Dental compositions comprising components containing resorcinol or catechol moieties and uses thereof

Abstract

The present invention relates to a composition comprising a resin matrix, an initiator system, and a filler system. The resin matrix comprises a polymerizable component comprising a backbone comprising a resorcinol or catechol moiety. The composition is particularly useful in the dental and orthodontic fields, for example as a dental filling material having advantageous properties.

Description

Technical Field

[0001] The present invention relates to a composition comprising a resin matrix, an initiator system and a filler system. The resin matrix comprises a polymerizable component comprising a backbone comprising a resorcinol or catechol moiety.

[0002] The composition is particularly useful in the dental and orthodontic fields, for example as a dental filling material having advantageous properties.

[0003] The dental compositions can also be used to produce mill blanks and as resins in laminate manufacturing processes. Background Art

[0004] Different dental filling materials are known for restorative purposes, including amalgam and dental composites.

[0005] In order to perform their primary function (replacing lost tooth structure), dental filling materials need to have adequate physical properties. In particular, they must be strong enough to absorb and resist chewing forces.

[0006] However, if the material is too hard, it will also become more brittle.

[0007] Therefore, dental filling materials need not only to be hard enough but also to be flexible to some extent.

[0008] To meet these requirements, commercially available dental composite filling materials generally contain a certain amount of resin matrix, filler and initiator.

[0009] A widely used polymerizable (meth)acrylate component contained in the resin matrix is ​​bisphenol A-glycidyl methacrylate (Bis-GMA) or other bisphenol-based (meth)acrylate monomers.

[0010] Compositions containing bisphenol-based monomers are said to possess a variety of advantageous properties such as high compressive strength, thus enabling practitioners to formulate a variety of different dental compositions for restorative purposes.

[0011] However, some literature seems to indicate that bisphenol-based monomers are not always recommended for all purposes. There is therefore a need for alternative polymerizable (meth)acrylate components.

[0012] US 2010 / 076115 A1 (Heraeus Kulzer) relates to compositions for dental composites, which contain acrylic esters of tricyclo[5.2.1.02.6]decane having urethane groups.

[0013] US 3,853,962 (Gander) relates to dental restorative cements comprising the methacrylate monomer 1,3-bis[2,3-di(methacryloyloxy)-propoxy]-benzene. Restorative compositions containing this monomer are said to have improved compressive strength and related physical properties.

[0014] No. 4,744,827 (Winkel) describes (meth)acrylic acid derivatives of tricyclodecane which exhibit relatively little polymerization shrinkage.

[0015] US Pat. No. 8,426,490 B2 (Bissinger et al.) describes methacrylate-based monomers containing urethane linkages which exhibit well-balanced properties with respect to viscosity, refractive index, molecular weight and shrinkage values.

[0016] US 2011 / 0315928 A1 (Jin et al.) relates to a low viscosity and low stress dental composition comprising at least one low stress polymerizable resin and at least one filler. The dental composition is said to have a high cure depth and self-leveling properties and can be applied in bulk.

[0017] WO 2012 / 106083 A1 (3M) describes a dental composition comprising a hardenable compound containing relatively rigid backbone units comprising aromatic or aliphatic cyclic moieties, spacer units, and units comprising polymerizable end groups. This composition can be used in dentistry to provide, for example, composite materials with reduced brittleness. Summary of the Invention

[0018] There remains a need for compositions with improved properties that are useful in the dental and orthodontic fields.

[0019] The composition should be easy to handle in its uncured state, in particular easy to apply to the surface to be treated.

[0020] This is also desirable if the composition allows for high filler loadings, if desired.

[0021] These properties should be achievable without the use of bisphenol A (BPA)-containing monomers.

[0022] Ideally, after hardening the composition, the composition should have adequate physical-mechanical properties, such as adequate flexural strength and depth of cure.

[0023] Furthermore, if possible, the polymerizable components of the curable composition should have sufficient refractive index for desired aesthetics and depth of cure properties.

[0024] One or more of these objectives are achieved by the present invention as described herein and in the claims.

[0025] In one embodiment, the invention features a dental composition comprising a) a resin matrix, b) an initiator system, c) a filler system, the resin matrix comprising a polymerizable component A1 characterized by any of the following formulas I, II, or III

[0026]

[0027] in

[0028] X = independently selected from H, alkyl, I, Br, Cl; Z = independently selected from H, CH3, CH2OH; n, m = independently selected from integers ranging from 1 to 10; (m+n) = 1 to 10, or 2 to 8, or 2 to 6; R = independently selected from H, CH3;

[0029]

[0030] wherein X=is independently selected from H, alkyl, I, Br, Cl; Z=is independently selected from H, CH3, CH2OH; k, n, m=are independently selected from integers ranging from 1 to 10; (k+m+n)=1 to 15, or 2 to 10, or 3 to 8; R=is independently selected from H, CH3;

[0031] and mixtures thereof, as described herein and in the claims.

[0032] Additional embodiments of the present invention are directed to a kit comprising a dental composition as described herein and in the claims and the following, alone or in combination: a dental adhesive; a dental primer; a dispensing device; a polishing apparatus; a dental curing light, as described herein and in the claims.

[0033] The dental compositions described herein may also be used to produce dental restorations, dental mill blanks or as a resin in a laminate manufacturing process as described herein and in the claims.

[0034] The dental compositions may also be used as composite filling materials, fixing materials for orthodontic appliances, cavity liners, or sealants.

[0035] In another embodiment, the present invention is directed to a dental composition for use in a method of treating hard dental tissue in a mammalian mouth, the method comprising the steps of applying the dental composition to the surface of the hard dental tissue and hardening the dental composition as described herein and in the claims.

[0036] Also described are packaging devices comprising the compositions described herein and in the claims.

[0037] Unless defined differently, for the purposes of this specification, the following terms shall have the given meanings:

[0038] A "hardenable or curable or polymerizable component" is any component that can be cured or solidified by a hardening reaction, in particular by polymerization initiated by radiation in the presence of a photoinitiator. A hardenable component may contain only one, two, three or more polymerizable groups. Typical examples of polymerizable groups include unsaturated carbon groups, such as vinyl groups, which are particularly present in (meth)acrylate groups.

[0039] As used herein, "hardening" or "curing" a composition are used interchangeably and refer to polymerization and / or cross-linking reactions involving one or more materials contained in the composition, including, for example, photopolymerization reactions and chemical polymerization techniques (e.g., ionic reactions or chemical reactions that form free radicals effective to polymerize ethylenically unsaturated compounds).

[0040] "Radiation curable" shall mean that the component (or composition, as the case may be) can be cured by applying radiation (preferably electromagnetic radiation having a wavelength in the visible spectrum) under ambient conditions and within a reasonable time frame (e.g., within about 15, 10 or 5 minutes).

[0041] The term "visible light" is used to refer to light having a wavelength of 400 to 700 nanometers (nm).

[0042] As used herein, "(meth)acryloyl" is a shorthand term that refers to "acryloyl" and / or "methacryloyl." For example, a "(meth)acryloyloxy" group is a shorthand term that refers to an acryloyloxy group (i.e., CH2=CH-C(O)-O-) and / or a methacryloyloxy group (i.e., CH2=C(CH3)-C(O)-O-).

[0043] The "resin matrix" comprises all hardenable compounds (monomers, oligomers and / or polymers) present in the hardenable composition. The resin may comprise only one hardenable compound or a mixture of different hardenable compounds.

[0044] The "filler system" comprises all fillers present in the hardenable composition. It is possible to use only one type of filler or a mixture of different fillers.

[0045] "Nanosized fillers" are fillers whose individual particles have a size in the nanometer range, for example an average particle size of less than 100 nm or less than 50 nm. Useful examples are given in US 6,899,948 (Zhang et al.) and US 6,572,693 (Wu et al.).

[0046] "Particle" means a solid substance having a geometrically definable shape. The shape can be regular or irregular. Particles can generally be analyzed with respect to, for example, particle size and particle size distribution.

[0047] As used herein, "aggregated" describes a strong association of particles typically held together by, for example, residual chemical treatment or partial sintering. The specific surface area of ​​the aggregated particles is typically smaller than that of the primary particles constituting the aggregate (see DIN 53206; 1972).

[0048] An "initiator or initiator system" is a component or combination of components that is capable of initiating the curing process of a hardenable component.

[0049] "Dispersed within the resin" means that the filler particles are present in the resin as discrete, non-associated (ie, non-agglomerated and non-aggregated) particles.

[0050] A "dental composition" is any composition which can be used or is intended for use in the dental field. In this respect, the composition should be harmless to the patient's health and therefore contain no hazardous and toxic components which can migrate from the composition.

[0051] Possible uses of the dental compositions are as or for the production of permanent and temporary crown and bridge materials, artificial crowns, dental filling materials, cavity liners, coating compositions, sealants, mill blanks, laboratory materials and orthodontic devices.

[0052] The dental composition is typically a hardenable composition that can be hardened under ambient conditions, including a temperature range of 15°C to 50°C or 20°C to 40°C, within a time range of 30 minutes, or 20 minutes, or 10 minutes.

[0053] Higher temperatures are not recommended as they may cause pain to the patient and may be harmful to the patient's health.

[0054] Dental compositions are typically provided to the practitioner in relatively small volumes (ie, volumes ranging from 0.1 ml to 100 ml, or from 0.5 ml to 50 ml, or from 1 ml to 30 ml).

[0055] "Dental article" means an article intended for use in the dental field, in particular as or for the production of dental restorations. Dental articles generally have two distinct surface parts, an outer surface and an inner surface. The outer surface is the surface that generally does not come into permanent contact with the tooth surface. In contrast, the inner surface is the surface that serves to attach or secure the dental article to the tooth. If the dental article has the shape of a crown, the inner surface generally has a concave shape, while the outer surface generally has a convex shape. Dental articles should not contain components that are harmful to the patient's health and therefore do not contain hazardous and toxic components that could migrate out of the dental or orthodontic article.

[0056] "Dental restoration" means a dental product used to repair a tooth to be treated. Examples of dental restorations include crowns, bridges, inlays, onlays, veneers, facings, copings, crown-bridge frameworks, and parts thereof.

[0057] By "dental mill blank" is meant a solid block of material (three-dimensional article) from which a dental article can be manufactured. A dental mill blank generally has a geometrically defined shape. A dental mill blank may have dimensions of 20 mm to 30 mm in two dimensions, for example, a diameter within this range, and a length in the third dimension. A block or blank for making a single crown may have a length of 15 mm to 30 mm, and a block or blank for making a dental bridge may have a length of 40 mm to 80 mm.

[0058] In addition to the aforementioned dimensions, dental mill blanks can also have a cubic, cylindrical, or cuboid shape. If more than one crown or bridge is to be manufactured from one blank, a larger milling block may be advantageous. For these cases, the diameter or length of the cylindrical or cuboid mill blank can be in the range of 80 mm to 200 mm, and the thickness in the range of 10 mm to 30 mm.

[0059] “Orthodontic appliances” include orthodontic brackets, buccal tubes, lingual retainers, orthodontic bands, bite openers, buttons, and splints.

[0060] "Additive manufacturing" or "3D printing" refers to a process that involves creating an object layer by layer from digital data. The article can be of almost any shape or geometry and is produced from a three-dimensional model or other electronic data source.

[0061] There are many 3D printing technologies, one of which is vat polymerization, which uses a radiation curing step to produce three-dimensional articles. Examples of vat polymerization technologies include stereolithography (SLA) and digital light processing (DLP).

[0062] "Stereolithography" is an example of an additive manufacturing technique, where two motors are typically used to aim a laser beam across the print area, thereby solidifying the printing resin. This process breaks down the design into a series of dots, layer by layer.

[0063] Digital light processing is another example of an additive manufacturing technique and typically involves using a digital projector screen to flash an image of each layer onto the build platform of the additive manufacturing unit. This image is typically composed of square pixels, resulting in a layer formed from small rectangular bricks called voxels.

[0064] "Ambient conditions" refers to the conditions to which the compositions described herein are typically subjected during storage and handling. Ambient conditions can be, for example, a pressure of 900 to 1,100 mbar, a temperature of 10° C. to 40° C., and a relative humidity of 10% to 100%. In the laboratory, ambient conditions are typically adjusted to 20° C. to 25° C. and 1,000 to 1,025 mbar (at sea level).

[0065] As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably. Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0066] Adding "plural form" to a term means that the term shall include both the singular and the plural forms. For example, the term "additive" refers to one additive and multiple additives (e.g., 2, 3, 4, etc.).

[0067] The terms "comprises" or "comprising" and variations thereof do not have a limiting meaning when these terms appear in the specification and claims. "Consisting essentially of means that certain additional components may be present, i.e., those components that do not materially affect the basic properties of the article or composition. "Consisting of means that no additional components should be present. The term "comprising" shall also encompass the terms "consisting essentially of" and "consisting of."

[0068] A composition is "substantially or essentially free" of a component if it does not contain that component as an essential characteristic. Thus, the component itself is not intentionally added to the composition, nor is it intentionally added to the composition together with other components or ingredients of other components. A composition that is substantially free of a component generally does not contain that component at all. However, the presence of small amounts of that component is sometimes unavoidable, for example due to impurities contained in the raw materials used. "Substantially free" generally means an amount of less than 1%, 0.5%, or 0.1% by weight. DETAILED DESCRIPTION

[0069] The compositions and methods described herein have been found to have several advantageous properties.

[0070] The di- and / or trifunctional (meth)acrylate components exhibit a high refractive index and a relatively low viscosity.

[0071] A high refractive index can contribute to the curing properties and aesthetics of the cured dental composition.

[0072] Due to the low viscosity, these (meth)acrylate components can be easily incorporated into the resin matrix and mixed with other components such as fillers, even at high filling rates.

[0073] Low viscosity, flowable compositions can now be formulated.

[0074] Furthermore, these components have been found to be suitable replacements for bisphenol A derived components, which are commonly used in dental preparations. By bisphenol A derived components is meant components containing a bisphenol A moiety.

[0075] Compositions containing these components exhibit advantageous mechanical properties, such as low polymerization shrinkage stress, improved tensile and flexural strength, and sufficient depth of cure.

[0076] The composition also exhibits favorable cusp deflection values ​​after curing (ie, low deformation of the aluminum block upon curing of a standardized filling).

[0077] The present invention relates to compositions useful in the dental and orthodontic fields.

[0078] The composition comprises a resin matrix, an initiator system, a filler system and optionally other components such as diluents and adjuvants.

[0079] The resin matrix contains a polymerizable component A1, and may contain an additional polymerizable component different from the polymerizable component A1.

[0080] Component A1 is found to generally contribute to or exhibit at least one or more of the following properties.

[0081] Component A1

[0082] a) generally have good filler wettability. This can be beneficial for achieving relatively high filler loadings if desired;

[0083] b) generally have a relatively low viscosity (e.g., 2.0 Pa*s to 40 Pa*s, or 2.0 Pa*s to 30 Pa*s; 23°C; shear rate: 100s -1 ). This may be beneficial to achieve proper processing of the final composition, if desired. Increasing the filler level, if desired, may also be beneficial, as the viscosity of the final composition will generally be within an acceptable range;

[0084] c) generally have a relatively high refractive index (e.g., 1.520 to 1.565 or 1.530 to 1.560 (n D 20 )). This may be beneficial to achieve appropriate aesthetics and / or a high depth of cure for the light-curable material, if desired;

[0085] d) generally have a relatively high hydrophobicity. This may be beneficial for achieving relatively low water absorption and / or exogenous staining, if desired;

[0086] e) can be used to provide compositions that exhibit reduced brittleness of the cured composition (ie relatively high impact strength and / or moderate E-modulus). This can be beneficial if the risk of failure due to cracks and / or fractures should be reduced.

[0087] f) can be used to provide compositions that exhibit a high depth of cure. This can be beneficial if batch curing applications of photocurable materials are desired.

[0088] Component A1 can be described as a component comprising a backbone unit comprising a di- or trihydroxybenzene moiety; and two or three spacer units connected to the backbone unit via ether bonds, the spacer unit comprising the structural element -CH2-CH-CH2-; comprising two or three (meth)acrylate moieties attached to the backbone via an alkyleneoxy moiety; comprising two or three phenoxy moieties as pendant groups attached to the backbone through the spacer units; and comprising no urethane moieties.

[0089] The molecular weight of component A1 is generally in the range from 500 g / mol to 1,200 g / mol.

[0090] Examples of component A1 include

[0091]

[0092]

[0093] in

[0094] m, n, k = independently selected integers ranging from 1 to 10,

[0095] and (m+n)=1 to 10, or

[0096] (m+n+k)=1 to 15,

[0097] and mixtures thereof.

[0098] The molecules of component A1 can generally be produced by reacting a phenolic compound (e.g., resorcinol or catechol), a glycidyl phenyl ether compound, and ethylene carbonate to produce an alkoxylated intermediate compound, which is hydrolyzed to produce an ethoxylated intermediate compound, which is further reacted with (meth)acrylic acid.

[0099] Component A1 is typically present in the composition in an amount of at least 3%, 5% or 8% by weight; up to 50%, 40% or 30% by weight; ranging from 3% to 50%, or from 5% to 40%, or from 8% to 30% by weight; the % by weight being relative to the weight of the entire composition.

[0100] The resin matrix may comprise further polymerizable components other than component A1. One or more of these further polymerizable components may be present.

[0101] These further polymerizable components are referred to as component A2.

[0102] Suitable components A2 contain at least one ethylenically unsaturated bond and are capable of addition polymerization.

[0103] Suitable polymerizable components may be characterized by the formula:

[0104] A n BA m

[0105] wherein A is an ethylenically unsaturated group, such as a (meth)acryloyl moiety,

[0106] B is selected from (i) a linear or branched C1 to C2 optionally substituted with other functional groups (eg, halogen (including Cl, Br, I), OH or a mixture thereof); 12 (ii) C6 to C6 alkyl, optionally substituted with other functional groups (e.g., halogen, OH or mixtures thereof) 12 aryl, or (iii) organic groups having 4 to 20 carbon atoms bonded to one another via one or more ether, thioether, ester, thioester, thiocarbonyl, amide, carbamate, carbonyl and / or sulfonyl bonds,

[0107] m and n are independently selected from 0, 1, 2, 3, 4, 5 or 6, with the proviso that n+m is greater than 0, ie, at least one A group is present.

[0108] Such polymerizable materials include mono-, di- or polyacrylates and methacrylates such as methyl acrylate, methyl methacrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, allyl (meth)acrylate, glycerol di(meth)acrylate, diurethane dimethacrylate known as UDMA which is a mixture of isomers (e.g., the reaction product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethyl-hexamethylene diisocyanate (TMDI), and methacrylates such as methyl acrylate, methyl methacrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, allyl (meth)acrylate, glycerol di(meth)acrylate, diurethane dimethacrylate known as UDMA which is a mixture of isomers (e.g., Plex 6661-0), glycerol tri(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-propylene glycol diacrylate, 1,3-propylene glycol dimethacrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate

[0014] Examples of free radical polymerizable materials include 1,4-cyclohexanediol di(meth)acrylate, 1,4-cyclohexanediol tri(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, 1,4-cyclohexanediol tri(meth)acrylate, 1,4-cyclohexanediol tetraacrylate, 1,4-pentaerythritol tetraacrylate, 1,4-pentaerythritol tetramethacrylate, 1,4-pentaerythritol hexa(meth)acrylate, 1,4-pentaerythritol tetraacrylate, 1,4-pentaerythritol hexa(meth) ...

[0109] If desired, an addition fragmentation monomer (AFM) may also be added. The addition fragmentation monomer may be characterized by the formula:

[0110]

[0111] in

[0112] R 1 、R 2 and R 3 Each independently is Z m -Q-, a (hetero)alkyl group or a (hetero)aryl group, provided that R 1 、R 2 and R 3 At least one of them is Z m -Q-; Q is a linking group with a valence of m+1; Z is an ethylenically unsaturated polymerizable group; m is 1 to 6; each X 1 are independently -O- or -NR 4 -, where R 4 is H or C1-C4 alkyl; and n is 0 or 1.

[0113] These monomers are said to have lower stress. Suitable monomers are also described in US 9,056,043 (Joly et al.).

[0114] Monomers containing hydroxyl moieties may also be added. Suitable compounds include 2-hydroxyethyl (meth)acrylate (HEMA), 2- or 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, dialkylene glycol mono(meth)acrylates (e.g., diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate), and further, (meth)acrylates. 1,2- or 1,3- and 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxypropyl-1,3-di(meth)acrylate, 3-hydroxypropyl-1,2-di(meth)acrylate, N-(meth)acryloyl-1,2-dihydroxypropylamine, N-(meth)acryloyl-1,3-dihydroxypropylamine, an adduct of phenol and glycidyl (meth)acrylate (e.g., 1-phenoxy-2-hydroxypropyl (meth)acrylate), 1-naphthyloxy-2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate are particularly preferred. If desired, a mixture of one or more of these components may be used.

[0115] Component A2 is typically present in the composition in an amount of at least 0 wt%, 1 wt% or 5 wt%; at most: 60 wt%, 50 wt% or 40 wt%; ranging from 0 wt% to 60 wt%, 1 wt% to 50 wt%, or 5 wt% to 40 wt%; the wt% being relative to the total composition.

[0116] The compositions described herein comprise an initiator system.

[0117] Initiator systems are able to start the curing process of the hardenable components present in the resin matrix.For curing one-component compositions, photoinitiator systems are usually used.

[0118] Suitable photoinitiator systems for free-radical polymerization are generally known to those skilled in the art of processing dental materials.

[0119] Suitable photoinitiator systems typically contain a sensitizer comprising an α-α diketone moiety, an anthraquinone moiety, a thioxanthone moiety, or a benzoin moiety. Sensitizers containing an α-α diketone moiety are generally preferred.

[0120] A typical photoinitiator system comprises a combination of a sensitizer and a reducing agent or donor component, which is generally referred to as a photoinitiator system.

[0121] As the sensitizer, those which can polymerize a polymerizable monomer by the action of visible light having a wavelength of 390 nm to 830 nm are preferred.

[0122] Examples of sensitizers that can be used include camphorquinone, benzil, diacetyl, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl di(2-methoxyethyl) ketal, 4,4,'-dimethylbenzyl dimethyl ketal, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-Methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis(4-dimethyl-amino-phenyl)ketone, 4,4,'-bisdiethylamino-benzophenone.

[0123] As the reducing agent or donor component, a tertiary amine or the like is generally used. Suitable examples of the tertiary amine include N,N-dimethyl-p-toluidine, N,N-dimethyl-aminoethyl methacrylate, triethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, methyldiphenylamine, and isoamyl 4-dimethylaminobenzoate.

[0124] Additional suitable reducing agents include diarylalkylamines characterized by the formula: Ar 1 Ar 2 RN, of which Ar 1 and Ar 2 independently selected from phenyl or alkyl (e.g., C1 to C4) substituted phenyl, R is an alkyl (e.g., C1 to C4) group, wherein one or more H atoms may be substituted by halogen, and N is nitrogen. These reducing agents are described in more detail in US 8,314,162 (Hailand et al.).

[0125] In addition, a sensitizer, an electron donor and and the like. Tertiary photopolymerization initiation systems composed of salts thereof, such as those described in U.S. Pat. No. 6,187,833 (Oxman et al.), U.S. Pat. No. 6,025,406 (Oxman et al.), U.S. Pat. No. 6,043,295 (Oxman et al.), U.S. Pat. No. 5,998,495 (Oxman et al.), U.S. Pat. No. 6,084,004 (Weinmann et al.), U.S. Pat. No. 5,545,676 (Palazzotto et al.), U.S. Pat. No. 8,314,162 B2 (Hailand et al.), and U.S. Pat. No. 6,765,036 (Dede et al.).

[0126] In the ternary photoinitiator system, the first component is Iodine is preferred Salt, i.e. diaryliodonium Salt.

[0127] iodine The salt is preferably soluble in the monomer and storage stable (ie, does not spontaneously promote polymerization) when dissolved therein in the presence of the sensitizer and the donor. The choice of salt may depend to some extent on the particular monomer, polymer or oligomer, sensitizer and donor selected. Suitable iodine Salts are described in US 3,729,313, US 3,741,769, US 3,808,006, US 4,250,053 and US 4,394,403. Iodine The salt can be a simple salt (e.g., containing an anion such as Cl - Br - , I - or C4H5SO3 - ) or metal complex salts (e.g., containing SbF5OH - or AsF6 - ). If necessary, iodine can be used A mixture of salts. Preferably iodine Salts including diphenyl iodide Salts such as diphenyl iodide Chloride, diphenyl iodide Hexafluorophosphate and diphenyl iodide Tetrafluoroborate.

[0128] The second component in the ternary photoinitiator system is the sensitizer.

[0129] The sensitizer is desirably soluble in the monomer and capable of light absorption in the wavelength range of greater than 400 nm to 1,200 nm, more preferably greater than 400 nm to 700 nm, and most preferably greater than 400 nm to 600 nm.

[0130] Suitable sensitizers can include compounds from the following classes: ketones, coumarin dyes (e.g., ketocoumarin), xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, para-substituted aminostyryl ketone compounds, aminotriarylmethanes, merocyanines, squarylium dyes, and pyridines. Dyes. Ketones (eg, monoketones or α-diketones), ketocoumarins, amino aromatic ketones, and p-substituted aminostyryl ketone compounds are preferred sensitizers.

[0131] For example, one preferred class of ketone sensitizers has the formula: ACO(X)b B, where X is CO or CR 5 R 6 , where R 5 and R 6 A and B may be the same or different and may be hydrogen, alkyl, alkaryl or aralkyl, b is zero or one, and A and B are different and may be substituted (with one or more non-interfering substituents) and may be the same or unsubstituted aryl, alkyl, alkaryl or aralkyl groups, or A and B together may form a cyclic structure which may be a substituted or unsubstituted alicyclic, aromatic, heteroaromatic or fused aromatic ring.

[0132] Suitable ketones of the above formula include monoketones (b=0) such as 2,2-, 4,4- or 2,4-dihydroxybenzophenone, di-2-pyridyl ketone, di-2-furyl ketone, di-2-thienyl ketone, benzoin, fluorenone, chalcone, Michler's ketone, 2-fluoro-9-fluorenone, 2-chlorothioxanthone, acetophenone, benzophenone, 1- or 2-acetonaphthone, 9-acetylanthracene, 2-, 3- or 9-acetylphenanthrene, 4-acetylbiphenyl, propiophenone, butyrophenone, valerophenone, 2-, 3- or 4-acetylpyridine, 3-acetylcoumarin, and the like. Suitable diketones include aralkyl diketones such as anthraquinone, phenanthrenequinone, o-, m-, and p-diacetylbenzene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, and 1,8-diacetylnaphthalene, 1,5-, 1,8-, and 9,10-diacetylanthracene, etc. Suitable α-diketones (b=1 and X=CO) include 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, benzil, 2,2′-3,3′- and 4,4′-dihydroxybenzil, furil, di-3,3′-indoleethyldione, 2,3-bornanedione (camphorquinone), biacetyl, 1,2-cyclohexanedione, 1,2-naphthoquinone, etc.

[0133] The third component of the ternary initiator system is the donor.

[0134] Preferred donors include, for example, amines (including aminoaldehydes and aminosilanes), amides (including phosphoramides), ethers (including thioethers), ureas (including thioureas), ferrocene, sulfinic acid and its salts, salts of ferrocyanide, ascorbic acid and its salts, dithiocarbamic acid and its salts, xanthates, ethylenediaminetetraacetates, and tetraphenylborate. The donor may be unsubstituted or substituted with one or more non-interfering substituents. Particularly preferred donors contain electron donor atoms such as nitrogen, oxygen, phosphorus, or sulfur atoms, and abstractable hydrogen atoms bonded to the alpha carbon or silicon atom of the electron donor atom. A variety of donors are disclosed in US Pat. No. 5,545,676. This reference is incorporated herein by reference.

[0135] Alternatively, free radical initiators useful in the present invention include acylphosphine oxides and bisacylphosphine oxides.

[0136] Suitable acylphosphine oxides can be described by the following general formula:

[0137] (R 9 )2-P(=O)-C(=O)—R 10

[0138] Each R 9 R is independently a hydrocarbon group such as alkyl, cycloalkyl, aryl and aralkyl, any of which may be substituted by a halogen, alkyl or alkoxy group, or both R 9 The groups may be joined to form a ring together with the phosphorus atom, and wherein R 10 is a hydrocarbon group, a five- or six-membered heterocyclic group containing S-, O- or N-, or -ZC(=O)-P(=O)-(R 9 )2 group, wherein Z represents a divalent hydrocarbon group such as an alkylene group or a phenylene group having 2 to 6 carbon atoms.

[0139] Preferred acylphosphine oxides are those in which R 9 and R 10 The groups are those of phenyl or lower alkyl or lower alkoxy substituted phenyl. By "lower alkyl" and "lower alkoxy" are meant such groups having 1 to 4 carbon atoms. Examples can also be found in, for example, US 4,737,593.

[0140] Examples include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-ethoxyphenyl-phosphine oxide, bis-(2,6-dichlorobenzoyl)-4-biphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthyl ... ,6-dichlorobenzoyl)-4-chlorophenyl-phosphine oxide, bis-(2,6-dichlorobenzoyl)-2,4-dimethoxy-phenyl-phosphine oxide, bis-(2,6-dichlorobenzoyl)decylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-octyl-phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethyl-phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-2,5-dimethyl-phenylphosphine oxide Phosphine oxide, bis-(2,6-dichloro-3,4,5-trimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichloro-3,4,5-trimethoxybenzoyl)-4-ethoxyphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)phenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-4-biphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-4-ethoxyphenylphosphine oxide, Bis-(2-methyl-1-naphthoyl)-2-naphthyl-phosphine oxide, bis-(2-methyl-1-naphthoyl)-4-propylphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-2,5-dimethylphosphine oxide, bis-(2-methoxy-1-naphthoyl)-4-ethoxy-phenyl-phosphine oxide, bis-(2-methoxy-1-naphthoyl)-4-biphenylphosphine oxide, bis-(2-methoxy-1-naphthoyl)-2-naphthylphosphine oxide and bis-(2-chloro-1-naphthoyl)-2,5-dimethylphenylphosphine oxide.

[0141] Tertiary amine reducing agents can be used in combination with acylphosphine oxides. Exemplary tertiary amines useful in the present invention include ethyl 4-(N,N-dimethylamino)benzoate and N,N-dimethylaminoethyl methacrylate.

[0142] Commercially available phosphine oxide photoinitiators capable of free radical initiation when irradiated at wavelengths greater than 400 nm to 1,200 nm include a 25:75 by weight mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (formerly known as Irgacure TM1700, Ciba), 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)-1-butanone (formerly Irgacure TM 369, Ciba), bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium (formerly known as Irgacure TM 784DC, Ciba), a 1:1 mixture by weight of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (formerly known as Darocur TM 4265, Ciba), ethyl-2,4,6-trimethylbenzylphenylphosphine oxide (formerly Lucirin TM LR8893X, BASF), and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (formerly Irgacure TM 819, BASF).

[0143] Another free radical initiator system that may alternatively be used comprises the class of ionic dye counterion complex initiators comprising a borate anion and a complementary cationic dye.

[0144] Borate photoinitiators are described, for example, in US 4,772,530 (Gottschalk et al.), US 4,954,414 (Adair et al.), US 4,874,450 (Gottschalk), US 5,055,372 (Shanklin et al.), and US 5,057,393 (Shanklin et al.).

[0145] The borate anions useful in these photoinitiators may generally have the formula R 1 R 2 R 3 R 4 B - , where R 1 、R 2 、R 3 and R 4 R can be independently an alkyl group, an aryl group, an alkaryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alicyclic group, and a saturated or unsaturated heterocyclic group. 2 、R 3 and R 4 is an aryl group and more preferably a phenyl group, and R 1 is an alkyl group and more preferably a secondary alkyl group.

[0146] The cationic counterions can be cationic dyes, quaternary ammonium groups, transition metal coordination complexes, etc. The cationic dyes used as counterions can be cationic methylene, polymethylene, triarylmethylene, indoline, thiazine, xanthene, oxazine or acridine dyes. More specifically, the dyes can be cationic cyanine, carbocyanine, hemicyanine, rhodamine and azomethine dyes. Specific examples of useful cationic dyes include methylene blue, safranin O and malachite green. The quaternary ammonium groups used as counterions can be trimethylhexadecylammonium, cetylpyridinium and tetramethylammonium. Other organophilic cations can include pyridine phosphonium and sulfonium.

[0147] The photosensitive transition metal coordination complexes that can be used include complexes of cobalt, ruthenium, osmium, zinc, iron and iridium with ligands such as pyridine, 2,2'-dipyridine, 4,4'-dimethyl-2,2'-dipyridine, 1,10-phenanthroline, 3,4,7,8-tetramethylphenanthroline, 2,4,6-tris(2-pyridyl-s-triazine) and related ligands.

[0148] In an alternative embodiment, heat can be used to initiate the hardening or polymerization of the free radical active groups.

[0149] Examples of heat sources suitable for the dental materials of the present invention include induction, convection and radiation. The heat source should be capable of generating a temperature of at least 40 °C to 15 °C under normal conditions or at elevated pressures.

[0150] Thermal curing procedures are sometimes preferably used to initiate the polymerization of materials that occur outside the oral environment, for example when the composition is used to produce grinding blanks or in the post-curing step of articles obtained by processing the composition into a resin in a layered manufacturing method.

[0151] The initiator system is generally present in the following amounts: at least 0.1 wt%, 0.2 wt% or 0.3 wt%; at most 4 wt%, 3 wt% or 2 wt%; in the range of 0.1 wt% to 4 wt%, 0.2 wt% to 3 wt%, or 0.3 wt% to 2 wt%; wt% is based on the entire composition.

[0152] The compositions described in this text contain a filler system. The filler system can contain one filler or a mixture of different types of fillers.

[0153] Adding fillers may be beneficial for example to adjust rheological properties such as viscosity.

[0154] The size of the filler particles should be such that a uniform mixture with the hardenable components forming the resin matrix can be obtained.

[0155] The average particle size of the filler may be in the range of 5 nm to 50 μm. If desired, the measurement of the particle size of the filler particles may be performed as described in the Examples section.

[0156] The filler is typically a non-acid reactive filler. A non-acid reactive filler is a filler that does not undergo an acid / base reaction with an acid.

[0157] Useful non-acid-reactive fillers include fumed silica, fillers based on non-acid-reactive fluoroaluminosilicate glasses, quartz, ground glass, water-insoluble fluorides such as CaF2, silica gels such as silicic acid, especially fumed silicic acid and particles thereof, cristobalite, calcium silicate, zirconium silicate, zeolites, including molecular sieves.

[0158] Suitable fumed silicas include, for example, those sold under the trade name Aerosil TM Products sold in the series OX-50, -130, -150 and -200 are available from Evonik's Aerosil TM R8200, R805, CAB-O-SIL from Cabot Corp (Tuscola) TM M5, and HDK types from Wacker, such as HDK TM -H2000, HDK TM H15, HDK TM H18, HDK TM H20 and HDK TM H30.

[0159] Fillers that can also be used and provide radiopacity to dental materials include heavy metal oxides and fluorides. As used herein, "radiopacity" describes the ability to distinguish hardened dental materials from tooth structure using standard dental X-ray equipment in a conventional manner. Radiopacity of dental materials is advantageous in certain situations where X-rays are used to diagnose dental conditions. For example, radiopaque materials will allow for the detection of secondary caries that may have formed in the tooth tissue surrounding the filling.

[0160] Oxides or fluorides of heavy metals with atomic numbers greater than 28 may be preferred. The heavy metal oxide or fluoride should be selected so that undesirable colors or shades are not imparted to the hardened resin in which the heavy metal oxide or fluoride is dispersed. For example, iron and cobalt are disadvantageous because they impart dark and contrasting colors to the neutral tooth color of the dental material. More preferably, the heavy metal oxide or fluoride is an oxide or fluoride of a metal with an atomic number greater than 30. Suitable metal oxides are oxides of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanides (i.e., elements with atomic numbers within the range of 57-71 (including end values)), cerium, and combinations thereof. Suitable metal fluorides are, for example, yttrium trifluoride and ytterbium trifluoride. Most preferably, oxides and fluorides of heavy metals with atomic numbers greater than 30 but less than 72 are optionally included in the material of the present invention. Particularly preferred radiopaque metal oxides include lanthanum oxide, zirconium oxide, yttrium oxide, ytterbium oxide, barium oxide, strontium oxide, cerium oxide, and combinations thereof. The heavy metal oxide particles may be aggregated. If so, preferably, the average diameter of the aggregated particles is equal to or less than 200 nm.

[0161] Other suitable fillers to increase radiopacity are barium and strontium salts, particularly strontium sulfate and barium sulfate.

[0162] Fillers that may also be used include nanosized fillers such as nanosized silica or a mixture of nanosized silica and zirconia particles. Suitable nanosized particles typically have an average particle size in the range of 5 nm to 50 nm.

[0163] The preferred nano-sized silica is available under the trade name NALCO TM Colloidal silica was purchased from Nalco Chemical Co. (Naperville, Ill.) (e.g., preferred silica particles can be obtained from Nalco using TMProducts 1040, 1042, 1050, 1060, 2327 and 2329 are available from Nissan Chemical America Company, Houston, Texas (e.g., SNOWTEX-ZL, -OL, -O, -N, -C, -20L, -40 and -50); available from Admatechs Co., Ltd., Japan (e.g., SX009-MIE, SX009-MIF, SC1050-MJM and SC1050-MLV); available from Grace GmbH & Co. KG, Worms, Germany (e.g., available under the trade name LUDOX TM available from Akzo Nobel Chemicals GmbH, Leverkusen, Germany (e.g., available under the trade name LEVASIL TM % and 500 / 15%), and are commercially available from Bayer MaterialScience AG, Leverkusen, Germany (e.g., available under the trade name DISPERCOLL TM S obtained, such as 5005, 4510, 4020 and 3030).

[0164] Surface treating the filler particles before loading into the dental material can provide a more stable dispersion in the resin. Preferably, the surface treatment stabilizes the particles so that the particles will disperse well in the resin and produce a substantially homogeneous composition.

[0165] Suitable surface treatments or surface modifiers include silane treatments that are capable of polymerizing with the resin. Preferred silane treatments include gamma-methacryloxypropyltrimethoxysilane (available commercially under the trade name A-174 (Momentive)) and gamma-glycidoxypropyltrimethoxysilane (available commercially under the trade name G6720 (United Chemical Technologies (Bristol, Pa.)).

[0166] Thus, silica particles, as well as other suitable non-acid reactive fillers, can be treated with a resin-compatible surface treatment agent.

[0167] Suitable fillers may also be characterized by the following properties, alone or in combination: Specific surface area (BET): 10 m 2 / g to 400m 2 / g, or 15m 2 / g to 300m 2 / g, or 20m 2 / g to 200m 2 / g; particles comprising SiO2, ZrO2 and mixtures thereof, especially mixtures thereof.

[0168] If desired, the specific surface area can be determined according to the method suggested by Brunauer, Emmet and Teller (BET) by using an apparatus (Monosorb) from Quantachrome.

[0169] The filler may comprise, contain, consist essentially of or consist of aggregated nanometer-sized particles. If desired, this may be demonstrated by transmission electron microscopy (TEM).

[0170] Once dispersed in the resin, the aggregated nanosized fillers are typically maintained in the aggregated stage. That is, the particles are not broken into discrete (ie, individual) and unassociated (ie, non-agglomerated, non-aggregated) particles during the dispersion step.

[0171] Agglomerated fillers and methods of their production and surface treatment are described, for example, in US 6,730,156 (Wu et al.) and US 6,730,156 (Windisch et al.).

[0172] The amount of filler used in the filler system generally depends on the purpose for which the composition is to be used.

[0173] The filler system is typically present in an amount of at least 20%, 30% or 40% by weight; up to 90%, 85% or 80% by weight; ranging from 20% to 90%, 30% to 85%, or 40% to 80% by weight; the weight % being relative to the total composition.

[0174] Depending on the application, the amount of filler system is generally adjusted.

[0175] Temporary crown and bridge materials (as examples of dental compositions) generally do not contain significant amounts of fillers. In these compositions, the filler content is generally in the range of 30% to 60% by weight relative to the total composition.

[0176] In dental filling materials (as an example of a dental composition; sometimes also called dental composites), which typically contain higher amounts of fillers than temporary crown and bridge materials, the filler content is typically in the range of 60 to 90 wt % relative to the total composition.

[0177] Lower viscosity dental filling materials (sometimes also referred to as "flowables") typically have a filler content in the range of 50% to 80% by weight relative to the total composition.

[0178] The compositions described herein may comprise additional components.

[0179] Additional components that may be present include plasticizers and adjuvants.

[0180] Plasticizers may contain hydroxyl groups, but generally do not contain polymerizable moieties.

[0181] If present, the plasticizer containing hydroxyl groups can contain two or more primary or secondary aliphatic hydroxyl groups (i.e., the hydroxyl groups are directly bonded to non-aromatic carbon atoms). The hydroxyl groups can be located at the terminal ends, or they can be pendant to the polymer or copolymer. The molecular weight of the hydroxyl-containing organic material can be changed from very low (e.g., 32 g / mol) to very high (e.g., one million or more g / mol). Suitable hydroxyl-containing materials can have a low molecular weight, i.e., 32 g / mol to 200 g / mol, a medium molecular weight, i.e., 200 g / mol to 10,000 g / mol, or a high molecular weight, i.e., greater than 10,000 g / mol. As used herein, all molecular weights are weight average molecular weights.

[0182] The plasticizer containing hydroxyl groups can be non-aromatic in nature or can contain aromatic functional groups. The plasticizer containing hydroxyl groups can optionally contain heteroatoms such as nitrogen, oxygen, sulfur, etc. in the molecular backbone. The plasticizer can, for example, be selected from naturally occurring or synthetically prepared cellulosic materials.

[0183] Representative examples of suitable hydroxyl group-containing plasticizers include alkanols, monoalkyl ethers of polyoxyalkylene glycols, monoalkyl ethers of alkylene glycols, and other plasticizers known in the art.

[0184] Representative examples of useful plasticizers include alkylene glycols (e.g., 1,2-ethanediol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 2-ethyl-1,6-hexanediol, bis(hydroxymethyl)cyclohexane, 1,18-dihydroxyoctadecane, 3-chloro-1,2-propanediol); polyhydroxyalkanes (e.g., glycerol, trimethylolethane, pentaerythritol, sorbitol) and other polyhydroxy compounds such as N,N-bis(hydroxyethyl)benzamide; 2-butyne-1,4-diol; 4,4-bis(hydroxymethyl)diphenyl sulfone; and castor oil.

[0185] Representative examples of useful plasticizers containing polymeric hydroxyl groups include polyoxyethylene and polyoxypropylene glycols, particularly polyoxyethylene and polyoxypropylene glycol diols and triols having a molecular weight of 200 g / mol to 10,000 g / mol, corresponding to a hydroxyl equivalent weight of 100 to 5,000 for the diols or 70 to 3,300 for the triols; polytetramethylene ether glycols of varying molecular weights, such as polytetrahydrofuran or "polyTHF"; copolymers of hydroxypropyl and hydroxyethyl acrylates and hydroxypropyl and hydroxyethyl methacrylates with other free radical polymerizable monomers such as acrylic esters, vinyl halides, or styrene; copolymers containing pendant hydroxyl groups formed by hydrolysis or partial hydrolysis of vinyl acetate copolymers, polyvinyl acetal resins containing pendant hydroxyl groups; modified cellulosic polymers such as hydroxyethylated and hydroxypropylated cellulose; hydroxyl terminated polyesters; hydroxyl terminated polylactones, particularly polycaprolactones; fluorinated polyoxyethylene or polyoxypropylene glycols; and hydroxyl terminated polyalkadienes.

[0186] Blends of various hydroxyl group-containing plasticizers are also included in this context.

[0187] The plasticizer is typically present in an amount of: 0 wt % or at least 1 wt % or 5 wt %; up to 20 wt %, 15 wt % or 10 wt %; ranging from 0 wt % to 20 wt %, 1 wt % to 15 wt %, or 5 wt % to 10 wt %; the wt % being relative to the weight of the entire composition.

[0188] The composition may also contain suitable adjuvants or additives such as surfactants, rheology modifiers, retarders, stabilizers, pigments, dyes, photobleachable colorants, fluoride-releasing agents and other ingredients known to those skilled in the art.

[0189] Surfactants that may be added include polyethylene glycol-modified silicones (e.g., Silwet TM type surfactants) and polyethylene glycol-modified carbosilanes (described, for example, in US 5,750,589 (Zech et al.)).

[0190] Rheology modifiers that may be added include surface-modified fumed silicas as described above, organophilic phyllosilicates, modified ureas, and polyhydroxycarboxamides (e.g., Rheobyk® available from Byk-Chemie, Wesel, Germany). TM type).

[0191] Retarder that may be added includes 1,2-diphenylethylene and its derivatives.

[0192] Stabilizers that can be used include, in particular, free radical scavengers such as substituted and / or unsubstituted hydroxyaromatic compounds (e.g., butylated hydroxytoluene (BHT), hydroquinone, hydroquinone monomethyl ether (MEHQ), 3,5-di-tert-butyl-4-hydroxyanisole (2,6-di-tert-butyl-4-ethoxyphenol), 2,6-di-tert-butyl-4-(dimethylamino)methylphenol or 2,5-di-tert-butylhydroquinone, 2-(2'-hydroxy-5'-methylphenyl)- 2H-Benzotriazole, 2-(2'-Hydroxy-5'-tert-octylphenyl)-2H-benzotriazole, 2-Hydroxy-4-methoxybenzophenone (UV-9), 2-(2'-Hydroxy-4',6'-di-tert-amyl-phenyl)-2H-benzotriazole, 2-Hydroxy-4-n-octyloxybenzophenone, 2-(2'-Hydroxy-5'-methacryloyloxy-ethylphenyl)-2H-benzotriazole, phenothiazine and HALS (hindered amine light stabilizers).

[0193] Pigments and / or dyes that may be used include titanium dioxide or zinc sulfide (lithopone), red iron oxide 3395, Bayferrox TM 920Z yellow, Neazopon TM Blue 807 (a copper phthalocyanine-based dye) or Helio TM Fast Yellow ER. These additives can be used for individual coloring of the composition.

[0194] Examples of photobleachable colorants include rose bengal, methylene violet, methylene blue, fluorescein, eosin yellow, eosin Y, ethyl eosin, eosin blue, eosin B, erythrosine B, erythrosine yellow blends, toluidine blue, 4',5'-dibromofluorescein, and blends thereof. Other examples of photobleachable colorants can be found in US 6,444,725 (Trom et al.).

[0195] Examples of fluoride-releasing agents include naturally occurring or synthetic fluoride minerals.These fluoride sources may optionally be treated with a surface treatment agent.

[0196] The adjuvant is typically present in an amount of at least 0%, 0.01% or 0.1% by weight; up to 15%, 10% or 5% by weight; ranging from 0% to 15%, or 0.01% to 10%, or 0.1% to 5% by weight; the % by weight being relative to the weight of the entire composition.

[0197] The compositions described herein may contain the following amounts of the respective components:

[0198] a) polymerizable component A1: 3% to 50% by weight,

[0199] b) polymerizable component A2: 0% to 60% by weight,

[0200] c) Initiator system: 0.1% to 4% by weight,

[0201] d) Filler system: 20% to 90% by weight,

[0202] e) Plasticizer: 0% to 20% by weight,

[0203] f) Adjuvant: 0% to 15% by weight,

[0204] Weight % is relative to the weight of the entire dental composition.

[0205] The compositions described herein may also contain the following amounts of the respective components:

[0206] a) polymerizable component A1: 5% to 40% by weight,

[0207] b) polymerizable component A2: 1% to 50% by weight,

[0208] c) Initiator system: 0.2% to 3% by weight,

[0209] d) Filler system: 30% to 85% by weight,

[0210] e) Plasticizer: 1 to 15 wt %,

[0211] f) Adjuvant: 0.01 wt% to 10 wt%,

[0212] Weight % is relative to the weight of the entire dental composition.

[0213] The compositions described herein may also contain the following amounts of the respective components:

[0214] a) polymerizable component A1: 8% to 30% by weight,

[0215] b) polymerizable component A2: 5% to 40% by weight,

[0216] c) Initiator system: 0.3% to 2% by weight,

[0217] d) Filler system: 40% to 80% by weight,

[0218] e) Plasticizer: 5 to 10 wt %,

[0219] f) Adjuvant: 0.1 wt% to 5 wt%,

[0220] Weight % is relative to the weight of the entire dental composition.

[0221] Certain embodiments of the compositions may also be characterized by the following physical-mechanical properties, alone or in combination, after hardening:

[0222] a) Flexural strength (FS): 140 MPa*s to 200 MPa*s, determined according to ISO 4049(2019);

[0223] b) E-modulus (EM): 4 GPa to 16 GPa, determined according to ISO 4049 (2019);

[0224] c) Depth of cure (DoC): 3 mm to 7 mm, determined according to ISO 4049 (2019);

[0225] d) Bonded disc shrinkage-strain (SHR): 1.50% to 1.80%;

[0226] e) Diaphragm tensile strength (DTS): 75 to 100, determined according to ISO 7489 (2019);

[0227] f) Cusp deflection (Cusp-D): <12μm.

[0228] Certain embodiments of the compositions are characterized by the following physical-mechanical properties, alone or in combination, after hardening:

[0229] a) Flexural strength (FS): 150 MPa*s to 200 MPa*s, determined according to ISO 4049(2019);

[0230] b) E-modulus (EM): 4 GPa to 10 GPa or 12 GPa to 16 GPa, determined according to ISO 4049 (2019);

[0231] c) Depth of cure (DoC): 4 mm to 6 mm, determined according to ISO 4049 (2019);

[0232] d) Bonded disc shrinkage-strain (SHR): 1.55% to 1.75%;

[0233] e) radial tensile strength (DTS): 80 to 100, determined according to ISO 7489 (2019);

[0234] a) Cusp deflection (Cusp-D): 8 to 11.

[0235] The following combinations of physical-mechanical properties are sometimes preferred: a) and b); a) and c); a), b) and c); a), c) and f); a), c) and d).

[0236] Certain embodiments of the compositions may also be characterized by the following physical-mechanical properties, alone or in combination, prior to hardening:

[0237] a) Viscosity: 5 Pa*s to 100 Pa*s at 23°C and a shear rate of 100 s-1,

[0238] b) pH value: 6 to 8;

[0239] c) It can be hardened within 10 minutes after irradiation with light with a wavelength in the range of 400nm to 700nm.

[0240] For flowable composites, the following combinations of physical-mechanical properties are sometimes preferred: a) and b) or a) and c).

[0241] A low viscosity can be advantageous because it allows the composition to flow also in deep cavities of the prepared tooth structure, which may otherwise be difficult to fill.

[0242] Since the composition generally does not contain acidic substances, the pH value is substantially in the neutral range.

[0243] All components used in the compositions described herein should be sufficiently biocompatible, that is, the compositions should not produce a toxic, deleterious, or immunological response in living tissue.

[0244] The compositions described herein typically do not contain the following components, alone or in combination: low boiling point solvents (e.g., boiling point below 150°C at ambient pressure) in an amount of 5 weight percent or more; Bis-GMA or bisphenol A partially derived components in an amount of 2 weight percent or more; polymerizable components containing acidic moieties in an amount of 2 weight percent or more.

[0245] The compositions described herein can be obtained by combining (including mixing and kneading) the individual components of the composition, preferably under "safe light" conditions. If desired, a speed mixer can be used.

[0246] The resulting composition can be hardened within an acceptable time frame, such as less than 10 minutes or less than 5 minutes or less than 2 minutes, and to a sufficient depth using visible light source equipment already available to practitioners.

[0247] Additional embodiments of the present invention include:

[0248] Implementation Plan 1

[0249] The composition may comprise, consist essentially of, or consist of:

[0250] a) a polymerizable component A1 in an amount of 3% to 50% by weight,

[0251] b) a polymerizable component A2 in an amount of 0% to 60% by weight,

[0252] c) an initiator system in an amount of 0.1% to 4% by weight, the initiator system comprising a ketone sensitizer and an amine donor,

[0253] d) a filler system comprising nanosized particles in an amount of 20% to 90% by weight,

[0254] e) a plasticizer in an amount of 0% to 20% by weight,

[0255] f) an adjuvant in an amount of 0% to 15% by weight,

[0256] The composition does not contain a component containing a bisphenol A moiety in an amount of 5% by weight or more, the % by weight being relative to the weight of the entire composition.

[0257] Implementation Plan 2

[0258] The composition may comprise, consist essentially of, or consist of:

[0259] a) a polymerizable component A1 in an amount of 5% to 40% by weight,

[0260] b) a polymerizable component A2 characterized by the formula:

[0261] A n BA m

[0262] wherein A is an ethylenically unsaturated group,

[0263] B is selected from (i) a linear or branched C1 to C2 optionally substituted with a halide or OH 12 Alkyl, (ii) C6 to C 12aryl, or (iii) organic groups having 4 to 20 carbon atoms bonded to one another via one or more ether, thioether, ester, thioester, thiocarbonyl, amide, carbamate, carbonyl and / or sulfonyl bonds,

[0264] m and n are independently selected from 0, 1, 2, 3, 4, 5 or 6, provided that n+m is greater than 0,

[0265] The amount thereof is 1% to 50% by weight,

[0266] c) an initiator system in an amount of 0.1% to 4% by weight, the initiator system comprising a ketone sensitizer and an amine donor,

[0267] d) a filler system comprising nanosized silica particles in an amount of 20% to 90% by weight,

[0268] e) a plasticizer in an amount of 0% to 20% by weight,

[0269] f) an adjuvant in an amount of 0% to 15% by weight,

[0270] The composition does not contain a bisphenol A-containing component in an amount of 5% by weight or more,

[0271] Weight % is relative to the weight of the entire composition.

[0272] Implementation Plan 3

[0273] The compositions described herein may comprise, consist essentially of, or consist of:

[0274] a) a polymerizable component A1 in an amount of 3% to 50% by weight,

[0275] b) a polymerizable component A2 in an amount of 5% to 60% by weight,

[0276] c) an initiator system in an amount of 0.1% to 4% by weight, the initiator system comprising a ketone sensitizer and an amine donor,

[0277] d) a filler system comprising nanosized particles in an amount of 60% to 90% by weight,

[0278] e) a plasticizer in an amount of 0% to 20% by weight,

[0279] f) an adjuvant in an amount of 0% to 15% by weight,

[0280] Weight % is relative to the weight of the entire composition.

[0281] Implementation Plan 4

[0282] The compositions described herein may comprise, consist essentially of, or consist of:

[0283] a) a polymerizable component A1 in an amount of 3% to 50% by weight,

[0284] b) a polymerizable component A2 in an amount of 0% to 60% by weight,

[0285] c) an initiator system in an amount of 0.1% to 4% by weight, the initiator system comprising a ketone sensitizer and an amine donor,

[0286] d) a filler system comprising nanosized particles in an amount of 50% to 80% by weight,

[0287] e) a plasticizer in an amount of 0% to 20% by weight,

[0288] f) an adjuvant in an amount of 0% to 15% by weight,

[0289] Weight % relative to the weight of the entire composition, the composition at 23 ° C and 100s -1 The viscosity is 5 Pa*s to 100 Pa*s.

[0290] The composition is typically provided to the practitioner under sanitary conditions. During storage, the composition is typically packaged in a suitable packaging and / or delivery device.

[0291] One possibility for achieving this involves packaging or storing the composition in a sealed container.

[0292] Suitable containers may have a front end and a rear end, a piston capable of moving within the container, and a nozzle or cannula for delivering or dispensing the composition located within the container. The container typically has only one compartment or reservoir.

[0293] The volume of the container is typically in the range of 0.1 ml to 100 ml, or 0.5 ml to 50 ml, or 1 ml to 30 ml.

[0294] Suitable disposable containers can have a volume in the range of 0.1 ml to 2 ml. This is the volume typically required for a single administration protocol. Such containers are typically used only once (e.g., disposable packaging).

[0295] The composition can be dispensed from the container by moving the piston in the direction of the nozzle.The piston can be moved manually or with the aid of an applicator or applicator designed to receive the container (for example, an applicator having a caulking gun design).

[0296] Examples of containers that can be used include pressurized capsules, syringes, and screw-on tubes.

[0297] The capsule typically has a cylindrical housing with a front end and a rear end and a nozzle. The rear end of the housing is typically sealed by a movable piston. Typically, an applicator with a movable plunger (e.g., an applicator in the shape of a caulking gun) is used to dispense the dental composition from the capsule or container.

[0298] Examples of suitable bladders or containers are described in US 5,624,260 (Wilcox et al.), EP 1 340 472 A1 (Centrix), US 2007 / 0172789 A1 (Mueller et al.), and US 5,865,803 (Major). Other suitable containers are exemplified in US 5,927,562 (Hammen et al.) and US 2011 / 151403 A1 (Pauser et al.).

[0299] It is advantageous if the container used comprises a nozzle of a certain shape and size, which allows the composition to be applied easily and safely to the soft tooth tissue surrounding the tooth to be restored, also in the vicinity of the interdental area.

[0300] The smaller the diameter of the nozzle, the easier it is to place the nozzle in the area between two teeth. However, a small diameter nozzle may result in an increase in the extrusion force required to dispense the composition out of the device. Therefore, not all cannula sizes and diameters are equally suitable. It has been found that devices with nozzles or cannulae having an outer diameter in the range of 0.6 mm to 1.3 mm and an inner diameter in the range of 0.2 mm to 0.9 mm are particularly useful.

[0301] Another embodiment of the present invention relates to a kit comprising at least two, three, four, five, six or more compositions that differ from each other at least in their color.As mentioned above, the compositions are typically stored in containers.

[0302] The compositions described herein are particularly useful in the dental and orthodontic fields.

[0303] The composition may be used as or for producing a dental restoration.Dental restorations are typically produced outside the patient's mouth and inserted later in a processing step.

[0304] Examples of dental restorations include direct restorative materials (eg, anterior and posterior restorations), prostheses, veneers, artificial crowns, artificial teeth, dentures, and the like.

[0305] As used herein, the term "prosthesis" refers to a composite that is shaped and polymerized for its ultimate use (eg, as a crown, bridge, veneer, inlay, onlay, etc.) prior to placement adjacent to a tooth.

[0306] When applying the dental material to the teeth, the teeth may optionally be pretreated with a primer such as a dentin or enamel adhesive by methods known to those skilled in the art.

[0307] More specifically, the composition can be used to treat hard dental tissue in the mouth of a mammal, particularly a human.

[0308] This approach typically involves the following steps:

[0309] a) contacting the composition described herein with the surface of hard tooth tissue

[0310] b) hardening the composition.

[0311] More particularly, the method may comprise the following steps:

[0312] c) applying the dental composition to the surface of the hard tooth tissue; if desired, the surface of the hard tooth tissue can be an etched surface (e.g., with phosphoric acid) or a non-etched surface,

[0313] d) optionally spreading the dental composition onto the film, preferably using a stream of air,

[0314] e) Radiation curing of dental compositions.

[0315] In particular, the composition can be used as a composite filling material, a cavity liner, a fixing material for an orthodontic appliance, or a sealant.

[0316] The term "composite filling material" refers to a dental composition that is filled. Dental composites are commonly used to repair missing tooth structure in a patient's mouth.

[0317] "Cavity liner" refers to a composition used to protect the dental pulp prior to the application of a composite filling material or dental restoration.

[0318] As used herein, the term "sealant" refers to a lightly filled dental composite material that cures after being placed adjacent to a tooth. Sealants are typically applied to back teeth and form a protective cap over the tooth's enamel.

[0319] In a preferred aspect, the dental material is a low viscosity dental filling material.

[0320] In further embodiments, the dental compositions described herein are used to produce dental mill blanks.

[0321] Dental mill blanks can be produced by placing a curable composition in a mold followed by a curing step.

[0322] In another embodiment, the dental composition is used as a resin in an additive manufacturing process for producing three-dimensional objects, such as dental articles, layer by layer, for example by applying 3D printing technology.

[0323] The present invention also relates to a kit comprising the composition described herein and the following items, alone or in combination: a dental adhesive; a dental primer; a dispensing device; a polishing device; a dental curing light; and optionally instructions for use.

[0324] Dental adhesives are typically acidic dental compositions with relatively low viscosities (e.g., 0.01 Pa*s to 3 Pa*s at 23°C). Dental adhesives interact directly with the enamel or dentin surface of the teeth. Dental adhesives are typically one-part compositions that are radiation-curable and comprise an ethylenically unsaturated component having an acidic moiety, an ethylenically unsaturated component not having an acidic moiety, water, a sensitizer, a reducing agent, and additives.

[0325] Examples of dental adhesives are described in US 2020 / 0069532 A1 (Thalacker et al.) and US 2017 / 0065495 A1 (Eckert et al.). Dental adhesives are also commercially available, such as 3M TM Scotchbond TM Universal (3M Oral Care).

[0326] Suitable dental primers are described in US 6,126,922 (Rozzi et al.) and WO 00 / 69393 A1 (3M). Dental primers are also commercially available, for example from 3M TM Transbond TM XT Primer (3M OralCare).

[0327] Suitable polishing equipment includes rubber pads, polishing pastes and polishing discs. Polishing devices are also commercially available, such as Soflex TM Tray (3M Oral Care).

[0328] Suitable dental curing lights are described in US 10,758,126 B2 (Geldmacher et al.) or US 10,231,810 B2 (Gramann et al.). Dental curing lights are also commercially available, for example from 3M TM Elipar TM S10 or 3M TM Elipar TM DeepCureS LED curing light (3M Oral Care).

[0329] Suitable dispensing devices are described in US 2021 / 113301 A1 (Pauser et al.). Dispensing devices are also commercially available, for example from 3M TM Capsule dispenser (3M Oral Care).

[0330] The instructions describe how the dental composition should be used in everyday practice, for example outlining the application steps and curing conditions.

[0331] The entire disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety, as if each were individually incorporated. Various modifications and variations of the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. The above specifications, examples, and data provide a description of the manufacture and use of the compositions of the present invention and the methods of the present invention. The present invention is not limited to the embodiments disclosed herein. It will be understood by those skilled in the art that many alternative embodiments of the present invention may be prepared without departing from the spirit and scope of the present invention.

[0332] The following examples are given to illustrate the present invention.

[0333] Example

[0334] Unless otherwise stated, all parts and percentages are based on weight, all water is deionized water, and all molecular weights are weight average molecular weight (g / mol). In addition, unless otherwise stated, all experiments were performed under ambient conditions (23° C.; 1013 mbar). In addition, almost all process steps were performed under a dry air atmosphere.

[0335] method

[0336] pH

[0337] If desired, the pH of the composition can be determined as follows: pH sensitive paper (Carl Ross TM Carl Roth TM Moisten a pH-sensitive paper strip. Place a small portion of the composition to be tested on the moistened pH-sensitive paper. After 5 seconds, determine the color change of the pH-sensitive paper.

[0338] Particle size distribution (non-nanosized particles)

[0339] If desired, the particle size distribution can be determined by light scattering, for example using the apparatus Horiba (Horiba, JP).

[0340] A light scattering particle size analyzer illuminates a sample with laser light and analyzes the intensity fluctuations of light scattered from particles at an angle of 173 degrees. This instrument can calculate particle size using photon correlation spectroscopy (PCS). PCS uses fluctuating light intensity to measure the Brownian motion of particles in a liquid. The particle size is then calculated as the diameter of a sphere moving at the measured velocity.

[0341] The intensity of light scattered by a particle is proportional to the sixth power of the particle diameter. The Z-average size, or cumulative mean, is the average value calculated from the intensity distribution and is based on the assumption that the particles are unimodal, monodisperse, and spherical. The correlation function calculated from the fluctuating light intensity is the intensity distribution and its mean. The mean of the intensity distribution is calculated based on the assumption that the particles are spherical. The Z-average size and the intensity distribution mean are more sensitive to larger particles than to smaller particles.

[0342] The volume distribution gives the percentage of the total particle volume that corresponds to particles within a given size range. The volume-average size is the size of the particle corresponding to the mean of the volume distribution. Since the volume of a particle is proportional to the cube of its diameter, this distribution is less sensitive to larger particles than the Z-average size. Therefore, the volume-average size is usually a smaller value than the Z-average size. Within the scope of this document, the Z-average size is referred to as the "average particle size."

[0343] Particle size distribution (nano-sized particles)

[0344] The measurement of the nanoparticle size is preferably based on the TEM (Transmission Electron Microscopy) method, whereby the population is analyzed to obtain the average particle size. The preferred method for measuring the particle size can be described as follows:

[0345] A sample approximately 80 nm thick was placed on a 200-mesh copper grid with a carbon-stabilized polyvinyl acetate substrate (SPI Supplies-Structure Probe, Inc., West Chester, PA). Transmission electron micrographs (TEM) were taken at 200 kV using a JEOL 200CX (JEOL, Ltd., Akishima, Japan, and sold by JEOL USA, Inc.). The overall size of approximately 50-100 particles was measured and the average diameter was determined.

[0346] Flexural strength (FS)

[0347] If necessary, flexural strength can be measured according to ISO 4049 (2019) using a universal testing machine (Zwick Z010, crosshead speed 1 mm / min). Flexural strength is usually given in MPa.

[0348] E-modulus (EM)

[0349] If desired, EM can be determined according to ISO 4049 (2019) and given in [GPa].

[0350] Shrinkage-strain of bonded disc (SHR)

[0351] If desired, the bond disc shrinkage-strain can be determined according to the Watts protocol described in more detail in: Dent. Mater. 1991, 7, 281-287. Unit: [%].

[0352] Depth of Cure (DoC)

[0353] The depth of cure (i.e., depth of cure) was determined according to ISO 4049 (2019) by filling the paste sample into a cylindrical metal curing mold (8 mm deep, 4 mm diameter) and using Elipar TM Trilight standard (800mW / cm 2 (3M Oral Care) samples were cured for 40 seconds for analysis. The cured samples were removed from the mold and, after curing for less than about one minute, the uncured paste was scraped off the sample with a plastic applicator. Results are reported as the average of three replicates.

[0354] Refractive index (n D 20 )

[0355] If desired, the refractive index can be measured with a Kruess AR 4D device (refractometer according to the Abbe measurement principle).The refractive index is typically measured at 20.0°C at a wavelength of 589 nm.

[0356] Viscosity (η)

[0357] If desired, viscosity can be measured using a Physica MCR 301 (Anton Paar Germany GmbH, Ostfildern-Scharnhausen, Germany). Monomers were tested using a 25 mm / 1° cone / plate system at 23.0°C and a shear rate of 100 g / s. Flowable composites were measured at 25.0°C using a 15 mm plate / plate system and a 0.2 mm gap at a shear rate of 100 g / s.

[0358] Cusp deflection (Cusp-D)

[0359] If desired, cusp deflection can be measured as follows:

[0360] A slot was machined into a rectangular 15×10×8 mm aluminum block. The slot was 8 mm long, 4.0 mm deep, and 4.0 mm wide and was located 2 mm from the edge, thus forming a 4 mm wide aluminum cusp adjacent to a 4 mm wide cavity containing the dental composition being tested. A linear variable displacement transducer (model GT 1000, used with an E309 analog amplifier, both from RDP Electronics, UK) was positioned to measure the displacement of the tooth cusp while the dental composition was light cured at room temperature. Prior to testing, a Rocatec TM Plus Special Surface with Sandblasting Material (3M OralCare) The slots in the aluminum block were sandblasted and the aluminum block was sandblasted with RelyX TM Ceramic primer (3M OralCare) and finally Scotchbond dental adhesive TM Universal (3M OralCare) Processing.

[0361] The slot was completely filled with the paste sample, which was equivalent to approximately 250 mg of material. The material was cured with a dental curing light (Elipar TM S10, 3M Oral Care) was irradiated for 1 minute with the dental curing light positioned close (approximately 2 mm) to the material in the slot, and the displacement of the tooth tip in microns was recorded 9 minutes after the light was turned off.

[0362] Radial tensile strength (DTS)

[0363] If necessary, DTS can be measured according to the following method:

[0364] The paste sample was injected into a 4 mm (inner diameter) glass tube; the tube was capped with a silicone rubber stopper; and then heated at approximately 2.88 kg / cm 2 The tube was compressed axially for 5 minutes. TM The samples were light cured for 4*20 s using a DeepCure dental curing light (3M Oral Care).

[0365] The cured samples were then cut with a diamond saw to form 2.5 mm long cylindrical plugs for compressive strength measurement. The plugs were stored in deionized water at 36°C for approximately 24 hours prior to testing. Measurements were performed according to ANSI / ADA specification 27 on a Zwick / Roell universal tester (Zwick / Roell GmbH & Co. KG, Ulm, Germany) at a crosshead speed of 1 mm / min using a 10 kilonewton (kN) load cell.

[0366] Composition

[0367] abbreviation

[0368] The names and / or structures of the components used are given in Table 1.

[0369]

[0370]

[0371]

[0372]

[0373]

[0374] Table 1; CE represents comparative examples, IE represents embodiments of the present invention.

[0375] Synthesis of compound (A)

[0376] Compound (A) can be prepared as follows:

[0377] General Procedure 1: Synthesis of alkoxylated intermediates using, for example, ethylene carbonate (EC)

[0378] Under a protective N2 atmosphere, a phenolic compound (e.g., resorcinol) and glycidyl phenyl ether (1 equivalent per phenolic OH group) and a basic catalyst (e.g., KOH or NaOH or KOtBu, at least 3 mol% relative to 1 phenolic OH group) are stirred at a temperature of at least 100°C until the epoxy groups are completely reacted (via the reaction in CD3OD). 1 H NMR measurement). Ethylene carbonate was then added (at least 1 ethylene carbonate per 1 initial phenolic OH group) and the mixture was stirred at a temperature of at least 140°C until the ethylene carbonate had reacted completely (via the 1H NMR detection). The two reaction steps can be carried out sequentially as a one-pot reaction or as two separate reactions. The synthesis of the alkoxylated intermediate can be carried out as a classic batch reaction (pressureless or pressurized) or continuously under pressure using a flow reactor.

[0379] The reaction mixture was then cooled to about 80°C and 130 wt% of 2N NaOH solution (relative to theoretical yield) was added. The mixture was heated to reflux for at least 2 hours, so that the carbonate in the EO side chain was hydrolyzed (via 1 (HNMR detection). The mixture is cooled to room temperature and diluted with 200% by weight of toluene or ethyl acetate (relative to the theoretical yield). The organic phase is separated and extracted several times with water. 10% by weight of NaCO and 10% by weight of charcoal (each relative to the theoretical yield) are then added to the organic phase, and the mixture is stirred overnight under air. After filtering from the NaCO / charcoal, the filtrate is filtered again through 20% by weight of neutral alumina (relative to the theoretical yield) and the solvent is stripped from the filtrate in vacuo. The yield of the ethoxylated intermediate is approximately 90%.

[0380] General procedure 2: Esterification of alkoxylated intermediates with, for example, methacrylic acid (MA)

[0381] To the ethoxylated intermediate in, for example, hexane and / or cyclohexane and / or toluene, BHT and / or HQME, optional methylene blue and / or PTZ, for example, methanesulfonic acid or H2SO4 as a catalyst and for example methacrylic acid are added. Water is removed using a Dean Starck apparatus under reflux. After the reaction is complete, the crude reaction mixture is extracted at least twice with an aqueous NaOH solution (4N or 2N), then washed at least once with water, optionally dried over anhydrous Na2SO4. After filtering, the filtrate is filtered through neutral alumina again. At least 100ppm of BHT and 100ppm of HQME are added to the filtrate. The solvent is then stripped under vacuum while air is bubbled through the crude sample. The final monomer yield is approximately 90%.

[0382] Synthesis of ERGP-MA (Comparative Example 1) :

[0383] ERGP-MA was synthesized according to WO 2012 / 106083 A1 (3M Company (3M)), page 45.

[0384] Synthesis of ERGP-A (Comparative Example 2) :

[0385] ERGP-A was synthesized according to WO 2012 / 106083 A1 (3M Company (3M)), page 45.

[0386] Synthesis of RGP2.2EO-DMA (Example 1 of the Present Invention) :

[0387] According to General Procedure 1, 25.0 g of R, 68.6 g of GP, and 79.9 g of EC were reacted using KOtBu as a catalyst. 112 g of RGP2.2EO (225 mmol, 98.9%) were isolated as a light yellow liquid. According to General Procedure 2, 49.9 g of RGP2.2EO, 25.8 g of MA, 94.7 mg of HQME, 3.80 mg of PTZ, and 2.30 g of MSA were reacted using cyclohexane:toluene = 92.5:7.50 as a solvent. 58.5 g of RGP2.2EO-DMA (92.2 mmol, 92.2%) were isolated as a light yellow oil: η = 5.5 Pa*s, n D 20 =1.542.

[0388] Synthesis of RGP3.3EO-DMA (Example 2 of the Present Invention) :

[0389] According to General Procedure 1, 60.0 g of R, 165 g of GP, and 288 g of EC were reacted using KOH as a catalyst. 290 g of RGP3.3EO (494 mmol, 90.7%) were isolated as a light yellow liquid. According to General Procedure 2, 96.0 g of RGP3.3EO, 43.7 g of MA, 175 mg of HQME, 7.00 mg of PTZ, and 4.20 g of MSA were reacted using cyclohexane:toluene = 70.0:30.0 as a solvent. 109 g of RGP3.3EO-DMA (140 mmol, 91.0%) were isolated as a light yellow oil: η = 3.8 Pa*s, n D 20 =1.538.

[0390] Synthesis of RGP3.4EO-DMA (Example 3 of the Present Invention) :

[0391] According to General Procedure 1, 25.0 g of R, 68.6 g of GP, and 120 g of EC were reacted using KOtBu as a catalyst. 120 g of RGP3.4EO (205 mmol, 90.2%) were isolated as a light yellow liquid. According to General Procedure 2, 109 g of RGP3.4EO, 49.8 g of MA, 199 mg of HQME, 8.00 mg of PTZ, and 4.80 g of MSA were reacted using cyclohexane:toluene = 70.0:30.0 as a solvent. 126 g of RGP3.4EO-DMA (180 mmol, 93.3%) were isolated as a light yellow oil: η = 3.6 Pa*s, n D 20 =1.538.

[0392] Synthesis of RGP3.8EO-DMA (Example 4 of the Present Invention) :

[0393] According to General Procedure 1, 20.0 g of R, 54.9 g of GP, and 118 g of EC were reacted using KOH as a catalyst. 102 g of RGP3.8EO (175 mmol, 96.3%) were isolated as a light yellow liquid. According to General Procedure 2, 102 g of RGP3.8EO, 45.6 g of MA, 185 mg of HQME, 7.40 mg of PTZ, and 6.30 g of MSA were reacted using cyclohexane:toluene = 70.0:30.0 as a solvent. 118 g of RGP3.8EO-DMA (165 mmol, 93.4%) were isolated as a light yellow oil: η = 3.3 Pa*s, n D 20 =1.538.

[0394] Synthesis of BCGP2.5EO-DMA (Example 5 of the Present Invention) :

[0395] According to General Procedure 1, 33.4 g of BC, 63.7 g of GP and 69.6 g of EC were reacted using KOH as a catalyst. 114 g of BCGP2.5EO (192 mmol, 95.5%) were isolated as a light yellow liquid. According to General Procedure 2, 114 g of BCGP2.5EO, 49.5 g of MA, 204 mg of HQME, 8.20 mg of PTZ and 7.00 g of MSA were reacted using cyclohexane:toluene = 70.0:30.0 as a solvent. 130.4 g of BCGP2.5EO-DMA (179 mmol, 93.5%) were isolated as a light yellow oil: η = 5.3 Pa*s, n D 20 =1.535.

[0396] Synthesis of PhloGP6EO-TMA (Example 6 of the Present Invention) :

[0397] According to General Procedure 1, 20.2 g of Phlo, 72.6 g of GP and 141 g of EC were reacted using KOH as a catalyst. 119 g of PhloGP6EO (142 mmol, 88.4%) were isolated as a light yellow liquid. According to General Procedure 2, 70.6 g of PhloGP6EO, 32.5 g of MA, 516 mg of HQME, 15.5 mg of PTZ and 3.09 g of MSA were reacted using cyclohexane:toluene = 20.0:80.0 as a solvent. 83.2 g of PhloGP6EO-TMA (79.6 mmol, 94.8%) were isolated as a light yellow oil: η = 14.6 Pa*s, n D 20 =1.538.

[0398] Synthesis of PhloGP6EO-TA (Example 7 of the Present Invention) :

[0399] According to General Procedure 1, 20.2 g of Phlo, 72.6 g of GP and 141 g of EC were reacted using KOH as a catalyst. 119 g of PhloGP6EO (142 mmol, 88.4%) were isolated as a light yellow liquid. According to General Procedure 2, 87.1 g of PhloGP6EO, 33.6 g of AA, 603 mg of HQME, 18.1 mg of PTZ and 3.70 g of MSA were reacted using cyclohexane:toluene = 20.0:80.0 as a solvent. 95.6 g of PhloGP6EO-TA (95.3 mmol, 92.0%) were isolated as a light yellow oil: η = 30.3 Pa*s, n D 20 =1.543.

[0400] Some properties of the synthesized components are given in Table 2.

[0401] Components Molecular weight Viscosity (Pa*s) Refractive index CE1 634.7 9.4 1.542 CE2 606.7 18.8 1.547 IE1 634.7 5.5 1.542 IE2 695.1 3.8 1.538 IE3 703.0 3.6 1.538 IE4 716.7 3.3 1.538 IE5 727.41 5.3 1.535 IE6 1045.2 14.6 1.538 IE7 1003.1 30.3 1.543

[0402] Table 2

[0403] The polymerizable components of the present invention are low in viscosity, have a sufficiently high refractive index and do not contain bisphenol-A moieties.

[0404] Synthesis of light-curable one-component compositions

[0405] Some of the synthesized compounds were used to produce (dental) compositions. The compositions produced and tested with regard to their mechanical properties are given in Table 3 below. In Table 3, the values ​​for components a) to i) represent the weight % of the respective component in the corresponding formulation.

[0406] General Procedure A :

[0407] The initiator system components were dissolved in the monomers under magnetic stirring and in the dark at a temperature not higher than 50°C (depending on the intrinsic viscosity of the monomers used).

[0408] General Procedure B :

[0409] The initiator system components were dissolved in the monomers according to General Procedure A. The filler was mixed in batches with the mixture of the initiator system and monomers using a double-arm kneader in the dark. The amount of filler was manually determined based on the desired handling properties of the dental composition. The curing was then performed using an 800 mW halogen curing lamp (3M Oral Care, Elipar TM The dental compositions were light cured using Trilight and tested according to the corresponding measurements listed above. The corresponding values ​​are given in Table 3.

[0410] Composition A contains component a) but does not contain compound (A) according to the present invention. In Table 2 below, compound (A) is represented by components b) to e). Therefore, composition A can be considered a comparative example, while compositions B to E can be considered examples of the present invention.

[0411]

[0412]

[0413] Table 3; “*” embodiment of the present invention

[0414] It can be seen that the composition containing the compound (A1) according to the present invention is superior in certain properties (e.g., FS, EM, DTS) or shows sufficient properties at a high level in other aspects (e.g., DoC, SHR, Cusp-D) compared to the composition not containing the compound (A1) according to the present invention.

Claims

1. A dental composition comprising a) a resin matrix, b) initiator system, c) Filler system, The resin matrix comprises a polymerizable component A1 characterized by any one of the following formulas (I), (II) or (III) in X = independently selected from H, alkyl, I, Br, Cl, Z = independently selected from H, CH3, CH2OH, n, m = independently selected integers ranging from 1 to 10, (m+n)=1 to 10, R = independently selected from H, CH3, in X = independently selected from H, alkyl, I, Br, Cl, Z = independently selected from H, CH3, CH2OH, k, n, m = independently selected integers ranging from 1 to 10, (k+m+n)=1 to 15, R = independently selected from H, CH3, and mixtures thereof.

2. The dental composition according to claim 1, wherein the polymerizable component A1 is selected from in m, n, k = independently selected integers ranging from 1 to 10, and (m+n)=1 to 10, or (m+n+k)=1 to 15, and mixtures thereof.

3. The dental composition according to claim 1 , wherein the polymerizable component A1 is characterized by the following properties, alone or in combination: a) Viscosity: 2Pa*s to 40Pa*s, at 23°C and 100s -1 At a shear rate of 25 mm / 1° cone / plate system; b) Refractive index: 1.520 to 1.565, measured at 20.0° C. at a wavelength of 589 nm.

4. The dental composition according to claim 1 or 2, wherein the resin matrix comprises one or more polymerizable components A2 different from the polymerizable component A1, wherein the polymerizable component A2 is characterized by the following formula: IN n NOT m wherein A is an ethylenically unsaturated group, B is selected from (i) a linear or branched C1 to C2 optionally substituted by halogen or OH 12 Alkyl, (ii) C6 to C 12 aryl, or (iii) organic groups having 4 to 20 carbon atoms bonded to one another via one or more ether, thioether, ester, thioester, thiocarbonyl, amide, carbamate, carbonyl and / or sulfonyl bonds, m and n are independently selected from 0, 1, 2, 3, 4, 5 or 6, with the proviso that n+m is greater than 0.

5. The dental composition of claim 1 or 2, wherein the initiator system comprises a photoinitiator system.

6. The dental composition according to claim 1 or 2, wherein the filler system comprises nano-sized particles and is present in an amount of 20% to 90% by weight relative to the weight of the entire composition.

7. The dental composition of claim 4, comprising the following amounts of components: a) polymerizable component A1: 3% to 50% by weight, b) polymerizable component A2: 0% to 60% by weight, c) Initiator system: 0.1% to 4% by weight, d) Filler system: 20% to 90% by weight, e) Plasticizer: 0% to 20% by weight, f) Adjuvant: 0% to 15% by weight, Weight % is relative to the weight of the entire composition.

8. The dental composition according to claim 1 or 2, which does not comprise the following components, alone or in combination: a solvent having a boiling point below 150° C. in an amount of 5% by weight or more; bisphenol A-derived components in an amount of 2% by weight or more; an amount of 2% by weight or more of a polymerizable component containing an acidic moiety, Weight % is relative to the weight of the entire composition.

9. The dental composition according to claim 1 or 2, characterized by the following features alone or in combination before hardening: a) Viscosity: 5Pa*s to 100Pa*s, at 25°C and 100s -1 At a shear rate of b) pH value: 6 to 8; c) It can be hardened within 10 minutes after irradiation with light with a wavelength in the range of 400nm to 700nm.

10. The dental composition according to claim 1 or 2, characterized by the following features after hardening, alone or in combination: a) Flexural strength: 140 MPa*s to 200 MPa*s, determined according to ISO 4049(2019); b) E-modulus (EM): 4 GPa to 16 GPa, determined according to ISO 4049 (2019); c) Cure depth: 3 mm to 7 mm, determined according to ISO 4049 (2019); d) Bonded disc shrinkage-strain: 1.50% to 1.80%, determined according to the Watts protocol; e) Radial tensile strength: 75 MPa to 100 MPa, determined according to ISO 7489 (2019); f)Curve deflection: <12μm.

11. The dental composition according to claim 4, characterized in that it comprises: a) a polymerizable component A1 in an amount of 3% to 50% by weight, b) a polymerizable component A2 in an amount of 0% to 60% by weight, c) an initiator system in an amount of 0.1% to 4% by weight, said initiator system comprising a ketone sensitizer and an amine donor, d) a filler system comprising nanosized particles in an amount of 20% to 90% by weight, e) a plasticizer in an amount of 0% to 20% by weight, f) an adjuvant in an amount of 0% to 15% by weight, Weight % relative to the weight of the entire composition, The composition does not include a component containing a bisphenol A moiety in an amount of 5 weight percent or more.

12. A kit comprising the dental composition according to claim 1 or 2 and the following items, alone or in combination: a dental adhesive; a dental primer; a dispensing device; a polishing device; a dental curing light.

13. Use of the dental composition according to claim 1 or 2 for producing dental restorations, for producing dental mill blanks, or as a resin in a laminated manufacturing process for producing dental articles.

14. The dental composition according to claim 1 or 2, which is used in a method for treating hard tooth tissue in a mammal's mouth, the method comprising the steps of applying the dental composition to the surface of the hard tooth tissue and hardening the dental composition.

15. The dental composition according to claim 1 or 2, which is used as a composite filling material, a fixing material for an orthodontic appliance, a cavity liner or a sealant.

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