WO2000047242A1 - Materiau de suture de plaies a base de methylidene malonate - Google Patents

Materiau de suture de plaies a base de methylidene malonate Download PDF

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Publication number
WO2000047242A1
WO2000047242A1 PCT/FR2000/000305 FR0000305W WO0047242A1 WO 2000047242 A1 WO2000047242 A1 WO 2000047242A1 FR 0000305 W FR0000305 W FR 0000305W WO 0047242 A1 WO0047242 A1 WO 0047242A1
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WO
WIPO (PCT)
Prior art keywords
weight
methylidene malonate
molecular weight
formula
equal
Prior art date
Application number
PCT/FR2000/000305
Other languages
English (en)
French (fr)
Inventor
Nicole Bru-Magniez
Pascal Breton
Claude Roques-Carmes
Isabelle Beliard
Original Assignee
Virsol
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Virsol filed Critical Virsol
Priority to US09/509,830 priority Critical patent/US6610078B1/en
Priority to AU25543/00A priority patent/AU767823B2/en
Priority to AT00903761T priority patent/ATE223739T1/de
Priority to DE60000437T priority patent/DE60000437D1/de
Priority to CA002361628A priority patent/CA2361628A1/en
Priority to KR1020017010027A priority patent/KR20010104341A/ko
Priority to PL00350244A priority patent/PL350244A1/xx
Priority to DK00903761T priority patent/DK1150723T3/da
Priority to BR0008091-8A priority patent/BR0008091A/pt
Priority to JP2000598193A priority patent/JP4863550B2/ja
Priority to EP00903761A priority patent/EP1150723B1/fr
Priority to SK1077-2001A priority patent/SK10772001A3/sk
Publication of WO2000047242A1 publication Critical patent/WO2000047242A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Definitions

  • the present invention relates to a new wound suture material based on methylidene malonate.
  • suture material is intended to denote a biocompatible material which makes it possible, by adhesion, to join the lips of wounds, to stop bleeding (hemostasis) and to promote the scarring of injured tissue.
  • the invention essentially finds application in the field of treatment of epidermal, dermo-epidermal or hypo-dermo-epidermal wounds, in particular frank dermo-epidermal wounds.
  • Wire suturing is generally used to bring together the superficial dermal and epidermal planes, in the case of non-absorbable threads, or to bring together the deep muscular and hypodermic planes in the case of absorbable threads. This treatment method is currently the most commonly used.
  • this mode of treatment is more or less traumatic psychologically for the patient, especially when it comes to children, for whom a quick and painless gesture is necessary.
  • the stapling poses, in practice, substantially the same problems as thread suturing.
  • the application of adhesive strips such as for example the product known under the trade name Stéri-Strip ® , makes it possible to treat minor wounds in a practically painless manner.
  • glues These adhesive materials generally designated by the term “glues” can be divided into two categories:
  • - synthetic glues mainly based on cyanoacrylate, and in particular, 2-octylcyanoacrylate, 2-ethylcyanoacrylate, 2-butylcyanoacrylate and 2-isobutylcyanoacrylate.
  • Biological glues are products chosen to reproduce the last phase of coagulation and to anchor the clot to the tissue via the supply of fibronectin ("junction protein") to the healing sites.
  • these adhesives are generally potentially allergenic and are very difficult to degrade in the body, generally forming products considered to be toxic for the latter, which considerably limits their interest.
  • the present invention aims to solve the technical problem consisting in the supply of a new wound suture material, of essentially synthetic nature, which has the same advantages as the abovementioned synthetic glues, which is of a easy implementation, which can be degraded relatively easily in the body without generating toxic products and which can be applied inside the wound in all the damaged skin layers.
  • the present invention also aims to solve the aforementioned technical problem in a manner applicable on an industrial scale.
  • compositions based on monomers and / or oligomers and / or polymers based on methylidene malonate have all the required properties, in particular in terms of bio-adhesion and viscosity before and / or after application, to make new wound suturing materials that meet this objective.
  • the subject of the present invention is a wound suturing material consisting of a biocompatible, bio-adhesive mixture comprising at least 50% by weight, and preferably at least 80% by weight, of a composition based on methylidene malonate containing:
  • Ri and R 2 independently represent a linear or branched alkyl group having from 1 to 6 carbon atoms, and n is an integer included between 1 and 5; and / or one or more methylidene malonate oligomer (s) having a molecular weight less than or equal to 6,000 and consisting of recurring units of formula (II):
  • A represents a group (a) in which R 1 represents an alkyl group having from 1 to 6 carbon atoms, preferably an ethyl group,
  • R represents an alkyl group having from 1 to 6 carbon atoms, preferably an ethyl group, and n is a number equal to 1.
  • the above-mentioned methylidene malonate composition contains:
  • methylidene malonate oligomer (s) having a molecular weight less than or equal to 6,000 preferably less than or equal to 3,000 and consisting of recurring units of formula (II) ,
  • the above-mentioned methylidene malonate composition contains: - from 55 to 65% by weight of one or more methylidene malonate oligomer (s) having a molecular weight less than or equal to 3,000, and preferably between 300 and 1,000 and consisting of recurring units of formula (II),
  • the wound suture material according to the present invention is essentially characterized in that it consists mainly of a composition based on methylidene malonate itself itself mainly consisting of monomer (s) and / or oligomer (s) of molecular weight less than or equal to 6000, preferably less than or equal to 3000.
  • Such a composition has viscosity and bioadhesion (or bonding) properties allowing its use in the treatment of dermo-epidermal wounds, alone or in admixture with other biocompatible components.
  • compositions based on methylidene malonate which can be used in the context of the invention are degradable by bioerosion, by releasing ethanol and glycolic acid which are generally considered to be non-toxic for the organism, glycolic acid even seems to act as a stimulator of cell growth.
  • These compositions based on methylidene malonate can be easily prepared by the skilled person, optionally by simple mixing in an appropriate solvent of its constituents (monomeric, oligomeric, polymeric) prepared separately, and subsequent evaporation of the solvent.
  • the methylidene malonate monomers can be prepared by following the process described in patent EP 0,283,346 corresponding to the patents
  • the oligomers and polymers of methylidene malonate can be synthesized anionically or radically from the abovementioned monomers.
  • compositions which are formed from a mixture of oligomer (s) and polymer (s)
  • these compositions can also be obtained in a single step; the relative proportions of the constituents can be adjusted by varying the concentration of anionic or radical initiator in the polymerization medium.
  • the physicochemical characteristics of the abovementioned methylidene malonate compositions can be easily adjusted by a person skilled in the art, in order to obtain a wound suturing material having the required bioadhesion and viscosity characteristics.
  • the constituents of the wound suturing material according to the invention may represent up to 50% by weight of this material.
  • These constituents will of course be chosen so as to form, with the compositions based on methylidene malonate mentioned above, intimate mixtures having the desired bio-adhesion and viscosity characteristics.
  • these constituents will represent only about 1 to 20%, more preferably 1 to 10% by weight, relative to the total weight of the suture material.
  • polycyanoacrylates preferably polyalkylcyanoacrylates
  • Preferred additional constituents are, for example, polyethylene glycol, a hydrophilic additive belonging to the family of polyoxyalkylenes capable of thwarting the role of plasticizer within the mixture, or alternatively poly (lactide-co-glycolide), a biodegradable additive belonging to the family of polylactate-co-glycolates capable of allowing an improvement in the biodegradability of the mixture.
  • these constituents will be present within the suture material in the form of mixtures with the compositions based on methylidene malonate mentioned above. It should be noted that, without departing from the scope of the present invention, these constituents may also be present within the suture material in the form of monomeric units in copolymers comprising methylidene malonate units of formula (II), as defined previously.
  • methylidene malonate-based copolymers can be prepared by conventional polymerization techniques well known to those skilled in the art, among which mention may be made of anionic polymerization, radical polymerization or else the technique of coupling the precursor sequences of the copolymer, these sequences having previously been adequately functionalized at the end of the chain.
  • the monomeric units forming the abovementioned constituents will be chosen from the constituent monomeric units of polyacrylates, polysaccharides, polyoxyalkylenes, polylactates and polylactate-co-glycolates.
  • alkylcyanoacrylates alkyl methacrylates and itaconates.
  • the copolymers based on methylidene malonate used in the context of the present invention will consist, for at least 50% of their monomeric units, by methylidene malonate units.
  • copolymers may be random or have block or grafted structures.
  • the suture material in accordance with the present invention may, where appropriate, comprise, among its constituents, biocompatible products capable of adjusting its viscosity, such as, for example, plasticizers, or even biocompatible products making it possible to improve adhesion, such as for example so-called "tackifying" resins.
  • biocompatible products capable of adjusting its viscosity such as, for example, plasticizers, or even biocompatible products making it possible to improve adhesion, such as for example so-called "tackifying" resins.
  • plasticizing agents which are suitable in the context of the present invention, there may be mentioned, for example, esters derived from adipic acid, azelaic acid, citric acid, oleic acid, stearic acid. , sebaccic acid; polyethylene glycol.
  • tackifying resins which are suitable in the context of the present invention, mention may be made of modified polyterpene or terpene resins, hydrocarbon resins, mixtures of aromatic and aliphatic resins.
  • the suture material in accordance with the present invention, can also comprise, among its constituents, one or more active ingredients chosen in particular from local anesthetics, such as lidocaine; bacteriostatic agents and antibiotic agents, such as, for example, streptomycin; analgesics, such as ketoprofen.
  • local anesthetics such as lidocaine
  • bacteriostatic agents and antibiotic agents such as, for example, streptomycin
  • analgesics such as ketoprofen.
  • the subject of the present invention is a method for treating epidermal, dermo-epidermal, hypo-dermo-epidermal wounds, characterized in that it consists in applying to the interior of said wound. a sufficient quantity of a wound suturing material as defined above, preheated if necessary to a temperature above its softening temperature.
  • the aforementioned preheating temperature is range from 35 ° C to 47 ° C.
  • the suture material according to the present invention will be packaged in a form allowing its application, such as for example inside a self-heating syringe.
  • PMM 2.1.2 oligomer or polymer consisting of recurring monomer units corresponding to the formula
  • PEG poly (ethylene glycol)
  • PLGA poly (lactide-co-glycolide)
  • molecular weight means the weight-average molar mass designated M w , expressed in g / mole of polystyrene equivalent (PS), and measured by the method of
  • CPG Gel Permeation Chromatography
  • glass transition temperature (Tg) was determined by differential enthalpy analysis with a scanning speed of 10 ° C per minute.
  • compositions based on methylidene malonate formed from mixtures of oligomers and polymers were prepared by anionic polymerization (0.1N NaOH) in solvent medium (acetone) from the monomer, in accordance with the following procedure:
  • Composition No. 2 consists for about 78% by weight of oligomers of molecular weight less than 3,100, and for about 22% by weight of polymers whose majority representative has a molecular weight of 13,000.
  • Composition No. 5 is made up of approximately 78% by weight of oligomers of molecular weight less than 5,100 and of approximately 22% by weight of polymers whose majority representative has a molecular weight of approximately 18,000.
  • a study carried out on flaps of human skin coming from surgical waste on abdominoplasties made it possible to confirm that all these compositions have all the qualities required, in particular in terms of bio-adhesion and viscosity, to be able to be used as suture material. , alone or in combination with other bio-compatible constituents, as defined above.
  • composition No. 1 It has been observed that a small amount of composition is sufficient to obtain satisfactory tackiness when manual compression of the two edges of the wound is carried out after application of said composition. The best results have been obtained with composition No. 1.
  • the glass transition temperature is less than 0 ° C., to prevent these compositions from solidifying too quickly before application inside the wound.
  • this glass transition temperature will be between - 10 and - 35 ° C. and more preferably between - 20 ° C and - 30 ° C.
  • compositions based on methylidene malonate formed from a mixture of oligomers and polymers and optionally incorporating one or more other constituents were prepared by mixing in an appropriate solvent. More specifically, the methylidene malonate oligomers, the methylidene malonate polymers and optionally an additional constituent were weighed in previously determined quantities, and dissolved in a common solvent (generally acetone) with magnetic stirring, then the solvent was evaporated using a rotary evaporator, and the mixture dried in a desiccator under primary vacuum.
  • a common solvent generally acetone
  • compositions 6 and 7 only consist of oligomers and polymers of methylidene malonate 2.1.2.
  • compositions n ° 8 and 9 also comprise a hydrophilic additive of the PEG type of low molar mass which can be used as a plasticizer within the mixture.
  • compositions 10 and 11 also contain a biodegradable additive of the PLGA type which can be used to modulate the bio-degradability of the mixture.
  • the PLGA used has the following characteristics:
  • Composition No. 11 also comprises a part consisting of methylidene malonate 2.1.2 monomers, this monomer having been added cold to a mixture in acetone consisting of the three other components.
  • the compositions no. 12 and 13 also comprise an amphiphilic additive, itself based on methylidene malonate 2.1.2 which has good affinity with the other components and makes it possible to improve the behavior of the adhesive on the wound.
  • This amphiphilic additive is a block copolymer having 250 ethylene oxide units and 43 MM 2.1.2 units prepared anionically by successive polymerization of ethylene oxide and then MM 2.1.2.
  • Composition No. 14 further comprises a bio-degradable additive based on MM 2.1.2 which is a PMM 2.1.2 - P ⁇ CL copolymer which has good affinity with the mixture and a biodegradable sequence enabling the kinetics of overall degradability to be modulated. of said mixture.
  • MM 2.1.2 which is a PMM 2.1.2 - P ⁇ CL copolymer which has good affinity with the mixture and a biodegradable sequence enabling the kinetics of overall degradability to be modulated. of said mixture.
  • This additive is a block copolymer having a PMM 2.1.2 sequence of 5800 g / mol, and a P ⁇ CL block of 2000 g / mol which was prepared by chemical coupling between the two homopolymers, PMM 2.1.2 ⁇ -hydroxy functionalized and functionalized P ⁇ CL ⁇ -carboxy, in the presence of DCC in dichloromethane.
  • composition No. 1 which has a glass transition temperature of -22 ° C., and in parallel against a reference system (suture by non-absorbable thread).
  • Betadine disinfection for a second shave
  • the temperature is taken in a control flask containing water.
  • a sample of the composition tested is taken from the dish using a fine spatula of a chemist (3 mm wide and 1 mm thick) for application, f - a digital approximation of s 2 banks of the wound for
  • each guinea pig is sutured using a Prolene Blue 4/0 monofilament equipped with a needle. P3 curve, 13 mm section.
  • the method of suturing the incision is as follows:
  • each guinea pig is returned to its cage, wakes up in less than 5 minutes after the operation, then is free to move.
  • the guinea pigs are sacrificed by intraperitoneal injection of a solution of phenobarbital after eleven days for the "glue” group and after twelve days for the "suture" group.
  • Two excision-biopsies, per guinea-pig, are carried out: a witness in healthy skin and one taking a global scar.
  • the total duration of the operations was 1 hour between the first and the last guinea pig in each group.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Materials For Medical Uses (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/FR2000/000305 1999-02-09 2000-02-09 Materiau de suture de plaies a base de methylidene malonate WO2000047242A1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US09/509,830 US6610078B1 (en) 1999-02-09 2000-02-09 Suture material for wounds based on methylidene malonate
AU25543/00A AU767823B2 (en) 1999-02-09 2000-02-09 Suture material for wounds based on methylidene malonate
AT00903761T ATE223739T1 (de) 1999-02-09 2000-02-09 Wundnahtmaterial auf der basis von methylidenmalonat
DE60000437T DE60000437D1 (de) 1999-02-09 2000-02-09 Wundnahtmaterial auf der basis von methylidenmalonat
CA002361628A CA2361628A1 (en) 1999-02-09 2000-02-09 Suture material for wounds based on methylidene malonate
KR1020017010027A KR20010104341A (ko) 1999-02-09 2000-02-09 메틸리덴 말로네이트를 기재로 한 상처 봉합 물질
PL00350244A PL350244A1 (en) 1999-02-09 2000-02-09 Suture material for wounds based on methylidene malonate
DK00903761T DK1150723T3 (da) 1999-02-09 2000-02-09 Sammenføjningsmateriale til sår baseret på methylidenmalonat
BR0008091-8A BR0008091A (pt) 1999-02-09 2000-02-09 Material de sutura de feridas, e, material
JP2000598193A JP4863550B2 (ja) 1999-02-09 2000-02-09 マロン酸メチリデンベース傷縫合材料
EP00903761A EP1150723B1 (fr) 1999-02-09 2000-02-09 Materiau de suture de plaies a base de methylidene malonate
SK1077-2001A SK10772001A3 (sk) 1999-02-09 2000-02-09 Materiál na zošitie rán na báze metylidénmalonátu

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR99/01485 1999-02-09
FR9901485A FR2789314B1 (fr) 1999-02-09 1999-02-09 Materiau de suture de plaies a base de methylidene malonate

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WO2000047242A1 true WO2000047242A1 (fr) 2000-08-17

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US (1) US6610078B1 (US06610078-20030826-C00008.png)
EP (1) EP1150723B1 (US06610078-20030826-C00008.png)
JP (1) JP4863550B2 (US06610078-20030826-C00008.png)
KR (1) KR20010104341A (US06610078-20030826-C00008.png)
CN (2) CN1559622A (US06610078-20030826-C00008.png)
AR (1) AR022549A1 (US06610078-20030826-C00008.png)
AT (1) ATE223739T1 (US06610078-20030826-C00008.png)
AU (1) AU767823B2 (US06610078-20030826-C00008.png)
BR (1) BR0008091A (US06610078-20030826-C00008.png)
CA (1) CA2361628A1 (US06610078-20030826-C00008.png)
CZ (1) CZ20012896A3 (US06610078-20030826-C00008.png)
DE (1) DE60000437D1 (US06610078-20030826-C00008.png)
DK (1) DK1150723T3 (US06610078-20030826-C00008.png)
ES (1) ES2183782T3 (US06610078-20030826-C00008.png)
FR (1) FR2789314B1 (US06610078-20030826-C00008.png)
HU (1) HUP0200330A2 (US06610078-20030826-C00008.png)
PL (1) PL350244A1 (US06610078-20030826-C00008.png)
PT (1) PT1150723E (US06610078-20030826-C00008.png)
RU (1) RU2241494C2 (US06610078-20030826-C00008.png)
SK (1) SK10772001A3 (US06610078-20030826-C00008.png)
TW (1) TW492883B (US06610078-20030826-C00008.png)
WO (1) WO2000047242A1 (US06610078-20030826-C00008.png)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017021785A1 (en) 2015-07-31 2017-02-09 Afinitica Technologies, S.L. Fast light curing cyanoacrylate compositions

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8795332B2 (en) 2002-09-30 2014-08-05 Ethicon, Inc. Barbed sutures
US6241747B1 (en) 1993-05-03 2001-06-05 Quill Medical, Inc. Barbed Bodily tissue connector
US5931855A (en) 1997-05-21 1999-08-03 Frank Hoffman Surgical methods using one-way suture
FR2774096B1 (fr) * 1998-01-29 2000-04-07 Virsol Nouveaux copolymeres tensioactifs a base de methylidene malonate
FR2812551B1 (fr) * 2000-08-07 2003-03-28 Virsol Forme pharmaceutique comprenant un materiau support a base de methylidene malonate et un facteur de regulation cellulaire
US7056331B2 (en) 2001-06-29 2006-06-06 Quill Medical, Inc. Suture method
US6848152B2 (en) 2001-08-31 2005-02-01 Quill Medical, Inc. Method of forming barbs on a suture and apparatus for performing same
US6773450B2 (en) 2002-08-09 2004-08-10 Quill Medical, Inc. Suture anchor and method
US20040088003A1 (en) 2002-09-30 2004-05-06 Leung Jeffrey C. Barbed suture in combination with surgical needle
US8100940B2 (en) 2002-09-30 2012-01-24 Quill Medical, Inc. Barb configurations for barbed sutures
US7624487B2 (en) 2003-05-13 2009-12-01 Quill Medical, Inc. Apparatus and method for forming barbs on a suture
RU2404717C2 (ru) 2004-05-14 2010-11-27 Квилл Медикал, Инк. Способы и устройства для наложения швов
JP2007100108A (ja) * 2007-01-22 2007-04-19 Dainippon Ink & Chem Inc 硬化性樹脂組成物
US8915943B2 (en) 2007-04-13 2014-12-23 Ethicon, Inc. Self-retaining systems for surgical procedures
EP2197501B8 (en) 2007-09-27 2012-10-03 Ethicon, LLC Self-retaining sutures including tissue retainers having improved strength
US8916077B1 (en) 2007-12-19 2014-12-23 Ethicon, Inc. Self-retaining sutures with retainers formed from molten material
JP5518737B2 (ja) 2007-12-19 2014-06-11 エシコン・エルエルシー 熱接触媒介リテーナを備えた留置縫合糸
US8118834B1 (en) 2007-12-20 2012-02-21 Angiotech Pharmaceuticals, Inc. Composite self-retaining sutures and method
WO2009097556A2 (en) 2008-01-30 2009-08-06 Angiotech Pharmaceuticals, Inc. Appartaus and method for forming self-retaining sutures
US8615856B1 (en) 2008-01-30 2013-12-31 Ethicon, Inc. Apparatus and method for forming self-retaining sutures
US9125647B2 (en) 2008-02-21 2015-09-08 Ethicon, Inc. Method and apparatus for elevating retainers on self-retaining sutures
US8216273B1 (en) 2008-02-25 2012-07-10 Ethicon, Inc. Self-retainers with supporting structures on a suture
US8641732B1 (en) 2008-02-26 2014-02-04 Ethicon, Inc. Self-retaining suture with variable dimension filament and method
BRPI0911132B8 (pt) 2008-04-15 2021-06-22 Angiotech Pharm Inc sutura para ser usada em um procedimento aplicado ao tecido
US8961560B2 (en) 2008-05-16 2015-02-24 Ethicon, Inc. Bidirectional self-retaining sutures with laser-marked and/or non-laser marked indicia and methods
BRPI0921810B8 (pt) 2008-11-03 2021-06-22 Angiotech Pharm Inc montagem para inserir um comprimento de sutura no interior do corpo de um mamífero
US8106234B2 (en) * 2009-05-07 2012-01-31 OptMed, Inc Methylidene malonate process
US8975435B2 (en) * 2009-05-07 2015-03-10 Optmed, Inc. Methylidene malonate process
KR101883143B1 (ko) 2010-05-04 2018-07-31 에티컨, 엘엘씨 자가-유지형 봉합재를 생성하기 위한 레이저 커팅 시스템 및 방법
BR112012031606B1 (pt) 2010-06-11 2020-11-10 Ethicon Llc distribuidor de sutura
MX2013004513A (es) 2010-10-20 2013-09-26 Bioformix Inc Síntesis de metilenmalonatos sustancialmente libres de impurezas.
US10414839B2 (en) 2010-10-20 2019-09-17 Sirrus, Inc. Polymers including a methylene beta-ketoester and products formed therefrom
US9279022B1 (en) * 2014-09-08 2016-03-08 Sirrus, Inc. Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions
US9249265B1 (en) 2014-09-08 2016-02-02 Sirrus, Inc. Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions
US9828324B2 (en) 2010-10-20 2017-11-28 Sirrus, Inc. Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom
AU2011323299B2 (en) 2010-11-03 2016-06-30 Ethicon Llc Drug-eluting self-retaining sutures and methods relating thereto
EP2637574B1 (en) 2010-11-09 2016-10-26 Ethicon, LLC Emergency self-retaining sutures
RU2659454C2 (ru) 2011-03-23 2018-07-02 ЭТИКОН ЭлЭлСи Самоудерживающиеся нити с регулируемой петлей
US20130172931A1 (en) 2011-06-06 2013-07-04 Jeffrey M. Gross Methods and devices for soft palate tissue elevation procedures
JP2014534969A (ja) 2011-10-19 2014-12-25 シラス・インコーポレイテッド メチレンβ−ケトエステルモノマー、メチレンβ−ケトエステルモノマーを製造するための方法、これらから作られる重合可能な組成物および製品
JP6553505B2 (ja) 2012-03-30 2019-07-31 シラス・インコーポレイテッド 複合材およびラミネート物品ならびにこれらを作製するための重合系
JP6188252B2 (ja) 2012-03-30 2017-08-30 シラス・インコーポレイテッド 重合性組成物の活性化方法、重合系およびこれにより形成される製品
US9234107B2 (en) 2012-03-30 2016-01-12 Sirrus, Inc. Ink coating formulations and polymerizable systems for producing the same
WO2013181600A2 (en) 2012-06-01 2013-12-05 Bioformix Inc. Optical material and articles formed therefrom
WO2014078689A1 (en) 2012-11-16 2014-05-22 Bioformix Inc. Plastics bonding systems and methods
US10607910B2 (en) 2012-11-30 2020-03-31 Sirrus, Inc. Composite compositions for electronics applications
CN105008321A (zh) 2013-01-11 2015-10-28 瑟拉斯公司 经过双(羟甲基)丙二酸酯的途径获得亚甲基丙二酸酯的方法
US9315597B2 (en) 2014-09-08 2016-04-19 Sirrus, Inc. Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US9416091B1 (en) 2015-02-04 2016-08-16 Sirrus, Inc. Catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US10501400B2 (en) 2015-02-04 2019-12-10 Sirrus, Inc. Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US9334430B1 (en) 2015-05-29 2016-05-10 Sirrus, Inc. Encapsulated polymerization initiators, polymerization systems and methods using the same
US9217098B1 (en) 2015-06-01 2015-12-22 Sirrus, Inc. Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound
EP3310821B1 (en) * 2015-06-19 2021-02-17 Sirrus, Inc. Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US9518001B1 (en) 2016-05-13 2016-12-13 Sirrus, Inc. High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation
US9617377B1 (en) 2016-06-03 2017-04-11 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US10428177B2 (en) 2016-06-03 2019-10-01 Sirrus, Inc. Water absorbing or water soluble polymers, intermediate compounds, and methods thereof
US9567475B1 (en) 2016-06-03 2017-02-14 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US10196481B2 (en) 2016-06-03 2019-02-05 Sirrus, Inc. Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof
US11591425B2 (en) 2017-06-02 2023-02-28 Arkema France Curable compositions and uses thereof
WO2021014219A2 (en) 2019-07-19 2021-01-28 Arkema France Curable compositions useful for obtaining non-sensitizing cured products

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996000760A1 (en) * 1994-06-28 1996-01-11 Tri-Point Medical Corporation pH-MODIFIED BIOCOMPATIBLE MONOMER AND POLYMER COMPOSITIONS
WO1996002278A1 (fr) * 1994-07-18 1996-02-01 Laboratoires Upsa Immunonanoparticules revetues d'anticorps monoclonaux anti-beta-2 microglobuline
DE19508049A1 (de) * 1995-02-23 1996-09-12 Schering Ag Verwendung von Methylenmalondiesterderivaten zur Herstellung von Mikropartikel
US5575997A (en) * 1993-03-31 1996-11-19 Tri-Point Medical Corporation Biocompatible monomer and polymer compositions
US5624669A (en) * 1993-03-31 1997-04-29 Tri-Point Medical Corporation Method of hemostatic sealing of blood vessels and internal organs
WO1998018455A1 (fr) * 1996-10-25 1998-05-07 Virsol Procede de preparation de nanoparticules de methylidene malonate, nanoparticules contenant eventuellement une ou plusieurs molecules biologiquement actives

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5550172A (en) * 1995-02-07 1996-08-27 Ethicon, Inc. Utilization of biocompatible adhesive/sealant materials for securing surgical devices

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5575997A (en) * 1993-03-31 1996-11-19 Tri-Point Medical Corporation Biocompatible monomer and polymer compositions
US5624669A (en) * 1993-03-31 1997-04-29 Tri-Point Medical Corporation Method of hemostatic sealing of blood vessels and internal organs
WO1996000760A1 (en) * 1994-06-28 1996-01-11 Tri-Point Medical Corporation pH-MODIFIED BIOCOMPATIBLE MONOMER AND POLYMER COMPOSITIONS
WO1996002278A1 (fr) * 1994-07-18 1996-02-01 Laboratoires Upsa Immunonanoparticules revetues d'anticorps monoclonaux anti-beta-2 microglobuline
DE19508049A1 (de) * 1995-02-23 1996-09-12 Schering Ag Verwendung von Methylenmalondiesterderivaten zur Herstellung von Mikropartikel
WO1998018455A1 (fr) * 1996-10-25 1998-05-07 Virsol Procede de preparation de nanoparticules de methylidene malonate, nanoparticules contenant eventuellement une ou plusieurs molecules biologiquement actives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017021785A1 (en) 2015-07-31 2017-02-09 Afinitica Technologies, S.L. Fast light curing cyanoacrylate compositions
US10626310B2 (en) 2015-07-31 2020-04-21 Afinitica Technologies, S.L. Fast light curing cyanoacrylate compositions

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DK1150723T3 (da) 2003-01-20
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FR2789314A1 (fr) 2000-08-11
AU767823B2 (en) 2003-11-27
JP2002536124A (ja) 2002-10-29
FR2789314B1 (fr) 2001-04-27
CA2361628A1 (en) 2000-08-17
CN1559622A (zh) 2005-01-05
US6610078B1 (en) 2003-08-26
KR20010104341A (ko) 2001-11-24
JP4863550B2 (ja) 2012-01-25
PL350244A1 (en) 2002-12-02
DE60000437D1 (de) 2002-10-17
BR0008091A (pt) 2001-11-13
TW492883B (en) 2002-07-01
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PT1150723E (pt) 2003-01-31
HUP0200330A2 (en) 2002-06-29
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RU2241494C2 (ru) 2004-12-10
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AU2554300A (en) 2000-08-29
ES2183782T3 (es) 2003-04-01

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