# US 5,344,456 A · Materials for living hard tissue replacements

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- Number: US 5,344,456 A
- Document ID: US5344456A
- Status: Granted
- Kind: A
- Application number: 07/872,950
- Filed: 1992-04-21
- Granted: 1994-09-06
- Earliest claimed: 1989-06-06
- Assignees: TDK Corporation
- Inventors: Tohru Nonami; Hiroyasu Noma; Shinya Nakajima
- Web page: https://patentgrep.com/patent/US5344456A

## CPC

- A61L 27/10: Ceramics or glasses
- C04B 35/22: rich in calcium oxide {, e.g. wollastonite (C04B35/195 takes precedence)}
- Y10S 623/901: Method of manufacturing prosthetic device
- A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

The materials for living hard tissue replacements of the present invention comprise a ceramic material which contain Cao and SiO.sub.2 as essential components, and MgO as an optional components, are substantially free from calcium phosphate and are capable of forming a compound based on calcium phosphate by contact with an aqueous solution containing phosphorus, and show high biological affinity.

## Claims

### Claim 1

A material for living hard tissue replacement, prepared by a process comprising the steps of:
coating a substrate with a layer of a ceramic material comprising CaO and SiO.sub.2 in a weight ratio of CaO to SiO.sub.2 of between 1:4 and 6:1, said ceramic material being substantially free from calcium phosphate and being selected from the group consisting of diopside, wollastonite, alite, belite, akermanite, monticellite, forsterite, protoenstatite and tridymite; and
contacting said coated substrate with an aqueous solution containing phosphorus to form a calcium phosphate-based compound.

### Claim 2

A material for living hard tissue replacement, comprising:
a metal or plastic substrate; and
a coat layer of a ceramic material comprising CaO and SiO.sub.2 in a weight ratio of CaO to SiO.sub.2 of between 1:4 and 6:1, said ceramic material being substantially free from calcium phosphate and being selected from the group consisting of diopside, wollastonite, alite, belite, akermanite, monticellite, forsterite, protoenstatite and tridymite, said ceramic material being capable of forming a calcium phosphate-based compound upon contact with an aqueous solution containing phosphorus.

### Claim 3 (depends on 1, 2)

The material for living hard tissue replacement of claim 1 or 2, wherein said ceramic material contains from 50 to 100% by volume of diopside.

### Claim 4 (depends on 1, 2)

The material as claimed in claim 1 or 2, wherein said ceramic material contains MgO in addition to the essential components of CaO and SiO.sub.2.

### Claim 5 (depends on 4)

The material as claimed in claim 4, wherein said ceramic material contains 10 to 88% by weight of CaO, 10 to 80% by weight of SiO.sub.2 and 2 to 35% by weight of MgO.

### Claim 6 (depends on 5)

The material as claimed in claim 5, wherein said ceramic material contains 18 to 47% by weight of CaO, 37 to 68% by weight of SiO.sub.2 and 10 to 25% by weight of MgO.

### Claim 7 (depends on 2)

The material as claimed in claim 2, wherein said ceramic material belongs to the field of diopside, wollastonite, alite, belite, akermanite or monticellite.

### Claim 8 (depends on 7)

The material as claimed in claim 7, wherein said ceramic material contains at least 40% by volume of a diopside composition, a wollastonite composition or a mixture of diopside and wollastonite compositions.

### Claim 9 (depends on 8)

The material as claimed in claim 8, wherein said ceramic material contains at least 40% by volume of a diopside composition.

### Claim 10 (depends on 8)

The material as claimed in claim 8, wherein said ceramic material contains at least 50% by volume of a diopside composition, a wollastonite composition or a mixture of diopside and wollastonite compositions.

### Claim 11 (depends on 10)

The material as claimed in claim 10, wherein said ceramic material contains 70% to 100% by volume of a diopside composition, a wollastonite composition or a mixture of diopside and wollastonite compositions.

### Claim 12 (depends on 1, 2)

The material as claimed in claim 1 or 2, wherein said coat layer has a thickness of 1 to 5000 .mu.m.

### Claim 13 (depends on 12)

The material as claimed in claim 12, wherein said coat layer has a thickness of 10 to 2000 .mu.m.

### Claim 14 (depends on 13)

The material as claimed in claim 13, wherein said coat layer has a thickness of 20 to 1000 .mu.m.

### Claim 15 (depends on 1, 2)

The material as claimed in claim 1 or 2, wherein said coat layer has a surface roughness of 1 to 200 .mu.m.

### Claim 16 (depends on 15)

The material as claimed in claim 15, wherein said coat layer has a surface roughness of 5 to 100 .mu.m.

### Claim 17 (depends on 1, 2)

The material as claimed in claim 1 or 2, wherein said coat layer is porous.

### Claim 18 (depends on 17)

The material as claimed in claim 17, wherein said porous coat layer has a pore diameter of 5 to 2000 .mu.m.

### Claim 19 (depends on 18)

The material as claimed in claim 18, wherein said porous coat layer has a pore diameter of 10 to 1000 .mu.m.

### Claim 20 (depends on 17)

The material as claimed in claim 17, wherein said porous coat layer has a porosity of 10 to 80%.

### Claim 21 (depends on 20)

The material as claimed in claim 20, wherein said porous coat layer has a porosity of 20 to 70%.

### Claim 22 (depends on 21)

The material as claimed in claim 21, where n said porous coat layer has a porosity of 25 to 60%.

### Claim 23 (depends on 1)

The material as claimed in claim 1, wherein said substrate comprises metal, ceramic, glass or plastic.

### Claim 24 (depends on 2, 23)

The material as claimed in claim 23 or 2, wherein said substrate comprises a metal selected from the group consisting of Ti, W, Ni--Cr alloy, Fe--Cr--Al alloy, Ti--Zr alloy, Fe--Ni--Cr alloy, Mo, Ti--Al--V alloy, Co--Cr--Mo alloy, Ti--Mo alloy, Co--Cr--Ni alloy, stainless steel 304, stainless steel 310 and stainless steel 316.

### Claim 25 (depends on 2, 23)

The material as claimed in claim 23 or 2, wherein said substrate comprises Ti or an alloy thereof.

### Claim 26 (depends on 23)

The material as claimed in claim 23, wherein said substrate comprises a ceramic selected from the group consisting of alumina, zirconia, silicon carbide, tungsten nitride and silicon nitride.

### Claim 27

A material for living hard tissue replacement comprising a ceramic material which (i) contains CaO and SiO.sub.2 as essential components, (ii) is substantially free from calcium phosphate and (iii) is capable of forming a compound based in calcium phosphate by contact with an aqueous solution containing phosphorous, said CaO and SiO.sub.2 being present in a weight ratio of CaO to SiO.sub.2 of between 1:4 and 6:1; said ceramic material being in the form of a porous body having a pore diameter of 5 to 2000 .mu.m and a porosity of 10 to 80%.

### Claim 28 (depends on 27)

The material as claimed in claim 27, wherein said ceramic material contains MgO in addition to the essential components of CaO and SiO.sub.2.

### Claim 29 (depends on 28)

The material as claimed in claim 28, wherein said ceramic material contains 10 to 88% by weight of CaO, 10 to 80% by weight of SiO.sub.2 and 2 to 35% by weight of MgO.

### Claim 30 (depends on 29)

The material as claimed in claim 29, wherein said ceramic material contains 18 to 47% by weight of CaO, 37 to 68% by weight of SiO.sub.2 and 10 to 25% by weight of MgO.

### Claim 31 (depends on 30)

The material as claimed in claim 30, wherein said ceramic material belongs to the field of diopside, wollastonite, alite, belite, akermanite or monticellite.

### Claim 32 (depends on 31)

The material as claimed in claim 31, wherein said ceramic material contains at least 40% by volume of a diopside composition, a wollastonite composition or a mixture of diopside and wollastonite compositions.

### Claim 33 (depends on 32)

The material as claimed in claim 32, wherein said ceramic material contains at least 40% by volume of a diopside composition.

### Claim 34 (depends on 32)

The material as claimed in claim 32, wherein said ceramic material contains at least 50% by volume of a diopside composition, a wollastonite composition or a mixture of diopside and wollastonite composition.

### Claim 35 (depends on 34)

The material as claimed in claim 34, wherein said ceramic material contains 70% to 100% by volume of a diopside composition, a wollastonite composition, a wollastonite composition or a mixture of diopside and wollastonite composition.

### Claim 36 (depends on 27)

The material as claimed in claim 27, wherein said porous body has a pore diameter of 10 to 1000 .mu.m.

### Claim 37 (depends on 27)

The material as claimed in claim 27, wherein said porous body has a porosity of 20 to 70%.

### Claim 38 (depends on 27)

The material as claimed in claim 27, wherein said porous body has a porosity of 25 to 60%.

### Claim 39 (depends on 27)

The material as claimed in claim 27, wherein said porous body is in the form of granules having diameters in the range of 0.05 to 5 mm.

### Claim 40 (depends on 39)

The material as claimed in claim 39, wherein said diameters are in the range of 0.1 to 3 mm.

### Claim 41 (depends on 40)

The material as claimed in claim 40, wherein said diameters are in the range of 0.1 to 2 mm.
