CA2368323A1 - Dental materials based on metal oxide clusters - Google Patents
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- CA2368323A1 CA2368323A1 CA002368323A CA2368323A CA2368323A1 CA 2368323 A1 CA2368323 A1 CA 2368323A1 CA 002368323 A CA002368323 A CA 002368323A CA 2368323 A CA2368323 A CA 2368323A CA 2368323 A1 CA2368323 A1 CA 2368323A1
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- 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
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- 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
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- 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
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Abstract
Dental material containing a cluster according to the general formula [(M1)a(M2)b O c (OH)d(OR)e(L-Sp-Z)f] (I) in which M1, M2, independently of each other, stand in each case for a metal atom of the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table; R is an alkyl group with 1 to 6 carbon atoms; L is a co-ordinating group with 2 to 6 complexing centres; Sp is a spacer group or is absent; Z is a polymerizable group; c is a number from 1 to 30; d, e, independently of each other, are in each case a number from 1 to 30; f is a number from 2 to 30, any charge of the cluster (I) present being equalized by counterions.
Description
Dental materials based on metal oxide clusters The invention relates to dental materials based on polymerizable metal oxide clusters.
Polymerizable compositions are known which, in addition to organic monomers, also contain poiymerizable metal compounds.
US 2,502,411 discloses compositions which, in addition to unsaturated polymerizable organic compounds, contain a zirconium acrylate which is obtainable by reacting a water_-soluble zirconium salt with a salt of (meth)acrylic acid.
The zirconium compound is said to improve 'the wettability of ceramics, metals and cellulose. Details of the structure of the zirconium acrylates are not given.
DE 3I 37 $40 C2 discloses crystalline zirconium methacrylate of the general formula Zr4{MAS)~oOzX,(H20)Z_4 in which MAS is the anion of methacrylic acid and X an anion from the group hydroxide, alkoxide, halide and carboxylate.
The compounds are said to be suitable as cross-linking agents in the preparation of vinyl polymers by radical polymerization of vinyl monomers.
Schubert et al., Chem. Mater 4 (1992) 291 describe the preparation and characterization.of methacrylate-modified titanium and zirconium alkoxides which are obtainable by reaction of the corresponding metal alcoholates with methacrylic acid, and Kiclcelbick and Schubert, Chem.
Ber./Recueil 130 (1997) 473, of crystalline oxozirconium methacrylate clusters of the formulae Zr~ ( OH ) 4O4 ( OMc ) .~~ and Zr40z ( OMc ) 1z in which OMc is the anion of methacrylic acid DE 41 33 494 C2 discloses dental resin compositions based on polymerizable polysiloxanes which are prepared by hydrolytic condensation of one or more silanes of which at least one is substituted by a 1,4,5-trioxaspiro-[4,4)-nonane radical or an ethylenically unsaturated group.
Hydrolyzable and polymerizable silanes are known from DE 44 16 857 Cl which contain one linear or branched organic radical with at least one C=C double bond and 4 to 50 carbon atoms.
EP I 022 012 A2 and US 6,096,903 disclose dental materials based on polymerizable and hydrolyzable methacrylate-modified or oxetane-group-r_ontaining silanes.
Silanes of the type described above can be condensed alone or together with another hydrolytically condensable compounds to form inorganic networks, which can then be cured via the C=C double bonds.contained in the silanes by ionic or radical polymerization accompanied by the formation of inorganic-organic networks.
_ j _ The ob;P~t of the invention is to provide dental materials with improved mechanical properties.
This object is achieved by dental materials which contain at least one cluster according to the general formula (I-) ~tMl~a~Mz)b~c~~H)dt~R~e~I'-Sp'~-')f~ ~I) in which Ml, MZ independently of each other, stand for a metal atom of the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
R is an alkyl group with 1 to 6 carbon atoms;
L is a coordinating group caith 2 to 6 complexing centres;
Sp is a spacer group or is absent;
Z is a polymerizabl e group;
a is a number from 1 20;
to b is a number from 0 10;
to c is a number from 1 30;
to d, a independently of eachother, are in each case a number from 0 to 30;
f is a number from 2 30.
to The respective values of the indices a to f can vary according to the type, number and valency of the metals and ligands. The indices c, d, a and f preferably assume such values that the positive charges of the metals M' and M' are completely equalized and the cluster is neutral. The cluster can however also be positively or negatively charged. In this case, the charge of the cluster is compensated by suitable counterions such as for example Hy, alkali or alkaline-earth metal ions, NH4+, NR°4+ with R° -alkyl, in particular C1 to C4 al)cyl, or OH-, R'-C00 with R' - alkyl, preferably C1 to C1° alkyl, particularly preferably C1 to C4 alkyl, or halide, preferably F- or C1-. The clusters (I) have for example a charge of -4 to +4, in particular +1 to +4:
The group L can be chelating or bridging, i.e. the complexing centres of the group L can be connected to the same mei.al atom or preferably with two or more different metal atoms.
The ligand (L-Sp-Z) can be neutral or have a negative charge. Neutral ligands or ligands with. a single to triple negative charge are preferred.
The ligands (L-Sp-Z) present in the cluster can be the same or different. Clusters which contain 1 to 4, preferably 1 or 2 kinds of ligands (L-Sp--Z) are preferred. For example, two methacrylate ligands can be replaced by allyl acetoacetate in the cluster Zr40Z(methacrylate)1z. The resul ting c 1 uster has the formula Zr40z (methacrylate ) 1Z ( allyl acetoacetate)Z, both'methacrylate and allyl acetoacetate _ 1 _ being ligands of the type (L-Sp-Z), i.e. the cluster contains two kinds of ligands of the type (L-Sp-Z).
Clusters which contain only a small proportion of alkoxy groups (d > e) are preferred. Preferably a _< (a+b), particularly preferably a = 0.
Preferred definitions, which can be selected independently of each other, for the individual variables are:
M1, MZ - independently of each other, Ti and/or Zr;
R - an alkyl group with 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms;
L - a-hydroxycarboxyiate (-CH(OH)-COO ), cx-aminoc arboxyl ate ( -CH { NHz ) -C00 ) , j3-diketonate { [ -C ( -0 ) =CH-C ( =0 ) R'~ ] ; with R~
- alkyl, preferably Ci to C~ alkyl, particularly preferably Ci to C3 alkyl, in particular methyl, sulfonate (-S03) or phosphonate (-P032), particularly preferably carboxylate (-C00 );
Sp - an alkylene group with 1 to 18 carbon atoms, an oxyalkylene group with 1 to 18 carbon atoms and 0 to 6 oxygen atoms or an arylene group with 6 to 14 carbon atoms, the spacer Sp being able to contain one or more, preferably 0 to 2 of the groups 0, S, CO-0, 0-C0, CO-NH; NH-C0, 0-CO-NH; NH-CO-0 and NH;
_ () particularly preferably, Sp is an alkylene group with i to 6~ in particular 1 to 3 carbon atoms or' is absent;
Z - an ethylenically unsaturated group, an epoxide, oxetane, vinyl ether, 1,3-dioxolane, spiroorthoester;
particularly preferably a methacrylic and/or acrylic group;
a - 2 to 11;
b - 0 to 4.
The values of the indices c, d, a and f again correlate to the number and charge of the metal atoms. Preferably, they assume values such that the charge of the cluster is equalized. Typical values for c are in the case of the preferred clusters 1 to 1f, in particular 2 to 5, for_ d and a 0 to 10 and in particular 0 to 8, for f 4 to 20 and in particular 6 to 15.
According to a particularly preferred version, M1 - Mz.
Clusters in which M1 and ~I' are each zirconium are particularly preferred.
The polymerizable groups Z are preferably bound to the metal centres direct or by a short spacer via carboxylate groups.
Particularly preferred ligands of the type {L-Sp-Z) are acrylate, methacrylate, oleate, allyl acetoacet.ate and acetoacetoxyethyl methacrylate.
Particularly preferred clusters are:
Zr6 ( OH ) 404 ( OMc ) 1z i Zr40z ( OMc ) 1z i Zr60z ( OC4H9 ) to ( OMc ) to i T1b04 ( OCZHS ) 3 ( OMC ) S i T14O2 ( O-~--C3H7 ) b ( OMC ) 6; T1402 ( O-1-C3H7)6(~MC)6; T190g{OCgH~)4(OMC)16i Zr4T1Z04(OC4H9)2(OMC)14i ZrzTi404 ( OC4H9 ) b ( OMc ) to i Zr4Ti406 ( OBu ) 4 ( OMc ) 16 and 2, r6Tiz06 ( OMc ) zo.
OMc in each case standing for a methacr_ylate group.
Similarly preferred are the clusters which contain acrylate groups instead of the methacrylate groups.
The clusters according to formula (I) can be prepared by reacting metal alkoxides with suitable polymerizable ligands, optionally with the addition of_ water. For example, the reaction of zirconium{IV)-propoxide (Zr{0-C3H~)4) with a quadruple molar excess of methacrylic acid (HOMe) produces dusters of the composition Zr40z(OMc)lz (G.
Kickelbick, U. Schubert, Chem. Ber./Recueil 130 (1997) 473):
4 Zr ( OC3H7 ) 4 + 14 HOMc ~ Zr40z ( OMc ) 1z + 2 C3H~OMc + 14 C3H70H
Moreover, suitable clusters can be prepared by the exchange of ligands for polymeri~.a.ble ligands. For example, the reaction of titanium oxide clusters TiaO~ ( OOCRa) ~ with unsaturated carboxylic acids (HOOCR''') produces clusters of the compos ition TiaO~ ( OOCRa ) e_a ( OOCRf' ) a . Spec i f ical 1y, the reaction of the titanium carboxylate cluster Tib04 ( OCZHS ) 8 ( acetate ) $ with methacrylic acid ( HOMc } produces the c luster Ti604 ( OCZHS ) s ( acetate ) 8_u ( OMc ) a .
Alternatively, suitable clusters can be obtained by the derivatization of inorganic clusters. For example, the reaction of SiW1103~$ with trichloro- or t:riethoxysilanes RYSiQ3 ( Q = Cl or -OC,HS ) in which RY contains a polymerizable group produces polymerizable clusters of the composition SiW11039 ( OSi.2R2) 4 The clusters according to formula (I) represent substances of high reactivity which can be processed alone or preferably in combination with other polymerizable components by polymerization to form mechanically stable layers, moulded bodies and fillers. These are characterized by a very small proportion of monomers which can be dissolved out by solvents and a high stability even in humid conditions. The mechanical properties of the cured materials are not impaired by water storage.
For curing; an initiator for ionic or radical polymerization is preferably added to the polymerizable clusters or mixtures of the clusters with other polymerizable components. Depending on the type of initiator used, the polymerization can be initiated thermally, by UV or visible light. In addition, the mixtures can contain further additives, such as for example colorants {pigments or dyes), stabilizers, flavoring agents, microbicidal active ingredients, plasticizers and/or UV absorbers. The clusters according to formula {I~) and their mixtures are suitable in particular for use as dental materials or for the preparation of dental materials. By dental materials are preferably meant adhesives, coating materials, cements and in particular filling materials.
The clusters according to formula (I) have only a low volatility because of their high molecular weight and can therefore largely be safely processed. Through the size and structure as well as the number of polymerizable groups of the clusters, the cross-linking density and thereby the mechanical properties such as E-modules and strength and the swelling behaviour in organic solvents of the cured materials can be selectively set. Size,and structure of the clusters as well as the number of polymerizable groups per metal atom can be monitored by variations in the synthesis parameters. The cluster size and structure are governed by the ratio of metal oxide to ligand in the- educt mixture, but also by the nature of the radicals R in the alkoxides Ml { OR } ~, or MZ ( OR ) n used . Furthermore, the mechanical properties such as strength and fle::ibility can be influenced via the distance between the metal centres and polymerizable radicals, i:e. via the length of the spacer groups -Sp-.
In the case of the clusters according to formula (I), the polymerizable groups are fixed to a compact particulate cluster structure. The result of this is that, upon polymerization, rigid products with a high cross-linking density are obtained. The clusters represent three-dimensional molecules with a defined spatial structure and size and allow, upon co-polymerization with other components, an optimum cross-linking density to be set for the purpose in question. The structure of the clusters guarantees a complete incorporation of the clusters into the polymer network. It ensures a uniform environment for all the polymerizable organic ligands, so that these are practically equivalent as regards their reaction with organic co-monomers, which results in a uniform polymer structure developing around each ligand.
In addition, the abrasiveness or the optical properties such as for example the refractive index can be varied via the type and number of metal atoms.
Substances in which the clusters are soluble, i.e. liquid materials in particular; are preferred as further polymerizable components. Radically o.r ionically polymerizable mono- and polyfunctional compounds can primarily be considered here, in particular polymerizable organic monomers and silanes and polysiloxanes with polymerizable groups as well as mixtures of these compounds.
Ethylenically unsaturated organic monomers, in particular monofunctional or polyfunctional methacrylates which can be used alone or in mixtures are preferred as polymerizable organic monomers. Mono(meth)acrylates such as methyl, ethyl, butyl, benzyl, furfuryL, phenyl(meth)acrylate, isobutyl(meth)acrylate, cyclohexyl(meth}acrylate and polyfunctional (meth)acrylates-such as tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethylene . glycol di~meth)acrylate; polyethylene glycol di(meth}acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, bisphenol-A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 2,2-bis-4-(3-methacryloxy-2-hydroxypropoxy)-phenylpropane (bis-GMA), pentaerythritol tetra(meth)acrylate as well as the reaction products from isocyanates, in particular di- and/or triisocyanates, and OH-group-containing (meth)acrylates can be considered as preferred examples of these compounds.
Examples of these are the reaction products of l mol 2,2,4-trimethylhexamethylene diisacyanate with 2 mol 2-hydroxyethylene methacrylate (UDMA) or 2 mol hydroxypropyl - I? -met:~acrylate as well as the reaction products of 2 mol glycerin dimethacrylate with 1 mol 2,2,4-trimethylhexamethylene diisocyanate, isophoron diisocyanate or re, a,cx' , cx' -tetramethyl-xylylene-m-diisocyanate . The use of polyfunctional (meth)acrylates is particularly preferred. By polyfunctional compounds are meant those with several polymerizable groups.
Further preferred polymerizable organic monomers are cationically polymerizable mono- or polyfunctional monomers such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, 3-ethyl-3-hydroxymethyl oxetane, 1;10-decanediylbis(oxymethylene)bis(3-ethyloxetane) and 3,3-(4-xylylenedioxy)-bis-(methyl-3-ethyl-oxetane).
Compounds which have polymerizable groups; preferably (meth)acryl groups, or rationally polymerizable groups, preferably epoxide, oxetane, spiroorthoesters or vinyl ether groups, are particularly suitable as polymerizable silanes and polysiloxanes. Suitable silanes and polysiloxanes and their preparation are described in DE 41 33 494 C2, DE 44 16 857 C1, EP 1 022 0?2 A2 and US
6,096,903. Preferred silanes are listed below.
Polysiloxanes based on these silanes are particularly preferred, the polysiloxanes being able to be present in the form of the homo- and co-condensates.
- LJ -Silanes of the general formula (1) are prefeT_red i Yinisl X miR 4_(nl-mi) ( ~-) in which the radicals X1, Y1 and Rl are the same or different and haves the following meanings:
R1 - alkyl, alkenyl, aryl, alkylaryl or arylalkyl, X1 - hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or DTRsz with RS -hydrogen, alkyl or aryl, Y1 - a substituent which contains a substituted or unsubstituted 1,4,6-trioxaspiro-[4,4]-nonane radical, n1 - 1, 2 or 3, ml - l, 2 or 3, with n1 + mi <_ 4, and silanes of the general formula (2), fXlnlRlltls~-[RZ(Al)1]4-(nl+ki)~~iBl (2) in which radicals Ai, R1, RZ and X1 are the same or different and have the following meanings:
AI - 0, S, PRE, PORE, NHC ( 0 ) 0 or NHC ( 0 ) ONRE, with RE - hydrogen, alkyl or aryl, B1 - a linear or branched organic radical which is -1=J-derived from a compound B-~ with at least one ( for 1 - l and A = NHC(0)0 or NHC(0)NR') or at least two C=C double bonds and 5 to 50 carbon atoms, with R~ = hydrogen, alkyl or aryl, Rl - alkyl, alkenyl, aryl, alkylaryl or arylalkyl, RZ - alkylene, arylene or alkylene arylene, X1 - hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkyicarbonyl, alkoxycarbonyl or NR~Z with R° -hydrogen, alkyl or aryl, n1 - l, 2 or 3, k1 - 0, 1 or 2, 1 - 0 or 1, X1 - an .integer the maximum value of which corresponds to the number of double bonds in the compound Bl minus 1 or is equal to the number of double bonds in the compound B1 when 1 = 1 and A
stands for NHC(0)0 or NHC{0)ONR'.
The silanes of the general formula (1) and (2) are hydrolyzable and polymerizable, the radicals Xi being hydrolyzable and the radicals Bl and Yi being polymerizable and in each case at least one radical B1, X~ and Yi with the above-named meaning being present in the silanes of the general formula {1} and (2). Polysiloxanes based on silanes {1) and/or {2) are preferred polymerizable components.
The alkyl radicals of the compounds ( 1 ) and ( 2 } are a . g .
linear, branched or cyclic radicals with 1 to 20~, _ j i _ preferably 1 to 10 carbon atoms, and Lower alkyl radicals with 1 to 6 carbon atoms are particularly preferred.
Special examples are methyl, ethyl, N-propyl, i-propyl, n-butyl, s-butyl, t-butyl, i-butyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl.
The alkenyl radicals are e.g. linear, branched or cyclical radicals with 2 to 20, preferably 2 to 10 carbon atoms and lower alkenyl radicals with 2 to 6 carbon atoms such as e.g. vinyl, allyl or 2-butenyl are particularly preferred.
Preferred aryl radicals are phenyl, biphenyl and naphthyl.
The alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl and amino radicals are preferably derived from the above-named alkyl and aryl radicals: Special examples are methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, methylamino, ethylamino, dimethylamino, diethylamino, N-ethylanilino, acetyloxy, propionyloxy, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenylethyl and tolyl.
The radicals named can optionally have one or more substituents; e.g. halogen, alkyl, hydroxyalkyl, alkoYy., aryl, aryloxy,. alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, alkylamino, dialkylamino, trialkylammonium, amido, hydroxy, formyl, carboxy, mercapto, cyano, isocyanato, nitro, epoxy, S03H and P04H2.
- l~ -Of the halogens, fluorine, chlorine and bromine are preferred.
The substituted or unsubstituted 1,4,6-trioxaspiro[4,4]-nonane groups are bound to the Si atom via alkylene or via alkenylene radicals which can be interrupted by ether or ester groups.
Further preferred are silanes according to the general formula (3) as well as polysiloxanes based on same B fA -~Z. )dl'R -IR -S1X a1R bl}cl in which the radicals and indices have the following meanings:
Bz - a linear or branched organic radical with at least one C=C double bond and 4 to 50 carbon atoms;
XZ - hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR'z;
R6 - alkyl, alkenyl, aryl, alkylaryl or arylalkyl;
R$ - alkylene, arylene, arylenealkylene or alkylenearylene with in each case 0 to 10 carbon atoms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups;
R' - hydrogen, alkyl or aryl;
AZ - 0, S or NH for di - Z and Z1 - CO
_ j% _ and R3 - al)cylene, arylene or a7 kylenearylene with in each case 1 to 10 carbon a oms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups, and R'' -COOH; or A2 - 0, S or NH for d1 - 1 and Z1 - CO
and R3 - alkylene, arylene or a7_kylenearylene with in each case I to 10 carbon atoms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups, and R~ - H~;
or AZ - 0, S, NH or C00 for dl - 1 and Z1 - CHR~, with R~ equal to H, alkyl, aryl or alkylaryl, and R3 - alkylene, arylene or allcylenearylene with in each case 1 to 10 carbon atoms, these radicals being able to be interrupted by oxygen and' sulphur atoms or by amino groups, and R4 - OH; or AZ - O, S, NH or COO for dl - 0 and R3 - alkylene, arylene or alkylenearylene with in each case 1to 10 carbon atoms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups, and R4 - OH; or AZ - S for dl - 1 and ZZ - CO and R3 - N and Rl' - H;
al - 1, 2 or 3;
b1 - 0, 1 or 2;
a1+bl - 3l c1 - 1, 2, 3 or 4.
The silanes of the formula (3} are polymerizable via the radicals ~~ and hydrolyzable via the radicals XZ.
The optionally present alkyl, alkenyl, aryl, alkoxy, acyloxy, alkylcarbonyl, aI)coxycarbonyl and amino radicals have the meanings defined for the formulae (1} and (2).
For al >_ 2 or b~ - 2, the radicals YZ and R' can in each case have tile Same or a different,meaning. The radical BZ is derived from a substituted or unsubstituted compound B'(A-H)~1 with at least one C=C double bond, such as a.g.
vinyl, alkyl, acryl and/or rnethacryl groups and 4 to 50, preferably 6 to 30 carbon atoms. Preferably, B' is derived from a substituted or unsubstituted compound with two or more acrylate or methacrylate groups. Such compounds are also called (meth)acrylates. If the compound B~(AZH)~; is substituted, the substituents can be selected from the substituents named above. The group AzH can be -OH, -SH, -NHZ or -COOH and c can assume values from 1 to 4.
Silanes according to formula (4} and polysiloxanes based on them are particularly preferred [ (Wq-R13 ZZ)P_Rlo]mZY2-R9-S1X3n2R83-n2 Formula (4}
in which X3 stands for.a halogen atom, a hydroxyl, alkoxy andlor acyloxy group;
n2 is equal to 1 to 3;
R8 stands for an alkyl, alkenyl, aryl, alkylaryl, arylallcyl group;
R9 stands for an alkylerie group;
R1° stands for a p-times substituted, linear, branched or cyclic, saturated or unsaturated, aromatic or aliphatic organic radical with 2 to 40 carbon atoms and optionally 1 to 6 heteroatoms;
R13 stands for a q-times substituted.linear, branched or cyclic organic radical with 1 to 20 carbon atoms or is absent;
p is equal to 1 or 2;
q is equal to 1 to 6;
Y2 stands for -NR11-; N or -(C=0)-NH-;
m2 is equal to 2 for YZ - N and equal to 1 for -Y --NR11- or -( C=0 } -NH-;
R11 stands for an alkyl or aryl group;
_ 'I <) _ Z~ stands for 0, S, -(C=0)-0-, -(C=0)-NH-, -0-(C=0)-P1H-or is absent;
W stands for CH,=CR~~ -{ C=0 ) -0-; and RlZ stands for a hydrogen atom or an alkyl group.
Suitable heteroatoms are phosphorus and preferably oxygen.
In connection with formula {4), by alkyl, acyloxy, alkoxy, alkenyl groups and allcylene groups are meant radicals which preferably contain 1 to 25 carbon atoms, particularly preferably 1 to 10 carbon atoms and quite particularly preferably 1 to 4 carbon atoms and optionally bear one or more substitutes such as for example halogen atoms, nitro groups or alkyloxy radicals. By aryl is meant radicals, groups or substituents which preferably have 6 to 10 carbon atoms and can be substituted as stated above. The above definitions also apply to composite groups such as for example alJcylaryl and arylalkyl groups . An aJ_l~ylaryl group thus designates for example an aryl group as defined above which is substituted with an alkyl group as defined above.
The alkyl, acyloxy, alkoxy, alkenyl groups and alkylene groups can be linear, branched or cyclical.
Preferred definitions, which can be selected independently of each other, for the individual variables of formula (4) are:
X3 - a methoxy and/or ethoxy croup;
n2 - 2 or 3;
R$ - a C1 to C3 alJcyl group, in particular a methyl group;
R9 - a C1 to C4 alkylene group;
R1° - a p-times substituted linear, branched or cyclic, saturated or unsaturated, aromatic or aliphatic organic radical with 2 to 10 carbon atoms and optionally a hetero atom, preferably an -ii) _ oxygen atom, particularly preferably a Ci to C~, alkenylene radical or a manocyclic radical with 4 to 10, in particular 5 to 8 carbon atoms;
R'' - a q-times substituted linear, branched or cyclical organic radical with 1 to 4 carbon atoms, particularly preferably a Ci to C3 alkylene radical;
p - 1 or 2, in particular l;
q - 1 or 2;
Yz - N or -(C=0)-NH-;
Zz - -(C=O)-; and/or R1z - a hydrogen atom or a methyl group.
Hydrolyzable and polymerizable oxetane silanes according to the general formula (5) and their stereoisomers as well as polysiloxanes based thereon are further preferred:
(5~ _ / \R16 R15 { R1~ SiX~R~? }
a Y :_a_~~ ~2 the variables R14 Rls Ri6 R:.7 Ris R'g Rzo ~l~ Ys az bz 1. , I I l 1 1 1 P 1 1 cz, and xz, unless otherwise stated, having the following meanings independently of each other:
R14 - hydrogen or substituted or unsubstituted C1 to C,o alkyl;
Rls - absent or substituted or unsubstituted C1 to Cls alkylene, C6 to Cls arylene, C~ to Cls alkylenearylene or arylenealkylene, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl, a~iide and urethane group;
R16 - absent or substituted or unsubstituted .
C1 to Cis alkylene, C6 to Cls arylene, C7 to Cls alkylenearylene or C7 to Cls arylenealkylene, , CA 02368323 2002-O1-17 these radi cals being able to be i nt~rrupted by at least one group selected from ether, thioether, ester, thioester, carbonyl, amide and urethane group or bear these in terminal position;
R~' - absent or substituted or unsubstituted Cl to C1$ alkyl, Cz to Cls alkenyl, C~ to C1$ aryl, C~ to C1$ alkylaryl or C~ to Clg arylalkyl, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl, amide and urethane group;
R1$ - absent or substituted or unsubstituted -CHRzo-CHRz°-, -CHRzo-CHRzo-S-R19-, -S-R19-, -Y3-CO-NH-R19- or -CO-0-R19-;
R19 - substituted or unsubstituted C1 to C1$ alkylene, C~ to Cls arylene, C~ to C18 alkylenearylene or C6 to C1$ arylenealkylene, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl; amide and urethane group;
~~zo - hydrogen or substituted or unsubstituted C1 to C1$ alkyl or C6 to Clo aryl;
X'' - a hydrolyzable group, namely halogen, hydroxy, allcoxy or acyloxy;
Y3 - 0 or S; ' az - 1, 2 or 3 ;
bz - l, 2 or 3;
c2 - 1 to 6; and x2 - 1, 2 or 3;
and on condition that ( i ) az+xz - 2 , . 3 or 4 and ( ii ) az and/or b2 - 1.
However, the above formulae cover only such compounds which are compatible with the doctrine of valence.
Normally, the silanes according to formula (5) are present as stereoisomer mixtures and in particular as racemic compounds.
The ether, thioether, ester, thioester, carbonyl, amide and urethane groups possibly present in the case of the radicals of formula (5) are defined by the following formulae: -0-, -S-, -CO-0-, -0-CO-, -CO-S-, -S-CO-, -CS-0-, -0-CS-, -CO-, -CO-NH-, -NH-CO-, -0-CO-NH- and -NH-CO-0-.
The non-aromatic radicals or non-aromatic parts of the radicals which can be present in formula (5) can be linear, branched or cyclic.
In the silanes according to formula (5), any alkyl radicals present have preferably I to 8 and particularly preferably 1 to 4 carbon atoms. Special examples of possible alkyl radicals are methyl, ethyl, n- and iso-propyl, sec.- and tert.-butyl, n-pentyl, cyclohexyl, 2-ethylhexyl and octadecyl.
In the silanes according to formula (5), any alkenyl 'radicals present have preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms. Special examples of possible alkenyl radicals are vinyl, allyl- and iso-butenyl.
Preferred examples of possible aryl radicals of the formula (5) are phenyl, biphenyl and naphthyl. Alkoxy,radicals have preferably l to 6 carbon atoms. Special examples of possible alkoxy radicals are methoxy, ethoxy, n-propoxy, iso-propoxy and tert.-butoxy. Acyloxy radicals have preferably 2 to 5 carbon atoms. Special examples are acetyloxy and propionyloxy.
Preferred alkylene radicals of formula (5) are derived from the above preferred alkyl radicals, and preferred arylene radicals are derived from the above preferred aryl radicals. Preferred radicals which consist of a combination of a non-aromatic and aromatic part are derived from the above preferred alkyl and aryl radicals. Special examples of this are benzyl, 2-phenylethyl and tolyl.
The named substituted R radicals of formula (5) bear one or more single substituents. Examples of these substituents are methyl, ethyl, phenyl, benzyl, hydroxymethyl, hydroxyethyl, methoxy, ethoxy, chlorine, bromine, hydroxy, mercapto, isocyanato, vinyloxy, acryloxy, methacryloxy, allyl, styryl, epoxy, carboxyl, S03H, P03Hz or P04HZ.
For a2, bZ, cZ or x2 ? 2, the radicals X4 as well as the individual R.radicals can in each case have the same or a different meaning.
In addition, preferred definitions exist for the variables of formula (5) set out above which, unless other~iise stated, can be selected independently of each other and are as follows:
R1'' hydrogen or C1 to CS allcyl;
-R15 C1 to Cs alkylene, these radicals being able to -be interrupted by at least one group selected from ether, thioether, ester and urethane group;
R16 absent or C1 to Cs alkylene, these radicals being -able to be interrupted by at least one group selected from ether, thioether, ester, thioester, carbonyl, amide and urethane group or bear these in terminal position;
Rl' absent or methyl, ethyl or phenyl;
-R1$ absent or -CHRZ-CHRZ-, -S-P.19-, --Y-CO-NH-R19- or --CO-0-R19-;
R19 C1 to Cs allcylene, these radicals being able to -be interrupted by at least one group selected from ether, thioether, ester, carbonyl, amide and urethane group;
R2 hydrogen or C1 to CS alJcyl;
-X4' methoxy, ethoxy or chlorine;
-Y~ - 0 or S ;
a- - 1;
'.~ z - 1 c2 - 1 to 6;
xz - 2 or 3; and/or az+xZ - 3.
The individual R radicals can in turn bear single substituents.
Preferred compounds according to formula (5) are accordingly those for which at least one of the variables of formula (5) meets the preferred definition described above.
Furthermore, oxetane silanes of formula (5) are preferred for which the indices az, b' and/or c' have the value 1.
The silanes (5) are polymerizable via the oxetane groups and hydrolyzable via the radicals X4.
The above-named silanes can be processed, either alone or together with other hydrolytically condensable compounds of silicon, aluminium, zirconium, titanium, boron, tin, vanadium and/or phosphorus to form polysiloxanes. These additional compounds can be used either per se or already in pre-condensed form.
Preferred further hydrolytically compounds of silicon are silanes of the general formula (6) Rzi~.z( z3Rzz)msSiX54-n;.z+m3) Formula ( 6 ) in which R-1 stands for a C, to Cs alkyl, C, to C-= all~enyl or C~ to Ci4 aryl group;
R" stands for a C1 to C$ al)cylene, Cz to Ci~ al)cenylene or C6 to C1,, arylene group;
XS stands for a hydrogen or halogen atom or a Ci to Cs alkoxy group;
Z3 stands for a glycidyl, acryl, methacryl, vinyl, allyl or vinylether group k2 is equal to 0, l, 2 or 3;
m3 is equal to 0, l, 2 or 3; and k2+m3 is equal to 0, l, 2 or 3.
Preferred definitions, which can be selected independently of each other, for the individual variables are:
R21 - a C1 to C3 alkyl, Cz to C5 alkenyl or a phenyl group;
a C1 to CS alkylene, CZ to C5 al)cenylene or a phenylene group;
XS - a halogen atom, a methoxy or ethoxy group;
Z3 - an acryl or methacryl group;
lcz - 0 and 1;
m3 - 0 and 1;
k2+m3 - 0, l or 2.
Such silanes are described for example in DE 34 07 087 A1.
Preferred zirconium, titanium compounds for the co-condensation with the named silanes are those according to formula (7) MeX6yRz3Z Formula ( 7 ) in which Me stands for Zr or Ti;
R'3 stands for a hydrogen atom, a substituted or unsubstituted C_ to C1~ alkyl, Ci to C15 alkylaryl or C~
to C1~ aryl group;
X6 stands for a halogen atom, a hydroxyl or C1 to C8 alkoxy group;
Y is equal to 1 to 4;
z is equal to 0 to 3.
Preferred definitions, which can be selected independently of each other, for the individual variables are:
Rz3 - a C1 to C5 alkyl or a phenyl group;
X6 - a halogen atom, a methoxy, ethoxy or propoxy group;
y - 4;
z - 0 or l, in particular 0.
Particularly preferred zirconium and titanium compounds are ZrCl4, Zr(OCZHS)4, Zr(OC3H7)4, Zr(OC4H9)4, ZrOClz, TiCl4, Ti ( OCZHS ) 4, Ti ( OC3H7 ),, and Ti ( OC4H~ ) 4 .
Preferred aluminium compozznds are those according to formula (8) AlRZ43 Formula ( 8 ) in which R24 stands for a halogen atom, a hydroxyl or C1 to C$
alkoxy group, preferably for a halogen atom or a C, to C; alkoxy group.
Particularly preferred aluminium compounds are Al(OCH3)3, A1 ( OCzH~ ) 3, A1 ( OC3H7 ) 3, Al ( OC4H9 ) 3 and AlCl3 .
'' ; _ In addition, boron trihalides, tin tetra.halides, tin tetraalkoxides and/or vanadyl compounds are suitable for co-condensation with the above-named silanes.
The curing of the materials takes place, depending on the initiator used, by thermal, photochemical or redoY-induced polymerization. , , Peroxides, in particular dibenzoyl peroxide, dilauroyl peroxide, tert.-butyl peroctoate and tert.-butyl perbenzoate are preferred as initiators for the hot-curing systems. Tn addition, azobisisobutyroethylester, 2,2'-azobisisobutyronitrile {AIBN}, benzopinacol and 2,2'-dialkylbenzopinacols are suitable.
Radical-supplying systems, for example benzoyl peroxide, lauroyl peroxide or preferably dibenzoyl peroxide, together with amines such as N,N-dimethyl-p-toluidine, N;N-dihydroxyethyl-p-toluidine, N,N-dimethyl-sym.-xylidine °or other structurally-related amines are used as initiators for cold polymerization. Amine and peroxide are usually distributed over two different components of the dental material. Upon mixing of the amine-containing base paste with the peroxide-containing initiator paste, the radical polymerization is initiated by the reaction of amine and peroxide.
Benzophenone and its derivatives as well as benzoin arid its derivatives can be used for example as initiators for photopolymerization. Further preferred photoinitiators are the a-dil:etones such as 9,10-phenanthrenquinone, diacetyl~, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil.
Camphorquinone and 2,2-methoxy-2-phenyl-acetophenone and in particular cx-diketones in combination wiyth amines as reduction agents are particularly preferably used.
Preferred amines are 4-(N,N-dimethylamino}--benzoic acid ester, N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine and triethanolamine. In addition, acyl phosphines such as e.g. 2,4,6-trimethylbenzoyldipher~yl- or bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphinic oxide are also particularly~suitable as photoinitiators.
For curing cationically polymerizable systems, diaryl-iodonium or triarylsulfonium salts such as e.g.
triphenylsulfonium hexafluorophosphate or hexafluoro-antimonate are particularly suitable as well as the photoinitiator systems described in X10 96/13538 and WO
98/47047.
Furthermore, the mixtures can be filled with organic or inorganic particles or fibres to improve the mechanical properties. In particular; amorphous, spherical materials based on mixed oxides of SiO~, ZrO~ and/or Ti02 with a mean average particle size of 0.005 to ?.0 Vim, preferably from 0.1 to 1 Vim, as disclosed for example in DE-PS 32 47 800, microfine fillers such as pyrogenic sili_cic acid ~or precipitation silicic acid as well as macro- or mini-fillers, such as quartz, glass ceramic or glaas powder with an average particle size of 0.01 to 20 Vim, preferably 0.5 to 5 ~cm as well as x-ray-opaque fillers such as ytterbium fluoride, are suitable as filler components. By mini-fillers are meant fillers with a parti cle s ize of 0 . 5 to 1.5 Vim, and by macro-fillers fillers with a particle size of l0 to 20 Vim.
Preferred compositions according to the invention contain, relative to their overall mass:
(a) 5 t~ 90% wt.-%, in particular 5 to 40 wt.-%, quite particularly preferably 10 to 20 wt.-% of one or more clusters according to formula (I), (b) 10 to 90 wt.-o, in particular 10 to 80 wt.-% of one or more further polymerizable components, (c) 0.1 to 5.0 wt.-%, in particular 0.2 to 2.0 polymerization initiator, and (d) 0 to 90 wt.-%, in particular 0 to 80 wt.-% filler.
The above composition can be further optimized in accordance with the desired use. Thus, a material which is particularly suitable as dental filling material preferably contains, in each case relative to the overaJ_l mass of the material:
( a ) 5 to 20 % wt . - % of one or more clusters according to formula (I), (b) 0 to 20 wt.-% of one or more further polymerizable components, (c) 0.2 to 2.0 wt.-% 2.0 polymerization initiator, and (d) 5 to 80 wt.-% filler.
A dental material which is particularly suitable as dental cement preferably contains, in each case relative to the overall mass of the material:
( a ) 5 to 30 % wt . - % of one or more clusters according to formula (I), (b) 0 to 30 wt.-% of one or more further polymerizable components, (c) 0.2 to 2.0 wt.-% 2.0 polymerization initiator, and (d) 5 to 50 wt.-% filler.
A dental material which is particularly suitable as dental coating material preferably contains, in each case relative to the overall mass of the material:
( a } 5 to 40 % wt . - % of one or more clusters according to formula ( I } , - .i() -{b) 5 to 80 wt.-~ of one or more further polymerizable components, {c) 0.2 to 2.0 wt.-% 2.O polymerization initiator, and (d) 0 to 40 wt.-% filler:
Quite particularly preferred are materials which contain, as further polymerizable component (b), 10 to 90 wt.-polysiloxane and 0 to 40 wt.-o polymerizable organic monomers, in each case relative to the overall mass of the dental material.
These compositions are particularly suitable as dental materials, quite particularly as adhesives, for example for inlays, coating materials, cements and in particular filling materials. In general, the compositions are particularly suitable for those uses in which the curing of the material takes place in the mouth cavity.
After polymerization, the dental material. s according to the invention have only a minimal content of unpolymerized constituents which can be dissolved out with aqueous or alcoholic solvents, which represents a significant improvement vis-a-vis conventional dental materials, as toxic side effects caused by monomeric constituents are suppressed.
According to the invention, clusters of a defined size and structure, i.e. pure, defined compounds of a known stoichiometry, are used for the preparation of dental materials, particularly preferably clusters with monodispersed mass distributiorx. In this way, the material properties of the dental materials, such as for example E-modulus, strength, hardness and abrasivity, can be set and improved in a controlled manner. Dental materials which contain 1 to 2 different.clusters are preferred.
In the following, the invention is explained in more detail using examples.
Example l:
Synthesis of the oxozirconium methacrylate cluster of composition Zr,,02( OMc ) 12 2.04 g (24 mmol) methacrylic acid were added to 1.73 g (3.6 mmol) of an 80% solution of zirconium butylate (Zr{OC4H9)4) in n-butanol. The reaction mixture was left to stand for a day at room temperature and the formed precipitate filtered off accompanied by the exclusion of moisture. I.09 g {86%
yield) of colourless cubic crystals resulted, which are soluble in chloroform, ethanol or toluene.
Example 2:
Synthesis of matrix substances based on silicic acid polycond.ensate A) Hydrolytic condensation of bis[(methacryloyloxy)pro-poxycarbonylethyl)-[3-{triethoxysilylpropyl))amine:
16.1g(26mmo1)bis[(methacryloyloxy)propoxy-carbonylethyl)-[3-(triethoxysilylpropyl)]amine which is obtainable by Michael addition of 3-aminopropyltriethoxysilane to 2-(acryloyloxyethyl)-propyl methacrylate (cf. ~P 1 022 022) were dissolved in 37.5 ml anhydrous ethanol and hydrolytically condensed accompanied by the addition of 2.81 g of an aqueous O.i N ammonium fluoride solution.
After 24 h stirring at room temperature, the volatile components were removed in vacuum and approx. 12 g of a relatively low-viscosity resin (SG-'1) with a viscosity of c = ca. 8 Pas {23°C) remained. This and all other viscosity data, unless otherwise stated, involves the rotation viscosity measured with a rotation rheometer with a _ j'7 _ paralle?-plate measuring system, CV = 120 (model CVO 120 of the company Bohlin).
B) Hydrolytic condensation of (3-triethoxysilyl-propylaminocarbonyl)butyric acid-(1,3{2)-bismethacryl-oyloxypropyl)ester:
10.9 g (20 mmol) {3-triethoxysilylpropylamido)butyric acid-(1,3-(2)-bismethacryloyloxypropyl)ester, which was obtained by amidation from 3-aminopropyltriethoxysilane with the adduct from glycerin dimethacrylate and glutaric acid anhydride ( cf . EP 1 022 012 ) , were dissolved in 98 . 2 mol anhydrous ethyl acetate and hydrolyticaJ_ly condensed accompanied by the addition of 1.08 g 0.5 N hydrochloric acid. After 30 minutes' 'stirring at 40°C, the volatile components were removed in vacuum. The resin obtained was then silylated after dissolving in a mixture of 35 g tert.-butylmethyl-ether, 12 g THF and 1.45 g {12 mmol) 2,4,5-trimethylpyridine by the dropwise additi_,on of 1 .96 g ( 18 mmol) trimethyichlorosilane. After st:L.r~rzng overnight at room temperature, the reaction mixt~.~re was washed with diluted hydrochloric acid and saturated NaCl solution and then dried over anhydrous sodium sulphate. After the evaporation of the solvent in vacuum, ca. 6 g of a viscous resin {SG-2} with a viscosity of r~ - ca. 75 Pas {23°C) remained.
Example 3:
Preparation of dental materials based on clusters according to example 1 ' various materials were prepared starting from the cluster Zr40z { OMc ) 1Z from example 1 and the matrix substances ST-1 and SG-2. The clusters were mixed with the matrix substances as 10% solution in ethanol and the solvent evaporated off in vacuum after the addition of the initiator components. The compositions (mass o) of the thus-prepared unfilled materials M-1 to M-5 are listed in Table 1. To determine the mechanical properties, testpieces with the dimens ions 2 5 x 2 x 2 mm were prepared from the compositions and cured by illumination with light of a wavelength of 390 to 500 nm (6 minutes). For this purpose, a dental radiation source~ of the Spectramat type from Vivadent was used. The bending strength (BS) and the bending E-modulus (BEM) were determined according to the ISO standard 4049 (2000), the testpieces having been previously stored in water at 37°C for 24 h. In addition, BS and BEM values were also measured for samples which were stored dry for 24 h at 37°C.
Table 1: Composition (mass %) of the unfilled materials M-1 to M-5 M-1* ) M-2 M-3* M-4 M_,-5 ) 9s.7 8s.7 _ -SG-2 - - 98.7 88.7 78.7 Zr-Cluster from - 10.0 - 10.0 20 Example 1 Photoinitiatora~ 1.3 1.3 1.3 1.3 1.3 *) Comparison example without clusters A mixture of 0.3o camphorquinone, 0.6% 4-(N,N-dimethylamino)-benzoic acid ethyl ester and 0.40 acryl phosphinic oxide (Lucerin TPO, BASF) was used as photoinitiator Table 2 : Bending strength ( BS ) and Bending E-modulus ( BEM) of materials M-1 to M-5 M-1* ~ 1"1-2M-3~ ~_.4 I M-5 ) )-i Dry BF {MPa) 46 47 48 59 70 - I
HZO storage BS (MPa) 31 52 36 60 60 Dry BEM (MPa) 1230 1900 1820 2100 2400 HZO storage BEM -(MPa) 1000 1920 1750 2270 2600 *) Comparison example without clusters To prepare the composite pastes C-1 to C-5, the unfilled materials'M-l to M-5 were mixed with the quantities of filler given in Table 3. Silanized pyrogenic silicic acid with an average primary particle size of 40 nm and a BET
surface of 50 mz/g (silanized Aerosil 0~-50, Degussa), ytterbium trifluoride with an average particle size of 5 ~m and a BET surface of < 7.5 m'/g (.YbF3, Auer Remy), silanized SiOZ-ZrOz mixed oxide with a primary particle size of 130 to 230 nm (Spharosil, Tokoyma Soda} and silznized barium silk ate glass (Ba-Si glass} with an average particle size of 1.2 ~m were used as fillers. The filler components are incorporated by means of a capsule vibrator.
The bending strength and the bending E-modulus were then measured, in each case after 24-hour storage in water or in the dry. The results are summarized in Table 4.
Table 3: Composition of the composite pastes C-1 to C-5 (values in mass o) R-1*) Y-2 K-3*) K-4 ~ IC-5 I.
Unfilled ma- 25.0 25.0 25.0 25.U 25.0 terial (M-1) (M-2) (M-3) {M-4) (M-5}
Aerosi:l OX-50 1.0 1.0 1.0 1.0 1.0 YbF3 15.0 15.0 15.0 15.0 15.0 Spharosil 15.0 15.0 15.0 15.0 15.0 i Ba-Si glass 44.0 44.0 44.0 44.0 44.0 *) Comparison example without clusters Table 4: Bending strength (BS) and bending E-modulus (BEM) of the composites C-1 to C-5 IZ_1* R_2 K_3* K_4 R-5 Dry BS (MPa) 94 96 89 101 103 HBO storage BS {MPa)' 68 100 89 110 113 Dry BEM (MPa) 6400 8900 8150 9100 9840 H20 storage BEM (MPa) 5500 9300 7160 9750 1.0900 *) Comparison without dusters The results show (Tables 2 and 4) that the addition of clusters of the composition Zr402(OMc)iz in each case leads to an improvement in strength and to an increase in E-modulus of the materials. In addition, in the case of the cluster-containing materials, an increase in the E-modulus after water storage can be observed, whereas the E-rnodulus _i(~ -decreases in the case of the non-modified samples M-1/C-1 and M-3/C-3 after water storage.
Samples of the cured composites C-2 and C-4 were crushed and the fragments dispersed in ethanol at 37°C. After 72 h, the solid constituents were filtered off and the filtrate concentrated to dryness. Almost no residue resulted, which indicates a complete incorporation of the polymerizabie components into the polymer network of the composite matrix.
Polymerizable compositions are known which, in addition to organic monomers, also contain poiymerizable metal compounds.
US 2,502,411 discloses compositions which, in addition to unsaturated polymerizable organic compounds, contain a zirconium acrylate which is obtainable by reacting a water_-soluble zirconium salt with a salt of (meth)acrylic acid.
The zirconium compound is said to improve 'the wettability of ceramics, metals and cellulose. Details of the structure of the zirconium acrylates are not given.
DE 3I 37 $40 C2 discloses crystalline zirconium methacrylate of the general formula Zr4{MAS)~oOzX,(H20)Z_4 in which MAS is the anion of methacrylic acid and X an anion from the group hydroxide, alkoxide, halide and carboxylate.
The compounds are said to be suitable as cross-linking agents in the preparation of vinyl polymers by radical polymerization of vinyl monomers.
Schubert et al., Chem. Mater 4 (1992) 291 describe the preparation and characterization.of methacrylate-modified titanium and zirconium alkoxides which are obtainable by reaction of the corresponding metal alcoholates with methacrylic acid, and Kiclcelbick and Schubert, Chem.
Ber./Recueil 130 (1997) 473, of crystalline oxozirconium methacrylate clusters of the formulae Zr~ ( OH ) 4O4 ( OMc ) .~~ and Zr40z ( OMc ) 1z in which OMc is the anion of methacrylic acid DE 41 33 494 C2 discloses dental resin compositions based on polymerizable polysiloxanes which are prepared by hydrolytic condensation of one or more silanes of which at least one is substituted by a 1,4,5-trioxaspiro-[4,4)-nonane radical or an ethylenically unsaturated group.
Hydrolyzable and polymerizable silanes are known from DE 44 16 857 Cl which contain one linear or branched organic radical with at least one C=C double bond and 4 to 50 carbon atoms.
EP I 022 012 A2 and US 6,096,903 disclose dental materials based on polymerizable and hydrolyzable methacrylate-modified or oxetane-group-r_ontaining silanes.
Silanes of the type described above can be condensed alone or together with another hydrolytically condensable compounds to form inorganic networks, which can then be cured via the C=C double bonds.contained in the silanes by ionic or radical polymerization accompanied by the formation of inorganic-organic networks.
_ j _ The ob;P~t of the invention is to provide dental materials with improved mechanical properties.
This object is achieved by dental materials which contain at least one cluster according to the general formula (I-) ~tMl~a~Mz)b~c~~H)dt~R~e~I'-Sp'~-')f~ ~I) in which Ml, MZ independently of each other, stand for a metal atom of the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
R is an alkyl group with 1 to 6 carbon atoms;
L is a coordinating group caith 2 to 6 complexing centres;
Sp is a spacer group or is absent;
Z is a polymerizabl e group;
a is a number from 1 20;
to b is a number from 0 10;
to c is a number from 1 30;
to d, a independently of eachother, are in each case a number from 0 to 30;
f is a number from 2 30.
to The respective values of the indices a to f can vary according to the type, number and valency of the metals and ligands. The indices c, d, a and f preferably assume such values that the positive charges of the metals M' and M' are completely equalized and the cluster is neutral. The cluster can however also be positively or negatively charged. In this case, the charge of the cluster is compensated by suitable counterions such as for example Hy, alkali or alkaline-earth metal ions, NH4+, NR°4+ with R° -alkyl, in particular C1 to C4 al)cyl, or OH-, R'-C00 with R' - alkyl, preferably C1 to C1° alkyl, particularly preferably C1 to C4 alkyl, or halide, preferably F- or C1-. The clusters (I) have for example a charge of -4 to +4, in particular +1 to +4:
The group L can be chelating or bridging, i.e. the complexing centres of the group L can be connected to the same mei.al atom or preferably with two or more different metal atoms.
The ligand (L-Sp-Z) can be neutral or have a negative charge. Neutral ligands or ligands with. a single to triple negative charge are preferred.
The ligands (L-Sp-Z) present in the cluster can be the same or different. Clusters which contain 1 to 4, preferably 1 or 2 kinds of ligands (L-Sp--Z) are preferred. For example, two methacrylate ligands can be replaced by allyl acetoacetate in the cluster Zr40Z(methacrylate)1z. The resul ting c 1 uster has the formula Zr40z (methacrylate ) 1Z ( allyl acetoacetate)Z, both'methacrylate and allyl acetoacetate _ 1 _ being ligands of the type (L-Sp-Z), i.e. the cluster contains two kinds of ligands of the type (L-Sp-Z).
Clusters which contain only a small proportion of alkoxy groups (d > e) are preferred. Preferably a _< (a+b), particularly preferably a = 0.
Preferred definitions, which can be selected independently of each other, for the individual variables are:
M1, MZ - independently of each other, Ti and/or Zr;
R - an alkyl group with 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms;
L - a-hydroxycarboxyiate (-CH(OH)-COO ), cx-aminoc arboxyl ate ( -CH { NHz ) -C00 ) , j3-diketonate { [ -C ( -0 ) =CH-C ( =0 ) R'~ ] ; with R~
- alkyl, preferably Ci to C~ alkyl, particularly preferably Ci to C3 alkyl, in particular methyl, sulfonate (-S03) or phosphonate (-P032), particularly preferably carboxylate (-C00 );
Sp - an alkylene group with 1 to 18 carbon atoms, an oxyalkylene group with 1 to 18 carbon atoms and 0 to 6 oxygen atoms or an arylene group with 6 to 14 carbon atoms, the spacer Sp being able to contain one or more, preferably 0 to 2 of the groups 0, S, CO-0, 0-C0, CO-NH; NH-C0, 0-CO-NH; NH-CO-0 and NH;
_ () particularly preferably, Sp is an alkylene group with i to 6~ in particular 1 to 3 carbon atoms or' is absent;
Z - an ethylenically unsaturated group, an epoxide, oxetane, vinyl ether, 1,3-dioxolane, spiroorthoester;
particularly preferably a methacrylic and/or acrylic group;
a - 2 to 11;
b - 0 to 4.
The values of the indices c, d, a and f again correlate to the number and charge of the metal atoms. Preferably, they assume values such that the charge of the cluster is equalized. Typical values for c are in the case of the preferred clusters 1 to 1f, in particular 2 to 5, for_ d and a 0 to 10 and in particular 0 to 8, for f 4 to 20 and in particular 6 to 15.
According to a particularly preferred version, M1 - Mz.
Clusters in which M1 and ~I' are each zirconium are particularly preferred.
The polymerizable groups Z are preferably bound to the metal centres direct or by a short spacer via carboxylate groups.
Particularly preferred ligands of the type {L-Sp-Z) are acrylate, methacrylate, oleate, allyl acetoacet.ate and acetoacetoxyethyl methacrylate.
Particularly preferred clusters are:
Zr6 ( OH ) 404 ( OMc ) 1z i Zr40z ( OMc ) 1z i Zr60z ( OC4H9 ) to ( OMc ) to i T1b04 ( OCZHS ) 3 ( OMC ) S i T14O2 ( O-~--C3H7 ) b ( OMC ) 6; T1402 ( O-1-C3H7)6(~MC)6; T190g{OCgH~)4(OMC)16i Zr4T1Z04(OC4H9)2(OMC)14i ZrzTi404 ( OC4H9 ) b ( OMc ) to i Zr4Ti406 ( OBu ) 4 ( OMc ) 16 and 2, r6Tiz06 ( OMc ) zo.
OMc in each case standing for a methacr_ylate group.
Similarly preferred are the clusters which contain acrylate groups instead of the methacrylate groups.
The clusters according to formula (I) can be prepared by reacting metal alkoxides with suitable polymerizable ligands, optionally with the addition of_ water. For example, the reaction of zirconium{IV)-propoxide (Zr{0-C3H~)4) with a quadruple molar excess of methacrylic acid (HOMe) produces dusters of the composition Zr40z(OMc)lz (G.
Kickelbick, U. Schubert, Chem. Ber./Recueil 130 (1997) 473):
4 Zr ( OC3H7 ) 4 + 14 HOMc ~ Zr40z ( OMc ) 1z + 2 C3H~OMc + 14 C3H70H
Moreover, suitable clusters can be prepared by the exchange of ligands for polymeri~.a.ble ligands. For example, the reaction of titanium oxide clusters TiaO~ ( OOCRa) ~ with unsaturated carboxylic acids (HOOCR''') produces clusters of the compos ition TiaO~ ( OOCRa ) e_a ( OOCRf' ) a . Spec i f ical 1y, the reaction of the titanium carboxylate cluster Tib04 ( OCZHS ) 8 ( acetate ) $ with methacrylic acid ( HOMc } produces the c luster Ti604 ( OCZHS ) s ( acetate ) 8_u ( OMc ) a .
Alternatively, suitable clusters can be obtained by the derivatization of inorganic clusters. For example, the reaction of SiW1103~$ with trichloro- or t:riethoxysilanes RYSiQ3 ( Q = Cl or -OC,HS ) in which RY contains a polymerizable group produces polymerizable clusters of the composition SiW11039 ( OSi.2R2) 4 The clusters according to formula (I) represent substances of high reactivity which can be processed alone or preferably in combination with other polymerizable components by polymerization to form mechanically stable layers, moulded bodies and fillers. These are characterized by a very small proportion of monomers which can be dissolved out by solvents and a high stability even in humid conditions. The mechanical properties of the cured materials are not impaired by water storage.
For curing; an initiator for ionic or radical polymerization is preferably added to the polymerizable clusters or mixtures of the clusters with other polymerizable components. Depending on the type of initiator used, the polymerization can be initiated thermally, by UV or visible light. In addition, the mixtures can contain further additives, such as for example colorants {pigments or dyes), stabilizers, flavoring agents, microbicidal active ingredients, plasticizers and/or UV absorbers. The clusters according to formula {I~) and their mixtures are suitable in particular for use as dental materials or for the preparation of dental materials. By dental materials are preferably meant adhesives, coating materials, cements and in particular filling materials.
The clusters according to formula (I) have only a low volatility because of their high molecular weight and can therefore largely be safely processed. Through the size and structure as well as the number of polymerizable groups of the clusters, the cross-linking density and thereby the mechanical properties such as E-modules and strength and the swelling behaviour in organic solvents of the cured materials can be selectively set. Size,and structure of the clusters as well as the number of polymerizable groups per metal atom can be monitored by variations in the synthesis parameters. The cluster size and structure are governed by the ratio of metal oxide to ligand in the- educt mixture, but also by the nature of the radicals R in the alkoxides Ml { OR } ~, or MZ ( OR ) n used . Furthermore, the mechanical properties such as strength and fle::ibility can be influenced via the distance between the metal centres and polymerizable radicals, i:e. via the length of the spacer groups -Sp-.
In the case of the clusters according to formula (I), the polymerizable groups are fixed to a compact particulate cluster structure. The result of this is that, upon polymerization, rigid products with a high cross-linking density are obtained. The clusters represent three-dimensional molecules with a defined spatial structure and size and allow, upon co-polymerization with other components, an optimum cross-linking density to be set for the purpose in question. The structure of the clusters guarantees a complete incorporation of the clusters into the polymer network. It ensures a uniform environment for all the polymerizable organic ligands, so that these are practically equivalent as regards their reaction with organic co-monomers, which results in a uniform polymer structure developing around each ligand.
In addition, the abrasiveness or the optical properties such as for example the refractive index can be varied via the type and number of metal atoms.
Substances in which the clusters are soluble, i.e. liquid materials in particular; are preferred as further polymerizable components. Radically o.r ionically polymerizable mono- and polyfunctional compounds can primarily be considered here, in particular polymerizable organic monomers and silanes and polysiloxanes with polymerizable groups as well as mixtures of these compounds.
Ethylenically unsaturated organic monomers, in particular monofunctional or polyfunctional methacrylates which can be used alone or in mixtures are preferred as polymerizable organic monomers. Mono(meth)acrylates such as methyl, ethyl, butyl, benzyl, furfuryL, phenyl(meth)acrylate, isobutyl(meth)acrylate, cyclohexyl(meth}acrylate and polyfunctional (meth)acrylates-such as tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethylene . glycol di~meth)acrylate; polyethylene glycol di(meth}acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, bisphenol-A di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 2,2-bis-4-(3-methacryloxy-2-hydroxypropoxy)-phenylpropane (bis-GMA), pentaerythritol tetra(meth)acrylate as well as the reaction products from isocyanates, in particular di- and/or triisocyanates, and OH-group-containing (meth)acrylates can be considered as preferred examples of these compounds.
Examples of these are the reaction products of l mol 2,2,4-trimethylhexamethylene diisacyanate with 2 mol 2-hydroxyethylene methacrylate (UDMA) or 2 mol hydroxypropyl - I? -met:~acrylate as well as the reaction products of 2 mol glycerin dimethacrylate with 1 mol 2,2,4-trimethylhexamethylene diisocyanate, isophoron diisocyanate or re, a,cx' , cx' -tetramethyl-xylylene-m-diisocyanate . The use of polyfunctional (meth)acrylates is particularly preferred. By polyfunctional compounds are meant those with several polymerizable groups.
Further preferred polymerizable organic monomers are cationically polymerizable mono- or polyfunctional monomers such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis-(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, 3-ethyl-3-hydroxymethyl oxetane, 1;10-decanediylbis(oxymethylene)bis(3-ethyloxetane) and 3,3-(4-xylylenedioxy)-bis-(methyl-3-ethyl-oxetane).
Compounds which have polymerizable groups; preferably (meth)acryl groups, or rationally polymerizable groups, preferably epoxide, oxetane, spiroorthoesters or vinyl ether groups, are particularly suitable as polymerizable silanes and polysiloxanes. Suitable silanes and polysiloxanes and their preparation are described in DE 41 33 494 C2, DE 44 16 857 C1, EP 1 022 0?2 A2 and US
6,096,903. Preferred silanes are listed below.
Polysiloxanes based on these silanes are particularly preferred, the polysiloxanes being able to be present in the form of the homo- and co-condensates.
- LJ -Silanes of the general formula (1) are prefeT_red i Yinisl X miR 4_(nl-mi) ( ~-) in which the radicals X1, Y1 and Rl are the same or different and haves the following meanings:
R1 - alkyl, alkenyl, aryl, alkylaryl or arylalkyl, X1 - hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or DTRsz with RS -hydrogen, alkyl or aryl, Y1 - a substituent which contains a substituted or unsubstituted 1,4,6-trioxaspiro-[4,4]-nonane radical, n1 - 1, 2 or 3, ml - l, 2 or 3, with n1 + mi <_ 4, and silanes of the general formula (2), fXlnlRlltls~-[RZ(Al)1]4-(nl+ki)~~iBl (2) in which radicals Ai, R1, RZ and X1 are the same or different and have the following meanings:
AI - 0, S, PRE, PORE, NHC ( 0 ) 0 or NHC ( 0 ) ONRE, with RE - hydrogen, alkyl or aryl, B1 - a linear or branched organic radical which is -1=J-derived from a compound B-~ with at least one ( for 1 - l and A = NHC(0)0 or NHC(0)NR') or at least two C=C double bonds and 5 to 50 carbon atoms, with R~ = hydrogen, alkyl or aryl, Rl - alkyl, alkenyl, aryl, alkylaryl or arylalkyl, RZ - alkylene, arylene or alkylene arylene, X1 - hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkyicarbonyl, alkoxycarbonyl or NR~Z with R° -hydrogen, alkyl or aryl, n1 - l, 2 or 3, k1 - 0, 1 or 2, 1 - 0 or 1, X1 - an .integer the maximum value of which corresponds to the number of double bonds in the compound Bl minus 1 or is equal to the number of double bonds in the compound B1 when 1 = 1 and A
stands for NHC(0)0 or NHC{0)ONR'.
The silanes of the general formula (1) and (2) are hydrolyzable and polymerizable, the radicals Xi being hydrolyzable and the radicals Bl and Yi being polymerizable and in each case at least one radical B1, X~ and Yi with the above-named meaning being present in the silanes of the general formula {1} and (2). Polysiloxanes based on silanes {1) and/or {2) are preferred polymerizable components.
The alkyl radicals of the compounds ( 1 ) and ( 2 } are a . g .
linear, branched or cyclic radicals with 1 to 20~, _ j i _ preferably 1 to 10 carbon atoms, and Lower alkyl radicals with 1 to 6 carbon atoms are particularly preferred.
Special examples are methyl, ethyl, N-propyl, i-propyl, n-butyl, s-butyl, t-butyl, i-butyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl.
The alkenyl radicals are e.g. linear, branched or cyclical radicals with 2 to 20, preferably 2 to 10 carbon atoms and lower alkenyl radicals with 2 to 6 carbon atoms such as e.g. vinyl, allyl or 2-butenyl are particularly preferred.
Preferred aryl radicals are phenyl, biphenyl and naphthyl.
The alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl and amino radicals are preferably derived from the above-named alkyl and aryl radicals: Special examples are methoxy, ethoxy, n- and i-propoxy, n-, i-, s- and t-butoxy, methylamino, ethylamino, dimethylamino, diethylamino, N-ethylanilino, acetyloxy, propionyloxy, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenylethyl and tolyl.
The radicals named can optionally have one or more substituents; e.g. halogen, alkyl, hydroxyalkyl, alkoYy., aryl, aryloxy,. alkylcarbonyl, alkoxycarbonyl, furfuryl, tetrahydrofurfuryl, amino, alkylamino, dialkylamino, trialkylammonium, amido, hydroxy, formyl, carboxy, mercapto, cyano, isocyanato, nitro, epoxy, S03H and P04H2.
- l~ -Of the halogens, fluorine, chlorine and bromine are preferred.
The substituted or unsubstituted 1,4,6-trioxaspiro[4,4]-nonane groups are bound to the Si atom via alkylene or via alkenylene radicals which can be interrupted by ether or ester groups.
Further preferred are silanes according to the general formula (3) as well as polysiloxanes based on same B fA -~Z. )dl'R -IR -S1X a1R bl}cl in which the radicals and indices have the following meanings:
Bz - a linear or branched organic radical with at least one C=C double bond and 4 to 50 carbon atoms;
XZ - hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR'z;
R6 - alkyl, alkenyl, aryl, alkylaryl or arylalkyl;
R$ - alkylene, arylene, arylenealkylene or alkylenearylene with in each case 0 to 10 carbon atoms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups;
R' - hydrogen, alkyl or aryl;
AZ - 0, S or NH for di - Z and Z1 - CO
_ j% _ and R3 - al)cylene, arylene or a7 kylenearylene with in each case 1 to 10 carbon a oms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups, and R'' -COOH; or A2 - 0, S or NH for d1 - 1 and Z1 - CO
and R3 - alkylene, arylene or a7_kylenearylene with in each case I to 10 carbon atoms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups, and R~ - H~;
or AZ - 0, S, NH or C00 for dl - 1 and Z1 - CHR~, with R~ equal to H, alkyl, aryl or alkylaryl, and R3 - alkylene, arylene or allcylenearylene with in each case 1 to 10 carbon atoms, these radicals being able to be interrupted by oxygen and' sulphur atoms or by amino groups, and R4 - OH; or AZ - O, S, NH or COO for dl - 0 and R3 - alkylene, arylene or alkylenearylene with in each case 1to 10 carbon atoms, these radicals being able to be interrupted by oxygen and sulphur atoms or by amino groups, and R4 - OH; or AZ - S for dl - 1 and ZZ - CO and R3 - N and Rl' - H;
al - 1, 2 or 3;
b1 - 0, 1 or 2;
a1+bl - 3l c1 - 1, 2, 3 or 4.
The silanes of the formula (3} are polymerizable via the radicals ~~ and hydrolyzable via the radicals XZ.
The optionally present alkyl, alkenyl, aryl, alkoxy, acyloxy, alkylcarbonyl, aI)coxycarbonyl and amino radicals have the meanings defined for the formulae (1} and (2).
For al >_ 2 or b~ - 2, the radicals YZ and R' can in each case have tile Same or a different,meaning. The radical BZ is derived from a substituted or unsubstituted compound B'(A-H)~1 with at least one C=C double bond, such as a.g.
vinyl, alkyl, acryl and/or rnethacryl groups and 4 to 50, preferably 6 to 30 carbon atoms. Preferably, B' is derived from a substituted or unsubstituted compound with two or more acrylate or methacrylate groups. Such compounds are also called (meth)acrylates. If the compound B~(AZH)~; is substituted, the substituents can be selected from the substituents named above. The group AzH can be -OH, -SH, -NHZ or -COOH and c can assume values from 1 to 4.
Silanes according to formula (4} and polysiloxanes based on them are particularly preferred [ (Wq-R13 ZZ)P_Rlo]mZY2-R9-S1X3n2R83-n2 Formula (4}
in which X3 stands for.a halogen atom, a hydroxyl, alkoxy andlor acyloxy group;
n2 is equal to 1 to 3;
R8 stands for an alkyl, alkenyl, aryl, alkylaryl, arylallcyl group;
R9 stands for an alkylerie group;
R1° stands for a p-times substituted, linear, branched or cyclic, saturated or unsaturated, aromatic or aliphatic organic radical with 2 to 40 carbon atoms and optionally 1 to 6 heteroatoms;
R13 stands for a q-times substituted.linear, branched or cyclic organic radical with 1 to 20 carbon atoms or is absent;
p is equal to 1 or 2;
q is equal to 1 to 6;
Y2 stands for -NR11-; N or -(C=0)-NH-;
m2 is equal to 2 for YZ - N and equal to 1 for -Y --NR11- or -( C=0 } -NH-;
R11 stands for an alkyl or aryl group;
_ 'I <) _ Z~ stands for 0, S, -(C=0)-0-, -(C=0)-NH-, -0-(C=0)-P1H-or is absent;
W stands for CH,=CR~~ -{ C=0 ) -0-; and RlZ stands for a hydrogen atom or an alkyl group.
Suitable heteroatoms are phosphorus and preferably oxygen.
In connection with formula {4), by alkyl, acyloxy, alkoxy, alkenyl groups and allcylene groups are meant radicals which preferably contain 1 to 25 carbon atoms, particularly preferably 1 to 10 carbon atoms and quite particularly preferably 1 to 4 carbon atoms and optionally bear one or more substitutes such as for example halogen atoms, nitro groups or alkyloxy radicals. By aryl is meant radicals, groups or substituents which preferably have 6 to 10 carbon atoms and can be substituted as stated above. The above definitions also apply to composite groups such as for example alJcylaryl and arylalkyl groups . An aJ_l~ylaryl group thus designates for example an aryl group as defined above which is substituted with an alkyl group as defined above.
The alkyl, acyloxy, alkoxy, alkenyl groups and alkylene groups can be linear, branched or cyclical.
Preferred definitions, which can be selected independently of each other, for the individual variables of formula (4) are:
X3 - a methoxy and/or ethoxy croup;
n2 - 2 or 3;
R$ - a C1 to C3 alJcyl group, in particular a methyl group;
R9 - a C1 to C4 alkylene group;
R1° - a p-times substituted linear, branched or cyclic, saturated or unsaturated, aromatic or aliphatic organic radical with 2 to 10 carbon atoms and optionally a hetero atom, preferably an -ii) _ oxygen atom, particularly preferably a Ci to C~, alkenylene radical or a manocyclic radical with 4 to 10, in particular 5 to 8 carbon atoms;
R'' - a q-times substituted linear, branched or cyclical organic radical with 1 to 4 carbon atoms, particularly preferably a Ci to C3 alkylene radical;
p - 1 or 2, in particular l;
q - 1 or 2;
Yz - N or -(C=0)-NH-;
Zz - -(C=O)-; and/or R1z - a hydrogen atom or a methyl group.
Hydrolyzable and polymerizable oxetane silanes according to the general formula (5) and their stereoisomers as well as polysiloxanes based thereon are further preferred:
(5~ _ / \R16 R15 { R1~ SiX~R~? }
a Y :_a_~~ ~2 the variables R14 Rls Ri6 R:.7 Ris R'g Rzo ~l~ Ys az bz 1. , I I l 1 1 1 P 1 1 cz, and xz, unless otherwise stated, having the following meanings independently of each other:
R14 - hydrogen or substituted or unsubstituted C1 to C,o alkyl;
Rls - absent or substituted or unsubstituted C1 to Cls alkylene, C6 to Cls arylene, C~ to Cls alkylenearylene or arylenealkylene, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl, a~iide and urethane group;
R16 - absent or substituted or unsubstituted .
C1 to Cis alkylene, C6 to Cls arylene, C7 to Cls alkylenearylene or C7 to Cls arylenealkylene, , CA 02368323 2002-O1-17 these radi cals being able to be i nt~rrupted by at least one group selected from ether, thioether, ester, thioester, carbonyl, amide and urethane group or bear these in terminal position;
R~' - absent or substituted or unsubstituted Cl to C1$ alkyl, Cz to Cls alkenyl, C~ to C1$ aryl, C~ to C1$ alkylaryl or C~ to Clg arylalkyl, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl, amide and urethane group;
R1$ - absent or substituted or unsubstituted -CHRzo-CHRz°-, -CHRzo-CHRzo-S-R19-, -S-R19-, -Y3-CO-NH-R19- or -CO-0-R19-;
R19 - substituted or unsubstituted C1 to C1$ alkylene, C~ to Cls arylene, C~ to C18 alkylenearylene or C6 to C1$ arylenealkylene, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl; amide and urethane group;
~~zo - hydrogen or substituted or unsubstituted C1 to C1$ alkyl or C6 to Clo aryl;
X'' - a hydrolyzable group, namely halogen, hydroxy, allcoxy or acyloxy;
Y3 - 0 or S; ' az - 1, 2 or 3 ;
bz - l, 2 or 3;
c2 - 1 to 6; and x2 - 1, 2 or 3;
and on condition that ( i ) az+xz - 2 , . 3 or 4 and ( ii ) az and/or b2 - 1.
However, the above formulae cover only such compounds which are compatible with the doctrine of valence.
Normally, the silanes according to formula (5) are present as stereoisomer mixtures and in particular as racemic compounds.
The ether, thioether, ester, thioester, carbonyl, amide and urethane groups possibly present in the case of the radicals of formula (5) are defined by the following formulae: -0-, -S-, -CO-0-, -0-CO-, -CO-S-, -S-CO-, -CS-0-, -0-CS-, -CO-, -CO-NH-, -NH-CO-, -0-CO-NH- and -NH-CO-0-.
The non-aromatic radicals or non-aromatic parts of the radicals which can be present in formula (5) can be linear, branched or cyclic.
In the silanes according to formula (5), any alkyl radicals present have preferably I to 8 and particularly preferably 1 to 4 carbon atoms. Special examples of possible alkyl radicals are methyl, ethyl, n- and iso-propyl, sec.- and tert.-butyl, n-pentyl, cyclohexyl, 2-ethylhexyl and octadecyl.
In the silanes according to formula (5), any alkenyl 'radicals present have preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms. Special examples of possible alkenyl radicals are vinyl, allyl- and iso-butenyl.
Preferred examples of possible aryl radicals of the formula (5) are phenyl, biphenyl and naphthyl. Alkoxy,radicals have preferably l to 6 carbon atoms. Special examples of possible alkoxy radicals are methoxy, ethoxy, n-propoxy, iso-propoxy and tert.-butoxy. Acyloxy radicals have preferably 2 to 5 carbon atoms. Special examples are acetyloxy and propionyloxy.
Preferred alkylene radicals of formula (5) are derived from the above preferred alkyl radicals, and preferred arylene radicals are derived from the above preferred aryl radicals. Preferred radicals which consist of a combination of a non-aromatic and aromatic part are derived from the above preferred alkyl and aryl radicals. Special examples of this are benzyl, 2-phenylethyl and tolyl.
The named substituted R radicals of formula (5) bear one or more single substituents. Examples of these substituents are methyl, ethyl, phenyl, benzyl, hydroxymethyl, hydroxyethyl, methoxy, ethoxy, chlorine, bromine, hydroxy, mercapto, isocyanato, vinyloxy, acryloxy, methacryloxy, allyl, styryl, epoxy, carboxyl, S03H, P03Hz or P04HZ.
For a2, bZ, cZ or x2 ? 2, the radicals X4 as well as the individual R.radicals can in each case have the same or a different meaning.
In addition, preferred definitions exist for the variables of formula (5) set out above which, unless other~iise stated, can be selected independently of each other and are as follows:
R1'' hydrogen or C1 to CS allcyl;
-R15 C1 to Cs alkylene, these radicals being able to -be interrupted by at least one group selected from ether, thioether, ester and urethane group;
R16 absent or C1 to Cs alkylene, these radicals being -able to be interrupted by at least one group selected from ether, thioether, ester, thioester, carbonyl, amide and urethane group or bear these in terminal position;
Rl' absent or methyl, ethyl or phenyl;
-R1$ absent or -CHRZ-CHRZ-, -S-P.19-, --Y-CO-NH-R19- or --CO-0-R19-;
R19 C1 to Cs allcylene, these radicals being able to -be interrupted by at least one group selected from ether, thioether, ester, carbonyl, amide and urethane group;
R2 hydrogen or C1 to CS alJcyl;
-X4' methoxy, ethoxy or chlorine;
-Y~ - 0 or S ;
a- - 1;
'.~ z - 1 c2 - 1 to 6;
xz - 2 or 3; and/or az+xZ - 3.
The individual R radicals can in turn bear single substituents.
Preferred compounds according to formula (5) are accordingly those for which at least one of the variables of formula (5) meets the preferred definition described above.
Furthermore, oxetane silanes of formula (5) are preferred for which the indices az, b' and/or c' have the value 1.
The silanes (5) are polymerizable via the oxetane groups and hydrolyzable via the radicals X4.
The above-named silanes can be processed, either alone or together with other hydrolytically condensable compounds of silicon, aluminium, zirconium, titanium, boron, tin, vanadium and/or phosphorus to form polysiloxanes. These additional compounds can be used either per se or already in pre-condensed form.
Preferred further hydrolytically compounds of silicon are silanes of the general formula (6) Rzi~.z( z3Rzz)msSiX54-n;.z+m3) Formula ( 6 ) in which R-1 stands for a C, to Cs alkyl, C, to C-= all~enyl or C~ to Ci4 aryl group;
R" stands for a C1 to C$ al)cylene, Cz to Ci~ al)cenylene or C6 to C1,, arylene group;
XS stands for a hydrogen or halogen atom or a Ci to Cs alkoxy group;
Z3 stands for a glycidyl, acryl, methacryl, vinyl, allyl or vinylether group k2 is equal to 0, l, 2 or 3;
m3 is equal to 0, l, 2 or 3; and k2+m3 is equal to 0, l, 2 or 3.
Preferred definitions, which can be selected independently of each other, for the individual variables are:
R21 - a C1 to C3 alkyl, Cz to C5 alkenyl or a phenyl group;
a C1 to CS alkylene, CZ to C5 al)cenylene or a phenylene group;
XS - a halogen atom, a methoxy or ethoxy group;
Z3 - an acryl or methacryl group;
lcz - 0 and 1;
m3 - 0 and 1;
k2+m3 - 0, l or 2.
Such silanes are described for example in DE 34 07 087 A1.
Preferred zirconium, titanium compounds for the co-condensation with the named silanes are those according to formula (7) MeX6yRz3Z Formula ( 7 ) in which Me stands for Zr or Ti;
R'3 stands for a hydrogen atom, a substituted or unsubstituted C_ to C1~ alkyl, Ci to C15 alkylaryl or C~
to C1~ aryl group;
X6 stands for a halogen atom, a hydroxyl or C1 to C8 alkoxy group;
Y is equal to 1 to 4;
z is equal to 0 to 3.
Preferred definitions, which can be selected independently of each other, for the individual variables are:
Rz3 - a C1 to C5 alkyl or a phenyl group;
X6 - a halogen atom, a methoxy, ethoxy or propoxy group;
y - 4;
z - 0 or l, in particular 0.
Particularly preferred zirconium and titanium compounds are ZrCl4, Zr(OCZHS)4, Zr(OC3H7)4, Zr(OC4H9)4, ZrOClz, TiCl4, Ti ( OCZHS ) 4, Ti ( OC3H7 ),, and Ti ( OC4H~ ) 4 .
Preferred aluminium compozznds are those according to formula (8) AlRZ43 Formula ( 8 ) in which R24 stands for a halogen atom, a hydroxyl or C1 to C$
alkoxy group, preferably for a halogen atom or a C, to C; alkoxy group.
Particularly preferred aluminium compounds are Al(OCH3)3, A1 ( OCzH~ ) 3, A1 ( OC3H7 ) 3, Al ( OC4H9 ) 3 and AlCl3 .
'' ; _ In addition, boron trihalides, tin tetra.halides, tin tetraalkoxides and/or vanadyl compounds are suitable for co-condensation with the above-named silanes.
The curing of the materials takes place, depending on the initiator used, by thermal, photochemical or redoY-induced polymerization. , , Peroxides, in particular dibenzoyl peroxide, dilauroyl peroxide, tert.-butyl peroctoate and tert.-butyl perbenzoate are preferred as initiators for the hot-curing systems. Tn addition, azobisisobutyroethylester, 2,2'-azobisisobutyronitrile {AIBN}, benzopinacol and 2,2'-dialkylbenzopinacols are suitable.
Radical-supplying systems, for example benzoyl peroxide, lauroyl peroxide or preferably dibenzoyl peroxide, together with amines such as N,N-dimethyl-p-toluidine, N;N-dihydroxyethyl-p-toluidine, N,N-dimethyl-sym.-xylidine °or other structurally-related amines are used as initiators for cold polymerization. Amine and peroxide are usually distributed over two different components of the dental material. Upon mixing of the amine-containing base paste with the peroxide-containing initiator paste, the radical polymerization is initiated by the reaction of amine and peroxide.
Benzophenone and its derivatives as well as benzoin arid its derivatives can be used for example as initiators for photopolymerization. Further preferred photoinitiators are the a-dil:etones such as 9,10-phenanthrenquinone, diacetyl~, furil, anisil, 4,4'-dichlorobenzil and 4,4'-dialkoxybenzil.
Camphorquinone and 2,2-methoxy-2-phenyl-acetophenone and in particular cx-diketones in combination wiyth amines as reduction agents are particularly preferably used.
Preferred amines are 4-(N,N-dimethylamino}--benzoic acid ester, N,N-dimethylaminoethyl methacrylate, N,N-dimethyl-sym.-xylidine and triethanolamine. In addition, acyl phosphines such as e.g. 2,4,6-trimethylbenzoyldipher~yl- or bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphinic oxide are also particularly~suitable as photoinitiators.
For curing cationically polymerizable systems, diaryl-iodonium or triarylsulfonium salts such as e.g.
triphenylsulfonium hexafluorophosphate or hexafluoro-antimonate are particularly suitable as well as the photoinitiator systems described in X10 96/13538 and WO
98/47047.
Furthermore, the mixtures can be filled with organic or inorganic particles or fibres to improve the mechanical properties. In particular; amorphous, spherical materials based on mixed oxides of SiO~, ZrO~ and/or Ti02 with a mean average particle size of 0.005 to ?.0 Vim, preferably from 0.1 to 1 Vim, as disclosed for example in DE-PS 32 47 800, microfine fillers such as pyrogenic sili_cic acid ~or precipitation silicic acid as well as macro- or mini-fillers, such as quartz, glass ceramic or glaas powder with an average particle size of 0.01 to 20 Vim, preferably 0.5 to 5 ~cm as well as x-ray-opaque fillers such as ytterbium fluoride, are suitable as filler components. By mini-fillers are meant fillers with a parti cle s ize of 0 . 5 to 1.5 Vim, and by macro-fillers fillers with a particle size of l0 to 20 Vim.
Preferred compositions according to the invention contain, relative to their overall mass:
(a) 5 t~ 90% wt.-%, in particular 5 to 40 wt.-%, quite particularly preferably 10 to 20 wt.-% of one or more clusters according to formula (I), (b) 10 to 90 wt.-o, in particular 10 to 80 wt.-% of one or more further polymerizable components, (c) 0.1 to 5.0 wt.-%, in particular 0.2 to 2.0 polymerization initiator, and (d) 0 to 90 wt.-%, in particular 0 to 80 wt.-% filler.
The above composition can be further optimized in accordance with the desired use. Thus, a material which is particularly suitable as dental filling material preferably contains, in each case relative to the overaJ_l mass of the material:
( a ) 5 to 20 % wt . - % of one or more clusters according to formula (I), (b) 0 to 20 wt.-% of one or more further polymerizable components, (c) 0.2 to 2.0 wt.-% 2.0 polymerization initiator, and (d) 5 to 80 wt.-% filler.
A dental material which is particularly suitable as dental cement preferably contains, in each case relative to the overall mass of the material:
( a ) 5 to 30 % wt . - % of one or more clusters according to formula (I), (b) 0 to 30 wt.-% of one or more further polymerizable components, (c) 0.2 to 2.0 wt.-% 2.0 polymerization initiator, and (d) 5 to 50 wt.-% filler.
A dental material which is particularly suitable as dental coating material preferably contains, in each case relative to the overall mass of the material:
( a } 5 to 40 % wt . - % of one or more clusters according to formula ( I } , - .i() -{b) 5 to 80 wt.-~ of one or more further polymerizable components, {c) 0.2 to 2.0 wt.-% 2.O polymerization initiator, and (d) 0 to 40 wt.-% filler:
Quite particularly preferred are materials which contain, as further polymerizable component (b), 10 to 90 wt.-polysiloxane and 0 to 40 wt.-o polymerizable organic monomers, in each case relative to the overall mass of the dental material.
These compositions are particularly suitable as dental materials, quite particularly as adhesives, for example for inlays, coating materials, cements and in particular filling materials. In general, the compositions are particularly suitable for those uses in which the curing of the material takes place in the mouth cavity.
After polymerization, the dental material. s according to the invention have only a minimal content of unpolymerized constituents which can be dissolved out with aqueous or alcoholic solvents, which represents a significant improvement vis-a-vis conventional dental materials, as toxic side effects caused by monomeric constituents are suppressed.
According to the invention, clusters of a defined size and structure, i.e. pure, defined compounds of a known stoichiometry, are used for the preparation of dental materials, particularly preferably clusters with monodispersed mass distributiorx. In this way, the material properties of the dental materials, such as for example E-modulus, strength, hardness and abrasivity, can be set and improved in a controlled manner. Dental materials which contain 1 to 2 different.clusters are preferred.
In the following, the invention is explained in more detail using examples.
Example l:
Synthesis of the oxozirconium methacrylate cluster of composition Zr,,02( OMc ) 12 2.04 g (24 mmol) methacrylic acid were added to 1.73 g (3.6 mmol) of an 80% solution of zirconium butylate (Zr{OC4H9)4) in n-butanol. The reaction mixture was left to stand for a day at room temperature and the formed precipitate filtered off accompanied by the exclusion of moisture. I.09 g {86%
yield) of colourless cubic crystals resulted, which are soluble in chloroform, ethanol or toluene.
Example 2:
Synthesis of matrix substances based on silicic acid polycond.ensate A) Hydrolytic condensation of bis[(methacryloyloxy)pro-poxycarbonylethyl)-[3-{triethoxysilylpropyl))amine:
16.1g(26mmo1)bis[(methacryloyloxy)propoxy-carbonylethyl)-[3-(triethoxysilylpropyl)]amine which is obtainable by Michael addition of 3-aminopropyltriethoxysilane to 2-(acryloyloxyethyl)-propyl methacrylate (cf. ~P 1 022 022) were dissolved in 37.5 ml anhydrous ethanol and hydrolytically condensed accompanied by the addition of 2.81 g of an aqueous O.i N ammonium fluoride solution.
After 24 h stirring at room temperature, the volatile components were removed in vacuum and approx. 12 g of a relatively low-viscosity resin (SG-'1) with a viscosity of c = ca. 8 Pas {23°C) remained. This and all other viscosity data, unless otherwise stated, involves the rotation viscosity measured with a rotation rheometer with a _ j'7 _ paralle?-plate measuring system, CV = 120 (model CVO 120 of the company Bohlin).
B) Hydrolytic condensation of (3-triethoxysilyl-propylaminocarbonyl)butyric acid-(1,3{2)-bismethacryl-oyloxypropyl)ester:
10.9 g (20 mmol) {3-triethoxysilylpropylamido)butyric acid-(1,3-(2)-bismethacryloyloxypropyl)ester, which was obtained by amidation from 3-aminopropyltriethoxysilane with the adduct from glycerin dimethacrylate and glutaric acid anhydride ( cf . EP 1 022 012 ) , were dissolved in 98 . 2 mol anhydrous ethyl acetate and hydrolyticaJ_ly condensed accompanied by the addition of 1.08 g 0.5 N hydrochloric acid. After 30 minutes' 'stirring at 40°C, the volatile components were removed in vacuum. The resin obtained was then silylated after dissolving in a mixture of 35 g tert.-butylmethyl-ether, 12 g THF and 1.45 g {12 mmol) 2,4,5-trimethylpyridine by the dropwise additi_,on of 1 .96 g ( 18 mmol) trimethyichlorosilane. After st:L.r~rzng overnight at room temperature, the reaction mixt~.~re was washed with diluted hydrochloric acid and saturated NaCl solution and then dried over anhydrous sodium sulphate. After the evaporation of the solvent in vacuum, ca. 6 g of a viscous resin {SG-2} with a viscosity of r~ - ca. 75 Pas {23°C) remained.
Example 3:
Preparation of dental materials based on clusters according to example 1 ' various materials were prepared starting from the cluster Zr40z { OMc ) 1Z from example 1 and the matrix substances ST-1 and SG-2. The clusters were mixed with the matrix substances as 10% solution in ethanol and the solvent evaporated off in vacuum after the addition of the initiator components. The compositions (mass o) of the thus-prepared unfilled materials M-1 to M-5 are listed in Table 1. To determine the mechanical properties, testpieces with the dimens ions 2 5 x 2 x 2 mm were prepared from the compositions and cured by illumination with light of a wavelength of 390 to 500 nm (6 minutes). For this purpose, a dental radiation source~ of the Spectramat type from Vivadent was used. The bending strength (BS) and the bending E-modulus (BEM) were determined according to the ISO standard 4049 (2000), the testpieces having been previously stored in water at 37°C for 24 h. In addition, BS and BEM values were also measured for samples which were stored dry for 24 h at 37°C.
Table 1: Composition (mass %) of the unfilled materials M-1 to M-5 M-1* ) M-2 M-3* M-4 M_,-5 ) 9s.7 8s.7 _ -SG-2 - - 98.7 88.7 78.7 Zr-Cluster from - 10.0 - 10.0 20 Example 1 Photoinitiatora~ 1.3 1.3 1.3 1.3 1.3 *) Comparison example without clusters A mixture of 0.3o camphorquinone, 0.6% 4-(N,N-dimethylamino)-benzoic acid ethyl ester and 0.40 acryl phosphinic oxide (Lucerin TPO, BASF) was used as photoinitiator Table 2 : Bending strength ( BS ) and Bending E-modulus ( BEM) of materials M-1 to M-5 M-1* ~ 1"1-2M-3~ ~_.4 I M-5 ) )-i Dry BF {MPa) 46 47 48 59 70 - I
HZO storage BS (MPa) 31 52 36 60 60 Dry BEM (MPa) 1230 1900 1820 2100 2400 HZO storage BEM -(MPa) 1000 1920 1750 2270 2600 *) Comparison example without clusters To prepare the composite pastes C-1 to C-5, the unfilled materials'M-l to M-5 were mixed with the quantities of filler given in Table 3. Silanized pyrogenic silicic acid with an average primary particle size of 40 nm and a BET
surface of 50 mz/g (silanized Aerosil 0~-50, Degussa), ytterbium trifluoride with an average particle size of 5 ~m and a BET surface of < 7.5 m'/g (.YbF3, Auer Remy), silanized SiOZ-ZrOz mixed oxide with a primary particle size of 130 to 230 nm (Spharosil, Tokoyma Soda} and silznized barium silk ate glass (Ba-Si glass} with an average particle size of 1.2 ~m were used as fillers. The filler components are incorporated by means of a capsule vibrator.
The bending strength and the bending E-modulus were then measured, in each case after 24-hour storage in water or in the dry. The results are summarized in Table 4.
Table 3: Composition of the composite pastes C-1 to C-5 (values in mass o) R-1*) Y-2 K-3*) K-4 ~ IC-5 I.
Unfilled ma- 25.0 25.0 25.0 25.U 25.0 terial (M-1) (M-2) (M-3) {M-4) (M-5}
Aerosi:l OX-50 1.0 1.0 1.0 1.0 1.0 YbF3 15.0 15.0 15.0 15.0 15.0 Spharosil 15.0 15.0 15.0 15.0 15.0 i Ba-Si glass 44.0 44.0 44.0 44.0 44.0 *) Comparison example without clusters Table 4: Bending strength (BS) and bending E-modulus (BEM) of the composites C-1 to C-5 IZ_1* R_2 K_3* K_4 R-5 Dry BS (MPa) 94 96 89 101 103 HBO storage BS {MPa)' 68 100 89 110 113 Dry BEM (MPa) 6400 8900 8150 9100 9840 H20 storage BEM (MPa) 5500 9300 7160 9750 1.0900 *) Comparison without dusters The results show (Tables 2 and 4) that the addition of clusters of the composition Zr402(OMc)iz in each case leads to an improvement in strength and to an increase in E-modulus of the materials. In addition, in the case of the cluster-containing materials, an increase in the E-modulus after water storage can be observed, whereas the E-rnodulus _i(~ -decreases in the case of the non-modified samples M-1/C-1 and M-3/C-3 after water storage.
Samples of the cured composites C-2 and C-4 were crushed and the fragments dispersed in ethanol at 37°C. After 72 h, the solid constituents were filtered off and the filtrate concentrated to dryness. Almost no residue resulted, which indicates a complete incorporation of the polymerizabie components into the polymer network of the composite matrix.
Claims (33)
1. Dental material containing a cluster according to the general formula (I) [(M1)a(M2)b O c(OH)d(OR)e(L-Sp-Z)f] (I) wherein M1 is a metal atom of the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
M2 is a metal atom of the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
R is an alkyl group with 1 to 6 carbon atoms;
L is a co-ordinating group with 2 to 6 complexing centres;
Sp is a spacer group or is absent;
Z is a polymerizable group;
a is an integer from 1 to 20;
b is an integer from 0 to 10;
c is an integer from 1 to 30;
d is an integer from 0 to 30;
e is an integer from 0 to 30;
f is an integer from 2 to 30, any charge of the cluster (I) present being equalized by counterions.
M2 is a metal atom of the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
R is an alkyl group with 1 to 6 carbon atoms;
L is a co-ordinating group with 2 to 6 complexing centres;
Sp is a spacer group or is absent;
Z is a polymerizable group;
a is an integer from 1 to 20;
b is an integer from 0 to 10;
c is an integer from 1 to 30;
d is an integer from 0 to 30;
e is an integer from 0 to 30;
f is an integer from 2 to 30, any charge of the cluster (I) present being equalized by counterions.
2. Dental material according to claim 1, wherein M1 is Ti or Zr;
M2 is Ti or Zr;
R is an alkyl group with 1 to 4 carbon atoms;
L is .alpha.-hydroxycarboxylate (-CH(OH)-COO-), .alpha.-aminocarboxylate (-CH (NH2) -COO-) or .beta.-diketonate ([-C (-O-)=CH-C(=O)R k], with R k = alkyl);
Z is an ethylenically unsaturated group, an epoxide, oxetane, vinyl ether, 1,3-dioxalane or a spiroorthoester;
a is 2 to 11;
b is O to 4; and the spacer group is an alkylene group with 1 to 18 carbon atoms, an oxyalkylene group with 1 to 18 carbon atoms and 0 to 6 oxygen atoms or an arylene group with 6 to 14 carbon atoms, the spacer group optionally containing one or more of the groups 0, S, CO-O, O-CO, CO-NH, NH-CO, O-CO-NH, NH-CO-O and NH.
M2 is Ti or Zr;
R is an alkyl group with 1 to 4 carbon atoms;
L is .alpha.-hydroxycarboxylate (-CH(OH)-COO-), .alpha.-aminocarboxylate (-CH (NH2) -COO-) or .beta.-diketonate ([-C (-O-)=CH-C(=O)R k], with R k = alkyl);
Z is an ethylenically unsaturated group, an epoxide, oxetane, vinyl ether, 1,3-dioxalane or a spiroorthoester;
a is 2 to 11;
b is O to 4; and the spacer group is an alkylene group with 1 to 18 carbon atoms, an oxyalkylene group with 1 to 18 carbon atoms and 0 to 6 oxygen atoms or an arylene group with 6 to 14 carbon atoms, the spacer group optionally containing one or more of the groups 0, S, CO-O, O-CO, CO-NH, NH-CO, O-CO-NH, NH-CO-O and NH.
3. Dental material according to claim 1 or 2, wherein R is an alkyl group with 1 to 2 carbon atoms.
4. Dental material according to any one of claims 1 to 3, wherein R K is C1 to C6 alkyl.
5. Dental material according to claim 4, wherein R K is C1 to C3 alkyl.
6. Dental material according to claim 5, wherein R k is methyl, sulfonate (-SO3-), phosphonate (-PO3 2-) or carboxylate (-COO-).
7. Dental material according to claim 6, wherein R k is carboxylate (-COO-).
8. Dental material according to claim 2, wherein the spacer group is an alkylene group with 1 to 5 carbon atoms, optionally containing one or more of the groups 0, S, CO-O, O-CO, CO-NH, NH-CO, O-CO-NH, NH-CO-O and NH.
9. Dental material according to claim 8, wherein the spacer group is an alkylene group with 1 to 3 carbon atoms, optionally containing one or more of the groups 0, S, CO-O, O-CO, CO-NH, NH-CO, O-CO-NH, NH-CO-O and NH.
10. Dental material according to claim 2, 8 or 9, wherein the spacer group optionally contains 1 or 2 of the groups 0, S, CO-O, O-CO, CO-NH, NH-CO, O-CO-NH, NH-CO-O and NH.
11. Dental material according to claim 2, wherein Z is a methacrylic and/or acrylic group.
12. Dental material according to claim 2, wherein:
R is an alkyl group with 1 to 2 carbon atoms;
L is .alpha.-hydroxycarboxylate (-CH(OH)-COO-), .alpha.-aminocarboxylate (-CH (NH2) -COO-) or .beta.-diketonate ([-C (-O-) =CH-C (=O) R K], with R K = C1 to C6 alkyl);
Z is a methacrylic and/or acrylic group; and the spacer group optionally contains 1 or 2 of the groups 0, S, CO-O, O-CO, CO-NH, NH-CO, O-CO-NH, NH-CO-O and NH.
R is an alkyl group with 1 to 2 carbon atoms;
L is .alpha.-hydroxycarboxylate (-CH(OH)-COO-), .alpha.-aminocarboxylate (-CH (NH2) -COO-) or .beta.-diketonate ([-C (-O-) =CH-C (=O) R K], with R K = C1 to C6 alkyl);
Z is a methacrylic and/or acrylic group; and the spacer group optionally contains 1 or 2 of the groups 0, S, CO-O, O-CO, CO-NH, NH-CO, O-CO-NH, NH-CO-O and NH.
13. Dental material according to claim 12, wherein R K is C1 to C3 alkyl.
14. Dental material according to claim 13, wherein R K is methyl, sulfonate (-SO3-), phosphonate (-PO3 2-) or carboxylate (-COO-).
15. Dental material according to claim 14, wherein R K is carboxylate (-COO-).
16. Dental material according to claim 12, wherein the spacer group is an alkylene group with 1 to 6 carbon atoms.
17. Dental material according to claim 16, wherein the spacer group is an alkylene group with 1 to 3 carbon atoms.
18. Dental material according to any one of claims 1 to 3, wherein L-Sp-Z stands for acrylate, methacrylate, oleate, allyl acetoacetate and/or acetoacetoxyethyl methacrylate.
19. Dental material according to any one of claims 1 to 18, wherein the clusters contain 1 to 4 kinds of ligands of the type L-Sp-Z.
20. Dental material according to claim 19, wherein the clusters contain 1 or 2 kinds of ligands of the type L-Sp-Z.
21. Dental material according to any one of claims 1 to 20, wherein the cluster has a monodisperse mass distribution.
22. Dental material according to any one of claims 1 to 21, wherein the indices c to f assume values such that the positive charges of the metal or metals are completely equalized.
23. Dental material according to any one of claims 1 to 22, wherein M1 = M2-
24. Dental material according to claim 23, wherein M1 and M2 are zirconium.
25. Dental material according to one of claims 1 to 24, further comprising one or more further polymerizable components.
26. Dental material according to claim 25, wherein the further polymerizable components comprise a polymerizable, polysiloxane, an sonically and/or radically polymerizable organic monomer or a mixture thereof.
27. Dental material according to any one of claims 1 to 26, further comprising an initiator for ionic and/or radical polymerization.
28. Dental material according to claim 27, further comprising a filler and optionally further additives.
29. Dental material according to claim 25, further comprising an initiator for ionic and/or radical polymerization.
30. Dental material according to claim 29, further comprising a filler and optionally further additives.
31. Dental material according to claim 30, containing, relative to its overall mass (a) 5 to 90% wt.-% of at least one cluster according to formula (I), (b) 10 to 90 wt.-% of further polymerizable components, (c) 0.1 to 5.0 wt.-% polymerization initiator, and (d) 0 to 90 wt.-% filler.
32. Use of a cluster of the general formula (I) [(M1)a(M2)b O c(OH)d(OR)e(L-Sp-Z)f] (I) wherein M1 is a metal atom of the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
M2 is a metal atom the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
R is an alkyl group with 1 to 6 carbon atoms;
L is a co-ordinating group with 2 to 6 complexing centres;
Sp is a spacer group or is absent;
Z is a polymerizable group;
a is a number from 1 to 20;
b is a number from 0 to 10;
c is a number from 1 to 30;
d is a number from 0 to 30;
e is a number from 0 to 30; and f is a number from 2 to 30, any charge of the cluster (I) present being equalized by counterions, as dental material or for the preparation of dental material.
M2 is a metal atom the IIIrd or Vth main groups or the Ist to VIIIth sub-groups of the periodic table;
R is an alkyl group with 1 to 6 carbon atoms;
L is a co-ordinating group with 2 to 6 complexing centres;
Sp is a spacer group or is absent;
Z is a polymerizable group;
a is a number from 1 to 20;
b is a number from 0 to 10;
c is a number from 1 to 30;
d is a number from 0 to 30;
e is a number from 0 to 30; and f is a number from 2 to 30, any charge of the cluster (I) present being equalized by counterions, as dental material or for the preparation of dental material.
33. Use according to claim 32 as adhesive, coating material, cement or filling material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10102297.2 | 2001-01-19 | ||
| DE10102297A DE10102297B4 (en) | 2001-01-19 | 2001-01-19 | Dental materials based on metal oxide cluster compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2368323A1 true CA2368323A1 (en) | 2002-07-19 |
Family
ID=7671076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002368323A Abandoned CA2368323A1 (en) | 2001-01-19 | 2002-01-17 | Dental materials based on metal oxide clusters |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1224926B1 (en) |
| JP (1) | JP4230700B2 (en) |
| AT (1) | ATE282393T1 (en) |
| CA (1) | CA2368323A1 (en) |
| DE (2) | DE10102297B4 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11992538B2 (en) | 2019-08-19 | 2024-05-28 | Voco Gmbh | Polymerizable dental composition based on condensed silanes |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7102972B2 (en) * | 2018-06-25 | 2022-07-20 | 住友ゴム工業株式会社 | Complex and method for producing complex |
| JP7151210B2 (en) * | 2018-06-25 | 2022-10-12 | 住友ゴム工業株式会社 | Complex and method for producing complex |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3137840A1 (en) * | 1981-09-23 | 1983-03-31 | Röhm GmbH, 6100 Darmstadt | Zirconium methacrylate, process for the preparation thereof, and the use thereof as crosslinking agent |
| US5662886A (en) * | 1991-01-08 | 1997-09-02 | Minnesota Mining And Manufacturing Company | Adhesive amalgam system |
| US5508342A (en) * | 1994-02-01 | 1996-04-16 | The United States Of America As Represented By The Secretary Of Commerce | Polymeric amorphous calcium phosphate compositions |
| JP3524233B2 (en) * | 1995-08-23 | 2004-05-10 | 株式会社ジーシー | Dental inorganic-organic composite filler |
| US6126922A (en) * | 1995-11-17 | 2000-10-03 | 3M Innovative Properties Company | Fluorid-releasing compositions and compositions with improved rheology |
| DE19846660A1 (en) * | 1998-10-09 | 2000-04-13 | Inst Oberflaechenmodifizierung | Polymerizable metal oxide particles, e.g. useful in coating compositions, adhesives or sealants, comprise a metal oxide core functionalized with reactive groups |
| US6194481B1 (en) * | 1999-05-19 | 2001-02-27 | Board Of Regents Of The University Of Texas System | Mechanically strong and transparent or translucent composites made using zirconium oxide nanoparticles |
-
2001
- 2001-01-19 DE DE10102297A patent/DE10102297B4/en not_active Expired - Fee Related
-
2002
- 2002-01-16 JP JP2002007852A patent/JP4230700B2/en not_active Expired - Fee Related
- 2002-01-17 CA CA002368323A patent/CA2368323A1/en not_active Abandoned
- 2002-01-18 EP EP02001045A patent/EP1224926B1/en not_active Expired - Lifetime
- 2002-01-18 DE DE50201534T patent/DE50201534D1/en not_active Expired - Lifetime
- 2002-01-18 AT AT02001045T patent/ATE282393T1/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11992538B2 (en) | 2019-08-19 | 2024-05-28 | Voco Gmbh | Polymerizable dental composition based on condensed silanes |
Also Published As
| Publication number | Publication date |
|---|---|
| DE10102297B4 (en) | 2006-04-13 |
| JP4230700B2 (en) | 2009-02-25 |
| DE10102297A1 (en) | 2002-08-08 |
| ATE282393T1 (en) | 2004-12-15 |
| EP1224926B1 (en) | 2004-11-17 |
| JP2002241210A (en) | 2002-08-28 |
| EP1224926A1 (en) | 2002-07-24 |
| DE50201534D1 (en) | 2004-12-23 |
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| EEER | Examination request | ||
| FZDE | Discontinued |