CA1160952A - Bone substitute and a method of production thereof - Google Patents
Bone substitute and a method of production thereofInfo
- Publication number
- CA1160952A CA1160952A CA000367006A CA367006A CA1160952A CA 1160952 A CA1160952 A CA 1160952A CA 000367006 A CA000367006 A CA 000367006A CA 367006 A CA367006 A CA 367006A CA 1160952 A CA1160952 A CA 1160952A
- Authority
- CA
- Canada
- Prior art keywords
- bone
- bone substitute
- collagen
- apatite
- granules
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/26—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
- A61L2300/406—Antibiotics
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
ABSTRACT OF THE DISCLOSURE
A bone substitute comprised of collagen material in the form of fleece or a spatial meshwork having apatite, the mineral component of bone material, admixed therewith. The structure of the collagen material may be strengthened by carbohydrate or starch or may be applied, in the form of a coating, to a honeycomb-like basic structure made from a variety of materials. Such a bone substitute has a good support quality, promotes bone growth and also has a good styptic or haemostatic effect.
A bone substitute comprised of collagen material in the form of fleece or a spatial meshwork having apatite, the mineral component of bone material, admixed therewith. The structure of the collagen material may be strengthened by carbohydrate or starch or may be applied, in the form of a coating, to a honeycomb-like basic structure made from a variety of materials. Such a bone substitute has a good support quality, promotes bone growth and also has a good styptic or haemostatic effect.
Description
~60ss2
- 2 -DESCRIPq`ION 0~ THE PRIOR ART
As a bone substitute, autologous bone material has, hitherto proved to be the most suitable. The bone material is removed from a different part of the body of the patient, such as the pelvis or shinbone and is transplanted into the region of the defect.
Autologous bone material has the major advantage that as individually identical albumen it may be rapidly implanted wlthout setting up any i~nunological reject-ion reaction. On the other hand, autologous bone material has the disadvantage that a Iurther wound is formed which additionally strains the patient biolog-- ically, for example, due to loss of blood, and may even cause a defect in the region from which the material i8 remo~ed. ~he wound thus caused may only heal slowly and may itselI cause a structural weakness in the skeletal portion from which the material has i~:
been removed.
For this reason, attempts have been made to employ homoioplastics, whereby bone material from different humans is used. q~e bone material may, in ~ fact, be obtained from corpses. The bone material may '5,`~ be preserved~ until it is required for use, in sterile saline solutions, such as Zialite or may be deep frozen. In homoioplastics, it is an identical, but individually differentt albumen which leads to ; oertain immunological rejection reactions~ Consequently, , ~ ; ' ~ ' ' ``` ~.~.60952 homoioplastics do not have such a good osteoplastic effect as autologous material. ~his material does stimulate bone regeneration but this is prevented by the necessary biological synthesis of the transplant.
Moreover, the obtaining and storage of such material in a sterile form poses difficulties for the clinics and hospitals concerned. Moreover, legal problems may well arise in connection with organ removal from corpses.
For a long time, it has also been a-ttempted to use bone material obtained from animals, this being a ready source. However, the unrelated type of albumen found in this heteroplaRtic leads to greater immun-ological rejection reactions with rejection or encapsulation o~ the transplant and only gi~es rise to sparse stimulation of bone regeneration.
It i9, however, al~o known to use heteroplastics, such as animal bone material in the form of bone splinters or dust or bone meal (Corticalis and Spongiosa), particularly that obtained from calves.
In this case, the albumenic substances of the bone marrow are washed out and the bone is degreased and `:
dealbumenised. However, the material still contains a certain amount of collagen and apatite. Thi~ mater-ial, known by the name "Kieler Knochenspan" has not, ;: :
however, successfully been used and, at present, autologous or homologous bone substitutes are usually used.
.
- .
, ' ' ' , , 60g5~ , SUMMARY OF THE INVENTION
The present invention seeks to provide a bone substitute which may be produced on an industrial scale at a uniform quality and having satisfactory sterility, whilst avoiding the disadvantages associated with autologous or homologous bone substitutes. How-ever, the invention also seeks to provide a bone substitute which s-timulates natural bone development better than heterologous bone substitutes.
According to the present invention, there is provided bone substitute comprising a mixture of spatial structured collagen and the mineral component of bone material, namely apatite.
Also according to the present invention there is provided a method of producing such a bone substitute wherein the collager. material is uniformly mixed with apatite powder or granules.
_ESCRIPTION OF THE PREFERRED EMBODIMENTS
For a long time, clinics have used styptic material in the form of collagen fleeces. Collagen is used herein to mean the supporting albumen of the connective tissues, skin, sinews and bones. ~hus, a chemical di~tinction is made between neutral salt and acid-soluble collagen and a more-or-less insoluble collagen fibre in which the collagen molecules are strongly bonded.
~' `
, , .
5 ~ 952 ~he chemical collagen unit has a high molecular weight of about ~00,000~ ~his macromolecular peptide is formed of three helical protein chains, each having a molecular weight of approximately 95,000. ~he collagen is predominantly obtained from animal skin and, in its correct compo~ition or formulation, causes immediate blood coagulation and hence is very useful for closing wounds. Accordingly, the use of this material is indicated in connection with injuries to organs such as, for example, the liver, and for covering burn wounds or wounds which granulate. In individual cases, the collagen material has been used as a bone substitute in jawbone surgery, but there are contrasting opinions regarding the success of such surgery. In those cases where the bone substitute is ; used in so-called "strong" mountings, such as within a bone cavity and in smaller gaps, both negative and also po~itive results have been given. In the case of so-called "weak" mountings, such as when the substitute material has to be implanted in a soft tissue gap after complete bone resection, no noticeable success -has been achieved using collagen fibres. In orthopaedic surgery, however~ it would therefore be desirab]e to have an effective bone-forming material for use in the so-called "weak" mounting.
~o obtain a bone substitute which is bone-forming in both of the above types of mounting and which is 9~Z
universally applicable, it is necessary to add sub-stances to the collagen fleece which cause or promote this effect. A substance which is particularly suitable for this purpose is the mineral component of paraplastic bone substances, namely apatite, which is predominantly hydrated tricalcium phosphate. ~rom many prior experiments, it is already known that apatite has a substa~ ial bone development effect. An essential feature of such material is that it occurs in particularly porous forms in order to promote the substitution of this material through vital bone tissue.
It is therefore stressed that the styptic effect of the collagen fleece is desirable. During bone operations, heavy bleeding occur~, in most cases, from the fine bone passages and from the blood vessels in distinction from the soft part tissue, cannot there be sealed off by electro-coagulation. Added to this is the fact that the styptic effect of the collagen fleece is improved by the apatite addition, since the apatite-calcium ions are liberated and calcium ions play a substantial part in the coagulation of the blood.
he collagen material is generally obtained from animal skin, such as pigskin, by treatment to the skin ; ~
~ 25 with proteolytic enzymes. Subsequently, the material , ~
;~ is cleansed, lyophiliæed and sterili~ed utilising gamma-~; radiation. ~or certain purposes, however, it may be ': :
!
~9~z ~
necessary to make the collagen material ~rom human tissue. ~his is particularly true for transplant purposes .
Preferably, the collagen material is first prod-uced in the form of a pressed fleece grid or network or in a plaited, knitted or~woven textile form or as spatial me~h or honeycomb grid, similar to the natural spongiosa structure. When producing a fleece network, the ~leece layer may pass through a screen press roller by means of which grid a pattern is impressed therein.
When producing the bone substitute, it is necessary to ensure that as thorough mixing as possible o~ the collagen material with the apatite powder or granules is achieved 80 as to produce a uniform product. Two differe~t methods of doing this may be used.
~irstly, the collagen fleece may be produced in two thin layers and is then dusted with apatite powder : ~ ~
or granules. The mixture is subjected to a pressing operation by passing it through a pair of rollers .
~ 20 which cause the apatite powder to be pressed into the ~f ~ ~ :
mesh of the M eece. ~his method may be carried out in either dry or wet conditions.
Alternatively, the collagen fibre material may ; be mixed with apatite powder or granule~ in a suitable mixture beiore being formed into layers and dried, In natural bone tissue, the ratio of collagen to apatite is approximately 1:1, but i~ a bone substitute , , : .
.
::; ' - 8 - ~ ~ 9~Z
according to the present invention, these proportions may be varied within a wide range depenaent upon its ultimate intended use. The material preferably has suitable antibiotics admixed therewith, which are part-icularly important in septic bone surgery. The end product may be produced in the form of granules, amorphous or shaped sections, chips, strips or tubes.
It is also possible to give the material the shape of natural human bones.
Collagen fleece material produced by conventional methods is generally very soft, which makes it possible for the material to be forced into bone cavities and apertures so that it readily abuts against the natural bone surface or is pressed thereagainst. ~his, however, is not desirable in the case where bridges to correct a defect have to be provided so as to have a certain pre-determined strength. It is therefore desirable to reinforce the structure of the collagen fleece. ~or this carbohydrate starch or fibrin may be used. To strengthen the structure still further, the collagen material-apatite mixture may also be applied in the form of a coating onto honeycomb-like basic structures, the structures themselves being formed from plastics materials, textiles, metal, aluminium oxide, ceramics, carbon-fibre fabrics, carbon or bone cement as desired.
; The structur0s may also be given the shape of the bnne section which they are to replace.
,
As a bone substitute, autologous bone material has, hitherto proved to be the most suitable. The bone material is removed from a different part of the body of the patient, such as the pelvis or shinbone and is transplanted into the region of the defect.
Autologous bone material has the major advantage that as individually identical albumen it may be rapidly implanted wlthout setting up any i~nunological reject-ion reaction. On the other hand, autologous bone material has the disadvantage that a Iurther wound is formed which additionally strains the patient biolog-- ically, for example, due to loss of blood, and may even cause a defect in the region from which the material i8 remo~ed. ~he wound thus caused may only heal slowly and may itselI cause a structural weakness in the skeletal portion from which the material has i~:
been removed.
For this reason, attempts have been made to employ homoioplastics, whereby bone material from different humans is used. q~e bone material may, in ~ fact, be obtained from corpses. The bone material may '5,`~ be preserved~ until it is required for use, in sterile saline solutions, such as Zialite or may be deep frozen. In homoioplastics, it is an identical, but individually differentt albumen which leads to ; oertain immunological rejection reactions~ Consequently, , ~ ; ' ~ ' ' ``` ~.~.60952 homoioplastics do not have such a good osteoplastic effect as autologous material. ~his material does stimulate bone regeneration but this is prevented by the necessary biological synthesis of the transplant.
Moreover, the obtaining and storage of such material in a sterile form poses difficulties for the clinics and hospitals concerned. Moreover, legal problems may well arise in connection with organ removal from corpses.
For a long time, it has also been a-ttempted to use bone material obtained from animals, this being a ready source. However, the unrelated type of albumen found in this heteroplaRtic leads to greater immun-ological rejection reactions with rejection or encapsulation o~ the transplant and only gi~es rise to sparse stimulation of bone regeneration.
It i9, however, al~o known to use heteroplastics, such as animal bone material in the form of bone splinters or dust or bone meal (Corticalis and Spongiosa), particularly that obtained from calves.
In this case, the albumenic substances of the bone marrow are washed out and the bone is degreased and `:
dealbumenised. However, the material still contains a certain amount of collagen and apatite. Thi~ mater-ial, known by the name "Kieler Knochenspan" has not, ;: :
however, successfully been used and, at present, autologous or homologous bone substitutes are usually used.
.
- .
, ' ' ' , , 60g5~ , SUMMARY OF THE INVENTION
The present invention seeks to provide a bone substitute which may be produced on an industrial scale at a uniform quality and having satisfactory sterility, whilst avoiding the disadvantages associated with autologous or homologous bone substitutes. How-ever, the invention also seeks to provide a bone substitute which s-timulates natural bone development better than heterologous bone substitutes.
According to the present invention, there is provided bone substitute comprising a mixture of spatial structured collagen and the mineral component of bone material, namely apatite.
Also according to the present invention there is provided a method of producing such a bone substitute wherein the collager. material is uniformly mixed with apatite powder or granules.
_ESCRIPTION OF THE PREFERRED EMBODIMENTS
For a long time, clinics have used styptic material in the form of collagen fleeces. Collagen is used herein to mean the supporting albumen of the connective tissues, skin, sinews and bones. ~hus, a chemical di~tinction is made between neutral salt and acid-soluble collagen and a more-or-less insoluble collagen fibre in which the collagen molecules are strongly bonded.
~' `
, , .
5 ~ 952 ~he chemical collagen unit has a high molecular weight of about ~00,000~ ~his macromolecular peptide is formed of three helical protein chains, each having a molecular weight of approximately 95,000. ~he collagen is predominantly obtained from animal skin and, in its correct compo~ition or formulation, causes immediate blood coagulation and hence is very useful for closing wounds. Accordingly, the use of this material is indicated in connection with injuries to organs such as, for example, the liver, and for covering burn wounds or wounds which granulate. In individual cases, the collagen material has been used as a bone substitute in jawbone surgery, but there are contrasting opinions regarding the success of such surgery. In those cases where the bone substitute is ; used in so-called "strong" mountings, such as within a bone cavity and in smaller gaps, both negative and also po~itive results have been given. In the case of so-called "weak" mountings, such as when the substitute material has to be implanted in a soft tissue gap after complete bone resection, no noticeable success -has been achieved using collagen fibres. In orthopaedic surgery, however~ it would therefore be desirab]e to have an effective bone-forming material for use in the so-called "weak" mounting.
~o obtain a bone substitute which is bone-forming in both of the above types of mounting and which is 9~Z
universally applicable, it is necessary to add sub-stances to the collagen fleece which cause or promote this effect. A substance which is particularly suitable for this purpose is the mineral component of paraplastic bone substances, namely apatite, which is predominantly hydrated tricalcium phosphate. ~rom many prior experiments, it is already known that apatite has a substa~ ial bone development effect. An essential feature of such material is that it occurs in particularly porous forms in order to promote the substitution of this material through vital bone tissue.
It is therefore stressed that the styptic effect of the collagen fleece is desirable. During bone operations, heavy bleeding occur~, in most cases, from the fine bone passages and from the blood vessels in distinction from the soft part tissue, cannot there be sealed off by electro-coagulation. Added to this is the fact that the styptic effect of the collagen fleece is improved by the apatite addition, since the apatite-calcium ions are liberated and calcium ions play a substantial part in the coagulation of the blood.
he collagen material is generally obtained from animal skin, such as pigskin, by treatment to the skin ; ~
~ 25 with proteolytic enzymes. Subsequently, the material , ~
;~ is cleansed, lyophiliæed and sterili~ed utilising gamma-~; radiation. ~or certain purposes, however, it may be ': :
!
~9~z ~
necessary to make the collagen material ~rom human tissue. ~his is particularly true for transplant purposes .
Preferably, the collagen material is first prod-uced in the form of a pressed fleece grid or network or in a plaited, knitted or~woven textile form or as spatial me~h or honeycomb grid, similar to the natural spongiosa structure. When producing a fleece network, the ~leece layer may pass through a screen press roller by means of which grid a pattern is impressed therein.
When producing the bone substitute, it is necessary to ensure that as thorough mixing as possible o~ the collagen material with the apatite powder or granules is achieved 80 as to produce a uniform product. Two differe~t methods of doing this may be used.
~irstly, the collagen fleece may be produced in two thin layers and is then dusted with apatite powder : ~ ~
or granules. The mixture is subjected to a pressing operation by passing it through a pair of rollers .
~ 20 which cause the apatite powder to be pressed into the ~f ~ ~ :
mesh of the M eece. ~his method may be carried out in either dry or wet conditions.
Alternatively, the collagen fibre material may ; be mixed with apatite powder or granule~ in a suitable mixture beiore being formed into layers and dried, In natural bone tissue, the ratio of collagen to apatite is approximately 1:1, but i~ a bone substitute , , : .
.
::; ' - 8 - ~ ~ 9~Z
according to the present invention, these proportions may be varied within a wide range depenaent upon its ultimate intended use. The material preferably has suitable antibiotics admixed therewith, which are part-icularly important in septic bone surgery. The end product may be produced in the form of granules, amorphous or shaped sections, chips, strips or tubes.
It is also possible to give the material the shape of natural human bones.
Collagen fleece material produced by conventional methods is generally very soft, which makes it possible for the material to be forced into bone cavities and apertures so that it readily abuts against the natural bone surface or is pressed thereagainst. ~his, however, is not desirable in the case where bridges to correct a defect have to be provided so as to have a certain pre-determined strength. It is therefore desirable to reinforce the structure of the collagen fleece. ~or this carbohydrate starch or fibrin may be used. To strengthen the structure still further, the collagen material-apatite mixture may also be applied in the form of a coating onto honeycomb-like basic structures, the structures themselves being formed from plastics materials, textiles, metal, aluminium oxide, ceramics, carbon-fibre fabrics, carbon or bone cement as desired.
; The structur0s may also be given the shape of the bnne section which they are to replace.
,
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A bone substitute, comprising a mixture of spatial structured collagen and the mineral component of bone material, namely apatite.
2. A bone substitute according to claim 1, additionally containing carbo-hydrate starch or fibrin as a strengthening agent for the structure.
3. A bone substitute according to claim 1, in the form of a coating applied to a honeycomb-like basic structure.
4. A bone substitute according to claim 3, wherein the honeycomb-like basic structure is made from a material selected from the group consisting of plastics materials, textiles, metals, ceramics, carbon fibre fabrics and carbon or bone cement.
5. A bone substitute according to claim 1 or 2 in the form of granules, amorphous or shaped sections, chips, strips or tubes.
6. A bone substitute according to claim 1 having the shape of natural bones.
7. A bone substitute according to claim 1 additionally containing antibiotics.
8. A method of producing a bone substitute comprising a mixture of spatial structured collagen and apatite, wherein the collagen material is uniformly mix-ed with apatite powder or granules.
9. A method according to claim 8 wherein the collagen material is in the form of thin layers which are dusted with apatite powder or granules and are subsequently subjected to a pressing operation.
10. A method according to claim 9, wherein the collagen material is in a form selected from the group consist-ing of fleeces, pressed meshes, plaited, knitted or woven textile form, and a honeycomb grid having a structure similar to spongiosa.
11. A method according to claim 8, wherein the collagen material is mixed with apatite powder or granules and subsequently moulded or shaped and dried.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP79810183A EP0030583B1 (en) | 1979-12-18 | 1979-12-18 | Bone replacement material and process for producing a bone replacement material |
| EP79810183.8 | 1979-12-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160952A true CA1160952A (en) | 1984-01-24 |
Family
ID=8186538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000367006A Expired CA1160952A (en) | 1979-12-18 | 1980-12-17 | Bone substitute and a method of production thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4516276A (en) |
| EP (1) | EP0030583B1 (en) |
| JP (1) | JPS56125042A (en) |
| CA (1) | CA1160952A (en) |
| DE (1) | DE2967060D1 (en) |
| ES (1) | ES8200223A1 (en) |
Families Citing this family (133)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2084468B (en) * | 1980-09-25 | 1984-06-06 | South African Inventions | Surgical implant |
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| US4472840A (en) * | 1981-09-21 | 1984-09-25 | Jefferies Steven R | Method of inducing osseous formation by implanting bone graft material |
| US4485096A (en) * | 1982-02-26 | 1984-11-27 | Massachusetts Institute Of Technology | Tissue-equivalent and method for preparation thereof |
| GB8328074D0 (en) * | 1983-10-20 | 1983-11-23 | Geistlich Soehne Ag | Chemical compositions |
| EP0166263A1 (en) * | 1984-05-31 | 1986-01-02 | Green Cross Corporation | Filler composition for filling in defect or hollow portion of bone and kit or set for the preparation of the filler composition |
| DE3479402D1 (en) * | 1984-06-12 | 1989-09-21 | Oscobal Ag | Method of producing a bone replacement material |
| JPS6168054A (en) * | 1984-09-10 | 1986-04-08 | 増原 英一 | Artificial bone and tooth |
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| US6559119B1 (en) | 1990-11-27 | 2003-05-06 | Loyola University Of Chicago | Method of preparing a tissue sealant-treated biomedical material |
| US7229959B1 (en) | 1990-11-27 | 2007-06-12 | The American National Red Cross | Supplemented fibrin matrix delivery systems |
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| US5397352A (en) * | 1993-08-27 | 1995-03-14 | Burres; Steven | Method of recollagenation |
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| DE2917446A1 (en) * | 1979-04-28 | 1980-11-06 | Merck Patent Gmbh | SURGICAL MATERIAL |
-
1979
- 1979-12-18 EP EP79810183A patent/EP0030583B1/en not_active Expired
- 1979-12-18 DE DE7979810183T patent/DE2967060D1/en not_active Expired
-
1980
- 1980-12-17 CA CA000367006A patent/CA1160952A/en not_active Expired
- 1980-12-17 ES ES497844A patent/ES8200223A1/en not_active Expired
- 1980-12-18 JP JP17963080A patent/JPS56125042A/en active Granted
-
1984
- 1984-03-26 US US06/593,174 patent/US4516276A/en not_active Expired - Lifetime
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|---|---|
| US4516276A (en) | 1985-05-14 |
| EP0030583B1 (en) | 1984-06-13 |
| JPS56125042A (en) | 1981-10-01 |
| JPS6341586B2 (en) | 1988-08-17 |
| DE2967060D1 (en) | 1984-07-19 |
| ES497844A0 (en) | 1981-11-01 |
| ES8200223A1 (en) | 1981-11-01 |
| EP0030583A1 (en) | 1981-06-24 |
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