US2664367A - Plasticized sponge material and method of making same - Google Patents

Plasticized sponge material and method of making same Download PDF

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US2664367A
US2664367A US116643A US11664349A US2664367A US 2664367 A US2664367 A US 2664367A US 116643 A US116643 A US 116643A US 11664349 A US11664349 A US 11664349A US 2664367 A US2664367 A US 2664367A
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sponge
polyvinyl alcohol
formaldehyde
solution
reaction
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US116643A
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Wilson Christopher Lumley
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Wilson Christopher Lumley
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36After-treatment
    • C08J9/40Impregnation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2329/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/14Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols

Description

Patented Dec. 29, 11953 P-LA STICIZED SPO METHOD OF NGE MATERIAL AND MAKING SAME Christopher Lumley Wilson, Columbus, Ohio No Drawing. A plication September 19,1949, Serial No. 116.643 '2. Claims. (Cl. 117-138.8)

"This invention relates to a sponge material comprising partially formalized polyvinyl alcohol, and relates particularly to such a sponge material having incorporated therein a plasticizer' to maintain the sponge in a soft and resilient condition.

Sponge and expanded materials comprising partially formalized polyvinyl alcohol and their preparation are described in my copending application Serial No. 29,657, filed Mayz l, 194$,and now Patent No. 2,609,347, which is a continuation-impart of my prior copend'ing application Serial No. 769,537, filed August 19, 1947, now abandoned. These sponge materials are prepared by reacting the formaldehyde with polyvinyl alcohol so that only a portion of the hydroxyl groups of the alcohol enters into the reaction. Preferably the solution of the materials is expanded as by beating air into the solution and the reaction is then permitted to proceedso that a solid is formed containing openings formerly occupied by the bubbles of air or other gas. is employed in order to speed up the reaction.

As further set forth in the above mentioned Patent 2,609,347, the sponge materials described therein are made by a process comprising providing an aqueous solution of formaldehyde, polyvinyl alcohol containing less than residual hydrolyzable material in the moleculean acid catalyst in which the acid functional group is inorganic and having a dissociation constant of at least 10- and a froth-stabilizing wetting agent soluble in and substantially stable to said solution; forming a substantially stable and homogeneous froth withsaid solution stabilized with the wetting agent; reacting the polyvinyl alcohol and the formaldehyde in the solution thereby causing gellation and solidification of the froth with the production of interconnected pores simultaneously with the progression of the" reaction, the froth being formed prior to appreciable reaction between the polyvinyl alcohol and the formaldehyde; and stopping the reaction when approximately 35-80% of the hydroxyl groups of the polyvinyl alcohol have beenreacted with the formaldehyde. I

Sponge materials prepared in the above mannor are soft and resilient when" they contain appreciable amounts of water. When the sponge materials become dry, however, they shrink to a certain extent and become hard and rigid. They are immediately softened as soon as water is re introduced into the sponge material. Although this re-wetting of the sponge material immediately changes it from a rigid solid to a resilient In the preferred procedure, an acid catalyst elastic material and the drying out of the material causes no deleterious eifects, the dry sponge material does not have as pleasing an appearance to the prospective purchaser.

I have discovered that the sponge material may be maintained soft and resilient if a plasticizer is incorporated therewith. These plasticizers are polyethylene glycols and polyalkanolamines and may be introduced by soaking the sponge material in either the heated plasticizer or in an aqueous solution of the plasticizer. After soak ing in the liquid, the excess liquid. is removed. These plasticizers, which are preferably liquid at ordinary room temperatures, maintain the sponge material in a soft, resilient condition.

One of the features of this invention is to provide a method of making a soft, resilient sponge material comprisingproviding a partially formalized polyvinyl alcohol sponge and soaking the sponge in a liquid including a member of the class consisting of polyethylene glycols and polyalkanolamines; another feature of this invention is the provision of a partially formalized polyvinyl alcohol sponge material containing as a plasticizer a member of the class consisting of polyethylene glycols and polyalkanolamines. Other features and advantages of the invention will become apparent from the following description and the accompanying claims.

The plasticizers of this inventionmay be intro du'c'e'd into the sponge material either in the form of a solution or as substantially anhydrous liquids. When a solution is used an aqueoussolution is preferred in which the sponge is soaked so as to absorb the maximum amount of solution and then. the excess solution is removed. When the plasticizers are added in substantially anhydrous form, the liquid plasticizer is heated and the sponge is immersed in the heated plasticizer for from a few seconds to several hours depending upon the temperature employed. The sponge is thenreinoved from the plasticizer and the excess plasticizer is removed.

Among the suitable plasticizers that have been discovered are diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol have ing a molecular weight of about 209, other polyethylene glycols having molecular weights of more than 200, triethanolamine and methyl diethanolamine. The plasticizers may be used alone or in combinations of two or more. When the substantially anhydrous plasticizer is employed, the liquid plasticizer is preferably heated at a temperature between about 37 to C. At the higher temperatures care must be used that the sponge is not immersed for too long a time, as ordinarily only a few seconds is required at the high temperatures. A temperature of about 50 C. is preferred.

Any amount of plasticizer desired may be used so long as a plasticizing effect is achieved. In general, the sponge should contain approximately 50% of the anhydrous plasticizer by weight of the dry sponge material. In actual practice, it has been found that excellent results have been achieved when at least 30% of the plasticizer is employed by weight of the dry sponge material. Ordinarily not more than about 100% is required, but in some instances it may be advisable to use more. Under conditions of high humidity, the minimum amount may be reduced below 30%. For example, 20% is satisfactory if the relative humidity of the atmosphere surrounding the sponge is at least 85-90%.

The following examples illustrate methods of practicing this invention:

Example 1 liquid. The sponge material retained about 6 grains of the solution and remained flexible in the atmosphere.

Example 2 A. partially formalized polyvinyl alcohol sponge made according to the above application was soaked overnight in triethylene glycol at 50 C. At the end of this time, the excess plasticizer was removed by squeezing the sponge. This sponge remained soft and flexible when exposed to air at room temperature.

Example 3 A portion of the sponge material Was soaked in a 30% by weight aqueous solution of triethanolamine. After the excess solution had been removed by squeezing, the sponge remained soft when exposed to air at room temperature. The sponge was found to contain 60% triethanolamine, calculated as anhydrous amine and based on the weight of the dry sponge.

Example 4 A portion of the sponge material was soaked in a 30% by weight aqueous solution of methyl diethanolamine. After the excess solution had been removed by squeezing, the sponge remained soft when exposed to air at room temperature. The sponge was found to contain 60% methyl diethanolarnine, calculated as anhydrous amine and based on the weight of the dry sponge.

Of the plasticizers described herein, the polyethylene glycols are preferred, and especially triethylene glycol. Diethylene glycol, triethylene glycol, tetraethylene glycol and other polyethylene glycols having a molecular weight of at least 200 may be employed. It is preferred, however, that the polyethylene glycol contain not more than 8 ethylene groups in the molecule.

Polyhydric alcohol plasticizers for partially formalized polyvinyl alcohol sponges are disclosed and claimed generally in my copending 4 application serial No. 116,642, filed September 19, 1949.

Having described my invention as related to various embodiments of the same, it is my intention that the invention be not limited by any of the details of description unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.

I claim:

1. The method of making a soft, resilient sponge material having interconnected pores by reacting polyvinyl alcohol and formaldehyde, which comprises: providing an aqueous solution of formaldehyde, polyvinyl alcohol containing less than 10% residual hydrolyzable material in the molecule, an acid catalyst in which the acid functional group is inorganic and having a dissociation constant of at least 10 and a frothstabilizing wetting agent soluble in and substantially stable to said solution; forming a substantially stable and homogeneous froth with said solution stabilized with the wetting agent; reacting the polyvinyl alcohol and formaldehyde in the solution thereby causing gellation and solidification of the froth with the production of interconnected pores simultaneously with the progression of the reaction, the froth being formed prior to appreciable reaction between the polyvinyl alcohol and the formaldehyde; stopping said reaction when approximately 35-80% of the hydroxyl groups of the polyvinyl alcohol have been reacted with the formaldehyde; whereby a sponge material is formed impregnating said sponge with a liquid including a mem ber of the class consisting of substantially anhydrous polyethylene glycols and polyalkanol' amines heated to a temperature of up to about 100 C. and aqueous solutions of said amines, and removing excess of said liquid until there remains deposited on said sponge about 20-100% of said liquid based on the dry weight of the p e.

2. A method according to claim 1 in which said liquid is triethylene glycol.

3. A method according to claim 1 in which said liquid is a polyethylene glycol having a molecular weight of approximately 200.

4. A method according to claim 1 in which said liquid is triethanolamine.

5. A method according to claim 1 in which said liquid is diethylene glycol.

6. A method according to claim 1 in which said liquid is methyl diethanolamine.

7. A sponge material prepared by the method of claim 1 and in which said liquid is a polyalkanolamine.

CHRISTOPHER LUMLEY WILSON.

References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. THE METHOD OF MAKING A SOFT, RESILIENT SPONGE MATERIAL HAVING INTERCONNECTED PORES BY REACTING POLYVINYL ALCOHOL AND FORMALDEHYDE, WHICH COMPRISES: PROVIDING AN AQUEOUS SOLUTION OF FORMALDEHYDE, POLYVINYL ALCOHOL CONTAINING LESS THAN 10% RESIDUAL HYDROLYZABLE MATERIAL IN THE MOLECULE, AN ACID CATALYST IN WHICH THE ACID FUNCTIONAL GROUP IS INORGANIC AND HAVING A DISSOCIATION CONSTANT OF AT LEAST 10-2 AND A FROTHSTABILIZING WETTING AGENT SOLUBLE IN AND SUBSTANTIALLY STABLE TO SAID SOLUTION; FORMING A SUBSTANTIALLY STABLE AND HOMOGENEOUS FROTH WITH SAID SOLUTION STABILIZED WITH THE WETTING AGENT; REACTING THE POLYVINYL ALCOHOL AND FORMALDEHYDE IN THE SOLUTION THEREBY CAUSING GELLATION AND SOLIDIFICATION OF THE FROTH WITH THE PRODUCTION OF INTERCONNECTED PORES SIMULTANEOUSLY WITH THE PROGRESSION OF THE REACTION, THE FROTH BEING FORMED PRIOR TO APPRECIABLE REACTION BETWEEN THE POLYVINYL ALCOHOL AND THE FORMALDEHYDE; STOPPING SAID REACTION WHEN APPROXIMATELY 35-80% OF THE HYDROXYL GROUPS OF THE POLYVINYL ALCOHOL HAVE BEEN REACTED WITH THE FORMALDEHYDE; WHEREBY A SPONGE MATERIAL IS FORMED IMPREGNATING SAID SPONGE WITH A LIQUID INCLUDING A MEMBER OF THE CLASS CONSISTING OF SUBSTANTIALLY ANHYDROUS POLYETHYLENE GLYCOLS AND POLYALKANOLAMINES HEATED TO A TEMPERATURE OF UP TO ABOUT 100* C. AND AQUEOUS SOLUTIONS OF SAID AMINES, AND REMOVING EXCESS OF SAID LIQUID UNTIL THERE REMAINS DEPOSITED ON SAID SPONGE ABOUT 20-100% OF SAID LIQUID BASED ON THE DRY WEIGHT OF THE SPONGE.
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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711969A (en) * 1954-02-25 1955-06-28 Us Rubber Co Method of treating sheet sponge rubber
US2993801A (en) * 1958-08-01 1961-07-25 Walter E Hoehne Method for conditioning extensible balloons
US3190843A (en) * 1960-03-17 1965-06-22 Kalle Ag Process of making a modified polyvinyl alcohol foam
US3491115A (en) * 1966-10-28 1970-01-20 Standard Oil Co Composition for degelling resins
US3661633A (en) * 1963-12-11 1972-05-09 Rolf Erhard Moren Process and composition for impregnating wood and wood products
US4098728A (en) * 1976-01-02 1978-07-04 Solomon Rosenblatt Medical surgical sponge and method of making same
US5284468A (en) * 1991-08-19 1994-02-08 M-Pact Worldwide Management Corporation Orthopedic splinting article
US5554658A (en) * 1991-08-06 1996-09-10 Rosenblatt; Solomon Injection molded PVA Sponge
US5567612A (en) * 1986-11-20 1996-10-22 Massachusetts Institute Of Technology Genitourinary cell-matrix structure for implantation into a human and a method of making
US5709854A (en) * 1993-04-30 1998-01-20 Massachusetts Institute Of Technology Tissue formation by injecting a cell-polymeric solution that gels in vivo
US5741685A (en) * 1995-06-07 1998-04-21 Children's Medical Center Corporation Parenchymal cells packaged in immunoprotective tissue for implantation
US5770417A (en) * 1986-11-20 1998-06-23 Massachusetts Institute Of Technology Children's Medical Center Corporation Three-dimensional fibrous scaffold containing attached cells for producing vascularized tissue in vivo
US5804178A (en) * 1986-11-20 1998-09-08 Massachusetts Institute Of Technology Implantation of cell-matrix structure adjacent mesentery, omentum or peritoneum tissue
US5843060A (en) * 1997-01-02 1998-12-01 Xomed Surgical Products, Inc. Non-adherent nasal, sinus and otic packing and method for processing sponge materials in fabrication of packings
US5851833A (en) * 1991-10-24 1998-12-22 Children's Medical Center Corp. Neomorphogenesis of urological structures in vivo from cell culture
US6129761A (en) * 1995-06-07 2000-10-10 Reprogenesis, Inc. Injectable hydrogel compositions
US6224630B1 (en) 1998-05-29 2001-05-01 Advanced Bio Surfaces, Inc. Implantable tissue repair device
US6281015B1 (en) 1994-12-16 2001-08-28 Children's Medical Center Corp. Localized delivery of factors enhancing survival of transplanted cells
US6309635B1 (en) 1986-11-20 2001-10-30 Children's Medical Center Corp. Seeding parenchymal cells into compression resistant porous scaffold after vascularizing in vivo
WO2004087862A2 (en) 2003-04-01 2004-10-14 Yissum Research Development Company Of The Hebrew University Of Jerusalem Tak1-mediated inhibition of osteogenesis
US7044957B2 (en) 1994-09-16 2006-05-16 Ethicon Endo-Surgery, Inc. Devices for defining and marking tissue
US7189235B2 (en) 1999-10-20 2007-03-13 Anulex Technologies, Inc. Spinal disc annulus reconstruction method and spinal disc annulus stent
EP2075015A1 (en) 1997-07-03 2009-07-01 Massachusetts Institute of Technology Tissue-engineered constructs
US7615076B2 (en) 1999-10-20 2009-11-10 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US7668582B2 (en) 1998-12-24 2010-02-23 Ethicon Endo-Surgery, Inc. Biopsy site marker
US7828850B2 (en) 1999-10-20 2010-11-09 Anulex Technologies, Inc. Methods and devices for spinal disc annulus reconstruction and repair
US7922768B2 (en) 1999-10-20 2011-04-12 Anulex Technologies, Inc. Spinal disc annulus reconstruction method and deformable spinal disc annulus stent
US7935147B2 (en) 1999-10-20 2011-05-03 Anulex Technologies, Inc. Method and apparatus for enhanced delivery of treatment device to the intervertebral disc annulus
US7951201B2 (en) 1999-10-20 2011-05-31 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US8128698B2 (en) 1999-10-20 2012-03-06 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US8454697B2 (en) 2008-10-14 2013-06-04 Anulex Technologies, Inc. Method and apparatus for the treatment of tissue
US8556977B2 (en) 1999-10-20 2013-10-15 Anulex Technologies, Inc. Tissue anchoring system and method
US9492570B2 (en) 1998-12-24 2016-11-15 Devicor Medical Products, Inc. Device and method for safe location and marking of a biopsy cavity
WO2017076782A1 (en) 2015-11-02 2017-05-11 Novahep Ab Compositions and methods for healing wounds
US9669113B1 (en) 1998-12-24 2017-06-06 Devicor Medical Products, Inc. Device and method for safe location and marking of a biopsy cavity
WO2018127554A1 (en) 2017-01-06 2018-07-12 Novahep Ab Methods of preparing bioengineered or bioprinted organ or tissue, and uses thereof
WO2018162328A1 (en) 2017-03-08 2018-09-13 Carl Freudenberg Kg Cleaning article

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1779011A (en) * 1928-06-07 1930-10-21 Railway Service & Supply Corp Method of conditioning waste
US2037049A (en) * 1933-10-04 1936-04-14 Theron P Sager Gas retaining fabrics and method of preparing the same
US2056796A (en) * 1934-04-26 1936-10-06 Du Pont Polyvinyl resin compositions and process of preparing same
US2370126A (en) * 1942-03-06 1945-02-27 Prophylactic Brush Co Process of making polyvinyl acetals
GB573966A (en) * 1943-07-27 1945-12-14 Revertex Ltd Cellular structures and methods of producing same
US2478879A (en) * 1946-02-23 1949-08-09 Wingfoot Corp Porous compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1779011A (en) * 1928-06-07 1930-10-21 Railway Service & Supply Corp Method of conditioning waste
US2037049A (en) * 1933-10-04 1936-04-14 Theron P Sager Gas retaining fabrics and method of preparing the same
US2056796A (en) * 1934-04-26 1936-10-06 Du Pont Polyvinyl resin compositions and process of preparing same
US2370126A (en) * 1942-03-06 1945-02-27 Prophylactic Brush Co Process of making polyvinyl acetals
GB573966A (en) * 1943-07-27 1945-12-14 Revertex Ltd Cellular structures and methods of producing same
US2478879A (en) * 1946-02-23 1949-08-09 Wingfoot Corp Porous compositions

Cited By (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711969A (en) * 1954-02-25 1955-06-28 Us Rubber Co Method of treating sheet sponge rubber
US2993801A (en) * 1958-08-01 1961-07-25 Walter E Hoehne Method for conditioning extensible balloons
US3190843A (en) * 1960-03-17 1965-06-22 Kalle Ag Process of making a modified polyvinyl alcohol foam
US3661633A (en) * 1963-12-11 1972-05-09 Rolf Erhard Moren Process and composition for impregnating wood and wood products
US3491115A (en) * 1966-10-28 1970-01-20 Standard Oil Co Composition for degelling resins
US4098728A (en) * 1976-01-02 1978-07-04 Solomon Rosenblatt Medical surgical sponge and method of making same
US5770417A (en) * 1986-11-20 1998-06-23 Massachusetts Institute Of Technology Children's Medical Center Corporation Three-dimensional fibrous scaffold containing attached cells for producing vascularized tissue in vivo
US6309635B1 (en) 1986-11-20 2001-10-30 Children's Medical Center Corp. Seeding parenchymal cells into compression resistant porous scaffold after vascularizing in vivo
US5567612A (en) * 1986-11-20 1996-10-22 Massachusetts Institute Of Technology Genitourinary cell-matrix structure for implantation into a human and a method of making
US5804178A (en) * 1986-11-20 1998-09-08 Massachusetts Institute Of Technology Implantation of cell-matrix structure adjacent mesentery, omentum or peritoneum tissue
US5554658A (en) * 1991-08-06 1996-09-10 Rosenblatt; Solomon Injection molded PVA Sponge
US5554659A (en) * 1991-08-06 1996-09-10 Rosenblatt; Solomon Injection molded PVA sponge
US5284468A (en) * 1991-08-19 1994-02-08 M-Pact Worldwide Management Corporation Orthopedic splinting article
US5851833A (en) * 1991-10-24 1998-12-22 Children's Medical Center Corp. Neomorphogenesis of urological structures in vivo from cell culture
US5709854A (en) * 1993-04-30 1998-01-20 Massachusetts Institute Of Technology Tissue formation by injecting a cell-polymeric solution that gels in vivo
US7807150B2 (en) 1993-04-30 2010-10-05 Massachusetts Institute Of Technology Injectable composition containing crosslinkable material and cells for forming animal tissue
US20040170612A1 (en) * 1993-04-30 2004-09-02 Griffith Linda G. Injectable polysaccharide-cell compositions
US7625397B2 (en) 1994-09-16 2009-12-01 Ethicon Endo-Surgery, Inc. Methods for defining and marking tissue
US7229417B2 (en) 1994-09-16 2007-06-12 Ethicon Endo-Surgery, Inc. Methods for marking a biopsy site
US8277391B2 (en) 1994-09-16 2012-10-02 Devicor Medical Products, Inc. Methods and devices for defining and marking tissue
US7044957B2 (en) 1994-09-16 2006-05-16 Ethicon Endo-Surgery, Inc. Devices for defining and marking tissue
US6281015B1 (en) 1994-12-16 2001-08-28 Children's Medical Center Corp. Localized delivery of factors enhancing survival of transplanted cells
US5741685A (en) * 1995-06-07 1998-04-21 Children's Medical Center Corporation Parenchymal cells packaged in immunoprotective tissue for implantation
US6129761A (en) * 1995-06-07 2000-10-10 Reprogenesis, Inc. Injectable hydrogel compositions
US5843060A (en) * 1997-01-02 1998-12-01 Xomed Surgical Products, Inc. Non-adherent nasal, sinus and otic packing and method for processing sponge materials in fabrication of packings
US6214895B1 (en) 1997-01-02 2001-04-10 Xomed Surgical Products, Inc. Method for making a polyvinyl acetal sponge packing for use in the nasal, sinus and otic cavities
US6169123B1 (en) 1997-01-02 2001-01-02 Xomed Surgical Products, Inc. Non-adherent nasal, sinus and otic packing and method for processing sponge materials in fabrication of packings
EP2075015A1 (en) 1997-07-03 2009-07-01 Massachusetts Institute of Technology Tissue-engineered constructs
US6224630B1 (en) 1998-05-29 2001-05-01 Advanced Bio Surfaces, Inc. Implantable tissue repair device
US9380998B2 (en) 1998-12-24 2016-07-05 Devicor Medical Products, Inc. Subcutaneous cavity marking device and method
US8600481B2 (en) 1998-12-24 2013-12-03 Devicor Medical Products, Inc. Subcutaneous cavity marking device
US7668582B2 (en) 1998-12-24 2010-02-23 Ethicon Endo-Surgery, Inc. Biopsy site marker
US8320994B2 (en) 1998-12-24 2012-11-27 Devicor Medical Products, Inc. Biopsy cavity marking device and method
US9986974B2 (en) 1998-12-24 2018-06-05 Devicor Medical Products, Inc. Biopsy cavity marking device
US9669113B1 (en) 1998-12-24 2017-06-06 Devicor Medical Products, Inc. Device and method for safe location and marking of a biopsy cavity
US8320993B2 (en) 1998-12-24 2012-11-27 Devicor Medical Products, Inc. Subcutaneous cavity marking device
US9492570B2 (en) 1998-12-24 2016-11-15 Devicor Medical Products, Inc. Device and method for safe location and marking of a biopsy cavity
US8306602B2 (en) 1998-12-24 2012-11-06 Devicor Medical Products, Inc. Biopsy cavity marking device
US7615076B2 (en) 1999-10-20 2009-11-10 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US7935147B2 (en) 1999-10-20 2011-05-03 Anulex Technologies, Inc. Method and apparatus for enhanced delivery of treatment device to the intervertebral disc annulus
US7951201B2 (en) 1999-10-20 2011-05-31 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US7963992B2 (en) 1999-10-20 2011-06-21 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US7985257B2 (en) 1999-10-20 2011-07-26 Anulex Technologies, Inc. Methods and devices for spinal disc annulus reconstruction and repair
US7993405B2 (en) 1999-10-20 2011-08-09 Anulex Technologies, Inc. Spinal disc annulus repair system and methods
US8034112B2 (en) 1999-10-20 2011-10-11 Anulex Technologies, Inc. Spinal disc annulus reconstruction method and spinal disc annulus stent
US8048160B2 (en) 1999-10-20 2011-11-01 Anulex Technologies, Inc. Intervertebral disc annulus stent
US8088165B2 (en) 1999-10-20 2012-01-03 Anulex Technologies, Inc. Spinal disc annulus reconstruction method and deformable spinal disc annulus stent
US8128698B2 (en) 1999-10-20 2012-03-06 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US7922768B2 (en) 1999-10-20 2011-04-12 Anulex Technologies, Inc. Spinal disc annulus reconstruction method and deformable spinal disc annulus stent
US7909879B2 (en) 1999-10-20 2011-03-22 Anulex Technologies, Inc. Intervertebral disc annulus stent
US7828850B2 (en) 1999-10-20 2010-11-09 Anulex Technologies, Inc. Methods and devices for spinal disc annulus reconstruction and repair
US7670379B2 (en) 1999-10-20 2010-03-02 Anulex Technologies, Inc. Spinal disc annulus reconstruction method
US9675347B2 (en) 1999-10-20 2017-06-13 Krt Investors, Inc. Apparatus for the treatment of tissue
US8556977B2 (en) 1999-10-20 2013-10-15 Anulex Technologies, Inc. Tissue anchoring system and method
US7189235B2 (en) 1999-10-20 2007-03-13 Anulex Technologies, Inc. Spinal disc annulus reconstruction method and spinal disc annulus stent
US8632590B2 (en) 1999-10-20 2014-01-21 Anulex Technologies, Inc. Apparatus and methods for the treatment of the intervertebral disc
US9095442B2 (en) 1999-10-20 2015-08-04 Krt Investors, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US9114025B2 (en) 1999-10-20 2015-08-25 Krt Investors, Inc. Methods and devices for spinal disc annulus reconstruction and repair
US7749273B2 (en) 1999-10-20 2010-07-06 Anulex Technologies, Inc. Method and apparatus for the treatment of the intervertebral disc annulus
US20100209400A1 (en) * 2003-04-01 2010-08-19 Dan Gazit TAK1-Mediated Regulation of Osteogenesis
US20070197457A1 (en) * 2003-04-01 2007-08-23 Dan Gazit Tak1-mediated inhibition of osteogenesis
WO2004087862A2 (en) 2003-04-01 2004-10-14 Yissum Research Development Company Of The Hebrew University Of Jerusalem Tak1-mediated inhibition of osteogenesis
US8454697B2 (en) 2008-10-14 2013-06-04 Anulex Technologies, Inc. Method and apparatus for the treatment of tissue
US9192372B2 (en) 2008-10-14 2015-11-24 Krt Investors, Inc. Method for the treatment of tissue
WO2017076782A1 (en) 2015-11-02 2017-05-11 Novahep Ab Compositions and methods for healing wounds
WO2018127554A1 (en) 2017-01-06 2018-07-12 Novahep Ab Methods of preparing bioengineered or bioprinted organ or tissue, and uses thereof
WO2018162328A1 (en) 2017-03-08 2018-09-13 Carl Freudenberg Kg Cleaning article

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