GB1565441A – Cavity liner for dental restorations
– Google Patents
GB1565441A – Cavity liner for dental restorations
– Google Patents
Cavity liner for dental restorations
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Publication number
GB1565441A
GB1565441A
GB2764/77A
GB276477A
GB1565441A
GB 1565441 A
GB1565441 A
GB 1565441A
GB 2764/77 A
GB2764/77 A
GB 2764/77A
GB 276477 A
GB276477 A
GB 276477A
GB 1565441 A
GB1565441 A
GB 1565441A
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GB
United Kingdom
Prior art keywords
metal
adhesive
composition
liner
amalgam
Prior art date
1976-01-26
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB2764/77A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Virginia UVA
Original Assignee
University of Virginia UVA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1976-01-26
Filing date
1977-01-24
Publication date
1980-04-23
1977-01-24
Application filed by University of Virginia UVA
filed
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University of Virginia UVA
1980-04-23
Publication of GB1565441A
publication
Critical
patent/GB1565441A/en
Status
Expired
legal-status
Critical
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Classifications
A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
A61K6/00—Preparations for dentistry
A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
A61K6/847—Amalgams
Description
PATENT SPECIFICATION
( 21) Application No 2764/77 ( 22) Filed 24 Jan 1977 ( 31) Convention Application No 652238 ( 32) ( 33) ( 44) ( 51) ( 11) 1 565 441 ( 19) Filed 26 Jan 1976 in United States of America (US)
Complete Specification published 23 April 1980
INT CL 3 C 08 L 33/02 C 09 D 5/38 ( 52) Index at acceptance C 3 V AC AP C 3 N 6 C 3 W 209 C 3 Y B 120 B 123 B 230 B 240 B 245 Fill F 581 F 583 ( 54) AN IMPROVED CAVITY LINER FOR DENTAL RESTORATIONS ( 71) We, THE UNIVERSITY OF VIRGINIA, a body corporate organised under the laws of the State of Virginia, United States of America, of Charlottesville, Virginia 22901, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-
The present invention relates to a method for filling prepared dental cavities in a manner which substantially reduces corrosion at the interface of the tooth-amalgam restorations.
More particularly, the present invention relates to a cavity lining material containing an adhesive which not only improves the tenacity of the bonding of a dental restoration to cavity surfaces, but also is effective in substantially reducing the susceptability of amalgam fillings to corrosion.
Normally, dental cavities are filled with a silver-tin amalgam With time, however, the amalgam restoration degenerates by corrosion and, as a result, it must be replaced.
Silver-tin dental amalgam is produced by triturating or mixing about equal quantities of the powdered silver-tin alloy, principally Ag 2 Sn, and Hg The mixture, when placed in a cavity, hardens to form several alloy phases.
Of the phases which form, the two which predominate are a silver-mercury phase, Ag 2 Hg,(y 1) and a tin-mercury phase, Sn 78 Hg(y) Over a period of time, the tin from the y phase dissolves or corrodes because tin is less noble (more easily oxidized) than either Ag or Hg and because of factors such as differential aeration This corrosion, of course, reduces the strength of the amalgam restoration, causes discolorization of the tooth, and contributes to marginal discrepancies and eventual partial extrusion of the restoration from the cavity.
Differential aeration causes the corrosion process (i e, tin dissolution) to occur most rapidly in areas of lower oxygen concentration.
Thus, the primary area of corrosion is at the restoration-tooth interface Corrosion of the margins (that part of the restoration-tooth interface that is exposed to saliva) is especially critical as such corrosion contributes to recurrent decay Thus, the corrosion process usually occurs from the inside-out, which weakens the restoration.
Differential aeration is a common oxidative phenomenon For instance, it is the mechanism which causes rust to spread circumferentially under the paint around a pin-hole blemish on painted steel In a dental restoration, the first step of differential aeration is the reduction of oxygen on the unexposed restoration-tooth interface Mercury and silver are relatively inert in comparison to tin and only participate as sites for oxygen reduction The anodic oxidation (corrosion) of the surface tin atoms causes an electron transfer to occur from the tin atoms at the surface of the amalgam restoration These electrons are conducted to the exposed (oxygen rich) surface of the amalgam through the amalgam -bulk, resulting in the cathodic reduction of oxygen atoms The net effect is that the oxidation of tin atoms, which occurs on the unexposed (to air) amalgam surface, results in the generation of tin ions within the interface In addition, the presence of the tin ions in the areas adjacent to the cavity surfaces promotes further deterioration of the dental restoration by the precipitation of tin hydroxides which cause the area to become more acid.
One of the reasons that the silver-tin (Ag 3 Sn) alloy is used is that the resulting amalgam is reasonably strong and expands or contracts very little upon hardening Because tin is less noble than silver or mercury, and because the atomic proportions of tin and mercury in the y, phase (Sn 7 r 8 Hg) are unfavourable, it is essentially the only part of the amalgam that corrodes Hence, the corrosion of dental amalgam restorations seems to be a result of differential aeration and of the presence of tin in the y 2 phase.
1,565,441 One object of the present invention is to provide a composition having improved adhesion to cavity surfaces while at the same time having improved resistance to deterioration.
According to the present invention a metal containing composition in the form of a paint suitable for application to the surfaces of a prepared cavity of a carious tooth to produce a corrosition resistant metal liner, consisting essentially of a combination of at least one finely divided metal or alloy of metals at a position higher than tin on the international EMF series, the said metal being capable of being amalgamated by diffusion of the mercury into said lining when the said lining is in contact with an Ag-Hg-Sn containing dental amalgam, the said metal having a particle size of less than 37 microns, with a dentally acceptable adhesive comprising a polycarboxylate cement, a zinc silico-phosphate, a zinc phosphate, a copper phosphate, a silicate, a zinc oxide-eugenol, or zinc oxide-eugenol-o-ethoxybenzoic acid, the amount of metal based on metal and adhesive being greater than 46 % by weight, and the amount of adhesive based on metal and adhesive being less than 54 % by weight, and up to 0 1 wt % based on metal and adhesive of a wetting agent and an amount of a volatile organic solvent such as to impart a paint like consistency to the composition.
In the process of forming dental restorations for carious teeth, a cavity is prepared in the carious tooth and the cavity is filled with a dental amalgam which is most usually a mixture of mercury, tin and silver As the metal mixture hardens in the cavity, a variety of interpenetration compounds or phases form, of which three predominate The predominant phases are a y phase, a silver mercury phase, Ag:Hg( y,) and a tin-mercury phase, Sn,,Hg(y 2) As the filling sets, the silver rich y, phase expands and the tin rich y 2 phase contracts which are counter-balancing forces resulting in a very small net change in volume.
Of the metals in the amalgam, silver and mercury are stable elements in that they are very resistant to oxidation and thus none of the y, phase dissolves or is removed from the filled tooth The other principal phase, that is the Y, phase, is not as stable as the y, phase, and will dissolve from the tooth because tin is relatively easily oxidized.
We have now found that certain adhesives, when mixed with an oxidation-resistant metal or alloy, form an adhesive-metal lining composition, which when applied to the surfaces of a tooth cavity, results in an exceptionally tightly bound dental restoration to the cavity surfaces and a restoration which exhibits a long effective lifetime The applied liner achieves two important objectives which are the inhibition of corrosion of the restoration and the improvement of the adhesion of the subsequently applied amalgam to the tooth by chemical or mechanical adhesion means Suitable polycarboxylate cements include polyacrylates containing zinc oxide and polyacrylic acid, zinc polyacrylate cements in which up to wt %O of the zinc oxide is substituted with magnesium oxide, bis-GMA which may be synthesized from the reaction of bisphenol A and glycidyl methacrylate, or polyacrylates containing mineral fillers.
Suitable silicate cements are those which are mixtures of complex glass aluminosilicates containing magnesium, fluorine, calcium, sodium and phosphorus The amount of adhesive combined with the metal or alloy is less than 55 wt % preferably 25 % to 50 .
If the amount of adhesive exceeds the maximum amount indicated, the adhesive will decrease the amount of silver in the liner that is available for amalgamation with the amalgam.
Bonding will take place but the improved bonding of the present composition will not be as readily attained If the amount of adhesive is less than 25 %, the amount of adhesive available for bonding at the tooth-liner interface decreases so that the improved bonding effects of the present invention are not as readily attained Instead, if less than 25 % adhesive is used, bonding of the liner to the cavity surface becomes increasingly dependent upon the mechanical bonding forces derived from contact of the irregular cavity walls with the surface of the liner.
The major criteria in the selection of a dental adhesive for the purposes of the present invention are that, besides its compatability with tooth structure and the necessity of the adhesive meeting FDA and ADA specifications, once the adhesive liner has formed in the tooth cavity, the applied lining must permit the diffusion of mercury from the subsequently applied amalgam into the liner whereupon the amalgam constituents interact with the metal of the liner to form an integral restoration.
The metal or alloy which is combined with adhesive in the composition applied to the cavity surfaces are those metals and alloys which will amalgamate by diffusion of the mercury from the subsequently applied dental amalgam, so as to become an integral part of the amalgam, and which are characterised by a corrosion resistance which is greater than the dental amalgam Suitable metals which are more positive than tin in the International Electromotive Series include platinum, gold, copper, silver, or alloys of platinum, gold, copper or silver inert to the system Most preferred, however, are silver and alloys containing silver.
The dental composition is completed by adding up to about 0 1 wt % of a wetting agent, such as lecithin and a solvent such as acetone, chloroform, methylchloroform, the lower alkyl alcohols, the lower alkyl ethers or the like, wherein the lower alkyl groups contain from 3 1,565,441 3 one to six carbon atoms, to the adhesive-metal combination The particle size of the metal particles is less than 400 mesh (i e less than 371 i), and preferably is less than 1 a The amount of metal or alloy in the liner composition based on metal and adhesive is greater than 46 wt %, preferably 50 to 75 wt %.
The adhesive-metal liner can be deposited on the surfaces of the cavity in the form of a paint or slurry which is fluent enough to form a homogeneous coat on the cavity The composition deposited can be a metal containing adhesive and the only materials in the liner composition are metal, adhesive and possibly a wetting agent and a solvent In actual practice the composition is formed by mixing the two parts of the adhesive immediately prior to application of the composition to the prepared cavity The two parts of the adhesive are mixed in the form of a liquid with powder or in the form of liquid with liquid The metal to be deposited as well as the wetting agent can be combined with either one or both of the adhesive components Once the adhesive components are mixed, the adhesive usually hardens rather quickly.
The composition which is applied to the surfaces of the cavity must be thin enough to be applied by such conventional techniques as brushing, swabbing, wiping or the like.
Usually, the composition, in whatever form, is best applied to the cavity by the application of a single coat with a small brush.
The total film thickness of the applied liner composition can vary depending upon the particular adhesive used Furthermore, complete amalgamation may not be necessary, but complete amalgamation at the amalgam-liner interface is imperative Generally, the thickness of the liner is less than 100 1 gm or less than 10 % of the smallest dimension of the restoration containing composite.
After the surfaces of the tooth cavity have been coated to the appropriate depth with a layer of the metal or metal alloy particles, a standard dental amalgam is then inserted into the remaining lined cavity by standard dental procedures The dental amalgams contain Ag, Hg, and Sn, and often small portions of Cu and Zn The basic composition of the amalgams used are conventional The Hg is usually present in an amalgam in an amount of from 45 to 60 ‘/, before insertion When the amalgam is packed into the cavity, free mercury will be expressed to the surfaces and to the amalgam-lining interface The free mercury is highly reactive and will quickly diffuse into the lining metal to form a metal-mercury phase, and to mutually fuse the particles together to form a continuous coating This process continues thereafter for some period due to the difference in Hg concentration between the applied amalgam and the lining The result of this amalgamation of the metal in the lining is to form an integral structure of applied amalgam and the lining amalgam, wherein the outermost layer of the integral structure is essentially free of tin, and consequently free of ‘Y 2 tin-mercury phase The restoration is therefore characterized by a continuous structural integrity and outstanding corrosion resistance.
In conventional restorations which do not use a liner, the free mercury which is expressed at the surface of the restoration increases the problem of deterioration of the restoration.
However, when the liner of the present invention is applied to a tooth cavity, the free mercury expressed when the amalgam is applied combines with the metal of the liner resulting in an overall decrease in the concentration of free mercury at the tooth-restoration interface Consequently, a more stable restoration is achieved.
The cavity liner further has the characteristic that the adhesive component of the applied composition results in a much stronger adhesion of the internal amalgam surfaces to the surfaces of the cavity Bonding of the restoration to the cavity walls is also enhanced by the fact that as the mercury diffuses into the metal lining, the metal tends to expand, and tends to fill any crevices or irregularities in the tooth walls This is an especially unique attribute in the technology of linings for dental fillings The successful amalgamation of the metal of the lining composition with the bulk of the applied dental amalgam is perhaps somewhat surprising since it might have been expected that the presence of the adhesive in the lining composition might interfere with the necessary amalgamation of the metal in the lining by the diffusion of mercury from the bulk of the applied amalgam Yet, successful amalgamation occurs It may be that the adhesives used are of sufficient porosity to achieve amalgamation, or perhaps the amalgamation is achieved due to the small metal particle size.
In addition, since the standard dental amalgams have particle sizes of the order of am, relatively large spaces exist at the tooth restoration interface Thus, by using liner compositions containing small metal particles, not only is the reaction time increased between amalgam and liner, but also much closer juxtaposition of the liner to the tooth wall is achieved.
The invention may be put into practice in various ways and some specific embodiments will be described to illustrate the invention with interface to the accompanying examples.
EXAMPLE 1
The purpose of this experiment was to determine if a dental amalgam could be bonded tc tooth structure A metal containing adhesive was prepared using < 1 Am Ag particles and two commercially available polycarboxylate dental cements, Durelon (Registered Trade 1,565,441 Mark) and PCA The cement was prepared using a 1:1 ratio of cement powder/liquid, to which was added the Ag powder to give a total wt Ag of 50 w/o To the mixture was added ethyl alcohol in amounts sufficient to make the liner composition thin enough to paint onto the surface of an extracted tooth.
After the mixture was allowed to set, a mm X 3 mm x 3 mm wax mold was placed on the painted tooth surface The mold exposed an area to be filled approximately one half of which was dentin and the other half of which was enamel A conventional dental amalgam having an original content of 53 w/o, Hg was then hand condensed (compressed) into a 2 Kg balance apparatus After two hours the wax mold was removed and the dental amalgam was bonded to the tooth structure.
EXAMPLE 2
The following experiment was conducted to determine if a bond between the silver containing dental adhesive and a conventional dental amalgam could be attained Metal containing adhesive was formed using < 1 aum spherical Ag particles and two commercially available dental polycarboxylate cements, Durelon and PCA The cement was prepared according to manufacturers specifications using a 1:1 wt ratio of powder to liquid To this was added < 1 'am Ag particles to give a total wt % Ag or 50 w/o To this mixture was added ethyl alcohol in amount sufficient to make the composition thin enough to paint onto the surface of a glass slide The painted glass slide was allowed to dry and used as the base of a 12 mm x 5 mm X 1 mm mold A conventional dental analgam was then hand condensed into the mold as per Example 1 The reaction between the mercury expressed during hand condensing and the silver in the liner was observed occurring through the glass slide and appeared to be complete after approximately 2 hours At this time the mold was removed and it was found that the amalgam was bonded to the metallic adhesive liner.
EXAMPLE 3
The procedure of Example 2 was followed with the exception that the w/o silver was varied to 54 w/o, and 61 w/o The same bonding results were obtained between liner and amalgam as were obtained in Example 2.
EXAMPLE 4
The same procedure described in Example 2 was followed with the exception that the polycarboxylate adhesive was replaced by a commercially available dental zinc phosphate cement "Tenicin" This cement was prepared using a powder to liquid ratio of approximately 2.5:1 and then adding distilled water in an amount equal to the liquid in the adhesive To the prepared adhesive was added the < 1 am Ag particles to give a final mixture of 50 w/o Ag The results obtained are the same as those obtained in Example 2.
EXAMPLE 5
The following tests were run to measure the shear strength of the amalgam composite liner interface A composite liner was prepared as per Example 1 except that in addition to a 50 w/o Ag containing adhesive, 45 w/o, 54 w/o and 61 w/o adhesives were prepared Each prepared metallic liner was painted onto the circumferential surface of a 4 mm diameter hole drilled through 3 mm Plexiglass (Registered Trade Mark) using a carbide drill Into all 80 of the holes plus 20 identically prepared nonlined holes was hand condensed a conventional dental amalgam as described in Example 1.
Samples and molds were placed in 1 0 w/o Na CI for 7 days The samples were then ejected from the molds using an Instron (Registered Trade Mark) Tensile Testing machine The results obtained are as follows:
a) A significant increase in the retention of lined samples over unlined samples was found with an increase in shear strength of 5 to 7 times.
b) Fracturing occurred through the liner or at the liner-mold interface above 45 w/o Ag.
EXAMPLE 6
The procedure of Example 6 was repeated execept that the liner was prepared as described in Example 4 The results showed a significant increase in shear strength of 2-3 times with fracture occurring through the liner or at the liner-mold interface.
EXAMPLE 7
X-ray energy analysis and Scanning Electron Microscopy of the samples described in Example 5 showed the following results: 100 1 The surface of the lined sample contained none of the corrosive Y 2 phase present in dental amalgam and only contained Ag and Hg.
2 The analysis showed that the liner thick 105 ness varied between 20 and 100 urn in all samples examined.
Claims (1)
WHAT WE CLAIM IS: -
1 A metal conitaining composition in the form of a paint suitable for application to the surfaces of a prepared cavity of a carious tooth to produce a corrosion resistant metal liner which consists essentially of a combination of at least one finely divided metal or alloy of metals at a position higher than tin on the international EMP series, the said metal being capable of being amalgamated by diffusion of the mercury into said lining, when the said lining is in contact with an Ag-Hg-Sn containing dental amalgam, the said metal having a particle size of less than 37 micron with a dentally acceptable adhesive comprising a polycarboxylate cement, a zinc silicophosphate, a 1,565,441 1,565,441 zinc phosphate, a copper phosphate, a silicate, a zinc oxide-eugenol, or zinc oxide eugenol-oethoxy benzoic acid, the amount of metal based on metal and adhesive being greater than 46 % by weight, and the amount of adhesive based on metal and adhesive being less than 54 % by weight, and up to 0 1 wt % based on metal and adhesive of a wetting agent and an amount of a volatile organic solvent such as to impart a paint like consistencey to the composition.
2 A composition as claimed in Claim 1 in which the said adhesive is a polycarboxylate cement.
3 A composition as claimed in Claim 1 in which the said adhesive is a zinc-silico-phosphate cement.
4 A composition as claimed in Claim 1 in which the said adhesive is a zinc phosphate cement 1 A composition as claimed in any one of Claims 1 to 4 which contains 25 % to 50 % by weight of the adhesive.
6 A composition as claimed in any one of Claims 1 to 5 in which the particle size of the finely divided metal is less than 1 micron.
7 A liner composition as claimed in any one of Claims 1 to 6 in which the metal is platinum, gold, copper, silver or alloys of platinum, gold, copper or silver.
8 A liner composition as claimed in Claim 1 substantially as specifically described herein with reference to the accompanying examples.
KILBURN & STRODE, Chartered Patent Agents, Agents for the Applicants.
Printed for Her Majesty's Stationery Office, by the Courier Press Leamington Spa, 1980 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A IAY, from which copies may be obtained.
GB2764/77A
1976-01-26
1977-01-24
Cavity liner for dental restorations
Expired
GB1565441A
(en)
Applications Claiming Priority (1)
Application Number
Priority Date
Filing Date
Title
US05/652,238
US4064629A
(en)
1976-01-26
1976-01-26
Cavity liner for dental restorations
Publications (1)
Publication Number
Publication Date
GB1565441A
true
GB1565441A
(en)
1980-04-23
Family
ID=24616075
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
GB2764/77A
Expired
GB1565441A
(en)
1976-01-26
1977-01-24
Cavity liner for dental restorations
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US
(1)
US4064629A
(en)
JP
(1)
JPS534393A
(en)
AT
(1)
AT353418B
(en)
AU
(1)
AU504819B2
(en)
CA
(1)
CA1090502A
(en)
DE
(1)
DE2702923A1
(en)
DK
(1)
DK32477A
(en)
FR
(1)
FR2338696A1
(en)
GB
(1)
GB1565441A
(en)
IL
(1)
IL51219A
(en)
NL
(1)
NL7700678A
(en)
SE
(1)
SE7700772L
(en)
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Adhesive composition and adhesion process of a restorative material to a substrate
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Method and composition for removing mercury vapor from dental restorations
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Minnesota Mining And Manufacturing Company
Oxidative pretreatment for improved adhesion
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1993-04-19
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Method and composition for adhering to metal dental structure
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Method for bonding non-amalgam restorative materials to dental surfaces
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US
US05/652,238
patent/US4064629A/en
not_active
Expired - Lifetime
1977
1977-01-04
CA
CA269,097A
patent/CA1090502A/en
not_active
Expired
1977-01-06
IL
IL51219A
patent/IL51219A/en
unknown
1977-01-24
NL
NL7700678A
patent/NL7700678A/en
unknown
1977-01-24
GB
GB2764/77A
patent/GB1565441A/en
not_active
Expired
1977-01-25
SE
SE7700772A
patent/SE7700772L/en
unknown
1977-01-25
AU
AU21622/77A
patent/AU504819B2/en
not_active
Expired
1977-01-25
FR
FR7702016A
patent/FR2338696A1/en
active
Pending
1977-01-25
DE
DE19772702923
patent/DE2702923A1/en
not_active
Withdrawn
1977-01-25
AT
AT43777A
patent/AT353418B/en
not_active
IP Right Cessation
1977-01-26
JP
JP689577A
patent/JPS534393A/en
active
Pending
1977-01-26
DK
DK32477A
patent/DK32477A/en
not_active
Application Discontinuation
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Publication date
DE2702923A1
(en)
1977-08-11
IL51219A
(en)
1980-03-31
IL51219A0
(en)
1977-03-31
DK32477A
(en)
1977-07-27
FR2338696A1
(en)
1977-08-19
CA1090502A
(en)
1980-12-02
US4064629A
(en)
1977-12-27
SE7700772L
(en)
1977-07-27
JPS534393A
(en)
1978-01-14
AU504819B2
(en)
1979-11-01
ATA43777A
(en)
1979-04-15
AU2162277A
(en)
1978-08-03
AT353418B
(en)
1979-11-12
NL7700678A
(en)
1977-07-28
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Legal Events
Date
Code
Title
Description
1980-07-09
PS
Patent sealed [section 19, patents act 1949]
1982-08-18
PCNP
Patent ceased through non-payment of renewal fee
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