JP2017093995A - Method for producing composite body, and composite body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite body having excellent strength and applicable to a centrum spacer capable of attaining initial bone union, and in which the degeneracy and deterioration of constituting materials involved therein are accurately suppressed or prevented, and a method for producing the composite body.SOLUTION: Provided is a method for producing a composite body provided with: a base material composed of a metallic material or the first ceramic material; and a covering layer composed of the second ceramic material, comprising: a step where slurry containing particles composed of the second ceramic material, water, an organic binder and a solvent, and a base material provided with ruggedness are prepared; a step where the surface of the base material is fed with the slurry, and, in a state where the particles are buried into the recessed parts, a liquid film is formed; and a step where, after the liquid film is dried, the particles are sintered to form a coating layer.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a composite and the composite.

  For example, in spinal canal stenosis, intervertebral disc degeneration between vertebral bodies and vertebral bodies, degenerative facet joints, secondary vertebral deformity, spinal deformity The cauda equina and nerve root disorder are recognized as pathological conditions.

  For the treatment of such spinal canal stenosis, vertebral body fusion is used, in which the degenerated disc is removed from the vertebrae, and autologous bone is transplanted between the vertebrae from which the intervertebral disc has been removed to fix the vertebral bodies together. It is done.

  However, if only bone transplantation is performed between the vertebrae, instability may occur due to resorption of the transplanted bone before bone fusion is obtained. In addition, the amount of bone collected from autologous bone is limited, and sufficient transplanted bone may not be secured.

  Therefore, by using a vertebral body spacer as a substitute for autologous bone, and inserting this into the intervertebral space (gap) between the vertebral body (bone) and the vertebral body (bone) together with the autologous bone, A technique that is fixed stably is used.

  Here, the vertebral body spacer is required to be able to stably support the vertebral body and to be easily fused with the vertebral body. In view of this, the constituent materials and shapes have been studied, and various vertebral body spacers have been proposed (see, for example, Patent Document 1).

  In such a vertebral body spacer, the stress applied to the vertebral body spacer differs depending on the physique of the case to which this vertebral body is applied, and also the position between vertebrae such as the lumbar vertebrae and the cervical vertebra, etc. For this purpose, the vertebral body spacer is composed mainly of a metal material such as titanium or titanium alloy having excellent strength.

  However, in the vertebral body spacer composed of such a metal material as the main material, the vertebral body spacer does not function as a scaffold for the proliferation and differentiation of bone cells, so bone fusion with the vertebral body with which the vertebral body spacer contacts is early. There was a problem that could not be achieved.

  On the other hand, as a vertebral body spacer capable of functioning as a scaffold for proliferation and differentiation of bone cells, a material composed mainly of a calcium phosphate-based material such as hydroxyapatite or tricalcium phosphate has been proposed. However, in this case, there arises a problem that excellent strength cannot be imparted to the vertebral body spacer.

  Therefore, by configuring the vertebral body spacer with a composite in which a coating layer composed mainly of a calcium phosphate-based material is formed on the surface of a base material composed mainly of a metal material, excellent strength and It is conceivable to use a vertebral body spacer having a function as a scaffold, and as a technique for obtaining a vertebral body spacer (composite) having such a configuration, for example, a flame spraying method as described in Patent Document 2 has been proposed. .

  However, in the method using the flame spraying method, the phosphorus contained in the calcium phosphate material evaporates due to the calcium phosphate material being heated to 1000 ° C. or higher, and as a result, included in the coating layer to be formed. Calcium phosphate material is altered and deteriorated.

  Therefore, the base material composed mainly of a metal material and the coating layer composed mainly of a calcium phosphate-based material are joined with excellent strength, and alteration and deterioration of the constituent materials contained in these are prevented. There is a need to develop a vertebral body spacer (composite).

  In addition, such a problem is not limited to a composite of a base material composed of a metal material as a main material and a coating layer composed of a calcium phosphate-based material as a main material, but a calcium phosphate-based material contained in the coating layer. In the case where the material is composed of another ceramic material, the same occurs even when the base material and the coating layer are composed of different ceramic materials as main materials.

Japanese Patent Laid-Open No. 2002-956885 Japanese Patent Publication No. 06-77599

  An object of the present invention is to bond a base material composed of a metal material or a first ceramic material as a main material and a coating layer composed of a second ceramic material as a main material with excellent strength, and An object of the present invention is to provide a composite in which alteration / deterioration in the constituent materials contained therein is appropriately suppressed or prevented, and a composite manufacturing method capable of manufacturing such a composite.

Such an object is achieved by the present invention described in the following (1) to (11).
(1) A base material composed mainly of a metal material or a first ceramic material, and a second ceramic material formed on the surface of the base material, which is different from the first ceramic material. A method for producing a composite comprising a coating layer,
First prepared is a slurry containing particles composed mainly of the second ceramic material, water, an organic binder, and a solvent having an affinity for water, and the base material having at least unevenness on the surface. And the process of
A second step of supplying the slurry to the surface of the base material to form a liquid film in a state where the particles are embedded in the concave and convex portions;
A third step of forming the coating layer made of a porous body formed by following the irregularities by heating the liquid coating, drying the liquid coating, and then sintering the particles; The manufacturing method of the composite_body | complex characterized by having.

  Thereby, the base material composed of the metal material or the first ceramic material as the main material and the coating layer composed of the second ceramic material as the main material are bonded with excellent strength and included in these. Thus, it is possible to obtain a composite in which alteration / deterioration in the constituent material is appropriately suppressed or prevented.

  (2) The said solvent is a manufacturing method of the composite_body | complex as described in said (1) which is a C2-C6 primary or secondary alcohol.

  These solvents exhibit excellent compatibility with water and can reliably reduce the viscosity of the slurry. Therefore, in the second step, the liquid is introduced in the state where the slurry is introduced into the recesses provided in the irregularities. A film can be reliably formed.

  (3) The method for producing a complex according to (1) or (2), wherein the content of the solvent in the slurry is 25% by mass or more and 75% by mass or less.

  Thereby, the viscosity of the slurry can be more reliably lowered, and in the second step, the slurry can be reliably introduced into the recess provided in the unevenness.

  (4) The method for producing a composite according to any one of (1) to (3), wherein the particles have a size that allows the recesses to be embedded.

  Thereby, in a 3rd process, a coating layer can be reliably formed into a film following an uneven | corrugated shape.

  (5) The method for producing a composite according to (4), wherein the particles have an average particle diameter of 0.1 μm or more and 10 μm or less.

  Thereby, particle | grains can be made into the magnitude | size which accept | permitted reliably of embedding of the particle | grain in the recessed part with the unevenness | corrugation of a base material.

  (6) The manufacturing method of the composite according to any one of (1) to (5), wherein the base is made of the metal material, and the second ceramic material is made of a calcium phosphate material.

  (7) In the third step, the liquid coating is heated in a non-oxidizing atmosphere after the liquid coating is dried at a first temperature capable of suppressing oxidation of the metal material in an oxidizing atmosphere. The method for producing a composite according to (6), wherein the particles are sintered at a second temperature higher than the first temperature.

  As a result, it is possible to obtain a composite as the coating layer is bonded to the base material with excellent strength while accurately suppressing or preventing deterioration and deterioration in the constituent materials contained in the coating layer and the base material. Can do.

  (8) The manufacturing method of the composite according to (7), wherein the first temperature is 200 ° C. or higher and 500 ° C. or lower.

  Thereby, decomposition | disassembly degreasing | defatting of components other than the particle | grains contained in a liquid film can be implemented more reliably, suppressing or preventing the oxidation of a metal material more reliably.

  (9) The method for producing a composite according to (7) or (8), wherein the second temperature is 600 ° C. or higher and 900 ° C. or lower.

  Thereby, since adjacent particle | grains can be sintered in the state connected more reliably, the formed coating layer can be more firmly joined with respect to the base material.

(10) A base material comprising a metal material or a first ceramic material as a main material, at least having a surface with irregularities, and a second ceramic formed on the surface of the base material and different from the first ceramic material A composite comprising a coating layer composed of a material as a main material,
The said coating layer is comprised with the porous body formed following the said uneven | corrugated shape, The composite body characterized by the above-mentioned.

  Thereby, the base material composed of the metal material or the first ceramic material as the main material and the coating layer composed of the second ceramic material as the main material are bonded with excellent strength and included in these. Therefore, it is possible to obtain a composite in which alteration / deterioration in the constituent material is appropriately suppressed or prevented.

(11) The composite body according to (9), wherein the porous body is formed by sintering particles composed of the second ceramic material as a main material.
Thereby, the coating layer can be bonded to the base material with excellent strength.

  According to the present invention, the base material composed of the metal material or the first ceramic material as the main material and the coating layer composed of the second ceramic material as the main material are bonded with excellent strength, and A composite in which alteration / deterioration in the constituent materials contained therein is appropriately suppressed or prevented can be produced.

  Therefore, by applying such a composite to a spacer including a base material composed of a metal material as a main material and a coating layer composed of a calcium phosphate-based material as a main material, such a spacer has excellent strength. It is possible to prepare and to achieve early bone fusion with the bone.

The top view (a), front view (b), side view (c), side surface partial enlarged view (d) which show 1st Embodiment of the block body which comprises the vertebral body spacer to which the composite_body | complex of this invention was applied. It is. It is a figure which shows the use condition of 1st Embodiment of the block body which comprises the vertebral body spacer shown in FIG. It is a figure which shows the use condition of 1st Embodiment of the block body which comprises the vertebral body spacer shown in FIG. It is a longitudinal cross-sectional view for demonstrating the manufacturing method which manufactures 1st Embodiment of the block body which comprises a vertebral body spacer. The top view (a), front view (b), side view (c), side surface partial expanded sectional view (d) which show 2nd Embodiment of the block body which comprises the vertebral body spacer to which the composite_body | complex of this invention was applied. ).

  Hereinafter, a method for producing a composite of the present invention and the composite will be described in detail based on preferred embodiments shown in the accompanying drawings.

  First, before explaining the manufacturing method of the composite_body | complex of this invention, the composite_body | complex of this invention is demonstrated.

  In the following, the case where the composite of the present invention is applied to a vertebral body spacer including a base material composed mainly of a metal material and a coating layer composed mainly of a calcium phosphate-based material is taken as an example. explain.

<Vertebral body spacer>
<< First Embodiment >>
First, a first embodiment of a vertebral body spacer to which the composite of the present invention is applied will be described.

  FIG. 1 is a plan view (a), a front view (b), a side view (c), and a side partial enlarged view showing a first embodiment of a block body constituting a vertebral body spacer to which a composite of the present invention is applied. FIG. 2D, FIG. 2 and FIG. 3 are views showing the usage state of the first embodiment of the block body constituting the vertebral body spacer, to which the composite of the present invention is applied.

  In the following description, unless otherwise specified, the direction is specified based on the state in which the vertebral body spacer is inserted between the vertebral bodies of the case (patient).

  That is, the ventral side of the case (the right side in FIGS. 1 (a), 1 (b) and 2 (b), the front side in FIG. 1 (c) and FIG. 2 (a), the lower side in FIG. Side) “front”, back side (left side in FIG. 1 (a), FIG. 1 (b) and FIG. 2 (b), back side in FIG. 1 (c) and FIG. 2 (a), FIG. The “upper side” is referred to as “rear”, and the head side of the case (the upper side in FIGS. 1B and 2, the front side in FIG. 1A and FIG. 3, the left side in FIG. 1C). ) Is “upper”, the leg side (lower side in FIGS. 1B and 2, the back side of the paper in FIGS. 1A and 3, the right side in FIG. 1C) is “lower”. say.

  As shown in FIG. 2, the vertebral body spacer 1 is provided between the vertebral body (bone) 101 and the vertebral body (bone) 102 when the upper and lower vertebral bodies 101 and 102 after the intervertebral disc is removed are fixed. It is inserted into the formed gap (hereinafter referred to as “vertebra”). In a state where the vertebral body spacer 1 is inserted between the vertebrae (hereinafter referred to as “inserted state”), the interval (separation distance) between the vertebral body 101 and the vertebral body 102 is properly maintained (held).

  As shown in FIGS. 2A and 3, the vertebral body spacer 1 (hereinafter sometimes simply referred to as “spacer 1”) is composed of a pair of block bodies 2 and 2 in this embodiment. Yes. Each block body 2 has substantially the same shape (configuration).

  Thus, since each block body 2 is made into the substantially same shape, below, one block body 2 is demonstrated to a representative.

  As shown in FIG. 1, the overall shape of the block body 2 is the first surface 31, the second surface 32, the third surface 33, the fourth surface 34, and the fifth surface 35. And a shape formed by being surrounded by the sixth surface 36.

  As shown in FIG. 3, in the block body 2, the first surface 31 is a contact surface that contacts the vertebral body 101 and the second surface 32 is the vertebral body 102 with the block body 2 inserted between the vertebrae. It becomes the contact surface which contacts. Further, the third surface 33 becomes a surface facing the inside of the space 103 formed by inserting the block body 2 between the vertebrae, and the fourth surface 34 becomes a surface facing the outside of the space 103.

  In the present embodiment, the third surface 33 is a curved concave surface, and the fourth surface 34 is a curved convex surface. Thereby, when the block body 2 is inserted between vertebrae, the block body 2 corresponding to the shape of the vertebra can be inserted more easily.

  The first surface 31, the second surface 32, the fifth surface 35, and the sixth surface 36 are substantially flat. Among these, in particular, when the first surface 31 and the second surface 32 are flat, the block body 2 can be surely brought into contact with the vertebral bodies 101 and 102.

  Further, the first surface 31 and the second surface 32 are formed with substantially the same length, and the third surface 33 and the fourth surface 34 are formed with substantially the same length, and the fifth surface The surface 35 and the sixth surface 36 are formed to have substantially the same length.

  From the above, the overall shape of the block body 2 is such that the rectangular parallelepiped is curved on the third surface 33 side in the third surface 33 and the fourth surface 34.

  In addition, chamfering is made in the vicinity of each corner formed by the surfaces contacting each other. Thereby, chipping (breakage) of the block body 2 is prevented, and the insertion of the block body 2 into the intervertebral space can be easily performed without being caught by the vertebral bodies 101 and 102.

In such a block body 2, the length of the third surface 33 (L _{1 in} FIG. ₁ ), the length of the fifth surface 35 (L _{2 in} FIG. 1), and the third surface 33 and the fourth surface Each dimension such as the (maximum) distance (L _{3 in} FIG. 1) from the surface 34 of the vertebra is appropriately determined according to the type of vertebral body such as the cervical vertebra and the lumbar vertebra, and the case. It is set within such a range.

That is, the length of the third surface 33 (L _{1 in} FIG. ₁ ) is preferably set to about 6 to 25 mm, more preferably about 8 to 22 mm.

Further, the length of the fifth surface 35 (L _{2 in} FIG. 1) is preferably set to about 4 to 25 mm, more preferably about 10 to 25 mm, and further preferably about 16 to 21 mm.

Furthermore, the (maximum) distance (L _{3 in} FIG. 1) between the third surface 33 and the fourth surface 34 is preferably set to about 6 to 15 mm, more preferably about 9 to 12 mm.

  The block body 2 having such a configuration includes a base material 21 composed of a metal material as a main material and a coating layer 25 formed on the surface of the base material 21 and composed of a calcium phosphate-based material as a main material. There is no. And in this embodiment, the base material 21 comprises the porous body formed by laminating | stacking the mesh which makes a some mesh shape, and comprises the structure provided with an unevenness | corrugation on the surface, and the coating layer 25 is such an unevenness | corrugation. It is comprised with the porous body formed following the shape of this.

  By providing the block body 2 with such a base material 21 and the coating layer 25, the base material 21 composed of a metal material as a main material has excellent strength, and a calcium phosphate material as a main material. Since the configured covering layer 25 functions as a scaffold for the proliferation and differentiation of bone cells, the block body 2 (vertebral body spacer 1) has excellent strength, and the vertebral body (bones) 101, 102 It is possible to achieve early bone fusion.

  Moreover, since this block body 2 (vertebral body spacer 1) can be manufactured by applying the composite manufacturing method of the present invention described later, the base material 21 and the coating layer 25 (particularly the coating layer 25) are used. The base material 21 and the coating layer 25 are bonded with excellent strength in a state in which the alteration / deterioration in the constituent materials contained is appropriately suppressed or prevented.

  As shown in FIG. 1, the base material 21 is substantially composed of a porous body formed by laminating a plurality of mesh-like meshes 22 in the thickness direction. Thereby, the surface is provided with unevenness. Note that the mesh 22 is formed by arranging a plurality of linear bodies 23 both in the vertical direction and in the horizontal direction and joining or weaving them at the contact points of each other.

  In this embodiment, the base material 21 (linear body 23) is composed of a metal material as a main material. Thereby, since the base material 21 becomes what has the outstanding intensity | strength, it can prevent or suppress the damage of the block body 2 in between vertebrae exactly.

  In addition, various materials can be used as the metal material, and titanium or a titanium alloy is particularly preferable. Titanium or titanium alloy is preferably used as a constituent material of the base material 21 because of its high biocompatibility and excellent strength. In addition, although it does not specifically limit as a titanium alloy, For example, Ti, such as Ti-6Al-4V and Ti-29Nb-13Ta-4.6Zr, has Al as a main component, Sn, Cr, Zr, Mo, Ni , Pd, Ta, Nb, V, Pt and the like are added. The metal material may be a shape memory alloy. By configuring the base material 21 with a shape memory alloy, the base material 21 returns to its original shape even if it is deformed by an external load.

  Furthermore, the porosity of the base material 21 is preferably about 3% to 50%, more preferably about 10% to 40%, and more preferably about 15% to 35%. preferable. Thereby, since the base material 21 can be provided with the especially outstanding intensity | strength, the failure | damage of the block body 2 in a vertebra can be prevented or suppressed exactly.

  The covering layer 25 is configured by a porous body that covers the base material 21 following the shape of the unevenness provided on the surface of the base material 21.

  In this embodiment, the coating layer 25 is composed of a calcium phosphate material as a main material. Thereby, since the covering layer 25 functions as a scaffold for the proliferation and differentiation of bone cells, the block body 2 (vertebral body spacer 1) can achieve early bone fusion with the vertebral bodies (bones) 101 and 102. It becomes.

  Examples of the calcium phosphate compound include apatites such as hydroxyapatite, fluorine apatite, and carbonate apatite, dicalcium phosphate, tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, and the like. These can be used alone or in combination of two or more. Of these calcium phosphate compounds, those having a Ca / P ratio of 1.0 to 2.0 are preferably used.

  Of such calcium phosphate compounds, hydroxyapatite is more preferable. Hydroxyapatite has an excellent biocompatibility because it has the same structure as the mineral main component of bone. In addition, since it functions as a scaffold for the growth and differentiation of bone cells, early fusion between the block body 2 itself and the vertebral bodies (bones) 101 and 102 can be expected.

  Furthermore, the porosity of the coating layer 25 is preferably set to about 1% to 20%, more preferably about 1% to 10%, and still more preferably about 1% to 5%.

  The thickness of the covering layer 25 is not particularly limited, but is preferably set to about 1 to 6 mm, more preferably about 2 to 4 mm.

  The covering layer 25 having such a porosity and thickness can be obtained by manufacturing the block body 2 using the composite manufacturing method of the present invention described later. By forming the coating layer 25 by applying such a manufacturing method, the coating layer 25 is applied to the base material 21 in a state where alteration or deterioration in the constituent materials included in the coating layer 25 is appropriately suppressed or prevented. It can form as what was joined by the outstanding intensity | strength.

  Further, the coating layer 25 preferably has an osteoinductive factor carried on its surface. Thereby, it becomes possible to aim at a bone fusion with the vertebral bodies 101 and 102 in the block body 2 at an earlier stage.

  The osteoinductive factor is not particularly limited as long as it has an activity of promoting osteogenesis by inducing differentiation into undifferentiated mesenchymal cells, and, for example, a bone morphogenetic protein. (BMP) is preferably used.

  Examples of BMP include BMP-1, BMP-2, BMP-3, BMP-4, BMP-5, BMP-6, BMP-7, BMP-8, BMP-9, BMP-12 (and above, Homodimers), or heterodimers or modified forms of these BMPs.

  The block bodies 2 as described above are inserted side by side between the vertebral body 101 and the vertebral body 102 (intervertebral) in pairs.

  By inserting the block body 2 into such an intervertebral space, a space 103 is formed in a region where the block body 2 is not inserted into the intervertebral space. By filling this space 103 with a transplanted bone (in particular, autologous bone) as a filling material, bone fusion between the vertebral body 101 and the vertebral body 102 via the block body 2 can be performed more reliably and quickly. It becomes.

  Further, since the spacer 1 is composed of a pair of block bodies 2 and 2, the arrangement of each block body 2 is changed, that is, the front end or the rear end of each block body 2 is separated or brought close to each other. For example, appropriate treatment can be performed according to the case.

  The spacer 1 as described above can be manufactured, for example, as follows by applying the composite manufacturing method of the present invention.

  FIG. 4 is a longitudinal sectional view for explaining the manufacturing method for manufacturing the first embodiment of the block body constituting the vertebral body spacer.

  This spacer 1 (block body 2) is produced by preparing a slurry containing particles composed mainly of a calcium phosphate-based material, water, an organic binder, and a solvent having an affinity for water, and a base material 21. And a second step of supplying the slurry to the surface of the base material 21 and forming a liquid film in a state where the particles contained in the slurry are embedded in the concave and convex portions provided in the base material 21. And a porous body formed by following the shape of the irregularities by heating the liquid film, drying the liquid film, and then sintering the particles composed mainly of the calcium phosphate material. And a third step of forming a coating layer 25 made of

Hereinafter, these steps will be sequentially described.
<1> First, a slurry containing a particle having a calcium phosphate-based material as a main material, water, an organic binder, and a solvent having an affinity for water, and a substrate 21 are prepared (first step).

  <1-1> First, a solvent having affinity for particles composed of a calcium phosphate-based material as a main material (hereinafter also referred to as “calcium phosphate-based particles”), water, an organic binder, and water. A slurry containing is prepared.

  Thus, the viscosity of a slurry can be reduced because the solvent provided with affinity with water is contained in the slurry. Therefore, in the next step <2>, when the slurry is supplied to the surface of the base material 21, the slurry is easily infiltrated (impregnated) into the inside of the base material 21, that is, into the recess provided on the surface of the base material 21. Can do.

  Specifically, the viscosity of the slurry varies depending on the size of the recess provided on the surface of the base material 21 and the type of the metal material included in the base material 21, for example, a viscosity at 25 ° C. of 100 Pa · s to 2500 Pa. It is preferably s or less, more preferably 150 Pa · s or more and 2000 Pa · s or less. Thereby, the said effect can be exhibited reliably.

  As the calcium phosphate particles, powders such as temporary particles and secondary particles composed of the calcium phosphate compound described above are used.

  Such calcium phosphate-based particles can be produced by a known method. For example, hydroxyapatite particles are synthesized by a wet method in which an aqueous phosphoric acid solution and a calcium hydroxide suspension are reacted by a known method, and then filtered. It can be obtained by pulverization by means such as centrifugation or spray drying. Depending on the particle size of the calcium phosphate particles to be obtained, the obtained powder is pulverized and then the obtained pulverized product is classified to obtain calcium phosphate particles having a target particle size. Good.

  The average particle size of the calcium phosphate particles is not particularly limited, but is preferably about 0.1 μm or more and 10 μm or less, and more preferably about 1 μm or more and 3 μm or less. By setting within such a range, the calcium phosphate-based particles can have a size that allows the calcium phosphate-based particles to be embedded in the recesses of the irregularities of the base material 21 with certainty. Therefore, in the post-process <3-2>, the coating layer 25 can be reliably formed following the uneven shape. The average particle diameter of the calcium phosphate particles can be measured by, for example, a laser diffraction method.

  The content of the calcium phosphate particles in the slurry is preferably about 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and more preferably 10% by mass to 30% by mass in the slurry. % Or less is more preferable. By setting within this range, in the post-process <3>, the coating layer 25 can be formed in a state of following the shape of the unevenness and bonded with an excellent strength to the unevenness. .

  In addition, as a solvent having an affinity for water (hereinafter, also simply referred to as “solvent”), as long as it exhibits compatibility with water and can reduce the viscosity of the slurry, Although not limited, for example, a primary or secondary alcohol having 2 to 6 carbon atoms is preferably used. Specifically, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol and the like can be mentioned, and one or more of these can be used in combination. Since these solvents show excellent compatibility with water and can reliably reduce the viscosity of the slurry, in the next step <2>, in a state where the slurry is introduced into the recesses provided in the unevenness, A liquid film can be reliably formed.

  The content of the solvent in the slurry is preferably about 25% by mass to 75% by mass, and more preferably 40% by mass to 60% by mass in the slurry. By setting within such a range, the viscosity of the slurry can be more reliably lowered, and in the next step <2>, the slurry can be surely introduced into the recess provided in the unevenness.

  Examples of organic binders (water-soluble resin binders) include acrylic resins such as polyacrylic acid esters and polymethacrylic acid esters, cellulose resins such as methylcellulose, hydroxymethylcellulose, nitrocellulose, and cellulose acetate butyrate, polyvinyl butyral, and polyvinyl alcohol. , Vinyl group-containing resins such as polyvinyl chloride, hydrocarbon resins such as polyolefin, oxygen-containing resins such as polyethylene oxide, etc., and one or more of these can be used in combination. By containing the organic binder, the calcium phosphate particles can be uniformly dispersed in the slurry.

  The content of the organic binder in the slurry is preferably about 0.2% by mass to 3% by mass and more preferably 0.4% by mass to 2% by mass in the slurry. By setting within this range, the calcium phosphate-based particles can be more uniformly dispersed in the slurry, so that the coating layer 25 having a more uniform thickness can be formed in the post-process <3>.

  This slurry can be obtained by mixing calcium phosphate-based particles, water, an organic binder, and a solvent having an affinity for water almost simultaneously, but the calcium phosphate-based particles, water, and organic binder It is preferable to mix a solvent having an affinity for water after mixing. As a result, a slurry having more excellent uniformity can be obtained.

<1-2> Next, the base material 21 is prepared.
For example, the substrate 12 includes a plurality of linear bodies (dense bodies) 23 each having a linear shape composed mainly of a metal material, and the plurality of linear bodies 23 are arranged in both the vertical direction and the horizontal direction. The mesh 22 is formed by joining or weaving at the contact points of each other.

  Next, after this mesh 22 is joined in a state of being stacked in the thickness direction to form a laminated body, the laminated body is subjected to a thin piece cutting method such as laser cutting, water jet, discharge wire processing, or ultrasonic cutting. It can be obtained by molding its shape, size, etc.

  <2> Next, a slurry is supplied to the surface of the base material 21, and a liquid film is formed in a state where the calcium phosphate particles contained in the slurry are embedded in the concave and convex portions provided in the base material 21 ( Second step).

  That is, in this embodiment, since the block body 2 is a laminated body in which a plurality of meshes 22 are stacked in the thickness direction, the block body 2 is composed of a porous body, and slurry is contained in the porous body. As a result, a liquid film is formed so as to cover the surface of the linear body 23 constituting the mesh 22.

  A method for supplying the slurry to the substrate 21 is not particularly limited, and examples thereof include a knife coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. .

  As described above, the slurry supplied to the base material 21 contains a solvent having an affinity for water, so that the viscosity is low. Therefore, when the slurry is supplied to the base material 21, a liquid film can be formed in a state where the slurry is embedded in the recess.

  Furthermore, when supplying the slurry to the base material 21, the calcium phosphate-based particles in the slurry have a size that allows embedding into the recesses of the unevenness of the base material 21. Therefore, when supplying the slurry to the base material 21, a liquid film may be formed in a state where the calcium phosphate-based particles contained in the slurry are embedded in the recess together with the liquid component contained in the slurry. it can.

  <3> Next, the liquid film is heated to dry the liquid film, and then the calcium phosphate-based particles are sintered, thereby forming a porous body formed by following the unevenness provided on the surface of the substrate 21. The covering layer 25 is formed (third step).

  Here, in this embodiment, the base material 21 is comprised with a metal material, and the particle | grains (2nd ceramic material) for forming the coating layer 25 are comprised with a calcium-phosphate type material. In this case, the heating of the liquid film is performed by drying the liquid film at a first temperature capable of suppressing the oxidation of the metal material contained in the base material 21 in an oxidizing atmosphere, and then in the non-oxidizing atmosphere. This is performed by sintering the calcium phosphate particles at a second temperature higher than the temperature.

  <3-1> First, in an oxidizing atmosphere, the liquid coating is dried by heating at a first temperature that can suppress oxidation of the metal material contained in the base material 21.

  In the heating at the first temperature, the liquid film is heated at a temperature (first temperature) at which oxidation of the metal material contained in the base material 21 is suppressed even in an oxidizing atmosphere. Is called. Therefore, it is possible to accurately suppress or prevent the metal material from being oxidized due to the heating of the metal material. Therefore, the structural material (metal material) included in the base material 21 can be appropriately altered and deteriorated. Can be suppressed or prevented.

  In addition, in the drying of the liquid film by heating at the first temperature, components other than the calcium phosphate particles contained in the liquid film are decomposed and degreased, whereby the liquid film is removed from the skeleton in which the calcium phosphate particles are aggregated. It can be set as the degreased body formed. That is, since the heating at the first temperature is performed in an oxidizing atmosphere, the carbon film contained in the solvent having an affinity for the organic binder and water is also surely separated from the liquid film, and the liquid film is formed. A defatted body formed from a skeleton in which calcium phosphate-based particles are aggregated can be obtained.

  For example, the first temperature is preferably about 200 ° C. or more and 500 ° C. or less, and more preferably about 250 ° C. or more and 450 ° C. or less.

  The time for heating at the first temperature is preferably about 0.1 hour or more and 2 hours or less, and more preferably about 0.1 hour or more and 0.5 hours or less.

  By performing drying of the liquid film at the first temperature under such conditions, decomposition and degreasing of components other than calcium phosphate-based particles contained in the liquid film (carbon) while more reliably suppressing or preventing oxidation of the metal material. (Detachment of atoms) can be carried out more reliably.

  <3-2> Subsequently, the calcium phosphate particles are sintered by heating at a second temperature higher than the first temperature in a non-oxidizing atmosphere.

  Thereby, the coating layer 25 which consists of a porous body formed following the uneven | corrugated shape with which the surface of the base material 21 is provided is obtained.

  The heating at the second temperature is performed in a state where the calcium phosphate-based particles are embedded in the recesses provided in the unevenness. That is, in the present embodiment, the calcium phosphate-based particles are performed in a state of covering the surface of the linear body 23 provided in the mesh 22 that forms the recess in the base material 21 (porous body).

  In this manner, the calcium phosphate particles are sintered in a state where the surface of the linear body 23 is covered. Therefore, as shown in FIG. 4, since the coating layer 25 is formed by sintering (connecting) adjacent calcium phosphate-based particles, the formed coating layer 25 is composed of the linear body 23 (base material 21). It will be firmly joined to.

  In addition, since the heating at the second temperature is performed in a non-oxidizing atmosphere, even if the heating is performed at a second temperature higher than the first temperature, the metal material is accurately suppressed or prevented from being oxidized. Therefore, alteration / deterioration of the constituent material (metal material) included in the base material 21 can be accurately suppressed or prevented.

  The average particle diameter of the calcium phosphate particles is preferably set to about 0.1 μm or more and 10 μm or less as described above. As described above, when the calcium phosphate particles are sintered, the calcium phosphate particles are more surely connected to each other when the calcium phosphate particles are sintered as shown in FIG. Since it can be in a state, the formed coating layer 25 can be more firmly bonded to the linear body 23 (base material 21). In addition, the calcium phosphate particles adhere to the surface of the linear body 23 when the slurry is supplied to the surface of the base material 21 and the slurry penetrates into the base material 21 in the step <2>. Among the calcium phosphate-based particles contained in, particles having a smaller particle size tend to adhere. Therefore, also from such a viewpoint, the coating layer 25 that is more firmly bonded to the linear body 23 (base material 21) can be obtained by forming the coating layer 25 using slurry. it can.

  Furthermore, the second temperature is preferably about 600 ° C. or higher and 900 ° C. or lower, and more preferably about 700 ° C. or higher and 850 ° C. or lower.

  The time for heating at the second temperature is preferably about 1 hour to 10 hours, more preferably about 2 hours to 8 hours.

  By sintering under such conditions, adjacent calcium phosphate-based particles can be sintered in a more reliably connected state, and thus the formed coating layer 25 is applied to the linear body 23 (base material 21). On the other hand, it can be more firmly joined.

  As calcium phosphate-based particles, one containing low-crystalline hydroxyapatite as a main material is prepared, and this low-crystalline hydroxyapatite is converted into tricalcium phosphate (TCP), and the calcium phosphate-based particles are converted into tricalcium phosphate. When included as a main material, the second temperature is preferably about 800 ° C. or higher and 850 ° C. or lower.

In addition, the degree of vacuum when the non-oxidizing atmosphere is set is preferably 5.0 × 10 ⁻² Pa or less, and the non-oxidizing atmosphere is preferably a nitrogen atmosphere or an argon atmosphere. Thereby, even if it heats at 2nd temperature higher than 1st temperature, since it can suppress or prevent that a metal material oxidizes more exactly, the constituent material (metal material) contained in the base material 21 can be prevented. ) Can be suppressed or prevented more accurately.

  By passing through the above steps, the coating layer 25 has an excellent strength against the base material 21 while accurately suppressing or preventing deterioration and deterioration in the constituent materials contained in the coating layer 25 and the base material 21. The spacer 1 (block body 2) can be obtained as what was joined.

Second Embodiment
Next, a second embodiment of the vertebral body spacer to which the composite of the present invention is applied will be described.

  FIG. 5 is a plan view (a), a front view (b), a side view (c), and a side partial enlarged view showing a second embodiment of a block body constituting a vertebral body spacer to which the composite of the present invention is applied. It is sectional drawing (d).

  Hereinafter, although the block body 2 shown in FIG. 5 is demonstrated, it demonstrates centering around difference with the block body 2 shown in FIGS. 1-3, and the description is abbreviate | omitted about the same matter.

  The block body 2 shown in FIG. 5 is the same as the block body 2 shown in FIGS. 1 to 3 except that the structure of the base material 21 is different.

  That is, in the present embodiment, the block body 2 has a dense central portion excluding the surface thereof and a non-smooth surface, and thereby has irregularities on the surface. This non-smooth surface can be obtained by subjecting the surface of a dense body made of a metal material to surface treatment such as blasting to form irregularities.

  Even if the unevenness formed by applying such a surface treatment to the substrate 21, as shown in FIG. 5, the coating layer follows the shape of the unevenness so that the coating layer 25 is embedded in the recess. By forming 25, the covering layer 25 can be firmly bonded to the recess (base material 21) due to the anchor effect on the recess of the coating layer 25.

  The block body 2 of the present embodiment having such a configuration is manufactured as the base body 21 except that a substrate 21 having surface irregularities formed thereon is prepared. It can be manufactured in the same manner as the manufacturing method, and by applying the manufacturing method, the coating layer 25 and the constituent materials contained in the base material 21 can be coated while accurately suppressing or preventing deterioration and deterioration. As the layer 25 bonded to the base material 21 with excellent strength, the block body 2 of the present embodiment can also be obtained.

  Furthermore, the block body 2 having such a configuration can be used in the same manner as the block body 2 of the first embodiment.

  As mentioned above, although the composite_body | complex of this invention was demonstrated about each embodiment of illustration, this invention is not limited to these.

  For example, in the composite of the present invention, the arbitrary configurations of the first and second embodiments can be combined.

  Moreover, although each embodiment demonstrated the case where a pair of block body 2 was inserted between vertebrae, it is not limited to this case, You may make it insert one block body 2 between vertebrae. In this case, the block body 2 is inserted to the front side of the intervertebral space so that the fourth surface 34 faces the front side and the third surface 33 faces the rear side.

  Furthermore, the filler is not limited to transplanted bone (autologous bone), and may be, for example, calcium phosphate compound powder.

  Moreover, in each embodiment, although the base material was comprised as a main material and the case where the coating layer was a calcium-phosphate type material was demonstrated, it is not limited to such a combination, For example, a base material, a coating layer, May be composed of a first ceramic material and a second ceramic material of different types as main materials. In this case, examples of the ceramic material include alumina, zirconia, silicon carbide, silicon nitride, boron nitride, barium titanate, ferrite, and zinc oxide in addition to the above-described calcium phosphate materials. Are selected as the first ceramic material and the second ceramic material.

  Further, in each embodiment, the case where the composite of the present invention is applied to a vertebral body spacer has been described. The present invention can be applied to a spinous process spacer, a skull spacer to be compensated for a defect of a skull, a bone plate addressed to a fracture site such as a femur.

Next, specific examples of the present invention will be described.
1. Preparation of slurry [Slurry 1A]
[1A] First, 2 g of hydroxypropylmethylcellulose (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., “Marporose”) was dissolved in 100 mL of water.

  [2A] Next, 30 g of pre-fired TCP powder (average particle size 2.3 μm, pre-sintering temperature 700 ° C.) was added and stirred for 1 day.

[3A] Next, 100 mL of ethanol was added, and the mixture was further stirred for 3 hours to obtain slurry 1A.
The obtained slurry 1A had a viscosity of 500 Pa · s.

[Slurry 2A]
In the step [3A], a slurry 2A was obtained in the same manner as the slurry 1A except that the amount of ethanol added was 300 mL.
In addition, the viscosity of the obtained slurry 2A was 200 Pa · s.

[Slurry 3A]
In the step [3A], a slurry 3A was obtained in the same manner as the slurry 1A except that the amount of ethanol added was 25 mL.
The obtained slurry 3A had a viscosity of 2000 Pa · s.

[Slurry 4A]
A slurry 4A was obtained in the same manner as the slurry 1A except that the addition of ethanol in the step [3A] was omitted.
The obtained slurry 4A had a viscosity of 5000 Pa · s.

[Slurry 1B]
[1B] First, 2 g of hydroxypropylmethylcellulose (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., “Marporose”) was dissolved in 100 mL of water.

  [2B] Next, 30 g of pre-fired TCP powder (average particle size 2.3 μm, pre-sintering temperature 700 ° C.) was added and stirred for 1 day.

  [3B] Next, 100 mL of ethanol was added, and the mixture was further stirred for 3 hours to obtain slurry 1B.

[Slurry 2B]
In the step [2B], a slurry 2B was obtained in the same manner as the slurry 1B, except that the temporarily calcined TCP powder to be added had an average particle size of 36 μm.

2. Manufacture of base material [1C] First, a plurality of 0.1 mm diameter linear bodies made of titanium are prepared, and the plurality of linear bodies are arranged in both the vertical and horizontal directions at a pitch of 0.2 mm. The mesh was obtained by heat welding at the contact points of each other.

  [2C] Next, a plurality of meshes 22 were stacked in the thickness direction and heat-welded to obtain a base material.

3. Evaluation 3-1. Evaluation of Permeability of Slurry to Base Material About each of the prepared slurries 1A to 4A, 1 mL was applied to the base material.

  Then, the degree of penetration of the slurry into the base material was visually confirmed, and evaluation was made based on the following evaluation criteria according to the degree.

<Evaluation criteria for permeability>
A: Almost all of the supplied slurry penetrates into the substrate.
◯: Less than 1/3 of the supplied slurry remains on the substrate without penetrating.
Δ: 1/3 or more and less than half of the supplied slurry remains on the substrate without penetrating.
X: Half or more of the supplied slurry remains on the substrate without penetrating.
The evaluation results are shown in Table 1.

  As is apparent from Table 1, by making ethanol contain in the slurry, the viscosity of the slurry can be lowered, and the viscosity of the slurry is preferably 2000 Pa · s or less, more preferably 500 Pa · s. It has been clarified that the slurry can be effectively infiltrated into the base material by setting it to s or less.

3-2. Evaluation of presence or absence of removal of coating layer 1 mL of each of the prepared slurries 1B and 2B was applied to the substrate.

  Next, the surface of the linear body was coated with the pre-fired TCP powder by burning off hydroxypropylmethylcellulose and ethanol by performing a degreasing treatment in an atmospheric furnace at 400 ° C. for 20 minutes.

  Next, a composite in which a coating layer is formed on the surface of the linear body included in the base material by sintering the pre-fired TCP powder by heating at 800 ° C. for 240 minutes in an argon furnace under an argon atmosphere. Got the body.

Then, the release of the coating layer in the composite was confirmed by rubbing the surface of the composite with a finger to determine whether the powder adhered to the finger.
The evaluation results are shown in Table 2.

  As can be seen from Table 2, by using a slurry containing a powder having an average particle size as small as 2.3 μm, a composite in which separation of the coating layer from the substrate is prevented can be obtained. It became clear.

3-3. Evaluation of powder sintering conditions [Composite 1C]
About the prepared slurry 1B, 1 mL was apply | coated with respect to the base material.

  Next, the surface of the linear body was coated with the pre-fired TCP powder by burning off hydroxypropylmethylcellulose and ethanol by performing a degreasing treatment in an atmospheric furnace at 400 ° C. for 20 minutes.

  Next, a composite in which a coating layer is formed on the surface of the linear body included in the base material by sintering the pre-fired TCP powder by heating at 800 ° C. for 240 minutes in an argon furnace under an argon atmosphere. Got the body.

[Composite 2C]
About the prepared slurry 1B, 1 mL was apply | coated with respect to the base material.

  Subsequently, by heating in an argon furnace under the conditions of 800 ° C. and 240 minutes in an argon atmosphere, hydroxypropylmethylcellulose and ethanol are burned off by degreasing treatment, and the pre-fired TCP powder is sintered. A composite in which a coating layer was formed on the surface of the linear body included in the material was obtained.

[Composite 3C]
About the prepared slurry 1B, 1 mL was apply | coated with respect to the base material.

  Next, by heating under an oxidizing atmosphere in an atmospheric furnace at 800 ° C. for 240 minutes, the hydroxypropyl methylcellulose and ethanol are burned off by degreasing and the pre-fired TCP powder is sintered. A composite in which a coating layer was formed on the surface of the linear body included in the material was obtained.

  And the intensity | strength of the composite_body | complex was calculated | required by folding a composite by hand and evaluated based on the following evaluation criteria.

<Evaluation criteria for composite strength>
A: The composite cannot be folded by hand, and no slight deformation is observed.
◯: The composite cannot be folded by hand, but some deformation is observed.
X: The composite can be folded by hand.
Furthermore, the presence or absence of carbon atoms remaining in the coating layer was visually confirmed.
The evaluation results are shown in Table 3.

  As is apparent from Table 3, the composites 1C and 2C both obtained sufficient strength, and the composite 3C did not provide sufficient strength. The composite 3C lost the toughness of the metal and was easily broken. In addition, in the composite 2C, although sufficient strength was obtained, the result of carbon remaining in the coating layer was shown.

DESCRIPTION OF SYMBOLS 1 Vertebral body spacer 2 Block body 12 Base material 21 Base material 22 Mesh 23 Linear body 25 Coating layer 31 1st surface 32 2nd surface 33 3rd surface 34 4th surface 35 5th surface 36 6th Face 101, 102 vertebral body 103 space

Claims (11)

A base material composed mainly of a metal material or a first ceramic material, and a coating formed on the surface of the base material and composed of a second ceramic material different from the first ceramic material. A method for producing a composite comprising a layer,
First prepared is a slurry containing particles composed mainly of the second ceramic material, water, an organic binder, and a solvent having an affinity for water, and the base material having at least unevenness on the surface. And the process of
A second step of supplying the slurry to the surface of the base material to form a liquid film in a state where the particles are embedded in the concave and convex portions;
A third step of forming the coating layer made of a porous body formed by following the irregularities by heating the liquid coating, drying the liquid coating, and then sintering the particles; The manufacturing method of the composite_body | complex characterized by having.   The method for producing a composite according to claim 1, wherein the solvent is a primary or secondary alcohol having 2 to 6 carbon atoms.   The method for producing a composite according to claim 1 or 2, wherein the content of the solvent in the slurry is 25% by mass or more and 75% by mass or less.   The method for producing a composite according to any one of claims 1 to 3, wherein the particles have a size that allows embedding in the concave portion.   The method for producing a composite according to claim 4, wherein the particles have an average particle diameter of 0.1 μm or more and 10 μm or less.   The method for producing a composite according to any one of claims 1 to 5, wherein the base material is made of the metal material, and the second ceramic material is made of a calcium phosphate material.   In the third step, the liquid coating is heated in a non-oxidizing atmosphere after the liquid coating is dried at a first temperature capable of suppressing oxidation of the metal material in an oxidizing atmosphere. The manufacturing method of the composite_body | complex of Claim 6 performed by sintering the said particle | grain at 2nd temperature higher than 1 temperature.   The method for producing a composite according to claim 7, wherein the first temperature is 200 ° C. or higher and 500 ° C. or lower.   The method for producing a composite according to claim 7 or 8, wherein the second temperature is 600 ° C or higher and 900 ° C or lower. A main material is a metal material or a first ceramic material, and a base material having at least unevenness on the surface, and a second ceramic material that is formed on the surface of the base material and is different from the first ceramic material. A composite comprising a coating layer configured as a material,
The said coating layer is comprised with the porous body formed following the said uneven | corrugated shape, The composite body characterized by the above-mentioned.   The composite according to claim 9, wherein the porous body is formed by sintering particles composed of the second ceramic material as a main material.

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