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EP0264917A2
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EP
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A biocompatible composite material and a method for producing the same
Assignee: Individual
•
Filing: 1987-10-20
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Granted: —
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Expires: 2007-10-20
Abstract
Abstract A biocompatible composite material comprising a substrate having a glass-hydroxyapatite ceramic layer disposed thereon, and optionally having an intermediate glass layer between the substrate and the layer. The glass-hydroxyapatite ceramic layer comprises a continous glass phase having a hydroxyapatite ceramic dispersed therein, said hydroxyapatite ceramic having a calcium/phosphorous molar ratio of 1.50 to 1.75, wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite. The surface portion of the layer is in a roughened state having voids and having the hydroxyapatite ceramic exposed. The composite material may be produced by a method comprising applying a blend of a powdery glass with a hydroxyapatite ceramic to the surface of a substrate with or without a glass layer disposed thereon, firing the resulting coated substrate and subjecting the fired coated substrate to an etching action with an acid. The composite material is useful as a bone substitute material for the reconstruction of bone defects.
Inventors
- 👤 Shigeo Maruno
- 👤 Seiji Ban
- 👤 Hisashi Iwata
- 👤 Haruo Ito
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-08 22:23
CPC Classifications
A; A61; A61L; A61L27/00; C; C23; C23D; C23D5/00; A61F; A61F2/00; A61F2/02; A61F2/28; A61F2/30; A61K; A61K6/00; A61K6/50; A61K6/54; A61K6/58; A61K6/70; A61K6/78; A61K6/80; A61K6/802; A61K6/807; A61K6/813; A61K6/816; A61K6/818; A61K6/831; A61K6/833; A61K6/838; A61L27/28; A61L27/30; A61L27/32; C03; C03C; C03C14/00; C03C14/004; C03C3/00; C03C3/04; C03C3/076; C03C3/089; C03C3/091; A61F2310/00; A61F2310/00389; A61F2310/00592; A61F2310/00796; C03C2214/00; C03C2214/04
Claims Analysis
Total Claims: 48
Claim 1
Independent Claim
76 words
A biocompatible composite material comprising a substrate having a glass-hydroxyapatite ceramic layer disposed thereon, said layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75, wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, and wherein the surface portion of said glass-hydroxyapatite ceramic layer is in a roughened state having voids and having the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer exposed.
Claim 2
Dependent Claim
76 words
A biocompatible composite material comprising a substrate having a glass-hydroxyapatite ceramic layer disposed thereon, said layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75, wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, and wherein the surface portion of said glass-hydroxyapatite ceramic layer is in a roughened state having voids and having the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer exposed.
Claim 3
Dependent Claim
79 words
The composite material according to claim 1, wherein said glass-hydroxyapatite ceramic layer comprises a plurality of sub-layers each comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said sub-layers having different hydroxyapatite ceramic contents which are increased from the innermost sub-layer toward the outermost sub-layer, and wherein the surface portion of the outermost sub-layer of said glass-hydroxyapatite ceramic layer is in a roughened state having voids and having the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer exposed.
Claim 4
Dependent Claim
146 words
The composite material according to claim 1, wherein said glass-hydroxyapatite ceramic layer comprises at least three sub-layers each comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said sub-layers including at least one combination of at least two mutually adjacent sub-layers of which the hydroxyapatite ceramic contents are identical with each other and having different hydroxyapatite ceramic contents between at least two mutually adjacent sub-layers, in which the hydroxyapatite ceramic contents of the sub-layers constituting the entire glass-hydroxyapatite ceramic layer are increased from the innermost sub-layer toward the outermost sub-layer through at least one sub-layer of which the hydroxyapatite ceramic content is identical with that of a sub-layer immediately preceding said sub-layer, and wherein the surface portion of the outermost sub-layer of said glass-hydroxyapatite ceramic layer is in a roughened state having voids and having the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer exposed.
Claim 5
Dependent Claim
47 words
The composite material according to any one of claims 1 to 3, having an intermediate layer between said substrate and said glass-hydroxyapatite ceramic layer, wherein said intermediate layer comprises glass and is bonded to each of the opposing surfaces of the substrate and the glass-hydroxyapatite ceramic layer.
Claim 6
Dependent Claim
28 words
The composite material according to any one of claims 1 to 4, wherein said glass of the glass-hydroxyapatite ceramic layer comprises a borosilicate glass or an aluminosilicate glass.
Claim 7
Dependent Claim
22 words
The composite material according to claim 4, wherein said glass of the intermediate layer comprises a borosilicate glass or an aluminosilicate glass.
Claim 8
Dependent Claim
82 words
The composite material according to claim 5 or 6, wherein said borosilicate glass comprises from 75 to 85 % by weight of a mixture of SiO₂, B₂O₃ and Al₂O₃, based on the weight of the glass, and from 14 to 20 % by weight, based on the weight of the glass, of at least one metal oxide, in which the metal of the metal oxide is a member selected from the group consisting of an alkali metal and an alkaline earth metal.
Claim 9
Dependent Claim
81 words
The composite material according to claim 5 or 6, wherein said aluminosilicate glass comprises from 60 to 75 % by weight of a mixture of SiO₂ and Al₂O₃, based on the weight of the glass, and from 14 to 20 % by weight, based on the weight of the glass, of at least one metal oxide in which the metal of the metal oxide is a member selected from the group consisting of an alkali metal and an alkaline earth metal.
Claim 10
Dependent Claim
29 words
The composite material according to any one of claims 1 to 8, wherein said substrate is selected from the group consisting of a metallic substrate and a ceramic substrate.
Claim 11
Dependent Claim
14 words
The composite material according to claim 9, wherein said substrate is a metallic substrate.
Claim 12
Dependent Claim
17 words
The composite material according to claim 10, wherein said metallic substrate comprises Ti or a Ti alloy.
Claim 13
Dependent Claim
15 words
The composite material according to claim 11, wherein said Ti alloy comprises Ti and Al.
Claim 14
Dependent Claim
42 words
The composite material according to any one of claims 10 to 12, wherein said glass of the glass-hydroxyapatite ceramic layer has a linear thermal expansion coefficient which corresponds to from about 80 to about 95 % of that of the metallic substrate.
Claim 15
Dependent Claim
37 words
The composite material according to claim 13, wherein said glass of the glass-hydroxyapatite ceramic layer has a linear thermal expansion coefficient which corresponds to from about 90 to about 95 % of that of the metallic substrate.
Claim 16
Dependent Claim
41 words
The composite material according to any one of claims 10 to 14, wherein said glass of the intermediate layer has a linear thermal expansion coefficient which corresponds to from about 80 to about 95 % of that of the metallic substrate.
Claim 17
Dependent Claim
36 words
The composite material according to claim 15, wherein said glass of the intermediate layer has a linear thermal expansion coefficient which corresponds to from about 90 to about 95 % of that of the metallic substrate.
Claim 18
Dependent Claim
37 words
The composite material according to any one of claims 1 to 3, wherein said glass-hydroxyapatite ceramic layer has a hydroxyapatite ceramic content of from 15 to 50 % by weight, based on the weight of the layer.
Claim 19
Dependent Claim
32 words
The composite material according to claim 4, wherein said glass-hydroxyapatite ceramic layer has a hydroxyapatite ceramic content of from 15 to 70 % by weight, based on the weight of the layer.
Claim 20
Independent Claim
158 words
A method for producing a biocompatible composite material which comprises the steps of: (1) applying a blend of a powdery glass with a hydroxyapatite ceramic to the surface of a substrate to form a substrate having the blend disposed thereon, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75 and wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, (2) firing the substrate having the blend disposed thereon to obtain a preliminary product comprising a substrate having a glass-hydroxyapatite ceramic layer disposed thereon, said layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, and (3) subjecting said preliminary product to an etching action with an acid so as to dissolve the glass at the surface portion of the glass-hydroxyapatite ceramic layer remote from the substrate, thereby causing said surface portion to be roughened so that the surface portion has voids and the hydroxyapatite ceramic of the glass-hydroxy apatite ceramic layer is exposed.
Claim 21
Independent Claim
158 words
A method for producing a biocompatible composite material which comprises the steps of: (1) applying a blend of a powdery glass with a hydroxyapatite ceramic to the surface of a substrate to form a substrate having the blend disposed thereon, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75 and wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, (2) firing the substrate having the blend disposed thereon to obtain a preliminary product comprising a substrate having a glass-hydroxyapatite ceramic layer disposed thereon, said layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, and (3) subjecting said preliminary product to an etching action with an acid so as to dissolve the glass at the surface portion of the glass-hydroxyapatite ceramic layer remote from the substrate, thereby causing said surface portion to be roughened so that the surface portion has voids and the hydroxyapatite ceramic of the glass-hydroxy apatite ceramic layer is exposed.
Claim 22
Dependent Claim
84 words
The method according to claim 19, wherein the sequence of steps (1) and (2) is repeated prior to step (3), wherein the hydroxyapatite ceramic content of said blend is increased with each repetition of said sequence, wherein the glass-hydroxyapatite ceramic layer of the preliminary product formed, comprises a plurality of sub-layers, each comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said sub-layers having different hydroxyapatite ceramic contents, in which said contents are increased from the innermost sub-layer toward the outermost sub-layer.
Claim 23
Dependent Claim
172 words
The method according to claim 19, wherein the sequence of steps (1) and (2) is repeated at least two times prior to step (3), wherein the hydroxyapatite ceramic, content of said blend is unchanged with at least one repetition of said sequence while the hydroxyapatite ceramic content of said blend is increased with at least one repetition of said sequence, wherein the glass-hydroxyapatite ceramic layer of the preliminary product formed comprises at least three sub-layers each comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said sub-layers including at least one combination of at least two mutually adjacent sub-layers of which the hydroxyapatite ceramic contents are identical with each other and having different hydroxyapatite ceramic contents between at least two mutually adjacent sub-layers, in which the hydroxyapatite ceramic contents of the sub-layers constituting the entire glass-hydroxyapatite ceramic layer are increased from the innermost sub-layer toward the outermost sub-layer through at least one sub-layer of which the hydroxyapatite ceramic content is identical with that of a sub-layer immediately preceding said sub-layer.
Claim 24
Independent Claim
28 words
The method according to any one of claims 19 to 21, wherein the firing in step (2) is conducted at a temperature of from 850 to 1150 °C.
Claim 25
Independent Claim
204 words
A method for producing a biocompatible composite material which comprises the steps of: (1) applying a powdery glass to the surface of a substrate to coat the substrate with the powdery glass, (2) firing the powdery glass coated substrate to form a glass coated substrate, (3) applying a blend of a powdery glass with a hydroxyapatite ceramic to the surface of the glass coated substrate to form a glass coated substrate having the blend disposed thereon, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75 and wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, (4) firing the glass coated substrate having the blend disposed thereon to obtain a preliminary product comprising a substrate having a glass layer disposed thereon, which in turn has a glass-hydroxyapatite ceramic layer disposed thereon, said layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, and (5) subjecting said preliminary product to an etching action with an acid so as to dissolve the glass at the surface portion of the glass-hydroxyapatite ceramic layer remote from the substrate, thereby causing said surface portion to be roughened so that the surface portion has voids and the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer is exposed.
Claim 26
Independent Claim
204 words
A method for producing a biocompatible composite material which comprises the steps of: (1) applying a powdery glass to the surface of a substrate to coat the substrate with the powdery glass, (2) firing the powdery glass coated substrate to form a glass coated substrate, (3) applying a blend of a powdery glass with a hydroxyapatite ceramic to the surface of the glass coated substrate to form a glass coated substrate having the blend disposed thereon, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75 and wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, (4) firing the glass coated substrate having the blend disposed thereon to obtain a preliminary product comprising a substrate having a glass layer disposed thereon, which in turn has a glass-hydroxyapatite ceramic layer disposed thereon, said layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, and (5) subjecting said preliminary product to an etching action with an acid so as to dissolve the glass at the surface portion of the glass-hydroxyapatite ceramic layer remote from the substrate, thereby causing said surface portion to be roughened so that the surface portion has voids and the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer is exposed.
Claim 27
Dependent Claim
88 words
The method according to claim 23, wherein following steps (1) and (2), the sequence of steps (3) and (4) is repeated prior to step (5), wherein the hydroxyapatite ceramic content of said blend is increased with each repetition of said sequence, wherein the glass-hydroxyapatite ceramic layer of the preliminary product formed, comprises a plurality of sub-layers, each comprising a continues glass phase having hydroxyapatite ceramic dispersed therein, said sub-layers having different hydroxyapatite ceramic contents, in which said contents are increased from the innermost sub-layer toward the outermost sub-layer.
Claim 28
Dependent Claim
178 words
The method according to claim 23, wherein following steps (1) and (2), the sequence of steps (3) and (4) is repeated at least two times prior to step (5), wherein the hydroxyapatite ceramic content of said blend is unchanged with at least one repetition of said sequence while the hydroxyapatite ceramic content of said blend is increased with at least one repetition of said sequence, wherein the glass-hydroxyapatite ceramic layer of the preliminary product formed comprises at least three sub-layers each comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said sub-layers including at least one combination of at least two mutually adjacent sub-layers of which the hydroxyapatite ceramic contents are identical with each other and having different hydroxyapatite ceramic contents between at least two mutually adjacent sub-layers, in which the hydroxyapatite ceramic contents of the sub-layers constituting the entire glass- hydroxyapatite ceramic layer are increased from the innermost sub-layer toward the outermost sub-layer through at least one sub-layer of which the hydroxyapatite ceramic content is identical with that of a sub-layer immediately preceding said sub-layer.
Claim 29
Independent Claim
25 words
The method according to any one of claims 23 to 25, wherein the firing is conducted at a temperature of from 850 to 1150 °C.
Claim 30
Independent Claim
187 words
A method for producing a biocompatible composite material which comprises the steps of: (1) applying a blend of a powdery glass with a hydroxyapatite ceramic to the glass layer surface of a glass coated substrate comprising a substrate having disposed thereon a glass layer remote from the substrate to form a coated substrate having the blend disposed thereon, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75 and wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, (2) firing the glass coated substrate having the blend disposed thereon to obtain a preliminary product comprising a substrate having a glass layer disposed thereon, which in turn has a glass-hydroxyapatite ceramic layer disposed thereon, said ceramic layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, and (3) subjecting said preliminary product to an etching action with an acid so as to dissolve the glass at the surface portion of the glass-hydroxyapatite ceramic layer remote from the substrate, thereby causing said surface portion to be roughened so that the surface portion has voids and the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer is exposed.
Claim 31
Independent Claim
187 words
A method for producing a biocompatible composite material which comprises the steps of: (1) applying a blend of a powdery glass with a hydroxyapatite ceramic to the glass layer surface of a glass coated substrate comprising a substrate having disposed thereon a glass layer remote from the substrate to form a coated substrate having the blend disposed thereon, said hydroxyapatite ceramic having a calcium/phosphorus molar ratio of 1.50 to 1.75 and wherein said hydroxyapatite ceramic is comprised mainly of hydroxyapatite, (2) firing the glass coated substrate having the blend disposed thereon to obtain a preliminary product comprising a substrate having a glass layer disposed thereon, which in turn has a glass-hydroxyapatite ceramic layer disposed thereon, said ceramic layer comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, and (3) subjecting said preliminary product to an etching action with an acid so as to dissolve the glass at the surface portion of the glass-hydroxyapatite ceramic layer remote from the substrate, thereby causing said surface portion to be roughened so that the surface portion has voids and the hydroxyapatite ceramic of the glass-hydroxyapatite ceramic layer is exposed.
Claim 32
Dependent Claim
84 words
The method according to claim 27, wherein the sequence of steps (1) and (2) is repeated prior to step (3), wherein the hydroxyapatite ceramic content of said blend is increased with each repetition of said sequence, wherein the glass-hydroxyapatite ceramic layer of the preliminary product formed, comprises a plurality of sub-layers, each comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said sub-layers having different hydroxyapatite ceramic contents, in which said contents are increased from the innermost sub-layer toward the outermost sub-layer.
Claim 33
Dependent Claim
172 words
The method according to claim 27, wherein the sequence of steps (1) and (2) is repeated at least two times prior to step (3), wherein the hydroxyapatite ceramic content of said blend is unchanged with at least one repetition of said sequence while the hydroxyapatite ceramic content of said blend is increased with at least one repetition of said sequence, wherein the glass-hydroxyapatite ceramic layer of the preliminary product formed comprises at least three sub-layers each comprising a continuous glass phase having a hydroxyapatite ceramic dispersed therein, said sub-layers including at least one combination of at least two mutually adjacent sub-layers of which the hydroxyapatite ceramic contents are identical with each other and having different hydroxyapatite ceramic contents at least between two mutually adjacent sub-layers, in which the hydroxyapatite ceramic contents of the sub-layers constituting the entire glass-hydroxyapatite ceramic layer are increased from the innermost sub-layer toward the outermost sub-layer through at least one sub-layer of which the hydroxyapatite ceramic content is identical with that of a sub-layer immediately preceding said sub-layer.
Claim 34
Independent Claim
28 words
The method according to any one of claims 27 to 29, wherein the firing in step (2) is conducted at a temperature of from 850 to 1150 °C.
Claim 35
Dependent Claim
21 words
The method according to claim 19, 23 or 27 wherein said powdery glass comprises a borosilicate glass or an aluminosilicate glass.
Claim 36
Dependent Claim
18 words
The method according to claim 27, wherein said glass layer comprises a borosilicate glass or an aluminosilicate glass.
Claim 37
Dependent Claim
83 words
The method according to claim 31 or 32, wherein said borosilicate glass comprises from 75 to 85 % by weight of a mixture of SiO₂, B₂O₃ and Al₂O₃, based on the weight of the powdery glass and from 14 to 20 % by weight, based on the weight of the powdery glass, of at least one metal oxide, in which the metal of the metal oxide is a member selected from the group consisting of an alkali metal and an alkaline earth metal.
Claim 38
Dependent Claim
82 words
The method according to claim 31 or 32, wherein said aluminosilicate glass comprises from 60 to 75 % by weight of a mixture of SiO₂ and Al₂O₃, based on the weight of the powdery glass, and from 14 to 20 % by weight, based on the weight of the powdery glass, of at least one metal oxide in which the metal of the metal oxide is a member selected from the group consisting of an alkali metal and an alkaline earth metal.
Claim 39
Independent Claim
28 words
The method according to any one of claims 19 to 34, wherein said substrate is selected from the group consisting of a metallic substrate and a ceramic substrate.
Claim 40
Dependent Claim
13 words
The method according to claim 35, wherein said substrate is a metallic substrate.
Claim 41
Dependent Claim
16 words
The method according to claim 36, wherein said metallic substrate comprises Ti or a Ti alloy.
Claim 42
Dependent Claim
14 words
The method according to claim 37, wherein said Ti alloy comprises Ti and Al.
Claim 43
Independent Claim
37 words
The method according to any one of claims 36 to 38, wherein said powdery glass has a linear thermal expansion coefficient which corresponds to from about 80 to about 95 % of that of the metallic substrate.
Claim 44
Dependent Claim
32 words
The method according to claim 39, wherein said powdery glass has a linear thermal expansion coefficient which corresponds to from about 90 to about 95 % of that of the metallic substrate.
Claim 45
Dependent Claim
35 words
The method according to claim 19, wherein said blend of powdery glass with hydroxyapatite ceramic has a hydroxyapatite ceramic content of from 15 to 50 % by weight based on the weight of the layer.
Claim 46
Dependent Claim
37 words
The method according to claim 23 or 27, wherein said blend of powdery glass with hydroxyapatite ceramic has a hydroxyapatite ceramic content of from 15 to 70 % by weight based on the weight of the layer.
Claim 47
Dependent Claim
47 words
The method according to claim 20 or 21, wherein said blends of powdery glass with hydroxyapatite ceramic for forming the sub-layers constituting the glass-hydroxyapatite ceramic layer have an average hydroxyapatite ceramic content of from 15 to 50 % by weight based on the weight of the layer.
Claim 48
Independent Claim
50 words
The method according to any one of claims 24, 25, 28 and 29, wherein said blends of powdery glass with hydroxyapatite ceramic for formingsub-layers constituting the glass-hydroxyapatite ceramic layer have an average hydroxyapatite ceramic content of from 15 to 70 % by weight based on the weight of the layer.
References Cited (Backward Citations)
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