promoter is uniformly dispersed by a technique selected from the group comprising milling and pre-reacting.

17. The electrochromic mirror of claim 1, where said seal member further comprises an inorganic filler in an amount sufficient to lower the coefficient of thermal expansion of said seal member, while allowing said seal member, in an uncured state, to be dispensed or screen printed.

18. The electrochromic mirror of claim 17, where said amount is greater than about 40 percent by weight of said seal member.

19. The electrochromic mirror of claim 18, where said amount is greater than about 60 percent by weight of said seal member.

20. The electrochromic mirror of claim 17, where said inorganic filler is glass beads and where the average dimension of said beads is less than 2/3 of the dimension that said front and rear elements are spaced apart.

21. The electrochromic mirror of claim 20, where said glass bead dimension is less than 1/2 of the dimension that said front and rear elements are spaced apart and greater than about 0.5 microns.

22. The electrochromic mirror of claim 21, where said glass bead dimension is less than about 50 microns.

23. An electrochromic device, comprising front and rear spaced elements, each having front and rear surfaces, said rear surface of said front element and said front surface of said rear element having a layer of transparent conductive material disposed thereon, where one of said layers of transparent conductive material is a layer of metal, said device further comprising a seal member bonding said front and rear spaced elements together in a spaced-apart relationship to define a chamber containing an electrochromic medium, said seal member comprising a sealing system and an adhesion promoter, where said adhesion promoter comprising a phosphorous- or sulfur-containing organic moiety.

24. The electrochromic device of claim 23, where said first region is a moiety selected from the group comprising phosphine, thiol, dithiol, thioacid, thioamide, thioester, sulfide, disulfide and tetrasulfide.

25. The electrochromic device of claim 24, where said adhesion promoter further comprises a second region that interacts with said seal member.

26. The electrochromic device of claim 23, where said first region interacts with said layer of metal through chemisorption or complexation.

27. The electrochromic device of claim 23, where said adhesion promoter further comprises a second region that interacts with said seal member.

28. The electrochromic device of claim 27, where said second region interacts with said seal member through a chemical reaction.

29. The electrochromic device of claim 23, where said adhesion promoter further comprises a second region that is compatible with said seal member.

30. The electrochromic device of claim 23, where said layer of transparent conductive material is selected from the group comprising:

fluorine-doped tin oxide, tin-doped indium oxide, gold, aluminum, silver, silver alloys, zinc indium oxide, and IMI.

31. The electrochromic device of claim 23, where said layer of transparent conductive material is selected from the group comprising gold, aluminum, silver, and silver alloys and where the layer is disposed in a pattern.

32. The electrochromic device of claim 31, where said layer of transparent conductive material covers less than 50 percent of the geometric area of said rear surface of said front element.

33. The electrochromic device of claim 23, where said adhesion promoter is uniformly dispersed throughout said seal member.

34. The electrochromic device of claim 33, where said adhesion promoter is uniformly dispersed by a technique selected from the group comprising milling and pre-reacting.

35. The electrochromic device of claim 23, where said seal member further comprises an inorganic filler in an amount sufficient to lower the coefficient of thermal expansion of said seal member, while allowing said seal member, in an uncured state, to be dispensed or screen printed.

36. The electrochromic device of claim 35, where said amount is greater than about 40 percent by weight of said seal member.

37. The electrochromic device of claim 36, where said amount is greater than about 60 percent by weight of said seal member.

38. The electrochromic device of claim 35, where said inorganic filler is glass beads and where the average dimension of said beads is less than 2/3 of the dimension that said front and rear elements are spaced apart.

39. The electrochromic device of claim 38, where said glass bead dimension is less than 1/2 of the dimension that said front and rear elements are spaced apart and greater than about 0.5 microns.

40. The electrochromic device of claim 39, where said glass bead dimension is less than about 50 microns.

41. The electrochromic device of claim 23, where said adhesion promoter is selected from the group comprising:

where n is an integer of 1 to 4, m is an integer of 1 or 2, and R₁ and R₂ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted alkyl-, aryl-, aralkyl- or alkoxy-silane having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted alkyl-, aryl-, aralkyl- or alkoxy-phosphine having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted straight or branched alkyl chains having 1-20 carbons, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted aryl, or aralkyl having a chain of 1-20 carbons which may be branched or straight, as well as amido and primary, secondary and tertiary amino derivatives thereof; and

where if R₁ and R₂ can form a substituted or unsubstituted cyclic alkyl of 2-20 carbons, as well as alkyl-, alkenyl, amido and primary, secondary and tertiary amino derivatives thereof; and

if R₁ and R₂ are substituted, they are substituted with a member of the group comprising;

acetals, acetoacetates, nitriles, alkynes, acid anhydrides, acyl halides, alcohols, aldehydes, alkyl halides, alkyl hydroperoxides, amides, primary, secondary and tertiary amines, 2-aminothiols, aryl dichloroarsines, carbamyl chloride, carboxylic acids, cyanates, cyanoacetates, epoxides, ethylene imines, halohydrins, ketones, malonates, metal alkoxides, phenols, phosphines, alkyl phosphonic acids, phthalimides, alkyl silicon halides, siloxanes, thiocyanates, thioacids, thiols and thionyl chlorides.

42. The electrochromic device of claim 41, where said adhesion promoter is selected from the group comprising:

##STR13## where R₃, R₄ and R₅ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted straight or branched alkyl, aralkyl or alkoxyalkyl having 1-10 carbons;

substituted and unsubstituted cyclic, polycyclic or heterocyclic, alkyl having 1-10 carbons;

R₆ is selected from the group comprising substituted and unsubstituted straight or branched alkyl or aralkyl having 1-14 carbons;

or substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, or alkoxy-alkyl having 1-14 carbons;

space="preserve" listing-type="equation">H.sub.2 N--R.sub.7 --(S--).sub.m --R.sub.8 --NH.sub.2 [V]

where m is an integer from 1 to 4, R₇ and R₈ are the same or different and are selected from the group comprising substituted and unsubstituted alkyl, aryl or aralkyl having a chain of 1-14 carbons which may be branched or straight;

or substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having 1-14 carbons which may be branched or straight;

if R₇ and R₈ are substituted then they are substituted with a member of the group comprising;

acetals, acetoacetates, nitriles, alkynes, acid anhydrides, acyl halides, alcohols, aldehydes, alkyl halides, alkyl hydroperoxides, amides, primary, secondary and tertiary amines, 2-aminothiols, aryl dichloroarsines, carbamyl chloride, carboxylic acids, cyanates, cyanoacetates, epoxides, ethylene imines, halohydrins, ketones, malonates, metal alkoxides, phenols, phosphines, alkyl phosphonic acids, phthalimides, alkyl silicon halides, siloxanes, thiocyanates, thioacids, thiols and thionyl chloride;

##STR14## where R₉ and R₁₀ are the same or different and are selected from the group comprising hydrogen;

straight or branched alkyl, aryl and aralkyl having 1-14 carbons;

or cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having 1-14 carbons; and

where R₉ and R₁₀ also form a cyclic alkyl of 4-12 carbons or a aryl of 6 to 10 carbons;

##STR15## where m is an integer from 1-4, R₁₁, R₁₂, R₁₃, R₁₆, R₁₇ and R₁₈ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted straight or branched alkyl, aralkyl or alkoxyalkyl having 1-10 carbons;

substituted and unsubstituted cyclic, polycyclic or heterocyclic alkyl having 1-10 carbons, and R₁₄ and R₁₅ is selected from the group comprising substituted and unsubstituted straight or branched alkyl or aralkyl having 1-14 carbons;

or substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, or alkoxy-alkyl having 1-14 carbons; and

##STR16## where R₁₉, R₂₀, R₂₁ and R₂₂ can be the same or different and selected from the group comprising hydrogen;

substituted and unsubstituted straight or branched alkyl, aryl or aralkyl having 1-14 carbons, as well as amido and primary, secondary and tertiary amino derivatives thereof;

substituted and unsubstituted cyclic-, polycyclic-, heterocyclo-, hydroxyl-, or alkoxy-alkyl having 1-14 carbons, as well as amido and primary, secondary and tertiary amino derivatives thereof.

43. The electrochromic device of claim 42, where said adhesion promoter is selected from the group comprising:

##STR17##