EP2374445A2

Dual hardening multi-component dental composition

Abstract

Die Erfindung betrifft primär eine dualhärtende, mehrkomponentige dentale Zusammensetzung umfassend: (a) ein oder mehrere photopolymerisierbare Monomere ausgewählt aus der Gruppe bestehend aus Acrylaten und Methacrylaten, vorzugsweise der Gruppe der Methacrylate, (b) ein oder mehrere Photoinitiatoren, ausgewählt aus der Gruppe bestehend aus alpha-Diketonen, Benzoinalkylethern, Thioxanthonen, Benzophenonen, Acylphosphinoxiden, Acetophenonen, Ketalen, Titanocenen, Boraten und sensibilisierenden Farbstoffen, (c) ein oder mehrere Molekulargewichtsregler ausgewählt aus der Gruppe bestehend aus Verbindungen, die mit einem Radikal eines Monomers des Bestandteils (a) umsetzbar sind, wobei die Umsetzung unter Abstraktion eines H-Radikals aus dem Molekulargewichtsregler in Allylposition erfolgt, (d) ein oder mehrere Polymerisationsinhibitoren zur Erhöhung der Lagerstabilität der Zusammensetzung, vorzugsweise ausgewählt aus der Gruppe bestehend aus Hydrochinonmonomethylether (HQME), Phenolen, dabei vorzugsweise 2,6-Di-tert.butyl-4-methylphenol (BHT) und tert.-Butylhydroxyanisol (BHA), 2,2-Diphenyl-1-picrylhydrazyl-Radikalen, Galvinoxyl-Radikalen, Triphenylmethyl-Radikalen, 2,3,6,6,-Tetramethylpiperidinyl-1-oxylradikal (TEMPO) sowie dessen Derivaten und Phenothiazin sowie dessen Derivaten, (e) ein oder mehrere anorganische Füllstoffe, (f) ein oder mehrere Initiatoren für eine chemische Aushärtung bei Umgebungstemperatur, vorzugsweise ein Redoxinitiatorsystem, sowie gegebenenfalls ein oder mehrere weitere Additive. Die Erfindung betrifft ferner ein entsprechendes Verfahren zur Herstellung einer solchen Zusammensetzung sowie die Verwendung bestimmter Molekulargewichtsregler zur Herstellung einer dualhärtenden, mehrkomponentigen dentalen Zusammensetzung.

EP2374445A2, drawing sheet 1 — Sheet 1 of 1

Term

4.5 yearsto projected expiry

Projected expiry 12 April 2031, counted from filing; an application has no term until it is granted.

15 claims: 12 independent, 3 dependent

1
Dualhärtende, mehrkomponentige dentale Zusammensetzung umfassend:(a) ein oder mehrere photopolymerisierbare Monomere ausgewählt aus der Gruppe bestehend aus Acrylaten und Methacrylaten, vorzugsweise der Gruppe der Methacrylate, (b) ein oder mehrere Photoinitiatoren, ausgewählt aus der Gruppe bestehend aus alpha-Diketonen, Benzoinalkylethern, Thioxanthonen, Benzophenonen, Acylphosphinoxiden, Acetophenonen, Ketalen, Titanocenen, Boraten und sensibilisierenden Farbstoffen, (c) ein oder mehrere Molekulargewichtsregler ausgewählt aus der Gruppe bestehend aus Verbindungen, die mit einem Radikal eines Monomers des Bestandteils (a) umsetzbar sind, wobei die Umsetzung unter Abstraktion eines H-Radikals aus dem Molekulargewichtsregler in Allylposition erfolgt, (d) ein oder mehrere Polymerisationsinhibitoren zur Erhöhung der Lagerstabilität der Zusammensetzung, vorzugsweise ausgewählt aus der Gruppe bestehend aus Hydrochinonmonomethylether (HQME), Phenolen, dabei vorzugsweise 2,6-Di-tert.butyl-4-methylphenol (BHT) und tert.-Butylhydroxyanisol (BHA), 2,2-Diphenyl-1-picrylhydrazyl-Radikalen, Galvinoxyl-Radikalen, Triphenylmethyl-Radikalen, 2,3,6,6,-Tetramethylpiperidinyl-1-oxylradikal (TEMPO) sowie dessen Derivaten und Phenothiazin sowie dessen Derivaten, (e) ein oder mehrere anorganische Füllstoffe, (f) ein oder mehrere Initiatoren für eine chemische Aushärtung bei Umgebungstemperatur, vorzugsweise ein Redoxinitiatorsystem, sowie gegebenenfalls ein oder mehrere weitere Additive.
2
Dentale Zusammensetzung nach Anspruch 1, wobei die dentale Zusammensetzung zweikomponentig ist und vorzugsweise in Form zweier Pasten vorliegt.
3
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, wobei die dentale Zusammensetzung zweikomponentig ist und in Form einer Basispaste und einer Katalysatorpaste vorliegt, wobei vorzugsweise die gewichtsbezogenen Mischungsverhältnisse von Basispaste zu Katalysatorpaste im Bereich von 1 :2 bis 10 : 1 liegen, bevorzugt im Bereich von 1 : 1 bis 10 : 1 und/oder vorzugsweise Bestandteil (d) teilweise oder vollständig in der Katalysatorpaste enthalten ist.
4
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, insbesondere nach Anspruch 1, wobei Bestandteil (f) umfasst:(f-a) - ein oder mehrere Initiatoren, die ausgewählt sind aus der Gruppe bestehend aus anorganischen Peroxiden, organischen Peroxiden, anorganischen Hydroperoxiden, organischen Hydroperoxiden, Barbitursäurederivaten, Malonylsulfamiden, Protonensäuren, Lewis- oder Broensted-Säuren, solche Säuren freisetzenden Verbindungen und Carbeniumionen-Donatoren;- ein oder mehrere Co-Initiatoren ausgewählt aus der Gruppe bestehend aus tertiären Aminen, Schwermetallverbindungen, Verbindungen mit ionogen gebundenen Halogenen oder Pseudohalogenen und schwachen Broenstedt-Säuren, und/oder (f-b) ein Redoxinitiatorsystem umfassend (f-b1) Barbitursäure, Thiobarbitursäure, ein Barbitursäure- und/oder ein Thiobarbitursäurederivat, (f-b2) gegebenenfalls eine Peroxodisulfat- und/oder eine Peroxodiphosphatverbindung, (f-b3) eine Kupferverbindung, (f-b4) eine Verbindung mit einem ionogen vorliegenden Halogenatom, wobei die Initiatoren des Bestandteils (f) so auf separate Komponenten der dentalen Zusammensetzung verteilt sind, dass eine chemische Initiierung durch Vermischen der besagten Komponenten ausgelöst wird.
5
Dentale Zusammensetzung nach Anspruch 3 oder 4, wobei die Katalysatorpaste einen oder mehrere Initiatoren des Bestandteils (f-a) enthält, vorzugsweise eine oder mehrere peroxidhaltige Komponenten, und die Basispaste einen oder mehrere Co-Initiatoren des Bestandteils (f-a) enthält, vorzugsweise eine oder mehrere aminhaltige Komponenten.
6
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass ein oder mehrere der Molekulargewichtsregler des Bestandteils (c) Verbindungen mit zwei oder mehr Doppelbindungen sind, die durch Abstraktion eines Allyl-H-Atoms ein delokalisiertes Elektronensystem ausbilden können, das sich über 5 oder mehr C-Atome erstreckt, und bevorzugt ausgewählt sind aus der Gruppe der Monoterpene, dabei bevorzugt aus der Gruppe bestehend aus α-Terpinen, β-Terpinen, γ-Terpinen, α-Phellandren, β-Phellandren und Terpinolen, oder ausgewählt sind aus der Gruppe bestehend aus Linolsäure, Linolensäure und sonstigen substituierten oder nicht substituierten Cyclohexadienen, insbesondere bevorzugt ausgewählt aus der Gruppe bestehend aus α-Terpinen und γ-Terpinen.
7
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, umfassend Bestandteil (a) in einer Menge von 19 bis 70 Gew.-%, vorzugsweise in einer Menge von 30 bis 65 Gew.-%, Bestandteil (c) in einer Menge von 0,05 bis 5,00 Gew.-%, vorzugsweise von 0,1 bis 2,0 Gew.-%, bevorzugt von 0,1 bis 0,5 Gew.-%, und Bestandteil (e) in einer Menge von 25 bis 80 Gew.-%, vorzugsweise von 30 bis 65 Gew.-%, sowie vorzugsweise Bestandteile (b) und (f) in einer Gesamtmenge im Bereich von 0,25 bis 3 Gew.-%, vorzugsweise in einer Gesamtmenge im Bereich von 0,35 bis 1,5 Gew.-%, jeweils bezogen auf die Gesamtmasse der dentalen Zusammensetzung.
8
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, umfassend Bestandteil (a) in einer Menge von 19 bis 70 Gew.-%, vorzugsweise in einer Menge von 30 bis 65 Gew.-%, Bestandteil (b) in einer Menge von 0,05 bis 1,00 Gew.-%, vorzugsweise von 0,05 bis 0,5 Gew.-%, bevorzugt von 0,05 bis 0,2 Gew.-%, Bestandteil (c) in einer Menge von 0,05 bis 5,00 Gew.-%, vorzugsweise von 0,1 bis 2,0 Gew.-%, bevorzugt von 0,1 bis 0,5 Gew.-%, Bestandteil (e) in einer Menge von 25 bis 80 Gew.-%, vorzugsweise von 30 bis 65 Gew.-%, und Bestandteil (f) in einer Menge von 0,2 bis 2 Gew.-%, vorzugsweise von 0,3 bis 1,0 Gew.-%, jeweils bezogen auf die Gesamtmasse der dentalen Zusammensetzung.
9
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, wobei die Zusammensetzung neben einem oder mehreren Photoinitiatoren des Bestandteils (b) zusätzlich einen oder mehrere von Bestandteil (b) verschiedene Initiatoren für eine chemische Aushärtung bei Umgebungstemperatur des Bestandteils (f) enthält.
10
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass Bestandteil (a) ein oder mehrere Dimethacrylat-Monomere enthält gewählt aus der Gruppe bestehend aus Ethylenglykoldimethacrylat (EGDMA), 1,6-Hexandioldimethacrylat (HEDMA), Triethylenglykoldimethacrylat (TEGDMA), 1,12-Dodecandioldimethacrylat (DODMA), ethoxyliertes Bisphenol-A-dimethacrylat, Polyethylenglykoldimethacrylat (PEGDMA), 7,7,9-Trimethyl-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydimethacrylat (UDMA), Butandioldimethacrylat, Tetraethylenglykoldimethacrylat, Neopentylglykoldimethacrylat, 2-Hydroxypropyl-1,3-dimethacrylat, 3-Hydroxypropyl-1,2-dimethacrylat, Pentaerythritoldimethacrylat, Glycerindimethacrylat, Bisphenol-A-Glycidyl-Methacrylat (Bis-GMA) und Dimethacrylaten des Dihydroxymethyltricyclo[5.2.1.0 2,6 ]decans.
11
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass diese Bestandteil (d) in einer Menge von 0,005 bis 0,100 Gew.-% umfasst, vorzugsweise von 0,005 bis 0,075 Gew.-%, bevorzugt von 0,010 bis 0,050 Gew.-%, bezogen auf die Gesamtmasse der dentalen Zusammensetzung, und/oder das Verhältnis der Gesamtmasse des Bestandteils (c) zu der Gesamtmasse des Bestandteils (d) im Bereich von 1 :5 bis 100 : 1 liegt, vorzugsweise im Bereich von 1 : 1 bis 20 : 1, bevorzugt im Bereich von 10 : 1 bis 20 : 1, weiter bevorzugt im Bereich von 11 : 1 bis 20 : 1, besonders bevorzugt im Bereich von 12 : 1 bis 18 : 1.
12
Dentale Zusammensetzung nach einem der vorangehenden Ansprüche als dentales Füllungsmaterial, als fließfähiges Kompositmaterial (Flow-Material), als Kronenmaterial, als Brückenmaterial und/oder als Stumpfaufbaumaterial.
13
Dentale Spritze, vorzugsweise Doppelkammerspritze oder Doppelkammerkartusche mit Mischaufsatz, enthaltend eine dentale Zusammensetzung nach einem der vorangehenden Ansprüche.
14
Verfahren zur Herstellung einer dentalen Zusammensetzung nach einem der vorangehenden Ansprüche, mit folgenden Schritten:- Herstellen eines mehrkomponentigen, vorzugsweise zweikomponentigen Systems umfassend sämtliche der Bestandteile (a), (b), (c), (d), (e) und (f) sowie gegebenenfalls weitere Additive, wobei die Initiatoren des Bestandteils (f) so auf separate Komponenten der dentalen Zusammensetzung verteilt sind, dass eine chemische Initiierung durch Vermischen der besagten Komponenten ausgelöst wird.
15
Verwendung einer Verbindung mit zwei oder mehr Doppelbindungen, die durch Abstraktion eines Allyl-H-Atoms ein delokalisiertes Elektronensystem ausbilden kann, das sich über 5 oder mehr C-Atome der Verbindung erstreckt, bevorzugt eines Diens, das durch Abstraktion eines Allyl-H-Atoms ein delokalisiertes Elektronensystem ausbilden kann, das sich über 5 C-Atome erstreckt, vorzugsweise ausgewählt aus der Gruppe bestehend aus α-Terpinen und γ-Terpinen, als Molekulargewichtsregler bei der Polymerisation von Monomeren ausgewählt aus der Gruppe bestehend aus Acrylaten und Methacrylaten, vorzugsweise aus der Gruppe der Methacrylate, zur Herstellung einer dualhärtenden, mehrkomponentigen dentalen Zusammensetzung, vorzugsweise nach einem der Ansprüche 1 bis 12.

Independent claims15

183 paragraphs, as filed

p0001The present invention relates to a dual-curing multicomponent dental composition containing one or more specific additives (molecular weight regulator), a corresponding method for preparing such a composition and to the use of specific molecular weight regulators for the production of a dual-curing multi-component dental composition.

p0002A photo-curable composite materials are the dental materials most commonly used. Modern dental composites are usually a combination of an organic polymer matrix with inorganic fillers, wherein the inorganic phase is connected to the organic phase. The not yet crosslinked composition thus contains free monomers or monomer, inorganic fillers or filler mixtures, initiators and mostly dyes.

p0003The curing light-curable dental composite materials is carried out by photo-initiated polymerization. Here, chain reactions are, after photochemical activation of an initiator system, is introduced, in which there is a three-dimensional cross-linking to a conversion of liquid monomer to a solid polymer.

p0004The supply of prepared teeth with temporaries example in the crown and bridge restorations for patients is essential, as it involves a proper aesthetics, phonetics and occlusion is ensured. You also protects both the tooth structure from caries and fractures as well as the pulp from trauma or injury. They have also preserved the dentine of the ground tooth against thermal, chemical, mechanical and bacteriological stimuli that can lead to inflammatory processes in the pulp within a very short time.

p0005In the production of temporaries different methods may be used:<ul><li>In the direct method, a situation impression is taken, for example, prior to preparation of alginate or a silicone compound. After the preparation, the plastic composition is introduced into the impression and then repositioned in the patient's mouth.</li></ul>

p0006Alternatively, for example, already prefabricated plastic sleeves can be used, the temporary is created without previous situation impression. The sleeves are individually adapted in the mouth with scissors and cutter, filled with a self-polymerizing plastic and then placed on the prepared tooth.

p0007Materials for making temporary crowns and bridges need during their mouthing ensure the functioning of the temporaries. For this, the materials must meet a number of requirements.

p0008Thus, the materials should during their operations do not release toxic substances. The emission of harmful substances in the oral cavity could be done by diffusion, abrasion, reduction, and by dental activities such as grinding. In particular, the release of plastic monomers is to prevent having allergenic potential and could escape in the form of unconverted residual monomers by diffusion into the oral cavity.

p0009Furthermore, the material good mechanical properties, particularly with respect to hardness, strength, modulus of elasticity and abrasion should have to ensure, together with an optimal adaptation to the occlusal relationships, trouble-free operation during the time spent.

p0010The surface of the temporary should be smooth and mirror polishing. The smoothness of the material serves to prevent the accumulation of plaque, the polishing properties, the aim is to operate aesthetic concerns. A rough surface can also cause irritation of the tongue and cause misperceptions.

p0011The temporary should furthermore show along with the fixing material, a high marginal integrity to prevent the ingress of bacteria and substances.

p0012Furthermore, the material should not cause thermal damage during intraoral phase polymerization. By liberated during crosslinking heat energy no pain in the patient's mouth should be caused. Simultaneously, the material should achieve a full and dense coverage of the polished tooth surface and so protect the tooth from thermal and mechanical irritation.

p0013The nowadays customary crown and bridge materials are plastic-based and quite different in their chemical structure. They usually contain methacrylates, acrylates, as well as catalysts, inhibitors, cross-linking agents, plasticizers, accelerators, UV absorbers, fillers, etc .. The curing of these products takes place either chemically by autopolymerization by mixing two pastes, the so-called base paste with the so-called catalyst paste in the static mixing tube of a double-chamber cartridge, or dual-curing, ie, both chemically and by means of radiation of a suitable wavelength.

p0014A decisive disadvantage of autopolymerisierbaren plastic composition is the generation of heat during the exothermic polymerization which constitutes a danger to the pulp. The amount of heat released is dependent on the dosage of the catalyst system employed, of the forming mass (Abformstoff) and of the processing amount. In the literature different temperature peaks for temporary crown and bridge materials were measured by various working groups, which differ depending on the test configuration and chemical composition 25-94 ° C. In addition to the maximum temperature of the polymerization is also the shape of the temperature development of meaning. For example, the temperature development of curing a composition of a provisional crown and bridge material in a temperature-time diagram extend relatively flat at the beginning of the cross-linking, and then to deliver the time of maximum temperature, short and sharply rise and a lot of heat in a very short time , On the other hand may also assume a shape such a curve that a relatively long-lasting, but weaker heat development takes place.

p0015Self-curing temporary crown and bridge materials are usually first applied into the impression. Here, the most of two-component composition is forced through a static mixing tube of a double-chamber cartridge. The components are mixed with each other in the process and so brought to reaction. The tray filled with mixed impression material is then placed in the mouth and pressed onto the prepared stump. After the radically curable plastic material in the impression passes through its elastic phase, it is about 1 minute away from the die and taken out of the mouth, where it hardens extraorally to end. Here the setting time reached its maximum temperature.

p0016Already during the elastic phase, where not even the maximum temperature is reached, a state of the dental composition is rapidly reached at which it begins to gel and the outer shape does not change fundamentally. The viscosity of the composition is now so high that it becomes harder for the not yet reacted unsaturated groups to include a sufficient mobility to meet implementation partners. Usually free monomers remain in the network, which will be issued later to the environment in the mouth.

p0017A further disadvantage is the change occurring during the crosslinking density in the material which may lead to a change of the outer shape in the worst case. When the crown and bridge material will not harden its shape, so it can later lead to inaccurate fit. The crown then covers the stump is no longer completely. At these points later microorganisms could invade and attack the tooth stump from inside. This change in density is referred to as shrinkage or volume shrinkage of the reaction resin compound. It depends primarily on the number of unreacted functional groups. The shrinkage occurs both in the liquid state, that is at the very beginning of the polymerization, as well as during and after the gelation. The total shrinkage is divided into a physical and a chemical moiety. During the physical shrinkage is directionally determined and spatially extending from the outer regions of the polymer analogously and in accordance with the built temperature gradient inside the center of the thermosetting molding material, the chemical component is not directionally oriented, results solely from the polymer formation and is strongly influenced by the geometric conformation and configuration parameters of the newly established macromolecule depends.

p0018In light curable materials analogous problems may occur. It was found that a lower heat release and lower shrinkage forces occur when it is possible to be used the polymerization initially delayed. Such a polymerization process can be achieved when initially lower light power and a later increase of the light output to a maximum value, the polymerization is deliberately delayed. Due to the lower light output at the beginning of curing the material remains flowable for longer, the gel point is reached later, the mobility of the functional groups is maintained longer, so that higher conversion rates can be achieved. The technology used here is called "soft-start polymerization". It is next to the so-called "incremental technique", are light-cured individually in thin layers (time consuming), another technique to reduce high heat peaks and coupled with the release of heat shrinkage can.

p0019Approaches to provide low-shrinkage dental materials, such as<ul><li>the use of ring-opening metathesis polymerization (ROMP) curing, bicyclic monomers (<patcit id="pcit0001" dnum="DE19905093A1"><text>DE 199 05 093 A1</text></patcit>)</li><li>the addition of certain additives (coumarone, Polyvinyacetat, alcohol surfactants) prior to curing of the composition (<patcit id="pcit0002" dnum="DE19851038A1"><text>DE 198 51 038 A1</text></patcit>)</li><li>the use of cationically polymerizable oxetanes (<patcit id="pcit0003" dnum="US5750590A"><text>US 5,750,590</text></patcit>)</li><li>The use of epoxy resins, which contain nanoscale inorganic oxides and</li><li>the combination of different sized fillers (<patcit id="pcit0004" dnum="US6709271B1"><text>US No. 6,709,271 B1</text></patcit>)</li></ul> have not been able to enforce in practice.

p0020For autopolymerizing and, to a much greater extent for dual-curing dental compositions provide factors such as heat release and shrink concerns, that is currently met primarily through process and less in the chemical formulation of the dental composition.

p0021In <patcit id="pcit0005" dnum="EP1720506A"><text>EP 1720506</text></patcit>. <patcit id="pcit0006" dnum="WO2009083168A1"><text>WO 2009/083168 A1</text></patcit>. <patcit id="pcit0007" dnum="DE102008028306A1"><text>DE 10 2008 028 306 A1</text></patcit>. <patcit id="pcit0008" dnum="EP1872767A1"><text>EP 1872767 A1</text></patcit> as <patcit id="pcit0009" dnum="EP2070506A"><text>EP 2070506</text></patcit> are described various polymerizable dental materials. The disclosed therein dental materials can be cured by reaction with the oral or humidity thermal, chemical, photochemical and / or. Among many other stabilizers these documents disclose in the respective List of stabilizers among other terpinenes. A combination of photopolymerizable monomers and Terpinenen is not disclosed in the aforementioned documents.

p0022On another dental application field, namely the field of dental masking compounds, the problem of high heat generation in some cases, in systems of free-radical polymerization of photocurable compositions addressed by either of the composition shall be included and / or monomers nonreactive organic additives of high molecular weight, ie compounds having a low double bond content to use. There are so far the<patcit id="pcit0010" dnum="US6305936B1"><text>US 6,305,936 B1</text></patcit>. <patcit id="pcit0011" dnum="US6800671B1"><text>US 6,800,671 B1</text></patcit> and <patcit id="pcit0012" dnum="WO2008096182A"><text>WO 2008/096182</text></patcit> called.

p0023<patcit id="pcit0013" dnum="DE4233886C1"><text>DE 42 33 886 C1</text></patcit> discloses polymerizable conditioners on methacrylic base and a method of pretreating the surface of moldings from polyacrylate, polymethacrylate and polycarbonate plastics before application of polymerisable methacrylate material and the use of the conditioning agent. The conditioning agent may contain monocyclic terpene hydrocarbon. An intraoral use seems impossible because of the use of included among the toxicological concern Alkylmonomethacrylaten.

p0024<patcit id="pcit0014" dnum="DE2727480A1"><text>DE 27 27 480 A1</text></patcit> discloses impact-resistant, glass-like plastic alloys of polymethacrylates and aliphatic polyurethane ureas, are disclosed methods for their preparation, in which monomer mixtures are employed consisting of sulfur-containing molecular weight regulators. are not disclosed compositions for the dental field.

p0025<patcit id="pcit0015" dnum="DE1795395A"><text>DE 17 95 395 A</text></patcit> discloses methods for the production of polymers and copolymers of (meth) acrylic esters and acrylonitrile in the presence of polymerization catalysts and of compounds with a six ring having two non-conjugated double bonds, of which semicyclisch (exocyclic) may be. The specifically disclosed polymerization are thermal catalysts. Photoinitiators or photopolymerizable dental compositions are not disclosed.

p0026<patcit id="pcit0016" dnum="US4490497A"><text>US 4,490,497 A</text></patcit> discloses powder-liquid systems for a surgical cement that can be used in the preparation of dental extraoral prostheses. A liquid component of the composition as a "chain stopper" for example, a double unsaturated monocyclic terpene or a monounsaturated bicyclic terpene. Not disclosed are dual-curing compositions, particularly no dual curing dental compositions which are suitable for immediate use in the oral cavity. Furthermore, the described powder-liquid systems are not suitable for application by means of dental syringes. In the<patcit id="pcit0017" dnum="US4490497A"><text>US 4,490,497 A</text></patcit> described systems also have very long setting times. A link between the use of "chain stopper" and polymerization (such as alkyl-substituted monophenols) is not disclosed.

p0027<patcit id="pcit0018" dnum="DE3010373A1"><text>DE 30 10 373 A1</text></patcit> discloses methods for the polymerization of methyl methacrylate or mixtures thereof with other vinyl monomers in the presence of enol ethers. The polymers prepared by the method disclosed, although referred to as particularly suitable for use in the dental field, for example for the production of prostheses according to the powder-liquid process, however, not disclosed are dual-curing multicomponent compositions.

p0028<patcit id="pcit0019" dnum="EP1720506B1"><text>EP 720 506 B1 1</text></patcit> discloses a filled and polymerizable dental material and a method for its preparation. The following examples are mentioned: dental filling materials, core materials, materials for temporary crowns and bridges, dental cements, adhesives, materials for artificial teeth, veneering, sealants and dental lacquers. It is disclosed that the dental material for certain properties may contain additives or modifiers; be found in a long list of examples, "terpinenes". however are not disclosed dual-curing, multi-component compositions comprising a molecular weight regulator.

p0029The skilled artisan, for example, the dentist, wants a (possible) long extraoral processing time and then the shortest possible intraoral setting time after insertion into the mouth (ie, generally at slightly elevated temperature). The cure must not be accompanied by a large exothermic reaction, since it may be permanently damaged at high temperatures living tooth.

p0030In order to influence processing time and setting time, a dental composition can be varied. If one increases with an otherwise identical composition, for example, the added amount of a polymerization inhibitor in a radical polymerizable composition, shall be extended regularly both the working time and the setting time, which is proportional to the delay of cure in approximately to the added amount of polymerization inhibitor.

p0031It was the object of the invention, dual-curing dental (dental chemical and simultaneously curing) to provide compositions, which have over the compositions of the prior art, a lower heat generation and reduced shrinkage.

p0032A special dental task was to provide a filled, dual-curing dental composition (especially a composite material, which is used as a dental filling material as the flowable composite, as crown material as bridge material and / or as core build-up material), which should be capable of application with a dental syringe and should preferably which are present in the form of two pastes, ie in the form of a paste-paste system.

p0033Further, the processing time should be sufficiently long setting time and at the same time as short as possible. This should take place, that is an acceptable maximum temperature during curing of dental composition in the oral cavity are not exceeded despite the shortest possible setting time the lowest possible temperature development.

p0034The present invention relates to a dual-curing, multi-component dental composition comprising:<ol><li>(A) one or more photopolymerizable monomers selected from the group consisting of acrylates and methacrylates, preferably the group consisting of methacrylates,</li><li>(B) one or more photoinitiators selected from the group consisting of alpha-diketones, benzoin alkyl ethers, thioxanthones, benzophenones, acylphosphine oxides, acetophenones, ketals, titanocene, borates and sensitizing dyes,</li><li>(C) one or more molecular weight regulator selected from the group consisting of compounds having a radical of a monomer of the component (a) be implemented, in which the reaction takes place under abstraction of a hydrogen radical from the molecular weight regulator in the allyl position,</li><li>(D) one or more polymerization inhibitors to improve storage stability of the composition, preferably selected from the group consisting of hydroquinone monomethyl ether (HQME), phenols, preferably 2,6-di-tert-butyl-4-methylphenol (BHT) and tert butylhydroxyanisole (BHA), 2,2-diphenyl-1-picrylhydrazyl radicals, galvinoxyl radicals, triphenylmethyl radicals, 2,3,6,6, 1-oxyl--Tetramethylpiperidinyl (TEMPO) and its derivatives, and phenothiazine as well as its derivatives .</li><li>(E) one or more inorganic fillers, </li><li>(F) one or more initiators for chemical curing at ambient temperature (preferably 23 ° C), preferably a redox initiator system,</li></ol>and optionally one or more further additives.

p0035It has surprisingly been found that it is possible to provide dental compositions based on photopolymerizable monomers from the group of acrylates and methacrylates in the form of the inventive dual-curing, multi-component dental compositions which do not emit large amounts of heat to the environment and low physical shrinkage and exhibit high crosslinking rates and no adverse amounts of unreacted monomers containing more after hardening of the material that can later accept a detrimental effect on the tissue.

p0036Surprisingly, it was further found that a combination of one or more molecular weight regulators of component (c) and one or more polymerization inhibitors of component (d) in the dual-curing inventive dental compositions leads to such a curing behavior and such a polymerization kinetics that after mixing (eg in a static mixing tube) a long extraoral processing of the dental material is possible (see. Notes to the processing time below), however, after intra-oral application, rapid curing and tying takes place (see FIG. Notes to the setting below).

p0037Since compositions of the invention are dual-curing, the polymerization or curing is usually accelerated by exposure to light.

p0038can Briefly by the compositions of the invention, in particular in one of the configurations identified below as preferred or particularly preferred, thus to a certain extent a comparatively long processing time can be achieved without causing the setting time would be extended accordingly.

p0039The terms and definitions of "working time" and "setting" and the methods of determination relate in the present context to the DIN EN ISO 4049 (March 2010).

p0040The working and setting times for different inventive dual cure, two-component dental compositions containing 0.02 wt .-% of the polymerization inhibitor BHT (2,6-di-tert-butyl-4-methyl phenol; compound of the component (d)) and different amounts of γ terpinene (compound of the component (c)) (an otherwise identical composition) are in <figref idrefs="f0001">Fig.1</figref> illustrated.

p0041The working and setting times for different non-inventive dual cure, two-component dental compositions containing various amounts of the polymerization inhibitor BHT (an otherwise identical composition) in the absence of a molecular weight regulator in accordance with component (c) are in <figref idrefs="f0001">Fig.2</figref> shown.

p0042According to the DIN EN ISO 4049 method, the processing time is 23 ° C measured at a (form) and the setting time at 37 ° C. This (form) temperatures correspond usual extraoral or intraoral conditions.

p0043<figref idrefs="f0001">Fig.1</figref> illustrates the working and setting times at a constant amount of BHT as a function of the content of γ-terpinene an otherwise identical inventive dental composition. The abscissa of<figref idrefs="f0001">Fig.1</figref> indicates the percentage content of γ-terpinene in the respective composition on the ordinate, the time in seconds. The processing times determined in accordance with the dashed line with triangles, the determined set times of the solid line with squares.

p0044<figref idrefs="f0001">Fig.2</figref> illustrates an example of the working and setting times, depending on the content of BHT in an otherwise identical composition. The abscissa of<figref idrefs="f0001">Fig.2</figref> indicates the percentage content of BHT in the respective composition on the ordinate, the time in seconds. The processing times determined in accordance with the dashed bottom line with triangles, the determined set times of the solid top line with squares.

p0045Out <figref idrefs="f0001">Fig.1</figref> is immediately apparent that the setting time increasingly with increasing content differs from the processing time of γ-terpinene, so to speak, there is a decoupling of setting time and processing time.

p0046Out <figref idrefs="f0001">Fig.2</figref> however, is immediately apparent that the curve for the Abbindezeitwerte for processing time values corresponds qualitatively and - in the examples specifically studied - the setting is each slightly longer than the corresponding processing time.

p0047The in <figref idrefs="f0001">Figures 1 and 2</figref> Results shown resulting from our own studies with compositions in accordance with or based on the recipe of the reference example and the formulations of the examples Exp invention. 1 to Exp. 4. Exact details are given below (see also the following Tables 1, 1A-1, 1A-2 and 1B).

p0048A preferred inventive dental composition has a set time (in accordance with DIN EN ISO 4049, as specified above) of at most 10 minutes, preferably not more than 6 minutes, more preferably of at most 3 minutes.

p0049A preferred inventive dental composition is two-component, and is preferably in the form of two pastes.

p0050Inventive dual-curing compositions are in the form of a base paste and a catalyst paste in general. A preferred inventive dental composition is two-component and is in the form of a base paste and a catalyst paste, wherein preferably the weight-related mixing ratios of base paste to catalyst paste is in the range of 1: 2 to 10: 1, preferably in the range from 1: 1 to 10: 1 ,

p0051In a preferred embodiment, component (d) partially or completely contained in the catalyst paste of a dental composition according to the invention.

p0052A preferred inventive dental composition is a dental syringe, in particular with a double syringe or double cartridge chamber, via a cannula, preferably a static mixing tube, and be discharged to apply.

p0053Preference is given to double-chamber syringes and double chamber cartridges with mixing attachment, because with these rapid and bubble-free mixing in well-defined mixing ratios is possible.

p0054A preferred dental composition according to the invention has application in the mouth at a flow behavior and such a stability, that a down-running or spreading of the applied dental composition does not occur.

p0055Preferably the viscosity is at least one component, but preferably the viscosity of each component of the dental composition according to the invention is greater than or equal to 10 Pas and preferably in the range of 10 Pas to 190 Pas, particularly preferably in the range from 20 to 140 Pas.

p0056At higher viscosity values, in particular above 190 Pas, the flow properties of the composition is significantly worse and is made of a conventional dental mixing tips only very poorly expressible.

p0057Dental compositions having a viscosity in the most preferred range from 20 to 140 Pas can be particularly comfortable using conventional dental mixing tips and apply in both the patient and for the dentist a pleasant manner in the oral cavity, without or unwanted drop formation comes to a flowing away.

p0058The viscosities reported here relate to the measurement at 23 ° C with a plate-plate rheometer (plate diameter: 25 mm) with a shear rate of 10 / sec. at a slit width of 1 mm.

p0059According to the invention also preferably is a dental composition, wherein component (f) comprises:<ul><li>(fa)<ul><li>one or more initiators, which are selected from the group consisting of inorganic peroxides, organic peroxides, inorganic hydroperoxides, organic hydroperoxides, barbituric, Malonylsulfamiden, proton acids, Lewis or Bronsted acids, such acids releasing compounds and carbenium ion donors such as preferably methyl triflate or triethyl;</li><li>one or more co-initiators selected from the group consisting of</li></ul>tertiary amines, heavy metal compounds, in particular compounds of the 8th and the 9th of the Periodic Table ( "iron and copper group"), compounds with ionic bonded halogens or pseudo halogens, preferably quaternary ammonium halides, and weak Brønsted acids such. as alcohols and water, and or</li><li>(Fb) a redox initiator system comprising</li><li>(F-b1) barbituric acid, thiobarbituric acid, a barbituric acid and / or a thiobarbituric acid derivative,</li><li>(F-b2) optionally, a peroxodisulfate and / or a peroxodiphosphate compound,</li><li>(F-b3) a copper compound,</li><li>(F-b4) a compound having a ionic present halogen atom,</li></ul>wherein the initiators of the component (f) are distributed to separate components of the dental composition that a chemical initiation by mixing the said components is triggered.

p0060The skilled person is known diverse initiator systems for chemical curing as well as corresponding redox initiator. It is so far to the example<patcit id="pcit0020" dnum="EP1720506A"><text>EP 1720506</text></patcit> and especially the <patcit id="pcit0021" dnum="EP1839640A"><text>EP 1839640</text></patcit> referenced and the documents cited therein.

p0061Molecular weight regulator (hereinafter referred to briefly as regulators) are known and commercially available per se. They are used, for example, in the solution polymerization of olefins, in the emulsion polymerization of methacrylates or for the production of moldings of PMMA molding compounds (PMMA = polymethyl methacrylate) by compression molding or injection molding. Molecular weight regulators are so-called transfer reagents which enter into a free radical reaction-transfer reactions and mechanistic H abstraction and transfer of the radical function includes the dial. The controller will then be due to its function in the form of end groups in the crosslinked polymer again.

p0062Conventional regulators are aldehydes and ketones such as formaldehyde, acetaldehyde, propionaldehyde, <i>n</i>Butyraldehyde, isobutyraldehyde, methyl ethyl ketone, acetone, methyl isobutyl ketone, formic acid, ammonium formate, hydroxylammonium sulfate and hydroxylammonium phosphate, compounds which contain sulfur in organically bound form, such as di-<i>n</i>-butylsulfid, di-<i>n-</i>octyl sulfide, diphenyl sulfide, Düsopropyldisulfid, di-<i>n</i>-butyldisulfid, di-<i>n</i>-hexyldisulfid, Diacetyldisulfid and di-tert-butyl trisulfide, compounds containing sulfur in the form of SH groups have, as <i>n</i>-Butylmercaptan, <i>n</i>-Hexylmercaptan and <i>n</i>Dodecyl mercaptan, octadecyl mercaptan, other sulfur compounds such as hydrogen sulfites, disulfites, compounds such as mercaptoethanol, mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioglycolic acid, Diethanolsulfid, thiodiglycol, ethylthioethanol, 2,2,4,6,6-pentamethylheptane-4- thiol, 2,2,4,6,6,8,8-heptamethylnonane-4-thiol, thiourea, dimethyl sulfoxide, ethylhexyl, pentaerythritol tetrathioglycolate, mercaptopropyltrimethoxysilane, then allyl compounds such as allyl alcohol, allyl bromide, or benzyl such as benzyl chloride or alkyl halides such as chloroform, or bromotrichloromethane carbon tetrachloride, carbon tetrabromide , methylene chloride, further lower and higher molecular weight monohydric or polyhydric alcohols such as methanol, ethanol,<i>n</i>-propanol, Isopropanol, tert-butanol, sec-butanol, <i>n</i>Butanol, amyl alcohol, cyclohexanol, octanol, dodecanol, 1-ethylhexanol, glycerol, stearyl alcohol, oleyl alcohol, hydroxyethyl methacrylate, or amines such as triethylamine and toluene or ethylbenzene.

p0063However, the regulator above are unsuitable for the intended use here. So have sulfur-containing molecular weight regulators intensive and typically unpleasant odor, separate them as a component of a dental material from. Dental compositions according to the invention therefore preferably do not comprise a sulfur-containing molecular weight regulator. Further, it was found that alcohols, lower- or higher-molecular, one-or multi-valued, develop any regulatory action in the compositions and remain ineffective. The same applies to aldehydes and ketones.

p0064The exact reason for the success in the invention using the above molecular weight regulator (c) is not known in detail. However, presumably, a particular advance not to be expected, the interaction between the monomer or monomers and the one or more molecular weight regulators, which makes it possible that, on during the photopolymerization, the composition of the invention the molecular weight regulator (c) in a manner and to an extent influence the polymerization process takes that chain length, crosslinking and residual monomer content of the polymer being formed are designed such that the desired properties are obtained.

p0065According to the invention suitable molecular weight regulators are, for example, various terpenes, particularly terpinenes (α-terpinene, β-terpinene, γ-terpinene), phellandrene (α-Phellandren, β-Phellandren) and terpinolene (also called δ-terpinene), 1,4-cyclohexadiene ( optionally substituted), substituted 1,3-cyclohexadiene (as appropriate), 1,4-Dihydronaphtalin, 1,4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran or dimeric α-styrene (2,4-diphenyl-4-methyl -1-pentene) and linoleic acid and α-linolenic acid.

p0066According to the invention as a component (c) a composition of the invention to be used molecular weight regulators are compounds having two or more double bonds, preferably compounds having two or more double bonds, which can form through abstraction of an allyl-H atom a delocalized electron system, extending over 5 or more C extends -atoms, preferably dienes which can form through abstraction of an allyl-H atom a delocalized electron system, extending over 5 carbon atoms.

p0067According to the invention as a component (c) a composition of the invention to be used molecular weight regulators are selected from the group of monoterpenes, preferably from the group of monoterpene dienes, preferably from the group consisting of α-terpinene, β-terpinene, γ-terpinene, α-Phellandren , β-phellandren and terpinolene or are selected from the group consisting of linoleic acid, linolenic acid and other substituted or unsubstituted cyclohexadiene.

p0068According to particularly preferred regulators are α-terpinene and γ-terpinene, particularly preferably γ-terpinene. These molecular weight regulators the best results were achieved according to the present invention.

p0069In a composition of the invention also relates to mixtures of molecular weight regulators can be used, of course.

p0070According to the invention comprise preferred dental compositions

p0071Component (a), in a quantity of 19 to 70 wt .-%, preferably in an amount of 30 to 65 wt .-%

p0072Component (c) in an amount of 0.05 to 5.00 weight .-%, preferably from 0.1 to 2.0 wt .-%, preferably from 0.1 to 0.5 wt .-%, and

p0073Component (e) in an amount of 25 to 80 wt .-%, preferably from 30 to 65 wt .-%,

p0074in each case based on the total mass of the dental composition.

p0075According to the invention comprise preferred dental compositions

p0076Constituents (b) and (f) in a total amount ranging from 0.25 to 3 wt .-%, preferably in a total amount in the range of 0.35 to 1.5 wt .-%, based on the total mass of the dental composition ,

p0077According to the invention comprise preferred dental compositions

p0078Component (e) in an amount of at least 10 wt .-%, preferably of at least 20 wt .-%, preferably of at least 25 wt .-%, and preferably at the same time

p0079Constituents (b) and (f) in a total amount ranging from 0.25 to 3 wt .-%, preferably in a total amount in the range of 0.35 to 1.5 wt .-%, and / or preferably at the same time

p0080Component (d) in an amount from 0.005 to 0.100 wt .-%, preferably 0.005 to 0.075 wt .-%, preferably from 0.010 to 0.050 wt .-%,

p0081in each case based on the total mass of the dental composition.

p0082According to the invention further include preferred dental compositions

p0083Component (a), in a quantity of 19 to 70 wt .-%, preferably in an amount of 30 to 65 wt .-%

p0084Component (c) in an amount of 0.05 to 5.00 weight .-%, preferably from 0.1 to 2.0 wt .-%, preferably from 0.1 to 0.5 wt .-%,

p0085Component (e) in an amount of 25 to 80 wt .-%, preferably from 30 to 65 wt .-%, and

p0086Constituents (b) and (f), in a total amount ranging from 0.25 to 3 wt .-%, preferably in a total amount in the range of 0.35 to 1.5 wt .-%

p0087in each case based on the total mass of the dental composition.

p0088According to the invention further include preferred dental compositions

p0089Component (a), in a quantity of 19 to 70 wt .-%, preferably in an amount of 30 to 65 wt .-%

p0090Component (b) in an amount of 0.05 to 1.00 wt .-%, preferably from 0.05 to 0.5 wt .-%, preferably from 0.05 to 0.2 wt .-%,

p0091Component (c) in an amount of 0.05 to 5.00 weight .-%, preferably from 0.1 to 2.0 wt .-%, preferably from 0.1 to 0.5 wt .-%,

p0092Component (e) in an amount of 25 to 80 wt .-%, preferably from 30 to 65 wt .-%, and component (f) in an amount of 0.2 to 2 wt .-%, preferably of 0.3 to 1.0 wt .-%,

p0093in each case based on the total mass of the dental composition.

p0094In the present text in a multicomponent system called the "total mass of the dental composition" the total mass of all the components of the dental composition.

p0095A preferred dental composition according to the invention contains one or more photoinitiators of component (b) additionally comprises one or more of component (b) various initiators for chemical curing at ambient temperature (preferably 23 ° C) of the component (f).

Component (a) - photopolymerizable monomers

p0096The radically photopolymerizable monomers, at least two ethylenic group-containing substances such as his, but are not limited to, those typically used in dental chemistry in composite materials (meth) acrylate monomers.

p0097In a variety of inventive compositions are preferably dispensed with the presence of methyl methacrylate as methyl methacrylate is considered of toxicological concern. Therefore an inventive dental composition preferably includes at most 5 wt .-% methyl methacrylate, preferably at most 2 wt .-%, more preferably at most 1 wt .-%, particularly preferably at most 0.5 wt .-%, each based on the total weight of the composition , In a further preferred embodiment of an inventive dental composition is free of methyl methacrylate.

p0098In a preferred embodiment, component (a) contains a dental composition according to the invention no Alkylmonomethacrylate. In a further preferred embodiment comprises an inventive dental composition is at most 5 wt .-% of Alkylmonomethacrylaten, preferably at most 2 wt .-%, preferably at most 1 wt .-%, more preferably at most 0.5 wt .-%. Particularly preferred is an inventive dental composition free from Alkylmonomethacrylaten.

p0099In the patent literature a number of other compounds is known (for example, in the <patcit id="pcit0022" dnum="DE3941629A1"><text>DE 39 41 629 A1</text></patcit>Which in the present application is by way of reference), which are diesters of acrylic or methacrylic all and are suitable for use in a composition of the invention.

p0100In a preferred dental composition according to the invention contains component (a) one or more dimethacrylate monomers selected from the group consisting of ethylene glycol dimethacrylate (EGDMA), 1,6-hexanediol dimethacrylate (Hedma), triethylene glycol dimethacrylate (TEGDMA), 1,12-dodecanediol dimethacrylate (DODMA) , ethoxylated bisphenol-A dimethacrylate, polyethylene glycol dimethacrylate (PEGDMA), 7,7,9-trimethyl-4,13-dioxo-5,12-diazahexadecan-1,16-dioxydimethacrylat (UDMA), butanediol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 2- hydroxypropyl-1,3-dimethacrylate, 3-hydroxypropyl-1,2-dimethacrylate, pentaerythritol dimethacrylate, glycerol dimethacrylate, bisphenol-A-glycidyl methacrylate (bis-GMA) and dimethacrylates of Dihydroxymethyltricyclo [5.2.1.0<sup>2.6</sup>] Decane.

p0101Explicitly preferably the corresponding dimethacrylates or diacrylates of Dihydroxymethyltricyclo [5.2.1.0 are<sup>2.6</sup>] Decane as described in the publications <patcit id="pcit0023" dnum="DE1816823"><text>DE 1816823</text></patcit>. <patcit id="pcit0024" dnum="DE2419887"><text>DE 2419887</text></patcit>. <patcit id="pcit0025" dnum="DE2406557"><text>DE 2406557</text></patcit>. <patcit id="pcit0026" dnum="DE2931926"><text>DE 2931926</text></patcit>. <patcit id="pcit0027" dnum="DE3522005"><text>DE 3522005</text></patcit>. <patcit id="pcit0028" dnum="DE3522006"><text>DE 3522006</text></patcit>. <patcit id="pcit0029" dnum="DE3703120"><text>DE 3703120</text></patcit>. <patcit id="pcit0030" dnum="DE102005021332"><text>DE 102005021332</text></patcit>. <patcit id="pcit0031" dnum="DE102005053775"><text>DE 102005053775</text></patcit>. <patcit id="pcit0032" dnum="DE102006060983"><text>DE 102006060983</text></patcit>. <patcit id="pcit0033" dnum="DE69935794"><text>DE 69935794</text></patcit> and <patcit id="pcit0034" dnum="DE102007034457"><text>DE 102007034457</text></patcit> described, which are part of the present application by way of reference.

p0102The free-radically photopolymerizable monomers can also be at least one ethylenic double bond-containing hydroxyl compounds. It all hydroxyl compounds of acrylates or methacrylates normally used in dental chemistry can be used. Preference is given to hydroxyl compounds of methacrylates, thereby in turn, preferably 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 1,2-dihydroxypropyl, 1,3-dihydroxypropyl, 2,3-dihydroxypropyl methacrylate, 2-hydroxypropyl-1,3-dimethacrylate, 3 hydroxypropyl-1,2-dimethacrylate, pentaerythritol dimethacrylate, glycerin dimethacrylate, 2,2-bis [4- [3-methacryloyloxy-2-hydroxypropoxy] phenyl] propane.

p0103In a further preferred embodiment, there is component (a) a dental composition according to the invention from monomers selected from the group consisting of (meth) acrylate monomers having at least two ethylenic groups and hydroxyl compounds of acrylates or methacrylates, or component (a) includes such monomers.

p0104In a further preferred embodiment is part of (a) a dental composition according to the invention from monomers selected from the group consisting of methacrylate monomers having at least two ethylenic groups and hydroxyl compounds of methacrylates, or component (a) includes such monomers.

p0105Furthermore, the so-called Ormocere that are known to those skilled and the example in the <patcit id="pcit0035" dnum="DE19903177"><text>DE 199 03 177</text></patcit> or in the <patcit id="pcit0036" dnum="DE4416857"><text>DE 44 16 857</text></patcit> are described, usable, which are part of the present application by way of reference.

p0106An inventive composition may further contain one or more acid group-containing curable substances. Acid group-containing monomers may preferably a carboxylic acid, phosphoric acid, a phosphonic acid, a sulfonic acid and / or a Thiophosphorsäurefunktion exhibit.

p0107The acid group-containing, photo-curable compound may be a polymerizable monomer containing one or more acid functional groups in one molecule.

p0108Suitable phosphoric acid group-containing monomers are, for example, 2- (meth) acryloyloxyethyldihydrogenphosphat, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphat, 6- (meth) -acryloyloxyhexyldihydrogenphosphat, 10- (meth) acryloyloxydecyldihydrogenphosphat (MDP) 6- (meth) -acryloyloxyhexylphenylhydrogenphosphat, 10- (meth) acryloyloxydecyldihydrogenphosphat, 1,3-di (meth) acryloyloxypropane-2-dihydrogenphosphate, 1,3-di (meth) acryloyloxypropane-2-phenylhydrogenphosphat and bis [5- ( 2- (meth) acryloyloxyethoxycarbonyl) heptyl] hydrogenphosphate.

p0109Suitable carboxylic acid group containing monomers are, for example, 4- (meth) acryloxyethyltrimellithsäure (4-MET), 4- (meth) acryloxyethyltrimellithsäureanhydrid (4-META), 4- (meth) acryloxydecyltrimellithsäure, 4- (meth) acryloxydecyltrimellithsäureanhydrid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di (meth) acryloyloxypyromellithsäure, 2- (meth) acryloyloxyethylmaleinsäure, 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethylhexahydrophthalic acid.

p0110Other suitable acid-functional monomers are for example in the <patcit id="pcit0037" dnum="EP0980682B1"><text>EP 980 682 B1 0</text></patcit> or the <patcit id="pcit0038" dnum="EP0948955A"><text>EP 0948955</text></patcit> called, which are part of the present application by way of reference.

p0111Further, the phosphoric esters can be used with glycerol or with hydroxyethyl methacrylate or hydroxypropyl methacrylate with.

p0112The aforementioned photopolymerizable monomers can be used individually or in mixtures.

Component (b) - photoinitiators

p0113Examples of a photo-curing initiator include catalysts that act solely a photo and combinations of sensitizer and accelerators.

p0114Examples of photosensitizers are alpha-diketones, benzoin, thioxanthones, benzophenones, acylphosphine oxides, acetophenones, ketals, titanocene, sensitizing dyes, etc. The sensitizers may be used alone or in combination. Specific substance examples of the different classes are found for example in the<patcit id="pcit0039" dnum="DE102006019092A1"><text>DE 10 2006 019 092 A1</text></patcit> or in the <patcit id="pcit0040" dnum="DE3941629C2"><text>DE 39 41 629 C2</text></patcit>Which are part of the present application by way of reference.

p0115Examples of accelerators which are used together with sensitisers, are tertiary amines, secondary amines, barbituric acids, tin compounds, aldehydes and sulfur compounds. Specific substance examples of the different classes are found in the<patcit id="pcit0041" dnum="DE102006019092"><text>DE 10 2006 019 092</text></patcit> or in the <patcit id="pcit0042" dnum="DE3941629C2"><text>DE 39 41 629 C2</text></patcit>Which are part of the present application by way of reference.

p0116Further suitable initiators and initiator combinations are <patcit id="pcit0043" dnum="DE60116142"><text>DE 601 16 142</text></patcit> described, which are part of the present application by way of reference.

p0117The usable in the present invention, photoinitiators are characterized in that they or by absorption of light in the wavelength range of 300 nm to 700 nm, preferably from 350 nm to 600 nm and particularly preferably from 380 nm to 500 nm, optionally in combination with a more coinitiators can effect curing of a composition according to the invention.

p0118The absorption maximum of camphorquinone (CC) is approximately 470 nm, which is in the range of blue light. Camphorquinone (CC) is one of the PI<sub>2</sub>Initiators and is regularly used together with a co-initiator.

p0119Preferably a composition of the invention includes the combination of an alpha-diketone and an aromatic tertiary amine, preferred is the combination of camphorquinone (CC) and ethyl<i>p</i>-<i>N, N</i>-dimethylaminobenzoat (DABE).

p0120Also preferred is the further combination of system "alpha-diketone / aromatic tertiary amine" with a phosphine oxide, in particular with the phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide and / or the 2,4,6-trimethylbenzoyl. With respect to the structures of suitable phosphine oxides for use in a composition of the invention is to the publications<patcit id="pcit0044" dnum="DE3801511C2"><text>DE 38 01 511 C2</text></patcit>. <patcit id="pcit0045" dnum="DE102006050153A1"><text>DE 10 2006 050 153 A1</text></patcit>. <patcit id="pcit0046" dnum="EP0184095B1"><text>EP 184 095 B1 0</text></patcit>. <patcit id="pcit0047" dnum="DE4231579C2"><text>DE 42 31 579 C2</text></patcit>. <patcit id="pcit0048" dnum="EP0366977B1"><text>EP 366 977 B1 0</text></patcit>. <patcit id="pcit0049" dnum="US7081485B2"><text>US 7,081,485 B2</text></patcit>. <patcit id="pcit0050" dnum="DE3236026A1"><text>DE 32 36 026 A1</text></patcit>. <patcit id="pcit0051" dnum="US20070027229A1"><text>US 2007/0027229 A1</text></patcit>. <patcit id="pcit0052" dnum="EP0262629B1"><text>EP 262 629 B1 0</text></patcit>. <patcit id="pcit0053" dnum="EP0073413A"><text>EP 0073413</text></patcit>. <patcit id="pcit0054" dnum="US7148382B2"><text>US 7,148,382 B2</text></patcit>. <patcit id="pcit0055" dnum="US5761169A"><text>US 5,761,169</text></patcit>. <patcit id="pcit0056" dnum="DE19708294A1"><text>DE 197 08 294 A1</text></patcit>. <patcit id="pcit0057" dnum="EP0057474A"><text>EP 0057474</text></patcit>. <patcit id="pcit0058" dnum="EP0047902A"><text>EP 0047902 A</text></patcit>. <patcit id="pcit0059" dnum="EP0007508A"><text>EP 0007508</text></patcit>. <patcit id="pcit0060" dnum="DE60029481T2"><text>DE 600 29 481 T2</text></patcit>. <patcit id="pcit0061" dnum="EP0980682B1"><text>EP 980 682 B1 0</text></patcit>. <patcit id="pcit0062" dnum="EP0948955B1"><text>EP 948 955 B1 0</text></patcit>. <patcit id="pcit0063" dnum="EP1236459B1"><text>EP 236 459 B1 1</text></patcit> and <patcit id="pcit0064" dnum="EP0173567A2"><text>EP 0173567 A2</text></patcit> referenced, which are part of the present application by way of reference.

p0121The phosphine oxides indicated in these documents are suitable. Especially alone or in combination with the system "alpha-diketone / amine" as photopolymerization in the inventive compositions

p0122Alternatively, borate salts, such as those in <patcit id="pcit0065" dnum="US4772530A"><text>US 4,772,530</text></patcit>. <patcit id="pcit0066" dnum="US4954414A"><text>US 4,954,414</text></patcit>. <patcit id="pcit0067" dnum="US4874450A"><text>US 4,874,450</text></patcit>. <patcit id="pcit0068" dnum="US5055372A"><text>US 5,055,372</text></patcit> and <patcit id="pcit0069" dnum="US5057393A"><text>US No. 5,057,393</text></patcit> are described, are used as photoinitiators use, which are part of the present application by way of reference.

p0123Further suitable photoinitiators are, in <nplcit id="ncit0001" npl-type="b"><text>J.-P. Fouassier, photoinitiation, Photopolymerization and Photocuring, Hanser Publishers, Munich, Vienna, New York 1995</text></nplcit> as in <nplcit id="ncit0002" npl-type="b"><text>JF Rabek (eds.), Radiation Curing in Polymer Science and Technology, Vol. 11, Elsevier Applied Science, London, New York 1993</text></nplcit> described, which are part of the present application by way of reference.

Component (f) - initiators for chemical curing

p0124The person skilled in various initiators known for chemical curing. It is so far to the example<patcit id="pcit0070" dnum="EP1720506A"><text>EP 1720506</text></patcit> referenced.

p0125Preferred initiators for chemical curing are benzoyl peroxide (BPO), lauroyl peroxide, especially dibenzoyl peroxide in combination with amines such as N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine as well as structurally related amines.

p0126The peroxides and the amines are thereby separated onto different components of the dental material. When mixing the amine-containing component (so-called base paste) to the peroxide component (the so-called initiator or catalyst paste) is initiated by the reaction of amine and peroxide (redox reaction), the free-radical reaction.

p0127Dual-curing systems comprise a combination of photoinitiators and initiators for chemical curing.

p0128For example, the base paste additionally contain a photoinitiator, so that the base paste can be used either alone as light-curing or together with the initiator paste as light- and self-curing dental material.

p0129In addition to the oxidative effect, organic peroxide compounds can be used as redox systems also barbituric or barbituric and Malonysulfamide.

p0130Of the barbituric acid systems the so-called "Bredereck systems" are of great importance. Examples of suitable "Bredereck systems" as well as references to the corresponding patent literature can be found in the<patcit id="pcit0071" dnum="EP1839640A"><text>EP 1839640</text></patcit> as in <patcit id="pcit0072" dnum="DE1495520"><text>DE 1495520</text></patcit>. <patcit id="pcit0073" dnum="WO02092021A"><text>WO 02/092021</text></patcit> or in <patcit id="pcit0074" dnum="WO02092023A"><text>WO 02/092023</text></patcit>Which are part of the present application by way of reference.

p0131Suitable Malonysulfamide are <patcit id="pcit0075" dnum="EP0059451A"><text>EP 0059451</text></patcit> describes what is in the present application by way of reference. Preferred compounds are 2,6-dimethyl-4-isobutylmalonylsulfamid, 2,6-DÜsobutyl-4-propylmalonylsulfamid, 2,6-dibutyl-4-propylmalonylsulfamid, 2,6-dimethyl-4-ethylmalonylsulfamid and 2, 6-Diocytyl- 4-isobutylmalonylsulfamid.

p0132Further, sulfur compounds in the oxidation state +2 or +4, such as sodium benzenesulfinate or Natriumparatoluolsulfinat can be used.

p0133To accelerate the curing, the polymerization in the presence of heavy metal compounds, such as Ce, Fe, Cu, Mn, Co, Sn, or Zn may be carried out, wherein copper compounds are especially preferred. The heavy metal compounds are preferably used in the form of soluble organic compounds. Preferred copper compounds are copper benzoate, copper acetate, Kupferethylhexanoat, Kupferdi (methacrylate), copper acetylacetonate and copper naphthenate.

Component (d) - polymerization

p0134The dental compositions of the invention contain one or more inhibitors, also known as stabilizers. These are added to a composition in order to avoid spontaneous polymerization. They react with prematurely forming radicals, which are intercepted, prevent premature polymerization and increase the storage stability of the photocurable dental composition. Common inhibitors include phenol derivatives such as hydroquinone monomethyl ether (HQME) or 2,6-di-tert-butyl-4-methylphenol (BHT). Further inhibitors such as 2,2-diphenyl-1-picrylhydrazyl-, galvinoxyl, triphenylmethyl radicals, 2,3,6,6, 1-oxyl radicals -Tetramethylpiperidinyl-(TEMPO) and derivatives of TEMPO or phenothiazine and derivatives of this compound are in of the<patcit id="pcit0076" dnum="EP0783880B1"><text>EP 783 880 B1 0</text></patcit> described which are part of the present application by way of reference. Alternative inhibitors are in the<patcit id="pcit0077" dnum="DE10119831A1"><text>DE 101 19 831 A1</text></patcit> or in the <patcit id="pcit0078" dnum="EP1563821A1"><text>EP 1563821 A1</text></patcit> indicated that they are in the present application by way of reference.

p0135An inventive dental composition further comprises (D) one or more polymerization inhibitors to improve storage stability of the composition, preferably selected from the group consisting of hydroquinone monomethyl ether (HQME), phenols, preferably 2,6-di-tert-butyl-4-methylphenol (BHT) and tert butylhydroxyanisole (BHA), 2,2-diphenyl-1-picrylhydrazyl radicals, galvinoxyl radicals, triphenylmethyl radicals, 2,3,6,6, 1-oxyl--Tetramethylpiperidinyl (TEMPO) and its derivatives, and phenothiazine as well as its derivatives ,

p0136According to the invention as component (d) a composition of the invention to be used molecular weight regulators are selected from the group consisting of phenols, particularly preferred are 2,6-di-tert-butyl-4-methylphenol (BHT) and tert-butyl hydroxyanisole (BHA). The polymerization of the component (d) are not capable of hydrogen abstraction in the allyl position in contrast to the molecular weight regulators of the component (c).

p0137If however, in individual cases, a polymerization inhibitor at the same time as one can be considered for hydrogen abstraction in allyl more capable molecular weight regulator, this is construed for the purposes of the present text as molecular weight regulator, in particular for quantitative considerations.

p0138The combination of one or more molecular weight regulators of component (c) and one or more polymerization inhibitors of component (d) in a dual-curing, the inventive dental composition multicomponent results, especially in the designated preferred embodiments that after mixing the two or more components a long extraoral processing of the composition is made possible in the mixed state and hardens after the intraoral application of the composition in the mixed state this quickly.

p0139The presence of one or more polymerization inhibitors of the component (d), preferably of BHT and / or TEMPO, in an inventive dental composition, in particular in the above preferred amounts and proportions, so is advantageous because the storage stability of a dental composition according to the invention significantly increased becomes. The relevant here or effect of the molecular weight regulator (c) is not impaired.

p0140An inventively preferred dental composition comprises component (d) in an amount from 0.005 to 0.100 wt .-%, preferably 0.005 to 0.075 weight .-%, preferably 0.010 to 0.050 wt .-%, in each case based on the total mass of the dental composition.

p0141Be markedly higher amounts of component (d) is used, the curing of the dental composition is slowed down appreciably.

p0142In further accordance with the invention preferred dental compositions, the ratio of the total mass of component (c) is to the total mass of the component (d) ranges from 1: 5 to 100: 1, preferably in the range from 1: 1 to 20: 1, preferably in the range from 10: 1 to 20: 1, more preferably in the range from 11: 1 to 20: 1, more preferably in the range from 12: 1 to 18: 1st

p0143In summary, ensuring such a combination of component (c) and (d) in addition to the effects already set out above, in particular in one of the embodiments identified as preferred, also<ul><li>a very good storage stability, </li><li>upon polymerization of the dental composition according to the invention, an adjustable / tailored molecular weight distribution after curing, and</li><li>an acceptable maximum temperature (T<sub>Max</sub>) In the polymerization of the dental composition in the oral cavity.</li></ul>

Ingredient (e) - inorganic fillers

p0144The inorganic fillers may be used alone or as mixtures. To optimize the product properties, the inorganic fillers may be incorporated in different grain sizes in the formulations. The fillers can have a unimodal or polymodal, for example a bimodal distribution.

p0145An inventively preferred dental composition comprises ingredient (s) in an amount of least 10 wt .-%, preferably at least 20 wt .-%, preferably at least 25 wt .-%, based on the total mass of the dental composition.

p0146The total amount of inorganic fillers in a dental composition according to the invention is preferably at most 95 wt .-%, preferably at most 90 wt .-%, more preferably at most 85 wt .-%, based on the total mass of the composition.

p0147The total amount of inorganic fillers in a dental composition according to the invention is preferably at least 25 wt .-%, preferably at least 30 wt .-%, more preferably at least 40 wt .-%, based on the total mass of the composition.

p0148As inorganic fillers compact glasses and different silicas come in various sizes and states (monodisperse, polydisperse) used.

p0149Suitable inorganic constituents are, for example, amorphous materials based on mixed oxides of SiO<sub>2</sub> ZrO<sub>2</sub> and / or TiO<sub>2</sub> microfine fillers such as pyrogenic silicic acid or precipitation silicic acid as well as macro- or mini-fillers such as quartz-glass ceramic or glass powder, barium silicate, Bariumfluorsilikatgläser, strontium silicate glasses, Strontiumborsilikat, Li / Al-silicate glasses, Bariumgläser, calcium silicates, sodium aluminum silicates, fluoroaluminosilicate glasses, oxides of aluminum or silicon, zeolites , apatite, zirconium silicates, hardly soluble metal salts such as barium sulfate or calcium fluoride and radiopaque fillers such as ytterbium fluoride.

p0150For better incorporation into the polymer matrix, the fillers can be surface-modified. An example is the surface treatment of fillers with a silane. As adhesion promoter is especially the methacryloxypropyltrimethoxysilane.

p0151To adjust the rheology, inventive dental compositions different silicas, preferably fumed silicas contain.

p0152In addition, reinforcing materials such as glass fibers, polyamide or carbon fibers can be used. The dental composition may further contain fine particle splinters or bead polymers, wherein the bead polymers can be homopolymers or copolymers organically curable monomers.

p0153In a variety of inventive compositions is preferably used no or a relatively small proportion of organic filler, because some dental applications certain, that require relatively high mechanical properties that are not achievable with organic filler.

p0154When present, the total amount of organic filler particles in a dental composition according to the invention preferably at most 40 wt .-%, preferably at most 35 wt .-%, based on the total mass of the composition.

p0155Where a dental composition according to the invention comprises organic filler particles, the proportion is preferably in the range of 5 to 35 wt .-%, based on the total mass of the composition.

p0156A variety of preferred inventive dental compositions comprising no organic filler.

p0157The total amount of inorganic and organic filler particles in a dental composition according to the invention is preferably at most 95 wt .-%, preferably at most 90 wt .-%, more preferably at most 85 wt .-%, based on the total mass of the composition.

p0158UV absorbers which are capable, for example, through their conjugate Doppelbindungssytemen and aromatic rings, to absorb UV radiation, may optionally be a component of a dental composition according to the invention. Examples of UV absorbers are 2-hydroxy-4-methoxybenzophenone, salicylic acid or 3- (2'-hydroxy-5'-methylphenyl) benzotriazole.

p0159Since the teeth are to restore as faithfully as possible, it is necessary to provide dental compositions of the invention in a variety of shades. We used for this purpose usually inorganic dyes and organic pigments in very small quantities.

p0160The marked respectively above as preferred or particularly preferred embodiments of a composition of the invention also apply in particular in combination with other as preferred or particularly marked preferred embodiments of an inventive composition.

p0161In accordance with the foregoing, includes a particularly preferred inventive dual-curing, two-component dental composition in the form of two pastes:<ol><li>(A) one or more photopolymerizable monomers selected from the group consisting of methacrylates,</li><li>(B) one or more photoinitiators selected from the group consisting of alpha-diketones, benzoin alkyl ethers, thioxanthones, benzophenones, acylphosphine oxides, acetophenones, ketals, titanocene and borates, preferably selected from the group of alpha-diketones, preferably camphorquinone,</li><li>(C) one or more molecular weight regulator selected from the group consisting of α-terpinene and γ-terpinene,</li><li>(D) one or more polymerization inhibitors to improve storage stability of the composition, preferably selected from the group consisting of hydroquinone monomethyl ether (HQME), phenols, preferably 2,6-di-tert-butyl-4-methylphenol (BHT) and tert butylhydroxyanisole (BHA), 2,2-diphenyl-1-picrylhydrazyl radicals, galvinoxyl radicals, triphenylmethyl radicals, 2,3,6,6, 1-oxyl--Tetramethylpiperidinyl (TEMPO) and its derivatives, and phenothiazine as well as its derivatives , preferably from the group of phenols,</li><li>(E) one or more inorganic fillers, preferably in an amount of at least 25 wt .-%, based on the total weight of the composition</li><li>(F) one or more initiators for chemical curing at ambient temperature, preferably dibenzoyl peroxide, preferably dibenzoyl peroxide in combination with N, N-dimethyl-p-toluidine or N, N-dihydroxyethyl-p-toluidine,</li></ol>wherein the composition is preferably at most 5 wt .-% of Alkylmonomethacrylaten and / or preferably at most 40 wt .-% of organic contains filler particles.

p0162A further particularly preferred inventive two-component dental composition in the form of two pastes comprises:<ol><li>(A) one or more photopolymerizable monomers selected from the group consisting of methacrylates, </li><li>(B) one or more photoinitiators selected from the group consisting of alpha-diketones, preferably camphorquinone, camphorquinone are preferred in combination with ethyl<i>p</i>-<i>N, N-</i>dimethylaminobenzoate,</li><li>(C) one or more molecular weight regulator selected from the group consisting of α-terpinene and γ-terpinene,</li><li>(D) one or more polymerization inhibitors to improve storage stability of the composition, preferably selected from the group consisting of phenols, preferably 2,6-di-tert-butyl-4-methylphenol (BHT),</li><li>(E) one or more inorganic fillers, in an amount of at least 30 wt .-%, preferably in an amount of at least 40 wt .-%, based on the total weight of the composition</li><li>(F) one or more initiators for chemical curing at ambient temperature, preferably dibenzoyl peroxide in combination with N, N-dimethyl-p-toluidine or N, N-dihydroxyethyl-p-toluidine,</li></ol>wherein the ratio of the total mass of the component (c) to the total mass of the component (d) ranges from 10: 1 to 20: 1, and wherein the composition is preferably at most 1 wt .-% of Alkylmonomethacrylaten and / or preferably at most 35 wt .-% of organic contains filler particles.

p0163The invention further relates to a dental syringe, preferably a double syringe or double cartridge chamber, preferably with a static mixing tube, comprising an inventive dental composition, preferably in one of the embodiments identified as preferred.

p0164The invention further relates to the use of a compound having two or more double bonds that can be formed by abstraction of allyl hydrogen atom a delocalized electron system, which is about 5 or more C-atoms of the connection extends, preferably a diene, which is one by abstraction allyl-H atom can form a delocalized electron system, extending over 5 carbon atoms, preferably selected from the group consisting of α-terpinene and γ-terpinene, as molecular weight regulator in the polymerization of monomers selected from the group consisting of acrylates and methacrylates, preferably from the group of methacrylates, for preparing a dual-curing, multi-component dental composition.

p0165The invention also relates to a method for producing a dental composition according to the invention, preferably in one of the embodiments indicated as being preferred or particularly preferred, comprising the steps of:<ul><li>Producing a multi-component, preferably two-component, system comprising all the components (a), (b), (c), (d), (e) and (f) and optionally further additives,</li></ul>wherein the initiators of the component (f) are distributed to separate components of the dental composition that a chemical initiation by mixing the said components is triggered.

p0166Furthermore, the invention relates to an inventive dental composition, preferably in one of the identified as preferred or particularly preferred, as dental filling material as the flowable composite (Flow-material), as the crown material as bridge material and / or as core build-up material.

p0167The invention further relates to a method for treating dental disease, wherein an inventive dental composition, preferably in one of the indicated as preferred embodiments, as dental filling material as the flowable composite (Flow-material), as the crown material as bridge material and / or as core build-up material becomes.

p0168The following examples the invention will be further explained. Unless otherwise stated, all data relate to the weight. There are thereby customary abbreviations are used.

p0169In the following examples the base paste (base) and the catalyst paste have been in the weight ratio 1 (Cat.): 1.

p0170Description of the method for determining the maximum temperature (T<sub>Max</sub>)

p0171The heat development during polymerization was determined with a relative measurement method: a thermocouple type L (Fe-CuNi) from Reckmann is embedded in a holder made of polyethylene so that 3 mm of the sensor protruding.. This free end of the thermal sensor is placed centrally in a polyethylene tube of 3 mm inner diameter and 5 mm height. The tube is filled to the brim with material. In the Tubes of a colorless, clear acetate sheet is placed so that any excess material to be pressed. To initiate the polymerization, is a dental LED lamp with 1000 mW / cm<sup>2</sup> Light power placed directly on the acetate sheet and turned on for 10 sec. The resulting from the temperature development voltage change of the thermocouple is recorded on an xy plotter L 250-2 of the Fa. Linseis with a sensitivity of 2 mV.

p0172The measurement is performed in a conditioned room at 23 ° C and 50% relative humidity under yellow light protection to prevent premature polymerization of the materials. Each individual measurement is not started (exposed) when after placing the acetate again a constant temperature is reached and the pen recorder was adjusted to the zero line. Measurements are the maximum deflection of the recorder in scale divisions (0 - 100 Skt.). For clarity, it should be noted that the scale divisions (Skt.) Although correlated with temperature (ie, within a series of measurements corresponding to a higher hexagon value a higher temperature), but numerically not match ° C values. The measurements given are the mean values from 3 individual measurements.<tables id="tabl0001" num="0001"><table frame="all"><title><b>Table 1: Exemplary embodiments with γ-terpinene</b></title><tgroup cols="7"><colspec colnum="1" colname="col1" colwidth="13mm" /><colspec colnum="2" colname="col2" colwidth="61mm" /><colspec colnum="3" colname="col3" colwidth="18mm" /><colspec colnum="4" colname="col4" colwidth="13mm" /><colspec colnum="5" colname="col5" colwidth="13mm" /><colspec colnum="6" colname="col6" colwidth="13mm" /><colspec colnum="7" colname="col7" colwidth="13mm" /><thead><row><entry namest="col1" nameend="col7" align="left" valign="top">The amount of information is parts by weight</entry></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">reference</entry><entry align="center" valign="middle">Exp. 1</entry><entry align="center" valign="middle">Exp. 2</entry><entry align="center" valign="middle">Exp.3</entry><entry align="center" valign="middle">Exp. 4</entry></row></thead><tbody><row><entry morerows="6" align="center" valign="middle">Kat.</entry><entry align="center" valign="middle">UDMA</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry></row><row><entry align="center" valign="middle">Ethoxylated bisphenol A dimethacrylate</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry></row><row><entry align="center" valign="middle">BHT</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry></row><row><entry align="center" valign="middle">BPO</entry><entry align="center" valign="middle">0.25</entry><entry align="center" valign="middle">0.25</entry><entry align="center" valign="middle">0.25</entry><entry align="center" valign="middle">0.25</entry><entry align="center" valign="middle">0.25</entry></row><row><entry align="center" valign="middle">glass powder</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry></row><row><entry align="center" valign="middle">Aerosil 1</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry></row><row><entry align="center" valign="middle">Aerosil 2</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry morerows="9" align="center" valign="middle">Base</entry><entry align="center" valign="middle">UDMA</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle">20,00</entry></row><row><entry align="center" valign="middle">Ethoxylated bisphenol A dimethacrylate</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry><entry align="center" valign="middle">40,00</entry></row><row><entry align="center" valign="middle">N, N-di (hydroxyethyl) -p-toluidine</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry></row><row><entry align="center" valign="middle">glass powder</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">35,00</entry></row><row><entry align="center" valign="middle">Aerosil 1</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry><entry align="center" valign="middle">2.00</entry></row><row><entry align="center" valign="middle">Aerosil 2</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry><entry align="center" valign="middle">3.50</entry></row><row><entry align="center" valign="middle">Dyes, pigments</entry><entry align="center" valign="middle">0.50</entry><entry align="center" valign="middle">0.50</entry><entry align="center" valign="middle">0.50</entry><entry align="center" valign="middle">0.50</entry><entry align="center" valign="middle">0.50</entry></row><row><entry align="center" valign="middle">camphorquinone</entry><entry align="center" valign="middle">0.34</entry><entry align="center" valign="middle">0.34</entry><entry align="center" valign="middle">0.34</entry><entry align="center" valign="middle">0.34</entry><entry align="center" valign="middle">0.34</entry></row><row><entry align="center" valign="middle">DABE</entry><entry align="center" valign="middle">0.51</entry><entry align="center" valign="middle">0.51</entry><entry align="center" valign="middle">0.51</entry><entry align="center" valign="middle">0.51</entry><entry align="center" valign="middle">0.51</entry></row><row><entry align="center" valign="middle">BHT</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle">γ-terpinene</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">0.20</entry><entry align="center" valign="middle">0.50</entry><entry align="center" valign="middle">1.00</entry><entry align="center" valign="middle">2.00</entry></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle">T<sub>Max</sub> [Skt]</entry><entry align="center" valign="middle">77</entry><entry align="center" valign="middle">66</entry><entry align="center" valign="middle">55</entry><entry align="center" valign="middle">48</entry><entry align="center" valign="middle">42</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title><b>Table 1A-1: Conversion of the parts by weight of BHT and γ-terpinene in percentages by weight of the compositions shown in Table 1</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="29mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><colspec colnum="3" colname="col3" colwidth="28mm" /><colspec colnum="4" colname="col4" colwidth="28mm" /><colspec colnum="5" colname="col5" colwidth="28mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">reference</entry><entry align="center" valign="middle">Exp. 1</entry><entry align="center" valign="middle">Exp. 2</entry><entry align="center" valign="middle">Exp.3</entry><entry align="center" valign="middle">Exp. 4</entry></row></thead><tbody><row><entry align="center" valign="middle">BHT (wt .-%)</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.02</entry></row><row><entry align="center" valign="middle">γ-terpinene (wt .-%)</entry><entry align="center" valign="middle">0.00</entry><entry align="center" valign="middle">0.10</entry><entry align="center" valign="middle">0.24</entry><entry align="center" valign="middle">0.49</entry><entry align="center" valign="middle">0.97</entry></row></tbody></tgroup></table></tables>

p0173The information for "BHT (wt .-%)" and "γ-terpinene (wt .-%)" in Table 1A-1, the amounts of BHT or, γ-terpinene in weight percent (rounded to two decimal places), based on the total weight of each composition shown in Table 1 by mixing of catalyst paste and base paste in a weight ratio 1: 1.<tables id="tabl0003" num="0003"><table frame="all"><title><b>Table 1A-2: setting and processing times for the compositions shown in Table 1</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="39mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><colspec colnum="3" colname="col3" colwidth="20mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><colspec colnum="5" colname="col5" colwidth="20mm" /><colspec colnum="6" colname="col6" colwidth="20mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">reference</entry><entry align="center" valign="middle">Exp. 1</entry><entry align="center" valign="middle">Exp. 2</entry><entry align="center" valign="middle">Exp. 3</entry><entry align="center" valign="middle">Exp. 4</entry></row></thead><tbody><row><entry align="center" valign="middle">processing time</entry><entry align="center" valign="middle">50 sec</entry><entry align="center" valign="middle">80 sec</entry><entry align="center" valign="middle">96 sec</entry><entry align="center" valign="middle">120 sec</entry><entry align="center" valign="middle">150 sec</entry></row><row><entry align="center" valign="middle">setting time</entry><entry align="center" valign="middle">53 sec</entry><entry align="center" valign="middle">57 sec</entry><entry align="center" valign="middle">60 sec</entry><entry align="center" valign="middle">64 sec</entry><entry align="center" valign="middle">70 sec</entry></row></tbody></tgroup></table></tables>

p0174According to DIN EN ISO 4049 (as specified above), the processing times at 23 ° C and the setting time at 37 ° C for the reference example and the examples Exp. 1 intended to Exp. 4 shown in Table 1. The respective times are given in Table 1A-2 in seconds.

p0175It can be seen from Table 1A-2 show that the setting time of the processing time increasingly deviates with increasing content of γ-terpinene. The data obtained for processing time and setting time - as stated above - in<figref idrefs="f0001">Fig. 1</figref> shown graphically. <tables id="tabl0004" num="0004"><table frame="all"><title><b>Table 1B: Comparative compositions Noninventive without γ-terpinene with varying content of BHT</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="30mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><colspec colnum="3" colname="col3" colwidth="28mm" /><colspec colnum="4" colname="col4" colwidth="28mm" /><colspec colnum="5" colname="col5" colwidth="28mm" /><colspec colnum="6" colname="col6" colwidth="28mm" /><thead><row><entry align="center" valign="middle">BHT (wt .-%)</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.12</entry><entry align="center" valign="middle">0.26</entry><entry align="center" valign="middle">0.51</entry><entry align="center" valign="middle">0.99</entry></row></thead><tbody><row><entry align="center" valign="middle">processing time</entry><entry align="center" valign="middle">50 sec</entry><entry align="center" valign="middle">65 sec</entry><entry align="center" valign="middle">81 sec</entry><entry align="center" valign="middle">96 sec</entry><entry align="center" valign="middle">118 sec</entry></row><row><entry align="center" valign="middle">setting time</entry><entry align="center" valign="middle">53 sec</entry><entry align="center" valign="middle">68 sec</entry><entry align="center" valign="middle">85 sec</entry><entry align="center" valign="middle">100 sec</entry><entry align="center" valign="middle">125 sec</entry></row></tbody></tgroup></table></tables>

p0176The information for "BHT (wt .-%)" in Table 1 B are the amounts of BHT in weight percent (rounded to two decimal places), based on the total weight of each composition, the formulation with the reference example shown in Table 1 - after mixing of catalyst paste and base paste in a weight ratio of 1: 1 - is identical, with the proviso that in each case the amounts of BHT shown in Table 1B above were used. The composition of the catalyst paste was identical in each case to that from the reference example, only the composition of the base paste was varied by changing the BHT fraction.

p0177According to DIN EN ISO 4049 (as specified above), the processing times were determined at 23 ° C and the setting time at 37 ° C for these comparative compositions. The respective times are given in Table 1B in seconds. The data obtained for processing time and setting time - as stated above - in<figref idrefs="f0001">FIG. 2</figref> shown graphically.<tables id="tabl0005" num="0005"><table frame="all"><title><b>Table 2: Further embodiments with γ-terpinene</b> The amount of information is parts by weight</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="22mm" /><colspec colnum="2" colname="col2" colwidth="56mm" /><colspec colnum="3" colname="col3" colwidth="22mm" /><colspec colnum="4" colname="col4" colwidth="22mm" /><colspec colnum="5" colname="col5" colwidth="22mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">Exp. 5</entry><entry align="center" valign="middle">Exp. 6</entry><entry align="center" valign="middle">Exp. 7</entry><entry align="center" valign="middle">Exp. 8</entry></row></thead><tbody><row><entry morerows="8" align="center" valign="middle">Kat.</entry><entry align="center" valign="middle">UDMA</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle">18,07</entry><entry align="center" valign="middle">15,00</entry><entry align="center" valign="middle">15,00</entry></row><row><entry align="center" valign="middle">Ethoxylated bisphenol A dimethacrylate</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">39,15</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">Bis-GMA</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">3.00</entry><entry align="center" valign="middle">3.00</entry></row><row><entry align="center" valign="middle">TEDMA</entry><entry align="center" valign="middle">15,00</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">DODMA</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">6.00</entry><entry align="center" valign="middle">6.00</entry></row><row><entry align="center" valign="middle">Hedma</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">6.00</entry><entry align="center" valign="middle">6.00</entry></row><row><entry align="center" valign="middle">PEG 300</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">0.60</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">softener</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">0.50</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">BHT</entry><entry align="center" valign="middle">0.06</entry><entry align="center" valign="middle">0.02</entry><entry align="center" valign="middle">0.04</entry><entry align="center" valign="middle">0.04</entry></row></tbody></tgroup><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="22mm" /><colspec colnum="2" colname="col2" colwidth="56mm" /><colspec colnum="3" colname="col3" colwidth="22mm" /><colspec colnum="4" colname="col4" colwidth="22mm" /><colspec colnum="5" colname="col5" colwidth="22mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">Exp. 5</entry><entry align="center" valign="middle">Exp. 6</entry><entry align="center" valign="middle">Exp.7</entry><entry align="center" valign="middle">Exp. 8</entry></row></thead><tbody><row><entry morerows="4" align="center" valign="middle" /><entry align="center" valign="middle">BPO</entry><entry align="center" valign="middle">0.50</entry><entry align="center" valign="middle">1.51</entry><entry align="center" valign="middle">0.70</entry><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">1,3-dimethyl-5-phenylbarbitur-acid sodium salt</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">1.20</entry></row><row><entry align="center" valign="middle">glass powder</entry><entry align="center" valign="middle">30,00</entry><entry align="center" valign="middle">35,13</entry><entry align="center" valign="middle">66,50</entry><entry align="center" valign="middle">66,00</entry></row><row><entry align="center" valign="middle">Fumed silica</entry><entry align="center" valign="middle">15,00</entry><entry align="center" valign="middle">5.02</entry><entry align="center" valign="middle">2.76</entry><entry align="center" valign="middle">2.76</entry></row><row><entry align="center" valign="middle">titania</entry><entry align="center" valign="middle">1.50</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry morerows="18" align="center" valign="middle">Base</entry><entry align="center" valign="middle">UDMA</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">18,30</entry><entry align="center" valign="middle">14,00</entry><entry align="center" valign="middle">14,00</entry></row><row><entry align="center" valign="middle">Ethoxylated bisphenol A dimethacrylate</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">37,89</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">TEDMA</entry><entry align="center" valign="middle">20,00</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">DODMA</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">6.00</entry><entry align="center" valign="middle">6.00</entry></row><row><entry align="center" valign="middle">Hedma</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">5.50</entry><entry align="center" valign="middle">5.50</entry></row><row><entry align="center" valign="middle">PEG 300</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">0.60</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">softener</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">0.52</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">Bis-GMA</entry><entry align="center" valign="middle">35,00</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">3.00</entry><entry align="center" valign="middle">3.00</entry></row><row><entry align="center" valign="middle">glass powder</entry><entry align="center" valign="middle">27,00</entry><entry align="center" valign="middle">35.24</entry><entry align="center" valign="middle">67,50</entry><entry align="center" valign="middle">67,50</entry></row><row><entry align="center" valign="middle">Fumed silica</entry><entry align="center" valign="middle">14,00</entry><entry align="center" valign="middle">4.38</entry><entry align="center" valign="middle">3.00</entry><entry align="center" valign="middle">3.00</entry></row><row><entry align="center" valign="middle">titania</entry><entry align="center" valign="middle">1.50</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">Dyes, pigments</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">0.34</entry><entry align="center" valign="middle">0.01</entry><entry align="center" valign="middle">0.01</entry></row><row><entry align="center" valign="middle">camphorquinone</entry><entry align="center" valign="middle">0.01</entry><entry align="center" valign="middle">0.07</entry><entry align="center" valign="middle">0.08</entry><entry align="center" valign="middle">0.04</entry></row><row><entry align="center" valign="middle">Cu (II) acetylacetonate</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">0.25</entry></row><row><entry align="center" valign="middle">benzyltributylammonium</entry><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle">0.25</entry></row><row><entry align="center" valign="middle">DABE</entry><entry align="center" valign="middle" /><entry align="center" valign="middle">0.10</entry><entry align="center" valign="middle">0.11</entry><entry align="center" valign="middle">0.1</entry></row><row><entry align="center" valign="middle">N, N-di (hydroxyethyl) -p-toluidine</entry><entry align="center" valign="middle">0.41</entry><entry align="center" valign="middle">2.24</entry><entry align="center" valign="middle">0.45</entry><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle">γ-terpinene</entry><entry align="center" valign="middle">0.70</entry><entry align="center" valign="middle">0.34</entry><entry align="center" valign="middle">0.35</entry><entry align="center" valign="middle">0.35</entry></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /><entry align="center" valign="middle" /></row><row><entry align="center" valign="middle" /><entry align="center" valign="middle">T<sub>Max</sub> [Skt]</entry><entry align="center" valign="middle">48</entry><entry align="center" valign="middle">46</entry><entry align="center" valign="middle">49</entry><entry align="center" valign="middle">43</entry></row></tbody></tgroup></table></tables>

p0178According to DIN EN ISO 4049 (as specified above), the processing times at 23 ° C and the setting time at 37 ° C for the examples Exp. 5 determined to Exp.. 8 The respective times are given in seconds.<tables id="tabl0006" num="0006"><table frame="all"><title><b>Table 3:</b> Processing and setting the examples Exp. 5 to Exp. 8</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="37mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="18mm" /><colspec colnum="4" colname="col4" colwidth="18mm" /><colspec colnum="5" colname="col5" colwidth="18mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Exp.5</entry><entry align="center" valign="middle">Exp.6</entry><entry align="center" valign="middle">Exp.7</entry><entry align="center" valign="middle">Exp.8</entry></row></thead><tbody><row><entry align="center" valign="middle">processing time</entry><entry align="center" valign="middle">90 sec</entry><entry align="center" valign="middle">105 sec</entry><entry align="center" valign="middle">80 sec</entry><entry align="center" valign="middle">110 sec</entry></row><row><entry align="center" valign="middle">setting time</entry><entry align="center" valign="middle">57 sec</entry><entry align="center" valign="middle">62 sec</entry><entry align="center" valign="middle">57 sec</entry><entry align="center" valign="middle">64 sec</entry></row></tbody></tgroup></table></tables>

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US5750590A	Cites	United States of America	Applicant
US5761169A	Cites	United States of America	Applicant
US5761169A	Cites	United States of America	Applicant
DE60029481T2	Cites	Germany	Applicant
DE60029481T2	Cites	Germany	Applicant
DE60116142T2	Cites	Germany	Applicant
DE60116142T2	Cites	Germany	Applicant

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6 members in 3 offices; this record represents the family

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Members6

Family members, oldest first
Document	Office	Kind
EP2374445A2This record	European Patent Office (EPO)	A2	2011-10-12
DE102010003884A1	Germany	A1	2011-10-13
US2011250558A1	United States of America	A1	2011-10-13
EP2374445A3	European Patent Office (EPO)	A3	2013-01-23
US8501834B2	United States of America	B2	2013-08-06
EP2374445B1	European Patent Office (EPO)	B1	2015-07-29

78 legal events, as 9 offices reported them to INPADOC

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Events

Legal events, newest first
	Event	Code	Office
2026-07-23	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2026-07-16	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2026-07-11	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2026-05-01	Full renewal or maintenance fee paidST27 STATUS EVENT CODE: U-0-0-U10-U11 (AS PROVIDED BY THE NATIONAL OFFICE)U11	U11	CH
2026-04-09	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2025-07-18	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2019-11-25	Amendment of ipc main classPREVIOUS MAIN CLASS: A61K0006083000R079	R079	DE
2018-10-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-07-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-06-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-06-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-06-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-06-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-05-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-05-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-05-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2018-04-24	Fee paymentPLFP	PLFP	FR
2017-08-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2017-06-15	Lapse because of not paying annual feesLapsedMM01	MM01	AT
2017-05-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2017-04-24	Fee paymentPLFP	PLFP	FR
2017-01-25	Patent lapsedLapsedMM4A	MM4A	IE
2016-12-30	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-08-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-08-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-07-06	No opposition filedOpposition26N	26N	EP
2016-06-03	No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE	PLBE	EP
2016-06-03	Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA	STAA	EP
2016-05-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-05-02	No opposition filed against granted patent, or epo opposition proceedings concluded without decisionGrantedR097	R097	DE
2016-04-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-04-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-04-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-04-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-04-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-04-22	Fee paymentPLFP	PLFP	FR
2016-03-31	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-02-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-02-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-02-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-02-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-02-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-02-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-02-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-01-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-01-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-01-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-01-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-01-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2016-01-06	Patent invalid in the netherlands as no translation has been filedMP	MP	NL
2015-12-28	Invalidated european patentMG4D	MG4D	LT
2015-09-10	Dpma publication of mentioned ep patent grantGrantedR096	R096	DE
2015-08-26	European patents granted designating irelandGrantedLANGUAGE OF EP DOCUMENT: GERMANFG4D	FG4D	IE
2015-08-15	Reference to at number (ep patent validated in austria)REF	REF	AT
2015-07-31	European patent takes effect as a national patent in ch/liEP	EP	CH
2015-07-31	New agentNV	NV	CH
2015-07-29	Designated contracting statesAK	AK	EP
2015-07-29	European patent grantedGrantedNOT ENGLISHFG4D	FG4D	GB
2015-07-29	Information on inventor provided before grant (corrected)RIN1	RIN1	EP
2015-07-29	Information on inventor provided before grant (corrected)RIN1	RIN1	EP
2015-07-29	Information on inventor provided before grant (corrected)RIN1	RIN1	EP
2015-06-26	(expected) grantORIGINAL CODE: 0009210GRAA	GRAA	EP
2015-06-24	Grant fee paidORIGINAL CODE: EPIDOSNIGR3GRAS	GRAS	EP
2015-04-08	Intention to grant announcedINTG	INTG	EP
2015-04-08	Information on inventor provided before grant (corrected)RIN1	RIN1	EP
2015-04-08	Information on inventor provided before grant (corrected)RIN1	RIN1	EP
2015-04-08	Information on inventor provided before grant (corrected)RIN1	RIN1	EP
2015-03-10	Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOSNIGR1GRAP	GRAP	EP
2014-06-18	First examination report despatched17Q	17Q	EP
2013-08-28	Request for examination filed17P	17P	EP
2013-08-28	Designated contracting states (corrected)RBV	RBV	EP
2013-01-23	Designated contracting statesAK	AK	EP
2013-01-23	Request for extension of the european patentAX	AX	EP
2013-01-23	Information provided on ipc code assigned before grantRIC1	RIC1	EP
2012-12-21	Search report despatchedORIGINAL CODE: 0009013PUAL	PUAL	EP
2011-10-12	Designated contracting statesAK	AK	EP
2011-10-12	Request for extension of the european patentAX	AX	EP
2011-09-09	Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI	PUAI	EP

Dual hardening multi-component dental composition

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