RU2575579C2 - Dental composition, method for manufacturing and use - Google Patents

Abstract

FIELD: medicine, pharmaceutics.

SUBSTANCE: group of inventions refers to dentistry and concerns a dental composition, a kit using it and use thereof. The presented composition contains a compound (A), an excipient (B), an initiator (C) and a polymerised compound (D) different from the compound (A). The compound (A) contains only one frame link (U) with 6-20 carbon atoms, at least 6 carbon atoms of which form an aromatic or aliphatic cyclic fragment, whereas the rest carbon atoms are either a part of substitutes suspended to the cyclic fragment, or a part of bridge groups of spacer links (S); one or more of the rest carbon atoms can be substituted by an oxygen atom with the frame link being free from a bisphenol structure. One or two spacer links (S) are coupled with the frame link (U) through an ester bond; at least one spacer link (S) contains the chain -CH2-CH2-CH2-CH2-O-CH2-CH(Q)-OG or the residue -CH2-CH(OG)-CH2-OM or a mix of these two types of spacers in one spacer link, wherein G contains at least one group specified in acryloyl, methacryloyl, acetyl, benzoyl and combinations thereof; M contains at least one aryl group; Q contains at least one group specified in hydrogen, methyl, phenyl, phenoxymethyl and combinations thereof. Presented is using the above composition as or for producing dental cement, a material for crowns or bridges, filling material, moulding material, filler liners, coating compounds, dental blanks, dental braces, sealant or combinations thereof, as well as a kit of components applicable in dentistry, containing at least two compositions specified above; the compositions have at least a different colour.

EFFECT: using the group of inventions provides the composites with the improved mechanical properties, particularly low fragility as compared to the compositions free from the compound (A).

12 cl, 7 tbl, 25 ex

Description

FIELD OF THE INVENTION

The present invention relates to a composition comprising a curable compound containing a comparatively rigid framework unit, a spacer unit and a unit containing polymerizable end groups linked to the spacer.

This composition is useful in the field of dentistry and can be used to provide, for example, composite materials with reduced brittleness.

State of the art

High strength dental composite materials are sometimes desired to provide appropriate functionality. In the case of high-strength filling materials, high fragility can contribute to the appearance of imperfections, such as cracks, for example during restoration, so that repair or replacement may be necessary. In the case of temporary materials, in particular temporary crown materials and bridges, brittleness can lead to destruction of the material so that the material needs to be replaced.

Typical physical parameters for determining the brittleness of a material are elastic modulus, elongation at break, and impact strength.

Various attempts have been made to solve this problem.

WO 01/44338 relates to dental compositions based on (meth) acrylates containing urethane prepolymers to reduce brittleness, as indicated by increased impact strength of the cured composition.

WO 2009/006282 relates to dental compositions based on polyfunctional (meth) acrylates containing urethane, urea or amide groups to reduce brittleness, as indicated by increased impact strength of the cured composition.

US 7,534,909 (Otsjui et al.) Relates to a (meth) acrylic ester compound having a specific formula. It is claimed that the compound can be used in dental materials and optical parts.

JP 63248811 (Mitshubichi) describes high refractive index compositions useful for optical lenses where the polymerizable components used contain halogenated aryl moieties.

However, there is still room for improvement, especially with regard to performance requirements with regard to modern dental materials.

Thus, there is still a need for an improved dental composition that can be used, inter alia, as a filling material or material for temporary or permanent crowns and bridges.

SUMMARY OF THE INVENTION

An object to which the present invention can be directed is to provide a composition having useful properties, for example with regard to reduced fragility.

In one embodiment, the present invention describes a dental composition or composition for use in dentistry, comprising

a) compound (A) with the following features:

only one framework unit (U) with 6-20 carbon atoms, at least 6 carbon atoms of which form an aromatic or aliphatic cyclic fragment, and the remaining carbon atoms are either part of the substituents suspended from the cyclic fragment, or are part of bridge groups of spacer units , while one or more of the remaining carbon atoms can be replaced by an oxygen atom, and the frame link does not contain a bisphenol structure,

one or two spacer units (S) connected to the frame unit (U) via an ether link, with at least one spacer unit (S) containing the chain -CH2-CH2-CH2-CH2-O-CH2-CH ( Q) -OG or the remainder of -CH2-CH (OG) -CH2-OM or a mixture of these two types of spacers in one spacer link,

Where

G contains at least one group selected from acryloyl, methacryloyl, acetyl, benzoyl, mixtures and combinations thereof,

M contains at least one aryl group, mixtures and combinations thereof,

Q contains at least one group selected from hydrogen, methyl, phenyl, phenoxymethyl, mixtures and combinations thereof,

especially provided that at least two G groups are present in compound (A), where if only one spacer link (S) is present, then the G group which is not part of said spacer link (S) is in another substituent suspended from an aromatic or aliphatic cyclic moiety,

b) filler (B) and

c) initiator (C).

The present invention also relates to a method for producing a dental composition comprising a mixing step.

In accordance with another implementation of the present invention relates to the use of the composition, as described in this application, as or for the production of dental cement, material of the crown or bridge, filling material, casting material, lining material for the sealant, composition for coating, billet, orthodontic devices sealant or combinations thereof.

The present invention is also directed to kits or parts containing at least 2 compositions, as described herein, wherein the compositions differ from each other by at least color.

The present invention is also directed to a method of using compound (A) as or for preparing a dental composition, the method typically comprising the steps of:

a) place the composition containing the compound (A) in contact with the surface,

b) curing the composition.

Definitions

In the description of the present invention, the following terms are defined as follows.

The term "visible radiation" is used in relation to light having a wavelength of from about 400 to about 800 nanometers (nm).

A “dental composition” is any composition that can or should be used in the field of dentistry. In this regard, the composition should not be harmful to the health of patients and, therefore, should be free from dangerous and toxic components that can migrate from the composition. Examples of dental compositions include permanent and temporary crowns and bridges materials, artificial crowns, filling materials, adhesives, molding materials, dental cements, fillings, fillings, sealants, blanks, laboratory materials and orthodontic devices.

Dental compositions are typically curable compositions that can be cured under ambient conditions, including a temperature range of from about 15 to 50 ° C or from about 20 to 40 ° C for a time interval of about 30 minutes or 20 minutes or 10 minutes.

Elevated temperatures are not recommended because they can cause pain to the patient and may be harmful to the patient's health.

Dental compositions are typically presented to a practitioner in relatively small volumes, i.e. volumes in the range of from about 0.1 to about 100 ml, or from about 0.5 to about 50 ml, or from about 1 to about 30 ml.

A "monomer" is any chemical substance that can be characterized by a chemical formula having polymerizable groups (including (meth) acrylate groups) that can polymerize into oligomers or polymers, thereby increasing molecular weight. The molecular weight of the monomers can usually be calculated simply based on a given chemical formula.

A “curable compound or material” is any compound that can be cured or cured, for example by heating, to cause polymerization, chemical crosslinking, radiation polymerization or crosslinking, or the use of a redox initiator. A curable compound may contain only two, three or more polymerizable groups. Typical examples of polymerizable groups include epoxy groups and unsaturated carbon groups, such as the vinyl group present, inter alia, in the (methyl) acrylate group.

A “resin” contains all curable compounds (monomers, oligomers and / or polymers) present in the curable composition. The resin may contain only one curable compound or a mixture of various curable compounds.

A “filler” contains all fillers present in the curable composition. Only one type of filler or a mixture of different fillers may be used.

"Dispersed in resin" means that the filler particles are present in the resin as discrete, unbound (i.e., non-agglomerated and non-aggregated) particles.

A “nanoscale filler” is a filler whose individual particles have a size in the nanometer region, for example, an average particle diameter of less than about 200 nm. Useful examples are given in US 6,899,948 and US 6,572,693, the contents of which are specifically included in relation to particles of nanosized silica in this application by reference.

An “initiator or initiator system” is a substance capable of initiating a solidification process of a curable compound.

The "hardening, curing or setting reaction" is used interchangeably and refers to a reaction in which physical properties, such as viscosity and hardness of a composition, change over time due to a chemical reaction between the individual components.

A “derivative” is a chemical compound that exhibits a chemical structure that is closely related to the corresponding basic compound, and that contains all the characteristic structural elements of the corresponding basic compound, but having minor modifications, for example, the content of, in addition, additional relatively small additional chemical groups, such as, for example, CH ₃ , Br, Cl or F, or the absence of relatively small chemical groups, such as, for example, CH ₃ compared with the corresponding basic compound by. The following examples can illustrate this: tetramethylbisphenol A having four additional methyl groups relative to the basic compound of bisphenol A, and bisphenol F having no two additional methyl groups relative to the basic compound of bisphenol A, which are derivatives of bisphenol with respect to this definition.

"Environmental conditions" means the conditions to which a composition in accordance with the present invention is usually exposed during storage and use. Environmental conditions may, for example, be a pressure of from about 900 to about 1100 mbar, a temperature of from about 10 to about 60 ° C, and a relative humidity of from about 10 to about 100%. In the laboratory, environmental conditions are adjusted to approximately 23 ° C and approximately 1013 mbar. In the field of dentistry and orthodontics, environmental conditions are correctly understood as pressure from about 950 to about 1050 mbar, temperature from about 15 to about 40 ° C and relative humidity from about 20 to about 80%.

As used in this application, the singular, “at least one” and “one or more” are used interchangeably. The terms “contains” or “consists” and their variants are not intended to be limiting, where these terms are given in this application and the claims of the present invention. Also in this application, indications of numerical ranges by endpoints include all numbers falling within this range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and etc.).

Unless otherwise specified, all numbers expressing the amounts of ingredients, the measurement of properties, such as contrast ratio, etc., used in this application and the claims of the present invention should be construed as modified in all cases by the term "approximately".

DETAILED DESCRIPTION OF THE INVENTION

The composition of the present invention is typically a polymerizable composition. That is, the composition typically — but not necessarily — contains polymerizable components or compounds.

The present invention also relates to a composition obtained or which can be obtained by polymerization or solidification of the polymerizable composition.

According to one embodiment, the composition comprises a compound (A) containing polymerizable fragments.

According to another embodiment, the composition comprises a compound (A) not containing polymerizable fragments, and further comprising a compound containing polymerizable fragments.

Thus, if the composition is a polymerizable composition, then it contains compound (A), provided that if compound (A) does not contain polymerizable fragments, then the composition further comprises a compound containing polymerizable fragments.

The composition in accordance with the present invention is useful for the dentist in a number of aspects.

For example, it was found that compound (A) is contained in a composition in accordance with the present invention and typically has at least one or more of the following properties:

a) Compound (A) typically has good (filler or pigment) wettability. This can be useful to achieve relatively high filler loads, if desired.

b) Compound (A) typically has a relatively low viscosity. This may be useful to achieve the appropriate properties of the finished composition, if desired. It may also be useful to increase the loading of the filler, if desired, since the viscosity of the finished composition will typically be in an acceptable range.

c) Compound (A) typically has a relatively high refractive index. This may be useful to achieve appropriate aesthetic properties and / or a high curing depth of the light curing materials, if desired.

d) Compound (A) typically has a relatively high hydrophobicity. This may be useful to achieve a relatively low water absorption and / or exogenous staining, if desired.

e) Compound (A) can be used to provide compositions exhibiting reduced brittleness of the cured composition (i.e., relatively high impact strength and / or moderate modulus). This can be useful if the risk of breaks due to cracks and / or splits should be reduced.

f) Compound (A) can be used to provide compositions exhibiting a high cure depth. This may be useful if volumetric curing application of light curing materials is desired.

g) Compound (A) typically exhibits a moderate modulus of elasticity with standard wear resistance (measured in accordance with ASTA). This may be useful if relatively low brittleness is desired.

One or more of these properties can be obtained by applying a compound having a comparatively rigid frame link and a flexible spacer link of a certain length.

The combination of appropriate mechanical properties, for example, moderate elastic modulus, high impact strength and sufficient curing depth (for example, for light-cured compositions) has been shown to be useful, especially in the field of dentistry.

Not wanting to be bound by a particular theory, it is believed that the nature and length of the spacer units contribute to the effect on the flexibility and / or viscosity of the compound.

A rigid framework containing a cyclic carbon fragment can contribute to hydrophobicity.

Thus, compound (A) exhibits a unique combination of features, which can help provide a dental composition having useful properties, in particular, exhibiting reduced fragility of the cured composition.

Compound (A) can be characterized by the following features.

- only one skeleton unit (U) with 6-20 carbon atoms, at least 6 carbon atoms of which form an aromatic or aliphatic cyclic fragment, and the remaining carbon atoms are either part of the substituents suspended from the cyclic fragment, or are part of spacer bridge groups units, wherein one or more of the remaining carbon atoms can be replaced by an oxygen atom, and the frame unit does not have a bisphenol structure,

- one or two spacer units (S) connected to the frame unit (U) via an ether link, at least one spacer unit (S) contains the chain -CH2-CH2-CH2-CH2-O-CH2-CH (Q) -OG or the remainder of -CH2-CH (OG) -CH2-OM or a mixture of these two types of spacers in one spacer link (where an example of such a mixture is shown in structure S3 below),

Where

G contains at least one group selected from acryloyl, methacryloyl, acetyl, benzoyl and mixtures thereof,

M contains at least one aryl group and mixtures thereof,

Q contains at least one group selected from hydrogen, methyl, phenyl, phenoxymethyl and mixtures thereof.

At least two groups G are present in the compound (A), in this case, if there is only one spacer unit (S), then the group G, which is not part of the specified spacer unit (S), is in the substituent suspended from the aromatic or an aliphatic cyclic moiety.

The term "frame link" means a link forming the Central part of the compound (A). To function as a wireframe link, the wireframe link must be at least bifunctional or divalent. That is, at least two, three or four substituents are attached to the frame link. A link containing only one substituent cannot be considered as a frame link. Such a link is most likely interpreted as a suspended deputy.

The framework unit (U) contains at least two substituents, which may be the same or different, where each substituent contains a polymerizable fragment. Thus, at least two polymerizable fragments are present in two different substituents attached to the framework unit (U).

Alternatively or in other words, compound (A) contains at least two groups G, which may be the same or different, where if only one spacer unit (S) is present, then the group G, which is not part of the specified spacer unit (S) is in a substituent suspended from an aromatic or aliphatic cyclic moiety.

The term “bisphenol structures” includes such structures as bisphenol A, bisphenol AR (4,4 ′ - (1-phenylethylidene) bisphenol), bisphenol C (bis (4-hydroxyphenyl) -2,2-dichloroethylene), bisphenol F (bis (2-hydroxyphenyl) methane), bisphenol TMS (4,4 ′ - (3,3,5-trimethyl-cyclohexylidene) bisphenol). These and other abbreviations are known to the person skilled in the art.

If desired, various compounds falling within the definition of compound (A) may be present in the composition. For example, the composition in accordance with the present invention may contain two, three, four or even more compounds that differ from each other, for example, the nature of the frame link and / or the nature of the spacer link (s).

Compound (A) may be typically characterized by at least one, two, three, four or five of the following:

a) Molecular mass (Mw): from about 550 to about 1000;

b) Reactive functional group: about 2, exactly 2 or not more than 2 ethylenically unsaturated reactive groups per molecule, attached via an ester bond to the backbone;

c) Non-reactive functional groups: approximately 2, exactly 2 or not more than 2 hydrocarbon non-reactive functional groups per molecule attached via an ester bond to the backbone;

d) Polar groups: essentially the absence of OH free groups in the molecule;

e) Secondary network: essentially the absence of urethane fragments in the molecule;

f) Refractive index: from about 1.495 to about 1.565 (n _D ²⁰ ).

Thus, the compound (A) can be characterized as described in this application and additionally by performing at least one of the characteristics a), b), c), d), e) or f).

For example, in accordance with one implementation, the compound (A) has, for example, features a), b) and c). According to another embodiment, compound (A) has, for example, features a), b) and d). According to a further embodiment, the compound (A) has, for example, features a), b), d) and e).

Frame link (U) may include a fragment selected from

,

,

,

,

,

,

,

,

,

,

,

,

where the symbol "*" indicates the bond of the molecular fragment. The spacer link (s) (S) may contain a fragment selected from

,S1:

,

where m = 1-3 and n = 1-3,

Q = hydrogen, methyl, phenyl, phenoxymethyl,

,S2:

,

where M = aryl or phenyl,

,

,

S3:

where m = 1-3 and n = 1-3,

Q = hydrogen, methyl, phenyl, phenoxymethyl and

M = aryl or phenyl.

"G" may contain a fragment selected from

,

,

,

и их комбинаций и их смесей.

,

,

,

and combinations thereof and mixtures thereof.

The symbol "*" indicates the connection of molecular fragments with other fragments. That is, two fragments, each of which may have a “*”, can be linked to each other via a chemical bond.

Aryl means a moiety containing 6 to 9 carbon atoms, including phenyl moieties substituted with alkyl (C1-C3). Fragments such as naphthyl or biphenyl are not included.

In accordance with a specific implementation, the compound (A) can be characterized by the structure in accordance with any of formulas (I), (II) and (III)

Where

a, b = 0-3, c, d = 0-3, (a + b) = 1-6, (c + d) = 1-6,

Q = independently selected from hydrogen, methyl, phenyl or phenoxymethyl,

,

,

Where

a, b = 0-3, c, d = 0-3, (a + b) = 1-6, (c + d) = 1-6,

Q = independently selected from hydrogen, methyl, phenyl or phenoxymethyl, where G is selected from

,

,

,

, и где U выбран из

,

,

,

, and where U is selected from

,

,

,

,

,

,

,

,

,

,

.

.

their combinations and their mixtures.

With respect to any of formulas (I) to (III), “U” and “G” may be any of the fragments described above in this application in connection with the description of “U” and “G”.

Compound (A) is typically present in the composition in an amount of at least about 5 wt.% Or at least about 10 wt.% Or at least about 20 wt.%.

The amount of compound (A) contained in the composition is typically up to about 50 wt.%, Or up to about 60 wt.%, Or up to about 70 wt.%.

Typical ranges include from about 5 to about 70, or from about 10 to about 60, or from about 10 to about 45, or from about 10 to about 30 wt.%.

Compound (A) can be obtained or manufactured, for example, in the following way:

the reaction of, for example, alcohols (such as, for example, TCD alcohol or ethoxylated resorcinol (ER) or ethoxylated hydroquinone (EN)) with epoxides (such as, for example, glycidylphenyl ether (GP)) or with mixtures containing epoxy fragments (such as for example, ethylene oxide (EO) in THF or propylene oxide (PO) in THF or styrene oxide (SO), or GP in THF) in a solvent (such as, for example, tetrahydrofuran (THF)), thereby obtaining an ester derivative,

reacting the resulting ester derivative with, for example, methacrylic acid (MA), or acrylic acid (AA), or acetic anhydride (AAA), or benzoic acid (BA) to form the corresponding esters.

Compound (A) can also be obtained or manufactured, for example, in the following way:

reacting OH an acidic compound (such as, for example, phenol, resorcinol) with epoxides (such as, for example, resorcyndiglycidyl ether (RDGE) or cyclohexane-1,4-dimethanolated diglycidyl ether (CDGE)), thereby obtaining an ether derivative;

reacting the obtained ester derivative with, for example, methacrylic acid (MA), or acrylic acid (AA), or acetic anhydride (AAA), or benzoic acid (BA) to form the corresponding esters.

The reaction of alcohols with epoxides can be carried out using the main catalyst (in particular, for example, for the reaction of alcohols with epoxides (such as, for example, GP) or using the Lewis acid catalyst (in particular, for example, for the reaction of alcohols with epoxy-containing mixtures (such as , for example, SW in THF)).

The reaction of OH acidic compounds with epoxides can be carried out using, for example, a soft nucleophilic catalyst or a basic catalyst.

Examples of basic catalysts include triethylamine (TEA), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), triethylammonium acetate (TEAA), sodium acetate (NaOAc), potassium acetate (KOAc), potassium tert-butoxide (KOtBu) and mixtures thereof.

Examples of acidic Lewis catalysts include boron fluoride esters, i.e. BF ₃ * THF, BF ₃ * OEt ₂ and mixtures thereof.

Examples of a nucleophilic solvent include triphenylphosphane (PPh ₃ ).

The reaction can typically be carried out in a temperature range of from about 40 to about 110 ° C., typically in dry conditions and a shielding gas atmosphere (i.e., excluding water and oxygen). The reaction can be carried out in conventional solvents, including hexane, cyclohexane, methylcyclohexane, toluene, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran and mixtures thereof, or without solvent.

If desired, the crude reaction product (s) can be treated with organic acids to reduce unwanted discoloration.

The esterification reaction can be carried out in a temperature range of from about 60 to about 110 ° C., preferably in an atmosphere of air, using general reaction procedures, such as, for example, acid-catalyzed esterification with water removal using a Dean Stark apparatus. The reaction can be carried out in common solvents, including hexane, cyclohexane, methylcyclohexane, toluene, methyl tert-butyl ether, and mixtures thereof.

By selecting the appropriate molar ratios of the reactive components (i.e., isolated substances), the desired molecular structure of the reaction product can be adjusted.

In the ideal case, if, for example, bifunctional alcohol (HO-X-OH) reacts with one equivalent of Y, then the final reaction product will typically contain a statistical mixture of the following components in appropriate amounts: HO-X-OH (25%), YOXOY ( 25%), YOX-OH (50%).

Ideally, if, for example, a bifunctional alcohol (HO-X-OH) reacts with two equivalents of Y, then the final reaction product will typically contain Y-O-X-O-Y (100%).

If desired, further purification of the product mixture can be achieved by means known to a person skilled in the art, including HPLC, distillation and fractional crystallization.

To prevent unwanted radical polymerization during synthesis, an appropriate amount of stabilizer (e.g., from about 50 to about 500 ppm), for example 3,5-di-tert-butyl-4-hydroxytoluene (BHT), 4- methoxyphenol (MOP) or hydroquinone (HQ), if desired.

If desired, compound (A) can be combined with surface-treated SiO2 and / or ZrO2 nanoparticles to obtain dispersions of surface-treated SiO2 and / or ZrO2 nanoparticles in compound (A).

The composition in accordance with the present invention may contain a filler or a matrix of filler. The filler matrix may consist of one filler or a mixture of different fillers.

The nature of the filler composition in accordance with the present invention is not particularly limited. The particle size of the filler must be such that a homogeneous mixture can be obtained with the curable component (s) forming the resin matrix.

Useful fillers include pyrogenic silica, fillers based on fluoroaluminosilicate glasses, quartz, ground glasses, water insoluble fluorides such as CaF ₂ , silica gels such as silicic acid, in particular pyrogenic silicic acid and its granules, cristobalite, calcium silicate, zirconium silicate zeolites, including molecular sieves, powders of metal oxides such as aluminum or zinc oxides or their mixed oxides, barium sulfate, yttrium fluoride, calcium carbonate.

Silica is usually dispersed in a resin matrix. The silica particles used in the dental compositions of the invention preferably have an average diameter of less than about 200 nm, more preferably, the particles have an average diameter of less than about 100 nm. These measurements are preferably based on the TEM method (transmission electron microscopy), in which the population is analyzed to obtain an average particle diameter. A preferred method for measuring particle diameter can be described as follows:

Samples of approximately 80 nm thick are placed on 200 mesh copper meshes with carbon-stabilized formwork substrates (SPI Supplies — a division of Structure Probe, Inc., West Chester, PA). A micrograph was obtained in a transmission microscope (TEM) using a JEOL 200CX (JEOL, Ltd. of Akishima, Japan and sold from JEOL USA, Inc.) at 200 kV. A population size of about 50-100 particles can be measured and the average diameter determined.

The average surface area of the silica particles is preferably greater than about 15 m ² / g, more preferably greater than about 30 m ² / g.

After dispersion in the resin, silica particles are in discrete (separate) and unbound (i.e., non-agglomerated, non-aggregated) states. "Agglomerated," as used in this application, is a description of a weak association of particles that are usually held together by charge or polarity and can be broken down into smaller fragments. “Aggregated,” as used herein, is a description of a strong association of particles that are often associated with each other, for example, residual chemical treatment; further destruction of aggregates into small fragments is very difficult to achieve.

Silica particles that can be used in dental materials in accordance with the present invention are preferably substantially spherical and substantially non-porous. Although silica is preferably substantially pure, it may contain small amounts of a stabilizing ion, such as ammonium and an alkali metal.

Suitable fumed silicas include, for example, products sold under the trade name AEROSIL of the OX-50, -130, -150 and -200 series, available from Degussa AG, (Hanau, Germany) and CAB-O-SIL M5, available from Cabot Corp (Tuscola, III.).

Useful fluoroaluminosilica glasses include silanol-treated fluoroaluminosilica glass fillers, as described in US 5,332,429, the description of which is obviously incorporated by reference in this application. For example, fluoride-releasing glass may be added to the dental composition to provide the beneficial effect of sustained release of fluoride when used, for example, in the oral cavity.

Optionally, heavy metal oxide may be included in the dental materials of the present invention to provide radiopaque dental material. Preferably, the heavy metal oxide is present in an amount effective to provide X-ray impermeability. As used herein, “X-ray tightness” describes the ability to distinguish cured dental material from tooth structure using standard dental x-ray techniques in a standard manner. The X-ray tightness in the dental material is useful in some cases when X-rays are used to diagnose a dental disease. For example, an X-ray-tight material will detect secondary caries, which may be formed in the tooth tissue surrounding the filling. The target degree of impermeability for x-rays can be changed depending on the specific application and the expectations of the practitioner evaluating the x-ray film.

Oxides of heavy metals having an atomic number greater than about 28 may be preferred. The heavy metal oxide should be selected so that unwanted colors or blackout is not present in the cured resin in which it is dispersed. For example, iron and cobalt may not be useful because they give dark and contrasting colors to the neutral color of the dental material. More preferably, the heavy metal oxide is an oxide of metals having an atomic number greater than 30. Suitable metal oxides are oxides of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanoid elements ( i.e., elements having atomic numbers 57-71, inclusive), cerium, and combinations thereof. More preferably, heavy metal oxides having an atomic number greater than 30 but less than 72 are optionally included in the materials of the present invention. Particularly preferred x-ray impermeable metal oxides include lanthanum oxide, zinc oxide, tin oxide, zirconium oxide, yttrium oxide, ytterbium oxide, barium oxide, strontium oxide, cerium oxide, and combinations thereof. Particles of heavy metal oxides can be aggregated. If so, it is preferred that the aggregated particles are less than about 200 nm, and more preferably less than about 90 nm in average diameter.

In a preferred embodiment, the filler matrix comprises a nanosized filler, including nanosized silica.

Preferred nanosized silicas are commercially available from Nalco Chemical Co. (Naperville, III.) Under the product name NALCO COLLOIDAL SILICAS (e.g., preferred silica particles can be obtained using NALCO products 1040, 1042, 1050, 1060, 2327 and 2329), Nissan Chemical America Company, Houston, Texas (e.g. SNOWTEX -ZL, -OL, -O, -N, -C, -20L, -40 and -50); Admatechs Co., Ltd., Japan (e.g., SX009-MIE, SX009-MIF, SCI 050-MJM, and SC1050-MLV); Grace GmbH & Co. KG, Worms, Germany (for example, available under the product name LUDOX, for example, P-W50, P-W30, P-X30, P-T40 and P-T40AS); Akzo Nobel Chemicals GmbH, Leverkusen, Germany (e.g. available under the product name LEVASIL, e.g. 50/50%, 100/45%, 200/30%, 10 200A / 30%, 200/40%, 200A / 40%, 300/30% and 500/15%), and Bayer MaterialScience AG, Leverkusen, Germany (e.g. available under the product name DISPERCOLL S, e.g. 5005, 4510, 4020 and 3030). In a preferred embodiment, if the curable resin uses a cationic initiator system, the starting silica is preferably acidic (such as Nalco 1042).

Surface treatment of nanosized silica particles before loading into the dental material can provide a stable dispersion in the resin. "Stable", as used in this application, means a dental material in which the particles do not agglomerate after incubation for a period of time, for example, approximately 24 hours, under standard environmental conditions, for example at room temperature (from about 20 to about 22 ° C), atmospheric pressure and the absence of extreme electromagnetic forces. Preferably, the surface treatment stabilizes the nanosized particles so that the particles are well dispersed in the curable resin, and results in a substantially homogeneous composition. Additionally, it is preferable that the silica has been modified, at least part of its surface, with a surface treatment agent so that the stabilized particle can copolymerize or otherwise interact with the curable resin during curing.

Silica particles can be treated with a surface-improving agent compatible with the resin. Particularly preferred surface treatment agents or surface modification agents include silane processing agents capable of polymerising with the resin. Preferred silane treatment agents include γ-methacryloxypropyltrimethoxysilane commercially available under the trade name A-174, commercially available from Witco OSi Specialties (Danbury, Conn.) And γ-glycidoxypropyltrimethoxysilane available under the trade name G6720 available from United Chemical Technologies ( , Pa.).

Alternatively, a combination of surface modifying agents may be useful if at least one of the agents has a functional group copolymerizable with a curable resin. For example, the polymerizing group may be an ethylenically unsaturated or cyclic functional group susceptible to ring opening polymerization. The ethylenically unsaturated polymerizing group may be, for example, an acrylate or methacrylate, or a vinyl group. A cyclic functional group susceptible to ring opening polymerization generally contains a heteroatom, such as oxygen, sulfur or nitrogen, and is preferably a 3-membered ring containing oxygen, such as epoxide. Other surface modifying agents that generally do not react with curable resins may be included to enhance dispersibility or rheological properties. Examples of this type of silane include, for example, alkyl or aryl polyesters, alkyl, hydroxyalkyl, hydroxyaryl or aminoalkyl functional silanes.

After surface treatment of the silica particles, they can then be combined with the corresponding curable resin to form a dental composition in accordance with the present invention.

The filler matrix may contain at least about 25 wt.%, Or at least about 30 wt.%, Or at least about 40 wt.%, Or at least about 50 wt.% the whole composition.

The amount of filler to be used in the filler matrix typically depends on the purpose for which the composition is to be used.

The filler matrix may contain up to about 90 wt.%, Or up to about 85 wt.%, Or up to about 80 wt.%, Or up to about 75 wt.% Of the whole composition.

Materials of temporary crowns and bridges (for example, for a dental composition) usually do not contain large amounts of fillers. With respect to such compositions, the filler content is usually in the range of from about 30 to about 60 wt.% Relative to the entire composition.

In filling materials (for example, a dental composition; sometimes also referred to as dental composite materials), which typically contain a greater amount of filler than temporary crowns and bridges, the filler content is usually in the range of about 60 to about 85% by weight relative to the total composition .

The dental composition in accordance with the present invention also contains an initiator or initiator system capable of initiating the curing process of the curable components present in the resin matrix.

Dental materials in accordance with the present invention may be chemically curable, heat curable or light curable. Light curing materials must have an appropriate initiator system. Chemically curable materials may be self-hardening (e.g., via redox initiators). Alternatively, the materials of the present invention can be cured by a combination of self-curing and light curing.

For free radical polymerization (curing), the initiator system can be selected from systems that initiate polymerization by radiation, heat or a redox / self-curing chemical reaction. The class of initiators capable of initiating the polymerization of free active functional groups includes photoinitiators generating free radicals, optionally in combination with a photosensitizer or a curing accelerator. Such initiators may typically be capable of generating free radicals for additive polymerization after exposure to light energy with a wavelength of from about 200 to about 800 nm.

Many systems of photoinitiators in the visible or near infrared region of the spectrum can be used for photopolymerization of free radical polymerizable materials useful in the present invention. For example, in free radical polymerization (curing), the photoinitiation system can be selected from systems that initiate polymerization through a two-component system of amine and α-diketone, as described in US 4,071,424 and WO 2009151957, which are incorporated herein by reference. Alternatively, the resin may be combined with three components or a three component photoinitiator system as described in US 5,545,676 and WO 2009151957, which are incorporated herein by reference.

In a three-component photoinitiator system, the first component is an iodonium salt, i.e. diaryl iodonium salt. The iodonium salt is preferably soluble in the monomer and stable over the period of use (i.e., does not spontaneously promote polymerization) when dissolved in the presence of a sensitizer and a donor. Accordingly, the choice of a particular iodonium salt may depend to some extent on the particular monomer, polymer or oligomer, sensitizer and donor selected. Suitable iodonium 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, the descriptions of which are incorporated herein by reference. The iodonium salt can be a simple salt (for example, containing an anion, such as Cl ^- , Br ^- , I ^- or С ₄ Н ₅ SO ₃ ^- ) or a salt of a metal complex compound (for example, containing SbF ₅ OH ^- or AsF ₆ ^- ). If desired, mixtures of iodonium salts can be used. Preferred iodonium salts include diphenyl iodonium salts such as diphenyl iodonium chloride, diphenyl iodonium hexafluorophosphate and diphenyl iodonium tetrafluoroborate.

The second component in the three-component photoinitiator system is a sensitizer. The sensitizer is desirably soluble in the monomer and is capable of absorbing light somewhere in the wavelength range higher than 400 to 1200 nm, more preferably higher than 400 to 700 nm, and most preferably higher than 400 to about 600 nm. The sensitizer may also be capable of sensitizing 2-methyl-4,6-bis (trichloromethyl) -s-triazine using the test procedures described in US Pat. No. 3,729,313, which is incorporated herein by reference. Preferably, in addition to this test, the sensitizer is also selected based in part on storage stability considerations. Accordingly, the choice of a particular sensitizer may depend to some extent on the selected specific monomer, oligomer or polymer, iodonium salt and donor.

Suitable sensitizers may include compounds in the following categories: ketones, coumarin dyes (e.g. ketocoumarins), xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic aminostroketone compounds, aminotriarylmethanes, merocyanins, squarilium dyes and pyridinium dyes. Preferred sensitizers are ketones (e.g., monoketones or alpha-diketones), ketocoumarins, amino aryl ketones and p-substituted aminostyrene ketones. For applications requiring high sensitivity, it is preferable to use a sensitizer containing a yulolidinyl fragment. For applications requiring deep curing (for example, curing highly filled composites), it is preferable to use sensitizers having an extinction coefficient of less than about 1000, more preferably less than about 100, at the desired radiation wavelength for photopolymerization. Alternatively, dyes that are reduced by absorbing light upon irradiation with an excitation wavelength can be used.

For example, a preferred class of ketone sensitizers has the formula: ASO (X) _b B, where X is CO or CR ⁵ R ⁶ , where R ⁵ and R ⁶ 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 can be substituted (having one or more non-interfering substituents) or can be the same or unsubstituted aryl, alkyl, alkaryl or aralkyl groups, or together A and B can form a cyclic structure, which can be replaced ennym or unsubstituted cycloaliphatic, aromatic, heteroaromatic or fused aromatic ring.

Suitable ketones of the above formula include mono-ketones (b = 0), such as 2,2-, 4,4- or 2,4 - 10 dioxibenzophenones, di-2-pyridylketone, di-2-furanylketone, di-2-thiophenylketone, benzoin , fluorenone, chalcone, tetramethyldiaminobenzophenone, 2-fluoro-9-fluorenone, 2-chlorothioxantone, acetophenone, benzophenone, 1- or 2 acetonaphton, 9-acetylanthracene, 2-, 3- or 9-acetylphenanthrene, 4-acetylbiphenone, propiophenone butyrophenone, valerophenone, 2-, 3- or 4-acetylpyridine, 3-acetylcoumarin and the like.

Suitable diketones include aralkyl diketones such as anthraquinone, phenanthrenquinone, 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 and the like. Suitable alpha 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, benzyl, 2,2′-, 3,3′- and 4,4′-dihydroxybenzyl, furyl, di-3,3′-indolylethanedione, 2,3-bornanedione ( camphorquinone), diacetyl, 1,2-cyclohexanedione, 1,2-naphthaquinone, acenaphtahinone and the like.

The third component of the ternary system of initiators is the donor. Preferred donors include, for example, amines (including aminoaldehydes and aminosilanes), amides (including phosphoramides), esters (including thioesters), ureas (including thioureas), ferrocene, sulfinic acids and their salts, ferrocyanide salts, ascorbic acid and its salts, dithiocarbamic acid acid and its salts, salts of xanthates, salts of ethylenediaminetetraacetic acid and salts of tetraphenylboronic acid. The donor may be unsubstituted or substituted by one or more non-interfering substituents. Particularly preferred donors contain an electron donor atom, such as a nitrogen, oxygen, phosphorus or sulfur atom, and a leaving atom of hydrogen bonded to a carbon or silicon atom located in alpha position relative to the electron donor atom. A wide variety of donors are disclosed in US 5,545,676, which is incorporated herein by reference.

Alternatively, free radical initiators useful in the present invention include a class of acylphosphine oxides as described in US 4,737,593. Such acylphosphine oxides have the general formula

where each R individually may be a hydrocarbyl group, such as alkyl, cycloalkyl, aryl and aralkyl, any of which may be substituted by a halo, alkyl or alkoxy group, or two R ⁹ groups may be joined to form a ring together with a phosphorus atom, and where R ¹ is a hydrocarbyl group, S-, O-, or N-containing five- or six-membered heterocyclic group, or a group -ZC (= O) -P (= O) - (R ⁹ ) ₂ , where Z is divalent a hydrocarbyl group such as alkylene or phenylene having from 2 to 6 carbon atoms.

Preferred acylphosphine oxides useful in the present invention are those in which the groups R ⁹ and R ¹⁰ are phenyl or lower alkyl or lower alkoxy substituted phenyl. By “lower alkyl” and “lower alkoxy” are meant those groups which have 1-4 carbon atoms. Most preferably, the acylphosphine oxide is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE ™ 819, Ciba Specialty Chemicals, Tarrytown, NY).

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

Commercially available phosphide oxide photoinitiators capable of free radical initiation upon irradiation at wavelengths greater than 400 nm to 1200 nm include a 25:75 mixture, by weight, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2- hydroxy-2-methyl-1-phenylpropan-1-one (IRGACURE ™ 1700, Ciba Specialty Chemicals), 2-benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) -1-butanone (IRGACURE ™ 369, Ciba Specialty Chemicals), bis (η5-2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (IRGACURE ™ 784 DC , Ciba Specialty Chemicals), a 1: 1 mixture, by weight, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2-hydro si-2-methyl-1-phenylpropan-1-one (DAROCUR ™ 4265, Ciba Specialty Chemicals), and ethyl 2,4,6-trimethylbenzylphenylphosphinate (LUCIRIN ™ LR8893X, BASF Corp., Charlotte, NC).

Another system of free radical initiators, which can alternatively be used in dental materials in accordance with the present invention, includes a class of initiators based on an ion-dye-counterion complex containing a borate anion and a complementary cationic dye.

Borate salt photoinitiators are described, for example, in US 4,772,530, US 4,954,414, US 25 4,874,450, US 5,055,372, and US 5,057,393, the disclosures of which are incorporated herein by reference.

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 independently can be alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups. Preferably, R ² , R ³ and R ⁴ are aryl groups and more preferably phenyl groups, and R ¹ represents an alkyl group and more preferably a secondary alkyl group.

Cationic counterions can be cationic dyes, quaternary ammonium groups, transition metal coordination complexes, and the like. Cationic dyes useful as counterions can be cationic methane, polymethine, triarylmethine, indoline, thiazine, xanthene, oxazine or acridine dyes. More specifically, the dyes can be cationic cyanine, carbocyanine, hemicianin, rhodamine and azomethine dyes. Specific examples of useful cationic dyes include Methylene Blue, Safranin O and Malachite Green. Quaternary ammonium groups useful as counterions can be trimethylacetyl ammonium, cetyl pyridinium and tetramethyl ammonium. Other organophilic cations may include pyridinium, phosphonium and sulfonium.

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′-bipyridine, 4,4′-dimethyl-2,2′- bipyridine, 1,10-phenanthroline, 3,4,7,8-tetramethyl-phenanthroline, 2,4,6-tri (2-pyridyl-5-triazine) and related ligands.

Another alternative class of initiators capable of initiating the polymerization of free radical active functional groups includes a standard chemical initiator system, such as a combination of peroxide and amine. These initiators, which are based on thermal redox reactions, are often referred to as "self-curing catalysts." They are typically presented as a two-component system in which the reagents are stored separately from each other and then mixed immediately before use.

In a further alternative embodiment, heat may be used to initiate curing or polymerization of the free radical active groups. Examples of heat sources suitable for the dental materials of the invention include inductive, convective, and by radiation. Heat sources must be capable of generating temperatures of at least 40 ° C-15 ° C under normal conditions or at elevated pressure. This procedure is preferred to initiate the polymerization of materials occurring outside the oral cavity.

Organic peroxide compounds, together with the so-called activators, are also suitable as redox initiator systems. In particular, compounds such as lauroyl peroxide, benzoyl peroxide, and p-chlorobenzoyl peroxide, and p-methylbenzoyl peroxide can be considered as organic peroxide compounds.

Suitable activators are, for example, tertiary aromatic amines, such as N, N-bis- (hydroxyalkyl) -3,5-xylidines, known from US 3,541,068, as well as N, N-bis- (hydroxyalkyl) -3,5 -di-tert-butylanilines, in particular N, N-bis - ([beta] -oxybutyl) -3,5-di-tert-butylaniline, as well as N, N-bis- (hydroxyalkyl-3,4,5- trimethylaniline.

Well-suitable activators are also barbituric acids and derivatives of barbituric acids, as described in US 2003/008967, DE 1495520, as well as malonyl sulfamides described in US 4,544,742 (corresponding to EP 0059451). Preferred malonyl sulfamides are 2,6-dimethyl-4-isobutyl malonyl sulfamide, 2,6-diisobutyl-4-propyl malonyl sulfamide, 2,6-dibutyl-4-propyl malonyl sulfamide, 2,6-dimethyl-4-ethyl malonyl sulfamide and 2,6-diocyl -isobutyl malonyl sulfamide.

To further accelerate the polymerization in this case, it is preferable to carry out in the presence of compounds of heavy metals with ionic halogen or pseudohalogen. The heavy metal is suitably used in the form of soluble organic compounds. Additionally, halide and pseudo-halide ions are respectively used in the form of soluble salts, and soluble amine hydrochlorides as well as quaternary ammonium chloride compounds can be mentioned as examples. Suitable accelerators, in particular, are metals, for example, iron or copper groups, preferably copper and iron complexes and, in particular, copper complexes. The heavy metal is preferably used in the form of soluble organic compounds. Suitable are, for example, iron carboxylates, copper carboxylates, iron protetonate, copper protetonate, copper naphthenate, copper acetate and iron naphthenate.

The initiator is typically present in the composition in an amount of at least about 0.1 wt.%, Or at least about 0.2 wt.%, Or at least about 0.3 wt.%.

The amount of initiator contained in the composition is typically up to about 3 wt.%, Or up to about 2 wt.%, Or up to about 1.8 wt.%.

Typical ranges include from about 0.1 to about 3, or from about 0.2 to about 2, or from about 0.3 to about 1.8 wt.%.

According to another embodiment, the composition may contain (optionally) a polymerizable component (D) other than compound (A). Component (D) is a typically free radical polymerizable material, including ethylenically unsaturated monomer, monomers or oligomers or polymers.

Suitable polymerizable components contain at least one ethylenically unsaturated bond and are capable of undergoing additive polymerization. Such free-radical polymerizable substances include mono-, di- or polyacrylates and methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, diurethane, 6-formulomethane, ), which is the reaction product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethylhexamethylene diisocyanate (TMDI), glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanedio ldiacrylate, 1,3-propanediol dimethacrylate, trimethylpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate [pentaerythritol tetra methacrylate-1-sorbite, 2) - (3-acryloxy-2-hydroxy)] - p-propoxyphenyl-dimethylmethane and trishydroxyethyl-isocyanurate trimethacrylate; bis-acrylates and bis-methacrylates of polyethylene glycols of molecular weight 200-500, copolymerizable mixtures of acrylated monomers, such as described in US 4,652,274, and acrylated oligomers, such as described in US 4,642,126; and vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate; polyfunctional (meth) acrylates containing urethane, urea or amide groups, such as those described in EP 2007111356, incorporated herein by reference. Mixtures of two or more of these free-radical polymerizable substances can be used if desired.

If desired, the polymerizable substance (a) can contain both cationically polymerizable and free radical polymerizable functional groups in one molecule. They can be prepared, for example, by reacting a di- or poly-epoxide with one or more equivalents of ethylenically unsaturated carboxylic acid. Examples of such substances include the reaction product UVR-6105 (available from Union Carbide) or DER 332 (available from Dow Chemical Co.) with one equivalent of methacrylic acid. Commercially available substances having epoxy and free-radical polymerizable functional groups include the "cyclomeric" series, for example the M100 or M101 Cyclomer, available from Daicel Chemical, Japan.

If present, component (D) is typically present in the composition in an amount of at least about 5 wt.%, Or at least about 10 wt.%, Or at least about 20 wt.%.

If present, the amount of component (D) contained in the composition typically is up to about 45 wt.%, Or up to about 55 wt.%, Or up to about 65 wt.%.

If present, typical ranges include from about 5 to about 65, or from about 10 to about 55, or from about 10 to about 40, or from about 10 to about 25 wt.%.

The polymerizable substance (a) may also contain a softener (E) that does not contain polymerizable groups.

The softener (E) may contain hydroxyl functional groups.

Preferably, a substance containing a hydroxyl group may contain two or more primary or secondary aliphatic hydroxyl groups (for example, a hydroxyl group is bonded directly to a non-aromatic carbon atom). Hydroxyl groups may be located terminally, or they may be suspended from a polymer or copolymer. The molecular weight of hydroxyl-containing organic substances can vary from very low (for example, 32) to very high (for example, one million or more). Suitable hydroxyl-containing substances may have low molecular weights, i.e. from about 32 to 200, intermediate molecular weights, i.e. from about 200 to 10,000, or high molecular weights, i.e. higher than about 10,000. As used in this application, all molecular weights are weight average molecular weights.

A substance containing hydroxyl groups may optionally contain other functional groups that do not substantially interfere with cationic polymerization at room temperature. Thus, substances containing hydroxyl groups may be non-aromatic in nature or may contain an aromatic functional group. A substance containing hydroxyl groups may optionally contain heteroatoms in the backbone of the molecule, such as nitrogen, oxygen, sulfur, etc., provided that the final substance containing hydroxyl groups does not substantially interfere with cationic polymerization at room temperature. A substance containing hydroxyl groups may, for example, be selected from natural or synthesized cellulosic materials. Of course, the substance containing hydroxyl groups also essentially does not contain groups that can be thermally or photolytically unstable, that is, the substance will not decompose or release volatile components at temperatures below about 100 ° C or in the presence of actinic light, which can occur during the time of the desired polymerization conditions for the photopolymerizable composition.

Representative examples of suitable hydroxyl group-containing substances having a hydroxyl functional group include alkanols, monoalkyl ethers of polyoxyalkylene glycols, monoalkyl ethers of alkylene glycols, and others known in the art.

Representative examples of useful monomeric polyhydroxyorganic substances include alkylene glycols (e.g., 1,2-ethanediol; 1,3-propanediol; 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, trimethylol ethane, pentaerythritol, sorbitol) and other polyhydroxy compounds such as N, N-bis (hydroxyethyl) benzamide; 2-butyn-1,4-diol; 4,4-bis (hydroxymethyl) diphenylsulfone; Castor oil; etc.

Representative examples of useful polymeric substances containing hydroxyl groups include polyoxyethylene and polyoxypropylene glycols, and in particular polyoxyethylene and polyoxypropylene glycol diols and triols having molecular weights of from about 200 to about 10,000, corresponding to a hydroxy equivalent mass of 100-5000 for diols or 70-3300 for triols ; polytetramethylene ether glycols, such as polytetrahydrofuran or "poly THF" with different molecular weights; copolymers of hydroxypropyl and hydroxyethyl acrylates and methacrylates with other free-radical polymerizable monomers such as acrylate esters, vinyl halides, or styrene; copolymers containing suspended hydroxy groups formed by hydrolysis or partial hydrolysis of vinyl acetate copolymers; polyvinyl acetal resins containing suspended hydroxyl groups; modified cellulose polymers such as hydroxyethylated and hydroxypropylated cellulose; hydroxy terminal polyesters; hydroxy-terminal polylactones and especially polycaprolactones; fluorinated polyoxyethylene or polyoxypropylene glycols; and hydroxy-terminal polyalkadiene.

Useful commercially available materials containing hydroxyl groups include the TERATHANE series of polytetramethylene ether glycols such as TERATHANE 650, 1000, 2000 and 2900 25 (available from du Pont de Nemours, Wilmington, DE), polytetrahydrofuran with an average molecular weight of 250 (available from Sigma-Aldrich, St. Louis, MO), "PEP" a series of polyoxyalkylenetetrols having secondary hydroxyl groups, for example, "PEP" 450, 550 and 650; "BUTVAR" a series of polyvinyl acetal resins, for example, "BUTVAR" B-72A, B-73, B-76, B-90 and B-98 (available from Monsanto Chemical Company, St. Louis, MO); and “FORMVAR” a series of resins such as 7/70, 12/85, 7 / 95S, 7 / 95E, 15 / 95S and 15 / 95E (available from Monsanto Chemical Company); "TONE" series of polycaprolactone polyols, such as "TONE" 0200, 0210, 0230,040, 0300 and 0301 (available from Union Carbide); PARAPLEX U-148 aliphatic polyester diol (available from Rohm and Haas, Philadelphia, PA), MULTRON R series of saturated polyester polyols such as MULTRON R-2, R-12A, R-16, R-18 R-38, R-68 35, and R-74 (available from Mobay Chemical Co.); "KLUCEL E" hydroxypropylated cellulose having an equivalent weight of about 100 (available from Hercules Inc.); “Alcohol soluble butyrate” a cellulosic acetate butyric ester having a hydroxyl equivalent weight of about 400 (available from Eastman Kodak Co., Rochester, NY); polyether polyols such as polypropylene glycol diol (e.g. ARCOL PPG-425, Arcol PPG-725, ARCOL PPG-1025, ARCOL PPG-2025, ARCOL PPG-3025, ARCOL PPG-4025 from ARCO Chemical Co.); polypropylene glycol triol (for example, ARCOL LT-28, ARCOL LHT-42, ARCOL LHT 112, ARCOL LHT 240, ARCOL LG-56, ARCOL LG-168, ARCOL LG-650 from ARCO Chemical Co.); polyoxypropylene triol or diol with ethylene oxide end groups (for example, ARCOL 11-27, ARCOL 11-34, ARCOL E-351, ARCOL E-452, ARCOL E-785, ARCOL E-786 "From ARCO Chemical Co.); ethoxylated bis-phenol A; propylene oxide or ethylene oxide polyols (for example, "VORANOL" polyether polyols from Dow Chemical Co.).

The amount of organic substance containing hydroxyl groups, optionally used in the compositions in accordance with the present invention, can vary in a wide range, depending on factors such as compatibility of the hydroxyl-containing substances with the resin, the equivalent weight and functionality of the hydroxyl-containing substances, the necessary physical properties in the final cured composition, desired photopolymerization rate, and the like.

Mixtures of various substances containing hydroxyl groups are also contemplated by the present invention. Examples of such mixtures include two or more molecular weight distributions of substances containing hydroxyl groups, for example, low molecular weights (less than 200), intermediate molecular weights (from about 200 to 10,000), or high molecular weights (higher than about 10,000). Alternatively or additionally, the hydroxyl-containing substance may comprise a mixture of hydroxyl-containing substances of different chemical nature, for example, aliphatic or aromatic, or functional groups, for example, polar or non-polar. As a further example, mixtures of two or more polyfunctional hydroxy substances or one or more monofunctional hydroxy substances with polyfunctional hydroxy substances can be used.

If present, component (E) is typically present in the composition in an amount up to about 10 wt.%, Or up to about 15 wt.%, Or up to about 20 wt.%.

If present, typical ranges include from about 0 to about 20 wt.%, Or from about 0 to about 15 wt.%, Or from about 0 to about 10 wt.%.

Compositions in accordance with the present invention may also contain suitable excipients, such as accelerators, inhibitors or retarders, absorbents, stabilizers, pigments, dyes, surface tension reducing agents, and wetting aids, antioxidants and other ingredients well known to those skilled in the art this technical field.

The amounts and types of each ingredient in the composition must be adjusted to provide the desired physical and processing properties before and after polymerization. For example, the polymerization rate, polymerization stability, fluidity, compressive strength, tensile strength and strength of the dental material are typically partially controlled by changing the type and amount of polymerization initiator (s) and, if present, by loading and distributing the particles according to the size of the filler (s) . Such adjustments are typically carried out empirically based on experience with dental materials known in the art.

Typical excipients include pigments, colorants and / or dyes. Examples include titanium dioxide or zinc sulfide (lithopones), red iron oxide 3395, Bayferrox 920 Z Yellow, Neazopon Blue 807 (copper phthalocyanine dye) or Helio Fast Yellow ER. These additives can be used for individual staining of dental compositions.

Additional additives that can be added include stabilizers, in particular free radical scavengers, such as substituted and / or unsubstituted hydroxyaromatics (e.g., bottled 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-methox ibenzo-phenone (UV-9), 2- (2′-hydroxy-4 ′, 6′-di-tert-pentylphenyl) -2H-benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′- hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, phenothiazine and HALS (hindered amine light stabilizers). Such excipients may optionally contain a reactive functional group so that they will be copolymerized with the resin.

There is no absolute need for these excipients, so excipients may be absent altogether. However, if present, they are typically present in an amount of at least about 0.01 wt.%, Or at least about 0.5 wt.%, Or at least about 1 wt.% Relative to the whole composition.

Excipients may be present in an amount up to about 25 wt.%, Or up to about 20 wt.%, Or up to about 15 wt.% Relative to the entire composition.

The composition, as described in the text in accordance with the present invention, may contain components in the following amounts:

- Compound (A): from about 5 to about 70, or from about 10 to about 60, or from about 10 to about 45, or from about 10 to about 30 wt.%,

- Filler (B): from about 25 to about 90 wt.%, Or from about 30 to about 85 wt.%, Or from about 40 to about 80 wt.%,

- Initiator (C): from about 0.1 to about 3, or from about 0.2 to about 2, or from about 0.3 to about 1.8 wt.%,

- Polymerizable compound (D): from about 0 to about 65, or from about 5 to about 55, or from about 10 to about 40, or from about 10 to about 25 wt.%,

- Softener (E): from about 0 to about 20 wt.%, Or from about 0 to about 15 wt.%, Or from about 0 to about 10 wt.%,

- Excipient (F): from about 0 to about 25 wt.%, Or from about 0.01 to about 20 wt.%, Or from about 0.5 to about 15 wt.%,

wt.% relative to the weight of the entire composition.

A curable composition in accordance with the present invention can be obtained by combining (including mixing and kneading) the individual components of the composition, preferably under “safe light” conditions.

Suitable inert solvents may be used, if desired, to provide the mixture. Any solvent that does not react markedly with the components of the composition in accordance with the present invention may be used. Examples of suitable solvents include acetone, dichloromethane, acetonitrile and lactones. The liquid substance to be polymerized can be used as a solvent for another liquid or solid substance to be polymerized.

The present invention provides a composition that can be cured within an acceptable time frame, for example, less than about 120 seconds (s) or less than about 100 seconds or less than about 60 seconds, and to a sufficient depth using a visible radiation source device, already available in the dental office, or using electronic devices.

Compositions in accordance with the present invention are particularly well suited for use as a variety of dental materials, which may be filling or non-filling. Such dental materials include direct aesthetic restoration materials (for example, for front and side reconstructions), prostheses, adhesives and primers for hard tissues of the oral cavity, sealants, veneers, underlay materials for fillings, adhesives for orthodontic brackets for use with any type of brackets (for example (metal, plastic and ceramic), cements for crowns and bridges, artificial crowns, artificial teeth, dentures, etc. These dental materials are used in the oral floor STI and they are adjacent to natural teeth. The phrase “adjacent to” as used in this application refers to the placement of dental material through temporary or permanent communication (eg, adhesive) or tangential (eg, occlusal or proximal) contact with a natural tooth. The term “composite,” as used herein in the context of a dental material, refers to a dental filling material. The term "restorative", as used in this application, refers to a dental composite that is polymerized after being placed next to the tooth. The term "prosthesis", as used in this application, refers to a composite that is formed and polymerized for its final use (for example, such as a crown, bridge, veneer, tooth filling tab, outer tab, etc.) before it will be located next to the tooth. The term “sealant” as used in this application refers to a slightly filled dental composite or unfilled dental material that is cured after being placed next to the tooth.

When the dental material is applied to the tooth, the tooth may optionally be pretreated with a primer, such as dentin or enamel adhesive, by methods known to those skilled in the art.

Dental compositions in accordance with the present invention can be used, for example, as artificial crowns, front or rear fillings, molding materials, lining materials for fillings, cements, coating compositions, blanks, orthodontic devices, restoration materials, dentures and sealants.

In a preferred aspect, the dental material is a filling material. Filling materials in accordance with the present invention can be placed directly in the oral cavity and hardened (hardened) in situ, or alternatively, can be made in the prosthesis outside the oral cavity and subsequently attached to a place inside the oral cavity.

If the composition is a light curing composition, it can typically be characterized by at least one of the following parameters after curing:

- Bending strength: at least about 70 MPa, or at least about 80 MPa, or at least about 100 MPa, determined in accordance with ISO 4049,

- Modulus of elasticity: from about 2 GPa to about 11 GPa or from about 4 GPa to about 10 GPa, determined in accordance with ISO 4049,

- Curing depth: at least about 4 mm, or at least about 4.1 mm, or at least about 4.6 mm, as determined in accordance with ISO 4049.

If the composition is a chemically curable composition, it can typically be characterized by at least one of the following parameters after curing:

- Bending strength: from about 50 MPa to about 100 MPa or from about 70 MPa to about 90 MPa, determined in accordance with ISO 4049,

- Modulus of elasticity: from about 0.4 GPa to about 2.0 GPa or from about 0.5 GPa to about 1.9 GPa, determined in accordance with ISO 4049,

Elongation at break: at least about 10%, or at least about 11%, or at least about 12%, determined in accordance with DIN 53455,

Impact strength: at least about 8 kJ / m ² , or at least about 10 kJ / m ² , or at least about 12 kJ / m ² , determined in accordance with ISO 179-1.

The present invention is also directed to the use of monomers or a mixture of monomers in accordance with the present invention to obtain a dental composition, the method of application comprising the steps of:

c) place the dental composition containing the monomer or a mixture of monomers in accordance with the formula (1) in contact with the tooth,

d) curing the composition.

The dental composition in accordance with the present invention is typically stored in a container until use. Depending on the selected initiator system, different containers may be appropriate.

If the dental composition is presented as a one-component system, it can be stored in a container having only one chamber, for example a syringe. The syringe has a typically cylindrical body with a front and rear end and a nozzle. The rear end of the housing is usually sealed by a movable piston. Typically, the dental composition is dispensed from the syringe or container using an applicator having a movable piston (for example, an applicator having the shape of a joint filling syringe). Examples of suitable syringes or containers are described in US 5,624,260, EP 1340472 A1, US 2007/0172789 A1, US 5,893,714, and US 5,865,803, the contents of which are incorporated by reference into the description of syringes or containers.

Alternatively, if the dental composition is presented as a two-component system, it can be stored in a container with a double chamber or cartridge and can be mixed before use.

Cartridges that can be used are described, for example, in US 2007/0090079 or US 5,918,772, the descriptions of which are incorporated herein by reference. Cartridges that can be used are commercially available from SulzerMixpac AG (Switzerland).

Static mixing syringe cannulas that can be used are described, for example, in US 2006/0187752 or US 105,944,419, the descriptions of which are incorporated herein by reference. Syringe mixing cannulas that can be used are commercially available from SulzerMixpac AG (Switzerland).

Thus, another implementation in accordance with the present invention is directed to a set of components containing at least two, three, four, five, six or more compositions that differ from each other, at least with respect to their color. As described herein above, the compositions are typically stored in a container.

The container may include a housing having a front end with a nozzle, and a rear end, and at least one piston movable in the housing.

The container volume will typically be typically in the range of from about 0.1 to about 100 ml, or from about 0.5 to about 50 ml, or from about 1 to about 30 ml.

Similar to the dental composition, the kit of components described in this application is intended for use in the field of dentistry, in particular for the production of dental materials, including dental restoration material. A dental composition and a set of components are typically used to treat and / or restore teeth.

Certain embodiments of the invention are substantially free of low boiling solvents (for example, with a boiling point of less than about 150 ° C. at ambient pressure). As used herein, “substantially free of” means that the content is typically less than about 1 wt.%, Or less than about 0.5 wt.%, Or less than about 0.1 wt.%, Relative to the total composition.

According to another embodiment, the compound (A) of the composition typically does not contain halogen atoms such as F, Cl, Br or I. According to a further embodiment, the compound (A) of the composition typically does not contain a urethane, amide and / or carbonate moiety. According to another embodiment, the compound (A) of the composition typically does not contain atoms such as S and / or Si. According to a further embodiment, the dental composition typically does not contain bis-GMA.

Full descriptions of patents, patent documents, and publications cited in this application are incorporated by reference in their entirety as if each were individually incorporated. The present invention is not limited to the implementations described in this application.

Examples

Unless otherwise indicated, all parts and percentages are given on a mass basis, all water is deionized water, and all molecular weights are weight average molecular weights. Additionally, unless otherwise indicated, all experiments were performed under ambient conditions (23 ° C; 1013 mbar). Additionally, almost all stages of the process are carried out in an atmosphere of dry air:

Measurements

Particle size

If desired, the average particle size can be determined using a commercially available granulometer (laser diffraction particle size analyzer, MASERSIZER 2000; Malvern Comp.) In accordance with the manufacturer's instructions for use.

Bending Strength 1 (FS 1)

If desired, bending strength measurements can be carried out in accordance with ISO 4049 using a universal analyzer (Zwick Z 010, traverse head speed 1 mm / min). Bending strength is typically given in MPa.

Bending Strength 2 (FS 2)

If desired, bending strength measurements can be carried out in accordance with ISO 4049 using a universal analyzer (Zwick Z 010, traverse head speed 1 mm / min) with a single deviation consisting in the use of a test sample of 4 × 6 × 25 mm size. Bending strength is typically given in MPa.

Elastic modulus 1 (E-M. 1)

If desired, EM 1 can be determined in accordance with ISO 4049 and is given in [GPa].

Elastic modulus 2 (E-M. 2)

If desired, E-M 2 can be determined in accordance with ISO 4049 with the only deviation consisting in the use of a test sample of size 4 × 6 × 25 mm and it is given in [GPa].

Elongation at Break (EB)

If desired, EB can be determined in accordance with DIN 53455 and is given in [%].

Impact Strength (IS)

If desired, IS can be determined in accordance with ISO 179-1 (Charpy) using notched samples (test sample size: 4 × 6 × 50 mm) and a 0.5 J pendulum. IS is given in [kJ / m ² ].

Depth of Cure (DoO)

If desired, the cure depth (i.e. cured depth) can be analyzed in accordance with ISO 4049 by packing the paste sample in a cylindrical mold to cure the metal (8 mm depth, 4 mm diameter) and curing the sample for 40 s at using ELIPAR ™ Trilight standard (800 mW / cm ² ) (3M ESPE Company). The cured sample was removed from the mold and the uncured paste was scraped from the sample using a plastic applicator after less than about one minute of curing. The results are reported as the average of three repetitions.

Refractive index (n _D ²⁰ )

If desired, the refractive index can be measured using a Kruess AR 4 D device (refractometer in accordance with the Abby measurement principle). The refractive index is typically measured at 20.0 ° C at a wavelength of 589 nm.

Viscosity (η)

If desired, the viscosity can be measured using a Haake RotoVisco RV1 device (C60 / 1 rotor for viscosities up to 8000 MPa or C20 / 1 rotor for viscosities above 8000 MPa together with the P61 stator). Viscosity is typically measured at 23.0 ° C between two plane-parallel plates (i.e., a stator and a rotor). After activation and rectification of the system, an appropriate rotor is installed. The rotor is then leveled and the distance between the stator and rotor is adjusted to 0.052 mm (using the RheoWin Pro Job Manager Software Version 2.94 software) for viscosity measurements. Then the rotor is lifted and the material for measurements is fed to the stator (1.0 ml for the C60 / 1 rotor or 0.04 ml for the C20 / 1 rotor). Without undue delay, the rotor is leveled to a preset measurement position. The measurement material is quenched at 23.0 ° C. The shear rate for the measurement must be adjusted to a value at which the torque is at least 5000 μNm (therefore, usually shear rates of 100, 200, 500 or 1000 s ^-1 are used depending on the viscosity of the material to be measured). The measurement is started and carried out for 60 s. The viscosity values (Pa) are recorded starting from 20 seconds after the start of the measurements, and the average value of the recorded values is presented as viscosity.

Songs

Abbreviated Names

The name and / or structure of the components used are shown in Table 1.

Table 1 BF ₃ * THF Bortrifluoride tetrahydrofuran adduct (CAS No. 462-34-0) VNT 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-p-cresol, 3,5-di-tert-butyl-4-hydroxytoluene (CAS No. 7637-07-2) VA4EO-MA

Бисфенол А этоксилированный, диметакрилат (CAS №56744-60-6) Mw=540,7

Bisphenol A ethoxylated, dimethacrylate (CAS No. 56744-60-6) Mw = 540.7 S.P.2 b)

VA20x-MA

SP.3 but) Bisphenol A oxetanylated, dimethyl acrylate, Example 11 on page 14 DE 1,921,869 (CAS No. 27689-12-9) Mw = 480.6 BA2EO-Ac

Bisphenol A ethoxylated, diacetate (CAS No. 19224-29-4) Mw = 400.5 S.P.4 m) Cdge

Cyclohexane-1,4-dimethanol (CAS No. 14228-73-0) CPh

Mw = 444.6 CPh-MA

Mw = 580.7; n _D ²⁰ = 1,520; η = 4.2 Pa * s E8 h) CPh-A

Mw = 552.7; n _D ²⁰ = 1.524; η = 8.6 Pa * s E19 j) CPh-Ac

Mw = 528.7 E20 ab)

CPh-DB

Mw=652,8

Mw = 652.8 CPQ Camphorquinone (CAS No. 10373-78-1] n) DESMA Urethane methacrylate, compare with Example 1 on page 35 of WO 2009/006282 r) DPI-PF6 Diphenyl iodonium hexafluorophosphate (CAS No. 58109-40-3) o) Edmab Ethyl 4-dimethylaminobenzoate (CAS No. 10287-53-3) p) Eh

Ethoxylated Hydroquinone (CAS No. 104-38-1) Ehgp

Mw = 498.6 EHGP-MA

Mw = 634.7 EHGP-A

Mw = 606.7 EHGP-Ac

Mw = 582.7 EHGP-DB

Mw=706,8

Mw = 706.8 Ehteo

(a + b) = 1 and (c + d) = 4,
Mw = 530.3 EHTEO-MA

(a + b) = 1 and (c + d) = 4,
Mw = 666.4 Ehteo-a

where (a + b) = 1 and (c + d) = 4,
Mw = 638.4 EHTEO-Ac

where (a + b) = 1 and (c + d) = 4,
Mw = 614.4 EHTEO-DB

where (a + b) = 1 and (c + d) = 4,
Mw = 738.5 Ehtgp

(a + b) = 1 and (c + d) = 2,
Mw = 492.6

EHTGP-MA

(a+b)=1 и (c+d)=2,
Mw=628,7

(a + b) = 1 and (c + d) = 2,
Mw = 628.7 EHTGP-A

where (a + b) = 1 and (c + d) = 2,
Mw = 600.7 EHTGP-AM

where (a + b) = 1 and (c + d) = 2,
Mw = 614.7 EHTGP-Ac

where (a + b) = 1 and (c + d) = 2,
Mw = 576.7 EHTGP-DB

where (a + b) = 1 and (c + d) = 2,
Mw = 700.8 Ehtso

(a + b) = 1 and (c + d) = 2,
Mw = 462.6

EHTSO-MA

(a+b)=1 и (c+d)=2,
Mw=598,7

(a + b) = 1 and (c + d) = 2,
Mw = 598.7 EHTSO-A

where (a + b) = 1 and (c + d) = 2,
Mw = 570.7 EHTSO-AM

where (a + b) = 1 and (c + d) = 2,
Mw = 584.7 EHTSO-Ac

where (a + b) = 1 and (c + d) = 2,
Mw = 546.7 EHTSO-DB

where (a + b) = 1 and (c + d) = 2,
Mw = 670.8 Eo Ethylene Oxide (CAS No. 75-21-8) Er

Ethoxylated Resorcinol (CAS No. 102-40-9) Ergp

Mw = 498.6

ERGP-MA

Mw=634,7; n_D ²⁰=1,542; η=9,4 Па*с

Mw = 634.7; n _D ²⁰ = 1.542; η = 9.4 Pa * s E1 e) ERGP-A

Mw = 606.7; n _D ²⁰ = 1.547; η = 18.8 Pa * s E2 i) ERGP-Ac

Mw = 582.7; n _D ²⁰ = 1,540; η = 22.6 Pa * s E3 aa) ERGP-DB

Mw = 706.8 ERTEO

(a + b) = 1 and (c + d) = 2,
Mw = 386.2 ERTEO-MA

(a + b) = 1 and (c + d) = 2, Mw = 522.3; n _D ²⁰ = 1,500; η = 0.2 Pa * s E10 f) ERTEO-A

where (a + b) = 1 and (c + d) = 2,
Mw = 494.3

ERTEO-Ac

где (a+b)=1 и (c+d)=2,
Mw=470,3; n_D ²⁰=1,496; η=0,3 Па*с

where (a + b) = 1 and (c + d) = 2,
Mw = 470.3; n _D ²⁰ = 1.496; η = 0.3 Pa * s E11 ERTEO-DB

where (a + b) = 1 and (c + d) = 2,
Mw = 594.4; η = 4.5 Pa * s E12 ERTGP

(a + b) = 1 and (c + d) = 1,
Mw = 420.5 ERTGP-MA

(a + b) = 1 and (c + d) = 1,
Mw = 556.6; n _D ²⁰ = 1.525; q = 1.1 Pa * s E16 ERTGP-A

where (a + b) = 1 and (c + d) = 1,
Mw = 528.6 ERTGP-AM

where (a + b) = 1 and (c + d) = 1,
Mw = 542.6 ERTGP-Ac

E17 z)

where (a + b) = 1 and (c + d) = 1,
Mw = 504.6; n _D ²⁰ = 1.516; η = 1.5 Pa * s ERTGP-DB

где(a+b)=1 и (c+d)=1,
Mw=628,7

where (a + b) = 1 and (c + d) = 1,
Mw = 628.7 ERTSO

(a + b) = 1 and (c + d) = 1,
Mw = 390.5 ERTSO-MA

(a + b) = 1 and (c + d) = 1,
Mw = 526.6 ERTSO-A

where (a + b) = 1 and (c + d) = 1,
Mw = 498.6 ERTSO-AM

where (a + b) = 1 and (c + d) = 1,
Mw = 512.6 ERTSO-Ac

where (a + b) = 1 and (c + d) = 1,
Mw = 474.6 ERTSO-DB

where (a + b) = 1 and (c + d) = 1,
Mw = 598.7 Filler 1 Spray-dried filler based on zirconia and silica, <1 μm, surface treated q) Fill Gel 2 Glass filler containing ground strontium <3 μm (Schott Glaswerke), surface treated w) Filler 3 Pyrogenic Silica (Wacker HDKH 2000) x) GAA Glacial Acetic Acid (CAS No. 64-19-7) Gma

Глицидилметакрилат (CAS №106-91-2)

Glycidyl methacrylate (CAS No. 106-91-2) GP

Glycidylphenyl ether (CAS No. 122-60-1) Hq Hydroquinone (CAS No. 75-21-8) Hqme Hydroquinone methyl ether, 4-methoxyphenol (MPA) (CAS No. 150-76-5) Inits. one 1-benzyl-5-phenyl-barbituric acid s) Inits. 2 tert-butyl peroxy-3,5,5-trimethylhexanoate t) Inits. 3 Dibutylphenylethylammonium chloride u) Inits. four Copper (II) bis (1-phenylpentane-1,3-dione) complex v) MA Methacrylic acid (CAS No. 79-41-4) MSA Methanesulfonic acid, 70% (CAS No. 75-75-2) NaERT EO-MA Monomodal dispersion of planned 15 nm silica nanoparticles in ERTEO-MA E21 Na2ER THEO-MA Bimodal dispersion of planned 15 nm and 55 nm silica nanoparticles in ERTEO-MA E25 NaTTE O-MA Monomodal dispersion of planned 15 nm silica nanoparticles in TTEO-MA E22 NaTTE O-AM Monomodal dispersion of planned 15 nm silica nanoparticles in TTEO-AM E23

Na2TTE O-MA Bimodal dispersion of planned 15 nm and 55 nm silica nanoparticles in TTEO-MA E24 PO Propylene oxide (CAS No. 75-56-9) PPh ₃ Triphenylphosphane (CAS No. 2136-75-6) RDGE

Резорциндиглицидиловый эфир (CAS №101-90-6)

Resorcindiglycidyl ether (CAS No. 101-90-6) RPh

Mw = 410.5 RPh-MA

Mw = 546.6 RPh-A

Mw = 518.6 RPh-Ac

Mw = 494.6 RPh-DB

Mw = 618.7 SO Styrene Oxide (CAS No. 96-09-3) TCD alcohol

3/4,8/9-трицикло[5.2.1.0^2,6]декандиметанол, смесь изомеров (CAS №26896-48-0)
Mw=196,3

3 / 4.8 / 9-tricyclo [5.2.1.0 ^2.6 ] decandimethanol, mixture of isomers (CAS No. 26896-48-0)
Mw = 196.3 T-a one

3 / 4.8 / 9-tricyclo [5.2.1.0 ^2.6 ] decanedimethanol diacrylate, mixture of isomers, Example 2 in column 6 of US 4,131,729 (CAS No. 42594-17-2)
Mw = 304.4 S.P. one from) Tea Triethylamine (CAS No. 121-44-8) Teaa In situ triethylamine acetate obtained by mixing TEA and a molar excess of GAA Tgp

Mw = 496.7 TGP-MA

Mw = 632.8; n _D ²⁰ = 1,520; η = 1.0 Pa * s E4 TGP-A

Mw = 604.8; n _D ²⁰ = 1.521; η = 12.0 Pa * s E5

TGP-Ac

Mw=580,8

Mw = 580.8 TGP-DB

Mw = 704.9 THF Tetrahydrofuran (CAS No. 109-99-9) Tteo

(a + b) = 1 and (c + d) = 1,
Mw = 312.5 TTEO-MA

(a + b) = 1 and (c + d) = 1,
Mw = 448.6; n _D ²⁰ = 1,499; η = 0.1 Pa * s E6 g) TTEO-A

where (a + b) = 1 and (c + d) = 1,
Mw = 420.6; n _D ²⁰ = 1,503; η = 0.2 Pa * s E7 k) TTEO-AM

where (a + b) = 1 and (c + d) = 1,
Mw = 434.6; n _D ²⁰ = 1,502; η = 0.2 Pa * s E8 i) TTEO-Ac

where (a + b) = 1 and (c + d) = 1,

Mw = 396.6 TTEO-DB

где (a+b)=1 и (c+d)=1,
Mw=520,7; η=3,8 Па*с

where (a + b) = 1 and (c + d) = 1,
Mw = 520.7; η = 3.8 Pa * s E9 y) TTGP

(a + b) = 1 and (c + d) = 1,
Mw = 418.6 TTGP-MA

(a + b) = 1 and (c + d) = 1,
Mw = 554.7; n _D ²⁰ = 1.515; η = 1.0 Pa * s E13 d) TTGP-A

where (a + b) = 1 and (c + d) = 1,
Mw = 526.7; n _D ²⁰ = 1.517; η = 1.4 Pa * s E14 TTGP-Ac

where (a + b) = 1 and (c + d) = 1,
Mw = 502.7; n _D ²⁰ = 1.513; η = 1.7 Pa * s E15

TTGP-DB

где (a+b)=1 и (c+d)=1,
Mw=626,8

where (a + b) = 1 and (c + d) = 1,
Mw = 626.8 Ttso

(a + b) = 1 and (c + d) = 1,
Mw = 388.6 TTSO-MA

(a + b) = 1 and (c + d) = 1,
Mw = 524.7 TTSO-A

where (a + b) = 1 and (c + d) = 1,
Mw = 496.7 TTSO-Ac

where (a + b) = 1 and (c + d) = 1,
Mw = 472.7 TTSO-DB

where (a + b) = 1 and (c + d) = 1,
Mw = 596.8

S.P. means a comparative example.

Synthesis of Compound (A)

Compound (s) (A) can be prepared as follows:

General Procedure 1: Reaction of a diol precursor, e.g. TCP alcohol with epoxy (e.g. GP) using, for example, TEAA as a catalyst

For example, TCD alcohol and GP as the corresponding epoxy functional reagent / s were mixed with stirring, for example, cyclohexane. For example, 1.5 wt.% TEA and 1.5 wt.% GAA (relative to the weight of the sum of all reagents, with in situ formation of 3.0 wt.% TEAA) were added with stirring. The mixture was then heated with stirring to a temperature of approximately 70 ° C until the completion of the addition reaction (measured by 1 H-NMR: no signals of residual epoxy groups were detected). Optionally, 3-5 wt.% MSA was slowly added with stirring, and stirring was continued for about 60 minutes at about 70 ° C. The mixture was then allowed to cool to room temperature with stirring. The crude reaction mixture was washed once with water, then extracted twice with 2N NaOH, then washed once with water, then dried over anhydrous Na ₂ SO ₄ . After filtration, the filtrate was again filtered through basic alumina. Then the solvent was distilled off in vacuo.

General Procedure 2: Reaction of the diol precursor, e.g., TCP alcohol with an epoxy-containing mixtures (e.g., EO in THF) with BF ₃ * THF as catalyst

For example, TCD alcohol was diluted in anhydrous THF, then BF ₃ * THF was added with stirring. Gaseous EO was added with stirring so that the temperature of the reaction mixture did not exceed about 30-40 ° C. After completion of the addition of EO, stirring was continued at room temperature for approximately 30 minutes. 13 wt.% Water was added (relative to the sum of the amounts of reactive excreted substances), after about 30 minutes, 13 wt.% Basic alumina was also added with stirring. After an additional approximately 60 minutes of stirring, a 13 wt.% Solution of sodium methanolate in methanol (30% in methanol) was added. Then the suspension was stirred at room temperature for approximately 12 hours. After filtration, the solvent was distilled off in vacuo.

General Procedure 3: Reaction of a di-epoxy functional precursor, for example, CDGE with an OH acid reagent, for example phenol, using, for example, potassium tert-butoxide (KOtBu) as a catalyst

For example, phenol was mixed with, for example, toluene and heated with stirring to a temperature of approximately 50 ° C. For example, 3.0 wt.% KOtBu was added with stirring, and stirring was continued until KOtBu was dissolved. At a temperature of approximately 80 ° C, CDGE was added with stirring so that the temperature did not exceed approximately 90 ° C. After complete addition, the reaction mixture was stirred at a temperature of from about 80 ° C until the completion of the addition reaction (measured by 1 H-NMR: no signals of residual epoxy groups were detected). Toluene was added with stirring. The mixture was then allowed to cool to room temperature with stirring. The crude reaction mixture was extracted at least twice with a 4N NaOH solution, then washed once with water, then dried over anhydrous Na ₂ SO ₄ . After filtration, the filtrate was again filtered through basic alumina. Then the solvent was distilled off in vacuo.

General Procedure 4: The esterification of diol (e.g., TCD) non-methacrylate functional intermediates, e.g., methacrylic acid (MA)

To the corresponding, for example, TCD non-methacrylate functional intermediate in, for example, hexane, BHT, HOME, optionally methylene blue, for example, MSA as a catalyst and, for example, MA, were added. At reflux, water was removed using a Dean-Stark apparatus. After completion of the reaction, the crude reaction mixture was extracted at least twice with a 4N NaOH solution, then washed once with water, then dried over anhydrous Na ₂ SO ₄ . After filtration, the filtrate was again filtered through basic alumina. 100 ppm was added to the filtrate. BHT and 100 ppm NOME. Then, the solvent was distilled off in vacuo while bubbling air through a crude sample.

General Procedure 5: Dispersions of Planned SiO ₂ Nanoparticles Inside the Described Diol (e.g. TCD) Monomers by Silanizing a Suspension of SiO ₂ Nanoparticles

Dispersions of surface-modified nanosized silicas were obtained, for example, in the corresponding, for example, TCD monomer / monomers. Nanosized silica particles can be surface treated and dispersed in a curable resin, as described in US 6,899,948 B2, incorporated herein by reference. A preferred method for surface treatment and dispersion is described in Example 3, column 32, lines 31-42, as summarized below. The desired amount of surface-modifying agent (s) was added to methoxypropanol and mixed. This alcohol solution was added to the silica sol slowly with stirring (1-2 minutes) and kept at a temperature of approximately 80 ° C for approximately 16 hours. In a surface-modified silica sol, the solvent was replaced by mixing the sol with an appropriate, for example, TCD monomer / s and heating the modified organic sol in an oven at about 85-90 ° C. for about 4 hours. As one skilled in the art will understand, such a procedure can be used with many sols, including Single described herein, including sodium and ammonium-stabilized silica sols. Other solvents such as ethanol, n-propanol and / or isopropanol can also be used in place of or with methoxypropanol. This process may also be suitable for a wide variety of surface-modifying agents, including both reactive and non-reactive surface-modifying agents. This process is also not limited to the resin into which the surface-modified nanoparticles are dispersed. Finally, a modification process may also be used. For example, in some implementations, lower temperatures and the use of vacuum may be desirable. For example, in a surface-modified silica sol, the solvent can be replaced by mixing the sol with the appropriate, for example, TCD monomer / s, and the modified organic sol can then be treated by applying vacuum and heating in an oven at about 40-60 ° C until completion.

Synthesis of ERGP-MA (Example in accordance with the present invention 1):

In accordance with General Procedure, 1116 g of ER, 172 g of GP were reacted using THF as a solvent and KOtBu as a catalyst. 239 g of ERGP (479 mmol, 82%) were isolated as a yellowish liquid. In accordance with General Procedure, 4,157 g of ERGP, 81.4 g of MA, 30.0 mg of BHT, 80.0 25 mg of HQME and 11.5 g of MSA were reacted using toluene as solvent. 76.4 g of ERGP-MA (120 mmol, 38%) were isolated as a yellowish oil: η = 9.4 Pa * s, n _D ²⁰ = 1.542.

Synthesis of ERGP-A (Example in accordance with the present invention 2):

In accordance with General Procedure, 1116 g of ER, 172 g of GP were reacted using THF as a solvent and KOtBu as a catalyst. 239 g of ERGP (479 mmol, 82%) were isolated as a yellowish liquid. Following the General Procedure, 4,165 g of ERGP, 71.5 g of acrylic acid (AA), 28.0 mg of BHT, 77.0 mg of HQME and 6.50 g of MSA were reacted using toluene as solvent. 172 g ERGP-A (284 mmol, 86%) was isolated as a yellowish oil: η = 18,8 Pa * s, n _D ²⁰ = 1.547.

Synthesis of ERGP-Ac (Example in accordance with the present invention 3):

In accordance with General Procedure, 1116 g of ER, 172 g of GP were reacted using THF as a solvent and KOtBu as a catalyst. 239 g of ERGP (479 mmol, 82%) were isolated as a yellowish liquid. Following General Procedure 4, 60.0 g of ERGP, 24.9 g of acetic anhydride (AAA) were first reacted using toluene as solvent, then 630 mg of p-toluenesulfonic acid (pTSA) was added and water was removed. 48.6 g of ERGP-Ac (84.0 mmol, 69%) were isolated as a yellowish oil: η = 22.6 Pa * s, n _D ²⁰ = 1.540.

Synthesis of TGP-MA (Example in accordance with the present invention 4):

In accordance with General Procedure 1100 g of TCD alcohol, 153 g of GP were reacted. 255 g of TGP (512 mmol, 100%) was isolated as a yellowish liquid. Following General Procedure 4, 70.0 g of TGP, 79.0 g of AA, 18.0 mg of BHT, 49.0 mg of HQME, 36.0 mg of methylene blue, and 3.52 g of MSA were reacted. 54.8 g of TGP-MA (188 mmol, 60%) was isolated as a yellowish liquid: η = 1,0 Pa * s, n _D ²⁰ = 1.520.

Synthesis of TGP-A (Example in accordance with the present invention 5):

In accordance with General Procedure 1100 g of TCD alcohol, 153 g of GP were reacted. 255 g of TGP (512 mmol, 100%) was isolated as a yellowish liquid. Following the General Procedure, 4100 g of TGP, 42.0 g of AA, 17.0 mg of BHT, 46.0 mg of HQME and 6.80 g of MSA were reacted using cyclohexane as solvent. 97.0 g of TGP-A (160 mmol, 80%) was isolated as a yellowish oil: η = 12.0 Pa * s, n _D ²⁰ = 1.521.

Synthesis of TTEO-MA (Example in accordance with the present invention 6):

In accordance with the General Procedure, 2300 g of TCD alcohol, 64.6 g of EO, 600 g of THF and 37.9 g of BF ₃ * THF were reacted. 429 g of TTEO was isolated as a colorless oil. Following the General Procedure, 4213 g of TTEO, 161 g of MA, 44.8 mg of BHT, 121 mg of HQME, 89.6 mg of methylene blue and 12.8 g of MS A were reacted using hexane as solvent. 237 g of 20 TTEO-MA (67%) was isolated as a colorless liquid: η = 0.1 Pa * s, n _D ²⁰ = 1.499.

Synthesis of TTEO-A (Example in accordance with the present invention 7):

In accordance with the General Procedure, 2300 g of TCD alcohol, 64.6 g of EO, 600 g of THF and 37.9 g of BF ₃ * iTO were reacted. 429 g of TTEO was isolated as a colorless oil. Following the General Procedure, 4119 g of TTEO, 83.7 g of AA, 24.3 mg of BHT, 65.8 mg of HQME, 48.6 25 mg of methylene blue and 9.76 g of MSA were reacted using hexane as solvent. 142 g of TTEO-A (88%) were isolated as a colorless liquid: η = 0.2 Pa * s, n _D ²⁰ = 1.503.

Synthesis of TTEO-AM (Example in accordance with the present invention 8):

Following the General Procedure, 2300 g of TCD alcohol, 64.6 g of EO, 600 g of THF and 37.9 g of BF ₃ * TFO were reacted. 429 g of TTEO was isolated as a colorless oil. In accordance with General Procedure 4, first 230 g of TTEO, 57.8 g of MA, 39.7 mg of BHT, 107 mg of HQME, 79.3 mg of methylene blue and 15.9 g of MSA were reacted using hexane as solvent and then another 72 , 5 g of AA was added, and the resulting mixture reacted further. 263 g of TTEO-AM (94%) was isolated as a colorless liquid: η = 0.2 Pa * s, n _D ²⁰ = 1.502.

Synthesis of TTEO-DB (Example in accordance with the present invention 9):

In accordance with the General Procedure, 2300 g of TCD alcohol, 64.6 g of EO, 600 g of THF and 37.9 g of BF ₃ * THF were reacted. 429 g of TTEO was isolated as a colorless oil. In accordance with the General Procedure, 4100 g of TTEO, 106 g of benzoic acid (BA) and 7.10 g of MS A were reacted using hexane as a solvent. 135 g of TTEO-DB (80%) was isolated as a colorless oil: η = 3.8 Pa * s.

Synthesis of ERTEO-MA (Example in accordance with the present invention 10):

In accordance with General Procedure, 2179 g of ER, 38.9 g of EO, 700 g of THF and 21.9 g of BF ₃ * THF were reacted. 338 g of ERTEO were isolated as a colorless oil. Following the General Procedure, 4304 g of ERTEO, 197 g of MA, 39.0 mg of BHT, 666 mg of HQME and 10.0 g of 10 pTSA were reacted using cyclohexane as solvent. 338 g of ERTEO-MA (83%) were isolated as a colorless liquid: η = 0.2 Pa * s, n _D ²⁰ = 1,500.

Synthesis of ERTEO-Ac (Example in accordance with the present invention 11):

In accordance with General Procedure, 2179 g of ER, 38.9 g of EO, 700 g of THF and 21.9 g of BF ₃ * THF were reacted. 338 g of ERTEO were isolated as a colorless oil. Following the General Procedure, 470.0 g of ERTEO and 34.0 g of AAA were first reacted using toluene as solvent, then 770 mg of pTSA was added and water was removed. 77.8 g of ERTEO-Ac (88%) was isolated as a colorless oil: η = 0.3 Pa * s, n _D ^{20 =} 1.496.

Synthesis of ERTEO-DB (Example in accordance with the present invention 12):

According to the General Procedure, 2179 g of ER, 38.9 g of EO, 700 g of THF and 21.9 g of 20 BF ₃ * THF were reacted. 338 g of ERTEO were isolated as a colorless oil. Following the General Procedure, 440.0 g of ERTEO, 52.9 g of BA and 1.67 g of pTSA were reacted using toluene as solvent. 59.1 g of ERTEO-DB (87%) were isolated as a colorless oil: η = 4.5 Pa * s.

Synthesis of TTGP-MA (Example in accordance with the present invention 13):

In accordance with the General Procedure, 2300 g of TCD alcohol, 221 g of GP, 600 g of THF and 37.9 g of BF ₃ * THF were reacted. 620 g of TTGP was isolated as a colorless oil. In accordance with the General Procedure, 4150 g of TTGP, 93.3 g of MA, 24.7 mg of BHT, 434 mg of HQME and 11.8 g of MSA were reacted. 139 g of TTGP-MA (70%) was isolated as a colorless liquid: η = 1.0 Pa * s, n _D ²⁰ = 1.515.

Synthesis of TTGP-A (Example in accordance with the present invention 14):

In accordance with the General Procedure, 2300 g of TCD alcohol, 221 g of GP, 600 g of THF and 37.9 g of BF ₃ * THF were reacted. 620 g of TTGP was isolated as a colorless oil. Following the General Procedure, 4160 g of TTGP, 84.0 g of AA, 29.0 mg of BHT, 79.0 mg of HQME, 58.0 mg of methylene blue and 11.7 g of MSA were reacted. 180 g of TTGP-A (89%) was isolated as a colorless liquid: η = 1.4 Pa * s, n _D ²⁰ = 1.517.

Synthesis of TTGP-Ac (Example in accordance with the present invention 15):

In accordance with the General Procedure, 2300 g of TCD alcohol, 221 g of GP, 600 g of THF and 37.9 g of BF ₃ * THF were reacted. 620 g of TTGP was isolated as a colorless oil. Following the General Procedure, 450.0 g of TTGP and 18.9 g of AAA were first reacted using toluene as solvent, then 510 mg of pTSA was added and water was removed. 55.0 g of TTGP-Ac (91%) 5 was isolated as a colorless liquid: η = 1.7 Pa * s, n _D ²⁰ = 1.513.

Synthesis of ERTGP-MA (Example in accordance with the present invention 16):

In accordance with General Procedure, 2151 g of ER, 110 g of GP, 300 g of THF and 19.0 g of BF ₃ * THF were reacted. 325 g of ERTGP were isolated as a colorless oil. Following the General Procedure, 4165 g of ERTGP, 65.0 g of MA, 28.0 mg of BHT, 75.0 mg of HQME and 11.1 g of MSA were reacted. 155 g of ERTGP-MA (78%) were isolated as a colorless liquid: η = 1.1 Pa * s, n _D ²⁰ = 1.525.

Synthesis ERTGP-Ac (Example according to the invention 17): In accordance with the General Procedure 2 151 g ER, 110 grams of GP, 300 g of THF and 19.0 g of BF ₃ * THF reacted. 325 g of ERTGP were isolated as a colorless oil. Following General Procedure 4, 70.0 g of ERTGP and 31.5 g of AAA were first reacted using toluene as solvent, then 750 mg of pTSA was added and water was removed. 61.2 g of ERTGP-Ac (74%) were isolated as a colorless liquid: η = 1.5 Pa * s, n _D ²⁰ = 1.516.

Synthesis of CPh-MA (Example in accordance with the present invention 18): In accordance with General Procedure, 3,250 g of CDGE and 194 g of phenol were reacted. 367 g of 20 CPh (825 mmol, 89%) was isolated as a yellowish oil. Following the General Procedure, 4,128 g CPh, 74.4 g MA, 24.3 mg BHT, 65.8 mg HQME and 5.65 g MSA were reacted using cyclohexane as solvent. 70.0 g of CPh-MA (121 mmol, 42%) was isolated as a yellowish liquid: η = 4.2 Pa * s, n _D ²⁰ = 1.520.

Synthesis of CPh-A (Example in accordance with the present invention 19): In accordance with General Procedure, 3,250 g of CDGE and 194 g of phenol were reacted. 367 g CPh (825 mmol, 89%) was isolated as a yellowish oil. In accordance with General Procedure, 4,121 g of CPh, 59.0 g of AA, 21.6 mg of BHT, 58.5 mg of HQME and 5.35 g of MSA were reacted using cyclohexane as solvent. 76.8 g of CPh-A (139 mmol, 51%) was isolated as a yellowish oil: η = 8.6 Pa * s, n _D ²⁰ = 1.524.

Synthesis of CPh-Ac (Example in accordance with the present invention 20): In accordance with General Procedure 3250 g of CDGE and 194 g of phenol were reacted. 367 g CPh (825 mmol, 89%) was isolated as a yellowish oil. Following the General Procedure, 470.0 g CPh and 32.2 g AAA were first reacted using toluene as solvent, then 760 mg pTSA was added and water was removed. 53.5 g of CPh-Ac (101 mmol, 64%) were isolated as a yellowish oil: η = 26.5 Pa * s, n _D ^{20 =} 1.512.

Synthesis of NaERTEO-MA (monomodal dispersion of planned silica nanoparticles in ERTEO-MA (Example in accordance with the present invention 21):

Following the General Procedure, 5,116 g of ERTEO-MA, 200 g of Bayer Dispercoll S 4020, 9.38 g of 3-methacryloyloxypropyltrimethoxysilane, 2.50 g of phenyltrimethoxysilane and 388 g of ethanol were reacted. 201 g of NaERTEO-MA (95%) was isolated as a yellowish gel.

Synthesis of Na2ERTE0-MA (bimodal dispersion of planned silica nanoparticles in ERTEO-MA (Example in accordance with the present invention 25):

In accordance with the General Procedure, 55.6 g of ERTEO-MA, 30.0 g of Bayer Dispercoll S 4020.170 g of Bayer Dispercoll S 5005, 3.81 g of 3-methacryloyloxypropyltrimethoxysilane, 3.04 10 g of phenyltrimethoxysilane and 459 g of ethanol were reacted. 154 g of Na2ERTEO-MA (95%) was isolated as a yellowish gel.

Synthesis of NaTTEO-MA (monomodal dispersion of planned silica nanoparticles in TTEO-MA (Example in accordance with the present invention 22):

In accordance with the General Procedure, 5,153 g of TTEO-MA, 300 g of Bayer Dispercoll S 4020, 14.4 15 g of 3-methacryloyloxypropyltrimethoxysilane, 11.5 g of phenyltrimethoxysilane and 581 g of ethanol were reacted. 270 g of NaTTEO-MA (88%) were isolated as a yellowish gel.

Synthesis of NaTTEO-AM (monomodal dispersion of planned silica nanoparticles in TTEO-AM (Example in accordance with the present invention 23):

In accordance with the General Procedure, 5 94.2 g of TTEO-AM, 200 g of Bayer Dispercoll S 4020, 20 6.25 g of 3-methacryloyloxypropyltrimethoxysilane, 4.99 g of phenyltrimethoxysilane and 387 g of ethanol were reacted. 172 g of NaTTEO-AM (91%) was isolated as a yellowish gel.

Synthesis of Na2TTEO-MA (bimodal dispersion of planned silica nanoparticles in TTEO-MA (Example in accordance with the present invention 24):

In accordance with the General Procedure, 5,136 g of TTEO-MA, 86.5 g of Bayer Dispercoll S 4020, 490 g of GraceDavison Ludox P-W50, 16.7 g of 3-methacryloyloxypropyltrimethoxysilane, 13.3 g of phenyltrimethoxysilane and 1.12 kg of ethanol were reacted. 385 g of Na2TTEO-MA (85%) was isolated as a yellowish gel.

Synthesis of light-curable one-component compositions Some of the synthesized compounds were used to produce a (dental) composition. Compositions were prepared and analyzed for their mechanical properties, as shown in Tables 2 and 3 below. In Tables 2 and 3, the values for components a) to s) represent wt. % of individual components in the respective dental compositions. General Method A:

With stirring with a magnetic stirrer and with the light off, the initiator system components were dissolved in monomers at temperatures not exceeding 50 ° C (depending on the internal viscosity of the monomers used).

General Method B:

In accordance with General Procedure A, the components of the initiator system were dissolved in monomers. With the lights off and using a two-handed mixer, the filler was mixed in portions with a mixture of a system of initiators and monomers. The amount of filler was determined manually depending on the desired operating properties of the dental composition. The dental composition was then cured with light using 800 mW halogen curing radiation (3M ESPE 10 EliparTM Trilight) and analyzed in accordance with the corresponding measurements given above in this application. The corresponding values are given in Tables 2 and 3.

Dental compositions A-E contain any of components a), b) or c), but not the compound (A) in accordance with the present invention. In Tables 2 and 3 below, compound (A) is represented by components d) -l) and y) -ab). Thus, dental compositions A-E can be considered as comparative examples, while dental compositions F-L can be considered as examples in accordance with the present invention.

table 2 Dental composition A B C D E F G H but) 18,4 9.15 b) 17.7 8.60 from) 17.0 9.15 8.60 d) 17.7 e) 19.6 f) 18,4 g) h) i) j) k) l) m) n) 0,03 0,03 0,03 0,03 0,03 0,03 0,03 0,03 about) 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 p) 0.09 0.09 0.09 0.09 0.09 0.09 0.09 0.09 q) 81.3 82.0 82.7 81.4 82.5 82.0 80.1 81.3 r) s) t) u) v) w) x) y) z) aa) ab) FS 1 [MPa] 155 ± 15.0 137 ± 18.0 142 ± 10.0 153 ± 26.0 134 ± 9.00 82.0 ± 14.0 137 ± 14.0 126 ± 23.0 E-M, 1 [GPa] 11.1 ± 0.20 11.7 ± 0.20 15.0 ± 0.30 13.5 ± 0.60 11.5 ± 0.40 8.50 ± 0.30 10.0 ± 0.30 7.60 ± 0.40 DoC [mm] 4.65 4.74 5.34 5.60 5.57 4.67 4.81 4.93

Table 3 Dental composition I J K L a) b) c) d) e) f) g) 18.2 h) 21.1 i) 19.7 j) 20.5 k) l) m) n) 0,03 0,03 0,03 0,03 about) 0.19 0.19 0.19 0.19 p) 0.09 0.09 0.09 0.09 q) 81.5 78.6 80.0 79.2 r) s) t) u) v) w) x) y) z) aa) ab) FS 1 [MPa] 157 ± 10.0 114 ± 15.0 91.0 ± 8.00 72.0 ± 9.00 E-m. 1 [GPa] 8.60 ± 0.30 7.80 ± 0.30 2.70 ± 0.10 4.10 ± 0.30 DoC [mm] 4.12 5.65 5.20 5.85

As you can see, compositions containing compound (A) in accordance with the present invention are superior in relation to certain properties compared to compositions not containing compound (A) in accordance with the present invention.

Synthesis of Chemically Curable Two-Component Compositions

Some of the synthesized compounds were used to obtain a (dental) composition.

Compositions were prepared and analyzed for their mechanical properties, as shown in Tables 4, 5, 6 and 7 below in this application.

In Tables 4 and 5, the values for components a) to s) represent wt.% Of the individual components in the respective dental compositions. In Tables 6 and 7, the values for the Base 1 - CAT 5 components represent the relative% of individual components in the respective dental compositions.

General Method C:

With the lights off, the components listed in Tables 4 and 5 were mixed in a three-handed laboratory mixer. Residual agglomerates were homogenized in a ceramic three-roller mill.

General Method D:

The pastes listed in Tables 6 and 7, obtained in accordance with General Method C, filled the appropriate compartments of the 10: 1 SulzerMixpac ™ cartridge. The material was then applied to the appropriate metal molds using a Garant ™ II 10: 1 cartridge equipped with a static mixer (Sulzer Mixpac Company). Curing was carried out under pressure between a plastic foil (Hostaphan ™ RN75) and Plexiglass plates for 1 hour at 23 ° C. Then the press, plexiglass plates and foil were removed and the samples in the molds were post-cured at 36 ° C. in demineralized water for 23 hours. Molds were removed immediately before measurements. Cured samples were analyzed in accordance with the relevant measurements listed above in this application. The corresponding values are given in Tables 6 and 7.

Dental composition - Base 1 - contains any of the components a), b) or c), but not the compound (A) in accordance with the present invention. In Tables 4 and 5 below in this application, compound (A) is represented by components d) -l) and y) -ab). Thus, the dental composition - Base 1 - can be considered as related to the comparative example, while the dental composition - Base 2-6 - can be considered as related to the examples in accordance with the present invention.

Table 4 Dental composition Base 1 Base 2 Base 3 Base 4 Base 5 Base 6 but) b) 52,4 from) d) 52,4 e) f) 52,4 g) 52,4 h) i) j) k) 52,4 l) 52,4 m) n) o) p) q) r) 13.1 13.1 13.1 13.1 13.1 13.1 s) t) u) 0.15 0.15 0.15 0.15 0.15 0.15 v) <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 w) 26.3 26.3 26.3 26.3 26.3 26.3 x) 8.00 8.00 8.00 8.00 8.00 8.00 y) z) aa) ab)

Dental composition - CAT 1 - contains component m), which is a component in accordance with the prior art, while dental compositions - CAT2 - CAT 5 - contain any of components y), z), aa) and bb), components, which fall within the definition of compound (A) in accordance with the present invention.

Table 5 Dental composition CAT 1 CAT 2 CAT 3 CAT 4 CAT 5 but) b) from) d) e) f) g) h) i) j) to l) m) 79.7 n) o) p) q) r) s) 10.0 10.0 10.0 10.0 10.0 t) 0.30 0.30 0.30 0.30 0.30 u) v) w) x) 10.0 10.0 10.0 10.0 10.0 y) 79.7 z) 79.7 aa) 79.7 ab) 79.7

Dental composition M contains Base 1 and CAT 1, compositions that both contain components in accordance with the prior art. Dental compositions N-V contain either a Base component containing compound (A) in accordance with the present invention, or a CAT component containing compound (A) in accordance with the present invention. Thus, dental compositions N-V can be considered as examples in accordance with the present invention.

Table 6 Dental composition M N ABOUT R Q R Base 1 90.9 Base 2 90.9 Base 3 90.9 Base 4 90.9 Base 5 90.9 Base 6 90.9 CAT 1 9.09 9.09 9.09 9.09 9.09 9.09 CAT 2 CAT 3 CAT 4 CAT 5 FS 2 [MPa] 102 ± 1.90 55.3 ± 6.10 55.1 ± 4.90 83.9 ± 3.10 90.4 ± 7.00 99.8 ± 9.60 EAT. 2 [GPa] 2.07 ± 0.11 0.70 ± 0.16 0.48 ± 0.07 1.43 ± 0.03 1.55 ± 0.07 1.85 ± 0.25 EB [%] 10.0 ± 1.20 15.4 ± 2.20 23.3 ± 2.80 13.8 ± 2.60 18.8 ± 2.90 10.2 ± 4.10 IS [kJ / m ² ] 7.40 ± 2.80 11.5 ± 2.20 16.6 ± 3.50 10.1 ± 0.70 16.9 ± 2.70 12.9 ± 3.40

Table 7 Dental composition S T U V Base 1 90.9 90.9 90.9 90.9 Base 2 Base 3 Base 4 Base 5 Base 6 CAT 1 CAT 2 9.09 CAT 3 9.09 CAT 4 9.09 CAT 5 9.09 FS 2 [MPa] 88.3 ± 7.70 89.9 ± 3.40 83.8 ± 5.00 92.8 ± 5.10 E-m. 2 [GPa] 1.81 ± 0.07 1.52 ± 0.03 1.70 ± 0.05 1.69 ± 0.04 EB [%] 12.8 ± 0.70 11.8 ± 1.60 12.0 ± 1.20 12.8 ± 2.40 IS [kJ / ^m2] 11.1 ± 0.70 10.6 ± 2.40 11.1 ± 4.40 13.2 ± 2.40

As you can see, compositions containing compound (A) in accordance with the present invention are superior in relation to certain properties compared to compositions not containing compound (A) in accordance with the present invention.

Claims (12)

1. Dental composition containing
a) compound (A), characterized by a structure in accordance with any of the formulas (I), (II) or (III)

Where
a, b = 0-3, s, d = 0-3, (a + b) = 1-6, (c + d) = 1-6,
Q = independently selected from hydrogen, methyl, phenyl and phenoxymethyl,
G is selected from

and U is selected from

and mixtures thereof,

Where
G is selected from

and U is selected from

and mixtures thereof,

Where
a, b = 0-3, s, d = 0-3, (a + b) = 1-6, (c + d) = 1-6,
Q = independently selected from hydrogen, methyl, phenyl and phenoxymethyl,
G is selected from

and U is selected from

and mixtures thereof,
where the symbol "*" indicates the attachment point of the fragment,
b) filler (B);
c) initiator (C); and
d) a polymerizable compound (D) other than compound (A). 2. The composition according to p. 1, characterized in that the compound (A) is characterized by at least one, two, three, four or five of the following:
- Molecular mass (Mw): from 550 to 1000;
- Reactive functional group: 2 ethylenically unsaturated reactive groups per molecule, attached via an ester bond to the framework;
- Non-reactive functional groups: 2 hydrocarbon non-reactive functional groups per molecule attached via an ester bond to the framework;
- Polar groups: lack of free OH groups within the molecule;
Secondary network: the absence of urethane fragments inside the molecule;
- Refractive index: from 1.495 to 1.565 (n _D ²⁰ ). 3. The composition according to p. 1 or 2, characterized in that the compound (A) is selected from

(a + b) = 1 and (c + d) = 4

where (a + b) = 1 and (c + d) = 4

where (a + b) = 1 and (c + d) = 4

where (a + b) = 1 and (c + d) = 4

(a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

(a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

(a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

where (a + b) = 1 and (c + d) = 2

(a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

(a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

(a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

(a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

(a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1

where (a + b) = 1 and (c + d) = 1
and mixtures thereof. 4. The composition according to p. 1 or 2, characterized in that the initiator (C) contains a redox initiator, photoinitiator, or a mixture thereof. 5. The composition according to p. 1 or 2, characterized in that it further comprises one or more of the following components:
softener (E), not containing the polymerizable group (s), excipients (F). 6. The composition according to p. 1 or 2, characterized in that it contains a polymerizable compound (D) containing at least one ethylenically unsaturated bond. 7. The composition according to p. 1 or 2, characterized in that it contains components in the following amounts:
- Compound (A): from 5 to 70 wt. %
- Filler (B): from 25 to 90 wt. %
- Initiator (C): from 0.1 to 3 wt. %
- Polymerizable compound (D): from more than 0 to 65 wt. %
- Softener (E): from 0 to 20 wt. %
- Excipient (F): from 0 to 25 wt. %
wt. % relative to the weight of the entire composition. 8. The composition according to p. 1 or 2, characterized in that it is a light-curing composition and is characterized by at least one of the following parameters after curing:
- Bending strength: at least 70 MPa, determined in accordance with ISO 4049,
- Modulus of elasticity: from 2 GPa to 11 GPa, determined in accordance with ISO 4049,
- Curing depth: at least 4 mm, determined in accordance with ISO 4049. 9. The composition according to p. 1 or 2, characterized in that it is a chemically curable composition and is characterized by at least one of the following parameters after curing:
- Bending strength: from 50 MPa to 100 MPa, determined in accordance with ISO 4049,
- Modulus of elasticity: from 0.4 GPa to 2.0 GPa, determined in accordance with ISO 4049,
- Elongation at break: at least 10%, determined in accordance with DIN 53455,
- Impact strength: at least 8 kJ / m ² , determined in accordance with ISO 179-1. 10. The composition according to p. 1 or 2, characterized in that it is contained in the container. 11. A set of components for use in dentistry, containing at least 2 compositions, as described in paragraph 1 or 2, while the compositions differ from each other by at least color. 12. The use of the composition as described in paragraph 1 or 2, as or for the production of dental cement, material for crowns or bridges, filling material, casting material, lining material for the sealant, composition for coating, billet, orthodontic devices, sealant or their combinations.