JPS61226035A - Tooth crown repairing material having natural tooth appearance and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application of I11' Industry 1 to J The present invention relates to a dental crown restorative material having an appearance similar to a natural tooth.

[Prior Art] As dental materials such as dentures, tooth roots, dental crowns, inlays, and puddings, as well as biomedical ceramic materials such as surgical materials and aggregates, for example, Japanese Patent Publication No. 1145! +-1+625 publication, Ca028-57wt%, P20r, ? 2-43w
t% of! + glass, or more than IOi+t%
Glass added with Ah03.5i02 or H203 is melted, molded and then heat treated to obtain a crystallinity of 20% or more.
Calcium phosphate-based crystallized glass crystallized in ... has been proposed.

This calcium phosphate crystallized glass is extremely similar in composition to natural teeth or natural aggregates, and its physical, chemical, and mechanical properties are also close to those of natural teeth or natural aggregates, and it is similar to that of natural teeth or natural aggregates. It has good stainability, and can be manufactured through an intensive process in which the raw material powder is melted into a glass-like form, poured into a mold, molded into the desired shape, and then crystallized, and the shrinkage rate during the manufacturing process is also low. Because precision machining is not required even for complex shapes within 1%, it has superior properties and can be mass-produced as a biomedical ceramic material such as dental materials and surgical artificial bone materials compared to conventional metal materials and ceramic materials. Sex is expected.

[Problem to be solved by the invention 1 However, although the dental crown restoration material or denture made of such calcium phosphate crystallized glass is white, translucent, and has a gloss similar to that of human teeth, it has a yellowish color to humans. There was a noticeable difference in color between the teeth and the natural teeth, and the appearance was not desirable.

Furthermore, by adding a coloring component to the dental crown restorative material made of this calcium phosphate-based crystallized glass, it is possible to uniformly impart a fungal-like color similar to natural teeth to the dental crown restorative material. However, actual natural teeth have a distribution of colors, and this coloring method cannot achieve aesthetics that can be put to practical use.

- Currently, with porcelain jacket crowns, etc., feldspathic glass powder added with a blue agent is applied to the crown surface and then subjected to appropriate heat treatment to form a foil-colored layer on the surface, giving it an appearance similar to that of natural teeth. ing. The present inventor attempted to form a colored layer on the surface of calcium phosphate crystallized glass using these feldspar-based glass powders for coloring, but deformation of the dental crown restoration material due to the high heat treatment temperature at which the glass powder was baked; It has been found that there are problems such as the occurrence of cracks in the colored layer due to the difference in expansion coefficient between the base material and the colored layer, and peeling of the colored layer due to weak adhesive strength between the base material and the colored layer.

[Means for Solving the Problems J] The present invention was invented as a result of research for the purpose of providing a calcium phosphate-based crystallized glass dental crown restorative material that is free from the above defects and has an appearance similar to natural tooth structure. The gist is a base material made of crystallized glass containing 90 wt % or more of calcium phosphate with a Ca/P atomic ratio of 0.35 to 0.7, and a part or part of the outer surface thereof. The whole contains calcium phosphate with a Ga/P atomic ratio of 0.1 to 0.7 at 70 wt% or more and a coloring component of 0.01 to 10 wt%.
The present invention relates to a dental crown restorative material having a structure that is provided with a colored layer of glass or crystallized glass containing 50% by weight and having an appearance similar to a natural tooth.

The present invention also relates to a method for producing the calcium phosphate-based crystallized glass dental crown restorative material having an appearance similar to natural tooth structure.

The present invention will be explained in more detail below.

The composition of the calcium phosphate-based crystalline glass used in the present invention (in the present invention, crystalline glass means one that has been uncrystallized, and crystallized glass means one that has undergone crystallization treatment) is as follows: Calcium metaphosphate (CaO・P?Q5J) has a chain structure both in the crystalline state and in the crystalline state. The atomic ratio with phosphorus is Ca/P or 0.
35 to 0.7, that is, the composition of the base calcium phosphate crystalline glass is Ca028 to 3 Bilt.
%.

The optimum composition is 572 to 84 wt% P2O.

If the Ca/P ratio exceeds 0.7, vitrification becomes difficult and undesirable, and if it is lower than 0.35, crystallization tends to occur, making it impossible to obtain homogeneous crystallized glass and reducing the phosphorus content. If the amount is excessive, the water resistance will deteriorate, which is undesirable. Calcium phosphate-based crystallized glass with this composition is based on the composition of natural teeth and aggregates, that is, calcium phosphate-based crystalline and amorphous materials, and contains calcium and phosphorus) L(X 1tCa/P or about 1.75~ It has a composition similar to that in the range of 2.0 and has good affinity with living organisms.According to the glass with the composition 1. A dental crown restorative material can be obtained by a simple process of pouring and crystallizing.This is a material with a Ca/P atomic ratio of 0.35 to 0.7, which is used as a base material in the present invention. It is a crystallized glass containing calcium phosphate in an amount of Hwt% or more.

In the present invention, Al1 [13 , B2O3, Ga
10wt of 2O3 etc. to calcium phosphate glass
% or less. ] Owt% or more, the melt viscosity becomes too high, making it difficult to mold by pouring into a mold, and cracks are likely to occur during the crystallization process, making it impossible to obtain a crown restorative material with high strength.

The present invention uses calcium phosphate having a composition of 0.1 to 0.7 in the Ca/P atomic ratio as a suitable MIr for glass or crystallized glass used as a colored layer.
This invention discloses a composition containing 0.0 l to 10 vt% of a coloring component. Glass or crystallized glass of this composition can form a colored layer at a temperature of 900'0 or higher, at which the base material, calcium phosphate crystallized glass, is not deformed, has high adhesive strength with the base material, and It has a thermal expansion coefficient equivalent to that of the material mentioned above, and an even higher +f
i) It has corrosion resistance and water resistance. If the calcium phosphate content is less than 70 wt%, the colored layer will not be dense at temperatures below 900°C and will not have good contact with the base material, which is not preferable. Also, Ga/P is O, IjifX14
If so, the water resistance of the colored layer will be net, and Ca/P will be 0.
．． If the temperature exceeds 700℃, the colored layer will not be dense and good adhesion to the material will not be obtained, which is undesirable.If the coloring component is less than 0.01wt%, the coloring properties will be poor. If it exceeds 10 t%, the color of the tooth becomes too dark and is not suitable.

The thickness of the colored layer is suitably 0.01 to 2.0 mm.

0. (If it is less than 111IIm, the coloring effect is not sufficient,
Even if the thickness is made thicker than 2.0■, no further effect can be expected. Further, the colored layer contains Al2O3 and B2O3 in order to improve the water resistance of the colored layer.

It can contain less than 20% of Ga203 or the like.

If it is 20 wt % or more, it becomes impossible to form a colored layer without deforming the base material made of calcium phosphate crystallized glass, which is not appropriate.

The method for forming such a surface colored layer is not particularly limited as long as it can form a strong contact 71 with the base material without deforming the material (made of calcium phosphate crystallized caramel), Glass powder of the composition is kneaded with liquid to form a slurry, which is made of calcium phosphate crystallized glass), (
A method in which the desired part of the outer surface of the material is coated, followed by drying and heat treatment and subsequent printing is preferred because it is easy to apply and can express a uniform color distribution. The average particle size of the glass powders 1 to 1 is 0. ] μm to 100 pLm is suitable, and 0.5 to 5 Qpm is particularly preferable.・V average particle size is 0
．． If it is less than 1 p-m, the bulk density of the powder layer after coating and drying will be small, and a dense colored layer will not be formed after heat treatment. Moreover, if the average particle size exceeds 11007 L, the subsequent printing will not be carried out every 1 to 1 minute, and a dense colored layer will not be formed. The liquid used for kneading this powder is not particularly limited as long as it has the ability to knead the powder and does not generate scum or combustion residue during heat treatment, but it can be used as a solvent such as water or glycerin. Or a mixture thereof is preferred. ^Rani base material-4-1
How to coat the slurry 7), also #1 i! There is no limit to this, and tipping, spraying, etc. can also be used, but they are suitable! , I.J.
To achieve a color distribution of 4.J'7', painting methods (painting with a brush, flange, etc.) are preferred.

Heat treatment stage 1 is a drying process, and the combustion process of IJ1 component can be adopted as appropriate, but the maximum heat treatment temperature is 600-9
00℃ is appropriate, especially 700-900℃ is 111
Delicious. At temperatures below 600°C, the formation of a dense six-color layer and the adhesion between the colored layer and the base material made of calcium phosphate crystallized glass do not proceed for 1 to 1 minute, and when the temperature is higher than 900°C, a calcium phosphorus-butyric layer is formed.

The deformation of the base material made of crystallized glass is undesirable. Also, there are no particular restrictions on the heat treatment time at this temperature (
It can be appropriately selected within the range of 1 second to IO time.

As the coloring component contained in the colored layer, NiO (brown color), Fe, +03 (brown color), Mn203 (pink color), W20y, (blue color), etc. can be used.

These coloring components may be used alone or in combination of two or more. In addition, two or more kinds of glass composition powders described in 1. containing one or more kinds of coloring components can be used.
It is also possible to bake (1) at the lower stage of the above after mixing.

In addition, as a method for forming a colored layer that exhibits a good color distribution by the method described above, for example, when coating the dental crown restoration base material of glass powder in -1 to 1 through coating by a method such as coating. By creating a distribution in the thickness of the coating layer, and thereby creating a distribution in the thickness of the colored layer formed after heat treatment, the color can be created such that thicker areas of the colored layer are darker in color and thinner areas are lighter in color. A color distribution method is applied to the colored layer formed after heat treatment by applying two or more types of glass powder with an appropriate distribution to the dental crown restoration base material. A method such as letting it stand is used. In general, the crown restoration material has a color distribution in which the part corresponding to the tip of the tooth is a light color, and the part corresponding to the root of the tooth is a dark color, thereby creating a crown restoration material that closely resembles a natural tooth. I can do things.

Roughly speaking, as a method for forming the colored layer, 80w of calcium phosphate having a Ga/P atomic ratio of 0.1 to 0.7 was used.
For a glass composition containing 90 parts by weight or more of t% or more, the coloring component is 0.01 to 1 (l) in terms of oxide. After covering the base material made of the above material, heat treatment is performed at a temperature of 600 to 900° C. in the same manner as in the formation method described in iii. be able to.

In this case, the coloring components include Ni, Fe, and Mn.

W, No, etc. and their compounds and mixtures thereof are used. As a compound, it is an oxide.

Those for halides, nitrates, fa salts, phosphoric acids, etc. are used.

The maximum heat treatment temperature of the heat treatment conditions for this method is suitably 600 to 900°C, as in the above method.

750-85 to achieve natural tooth-like coloration of 10,000 to 10,000.
0°C is particularly preferred. In addition, the average condyle diameter of the glass Nl acid powder and colorant powder used for this force 1 is 0.1 m - 100 m LI11 or suitable 1) as in the previous i distribution V:
However, in order to exhibit natural tooth-like coloring within 1 minute, a range of 0.1 to ]0 μm is particularly preferable.

1 (Example 1) Powder of CaCO2 corresponding to 25 wt% as CaO and A I (OH) corresponding to 2 wt% as Al2O3
The reaction product obtained by dropping phosphoric acid containing prior PO4 corresponding to 73 wt% as P2O5 in the P.3 powder and P.1 mixture was dried and then crushed, and this powder was heated at 400°C for 50 minutes.
After firing for hr and melting this fired product in a platinum crucible at 1250°C with stirring for 2 hr, after pouring it out onto a graphite plate H,
Slow cooling was performed. Approximately 2 g of glass was cut out from the thus obtained phosphorus-calcium glass with a Ca/P atomic ratio of 0.425 and phosphorus-calcium substance or 98 wt%, and melted at 1200°C in a platinum crucible. Based on lost wax 1, the whole crown-shaped wax was embedded in advance, the wax was incinerated, and the wax was centrifugally cast in a phosphoric acid burial material maintained at 600°C. It was molded. By crystallizing the molded body together with the investment material at 700°C for 2 hours, the total crown of phosphoric acid-based crystallized glass is 111%.

On the other hand, CaC0 corresponding to 18 wt% as CaO: +
AI(DH) corresponding to 7 wt% as powder and AhOa
) 3 powder and NiO powder corresponding to 2 wt% as NiO, P2O5 and 1. The reaction product obtained by adding phosphoric acid containing 73iit% of prior PO4 was dried, crushed, and then calcined at 400° C. for 5 hours. This fired product was melted in a platinum crucible at 1350° C. with stirring for 2 hours, poured out onto graphite plates-1 and then discarded.

The glass of 78 colors with Ga/P of 0.31 and calcium phosphate Ga of 90 wt% thus njed is ground in a ball mill to produce colored glass powder with a Vli average particle size of 1.57z+a. ! ) f:. 3 m of 0.5 g of the glass powder
After mixing with M water to form a slurry, the tip of the tooth is thinly coated on the surface of the calcium phosphate crystallized glass whole tooth crown.
The root xylem of the tooth is J! It was applied with a brush in a Z-shape.

After keeping the coated body in an electric furnace at 120°C for 10 minutes,
0℃/m1n (7) Speed TeSI temperature, ? 50℃Te10
After being kept for 1 minute, it was cooled for 10 minutes. All the teeth obtained were carious.

Examples 2 to 4 Averages obtained by crushing glass obtained by using a ball mill to create a glass having the composition shown in Table 1 in the same manner as in Example 1 on the tooth crown surface obtained in the same manner as in Example 1. Powder having a particle size of 1.1 μm was applied in the same manner as in Example 1, dried, kept at 900° C. for 5 minutes, and then cooled for 20 minutes. The obtained whole tooth crown has 5 on the surface.
A colored layer with a thickness of 0 to 300 μm was formed, and the properties of the tooth crown were as shown in Table 1.

Example 5 On the surface of the tooth crown obtained in the same manner as in Example 1, glasses prepared in the same manner as in Example 1 to have the compositions 9) and 2 in Table 1 were crushed using a ball mill. The powders with average particle diameters of 1.0p, 1.1p, and 1.1p1m were respectively 0.0p, m, and 1.1p1m.
1 g and 0.2 g of i+star were mixed to obtain a mixed glass powder. This mixed glass powder was mixed with 2 mA of water to form a slurry, and then applied to the crown surface of the tooth with a brush.
The same heat treatment as in Example 1 was performed to form a P+' color layer. The thickness of the six color layers was 60-200 ILm. The properties of this tooth crown were as shown in Table 1.

Example 6 On the surface of the tooth crown obtained in the same manner as in Example 1, glass obtained by the same method as in Example 1 to have the composition shown in Table 1 was ground with a ball mill to have an average particle size of 0.9 μm. powder of 111
Ta. For 1g of this white glass powder, Fe2030.0
After adding 0.01 g of NiO powder and mixing for 1 minute in a mortar, 0.5 g of this mixed powder was kneaded with 3 mM water to form a slurry, which was then applied to the tooth crown surface with a brush. The same heat treatment was performed. All the tooth crowns obtained had a colored layer of 30 to 80 μl formed on the surface, and the properties of the tooth crowns were as shown in Table 751.

Example 7 Example 3 was applied to the tip of the crown surface obtained in the same manner as Example 1.
The glass powder used in Example 4 was applied to the root part in the same manner as in Example 1, and after drying, the glass powder was heated at 750°C.
It was kept for 5 minutes and then cooled for 10 minutes. A colored layer with a thickness of 100 to 200 μm was formed on the surface of all the tooth crowns that were flattened, and the properties of the tooth crowns were as shown in Table 1.

Comparative Example 1 A calcium phosphate crystallized glass whole dental crown was obtained in the same manner as in Example 1 using a glass obtained by the same method as in Example 1 so as to have the composition shown in Table 1. The properties of this tooth crown were as shown in Table 1.

Comparative Example 2 Hard resin (Thermoresin manufactured by Zenzen Dental Industry Co., Ltd.) was colored and applied to the surface of the tooth crown obtained in the same manner as in Example 1.
Polymerization was carried out at 160° C.lhr to obtain a whole tooth crown with a hard resin surface layer. The thickness of the hard resin surface layer is 0.3~
It was 0.8 mm, and the properties of this tooth crown were as shown in Table 1.

Comparative Example 3 A feldspathic glass flint (Ceracolor manufactured by Towa Giken Co., Ltd.) was colored and mixed with a special mixing solution according to the usual prescription on the surface of a tooth crown obtained in the same manner as in Example 1, and after application and drying. 90
Heat treatment was performed at 0°C for 5 minutes. (A surface layer of 60 to 3008 Lm was formed on the surface of all the tooth crowns prepared, and the properties of the tooth crowns were as shown in Table 1.

[Effect of the invention] Conventional calcium phosphate-based crystallized glass dental crown restorative materials are
The difference in color between white and yellowish human natural teeth was unfavorable. Also. By adding a coloring agent to this calcium phosphate-based crystallized glass dental crown restorative material, the crystallized glass dental crown restorative material has a uniform, natural-tooth-like color. There was still a difference in appearance compared to teeth, which was not desirable.

In contrast, the dental crown restorative material of the present invention is an excellent dental crown restorative material that has an appearance with a color distribution similar to that of natural teeth.

Furthermore, the manufacturing method of the present invention makes it possible to form a dense colored layer with high adhesive strength and water resistance on part or all of the surface of a dental crown restoration base material made of calcium phosphate crystallized glass. This makes it possible to obtain an excellent crown restorative material that has an appearance with a color distribution similar to that of natural teeth.

Claims (10)

[Claims] (1) A base material made of crystallized glass containing 90 wt% or more of calcium phosphate with a Ca/P atomic ratio of 0.35 to 0.7, and a part or all of its outer surface containing Ca.
Natural tooth-like structure with a colored layer of glass or crystallized glass containing 70 wt% or more of calcium phosphate with an atomic ratio of /P of 0.1 to 0.7 and 0.01 to 10 wt% of a coloring component. A dental crown restoration material with the appearance of (2) The colored layer according to claim 1, wherein the thickness of the colored layer is in the range of 0.01 to 2.0 mm.
A dental crown restoration material that looks like a natural tooth. (3) Part or all of the outer surface of a substrate made of crystallized glass containing 90 wt% or more of calcium phosphate with a Ca/P atomic ratio of 0.35 to 0.7. 70 wt% or more of calcium phosphate with a carbon content of 0.1 to 0.7 and a coloring component of 0.01 to 10
coated with a colored glass composition containing 600 to 90 wt%
forming a colored layer by heat treatment at a temperature of 0°C;
A method for manufacturing a dental crown restoration material that has a natural tooth-like appearance. (4) The method for producing a dental crown restoration material having a natural tooth-like appearance according to claim 3, wherein the colored layer has a thickness in the range of 0.01 to 2.0 mm. (5) The average particle size of the colored glass composition is 0.1 to 10
4. The method for producing a dental crown restoration material having a natural tooth-like appearance according to claim 3, wherein the thickness is in the range of 0 μm. (6) The thickness of the colored layer is in the range of 0.01 to 2.0 mm, and the average particle size of the colored composition is 0.1 to 100 μm.
4. The method for producing a dental crown restorative material having a natural tooth-like appearance according to claim 3, characterized in that the amount is within the range of m. (7) Ca/P original f 90 parts by weight of a glass composition containing 80 wt% or more of calcium phosphate having a ratio of 0.1 to 0.7 is coated with a mixed composition in which 0.01 to 10 parts by weight of a coloring component is mixed in terms of oxide. A method for producing a dental crown restoration material having a natural tooth-like appearance, which forms a colored layer by heat treatment at a temperature of ~900°C. (8) The method for producing a dental crown restoration material having an appearance similar to a natural tooth according to claim 7, wherein the thickness of the colored layer is in the range of 0.01 to 2.0 mm. (9) The average particle size of the above mixed composition is 0.1 to 100 μm
8. The method for producing a dental crown restoration material having a natural tooth-like appearance according to claim 7, wherein (10) The thickness of the colored layer is in the range of 0.01 to 2.0, and the average particle size of the mixed composition is 0.1 to 100 μm.
8. The method for producing a dental crown restoration material having a natural tooth-like appearance according to claim 7, wherein