WO2001012679A1

WO2001012679A1 - Composition that hardens with visible light and use thereof

Info

Publication number: WO2001012679A1
Application number: PCT/EP2000/007317
Authority: WO
Inventors: Michael Zimmermann; Rüdiger Lange
Original assignee: Deltamed Medizinprodukte Gmbh
Priority date: 1999-08-13
Filing date: 2000-07-28
Publication date: 2001-02-22
Also published as: EP1203033A1; JP2003507499A

Abstract

The invention relates to a composition that can be hardened with visible light, comprising (a) 2-99 wt. % of at least one compound containing acrylate and/or methacrylate groups and/or vinyl- and/or epoxide and/or oxetane groups and/or acryl-epoxy-oligomer groups and/or methacryl-epoxy-oligomer groups, and/or at least one resinous compound with a polymeriseable polsiloxane base; (b) 0,01-7 wt. % of at least one initiator, (c) 0-5 wt. % of at least one co-initiator, (d) 0-85 wt. % of one or more modifiers, such as fillers, dyes, pigments, flow improvers, thixotropic agents, polymeric thickeners, oxidising additives, stabilizing agents and retarders.

Description

Visible light curing composition and its use

The invention relates to a composition curable with visible light and its use in a shaping process.

Plastics that harden with visible light are made of

EP 0 897 710 A2 known for use in dental products.

In addition, it is known to use plastics curing with UV light in the shaping process of stereolithography.

The object of the invention is to provide an improved plastic which cures in visible light and which is particularly suitable for shaping processes such as microphotopinning, for other rapid prototyping processes such as stereolithography or for the production of dental products.

This object is achieved by a composition according to claim 1, a use of the composition according to one of claims 17 to 20, a method according to one of claims 21 to 24 or an object according to claim 25. Developments of the invention are specified in the subclaims.

Further features and expediencies result from the following description of exemplary embodiments of the invention with reference to the figure.

1 shows a device for the method of producing a three-dimensional object by means of microphotographic bonding from a plastic according to the invention which cures under the action of visible light.

The composition according to the invention is explained below using an exemplary embodiment of its use, namely the production of a three-dimensional object by means of microphotopinning.

As can be seen from FIG. 1, the device has a container 1 with an upper edge 2 that is open on its upper side. A carrier 3 for carrying an object 4 to be formed is arranged in the container with an essentially flat and horizontally oriented construction platform 5 which can be moved and positioned in the container 1 by means of a height adjustment device. The entire container 1 is filled to the level below the upper edge 2 with the composition according to the invention in the form of a liquid plastic 6 which cures in visible light. At a predetermined distance below the upper edge 2 of the container 1, a flat transparent plate 7 made of a material transparent to visible light is provided in such a way that, while the container 1 is filled with the liquid plastic 6, it has a predetermined amount in the liquid Immerse plastic 6.

Above the container 1 there is an exposure device 8 with a light source 9, such as a halogen, deuterium, plasma, Mercury vapor lamp or a laser, for generating visible light in a wavelength range from 350 to 700 nm, for example. The exposure device 8 also has a Pro optics and a mask generating device and a mask 10 for the selective exposure of a respective layer of the three-dimensional object 4 to be formed in a corresponding cross section. Provided between the exposure device 8 and the container 1 is an aperture 11 which can be pivoted into the beam path. Furthermore, a controller 12 is provided, which is designed in such a way that it controls the diaphragm 11, the mask generating device 10 and the height adjustment device of the carrier 3 or the construction platform as a function of predetermined object data.

In the process for producing the three-dimensional object 4, the container 1 is filled with the liquid plastic 6 which cures with visible light, and the building platform 5 is displaced by the associated height adjustment device in such a way that there is between the top of the building platform 5 and the bottom of the transparent Plate 7 forms a layer of the liquid plastic 6 which cures with visible light in a predetermined layer thickness. The plastic layer is then exposed in a cross section corresponding to the three-dimensional object 4 to be formed. Subsequently, the construction platform 5 is shifted vertically downward in order to form the next layer of the liquid light-curable plastic 6 between the upper surface of the object 4 and the transparent plate 7. These steps are repeated successively until the object 4 is formed in its entire height. The mask generating device 10 is controlled via the controller 12 in such a way that the exposure takes place with a light intensity which is sufficient to penetrate the layer of the liquid plastic 6 between the upper surface of the object 4 and the transparent plate 7 and with the layer which has already solidified underneath to connect the object 4. The plastic 6 consists of a composition that cures with or in visible light

(a) 2-99% by weight of at least one compound, the acrylate and / or methacrylate groups, and / or vinyl and / or epoxy and / or oxetane groups and / or acrylic-epoxy-oligomer groups and / or methacrylic-epoxy-oligomer groups contains, and / or at least one resin composition based on polymerizable polysiloxanes, in particular Ormocere,

(b) 0.01-7% by weight of at least one initiator,

(c) 0-5% by weight of at least one coinitiator,

(d) 0-85% by weight of modifiers, such as fillers, dyes, pigments, flow improvers, thixotropy agents, polymeric thickeners, oxidizing additives, stabilizers and retarders.

The compound or compounds of component (a) of the composition, which contain acrylate and / or methacrylate groups, harden in the visible light by radical polymerization. The following crosslinkable and non-crosslinkable monomers are particularly suitable: aliphatic diurethane methacrylate, tetra-ethoxylated bisphenol A diethyl acrylate, aliphatic urethane methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-butyl methacrylate, iso-propyl methacrylate

2-ethylhexyl methacrylate, methacrylic acid ester with an ester group of 1 to 13 carbon atoms, isobornyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, ethyl triglycol methacrylate, tetrahydrofurfuryl methacrylate, hydroxyalkyl methacrylate with an alkyl group from 1 to 4 methacrylate, such as 2-C-A, such as 2-C-A , Alkoxyethyl methacrylate with an alkoxy group of 1 to 4 carbon atoms, allyl methacrylate, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedimate acrylate, 1,4-butanediacrylate, 1,4-butanediacrylate , 1, 12-dodecanediol dimethacrylate, glycerol-l, 3-dimethacrylate, diurethane dimethacrylate, trimethylolpropane trimethyl acrylate. The epoxy and / or an oxetane group-containing compound or compounds of component (a) cure under the action of visible light by cationic polymerization. Examples include aliphatic or aromatic epoxides, cycloaliphatic epoxides or oxetanes, such as 1,3, 5, 7-tetrakis (2, 1-ethanediyl-3, 4-epoxycyclohexyl) -l, 3, 5, 7-tetramethylcyclo- tetrasiloxane, 1, 10-decanediylbis (oxymethylene) bis (3-ethyloxetane), 1,3,5,7, 9-pentakis (2, l-ethanediyl-3, 4-epoxycyclohexyl) - 1,3,5,7, 9-pentamethylcyclopentasiloxane, vinylcyclohexene oxide, vinylcyclohexene dioxide, 3,4-epoxy-6-methylcyclohexylmethyl-3,4,4-epoxy-6-methylcyclohexane carboxylate, bis (2,3-epoxycyclopentyl) ether; 3,4-epoxy-6-methylcyclohexylmethyl adipate, 3,4-epoxycyclohexyl-5, 5-spiro-3,4, epoxy (cyclohexane metadioxane), 1,4-butanediylbis (oxyethylene) bis (3-ethyloxetane), 3,4 - Epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, 1,1,3,3-tetramethyl-l, 3-bis (2, l-ethanediyl-3, 4-epoxycyclohexyl) disiloxane and / or bis- (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3 '-4' epoxycyclohexane carboxylate.

The compound containing vinyl groups or compounds of component (a) of the composition, such as, for example, monovinyl ether, divinyl ether, hydroxyvinyl ether, aminovinyl ether, trivinyl ether, cure by free radicals and cationically (mostly cationically) by light. Examples are triethylene glycol divinyl ether, 4-hydroxybutyl vinyl ether, propenyl ether of propylene carbonate, dodecyl vinyl ether, triethylene glycol divinyl ether, alkyl vinyl ether with an alkyl group of 2 to 18 carbon atoms, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, butanediol , Butanediol divinyl ether, hexanediol divinyl ether, ethylene glycol butyl vinyl ether, cyclohexane dimethanol mono- and divinyl ether, 2-ethyl hexyl vinyl ether, poly-THF divinyl ether, cyclohexyl vinyl ether, tert-butyl vinyl ether, Tert. -a yl vinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, hexanediol monovinyl ether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, aminopropyl vinyl ether, 2-diethylaminoethyl vinyl ether. The compound or compounds of component (a) which contain or contain acrylic-epoxy-oligomer groups and / or methacrylic-epoxy-oligomer groups polymerize under the action of visible light both cationically and radically in the form of a so-called dual curing. The combination of one or more of the above-mentioned cationically polymerizing compounds with one or more of the above-mentioned free-radically polymerizing compounds also leads to dual curing.

The resin composition or resin compositions based on polymerizable polysiloxanes, in particular Ormocere, contains or contain, for example, compounds as described in the patents DE 4133494 C2 or DE 3903407 A1. For example, it is a photochemically or thermally curable or self-curing resin composition based on polymerizable polysiloxanes in the presence of initiators, obtainable by hydrolytic condensation of one or more hydrolytically condensable compounds of silicon and optionally other elements from the group B, Ba, Ti, Zr, Al, Sn, the transition metals, the lanthanides and the actinides, and / or precondensates derived from the abovementioned compounds, optionally in the presence of a catalyst and / or a solvent, by the action of water or moisture, 1 to 100 mol%, based on monomeric compounds, from silanes of the general formula (I),

Y _n SiX _n R _< _ _{(n + n)} (I)

in which the radicals X, Y and R are identical or different and have the following meaning:

R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl

X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, or NR ' ₂ with

R '= hydrogen, alkyl or aryl,

Y = a substituent which contains a substituted or unsubstituted 1, 4, 6-trioxyaspiro [4, 4] nonane radical, n = 1, 2 or 3, m = 1, 2 or 3, with n + m <.4,

and / or from silanes of the general formula (II),

{X _n R _k Si [R ² (A) ₁ ] 4- (n + k)} _x B (II)

in which the radicals A, R, R ₂ and X are identical or different and have the following meaning:

A = 0, S, PR ', POR', NHC (0) 0 or NHC (0) NR ', with R' = hydrogen, alkyl or aryl,

B = straight-chain or branched organic radical, which is derived from a compound B 'with at least one (for 1 = 1 and A = NHC (0) 0 or NHC (0) NR') or at least two C = C double bonds and 5 derives up to 50 carbon atoms, with R '= hydrogen, alkyl or aryl,

R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl,

R = alkylene, arylene or alkylene arylene,

X = hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR ' ₂ , with

R '= hydrogen, alkyl or aryl, n = 1,2, or 3, k = 0, 1 or 2, 1 = 0 or 1, x = an integer, the maximum value of which is the number of double bonds in the compound B' minus 1 corresponds to, or is equal to the number of double bonds in the compound B 'when 1 = 1 and A is NHC (O) or NHC (0) NR',

are selected, optionally containing fillers and / or copolymerizable monomers.

In another example, one of the structural element E 2 and at least one of the structural elements is in the resin composition; E 1 and / or E 3 and / or E 4 compound of the general formula

El E2 E3 E4

O-— —O

where R _{x is} a methyl, ethyl, n-propyl, isopropyl or an optionally CH ₃ -C ₃ H ₇ -substituted phenyl radical, R _{2 is} a CH ₂ = -CH-, CH ₂ = CHC00 (CH ₂ ) _n - or

CH _j = C - COO (CH _a VRcst

I

CH ₃

or Rl, n 0,1,2 or 3, and M means titanium or zirconium. The molar ratio of the structural element E 2 to the structural elements E 1 and / or E 3 and / or E 4 is in each case between 50: 1 and 10: 1 or the molar ratio of the structural elements E2: E1: E3: E4 is approximately 25 : 1: 1: 1. The polymerisation of the polysiloxanes takes place radically and / or cationically.

In the case of radical curing, one or more of the following compounds which initiate the polymerization are provided as component (b) of the composition: phosphine oxides, acylphosphine oxides, diphenyl-2, 4, 6-trimethylbenzoylphosphine oxide; Benzoin ethers, such as benzoin or the benzoin alkyl ether; Benzil ketals such as benzil dialkyl ketal; α-hydroxyketones; aminoketones; Acetophenones, such as .alpha.-hydroxyacetophenones, dialkoxyacetophenones, .alpha.-aminoacetophenones, benzophenones; Thioxanthones such as i-propylthioxanthone; α-dicarbonyl compounds such as camphorquinone; bisimidazoles; Metallocenes such as titanocenes and ferrocenes; Aryl tert. -butyl-peresters; xanthenes; fluorenes; and / or fluorones, such as 5, 7-diiodo-3-butoxy-6-fluorones.

In the case of cationic curing, constituent (b) of the composition contains one or more of the following compounds as initiator: aryldiazonium salts, arylsulfonium salts, aryliodonium salts, ferrocenium salts and / or phenylphosphonium benzophenone salts.

In the case of a dual-curing compound or combination of components (a), component (b) is a combination of one or more of the above-mentioned, the radical see polymerization initiating compounds provided with one or more of the above, the cationic polymerization initiating compounds. The dual-curing composition and / or desired properties can thus be set.

Component (c) may contain one or more of the following compounds as co-initiators for radical curing: tertiary amines, preferably N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, N, N-dialkyl dialkylaniline and other structurally related amines, preferably in combination with initiators such as benzophenones and α-dicarbonyl compounds such as camphorquinone; Diaryliodonium compounds, preferably in combination with the fluorone initiators; Borates such as butyrylcholine triphenylbutyl borate and other structurally related borates; organic phosphites; Thioxanthones as a sensitizer for the α-aminoacetophenone initiators.

One or more of the following compounds can be provided as the co-initiators of component (c) for the cationic curing: xanthenes; fluorenes; fluorones; α-dicarbonyl compounds, such as. B. camphorquinone as a sensitizer for the diaryliodonium initiators.

In the case of a dual-curing composition, together with corresponding initiators of component (b) as component (c), a combination of one or more of the above-mentioned co-initiators for free-radical polymerization with one or more of the above-mentioned co-initiators for cationic polymerization, such as e.g. a combination of fluorones, diaryliodonium salts, tert. Amines and / or borates can be provided.

The component (d) can contain at least one modifier, for example at least one pigment and / or a dye such as anthraquinone, preferably in an amount of 0-3% by weight. The dye / pigment is precisely matched to the light source used or its emission spectrum. The that is, if you use a different light source, the dye / pigment may also have to be changed.

At least one of the following substances can be provided as a suitable filler of the component (d) of the composition: silicon dioxide, such as pyrogenic silicon dioxide and / or amorphous silica, aluminum oxide, ceramic, quartz, ground glasses, splinter polymers, silica gels and minerals. To improve the bond with the other constituents of the composition, the filler can be pretreated with a silane, such as 3-methacryloyloxypropyltrimethoxysilane. The grain sizes of the inorganic fillers are usually 0.01-100 μm, preferably 0.01-20 μm.

Fibers and fabrics, such as glass fiber, carbon fiber, textile fiber, metal fiber, can also be embedded as fillers. This includes fibers and fabrics individually or in ribbon, mat, tube or cord form or a bundle of continuous fibers. It does not matter whether the filler is contained in the plastic from the outset or whether the polymerization process is interrupted, for example to insert a glass fiber mat. If the plastic preparation contains the filler, a liquid, semi-solid to solid paste is obtained depending on the filler content. Deviating from Fig. 1, semi-solid or solid pastes are brought to the defined layer thickness (e.g. 10 - 150 μm) with a roller system. The introduction of fillers enables a variety of other areas of application, such as dental, otoplastic, facial and bone surgery applications.

In addition, component (d) of the composition can contain stabilizers such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and / or 2,6-di-tert. -butyl-4-methylphenol, preferably contained in an amount of 0-5% by weight.

The following table lists examples of a composition according to the invention.

When using the composition given in Example 1 as plastic 6 in the process described above, curing depths of 115-211 μm can be obtained with exposure times of 4-12 seconds. This results in layer thicknesses of 55-105 μm with the above arrangement. By varying the plastic composition, layer thicknesses of 1 - 250 μm are achieved. A halogen lamp is used.

The composition is produced by the following essential steps: First, prescribed amounts of the initiators, co-initiators, dyes, pigments and stabilizers are dissolved in a low-viscosity part of component (a) of the composition, for example in the monomer ethyl methacrylate or butanediol dimethacrylate, the resulting mixture depending on the solubility of the ingredients used, stirred between 1-36 h at 20-80'C. The resulting solution is then mixed with the rest of component (a) of the composition in 10-60 minutes. One or more fillers are then optionally added to the resulting solution in small portions and mixed intensively after each addition. During production, the choice of the type and the amount of fillers, pigments, dyes and stabilizers of the composition can influence physical properties, such as the hardness or depth hardness of a layer, the modulus of elasticity, the color, the layer thickness and the durability of the object to be formed and set as needed. Furthermore, the initiators and / or co-initiators can be used in various combinations in order to vary them in accordance with the type of shaping process, the light source used and the desired physical properties of the object to be formed therewith.

In the case of a dual-curing composition, the accuracy of fit of the object to be formed can be improved, since, for example, the polymerization shrinkage and the disruptive influence of an oxygen inhibition layer are reduced in comparison with a purely radical-curing composition.

By precisely matching the composition of the plastic used in the shaping process to the light source used, the mask, the type and / or the intensity of the incident light, the thickness of a layer to be hardened in the shaping process can be adjusted to the desired thickness. In addition, by adding suitable dyes and / or by varying the concentrations of the initiators and / or co-initiators or by selecting and combining one or more initiators and / or one or more co-initiators, the layer thickness and the depth hardness can be influenced via the polymerization depth and the polymerization time ,

The plastic of the abovementioned composition can be used in the above-described method for forming a three-dimensional object, that is to say in microphotopinning, as in other rapid prototyping methods, for example in laser sintering or in stereolithography.

The use of the composition according to the invention is not based on microphotopinning or on rapid prototyping. Procedure limited. The composition of the invention is rather also in other shaping processes, such as. B. in film casting of plastics, in the production of plastic sintered parts or in microstructuring, such as. B. in photolithography in semiconductor technology. In addition, the composition according to the invention can be used in the dental, facial and bone surgery and otoplastic fields for the production of inlays, onlays, tooth fillings, attachments, crowns, bridges, artificial teeth, pin teeth, dental prostheses, dental implants, facial implants, bone implants and hearing aids (otoplastic). Accordingly, both models and individually manufactured individual products or mass-produced sales products can be produced with the composition according to the invention.

A specific use of the composition according to the invention is given in dental technology in a method for producing plastic inlays. In the method, a camera is first used to record a cavity of a tooth to be filled and a computer model of the inlay to be inserted into the cavity is produced. The computer model is then broken down into flat layers by means of software, the layer data generated in this way being fed to the control of a microphotographic consolidation system described above, where the inlay is built up layer by layer in accordance with the layer data. Due to the good resolution in the process of microphotopinning, inlays can be produced in a precise manner. In the method according to the invention, a plastic is used as described above, which is tooth-colored by the addition of appropriate dyes / pigments.

Alternatively, the inlay can also be produced by using a plastic which is pasty through a filler of component (d), each layer being produced by rolling out the pasty material. A special rigidity of the inlay produced can be achieved if glass fiber components are added to the plastic mass to be cured. Alternatively, one or glass fiber mat can be placed in between several plastic layers.

Claims

1. Containing composition curable with visible light

(a) 2-99% by weight of at least one compound which has at least one acrylate group and / or at least one methacrylate group and / or at least one vinyl group and / or at least one epoxy group and / or at least one oxetane group and / or at least one acrylic-epoxy-oligomer group and / or contains at least one methacrylic epoxy oligomer group, and / or at least one resin composition based on at least one polymerizable polysiloxane,

(b) 0.01-7% by weight of at least one initiator,

(c) 0-5% by weight of at least one co-initiator,

(d) 0-85% by weight of one or more modifiers, such as fillers, dyes, pigments, flow improvers, thixotropic agents, polymeric thickeners, oxidizing additives, stabilizers and retarders.

2. Composition according to claim 1, characterized in that at least one Ormocer is contained in the resin composition as a polymerizable polysiloxane.

3. Composition according to claim 1 or 2, characterized in that a resin composition in the presence of initiators photochemically or thermally curable or self-curing resin composition based on polymerizable polysiloxanes, obtainable by hydrolytic condensation of one or more hydrolytically condensable compounds of silicon and optionally other elements the group B, Ba, Ti, Zr, Al, Sn, the transition metals, the lanthanides and the actinides, and / or precondensates derived from the abovementioned compounds, optionally in the presence of a catalyst and / or a solvent, by the action of water or Moisture, 1 to 100 mol%, based on monomeric compounds, of silanes of the general formula (I),

Y _n SiX _m R ₄ . _(ntm) (I) in which the radicals X, Y and R are identical or different and have the following meaning:

R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl

R '- hydrogen, alkyl or aryl,

Y = a substituent which contains a substituted or unsubstituted 1,4,6-trioxyaspiro- [4, 4] -nonane radical, n = 1,2 or 3, m = 1,2 or 3, with n + m < _. 4,

and / or from silanes of the general formula (II),

{X _n R _k Si [R ² (A) ₁ ] 4- (n + k)} _x B (II)

A = 0, S, PR ', P0R', NHC (0) 0 or NHC (0) NR ', with R' = hydrogen, alkyl or aryl,

B = straight-chain or branched organic radical, which is derived from a compound B 'with at least one (for 1 = 1 and A = NHC (0) 0 or NHC (0) NR') or at least two C = C double bonds and 5 derives up to 50 carbon atoms, with R ¹ = hydrogen, alkyl or aryl,

R = alkyl, alkenyl, aryl, alkylaryl or arylalkyl,

R ² = alkylene, arylene or alkylene arylene,

R '= hydrogen, alkyl or aryl, n = 1,2, or 3, k = 0, 1 or 2, 1 = 0 or 1, x = an integer, the maximum value of which is the number of double bonds in the compound B' minus 1 corresponds to or is equal to the number of double bonds in the compound B 'when 1 = 1 and A is NHC (O) or NHC (0) NR',

are selected, optionally containing fillers and / or copolymerizable monomers.

4. Composition according to one of claims 1 to 3, characterized in that one of the structural element ^' E 2 and at least one of the structural elements in the resin composition

E 1 and / or E 3 and / or E 4 compound of the general formula

El | E2 | E3 and E4

O -O

where R _{: is} a methyl, ethyl, n-propyl, isopropyl or an optionally CH ₃ -C ₃ H ₇ -substituted phenyl radical, R _{2 is} a CH ₂ = CH-, CH ₂ = CHCOO (CH ₂ ) _n - or

or Rl, n 0, 1, 2 or 3, and M denotes titanium or zirconium.

5. Composition according to one of claims 1 to 4, characterized in that it contains the compound of component (a) in an amount of 10-95% by weight.

6. Composition according to one of claims 1 to 5, characterized in that the composition is curable in a wavelength range of 350-700nm.

7. Composition according to one of claims 1 to 6, characterized in that the component (a) aliphatic diurethane methacrylate, tetra-ethoxylated bisphenol A dimethacrylate, aliphatic urethane methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso -Propyl methacrylate, butyl methacryla, 2-ethylhexyl methacrylate, methacrylic acid ester, isobornyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate,

n-hexyl methacrylate, ethyl triglycol methacrylate, tetrahydrofurfuryl methacrylate, hydroxyalkyl methacrylates,

2-hydroxyethyl methacrylate, alkoxyethyl methacrylate, allyl methacrylate, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butane diol dimethacrylate, 1,4-butane diol dimethacrylate, 1-diol dimethacrylate rin-1, 3-dimethacrylate, diurethane dimethacrylate, trimethylolpropane trimethyl acrylate, 1,3,5, 7-tetrakis (2, l-ethanediyl-3, 4-epoxycyclohexyl) -l, 3, 5, 7-tetramethylcyclotetrasiloxane, 1, 10-decanediylbis (oxymethylene) bis (3-ethyloxetane), 1,3,5,7,9-pentakis (2, l-ethanediyl-3, 4-epoxycyclohexyl) -l, 3, 5, 7, 9-pentamethylcyclopentasiloxane, Vinylcyclohexene oxide, vinylcyclohexene dioxide, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carboxylate, bis (2,3-epoxycyclopentyl) ether; 3, 4-epoxy-6-methylcyclohexylmethyl adipate, 3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy (cyclohexane metadioxane), 1,4 butanediyl-bis (oxymethylene) bis (3-ethyloxetane), 3, 4 Epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, 1,1,3,3-tetramethyl-1,3-bis (2,1-ethanediyl-3,4-epoxycyclohexyl) disiloxane, bis- (3,4-epoxycyclohexylmethyl) adipate, Monovinyl ether, divinyl ether, hydroxy vinyl ether, aminovinyl ether, trivinyl ether, triethylene glycol divinyl ether, 4-hydroxybutyl vinyl ether, propenyl ether of propylene carbonate, dodecyl vinyl ether, triethylene glycol divinyl ether, alkyl vinyl ether, ethylene glycol monovinyl ether, diethylene glycol diol ether, diethylene glycol diol ether, diethylene glycol diol ether Hexanediol divinyl ether, ethylene glycol butyl vinyl ether, cyclohexanedimethanol mono and divinyl ether, 2-ethyl hexyl vinyl ether, poly-THF divinyl ether, cyclohexyl vinyl ether, tert. -butyl vinyl ether, Ter. -amyl vinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, hexanediol monovinyl ether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, aminopropyl vinyl ether and / or 2-diethylaminoethyl vinyl ether.

8. Composition according to one of claims 1 to 7, characterized in that the component (b) for a radical hardening phosphine oxides, benzoin ethers, benzil ketals, acetophenones, benzophenones, thioxanthones, α-dicarbonyl compounds, bisimidazoles, metallocenes, aryl tert. -butyl-perester and / or fluorones, for a cationic curing aryldiazonium salts, arylsulfonium salts, aryliodonium salts, ferrocenium salts and / or phenylphosphonium benzophenone salts or a mixture thereof.

9. The composition according to claim 8, characterized in that as phosphine oxide diphenyl-2,4, 6-trimethylbenzoyl-phosphine oxide, as benzoin ether benzoin and / or benzoin alkyl ether, as benzil ketals benzil dialkyl ketals, as acetophenones α-hydroxy-acetophenones, dialkoxyacetophenones and / or α-aminoacetophenones, as thioxanthone i-propylthioxanthone, as α-dicarbonyl compound camphorquinone, as metallocenes titanoecenes and / or ferrocenes, as fluorones 5, 7-diiodo-3-butoxy-6-fluorones are contained.

10. Composition according to one of claims 1 to 9, characterized in that the component (c) for a radical hardening tertiary amines, diaryliodonium compounds, borates, organic phosphites and / or thioxanthones, for a cationic hardening xanthenes, fluorenes, fluorones and / or contains α-dicarbonyl compound or a mixture thereof.

11. The composition according to claim 10, characterized in that as tert. Amine N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, N, N-dialkyl-alkyl-aniline and / or other structure related amines, as borates butyrylcholine triphenylbutyl borate and / or other structurally related borates are contained.

12. Composition according to one of claims 1 to 11, characterized in that the component (d) contains an anthraquinone dye.

13. Composition according to one of claims 1 to 12, characterized in that the component (d) as a filler silicon dioxide, fumed silicon dioxide, amorphous silica, aluminum oxide, ceramic, quartz, ground glass, fragment polymer, silica gel, minerals, fibers and / or tissue contains.

14. Composition according to claim 13, characterized in that the fibers and / or fabrics glass fibers, carbon fibers, textile fibers and / or metal fibers are contained individually or in tape, mat, tube or cord form or in the form of a bundle of continuous fibers.

15. The composition according to claim 14, characterized in that one or more of the fillers contained are silanized.

16. The composition according to any one of claims 1 to 15, characterized in that the component (d) hydroquinone, hydroquinone mono ethyl ether, pyrocatechol, 2, 6-di-tert. -butyl-4-methylphenol contains.

17. Use of a composition according to any one of claims 1 to 16 in a molding process.

18. Use of a composition according to any one of claims 1 to 16 for the production of models, individually manufactured individual products and mass-produced sales products.

19. Use of a composition according to any one of claims 1 to 16 in a process of microfixing, rapid prototyping, film casting, the production of art Sintered parts, microstructuring, photolithography, the manufacture of dental products, the manufacture of surgical implants and / or the manufacture of otoplastic products.

20. Use of a composition according to one of claims 1 to 16 in a method for producing a three-dimensional object by successively selectively solidifying layers of the composition at locations corresponding to the cross section of the object under the action of visible light.

21. A method for producing a tooth filling by successive layer-by-layer solidification of a composition according to one of claims 1 to 13, at the corresponding cross-section of the filling in the respective layer.

22. The method according to claim 21, characterized by the steps a) generating a computer model of the filling to be produced, b) disassembling the computer model into layers, each of which corresponds to a cross section of the filling, c) layer-by-layer curing of the composition at locations corresponding to the cross section of the filling Exposure to visible light.

23. The method according to claim 21 or 22, characterized in that a pasty composition is used.

24. The method according to claim 23, characterized in that glass fiber components are added to the composition.

25. Object made by curing the composition of any one of claims 1 to 13 using visible light.