US4400485A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Rubber composition
Assignee: BP Corp North America Inc
•
Filing: 1981-08-28
•
Granted: 1983-08-23
•
Expires: 2001-08-28
Abstract
Abstract A rubber composition containing a phyllosilicate mineral filler is disclosed.
Inventors
- 👤 Harold Mukamal
- 👤 Richard S. Lamar
- 👤 Laurence E. Ferreira
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 20:32
CPC Classifications
C; C08; C08K; C08K3/00; C08K3/34; C08K9/00; C08K9/04; C08K9/06; Y; Y10; Y10T; Y10T428/00; Y10T428/29; Y10T428/2982; Y10T428/2991; Y10T428/2993; Y10T428/2995
Claims Analysis
Total Claims: 50
Claim 1
Independent Claim
894 words
A rubber composition formed according to an improved rubber compounding process, wherein the improvement comprises vulcanizing natural rubber, polybutadiene rubber, polyisoprene rubber, or styrene-butadiene rubber containing a substantially uniform dispersion of: A. 1. particulate Agent E at a level of from about 5 to about 200 phr, 2. Agent F at a level of from about 0.005 to about 15 phr, and 3. Agent G at a level of from about 0.005 to about 15 phr; or B. 1. a particulate adduct of Agents E and F having a median particle size in the range of from about 0.01 to about 20 microns and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr and the portion thereof contributed from Agent F is at a level of from about 0.005 to about 15 phr, and 2. Agent G at a level of from about 0.005 to about 15 phr; or C. 1. a particulate adduct of Agents E and G having a median particle size in the range of from about 0.01 to about 20 microns and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr and the portion thereof contributed from Agent G is at a level of from about 0.005 to about 15 phr, and 2. Agent F at a level of from about 0.005 to about 15 phr; or D. a particulate adduct of Agents E, F, and G having a median particle size in the range of from about 0.01 to about 20 and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr, the portion thereof contributed from Agent F is at a level of from about 0.005 to about 15 phr and the portion thereof contributed from Agent G is at a level of from about 0.005 to about 15 phr; wherein Agent E comprises phyllosilicate mineral particles having a median particle size in the range of from about 0.01 to about 20 microns; wherein Agent F comprises an organosilane of formula I ##STR3## wherein X is a group which is, or which upon hydrolysis forms a group which is, capable of reacting with a reactive site on the phyllosilicate mineral particles so as to form a bond between the organosilane of formula I and the phyllosilicate mineral particles, wherein Y is an alkyl, aryl or alkyl-substituted aryl group containing from 1 to 20 carbon atoms and bears a functional group capable of reacting with a reactive site on the rubber so as to form a bond between the organosilane of formula I and the rubber, and wherein R 1 and R 2 are the same or different and are each selected from the group consisting of the groups described by X and Y, an alkyl group containing from 1 to 20 carbon atoms, an aryl group, and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms; and wherein Agent G comprises an amine of formula II ##STR4## wherein Z is zero or a positive integer from 1 to 12, wherein R 3 , R 4 , R 6 and R 7 are the same or different and are each selected from the group consisting of hydrogen, an alkyl group containing from 1 to 20 carbon atoms, an aryl group and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms, wherein R 5 is an alkylene group containing from 2 to 16 carbon atoms, wherein, when Z is zero, at least one of R 3 , R 4 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and at least one of R 3 , R 4 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is located at a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and wherein, when Z is not zero, at least one of R 3 , R 4 , R 6 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, a group hydrolyzable to a hydroxy group, and, in addition, when R 5 contains more than 3 carbon atoms, at least one of R 3 , R 4 , R 6 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is attached to a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II.
Claim 2
Dependent Claim
894 words
A rubber composition formed according to an improved rubber compounding process, wherein the improvement comprises vulcanizing natural rubber, polybutadiene rubber, polyisoprene rubber, or styrene-butadiene rubber containing a substantially uniform dispersion of: A. 1. particulate Agent E at a level of from about 5 to about 200 phr, 2. Agent F at a level of from about 0.005 to about 15 phr, and 3. Agent G at a level of from about 0.005 to about 15 phr; or B. 1. a particulate adduct of Agents E and F having a median particle size in the range of from about 0.01 to about 20 microns and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr and the portion thereof contributed from Agent F is at a level of from about 0.005 to about 15 phr, and 2. Agent G at a level of from about 0.005 to about 15 phr; or C. 1. a particulate adduct of Agents E and G having a median particle size in the range of from about 0.01 to about 20 microns and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr and the portion thereof contributed from Agent G is at a level of from about 0.005 to about 15 phr, and 2. Agent F at a level of from about 0.005 to about 15 phr; or D. a particulate adduct of Agents E, F, and G having a median particle size in the range of from about 0.01 to about 20 and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr, the portion thereof contributed from Agent F is at a level of from about 0.005 to about 15 phr and the portion thereof contributed from Agent G is at a level of from about 0.005 to about 15 phr; wherein Agent E comprises phyllosilicate mineral particles having a median particle size in the range of from about 0.01 to about 20 microns; wherein Agent F comprises an organosilane of formula I ##STR3## wherein X is a group which is, or which upon hydrolysis forms a group which is, capable of reacting with a reactive site on the phyllosilicate mineral particles so as to form a bond between the organosilane of formula I and the phyllosilicate mineral particles, wherein Y is an alkyl, aryl or alkyl-substituted aryl group containing from 1 to 20 carbon atoms and bears a functional group capable of reacting with a reactive site on the rubber so as to form a bond between the organosilane of formula I and the rubber, and wherein R 1 and R 2 are the same or different and are each selected from the group consisting of the groups described by X and Y, an alkyl group containing from 1 to 20 carbon atoms, an aryl group, and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms; and wherein Agent G comprises an amine of formula II ##STR4## wherein Z is zero or a positive integer from 1 to 12, wherein R 3 , R 4 , R 6 and R 7 are the same or different and are each selected from the group consisting of hydrogen, an alkyl group containing from 1 to 20 carbon atoms, an aryl group and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms, wherein R 5 is an alkylene group containing from 2 to 16 carbon atoms, wherein, when Z is zero, at least one of R 3 , R 4 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and at least one of R 3 , R 4 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is located at a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and wherein, when Z is not zero, at least one of R 3 , R 4 , R 6 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, a group hydrolyzable to a hydroxy group, and, in addition, when R 5 contains more than 3 carbon atoms, at least one of R 3 , R 4 , R 6 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is attached to a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II.
Claim 3
Dependent Claim
15 words
The rubber composition of claim 1 wherein a sulfur or sulfur-donating curing agent is employed.
Claim 4
Dependent Claim
62 words
The rubber composition of claim 1 wherein the phyllosilicate mineral is selected from the group consisting of a member of the kaolin group, a member of the mica group, a member of the group characterized by a primitive three-layer structure, a member of the group characterized by an expandable three-layer structure and a member of the group characterized by a four-layer structure.
Claim 5
Dependent Claim
23 words
The method of claim 3 wherein the phyllosilicate mineral is selected from the group consisting of kaolinite, muscovite, pyrophyllite, talc, vermiculite and chlorite.
Claim 6
Dependent Claim
12 words
The rubber composition of claim 4 wherein the phyllosilicate mineral is talc.
Claim 7
Dependent Claim
18 words
The rubber composition of claim 1 wherein X is a group which upon hydrolysis forms a hydroxyl group.
Claim 8
Dependent Claim
36 words
The rubber composition of claim 1 wherein X is selected from the group consisting of a halogen radical and --OR 8 and wherein R 8 is an alkyl group containing from 1 to 20 carbon atoms.
Claim 9
Dependent Claim
21 words
The rubber composition of claim 7 wherein X is --OR 8 and R 8 contains from 1 to 7 carbon atoms.
Claim 10
Dependent Claim
53 words
The rubber composition of claim 1 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, and an amino group having an active hydrogen atom.
Claim 11
Dependent Claim
46 words
The rubber composition of claim 9 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of a mercapto group, a vinyl group and an amino group having an active hydrogen atom.
Claim 12
Dependent Claim
15 words
The rubber composition of claim 10 wherein Y contains from 1 to 6 carbon atoms.
Claim 13
Dependent Claim
31 words
The rubber composition of claim 1 wherein R 1 and R 2 are the same or different and are each selected from the group consisting of the group described by X.
Claim 14
Dependent Claim
47 words
The rubber composition of claim 12 wherein R 1 and R 2 are the same or different and are each selected from the group consisting of a halogen radical and --OR 8 and wherein R 8 is an alkyl group containing from 1 to 20 carbon atoms.
Claim 15
Dependent Claim
16 words
The rubber composition of claim 13 wherein X, R 1 and R 2 are the same.
Claim 16
Dependent Claim
24 words
The rubber composition of claim 1 wherein the organosilane of formula I is selected from the group consisting of 3-aminopropyl-triethoxysilane, 3-mercaptopropyl-trimethoxysilane and vinyl-tri-(2-methoxyethoxy) silane.
Claim 17
Dependent Claim
27 words
The rubber composition of claim 1 wherein the alkoxy group is --OR 8 wherein R 8 is an alkyl group containing from 1 to 20 carbon atoms.
Claim 18
Dependent Claim
32 words
The rubber composition of claim 1 wherein, when Z is not zero, at least one of R 3 , R 4 , R 6 and R 7 bears said second functional group.
Claim 19
Dependent Claim
15 words
The rubber composition of claim 1 wherein Z in formula II is 0 or 1.
Claim 20
Dependent Claim
15 words
The rubber composition of claim 1 wherein R 5 contains 2 or 3 carbon atoms.
Claim 21
Dependent Claim
17 words
The rubber composition of claim 1 wherein the amine of formula II is triethanolamine and N,N,N',N'-tetra-(2-hydroxypropyl) ethylenediamine.
Claim 22
Dependent Claim
30 words
The rubber composition of claim 1 wherein the median particle size of Agent E and of the adducts is in the range of from about 0.1 to about 1 micron.
Claim 23
Dependent Claim
32 words
The rubber composition of claim 1 wherein Agent E and the portions of the adducts contributed from Agent E are each at a level of from about 50 to about 150 phr.
Claim 24
Dependent Claim
32 words
The rubber composition of claim 1 wherein Agent F and the portions of the adducts contributed from Agent F are each at a level of from about 0.25 to about 3 phr.
Claim 25
Dependent Claim
32 words
The rubber composition of claim 1 wherein Agent G and the portions of the adducts contributed from Agent G are each at a level of from about 0.25 to about 3 phr.
Claim 26
Dependent Claim
640 words
A rubber composition comprising phyllosilicate mineral particles substantially uniformly distributed in natural rubber, polybutadiene rubber, polyisoprene rubber or styrene-butadiene rubber at a level of from about 5 to about 200 phr and having a median particle size of from about 0.01 to about 20 microns, and (1) an Adduct A of the rubber and phyllosilicate mineral particles with an organosilane of formula I ##STR5## wherein X is a group which is, or which upon hydrolysis forms a group which is, capable of reacting with a reactive site on the phyllosilicate mineral particles so as to form a bond between the organosilane of formula I and the phyllosilicate mineral particles, wherein Y is an alkyl, aryl or alkyl-substituted aryl group containing from 1 to 20 carbon atoms and bears a functional group capable of reacting with a reactive site on the rubber so as to form a bond between the organosilane of formula I and the rubber, and wherein R 1 and R 2 are the same or different and are each selected from the group consisting of the groups described by X and Y, an alkyl group containing from 1 to 20 carbon atoms, an aryl group, and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms, the portion of Adduct A contributed from the organosilane of formula I being at a level of from about 0.005 to about 15 phr; and (2) an Adduct B of the rubber and phyllosilicate mineral particles with an amine of formula II ##STR6## wherein Z is zero or a positive integer from 1 to 12, wherein R 3 , R 4 , R 6 and R 7 are the same or different and are each selected from the group consisting of hydrogen, an alkyl group containing from 1 to 20 carbon atoms, an aryl group and an alkyl-substituted aryl group wherein the aryl substituents contain a total of from 1 to 20 carbon atoms, wherein R 5 is an alkylene group containing from 2 to 16 carbon atoms, wherein, when Z is zero, at least one of R 3 , R 4 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and at least one of R 3 , R 4 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is located at a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and wherein, when Z is not zero, at least one of R 3 , R 4 , R 6 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and, in addition, when R 5 contains more than 3 carbon atoms, at least one of R 3 , R 4 , R 6 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is attached to a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and the portion of Adduct B contributed from the amine of formula II being at a level of from about 0.005 to about 15 phr.
Claim 27
Dependent Claim
640 words
A rubber composition comprising phyllosilicate mineral particles substantially uniformly distributed in natural rubber, polybutadiene rubber, polyisoprene rubber or styrene-butadiene rubber at a level of from about 5 to about 200 phr and having a median particle size of from about 0.01 to about 20 microns, and (1) an Adduct A of the rubber and phyllosilicate mineral particles with an organosilane of formula I ##STR5## wherein X is a group which is, or which upon hydrolysis forms a group which is, capable of reacting with a reactive site on the phyllosilicate mineral particles so as to form a bond between the organosilane of formula I and the phyllosilicate mineral particles, wherein Y is an alkyl, aryl or alkyl-substituted aryl group containing from 1 to 20 carbon atoms and bears a functional group capable of reacting with a reactive site on the rubber so as to form a bond between the organosilane of formula I and the rubber, and wherein R 1 and R 2 are the same or different and are each selected from the group consisting of the groups described by X and Y, an alkyl group containing from 1 to 20 carbon atoms, an aryl group, and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms, the portion of Adduct A contributed from the organosilane of formula I being at a level of from about 0.005 to about 15 phr; and (2) an Adduct B of the rubber and phyllosilicate mineral particles with an amine of formula II ##STR6## wherein Z is zero or a positive integer from 1 to 12, wherein R 3 , R 4 , R 6 and R 7 are the same or different and are each selected from the group consisting of hydrogen, an alkyl group containing from 1 to 20 carbon atoms, an aryl group and an alkyl-substituted aryl group wherein the aryl substituents contain a total of from 1 to 20 carbon atoms, wherein R 5 is an alkylene group containing from 2 to 16 carbon atoms, wherein, when Z is zero, at least one of R 3 , R 4 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and at least one of R 3 , R 4 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is located at a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and wherein, when Z is not zero, at least one of R 3 , R 4 , R 6 and R 7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and, in addition, when R 5 contains more than 3 carbon atoms, at least one of R 3 , R 4 , R 6 and R 7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is attached to a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and the portion of Adduct B contributed from the amine of formula II being at a level of from about 0.005 to about 15 phr.
Claim 28
Dependent Claim
18 words
The rubber composition of claim 25 formed by a vulcanization process employing a sulfur or sulfur-donating curing agent.
Claim 29
Dependent Claim
62 words
The rubber composition of claim 25 wherein the phyllosilicate mineral is selected from the group consisting of a member of the kaolin group, a member of the mica group, a member of the group characterized by a primitive three-layer structure, a member of the group characterized by an expandable three-layer structure and a member of the group characterized by a four-layer structure.
Claim 30
Dependent Claim
24 words
The rubber composition of claim 27 wherein the phyllosilicate mineral is selected from the group consisting of kaolinite, muscovite, pyrophyllite, talc, vermiculite and chlorite.
Claim 31
Dependent Claim
12 words
The rubber composition of claim 28 wherein the phyllosilicate mineral is talc.
Claim 32
Dependent Claim
18 words
The rubber composition of claim 25 wherein X is a group which upon hydrolysis forms a hydroxyl group.
Claim 33
Dependent Claim
36 words
The rubber composition of claim 25 wherein X is selected from the group consisting of a halogen radical and --OR 8 and wherein R 8 is an alkyl group containing from 1 to 20 carbon atoms.
Claim 34
Dependent Claim
21 words
The rubber composition of claim 31 wherein X is --OR 8 and R 8 contains from 1 to 7 carbon atoms.
Claim 35
Dependent Claim
53 words
The rubber composition of claim 25 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group and an amino group having an active hydrogen atom.
Claim 36
Dependent Claim
42 words
The rubber composition of claim 33 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of mercapto, vinyl and an amino group having an active hydrogen atom.
Claim 37
Dependent Claim
15 words
The rubber composition of claim 34 wherein Y contains from 1 to 6 carbon atoms.
Claim 38
Dependent Claim
31 words
The rubber composition of claim 25 wherein R 1 and R 2 are the same or different and are each selected from the group consisting of the group described by X.
Claim 39
Dependent Claim
47 words
The rubber composition of claim 36 wherein R 1 and R 2 are the same or different and are each selected from the group consisting of a halogen radical and --OR 8 and wherein R 8 is an alkyl group containing from 1 to 20 carbon atoms.
Claim 40
Dependent Claim
15 words
The rubber composition of claim 37 wherein X, R and R 2 are the same.
Claim 41
Dependent Claim
18 words
The rubber composition of claim 25 wherein the agent of formula I is 3-aminopropyl-triethoxysilane, 3-mercaptopropyl-trimethoxysilane, and vinyl-tri-(2-methoxyethoxy) silane.
Claim 42
Dependent Claim
27 words
The rubber composition of claim 25 wherein the alkoxy group is --OR 8 wherein R 8 is an alkyl group containing from 1 to 20 carbon atoms.
Claim 43
Dependent Claim
32 words
The rubber composition of claim 25 wherein, when Z is not zero, at least one of R 3 , R 4 , R 6 and R 7 bears said second functional group.
Claim 44
Dependent Claim
15 words
The rubber composition of claim 25 wherein Z in formula II is 0 or 1.
Claim 45
Dependent Claim
16 words
The rubber composition of claim 25 wherein R 5 contains from 2 or 3 carbon atoms.
Claim 46
Dependent Claim
17 words
The rubber composition of claim 25 wherein the amine of formula II is triethanolamine and N,N,N',N'-tetra-(2-hydroxypropyl) ethylenediamine.
Claim 47
Dependent Claim
25 words
The rubber composition of claim 25 wherein the phyllosilicate mineral median particle size is in the range of from about 0.1 to about 1 micron.
Claim 48
Dependent Claim
23 words
The rubber composition of claim 25 wherein the phyllosilicate mineral particles are at a level of from about 50 to about 150 phr.
Claim 49
Dependent Claim
31 words
The rubber composition of claim 25 wherein the portion of Adduct A contributed from the organosilane of formula I is at a level of from about 0.25 to about 3 phr.
Claim 50
Dependent Claim
31 words
The rubber composition of claim 25 wherein the portion of Adduct B contributed from the amine of formula II is at a level of from about 0.25 to about 3 phr.
References Cited (Backward Citations)
US3350345A
Cited
US3290165A
Cited
GB1236901A
Cited
US3737334A
Cited
US3649320A
Cited
US3953223A
Cited
US3862259A
Cited
US4143027A
Cited
JPS5233931A
Cited
JPS53115769A
Cited
US4156677A
Cited
DD136848A1
Cited
US4233366A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-08-22 | 1987-02-21 | 1987-08-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-22 | 1991-02-21 | 1991-08-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-22 | 1995-02-21 | 1995-08-23 | $7700.00 | Window Closed / Lapsed |