CH682214A5 - - Google Patents

Description

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

Description

The present invention relates to a modeling liquid for dental porcelain used for the preparation of various prostheses composed partially or entirely of porcelain in the work of crowns and bridges, while taking into account the shape of the teeth, their harmony with the other teeth, occlusion and chewing, their aesthetic appearance, their influence on the periodontium, the good progress of healing, their dynamic properties, their ease of preparation, improvements with regard to quality and reliability and lower production costs.

As for crown and bridge work, dust jacket crowns, inlays and onlays, they are increasingly made of ceramics, such as wettable ceramics and sintered all-purpose ceramics. In addition to techniques employing wettable ceramics made by molding, the refractory model and platinum sheet methods have so far been well used. The refractory model process involves the manufacture of a tooth mold made of a refractory molded material developed exclusively for mounting and firing porcelain, mounting and firing porcelain on the tooth mold, removing the tooth mold from the refractory model and finally rest the porcelain on the tooth mold to correct the shape, while the platinum sheet process involves pressing a platinum sheet of about 25 µm on a tooth model, mounting and the firing of all the porcelain parts including a perignatic part on the tooth mold and the removal of the porcelain located on the internal face of the crown after completion of all dental work, such as polishing and before cementation . On the other hand, in addition to these methods, the mounting and firing of porcelain on a metal screed is also a process of great importance when considering the shape of the teeth, their harmony with the teeth in place , occlusion and chewing, their aesthetic aspect, their influence on the periodontium, the good evolution of healing, their dynamic properties and their durability etc. If the crown or bridge work is performed with this type of metal coping, the dynamic properties of the prosthesis are then improved, a reduction of natural teeth or supporting teeth being eliminated. This allows the prosthesis to have a good influence on the periodontium and to be in harmony with the other teeth, so that the oral cavity is healthy in its entirety. Other possibilities: such aesthetic improvements can be obtained by bonding or adding porcelain to resin and, more particularly, hard resin.

However, although bonding or adding porcelain to hard resin can be easily carried out in a short time and at a reasonable cost, this operation has certain drawbacks, as described more precisely below:

1. this material is very inferior to porcelain in terms of wear resistance,

2. this material absorbs a lot of water and is so chemically unstable that it will likely discolor or stain in the oral cavity;

3. the aesthetic appearance of this material is far from that of natural teeth; and

4. this material has poor adhesion to a metal screed and it is also characterized by an insufficient duration.

For these reasons, there has recently been an increase in the demand for prostheses having an improved aesthetic appearance and more particularly a high quality. Thus, prostheses used in the work of crowns and bridges and comprising porcelain mounted and fired on a metal screed were used intensively in dentistry.

For this type of prosthesis, a metal cap is first fixed on a tooth mold. Next, opaque dentin and enameled porcelain are basically applied to the tooth mold in this order from its cervical edge using a brush or spatula directly. Each porcelain material is thus made, we proceed to the condensation operation to remove moisture and cooking, the metal cap being fixed to the tooth mold. However, the problems encountered in this area are due to the fact that, because it rests on the metal cover, the porcelain cannot be completely assembled and that it contracts during cooking. As a result, the porcelain deposited on the cervical edge is of insufficient thickness, so that the metallic color of the screed shines through it. In addition, the metal yoke is often exposed to view in the region of the cervical margin due to a gingival recession extending over a long period of time into the oral cavity. These phenomena not only cause a considerable lack of naturalness from the aesthetic point of view, but they also imply gingival discoloration or periodontitis. In order to be able to solve such problems, use has recently been made of a marginal porcelain technique in which no metal part is provided in the shoulder area of the cervical edge of the metal cap. With this method in which porcelain materials are applied to an area not covered with metal, it is possible to solve the problems caused by the fact that the color of the metallic screed is visible through the porcelain and that the metallic screed is exposed to view. However, to achieve this end, some skill is required, due to the considerable technical difficulties encountered in performing this process from the conventional techniques available. For example, considerable skill is required to condense each porcelain material each time it is mixed with water and then to remove it2

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

ment of these porcelain materials from the tooth impression of the working model without damaging the part which is in the region not lined with metal. In order to achieve this, different measures were taken and different methods were used to allow easy separation of the porcelain materials from the tooth model. The first method, called the refractory model method, as already indicated above, involves mounting and baking the cervical edge on a tooth model formed from refractory material. The second method, called the platinum sheet method, as also mentioned above, involves pressing a platinum sheet on the cervical edge and mounting the porcelain thereon, followed by a removal operation and cooking. The third method is a method called method of manufacturing a water-repellent model according to which the porcelain is mounted on a tooth model formed of epoxy resin or on a plaster working model on which water-repellent materials or surface treatment materials have been applied to make it water repellent. Porcelain mixed with water moistens the water-repellent tooth model so little that its removal is much easier than with conventional plaster working models. The 4th method consists of mixing an oven-dried wax without melted residue with porcelain, immediately mounting this mixture of wax on the shoulder and cooling and removing this wax from the model by plaster together with the metal screed. Generally, the wax is mixed with porcelain in a weight ratio of one to six or seven. The 5th method uses an exclusive modeling liquid treated with hot air, said modeling liquid being subjected to a reaction of treatment by heater. Since this modeling liquid cannot be treated at room temperature, it is mixed with porcelain and this mixture is treated with hot air and then removed from the plaster working model. The 6th method is based on a treatment by exposure to light. Although based on the same principle as that used in the 5th method, it is characterized by the use of light instead of heat.

Let us now turn to certain particular effects of the porcelain used until now and having a relationship with the present invention. As is normal, natural teeth are subject to various changes depending on their age and their intraoral environment. In recent years, there has therefore been a growing demand for dental prostheses that are individually adapted to different patients and as close as possible to natural teeth. This specifically resulted in a dental technique specially adapted and used to provide each patient with personal characteristics in terms of color, shape and environment. For example:

1. the cervical edge effect for the reproduction of the dentine of the root or the gingival color effect intended to achieve a certain harmony with the gum;

2. the effect of dentin by reproducing insufficient calcification, structural deficiency or differences in the thickness of the dentin core or the enamel layer;

3. the cutting effect to reproduce a lack of calcification and internal stains; and

4. the surface coloring effect to reproduce spots naturally caused on the teeth by tobacco, food, drink, cavities or other reasons.

In order to obtain such effects, the coloring can be carried out with a porcelain material of the desired color after having practically completed the assembly of a material based on porcelain or during this assembly. For example, the porcelain material reserved exclusively for internal coloring, can be included in the porcelain material and cut according to the line or points of the desired shape, during assembly or layered over the porcelain material after its assembly by providing personalized characteristics to the teeth of each patient. Then, the porcelain material can be pre-dried for 5-10 minutes, then heated in the oven at a temperature ranging from about 600 ° C to about 900 ° C, according to a heating sequence of 50-60 ° C per minute .

Conventional porcelain mounting techniques encounter certain problems and are generally subdivided into two types of cases.

First case: Without having a metal cap in the region of the cervical edge, a porcelain is mounted according to the marginal porcelain technique, while ensuring that the color is not visible by transparency; and

Second case: in order to obtain dental prostheses as close as possible to natural teeth, the specific effects are added to it thanks to a porcelain material intended to bring an internal or external color.

The explanation of the problems relating to these different cases is given below. Regarding the first case:

1. The refractory model process requires placing the porcelain of the plaster working model on the refractory model and requires about three hours more than the direct process, since considerable time is required for the operation of impression and drying and that very careful dental work is necessary. Consequently, an impression of less precision results in a reduction in the precision in the adaptation.

2. The platinum sheet process, in which a platinum sheet is pressed onto the cervical edge of the plaster working model, offers lower fitting precision due to the thickness of the

3

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

platinum sheet. Intended to be removed or discarded after use, the platinum foil gives rise to a considerable increase in costs.

3. The process in which porcelain is applied directly using a brush or spatula with condensation, cannot be used without considerable skill, since the shape of the cervical edge tends to be 'deviate from the model. This method is also not usable for a bridge prosthesis using a certain number of supporting teeth. It is also necessary to allow the condensed porcelain to be easily removed from the plaster working model by placing on its cervical edge a layer of water-repellent or surface treatment materials. In this case, however, the adaptation of the porcelain to the cervical edge is more difficult, because of the thickness of the layer of water-repellent or surface treatment material.

4. With the process in which a mixture of melted wax with porcelain is mounted, cooled and removed from a wax working model, the wax should be melted as many times as necessary because it trades to be treated during assembly, since the crystallinity of the wax is very high. As the wax is unable to be condensed, the porcelain contracts significantly. When large quantities of wax are used, a large quantity of carbon is produced which contaminates the oven or causes it to deteriorate.

5. In the process in which the porcelain is mounted with a heating processable liquid, the mounted porcelain which is treated with hot air, is cooled by heating and introduced by compressed air into the metal screed where it starts to be treated. This type of porcelain should preferably be removed before or after firing. However, it is impossible to remove it completely since the adaptation of the metal yoke becomes worse. This is due to the process in which a mixture of melted wax with porcelain is mounted, cooled and removed from the plaster working model.

6. The process in which the porcelain is mounted with a light-treatable modeling liquid is now commercially available. However, in the case of using this method, the porcelain cannot be condensed at all. After firing, there is in most cases carbon residues which add to the porcelain a gray or possibly black coloring, depending on the firing conditions. This process is therefore not applicable at all to porcelain fired on metal when great importance is attached to the aesthetic appearance.

Regarding the second case:

1. In order to add special effects to porcelain in which complex color tones are to be expressed, porcelain materials with multiple internal and external colorings are generally mixed with dentin or glazed porcelain, depending on Requirement. In this case, we even used water as a modeling liquid. And although a mixture with internally or externally colored porcelain water was assembled and well condensed, it was however impossible to make a precise estimate of the shade of color which would emerge after firing. This is due to the fact that the refractive index (1.3327 at 23 ° C) of water is very different from that (1.47-1.50) of porcelain. This is why porcelains are often also colored with a dye. In this case, it is impossible to estimate the proper color of the porcelain in advance, unless the dye is heated. The realization of such special effects which is often obtained thanks to the sixth sense of dental technicians, gives rise to very clumsy results on the part of novices and can be carried out cHnically only by a few specialists. Even when porcelain can be successfully made from the porcelain material of internal or external coloring chosen, the desired color tone is not always finally obtained after firing. In this case, the porcelain must be removed, in order to mount and cook a new porcelain having an internal or external porcelain coloring material of a different color tone. The color tone and the quality of the prosthesis after curing are deteriorated and the repetition of such operations is very costly in time.

2. In order to reproduce internal and external stains caused by cracks, yellowing, etc. and by insufficient calcification, special effect colors are applied to the porcelain by means of a fine brush. In this case, however, the laminated structure of several porcelain materials for internal coloring or the application of a porcelain material for external coloring gives rise to a mixture of colors. It also happens that the line thus drawn is made so thick that it becomes blurred. Even if coloring porcelain materials are applied over a limited area, they tend to drip and spread on the porcelain. Thus, porcelain materials with internal or external coloring cannot be used without referring to specialists. It is also not possible to reproduce the special effects requested with a certain quality at the desired time.

As a result of extensive and intensive studies carried out with a view to solving the above problems, the authors of the invention have discovered that these problems can be successfully solved by developing a modeling liquid as defined in claim 1 .

When mixed with porcelain, this liquid can be cooked on a metal and sintered without leaving any incineration residue and causing no change in the color tone desired for the porcelain. An explanation, illustrated with examples, of how to solve the above problems is given below.

(In order to prevent the metallic color of the cervical edge of a metallic screed from being

4

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

seen by transparency or exposed to view, porcelains are mounted with the marginal porcelain technique, but without applying the metal screed to the cervical edge).

1. In order to mount porcelain directly on a metal screed without a shoulder instead of using a refractory material, the porcelain mounted in a certain form on the cervical edge must be kept in the desired form. After having been mixed with the porcelain, the modeling liquid for dental porcelain referring to the present invention is mounted on the cervical edge and then exposed to light, or else it reacts with organic peroxide or a pyrimidinetrione derivative and an organo-metallic compound contained in porcelain. The porcelain thus treated is temporarily bonded with the metal screed and is thus easily removed from a plaster working model, so that its shape, as it was mounted on the cervical edge, can be retained until the end. Thus, delicate dental operations, such as mounting and sintering porcelain on a refractory model, can be performed. As a result, the time used, including the time spent removing the porcelain from the plaster working model and placing it on the refractory model, can be considerably reduced with, in addition, improvements in the precision of assembly.

2. The mounting of porcelain on a metal screed without shoulder covered with a platinum sheet, is delicate and costly in time, does not keep the cervical edge in good condition and involves considerable expenditure due to the cost of the sheet of platinum. The modeling liquid for dental porcelain relating to the present invention is much less expensive than the platinum sheet, say in proportions varying between one tenth and a few tenths and one hundredth and a few hundredths.

3. When porcelains are condensed with water in order to be removed, as is conventionally done, the shape of the cervical edge is preserved thus, only in the case of a wet connection, so that it loses its shape, even if it is subjected to slight vibrations or impacts. Thus, this cannot be applied to a bridge work using several support teeth. Five to ten years of experience are necessary to master this method. After having been mixed with porcelains and put in place, the modeling liquid for dental porcelain relating to the present invention is treated by exposure to light or by reaction with organic peroxide or a pyrimidinetrione derivative and an organic compound. metallic content in porcelain. Thus, porcelain can be removed so easily from a plaster working model that the shape of the cervical edge can be retained until the end. This technique makes it possible to immediately remove the porcelain mounted on the cervical edge of the plaster working model without any manual dexterity and can be easily used for bridge work using several supporting teeth. When porcelains are condensed with water in order to be removed, as is conventionally done, it is necessary to apply to the cervical edge of the plaster working model, a water-repellent separating or treatment material. surface, in order to easily remove the condensed porcelain. Thus, the adaptation of the porcelain on the cervical edge becomes relatively less good depending on the thickness of the separation or surface treatment material used. The porcelains thus mixed being put in place, the modeling liquid for dental porcelain relating to the present invention is treated by exposure to light or reaction with the organic peroxide or a derivative of pyrimidinetrione and an organometallic compound contained in porcelain. Thus, porcelain can be easily removed from the plaster working model without the need to use a water-repellent separating material or a surface treatment material. As a result, the adaptation of the cervical edge of fired porcelain to the plaster working model or even to a patient's supporting teeth is considerably improved.

4. In the case of the wax technique, a melted wax is mixed with porcelain, then placed and cooled, then removed from the plaster working model. However, the porcelain solidifies immediately after being applied and cannot therefore be mixed, the crystallization of the wax being very high. Since the wax cannot be condensed, it is also not possible to remove excess wax with tissue paper or gauze. Thus the mounted porcelain contracts strongly after firing and produces a large amount of carbon at the time of firing, which stains the stove or causes its deterioration. However, the porcelain modeling liquid has a viscosity sufficient to allow condensation after having been mixed with porcelain and put in place and before exposure to light or reaction with organic peroxide or a pyrimidinetrione derivative and an organo compound. metallic content in porcelain. Thus, when there is an excess of modeling liquid, this liquid can be removed with tissue paper or gauze. In connection with the present invention, solid or semi-solid organic matter at normal temperature, generally called "wax", is not used as such. This organic material is diluted with an organic solvent capable of dissolving the wax even slightly and is then condensed with porcelain, while a proportional amount of wax is reduced. After being mounted, the porcelain is heated to a temperature higher than the boiling point of the organic solvent, in order to volatilize only the organic solvent, the shape of the porcelain can thus be preserved with a small amount of wax residue. The incineration that follows, can further improve the fired porcelain, due to the small amount of the wax residue. Thus, since the amount of photopolyerizable compound having at least one unsaturated ethylenic double bond, which still contains carbon, can be reduced as much as possible depending on the amount of porcelain, there is no risk that a lot of carbon is produced at the time of incineration by contaminating the stove or causing its deterioration.

5

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

5. In the case of the technique of making porcelains with a modeling liquid which can be treated by heating, the porcelain thus produced flows in a metallic screed, while being treated with hot air, where it is processed. It is therefore necessary that an excess quantity of the modeling liquid is removed before cooking or at the end of the operation. If this removal operation is not successful, the adaptation of the porcelain on a plaster working model at the cervical edge of a metal cap or even on the patient's support teeth becomes less good. Anyway, with the dental porcelain modeling liquid relating to the present invention, it is not necessary to use hot air, since the treatment is carried out by exposure to light or reaction with the organic peroxide or a pyrimidinetrione derivative and an organometallic compound contained in porcelain. As a result, the adaptation of porcelain to a plaster working model at the cervical edge of a metal coping or even on the patient's support teeth is considerably improved.

6. The technique of mounting porcelain with a light-treatable modeling liquid is commercially available. Since this operation uses a polyfunctional monomer having a high viscosity, no condensation is possible. After firing, there is almost always carbon remaining which gives a gray tone to the color of the porcelain or which even blackens it depending on the firing conditions. This technique therefore does not apply at all to porcelain fired on a metal, for which particular importance is given to the aesthetic aspect. However, the dental porcelain modeling liquid relating to the present invention can be well condensed, its viscosity being equal to or less than 0.1 Pa.s at 23 ° C. In addition, it can be sintered after removal of an excess quantity using tissue paper or gauzes of the photopolymerizable compound having at least one ethylenic double bond unsaturated or the solid or semi-solid organic matter at normal temperature. . When the photopolymerizable compound having at least one unsaturated ethylenic double bond, has a high viscosity or the photopolymerization reaction or the reaction with the organic peroxide or pyrimidinetrione and an organometallic compound contained in the porcelain is very slow, the solid or semi-solid organic matter at normal temperature and the photopolymerizable compound are dissolved beforehand in an organic solvent which is not volatilized at room temperature but which has a boiling point sufficiently high to be volatilized by heating from 100 ° C. to 150 ° C. or more. After assembly and condensation, the porcelain is heated to 100 ° C-150 ° C or more, in order to remove the organic solvent mentioned above. Since the remaining organic material, solid or semi-solid at normal temperature, solidifies, it is however possible to keep the shape of the porcelain as it was assembled. In addition, since the refractive index of the organic solvent used can be adjusted within a range of 1.4 to 1.6, it is possible to make a preliminary estimate of the color tone of the porcelain before firing. Consequently, it is possible to obtain that the porcelain fired on a metal has a tone of color quite identical to that of the porcelain as it was mixed with water and put in place.

(In order to obtain dentures as close as possible to natural teeth, special effects are added to porcelain, using porcelain materials for internal and external coloring).

1. The modeling porcelain for dental porcelain relating to the present invention has a refractive index of 1.4 to 1.6 at 23 ° C, while porcelains have a refractive index of 1.47 to 1.50. This modeling liquid is not subject to any substantial change in its refractive index before and after exposure to light or reaction with organic peroxide or a pyrimidinetrione derivative and an organometallic compound contained in porcelain, i.e. d. before and after treatment. So when certain materials are chosen from a number of porcelain materials of internal or external coloring, so as to produce the special effect desired for the porcelain, by reproducing sophisticated color tones, it is possible even for people novices, to make a preliminary estimate of the color tone of the porcelain after firing. This is why it is possible to prevent the defects which cause the porcelains to be peeled off and replaced as often as necessary, because of the fact that the color tone of the porcelain cannot be estimated, as is the case by mixing the porcelain with water. This allows anyone to be able to obtain the production of special effects, production which, until now, had only been carried out by specialists. The internal and external coloring porcelain materials mixed with the modeling liquid relating to the present invention can be treated by exposure to light or reaction with the organic peroxide or a pyrimidinetrione derivative and an organometallic compound contained in the porcelain. . This also allows anyone to be able to make or apply porcelain on the desired location with the desired thickness and the desired extension. In addition, the time required for the dental operation is from one tenth to a few tenths of that usually required and the porcelain materials of internal or external coloring in the desired color tones can be selected with precision. For this reason, the special effects can be so easily applied to porcelain that the prosthesis can be improved in its aesthetic appearance with improvements in the quality and productivity of the work.

2. The modeling porcelain for dental porcelain relating to the present invention is designed to be produced by exposure to light or reaction with organic peroxide or a pyrimidinetrione derivative and an organometallic compound contained in the porcelain for its treatment. For this reason, when the special effects produced on the porcelain are internal or surface stains such as

6

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

those produced by cracks, yellowing and insufficient calcification etc., these effects can be applied or spread with a fine brush. It is therefore possible for anyone to perform the required operations, with ease and without any manual dexterity. Consequently, it is possible to produce these special effects with constant quality on porcelains based on porcelain materials of internal or external coloring and at any desired time, provided that no mixing of colors or thickening of the line or no blurring can occur as it does in mixing with water.

The modeling liquid relating to the present invention which has a refractive index of 1.4 to 1.6 inclusive at 23 ° C and a maximum viscosity of 0.1 Pa.s at 23 ° C can be prepared from compounds photopolymerizable having at least one ethylenic double bond unsaturated. Of these compounds, examples of functional methacrylates and acrylates include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyline methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate , tridecule methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hy-droxypropyl methacrylate, glycidyl methacrylate, tetrahydrofuryl methacrylate, methacrylate methacrylate methoxydiethylene glycol methacrylate, methoxytetra-ethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, phenoxydiethylene glycol methacrylate, phenoxyhexaneethylene glycol methacrylate methacrylate, methacrylate methacrylate, methacrylate, tetrahydrate , phenyl methacrylate, dipentaerythritole-monohydroxyl methacrylate, tetrahydrofurfuryl methacrylate modified with caproic acid, dipentaerythritole methacrylate modified with caproic acid, 2-hydroxyethyl methacrylate modified with caproic acid 2- methacrylate hy-droxypropyle modified with caproic acid, 2-ethoxyethyl methacrylate and lau-ryltridecyl methacrylate as well as their acrylates.

Examples of polyfunctional methacrylates and acrylates include: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1-3-butylene dimethacrylate dimethacrylate 1-6 hexanediol, neopentyl dimethacrylate, tripopylene glycol dimethacrylate, polypropylene glycol dimethacrylate, glycerol dimethacrylate, bisphenol A dimethacrylate, bisphenol A glycidyl dimethacrylate, modified ethylene bisphenyl dimethylacethacrylate dimethylacethacrylate by oxidation, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 2,2-bis (methacryloxyphenyl) propane, 2,2- 4- (2-hydroxy-3-metha-cryloxyethoxyphenyl propane, propane 2,2-bis (4-methacryloxyoxyoxyphenyl), 2,2-bis (4-meth-acryloxyethoxydiethoxyphenyl) propane, p 2,2-bis (4-methacryloxpropoxyphenyl) ropane, 7,7,9-trimethyl-4,13-dioxo-3,14-dioxo-5,12-diasahexadecane-1,6-diol dimethacrylate, neopentyl dimethacrylate glycol hydroxypivalate ester, hydroxypivalic dimethacrylate neopentyl glycol ester modified with caproic acid, oxidation-modified ethylene bisphenol A dimethacrylate, tri-methylololethane dimethacrylate, trimethylolpropane dimethacrylate, trimethyl methacrylate, trimethyl methacrylate trimethylolpropane, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, pentaerythritol hexamethacrylate and dipentaerythritol hexamethacrylate; compounds having the following structural formulas; and their acrylates. These compounds can be used alone or in combination of two or more and can optionally contain photopolymerization initiators, reducing agents, polymerization inhibitors, organic solvents, solid or semi-solid organic materials at normal temperature, amines tertiary, or-gano-halogen compounds etc.

Product of the reaction of 3-chloro-2-hydroxypropyl methacrylate with methylcyclohexane diiso-cyanate.

chzcfi 0 h I 1 i ch2 = c (ch3) cooch2-ch-oc-n-chz cha = c (cii3) c00ciu-ch-0c-n-chz i i i chz cû 0 h

7

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

Product of the reaction of 2-hydroxypropyl methacrylate with trimethylhexamethyiene diisocyanate.

CHa 0 H I S I

CH2 = C (CH3) C00CH2-CH-0C-N-CH2-C (CH3) 2v

/ CHj

CHz = C (CH3) C00C1I2-CH-0C-N- (CH2) 2 -Cir

I 11 I I

CH, 0 H CHa

2-hydroxypropy reaction product! methacrylate with methylcyclohexane diisocyanate.

CH3 0 H I I I

CHz = C (CH3) C00CH2-Cil-0C-N-CH2vv ^

TllJ

CII2 = C (CII3) C00ClI2 - CII-OC-N-CHz ^^

I I I CHa 0 l!

Product of the reaction of 2-hydroxypropyl methacrylate with methylene-bis (4-cyclohexyl isocya-nate).

CH3 0 H I I I

ch2 = c (ch3) cooch2-ch-oc-n- (FY

^> h2

ch2 = c (ch3) coochz-ch-oc-n- {h /

I IF CHa 0 II

Product of the reaction of 2-hydroxymethyl methacrylate with trimethylhexamethyiene diisocyanate.

0 h

1 I

ch2 = c (ch3) cooch2ch2o-c-n-ch2-c (ch3) 2 v

CH

ch2 = c (ch3) cooch2ch2o-c-n- (ch2) 2-ch //

I I I

0H CH3

8

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

Product of the reaction of 2-hydroxypropyl methacrylate with isofluorodiisocyanate.

CII3 0 H I fi I

CH2 = C (CH3) C00CH * -CH-0C-N-CHz

CH2 = C (CH3) COOCHz-CH-0C-N

I II I Cll3 0 II

CHa ch3

ch3

Product of the reaction of 3-chloro-2-hydroxypropyl methacrylate with isofluorodiisocyanate.

ch2cfl 0 h i 5 i cii3

ch2 = c (ch3) cooch2-ch-oc-n-ch2.

chz = c (ch3) c00CIIz-ch-0c-n "vpcn3

i 5 i ch3 CH2cû 0 h

Di- (2-methacryloyoxyethyl) dihexamethylene-7-alkyl-tetracarbamate.

He says

ch2 = c (ch3) -c00ch2ch2-0c-n- (chz) coc-nv ch2 = c (ch3) -c00CHzch2-0c-n- (ch2) s0c-pt

Ol II

0 ii oh

(R: an alkyl group)

Product of the reaction of 2-hydroxyethyl methacrylate with methylene-bis (4-cyclohexyl isocyana-te).

0 h

Of

ch2 = c (ch3) -cooch2ch2oc-n ^ 1Y1 ch2 = c (ch3) -cooch2ch2oc-n n i 0 h g

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

Product of the reaction of 3-chloro-2-hydroxypropyl methacrylate with hexamethylene diisocyanate.

ch2 = c (ch3) -cooch2cii-o-c-n

CH2CÛ 0 H g i

_ n _ r _ m ch2 = c (ch3) -cooch2ch-o-c-n

! I I ch2cû 0 h

/ (CH2) e

Product of the reaction of 2-hydroxypropyl methacrylate with hexamethylene diisocyanate.

ch3 0 h I I

pi r _ m

I [

CH2 = C (CH3) -C00CH2CH-0C-N

> (ch2)

ch2 = c (ch3) -cooch2ch-oc-n /

ch3 0 h

Product of the reaction of 2-hydroxyethyl methacrylate with hexamethylene diisocyanate.

0 h

1 I

ch2 = c (ch3) -c00ch2ch2-0c-nv

) (ch2) 6 ch2 = c (ch3) -cooch2ch2-oc-n '

1 I 0 h

Product of the reaction of 2-hydroxyethyl methacrylate with isophorone diisocyanate.

0 11 c1i3

1! 1

cii2 = c (ch3) -cooch2ch2oc-n-ch2v ^

ch2 = c (ch3) -c00ch2ch20c-n '^^^ ch3

i i ch3 0 h

10

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

Product of the reaction of 2-hydroxyethyl methacrylate with methyicyclohexane diisocyanate.

0 H! I

ch2 = c (ch3) -cooch2 ch2 oc-n-ch2v ^

jju chz = c (ch3) -COOCH2ch2oc-N-ch2 ^ x ^

1 l 0 h

Product of the reaction of 2-hydroxypropyl methacrylate and glycidol dimethacrylate with isophorone diisocyanate.

CH3 0 H I 5 I CHa CHz = C (CH3) -C00CH2-CH-0C-N-CHz

Cl (2 = C (CHa) -C00CHz v 'H

/ CH-C-N CIlz = C (CHa) -C00CHz!

0 h

Product of the reaction of glycidol dimethacrylate with methyicyclohexane diisocyanate.

0 h

cha = c (cha) -c00chzv i i

/ CII-C-N-CH Cil2 = C (CIIa) -COOCII2 X

ch2 = c (ch3) -cooch2x

/ CH-C-N-CHz CHz = C (CH3) ~ C00CHzX I I

0 h

Product of the reaction of glycidol dimethacrylate with hexamethylene diisocyanate.

0 h ch * = c (ch3) -c00ch2v i i

XCH-C-N

ch2 = c (ch3) -cooch

'\

CH2 = C (CH3) -C00CH2v (CHz)

/ CH-C-N

CH2 = C (CH3) -C00CHz S I

0 h

11

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

Product of the reaction of glycidol dimethacrylate with isophorone diisocyanate.

0 h ch2 = c (ch3) -cooch2 v i! i ch3

/ ch-c-n-ch x ch2 = c (ch3) -cooch2x

CH2 = C (CH3) -C00CHz v

/ CH-C-N V „CH3 CH2 = C (CH3) -C00CII2 x S I CH3

0 h

Product of the reaction of 2-hydroxypropyl methacrylate with methyibenzene diisocyanate.

CH3 0 H! D!

CHz = c (CHa) C00CHz-CH-0C-N-CH2 ^^

CHz = C (CHa) C00CHz-CH-0C-N-CHz ^^

i; i CH3 0 H

Product of the reaction of 3-chloro-2-hydroxypropyl methacrylate with methyibenzene diisocyanate.

CHz CJ2 0 H l 1!

CH2 = C (CH3) C00CHz-CH-0C-N-CHz \ ^

Toj

CH2 = C (CH3) C00CHz-CH-0C-N-CHz ^^

I 1 I CHz Cß 0 H

Product of the reaction of 2-hydroxyethyl methacrylate with methyibenzene diisocyanate.

0 H n i

CHz = C (CH3) C00C1Iz-CH-0C-N-CII2 ^^

Jo)

CHz = c (C1I3) C00CHz-CH-0C-N-CH2 ^^

He i 0 11

12

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

Product of the reaction of glycidol dimethacrylate with methyibenzene diisocyanate.

0 h

CH2 = C (CH3) -C00CH2v l I

n r n _ r _ v

CHz = C (CH3) -C00CHz /

CH-C-N-CHz

CH-C-N-CHz

CHa = C (CHa) -C00CHz \

CHz = C (CH3) -COOCHz / 1 1

0 h

Product of the reaction of glycidol dimethacrylate with hexamethylane diisocyanate.

OH HO

CHz = C (CH3) -C00CHzv i 1 11 yHzCOOC- (Cll3) C = 11ZC

; CH-CHOC-N (CH2) E N-COHC-HCy C1I2 = C (Cll3) -COOCIîz c00c "(CH: i) c = Hz C

13

Ol Ol

Ol

■ p *

o

CO Ol co o

KD Ol ro o

1,6-di methacryl ethyl oxycarbonylaminohexyl arninocarbonyloxy (3-methyl> propyloxycarbonylaminohexane

CIK

Cll3 I

CU,

Cll3

CH, = CC0CII2 CHz OCNH- (CII2) 6 -NIICOCII, Cll2 CHOCNII- (CHZ) B -NIICOCII, CH, CHOCNII- (Cil,) B -NIICOCII, CH2 0CC = CII2 I 1 II II II 1 1

00 00 00 00

Product of the reaction of hexamethylene diisocyanate with an addition of 6-hexanolide, an addition of a product of 2,2'-di <4 ~ hydro>: ycyclohexyl) propane with 2-hydroxyethyl methacrylate.

CII3 I

CI! 2 = CC0CH2CH20 I 0

Eyelash,

(0CIINI1- (CHa) e -NliC {0 (CH2) s -CO) m0 - <T> - C - (ÏÏ) - 0 {0 (CHZ) s-CO) n

Cll3 I

0CIIN- (Cl | 2) c -NII-COCHz Cll2 0CC = CH2

CHa

I

0

I

0

m + n = 0—10, m + n = 6, p = 0 ~ 3, p = l

0

1

a> 00

isï N)

■ t *>

Ul

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

The organic solvents used in the present invention can advantageously be those based on hydocarbons, halogenated hydrocarbons, alcohols, ethers / acetals, ketones, esters, polyhydric alcohols and their derivatives and nitrogen compounds.

In a more explanatory manner, the organic solvents based on hydrocarbon can advantageously be: n-pentane, n-hexane, isohexane, n-heptane, n-octane, iso-octane, n-decane, 2,2-dimethylbu-tane , petroleum ether, benzyl petroleum, ligroin gasoline, kerosene, mineral spirits, naphtha 2-pentene, pentenes mixed cyclohexane, méthyicyclohexane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamylbenzène, triamylbenzène, tétraamylbenzène, dodécylbentène, didodecylbenzene , amyltoluene, tar naphtha, naphthe solvent, p-cymene, tetralin, dipentene decalin, turpentine, pinene, p-menthane, pine essence and camphor oil. Special preference is given to: n-octane, n-decane, kerosene, mineral spirits, naphtha, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamylbenzene triamylbenzene, tetraamylbenzene, p-cymene, pinene and p-menthane.

The halogenated organic solvents based on hydrocarbon can advantageously be: methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, ethylidene chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1 , 1,1,2-tetrachloroethane, 1,1,2,2, -tetrachloroethane, pentachlo-roethane, vinylidene chloride, 1,2-dichloroethylene, trichlorethylene, tetrachlorethylene, 1,2,3-tri-chloropropane, chloride d 'isopropyl, allyl chloride, 1,2-dichloropropane, butyl chloride, amyl chloride, dichloropentane, hexylchloride, 2-ethylhexylchloride, ethyl bromide, ethylene bromide, t-trabromoethane, chlorobromoethane, chlorobromide ethylene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, o-dibromobenzene, o-chlorotoluene, p-chlorotouene, a-chloro-naphthalene, chlorinated naphthalene, fluorotrichloromethane and 1,1,2-trichloro-1 , 2,2-trifluoroethane. Special preference is given to: 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroé-thane, pentachloroethane, tetrachlorethylene, 1,2,3-trichloropropane, chloride hexyl, 2-ethylhexyl chloride, ethylene bromide, tetrabromoethane, chlorobromoethane, ethylene chlorobromide, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene, o-dibromobenzene, o-chlo-rotoluene and a-chloronaphthalene.

The alcoholic organic solvents can advantageously be: methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, 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-ethyl butanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 2-ethyl hexanol, 3.5 , 5-trimethyl hexanol, nonanol, n-decanol, undecanol, trimethylnonyl alcohol, heptadeca-nol, 2-methyl cyclohexanol, benzyl alcohol, glycidol, furfuryl alcohol, tetrahydro-furyl alcohol and abietinol, all of which are preferable.

The organic solvents based on ethers and acetals can advantageously be: ethyl ether, dichloroethyl ether, isopropyl ether, n-butyl ether, di-iso amyl ether, n-hexyl ether, methylphenyl ether, ethylphenyl ether , n-butylphenyl ether, amylphenyl ether, cresylmethyl ether, p-tertiary amylphenyl-n-amyl ether, ethylbenzyl ether, 1,2-propylene oxide, epichlorohydrin, diglycidyl ether, 1,4-dioxane, furan, furan , 2-methylfuran, tetrahydrofuran, tetrahydropyran, cineol, methylal, diethyl acetal, all of which are preferable.

The organic solvents based on ketone can advantageously be: acetone, methyl acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl iso-butyl ketone, methyl n-amyl ketone, methyl n- exyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, di-iso butyl ketone, 2,6,8-trimethylnonanone-4, oil with acetone, acetonylacetone, diacetone alcohol, mesityli-oxide , isophorone, cyclohexane, methyicyclohexane, acetophenone and dypnone, all of which are preferable.

The organic solvents based on ester can advantageously be: methyl formate, ethyl formate, propyl formate, n-butyl formate, iso-butyl formate, amyl formate, methyl acetate, n- acetate butyl, iso-butyl acetate, secondary butyl acetate, n-amyl acetate, iso-amyl acetate, iso-amyl methyl acetate, methoxybutyl acetate, secondary hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexy-acetate, benzyl acetate, methyl propionate, ethyl propionate, n-butyl propionate, iso-amyl propionate, methyl butyrate, ethyl butyrate , n-butyl butyrate, iso-amyl butyrate, butyl stearate, methyl acetoacetate, ethyl acetoacetate, isoamyl iso-valerate, methyl lactate, ethyl lactate, n-butyl lactate, lactate isobutyl, n-amyl lactate, isoamyl lactate, methyl benzoate, eth benzoate yl, propyl benzoate, butyl benzoate, isoamyl benzoate, benzyl benzoate, ethyl cinnamate, methyl salicylate, ethyl abietate, benzyl abietate, dioctyl adipate, Diethyl oxalate, Dibutyl oxalate, Oxalate diamyl, dediethyl maloate, dibu-tyle tartrate, tributyl citrate, dioctyl sebacate, diamethyl phthalate, diethyl phthalate, dibutyl phtphalate, di-2-ethylhexy phthalate and dioctyl phthalate, all preferably used.

The organic solvents based on polyhydric alcohols and their derivatives can advantageously be: ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol acetate monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monodiethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol dibutyl ether, ethylene glycol acetate monobu-tyl ether, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, ethylene glycol acetate mo-nophenyl ether, ethylene glycol benzyl ether, ethylene glycol mono methoxymethoxy ethanol,

15

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

ethylene glycol monoacetate, ethylene glycol diacetate, formic acid monoester, formic acid diester, butyrate monoester, butyrate diester, propionic acid diester, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , diethylene glycol acetate monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol acetate monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dibu-tyl ether, diethylene glycol acetate, triethylene glycol Methylene glycol monomethyl ether, Methylene glycol monethyl ether, trigycol dichloride, tetraethylene glycol, polyethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 1-buroxyethoxy propano !, propylene glycol derivatives, propylene chlorohydrin , di propylene glycol, di-propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, poly (oxyethylene-oxypropilene) derivatives, trimethylene glycol, butanediol, 1,5-pentanediol, hexylene glycol, octylene glycol, glycerin , acetine, diacetin, triacetin, glyceryl mono-butyrate, glycerine ether, glycerin a-monochlorohydrin, glycerin a, -r, dichlorohydrin and 1,2,6-hexa-netriol, all being preferably used.

The organic solvents based on nitrogen compounds can advantageously be: nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, O-nitroanisole, monoethylamine, diethylamine, triethylamine, isopropylamine, di-isopropyiamine, n-butylamine, n-dibutylamine, n-tributylamine, iso-butylamine, di-isobutylamine, secondary butylamine, n-amylamine, diamylamine, triamylamine, secondary amylamine, secondary hexylamine, ethylbutylamine, n-heptylamine, 2-ethylhexylamine, diocylamine, ethylene diamine, propylene diamine , Marnine diethylene, tetraethylene pentamine, diethylanelin, diethyl benzylamine, monoethanolamine, diethanolamine, triethanolamine, ethyl monoethanolamine, n-butyl mo-noethanolamine, diethyl ethanolamine, ethyl diethanolamine, n-butyl diethanolamine, di-n-butyl ethanolamine, isopropylamine , formamide, N, N-dimethylformamide, acetomitrile, benzonitrile, cyany-drine acetone, Pyridine, picoline-a, picoline-ß, picol ine-t, 2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, morpholine and ethyl morpholine, all preferably used. These organic solvents can be used in mixture or in dissolution and alone or in combination of two or more. It should be noted that the present invention is not limited to the organic solvents mentioned above as an example. In the present invention, it is possible to use any organic solvent which can easily dissolve the photopolymerizable compound having at least one ethylenic double bond unsaturated, not participating in chemical reactions and evaporating rapidly at a temperature below the cooking temperature . When the quantity of porcelain to be made is small or depends on the conditions of incineration and cooking, these organic solvents can be removed. Accordingly, the amount of organic solvents added to 100 parts by weight of the photopolymerizable compound is conveniently in the range of 0 to 9900 parts by weight. The solid or semi-solid organic materials used in the present invention can, for example, include natural waxes, petroleum waxes, synthetic waxes based on carbon, synthetic polyolefinical waxes, synthetic waxes based on fats and oils, as well as alcohol-based waxes (having 13 or more carbon atoms).

Advantageously included in natural waxes are fatty acids, fatty alcohols, hydrocarbons, triglyceride, saturated fatty acids, monoene acids, polyene acids, unsaturated fatty acids, hydroxy fatty acids, branched fatty acids, and bibasic acids.

Petroleum waxes, for example, can advantageously be paraffin wax, microcrystalline wax, flaked wax, petrolactam wax, petrolatum and petroleum ceresin.

Synthetic charcoal waxes, for example, mineral wax, acid wax, ester wax, partially saponified ester wax and soft mineral-type wax. As for polyolefinical waxes, it is advantageous to use those which are based on high, medium and low density polyethylene.

It is advantageous to include in fats and synthetic waxes based on oils: hardened beaver oil, 12-hydroxystearic acid, 12-hydroxystearic acid amide, N- (2-hydroxyethyl-thyl) acid amide hydroxystearic, N acid amide, N'-ethylene-bis-12-hydroxystearic, N acid amide, N'-hexamethylene-bis-12-hydroxystearic, N acid, N'-xylene-bis-12-hydroxystearic, methyl acid 12-hydroxystearic, butyl acid 12-hydroxystearic, propylene glycol mono-12-hydroxystearate, glycerol monohydroxystearate, ethylene glycol mono-12-hydroxystearate, lithium 12-hydroxystearic acid, calcium 12-hydroxystearic acid, laurate amide, amide stearate, amide oleate, erucic acid amide, amide ricinoleate, special fatty acid, N acid amide, N'ethylene-bis-lauri-que, amide N.N'methylene-bis-stearic acid, N.N'ethylene-bis-stearic acid amide, N acid amide, N'ethylene-bis-stearic acid, N acid amide, N'ét hylene-bis-oleic, amide of N.N ethylene-bis-behenic acid, amide of N acid, N'butylene-bis-stearic acid amide N, N'hexamethylene-bis-stearic acid, N acid amide, N'hexamethylene-bis-oleic acid, N acid amide, N'xylene-bis-stearic acid, monomethylolamide stearate, coconut oil fatty acid monoethanaol amide, diethanolamide stearate, amide N-oleyl stearic acid, N-oleyl oleic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide , N acid amide, N'-diolene adipic, N acid amide, N'-distearyl adipic, N acid amide, N'-dioleyl sebacic, N acid amide, N'-disearyl sebacic, amide N, N'-distearyl terephthalic acid, N, N'-dis-tearyl isophthalic acid amide, ketone diheptadecy, ketone diundecyl, dodecylamine, tetradecylamine, octadecyla-

16

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

mine, oieylamine, dioctadecylamine, methyl laurate, methyl myrsistate, methyl palmitate, methyl stearate, coconut oil fatty acid methyl, isoproyl myristate, butyl stearate, octadecyl stearate, oleate oleyl, glycerin monostearate, glycerin mono-oleate, glycerin docosanoate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan mono-oleate, propylene glycol monopalmitate, propylene glycol monostearate, propylene glycol monostearate polyoxyethylene monostearate.

As for alcoholic waxes (having 13 carbon atoms), it is advantageous to use, for example: tridecyl alcohol, myristic alcohol, pentadecyl alcohol, cetyl alcohol, heptadecylic alcohol, octadecyl alcohol, nonaadecyl alcohol and aralkyl alcohol. These solid or semi-solid organic materials at normal temperature can be used in mixture or in dissolution, alone or in combination of two or more materials. It should be noted that this invention is not limited to solid or semi-solid organic materials at normal temperature given above as an example. In other words, it is possible to use any solid or semi-solid organic material at normal temperature, which is soluble, even partially, in the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond and the solvents mentioned. above, which does not participate in the chemical reactions at all, leaves no incineration residue at the firing temperature of the porcelain and has no negative influence on the porcelain mounted on the metal after firing. Depending on the type of photopolymerizable compound or the incineration or even the cooking conditions, these solid or semi-solid organic materials can be dispensed with at normal temperature. Thus, the amount of solid or semi-solid organic matter at normal temperature added to 100 parts by weight of the photopolymerizable compound is suitable in a range from 0 to 900 parts (inclusive) by weight.

The photopolymerization initiators used in this invention can advantageously be compounds based on diketone-a, ketal, anthraquinone, thioxanthone and benzoin alkyl ether. To be more explicit, d, l-comphorquinone, benzyl, diacetyl, acenaphthenequinone, 9-10-phenanthrene quinone etc. can advantageously be used as α-di-ketone compounds. However, special preference is given to d, l-camphorquinone and benzyl. The ketal compounds, for example, can advantageously be: benzyldimethyl ketal, benzyldiethyl ketal, benzyldipropyl ketal, benzyldi (p-phenylethyl) ketal, benzyldi (2-methoxyethyl) ketal, benzyldi (2-ethoxyethyl-thyl) ketal, benzyldi ketal, benzyldi (2-ethoxyethoxyethyl) ketai, 4,4'-dimethyl-benzyldimethyl ketal, 2,2, '- dimethoxybenzyldiethyl ketal, 4,4'-dichlorobenzyldiethyl ketal and 4,4'-dichlo-robenzyldipropyl ketal. However, a preference is given to: benzyldimethylketal, benzyldiethylketal, benzyldi (2-methoxyethyl) ketal and 4,4'-dimethylbenzyldimethylketal.

The anthraquinone compounds can advantageously be: anthraquinone, 1-chloroantraquino-ne, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone and 1-bromoanthraquinone. However, preference is given to: anthraquinone, 1-chloroanthraquinone and 1,2-benzanthraquinone. The thioxanthose compounds can advantageously be: thioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methyl-thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylxanthone, 2,4-diisopropylthioxanthone, 2-chloro- 7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide and thioxanthone-10-oxide. However, preference is given to: thioxanthone, 2-chlorothioxanthone, 2,4-dimethylxanthone, 2,4-diethylxanthone and 2,4-di-isopropylthioxanthone.

The benzoïnalkyléther compounds can advantageously be: benzoïméthyléther, benzoïné-thyléther, benzoïnisopropyléther, benzoïn-n-butyléther and benzoïnbutyléther. However, preference is given to benzoïbutbutéther.

The photopolymerization initiators mentioned above can be used alone or in a singular combination of two or more.

Of these photopolymerization initiators, those based on a-diketone, anthraquinone, thioxanthone and benzoalkyl ether can be added within the range of 0.001 part by weight inclusive to 15 parts by weight exclusively per 100 parts by weight of compound photopolymerizable having at least one ethylenically unsaturated double bond. Below 0.001 part by weight, no satisfactory processing property is obtained, due to lower photopolymerization. At 15 parts by weight or more, the photopolymerization compound is colored with a yellow tint, inherent in the photopolymerization initiators, to such an extent that, when mixed with porcelain, a color tone is not obtained suitable.

The ketal compound can be added in the range of 0.001 part by weight inclusive to 20 parts by weight exclusively per 100 parts by weight of the photopolymerizable compound having at least one unsaturated ethylenic double bond. Below 0.001 part by weight, no satisfactory processing property is obtained due to lower photopolymerization. At 20 parts by weight or more, the solubility at room temperature is obtained so substantially that when the temperature of the modeling liquid decreases, the ketal compound precipitates, making the mixing operation difficult.

The reducing agents used in the present invention serve to reduce a photosensitizer when it is excited, but cannot reduce it when it is not excited by rays of active energy. The reducing agents can be primary, secondary or tertiary amines, as expressed by:

17

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

R *

R - N - R "

formula in which one or no group R, R 'and R "may be hydrogen. At least one of the elements R, R' and R" may be an identical or different hydrocarbon group. The hydrocarbon group can then be an alkyl, cycloalkyl or hydroxyalkyl group. Preferably, R, R 'and R "can be an alkyl group having 1 to 10 carbon atoms.

Suitable examples of reducing agents in which at least one or two R, R 'and R "units is a hydrocarbon are: propylamine, n-butylamine, pentylamine, hexylamine, diethylamine, dipropylamine, di-n-butylamine , dipentylamine, 2-dimethylaminoethanol, trimethylamine, triethylamine tripropyiami-ne tri-n-butylamine, tripentylamine, dimethylaminoethyl methacrylate, diethylamino-noethyl methacrylate, triethanolamine and aliphatic long chain amines.

Examples of reducing agents comprising an aromatic group are: N, N'-dimethylaniline, N, N'-dimethyl-p-toluidine, p-tolyldiethanolamine, m-tolydiethanolamine, N-methyldiphenylamine, 2-dimethylaminobenzoic acid, 4- ethyl acid, dimethylaminobenzoic acid, 4- butyl acid, dimethylaminobenzoic acid, 4- 2-ethylhexylic acid, dimethylaminobenzoic acid and 4- isoamylic acid, dimethylaminobenzoic acid.

It is also possible to use a diamine having the following structural formula:

in which n is an integer of 2 or more and groups R, R ', R "and R'", which may be the same or different from each other, each being a hydrogen atom or a hydrocarbon group , especially an alkyl group. Examples of such reducing agents are ethylene diamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine or hexamethylenediamine or their N-hydrocarbon derivatives, and in particular, an N-alkyl derivative.

Examples of the reducing agents, in which the element N constitutes a part of the cyclic compounds, are piperidine or its N-hydrocarbon derivatives. Other reducing agents, for example, are triarylamines, allylthiourea, salts of aromatic sulfinic acid and 5-alkyl or 5-allyl barbituric acid.

Of these reducing agents, preference is given to dimethylaminoethyl methacrylate, triethanolamine, 4-dimethylaminobenzoic methyl acid and 4-dimethylaminobenzoic ethyl acid. The abovementioned reducing agents can be used alone, or in combination of two or more.

Preferably, the amount of these reducing agents added to 100 parts by weight of photopolymerizable compound having at least one unsaturated ethylenic double bond is in the range from 0.001 by weight inclusive to 20 parts by weight exclusively. Above 0.001 part by weight, there is an increase in the processing time due to lower photopolymerization. At 20 parts by weight or more, the storage stability of the modeling liquid becomes so poor that the time devoted to dental work under a normal interior light is markedly reduced.

Preferably the tertiary amines employed in the present invention are aromatic tertiary amines. More specifically, the following substances: N, N'-dimethy! -P-toluidine, N-dimethy-Ianiline, N-methyl-Np-hydroxyethylaniline, N-di (p-hydroxyethyl) -aniline and N-di ( p-hydroxyethyl) -p-to-luidin, although not critical, are preferred. These tertiary aromatic amines can be used in mixture or in dissolution, alone or in combination of two or more and can be added in the range of 0.05 part by weight inclusive to 5 parts by weight exclusively for 100 parts by weight of the photopolymerizable compound having at least one unsaturated ethylenic double bond. At less than 0.05 parts by weight, the treatment becomes so insufficient, due to the low polymerization that the marginal zone cannot be preserved. At 5 parts by weight or more, on the other hand, the color tone derived from porcelain cannot be distinguished from that of aromatic tertiary amines. Whenever a modeling liquid containing a tertiary amine is used, it is absolutely essential that an organic peroxide is added to the porcelain.

The organic peroxides used in the present invention can advantageously be: benzoyl peroxide, dilauroyl peroxide, peroxide, 4,4-dichlorobenzoyl, 2,4-dichloro-benzoyl peroxide and methyl ethyl ketone peroxide, although the present invention is not limited to these substances. These organic peroxides can be used in mixture or in dissolution, alone or in combination of two or more, and can suitably be added in the range of 0.1 part.

R- -

18

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

weight exclusively to 100 parts by weight of porcelain, if the reactivity of a mixture of 1.5 of porcelain with 1 ml of the present modeling liquid is taken. Below 0.1 part by weight, the treatment becomes so insufficient, due to the low reactivity, that the shape of the marginal zone cannot be maintained. At 5 parts by weight or more, on the other hand, a reaction at room temperature takes place so quickly that the time allowed for assembly is insufficient.

The organic halogen compounds used in the present invention, for example, can be: dilauryl dimethylammonium chloride, lauryldimethyl-benzylammonium chloride, benzyl-trimethyl-ammonium chloride, diisobutylamine hydrochloride, tetra-n-butylammonium chloride, triethylamine hydrochloride , trimethylamine hydrochloride, diethylamine hydrochloride, methylamine hydrochloride, ethylamine hydrochloride, isobutylamine hydrochloride, triethanola-mine hydrochloride, p-phenylethylamine hydrochloride, acetylcholine chloride, 2-chlorotriethylamine, (2-chloroethyl chloride) ) trimethylammonium, tetradecyldimethylbenzylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, tetrabutylammonium fluoride and tetrabutylammonium iodide or ammonium tetra butyl in mela nge. Among these organic halogenated compounds, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tetra-n-butylammonium chloride are preferred, since they are soluble at normal temperature in an amount of up to 5 parts by weight in 100 parts by weight of the polymerizable compound having at least one unsaturated ethylenic double bond. Other organic halogen compounds which have lower solubility at normal temperature can be filtered for practical use. Preferably, the amount of these organic halogenated compounds added to 100 parts by weight of polymerizable compound having at least one ethylenic double bond unsaturated, is in the range of 0.01 part by weight inclusive to 5 parts by weight exclusively. Below 0.01 parts by weight, the treatment becomes so insufficient due to the low reactivity, that the shape of the marginal zone cannot be maintained. At 5 parts by weight or more, on the other hand, not only is the liquid colored with a color close to yellow, characteristic of the organic halogen compound, but also the reaction at room temperature is carried out so rapidly that the duration of the the working time required to assemble the porcelain becomes insufficient. Whenever a modeling liquid containing an organic halogen compound is used, it is absolutely essential that a pyrimidinetrione derivative and an organometallic compound be added to the porcelain.

The pyrimidinetriones derivatives used in the present invention, for example can include: N-cyclohexyl-5-ethylpyrimidinetrione, N-benzyl-5-phenylpyrimidinetrione, 5-butylpyrimidinetrione, 5,5'-diethylpyrimidinetrione, 1,3,5-trimethylpyrimidinetrione, 2,4,6- (1h, 3h, 5h) pyrimidinétrione and 1,3-dimethyl-pyrimidinétrione. Among them, the best is N-cyclohexyl-5-ethylpyrimidinetrione. To obtain the reactivity of a mixture of 1.5 g of porcelain with 1.5 ml of the present modeling liquid, the amount of these pyrimidinetrione derivatives added to 100 parts by weight of porcelain is preferably within the range of 0 , 1 part by weight inclusive to 10 parts by weight exclusively. Below 0.1 part by weight, the treatment becomes so insufficient due to the low reactivity, that the shape of the marginal zone cannot be preserved. On the other hand, at 10 parts by weight or more, the reaction at room temperature takes place so quickly that the time required for assembly becomes insufficient.

The organometallic compounds used in this invention can be: copper acetylacetone, cubic acetate, copper oleate, manganese acetylacetone, manganese naphthenate, manganese octylic acid, cobalt (III) acetylacetone, cobalt naphthenate, lithium acetylacetone, naphthen zinc, acetylacetone nickel, nickel acetate, acetylacetone aluminum, acetylacetone calcium, acetylacetone chromium (III), acetylacetone iron (III), sodium naphthenate and rare earth octoate, although this invention is not limited to these materials. Although used alone or as an added material, these organometallic compounds must be added to the porcelain at the same time as the pyrimidinetrione derivative. To obtain the reactivity of a mixture of 1.5 g of porcelain with 1 ml of the present modeling liquid, the amount of organometallic compound added to 100 parts by weight of porcelain, is preferably in the range of 0.001 part by weight inclusive to 0.2 parts by weight exclusively. At less than 0.001 part by weight, the treatment becomes so insufficient, due to the low reactivity, that the shape of the marginal zone cannot be preserved. However, at 0.2 part by weight or more, not only the reaction at room temperature takes place so quickly that the time necessary for assembly becomes insufficient, but the porcelain is also tinted with the color characteristic of the organometallic compound. , for example in blue in the case of acetylacetone copper and in red brown in the case of acetylacetone iron (III).

Examples

Modeling fluid samples relating to the present invention were prepared for comparison and evaluated using the following experiments 1-8. It is understood that the present invention is not limited to these samples. The results for the samples relating to the present invention are shown in Table 1 for comparison. Experiments 1-8 were carried out as follows.

19

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

Experience 1 - Characteristics of detachment and detachment compared to the plaster and shaping working model.

A metal screed without shoulder (for the central incisor tooth of the maxilla) was prepared on an anhydrite working model and a Unibond marginal porcelain produced by Shofu Co. Ltd. and was mixed with samples of modeling liquid shown in Table 1. In Examples 1-10,14 and 15 and in Comparative Examples 1-4 and 14, the samples were exposed to light from GC light VL -1 performed by GC Dental Industriai Corporation for 40 seconds. In Examples 11-25 and Comparative Examples 5-9 and 13, condensation was carried out for 30 seconds with hot air at a temperature of 80 ° C. from the condenser GC Ultra UL-1 manufactured by GC Dental Industriai Corporation, and in Comparative Examples 10 and 11, the condensation was performed with the same condenser. In Example 12, one part by weight of Plastodent (orange) manufactured by Degussa Company was mixed with 6 parts by weight of Unibond marginal porcelain manufactured by Shofu Co. Ltd., these materials being brought to the state of using a gas burner. These marginal areas thus formed were attached to or detached from the anhydrite working model in order to assess whether the shapes of the porcelain samples were preserved or not. It is noted that in Examples 18-21 and Comparative Examples 6 and 7 in which said modeling liquids contained di-methyl-p-toluidine -N, N 'as the tertiary amine, 0.25 parts by weight of benzoyl peroxide as organic peroxide were previously incorporated into 100 parts by weight of Unibond marginal porcelain manufactured by Shofu Co. Ltd., using a mortar and only in Examples 22-25 and in Comparative Examples 8-9 in which said liquids containing the halogenated organic compound, 0.2 part by weight of N-cyclohexyl-5-ethylpyrimidinetrione as a pyrimidinetrione derivative and 0.01 part by weight of acetylacetone copper as the organometallic compound were previously incorporated into 100 parts by weight Unibond marginal porcelain made by Shofu Co. Ltd., using a mortar.

Experiment 2 - Viscosity.

In all the examples and in the comparative examples with the exception of Comparative example 12, viscosities were measured at a constant temperature / humidity, the room being maintained at 23 ° C. ± 0.5 ° C. and at a humidity 50% ± 5% relative and illuminated with red light (having an average light intensity of approximately 50 Lx) using a DVL-B type digital viscometer manufactured by Tokyo Keiki KK A preliminary experiment allowed establish that the maximum viscosity (limit) to which the porcelain could be condensed was approximately 0.1 Pa.s at 23 ° C. Consequently, the viscosity values lower than 0.1 Pa.s were considered as "good" (which means that the porcelain could be condensed) and the viscosity values higher than 0.1 Pa.s were considered as "bad" (which means that the pocrelaine couldn't be condensed).

Experiment 3 - Treatment properties

A metal screed without a shoulder (for the central incisor tooth of the maxilla) was prepared and a marginal Unibond porcelain manufactured by Shofu K.K. was mixed with the samples of modeling liquid relating to the present invention for comparison purposes. After being treated under the same conditions as those indicated in experiment 1, the degree of treatment of the samples was evaluated by lightly touching them with a plastic spatula.

Experiment 4 - State after incineration and cooking

Test discs each having a diameter of 15 mm and a thickness of 2 mm were previously prepared with GC Ceramibond E58 manufactured by GC Toshi Kogyo Corporation. In all of the examples and in the comparative examples with the exception of Comparative Example 12, the test discs were covered on one of their faces with simple layers of the samples of modeling liquid by means of a brush. . Then, a mixture of 0.15 g of GC Ceramibond E58 with 0.1 ml of each sample of modeling liquid was applied to each test disc to a thickness of approximately 1 mm using a special brush. In the comparative example 12.6 parts by weight of GC Ceramibond E58 were mixed with one part by weight of Plastodent (orange) manufactured by Degussa KK, these materials being brought to the molten state using a gas burner, the mixture being applied in the same manner as described above. For incineration and cooking, each of the samples thus obtained was dried beforehand for 5 minutes at 150 ° C then heated for 1 minute at 600 ° C and heated under a reduced pressure of 730 mmHg from 600 ° C to 830 ° C at a heating rate of 60 ° C per minute and, finally maintained at 830 ° C for 1 minute using the Furnace KDF Master Spirit 120 porcelain stove manufactured by Denken KK For estimation purposes, these samples were observed visually regarding blackening due to carbon residue, cracks, color changes etc. It is noted that in Examples 18-21 and Comparative Examples 6 and 7 in which said modeling liquids contained dimethyl-p-toluidine -N, N 'as tertiary amine, 0.25 parts by weight of pe20

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

Benzoyl oxide as organic peroxide was previously incorporated into 100 parts by weight of GC Ceramibond E58, using a mortar and that in Examples 22-25 and in Comparative Examples 8-9 in which said modeling liquids contained the halogenated organic compound, 0.2 part by weight of N-cycohexyl-5-ethyl-pyrimidinetrione as derivative of pyrimidinétrione and 0.01 part by weight of copper acetylacetone as organometallic compound were previously incorporated into 100 parts by weight of GC Ceramibond E58, using a mortar.

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

In order to be able to establish a visual estimate for comparison purposes, the color tones of the modeling liquid samples relating to the present invention, the color tone of the latter before mixing with porcelains, was evaluated visually; about 1 ml of each sample was added dropwise to a tooth in a G-CERA 0 (dry) palette manufactured by GC Toshi Kogyo Corporation, the appearance of which was white under a standard C light source. transparent colors and tones were considered and designated as "good".

Experiment 6 - Refractive index

In all examples and comparative examples except Comparative Example 12, the refractive indices were measured in a constant temperature / humidity chamber maintained at 23 ° C ± 0.5 ° C and a relative humidity of 50% ± 5 % with an Abbe type 3 refractometer manufactured by Atago KK From preliminary experiments, it was found that due to the fact that the refractive index of porcelains was 1.47-1.50, the liquids of modeling visually agree with porcelain, if their refractive index is 1.4-1.6.

Experiment 7 - Reproducibility of the color tone when mixed with GC Ceramibond M67 manufactured by GC Toshi Corporation.

GC Ceramibond M67 was mixed for comparison with the modeling liquid samples relating to the present invention. Then, the color tones of the mixtures before treatment by exposure to light, drying and heating, were compared under a standard light source C with those of the heated porcelain of GC Ceramibond M67 with pure water. The estimate was considered good when the color tones of the mixtures tested were visually in coincidence with heated porcelain of GC Ceramibond M67 with pure water.

Experience 8 - Authorized duration of dental operations.

About 1 ml of each of the modeling samples relating to the present invention was added dropwise for comparison to a tooth in a G-CERA 0 (dry) manufactured by GC Toshi Kogyo Corporation and was left in a constant temperature / humidity chamber maintained at 23 ° C ± 0.5 ° C and at a relative humidity of 50% ± 5% with current interior lighting (approximately 300Lx) for 5 hours or more. The observation concerned whether or not the samples were made too hard to be used.

21

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE I

Example • 1

Example 2

Example 3

Example 4

A polymerizable compound having at least one unsaturated ethylenic double bond

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

80

50

20

20 20

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

20

50

80

60

Organic solvent

Hydrocarbon based

Iso-propylbenzoin

Based on halogenated hydrocarbon

1,2,3-trichloropropane tetrachlorethylene

Alcohol-based

2-methyl cyclohexanol

Based on acetal ether

Methylphenyl ether Û-crésy! Methyte ether

Based on ketone

Isophorone

Ester-based

Methyl benzoate

Based on polyhydric alcohol l-ropyicne glycol rnonotilhyi ether

A.basç of nitrogen compounds r

Monoethanolamine

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

Petroleum wax

Microcrystalline wax

Synthetic wax based on carbon

Fisher-Tropsch wax

Polyolefinical synthetic wax

High-density polyethylene wax

Synthetic wax based on rails and oils

Hardened Beaver Oil

Alcoholic urea having 'U or more carbon atoms

Myristyl alcohol

Photopolymer initiator

station

Reduction agent

Based on diketone-c <.

Quinone camphor

0.01

0.01

0.005

0.005

Based on ketal

Benzyl dimethyl ketal

Based on anthraquinone

1,2-benzanthraquinone

Based on thioxanthone

Thioxanthone

Based on benzoic alkyl ether

Benzoino isopropyl ether

Dimethylamlnoethyl methacrylate

0.01

A-dimethylaminobenzoate methyl

0.01

0.01

0.01

Tertiary amine

N, N'-dirnethyl-p ~ toluïdine (NB 1)

Alogenous organic compound

Dilauryldimethylammonium chloride (NB 2)

Polymerization inhibitor

Butyl hydroxytoluene

0.03

0.03

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain from plaster models

Well

Well

Well

Don

Visibility (23 ° C, digital DVL B type visometer made by Tokyo KeiUi K.K.) Pa.s

0.00672

0.00499

0.00269

0.00528

Treatment properties (touch sen3 with a spatula)

Don

Well

Well

Well

State of the porcelain after incineration and firing (15û ° Ç, 5 minutes ò 6QQ ° C, 1 minute "h Ü30 ° C, -1. Minute h 73QmmHq)

Well

Well

Well

Well

Color tones of the modeling liquid before melanqo with colorless / Transparent porcelain

Colorless / Transparent

Colorless / Transparent

Colorless / transparent

Refractive index (23UC Abbe precision refractometer, type three, manufactured by Atago K.K.)

1.4525

1.4545

1.4545

1.4640

Color rendering when mixed with GC Ceramibond M67

nipple

Well

Well

Well

Uuree necessary for the technical operation (under normal interior lighting: approx. 300 LX)

More than 5 hours

More than 5 hours

More than 5 hours

More than 5 hours

22

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE 1 (CONTINUED)

Example 5

Example 6

Example 7

Example S

A polymerizable compound having at least one functional unsaturated ethylenic double bond

2-hydroxyethyl methacrylate Phenoxyethylacrylate

50

60

60

60

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane triacrylate

50

40

40

40

Organic solvent

Hydrocarbon based

Iso-propylbenzoîne

100

Based on halogenated hydrocarbon

1,2,3-trichloropropane tetrachlorethylene

Alcohol-based

2-methyl cyclohexanol

120

Based on acetal ether

Methylphenyl ether 0-cresylmethyl ether

100

Based on ketone lsophorone

Ester-based

Methyl benzoate

Based on polyhydric alcohol

Hropylene glycol monoethyl ether

Atbase of nitrocjenes compounds

Monoethanolamine

100

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

0.5

Petroleum wax

Microcrystalline wax

Synthetic wax based on carbon

Fisher-Tropsch wax

Polyolefinic synthetic wax

High-density polyethylene wax

Synthetic wax based on rails and oils

Hardened Beaver Oil

Alcoholic ire having iJ> or more carbon atoms

Myristyl alcohol

Light-curing initiator

Reduction agent

Based on diketone-c <.

Quinone camphor

0.01

Based on ketal

Benzyl methyl ketal

0.02

Based on anthraquinone

1,2-benzanthraquinone

0.02

1

Based on thioxanthone

Thioxanthone

0.02

Based on benzoic alkyl ether

Benzoin isopropyl ether

Dimethylaminoethyl methacrylate

0.01

4-dimethylaminobenzoote methyl

0.01

0.01

0.01

Tertiary amine

N, N'-dimethyl-p-toluidine (NB 1)

Alogenous organic compound

Dilauryldimethylammonium chloride (NB 2)

Polymerization inhibitor

Hydroxytolu & butyl

0.03

0.03

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain from plaster models

Well

Well

Well

Well

Visibility (23 ° C, digital DVL B type viscometer manufactured by Tokyo Keikt K.K.) Pa.s

0.00287

0.01400

0.02531

0.01404

Treatment properties (sense of touch with a spatula)

Well

Well

Well

Well

State of the porcelain after incineration and firing (1D0UC, 5 minutes h 60Ü ° Cf 1 minute h 030aC, 1. minute at 730mmHq)

Well

Well

Well

Well

Color tones of the modeling liquid before mixing with the colorless / transparent porcelain

Colorless / T ransoarent ncolore / Transparent icolore / riannparenl

Refractive index (23 ° C Abbe precision refractometer, type three, manufactured by Atago K.K.)

1.4695

1.4530

1.4796

1.4872

Color kendu in mixture with GC Ceramibond M67

Well

Well

Well

Well

Duration required for the technical operation Under normal interior lighting: approx. 300 LX)

More than 5 hours

More than 5 hours

3 over 5 hours

More than 5 hours

23

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

TABLE 1 (CONTINUED)

Example 9

Example 10

Example 11

Example 12

A polymerizable compound

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

50

20

90

50

saturated ethylene linkage eu. ' no

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

50

80

10

50

Organic solvent

Hydrocarbon based

Iso-propylbenzoîne

Based on halogenated hydrocarbon

1,2,3-trichloropiopane E-trachloroethyene

20

150

100 50

Alcohol-based

2-methyl cyclohexanol

Based on acetal ether

Methylphenyl ether 0-cresylmethyl ether

80

Based on ketone

Isophorone

50

Ester-based

Methyl benzoate

Based on polyhydric alcohol l Propylene glycol monoethyl ether

50

A., base of nitrogen compounds

Monoethanolamine

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

Petroleum wax

Microcrystalline wax

I

Synthetic charcoal wax

Fisher-Tropsch wax

2

Polyolefinic synthetic wax

High density polyethylene wax

0.5

Synthetic wax based on rails and oils

Hardened Beaver Oil

3.5

Alcoholic wax with carbon atoms or more

Myristyl alcohol

150

Light-curing initiator

Reduction agent

Based on diketone-cC

Quinone camphor

0.01

Based on ketal

Benzyl dimethyl ketal

Based on anthraquinone

1,2-benzanthraquinone

i

Based on thioxanthone

Thioxanthone

Low £ alkyl ether bcnzotquc

Benzoïl isopropyl ether

0.02

Dimethylaminoethyl methacrylate

0.01

Methyl 4-dimethylaminobenzoate

0.005

Tertiary amine

NjN'-dimethyl-p-toluidine (NB 1)

Alogenous organic compound

Dilauryldimethylammonium chloride (NQ 2)

Polymerization inhibitor

Butyl hydroxytoluene

0.03

0.03

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain from plaster models

Well

Well

Well

Well

Visibility (23 ° C, digital DVL B type DV meter made by Tokyo Keiki K.K.) Pa.s

0.04000

0.00308

0.00310

0.00255

Treatment properties (sense of touch with a spatula)

Well

Well

Well

Well

State of the porcelain after incineration and firing (150 ° C, 5 minutes at 60 ° C, 1 minute at 030nC, 1. minute & 730mmHq)

Well

Well

Well

Well

Color tones of the modeling liquid before mixing with porcelain

Colorless / Transparent colorless / Transparent colorless / 1 ransoarent neelorc / IransDarenl

Refractive index (23 ° C Abbo precision refractometer, type three * manufactured by Atago K.K.)

1.4951

1.4458

1.4831

1.4792

Color rendering when mixed with GC Ceramibond M67

Well

Well

Well

Well

Urea necessary for the technical operation of all normal interior lighting: approx. 300 LX)

More laughs 5 hours

More than 5 hours

More than 5 hours

More than 5 hours

24

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE 1 (CONTINUED)

Example 13

Example 14

Example 15

Example 16

i

A polymerizable compound having at least one ethylenic double bond - unsaturated

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

60

90

50

50

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

40

10

50

50

Organic solvent

Hydrocarbon based

Iso-propylbenzoTne

Based on halogenated hydrocarbon

1,2,3-trichloropropane tetrachlorethylene

Alcohol-based

2-methyl cyclohexanol

100

Based on acetal ether

Methylphenyl ether G-cresylmethyl ether

Based on ketone

Isophorone

Ester-based

Methyl benzoate

50

Based on polyhydric alcohol l Propylene glycol monoethyl ether

A, basques of nitrugene compounds r

Monoethanolamine

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

Petroleum wax

Microcrystalline wax

Synthetic charcoal wax

Fisher-Tropsch wax

Polyolefinic synthetic wax

High-density polyethylene wax

0.5

Synthetic wax based on rails and oils

Hardened Beaver Oil

3.5

Alcoholic alcohol with carbon atoms or more

Myristyl alcohol

150

100

photopolymer initiator

station

Reduction agent

Based on diketone-oC

Quinone camphor

4.5

0.01

Based on ketal

Benzyl dimethyl ketal

Based on anthraquinone

1,2-benzanthraquinone

Based on thioxanthone

Thioxanthone

Basj? of benzoic alkyl ether

Benzoin isopropyl ether

Dimethylaminoethyl methacrylate

Methyl 4-dimethylaminobenzoate

0.01

5.0

Tertiary amine

N, N'-dimethyl-p-toluidine (NB 1)

Alogenous organic compound

Dilauryldimethylnmmonium chloride (NB 2)

Polymerization inhibitor

Butyl hydroxytoluene

0.03

0.03

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain from plaster models

Well

Well

Well

Well

Visibility (23 ° C, DVL B type digital viscometer manufactured by Tokyo Keiki K.K.) Pa.s

0} 01150

0.00643

0.00499

1.00877

Treatment properties (sense of Loucher with a spatula)

Well

Well

Well

Well

State of the porcelain after incineration and firing (150 ° C, 5 minutes at 60 ° C, 1 minute at 030 "C, - 1. minute at 730tnmHcj)

Well

Well

Well

Well

Color tones of the modeling liquid before mixing with porcelain

Colorless / Transparent

Colorless / Transparent

Colorless / Transparent *

ncolore / 'ransparen

Refractive index (23UC Abbe precision refractometer, type three, manufactured by Atago K.K.)

lj4685

1.4283

1.4551

1; 4295

Color rendering when mixed with GC Ceramibond M67

Well

Well

Well

Well

Urea necessary for the technical operation (under normal interior lighting: approx. 300 LX)

More than 5 hours

More than 5 hours

More than 5 hours

More than 5 hours

25

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE 1 (CONTINUED)

Example 17

Example 18

Example 19

Example 20

A polymerizable compound

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

60

60

50

saturated ethylene linkage. no

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

40

40

50

Organic solvent

Hydrocarbon based

Iso-propylbenzoîne

Baso of halogenated hydrocarbon

1,2,3-trichloropropane tetrachlorethylene

Alcohol-based

2-methyl cyclohexanol

100

Based on aceal ether

Methylphenyl ether 0-cresylmethyl ether

Based on ketone

Isophorone

Ester-based

Methyl benzoate

Based on polyhydric alcohol lJropyiene glycol monuiilhyl éLher

Absence of nitrogen compounds

Monoethanolamine

100

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

Petroleum wax

Microcrystalline wax

Synthetic wax 5 base key chnrbon

Fisher-Tropsch wax

Polyolefinic synthetic wax

High density polyethylene wax

0.5

Synthetic wax based on rails and oils

Hardened Beaver Oil

3.5

Alcoholic alcohol having 1> or more carbon atoms

Myristyl alcohol

Photopolymer initiator

station

Reduction agent

Based on diketone-oC.

Quinone camphor

Based on ketal

Benzyl dimethyl ketal

OnLhraquinone-based

1,2-benzanthraquinone

1

Based on thioxanthone

Thioxanthone

Down # of alkyl benzotque

Benzoin isopropyl ether

Dimethylaminoethyl melhacrylate

Methyl 4-dimethylaminobenzoate

Tertiary amine

N, N'-dirnethyl-p-toIuïdine (NÜ 1)

0.1

3.5

0.05

Alogenous organic compound

Dilauryjdimethylammonium chloride (NB 2)

inhibitor

I polymerization

Butyl hydroxytoluene

0.03

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain to go. of models we think

Well

Well

Well

Well

Visibility (23DC, DVL B type digital viscometer manufactured by Tokyo Keiki K.K.) Pa.s

0.02235

0.00520

0.01398

0.00880

Treatment properties (sense of touch with a spatula)

Well

Well

Well

Well

State of the porcelain after incineration and firing (1! 30UC, 5 minutes at 600nC, 1 minute at 030 "C, 1. minute at 730mmHq)

Well

Well

Well

Well

Color tones of the modeling liquid before mixing with porcelain

Colorless / Transparent colorless / Transparent

Colorless / Transparent

Colorless / Transparen

Refractive index (23 ° C Abbe precision refractometer, type three, manufactured by Atago K.K.)

1.4612

1.4533

1.4530

1.4551

Color rendering in mixture with GC Ceramibond Mf »7

Well

Well

Well

Well

Urea necessary for the thermal operation (under normal interior lighting: approx. 300 LX)

More than 5 hours

More than 5 hours

More than 5 hours

More than 5 hours

26

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE 1 (CONTINUED)

Example 21

Example 22

Example 23

Example 24

A polymerizable compound having at least one ethylenically unsaturated double bond

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

50

60

60

50

Pûly works!

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

50

40

40

50

Organic solvent

Hydrocarbon based

Iso-propylbenzoîne

Based on halogenated hydrocarbon

1,2,3-trichloropropane tetrachlorethylene

100 50

Alcohol-based

2-methyl cyclohexanol

Based on acetal ether

Methylphenyl ether 0-cresylmethyl ether

Based on ketone

Isophorone

Ester-based

methyl ßen2oate

Based on polyhydric alcohol iJropyine glycol monoethyl ether

A. base of nitrogen compounds

Monoethanolamine

100

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

Petroleum wax

Microcrystalline wax

Synthetic charcoal-based wax

Fisher-Tropsch wax

Polyolefinic synthetic wax

High density polyethylene wax

0.05

Synthetic wax based on qroisses and oils

Hardened Beaver Oil

3.5

Alcoholic urea having i-> carbon atoms or more

Myristyl alcohol

150

photopolymerization initiator

Reduction agent

Diketone-based - <* w

Quinone camphor

Based on ketal

Benzyl dimethyl ketal

Based on anthraquinone

1,2-benzanthraquinone

l

Based on thioxanthone

Thioxanthone

Basj? of benzoic alkyl ether

Benzoin isopropyl ether

Dimethylaminoethyl methacrylate

Methyl 4-dimethylaminobcnzoate

Tertiary amine

N, N'-dimethyl-p-toluidine (NB 1)

0.05

Alogenous organic compound

Dilauryldimethylammonium chloride (NB 2)

0.1

4.0

0.01

Polymerization inhibitor

Butyl hydroxytoluene

0.03

0.03

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain from plaster models

Well

Well

Well

Well

Visibility (23 ° C, DVL B type digital viscometer manufactured by Tokyo Keiki K.K.) Pa.s

0f00255

0.00520

0.01400

), 00885

Treatment properties (sense of touch with a spatula)

Well

Well

Well

Well

State of the porcelain after incineration and firing (150 ° C, 5 minutes at 600 ° C, 1 minute at 030 "C, 1. minute at 730mmHg)

Well

Well

Well

Well

Color tones of the modeling liquid before mixing with ncolore / fransparent ncolore / Transparent porcelain

Colorless /, ransparent ncolore / ransparen

Refractive index (23 ° C Abbe precision refractometer, type three, manufactured by Atago K.K.)

1.4792

1.4533

1.4530

U4551

Color rendering when mixed with GC Ceramibond M67

Well

Well

Well

Well

Uuróc necessary for the technical operation (under normal interior lighting: approx. 300 LX)

More than 5 hours

3lu5 of 5 hours

More than 5 hours 5

More than hours

27

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE 1 (CONTINUED)

Example 25

Comparative example 1

Comparative example 2

Comparative example 3

A polymerizable compound having at least one ethylenic double bond - unsaturated

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

50

80

50

20

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

50

20

50

80

Organic solvent

Hydrocarbon based

Iso-propylbenzoin

Based on halogenated hydrocarbon

1,2,3-trichloropropane tetrachlorethylene

100 50

Alcohol-based

2-methyl cyclohexanol

Based on acetal ether

Methylphenyl ether O-cresylmethyl ether

Based on ketone laophorone

Ester-based

Methyl benzoate

Based on polyhydric alcohol prapyienis glycol monoethyl ether

ALbasp of nitrogen compounds

Monoethanolamine

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

Petroleum wax

Microcrystalline wax

Synthetic charcoal-based wax

Fisher-Tropsch wax

Polyolefinic synthetic wax

High density polyethylene wax

Wax, synthetic based on rails and oils

Hardened Beaver Oil

alcoholic wax having l-> carbon atoms or more

Myristyl alcohol

150

Light-curing initiator

Reduction agent

Based on ketone-cC

Camphor quinonc

0.0005

6

0.01

Based on ketal

Benzyl dimethyl ketal

Based on anthraquinone

1,2-benzanthraquinone

1

Based on thioxanthone

Thioxanthone

Basj? of benzoic alkyl ether

Benzoino isopropyl ether

Dimethylaminoethyl methacrylate

0.01

Methyl 4-dimethylaminobenzoate

0.01

0.0005

Amine tertiniro

NjN'-dimethyl-p-toluTdinc (NB 1)

Alogenous organic compound

Dilauryldimethylammonium chloride (NB 2)

0.01

Polymerization inhibitor

Butyl hydroxytoluene

0.03

0.03

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain from plaster models

Well

Bad

Well

Bad

Visibility (23 ° C, digital DVL B type vmeter made by Tokyo Keiki K.K.) Pa.s

0.00261

0.00672

0.00499

0.00269

Treatment properties (sense of touch with a spatula)

Well

Bad

Well

Bad

State of the porcclainc after incineration and cooking (150UC, 5 minutes at 600 ° C, 1 minute at B30 ° C, 1. minute h 730mmHg)

Well

Well

Well

Well

Color tones of the modeling liquid before mixing with the porcelain

Colorless / T ransDarent

Colorless / Transparent

Yellow / 1ransparcnl

Colorless / Transoaren

Refractive index (23 ° C Abbe precision refractometer, type three, manufactured by Atago K.K.)

1.4792

1.4525

1.4545

1.4545

Color rendering in mixture with GC Ceramibond M67

Well

Well

Bad

Well

Uuree necessary for the technical operation (under normal interior lighting: approx. 300 LX)

More than 5 hours

More than 5 hours

About 10 minutes

More than 5 hours

28

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE 1 (CONTINUED)

Comparative example 4

Comparative example 5

Comparative example 6

Comparative example 7

A polymerizable compound having at least one unsaturated ethylenic double bond

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

20 20

50

60

60

Pol y functional

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

60

50

40

40

Organic solvent

Hydrocarbon based

Iso-propylbenzoin

Based on halogenated hydrocarbon

T Etrachloroeth ^ I 1,2,3-trichloropropane

Alcohol-based

2-methyl cyclohexanol

100

Based on acetal ether

Methylphenyl ether 0-cresyimethyl ether

Based on ketone

Isophorone

Ester-based

Methyl benzoate

Based on polyhydric alcohol

Clear propylene glycol LUyl ether

A ^ bnsç of nitrogen compounds

Monoethanolamine

100

Solid or semi-solid organic matter at normal temperature

Natural wax

Alba wax

Petroleum wax

Microcrystalline wax

SynLhetic wax based on charcoal

Fisher-Tropsch wax

Polyolefinic synthetic wax

High polyethylene wax

Synthetic wax based on oils and oils

Hardened Beaver Oil

Read alcoholic having 1J or more carbon atoms

Myristyl alcohol

Photopolymer initiator

station

Reduction agent

Based on diketone-c <.

Quinone camphor

0.01

Based on ketal

Benzyl dirnethyl ketal

Based on anthraquinone

1,2-benzanthraquinone

Based on thioxanthone

Thioxanthone

Based on benzoic alkyl ether

Benzoin isopropyl ether

Dimethylaminoethyl methacrylate

Methyl 4-dimethylaminobcnzoatc

12

Tertiary amine

N, N'-dimethyl-p-toIuTdine (NB 1)

0.01

6

Alogenous organic compound

Dilauryldimethylammonium chloride (NB 2)

Polymerization inhibitor

Butyl hydroxytoluene

0.03

0.03

0.03

0.03

Evaluation criteria

Attachability and formaliLity of porcelain from plaster models

Well

Bad

Bad

Well

Visibility (23DC, digital vtscometer type DVL D manufactured by Tokyo Keiki K.K.) Pa.s

0.00528

0.01370

0.00515

3.01399

Treatment properties (sense of touch with a spatula)

Good n'h treated

Bad

Well

State of the porcelain after incineration and firing (15DUC, 5 minutes at 60 ° C, 1 minute at 83GDC, 1. minute at 730mmHg)

Well

Well

Well

Well

Color tones of the modeling liquid before mixing with porcelain

Yellow / Transparen

Colorless / Transparent

Colorless / Transparent

Yellow / ranSDaren

Refractive index (23 "C Abbe precision reïctor, type three, manufactured by Atago K.K.)

1.4640

1.4555

1.4533

1.4530

Color rendering when mixed with GC Ceramibond M67

Bad

Well

Well

Bad

Urea necessary for Lechnique operation (under normal interior lighting: approx. 300 LX)

About 10 minutes

Within hours

More than 1? '5 hours

About minutes

29

5

10

15

20

25

30

35

40

45

50

55

60

CH 682 214 A5

TABLE 1 (CONTINUED)

Comparative example

0

Comparative example 9

Comparative example 10

Comparative example 11

A polymerizable compound having at least one functional unsaturated ethylenic double bond

2-hydroxyethyl methacrylate Phenoxyethylacrylate

50

50

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane. triacrylate

_ 50_ _

50

Pure water

Case, in which i \ is not

Pure water

Case in which a margina separator made by Ishifuki Kinzoku K.I is used for the working model in Plaster

Organic solvent

Based on lso-propylbenzo7ne hydrocarbon

no separation material used for the plAtm working model

Based on halogenated hydrocarbon

1,2,3-trichloropropane tetrachlorethylene

. _ 100_ _

50

Alcohol-based

2-methyl cyclohexanol

Based on acetal ether

Methylphenyl ether O-cresylinethyl éLhcr

Based on ketone

Isophorone

Ester-based

Methyl benzoate

Based on polyhydric alcohol l Propylene glycol monoethyl ether

A ^ bnse of nitrogen compounds r

Monoethanolamine

Solid or semi-solid organic matter b normal temperature

Natural wax

Nlba wax

Petroleum wax

Microcrystalline wax

Synthetic wax based on carbon

Fishcr-Tropsch wax

Synthetic wax Polyolefinic wax

High density polyethylene wax

0.5

Synthetic wax based on rails and oils

Hardened Beaver Oil

3.5

Read alcoholic having '1J carbon atoms or more

Myristyl alcohol

150

Light-curing initiator

Reduction agent

Based on diketone-c <»

Quinone camphor

Based on ketal

Benzyl dimethyl ketal

Based on nnthrnquinone

1,2-benznnLhraquinone

f

Based on thioxanthone

Thioxanthone

Based on benzoic alkyl ether

BenzoTne isopropyl ether

Dimethylaminoethyl methacrylate

Methyl 4-dimethylaminobenzoate

Terine amine

NjN'-diinethyl-p-toluidine (NB 1)

Alogenous organic compound

Dilauryldimethylammonium chloride (NB 2)

0.005

6

Inhibitor

1st polymerization

Butyl hydroxytoluene

0.03

0.03

Evaluation criteria

Attachability and formality of porcelain 5 from plaster models

Mauvaix

Well

Visibility (23 ° C, digital viscometer type DVL B manufactured by Tokyo Kciki K.K.) Pn.s

0.00878

0.00250

Treatment properties (sense of touch with a spatula)

Mauvaix

Well

State of the porcelain after incineration or firing (15I) UC, xj minutes h 60Ü "C, 1 minute h B3CJnC, 1. minute h 730inmHq)

Well

Well

Color tones of the modeling liquid before mixing with porcelain

Colorless / Transparent

Yellow / Transparent

Colorless / Transparent

Colorless / rransparenl

Refractive index (23 "C Abbe precision refractometer, type three, manufactured by Atago K.K.)

1.4550

1.4791

Color rendering when mixed with GC Ceramibond M67

Rnn

Bad

Urea necessary for the technical operation (under normal interior lighting: approx. 3UÜ LX)

More than 5 hours

About 5 minutes

More than 5 hours

More than 5 hours

30

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

TABLE 1 (CONTINUED)

Comparative example 12

Comparative example 13

Example, comparison n

A polymerizable compound

Functional

2-hydroxyethyl methacrylate Phenoxyethylacrylate

Case, in which - which 1 part by weight of

• SM liquid manufactured for Ducer

, Co. Ltd (liquid which may be

• cooked by cooking)

Spectrum Shoulder a Porcelain VLC Mediur manufactured by uentspl Co. Ltd (liquid which can be treated for light emission

saturated ethylene bond

\ Ue. no

Poly functional

Ethylene glycol dimethacrylate Trimethylolpropane. plastodent triacrylate (orang wax "made by Degussa K.K

n y

Organic solvent

Hydrocarbon based

Iso-propylbenzoin is fused for mixing

Based on halogenated hydrocarbon

1,2,3-Trichloropropane Tetrachlorethylene

Alcohol-based

2-methyl cyclohexanol

Based on acetal ether

Methylphenyl ether 0-cresylmethyl ether

Based on ketone

Isophorune

Ester-based

methyl methyl

Based on polyhydric alcohol

Propylone glycol monotiLhyl éLher

ALbasç of nitrugunea compounds

Monoethanolamine

Solid or semi-solid organic matter at normal temperature

Natural wax

Nlba wax

Petroleum wax

Microcrystalline wax

Synthetic charcoal wax

Fishcr-Tropsch wax

Polyolefinic synthetic wax

High density pnlyetlwlene wax

Synthetic wax based on ciraissea and oils

Hardened Beaver Oil

Alcoholic alcohol with carbon otomes or more

Myristyl alcohol

Photopolymer initiator

station

Reduction agent

Based on diketone-c <.

Camphor quinonc

Based on ketal

Denzyle dimethyl ketal

Based on anthraquinone

1,2-benzanthraquinone

t

Based on thioxanthone

1 hioxanLhone

Down # of benzoic alkyl ether

BenzoTne isopropyl ether

Dimethylaminoethyl methacrylate

4-dimethylaminûbenzoatc methyl

Tertiary amine

NjN'-dimethyl-p-toluTdine (NÜ 1)

Alogenous organic compound

Dilauryldimethylammonium chloride (NB 2)

Polymerization inhibitor

Butyl hydroxytoluene

Evaluation criteria

Attachability and formality of porcelain from plaster models

Well

Bad

Well

Visibility (23nC, digital viscometer type DVL B manufactured by Tokyo Keiki K.K.) Pa.s

-

0.00922

0.97997

Treatment properties (sense; touch with a spatula)

Well

ßon

&we

State of the porcelain after incineration and firing (15UUC,!> Minutes at 600 ° C, 1 minute n3n ° C, 1. minute? D 730mmHq)

Bad

Well

Bad

Color tones of the modeling liquid before mixing with the porcelain

Colorless orange /. _ ransparent l

Yellow / transparent

Refractive index (23 "C Abbe precision refractometer, Lype three, manufactured by Atago K.K.)

-

1.33S1

1.4800

Color Keridu in mixture with GC Ceramibuiul M67

Bad

Bad

Bad

Duration required for the technical operation (under normal interior lighting: approx. 30U LX)

1-2

minutes

^ read from E? hours 2

about hours

(NB 1): In the case of modeling liquids in which N, N'-dimethyl-p-toluidine was used, 0.25 part by weight of benzoic peroxide was used as organic peroxide previously incorporated using a mortar in 100 parts by weight of a porcelain material having the characteristics of the evaluation.

(NB 2): In the case of modeling liquids in which dilaurylmethylammonium chloride was used, 0.2 part by weight of N-cyclohexyl-5-ethylpyrimidine-trione was used as derivative of pyrimidinetrione and 0.01 part by weight of acetylacetone copper as organometail compound previously incorporated using a mortar in 100 parts by weight of a porcelain material having the characteristics of the evaluation.

31

5

10

15

20

25

30

35

40

45

50

55

CH 682 214 A5

The modeling liquid samples of Examples 1-4 each include the photopolymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator, a reducing agent and a ploymerization inhibitor. Examples 5-7 each include the photopolymerizable compound having at least one unsaturated ethylenic double bond, an organic solvent, a photopolymerization initiator, a reducing agent and a photopolymerization inhibitor. Examples 8-10 each include the photopolymerizable compound having at least one unsaturated ethylenic double bond, an organic solvent, a solid or semi-solid organic material at normal temperature, a photopolymerization initiator, a reducing agent and a polymerization inhibitor . Examples 11-13 each include the photopolymerizable compound having at least one unsaturated ethylenic double bond, an organic solvent, a solid or semi-solid organic material at normal temperature and a polymerization inhibitor. Examples 14-15 each include the photopolmerizable compound having at least one unsaturated ethylenic double bond, a solid or semi-solid organic material at normal temperature, a photopolymerization initiator, a reducing agent and a polymerization inhibitor. Example 16 includes the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond, a solid or semi-solid organic material at normal temperature and a polymerization inhibitor. Example 17 includes the organic solvent and the solid or semi-solid organic material at normal temperature. Examples 18-21 each include the polymerizable compound having at least one unsaturated ethylenic double bond and toludine-N, N'-dimethyl-p as the tertiary amine, which allows a reaction with the organic peroxide added to the porcelains for treatment. . Finally, Examples 22-25 each comprise the polymerizable compound having at least one ethylenically unsaturated double bond and dilauryldimethylammonium chloride as halogenated organic compound, which allows a reaction with the pyrimidinetrione derivative and the organometallic compound added to the porcelains. for treatment. The modeling liquids relating to examples Nos 1—10 and 14-15 are treated under exposure to light, while the liquids relating to examples Nos 11-13 and 16-17 are treated by allowing the solid or semi-organic matter solid at normal temperature either precipitated by volatilization of the organic solvent or of the photopolymerizable or polymerizable compound having at least one ethylenic double bond unsaturated. The modeling liquids relating to examples Nos 18-25 are treated by reaction of the polymerization promoter which they contain, the polymerization initiator contained in the porcelain not being exposed to light. In Examples 3-4, the amount of incorporated photopolymerization initiator is smaller, while in Example 14, the amount of incorporated photopolymerization initiator is larger. In Example 10, the amount of reducing agent contained is smaller, while in Example 15, the amount of reducing agent contained is greater. In Example 19, the amount of tertiary amine incorporated is smaller, while in Example 20, the amount of tertiary amine incorporated is greater. In Example 23, the amount of halogenated organic compound added is smaller, while in Example 22, the amount of halogenated organic compound is larger. However, since these examples are all situated within the ranges defined in the appended claims, the quantities being smaller or larger than the average value of the range, there are no problems arising in relation to the properties assessed. In Example 17, no polymerization inhibitor is added, due to the absence of the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond. All the modeling liquids relating to these examples are satisfactory with regard to the properties evaluated.

Comparative examples 1-4 were carried out so as to define the amounts of the photopolymerization initiator and of the reducing agent, while comparative examples 6-9 were carried out so as to define the amounts of tertiary amine and halogenated organic compound. In Comparative Example 1, the amount of photopolymerization initiator is smaller than the lower limit defined in claim, while in Comparative Example 2, the amount of photopolymerization initiator is larger than the upper limit defined in the claims. In Comparative Example 3, the amount of reducing agent is less than the lower limit defined in claim, while in Comparative Example 4, the amount of reducing agent is greater than the upper limit defined in the claim. When the quantities of initiators and reducing agents are smaller than the lower limits, the treatment by exposure to light becomes so bad that the toughness or detachability of the porcelain compared to the plaster working model is lower and is accompanied by a decrease in its formability. When, on the other hand, these values are greater than the upper limits, the modeling liquids take on a yellow coloring before being mixed with porcelains. In addition, under exposure to normal indoor light, the light reactivity of modeling liquids is so high that when mixed with porcelain, they start to react immediately and cannot be used. In Comparative Example 6, the amount of the tertiary amine is smaller than the lower limit defined in claim, while in Comparative Example 7, the amount of the tertiary amine is greater than the upper limit defined in claim. In Example 8, the amount of the halogenated organic compound is smaller than the lower limit defined in claim, while in Comparative Example 9 the amount of tertiary amine is greater than the upper limit defined in claim . When the amounts of the halogen compound and the amine are smaller than the lower limits, the treatment by exposure to light becomes so bad that the attachability or detachability of the porcelain compared to the working model

32

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

plaster is lower and is accompanied by a decrease in its formability. When these values are greater than the upper limits, the modeling liquids take on a yellow color before being mixed with porcelain. On the other hand, in an environment of 23 ° C, the light reactivity of modeling liquids is so high that when mixed with porcelain, they start to react immediately and cannot be used. In Comparative Example 5, the modeling liquid consists solely of a photopolymerizable or polymerizable compound having at least one unsaturated ethylenic double bond and the organic solvent, and contains no component contributing to its treatment. As a result, it can be condensed with its low viscosity, but cannot give porcelains a better attachability or detachability compared to the plaster working model, any more than better forming properties. In Comparative Examples 10 and 11, pure water generally used in other cases relating to the present invention is used. In Comparative Example 10, no separating agent is applied to the plaster model, while in Comparative Example 11, use is made of the Margin Separator manufactured by Ishifuku Konzoku Co. Ltd. as separation material for the plaster model. In Comparative Example 10, since the applied porcelain is inclined to be deposited on the plaster model, even specialists can neither attach it, detach it from the model, nor form it. In Comparative Example 11, some specialists can carefully form the porcelain by attaching or detaching it from the plaster model, since the separating agent is applied to it; but this operation often fails. In some cases, the modeling liquids differ considerably in terms of their refractive index with respect to water (1.3327 at 23 ° C). As a result, it is impossible to make a preliminary estimate of the color tones that the modeling liquids will take when mixed with the GC Ceramibond M67 manufactured by GC Toshi Kogyo Corporation. In Comparative Example 12, 1 part by weight of Plastodent (orange wax) manufactured by Degussa Company is melted using a gas burner and mixed with 6 parts by weight of GC Ceramibond M67. It is absolutely impossible to make a prior estimate of the color of the porcelain after it has been sintered, since the orange tone of this wax is reflected. In addition, since the wax is not condensed, but produces a lot of carbon, the carbon thus produced can contaminate the interior of the porcelain stove and cause its deterioration, when the porcelain is subjected to the operation. incineration. On the other hand, even when the wax is melted using a gas burner, then incorporated into the procelaine, it solidifies immediately after being cooled to room temperature, due to its high degree of crystallinity and therefore cannot be used. This is why the time granted for this dental operation does not exceed 1-2 minutes when the total quantity of porcelain is approximately 2 grams. The wax is then very difficult to handle. In Comparative Example 13, SM Liquid manufactured by Ducerà Co. Ltd. is used. Designed to be heated and treated with hot air from a dryer, etc., the liquid is capable of being deposited on the plaster model during the treatment, so that its detachability compared to the plaster model is much lower. It is also impossible to make a preliminary estimate of the color that this liquid will take when it is mixed with GC Ceramibond M67 and sintered, since its refractive index (from 1.3381 to 23 ° C) is very close to that of water. In Comparative Example 14, the Spectrum Shoulder Porcelain VLC Medium made by Dentsply Co. Ltd. is used. Although having good processing properties, this liquid has a viscosity of 0.9799 Pa.s, so that it cannot be condensed, making it impossible to remove excess parts. This is why the black carbon remains after incineration and cooking. Due to the fact that it contains many catalysts such as photopolymerization initiators and reducing agents, the liquid itself takes on a yellow color and it is perfectly impossible to estimate the color which it will take when it is mixed with GC Ceramibond M67 and then baked.

We will now expose the effects of the modeling liquid for dental porcelain realtifs to the present invention.

(In order to prevent the metallic color of the cervical edge of a metallic screed from appearing by transparency or being exposed directly to the view, porcelains are applied with the marginal porcelain technique but without adapting the metallic screed to the cervical edge) .

1. After having been mixed with the porcelain, the modeling liquid for dental porcelain relating to the present invention is mounted on the cervical edge and then exposed to light or reacted with the organic peroxide or the pyrimidinetrione derivative and the compound organo-metallic contained in porcelain; or other possibility: the organic solvent is volatilized. The porcelain thus treated is temporarily linked to the metal screed and is thus easily removed from the plaster working model. Therefore, delicate dental operations, such as the mounting and sintering of refractory porcelain, can be eliminated. As a result, the time allowed for this dental work can be considerably reduced with further improvements in the accuracy of the fitting.

2. The mounting of porcelain on a metal screed covered with a platinum sheet is delicate and time-consuming. It does not keep the cervical edge in good condition and involves considerable expense due to the cost of the platinum sheet. The modeling porcelain for dental porcelain relating to the present invention is much less expensive than the platinum sheet, say in proportions varying between one tenth and a few tenths and one hundredth and a few hundredths, which leads to cost reductions.

3. When porcelains are condensed with water in order to be removed, as is done with

33

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

conventionally, the shape of the cervical edge is retained as well, only in the case of a wet connection, so that it loses its shape, even if it is subjected to a slight vibration or a small impact. Thus, this method cannot be used for a bridge work using several support teeth. In addition, this method requires a lot of skill. Thus, porcelain can be removed so easily from a plaster working model that the shape of the cervical edge can be retained until the end. This technique makes it possible to immediately remove the porcelain shown on the cervical edge of the plaster working model without any manual dexterity and can be easily used for bridge work using several supporting teeth. When porcelains are condensed with water in order to be removed, as is conventionally done, it is necessary to apply to the cervical edge of the plaster working model, a water-repellent separating or treatment material. surface, in order to easily remove the condensed porcelain. Thus, the adaptation of the porcelain on the cervical edge becomes relatively less good depending on the thickness of the separation or surface treatment material used. After having been mixed with porcelains and placed, the dental porcelain modeling liquid relating to the present invention is treated by exposure to light or by reaction with the organic peroxide or the pyrimidinetrione derivative and an organometallic compound contained in porcelain. Porcelain can therefore easily be removed from a plaster working model without the need to use a water-repellent separating material or a surface treatment material. Consequently, the adaptation of the cervical edge of the porcelain bonded by firing on the plaster working model or even on the support teeth of a patient is considerably improved.

4. The modeling liquid for dental porcelain relating to the present invention has a viscosity sufficient for condensation after having been mixed with porcelain and put in place and before exposure to light or reaction with the organic peroxide or the pyrimidinetrione derivative and the organo-metallic compound contained in porcelain. So, when there is an excess of moderation liquid, this can be removed with tissue paper or gauze. In accordance with the present invention, the solid or semi-solid organic material at normal temperature is diluted with an organic solvent. After having been mounted, the porcelain is heated to a temperature higher than the boiling point of the organic solvent in order to volatilize only the organic solvent, an operation during which the shape of the porcelain can be preserved with a small amount of the residue of wax. The following incineration, on the other hand, can improve the fired porcelain due to the small amount of the wax residue. Therefore, it is not to be feared that a significant quantity of carbon will be produced during the incineration at the risk of contaminating or damaging the stove.

5. The modeling porcelain for dental porcelain relating to the present invention must not be softened by heat and the liquid will not be softened by heat or will not flow under the effect of compressed air, so that the porcelain will not have to flow on the metal screed. This is why, the adhesion of porcelain on the plaster model on the cervical edge of the metal cap or even on the support teeth of a patient is considerably improved.

6. The modeling liquid for dental porcelain relating to the present invention can be well condensed. In addition, it can be sintered after removing an excess amount of the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond. When the photopolymerizable or polymerizable compound having at least one ethylenically unsaturated double bond has a high viscosity or the photopolymerization reaction, or when the reaction with the organic peroxide or pyrimidinetrione and the organometallic compound contained in the porcelain is very slow, the solid or semi-solid organic matter at normal temperature and the photopolymerizable or polymerizable compound having at least one unsaturated ethylenic double bond, are dissolved beforehand in an organic solvent having a high boiling point. After assembly and condensation, the porcelain is heated in order to remove the solvent indicated above. Since the remainder of solid or semi-solid organic matter at normal temperature solidifies, it is possible to keep the shape of the porcelain as it was assembled.

(In order to obtain dental prostheses as close as possible to natural teeth, special effects are added to porcelains using porcelain materials, internal or external coloring).

1. The modeling porcelain for dental porcelain relating to the present invention has a refractive index of 1.4 to 1.6 at 23 ° C, while porcelains have a refractive index of 1.47 to 1.50. This modeling liquid is not subject to any substantial change in its refractive index before and after exposure to light or reaction with organic peroxide or a pyrimidinetrione derivative and an organometallic compound contained in porcelain, i.e. d. before and after treatment. Thus, when certain materials are chosen from a number of porcelain materials of internal or external coloring, so as to produce the special effect desired for the porcelain, by reproducing sophisticated color tones, even novice people can make an estimate. prior to the color tone of porcelain after firing. This is why it is possible to prevent the defects which cause the porcelains to be reassembled as often as necessary, in a mixture with water, since the color tone of the porcelain can be estimated beforehand. This allows anyone to be able to obtain the production of special effects, production which until now had only been carried out by specialists. Internal and external coloring porcelain materials mixed with fashion liquid-

34

5

10

15

20

25

30

35

40

45

50

55

60

65

CH 682 214 A5

The age of the present invention can be treated by exposure to light or reaction with organic peroxide or a pyrimidinetrione derivative and an organometallic compound contained in porcelain. This also allows anyone to be able to make or apply porcelain on the desired location with the desired thickness and the desired extension. In addition, the time required for the dental operation is from one tenth to a few tenths of that usually required and the porcelain materials of internal or external coloring in the desired color tones can be selected with precision. For this reason, the special effects can be so easily applied to porcelain that the prosthesis can be improved in its aesthetic appearance with improvements in the quality and productivity of the work.

2. The modeling porcelain for dental porcelain relating to the present invention is designed to be mounted by exposure to light or reaction with organic peroxide or a pyrimidinetrione derivative and an organometallic compound contained in the porcelain for its treatment. For this reason, when these special effects such as internal defects including cracks, yellowing etc. or external defects and insufficient calcification are reproduced on porcelain, these can be carried out using a fine brush, so as to easily cover such internal stains without any dexterity. It is therefore possible for anyone to carry out the required operations with ease and without any manual dexterity. Consequently, it is possible to produce these special effects with constant quality on porcelains based on porcelain materials of internal or external coloring and at any desired time, provided that no mixing of colors or thickening of the no line or blurring effect can occur, as is the case with mixing with water.

Claims (15)

Claims 1. Modeling liquid used for the manufacture of dental porcelain and comprising: (A) a photopolymerizable compound having at least one unsaturated ethylenic double bond, (B) a photopolymerization initiator, (C) a reducing agent, and (D) a polymerization inhibitor. 2. Liquid according to claim 1, characterized in that it comprises an organic solvent. 3. Liquid according to claim 1, characterized in that it comprises a solid or semi-solid organic material at normal temperature. 4. Liquid according to claim 1, characterized in that it comprises an organic solvent and a solid or semi-solid organic material at normal temperature. 5. Liquid according to one of claims 1 to 4, characterized in that it has a refractive index of 1.4 to 1.6 at 23 ° C. 6. Liquid according to one of claims 1 to 5, characterized in that it has a viscosity of 0.1 Pa.s or less at 23 ° C. 7. Liquid according to one of claims 1 to 6, characterized in that the photopolymerizable compound is a monofunctional methacrylate. 8. Liquid according to one of claims 1 to 6, characterized in that the photopolymerizable compound is a polyfunctional methacrylate. 9. Liquid according to one of claims 1 to 6, characterized in that the photopolymerizable compound is a monofunctional acrylate. 10. Liquid according to one of claims 1 to 6, characterized in that the photopolymerizable compound is a polyfunctional acrylate. 11. Liquid according to one of claims 2, 4, 5, 6, 7, 8, 9 or 10, characterized in that the organic solvent comprises at least one solvent chosen from the group of solvents comprising solvents based on hydrocarbons, halogenated hydrocarbons, alcohol, ether-acetal, ketone, ester, polyhydric alcohol and its derivatives, and a nitrogen compound. 12. Liquid according to one of claims 3 to 10, characterized in that the solid or semi-solid organic material comprises at least one material chosen from the group comprising natural waxes, petroleum waxes, synthetic waxes based on carbon, polyolefin synthetic waxes, synthetic fats based on fats and oils, alcohol waxes having at least 13 carbon atoms. 13. Liquid according to one of claims 1 to 12, characterized in that the photopolymerization initiator comprises at least one initiator chosen from the group comprising compounds based on diketo-ne-a, ketal, anthraquinone, thioxanthone, alkyl ether banzoin and their derivatives. 14. Liquid according to one of claims 1 to 13, characterized in that the photopolymerization initiator is added in a range of 0.001 part by weight inclusive to 15 parts by weight exclusively per 100 parts by weight of the photopolymerizable compound. 15. Liquid according to one of claims 1 to 14, characterized in that the reducing agent is added in a range from 0.001 part by weight inclusive to 20 parts exclusively per 100 parts by weight of the photopolymerizable compound. 35