DD253180A1 - PROCESS FOR THE PRODUCTION OF COMPOSITES, ESPECIALLY FOR THE DENTAL PRACTICE - Google Patents

Abstract

The invention relates to light or thermally curable Kompositmassen based on specific dioxolane methacrylates and fillers. The process is characterized in that the polymerizable matrix-forming material contains dioxolane methacrylates or dioxolane acrylates having more than one dioxolane moiety and / or more than one methacrylate or acrylate moiety and that these mixtures are formed by free-radical or ionic polymerization processes be hung up. As inorganic fillers, the composites contain spherical silica particles of a narrow grain size distribution (0.1-2.5 m) obtained by ultrasonic atomization of silica sols, especially with an average of 0.9 m particle diameter. The composites of the invention are suitable as dental filling material and for building crowns and bridges.

Description

CH ,.

CHO

I ³

CH ₂ - OCO- C = CH ₂

CH - 0 / CH ₃

C OH -O ^ OH ₃

: ₂ - oco - c = CH ₀ I ²

CHO

14. A process for the preparation of composts according to claim 1 to 12, characterized in that a Bisdioxolanmonomethacrylat of formula 3 is used.

CH ₀ -CH-CH ₀ -O-CH ₀ -CH-CH ₀ -O-CH ₀ -CH-CH ₀

d \ d d , d d _r . id

CO - C = CHo

Q 0

CH ₃ ^ C

I CH

0 0

C / _χ

CH ₃ CH ₃

15. A process for the preparation of composites according to claim 1 to 12, characterized in that a Bisdioxolanbismethacrylat of formula 4 and / or 5 is used.

CH ₀ -CH-CH ₀ -O-CH ₀ -CH-CH ₀ -O-CH ₀ -CH-CH ₀ -O-Ch ₀ -C ¹ H-CH ₀

id ιd d, d d \ d dl ld

.0

CH,

I CO-C = CH,

I 'CH-,

CO-C-CH,

CH,

0 0

CH,

CH ₃ C-COOCHo-CH-O '

Ch-ch

O-CH

CH,

-O-CH-CH ₂ OOC-C = CH ₂

16. A process for the preparation of composites according to claim 1 to 15, characterized in that mixtures of the compounds 1,3,4 and corresponding Dioxolanmethacrylate be used by higher oligomers of polyglycerol.

17. A process for the preparation of composites according to claim 1 to 16, characterized in that corresponding acrylates are used in place of the aforementioned methyl acrylates.

Field of application of the invention

The invention relates to light or thermally curable composite materials based on specific dioxolane methacrylates and fillers. The composite masses harden by brief irradiation from a suitable light source.

They are of a consistency such that they can be modeled as tooth filling or reconstruction of tooth defects, and can be modeled in the mouth in, e.g. can be cured by irradiation by means of a light guide. The composites according to the invention are also particularly suitable as highly filled polymer material for the construction of dental crowns and bridges in prosthetics or as a filling material in place of metals or of inorganic filling cement.

Characteristic of the known technical solutions

Composites for dental practice are known and have been in use for a long time. They consist of mixtures of liquid polymerizable organic binders and inorganic or inorganic / organic fillers. The polymerisable binders used are predominantly methacrylic acid esters of relatively high molecular weight polyhydric alcohols, as described, for example, in US Pat. Nos. 3,066,112,216,468 or DE 2,126,419. Also mentioned are DE 3001616A1, GB 1072689, GB 2033822, DE 3301 012A1. Often the bis-GMA introduced by Bowen is used and in many cases methyl methacrylate serves as the reactive diluent.

) ₂ - ^> - o-ch ₂ -ch ₂ -ooc-c = ch ₂

OH

The good properties of these composites, such as high tensile strength, compressive strength, hardness, good adaptability of the composite mass to cavities and good processability, deserve special mention. For suitable fillers, polishability is given to smooth, glossy surfaces. As fillers, various silicas or glass and ceramic powders have been introduced, but also so-called. Splitter polymers. These are inorganic filler-containing composites with organic polymer networks that are ground to an appropriate size. Particularly advantageous is the use of a filler which consists of disperse silica, with an average particle diameter of 0.1 / xm to 2 ^ m (eg 0.9 / xm), and which can be easily obtained by ultrasonic atomization of silica sols , This makes it possible to sufficiently finely divided filler particles in a high proportion, z. B. 70Gew .-%, directly incorporated into the mass (DE 3532997A1, DD-WP 248 281). The properties of the composite pastes and of the cured composites are determined in a complex manner by the combination of organic monomer (binder) and inorganic filler, or by the combination of organic polymer / inorganic filler (see F. Lutz et al .: Swiss Dent. 2 [1981] Nos. 1-2,4 and 2126419). From the adaptation of the refractive indices of polymerisable binder / polymer matrix on the one hand and filler on the other hand, the transparency of the material depends and thus both the curing depth to be achieved by light (see R.Dowbenko et al .: Progress in Organic Coatings 11 [1983] 71) also the melt-like, translucent appearance of the cured composites. The fineness of the fillers (if possible <1μη \) is of great influence on the properties of the composites. A major problem for transparency is still the adaptation of the refractive indices of organic matrix and the most suitable filler. Considering, for example, the refractive indices of bis-GMA (nc ⁰ = 1.549) and silicic acid (silanized) (no ⁰ = 1.46-1.47), it is readily apparent that it is necessary to have low refractive reactive diluents, eg, methacrylates of aliphatic alcohols, or to regulate the refractive index by a suitable splinter polymer. To solve this problem has recently been proposed that low-breaking Isopropylidenglyzerinmethacrylat (no ° = 1.4425-1.4440) to use as a polymerizable binder (WP 245 814). However, to achieve good modeling, the binder properties continue to be in need of improvement.

Object of the invention

From the above-mentioned influences of refractive index and consistency (viscosity) of the polymerizable binder, there is a need to find new methacrylates of aliphatic polyalcohols. These target materials should disperse on the preferred silica filler (DK silanized no ⁰ = 1.468) have approximate refractive index. These compounds should have a favorable binder character due to a sufficiently high molecular weight (MW preferably 300-600 g / mol), so that the composite pastes provided with the superficial filler obtain the corresponding consistency and good modeling ability. On the other hand, the Grundmonomer / Grundmonomerengemisch must still have such a viscosity (ie, the viscosity must again not be too high) that a high proportion of finely divided filler (50-80%) can be included without the uniform intermiscibility and pasty character lost goes. Finally, good chemical accessibility and durability of these chemicals must be ensured. The bis-GMA preferably used previously for dental composites has an unfavorably high viscosity with the refractive index no ° = 1.5490 at a MW of about 512. It must therefore z. B. reactive low-boiling thinner can be used. The object of the invention is to provide dental composites based on new binders, which have the above favorable property combinations, ie at a high filler content (50-80%) of finely divided fillers (as possible to disperse silica), thermally or by possible short-term irradiation with a suitable light (UV-visible) to form mechanically solid, non-brittle dental moldings and in the cured state have a favorable transparency and polishability.

Explanation of the essence of the invention

The object is achieved by a method for producing composites, in particular for dental practice, based on liquid, polymerizable organic monomers / binders and solid inorganic / organic fillers with additions of polymerization initiators, stabilizers, adhesion promoters and pigments, characterized in that the polymerizable matrix-forming material contains dioxolane methacrylates or dioxolane acrylates having more than one dioxolane moiety and / or more than one methacrylate or acrylate moiety, such as monodioxolane bismethacrylate

Bisdioxolan monomethacrylates

Bisdioxolan-Bismethacrylates

and that these mixtures are cured by free-radical or ionic polymerization processes.

Recently, suitable precursors for the synthesis of monodioxolane bismethacrylates, bisdioxolane monomethacrylates and bisdioxolane bismethacrylates have become technically accessible (products or experimental products of Deutsche Solvay-Werke, FRG). From the monoisopropylidene diglycerol MIPDG, the diisopropylidene triglycerol DIPTG and the diisopropylidenetraglycerol DIPTEG, it was possible, for example, to obtain B. by transesterification with methyl methacrylate, the new monomers of the invention 1.3 and 4 produce. Furthermore, the dioxolane bismethacrylates 2 and 5 have been prepared by other syntheses.

CH ₀ -CH-CH ₀ -O-CH ₀ -CH-Gh ₀ I 2 ι 2 di] d

0 0 OH OH MiPDG

CHq CHq

0 CH ₀ -CH-CH ₀ -O-CH ₀ -CH-Ch ₀ -OCC = CH ₀

I 2 j 2 2 I d \ d

0 0 0 CHq 1

\ / O = CC = CH ₀

/ \ I ²

CH

CH ₀ -CH-CH ₀ -O-CH ₀ -CH-CH ₀ -O-Ch ₀ -CH-CH ₀ t 2 ι 2 2 (2 2 jj 2

0 _v 0 OH 0 0

\ / \ / DlPTG

CHq CHq 'CHq CHq

CH₀-CH-CH₀-O-CH₀-CH-CH₀-O-CH₀-CH-Ch₀| 2 | 2c \ d έ \\ £

0. 0 0 0 0

\ ^y O = CC = CH ₀ V

CHq CHq CHq CHq CHq

CH ₀ -CH-CH ₀ -O-CH ₂ -CH-CH ₂ -O-CH ₂ -CH-CH ₂ -O-CH ₂ -Ch-CH ₂ O ² OH OH 0 0

χ χ

CH ₃ · ^CH 3 ^GH 3 ^DiPTEG

CH ₂ -CH-CH ₂ -O-CH ₂ -CH-CH ₂ -O-CH ₂ -CH-CH ₂ -O-CH ₂ -CH-Ch ₂

o _{n /} o

₂ ρ _x

CH ₃ CH ₃ CH ₃ CH

ο ο _{n /}

O = CC = CH ₂ O = CC = CH ₂ ρ

CH C

₃ . CH ₃ CH ₃ CH ₃

_{3 3}

CH _n = C-CO-O-CH ₀ -CH-CH-CH ₀ -OCO-C = CH ₀ 2 -. 2 ι dd

0 0 \ /

CH-CH CH ₂ = C-CO-O-CH ₂ -CH-O-O-CH-CH ₂ -O-CO-C = CH ₂

Diedualfunctional monomers 1,3,4 represent low viscous colorless liquids with molecular weights between 300 and 600 g / mol, and they are characterized by a required favorable refractive index in the range ηέ ⁰ = 1.45-1.47. They polymerize with suitable known initiator systems both thermally and photochemically or by redox initiation. Due to their relatively low viscosity, they can be filled without the use of thinners with high proportions of finely divided fillers to form a paste-like composite material which is very easy to model. It is also possible to use mixtures of the monomers according to the invention. This polymerizable matrix material can be further modified by addition of known methacrylates such. Bis-GMA, butanediol bismethacrylate, furfuryl acrylate or 2,2-dimethyl-1,3-dioxolan-4-ylmethyl methacrylate (isopropylidene glycerol methacrylate).

Particularly suitable as inorganic filler is disperse silica (according to WP 247 884), which can be prepared by ultrasonic atomization of silica sols as spherical silica particles of a narrow particle size distribution with an average value between 0.1 and 2.5 μm. It is advantageously contained in a proportion of 51-80 wt .-% in the composite material, and the average particle diameter is advantageously Ο, θμ, ΐΌ or 0.4 / * m. However, traditional fillers are also usable, such as amorphous silica having a particle diameter of 2-15 / μm or fumed silica or ground silicates, glasses, ceramics of various particle sizes, especially having a particle diameter of 0.5 to 100 / μm. Furthermore, organic fillers, such as polymerized and ground methacrylates or prepigmented and filled with inorganic fillers polymethacrylates can be used in ground form. The usual incorporation of pigments, preferably CaF ₂ , BaSO ₄ , TiO ₂ is possible.

A particularly valuable embodiment of the invention is the incorporation of a photosensitive catalyst / initiator which, upon activation by light, especially by light of wavelengths 250-500 nm, causes the rapid curing / polymerization of the polymerizable constituents. As initiator systems are suitable for the photopolymerization z. B. benzil ketal, camphorquinone / tert. Amine, thioxanthones / tert. Amine, as well as other known photoinitiators. For example, 2-isopropylthioxanthone / N, N-dimethylaminoethyl benzoate is well suited. However, it is also possible to use thermally activatable initiators, such as benzoyl peroxide, and redox initiator systems, such as benzoyl peroxide / N, N-dimethyl-p-toluidine. The photopolymerization of a composite according to the invention from the bis-dioxolane bismethacrylate 4, which is filled to 68% with disperse silica (mean particle diameter Ο, θμητι) with 2-isopropylthioxanthone / triethanolamine as a photo initiator at a 2 χ 90s irradiation with light of the wavelength range 250- 500 nm to a hard, mechanically strong, smooth glossy and polishable composite material. It is achieved under these conditions, a tack-free curing in a layer thickness> 3 mm

 Instead of the described methacrylates, the corresponding acrylates can also be used.

embodiments

Preparation of Monomers 1,3 and 4

The mono- and dimethacrylates according to the invention, which are derived from monoisopropylidenediglycerol, diisopropylidenetriglycerol and diisopropylidenetraglycerol, have been prepared by transesterification with excess methyl methacrylate according to the following general procedure:

50 g of isopropylidenoligoglycerol (products of the German Solvay-Werke, Rheinsberg, Germany) are mixed with 350 ml of methyl methacrylate and 1.0 g of hydroquinone. Through this solution, a weak stream of argon is passed, which is also continued during the transesterification reaction. Then 1.3 g of sodium methoxide are added and the reaction mixture is conducted at 82-85 ° C hours. After 2 and 4.5 hours of reaction, 0.7 g of sodium methoxide are again added in each case. By addition of the alcoholate, the reaction mixture turns dark green and after some time slowly distilled off methanol. After the reaction is allowed to cool under argon, the mixture is filtered through a glass frit and washed the filter residue with a little MMA. The excess MMA is distilled off in a water-jet vacuum from the combined filtrate. The remaining distillation residue is then taken up in 50 ml of ether, with 50 ml

Water, then shaken with 50 ml of dilute sodium hydroxide solution and again twice with 50 ml of water. The ether phase is optionally filtered for decolorization several times over 10 g of silica gel H or aluminum oxide (acidic) and then dried over magnesium sulfate. After removal of the ether in a rotary evaporator is further 1 h at a bath temperature of 4O ⁰ C moves. The remaining nearly colorless liquid is degassed in an oil pump vacuum for 4 h at room temperature. The yield is about 50%

 Monoisopropylidenediglycerol dimethacrylate 1:

The compound is distilled under vacuum (0.2 Torr) and passes at 145-150 ° C. Colorless slightly viscous liquid, ng ⁰ = 1.4686, MW (VPO) 330

C ₁₇ H ₂₆ O ₇ (342.4) Calc .: C 59.64 H 7.65 Found: C 58.62 H 7.56

Diisopropylidene triglycerol monomethacrylate S: Colorless liquid, ng ⁰ 1.4568-1.4571, MW (VPO) 400 C ₁₉ H ₃₂ O ₈ (388.5) Calcd. C, 58.75, H, 8.30

Found: C59.36 H8.51 IR (Film on KBr): 940, 980cm ^-1 (COC), 1640 (C = C), 1 720cm ^-1 (C = O).

Diisopropylidenetraglycerol dimethacrylate 4:

Colorless, slightly viscous liquid, n ° = 1.4660, MW (VPO) = 526, IR (Film on KBr): 940, 980cm " ¹ (COC), 1 640cm" ¹ (C = C) 1715cm " ¹ ( C = O).

C ₂₆ H ₄₂ O ₁₁ (530.6) Calc .: C58,85 H7,98 Found .: C58,54 H8,23

Monoisopropylidenerythritol-dimethacrylat2:

60.0 g (0.37 mol) of 2,3-isopropylidenerythritol, 400 ml of methyl methacrylate (dried over CaH ₂ ), 40 mg of hydroquinone and 4 g of sodium methylate in a 750 ml two-necked flask with stirrer and distillate distilled with exclusion of air (argon) for 8 hours 90-100 ⁰ C heated in an oil bath. During this process, methanol and partly also methyl methacrylate distils off. The brown solution is filtered, excess MMA distilled off and the remaining viscous residue is fractionated in vacuo.

Yield: 39.7 g (36% of theory) of colorless viscous liquid.

Kp ₀ ,! = 115-12O ⁰ C

If 1% by mass of benzil dimethyl ketal is dissolved in the substance and then irradiated with the unfiltered light of a high-pressure mercury lamp (HBO 500), a transparent, insoluble polymer body is formed.

Bisdioxolane bismethacrylate 5:

a) bis-2,2 '- (4-hydroxymethyl-dioxolane)

To 600 g of 30% aqueous Glyoxallösurig, corresponding to 3.1 moles of dialdehyde, are added 607.8 g (6.6 mol) of glycerol and adds 11 toluene and about 5 ml of conc. H ₂ SO4 added. Using a suitable stirring apparatus with condenser and water separator 520-53OmI of water are then split off within 2V2-3 hours. The outside temperature should be adjusted so that the distillation of the azeotrope proceeds as quickly as possible. After cooling the reaction mixture to room temperature is neutralized with aqueous sodium carbonate solution, filtered and then the toluene is distilled off and fractionated in vacuo

Kp ₂ _3 = 146-15O ⁰ C viscous, colorless liquid Yield: 580g

b) transesterification

In a 750 ml sulfonating flask equipped with stirrer, reflux condenser, Gaseinieitung, distillery are 350ml of methyl methacrylate, 0.1 g of hydroquinone and 50 g of bis-2,2 '- (4-hydroxymethyl-dioxolane) and heated to 80-90 ⁰ C 1.3 g of sodium methylate. After each 2.5 hours add 0.7 g of sodium methylate (total 2.1 g). It is filtered, distilled off excess MMA and fractionated in vacuo.

Kpo, 2 = 110-12O ⁰ C (oily colorless liquid) Yield: (. 24% of theory.) 20.0 g of C ₆ H ₂₂ O ₃ (342.34) Calc .: C56,13 H6,48 Found .: C 56.20 H 5.93

Embodiment 1

4.3 g of disperse silica (mean particle diameter 0.9 ± .m) are silanized in the usual way with A-174 and made into a solution consisting of 2.0 g of bis-dioxolane bismethacrylate 4, 0.01 g of 2-isopropylthioxanthone and 0.04 g of triethanolamine given. After thorough mixing, a transparent composite material with excellent consistency and modeling properties is created. For processing, the composite z. For example, it is modeled as a layer and irradiated for 90 seconds in the Dentacolor XS light unit. The cured dental material is translucent, hard and has a high gloss smooth surface. The cured composite shows good mechanical properties.

Embodiment 2

To a solution consisting of 1.6 g of monodioxolane bismethacrylate, 1.0.4 g of 2,2-bis [p- (2-hydroxy-3-methacryloxy-propoxy) -phenyl] propah (bis-GMA), 0.01 g Camphorquinone and 0.05 g of triethanolamine are added to 4.2 g in the usual way with -y-methacryloxypropyltrimethoxysilane (A-174) silanized disperse silica (average particle diameter 0.9 μηl) obtained by ultrasonic nebulization of silica sols and mixed thoroughly. The pasteuse thus obtained

and transparent composite material is storage stable and very easy to model. Full curing of the composite takes place after 90s irradiation time in the Dentacolor XS illuminator (spectral range 320-520 nm). This results in completely tack-free, hard and translucent layers. The hardening depths are> 3mm.

Embodiment 3

A solution consisting of 1.7 g of bis-dioxolane monomethacrylate S, 0.3 g of bis-GMA, 0.02 g of dibenzoyl peroxide with 0.25 g of CaF ₂ and 1.85 g of fumed silica (particle diameter> 0.9 / xm), according to the usual Were silanized with cyclohexenylethyltriethoxysilane, homogeneously mixed. The transparent composite material is easy to model. After 30 minutes of polymerization at 100 ^° C., hard, glossy composites are produced with smooth surfaces which can be polished to a high gloss using the conventional techniques.

Embodiment 4

To a solution consisting of 1.6 g Bisdioxolan bismethacrylate ^ 0.4 g Bis-GMA, 0.01 g camphorquinone and 0.05 g triethanolamine are 4.2 g disperse silica (average particle diameter 0.9μ.ηη), in the usual manner silanized with A-174, added and mixed homogeneously. The paste-like transparent composite material is very easy to model. After 90s irradiation time in the Dentacolor XS light unit, complete and tack-free hardened dental materials with hardening depths> 3 mm are produced. The composites are hard, translucent and have a high glossy smooth surface.

Embodiment 5

3.7 g of amorphous silica (mean particle diameter 2-15 μm) silanized in the usual manner with A-174 are added to a solution consisting of 1.1 g of bis-dioxolane-bismethacrylate, 4.09 g of monodioxolane-bismethacrylate 1 and 0 , 02g benzil dimethyl ketal added and mixed homogeneously. The resulting transparent and very easy to model paste is completely cured after 90s exposure time in the Dentacolor XS light unit. The composite material is very hard, shiny and translucent.

Embodiment 6

To a solution consisting of 1.1 g of bis-dioxolane monomethacrylate S, 0.4 g of (2,2-dimethyl-1,3-dioxolan-4-yl) methyl methacrylate, 0.5 g of butanediol bismethacrylate and 0.014 g of dibenzoyl peroxide are added 3.9 g Borosilicate glass powder (average particle diameter 0.6 μιπ), which was silanized in a conventional manner with A-174, added and mixed to form a homogeneous paste (paste A). Another solution consisting of 1.5 g of bis-dioxolane monomethacrylate S, 0.5 g of butanediol-bismethacrylate and 0.005 g of N, N-dimethyl-p-toluidine is processed with 2.8 g of silanized borosilicate glass powder to form a homogeneous paste (paste B). Mixing equal amounts of paste A and B on a mixing block, we obtain a hard composite material. The processing width is 2 minutes. After polishing the composite, the surface is homogeneous, smooth and free of pores.

Embodiment 7

To a solution consisting of 1.3 g monodioxolane-bismethacrylate 2, 0.4 g bis-GMA, 1.3 g monodioxolane acrylate 1, 0.005 g camphorquinone and 0.05 g triethanolamine are added 0.45 g prepigmented polymethyl methacrylate and 3.8 g, usually with A- 174 silanized disperse silica (average particle diameter 0.4 / xm) added. After homogenization, a well-mouldable paste of good transparency is produced. The composite cures completely after curing for 90s in the Dentacolor XS illuminator with a depth of cure> 3mm. The result is hard, tack-free and translucent composites with a smooth shiny surface.

Embodiment 8

4.0 g of disperse silica (average particle diameter 0.4p, m), which was silanized in the usual way with A-174, are treated with a solution consisting of 0.9 g of bis-dioxolan bismethacrylate 5, 0.4 g (2,2-dimethylformamide). 1,3-dioxolan-4-yl) -methylmethacrylate, 0.7 g of bisdioxolane-bismethacrylate 4.0.01 g of 2-isopropylthioxanthone and 0.04 g of Ν, Ν-dimethylaminoethylbenzoate were mixed homogeneously to form a paste-like composite material. The transparent paste cures for a total of 90s in the Dentacolor XS illuminator. The result is hard composites with a smooth shiny surface that can be polished to a high gloss.

Claims (13)

1. A process for the preparation of composites, in particular for dental practice, based on liquid, polymerizable organic monomers / binders and solid inorganic / organic fillers with additions of polymerization initiators, stabilizers, · adhesion promoters and pigments, characterized in that the polymerizable matrix-forming material dioxolane containing methacrylates or dioxolane acrylates having more than one dioxolane moiety and / or more than one methyl acrylate or acrylate moiety, such as - Monodioxolane bismethacrylate - Bisdioxolan monomethacrylates - bisdioxolane bismethacrylate and that these mixtures are cured by free-radical or ionic polymerization processes. 2. A process for the preparation of composites according to claim 1, characterized in that the polymerizable matrix-forming material additionally known polymerizable compounds, such as preferably mono-dioxolane-mono-methacrylates (2,2-dimethyl-1,3-dioxolan-4-yl-methyl methacrylate) Bis-GMA, butanediol bismethacrylate, furfuryl acrylate. 3. A process for the preparation of composites according to claim 1 and 2, characterized in that as inorganic fillers obtained by ultrasonic atomization of silica sols spherical silica particles of a narrow particle size distribution with an average value between 0.1 and 2.5 / xm, especially with a mean value of 0 , 9μΐη particle diameter are used and are particularly contained in a proportion of 51-80 Ma .-%. 4. A process for the preparation of composites according to claim 1 and 2, characterized in that the inorganic fillers amorphous silica having an average particle size of 2-15μΐη are included. 5. A process for the preparation of composites according to claim 1 and 2, characterized in that are included as inorganic fillers fumed silica. 6. A process for the preparation of composites according to claim 1 and 2, characterized in that they contain as inorganic fillers milled silicates, glasses, ceramics, especially with a particle diameter of 0.7 to 10Ομηη. 7. A process for the preparation of composites as claimed in claims 1 and 2, characterized in that polymerized (methyl) acrylates, in particular polymerized dioxolane (meth) acrylate and / or prepigmented poly (methyl methacrylate), are contained as organic fillers. 8. A process for the preparation of composites according to claim 1-7, characterized in that pigments, preferably CaF ₂ , BaSO ₄ , TiO _{2 are} included. 9. A process for the preparation of composites according to claim 1 to 8, characterized in that the curing is followed by lights, in particular the wavelengths 250-500 nm, wherein as initiators photoactive compounds are added. 10. A process for the preparation of composites according to claim 1 to 8, characterized in that the curing takes place thermally, in particular by temperatures of 50-15O ⁰ C, wherein thermally activatable initiators are added. 11. A process for the preparation of composites according to claim 1 to 8, characterized in that the curing takes place at room temperature by addition of redox initiator systems. 12. A process for the preparation of composites according to claim 1 to 11, characterized in that the fillers are pretreated with adhesion promoters, in particular with Silanhaftvermittlern. 13. A process for the preparation of composites according to claim 1 to 12, characterized in that a Monodioxolanbismethacrylat of formula 1 and / or 2 is used. CH ₉ -CH-CH ₅ -O-CH ₀ -CH-CH ₀ I ² i ^{2 2}I i² α o CHo ^ Ci 0 - CO - C = CH, COC = CH, CH,