DE4039382A1 - Modelling liq. for building up dental porcelain - contg. photopolymerisable cpd., photopolymerisation inhibitor, reducing agent and polymerisation inhibitor - Google Patents

Abstract

Modelling liq for building up of dental porcelain contains (A) a photopolymerisable cpd with at least 1 C=C bond, (B) a photopolymerisation initiator, (C) a reducing agent, and (D) a polymerisation inhibitor. Further components include (E) an organic solvent, (F) (semi)solid organic material, (G) a tert amine and (H) an organic halo cpd. Pref components are: (A) a mono-or poly-functional (meth)acrylate, (B) an alpha-diketone, ketal benzolin alkyl ether, or deriv, in amt of 0.001-15 wt% wrt (A), (C) 0.001-20% of reducing agent, (E) a (halo)hydro-carbon, alcohol, ether, ketone, ester, or a N cpd, (F) natural wax, petroleum wax, synthetic wax based on C, polyolefins, or fats and oils, (G) 0.05-5% of a tert amine, and (H) 0.01-5% of halo cpd.. ADVANTAGE - The liq can be burned and sintered without residual ash and without altering the colour of the porcelain.

Description

The present invention relates to a modeling fluid for Dental porcelain that is used to manufacture various Prostheses used in the production of crowns and bridges partially or entirely made of porcelain, is used, paying attention to the Shape of the teeth, their correspondence with the rest Teeth, occlusion and chewing ability aesthetic appearance, the influence on the Periodontium, the preservation of regenerability, the dynamic properties, their ease of manufacture, Improvements in their quality and reliability and Savings in production costs.

For crown and bridge production, jacket crowns, Inlays and overlays increasingly made of ceramic Materials made, e.g. B. castable ceramic material and sintered pure ceramic material. Except for techniques, at pourable ceramic material for casting production has so far typically found refractory models and Platinum foil process widely used. At the Refractory model procedure becomes a denture shape from one fireproof model material used exclusively for education and was developed for firing porcelain, Porcelain is processed and fired on the denture mold, the bit form is taken from the refractory model and finally the porcelain is used for shape corrections in the Denture form returned, and the platinum foil process comprises the pressing on of an approximately 25 µm thick platinum foil on a bit form, training and firing all parts of the porcelain including a perignatic part the shape of the teeth and the removal of the porcelain from the Inner surface of the crown after all dental work like Glazing is finished and before cementing.  

Aside from these procedures, however, is burning of porcelain on a metallic cover or frame part also of great importance when the shape of the teeth, their correspondence with existing other teeth, Occlusion and chewing ability, aesthetic appearance, Influence on periodontium, preservation of regeneration, dynamic properties and durability and the like be taken into account. Becomes crown or bridge processing with such a metallic cover or such Frame, so are the dynamic properties the prosthesis improved by reducing the size natural teeth or abutment teeth to be cut. This also means that the prosthesis has a good one Has an influence on the periodontium and in accordance with the remaining teeth, which leads to the oral cavity overall is in good health. You can choose such aesthetic improvements are achieved that porcelain on resin, especially a hard resin, is bound or combined with it. However, although binding or combining porcelain with the hard resin inside in a short period of time and easily at reasonable cost is achievable, it has numerous disadvantages, one of which typical are listed below:

• 1. The material is porcelain in terms of Strongly inferior to abrasion resistance;
• 2. The material absorbs a lot of water and is so chemical unstable that it is obvious that it is in the oral cavity is discolored or colored;
• 3. The aesthetic appearance of the material is from that of natural teeth far away; and
• 4. The material has poor adhesion to one metallic cover or frame part and it is missing also the durability.

For these reasons, there has been an increasing trend lately Need for prostheses with an improved aesthetic Appearance, especially with a high quality. To crowns and bridges processed prostheses with a metallic Porcelain cover or frame part can be found in the Widely used dentistry.

For such prostheses, a metal cover or a Metal frame first adapted to a denture shape. Then are opaque dentine and enamel porcelain materials from Get started on the bit form in that order from their Cervical periphery using a brush or a spatula. When building each Porcelain material becomes a condensation for removal of moisture and a burning sensation with that on the denture mold attached metallic cover or frame part carried out. However, the problem arises that because of the support on the metallic cover or frame part Porcelain cannot be built up completely and itself contracted by burning. As a result, this is the case Porcelain built up cervical periphery insufficiently thick or thinly formed so that the metal color of the cover or the frame is visible through the porcelain. Furthermore, the metal cover or frame is often through the cervical periphery in the case of a Gingival recession in the oral cavity over a longer period Period visible. This is not only proving very much unnatural from an aesthetic point of view, but leads also to gingival discoloration or periodontitis.

To solve these problems has been recently by one Marginal porcelain technology made use of, in which no Metal part on the shoulder region of the cervical periphery of the metallic cover or frame part is provided. With Help this procedure with the porcelain materials  built on a non-metal area be, it is possible to solve the problems that the color of the metallic cover or frame part through the Porcelain materials are seen and that the metallic Cover or frame part is visible. However, this is a certain skill is required because with the Carrying out this procedure using the usual, currently techniques available considerable technical Difficulties are connected. So z. B. a special one Skill necessary to handle every porcelain material Mix with water to condense and then the Porcelain materials from the denture model to the working model too remove without removing it from the metal Damage the area located.

As a result, various measures have been taken and different procedures applied to make separation easy to achieve the porcelain materials from the denture model. The first method - called the refractory model method like already mentioned - consists of the cervical periphery a denture model made of a refractory material build up and burn. The second method - called the Platinum foil method as also mentioned above - involves pressing a platinum foil onto the Cervical periphery and build up of porcelain on this with subsequent removal and burning operation. The third Method is called a model hydrophobization method referred to in the porcelain on a hydrophobic Epoxy material formed denture model or on a Gypsum working model that with hydrophobic release materials or Surface hardening materials have been coated to it to make hydrophobic. That with water mixed porcelain is so little wettable with the hydrophobic denture model that its removal easier can be done as with conventional plaster work models is possible. The fourth method involves mixing one  Fuel from residue-free wax melt with Porcelain, instant build-up of the wax mixture on the Shoulder part and cooling and removal from the plaster model together with the metallic cover or frame part. The wax is usually combined with porcelain in one Weight ratio of 1 to 6 or 7 mixed. The fifth Method makes use of an exclusive Modeling liquid that can be hardened by warm air, whereby this modeling fluid undergoes a heat curing reaction suffers. The modeling liquid that is at room temperature is not hardenable, is mixed with porcelain and that Mixture is hardened with warm air and then by the Plaster work model removed. The sixth method is based on a hardening that can be achieved by in visible Light is exposed. Based on the same principle however, it is like that of the fifth method characterizes that light is used instead of heat.

The following are some special effects that have so far been based on Porcelain were applied and also with the present one Invention have to be addressed.

Naturally, natural teeth suffer differently Changes depending on age and oral cavity influences. In the In recent years there has been a growing need for Dental prostheses that the individual patient as far as are adapted as possible and as close as possible to natural teeth come. The special effects concern this purpose serving dental technology that is applied to everyone Patients individual characteristics under Offer consideration of color, shape and area. These are e.g. B .:

• 1. The cervical effect for the reproduction of the dentine Root or the gingival color effect to achieve a Conformity with the gums;  
• 2. the dentinal effect is insufficient for regeneration Calcification, structural defects or differences in the thickness of the dentine centerpiece or the upper enamel;
• 3. the incisal effect for the regeneration of Lack of calcification and internal discoloration; and
• 4. the surface coloring effect for the regeneration of Discoloration that naturally occurs on teeth Exposure to tobacco, food, beverages, tooth decay and for other reasons.

To achieve such effects, the coloring with a Porcelain material of the desired color can be made after building a porcelain base material almost has ended or during its construction. So z. B. that Porcelain material exclusively for internal coloring cut out or along a desired shape line or point marker open Porcelain material incorporated in the course of the construction work or the porcelain material can be used after construction be coated, creating the teeth of every patient individual characteristics are awarded. After that you can the porcelain material pre-dried for 5 to 10 minutes and then at about 600 to 900 ° C at a heating rate be burned from 50 to 60 ° C per min.

Common techniques for building porcelain molds, of which turned out to have some problems, are usually in the following two cases broken down:

The first case: without a metallic cover or frame part to attach to the cervical area, a porcelain after the Marginal porcelain technology built up, which prevents is that their color is seen through the porcelain becomes;  

Second case: to receive dental prostheses, the Natural teeth will come as close as possible to them special effects imparted with the help of a Porcelain material for internal or external coloring.

The problems that occur in the specified cases are shown below.
The first case:
1. The refractory model process requires the porcelain to be transferred from the plaster work model to the refractory model and takes about three hours longer than the direct process, since it takes a considerable amount of time for impression taking and drying, and complicated dental work is required. This results in an imprint with poorer accuracy, which results in a decrease in the accuracy of fit.
2. The platinum foil process, in which a platinum foil is pressed onto the cervical periphery of the plaster work model, leads to a deterioration in the accuracy of fit due to the thickness of the platinum foil. Since the platinum foil is intended to be discarded or discarded after use, this entails a considerable increase in costs.
3. The method in which porcelain is built up directly with the aid of a brush or a spatula with condensation cannot be used without particular skill, since the shape of the cervical periphery tends to get out of shape. This method is also not applicable to a bridge prosthesis using a variety of abutment teeth. It also requires making the condensed porcelain easily removable from the plaster work model by coating its periphery of the cervical with a hydrophobic release or surface hardening material. However, the adaptation of the porcelain to the cervical periphery deteriorates due to the thickness of the applied hydrophobic detachment or surface hardening material.
4. In the process in which a mixture of a wax melt with porcelain is built up, cooled and removed from a plaster work model, the wax has to be melted as often as necessary since it starts to harden immediately in the course of processing due to the crystallinity of the wax that is very high. Because wax cannot be condensed, the porcelain contracts very strongly. If the wax is used in large quantities, a large amount of carbon is generated which contaminates the furnace or causes it to malfunction.
5. In the process in which porcelain is built with a heat-curable modeling liquid, the porcelain structure, which is hardened by warm air, is softened by heat and reaches the metallic cover or frame part by blower wind pressure, where it tends to harden. Such porcelain should preferably be removed before or after firing. However, it is impossible to remove it completely, so that the accuracy of fit of the metallic cover or frame part is deteriorated. This also applies to the process in which a mixture of a wax melt with porcelain is built up, cooled and removed from a plaster work model.
6. The process of building porcelain with a light-curable modeling fluid is now also commercially available. In the case of this method, however, the porcelain cannot be condensed at all. In most cases, after the firing, there remains coal residues which give the porcelain a gray tone or possibly a black tone depending on the firing conditions. The method is therefore not applicable at all to porcelain, which is fired on a metal, because of the aesthetic appearance, which is very important.
The second case:
1. In order to give the porcelain the special effects for which complicated color tones have to be expressed, internally or externally acting multicolor porcelain materials are usually mixed with dentine or enamel porcelain as required. In this case, water has been used as a modeling liquid. Although a mixture of the inside or outside coloring porcelain is easily built up with water and condensed well, it is impossible to estimate exactly which shade will come out after firing. This is because the refractive index of water (1.3327 at 23 ° C) is very different from that of porcelain (1.47-1.50). Porcelain is also often stained with a dye. In this case, it is impossible to estimate the color inherent in the porcelain from the outset, provided the dye has not burned. The creation of such special effects, which is often only achieved with the sixth sense of the dental technician, is rather hopeless for newbies and can only be achieved clinically by a few experts. Even if porcelain is successfully built with the selected inside or outside coloring porcelain material, the desired color is not always obtained after firing. In this case, the porcelain must be separated in order to build up and burn fresh porcelain with an internally or externally coloring porcelain material of different colors. The color and quality of the prosthesis thus deteriorate after firing and repeating such procedures is very time-consuming.
2. To treat internal or external discoloration caused by soot formation, yellowing and the like, as well as insufficient calcification, special effect paints are applied to porcelain using a thin brush. In this case, however, the lamination of a plurality of internally coloring porcelain materials or the application of an externally coloring porcelain material leads to a mixing of the colors. The line drawn in this way is also so thick that it is smeared. Even if the coloring porcelain materials are built up or applied to a limited area, they tend to flow and spread over the porcelain. The internal or external coloring porcelain materials can therefore only be used if appropriate experts are available. It is also not possible to bring about the special effects, which must meet certain quality requirements, in a predetermined, desired time period.

Extensive and intensive studies to solve the problems now have to the knowledge performed that the modeling fluid according to the invention for Dental porcelain successfully solves these problems.

The modeling liquid according to the invention comprises a photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond or an organic solvent and an organic Material that is solid or semi-solid at normal temperature, and it has a refractive index from 1.4 to including 1.6 at 23 ° C and a viscosity of 0.1 Pa · s or less at 23 ° C. Can be mixed with porcelain this liquid  are fired on a metal and sintered without any ash residue remains and without any change in the desired hue of the porcelain he follows.

The solution according to the invention to the problems shown is explained in more detail below:
(In order to prevent the metal color of the cervical periphery of a metallic cover or frame part from being seen through or seen, porcelain is built using the marginal porcelain technique, but without applying the metal cover or frame part to the cervical periphery).
1. In order to build porcelain directly on a metal covering or frame part that does not belong to the shoulder area, instead of using a fire-proof model material, the porcelain, which is built up in some form, must be held in the desired shape on the cervical periphery. After mixing porcelain, the modeling liquid for dental porcelain according to the invention is built up on the cervical periphery and then exposed to light or it reacts with the organic peroxide or pyrimidine trione derivative and the organometallic compound which is contained in the porcelain. The porcelain hardened in this way is temporarily bonded to the metal cover or frame part and is thus easy to remove from a plaster working model, so that its design, as it was formed on the cervical periphery, can be retained until the end. Laborious dental operations such as building and sintering porcelain on a refractory model can thus be dispensed with. As a result, the time period including the time for transferring the porcelain from the plaster work model to the refractory model can be greatly shortened while improving the fit.
2. Building porcelain on a non-shoulder metal cover or frame part covered with platinum foil is cumbersome and time consuming, does not allow the cervical periphery to be kept in good condition, and incurs significant costs because the platinum foil is expensive. The modeling liquid for dental porcelain according to the invention is much cheaper than the platinum foil and its price is on the order of only about 1/10 to several tenths or one 1/100 to several hundredths.
3. When porcelain is condensed with water for its removal, as is usually the case, the shape of the cervical periphery is only maintained by wet bonding so that it loses its original shape even when there is little vibration or impact. This procedure cannot therefore be applied to a bridge in which a large number of counter bearing teeth are used. It takes 5 to 10 years of experience to master this method. After mixing with porcelain and building up in place, the modeling liquid for dental porcelain according to the present invention is hardened by being exposed to light or being reacted with the organic peroxide or the pyrimidine trione derivative and the organometallic compound contained in the porcelain. Thus, the porcelain can be removed from a plaster work model so easily that the shape of the ceremonial periphery can be maintained until the end. This technique enables the porcelain structure on the cervical periphery to be immediately removed from the plaster model without any particular skill and is therefore easy to use on bridges where a large number of counter bearing teeth are used. If porcelain is condensed with water to remove it, as is usually the case, it is necessary that a hydrophobic release material or a surface hardening agent be applied to the cervical periphery of the plaster work model for easy removal of the condensed porcelain. In this way, the accuracy of fit of the porcelain on the cervical periphery is deteriorated due to the thickness of the release material or surface hardening material applied. The modeling liquid is mixed with porcelain and the porcelain mixed in this way is assembled on site, whereupon the modeling liquid according to the invention for dental porcelain is hardened by light exposure or reaction with the organic peroxide or pyrimidine trione derivative and the organometallic compound contained in the porcelain. In this way, the porcelain can be easily removed from the plaster work model without the need to use such a hydrophobic release material or surface hardening material. As a result, the accuracy of fit of the cervical periphery of the porcelain burned to a metal on the plaster work model or even on the patient's abutment teeth is greatly improved.
4. In the case of the techniques using wax, a wax melt is mixed with porcelain, whereupon the mixture is built up and cooled in place, followed by its removal from the plaster work model. However, the porcelain solidifies immediately after it is built up and therefore cannot be mixed due to the crystallization of the wax, which is very high. Because the wax cannot be condensed and it is also not possible to remove excess wax with paper towels or gauze swabs, the built-up porcelain contracts strongly after firing and generates a lot of carbon at the time of firing, which contaminates the furnace or causes it to malfunction . The modeling liquid according to the invention for dental porcelain, on the other hand, shows a sufficient viscosity for the condensation after mixing with porcelain and the on-site build-up and before the light is exposed or with the organic peroxide or pyrimidine trione derivative and the organometallic compound contained in the porcelain, has reacted. If the modeling liquid is in excess, this liquid can be removed with paper towels or gauze pads. According to the invention, the material which is solid or semi-solid at normal temperature and which is generally referred to as "wax" is not used as such. This organic material is diluted with an organic solvent suitable for easy solubilization of the wax, and is then condensed with porcelain while reducing the relative amount of the wax. After assembly, the porcelain is heated to a temperature higher than the boiling point of the organic solvent to volatilize the organic solvent alone, whereby the shape of the porcelain can be obtained with a small amount of the wax residue. Subsequent ashing can further improve the fired porcelain because of the small amount of wax residue. Thus, since the amount of the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond which always contains carbon can be reduced as much as possible with respect to the amount of porcelain, there is no fear that a lot of carbon can be generated during ashing and one Contamination or failure of the oven occurs.
5. In the case of the technique in which porcelain is built up with a heat-curable modeling liquid, the built-up porcelain flows during the hardening by warm air into the metal cover or frame part, where it hardens. It is therefore necessary to remove an excess portion of the modeling fluid before firing or at the end of the operation. If this removal is not successful, the accuracy of fit of the porcelain to a plaster work model on the cervical periphery of a metal cover or frame part or also on the counter-teeth of a patient is deteriorated. With the modeling liquid for dental porcelain according to the invention, however, it is not necessary to use warm air, since this liquid is hardened by exposing it to light or by reacting it with the organic peroxide or pyrimidine trione derivative and the organometallic compound also contained in the porcelain. The accuracy of fit of the porcelain to the plaster model on the cervical periphery of the metal cover or frame part or also on the counter bearing teeth of a patient is therefore greatly improved.
6. The technique of building porcelain with the help of a photo-curable modeling liquid is commercially applicable. Since use is made of a high viscosity polyfunctional monomer, any condensation is not possible at all. After firing, carbon almost always remains, which, depending on the firing conditions used, makes the color of the porcelain gray or possibly black. This procedure is therefore not applicable at all to porcelain that is burned to a metal if special attention is paid to the aesthetic appearance. In contrast, the modeling liquid according to the invention for dental porcelain can be condensed well because its viscosity is 0.1 Pa · s or less at 23 ° C. Furthermore, after removal of an excess portion of the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond or the organic material which is solid or semi-solid at normal temperature, it can be sintered with the aid of paper towels or gauze swabs. If the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond has a high viscosity or the photopolymerization reaction or the reaction with the organic peroxide or pyrimidine trione contained in the porcelain and the organometallic compound is very slow, the organic material which is solid or semi-solid at normal temperature and that Photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond previously dissolved in an organic solvent which is not volatile at room temperature, but has a boiling point so high that it evaporates when heated to 100 to 150 ° C or higher. After assembly and condensation, the porcelain is heated to 100 to 150 ° C or higher to remove the specified organic solvent. However, since the remaining organic material, which is solid or semi-solid at normal temperature, solidifies, it is possible to maintain the shape of the porcelain in the same way as it was built up. Furthermore, since the refractive index of the organic solvent used can be controlled in the range from 1.4 to 1.6, it is possible to estimate the color tone of the porcelain before firing. As a result, it is possible to obtain a porcelain fired to a metal which takes on a hue that is practically identical to that of the porcelain as it was mixed with water and assembled in place.
(In order to obtain dental prostheses that come as close as possible to natural teeth, the porcelain is given special effects with the help of porcelain materials that color internally or externally).
1. The modeling liquid for dental porcelain according to the invention has a refractive index of 1.4 to 1.6 at 23 ° C., while porcelain has a refractive index of 1.47 to 1.50. This modeling fluid does not undergo any significant change in the refractive index before or after it has been exposed to light or has reacted with the organic peroxide or pyrimidine trione derivative and the organometallic compound contained in the porcelain, ie before and after the hardening. Therefore, as soon as some have been selected from a larger number of internally or externally coloring porcelain materials in order to give the porcelain the desired special effect with the production of complicated shades, even novices in this field can estimate the color of the porcelain after firing. It is therefore possible to prevent such failures from having processed porcelain cut off and rebuilt as often as necessary due to the fact that the color tone of the porcelain cannot be estimated, as is the case when the porcelain is mixed with Water is the case. This also enables everyone to achieve the creation of special effects, which was previously reserved only for experts. The internally or externally coloring porcelain materials which have been mixed with the modeling liquid according to the invention can be hardened by being exposed to light or by reaction with the organic peroxide or pyrimidine trione derivative contained in the porcelain and the organometallic compound. This also makes it possible for everyone to build up or attach porcelain at the desired location in the desired thickness and to the desired extent. Furthermore, the time period required for dental work is one to several tenths of the time normally required and the inside or outside coloring porcelain materials of the desired colors can be selected precisely.
The special effects can therefore be imparted to the porcelain so easily that the prosthesis is improved in aesthetic appearance while at the same time achieving improvements in terms of quality and work efficiency.
2. The modeling liquid for dental porcelain according to the invention is designed for a structure which is carried out by exposure to light or reaction with the organic peroxide or pyrimidine trione and the organometallic compound which are contained in the porcelain for their hardening. If, therefore, the special effects on the porcelain are brought about by eliminating internal or external discolorations, such as those caused by cracking, yellowing and insufficient calcification and the like, the application or coating can be carried out with a fine brush. Thus, it is possible for anyone to easily perform the required operations without any special workmanship. As a result, it is possible to impart the special effects of constant quality to the porcelain with internally or externally coloring porcelain materials at any desired time since neither color mixing nor color line thickening or color smearing takes place, as is the case when mixing with water.

The modeling liquid according to the invention, the one Refractive index from 1.4 up to and including 1.6 at 23 ° C and has a viscosity of at most 0.1 Pa · s at 23 ° C, can be made from photopolymerizable or polymerizable Compounds with at least one ethylenically unsaturated Double bond can be made. Of these connections can be used as examples of monofunctional methacrylates and  Acrylates are called

Methyl methacrylate,
Ethyl methacrylate, n-butyl methacrylate,
iso-butyl methacrylate, t-butyl methacrylate,
2-ethylhexyl methacrylate, lauryl methacrylate,
Tridecyl methacrylate, stearyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
Glycidyl methacrylate, tetrahydrofurfuryl methacrylate,
Allyl methacrylate, 2-ethoxyethyl methacrylate,
Methoxydiethylene glycol methacrylate,
Methoxytetraethylene glycol methacrylate,
Methoxypolyethylene glycol methacrylate,
Phenoxy diethylene glycol methacrylate,
Phenoxyhexane-ethylene-glycol-methacrylate,
Glycerol methacrylate, tetrahydrofurfuryl methacrylate,
Dicyclopentenyl methacrylate, dicyclopentanyl methacrylate,
iso-bornyl methacrylate, phenyl methacrylate,
Dipentaerythritol monohydroxyl methacrylate,
Caprolactone-modified tetrahydrofufuryl methacrylate,
Caprolactone-modified dipentaerythritol methacrylate,
Caprolactone-modified 2-hydroxyethyl methacrylate,
Caprolactone-modified 2-hydroxypropyl methacrylate,
2-ethoxyethyl methacrylate and lauryltridecyl methacrylate
as well as their acrylates.

As examples of polyfunctional methacrylates and acrylates can be named

Ethylene glycol dimethacrylate,
Diethylene glycol dimethacrylate,
Triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate,
Polyethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate,
1,6-hexane-diol-dimethacrylate,
Neopentyl glycol dimethacrylate,
Tripropylene glycol dimethacrylate,
Polypropylene glycol dimethacrylate, glycerin dimethacrylate,
Bisphenol A dimethacrylate, bisphenol
A-glycidyl dimethacrylate, ethylene oxide modified
Bisphenol A dimethacrylate, ethylene oxide modified
Glycidyl dimethacrylate, 1,3-butanediol dimethacrylate,
1,4-butanediol dimethacrylate,
2,2-bis (methacryloxyphenyl) propane,
2,2- [4- (2-hydroxy-3-methacryloxyethoxyphenyl)] propane,
2,2-bis (4-methacryloxyethoxyphenyl) propane,
2,2-bis (4-methacryloxyethoxydiethoxyphenyl) propane,
2,2-bis (4-methacryloxypropoxyphenyl) propane,
7,7,9-trimethyl-4,13-dioxo-3,14-dioxo-5,12-diazahexadecane-1,6-diol-dimethacrylate, neopentyl-glycol-hydroxypivalate ester dimethacrylate, caprolactone-modified
Hydroxypivalic acid neopentyl glycol ester dimethacrylate,
Ethylene oxide-modified bisphenol A dimethacrylate,
Trimethylol ethane dimethacrylate,
Trimethylolpropane dimethacrylate,
Trimethylolmethane trimethacrylate,
Trimethylolethane trimethacrylate,
Trimethylolpropane trimethacrylate,
Pentaerythritol trimethacrylate,
Dipentaerythritol trimethacrylate,
Pentaerythritol tetramethacrylate,
Dipenta-erythritol tetramethacrylate,
Pentaerythritol hexamethacrylate and
Dipentaerythritol hexamethacrylate.

Compounds of the following structural formulas and their Acrylates. These compounds can work alone or in Combination of two or more can be used and if necessary, they contain photo polymerization initiators, Reducing agents, polymerization inhibitors, organic Solvent, solid or semi-solid at normal temperature organic materials, tertiary amines, Organohalogen compounds and the like.  

Reaction product of 3-chloro-2-hydroxypropyl methacrylate with methylcyclohexane diisocyanate. Reaction product of 2-hydroxypropyl methacrylate with trimethylhexamethylene diisocyanate. Reaction product of 2-hydroxypropyl methacrylate with methylcyclohexane diisocyanate. Reaction product v. 2-hydroxypropyl methacrylate with methylene bis (4-cyclohexyl isocyanate). Reaction product of 2-hydroxymethyl methacrylate with trimethylhexamethylene diisocyanate. Reaction product of 2-hydroxypropyl methacrylate with isofluorodiisocyanate. Reaction product of 3-chloro-2-hydroxypropyl methacrylate with isofluorodiisocyanate. Di- (2-methacrylicoxyethyl) dihexamethylene-7- alkyl tetracarbamate. Reaction product of 2-hydroxyethyl methacrylate with methylene bis (4-cyclohexyl isocyanate). Reaction product of 3-chloro-2-hydroxypropyl methacrylic with hexamethylene diisocyanate. Reaction product of 2-hydroxypropyl methacrylate with hexamethylene diisocyanate. Reaction product of 2-hydroxyethyl methacrylate with hexamethylene diisocyanate. Reaction product of 2-hydroxyethyl methacrylate with isophorone diisocyanate. Reaction product of 2-hydroxyethyl methacrylate with methylcyclohexane diisocyanate. Reaction product of 2-hydroxypropyl methacrylate and glycidol dimethacrylate with isophorone diisocyanate. Reaction product of 2-glycidol dimethacrylate with methylcyclohexane diisocyanate. Reaction product of glycidol dimethacrylate with hexamethylene diisocyanate. Reaction product of glycidol dimethacrylate with isophorone diisocyanate. Reaction product of 2-hydroxypropyl methacrylate with methylbenzene diisocyanate. Reaction product of 3-chloro-2-hydroxypropyl methacrylate with methylbenzene diisocyanate. Reaction product of 2-hydroxyethyl methacrylate with methylbenzene diisocyanate. Reaction product of glycidol dimethacrylate with Methylbenzene diisocyanate. Reaction product of glycidol dimethacrylate with hexamethylane diisocyanate. 1,6-dimethacrylethyloxycarbonylaminohexylaminocarbonyloxy (3-methyl) propyloxycarbonylaminohexane Reaction product of a hexamethylene diisocyanate addition product of a 6-hexanolide Addition product of 2,2'-di (4-hydroxycyclohexyl) propane with 2-hydroxyethyl methacrylate.

In the organic used according to the invention Solvents are preferably such based on hydrocarbons, halogenated Hydrocarbons, alcohols, ethers / acetals, ketones, Esters, polyhydric alcohols and their derivatives and Nitrogen compounds.

The hydrocarbon based organic Solvents are advantageously n-pentane, n-hexane, iso-hexane, n-heptane, n-octane, iso-octane, n-decane, 2,2-dimethylbutane, petroleum ether, petroleum benzyl; Ligroin, Gasolin, kerosene, petroleum spirit, petroleum naphtha, 2-pentene, mixed pentenes, cyclohexane, methylcyclohexane, Benzene, toluene, xylene, ethylbenzene, diethylbenzene, iso-propylbenzene, amylbenzene, diamylbenzene, triamylbenzene, Tetraamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, Kohleteer-naphtha, solvent-naphtha, p-Cymol, tetralin, Decalin, dipentene, turpentine, pinene, p-methane, pine oil and camphor oil. N-octane, n-decane, Kerosene, petroleum spirit, petroleum naphtha, ethylbenzene, Diethylbenzene, iso-propylbenzene, amylbenzene, diamylbenzene, Triamylbenzene, tetra-amylbenzene, p-cymene, pinene and p-menthan.

The halogenated organic solvents Hydrocarbon bases are advantageous Methylene chloride, chloroform, carbon tetrachloride, Ethylene chloride, ethylidene chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetra-chloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, vinylidene chloride,  1,2-dichloroethylene, trichlorethylene, Tetrachloroethylene, 1,2,3-trichloropropane, Isopropyl chloride, allyl chloride, 1,2-dichloropropane, Butyl chloride, amyl chloride, dichloropentane, hexyl chloride, 2-ethylhexyl chloride, ethyl bromide, ethylene bromide, Tetrabromoethane, chlorobromoethane, ethylene chlorobromide, Chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, Bromobenzene, o-dribromobenzene, o-chlorotoluene, p-chlorotoluene, alpha-chloro-naphthalene, chlorinated Naphthalene, fluorotrichloro-methane and 1,1,2-trichloro-1,2,2-trifluoroethane. Particularly preferred are 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, Tetrachloroethylene, 1,2,3-trichloropropane, dichloropropane, Hexyl chloride, 2-ethylhexyl chloride, ethylene bromide, Tetrabromethane, chlorobromoethane, ethylene chlorobromide, Chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, Bromobenzene, o-dibromobenzene, o-chlorotoluene and alpha-chloronaphthalene.

Organic solvents based on alcohol are in advantageously methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanoma, secondary butanol, n-amyl alcohol, active amyl alcohol, iso-amyl alcohol, secondary amyl alcohol, 3-pentanol, tertiary amyl alcohol, Fusel oil, n-hexanol, methylamyl alcohol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethyl-hexanol, 3,5,5-trimethyl-hexanol, nonanol, n-decanol, undecanol, trimethylnonyl alcohol, heptadecanol, 2-methyl-cyclohexanol, benzyl alcohol, glycidol, Furfuryl alcohol, tetrahydrofurfuryl alcohol and abietinol, all of which can be used preferentially.  

The organic solvents based on ethers and Acetals are advantageously ethyl ethers, Dichloroethyl ether, isopropyl ether, n-butyl ether, Di-iso-amyl ether, n-hexyl ether, methylphenyl ether, Ethylphenyl ether, n-butylphenyl ether, amylphenyl ether, Cresyl methyl ether, p-tertiary amylphenyl-n-amyl ether, Ethylbenzyl ether, 1,2 propylene oxide, epichlorohydrin, Diglycidyl ether, 1,4-dioxane, furan, furfural, 2-methylfuran, tetrahydrofuran, tetrahydropyran, cineol, Methylal and diethyl acetal, all of which are preferred are.

Organic solvents based on ketone are in advantageously acetone, methyl acetone, Methyl ethyl ketone, methyl n-propyl ketone, Methyl-n-butyl-ketone, methyl-iso-butyl-ketone, Methyl n-amyl ketone, methyl n-hexyl ketone, diethyl ketone, Ethyl n-butyl ketone, di-n-propyl ketone, di-iso-butyl ketone, 2,6,8-trimethylnonanon-4, acton oil, acetonylacetone, Diacetone alcohol, mesityl oxide, isophorone, cyclohexane, Methylcyclohexane, acetophenone and dypnone, all preferred can be used.

Organic ester-based solvents are particularly popular advantageously methyl formate, ethyl formate, Propyl formate, n-butyl formate, iso-butyl formate, Amyl formate, methyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate, n-amyl acetate, iso-amyl acetate, methyl-iso-amyl acetate, Methoxybutyl acetate, secondary hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, Methylcyclohexyl acetate, benzyl acetate, methyl propionate, Ethyl propionate, n-butyl propionate, isoamyl propionate, Methyl butyrate, ethyl butyrate, n-butyl butyrate, Isoamyl butyrate, butyl stearate, methyl acetoacetate, Ethyl acetoacetate, isoamyl iso valerate, methyl lactate, Ethyl lactate, n-butyl lactate, isobutyl lactate,  n-amyl lactate, isoamyl lactate, methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate, Isoamyl benzoate, benzyl benzoate, ethyl cinnamate, Methyl salicylate, ethyl abietate, benzyl abietate, Dioctyl adipate, diethyl oxalate, dibutyl oxalate, Diamyl oxalate, diethyl maloate, dibutyl tartrate, Tributyl citrate, dioctyl sebacate, dimethyl phthalate, Diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate and dioctyl phthalate, all of which can preferably be used.

Organic solvents based on polyvalent Alcohols and their derivatives are advantageous Ethylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether, ethylene glycol diethyl ether, Ethylene glycol monoethyl ether acetate, Ethylene glycol isopropyl ether, Ethylene glycol dibutyl ether, Ethylene glycol monobutyl ether acetate, Ethylene glycol isoamyl ether, Ethylene glycol monophenyl ether, Ethylene glycol monophenyl ether acetate, Ethylene glycol benzyl ether, ethylene glycol monohexyl ether, Methoxymethoxyethanol, ethylene glycol monoacetate, Ethylene glycol diacetate, monoesters of formic acid, diesters of formic acid, monoesters of butyrate, diesters of Butyrate, diester of propionic acid, diethylene glycol, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, Diethylene glycol dimethyl ether, Diethylene glycol methyl ethyl ether, Diethylene glycol diethyl ether, Diethylene glycol dibutyl ether, diethylene glycol acetate,  Triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, triglycol dichloride, Tetraethylene glycol, polyethylene glycol, propylene glycol, Propylene glycol monomethyl ether, Propylene glycol monoethyl ether, Propylene glycol monobutyl ether, 1-butoxyethoxy propanol, Propylene glycol derivatives, propylene chlorohydrin, Dipropylene glycol, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, Tripropylene glycol monomethyl ether, polypropylene glycol, Poly (oxyethylene oxypropylene) derivatives, trimethylene glycol, Butanediol, 1,5-pentane-diol, hexalen-glycol, octylene-glycol, Glycerin, glyceryl monoacetate, glyceryl diacetate, Glyceryl triacetate, glyceryl monobutyrate, glycerin ether, Glycerin-alpha-monochlorohydrin, glycerin-α, γ- dichlorohydrin and 1,2,6-hexanetriol, all preferred can be used.

Organic solvents based on Nitrogen compounds are advantageous Nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, Nitrobenzene, o-nitroanisole, monoethylamine, diethylamine, Triethylamine, isopropylamine, di-isopropylamine, n-butylamine, n-dibutylamine, n-tributylamine, isobutylamine, Di-isobutylamine, secondary butylamine, n-amylamine, diamylamine, Triamylamine, secondary amylamine, secondary hexylamine, 2-ethylbutylamine, n-heptylamine, 2-ethylhexylamine, Dioctylamine, ethylene diamine, propylene diamine, Diethylene triamine, tetraethylene pentamine, diethylaniline, Diethylbenzylamine, monethanolamine, diethanolamine, Triethanolamine, ethyl monoethanolamine, n-butyl monoethanolamine, diethylethanolamine, Ethyl diethanolamine, n-butyl diethanolamine, Di-n-butylethanolamine, isopropanolamine, formamide, N, N-dimethylformamide, acetonitrile, benzonitrile, Acetone-cyanohydrin, pyridine, alpha-picoline, β-picoline,  Gamma-picoline, 2,4-lutidine, 2,6-lutidine, quinoline, Isoquinoline, morpholine and ethyl morpholine, all are preferably used.

These organic solvents are in a mixture or as Solution and by itself or in combination of two or several usable. It must be emphasized that the Invention does not apply to the use of the above organic solvent is limited. According to the invention any organic solvent can be used that the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond is easy to solve, but not in the chemical reactions participates and at a temperature that is lower than the burning temperature, quickly evaporated. If the crowd of porcelain to be built is low or of the Ashing and firing conditions may depend on this organic solvents can be dispensed with. That's the way it is Amount of organic solvents that make up 100 Parts by weight of the photopolymerizable or polymerizable Connection with at least one ethylenically unsaturated Double bond is added, suitably in the range from 0 to 9900 parts by weight.

In the solid or semi-solid used according to the invention organic materials are e.g. B. natural Waxes, petroleum waxes, synthetic waxes Carbon base, pole olefinic synthetic waxes, synthetic waxes based on fat and oil and waxes Alcohol base (with 13 or more carbon atoms).

Among the natural ones that can be used advantageously Waxes include fatty acids, fatty alcohols, Hydrocarbons, triglyceride, saturated fatty acids, Mono acids, polyene acids, unsaturated fatty acids, Hydroxy fatty acids, branched fatty acids and dibasic Acids.  

To the petroleum waxes that can be used advantageously include z. B. paraffin wax, microcrystalline wax, Dandruff paraffin wax, petrolactam wax, natural petroleum jelly and petroleum ceresin.

The synthetic waxes are based on coal z. B. advantageously montan wax, acid wax, Ester wax, partially saponified ester wax and soft wax of the mountain base type. Of the polyolefinic waxes are in advantageously those based on high, medium and low-density polyethylene.

To synthetic waxes based on fats and Oils advantageously include hardened castor oil, 12-hydroxystearic acid, 12-hydroxystearic acid, N- (2-hydroxyethyl) -12-hydroxysteric acid amide, N, N'-ethylene-bis-12-hydroxysteric acid amide, N, N'-hexamethylene-bis-12-hydroxysteric acid, N, N'-xylene-bis-12-hydroxystearic acid amide, 12-hydroxystearic acid methyl, 12-hydroxystearic acid butyl, Propylene glycol mono 12 hydroxystearate, Glycerol monohydroxystearate, Ethylene glycol mono 12 hydroxystearate, 12-hydroxystearic acid lithium, 12-hydroxystearic acid calcium, amide laurate, amide stearate, Amide oleate, erucic acid amide, amide ricinoleate, Special fatty acid amide, N, N'-ethylene-bis-lauric acid amide, N, N'-methylene-bis-stearic acid amide, N, N'-ethylene-bis-stearic acid amide, N, N'-ethylene-bis-oleic acid amide, N, N'-ethylene-bis-behenic acid amide, N, N'-butylene-bis-stearic acid amide, N, N'-hexamethylene-bis-stearic acid amide, N, N'-hexamethylene-bis-oleic acid amide, N, N'-xylene-bis-stearic acid amide, monomethylolamide stearate, Coconut oil fatty acid monoethanol amide,  Diethanolamide stearate, N-oleylstearic acid amide, N-oleyl-oleic acid amide, N-stearylstearic acid amide, N-stearyl-oleic acid amide, N-oleyl-palmitic acid amide, N-stearyl erucic acid amide, N, N′-diolein adipic acid amide, N, N′-distearyl adipic acid amide, N, N'-dioleyl-sebacic acid amide, N, N′-distearyl-sebacic acid amide, N, N′-distearyl-terephthalic acid amide, N, N-distearyl isophthalic acid amide, diheptadedyl ketone, Diundecyl ketone, dodecylamine, tetradecylamine, octadecylamine, Oleylamine, dioctadecylamine, methyl laurate, methyl myristate, Methyl palmitate, methyl stearate, Coconut oil fatty acid methyl, isopropyl myristate, Butyl stearate, octadecyl stearate, oleyl oleate, Glycerol monostearate, glycerol monooleate, Glycerin docosanoate, sorbitan monopalmitate, Sorbitan monostearate, sorbitan tristearate, Sorbitan mono-oleate, propylene glycol monopalmitate, Propylene glycol monostearate, ethylene glycol monostearate and Polyoxyethylene monostearate.

Alcohol-based waxes (with 13 or more Carbon atoms) can e.g. B. in an advantageous manner Use of tridecyl alcohol, Myristyl alcohol, pentadecyl alcohol, cetyl alcohol, Heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol and Aralkyl alcohol. These fixed at normal temperature or semi-solid organic materials are mixed or as Solution by itself or in combination of two or several usable. It should be emphasized that the present Invention does not apply to the use of the above organic materials that solid at normal temperature or are semi-solid, is limited. In other words, it is any organic solid or semi-solid at normal temperature Material usable in the photopolymerizable or polymerizable compound with at least one ethylenic  unsaturated double bond and those given above Solvents is only slightly soluble in the does not participate in chemical reactions at all no incineration residue at the firing temperature of Porcelain leads and has no adverse influence on that has a metal fired porcelain after firing. In Depending on the type of photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond or Ashing or burning conditions can affect this Normal temperature solid or semi-solid organic Materials are dispensed with. So the amount is included Normal temperature solid or semi-solid organic Materials made up of 100 parts by weight of the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond is suitably added in the range of 0 to including 900 parts by weight.

In the photopolymerization initiators used according to the invention can be advantageous Compounds based on alpha-diketone, ketal, Trade antrachinone, thioxanthone and benzoin alkyl ether. So are z. B. as the alpha-diketone compounds in particular advantageously d, 1-camphorquinone, benzyl, diacetal, Acenaphthene quinone, 9,10-phenanthrene quinone and the like usable. However, it is particularly preferred d, 1-camphorquinone and benzyl. The usable ones Ketal compounds are e.g. B. in an advantageous manner Benzyl dimethyl ketal, benzyl diethyl ketal, Benzyl dipropyl ketal, benzyldi (β-phenylethyl) ketal, Benzyldi (2-methoxyethyl) ketal, Benzyl-di (2-ethoxyethyl) ketal, Benzyldi (2-methoxyethoxyethyl) ketal, Benzyldi (2-ethoxyethoxyethyl) ketal,  4,4'-dimethylbenzyldimethylketal, 2,2′-dimethoxybenzyldiethyl-ketal, 4,4'-dichlorobenzyldiethyl ketal and 4,4'-dichlorobenzyl dipropyl ketal. Be particularly preferred however, benzyldimethylketal, benzyldiethyl-ketal, Benzyldi (2-methodyethyl) ketal and 4,4'-dimethylbenzyl dimethyl ketal.

The anthraquinine compounds that can be used are in advantageously anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone and 1-bromoanthraquinone. Especially however, anthraquinone, 1-chloroanthraquinone are preferred and 1,2-benzanthraquinone. It is advantageous the tioxanthone compounds are thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di-isopropylthioxanthone, 2-chloro-7-trifluoromethylthioxanthone, Thioxanthone-10,10-dioxide and Thioxanthone-10-oxide. Especially however, preference is given to thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-di-isopropylthioxanthone.

Advantageously, it can Benzoin alkyl ether compounds around benzoin methyl ether, Benzoin ethyl ether, benzoisopropyl ether, benzoin n-butyl ether and act on benzoin butyl ether. Is particularly preferred however, benzoin butyl ether.

The specified photopolymerization initiators can be used for alone or in combination of two or more be used.  

Of these photo polymerization initiators, those on the Base of alpha diketone, anthraquinone, and thioxanthone Benzoin alkyl ether suitably in the range of including 0.001 part by weight up to 15 Parts by weight per 100 parts by weight of the photopolymerizable Connection with at least one ethylenically unsaturated Double bond added. For quantities below 0.001 parts by weight will not have satisfactory curing properties obtained due to weaker photopolymerization. At It is 15 parts by weight or higher Photopolymerization compound so strong in a yellow tint, which is inherent in the photopolymerization initiators, colored, that when mixing with porcelain there is no perfect shade is achieved.

The ketal compound can suitably range from including 0.001 part by weight up to 20 Parts by weight per 100 parts by weight of the photopolymerizable Connection with at least one ethylenically unsaturated Double bond can be added. At less than 0.001 parts by weight will not have satisfactory curing properties obtained due to weaker photopolymerization. At The solubility is 20 parts by weight or higher Room temperature so high that if the The temperature of the modeling liquid drops Ketal compound fails, making the mixing operation difficult makes.

The reducing agents used according to the invention serve a reduction of a photosensitizer when stimulated is, but no reduction can take place if none Excitation by active energy rays has occurred. The Reducing agents can be primary, secondary or tertiary Amines expressed by the general formula

be in which two or one or none of the groups R, R 'and R '' represents hydrogen. At least one of the radicals R, R ′ and R '' can be identical or different Be a hydrocarbon group. In the Hydrocarbon group can then be an alkyl, Act cycloalkyl or hydroxyalkyl group. Preferably R, R ′ and R ′ ′ represent an alkyl group with 1 to 10 Carbon atoms.

Examples of suitable reducing agents in which at least one of the radicals R, R ′ and R ′ ′ is one Is hydrocarbon group are propylamine, n-butylamine, Pentylamine, hexylamine, dimethylamine, diethylamine, Dipropylamine, di-n-butylamine, dipentylamine, 2-dimethylaminoethanol, trimethylamine, triethylamine, Tri-propylamine, tri-n-butylamine, tripentylamine, Dimethylaminoethyl methacrylate, Diethylaminoethyl methacrylate, triethanolamine and long chain aliphatic amines.

Examples of reducing agents with an aromatic group are N, N'-dimethylaniline, N, N'-dimethyl-p-toluidine, p-tolyldiethanolamine, m-tolyldiethanolamine, N-methyldiphenylamine, 2-dimethylaminobenzoic acid-ethyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid butyl, 4-dimethylaminobenzoic acid-2-ethylhexyl and 4-dimethylaminobenzoic acid isoamyl.

A diamine of the following can also be used Structural formula:

where n is an integer of 2 or more and the groups R, R ', R' 'and R' '', the same or different can be, each a hydrogen atom or one Hydrocarbon group, especially an alkyl group mean. Examples of such reducing agents are Ethylene diamine, trimethylene diamine, tetramethylene diamine, Pentamethylenediamine or hexamethylenediamine or their N-hydrocarbon derivatives, especially N-alkyl derivatives.

Examples of reducing agents in which the element N is a Part of the rings are piperidine or its N-hydrocarbon derivatives. Other suitable Reducing agents are e.g. B. triarylamines, allylthiourea, aromatic sulfinic acid salts and 5-alkyl or 5- Allyl barbituric acid.

Of these reducing agents Dimethylaminoethyl methacrylate, triethanolamine, 4-dimethylaminobenzoic acid methyl and 4-Dimethylaminobenzoesäureethyl preferred. The above mentioned reducing agents can be used alone or in Combination of two or more can be used.

The amount of these reducing agents is preferably to 100 parts by weight of the photopolymerizable compound with at least one ethylenically unsaturated double bond is added in the range of 0.001 inclusive Parts by weight up to 20 parts by weight only. At under 0.001 part by weight is due to an increase in the curing time the weaker photopolymerization. At 20 parts by weight or the storage stability of the modeling liquid becomes higher  so worsened that for dental work under one period of time available for normal interior lighting is pretty much degraded.

The tertiary amines used according to the invention are preferably aromatic tertiary amines. To be favoured e.g. B. N, N'-dimethyl-p-toluidine, N-dimethylaniline, N-methyl-N-β-hydroxyethylaniline, N-di (β-hydroxyethyl) aniline and N-di (β-hydroxyethyl) -p-toluidine, although not is critical. These aromatic tertiary amines can in Mixture or in solution alone or in combination used by two or more and they will be in suitably in the range of 0.05 inclusive Parts by weight with only 5 parts by weight per 100 Parts by weight of the polymerizable compound with at least added to an ethylenically unsaturated double bond. At below 0.05 part by weight, the hardening is due to a poor polymerization so insufficient that the Marginal area cannot be kept in shape. At 5 On the other hand, parts by weight or higher may be the desired one Hue of porcelain from that of aromatic tertiary amines can no longer be distinguished. If one a modeling liquid containing a tertiary amine is used, it is imperative that a organic peroxide is added to the porcelain.

Advantageously, the invention used organic peroxides Benzoyl peroxide, dilauroyl peroxide, 4,4-dichlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide and Methyl ethyl ketone peroxide, although the invention is based on the Use of the peroxides mentioned is not restricted. The Organic peroxides can be used in a mixture or in solution alone or in combination of two or more are used and they are used in a suitable manner Range from 0.1 parts by weight to exclusively 5 parts by weight to 100 parts by weight of porcelain  added when the reactivity of a mixture of 1.5 g Porcelain with 1 ml of the invention Modeling liquid is used as a basis. At less than 0.1 Parts by weight will harden due to a low Reactivity so insufficient that the shape of the Marginal areas cannot be maintained. At 5 On the other hand, parts by weight or higher is a Room temperature reaction so quickly that the for the time available to build up is insufficient is.

The halogen compounds which can be used according to the invention are e.g. B. dilauryl-dimethylammonium chloride, Lauryldimethylbenzylammonium chloride, Benzyltrimethylammonium chloride, Di-isobutylamine hydrochloride, tetra-n-butylammonium chloride, Triethylamine hydrochloride, trimethylamine hydrochloride, Dimethylamine hydrochloride, diethylamine hydrochloride, Methylamine hydrochloride, ethylamine hydrochloride, Isobutylamine hydrochloride, triethanolamine hydrochloride, β-phenylethylamine hydrochloride, acetylcholine chloride, 2-chlorotriethylamine, (2-chloroethyl) trimethylammonium chloride, Tetradecyl-dimethylbenzylammonium chloride, Tetraethylammonium chloride, tetramethylammonium chloride, Tetrabutylammonium bromide, benzyltriethylammonium bromide, Benzyl trimethyl ammonium chloride, tetrabutyl ammonium fluoride and tetrabutyl ammonium iodide, which by itself, in Mixture with each other, can be used.

Of these organic halogen compounds Dilauryldimethylammonium chloride, Lauryl-dimethyl-benzyl-ammonium chloride and Tetra-n-butylammonium chloride is preferred as it is Normal temperatures in amounts of up to about 5 parts by weight in 100 parts by weight of the polymerizable compound with at least one ethylenically unsaturated double bond  are soluble. Other inorganic halogen compounds, their Solubility at normal temperature is lower for be filtered for practical use. Preferably is the amount of these organic halogen compounds, with 100 parts by weight of the polymerizable compound at least one ethylenically unsaturated double bond is added in the range of 0.01 inclusive Parts by weight up to 5 parts by weight only. At less than 0.01 Parts by weight will harden due to the low Reactivity so insufficient that the shape of the Marginal area cannot be maintained. At 5 On the other hand, the liquid is parts by weight or higher not just in a shade that matches the yellow of the organic halogen compound comes close, but the at The reaction taking place at room temperature is so rapid that the length of working time required to set up becomes insufficient. Unless a modeling liquid, the one contains organic halogen compound, is used absolutely necessary that both a pyrimidine trione derivative as well as an organometallic compound to the porcelain is added.

The pyrimidine trione derivatives which can be used according to the invention include z. B. N-cyclohexyl-5-ethylpyrimidine trione, N-benzyl-5-phenylpyrimidine trione, 5-butylpyrimidine trione, 5,5′-diethylpyrimidine trione, 1,3,5-trimethylpyrimidine trione, 2,4,6- (1H, 3H, 5H) pyrimidine trione and 1,3-dimethylpyrimidine trione. Of these is N-Cyclohexyl-5-ethylpyrimidintrione the most outstanding. in the With regard to the reactivity of a mixture of 1.5 g Porcelain with 1.5 ml of the invention Modeling liquid is the amount of these Pyrimidine trione derivatives, 100 parts by weight of porcelain added, preferably in the range of inclusive 0.01 parts by weight to only 10 parts by weight. At under The hardening becomes 0.1 parts by weight due to the low  Reactivity so insufficient that the shape of the Marginal area cannot be maintained. At 10 On the other hand, parts by weight or higher is the reaction Room temperature so quickly that for building time required becomes insufficient.

The organometallic that can be used according to the invention Connections are e.g. B. Acetylacetone copper, copper (II) acetate, copper oleate, acetylacetone-manganese, Manganese naphthenate, octyl acid manganese, Acetyl-acetone-cobalt (III), cobalt-naphthenate, Acetylacetone lithium, zinc naphthenate, acetylacetone nickel, Nickel acetate, acetylacetone aluminum, acetylacetone calcium, Acetylacetone-chrome (III), acetylacetone-iron (III), Sodium naphthenate and rare earth octoate, although the Invention on the use of these compounds is not is limited. Whether alone or in a mixture used, these organometallic compounds should Porcelain added along with the pyrimidine trione derivative will. With regard to the reactivity of a mixture 1.5 g of porcelain with 1 ml of the invention Modeling liquid is the amount of organometallic Compound added to 100 parts by weight of porcelain preferably in the range of 0.001 parts by weight up to only 0.2 parts by weight. At less than 0.001 Parts by weight will harden due to the weak Reactivity so insufficient that the shape of the Marginal area cannot be maintained. At 0.2 Parts by weight or higher, on the other hand, is not the only one running Reaction at room temperature so quickly that for the Build-up time is insufficient, but that Porcelain is also with the hue of organometallic Connection, e.g. B. with blue in the case of acetylacetone copper and reddish brown in the case of acetylacetone iron (III) stained.

Examples

Modeling liquid samples according to the present invention and those for comparison purposes were made and evaluated as in the following experiments 1 to 8 described. Of course, the present invention not limited to these test samples. In Table 1 are the results of the samples according to the invention and the Comparative samples listed. At the end of the table some of the products used to conduct the experiment explained in more detail. Experiments 1 to 8 were as follows carried out.

Experiment 1 - Attachability and Removability from the Plaster Work Model and Deformability

A metal cover not intended for the shoulder area (for the central incisor of the upper jaw) was on made of an anhydrite working model and porcelain (Unibond Margin Porcelain, commercial product from Shofu Co., Ltd.) was with those listed in Table 1 Modeling liquid samples mixed. In Examples 1 to 10, 14 and 15 and Comparative Examples 1 to 4 and 14, the samples were exposed to light from an exposure device (GC Light VL-1, commercial product of GC Dental Industrial Corp.) exposed for 40 s. In Examples 11 to 25 and Comparative Examples 5 to 9 and 13 was a 30 s long condensation with warm air of about 80 ° C from one Condenser (GC Ultra Condenser UL-1, commercial product of the GC Dental Industrial Corp.), and in the Comparative Examples 10 and 11 became a condensation with made the same condenser. In Comparative Example 12 1 part by weight of wax (plastodent (orange), Commercial product from Degussa Comp.) Mixed with 6 Parts by weight of porcelain (Unibond Margin Porcelain, Commercial product of Shofu Co., Ltd.) while using a Melted gas burner  were. The marginal areas formed in this way were attached to or by the anhydrite working model removed to see if the shapes of the Porcelain samples were retained. It should be noted that in Examples 19 to 21 and the Comparative Examples 6 and 7, in which the invention Modeling liquids N, N'-dimethyl-p-toluidine as that tertiary amine contained 0.25 parts by weight of benzoyl peroxide as the organic peroxide previously in 100 parts by weight of Porcelain (Unibond Margin Porcelain, commercial product Shofu Co., Ltd.) with the help of a mortar; and that in Examples 22 to 25 and Comparative Examples 8 to 9, in which the inventive Modeling liquids the organic halogen compound contained 0.2 parts by weight N-Cyclohexyl-5-ethyl-pyrimidintrione as that Pyrimidine trione derivative and 0.1 part by weight Acetylacetone copper as the organometallic compound previously in 100 parts by weight of the porcelain (Unibond Margin Porcelain, commercial product of Shofu Co., Ltd.) with the help a mortar had been incorporated.

Experiment 2 - viscosity

In all examples and comparative examples with one exception of Comparative Example 12 were viscosities in one room of constant temperature / humidity, which at 23 ° C ± 0.5 ° C and at a relative humidity of 50% ± 5% held and with red light (which is an average Light intensity of about 50 Lx) was illuminated with Using a viscometer (DVL-B type digital viscometer, Commercial product of Tokyo Keiki K.K.) measured. From a Preliminary tests showed that the maximum (limit range) Viscosity at which Prozellan could be condensed was about 0.1 Pa · s at 23 ° C. As a result Viscosity values below 0.1 Pa · s classified as "good" (which means porcelain could be condensed) and Viscosity values  of higher than 0.1 Pa · s were classified as "bad" (which means that porcelain could not be condensed).

Experiment 3 - curing properties

A metal cover that does not affect the shoulder area (for the central incisor of the upper jaw made and porcelain (Unibond Margin Porcelain, Commercial product of Shofu K.K.) was with the Modeling liquid according to the present invention and to Mixed for comparison purposes. After hardening among the same conditions as given in Experiment 1 the degree of hardening of the samples is determined by using a Plastic spatulas have been lightly touched.

Experiment 4 - state after ashing and burning

Test disc pieces each 15 mm in diameter and 2 mm Thicknesses were previously made with porcelain (GC Ceramibond E58, commercial product of GC Toshi Kogyo Corporation). In all examples and comparative examples with the exception of Comparative Example 12, the test disks were on a of their pages with individual layers of Modeling liquid samples with the help of a brush coated. Then a mixture of 0.15 g Porcelain (GC Ceramibond E58) with 0.1 ml each Modeling liquid sample over each test disc in one About 1 mm thick with the help of an exclusive brush built up. In Comparative Example 12, 6 parts by weight Porcelain (GC Ceramibond E58) with 1 part by weight of wax (Plastodent (orange), commercial product from Degussa K.K.), mixed while being melted with a gas burner and the mixture was made in the same manner as above described, built.  

For ashing and burning, each was made in this way samples obtained previously dried at 150 ° C for 5 min, then heated to 600 ° C for 1 min and under one reduced pressure of 730 mmHg from 600 ° C to 830 ° C at heated to a heating rate of 60 ° C per min, and finally up to 830 ° C for 1 min using a Oven (Porcelain Furnace KDF Master Spirit 120, Commercial product of thinking K.K.). To the results the samples were visually inspected for Blackening due to carbon residues, cracking, Change in hue and the like. It should be noted that in Examples 18 to 21 and the Comparative Examples 6 and 7, in which the invention Modeling liquids N, N'-dimethyl-p-toluidine as that tertiary amine contained 0.25 parts by weight of benzoyl peroxide as the organic peroxide previously in 100 parts by weight of porcelain (GC Ceramibond E58) was added using a mortar; and that in Examples 22 to 25 and Comparative Examples 8 to 9, in which the invention Modeling liquids the organic halogen compound contained 0.2 parts by weight N-Cyclohexyl-5-ethyl-pyrimidintrione as that Pyrimidine trione derivative and 0.01 part by weight of acetylacetone copper than the organometallic compound previously in 100% by weight Porcelain (GC Ceramibond E58) using a mortar were incorporated.

Experiment 5 - Color shades of the modeling liquid before mixing with porcelain

To make a visual determination of the Color shades of the modeling liquid samples according to the invention to be able to make, the color of the same before Mix visually examined with porcelain, about 1 ml each sample was dropped into a well in a Test range (G-CERA Pallet O (dry), commercial product of GC Toshi Kogyo Corp.) introduced under a Standard light source C (designation according to CIE Commission International de l'Eclairage) looked white. Colorless and  transparent tones were found and rated as "good" designated.

Experiment 6 - refractive index

In all examples and comparative examples with the exception of Comparative Example 12, the refractive indices in a chamber with constant temperature / humidity, which at 23 ° C ± 0.5 ° C and a relative humidity of 50% ± 5% was kept with an accurate refractometer (Abbe Refractometer type 3, commercial product from Atago K.K.) measured. In previous experiments it was found that due to the fact that the refractive index of Porcelain is 1.47-1.50 which Modeling fluids are visually in accordance with Porcelain if it has a refractive index of 1.4-1.6 to have.

Experiment 7 - Color reproducibility when mixing with porcelain (GC Ceramibond M67, commercial product from GC Toshi Corp.)

Porcelain (GC Ceramibond M67) was used for comparison the modeling liquid samples according to the invention mixed. Then the shades of the mixtures were made before Exposure to curing, drying and exposure Heating under a standard light source C compared to those of the fired porcelain from GC Ceramibond M67 with pure water. The assessment is "good" if the shades of the tested mixtures visually in There was agreement with the porcelain from GC Ceramibond M67 with pure water.

Experiment 8 - time available for dental work

About 1 ml of each of the invention Modeling liquid samples were added dropwise Comparative purposes in a well in a test palette G-CERA Pallet O (dry), commercial product from GC Toshi Kogyo  Corp., and then in a chamber with a constant temperature / humidity at 23 ° C ± 0.5 ° C and a relative humidity of 50% ± 5% below usual interior lighting (about 300 Lx) was held, 5 h left for longer or longer. It was determined whether the samples were too hardened for use.  

Table 1

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Footnotes to Table 1
(NB 1) When modeling liquids containing N, N′-dimethyl-p-toluidine were used, use was made of 0.25 part by weight of benzoyl peroxide as organic peroxide, which had previously been mixed with a mortar in 100 parts by weight. Parts of a porcelain material of the type specified under "Rating information" were incorporated.
(NB 2) When modeling liquids containing dilaurylmethylammonium chloride were used, use was made of 0.2 part by weight of N-cyclohexyl-5-ethylpyrimidine trione as a pyrimidine trione derivative and 0.01 part by weight of acetylacetone copper as an organometallic compound which were previously incorporated with the aid of a mortar into 100 parts by weight of a porcelain material of the type specified under "evaluation information".

Explanations of the commercial products used:

• - Unibond Margin Porcelain from Shofu Co. Ltd .:
  Porcelain intended for the marginal part of metal surfaces, for example with the following composition:
  58.89 SiO₂, 17.70 Al₂O₃, 1.20 CuO, 0.02 MgO, 5.90 Na₂O, 11.42 K₂O, 3.62 B₂O₃
• - GC Ceramibond E58 and GC Ceramibond M67 from GC Toshi Kogyo Corp .:
  Enamel or modifying color porcelain for metal surfaces with the colors represented by E58 or M67 and with the following composition, for example:
  62.32 SiO₂, 17.18 Al₂O₃, 0.14 CuO, 0.01 MgO, 7.06 Na₂O, 10.38 K₂O, 1.55 B₂O₃
• - G-CERA Pallet O (dry) from GC Toshi Kogyo Corp .:
  Test range that is suitable for mixing opaque porcelain with water.
• - Margin Separator from Ishifuku Kinzoku Co. Ltd .:
  Release agent between porcelain and plaster.

The modeling liquid samples of Examples 1 to 4 each contain the photopolymerizable compound at least one ethylenically unsaturated double bond, a photopolymerization initiator, a reducing agent and a polymerization inhibitor.

Examples 5 to 7 each contain the photopolymerizable compound with at least one ethylenically unsaturated double bond, an organic Solvent, a photopolymerization initiator Reducing agent and a polymerization inhibitor.

Examples 8 to 10 each contain the photopolymerizable compound with at least one ethylenically unsaturated double bond, an organic Solvent, a solid or at normal temperature semi-solid organic material, a photopolymerization initiator, a reducing agent and one Polymerization inhibitor.

Examples 11 to 13 each contain the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond, an organic solvent, one at normal temperature solid or semi-solid organic material and one Polymerization inhibitor.

Examples 14 to 15 each contain the photopolymerizable compound with at least one ethylenically unsaturated double bond, one at Normal temperature solid or semi-solid material, one Photopolymerization initiator, a reducing agent and one Polymerization inhibitor.  

Example 16 contains the photopolymerizable or polymerizable compound with at least one ethylenic unsaturated double bond, a solid at normal temperature or semi-solid organic material and one Polymerization inhibitor.

Example 17 contains the organic solvent and a Normal temperature solid or semi-solid organic material.

Examples 18 to 21 each contain the polymerizable compound with at least one ethylenic unsaturated double bond and N, N'-dimethyl-p-toluidine as tertiary amine, which allowed a reaction with the organic peroxide that the porcelain for hardening was admitted.

Examples 22 to 25 each contain the polymerizable compound with at least one ethylenic unsaturated double bond and Dilauryldimethylammonium chloride as the organic Halogen compound that enables reaction with the Pyrimidine trione derivative and the organometallic compound, added to the porcelain for hardening.

The modeling liquids according to Examples 1 to 10 and 14 to 15 are hardened when exposed to light whereas the modeling liquids according to the examples 11 to 13 and 16 to 17 are hardened in that the Normal temperature solid or semi-solid organic material is precipitated by the volatilization of the organic Solvent or the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond.  

The modeling liquids according to Examples 8 to 25 are hardened by implementing the contained therein Polymerization promoter with the one contained in the porcelain Polymerization initiator without being exposed to the light will. In Examples 3 to 4 the amount is introduced photopolymerization initiator lower while in example 14 the amount of incorporated Photopolymerization initiator is larger. In example 10 is the amount of reducing agent used is lower, while in Example 15 the amount of contained therein Reducing agent is larger. In example 19 the amount is incorporated tertiary amine less while in the example 20 the amount of tertiary amine introduced is greater. in the Example 23 is the amount of organic added Halogen compound less, while in Example 22 the amount organic halogen compound introduced is larger. However, since the components used in these examples all within those specified in the claims Ranges and the amounts applied are less or are greater than the mean values of the range, none occurs Problem with the properties found. in the Example 17 no polymerization inhibitor is added because of the absence of a photopolymerizable or polymerizable compound with at least one ethylenically unsaturated double bond. All Modeling liquids according to the invention prove to be satisfactory in terms of the properties found.

Comparative Examples 1 to 4 were carried out in such a way that the amounts of photopolymerization initiator and Reducers could be set during the Comparative Examples 6 to 9 were carried out so that the Amounts of tertiary amine and organic halogen compound could be defined. In Comparative Example 1 Amount of photo polymerization initiator less than that in lower limit defined in the examples, while in Comparative Example 2 the amount of Photopolymerization initiator larger than that in the claims  defined upper limit. In Comparative Example 3 is the amount of reducing agent less than that in the claims defined lower limit, while in Comparative Example 4 the Amount of reducing agent is greater than that in the Defined upper limit. If the amounts at Initiator and reducing agent are less than the lower ones Limits, the hardening by exposure to light is like this bad that the applicability and removability of the Porcelain on or from the plaster work model becomes weaker while reducing its deformability. are the amounts are larger than the upper limits on the other hand, the modeling liquids before mixing a shade of yellow with porcelain. Furthermore, under one usual indoor lighting the reactivity of the Modeling liquids with light so high that they Mix with porcelain immediately and begin to harden therefore cannot be used.

In Comparative Example 6, the amount of tertiary amine lower than the lower limit defined in the claims, while in Comparative Example 7 the amount of tertiary amine is greater than the upper limit defined in the claims. In Comparative Example 8, the amount of organic Halogen compound less than that in the claims defined lower limit, while in Comparative Example 9 the Amount of organic halogen compound is larger than that in upper limit defined in the claims. If the amounts at Halogen compound and amine are smaller than the lower ones Limits become so bad when exposed to light that that the attachment or detachment of the porcelain to one or from becoming weaker under a plaster work model simultaneous decrease in its deformability. Are the Quantities larger than the upper limits, so take Modeling liquids before mixing with porcelain a shade of yellow. Furthermore, in an environment of 23 ° C Reactivity of the modeling liquids with light so high that she  begin to harden immediately when mixed with porcelain and therefore cannot be used.

In Comparative Example 5, the modeling liquid only exists from the photopolymerizable or polymerizable Connection with at least one ethylenically unsaturated Double bond and the organic solvent and them contains no hardening K 14684 00070 552 001000280000000200012000285911457300040 0002004039382 00004 14565 component at all. It is therefore a condensation due to the low Viscosity possible, but no porcelain can improved attachability or detachability from Preserved plaster work model and better deformability will.

In comparative examples 10 and 11, pure water, which was generally used according to the state of the art, used. In comparative example 10 there is no release agent attached to the plaster model, while in Comparative Example 11 a separator (margin Separator, commercial product from Ishifuku Kinzoku Co., Ltd.) is used. In Comparative Example 10, since that Building porcelain tends to deposit on the plaster model, even experts neither attach this to the model nor detach still deform. In example 11 it can agree Experts succeed in attaching the porcelain to or Carefully deform the detachment from the plaster model, as that Peeling agent is applied to it, but these too often unsuccessful. In any case, they are Modeling fluids considerable in the refractive index different from water (1.327 at 23 ° C). It is therefore impossible to predict in advance which shades the Accept modeling liquids if they are mixed with porcelain (GC Ceramibond M67, commercial product of GC Toshi Kogyo Corp.) be mixed.

In comparative example 12, 1 part by weight of wax (plastodent orange wax, commercial product of Degussa-Comp.) with one  Melted gas burner and with 6 parts by weight of porcelain (GC Ceramibond M67) mixed. It is absolutely impossible To predict the hue of the porcelain after sintering because the orange tone of the wax is reflected. Furthermore, since the wax is not condensed, but a lot of carbon generated, carbon are formed, the inside of a Porcelain oven contaminated and damage the oven can if the porcelain has an ashing reaction is subjected. Add to that the wax, even if it is melted with a gas burner and the porcelain is incorporated when cooling to room temperature due to its high crystallinity immediately solidified and thus is not applicable. The available for dental work standing period is therefore only 1 to 2 minutes if the The total amount of porcelain is about 2 g. The wax is therefore very difficult to handle.

In Comparative Example 13, a thermosetting Modeling liquid (SM Liquid Duceram, commercial product of Ducera Co., Ltd.) used. Because this liquid does this is determined, heated and by hot air from one Drying device tends to harden it deposit on the plaster model in the course of the hardening process, see above that their detachability from the plaster model is greatly reduced. It is also absolutely impossible to estimate in advance what color this liquid takes on when it comes with Porcelain (GC Ceramibond M67) is mixed and sintered, because their refractive index (1.3381 at 23 ° C) is very close to that of water.

In comparative example 14, a highly viscous Porcelain liquid (Spectrum Shoulder Porcelain VLC Medium, commercial product of Dentsply Co., Ltd.) applied. Although this liquid has good curing properties, it has a high viscosity of 0.9799 Pa · s, so that it cannot be condensed, which makes it impossible to remove excess shares. Soot remains after ashing and  the burning. Since the liquid like a lot of catalyst Photo polymerization initiators and reducing agents contains, it takes on a shade of yellow and it is practical impossible to predict what color it will be assumes when mixed with GC Ceramibond M67 and after is burned.

The effects of the modeling liquid according to the invention for Dental porcelain will now be shown.

(To prevent the metallic color of the cervical periphery of a metallic cover or frame part from being seen through or seen, porcelain is built using marginal porcelain technology, but without attaching the metal cover or frame part to the cervical periphery.)
1. After mixing with porcelain, the modeling liquid for dental porcelain according to the invention is built up on the cervical periphery and then exposed to light or reacted with the organic peroxide or pyrimidine trione derivative and the organometallic compound contained in the porcelain, or optionally the organic solvent is evaporated off . The porcelain hardened in this way is temporarily bound to the metal cover or frame part and is therefore easily removable from a plaster work model. Laborious dental work, such as building and sintering porcelain on a refractory model, can thus be dispensed with. The amount of time available for dental work can therefore be greatly reduced with improvements in terms of fit.
2. The porcelain construction on a metal covering or frame part provided with a platinum foil is laborious and time-consuming, does not allow the cervical periphery to be kept in good condition and causes considerable costs because of the high price of the platinum foil. The modeling liquid for dental porcelain according to the invention is much cheaper than the platinum foil and its price is approximately in the order of one tenth to several tenths or one tenth to several hundredths and thus leads to cost savings.
3. When porcelain is condensed with water to remove it, as is usually the case, the shape of the cervical periphery is maintained only by wet bonding, so that it becomes out of shape when it experiences only slight vibration or impact. This procedure cannot therefore be applied to bridges where a large number of counter bearing teeth are used. This method also requires skill. After mixing with porcelain and building up in place, the modeling liquid for dental porcelain according to the present invention is hardened by being exposed to light or being reacted with the organic peroxide or the pyrimidine trione derivative and the organometallic compound contained in the porcelain. The porcelain can therefore be removed from a plaster work model so easily that the shape of the cervical periphery can be retained to the end. This technique makes it possible to immediately remove the porcelain built up on the cervical periphery from the plaster work model without any workmanship, which is why it can also be easily used for the production of bridges using a large number of counter bearing teeth. If porcelain is condensed with water to remove it, as is usually the case, it is necessary that a hydrophobic release material or surface hardening agent be applied to the cervical periphery of the plaster work model for easy removal of the condensed porcelain. The fit of the porcelain on the cervical periphery therefore deteriorates due to the thickness of the release material or surface hardening material applied. After mixing with porcelain and building up in place, the modeling liquid for dental porcelain according to the invention is hardened by light exposure and reaction with the organic peroxide or with pyrimidine trione derivative and the organometallic compound contained in the porcelain. The porcelain can therefore be easily removed from the plaster work model without the need to use a hydrophobic release material or surface hardening material. As a result, the accuracy of fit of the cervical periphery of the porcelain burned to a metal on the plaster work model or even on a patient's abutment teeth is greatly improved.
4. The modeling liquid for dental porcelain according to the invention has a sufficient viscosity for condensation after mixing with the porcelain and building up on the spot and before exposure to light or reaction with the organic peroxide or the pyrimidine trione derivative and the organometallic compound which are contained in the porcelain . If there is an excess of modeling liquid, this can be removed with paper towels or gauze pads. According to the invention the solid or semi-solid organic material at normal temperature is diluted with the organic solvent. After the construction, the porcelain is heated to a temperature higher than the boiling point of the organic solvent only to volatilize the organic solvent, whereby the shape of the porcelain can be obtained with a small amount of the wax residue. Subsequent ashing can also improve the fired porcelain because of the small amount of wax residue present. Therefore, there is no fear that a lot of carbon can be generated at the time of ashing, which leads to contamination or malfunction of the furnace.
5. The modeling liquid for dental porcelain according to the invention is not hardened by heat and the liquid is not softened by heat or caused to flow by air pressure, so that the porcelain material does not flow into the metallic cover or frame part. As a result, the accuracy of fit of the porcelain on the plaster model on the cervical periphery of the metal cover or frame part or even on the counter bearing teeth of a patient is greatly improved.
6. The modeling liquid for dental porcelain according to the invention can be condensed well. Furthermore, it can be sintered with at least one ethylenically unsaturated double bond after removal of an excess proportion of photopolymerizable or polymerizable compound. If the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond has a high viscosity or the photopolymerization reaction or the reaction with the organic peroxide or the pyrimidine trione and the organometallic compound contained in the porcelain is very slow, then it becomes solid at normal temperature or semi-solid organic material and the photopolymerizable and polymerizable compound having at least one ethylenically unsaturated double bond previously dissolved in an organic solvent having a high boiling point. After building up and condensing, the porcelain is heated to remove the solvent mentioned. Since the remaining organic material, which is solid or semi-solid at normal temperature, solidifies, it is possible to maintain the shape of the porcelain as it was built.

(In order to obtain dentures that are as close as possible to the appearance of natural teeth, the porcelain is given special effects using porcelain materials that color internally or externally.)
1. The modeling liquid for dental porcelain according to the invention has a refractive index of 1.4 to 1.6 at 23 ° C., while porcelain has a refractive index of 1.47 to 1.50. This modeling liquid does not undergo a significant change in the refractive index before and after it is exposed to light or reacted with the organic peroxide or the pyrimidine trione derivative and the organometallic compound contained in the porcelain, ie before and after the hardening. Therefore, if some of a number of internally or externally coloring porcelain materials are selected to impart the desired special effect to the porcelain, thereby producing complex color tones, even novices can make a prediction about the color tone of the porcelain after firing. It is therefore possible to avoid such failures that porcelain has to be rebuilt as often as necessary, as is the case when mixing with water, since the color of the porcelain can be estimated in advance. This makes it possible for everyone to bring out the special effects, which previously could only be done by experts. The internally or externally coloring porcelain materials can be hardened in a mixture with the modeling liquid according to the invention by light exposure or reaction with the organic peroxide or the pyrimidine trione derivative and the organometallic compound which are contained in the porcelain. This also makes it possible for anyone to build up or apply porcelain in the desired thickness and to the desired extent. Furthermore, the period of time required for dental work is only one tenth to a few tenths of that which was previously necessary and the inside or outside coloring porcelain materials of the desired colors can be selected exactly. The special effects can therefore be imparted to the porcelain so easily that the prosthesis can be improved in terms of aesthetic appearance while at the same time achieving improvements in quality and work efficiency.
2. The modeling liquid for dental porcelain according to the invention is designed so that it is exposed to light for its hardening or is reacted with the organic peroxide or the pyrimidine trione and the organometallic compound contained in the porcelain. Therefore, if such special effects as the elimination of internal defects including cracking, yellowing and the like, or external defects and insufficient calcification are to be imparted to the porcelain, this can be done with the help of a fine brush to cover up such internal discoloration without being responsible for it special skill is required. As a result, it is possible to impart the special effects to the porcelain with internally or externally coloring porcelain materials of constant quality at any desired time, since neither color mixing nor line thickening or smearing takes place, as is the case when mixing with water.

Claims (28)

1. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a photopolymerizable compound with at least one ethylenically unsaturated double bond,
• (B) a photopolymerization initiator,
• (C) a reducing agent, and
• (D) a polymerization inhibitor.

2. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a photopolymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic solvent,
• (C) a photopolymerization initiator,
• (D) a reducing agent, and
• (E) a polymerization inhibitor.

3. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a photopolymerizable compound with at least one ethylenically unsaturated double bond,
• (B) a solid or semi-solid organic material at normal temperature,
• (C) a photopolymerization initiator,
• (D) a reducing agent, and
• (E) a polymerization inhibitor.

4. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a photopolymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic solvent,
• (C) a solid or semi-solid organic material at normal temperature,
• (D) a photopolymerization initiator,
• (E) a reducing agent, and
• (F) a polymerization inhibitor.

5. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) a tertiary amine, and
• (C) a polymerization inhibitor.

6. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic solvent,
• (C) a tertiary amine, and
• (D) a polymerization inhibitor.

7. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) a solid or semi-solid organic material at normal temperature,
• (C) a tertiary amine, and
• (D) a polymerization inhibitor.

8. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic solvent,
• (C) a solid or semi-solid organic material at normal temperature,
• (D) a tertiary amine, and
• (E) a polymerization inhibitor.

9. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic halogen compound, and
• (C) a polymerization inhibitor.

10. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic solvent,
• (C) an organic halogen compound, and
• (D) a polymerization inhibitor.

11. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) a solid or semi-solid organic material at normal temperature,
• (C) an organic halogen compound, and
• (D) a polymerization inhibitor.

12. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic solvent,
• (C) a solid or semi-solid organic material at normal temperature,
• (D) an organic halogen compound, and
• (E) a polymerization inhibitor.

13. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) an organic solvent,
• (C) a solid or semi-solid organic material at normal temperature, and
• (D) a polymerization initiator.

14. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) a polymerizable compound with at least one ethylenically unsaturated double bond,
• (B) a solid or semi-solid organic material at normal temperature, and
• (C) a polymerization inhibitor.

15. Modeling liquid for use in the construction of dental porcelain, containing:

• (A) an organic solvent,
• (B) a solid or semi-solid organic material at normal temperature.

16. Modeling liquid for dental porcelain according to one of the Claims 1 to 15 having a refractive index of 1.4 up to and including 1.6 at 23 ° C.   17. Modeling liquid for dental porcelain according to one of the Claims 1 to 16 having a viscosity of 0.1 Pa · s or less at 23 ° C. 18. Modeling liquid for dental porcelain according to one of the Claims 1 to 14, 16 and 17, wherein the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated Double bond is a monofunctional methacrylate. 19. Modeling liquid for dental porcelain according to one of the Claims 1 to 14, 16 and 17, wherein the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated Double bond is a polyfunctional methacrylate. 20. Modeling liquid for dental porcelain according to one of the Claims 1 to 14, 16 and 17, wherein the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated Double bond is a monofunctional acrylate. 21. Modeling liquid for dental porcelain according to one of the Claims 1 to 14, 16 and 17, wherein the photopolymerizable or polymerizable compound with at least one ethylenically unsaturated Double bond is a polyfunctional acrylate. 22. Modeling liquid for dental porcelain according to one of the Claims 2, 4, 6, 8, 10, 12, 13 and 15-21, wherein the organic solvents at least one from the group consisting of solvents based on Hydrocarbon, halogenated hydrocarbon, alcohol, Ether, acetal, ketone, ester, polyhydric alcohol and its derivatives, and nitrogen compound.   23. Modeling liquid for dental porcelain according to one of the Claims 3, 4, 7, 8 and 11-22, wherein the at Normal temperature solid or semi-solid organic Material at least one from the group consisting of natural waxes, petroleum waxes, on coal based synthetic waxes, polyolefinic synthetic waxes, based on fats and oils synthetic waxes and alcoholic waxes at 13 or more carbon atoms. 24. Modeling liquid for dental porcelain according to one of the Claims 4 and 16-23, wherein the At least one photopolymerization initiator from the Group consisting of compounds based on alpha-diketone, ketal, anthraquinone, thioxanthone, Is benzoin alkyl ether and their derivatives. 25. Modeling liquid for dental porcelain according to one of the Claims 1-4 and 16-24, wherein the Photo polymerization initiator in the range of including 0.001 part by weight up to 15 Parts by weight per 100 parts by weight of the photopolymerizable Connection with at least one ethylenic unsaturated double bond is present. 26. Modeling liquid for dental porcelain according to one of the Claims 1-4 and 16-25, wherein the reducing agent in the range of 0.001 parts by weight to only 20 parts by weight per 100 parts by weight of photopolymerizable compound with at least one ethylenically unsaturated double bond is present. 27. Modeling liquid for dental porcelain according to one of the Claims 5-8 and 16-23, wherein the tertiary amine in Range from 0.05 parts by weight up to only 5 parts by weight per 100 parts by weight of  polymerizable compound with at least one ethylenically unsaturated double bond is present. 28. Modeling liquid for dental porcelain according to one of the Claims 9-12 and 16-23, wherein the organic Halogen compound in the range of 0.01 inclusive Parts by weight up to 5 parts by weight per 100 Parts by weight of the polymerizable compound at least one ethylenically unsaturated double bond is present.