GB2291060A - Cement compositions - Google Patents

Cement compositions Download PDF

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Publication number
GB2291060A
GB2291060A GB9513352A GB9513352A GB2291060A GB 2291060 A GB2291060 A GB 2291060A GB 9513352 A GB9513352 A GB 9513352A GB 9513352 A GB9513352 A GB 9513352A GB 2291060 A GB2291060 A GB 2291060A
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United Kingdom
Prior art keywords
acid
composition according
mole
unsaturated carboxylic
cement
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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.)
Granted
Application number
GB9513352A
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GB9513352D0 (en
GB2291060B (en
Inventor
Christopher Eagleton Wilde
Michael John Williams
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.)
Solvay Solutions UK Ltd
Original Assignee
Albright and Wilson UK Ltd
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Publication date
Priority claimed from GB9413872A external-priority patent/GB9413872D0/en
Application filed by Albright and Wilson UK Ltd filed Critical Albright and Wilson UK Ltd
Priority to GB9513352A priority Critical patent/GB2291060B/en
Publication of GB9513352D0 publication Critical patent/GB9513352D0/en
Publication of GB2291060A publication Critical patent/GB2291060A/en
Application granted granted Critical
Publication of GB2291060B publication Critical patent/GB2291060B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/0047—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L24/0073—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material with a macromolecular matrix
    • A61L24/0089—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material with a macromolecular matrix containing inorganic fillers not covered by groups A61L24/0078 or A61L24/0084
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • 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
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/853—Silicates
    • 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
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/889—Polycarboxylate cements; Glass ionomer cements

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Surgery (AREA)
  • Dental Preparations (AREA)

Abstract

A cement composition includes a copolymer of vinylphosphonic acid or ester thereof with an unsaturated carboxylic acid (e.g. acrylic acid), or ester thereof and/or an unsaturated phosphonic acid ester, and an ion-leachable glass or other ion-leach able refractory material. The copolymer may be in salt form. The composition may be used as a dental cement or in connection with surgical implants or prostheses.

Description

CEMENT COMPOSITIONS This invention relates to cement compositions and in particular to cement compositions for use as or in connection with dental cements, surgical implants, surgical prostheses and the like.
The present invention will be described herein with particular reference to dental cements, but it is not to be construed as being limited thereto.
Dental cements generally comprise a polymeric species together with an ion-leachable glass powder. Cement compositions are known in which the polymeric species comprises a blend of a polymeric phosphorus-containing acid and a polymeric unsaturated carboxylic acid, for example, a blend of poly(vinylphosphonic) acid and poly(acrylic) acid.
A significant disadvantage of such known cement compositions is the rapid speed of reaction between the polymeric species and the ion-leachable glass powder. Consequently, such compositions require further treatment and/or further ingredients to retard the reaction if they are not to become unworkable.
We have now found that a cement composition in which the polymeric species comprises a copolymer of a vinylphosphonic acid and/or ester, with an unsaturated carboxylic acid and/or ester, and/or an unsaturated phosphonic acid ester, has the necessary mechanical properties for use as or in connection with dental cements, surgical implants, surgical prostheses and the like, without the disadvantage of the previously-described compositions.
Accordingly, the present invention provides, in a first embodiment, a cement composition including a polymeric species and an ion-leachable glass powder or other ion-leachable refractory material, in which the polymeric species comprises a copolymer of a vinylphosphonic acid and/or ester, with an unsaturated carboxylic acid and/or ester, and/or an unsaturated phosphonic acid ester, or a salt of said polymeric species.
In a second embodiment, the present invention provides a cement composition as described in the immediately-preceding paragraph, in which up to 50% of the ion-leachable glass powder or other ion-leachable refractory material has been replaced by a photosensitive monomer. The photosensitive monomer may be for example bis-glycidyl methacrylate or ethylene methacrylate phosphate. Alternatively, the photosensitive monomer may be hydroxyethyl methacrylate phosphate or penta-erythrityl methacrylate phosphate or penta-erythrityl acrylate phosphate. Some photosensitive monomers require the presence of an initiator.
The present invention also provides a dental cement comprising a composition described in either of the two immediately-preceding paragraphs and further provides a surgical implant or surgical prosthesis made from any ofthe aforesaid compositions. Examples of dental cements comprising such compositions include glass-ionomer cements and dental silicate cements.
We have also found that a composition according to either aforesaid embodiment of the present invention, which composition has been diluted by means of a system-compatible diluent and/or by reduction of the proportion of glass powder or other refractory material therein, can be used in a variety of dental and non-dental applications. An example of a suitable diluent is polyacrylic acid.
Thus, the present invention further provides a bonding agent, denture fixative, dentine primer fissure sealant, lacquer adhesive or metal primer for dental and non-dental uses and prostheses, comprising a composition according to either aforesaid embodiment of the present invention.
Suitably, a composition according to the present invention comprises, as the copolymer, from 0.1 to 66 mole % ofthe vinylphosphonic acid and correspondingly from 99.9 to 34 mole % of the unsaturated carboxylic acid or phosphonic acid ester, preferably from 2.5 to 50 mole % (e.g. 4 to 46 mole %) ofthe vinylphosphonic acid and correspondingly from 97.5 to 50 mole % (e.g. 96 to 54 mole %) ofthe unsaturated carboxylic acid and/or phosphonic acid ester.
The copolymer may especially comprise about 66 mole % of the vinylphosphonic acid and about 34% of the unsaturated carboxylic acid.
In a preferred embodiment of the present invention, the unsaturated carboxylic acid is acrylic acid.
The acrylic acid may comprise a polyacrylic acid homopolymer or may contain an acrylate-based copolymer.
Alternatively, the unsaturated carboxylic acid may be methacrylic acid, hydroxyethyl acrylic acid, hydroxyethyl methacrylic acid, hydroxypropyl acrylic acid, itaconic acid or maleic acid.
The vinylphosphonic acid may be, for example, a-methyl vinylphosphonic acid or styrene vinylphosphonic acid.
The salt of the polymeric species may suitably be any stable salt thereof, preferably an alkali metal salt or alkaline earth metal salt.
The ion-leachable glass powder may be any conventional ion-leachable glass powder typically used in dental cements. Suitable examples include amongst others, fluoride and non-fluoride alumino silicate glass e.g. alumino silicate glass and calcium alumino silicate fluoride glass.
Instead of all or part of the ion-leachable glass powder, an ion-leachable refractory material such as an oxide, for example alumina, silica, calcium oxide, or magnesium oxide may be used.
The present invention will be illustrated, merely by way of example, as follows: EXAMPLES 1 to 3 Comparative tests were carried out on the following materials.
EXAMPLE 1 Poly(vinylphosphonic) acid (PVPA) EXAMPLE 2 A commercial dental cement comprising polyacrylic acid and an ion-leachable glass powder, available from Espe-Seefeld (Germany) under the name CHELON-FILL.
EXAMPLE 3 A dental cement comprising: (i) vinylphosphonic acid/ acrylic acid copolymer (0.0085 g ) (a) (ii) solution of polyacrylic acid in water (0.1402g ) (b) (iii) ion-leachable glass powder (0.4868 g ) (c) Example 3 is a dental cement comprising a composition according to the present invention.
(a) A copolymer wherein the molar ratio of vinyl phosphonic acid to acrylic acid is 66:34.
(b) A solution of polyacrylic acid (35%) in water, available from G C Corporation (Japan) asGCFUJI 1 LIQUID.
(c) Available from G C Corporation (Japan) as FUJI GLASS IONOMER LUTING CEMENT POWDER.
TEST RESULTS(TYPICAL MAXIMUM VALUES) EXAMPLE 1 2 3 Hardness (*) - 137 323 Strength (+) 90 MPa 122 MPa 224 MPa (*) Vickers Standard Hardness (+) Compressive strength measured using a Houndsfield tensometer.
The Vickers Standard Hardness ofthe cement of Example 3 (above) approximates to that of human dental enamel.
EXAMPLES 4 TO 8 Cement compositions according to the present invention, comprising an ion-leachable glass powder, polyacrylic acid and a copolymer of vinylphosphonic acid and acrylic acid wherein the amount of vinylphosphonic acid was varied between 4% and 46 mole % by weight of the copolymer, were made up in the proportions shown in the TABLE (below). The compositions further comprised a minor amount of tartaric acid as a retarder.
The mean compressive strength of each of the compositions was determined using a Houndsfield tensometer. The test method was based upon BS6039:198l.
In addition to enhancement of Compressive Strength arising from the use of vinylphosphonic acid/acrylic acid copolymers in compositions according to the present invention, we have found that the degree of adhesion between the cement composition and dental enamel or bone is similarly enhanced. Furthermore, we have found that the use of copolymers enhances the capability of the cement to be carved, after setting, to acceptable anatomical forms. EXAMPLES 4 TO 8
Ex 4 5 6 7 8 Formnlation Control 4A 4B 4C 4D 5A 5B 6A 6B 7A 7B 8A 8B (a) Glass Powder (g) 4.82 4.82 4.82 4.82 4.82 4.82 4.82 4.82 4.82 4.82 4.82 4.82 4.82 (b) PAA (Polyacrylic Acid) Powder(g) 0.68 0.61 0.54 0.47 0.41 0.61 0.54 0.61 0.54 0.61 0.54 0.61 0.54 (c) VPA-AA Copolymer (4% VPA)(g) 0.07 0.14 0.20 0.27 VPA-AA Copolymer (10% VPA)(g) 0.07 0.14 VPA-AA Copolymer (20% VPA)(g) 0.07 0.14 VPA-AA Copolynmer (30% VPA)(g) 0.07 0.14 VPA-AA Copolymer (46% VPA)(g) 0.07 0.14 5% m/m (+) tartaric acid soln. (ml) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Ratio PAA:Copolymer 100:0 90:10 80:20 70:30 60:40 90:10 80:20 90:10 80:20 90:10 80:20 90:10 80::20 Compressive Strength (MPa) #1 106.95 104.91 128.34 128.34 100.84 112.05 131.40 82.51 123.25 111.03 122.23 #2 103.90 115.10 97.78 120.19 114.08 113.06 110.01 76.39 96.77 133.44 122.23 121.21 101.86 #3 105.93 91.67 106.95 121.21 99.82 92.69 102.88 91.67 82.51 112.05 119.18 119.18 124.78 #4 84.54 106.95 122.23 92.69 110.01 128.34 97.78 98.80 116.12 104.91 101.86 99.31 #5 107.97 117.14 101.85 126.31 127.32 128.34 124.27 91.67 90.65 125.29 104.91 109.50 # ;6 99.82 110.01 118.16 124.27 122.23 97.78 92.69 91.67 122.23 102.88 113.06 122.23 #7 96.77 102.88 101.86 93.71 105.93 102.88 90.65 110.01 120.19 120.19 Mean Compressive Strength (MPa) 101.5 105.4 110.0 115.5 111.3 112.4 113.9 88.8 91.8 120.3 113.9 113.1 113.3 Standard Deviation 8.8 10.0 11.3 13.2 11.8 12.5 13.8 7.8 5.7 8.2 9.2 7.6 11.3 Notes (a) A standard ion-leachable glass powder, available as G338 (b) A polyacrylic acid powder of average molecular weight # 50000 (c) "VPA"=vinylphosphonic acid; "AA"=acrylic acid

Claims (20)

  1. CLAIMS 1. A cement composition including a polymeric species and an ion-leachable glass powder or other ion-leachable refractory material, in which the polymeric species comprises a copolymer of a vinylphosphonic acid and/or ester, with an unsaturated carboxylic acid and/or ester, and/or an unsaturated phosphonic acid ester, or a salt of said polymeric species.
  2. 2. A composition according to Claim 1, in which the copolymer comprises from 0.1 to 66 mole % ofthe vinylphosphonic acid and correspondingly from 99.9 to 34 mole % of the unsaturated carboxylic acid or phosphonic acid ester.
  3. 3. A composition according to Claim 1 or 2, in which the copolymer comprises from 2.5 to 50 mole % ofthe vinylphosphonic acid and correspondingly from 97.5 to 50 mole % ofthe unsaturated carboxylic acid or phosphonic acid ester.
  4. 4. A composition according to Claim 1, 2 or 3, in which the copolymer comprises from 4 to 46 mole % of the vinylphosphonic acid and correspondingly from 96 to 54 mole % ofthe unsaturated carboxylic acid or phosphonic acid ester.
  5. 5. A composition according to Claim 1 or 2, in which the copolymer comprises about 66 mole % of the vinylphosphonic acid and about 34 mole % of the unsaturated carboxylic acid.
  6. 6. A composition according to any one of Claims 1 to 5, in which the unsaturated carboxylic acid is acrylic acid.
  7. 7. A composition according to any one of Claims 1 to 5, in which the vinylphosphonic acid is a-methyl vinylphosphonic acid or styrene vinyl phosphonic acid.
  8. 8. A composition according to any one of Claims 1 to 5, in which the unsaturated carboxylic acid is methacrylic acid, hydroxyethyl acrylic acid, hydroxyethyl methacrylic acid, hydroxypropyl acrylic acid, itaconic acid or maleic acid.
  9. 9. A composition according to Claim 6, in which the acrylic acid comprises a polyacrylic acid homopolymer.
  10. 10. A composition according to Claim 6, in which the acrylic acid also contains an acrylate-based copolymer.
  11. 11. A composition according to any one of the preceding claims, in which the salt of the polymeric species is an alkali metal salt, or an alkaline earth metal salt.
  12. 12. A cement composition, substantially as hereinbefore described with reference to any one of the Examples.
  13. 13. A composition according to any one of Claims 1 to 12, in which up to 50% of the ion-leachable glass powder or other ion-leachable refractory material has been replaced by a photosensitive monomer.
  14. 14. A composition according to Claim 13, in which the photosensitive monomer is bis-glycidyl methacrylate or ethylene methacrylate phosphate.
  15. 15. A composition according in Claim 13, in which the photosensitive monomer is hydroxyethyl methacrylate phosphate, penta-erythrityl methacrylate phosphate or penta-erythrityl acrylate phosphate.
  16. 16. A composition according to any one of the preceding claims, in which the ion-leachable refractory material is alumina, silica, calcium oxide or magnesium oxide.
  17. 17. A dental cement comprising a composition according to any one of Claims 1 to 16.
  18. 18. A dental cement according to Claim 17 which is an glass-ionomer cement or a dental silicate cement.
  19. 19. A surgical implant or surgical prosthesis made from a composition according to any one of Claims 1 to 16.
  20. 20. A bonding agent, denture fixative, dentine primer, fissure sealant, lacquer adhesive or metal primer for dental and non-dental uses and prostheses, comprising a composition according to any one of Claims 1 to 16.
GB9513352A 1994-07-09 1995-06-30 Cement compositions Expired - Fee Related GB2291060B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9513352A GB2291060B (en) 1994-07-09 1995-06-30 Cement compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9413872A GB9413872D0 (en) 1994-07-09 1994-07-09 Cement composition
GB9513352A GB2291060B (en) 1994-07-09 1995-06-30 Cement compositions

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GB9513352D0 GB9513352D0 (en) 1995-09-06
GB2291060A true GB2291060A (en) 1996-01-17
GB2291060B GB2291060B (en) 1998-11-25

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7264665B2 (en) 2000-12-20 2007-09-04 3M Espe Ag Inert dental glass
DE102008030326A1 (en) 2008-06-30 2009-12-31 S&C Polymer, Silicon- und Composite Spezialitäten GmbH Polyalkenoate cements with improved properties
US20130071464A1 (en) * 2009-08-14 2013-03-21 The University Of Manchester Composition comprising phosphonic acid polymer for use as tissue engineering fibrous scaffold
WO2014075996A1 (en) * 2012-11-13 2014-05-22 Sika Technology Ag Improved dispersant for hydraulically setting systems
EP2794503A1 (en) * 2011-12-23 2014-10-29 Queen Mary and Westfield College A composition for making a cement or an implant
EP3205326A1 (en) * 2016-02-15 2017-08-16 Shofu Inc. Two-paste type sealer composition for root canal filling
EP3205327A1 (en) * 2016-02-15 2017-08-16 Shofu Inc. Sealer composition for root canal filling

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58177907A (en) * 1982-04-12 1983-10-18 Tokuyama Soda Co Ltd Hardener for dental cement
JPS59122411A (en) * 1982-12-29 1984-07-14 Tokuyama Soda Co Ltd Dental cement composition
JPS59122410A (en) * 1982-12-28 1984-07-14 Tokuyama Soda Co Ltd Dental cement composition
JPS6078906A (en) * 1983-10-07 1985-05-04 Tokuyama Soda Co Ltd Hardener for dental cement
GB2219289A (en) * 1988-04-27 1989-12-06 Nat Res Dev Poly-vinylphosphonic acid and metal oxide or cermet or glass ionomer cement
GB2237278A (en) * 1989-10-26 1991-05-01 Nat Res Dev Poly-vinylphosphonic acid glass ionomer cement
GB2272222A (en) * 1992-11-04 1994-05-11 British Tech Group Command curable composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58177907A (en) * 1982-04-12 1983-10-18 Tokuyama Soda Co Ltd Hardener for dental cement
JPS59122410A (en) * 1982-12-28 1984-07-14 Tokuyama Soda Co Ltd Dental cement composition
JPS59122411A (en) * 1982-12-29 1984-07-14 Tokuyama Soda Co Ltd Dental cement composition
JPS6078906A (en) * 1983-10-07 1985-05-04 Tokuyama Soda Co Ltd Hardener for dental cement
GB2219289A (en) * 1988-04-27 1989-12-06 Nat Res Dev Poly-vinylphosphonic acid and metal oxide or cermet or glass ionomer cement
GB2237278A (en) * 1989-10-26 1991-05-01 Nat Res Dev Poly-vinylphosphonic acid glass ionomer cement
GB2272222A (en) * 1992-11-04 1994-05-11 British Tech Group Command curable composition

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
WPI Abstract Accession No 83-824549/47 & JP 58177907 A (TOKUYAMA) 18.10.83 (see abstract) *
WPI Abstract Accession No 84-210421/34 & JP 59122410 A (TOKUYAMA) 14.07.84 (see abstract) *
WPI Abstract Accession No 84-210422/34 & JP 59122411 A (TOKUYAMA) 14.07.84 (see abstract) *
WPI Abstract Accession No 85-144069/24 & JP 60078906 A (TOKUYAMA) 04.05.85 (see abstract) *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7264665B2 (en) 2000-12-20 2007-09-04 3M Espe Ag Inert dental glass
DE102008030326A1 (en) 2008-06-30 2009-12-31 S&C Polymer, Silicon- und Composite Spezialitäten GmbH Polyalkenoate cements with improved properties
WO2010000438A2 (en) * 2008-06-30 2010-01-07 S&C Polymer, Silicon- Und Composite-Spezialitäten Gmbh Polyalkenoate cements having improved properties
WO2010000438A3 (en) * 2008-06-30 2010-04-29 S&C Polymer, Silicon- Und Composite-Spezialitäten Gmbh Polyalkenoate cements having improved properties
US20130071464A1 (en) * 2009-08-14 2013-03-21 The University Of Manchester Composition comprising phosphonic acid polymer for use as tissue engineering fibrous scaffold
EP2794503A1 (en) * 2011-12-23 2014-10-29 Queen Mary and Westfield College A composition for making a cement or an implant
WO2014075996A1 (en) * 2012-11-13 2014-05-22 Sika Technology Ag Improved dispersant for hydraulically setting systems
US20160130182A1 (en) * 2012-11-13 2016-05-12 Michael DANZINGER Improved dispersant for hydraulically setting systems
US9446986B2 (en) * 2012-11-13 2016-09-20 Sika Technology Ag Dispersant for hydraulically setting systems
EP3205326A1 (en) * 2016-02-15 2017-08-16 Shofu Inc. Two-paste type sealer composition for root canal filling
EP3205327A1 (en) * 2016-02-15 2017-08-16 Shofu Inc. Sealer composition for root canal filling
US10307344B2 (en) 2016-02-15 2019-06-04 Shofu Inc. Two-paste type sealer composition for root canal filling
US10463581B2 (en) 2016-02-15 2019-11-05 Shofu Inc. Sealer composition for root canal filling

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