JPH0663114A - Joining paste and manufacture of artificial bone using it - Google Patents

Abstract

PURPOSE:To provide joining paste good for joining artificial bone members and a manufacture of an artificial bone by which a bone of a complicated form can be easily manufactured by using the joining paste and characteristics such as mechanical strength or the like may not be damaged. CONSTITUTION:A rectangular glass sintered body 11 and semi-cylindrical glass sintered bodies 12, 13, 14, 15 are prepared from SiO2-P2O5-CaO-MgO base crystalline glass. On the other hand, joining paste is prepared from SiO2-P2O5-CaO-MgO base crystalline glass powder, ethanol, propanol and polyvinylbutyral. Subsequently, the joining paste is applied to the lower surface 12a, 13a, 14a, 15a of semi- cylindrical glass sintered bodies 12, 13, 14, 15, and forced to be in contact with the upper surface 11a and the lower surface 11b of the rectangular glass sintered body 11 and dried. After that, the above bodies are treated by heat to obtain an artificial bone 10 having semi-cylindrical projections at the upper and lower surfaces.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bonding paste and a method for manufacturing artificial bone using the same.

[0002]

_2. Description of the Related Art At present, artificial bone materials include metals such as Ti alloys, ceramics such as alumina, apatite and calcium phosphate, SiO ₂ —P ₂ O ₅ —CaO—MgO based materials,
Crystallized glass such as SiO ₂ —CaO—MgO system is known. SiO Among these ₂ -P ₂ O ₅ -CaO-
The MgO-based crystallized glass and the SiO ₂ —CaO—MgO-based crystallized glass are useful materials having high strength and excellent bioactivity, and are particularly attracting attention.

By the way, the crystallized glass as described above is a so-called surface crystallized type of crystallized glass in which crystals are precipitated from the surface to the inside. Therefore, when the glass molded by the casting method is heat-treated for crystallization, volume shrinkage occurs. Occurs and cracks occur. Therefore, in the case of producing an artificial bone using such a material, glass molded into a thin plate is pulverized into powder of 200 mesh or less, which is pressure-molded by a rubber press method or the like, and then the molded product is obtained. Is used to sinter the glass powder to crystallize it, and further to cut it into a desired shape.

[0004]

However, in such a method, a great deal of labor and time are required for processing, and the productivity is low due to the need for advanced processing technology, and the degree of freedom of shape due to processing is limited. However, there are problems that it is difficult to obtain a complicated shape and that the mechanical strength of the artificial bone obtained by cracking due to the large amount of processing is likely to decrease.

Under these circumstances, it has been attempted to join a plurality of glass members to produce an artificial bone having a complicated shape, but there is no suitable adhesive for joining. The current situation.

That is, conventionally, various adhesives have been proposed for joining a high-strength member such as titanium and a bioactive member such as calcium phosphate. For example, Japanese Patent Publication No. 2-3778
No. 6 contains 2,2 bis [4- (3methacryloxy-2-
Hydroxypropoxy) phenyl] propane (BiS
-GMA), triethylene glycol dimethacrylate (TEGDMA), benzol peroxide (BP)
O), 4-methacryloxyethyl trimellitic acid and / or its anhydride (4-META), and a filler for biomaterials containing a filler are disclosed. Further, JP-A-2-225382 discloses a bonding material containing a ceramic raw material as a filler in an aqueous solution of a water-soluble polymer substance.

However, the adhesive of Japanese Patent Publication No. 2-37786 mentioned above does not allow Bis-GMA in vivo due to long-term implantation.
May deteriorate and the filler may fall off. Further, when resin powder is used as the filler, there is a drawback that the adhesive does not exhibit bioactivity, and thus the bioactivity of the glass member is impaired if the adhesive protrudes from the adhesive surface. In particular, when a porous glass member having bioactivity is adhered, there is a problem that the adhesive enters the pores to inhibit the bioactivity inside the pores or inhibit the invasion of new bone into the pores. . On the other hand, the joining material disclosed in JP-A-2-22538 is for joining artificial bone members to each other by sintering of a ceramic filler, and can be applied only to joining artificial bone members made of the same material as the filler. Therefore, it is impossible to join the glass members together. Further, since the joining is performed by sintering, there is a problem that the strength of the joining portion is low.

An object of the present invention is to provide a bonding paste suitable for bonding an artificial bone member, particularly an artificial bone member made of glass,
An object of the present invention is to provide a method for producing an artificial bone, which can easily obtain a complicated shape by using this bonding paste and does not impair properties such as mechanical strength.

[0009]

The bonding paste of the present invention is characterized in that it contains SiO ₂ and CaO as main components and comprises a crystalline glass powder exhibiting bioactivity, an organic solvent, and a binder. To do.

The method for producing an artificial bone according to the present invention comprises the steps of preparing a plurality of glass members exhibiting bioactivity, a crystalline glass powder containing SiO ₂ and CaO as main components and exhibiting bioactivity, and an organic compound. A step of preparing a bonding paste comprising a solvent and a binder, and a step of applying the bonding paste to the surface of at least one glass member,
Another glass member is brought into contact with the portion of the glass member where the bonding paste is applied, and then heat-treated to burn and remove the binder, and the crystalline glass powder is softened to bond the glass members together. And crystallization process.

[0011]

When the bonding paste of the present invention is heat-treated, the crystalline glass powder in the paste is softened so that the artificial bone members are fused and integrated with each other and the glass powder is crystallized. Can be joined to.

Further, the joint portion made of crystallized glass thus formed exhibits bioactivity, and it is possible to elute silica ions, calcium ions and the like in the living body to precipitate hydroxyapatite from the body fluid. Therefore, the biological activity of the artificial bone member that is the object to be bonded is not impaired. Even when the artificial bone member has no bioactivity, silica ions and calcium ions eluted from the joint portion cause hydroxyapatite to deposit on the surface of the artificial bone member, enabling bonding with natural bone.

The crystalline glass powder used in the present invention is apatite (Ca ₁₀ (PO ₄ ) ₆
O), wollastonite (CaO · SiO ₂ ), diopside (CaO · MgO · 2SiO ₂ ), etc., has the property of precipitating crystals, and it also elutes silica and calcium ions from the glass and is bioactive. Is shown. The composition of the crystalline glass powder is not limited, but particularly SiO ₂ 22.0 to 50.0%, P ₂ O ₅ 8.
0-30.0%, CaO20.0-53.0%, MgO
1.0 to 16.0%, Al ₂ O _{3 0 to} 9.0%, F ₂
SiO ₂ —CaO—MgO—P ₂ O _{5 which} consists of 0 to 2.0% and B ₂ O _{3 to} 5.0% and precipitates apatite and at least one of wollastonite and diopside.
System glass and at least 90% or more of SiO ₂ 40.0
~ 60.0%, CaO 30.0-45.0%, MgO
A SiO ₂ —CaO—MgO-based glass or the like that is 1.0 to 17.0% and precipitates wollastonite is preferable because it has high strength and exhibits high bioactivity.

As the organic solvent, it is preferable to use alcohols such as methanol, ethanol, propanol, butanol and isopropyl alcohol, which have good dispersibility of glass powder, alone or in combination. In the present invention, the reason for using an organic solvent as a solvent (the reason for not using water) is that the crystalline glass powder having bioactivity as described above does not react with an organic solvent, but easily reacts with water, This is because the sinterability and crystallization characteristics are deteriorated.

As the binder, it is preferable to use polyvinyl butyral (hereinafter abbreviated as PVB) or ethyl cellulose which has excellent binding force and dispersibility.

The mixing ratio of the crystalline glass powder, the organic solvent and the binder is 5% by weight of the crystalline glass powder.
~ 90%, organic solvent 10 ~ 95%, binder 0.1 ~
20%. The reason why these ratios are limited as described above is as follows. If the amount of the crystalline glass powder is less than 5%, the artificial bone member cannot be sufficiently joined, and if it is more than 90%, the paste is not formed. If the organic solvent is less than 10%, the paste will not be formed, and if it is more than 95%, the artificial bone member cannot be sufficiently joined. If the amount of the binder is less than 0.1%, the adhesive strength is weak and the glass powder cannot be fixed to the artificial bone member. If the amount of the binder is more than 20%, the sinterability of the glass powder is excluded and the strength of the joint is lowered. .

The bonding paste of the present invention is not only used for bonding glass members to each other, but also to ceramic members, metal members, glass members and ceramic members, glass members and metal members, ceramic members and metal members, and the like. It can also be used when producing an artificial bone using the above materials.

Next, a method of manufacturing the artificial bone of the present invention using the above-mentioned bonding paste will be described.

First, for a plurality of glass members exhibiting bioactivity
I mean. The glass used for the glass member shows bioactivity
There is no limitation as long as it is one, but especially the above-mentioned SiO₂ -P
₂ O _Five -CaO-MgO system and SiO₂ -CaO-MgO
Use of crystalline glass or crystallized glass
Preferably. These glasses are as described above
Elute silica ions and calcium ions in vivo
Therefore, it exhibits high bioactivity. Note that the glass members are
In order to prevent volume shrinkage due to heat treatment of
Use powder that is sintered or sintered and crystallized
Is desirable.

Further, the above-mentioned bonding paste is prepared.

Next, the bonding paste is applied to the surface of at least one glass member.

Further, another glass member is brought into contact with the portion of the glass member coated with the bonding paste and dried. Then, these are heat-treated to burn and remove the binder, and the crystalline glass powder is softened to bond the glass members together and crystallize. The heat treatment temperature is such that the crystalline glass powder contained in the paste is SiO ₂ -P
₂ O ₅ -CaO-MgO glass and SiO ₂ -CaO-
In the case of MgO-based glass, 1000 to 1200 ° C is suitable. When the glass member is made of crystalline glass,
At this time, it may be crystallized at the same time.

The artificial bone thus produced is used after being sterilized and washed, but it may be subjected to post-processing such as punching or chamfering if necessary.

[0024]

EXAMPLES The present invention will be described below based on examples.

Example 1 First, as a glass member exhibiting bioactivity, a rectangular glass sintered body 11 and semi-cylindrical glass sintered bodies 12, 13, 14, 1 as shown in FIG.
5 were prepared respectively. Also, a bonding paste P ₁ was prepared.

The rectangular glass sintered body 11 and the semi-cylindrical glass sintered bodies 12, 13, 14, and 15 were manufactured as follows.

% By weight of SiO ₂ 34.0%, CaO 4
4.7%, MgO 4.6%, P ₂ O ₅ 16.2%, F ₂
Formulate the glass raw material so as to have a composition of 0.5%,
The mixture was placed in a platinum crucible and melted at 1400 to 1600 ° C. for 3 hours, then roll-formed and crushed by a ball mill. Further, this pulverized product was classified with a 200-mesh sieve to obtain glass powder G ₁ . Note the glass powder G ₁ is 1,000 to
It is a crystalline glass that exhibits bioactivity by precipitating apatite, wollastonite and diopside when heat-treated at 200 ° C. for 1 to 4 hours.

Next, the glass powder G ₁ was pressed into a rectangular shape and a semi-cylindrical shape. Further, the temperature is raised at a rate of 60 ° C./hour,
By firing at 750 ° C. for 2 hours, 30 × 15 ×
Rectangular glass sintered body 11 having a size of 10 mm, and 5φ
Semi-cylindrical glass sintered body 12, 1 with a size of 15 mm
3, 14, and 15 were produced.

The bonding paste P ₁ is a glass powder G.
₁ , ₁ %, ethanol, propanol, and PVB were 83.0%, 8.3%, 8.3%, and 0.
It was prepared by kneading at a ratio of 4%.

Next, the semi-cylindrical glass sintered bodies 12, 13,
The bonding paste P ₁ is applied to the lower surfaces 12a, 13a, 14a, 15a of the respective 14, 15 to form the upper surface 11a and the lower surface 1 of the rectangular glass sintered body 11 as shown in FIG. 1 (a).
It was contacted with 1b and dried.

Further, these are heated at a rate of 60 ° C./hour and heat-treated at 1100 ° C. for 2 hours to obtain PV.
B is burned and removed, and the glass powder contained in the paste is softened to fuse and integrate the rectangular glass sintered body 11 and the semi-cylindrical glass sintered bodies 12, 13, 14, and 15. , The entire body is crystallized, and a dense artificial bone 1 having semi-cylindrical protrusions on the upper and lower surfaces as shown in FIG. 1 (b)
I got 0.

(Example 2) First, as glass members exhibiting bioactivity, pelletized crystallized glass compacts 21, 22 and columnar crystallized glass compacts 2 as shown in FIG.
3 and semi-cylindrical crystallized glass porous bodies 24 and 25 were prepared, respectively. Also, a bonding paste P ₂ was prepared.

Pelletized crystallized glass dense bodies 21, 22
The columnar crystallized glass dense body 23 was manufactured as follows.

By weight percentage, SiO ₂ 53.0%, Ca
A glass raw material was prepared so as to have a composition of O 39.5% and MgO 7.5%, and then melted, shaped, crushed and classified in the same manner as in Example 1 to obtain a glass powder G ₂ . Note the glass powder G ₂ is deposited a wollastonite Heat treatment for 1 to 4 hours at 1000 to 1200 ° C., a crystalline glass showing the biological activity.

Next, the glass powder G ₂ was press-molded into pellets and cylinders, further heated at a rate of 60 ° C./hour and fired at 1100 ° C. for 2 hours to be crystallized. Thus, pelletized crystallized glass compacts 21 and 22 having a size of 10φ × 3 mm and columnar crystallized glass compacts 23 having a size of 4φ × 14 mm were obtained.

Semi-cylindrical crystallized glass porous bodies 24 and 25 were prepared as follows. First, glass powder G ₂ , ethanol, propanol, and PVB were kneaded at a weight percentage of 76.3%, 7.6%, 15.3%, and 0.8% to form a slurry, This was impregnated in a semi-cylindrical urethane foam and dried. Then, these are heated at a rate of 60 ° C./hour and baked at 1100 ° C. for 2 hours to give an outer diameter of 10 mm, an inner diameter of 4 mm and a height of 14 mm.
mm cylindrical semi-cylindrical crystallized glass porous bodies 24 and 25 were produced.

The bonding paste P ₂ is a glass powder G.
₂ , ethanol, propanol, butanol,
PVB and ethyl cellulose are each 7% by weight.
9.4%, 7.9%, 7.9%, 4.0%, 0.4%,
It was prepared by kneading at a ratio of 0.4%.

Next, the bonding paste P ₂ is applied to the upper surface 23a and the lower surface 23b of the cylindrical crystallized glass compact body 23, and as shown in FIG. 2A, two pelletized crystallized glass compact bodies 21 are formed. , 22 were contacted and dried. Further, the bonding paste P ₂ is applied to the side surface 23c of the columnar crystallized glass dense body 23, the upper surfaces 24a and 25a and the lower surfaces 24b and 25b of the semi-cylindrical crystallized glass porous bodies 24 and 25, respectively, as shown in FIG. As shown in (2), two semi-cylindrical crystallized glass porous bodies 24 and 25 were brought into contact with the side surface 23c of the columnar crystallized glass dense body 23 and dried.

Thereafter, these are heated at a rate of 60 ° C./hour and baked at 1100 ° C. for 2 hours to obtain PVB.
And ethyl cellulose are burned and removed, and the glass powder contained in the paste is softened to give pellet-shaped crystallized glass compacts 21, 22, a columnar crystallized glass compact 23, and a semi-cylindrical crystallized glass. The porous bodies 24 and 25 were fused and integrated to obtain an artificial bone 20 having a porous portion on the side surface as shown in FIG. 2 (c).

The artificial bone 20 thus obtained is embedded in a defect portion artificially formed in the femur of a beagle dog,
When the postoperative course was observed, it was confirmed that the bone was tightly bound to natural bone after 8 weeks.

In Examples 1 and 2, the crystalline glass powder of the bonding paste and the glass member have the same composition, but the present invention is not limited to this, and different glass compositions are used. But it can be applied.

[0042]

As described above, by using the bonding paste of the present invention, it is possible to firmly bond an artificial bone member, particularly an artificial bone member made of glass. Further, the crystalline glass powder to be used exhibits bioactivity and contributes to the bond with the natural bone, and thus is suitable for joining the artificial bone member.

According to the method for producing an artificial bone of the present invention,
By using the glass members in an appropriate combination, it is possible to easily manufacture an artificial bone having a complicated shape without impairing the characteristics such as mechanical strength. Further, since the glass member and the bonding paste exhibiting bioactivity are used, it is possible to obtain an artificial bone exhibiting high bioactivity.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an embodiment of the method for manufacturing an artificial bone of the present invention.

FIG. 2 is an explanatory view showing another embodiment of the method for manufacturing an artificial bone of the present invention.

[Explanation of symbols]

 10 Artificial bone having semi-cylindrical projections on the upper and lower surfaces 11 Rectangular glass sintered body 12, 13, 14, 15 Semi-cylindrical glass sintered body 20 Artificial bone having a porous portion on the side surface 21, 22 Pellet shape Crystallized glass dense body 23 Columnar crystallized glass dense body 24, 25 Semi-cylindrical crystallized glass porous body

Claims (3)

[Claims] 1. A crystalline glass powder containing SiO ₂ and CaO as main components and exhibiting bioactivity, and an organic solvent,
A bonding paste comprising a binder. 2. The crystalline glass powder is SiO ₂ —P ₂ O.
₅ -CaO-MgO based glass or SiO ₂ -CaO-M
The bonding paste according to claim 1, which is made of gO-based glass. 3. A process of preparing a plurality of bioactive glass members, containing SiO ₂ and CaO as main components,
A step of preparing a bonding paste composed of a crystalline glass powder exhibiting bioactivity, an organic solvent, and a binder, a step of applying the bonding paste to the surface of at least one glass member, and a step of applying the glass member. Other glass members are brought into contact with the portion where the bonding paste is applied, and then these are heat-treated to burn and remove the binder, and the crystalline glass powder is softened to bond the glass members to each other and crystallize them. A method for producing an artificial bone, which comprises the steps of: