EP0022772A1 - Hardenable compositions - Google Patents

Hardenable compositions

Info

Publication number
EP0022772A1
EP0022772A1 EP79900975A EP79900975A EP0022772A1 EP 0022772 A1 EP0022772 A1 EP 0022772A1 EP 79900975 A EP79900975 A EP 79900975A EP 79900975 A EP79900975 A EP 79900975A EP 0022772 A1 EP0022772 A1 EP 0022772A1
Authority
EP
European Patent Office
Prior art keywords
composition according
acid
iii
alloy
particles
Prior art date
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.)
Withdrawn
Application number
EP79900975A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ian Robert Sced
Alan Donald Wilson
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.)
Individual
Original Assignee
Individual
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.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0022772A1 publication Critical patent/EP0022772A1/en
Withdrawn legal-status Critical Current

Links

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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients

Definitions

  • This invention relates to hardenable compositions; more particularly, this invention relates to such compositions containing a polymeric component which comprises a water-soluble polymer of one or more unsaturated mono- or poly carboxylic acids (hereinafter referred to as a "poly (carboxylic acid)").
  • a polymeric component which comprises a water-soluble polymer of one or more unsaturated mono- or poly carboxylic acids (hereinafter referred to as a "poly (carboxylic acid)").
  • poly (carboxylic acid) unsaturated mono- or poly carboxylic acids
  • Dental amalgam (which is an extemporaneously compounded amalgam of mercury with the intermetallic phase Ag Sn) has proved to be a very satisfactory material for posterior oral restorative work notably on account of its very good mechanical properties, such as compressive strength and hydrolytic stability. Nonetheless it has several serious disadvantages _ thus, it does not adhere to freshly-cut dentine nor does it provide in situ resistance against caries; it provides no resistance to thermal shock thereby necessitating the provision of an intermediate insulating cavity liner; and it initially provides a poor seal at the margins thereby permitting marginal percolation and concomitant secondary caries to occur.
  • a hardenable composition comprising: (i) a poly (carboxylic acid) or a hydrolysable precursor thereof; (ii) a particulate ion-leachable material; and (iii) a filler, different from (ii), the particles of which have a high flexural modulus and are anisotropicaUy dimensioned, (ii) being reactible with (i) in the presence of water to form a cement.
  • high flexural modulus in (iii) is meant a flexural modulus which is at least that of the cement matrix formed by reacting (ii) with (i). This will generally be greater than 20 GPa, suitably greater than JO GPa, and preferably very much greater, for example from 75 GPa to 400 GPa.
  • anisotropicaUy dimensioned in (iii) is meant that the particle has one dimension differing substantially from the others; for example, the length of a fibre or acicular or columnar crystal or the thickness of metal flake. It is envisaged that (iii) may comprise metals or high modulus inorganic or organic materials.
  • metals suitable as such for use as (iii) include aluminium, chromium, cobalt, copper, indium, iron, nickel, silver, tin, titanium, tungsten or zinc; alloys thereof, for example, copper-tin alloys, gold-indium alloys, gold-tin alloys, gold-zinc alloys, nickel-aluminium alloys, cobalt-chromium alloys, nickel- chromium alloys, nickel-titanium alloys, stainless and other steels, silver-tin alloys; intermetallics, such as NiAl and Ag Sn, preferably Ag Sn, are particularly preferred.
  • Mixtures of particulate metal may be particularly desirable, in the dental material art, where one such metal (for example Ag Sn) imparts strength to the cement while the other, more ductile such metal (for example dental gold) imparts burnishability and improved appearance.
  • Particularly preferred metals are fibrous metals spun from the melt, particularly by melt extraction techniques.
  • high modulus inorganic or organic materials suitable for use as (iii) include fibrous refractory oxides, nitrides or carbides, or glass fibres; or carbon fibres or polyalkylene fibres.
  • fibrous refractory oxides nitrides or carbides, or glass fibres; or carbon fibres or polyalkylene fibres.
  • specific examples are alkali metal titanates,
  • OMPI for example potassium titanate, alumina, carburised tungsten wire, glass, silica, silicon carbide, silicon (oxy)nitride, titanium nitride and zirconia, all in fibrous form; carbon fibres and high modulus homo- and co-polyalkylenes (for example as disclosed in UK 1469526, 1498628, 1506565, 45920/75 and 7919737).
  • Particularly preferred such materials are glass fibres reactible with (i) in the presence of water to form a cement, and carbon fibre.
  • the metals for example gold, platinum or rhodium
  • the high modulus inorganic or organic materials are not reactive with (i) and it is desirable that the bonding to the cement matrix is enhanced
  • it may be coated with a metal or metal oxide which does so react.
  • coatings include indium, iron, nickel, tin, zinc or an oxide thereof.
  • at least 50 by weight, preferably 60% to 90%, of (iii) is in the form of rod- shaped particles.
  • such particles have a length: thickne ratio of at least 4:1.
  • the mean length will be no more than about 1mm while the mean thicknes will be from lQ ⁇ to 2O0 ⁇ , preferably less than 50/** m, though larger particles may be used in other applications.
  • (iii) is present in an amount of up to 50 volume fraction preferably 20 to 4 ⁇ %, especially 25% to 30%, based on the weight of (ii).
  • the powder: liquid ratio of (ii) to (i), the latter being present as a 0 by weight aqueous solution is from 0.8 to 4.5 (g/ml), preferably 1.3 to 2.0 (g/ml).
  • Typical volume fractions of (iii) : (ii) : (i) are about 25%: 25%- 50% (in
  • (iii) is also a particulate, ion-leachable material, for example a fluoraluminosilicate glass fibre, reactible with (i) in the presence of water
  • the amount of (iii) may be substantially higher replacing a part of all of (ii).
  • (iii) should be readily wettable by (i) to ensure a homogeneous mix; surface treatment of (iii) , such as etching and/or oxidation, may facilitate this.
  • the preferred poly(carboxylic acids) suitable for use as (i) are those prepared by the homopolymerisation and copolymerisation
  • unsaturated aliphatic carboxylic acids for example aconitic acid, acrylic acid, citraconic acid, fumaric acid, glutaconic acid, itaconic acid, maleic acid, mesaconic acid, methacrylic acid, muconic acid and tiglic acid;- and the copolymerisation of these acids with other unsaturated aliphatic monomers for example vinyl
  • hydrolysable precursor of a poly(carboxylic acid) means a polymer which will be transforme into the poly(carboxylic acid) on hydrolysis, for example a poly(carboxylic acid anhydride); ftirthermore, polyacrylic acids may be prepared by hydrolysis of corresponding polyacrylonitriles
  • the hydrolysable precursor of a poly(carboxylic acid). may be a homopolymer of an unsaturated carboxylic acid anhydride or a copolymer with an above mentioned other carboxylic acid or anhydride thereof; or a copolymer of an unsaturated carboxylic acid anhydride with an unsaturated aliphatic monomer, for example vinyl monomers, such as vinyl hydrocarbon monomers, vinyl ethers, acrylamide or acrylonitrile.
  • Good ' results may be obtained by using homopolymers of maleic anhydride or vinyl orthophthalic anhydride, or copolymers thereof, especially block copolymers thereof, with ethylene, propylene, butenes, styrene and vinyl methyl ether.
  • the poly(carboxylic acid) or hydrolysable precursor thereof is preferably linear, although branched polymers may also be used.
  • the polymer has an average molecular weight from 1,000 to 1,000,000, more preferably from 1,000 to 250,000, and most preferably from 5,000 to 100,000, especially from 10,000 to 25,000. In this specification the average molecular weight is defined as being that measured by ultracentrifuging.
  • the preferred components (ii) are aluminosilicates or fluoraluminosilicates, particularly glasses thereof, wherein the ratio by weight of acidic to basic oxides in the glass is such that the glass will react with (i) in the presence of water and, desirably, a water-soluble complexing agent, for example a water- soluble chelating agent such as tartaric, citric or mellitic acid, to set to a hardened composition.
  • a water-soluble complexing agent for example a water- soluble chelating agent such as tartaric, citric or mellitic acid
  • the principal acidic oxide in the glass is a silica, although the glass may also contain minor amounts of other anhydrides such as phosphorus pentoxide and boric oxide.
  • the principal basic oxide in the glass is alumina which, although it has amphoteric properties, can be considered for the purposes- of the present invention solely as a basic oxide.
  • Particularly preferred glasses fall within the composition range of 10 to 65% w/w silica " and 15 to 50% w/w alumina.
  • the glass desirably contains at least one other basic oxide, preferably calcium oxide, which may be present in the glass composition in an amount from 0 to 50% w/w.
  • the calcium oxide may be partly or wholly replaced by sodium oxide or other basic oxide or a mixture of basic oxides, although in some applications the presence of sodium oxide may be undesirable as this oxide tends to increase the solubility of the resulting cement.
  • Preferred glasses for use in the present invention containing alumina, silica and calcium oxide are the gehlenite and anorthite glasses, and in general glasses falling within the composition range 10 to 65% w/w silica, 1 to 0 w/w alumina and 0 to 50% w/w calcium oxide.
  • OMPI Other glasses suitable for use in the present invention may contain fluoride, suitably up to 15% by weight, preferably less than 10% by weight.
  • a class of fluoraluminosilicate glasse particularly suited to dental applications are those wherein the ratio by weight of silica to alumina is from 1.5 to 2.0 and the ratio by weight of silica to alumina is from 0.5 to 1.5 and the ratio by weight of fluorine to alumina is from 0.25 to 2.0.
  • the glasses suitable for use in the present invention may be prepared by fusing mixtures of the components in the appropria o proportions at temperatures above 900 C and preferably in the range of 1050 C to 1550 C.
  • the mixture is preferably fused from
  • Silica and alumina may be included in the mixture as oxides, though it is convenient to add calcium oxide and sodium oxide as calcium carbonate and sodium carbonate respective and reference to the presence of these oxides in a glass fusing mixture includes the possibilities that they may be added as carbonates or as other compounds which decompose similarly under glass fusion conditions to give the oxides.
  • the addition of carbonates to the fusion mixture lowers the fusion temperature and thus these can be considered as fluxing agents.
  • the mixture may contain an additional fluxing agent, and this has been found to be important with glass compositions containing less than 10% w/w of calcium oxide.
  • fluorides such as fluorite and cryolite have been found to be especially useful as fluxing agents, although it is desirable not to use large amounts of fluorides in the fusion mixture.
  • Other fluxing agents for example calcium phosphate and aluminium phosphate may also be used.
  • the total amount of fluxing agents present in the mixture, including carbonates may be up to 50% by weight, based on the total weight of mixture.
  • the glass After fusion the glass may be poured off and cooled rapidly, for example, in air or water or some combination of both. To a first approximation the proportions of the different elements in the glass may be taken as the proportions of the same elements present in the mixture. Some fluorine may, however, be lost from the fluoride fluxing agent during the reaction.
  • Glasses used in the present invention may be readily obtained in fine powder form.
  • the degree of fineness of the powder should preferably be such that it produces a smooth cement paste which sets within an acceptable period when mixed with the poly(carboxylic acid) in the presence of water.
  • the degree of fineness of the powder is such that it will pass through a 150 mesh B.S. sieve and most preferably such that it will pass through a 350 mesh B.S. sieve. Mixtures of different glasses may be used if desired.
  • the silicate may also be a naturally-occurring orthosilicate, pyrosilicate, cyclic or chain silicate comprising recurring metasilicate units, or aluminosilicate having an Al-Si molar ratio greater than 2-3- or blast furnace slags; or Portland cement.
  • the hardenable composition of the invention may be stored in any suitable manner providing that means are provided to prevent premature reaction of the components (ii) (and where possible (iii) ⁇ with (i) in the presence of water.
  • the composition may be stored as a dry powder, suitably comprising an intimate mixture of the poly(carboxylic acid) or hydrolysable precursor thereof (i) in particulate form with (ii) and (iii).
  • an aqueous solution of (i) can be dried on to (iii) which is then powdered and blended with (ii).
  • mixing is improved by using the poly (carboxylic acid) (i) in the form of an aqueous solution, which may contain from 20 to 65% by weight of the poly(carboxylic acid).
  • (iii) may be included in admixture with (ii) or be separate therefrom.
  • any water-soluble complexi agent present may be included with one or more of (i), (ii) or (iii) in an amount from 0.01% to 30% by weight of (i).
  • the hardenable compositions of this invention may be used as dental cements for use as filling materials for restoring posterior teeth. They may also be formed as hardenable sheet materials, for example by depositing the components, optionally in intimate admixture, upon a flexible support web which may be woven, laid down as a non-woven fabric, cast or extruded.
  • the hardenable compositions may also be used in the building industry as. surface coatings, flooring materials, speciality cements, including groutings, panellings, shuttering and adhesives. They may also be used to seal exposed and hazardous asbestos surfaces and claddings.
  • Titanium (oxidised 1:1 2.8-1 0.5g 20.6 at 0 C for 1 mins )
  • FILLER FILLER GLASS SOLID:LIQUID LIQUID MEAN PREMIX WEIGHT MIX WEIGHT WEIGHT TRANSVERSE RATIO RATIO STRENGTH
  • Titanium (etched 1-1 2.3:1 o.5g 22.0 in Tucker's etch)
  • Titanium (etched 1:1 2.3:1 o.5g 22.4 and oxidised)
  • Atomised Al 8201-30 stated to be >99«9 ⁇ % Al ex Koch-Light Ltd. ⁇ 45 ⁇ fraction was sieved out and used in the experiment.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Dermatology (AREA)
  • Transplantation (AREA)
  • Dental Preparations (AREA)
EP79900975A 1978-08-29 1980-03-25 Hardenable compositions Withdrawn EP0022772A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB3489278 1978-08-29
GB7834892 1978-08-29

Publications (1)

Publication Number Publication Date
EP0022772A1 true EP0022772A1 (en) 1981-01-28

Family

ID=10499324

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79900975A Withdrawn EP0022772A1 (en) 1978-08-29 1980-03-25 Hardenable compositions

Country Status (3)

Country Link
EP (1) EP0022772A1 (enrdf_load_stackoverflow)
JP (1) JPS55500593A (enrdf_load_stackoverflow)
WO (1) WO1980000409A1 (enrdf_load_stackoverflow)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3248357A1 (de) * 1982-12-28 1984-07-05 ESPE Fabrik pharmazeutischer Präparate GmbH, 8031 Seefeld Pulverfoermiger dentalwerkstoff, verfahren zu seiner herstellung und seine verwendung
GB2190383B (en) * 1986-04-08 1990-03-28 Dentsply Ltd Glass/poly (carboxylic acid)cement compositions
GB2190372B (en) * 1986-04-08 1991-05-15 Dentsply Ltd Glasses and poly(carboxylic acid)cement compositions containing them
DE4024322A1 (de) * 1990-07-31 1992-02-06 Thera Ges Fuer Patente Verformbare masse und deren verwendung als fuellmaterial fuer zahnwurzelkanaele
US5435248A (en) * 1991-07-09 1995-07-25 The Ensign-Bickford Company Extended range digital delay detonator
JP7278957B2 (ja) * 2017-03-15 2023-05-22 スリーエム イノベイティブ プロパティズ カンパニー グラスアイオノマー組成物及び無機繊維を含む方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1087680A (fr) * 1953-11-20 1955-02-28 Plastiques Dentaires & Medicau Procédé de fabrication des agglomérats métallo-plastiques pour prothèses et obturations dentaires
US3518762A (en) * 1965-10-29 1970-07-07 Mitsuharu Takeuchi Sealing materials useful in dental practice
AT293623B (de) * 1969-10-08 1971-10-25 Herbert Mueller Verfahren zur Herstellung eines Zahnfüll- bzw. Befestigungsmaterials
US3814717A (en) * 1970-12-04 1974-06-04 Dental Materials Section Labor Poly(carboxylic acid)-fluoroalumino-silicate glass surgical cement
ZA728928B (en) * 1972-01-03 1973-09-26 Lee Pharmaceuticals Dental adhesive composites
GB1495255A (en) * 1973-12-18 1977-12-14 Nat Res Dev Cements
NL7604906A (nl) * 1975-05-13 1976-11-16 Smith & Nephew Res Hardbare samenstellingen.
GB1504520A (en) * 1975-10-31 1978-03-22 Nat Res Dev Poly-(carboxylate) cements
GB1548419A (en) * 1976-08-12 1979-07-11 British Petroleum Co Fabrication of polymer cements
GB1587904A (en) * 1976-11-12 1981-04-15 Ici Ltd Surgical cement compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8000409A1 *

Also Published As

Publication number Publication date
JPS55500593A (enrdf_load_stackoverflow) 1980-09-04
WO1980000409A1 (en) 1980-03-20

Similar Documents

Publication Publication Date Title
CA1273028A (en) Glasses and poly (carboxylic acid) cement compositions containing them
US4900697A (en) Glass powders for dental glass ionomer cements
US4775592A (en) Fluoroaluminosilicate glass powder for dental glass ionomer cement
CA1037703A (en) X-ray opaque, enamel-matching dental filling composition
US4758612A (en) Cement-forming compositions
Smith Development of glass-ionomer cement systems
EP0340016B1 (en) Poly-vinylphosphonic acid and metal oxide or cermet or glass ionomer cement
GB2028855A (en) Poly(Carboxylic Acid) Hardenable Compositions
EP0430705A1 (en) Dental cement composition
EP0620804A4 (en) FLUORIDION-EXHAUSTABLE GLASSES AND TOOTH-CEMENT COMPOSITIONS.
US4337186A (en) Hardenable compositions
EP0022772A1 (en) Hardenable compositions
NZ204975A (en) Polymerisable dental restorative compositions having improved mechanical properties and hydrolytic stability
GAO et al. Erosion process of light-cured and conventional glass ionomer cements in citrate buffer solution
JPH0672028B2 (ja) グラスアイオノマ−セメント用ガラス組成物
EP0119062B1 (en) Storable dental porcelain paste
CHUNG The properties of metal‐reinforced glass ionomer materials
CA3101605C (en) Dental fluoroaluminosilicate glass powder
Bansal et al. Modified polyalkenoate (glass‐ionomer) cement–a study
JPH0624927A (ja) 歯科用セメント硬化剤
JPH07206470A (ja) エックス線不透明性フッ化物イオン徐放性ガラスおよびそれを含む歯科用材料
JP3450059B2 (ja) 歯科セメント用ガラス粉末
SU1094711A1 (ru) Состав электродного покрыти
JPS60135547A (ja) 歯科用金属材料
PL188324B1 (pl) Stomatologiczna kompozycja szkło-jonomerowa

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19800923

AK Designated contracting states

Designated state(s): CH DE FR GB SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19821213