KR20070032377A - Dental Composition Containing Unsaturated Carbosilane Containing Components - Google Patents

Abstract

The present invention comprises a) a carbosilane containing component (A), b) initiator (B), c) optionally comprising at least one Si-aryl bond, at least one silicon atom, at least one unsaturated moiety, and free of Si-oxygen bonds; Filler (C) and d) optionally a dental composition comprising a component (D) selected from a modifier, a dye, a pigment, a thixotropic agent, a flow modifier, a polymer thickener, a surfactant, an aromatic substance, a diluent (s) and a perfume. It is about.

Dental compositions, carbosilane-containing components, initiators, curing

Description

Dental Composition Containing Unsaturated Carbosilane-Containing Components {Dental Composition Containing Unsaturated Carbosilane Containing Components}

The present invention relates to a curable dental composition containing an unsaturated carbosilane component. The composition has improved properties and can be used, for example, as a dental filling material.

Commercially available dental filler materials can be separated into resin modified glass ionomer cements and glass ionomer cements (GIZ), which are generally composites. Composites are typically cured by light induced radical polymerization of unsaturated components, especially (meth) acrylates. Glass ionomer cements are cured by cement curing reactions, while curing of resin modified glass ionomer cements is accomplished using both mechanisms.

Of particular interest are dental composites that produce materials that are very hard compared to glass ionomer cements, where curing is particularly useful for filling cavities. However, a known disadvantage of commercial dental composites is that the compositions shrink upon curing. Another disadvantage is that some of the dental composite components are not very stable to hydrolysis and / or are relatively hydrophilic. Hazardous substances may therefore be released over the years from the cured composition.

Attempts have been made to solve the problems mentioned above.

In this regard, U.S. Patent 6,653,375 B2 describes urethane di (meth) acrylate derivatives of 1,3-bis (1-isocyanato-1-1methylethyl) benzene. It is described that the monomer has a refractive index compatible with conventional dental filler materials, does not tend to discolor and can replace bis-GMA in dental materials without compromising the mechanical properties of the materials.

U.S. Patent 6,624,236 B1 relates to cyclosiloxane based crosslinkable monomers, their preparation, and their use in polymerizable materials, in particular polysiloxanes from sol-gel-condensable cyclosiloxane (meth) acrylates, and resinous compositions. .

U.S. Patent 6,566,413 B1 relates to polymerizable materials based on curable siloxane compounds useful in dental compositions. This describes that the siloxane compounds used exhibit low viscosity, allow high filler absorption, and produce compositions with low polymerization shrinkage.

WO 01/92271 A1 describes prepolymer (meth) acrylates having polycyclic or aromatic fragments as useful for the preparation of dental materials. It is described that siloxane monomers have a high molecular weight (eg greater than 600 g / mol) and have high (meth) acrylate functionality and low viscosity.

WO 01/095862 A1 is a low shrinkable polymerizable, comprising di- or poly (meth) acrylates, alkoxylated bisphenol dimethacrylates, polymerizable monomers, polymerization initiators and / or mixtures of photosensitizers, stabilizers and fillers. It relates to a dental material. It is mentioned here that the volume shrinkage during the polymerization is less than 2% by volume.

EP 0 451 709 A2 describes silanes of certain formulas which may include groups containing (meth) acrylate residues. It describes that silanes can be used on their own or as a composition for additives, bulk materials, adhesives and injection molding for coating compositions.

However, the solution described above is not completely satisfactory.

Thus, there is a need for alternatives. In particular, there is a need for alternative materials with improved properties.

Accordingly, it is an object of the present invention to alleviate one or more of the problems mentioned above.

It is also an object of the present invention to provide compositions having aesthetic properties useful in the dental field.

Another object of the present invention is to provide a lipophilic composition.

It is a further object of the present invention to provide compositions which can provide compositions with improved properties, in particular compositions with low shrinkage values.

It has been found that one or more of the above-mentioned objects can be achieved by providing the compositions described below.

Surprisingly, it has been found that the use of aromatic carbosilane-containing components that include polymerizable groups such as (meth) acrylates and that do not contain carbosiloxane structures can provide curable dental compositions with improved properties.

That is, the present invention

a) at least one Si-aryl bond,

One or more silicon atoms,

At least one unsaturated moiety,

Carbosilane-containing component (A) that does not contain Si-oxygen bonds,

b) initiator (B),

c) optionally filler (C),

d) a dental composition optionally comprising component (D) selected from modifiers, dyes, pigments, thixotropic agents, rheology modifiers, polymer thickeners, surfactants, fragrances, diluent (s) and perfumes.

The invention also relates to a process for preparing the compositions described below.

Further, the present invention relates to a method of using the composition described below.

The carbosilane containing component (A) can be used alone or as a mixture with other (meth) acrylate functional components as a reactive compound in dental materials that may also contain other reactive and / or non-reactive compounds if desired. have.

Carbosilane-containing component (A) typically exhibits a relatively high refractive index with a relatively low viscosity, such that commonly provided dental compositions have good opacity and are therefore very aesthetic. In addition, the compositions typically exhibit relatively low shrinkage after curing, as well as low absorption of water and / or water soluble dyes (eg from coffee, tea, red wine) compared to other commercial dental compositions.

Within the meaning of the present invention the terms "comprising" and "containing" refer to a non-exclusive list of features. Likewise, the term "one or a" is understood to mean "one or more."

The term “dental composition” according to the invention is typically a curable composition to be used in the dental field for different purposes in small amounts of several grams.

The term "initiator" according to the invention is a substance or mixture of substances capable of initiating a curing reaction, preferably a radical curing reaction.

The term "unsaturated moiety" according to the invention preferably comprises a (meth) acrylate group and refers to a polymerizable, especially radically polymerizable moiety.

The term "aryl" according to the invention refers to aromatic moieties (including C ₆ to C ₁₄ carbon atoms), preferably phenyl, naphthyl, alkoxyphenyl, alkoxy naphthyl, bisphenol A ether, bisphenol F ether . Besides an attached Si atoms, aryl moieties include one or two substituents, preferably alkyl and / or aryl ether groups (e.g., C _{1 -8} alkyl, C _{2 -10} alkenyl, C _{3 -6} cycloalkyl, C _{4 -6} cycloalkenyl, may have a C _{6 -10} aryl group).

Carbosilane-containing component (A) can be synthesized, for example, by hydrosilylation reactions (see Marciniec, B., Comprehensive Handbook on Hydrosilylation, Pergamon Press, Oxford, 1992).

The hydrosilylation reaction adds a Si—H functional component (i) to the olefin functional component (ii) in the presence of a catalyst, as shown in Scheme I, to form a new Si—C single bond, containing silicon Addition reaction to generate component (iii).

In the formula,

R ₁ , R ₂ , R ₃ , R ₄ = (cyclo) aliphatic or aromatic or (cyclo) aliphatic aromatic or aromatic (cyclo) aliphatic residues, wherein the C and / or H atoms may also be for example O, Br, Cl and Si May be substituted by an atom, and may contain other functional groups such as (meth) acrylate groups).

That is, the carbosilane compound (A) of the present invention is described, for example, in WO 01/92271 (Preparation Examples 1 to 5 of p23 to p25), U.S. Pat. Patent 2003/0166816 (Preparations 1 to 5 of p8 to p9) or WO 00/38619 (Example of p26), U.S. Pat. As described for analogous siloxane based compounds of patent 6,566,413 (Preparation of column 22), using a conventional noble metal compound as a catalyst, the poly Si-H functional carbosilane component (i) is olefin substituted (meth It can be obtained by the hydrosilylation reaction according to Scheme I by reacting with an acrylate residue containing component (ii).

Poly Si-H functional carbosilane components (i) such as 1,3,5-tris (dimethylsilyl) benzene and 2,4,6-tris (dimethylsilyl) anisole are described, for example, in Beck, H., N ., Chaffee, R., G., J. Chem. Eng. Data 1963, 8 (3), 453-454, can be synthesized by in situ Grignard reaction.

Olefin substituted (meth) acrylate moieties containing component (ii), such as, for example, 5-vinyl-2 (3) -norbornanyl-methacrylate, are described in U.S. Pat. It may be synthesized by addition reactions as described in patent 3,927,116, or may be purchased, for example, as (2-allyloxyethyl) methacrylate.

The carbosilane containing component (A) of the composition of the present invention preferably comprises the following structural elements.

Si-aryl bonds: at least 1, 2, 3 or 4

Silicon atoms: at least 1, 2, 3, 4, 5 or 6, preferably 2 to 4

Unsaturated residues: at least 1, 2, 3, 4, 5, 6, preferably 2 to 4

Si-oxygen bonds: none

Aromatic residues: at least 1, 2, 3 or 4

Optionally, bicyclic residues

Optionally a bisphenol derived spacer residue.

The carbosilane containing component (A) may be at least about 1% by weight, preferably about 3% by weight, more preferably about 10% by weight relative to the cured composition.

The amount of carbosilane-containing component (A) may be up to about 90% by weight, preferably about 65% by weight, more preferably about 30% by weight relative to the cured composition.

The amount of initiator (B) may be at least about 0.01% by weight, preferably about 0.1% by weight, more preferably about 0.5% by weight relative to the cured composition.

The amount of initiator (B) may be up to about 25% by weight, preferably about 10% by weight, more preferably about 3% by weight relative to the cured composition.

The amount of filler (C) may be at least about 3% by weight, preferably about 25% by weight, more preferably about 50% by weight relative to the cured composition.

The amount of filler (C) may be up to about 90% by weight, preferably about 80% by weight, more preferably about 75% by weight relative to the cured composition.

The amount of optional component (D) may be up to about 25% by weight, preferably about 15% by weight, more preferably about 3% by weight relative to the cured composition.

Dental compositions of the present invention preferably satisfy one or more of the following features.

The viscosity of the carbosilane containing component (A) may typically be at least about 0.1 Pa * s, at least about 1 Pa * s, at least about 2 Pa * s.

The viscosity of the carbosilane containing component (A) may typically be about 80 Pa * s or less, about 20 Pa * s or less, or about 5 Pa * s or less.

The refractive index of the carbosilane containing component (A) may typically be at least about 1.500, at least about 1.510, or at least about 1.520.

The refractive index may typically be about 1.600 or less, less than about 1.580, or less than about 1.560.

The opacity of the cured dental composition may be greater than about 10%, greater than about 40%, or greater than about 70%.

Opacity may typically be about 92% or less, less than about 90%, or less than about 88%.

The molecular weight (Mw) of the carbosilane containing component (A) may typically be greater than about 500, greater than about 800, or greater than about 1200.

The molecular weight (Mw) may typically be about 10,000 or less, less than about 5,000, or less than about 2,000.

Compressive strength may typically be greater than about 150 MPa, greater than about 200 MPa, or greater than about 250 MPa.

Flexural strength may typically be greater than about 50 MPa, greater than about 65 MPa, or greater than about 80 MPa.

Unless indicated otherwise, measurements were made at standard temperature and pressure (“STP”, ie 23 ° C. and 1023 hPa) according to the method described below.

The refractive index of the carbosilane containing component (A) can be measured with a Kruess AR 4D device (refractometer according to the Abbe measuring principle). The refractive index is measured at 20.0 ° C. The refractive index is measured at a wavelength of 589 nm.

The viscosity of the carbosilane-containing component (A) is determined by the Hake RotoVisco RV1 device (with stator P61, rotor C60 / 1 for viscosity below 8000 mPa * s, or rotor for viscosity above 8000 mPa * s). C20 / 1). Viscosity is measured at 23.0 ° C. between two flat parallel plates (ie stator and rotor). After activation and rectification of the system, the appropriate rotor is installed. The rotor is then lowered and the distance between the stator and the rotor is adjusted to 0.052 mm for viscosity measurement (using Software RheoWin Pro Job Manager Software Version 2.94). The rotor is then lifted and the material to be measured is placed on the stator (1.0 mL with rotor C60 / 1, or 0.04 mL with rotor C20 / 1). Without excessive delay, the rotor is lowered back to the pre-adjusted measuring position. The material to be measured is adjusted to 23.0 ° C. The shear rate for the measurement is adjusted to a value that produces a torque of 5000 μNm or more (thus typically a shear rate of 100, 200, 500 or 1000 s ⁻¹ is used depending on the viscosity of the material to be measured). Initiate the measurement and perform 60 seconds. The viscosity value (Pa * s) is recorded 20 seconds after the start of the measurement, and the average value of the recorded values is provided as the viscosity.

The molecular weight (Mw) of the carbosilane containing component (A) can be measured by GPC. Appropriate methods are known to those skilled in the art. In addition, the measurement of molecular weight can also use nuclear magnetic resonance spectroscopy (terminal measurement).

The opacity of the cured dental composition can be measured by a test piece of defined height of 3.6 (+/- 0.1) mm and a diameter of 20 (+/- 0.1) mm. They fill the material to be measured with a uniform, bubble-free, ring of suitable height and contact it every 40 seconds with a lighting device (Trilight®, 3M ESPE) between flat and transparent silicone oiled glass slides. This is done by examining the overlapped areas. The opacity was then measured with the Hunter Lab LabScan Spectralcolorimeter (HunterLab LabScan Spectralcolorimeter) from Hunter Lab Associates Laboratories Inc. (USA),% Provided by the device as a value.

Compressive strength and flexural strength can be measured similarly to ISO 9917 according to ISO 4049 respectively. For the measurement of compressive strength, ten test pieces (3 × 3 × 5 mm) of each material were prepared according to the manufacturer's recommendations, and the universal test machine (Zwick Z 010, crosshead speed 4 mm / min) The measurement is carried out similarly to ISO 9917. Compressive strength is given in MPa. Measurement of flexural strength is carried out in accordance with ISO 4049 using a universal test machine (Zwick Z 010, crosshead speed 2 mm / min). Flexural strength is given in MPa.

Carbosilane containing component (A) of the composition of this invention can be represented by following formula (A).

Aryl- [Si (A) _a (DB) _b ] _n

In the formula,

A = aliphatic or alicyclic moiety (e.g. C ₁ to C ₆ , methyl, ethyl, propyl, butyl, pentyl or hexyl, preferably C ₁ ) or aromatic moiety (e.g. C ₆ To C ₁₄ , phenyl, naphthyl, alkoxyphenyl, alkoxy naphthyl, preferably phenyl);

B = (meth) acrylate residue (preferably methacrylate) attached to spacer D;

D = spacer = aliphatic or cycloaliphatic residue (alkadiyl of C ₂ to C ₁₀ , preferably C ₆ and C ₉ ), wherein the C and / or H atoms may be substituted with O, Br, Cl and Si atoms And bicyclic structural elements described in the following specification)

[Br = bromine atom,

C = carbon atom,

Cl = chlorine atom,

H = hydrogen atom,

O = oxygen atom,

Si = silicon atom];

Aryl = aromatic residues (eg C ₆ to C ₁₄ , phenyl, naphthyl, alkoxyphenyl, alkoxy naphthyl, bisphenol A ether or bisphenol F ether, preferably phenyl);

a + b = 3;

a = 0, 1 or 2 (preferably 2);

b = 1, 2 or 3 (preferably 1);

n = 1, 2, 3, 4, 5 or 6 (preferably 2 to 4).

The carbosilane containing component (A) of the composition of the present invention has a relatively high refractive index with a relatively low viscosity. Carbosilane containing component (A) also has a relatively high molecular weight. Carbosilane-containing component (A) may also have relatively high lipophilic properties.

Without wishing to be bound to any particular mechanism, due to the presence of aromatic moieties in the carbosilane-containing component (A), the refractive index and lipophilic properties are relatively high, which can lead to water and / or (eg from coffee, tea, red wine) It is believed that it may be important for dental materials to avoid pigmentation and / or swelling due to absorption of water soluble dyes as well as to achieve an appropriate aesthetic appearance.

Depending on the chemical structure of the spacer D used, or the chemical structure of the different types of mixtures of the spacer D used, the relatively low viscosity of the carbosilane containing component (A) can be adjusted, which is used for dental purposes to achieve appropriate handling properties. It can be important for materials.

In addition, without wishing to be limited to any particular mechanism, due to the relatively high molecular weight of the carbosilane containing component (A) and / or the different reactivity of the (meth) acrylate residues used in the carbosilane compound (A), the induced dental It is thought that the volume shrinkage of the composition for the present invention is reduced compared to the conventional (meth) acrylate composite.

Spacer D may be a mixture of different types of spacers having similar and / or dissimilar chemical structures within the same molecule. The use of mixtures of different types of spacers D in the same molecule is tailored to the properties of the cured dental composition, such as stiffness, as well as the viscosity and / or reactivity and / or polarity and / or refractive index of the carbosilane containing component (A). This can be especially important with regard to doing.

In a preferred embodiment, the carbosilane-containing component (A) comprises the molecular structure of the carbosilane-containing component (A) and the structural elements of the carbosilane-containing component (A) {aryl- [Si (A) _a (DB) _b ] _n } according to the number m of _m it can be represented by the formulas I to IV.

In a preferred embodiment, the carbosilane containing component (A) contains only one aromatic moiety (ie m = 1), and only in the molecule of the structural element {aryl- [Si (A) _a (DB) _b ] _n } _m It contains one aryl-Si bond (ie n = 1) and can be represented by Formula I, the index of which is as defined above.

BDE- {aryl- [Si (A) _a (DB) _b ] _n } _m

In the formula,

m = 1;

n = 1;

E = (cyclo) aliphatic moiety (eg, alkadiyl of C ₅ to C ₁₁ , preferably C ₇ and C ₉ ), where one or more C atoms may be substituted with Si atoms and other C and / or H atoms May be substituted with O, Br, Cl and Si atoms) independently of one another;

The index is as defined above.

B =

D =

MA = (D-B)

인 화학식 I에 따른 카르보실란 함유 성분 (A)의 바람직한 예는 하기와 같다.

Preferred examples of carbosilane-containing component (A) according to formula (I) are as follows.

Where A = C ₁ , a = 2, b = 1, E = C is C ₇ partially substituted with O and Si, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, E = C is C ₇ partially substituted with O and Si, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, E = C is C ₇ partially substituted with O and Si, aryl = phenyl

Wherein A = C ₁ , a = 2, b = 1, E = C is C ₇ partially substituted with O and Si, aryl = naphthyl

Wherein A = C ₁ , a = 2, b = 1, E = C is C ₇ partially substituted with O and Si, aryl = naphthyl

The following compounds are examples of preferred poly Si-H functional carbosilane components (i) which can be used according to Scheme I for the synthesis of carbosilane-containing components (A) which meet the requirements according to formula (I).

The following compounds are examples of preferred olefin substituted (meth) acrylate residue containing component (ii) which can be used according to Scheme I for the synthesis of carbosilane containing component (A) which meets the requirements according to formula (I).

In a further preferred embodiment, the carbosilane containing component (A) comprises only one aromatic moiety (ie m = 1) in the molecule of the structural element {aryl- [Si (A) _a (DB) _b ] _n } _m , and It contains more than one aryl-Si bond (ie n ≧ 2) and can be represented by Formula II.

{Aryl- [Si (A) _a (DB) _b ] _n } _m

In the formula,

m = 1,

n is selected independently from each other from 2, 3, 4, 5 or 6 (preferably 2 to 4),

The index is as defined above.

B =

D =

MA = (D-B)

인 화학식 II에 따른 카르보실란 함유 성분 (A)의 바람직한 예는 하기와 같다.

Preferred examples of carbosilane-containing component (A) according to the formula (II) are as follows.

Where A = C ₁ , a = 2, b = 1, n = 2, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 2, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 2, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 3, and aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 3, and aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 2, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 3, and aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 4, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, n = 2, aryl = naphthyl

Where A = C ₁ , a = 2, b = 1, n = 2, aryl = naphthyl

The following compounds are examples of preferred poly Si-H functional carbosilane components (i) used according to Scheme I for the synthesis of carbosilane-containing components (A) which meet the requirements according to formula (II).

The following compounds are examples of preferred olefin substituted (meth) acrylate residue containing component (ii) used according to Scheme I for the synthesis of carbosilane-containing component (A) which meets the requirements of formula II.

In a further preferred embodiment, the carbosilane containing component (A) comprises more than one aromatic moiety (ie m> 2) in the molecule of the structural element {aryl- [Si (A) _a (DB) _b ] _n } _m It may be represented by the following formula (III).

F- {aryl- [Si (A) _a (DB) _b ] _n } _m

In the formula,

m = 2, 3 or 4 (preferably 2);

n = 1, 2, 3, 4, 5 or 6 (preferably 2);

F = (cyclo) aliphatic residue (alkadiyl of C ₀ to C ₂₅ , preferably C ₀ to C ₉ ), where C and / or H atoms may be substituted with O, Br, Cl and Si atoms (eg F may be selected independently from each other)), and the index is as defined above.

B =

D =

MA = (D-B)

인 화학식 III에 따른 카르보실란 함유 성분 (A)의 바람직한 예는 하기와 같다.

Preferred examples of carbosilane-containing component (A) according to the formula (III) are as follows.

Where A = C ₁ , a = 2, b = 1, m = 2, n = 1, F = C is C ₁ substituted with O, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 1, F = C ₁ , aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 1, 2, F = C ₃ , aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, F = C ₃ , aryl = phenyl)

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, F = C ₃ , aryl = phenyl)

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, F = C ₃ , aryl = phenyl)

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, and F = C is C ₇ partially substituted with O, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, and F = C is C ₅ partially substituted with O, aryl = naphthyl

Where A = C ₁ , a = 2, b = 1, m = 3, n = 2, and F = C is C ₈ partially substituted with O, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 4, n = 2, and F = C is C ₉ partially substituted with O, aryl = phenyl

The following compounds are examples of preferred poly Si-H functional carbosilane components (i) used according to Scheme I for the synthesis of carbosilane-containing components (A) which meet the requirements according to formula III.

The following compounds are examples of preferred olefin substituted (meth) acrylate residue containing component (ii) used according to Scheme I for the synthesis of carbosilane containing component (A) which meets the requirements according to formula (III).

In another preferred embodiment, the carbosilane containing component (A) comprises more than one aromatic moiety in the structural element {aryl- [Si (A) _a (DB) _b ] _n } _m molecule, which may be represented by Formula IV have.

G- {aryl- [Si (A) _a (DB) _b ] _n } _m

In the formula,

m = 2, 3 or 4 (preferably 2);

n = 1, 2, 3, 4, 5 or 6 (preferably 2 to 4);

G = (cyclo) aliphatic or aromatic or (cyclo) aliphatic aromatic or aromatic (cyclo) aliphatic residue (diyl of C ₁ to C ₁₀₀ , preferably C ₃ to C ₆₃ ), wherein C and / or H atoms are O , Br, Cl and Si atoms may be substituted), and the indices are as defined above.

B =

D =

MA = (D-B)

인 화학식 IV에 따른 카르보실란 함유 성분 (A)의 바람직한 예는 하기와 같다.

Preferred examples of carbosilane-containing component (A) according to the formula (IV) are as follows.

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C ₃ , aryl = phenyl)

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C ₃ , aryl = phenyl)

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₁₀ partially substituted with O, aryl = naphthyl

The following compounds are examples of preferred poly Si-H functional carbosilane components (i) used according to Scheme I for the synthesis of carbosilane containing components (A) which meet the requirements according to formula IV.

In a more detailed embodiment, the carbosilane containing component (A) according to formula IV can be represented by formula IVa, the index of which is as defined above.

In the formula,

p = 0, 1, 2, 3 or 4;

o = 0, 1, 2, 3, 4 or 5;

Q = H or CH ₃ ;

_{R, S = H, CH 3} , phenyl or C _{5 -9} alkadi _{(e, R + S = (CH 2} ) 5, CH 2 -CH (CH 3) -CH 2 -CH 2 -CH 2, CH 2 -CH ₂ -CH (CH ₃ ) -CH ₂ -CH ₂ , CH ₂ -C (CH ₃ ) ₂ -CH ₂ -CH (CH ₃ ) -CH ₂ );

T, U = H or CH ₃ ;

V, W, X, Y = H, Br or Cl,

The index is as defined above.

Preferred examples of carbosilane-containing component (A) according to formula (IVa) are as follows.

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₄₉ partially substituted with O and Si, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₅₉ partially substituted with O and Si, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₅₇ , aryl = phenyl partially substituted with Br, O and Si)

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₆₃ partially substituted with Br, O and Si, aryl = phenyl

In another embodiment, the carbosilane containing component (A) according to formula IVa with o = 0 may be represented by formula IVb, the index of which is as defined above.

Wherein the index is as defined above.

Preferred examples of carbosilane-containing component (A) according to formula (IVb) are as follows.

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₂₉ , aryl = phenyl partially substituted with O and Si)

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₃₄ partially substituted with O and Si, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₃₃ partially substituted with Br, O and Si, aryl = phenyl

Where A = C ₁ , a = 2, b = 1, m = 2, n = 2, G = C is C ₃₇ partially substituted with Br, O and Si, aryl = phenyl

The following compounds are examples of preferred poly Si-H functional carbosilane components (i) used according to Scheme I for the synthesis of carbosilane containing components (A) which meet the requirements according to formulas IVa and IVb.

These poly Si-H functional carbosilane components (i) are, for example, poly Si-H functional carbosilane components (ib) and silicon free, used according to Scheme I for the synthesis of Si-H compounds (i). It can be synthesized by hydrosilylation of the containing diolefin precursor (ia).

Preferred examples of the silicon-free diolefin precursor (ia) are as follows.

Examples of preferred poly Si-H functional carbosilane component (ib) are as follows.

The following compounds are examples of preferred olefin substituted (meth) acrylate residue containing component (ii) used according to Scheme I for the synthesis of carbosilane-containing component (A) that meets the requirements according to formulas IV, IVa and IVb. .

Useful initiators (B) may initiate curing of the carbosilane compound (A) of the composition. The initiator may be a photo cure or redox cure initiator. Both types of initiators are known to those skilled in the art.

Examples of photoinitiators are benzoin alkyl ethers, benzyl ketals, acylphosphine oxides or aliphatic and aromatic 1,2-diketone compounds, for example camphorquinone, and photopolymerization is an activator such as tertiary amines or organic phosphates. It can be facilitated by the addition of the pit.

Suitable initiator systems for the induction of polymerization through the redox mechanism are, for example, peroxide / amine and peroxide / barbituric acid derivative systems.

When the initiator system is used, it is advantageous to keep the initiator (eg peroxide) and catalyst component (eg amine) separately. The two components are usually mixed homogeneously with each other immediately before use.

The composition of the invention may also comprise filler (C), preferably inorganic fillers such as quartz, fine glass, silica gel, and pyrogenic silicic acid and precipitated silicic acid or granules thereof. X-ray opaque fillers are also preferably used at least partially. These may be, for example, X-ray impermeable glasses, ie glasses containing strontium, barium or lanthanum (ie according to US Pat. No. 3,971,754), or some fillers may be X-ray impermeable additives, such as Yttrium trifluoride, strontium hexafluorozirconate or fluoride of rare earth metals (for example according to EP 0 238 025 A1). For better incorporation into the polymer matrix, it is advantageous to hydrophobize the inorganic fillers. Typical hydrophobization agents are silanes such as (3-methacryloyloxypropyl) trimethoxysilane. The filler preferably has an average particle size of <20 μm, in particular <5 μm, more particularly <2 μm, and an upper particle limit of 150 μm, preferably 70 μm, more particularly 25 μm. The filler may be present in an amount of about 3 to about 90 weight percent, in particular about 25 to about 80 weight percent, or about 50 to about 75 weight percent of the composition.

Non-reinforcing fillers such as quartz, cristobalite, calcium silicate, diatomaceous earth, zirconium silicate, montmorillonite such as bentonite, zeolites, molecular sieves such as sodium aluminum silicate, metal oxide powders such as aluminum oxide or zinc oxide, or mixtures thereof Oxides, barium sulphate, calcium carbonate, plaster, glass and plastic powders may also be used in the present invention.

Suitable fillers also include reinforcing fillers such as pyrogenic or precipitated silicic acid and silica aluminum mixed oxides. The abovementioned fillers can be hydrophobized, for example, by treatment with organosilanes or siloxanes, or by etherification of hydroxyl groups to alkoxy groups. One type of filler or a mixture of two or more fillers may be used.

Particular preference is given to a combination of reinforcing and non-reinforcing fillers. In this regard, the amount of reinforcing filler may vary from about 1 to about 10 weight percent, in particular about 2 to about 5 weight percent.

The difference in the entire range specified, ie from about 2 to about 89% by weight, is due to the non-reinforcing filler.

Exothermically produced highly disperse silicic acid, preferably hydrophobized by surface treatment, is preferred as reinforcing filler. Surface treatment can be carried out, for example, with dimethyldichlorosilane, hexamethyldisilazane, tetramethylcyclotetrasiloxane or polymethylsiloxane.

Particularly preferred non-reinforcing fillers are quartz, cristobalite, calcium carbonate and sodium aluminum silicate, which can be surface treated. Surface treatment can generally be carried out in the same manner as described for the reinforcing fillers.

Optionally, component (D) such as stabilizers, modifiers, dyes, pigments, thixotropic agents, rheology modifiers or solvents, polymer thickeners, surfactants and diluent (s) may be added alone or in suitable mixtures.

The carbosilane containing component (A) described above may preferably be used as monomer in the dental composition curable via radical polymerization of unsaturated groups, in particular (meth) acrylate groups.

The dental compositions of the present invention can be used, for example, as dental filling materials, crown and interdental materials, veneer materials, inlays or onlays.

The dental composition of the present invention may be provided as a one part mixture or a two part mixture. This usually depends on the initiator used. If the initiator is photocurable, the dental composition may be provided as a one part mixture, and if the initiator is redox curable, the dental composition should be provided as a two part mixture.

Accordingly, the present invention also includes a base part (I) comprising a carbosilane containing component (A) and a filler (C), and a catalyst part (II) comprising an initiator (B), wherein component (D) Relates to a kit of parts, which is present in the base part, or the catalyst part, or both the base part and the catalyst part.

The dental compositions of the invention are usually packaged in containers or cartridges, preferably in dental complexes. Examples of such combs include U.S. Patent 5,322,440 A1 or 4,391,590 or 5,165,890.

The invention also

a) providing a dental composition comprising the carbosilane containing component (A) described above;

b) applying the dental composition to the surface;

c) a method of using a dental composition, comprising curing the dental composition.

The surface is typically the surface of a tooth, crown or dental plaque.

The invention also

a) providing components (A), (B), optionally (C) and optionally (D) described above,

b) mixing the components of step a),

The component (A) relates to a process for the preparation of a curable dental composition, which is obtainable by a hydrosilylation reaction.

The hydrosilylation reaction involves reacting the poly Si-H functional carbosilane component (i) and the olefin substituted (meth) acrylate residue containing component (ii), as described above.

The present invention will be described below by way of examples. The examples are for illustrative purposes only and are not intended to limit the invention.

The compounds listed in Table 1 were prepared according to the references described above and their refractive indices and viscosities were measured.

Example of a compound Refractive index Viscosity [mPa * s] Molecular weight [g / mol] Reference compound 1: 1,3,5,7-tetrakis- [3- (2-methcroyloxy-ethyloxy) -propyl] -1,3,5,7-tetramethyl-cyclotetrasiloxane 1.465 100 921.3 Example Compound 1: 2,2-bis {3,5-bis [dimethyl- [3- (2-methacryloyloxy-ethyloxy) -propyl] -silyl] -4- (3-methylbutyloxy) phenyl } -Propane 1.505 1200 1282 Reference Compound 2: Bis {dimethyl- [3- (2-Methacroyloxy-ethyloxy) -propyl] -siloxy} -hexakis {dimethyl- [2- (5 / 6-methacryloyloxy-bicyclo [2.2.1] hept-2-yl) -ethyl] -siloxy} -T8-silsesquioxane 1.480 3700 2596 Example Compound 2: 1- {Dimethyl- [3- (2-Methacroyloxy-ethyloxy-propyl] -silyl} -6- {dimethyl- [2- (5 / 6-Metacroyloxy-bicyclo [2.2.1] hept-2-yl) -ethyl] silyl} -2-methoxy-naphthalene 1.536 4700 651.0 Example Compound 3: 2- {3- [Dimethyl- [2-5 / 6-Metacroyloxy-bicyclo [2.2.1] hept-2-yl) -ethyl] -silyl] -4-butyloxy- 5- [dimethyl- [3- (2-methacryloyloxy-ethyloxy) propyl] -silyl] -phenyl} -2- {3- [dimethyl- [3- (2-methacryloyloxy-ethyloxy) Propyl} -silyl] -4-butyloxy-phenyl} -propane 1.521 11400 1061.7 Example Compound 4: 1- {2,4,6-tris [dimethyl- [2- (5 / 6-methacryloyloxy-bicyclo [2.2.1] hept-2-yl) -ethyl] -silyl] -Phenoxy} -3- {dimethyl- [2- (5 / 6-methacryloyloxy-bicyclo [2.2.1] hept-2-yl) -ethyl] -silyl} -propane 1.518 68000 1194

A dental composition containing a carbosilane compound according to the present invention, and a dental composition containing a reference compound of the art were prepared, and the opacity thereof was measured.

Volume (% by weight) Examples of Dental Compositions One 2 3 4 5 6 Reference compound 1 29.9 Example Compound 1 29.9 Reference compound 2 29.9 Example Compound 2 29.9 Example Compound 3 29.9 Example Compound 4 29.9 Bis (2,6-dichlorobenzoyl)-(4-butyl-phenyl) -phosphane oxide 0.1 0.1 0.1 0.1 0.1 0.1 Silaneized quartz, average particle size <2 μm 70.0 70.0 70.0 70.0 70.0 70.0 Opacity (%) Accurate Height of Test Specimen (mm) 94.6 (3.5) 89.3 (3.6) 94.9 (3.5) 83.0 (3.5) 79.8 (3.5) 84.9 (3.7)

Claims (15)

a) at least one Si-aryl bond, One or more silicon atoms, At least one unsaturated moiety, Carbosilane-containing component (A) that does not contain Si-oxygen bonds, b) initiator (B), c) optionally filler (C), and d) Dental composition optionally comprising component (D) selected from modifiers, dyes, pigments, thixotropic agents, rheology modifiers, polymer thickeners, surfactants, fragrances, diluent (s) and perfumes. The method of claim 1, a) the requirement that component (A) has a refractive index of greater than about 1.500, b) component (A) has a viscosity of greater than about 0.1 Pa * s, c) component (A) has a molecular weight greater than about 500, d) a requirement that the opacity of the cured composition is greater than about 10%, e) the compressive strength of the cured composition is at least about 150 MPa, and f) the flexural strength of the cured composition is at least about 50 MPa Dental composition that satisfies at least one of. The composition according to claim 1 or 2, wherein a) carbosilane-containing component (A) is present in an amount of at least 1% by weight, b) the initiator (B) is present in an amount of at least 0.01% by weight, c) optional filler (C) is present in an amount of at least 3% by weight, d) A dental composition wherein the optional component (D) is present in an amount of less than 25% by weight. The dental composition according to any one of claims 1 to 3, wherein component (A) is represented by the following formula (A). <Formula A> Aryl- [Si (A) _a (DB) _b ] _n In the formula, A = aliphatic or alicyclic moiety (C ₁ to C ₆ ) or aromatic moiety (C ₆ To C ₁₄ ); B = (meth) acrylate residue attached to spacer D; D = aliphatic or cycloaliphatic residue (alkadiyl of C ₂ to C ₁₀ ), where C and / or H atoms may be substituted with O, Br, Cl and Si atoms and may include bicyclic structural elements [Br = bromine atom, C = carbon atom, Cl = chlorine atom, H = hydrogen atom, O = oxygen atom, Si = silicon atom]; Aryl = aromatic residues (C ₆ to C ₁₄ ); a + b = 3; a = 0, 1 or 2; b = 1, 2 or 3; n = 1, 2, 3, 4, 5 or 6 independently selected from each other. The dental composition of claim 4 wherein compound (A) is represented by one of formulas (I), (II), (III) and (IV). <Formula I> BDE- {aryl- [Si (A) _a (DB) _b ] _n } _m In the formula, m = 1; n = 1; E = (cyclo) aliphatic moiety (alkadiyl of C ₅ to C ₁₁ ), wherein one or more C atoms may be substituted with Si atoms and other C and / or H atoms replaced with O, Br, Cl and Si atoms May be independently of one another; The other indices are as defined in claim 4. <Formula II> {Aryl- [Si (A) _a (DB) _b ] _n } _m In the formula, m = 1; n is independently selected from 2, 3, 4, 5 or 6, The other indices are as defined in claim 4. <Formula III> F- {aryl- [Si (A) _a (DB) _b ] _n } _m In the formula, m = 2, 3 or 4; n = 1, 2, 3, 4, 5 or 6; F = (cyclo) aliphatic moiety (alkadiyl of C ₀ to C ₂₅ ), wherein C and / or H atoms may be substituted independently of O, Br, Cl and Si atoms; The other indices are as defined in claim 4. <Formula IV> G- {aryl- [Si (A) _a (DB) _b ] _n } _m In the formula, m = 2, 3 or 4; n = 1, 2, 3, 4, 5 or 6; G = (cyclo) aliphatic or aromatic or (cyclo) aliphatic aromatic or aromatic (cyclo) aliphatic moiety (diyl of C ₁ to C ₁₀₀ ), where C and / or H atoms are to be substituted with O, Br, Cl and Si atoms May be independently of one another; The other indices are as defined in claim 4. The dental composition according to any one of claims 1 to 5, wherein compound (A) is represented by one of the following formulas (IVa) and (IVb). <Formula IVa>

<Formula IVb>

In the formula, p = 0, 1, 2, 3 or 4; o = 0, 1, 2, 3, 4 or 5; Q = H, CH ₃ ; R, S = H, methyl, ethyl, phenyl or C ₅ to C ₈ alkadiyl; T, U = H, methyl or ethyl; V, W, X, Y = H, Br, Cl or F are independently selected from each other, The remaining indices are as defined in claim 4. The dental composition according to any one of claims 1 to 6, wherein the carbosilane-containing component (A) is selected from the following.

In the formula, MA

to be. The dental composition according to claim 1, wherein the initiator (B) comprises a photocuring initiator or a redox curing initiator or a combination thereof. The dental composition of claim 1, wherein the filler (C) comprises reinforcing and / or non-reinforcing fillers. 10. A dental composition according to any one of the preceding claims filled in a container or cartridge. A base part (I) comprising a carbosilane containing component (A), and a catalyst part (II) comprising an initiator (B), wherein components (C) and (D) are base parts, or catalyst parts, Or a kit consisting of parts, which is present in both the base part and the catalyst part, wherein components (A), (B), (C) and (D) are as defined in any one of claims 1 to 9. . a) providing the compound (A), (B), optionally (C), and optionally (D) according to any one of claims 1 to 9, and b) mixing the compounds of step a), Component (A) is obtainable by hydrosilylation reaction, Method for producing a dental composition. The method of claim 12, wherein the hydrosilylation reaction comprises reacting a poly Si-H functional carbosilane component with an olefin substituted (meth) acrylate residue containing component. Use of a dental composition according to any one of claims 1 to 9 as a dental filling material, crown and interdental material, veneer material, inlay or onlay. a) providing a dental composition comprising a carbosilane compound (A) and an initiator (B), b) applying the dental composition to the surface, and c) Use of the carbosilane-containing component (A) according to any one of claims 1 to 7 for preparing a dental material in a method comprising curing the dental composition.