JPH0622569B2 - Porcelain composition for human body hard material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a porcelain composition for a human body hard material, and in particular, a human body hard material having good physical properties and excellent seizure property on a metal substrate such as titanium. The present invention relates to a porcelain composition.

The porcelain composition according to the present invention can be effectively used as a dental prosthesis material, artificial tooth, artificial bone, etc., but the case of using it as a dental material will be representatively described below.

[Prior Art] Porcelain used in dentistry includes porcelain commercially available as artificial teeth and porcelain used for producing porcelain inlays, jacket crowns, and the like. The most widely used porcelains are orthoclase (KAISi ₃ O ₈ ) and albite (NaAI).
Si ₃ O ₈ ), which usually contains a suitable amount of kaolin (Al ₂
O ₃ · SiO ₂ · 2H ₂ O) is compounded to give the material plasticity to facilitate molding and improve the strength of porcelain.

On the other hand, the metals used as dental prostheses are gold, silver-palladium alloy, nickel-chromium alloy, cobalt-
Examples include chromium alloys, but among these metals, gold and palladium have problems in terms of economy, and nickel-based alloys have problems such as affinity with living tissues or elution of harmful metal ions. ing. On the other hand, titanium and titanium alloys (represented below by titanium alloys)
It is considered that it can be effectively used as a dental prosthesis because it is lower in price than gold and palladium, has a good affinity with living organisms, and is harmless.

[Problems to be Solved by the Invention] The present inventors have conducted research aiming for effective use as a metal for dental prosthesis by taking advantage of the above characteristics of titanium alloy, but encountered the following problems in the course of the research. did. That is, when using a titanium alloy for dental prosthesis, it is essential to improve the adhesion with the porcelain that will be the main body of the artificial tooth. Due to its low strength, the porcelain may peel off from the titanium alloy and fall off when the both are baked and joined to be used for artificial teeth or the like. Therefore, in order to effectively utilize the properties of titanium alloy, it is necessary to improve the bake bondability with porcelain.

The present inventor has been made under such circumstances, and the purpose thereof is to improve the seizure bondability with a titanium alloy by adding a device to the porcelain from the viewpoint of the composition of the composition, thereby making the titanium alloy a metal for dental prosthesis. It aims to make it practical.

[Means for Solving Problems] The composition of the porcelain composition for a human body hard material according to the present invention is as follows: SiO ₂ : 15 to 60% (wt%: the same hereinafter) B ₂ O ₃ : _{3 to} 35% ZnO : 3 to 30% Al ₂ O ₃ : 3 to 20% is contained as an active ingredient. This porcelain composition is titanium (and titanium alloy) as described above.
It was developed with a focus on bake bondability to, but the porcelain composition is also very excellent in bake bondability to other metal materials such as stainless steel,
Moreover, it has excellent hardness and wear resistance, so it can be effectively used as a substitute for general dental porcelain, and it can also be artificially combined with titanium (or titanium alloy) or stainless steel. It can be widely applied as a hard material for human body, such as being usable as an aggregate.

[Operation] Hereinafter, the reason why the constituents and the content of the porcelain composition according to the present invention are determined will be described in detail.

SiO _2: by 15-60% sintering is the most important component as a network former for forming a vitreous or ceramic substance, as well as water resistance of the porcelain is deteriorated less than 15%, the thermal expansion coefficient However, the bake bondability with titanium alloys becomes insufficient. That is, when the porcelain material of the present invention is used in combination with a titanium alloy or the like, the porcelain raw material powder is laid on the surface of the titanium alloy base material in an arbitrary shape, and then heat-treated to sinter the porcelain raw material powder. Bake-bonding to the surface of titanium alloy base material is performed. However, if the coefficient of thermal expansion of the porcelain is large, the amount of shrinkage during cooling is large, so that peeling easily occurs at the bonding interface and sufficient bake-bonding strength cannot be obtained. . On the other hand, Si
When the amount of O ₂ exceeds 60%, the softening point of the raw material powder becomes too high and the workability deteriorates. However, the amount of SiO ₂ is 15 to 6
If set to 0%, more preferably 20 to 50%,
It is possible to obtain a porcelain material having an appropriate softening point, good baking workability, excellent water resistance and physical properties (hardness, abrasion resistance, etc.), and an appropriate thermal expansion coefficient.

_{B 2 O 3: 3~35% B} 2 is _{O 3} is also a component of the network former for forming a SiO ₂ and similar _glassy, if the 3 B 2 _{O 3}
If it is less than%, the softening point becomes too high and the handleability deteriorates,
On the other hand, if it exceeds 35%, the water resistance becomes poor, so 3 to 3
It is necessary to set it in the range of 5% to 5%, preferably 5 to 25%.

ZnO: 3 to 30% A component that is indispensable for improving fluidity during heating to improve wettability with respect to titanium alloys and for enhancing the bake-bonding strength. If it is less than 3%, the above effect cannot be effectively exhibited. . However, if it exceeds 30%, the softening point is excessively lowered to deteriorate the physical properties of the cured product, and the thermal expansion coefficient is also increased, so that a satisfactory bake-bonding force cannot be obtained. The more preferable content of ZnO is 5 to 20%.

_{Al 2 O 3: 3~20% Al} 2 O 3 is to increase the water resistance of the porcelain, by suppressing the lowering of excessive thermal expansion coefficient has the effect of relaxing the internal stress generated in the baking interface between the metal , At least 3% must be contained. However, if it is too large, the softening point becomes high and the handleability is deteriorated. Therefore, it must be kept to 20% or less. The more preferable content rate of Al ₂ O ₃ is 5 to
15%.

The essential constituents of the porcelain composition of the present invention are described in the above 4
Although it is a kind of oxide, the performance can be improved by adding the following components, if necessary.

BaO: 15% or less It has the effect of enhancing the wettability to titanium alloys and the like to further enhance the bake-bonding force. However, if too much, the coefficient of thermal expansion will increase and the bake-bonding force will decrease. I won't.

SnO ₂ : 25% or less It has the effect of enhancing the water resistance of porcelain and enhancing the adhesiveness with titanium alloys, etc. Especially when manufacturing artificial teeth in combination with titanium alloys etc., the opaque part is composed as a cassiterite mineral. The effect is remarkably exhibited by including it in the porcelain. However, if too much, the softening point becomes high and handling becomes difficult, so 25% or less, more preferably 15%.
% Should be kept below.

TiO ₂ : 10% or less When contained in the porcelain forming the opaque portion, it has a function of concealing the metallic color, and is an effective component particularly when an artificial tooth is obtained. TiO ₂ can be contained as a rutile mineral, but if it is too much, it causes a decrease in handleability due to an increase in the softening point, and since the thermal expansion coefficient tends to be large and the seizure bondability to metal tends to deteriorate, It is necessary to suppress it to 10% or less, more preferably 5% or less.

Alkali metal oxide: 13% or less Na ₂ O, K ₂ O, Li ₂ O and the like are mentioned as specific examples, and can be contained for the purpose of lowering the softening point and improving the fluidity. However, if too much, foaming occurs during bake-bonding with metal, or the coefficient of thermal expansion of the porcelain becomes large and the bake-bondability decreases, so it should be suppressed to 13% or less, more preferably 9% or less.

BaO: 15% or less, CaO: 5% or less, MgO: 5% or less, at least one of these alkaline earth metal oxides enhances the fluidity of porcelain to improve the wettability with a metal and bake-bonding strength. It has an effect of further enhancing the effect of the addition, and an appropriate amount of the compound brings good results. However, if the content exceeds the above-specified range, the coefficient of thermal expansion becomes too high, and the bake-bondability is adversely affected.

ZrO ₂ : 5% or less It is a component that contributes to the improvement of water resistance of porcelain and the adhesion strength with a titanium alloy, and its effect is remarkably exhibited especially when it is contained in the porcelain constituting the opaque portion.
However, if it is too large, the fluidity and wettability at the time of heating will be deteriorated and the bake-bondability will be adversely affected. Therefore, it must be suppressed to 5% or less.

The above inorganic oxides can be blended as a single compound or as a natural mineral, and accordingly Fe ₂ O ₃ , MnO, CuO, Cr ₂ O ₃ , In ₂ O can be blended.
Other oxides such as ₃ , V ₂ O ₅ , PbO and Bi ₂ O ₃ may be mixed in, but these oxides have a direct and detrimental effect on the object of the present invention as long as the amount is small. However, an amount of 5% or less is acceptable.

The component composition of the porcelain in the present invention is as described above, but in the preparation of the above-mentioned raw materials, the coefficient of thermal expansion of the obtained porcelain is within the range of 7.5 × 10 ^{−6 to} 11.0 × 10 ⁻⁶ / ° C. It is desirable to prepare it so that it fits in. The reason is as follows. That is, the porcelain material of the present invention can of course be used in a form independent of a metal material such as a titanium alloy, but as will be described later in detail, it is built and burned on the outer peripheral surface of a trunk material made of a metal such as a titanium alloy. When used as a composite artificial tooth, etc., it exerts its maximum effect.When considering such an application form, seizure with metal due to thermal contraction in the process of cooling from the end of heating and sintering The occurrence of tensile stress at the interface must be avoided as much as possible. For that purpose, it is desired that it has an appropriate coefficient of thermal expansion in relation to the coefficient of thermal expansion of the metal to be composited, but most of the porcelain when the present inventors combine it with titanium or a titanium alloy. When the preferable coefficient of thermal expansion was examined, it was in the above range (value close to that of titanium or titanium alloy)
The result shows that porcelain having a coefficient of thermal expansion of 1 can be most strongly baked and joined to titanium or a titanium alloy. However, the above-mentioned preferable coefficient of thermal expansion is determined on the premise of the combination with titanium or a titanium alloy, and therefore, when changing the metals to be combined, the optimum coefficient of thermal expansion should be determined each time.

Next, the production of the porcelain according to the present invention will be briefly described by taking as an example the case of producing an artificial tooth in combination with a titanium alloy.

As shown in FIG. 1 (perspective explanatory view), a titanium alloy rod 1 constituting a stem material is prepared. On the other hand, porcelain raw materials corresponding to opaque and body (translucent or the like in some cases) are blended within a range satisfying the requirements for the component composition. Then, the porcelain raw material prepared for the base opaque 2 is first built up on the outer periphery of the titanium alloy rod 1 on one end side, and then the porcelain raw material prepared for the body 3 is built up and shaped. The building process itself can be carried out in the same manner as when obtaining a conventional porcelain, water is the most common kneading medium, and a small amount of a binder or a fluidity modifier may be blended if necessary.

After building and shaping each part layer, each part layer is heated in a vacuum or an inert atmosphere to make each build layer porcelain and to bake-bond it to a titanium alloy. In this case, it is preferable to use a low temperature in order to prevent the oxidation of the titanium alloy, while it is preferable to heat-treat at a temperature as high as possible in order to enhance the bake-bonding strength and the gloss and physical properties of the porcelain, and it is most preferable in terms of the balance between the two. No is 600-980
It is in the range of ° C. If a bar material having a titanium nitride film formed on the surface is used as the titanium alloy rod 1, oxidation of the titanium alloy rod 1 during the heat treatment can be minimized, and as a result, the heat treatment temperature can be increased. The luster and physical properties of the material as well as the baking and joining strength can be further enhanced.

As described above, the porcelain of the present invention has an excellent bake-bonding property with respect to titanium and titanium alloys, and thus is very excellent as a dental material compounded with titanium (or titanium alloy). If the expansion coefficient is properly adjusted, it can be combined with other metal materials such as stainless steel to form a composite material. Further, its application is not limited to the dental one, and it can be widely used for a hard human body material for surgery or orthopedic surgery such as artificial bone by combining with titanium alloy or the like.

[Example] As shown in Table 1, porcelain raw material pastes (dispersion medium: water) were prepared for opaque and body, respectively, and each was applied to the surface of a pure titanium rod (diameter 3 mm) according to the method shown in FIG. Build up porcelain raw materials. The wall thickness was 1 mm for the opaque part and 2.5 mm for the body part. After each part layer was built up and shaped, each part layer was moored in a vacuum atmosphere at 600 to 930 ° C. for 1 minute each to porcelain the opaque part and body part and burned to a pure titanium rod.

The shear welding strength of the opaque portion and the pure titanium rod and the coefficient of thermal expansion of the porcelain portion in each of the obtained samples were measured to examine the compatibility between each porcelain and the pure titanium rod.

The results are collectively shown in Tables 1 (A) and (B).

For sample Nos. 7, 9, 11, and 12 in Table 1 (B), the build-up and seizure of the opaque part were defective, or the body part was not built up due to poor performance. In the case of sample No. 8, the body part loses its shape-retaining property by flowing in the firing process, and in the case of sample No. 10, the body part foams, and it is not necessary to measure the surface hardness or the like. It was judged as defective.

[Advantages of the Invention] The present invention is configured as described above, and not only has good seizure properties on metals such as titanium and titanium alloys, but is also extremely excellent in surface hardness and wear resistance. Therefore, by being combined with a metal material, it can be used as an excellent artificial tooth material, and can be effectively used as an artificial bone for not only dentistry but also surgery and orthopedic surgery. In particular, since the porcelain material of the present invention has excellent seizure bondability with respect to titanium and titanium alloys, by utilizing these characteristics, the characteristics of titanium and titanium alloys (having good biocompatibility, no harm, and excellent corrosion resistance) Has the advantage that it can be widely used as a material for a hard human body, and its utility value as a synthetic biomaterial is extremely large, including applications resulting from the characteristics of porcelain itself.

[Brief description of drawings]

FIG. 1 is a perspective view showing a practical example of the porcelain material according to the present invention. 1 ... Titanium alloy rod, 2 ... Opaque part 3 ... Body part

Claims (6)

[Claims] 1. SiO ₂ : 15-60% (weight%: the same applies hereinafter) B ₂ O ₃ : 3-35% ZnO: 3-30% Al ₂ O ₃ : 3-20% as an active ingredient. A porcelain composition for a human body hard material characterized by: 2. A porcelain composition for human body hard material according to claim 1 or 2, which contains 25% or less of SnO ₂ as an active ingredient. 3. A porcelain composition for a hard human body according to any one of claims 1 to 3, which contains 10% or less of TiO ₂ as an active ingredient. 4. A porcelain composition for a hard human body according to any one of claims 1 to 4, which contains 13% or less of an alkali metal oxide as an active ingredient. 5. BaO: 15% or less as an active ingredient, Ca
The porcelain composition for a human body hard material according to any one of claims 1 to 5, which contains at least one of O: 5% or less and MgO: 5% or less. 6. A porcelain composition for a hard human body according to any one of claims 1 to 6, which contains 5% or less of ZrO ₂ as an active ingredient.