CA2049055C - Biodegradable superabsorbing sponge - Google Patents
Biodegradable superabsorbing spongeInfo
- Publication number
- CA2049055C CA2049055C CA002049055A CA2049055A CA2049055C CA 2049055 C CA2049055 C CA 2049055C CA 002049055 A CA002049055 A CA 002049055A CA 2049055 A CA2049055 A CA 2049055A CA 2049055 C CA2049055 C CA 2049055C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- cross
- linking agent
- group
- carboxylic acid
- 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 - Fee Related
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
-
- 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
-
- 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
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/15203—Properties of the article, e.g. stiffness or absorbency
- A61F13/15252—Properties of the article, e.g. stiffness or absorbency compostable or biodegradable
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
- A61F2013/530583—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the form
- A61F2013/530649—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the form in sponge or foam
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
- A61F2013/530795—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials being biodegradable
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F13/534—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having an inhomogeneous composition through the thickness of the pad
- A61F2013/53481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having an inhomogeneous composition through the thickness of the pad being biodegradable
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/84—Accessories, not otherwise provided for, for absorbent pads
- A61F13/8405—Additives, e.g. for odour, disinfectant or pH control
- A61F2013/8438—Additives, e.g. for odour, disinfectant or pH control being enzymes, e.g. proteolysis, cellulase
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/84—Accessories, not otherwise provided for, for absorbent pads
- A61F13/8405—Additives, e.g. for odour, disinfectant or pH control
- A61F2013/8447—Additives, e.g. for odour, disinfectant or pH control in using different incompatible substances
- A61F2013/8452—Additives, e.g. for odour, disinfectant or pH control in using different incompatible substances being contained in microcapsules
Abstract
Abstract of the Invention new superabsorber which gels and cross-links as hydrated has been developed. The superabsorber contains a branched-chain polyanionic carbohydrate such as carboxymethylcellulose,a cross-linking agent, and a hydrophobic carboxylic acid. The superabsorber is biodegradable and non-toxic.
Description
~ : :
2 0 ~ 9 ~
~IODEeRA12AE~LE~ SQRE~INQ~Q~ ~ ' :'-. ~. ;', ' Ba~rQuna Qf~e Inven~Qa The present ~nvent~or~ r~l~te~ to bi~egra~abl~ gel~ wh~ch ~ct ~ sup~absorblng 5 spon~e~. Moro particularly, ~ha 9~l o~E th~ ~nYention has ~s h~gh, or hl~her, ligul~ an~ ~aline uptake t~n the p~lyacryl~ts superabsorber~ now being use~ wh~
~aving the advant~ge o~ be~ng comple~ely biodegra~a~
Biodegradabil~ty ha~ become a necessity ~n . ~;:
society in the la~t few years. As ~ore and more .
pro~uct~ are maae aisposable, the waste problems associatea with these ~isposables have become increasingly important. One example o thi~ I~ the ;
15 disposable ~iaper ~iel~. Unti~ a few y~3r~ ago, .
disposable aiapers, though convenient, ha~ not received widesprea~ use beeause the amou~t o~ l~qu~
whi~h cou~ be a~sorbe~ was limit~q Thi~ limi~t~on ;~-lea~ to use of the ~i~per~ ~or eactraor~in~ry 20 circumstarlces but they wer~ not feas~ble for most people on ~ day-to-~2y ba~i~ because o~ the le~k~ge ~:
and result~ng diaper ra~h pro~lem. In or~e~ to ~olQ~re these problems, tho l~aper manuf~turer fir~t uEe~
~ery thicl~ pers, placlng l~rge amou~lts of i~er ;
25 such as eellulo~ in the ~i3per to ~ICt ~ a liqu~
pr~ma~ly ~ n~ an~ ur~ne, absorber. The~e bulky diapers ~t~ll h~d ï~mlt~t~on~ on :tbe amount o . .
, ~ .
,~
- 2 - 2 ~ ~ 9 ~ 5 ~
l~qu~s they coul~ retaln whlle tb~ ~ulk m~ the~ ;
uncomfortable ~or the ~nfant~ to wear.
The ir~t ma~o~ ~mprovemen~ ~n t~o di~posable ~iaper f~el~ wa~ the ad~ition o th~
~o-calle~ ~uperabsorbers~ a8 l~u~ trap8. The8 superabsorbe~ ar~ primarlly polyacryl~te part~cle~
which ar~ plaee~ he ~aper in loo~ or~ or ~r~
entrappe~ amonq celluloso ~ber~. Theso polyacrylat~
particles absor~ larg~ quan~t~e~ of wa~er ~q I 10 swelling ~n~ act~ng a~ in~ ual pseuao-spo~e~
¦ ,Since t~e amount of ~allne and ur~ne which c~n be absorbe~ by these superabsorber~ ~ so much greater than cellulo~e or other natural fiber~, ~ery thi~
diaper~ coul~ be use~, minimizlng the problems to 15~ infants and ma~ing di~posables the ~iaper of choice.
. The polyacrylate gel beads move freely relative to ~ .
each other ana ~orm large ~paces between each other.
~owever, once fully hydrate~, these polyacryl~to .~
~uper~bsorber~ ten~ to clump, causing a lumpy ~i~per ~. .p ~.
20 an~ discomfort to the inf ant. ~ f In aadition to the use ~n ~apers, the super~bsorbers ha~e other uses. ~ny other items wh~ch are usea for absorptlon ~ liqu~ are ~ gertile .
groun~ for use o the superabsorber~. Howe~er, the polyacrylate super~b~or~er~ have on~ ma~or ~sa~ant~ge; th~y are not b~o~e~ra~abl~. ~h~ m~ns .
th~ the ~oper~ all other ~ro~ucts ma~e u~ln~
th~se ~uperabsorber~ ara not te~r3~e~ ~o~ ~e~a~es; ~n :~
f~et, th~y nee~ hun~re~s o~ yeaEs to bre~down. This 3Q lsad~ to the ~forement~sne~ ~ste pro~lem. ~o her d~adv~ntag2 of the poly~cryl~te~ i5 th~t they a~sorb '.'~.,.~ ' . ,. '~.
: ," , ...... ..
~ , ~ '`. ,, . `':
~IODEeRA12AE~LE~ SQRE~INQ~Q~ ~ ' :'-. ~. ;', ' Ba~rQuna Qf~e Inven~Qa The present ~nvent~or~ r~l~te~ to bi~egra~abl~ gel~ wh~ch ~ct ~ sup~absorblng 5 spon~e~. Moro particularly, ~ha 9~l o~E th~ ~nYention has ~s h~gh, or hl~her, ligul~ an~ ~aline uptake t~n the p~lyacryl~ts superabsorber~ now being use~ wh~
~aving the advant~ge o~ be~ng comple~ely biodegra~a~
Biodegradabil~ty ha~ become a necessity ~n . ~;:
society in the la~t few years. As ~ore and more .
pro~uct~ are maae aisposable, the waste problems associatea with these ~isposables have become increasingly important. One example o thi~ I~ the ;
15 disposable ~iaper ~iel~. Unti~ a few y~3r~ ago, .
disposable aiapers, though convenient, ha~ not received widesprea~ use beeause the amou~t o~ l~qu~
whi~h cou~ be a~sorbe~ was limit~q Thi~ limi~t~on ;~-lea~ to use of the ~i~per~ ~or eactraor~in~ry 20 circumstarlces but they wer~ not feas~ble for most people on ~ day-to-~2y ba~i~ because o~ the le~k~ge ~:
and result~ng diaper ra~h pro~lem. In or~e~ to ~olQ~re these problems, tho l~aper manuf~turer fir~t uEe~
~ery thicl~ pers, placlng l~rge amou~lts of i~er ;
25 such as eellulo~ in the ~i3per to ~ICt ~ a liqu~
pr~ma~ly ~ n~ an~ ur~ne, absorber. The~e bulky diapers ~t~ll h~d ï~mlt~t~on~ on :tbe amount o . .
, ~ .
,~
- 2 - 2 ~ ~ 9 ~ 5 ~
l~qu~s they coul~ retaln whlle tb~ ~ulk m~ the~ ;
uncomfortable ~or the ~nfant~ to wear.
The ir~t ma~o~ ~mprovemen~ ~n t~o di~posable ~iaper f~el~ wa~ the ad~ition o th~
~o-calle~ ~uperabsorbers~ a8 l~u~ trap8. The8 superabsorbe~ ar~ primarlly polyacryl~te part~cle~
which ar~ plaee~ he ~aper in loo~ or~ or ~r~
entrappe~ amonq celluloso ~ber~. Theso polyacrylat~
particles absor~ larg~ quan~t~e~ of wa~er ~q I 10 swelling ~n~ act~ng a~ in~ ual pseuao-spo~e~
¦ ,Since t~e amount of ~allne and ur~ne which c~n be absorbe~ by these superabsorber~ ~ so much greater than cellulo~e or other natural fiber~, ~ery thi~
diaper~ coul~ be use~, minimizlng the problems to 15~ infants and ma~ing di~posables the ~iaper of choice.
. The polyacrylate gel beads move freely relative to ~ .
each other ana ~orm large ~paces between each other.
~owever, once fully hydrate~, these polyacryl~to .~
~uper~bsorber~ ten~ to clump, causing a lumpy ~i~per ~. .p ~.
20 an~ discomfort to the inf ant. ~ f In aadition to the use ~n ~apers, the super~bsorbers ha~e other uses. ~ny other items wh~ch are usea for absorptlon ~ liqu~ are ~ gertile .
groun~ for use o the superabsorber~. Howe~er, the polyacrylate super~b~or~er~ have on~ ma~or ~sa~ant~ge; th~y are not b~o~e~ra~abl~. ~h~ m~ns .
th~ the ~oper~ all other ~ro~ucts ma~e u~ln~
th~se ~uperabsorber~ ara not te~r3~e~ ~o~ ~e~a~es; ~n :~
f~et, th~y nee~ hun~re~s o~ yeaEs to bre~down. This 3Q lsad~ to the ~forement~sne~ ~ste pro~lem. ~o her d~adv~ntag2 of the poly~cryl~te~ i5 th~t they a~sorb '.'~.,.~ ' . ,. '~.
: ," , ...... ..
~ , ~ '`. ,, . `':
- 3 - ~ :
- 20g~05~ -ma~mally at 0% ~ ne while u~n~ ~nd most ~o~y ~lu~ ar~ ~bout 0.~5 ~ ~alino. ~ ~
....
Mater~als wh~ch ~bsorb ligul~ ~n~ a~o bio~egradable such ~ ~hose o~ th@ present ~nventio~
5 have other possible uses as well. ~he~ entrapment o part~cles, ~nclu~lng macromoleeule~ ~uc~
hemoglobln and c~ uch a~ orythroc~te~
parti~ul~rly ~mportank ~o~ ~eminine ~pkin~ ~nd -~
c~m~lar psoducts. ~uperabsoxbe~ ba~o not ma~e ~
lO 9reat ~ent ~n this f~el~ even th~ugh tbey have the hecessary liqui~ absorpt~on because they cannot entrap lsrge p3rticulates.
Another possible use for a biodeqradable ~;~
material which will entrDp ligui~ an~/or particles is as a sustaine~ release vehicle. In certDin instances, the molecule~ to be ~elivered c~n be part '~
of the structural materi~l of the sp~nge itself. .
Nost mater~als which are presently ~e~ng teste~ as :~
sustained release vehicles, e.g., microcapsules, liposomes an~ relate~ cap~ular type ~ro~u~t~, have substanti~l costs an~ tlme ~5~0ci~te~ with their manuacture. The ~bil~ty to make ~ pro~u~t in fi~
npply ~t to ~ given area, ~n~ then let ~t ~egr~e under or~inary conditions to release entrapped m~terial, woul~ solve many problems.
A ~urthe~ u~e o~ a gel wh~eh entraps l~qui~s ~n~ part~cles ~s as ~ ~ologic~l protectiY~ h~rrier.
For esample, a gel wh~c~ ~ntr3ps bacter~a ~s ~t ~s hy~rate~, or provents the~r pass~ge o~c~ ~or~ea, c~n 3~ be use~ ns a wouna ~ressing, protect~ng the woun~
~: , '-".`' . .
' -2 ~ ~ 9 ~
~rom bDcteria while ollowin~ ~r flo~ ~n~or fre~
10w o~ liquid to th~ ~n~u~y. A fu~ther U8e ~ ~n a ~iaper wher~ coli~orm ~acteria can ~reakdown urea in -~
ur~ne to ammon~, chang~ng tha pH ~n~ promotinq s ~i~per ra~
Accor~n~ly, 8~ ob~e~t o~ ~hle ~nvent~on to provid2 ~ biodegra~ble mater~l that has high uptak~ fo~ wator ~n~ ~AllnQ. .
~ r~other ob~t of t~e inverlt~o~ to lo,prov~e ~ b~o~egradable carr~er or ~ust~rJe~ rele~se ~el~very system for ~rugs ana other moleculeE. . -:
A further ob~ect of the invent~o~ is to:
provi~e a material and metho~ for entrapment of part~culates such as erythrocytes an~ proteln 15 molecules ~uch as hemoglobin.
A st~ll further object o~ the ~nvention i~
to provide ~ proteetive barrier wh~ch prevent~ the passage o p~rticles ~uch as b~cter~a or ~-macromolecules, eOg., for use as ~ woun~ bandage. r,~
These tn~ other object~ ~n~ feature~ o~ the in~ention w~ll be apparent ~rom the ~ollow~ng ~escription.
~umm3rY o~ the In~n~Qn The present ~n~ention ~e2~ure6 a ~o~po8ition 25 of matter which ~Ct~ ~ a ~ynthetic ~ponge a~ well ~s metho~s ~f ~b~or~ing ~gueou~ or 5alin~ ~olut~ons.
-::.. :~.:~.,:--:, .: ~, _ 5 _ 2 3 ~ 9 ~
, .
The ~nvent~on ~urth~r featur~ metho~ o gntr~pp~ngparticle~ ~n a 9~1~ Th~ gel-l~ke compo~tion of matter ~an ba u~e~ a~ a protect~ve barrier an~ ~ a susta~ned release ~eh~cle which release~ entrappe~
5 particles or molecul~ ~uch ~ ugs o~er t~
~ n br~e, ~ sompos~tlo~ of m~ltter h~ bee~
aevelope~ wh~eh DCt~l 19S a 6ynthetlG spon~e wher~
allowe~ to hy~rato. ~ h~gh molecul~r w~ght, e~mplos carbo~ydrate w~th mult~ple anion-terminat~ branche~
lo an~ a ~ross-l~n~g agent are blen~ed ~n~er ~substant~ally anhy~rous conait~ons, preferably w1th a carbo~ylic ac~d with a substantial hy~rophobi~
region. Preferre~ carboxyl~c acids with su~s~antial hy~rophobic regio~ Are ~atty Dcids ~electea rom a :~
group consist~ng of lauric ac~d, palmitic 3cid, oleic acia, stear~c acid, benzoic ac~, or mi~tures thereof. A substant~al hydrophobic region me~n~ ana -~
implies a region with ~ substantial hy~rocarbon cha~n or ring ~tructure. Preferre~ br~nch comple~
carbohy~r~tes inclu~e carbosymethylcellulose, ~n~
chemical ~nalogues thereofO ~inear comple~
carbohydrates such as Gellulose, gum santhan~ ~um -~
kar~ya, or algln~c ~ci~ m~y ~l~o be inclu~e~
Once the component~ ~re intimately blen~e~, :
e.g., m~lle~ to~ethe~, the component~ o the mi~ture can be hy~rate~ ~n~ ~ro~-linke~ su~t~nt~lly ~multaneously when ~n the pres2nc~ o~ tha hy~r~tin~
: ~olution. Any o the component~ m~y be premise~
together or impregn~te~ wlth one another. In .
~it~on, the other re~Gtant~ m~y ~e ~erivatl~e~ W~t~
~he comples or l~near c~rbohydr~t-s us~ng an :
`~
20~0~
~ ~-isopropo~e or other ~imilar reac~on. ~,ome or all :7 o~ t~e ~atty aci~ can be repl~ced wit~ a ~~nction~
~atty aci~ or a long-ch2in car~o~yli~ ac~. A~
use~ herein, the ter~ ~func~lonal ~atty ~c~ m~an~
S ~nclu~es and ~efines a mo~ecule having a term~n~l carbo~yli~ ac~, a substant~al al~phat$c portlon, ~n~
5 b~olog~cal funct~on other than ~ ~ break~own pro~uct or precur~or in ~h~ ~oOa ~ha~a. Funot~on~
fatty ac~ nclu~e ~Ci~8 such as undecylen~c ~c~
10 arachi~onic a~i~, p~ostaglana~ns, pros~cycl~ns, thrombo~anes, an~ their ~er~ati~e~, chemic~
analogue~ ana precursor~
As noted, the composit~on of matter of the invention ~ncludes ~ cross-linking ~gent as ~n : :
15 essent~al component. The preferred ~ross-link~ng agents ore~metallo-organic compoun~s o mult~valent metal~, Organ~c cross-l~nk~ng agent~ ~uch as .:. -~ .
ch~tosan, ~oly-Cup* cbymene, an~ ~eff~mlne m~y be us,ed, bu~ are les~ eff~cient than the metal~o-or~ni~
20 comple~e~. O~ytetracyl~n~ ~ a h~ghly efect~ve ~ -~
cros~-lin~ing 2gent but ~as l~mite~ ~pplic~t~on because of ~ts biological ~CtiY~ty. Althou~h .
bivalent molecules ~uch ~s cdlcium might be use~ in certain ~ir~umst~nce~, the multivalent metal~
25 ~valence 3 an~ o~er) sUch ~s Dluminum or chrom~um are ~:.
preerre~. For m~ny appllcations aluminum ~n the form ~f hydroxy-~lumlnum d~et~te, borate-stabll~zed dihy~ro~y-~luminum ~cet~t~ ~n~or ~lum~nu~
6ulfate~cit~te, m~y be ~at~5factory~ A mo~t ~ ~-30 preferre~ ~oss-linking ~gent pro~id~ng superior performance ~ ~n ~luminum metallo-~rgan~c comple~ of the hy~ro~y-aluminum/hy~rophob~c earbosylate form *Trade Mark : ~'`'`
- 7 - 2~9~5~
., ~uch as hy~ro~y-~umlnum ben~osto. Th~ ~yent ean a~t as both the hyarophoblc car~o~yl~c aci~ ~n~ the cross-linkin~ agent ~n ~ ~in~le moleclulo. O~her hydrophobic c~rbo~yli~ ~ci~ ~uch a~ ~ur~o, ~ 5 ~tearat~, oleate or benzo~te can ~l~o b~ use~ ~ the ,Yj metallo-orsanie eompl~
i The in~ent~on ~urther feature~ ~ metho~ o~
; absor~ing agueou~ or ~al~ne solut~on~ uslng tho ~ b~o~eyr~ble ~ynthetl~ ~ponge compo~it~on of th~
`~ 10 invent~on. ~he synthe~lc ~ponge compos~t~on 1~
pro~ed ~n a ~ubst~ntially unhyBr~te~ o~m, or .~ esample, by blen~ing the components togetber to obtAin particles of the ~esired size, an~ then the -~
solution i8 absorbe~ by contacting the solution w~th 15 the synthetic sponse composition. ~he ~ynthetic sponge composition hydrates to ~bsorb t~e solution an~ substantially simult~neously cross-llnks into a gel which bin~s tbe ~olution.
The same basic materi~l m~y be u~e~ to 20 encapsul~te part~cle~ ~n ~ 9el. The synthetic ~ponqe eomposition i8 prov~e~ ~n a ~ubstantially unby~rate~
form ~na a solut~on cont~ining ~he particles to be entrappe~ within the gel i~ mi2ed with the composition, The gel form~ by Gross-linking, 25 absorbing the ligui~ ~n~ entrapp~ng the part~cles ~: :
wit~n the qel. P~rt~cl~s ~h~ch can be 2ntrappe~ ~n th~s way ~nclu~e ma~rom~lecule~ os prot~ns ~uch hemoglo~in, bicter~a, os Gell6 ~ueh ~s erythrocyte~
-, :
3 ~ub~t~nti~lly the ~me ~ntrapment ~roce~ure 30 ~an be used to creato a ~u~t~ined rele~se vehlcl~
J
2 ~ 5 ~
For esample, ~el~ cros~ n~e~ by oxytetr~cycl~n~ c~ p;
b~ use~ a~ ~ ~u~t~ne~ rele~ ehicle ~or thl~
~rug. Many po~tl~tely ch~rge~ ~rugs can ~o hell~ ~n polydnioll~c gel8 ~or ~ust~ine~ releAse. By mo~i~ying 5 the r~t~o~ o~ the ~ferent ~omponent~, an~ ~elect~0 the ~pec~f~ materi~ls wh~ch mak~ up thle 9~1, th~
~tabillty, zbsorp~cion 9.~rel~, ~n~ irmnle~ o~ t~ g~
can be mo~ e~. ~o~ e~ mpl~, chanç~ th~ atty ~c~carbohy~rAt~ r~t~Lo can ~ramdtically c2 ~ng~ th0 10 absorption, ar~l~ ths ~ubsequent relea~o ~at~, o l~gu~ rom the gel. Further, ~he a~tion o~ ot~er materi~ls to the gel, ~.9., surfactant~ ~u~h ~8 -~
polyosyethylene fatty a~ ether~ or spacer~ such as `~
5ilic3 or clays, c~n ch~nge the properties of the 15 9el. This chdnse of properties ~s mor0 ~learly e~plaine~ ~n the de~cription ~n~ the E~amples. ;
. . .. .
.,-~ ~ . , -, ,, petailed Description o~ ~he I~ventiQn The hydrate~ gel descr~be~ here~n ~8 ~ormea by the ~multaneou~ hyar~t~on an~ cross-l~n~ng by 20 cross-linkin~ a~ent of polyan~onic c~rbohydr~te~
pre~erably together with hydrophobis car~o~yl~t~
In contrast to the polyacrylste ~uperabsorber~, whi~h necessarily form ~i~crete particles ~s ~o ~ov~lently c~oss-linked moleeules ~uch a~ cro~s-l~nke~
25 carbosymethylcellulose, gel~t~ns, an~ ~lgin~te~), the materi~l of the present ~nvent~on ~ ts ln uncro~-llnked form pr~or to hy~r~tlon. Upon '~
hy~r~tion, the m~terial gorms e~tena, w~ter-binB~ng network~ of b~o~e~r~fl~ble ~arbohy~rate ~olymer, 30 prefer~bly ~urther cro~ nked w~th est~n~
multll~mell~r ~hee~ o~ ~egr~bl~, an~onic llpl~
.,. ~ - ~ ,.,~
,; . ;.~:
9 - 2 ~ '1 9 ~
Macroscoplcally, th~ 9~1~ ar~ ~t~le ~nd ~an e~ten~ -~
se~er~l ~ent~me~er~ ~n ~ever~ re~t~ons upon hy~rat~on. Thes~ gel~ ~an al~o be ~orme~ ln o a - ~ariety o~ geome~rle~ 6uch ~ ro~5, ~i~;kst on~
5 ~la~s. The consist~ncy o~ the gel, ~n~ th~ ~mount of li~ui~ ab~srbe~, ~an be ~hanged by mo~fy~g tho in~t~al compos~tlon. ~n ~dit1on, a ~rt~ally hy~rate~ 9~1 ~an bg further ~y~r~tg~ at ~ l~ter t~m~
~y absorpt~on of more l~qu~
~he c~p~city for upt~ke o~ l~qu~ o the composft~ons of the prese~t ~n~ention ~urthermore depen~s on the ratio of ~ctiv~ ac~, e.g., lipi~s, to a~tive carbohydrate. At low l~pia/carbohyarate .: :~
ratios ton a weight ~as~s), e.~., a 0.1 - 0.2 rat~o, 15 h~gh flui~ absorptlon ~s observe~. ~n fact, ~s m~y be seen frDm the follow~ng E~amples, the uptake of ~ .
0.15 N saline ~s considerably greater than that of ~, the polya~ry~ate ~upera~sorberL. When the rat~o of fatty aci~ to carbohy~rate ~ much higher, ~.9., 20 appros~mately 1, the ~els ~o not a~sorb ~s much liqui~, give up ths l~qu~ easier, ~n~ ~ct a~ better del~very systems.
Funct~onal ~tty ~ci~ c~n be use~ to repla~e ~ome or ~11 o~ the fatty Doi~. Tho mD~or a~ant~ge o~ us1ng the~e ~unct~onal gatty ~c~
that a~ the gel~ ~ro ~egrD~e~, the unct~onal atty ac~ rele~se~. Th~ ~ct~ as a typ~ o Aeli~eIy ~ystem wh~ch c~n have ~ much hi~her ~oncentr~t~on o the materi~l to be ~ell~erea than ~oul~ b~ po~ le 3~ in another type o~ enc~psulat~on or entr~pment .
~y~tem. In fact, ~ cert~n proport~on of the ~atty ;~
.,. ~':
' :. , .~.'.. .:`':
- lQ o 2 ~ 4 9 ~
ac~ ean ba replacs~ by any carbo~yl term~nat~
molecula.
Althoug~ ~r~nohe~ ~omple~ carbohy~rates ~ro nece~sary ~o~ p~ctic~ o~ ~he ~n~ent~on, ~om~ o~ ~ -5 ~hese branchea carhohy~rate ~ractions ~an be repl~ce~
by l~near ca~bohy~rate~ 8uch a~ ~llulo~. Th~
a~d~t~on of the~s l~ne~r c~rbohy~r~tes sppe~r~ to improYe tha ~bsorçt~on eap~bll~ty of the ~y~te~
~ct~n~ syner~st~c~lly with the other component~O ~: ;
10 Other l~ea~ c~rbohy~r~tes wh~ch ha~ bee~ shown to ~-~
be e~fect~e inclu~e ~arbohyarate~ w~th terminal glucoron~c aci~ ~uch a~ algin~ aci~, gum santhan ~n~
gum karaya. Non-cross-linkable ~oluble c~rbo~yli~ :
acida do not Dppear to work. . . ~
;,.. ' ''"'' . .'' ffrhe following E~amples will m~re clearly esplain the proceBures sn~ processes of the present invention.
E~amPle 1, ..?~
Th~'s Esample ~hows the flui~ uptake of .
20 saline for ~ compos~tion o~ the ~nvention w~th low --l~pin~carbohydrate rat~o un~er pressur~ eon~ition~
~esigne~ for testing polyacryl~te ~uperabsorber~
Approsim~tely 0.05 9 (0.2 mmol) o p~lmitic ac~ W~8 blende~ w~th 0.5 9 carbo~ymethyl~ellulo~e an~ 0.02 9 (0.14 mmol) bor~te-~t~b~ ze~ ~ihydro~y ~lu~lnum~
~cetate an~ 1.5 g og cellulose f~ber,. U en~ing too~
pl~ce ~t roo,m temper~ture by mi~ing the materi~
togetber until they were uniformlr blen~e~. Th~
material~,~, wer~ then ~ille~ into 500 micron p~rtioles.
: ~.. - ..-., . . .; ~, ..
. ~ .. - . - .. .. .
.. -. ~,. . ..
11 - 2 ~ ~ 9 ~
Sn a paralleI e~per~me~t9 s ~igh lip~L~/carbohy~rate materi~ m~ n~l te~ted un~or ths ~ame con~t~on2. Th~s hlgh r~t~o mat~ri~
made by blen~ing 1 g of ~s~m~tic aci~ with 1 9 o ~:
5 carbo~ymethylcellulo~e ~nd 0~04 g o the borate-sta~ Lze~ ~ihydro~y ~lumiLnu~ ac~t~t~
comple~. ~mall portiLon~ o~ th~ sampl~ ~ppro~ma~ly 0.1 9) were ~lende~ wlth 0.5 9 o~ cellulo~e ib~r.
~he two ~ample~ WBr9 te6te~ un~er t~e ~em~
10 procedure, ~ ~a~ polyacrylate i~upera~or~er. ~he ~est proceaure hy~ra~e~ the mater~al~ by eap~lla~y action with 0.15 M NaCl un~er ~ppl~ea loa~ of 0.22 lbs.~n2 for s~s~y m~nutes a~ room tempera~ure. The . : .
amount o ~lui~ ta~e up was then determlne~
15 gravimetrically. ~he tat~ shown ln all the lrDbl2s of ;~
E~ample~ ~how the amount o ~lula uptake for the :
synthet~c 6ponge, determine~ ~y corre~t~ng ~or the amount of flu~fl taken up ~y the cellulose ~o~e which was determine~ ~eparately. ;~
TABLE~
SYStem FlYid UDt ak~ ~mL~Q~ *
L~w ~ipi~Carbohydrate 37~3 ;
~igh Lipia~C~rbohy~r~te 21.1 .~
8up~r~b~orb~ 30O4 .. s ~able 1 ~hows that the ~lu~a upt~ke for the low l~pi~/csrbohyarate r~tio, ~n ml of l~qu~g of ~.~.
~b~orber, 1~ he~ th-- the uDer~bsorber ~hile ~
- 12 - 2 ~ ~ 9 ~
, . ., -lower ~mount, but ~tlll ~ni~unt~ 18 ~bsorbe~ by the hi~h lipid~carbohydrat~ rat~o ma~er~alO ~h~
shows that ~ ~lmpl~ mo~if~cat~on of riDt~o~, ~slng ' e~actly the same mater~31~, ~an le~ ~to ~ control ~n -~
s the amount of llqui~ tJ~en up ~y the l~el. .. ~ -E~ampXe ~ thi~ Esampls, ~ ~ere~t te~ w~ u~
to ~etesmin~ ~lui~ ~etention by two diferent ~els o~
the in~ention ~na a poly~cryl~t~ ~uperabsorberO ~he 10 ,fi~st ~ low lipi~carbohy~r~te rat~o gel, w~
maae by blen~ing 0.05 9 palmit~ ac~ w~th 0.5 g carbo~ymethylcellulose dnd 0.02 9 of the borate-stabilized ~ihy~rosy aluminum acetate .
comple2. Appro~imat~ly 0.3 g of th~s misture W25 then blended with 1.5 ~ of cellulose ~iber.
..'.: ':.' ~, ' ;
The second gel o~ the ~n~ention w~s made by blending ~.0 9 of palm~tic aei~ w~th 1.0 9 of carbo~ymethylcellulose ~n~ 0.04 9 of the ;~
borate-~tabilize~ dihydrosy aluminum hcetate comple~. Again, 0.3 9 of ~h~ mi~ure ~A~ blen~
with 0.5 0 o~ cellulo~ flber.
Samples o~ each of the two ~ompos~tio~s ~f the lnventlon ~n~ a superabsQrber ~0.3 ~ e~ch) were ~ n, ~eale~ ~n tea b~g~ ~n~ lmmer~ ln 0.1~ ~ ~ali~Q for.'.
thirty m~nute at room temper~ture. Aft~r remov~
from the ~sl~ne, th~ tea ~gs wer~ centr~fuge~ at'',.,t~.,~'."~,,''',.',''~, 300 X q for thirty minute8 ~n~ th~ amou~t of saline ret~ine~ w~th~n th~ m~t~r~al wa~ ~eter~ned grav~metrically- A~ain, th~re wa~ a corre~tion ~ade.,,,",~,,"!,, ,''''~''.','.','',"~"'"".''''`'~
':' ';.
''. '` ` '` - ' ''.`~'~' ~ ', 2~490~
for th~ e~ces~ cellulo~. Tabl0 2 ~how~ the re~ult~
of this test~n~
5 ~o~ ~pl~Carbohy~r~o 43.0 High ~ipi~Carbohy~r~t~ 21.1 :
Superabsorber 36 . 5 As is clear, the low l~p~carbohy~r~
ratio mater~al ha~ a greater flui~ retent~on than ~he 10 superabsorber while the h~h l~pi~carbohy~rate ratio material ha~ a lower retention.
.,: ~ ,. , E~ample 3.
In th~ ser~es of esperiments~ the retention of particulate materi~l by the gels of the ~nvent~on ~.-15 were teste~. In each esperiment, 1.0 g of palmitic .. ~
aci~ was uniformly ~len~e~ w~th 1.0 9 o~ m -., carbosymethylcellulo~e an~ 0.04 9 of the .-.
borate-~tabili~e~ dihydro~y ~lumi~um acet~te comples, making ~ high r~t~o ~el. About 0.5 9 o the m~ture .
20 was hydr~te~ w~th 25 ml of the te~t ~u~pensio~. In the ~r~t ts~t, the hy~ration mater~al w~
~u~pen~o~ of huma~ ~e~ cells ~n 0.15 ~ ~line. Tbe .. -~
gelat~on occurre~ with~n t~rty m~nuto~O Ater two hou~, the re~ult~ng ~el W98 ~ent~ifuqally w~she~
~th ~e volumes ~ 20% ~e~tran (140,000 ~ol. Wt.) ~issol~e~ ~n 0.15 ~ sal~ne. Each wash ha~ the ~mple .. .
cent~ifuge~ for th~rty m~nutes at 3,000 ~pm in ~
- lq - 2 0 4 ~ 0 5 5 , . " ,; ~ . . ~ . -Be~kman centrlfuge. The re~ cell-containing gel :~
contracte~ an~ 10ate~ t9 the top hDlf o~ th~
centrifuge tube while there wa8 ~ubstantially no ' ~`
release o~ red cells. If the cell~ ha~ been free, 5 they would pellet ~t the bottom of the centrifuq~
tu~ h~ s~ows the ~etent~on ~4 the partlculag~
matter, in part~uldr erythrocytes, by the 9~1 of the ~nven~on. O~r 99~ o ~he cell~ wero cont~e~
within the gel, as ~eterm~ne~
10 6pectrophot~metr~cally. Th~ was true ~or re~ cell ., suspension o~ 2.5-12.5 t~me~ the misture ~mount ,u~e~. In a ~im~l~r e~per~men~ with heparin-tre~tea whole blood, the gel was ~ble to absor~ 20 times it~
weight with ~im~lar retention characterist~cs. -~
Similar experiments were carrie~ out i.
replacing the re~ cell suspension with a solution of human hemoglobin ~n normal ~al~ne. Gelation lea~ to complete incorporation o~ the hemoglobin ~olution. ~ ~'`''"'`?''`'''''`'' After standing for two days, the ~el wa~ r~
centrifugally washed ~i~e t~mes at the 3,000 rpm for thirty minutes in the ~ec~man centrifuge ~n a de~tran -~
gradient. Only traces of hemo~lobin were obser~e~
released into the de~tran barrier while substantially all of the rest of the hemoglobin was retaine~ within ~ - :
the gel. By spectrophoto~raphic~ measurement, about 88~ o the hemoglQbin wa~ retaine~
A further experiment wa~ cdrr~ed out u~ng ;~
the ~me ~roce~ure but repl~cin9 the re~ ~ell .~
~uspenslon with a ~uspension of p~uc~lamellar lipi~ ~t ~esicles, ma~e using the mater~al~ ~n~ proce~ures descri~zed in co pendi~ C~adian Patent Applicaticsn Serial -, -~. . . ~ . .
,' ~, .
204~055 ~o.56l,290, with an ~ver3g2 ~ameter o ~bout 0.5 ~. These Yesi~les ha~ an oil-bas~ center with the liposoluble ~e~ ~ye ~Oil Re~ O~ ~ncorporated ~n : :
- the oil ~s ~ marke~. ~elat~on ~n the presence of the 5 vesi~le~ lea~ to eompl~e ~ncorpsrat~on of th~
ves~cles. Over ~wo ~ay3, five cen~riu~al wash~n~
of th~ qel~ showea a gr~u~l r~l~a~ of th~
~ye-containing ~esicles without fr~ct~on~t~n os ~reakao~n of the ~eslcl~ hls ~how~ tbat th~ typ@
0 of gel coul~ be use~ susta~ne~ relea~e ~ehicl~
or th~t ~t can ~ct ~ ~ protecti~e b~rrier to large .
part~cle~. Other paucildmellar l~pl~ ves~cl~s h~vo also been encapsulatea. ~ ~-E~amPle 4.
In thls e~perlment, the same blgh '',',''.,'!' lipl~carbohy~ra~e ratio ~el ~s used ~n E~ample 3 was use~ to ~how the effect~ of i~otonic changes and .
permeab~llty o ~mall particle~. The gel wa~
. manufactured as ~escribed above an~ wa~ hydr~te~ with ~ m~ ~.
20 25 ml of plain water. The 9¢l was then ~oake~
alternately ~n sever~l çhanges o~ 0.5 ml o 1 ~ucrose then water~ ..
The s~fts from the hypertonic to hypotonic me~ium an~ back cau~ed only tr2nsient ch~nge~ in gel ~ i ~s ~ol~me ~t the t~me of the change o~ the medium, in~icat~ng ~ree permea~ ty o~ the gel~ to ~ucro~e. ..
~herefore, it i~ e~pecte~ that the ~el~ woul~ al~o be ;~
permeable to molecule~ of ~pproYirn~tely the s~me ~ze ~s ~ucro~e~nclu~ing many ~rug6. Accor~ngly, the gel~ ~oul~ be u~e~ as a woun~ ban~age which ~llow~
x:
2 ~ ~L 9 pa~age o~ a arug throug~ ~h~ ~1 to wher~ ~t l~
necessary but prot~ct~on 3g~in~t l~r~
partlculste-typ~ matto~ 6uch a~ b~cteri~l cell~. ln contrast, esQo~ure o gel~ ~o a 20~ ~olution o h~gh ;~
5 molecular weigh~ De~tran (1~0,000 Mol. Wt.~ eau~e~
revers~ble 6hrinkln~, ~ugge~t~ng t~at thes~ molecul~
~o not penetr3t~ the gel~ an~ c~us~ o~rnoti~ 108~ 0 water f~om the gel~
Ex~mPle 5 10 , In ~hi~ Esampl~, ~ functional atty a~
undecylenic aci~, ~5 usea ~n place of a ~tanaar~
fatty AC~ in form~ng the gel of the invent~on. Th~s functional fatty aci~ i8 a pot~nt fungi~l~e.
, :, . i,. ,,.,., ,.i "~ ,~
To make thi~ gel, 1~0 g o undecylenic aci~
15 was un~formly blen~e~ with 1.0 g of ..
carbo~ymethylcellulose ana 0~036 9 o~ th~
borate~tabilize~ ~luminum ~cetate comples. The `~
~ample wa~ ~ydrated by mi~ing 25 ~1 of water wlth 0.5 .
g of the misture. Hy~r~t~on w~ ~ompl~te with~n 20 thirty minute~, ~orm~ng ~ sot gal. The gel ~lowly . .
release~ the undecylen~c a~i~ over t~me. A mo~e .~`
rig~d qel can be ~orme~ by us~n~ blen~ of th~
unct~onal fatty ~cia w~th p~lmitic or tearlc ~c~d~
~he ~o~t ~el ~ slightly turb~ pre~a~
e~ly, nd ~tick~ to the ~k~n. Bec~u~e o~ th~4, a ban~ge or wouna coverin~ o the un~ecyle~ic aci~ gel ~oul~ be 3ppli~ to th~ n, ~ro~ ng ~un~ l ~ r~i benef~t~ a~ ~ell a~ prote~t~on ~a~nst part~ul2te bacter~a ~n~ ~n~eet~on. .
' '`,'' "`.' `:
. ~ . . -...
- 17 - 2 ~ ~ ~ V~ 3 ~ n thi~ Esampl~, two ~ffero~t me'csllo-org~nic complea:e~ useul ~ cro~-linl~
agentæ with~ln ~he BCOpl~ O~ the ~nv~nt~on w~r~ m0~0.
5 The f~r~t, a palm~tatQ-~age~ alum~num metallo-org~n~C
GOmple~ (~?X-I.), ~8 maa~ ~ m~inSJ 0.6A g palm~t~
aci~ ~0.25 mmol~ olve~ a 5 lol o~ ~t~anol w~h 1.4 9 ~10 nunol) ~lum~num morloacetn~e ~t~b~ e~ wlth borlc ac~ ln S ml o wat~r. ~n op~leæoeslt Isolut~
10 resulte~, Th~ opalesc:ent ~uspens~on c:an be m~e with carbo:~ymethylc:ellulo~e (C~C~, with or w~thQut : ;~
cellulose ~ber, to prl~vi~e a cross-linkinq agent - . ~ `
impregnate~ ~n the CMC. Th~ æame procedure may be use~ w~th equ~l molar amounts o~ laur~c or ~eari~ :
15 aci~ to form ~im~lar comple~es.
. .~,. .: ;." ,", ~o fo.m ~n benzoate~baseD aluminum .
metallo-~rganic comple~ ~BX-~), a more ~llute ~olution i~ use~. Spe~l~ically, O.Cl g of benzo~c acid (0.50 mmo}) was dissolvea in 7.5 ml of ethanol.
20 The benzoi~ ~ia ~olu~on was ~i~ed with a solution ~ontain~ng 1.4 9 ~10 mmol) ~luminum monoacet~te .
stabilized with boric aci~ ln 7.5 ~1 o water.
Again, ~n op~lescent ~u~pens~on resulte~. ~his cros~-linking agent c~n ~l~o be impregnate~ ~nto or 25 der~v~t~zed with CM~ or cellulo~e f~ber. ::
~. ., .. ~..~ ., In th~s E-~mple, the or~no-~et~ e -cro~sl~n~in~ ag2nt6 orme~ ~n E~mple C w~r~ u~e~ to form the sponge-like ~ater~al o~ the ~nvention. In . ' ' . ' .' ~' '' ~, , ~....
', '`~', ' ~`.
- 18 - 20~0~
the irst ~uch test, o.a 9 0~ c~rbo~ymeth~lcelluloise (CMC), 0.04 9 of palmit~ ~ci~ ~P~?, 0.2 ml of the benzoate-based alumi~num metallo-orqanic cross-linking agent (BX-~ ma~e in E~ampla 6, an~ 50 ml of 0.15 W
5 salSne wer~ b~ende~. ~8 one o~ the two variat~orls of th~ e~periment, 0~6 g of cellulo~e w~ ~lso use~O
, ~, ." ",',', ~5""'~
The mi~ture wa~ hy~rate~ by th~ty ~econ~s o~ ma~net~ irring ~n~ the st~ll liQui~ m xture wa~
transferre~ to 50 ~1 cen~r~uge tubes ~n~ centriugea 10 at 300 X ~ fos thirty minutes. ~t the en~ o~ th~
thirty minute centrifuge per~o~, any free flu~ wa~
collecte~ by filtration throuQh a 150 ~ pore s~ze : : .
nylon mesh. ~iqhly cohes~ve, firm gets form within the thirty minute centrifuqation. .,.
Retention of ligui~ was me~sured at least :.
twenty-four hours ~ter formation. Gel piece aliquots were cut out, weighed, ~n~ place~ in a centrifuge tube: insert, close~ its bottom by perforated ~creen ~upporting D piece o non-woYen -~
20 tea-ba~ paper. After centrifuyat~o~ at 300 X ~ for .
thirty minute~, the am~unt o l~Qui~ release~ from `
the qel was determined grav~metr~cally. TabIe 3 ~hows the results of this testing ~or the material of . ~
the ~n~ent~ on (CMC~PA~BX-L), with or w~thout .`:
25 cell~lo6e. ~he ~ame test was carrle~ out usinq a ~imil~r amount o~ ~anwet*~MlS~0 U.S.~ ~ p~ly~cryl~c super~bsor~er, ~s ~ control. ~11 v~lue~ w~th ~ellulose ars correctea to non-cellulo~ ~cti~tie~
~n thi~ an~ the ~ollow~ E~ample6. ;
*Trade Mark -: - . .-:. . .
''' `''''~''~''.`'.
2 ~ ~ 9 ~
CMC~Palmitate~Ben~sa~e X~ 162 ~ 10 .. `~
~llulo~ 201 ~
5 Polyacryli~ ~uper~bso~bor C0 *
~Ce~lulos~ 70 ~
.... " .
A~ ca~ een ~rom the re~ult~ of ~abl~ 3, .
~he compos,~t~on o~ ~hs l~vention, eithe~ ~ith o~
,without cellulose, clearly:~s ~uper~or to the : ,".. ,.. ,,:!j",~.,',",.,", 10 polyacryli~ superab~orber~ in ~erms of retention of ..
0.15 N saline. ~`
.,,. ~ .,.~ ,....
The i~entic~l esperiment WDS performe~ us~ng .
a compositlon o the ~nvention which had the palmitate-base~ cross-linking agent ~PX-~) in plwe ?:
of the benzoate-ba~e~ cros~-llnking 2gent (~X~
Table ~ shows the result~, of this esperiment, nqain .`~
~ompare~ to the ~uper~bsorber re~ult~
!, ~
i' .; '~,. !, 20 CMC~Palmit~te~Palm~t~ X-lin~ 207 ICellulo~ 205 : . Poly~r~lic ~uper~b~or~er 60 ~ ~Cellulo~e 70 ,," . ~j,, "
- 20 - 2 a ~ 9 ~
In ~his E~ampl~, ~ 20~ whoie ~loo~ colut~on was teste~ fnr absgrpt~on by a compo~ition of th0 ~nY~nt~on made w~th th~ benzoate-base~ crosg~ ing : -sagent (BX-~) of ~sampl~ 6. Th~ compo~tion wa m~e by mising 0.2 g o~ carbo~ymethylcellulo~o, 0.04 9 o~
palm~t~ , 50 ml o~20~ whol~ bloo~ .15 ~
sallne ~n~ 1 ml of the crg~ nkin~ ~entO hg~n, tbe mater~al w~ ~este~ ~th An~ withou~ 0.6 ~ ~ ; W -c~llulo~2. After hy~r~tion, the ~tlll-ligu~ ml~
~ivide~ ~nto to ~wo 25 ml port~on~, these were -~ - r.
tran~ferre~ to 50 ml centri~uge tu~e~, and ~elation ` .
was allowe~ to proceed under ~entr~fugat~on at 300 X
g ~aver2ge 4800 lbs.~in2) ~or thirty m~nute3. At the 15 end of the centriugation, any free 1u~d was collecte~ by filtr~t~on though 150 ~ pore ~i~e nylon .~
mesh. Ta~le 5 ~hows the result~ o~ th~ te~t. The . `-:.. `
value without the cellulose ~s equ~valent to ~n .:
absorption of 3~ ml of whole blooa, while the .,~
20 cellulose aaded value i5 even higher.
' ~ :'.' '.
CMC~Palmit~te~enzoate X-l~nk 175 ~ 1 ~Cellulo~ 223 ~
. ; - ~
25 E~amPle 9.
In thlE E~ample, un~ecylen~c acl~
~ncorporated ~nto ~ gel ~ontain~ng the benzo~te-ba~e~
. ,-; ~.:
.~ .
- 21 2 ~ ll 9 ~ ~ 3 ~
æluminu~ metallo-org~n~ c~mple~ of E~amplQ 6.
~ppros~mately 0.5 ml o the cross-link~ng compl~ was combine~ with 0.5 ml c~rboxymethylcellulo~e an~ 0.5 g of undecy~enic ~ci~. The mater~al was ~ydrate~ w~th S 70 ~1 wlth ~elon~ze~ w~ter. A high cohe~ve ~ut ~:~
mobile gel forme~ with~n thir~y m~nute~. There W8~
no relea~e of ~at~r o~er a perio~ of mc,~ th~n thr@~ ~ -hour~ an~ ther~ wa~ no separat~on o ree un~e~ylen~
~c~
lo The 6~me ~pproach ~oul~ b~ u~ea to .
~corporate a ~ar~e~y o~ carboYyl termin~l ~unct~onal molecules such as prostaglana~ns, prsstacycl~ns, . ;~
thrombosanes ~n~ thei~ precursors such as arach~onic .
acid. In addition, certain antibiotics ~uch as 15 oYytetracyline can be use~ in place of some or all oE ... ~.
the cross-linking agents.
.: . ,,. :-.. ..
Other materials which coul~ be use~ to replace part the fatty ~ci~ inclu~e carbosyl~ acids, carbo~ylic pepti~es, nonionic surfactants, an~
20 ~teroifls such as cholesterol or hydrocortisone. :~ ~
Selection o~ proper ~ci~ic const~tuents can mod1y ~.:;~ ` .
gel propert~es. ~he Eiteroi~ can ~e present ~n the system up to at le~st 10~ o the atty ac~ w~thout d~turb~ng the gel. ~herefore, these gels coula be 25 u~ed a~ a ~el~ry 5y8tem5 ~or a va~ety o molecul~
u~h as i~tero~
'"~` ''' '" ' In a~it~on, ~ hown pre~iously, lipi~
vesicles can be lncorp~rate~ ~nto the gels a~
p~rt~cul~e ~att~. 8~nc~ these l~p~ veslcl~ c~n 30 ~l~o be ~es~ne~ to carry ~ v~r~ety of materl~li6i . . ~. .
: ~
- 22 - 2 ~ 4 9 ~
wh~ch ~oul~ not othe~w~se bQ c~rr~ n the woun~ patc:h c~ other ~:overlng mad6~ o~ th0 g~l w~th ..
the ~res~cles diispersed. there~n coul~ be used to ~pply ~rugs on a t~me-releasea basi~i to a i~;electel~ ~1t~. -Those 6k~ d ~n ~che art wl~l bo ~ to ~eterm~ne other mod~f~ca~cio~i of t~e ~a~empla~y proceâures an~ mater~al~. ~u~h ot~e~ mo~~t~on~
~re w~t~ tbe scope of the o~10w~n~ cl~m~
Wh~t ~s ~ me~
.`.,~ . ,,' ~' ,.
,~ .. ., ~ .
., ~, :: ,'',' ,'' ~: .
:
~ ~' -"`. .''
- 20g~05~ -ma~mally at 0% ~ ne while u~n~ ~nd most ~o~y ~lu~ ar~ ~bout 0.~5 ~ ~alino. ~ ~
....
Mater~als wh~ch ~bsorb ligul~ ~n~ a~o bio~egradable such ~ ~hose o~ th@ present ~nventio~
5 have other possible uses as well. ~he~ entrapment o part~cles, ~nclu~lng macromoleeule~ ~uc~
hemoglobln and c~ uch a~ orythroc~te~
parti~ul~rly ~mportank ~o~ ~eminine ~pkin~ ~nd -~
c~m~lar psoducts. ~uperabsoxbe~ ba~o not ma~e ~
lO 9reat ~ent ~n this f~el~ even th~ugh tbey have the hecessary liqui~ absorpt~on because they cannot entrap lsrge p3rticulates.
Another possible use for a biodeqradable ~;~
material which will entrDp ligui~ an~/or particles is as a sustaine~ release vehicle. In certDin instances, the molecule~ to be ~elivered c~n be part '~
of the structural materi~l of the sp~nge itself. .
Nost mater~als which are presently ~e~ng teste~ as :~
sustained release vehicles, e.g., microcapsules, liposomes an~ relate~ cap~ular type ~ro~u~t~, have substanti~l costs an~ tlme ~5~0ci~te~ with their manuacture. The ~bil~ty to make ~ pro~u~t in fi~
npply ~t to ~ given area, ~n~ then let ~t ~egr~e under or~inary conditions to release entrapped m~terial, woul~ solve many problems.
A ~urthe~ u~e o~ a gel wh~eh entraps l~qui~s ~n~ part~cles ~s as ~ ~ologic~l protectiY~ h~rrier.
For esample, a gel wh~c~ ~ntr3ps bacter~a ~s ~t ~s hy~rate~, or provents the~r pass~ge o~c~ ~or~ea, c~n 3~ be use~ ns a wouna ~ressing, protect~ng the woun~
~: , '-".`' . .
' -2 ~ ~ 9 ~
~rom bDcteria while ollowin~ ~r flo~ ~n~or fre~
10w o~ liquid to th~ ~n~u~y. A fu~ther U8e ~ ~n a ~iaper wher~ coli~orm ~acteria can ~reakdown urea in -~
ur~ne to ammon~, chang~ng tha pH ~n~ promotinq s ~i~per ra~
Accor~n~ly, 8~ ob~e~t o~ ~hle ~nvent~on to provid2 ~ biodegra~ble mater~l that has high uptak~ fo~ wator ~n~ ~AllnQ. .
~ r~other ob~t of t~e inverlt~o~ to lo,prov~e ~ b~o~egradable carr~er or ~ust~rJe~ rele~se ~el~very system for ~rugs ana other moleculeE. . -:
A further ob~ect of the invent~o~ is to:
provi~e a material and metho~ for entrapment of part~culates such as erythrocytes an~ proteln 15 molecules ~uch as hemoglobin.
A st~ll further object o~ the ~nvention i~
to provide ~ proteetive barrier wh~ch prevent~ the passage o p~rticles ~uch as b~cter~a or ~-macromolecules, eOg., for use as ~ woun~ bandage. r,~
These tn~ other object~ ~n~ feature~ o~ the in~ention w~ll be apparent ~rom the ~ollow~ng ~escription.
~umm3rY o~ the In~n~Qn The present ~n~ention ~e2~ure6 a ~o~po8ition 25 of matter which ~Ct~ ~ a ~ynthetic ~ponge a~ well ~s metho~s ~f ~b~or~ing ~gueou~ or 5alin~ ~olut~ons.
-::.. :~.:~.,:--:, .: ~, _ 5 _ 2 3 ~ 9 ~
, .
The ~nvent~on ~urth~r featur~ metho~ o gntr~pp~ngparticle~ ~n a 9~1~ Th~ gel-l~ke compo~tion of matter ~an ba u~e~ a~ a protect~ve barrier an~ ~ a susta~ned release ~eh~cle which release~ entrappe~
5 particles or molecul~ ~uch ~ ugs o~er t~
~ n br~e, ~ sompos~tlo~ of m~ltter h~ bee~
aevelope~ wh~eh DCt~l 19S a 6ynthetlG spon~e wher~
allowe~ to hy~rato. ~ h~gh molecul~r w~ght, e~mplos carbo~ydrate w~th mult~ple anion-terminat~ branche~
lo an~ a ~ross-l~n~g agent are blen~ed ~n~er ~substant~ally anhy~rous conait~ons, preferably w1th a carbo~ylic ac~d with a substantial hy~rophobi~
region. Preferre~ carboxyl~c acids with su~s~antial hy~rophobic regio~ Are ~atty Dcids ~electea rom a :~
group consist~ng of lauric ac~d, palmitic 3cid, oleic acia, stear~c acid, benzoic ac~, or mi~tures thereof. A substant~al hydrophobic region me~n~ ana -~
implies a region with ~ substantial hy~rocarbon cha~n or ring ~tructure. Preferre~ br~nch comple~
carbohy~r~tes inclu~e carbosymethylcellulose, ~n~
chemical ~nalogues thereofO ~inear comple~
carbohydrates such as Gellulose, gum santhan~ ~um -~
kar~ya, or algln~c ~ci~ m~y ~l~o be inclu~e~
Once the component~ ~re intimately blen~e~, :
e.g., m~lle~ to~ethe~, the component~ o the mi~ture can be hy~rate~ ~n~ ~ro~-linke~ su~t~nt~lly ~multaneously when ~n the pres2nc~ o~ tha hy~r~tin~
: ~olution. Any o the component~ m~y be premise~
together or impregn~te~ wlth one another. In .
~it~on, the other re~Gtant~ m~y ~e ~erivatl~e~ W~t~
~he comples or l~near c~rbohydr~t-s us~ng an :
`~
20~0~
~ ~-isopropo~e or other ~imilar reac~on. ~,ome or all :7 o~ t~e ~atty aci~ can be repl~ced wit~ a ~~nction~
~atty aci~ or a long-ch2in car~o~yli~ ac~. A~
use~ herein, the ter~ ~func~lonal ~atty ~c~ m~an~
S ~nclu~es and ~efines a mo~ecule having a term~n~l carbo~yli~ ac~, a substant~al al~phat$c portlon, ~n~
5 b~olog~cal funct~on other than ~ ~ break~own pro~uct or precur~or in ~h~ ~oOa ~ha~a. Funot~on~
fatty ac~ nclu~e ~Ci~8 such as undecylen~c ~c~
10 arachi~onic a~i~, p~ostaglana~ns, pros~cycl~ns, thrombo~anes, an~ their ~er~ati~e~, chemic~
analogue~ ana precursor~
As noted, the composit~on of matter of the invention ~ncludes ~ cross-linking ~gent as ~n : :
15 essent~al component. The preferred ~ross-link~ng agents ore~metallo-organic compoun~s o mult~valent metal~, Organ~c cross-l~nk~ng agent~ ~uch as .:. -~ .
ch~tosan, ~oly-Cup* cbymene, an~ ~eff~mlne m~y be us,ed, bu~ are les~ eff~cient than the metal~o-or~ni~
20 comple~e~. O~ytetracyl~n~ ~ a h~ghly efect~ve ~ -~
cros~-lin~ing 2gent but ~as l~mite~ ~pplic~t~on because of ~ts biological ~CtiY~ty. Althou~h .
bivalent molecules ~uch ~s cdlcium might be use~ in certain ~ir~umst~nce~, the multivalent metal~
25 ~valence 3 an~ o~er) sUch ~s Dluminum or chrom~um are ~:.
preerre~. For m~ny appllcations aluminum ~n the form ~f hydroxy-~lumlnum d~et~te, borate-stabll~zed dihy~ro~y-~luminum ~cet~t~ ~n~or ~lum~nu~
6ulfate~cit~te, m~y be ~at~5factory~ A mo~t ~ ~-30 preferre~ ~oss-linking ~gent pro~id~ng superior performance ~ ~n ~luminum metallo-~rgan~c comple~ of the hy~ro~y-aluminum/hy~rophob~c earbosylate form *Trade Mark : ~'`'`
- 7 - 2~9~5~
., ~uch as hy~ro~y-~umlnum ben~osto. Th~ ~yent ean a~t as both the hyarophoblc car~o~yl~c aci~ ~n~ the cross-linkin~ agent ~n ~ ~in~le moleclulo. O~her hydrophobic c~rbo~yli~ ~ci~ ~uch a~ ~ur~o, ~ 5 ~tearat~, oleate or benzo~te can ~l~o b~ use~ ~ the ,Yj metallo-orsanie eompl~
i The in~ent~on ~urther feature~ ~ metho~ o~
; absor~ing agueou~ or ~al~ne solut~on~ uslng tho ~ b~o~eyr~ble ~ynthetl~ ~ponge compo~it~on of th~
`~ 10 invent~on. ~he synthe~lc ~ponge compos~t~on 1~
pro~ed ~n a ~ubst~ntially unhyBr~te~ o~m, or .~ esample, by blen~ing the components togetber to obtAin particles of the ~esired size, an~ then the -~
solution i8 absorbe~ by contacting the solution w~th 15 the synthetic sponse composition. ~he ~ynthetic sponge composition hydrates to ~bsorb t~e solution an~ substantially simult~neously cross-llnks into a gel which bin~s tbe ~olution.
The same basic materi~l m~y be u~e~ to 20 encapsul~te part~cle~ ~n ~ 9el. The synthetic ~ponqe eomposition i8 prov~e~ ~n a ~ubstantially unby~rate~
form ~na a solut~on cont~ining ~he particles to be entrappe~ within the gel i~ mi2ed with the composition, The gel form~ by Gross-linking, 25 absorbing the ligui~ ~n~ entrapp~ng the part~cles ~: :
wit~n the qel. P~rt~cl~s ~h~ch can be 2ntrappe~ ~n th~s way ~nclu~e ma~rom~lecule~ os prot~ns ~uch hemoglo~in, bicter~a, os Gell6 ~ueh ~s erythrocyte~
-, :
3 ~ub~t~nti~lly the ~me ~ntrapment ~roce~ure 30 ~an be used to creato a ~u~t~ined rele~se vehlcl~
J
2 ~ 5 ~
For esample, ~el~ cros~ n~e~ by oxytetr~cycl~n~ c~ p;
b~ use~ a~ ~ ~u~t~ne~ rele~ ehicle ~or thl~
~rug. Many po~tl~tely ch~rge~ ~rugs can ~o hell~ ~n polydnioll~c gel8 ~or ~ust~ine~ releAse. By mo~i~ying 5 the r~t~o~ o~ the ~ferent ~omponent~, an~ ~elect~0 the ~pec~f~ materi~ls wh~ch mak~ up thle 9~1, th~
~tabillty, zbsorp~cion 9.~rel~, ~n~ irmnle~ o~ t~ g~
can be mo~ e~. ~o~ e~ mpl~, chanç~ th~ atty ~c~carbohy~rAt~ r~t~Lo can ~ramdtically c2 ~ng~ th0 10 absorption, ar~l~ ths ~ubsequent relea~o ~at~, o l~gu~ rom the gel. Further, ~he a~tion o~ ot~er materi~ls to the gel, ~.9., surfactant~ ~u~h ~8 -~
polyosyethylene fatty a~ ether~ or spacer~ such as `~
5ilic3 or clays, c~n ch~nge the properties of the 15 9el. This chdnse of properties ~s mor0 ~learly e~plaine~ ~n the de~cription ~n~ the E~amples. ;
. . .. .
.,-~ ~ . , -, ,, petailed Description o~ ~he I~ventiQn The hydrate~ gel descr~be~ here~n ~8 ~ormea by the ~multaneou~ hyar~t~on an~ cross-l~n~ng by 20 cross-linkin~ a~ent of polyan~onic c~rbohydr~te~
pre~erably together with hydrophobis car~o~yl~t~
In contrast to the polyacrylste ~uperabsorber~, whi~h necessarily form ~i~crete particles ~s ~o ~ov~lently c~oss-linked moleeules ~uch a~ cro~s-l~nke~
25 carbosymethylcellulose, gel~t~ns, an~ ~lgin~te~), the materi~l of the present ~nvent~on ~ ts ln uncro~-llnked form pr~or to hy~r~tlon. Upon '~
hy~r~tion, the m~terial gorms e~tena, w~ter-binB~ng network~ of b~o~e~r~fl~ble ~arbohy~rate ~olymer, 30 prefer~bly ~urther cro~ nked w~th est~n~
multll~mell~r ~hee~ o~ ~egr~bl~, an~onic llpl~
.,. ~ - ~ ,.,~
,; . ;.~:
9 - 2 ~ '1 9 ~
Macroscoplcally, th~ 9~1~ ar~ ~t~le ~nd ~an e~ten~ -~
se~er~l ~ent~me~er~ ~n ~ever~ re~t~ons upon hy~rat~on. Thes~ gel~ ~an al~o be ~orme~ ln o a - ~ariety o~ geome~rle~ 6uch ~ ro~5, ~i~;kst on~
5 ~la~s. The consist~ncy o~ the gel, ~n~ th~ ~mount of li~ui~ ab~srbe~, ~an be ~hanged by mo~fy~g tho in~t~al compos~tlon. ~n ~dit1on, a ~rt~ally hy~rate~ 9~1 ~an bg further ~y~r~tg~ at ~ l~ter t~m~
~y absorpt~on of more l~qu~
~he c~p~city for upt~ke o~ l~qu~ o the composft~ons of the prese~t ~n~ention ~urthermore depen~s on the ratio of ~ctiv~ ac~, e.g., lipi~s, to a~tive carbohydrate. At low l~pia/carbohyarate .: :~
ratios ton a weight ~as~s), e.~., a 0.1 - 0.2 rat~o, 15 h~gh flui~ absorptlon ~s observe~. ~n fact, ~s m~y be seen frDm the follow~ng E~amples, the uptake of ~ .
0.15 N saline ~s considerably greater than that of ~, the polya~ry~ate ~upera~sorberL. When the rat~o of fatty aci~ to carbohy~rate ~ much higher, ~.9., 20 appros~mately 1, the ~els ~o not a~sorb ~s much liqui~, give up ths l~qu~ easier, ~n~ ~ct a~ better del~very systems.
Funct~onal ~tty ~ci~ c~n be use~ to repla~e ~ome or ~11 o~ the fatty Doi~. Tho mD~or a~ant~ge o~ us1ng the~e ~unct~onal gatty ~c~
that a~ the gel~ ~ro ~egrD~e~, the unct~onal atty ac~ rele~se~. Th~ ~ct~ as a typ~ o Aeli~eIy ~ystem wh~ch c~n have ~ much hi~her ~oncentr~t~on o the materi~l to be ~ell~erea than ~oul~ b~ po~ le 3~ in another type o~ enc~psulat~on or entr~pment .
~y~tem. In fact, ~ cert~n proport~on of the ~atty ;~
.,. ~':
' :. , .~.'.. .:`':
- lQ o 2 ~ 4 9 ~
ac~ ean ba replacs~ by any carbo~yl term~nat~
molecula.
Althoug~ ~r~nohe~ ~omple~ carbohy~rates ~ro nece~sary ~o~ p~ctic~ o~ ~he ~n~ent~on, ~om~ o~ ~ -5 ~hese branchea carhohy~rate ~ractions ~an be repl~ce~
by l~near ca~bohy~rate~ 8uch a~ ~llulo~. Th~
a~d~t~on of the~s l~ne~r c~rbohy~r~tes sppe~r~ to improYe tha ~bsorçt~on eap~bll~ty of the ~y~te~
~ct~n~ syner~st~c~lly with the other component~O ~: ;
10 Other l~ea~ c~rbohy~r~tes wh~ch ha~ bee~ shown to ~-~
be e~fect~e inclu~e ~arbohyarate~ w~th terminal glucoron~c aci~ ~uch a~ algin~ aci~, gum santhan ~n~
gum karaya. Non-cross-linkable ~oluble c~rbo~yli~ :
acida do not Dppear to work. . . ~
;,.. ' ''"'' . .'' ffrhe following E~amples will m~re clearly esplain the proceBures sn~ processes of the present invention.
E~amPle 1, ..?~
Th~'s Esample ~hows the flui~ uptake of .
20 saline for ~ compos~tion o~ the ~nvention w~th low --l~pin~carbohydrate rat~o un~er pressur~ eon~ition~
~esigne~ for testing polyacryl~te ~uperabsorber~
Approsim~tely 0.05 9 (0.2 mmol) o p~lmitic ac~ W~8 blende~ w~th 0.5 9 carbo~ymethyl~ellulo~e an~ 0.02 9 (0.14 mmol) bor~te-~t~b~ ze~ ~ihydro~y ~lu~lnum~
~cetate an~ 1.5 g og cellulose f~ber,. U en~ing too~
pl~ce ~t roo,m temper~ture by mi~ing the materi~
togetber until they were uniformlr blen~e~. Th~
material~,~, wer~ then ~ille~ into 500 micron p~rtioles.
: ~.. - ..-., . . .; ~, ..
. ~ .. - . - .. .. .
.. -. ~,. . ..
11 - 2 ~ ~ 9 ~
Sn a paralleI e~per~me~t9 s ~igh lip~L~/carbohy~rate materi~ m~ n~l te~ted un~or ths ~ame con~t~on2. Th~s hlgh r~t~o mat~ri~
made by blen~ing 1 g of ~s~m~tic aci~ with 1 9 o ~:
5 carbo~ymethylcellulo~e ~nd 0~04 g o the borate-sta~ Lze~ ~ihydro~y ~lumiLnu~ ac~t~t~
comple~. ~mall portiLon~ o~ th~ sampl~ ~ppro~ma~ly 0.1 9) were ~lende~ wlth 0.5 9 o~ cellulo~e ib~r.
~he two ~ample~ WBr9 te6te~ un~er t~e ~em~
10 procedure, ~ ~a~ polyacrylate i~upera~or~er. ~he ~est proceaure hy~ra~e~ the mater~al~ by eap~lla~y action with 0.15 M NaCl un~er ~ppl~ea loa~ of 0.22 lbs.~n2 for s~s~y m~nutes a~ room tempera~ure. The . : .
amount o ~lui~ ta~e up was then determlne~
15 gravimetrically. ~he tat~ shown ln all the lrDbl2s of ;~
E~ample~ ~how the amount o ~lula uptake for the :
synthet~c 6ponge, determine~ ~y corre~t~ng ~or the amount of flu~fl taken up ~y the cellulose ~o~e which was determine~ ~eparately. ;~
TABLE~
SYStem FlYid UDt ak~ ~mL~Q~ *
L~w ~ipi~Carbohydrate 37~3 ;
~igh Lipia~C~rbohy~r~te 21.1 .~
8up~r~b~orb~ 30O4 .. s ~able 1 ~hows that the ~lu~a upt~ke for the low l~pi~/csrbohyarate r~tio, ~n ml of l~qu~g of ~.~.
~b~orber, 1~ he~ th-- the uDer~bsorber ~hile ~
- 12 - 2 ~ ~ 9 ~
, . ., -lower ~mount, but ~tlll ~ni~unt~ 18 ~bsorbe~ by the hi~h lipid~carbohydrat~ rat~o ma~er~alO ~h~
shows that ~ ~lmpl~ mo~if~cat~on of riDt~o~, ~slng ' e~actly the same mater~31~, ~an le~ ~to ~ control ~n -~
s the amount of llqui~ tJ~en up ~y the l~el. .. ~ -E~ampXe ~ thi~ Esampls, ~ ~ere~t te~ w~ u~
to ~etesmin~ ~lui~ ~etention by two diferent ~els o~
the in~ention ~na a poly~cryl~t~ ~uperabsorberO ~he 10 ,fi~st ~ low lipi~carbohy~r~te rat~o gel, w~
maae by blen~ing 0.05 9 palmit~ ac~ w~th 0.5 g carbo~ymethylcellulose dnd 0.02 9 of the borate-stabilized ~ihy~rosy aluminum acetate .
comple2. Appro~imat~ly 0.3 g of th~s misture W25 then blended with 1.5 ~ of cellulose ~iber.
..'.: ':.' ~, ' ;
The second gel o~ the ~n~ention w~s made by blending ~.0 9 of palm~tic aei~ w~th 1.0 9 of carbo~ymethylcellulose ~n~ 0.04 9 of the ;~
borate-~tabilize~ dihydrosy aluminum hcetate comple~. Again, 0.3 9 of ~h~ mi~ure ~A~ blen~
with 0.5 0 o~ cellulo~ flber.
Samples o~ each of the two ~ompos~tio~s ~f the lnventlon ~n~ a superabsQrber ~0.3 ~ e~ch) were ~ n, ~eale~ ~n tea b~g~ ~n~ lmmer~ ln 0.1~ ~ ~ali~Q for.'.
thirty m~nute at room temper~ture. Aft~r remov~
from the ~sl~ne, th~ tea ~gs wer~ centr~fuge~ at'',.,t~.,~'."~,,''',.',''~, 300 X q for thirty minute8 ~n~ th~ amou~t of saline ret~ine~ w~th~n th~ m~t~r~al wa~ ~eter~ned grav~metrically- A~ain, th~re wa~ a corre~tion ~ade.,,,",~,,"!,, ,''''~''.','.','',"~"'"".''''`'~
':' ';.
''. '` ` '` - ' ''.`~'~' ~ ', 2~490~
for th~ e~ces~ cellulo~. Tabl0 2 ~how~ the re~ult~
of this test~n~
5 ~o~ ~pl~Carbohy~r~o 43.0 High ~ipi~Carbohy~r~t~ 21.1 :
Superabsorber 36 . 5 As is clear, the low l~p~carbohy~r~
ratio mater~al ha~ a greater flui~ retent~on than ~he 10 superabsorber while the h~h l~pi~carbohy~rate ratio material ha~ a lower retention.
.,: ~ ,. , E~ample 3.
In th~ ser~es of esperiments~ the retention of particulate materi~l by the gels of the ~nvent~on ~.-15 were teste~. In each esperiment, 1.0 g of palmitic .. ~
aci~ was uniformly ~len~e~ w~th 1.0 9 o~ m -., carbosymethylcellulo~e an~ 0.04 9 of the .-.
borate-~tabili~e~ dihydro~y ~lumi~um acet~te comples, making ~ high r~t~o ~el. About 0.5 9 o the m~ture .
20 was hydr~te~ w~th 25 ml of the te~t ~u~pensio~. In the ~r~t ts~t, the hy~ration mater~al w~
~u~pen~o~ of huma~ ~e~ cells ~n 0.15 ~ ~line. Tbe .. -~
gelat~on occurre~ with~n t~rty m~nuto~O Ater two hou~, the re~ult~ng ~el W98 ~ent~ifuqally w~she~
~th ~e volumes ~ 20% ~e~tran (140,000 ~ol. Wt.) ~issol~e~ ~n 0.15 ~ sal~ne. Each wash ha~ the ~mple .. .
cent~ifuge~ for th~rty m~nutes at 3,000 ~pm in ~
- lq - 2 0 4 ~ 0 5 5 , . " ,; ~ . . ~ . -Be~kman centrlfuge. The re~ cell-containing gel :~
contracte~ an~ 10ate~ t9 the top hDlf o~ th~
centrifuge tube while there wa8 ~ubstantially no ' ~`
release o~ red cells. If the cell~ ha~ been free, 5 they would pellet ~t the bottom of the centrifuq~
tu~ h~ s~ows the ~etent~on ~4 the partlculag~
matter, in part~uldr erythrocytes, by the 9~1 of the ~nven~on. O~r 99~ o ~he cell~ wero cont~e~
within the gel, as ~eterm~ne~
10 6pectrophot~metr~cally. Th~ was true ~or re~ cell ., suspension o~ 2.5-12.5 t~me~ the misture ~mount ,u~e~. In a ~im~l~r e~per~men~ with heparin-tre~tea whole blood, the gel was ~ble to absor~ 20 times it~
weight with ~im~lar retention characterist~cs. -~
Similar experiments were carrie~ out i.
replacing the re~ cell suspension with a solution of human hemoglobin ~n normal ~al~ne. Gelation lea~ to complete incorporation o~ the hemoglobin ~olution. ~ ~'`''"'`?''`'''''`'' After standing for two days, the ~el wa~ r~
centrifugally washed ~i~e t~mes at the 3,000 rpm for thirty minutes in the ~ec~man centrifuge ~n a de~tran -~
gradient. Only traces of hemo~lobin were obser~e~
released into the de~tran barrier while substantially all of the rest of the hemoglobin was retaine~ within ~ - :
the gel. By spectrophoto~raphic~ measurement, about 88~ o the hemoglQbin wa~ retaine~
A further experiment wa~ cdrr~ed out u~ng ;~
the ~me ~roce~ure but repl~cin9 the re~ ~ell .~
~uspenslon with a ~uspension of p~uc~lamellar lipi~ ~t ~esicles, ma~e using the mater~al~ ~n~ proce~ures descri~zed in co pendi~ C~adian Patent Applicaticsn Serial -, -~. . . ~ . .
,' ~, .
204~055 ~o.56l,290, with an ~ver3g2 ~ameter o ~bout 0.5 ~. These Yesi~les ha~ an oil-bas~ center with the liposoluble ~e~ ~ye ~Oil Re~ O~ ~ncorporated ~n : :
- the oil ~s ~ marke~. ~elat~on ~n the presence of the 5 vesi~le~ lea~ to eompl~e ~ncorpsrat~on of th~
ves~cles. Over ~wo ~ay3, five cen~riu~al wash~n~
of th~ qel~ showea a gr~u~l r~l~a~ of th~
~ye-containing ~esicles without fr~ct~on~t~n os ~reakao~n of the ~eslcl~ hls ~how~ tbat th~ typ@
0 of gel coul~ be use~ susta~ne~ relea~e ~ehicl~
or th~t ~t can ~ct ~ ~ protecti~e b~rrier to large .
part~cle~. Other paucildmellar l~pl~ ves~cl~s h~vo also been encapsulatea. ~ ~-E~amPle 4.
In thls e~perlment, the same blgh '',',''.,'!' lipl~carbohy~ra~e ratio ~el ~s used ~n E~ample 3 was use~ to ~how the effect~ of i~otonic changes and .
permeab~llty o ~mall particle~. The gel wa~
. manufactured as ~escribed above an~ wa~ hydr~te~ with ~ m~ ~.
20 25 ml of plain water. The 9¢l was then ~oake~
alternately ~n sever~l çhanges o~ 0.5 ml o 1 ~ucrose then water~ ..
The s~fts from the hypertonic to hypotonic me~ium an~ back cau~ed only tr2nsient ch~nge~ in gel ~ i ~s ~ol~me ~t the t~me of the change o~ the medium, in~icat~ng ~ree permea~ ty o~ the gel~ to ~ucro~e. ..
~herefore, it i~ e~pecte~ that the ~el~ woul~ al~o be ;~
permeable to molecule~ of ~pproYirn~tely the s~me ~ze ~s ~ucro~e~nclu~ing many ~rug6. Accor~ngly, the gel~ ~oul~ be u~e~ as a woun~ ban~age which ~llow~
x:
2 ~ ~L 9 pa~age o~ a arug throug~ ~h~ ~1 to wher~ ~t l~
necessary but prot~ct~on 3g~in~t l~r~
partlculste-typ~ matto~ 6uch a~ b~cteri~l cell~. ln contrast, esQo~ure o gel~ ~o a 20~ ~olution o h~gh ;~
5 molecular weigh~ De~tran (1~0,000 Mol. Wt.~ eau~e~
revers~ble 6hrinkln~, ~ugge~t~ng t~at thes~ molecul~
~o not penetr3t~ the gel~ an~ c~us~ o~rnoti~ 108~ 0 water f~om the gel~
Ex~mPle 5 10 , In ~hi~ Esampl~, ~ functional atty a~
undecylenic aci~, ~5 usea ~n place of a ~tanaar~
fatty AC~ in form~ng the gel of the invent~on. Th~s functional fatty aci~ i8 a pot~nt fungi~l~e.
, :, . i,. ,,.,., ,.i "~ ,~
To make thi~ gel, 1~0 g o undecylenic aci~
15 was un~formly blen~e~ with 1.0 g of ..
carbo~ymethylcellulose ana 0~036 9 o~ th~
borate~tabilize~ ~luminum ~cetate comples. The `~
~ample wa~ ~ydrated by mi~ing 25 ~1 of water wlth 0.5 .
g of the misture. Hy~r~t~on w~ ~ompl~te with~n 20 thirty minute~, ~orm~ng ~ sot gal. The gel ~lowly . .
release~ the undecylen~c a~i~ over t~me. A mo~e .~`
rig~d qel can be ~orme~ by us~n~ blen~ of th~
unct~onal fatty ~cia w~th p~lmitic or tearlc ~c~d~
~he ~o~t ~el ~ slightly turb~ pre~a~
e~ly, nd ~tick~ to the ~k~n. Bec~u~e o~ th~4, a ban~ge or wouna coverin~ o the un~ecyle~ic aci~ gel ~oul~ be 3ppli~ to th~ n, ~ro~ ng ~un~ l ~ r~i benef~t~ a~ ~ell a~ prote~t~on ~a~nst part~ul2te bacter~a ~n~ ~n~eet~on. .
' '`,'' "`.' `:
. ~ . . -...
- 17 - 2 ~ ~ ~ V~ 3 ~ n thi~ Esampl~, two ~ffero~t me'csllo-org~nic complea:e~ useul ~ cro~-linl~
agentæ with~ln ~he BCOpl~ O~ the ~nv~nt~on w~r~ m0~0.
5 The f~r~t, a palm~tatQ-~age~ alum~num metallo-org~n~C
GOmple~ (~?X-I.), ~8 maa~ ~ m~inSJ 0.6A g palm~t~
aci~ ~0.25 mmol~ olve~ a 5 lol o~ ~t~anol w~h 1.4 9 ~10 nunol) ~lum~num morloacetn~e ~t~b~ e~ wlth borlc ac~ ln S ml o wat~r. ~n op~leæoeslt Isolut~
10 resulte~, Th~ opalesc:ent ~uspens~on c:an be m~e with carbo:~ymethylc:ellulo~e (C~C~, with or w~thQut : ;~
cellulose ~ber, to prl~vi~e a cross-linkinq agent - . ~ `
impregnate~ ~n the CMC. Th~ æame procedure may be use~ w~th equ~l molar amounts o~ laur~c or ~eari~ :
15 aci~ to form ~im~lar comple~es.
. .~,. .: ;." ,", ~o fo.m ~n benzoate~baseD aluminum .
metallo-~rganic comple~ ~BX-~), a more ~llute ~olution i~ use~. Spe~l~ically, O.Cl g of benzo~c acid (0.50 mmo}) was dissolvea in 7.5 ml of ethanol.
20 The benzoi~ ~ia ~olu~on was ~i~ed with a solution ~ontain~ng 1.4 9 ~10 mmol) ~luminum monoacet~te .
stabilized with boric aci~ ln 7.5 ~1 o water.
Again, ~n op~lescent ~u~pens~on resulte~. ~his cros~-linking agent c~n ~l~o be impregnate~ ~nto or 25 der~v~t~zed with CM~ or cellulo~e f~ber. ::
~. ., .. ~..~ ., In th~s E-~mple, the or~no-~et~ e -cro~sl~n~in~ ag2nt6 orme~ ~n E~mple C w~r~ u~e~ to form the sponge-like ~ater~al o~ the ~nvention. In . ' ' . ' .' ~' '' ~, , ~....
', '`~', ' ~`.
- 18 - 20~0~
the irst ~uch test, o.a 9 0~ c~rbo~ymeth~lcelluloise (CMC), 0.04 9 of palmit~ ~ci~ ~P~?, 0.2 ml of the benzoate-based alumi~num metallo-orqanic cross-linking agent (BX-~ ma~e in E~ampla 6, an~ 50 ml of 0.15 W
5 salSne wer~ b~ende~. ~8 one o~ the two variat~orls of th~ e~periment, 0~6 g of cellulo~e w~ ~lso use~O
, ~, ." ",',', ~5""'~
The mi~ture wa~ hy~rate~ by th~ty ~econ~s o~ ma~net~ irring ~n~ the st~ll liQui~ m xture wa~
transferre~ to 50 ~1 cen~r~uge tubes ~n~ centriugea 10 at 300 X ~ fos thirty minutes. ~t the en~ o~ th~
thirty minute centrifuge per~o~, any free flu~ wa~
collecte~ by filtration throuQh a 150 ~ pore s~ze : : .
nylon mesh. ~iqhly cohes~ve, firm gets form within the thirty minute centrifuqation. .,.
Retention of ligui~ was me~sured at least :.
twenty-four hours ~ter formation. Gel piece aliquots were cut out, weighed, ~n~ place~ in a centrifuge tube: insert, close~ its bottom by perforated ~creen ~upporting D piece o non-woYen -~
20 tea-ba~ paper. After centrifuyat~o~ at 300 X ~ for .
thirty minute~, the am~unt o l~Qui~ release~ from `
the qel was determined grav~metr~cally. TabIe 3 ~hows the results of this testing ~or the material of . ~
the ~n~ent~ on (CMC~PA~BX-L), with or w~thout .`:
25 cell~lo6e. ~he ~ame test was carrle~ out usinq a ~imil~r amount o~ ~anwet*~MlS~0 U.S.~ ~ p~ly~cryl~c super~bsor~er, ~s ~ control. ~11 v~lue~ w~th ~ellulose ars correctea to non-cellulo~ ~cti~tie~
~n thi~ an~ the ~ollow~ E~ample6. ;
*Trade Mark -: - . .-:. . .
''' `''''~''~''.`'.
2 ~ ~ 9 ~
CMC~Palmitate~Ben~sa~e X~ 162 ~ 10 .. `~
~llulo~ 201 ~
5 Polyacryli~ ~uper~bso~bor C0 *
~Ce~lulos~ 70 ~
.... " .
A~ ca~ een ~rom the re~ult~ of ~abl~ 3, .
~he compos,~t~on o~ ~hs l~vention, eithe~ ~ith o~
,without cellulose, clearly:~s ~uper~or to the : ,".. ,.. ,,:!j",~.,',",.,", 10 polyacryli~ superab~orber~ in ~erms of retention of ..
0.15 N saline. ~`
.,,. ~ .,.~ ,....
The i~entic~l esperiment WDS performe~ us~ng .
a compositlon o the ~nvention which had the palmitate-base~ cross-linking agent ~PX-~) in plwe ?:
of the benzoate-ba~e~ cros~-llnking 2gent (~X~
Table ~ shows the result~, of this esperiment, nqain .`~
~ompare~ to the ~uper~bsorber re~ult~
!, ~
i' .; '~,. !, 20 CMC~Palmit~te~Palm~t~ X-lin~ 207 ICellulo~ 205 : . Poly~r~lic ~uper~b~or~er 60 ~ ~Cellulo~e 70 ,," . ~j,, "
- 20 - 2 a ~ 9 ~
In ~his E~ampl~, ~ 20~ whoie ~loo~ colut~on was teste~ fnr absgrpt~on by a compo~ition of th0 ~nY~nt~on made w~th th~ benzoate-base~ crosg~ ing : -sagent (BX-~) of ~sampl~ 6. Th~ compo~tion wa m~e by mising 0.2 g o~ carbo~ymethylcellulo~o, 0.04 9 o~
palm~t~ , 50 ml o~20~ whol~ bloo~ .15 ~
sallne ~n~ 1 ml of the crg~ nkin~ ~entO hg~n, tbe mater~al w~ ~este~ ~th An~ withou~ 0.6 ~ ~ ; W -c~llulo~2. After hy~r~tion, the ~tlll-ligu~ ml~
~ivide~ ~nto to ~wo 25 ml port~on~, these were -~ - r.
tran~ferre~ to 50 ml centri~uge tu~e~, and ~elation ` .
was allowe~ to proceed under ~entr~fugat~on at 300 X
g ~aver2ge 4800 lbs.~in2) ~or thirty m~nute3. At the 15 end of the centriugation, any free 1u~d was collecte~ by filtr~t~on though 150 ~ pore ~i~e nylon .~
mesh. Ta~le 5 ~hows the result~ o~ th~ te~t. The . `-:.. `
value without the cellulose ~s equ~valent to ~n .:
absorption of 3~ ml of whole blooa, while the .,~
20 cellulose aaded value i5 even higher.
' ~ :'.' '.
CMC~Palmit~te~enzoate X-l~nk 175 ~ 1 ~Cellulo~ 223 ~
. ; - ~
25 E~amPle 9.
In thlE E~ample, un~ecylen~c acl~
~ncorporated ~nto ~ gel ~ontain~ng the benzo~te-ba~e~
. ,-; ~.:
.~ .
- 21 2 ~ ll 9 ~ ~ 3 ~
æluminu~ metallo-org~n~ c~mple~ of E~amplQ 6.
~ppros~mately 0.5 ml o the cross-link~ng compl~ was combine~ with 0.5 ml c~rboxymethylcellulo~e an~ 0.5 g of undecy~enic ~ci~. The mater~al was ~ydrate~ w~th S 70 ~1 wlth ~elon~ze~ w~ter. A high cohe~ve ~ut ~:~
mobile gel forme~ with~n thir~y m~nute~. There W8~
no relea~e of ~at~r o~er a perio~ of mc,~ th~n thr@~ ~ -hour~ an~ ther~ wa~ no separat~on o ree un~e~ylen~
~c~
lo The 6~me ~pproach ~oul~ b~ u~ea to .
~corporate a ~ar~e~y o~ carboYyl termin~l ~unct~onal molecules such as prostaglana~ns, prsstacycl~ns, . ;~
thrombosanes ~n~ thei~ precursors such as arach~onic .
acid. In addition, certain antibiotics ~uch as 15 oYytetracyline can be use~ in place of some or all oE ... ~.
the cross-linking agents.
.: . ,,. :-.. ..
Other materials which coul~ be use~ to replace part the fatty ~ci~ inclu~e carbosyl~ acids, carbo~ylic pepti~es, nonionic surfactants, an~
20 ~teroifls such as cholesterol or hydrocortisone. :~ ~
Selection o~ proper ~ci~ic const~tuents can mod1y ~.:;~ ` .
gel propert~es. ~he Eiteroi~ can ~e present ~n the system up to at le~st 10~ o the atty ac~ w~thout d~turb~ng the gel. ~herefore, these gels coula be 25 u~ed a~ a ~el~ry 5y8tem5 ~or a va~ety o molecul~
u~h as i~tero~
'"~` ''' '" ' In a~it~on, ~ hown pre~iously, lipi~
vesicles can be lncorp~rate~ ~nto the gels a~
p~rt~cul~e ~att~. 8~nc~ these l~p~ veslcl~ c~n 30 ~l~o be ~es~ne~ to carry ~ v~r~ety of materl~li6i . . ~. .
: ~
- 22 - 2 ~ 4 9 ~
wh~ch ~oul~ not othe~w~se bQ c~rr~ n the woun~ patc:h c~ other ~:overlng mad6~ o~ th0 g~l w~th ..
the ~res~cles diispersed. there~n coul~ be used to ~pply ~rugs on a t~me-releasea basi~i to a i~;electel~ ~1t~. -Those 6k~ d ~n ~che art wl~l bo ~ to ~eterm~ne other mod~f~ca~cio~i of t~e ~a~empla~y proceâures an~ mater~al~. ~u~h ot~e~ mo~~t~on~
~re w~t~ tbe scope of the o~10w~n~ cl~m~
Wh~t ~s ~ me~
.`.,~ . ,,' ~' ,.
,~ .. ., ~ .
., ~, :: ,'',' ,'' ~: .
:
~ ~' -"`. .''
Claims (33)
1. A composition of matter which acts as a synthetic sponge when allowed to hydrate comprising a non-hydrated mixture of:
a carboxylic acid with a substantial hydrophobic region; and a branched complex carbohydrate; and a separate cross-linking agent;
whereby said composition can be hydrated and cross-linked simultaneously in the presence of a hydrating solution.
a carboxylic acid with a substantial hydrophobic region; and a branched complex carbohydrate; and a separate cross-linking agent;
whereby said composition can be hydrated and cross-linked simultaneously in the presence of a hydrating solution.
2. The composition of claim 1 wherein said carboxylic acid comprises a fatty acid.
3. The composition of claim 2 wherein said fatty acid is selected from the group consisting of lauric acid, palmitic acid, stearic acid, oleic acid, and mixtures thereof.
4. The composition of claim 1 wherein said carboxylic acid comprises a functional fatty acid.
The composition of claim 4 wherein said functional fatty acid is selected from the group consisting of arachidonic acid, prostaglandins, prostacyclins and thromboxanes.
6. The composition of claim 1 wherein said branched complex carbohydrate is selected from the group consisting of carboxymethylcellulose and chitosan.
7. The composition of claim 1 further comprising a linear carbohydrate.
8. The composition of claim 1 wherein said cross-linking agent is a metallo-organic cross-linking agent which includes a multivalent metal ion.
9. The composition of claim 8 wherein said multivalent metal ion is selected from the group consisting of aluminum ions, chromium ions, and other metal ions with a valence greater than 2.
10. The composition of claim 8 wherein said metallo-organic cross-linking agent also acts as said cross-linking agent.
11. The composition of claim 1 wherein said cross-linking agent is an organic cross-linking agent contains a metal having an effective valence of at least 3.
12. The composition of claim 2 wherein said fatty acid is selected from the group consisting of lauric, palmitic, oleic, and stearic acids, said branched complex carbohydrate is selected from the group consisting of carboxymethylcellulose, chitosan, and mixtures thereof, and said cross-linking agent is selected from the group consisting of aluminum acetate, aluminum borate, benzoate-based aluminum metallo-organic complex, palmitate-based aluminum metallo-organic complex, and mixtures thereof.
13. A method of absorbing aqueous or saline solution using a biodegradable synthetic sponge composition comprising the steps of:
providing said synthetic sponge composition in a substantially unhydrated form, said synthetic sponge composition containing a carboxylic acid with a substantial hydrophobic region, a separate cross-linking agent, and a branched complex carbohydrate;
contacting said solution to be absorbed with said synthetic sponge composition;
whereby said synthetic sponge composition hydrates to absorb said solution and cross-links into a gel substantially simultaneously.
providing said synthetic sponge composition in a substantially unhydrated form, said synthetic sponge composition containing a carboxylic acid with a substantial hydrophobic region, a separate cross-linking agent, and a branched complex carbohydrate;
contacting said solution to be absorbed with said synthetic sponge composition;
whereby said synthetic sponge composition hydrates to absorb said solution and cross-links into a gel substantially simultaneously.
14. The method of claim 13 wherein said carboxylic acid comprises a fatty acid.
15. The method of claim 14 wherein said fatty acid is selected from the group consisting of lauric, palmitic, and stearic acids, and mixtures thereof.
16. The method of claim 13 wherein said branched complex carbohydrate is selected from the group consisting of carboxymethylcellulose and chitosan.
17. The method of claim 13. wherein said composition further comprises a linear carbohydrate.
18. The method of claim 13 wherein said cross linking agent is selected from a group consisting of metallo-organic complexes containing aluminum ions, chromium ions, and other metal ions with a valence of at least 3.
19. The method of claim 13 wherein said carboxylic acid and said cross-linking agent comprise the same molecule.
20.. The method of entrapping particles in a gel comprising the steps of:
providing a synthetic sponge composition in a substantially unhydrated form, said synthetic sponge composition containing a carboxylic acid with a substantial hydrophobic region, a branched complex carbohydrate and a separate cross-linking agent;
contacting a solution containing said particles to be entrapped with said synthetic sponge composition;
whereby said gel is formed by the combined hydration and cross-linking of said synthetic sponge composition, thereby entrapping the particles.
providing a synthetic sponge composition in a substantially unhydrated form, said synthetic sponge composition containing a carboxylic acid with a substantial hydrophobic region, a branched complex carbohydrate and a separate cross-linking agent;
contacting a solution containing said particles to be entrapped with said synthetic sponge composition;
whereby said gel is formed by the combined hydration and cross-linking of said synthetic sponge composition, thereby entrapping the particles.
21. The method of claim 20 wherein said carboxylic acid comprises a fatty acid.
22. The method of claim 20 wherein said particles to be entrapped are selected from the group consisting of cells, bacteria, and macromolecules.
23. The method of claim 21 wherein said fatty acid is selected from the group consisting of lauric, palmitic, and stearic acids, and mixtures thereof.
24. The method of claim 20 wherein said branched complex carbohydrate is selected from the group consisting of carboxymethylcellulose and chitosan.
25. The method of claim 20 wherein said composition further comprises a linear carbohydrate.
26. The method of claim 20 wherein said cross-linking agent is selected from the group consisting of metallo-organic complexes containing aluminum ions, chromium ions, and other metal ions with a valence of at least 3.
27. The method of claim 20 wherein said entrapment acts as a barrier to the passage of said entrapped particles.
28. The method of claim 20 wherein said entrapped particles are released over time from said gel, whereby said gel acts as a sustained release vehicle.
29. The method of claim 20 wherein said carboxylic acid and said cross-linking agent comprise the same molecule.
30. A composition of matter which acts a synthetic sponge when allowed to hydrate and releases undecylenic acid upon degradation comprising a non-hydrated mixture of:
undecylenic acid; and carboxymethylcellulose;
whereby said composition can be hydrated and cross-linked simultaneously in the presence of a hydrating solution.
undecylenic acid; and carboxymethylcellulose;
whereby said composition can be hydrated and cross-linked simultaneously in the presence of a hydrating solution.
31. The composition of claim 1 wherein said carboxylic acid comprises benzoic acid.
32. The method of claim 13 wherein said carboxylic acid comprises benzoic acid.
33. The method of claim 20 wherein said carboxylic acid comprises benzoic acid.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US320,944 | 1989-03-09 | ||
US07/320,944 US4959341A (en) | 1989-03-09 | 1989-03-09 | Biodegradable superabsorbing sponge |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2049055A1 CA2049055A1 (en) | 1990-09-10 |
CA2049055C true CA2049055C (en) | 1994-07-05 |
Family
ID=23248525
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002049054A Abandoned CA2049054A1 (en) | 1989-03-09 | 1990-03-08 | Particulate absorbent material |
CA002049055A Expired - Fee Related CA2049055C (en) | 1989-03-09 | 1990-03-08 | Biodegradable superabsorbing sponge |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002049054A Abandoned CA2049054A1 (en) | 1989-03-09 | 1990-03-08 | Particulate absorbent material |
Country Status (10)
Country | Link |
---|---|
US (1) | US4959341A (en) |
EP (2) | EP0462178B1 (en) |
JP (2) | JPH0720547B2 (en) |
KR (1) | KR920700020A (en) |
AU (2) | AU627014B2 (en) |
BR (2) | BR9007212A (en) |
CA (2) | CA2049054A1 (en) |
DE (1) | DE69003810T2 (en) |
WO (2) | WO1990010426A1 (en) |
ZA (2) | ZA901853B (en) |
Families Citing this family (77)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5269979A (en) * | 1988-06-08 | 1993-12-14 | Fountain Pharmaceuticals, Inc. | Method for making solvent dilution microcarriers |
US4959341A (en) * | 1989-03-09 | 1990-09-25 | Micro Vesicular Systems, Inc. | Biodegradable superabsorbing sponge |
US5234621A (en) * | 1989-03-09 | 1993-08-10 | Micro Vesicular Systems, Inc. | Rinse-free shampoo containing cross-linked carboxymethylcellulose |
US5510117A (en) * | 1989-03-09 | 1996-04-23 | Micro-Pak, Inc. | Entrapment vehicle and method |
US5049395A (en) * | 1989-03-09 | 1991-09-17 | Micro Vesicular Systems, Inc. | Controlled release vehicle |
US5252340A (en) * | 1989-12-14 | 1993-10-12 | Isolyser Company, Inc. | Method of producing an absorbent composition |
US5650219A (en) * | 1991-04-10 | 1997-07-22 | Isolyser Co. Inc. | Method of disposal of hot water soluble garments and like fabrics |
US6048410A (en) * | 1991-04-10 | 2000-04-11 | Isolyser Company, Inc. | Method of disposal of hot water soluble garments and like fabrics |
US5871679A (en) * | 1991-04-10 | 1999-02-16 | Isolyser Company, Inc. | Method of producing hot water soluble garments and like fabrics |
CA2073292C (en) † | 1991-10-25 | 2004-06-29 | Xin Ning | Carboxyalkyl polysaccharides having improved absorbent properties and process for the preparation thereof |
DE4206856C2 (en) * | 1992-03-05 | 1996-08-29 | Stockhausen Chem Fab Gmbh | Polymer composition, absorbent material composition, their preparation and use |
DE4206850C2 (en) * | 1992-03-05 | 1996-08-29 | Stockhausen Chem Fab Gmbh | Polymer compositions, preparation of polymer compositions, in particular absorption materials and their use |
DE4206857C2 (en) * | 1992-03-05 | 1996-08-29 | Stockhausen Chem Fab Gmbh | Polymer composition, absorbent material composition, their production and use |
CA2076732C (en) † | 1992-04-17 | 2006-05-09 | Kimberly-Clark Worldwide, Inc. | Modified polysaccharides having improved absorbent properties and process for the preparation thereof |
US5620786A (en) * | 1993-04-29 | 1997-04-15 | Isolyser Co. Inc. | Hot water soluble towels, sponges and gauzes |
US5885907A (en) * | 1993-04-29 | 1999-03-23 | Isolyser Company, Inc. | Method of disposal of hot water soluble garments and like fabrics |
JP4032261B2 (en) * | 1993-05-03 | 2008-01-16 | ストックハウゼン ゲーエムベーハー | Polymer composition, absorbent composition, production and use thereof |
DE4318094B4 (en) * | 1993-06-01 | 2004-03-04 | Stockhausen Gmbh & Co. Kg | Superabsorbents, processes for their preparation and their use |
EP0674920A1 (en) * | 1994-03-31 | 1995-10-04 | Bio-Sep Inc. | Process and apparatus for digesting solid waste |
US5661217A (en) * | 1994-08-05 | 1997-08-26 | Isolyser Company, Inc. | Method of manufacturing monolithic structures from polyvinyl alcohol |
US5470653A (en) * | 1994-08-05 | 1995-11-28 | Isolyser Company, Inc. | Disposable mop heads |
MY132433A (en) * | 1995-01-10 | 2007-10-31 | Procter & Gamble | Foams made from high internal phase emulsions useful as absorbent members for catamenial pads |
US5849805A (en) * | 1995-01-10 | 1998-12-15 | The Procter & Gamble Company | Process for making foams useful as absorbent members for catamenial pads |
US5563179A (en) * | 1995-01-10 | 1996-10-08 | The Proctor & Gamble Company | Absorbent foams made from high internal phase emulsions useful for acquiring and distributing aqueous fluids |
US5650222A (en) * | 1995-01-10 | 1997-07-22 | The Procter & Gamble Company | Absorbent foam materials for aqueous fluids made from high internal phase emulsions having very high water-to-oil ratios |
US5618554A (en) * | 1995-06-07 | 1997-04-08 | Kimberly-Clark Corporation | Inhibition of exoprotein using amine compositions in absorbent article and method thereof |
US5633291A (en) * | 1995-06-07 | 1997-05-27 | The Procter & Gamble Company | Use of foam materials derived from high internal phase emulsions for insulation |
US5770634A (en) * | 1995-06-07 | 1998-06-23 | The Procter & Gamble Company | Foam materials for insulation, derived from high internal phase emulsions |
US5612045A (en) * | 1995-06-07 | 1997-03-18 | Kimberly-Clark Corporation | Inhibition of exoprotein in absorbent article |
US5685872A (en) * | 1995-06-07 | 1997-11-11 | Kimberly-Clark Worldwide, Inc. | Inhibition of exoprotein using amide compositions in absorbent article |
US5550167A (en) * | 1995-08-30 | 1996-08-27 | The Procter & Gamble Company | Absorbent foams made from high internal phase emulsions useful for acquiring aqueous fluids |
US5707731A (en) * | 1996-05-09 | 1998-01-13 | Isolyser Company, Inc. | Disposable cleaning articles |
US5806668A (en) * | 1996-07-01 | 1998-09-15 | Bixby; Steven H. | Containment, collection and disposal device |
JP3378256B2 (en) * | 1996-09-11 | 2003-02-17 | ザ、プロクター、エンド、ギャンブル、カンパニー | Modified porous starch |
US5891812A (en) * | 1996-10-11 | 1999-04-06 | Isolyser Company, Inc. | Liquid absorbable non-permeable fabrics and methods of making, using, and disposing thereof |
US5844007A (en) * | 1996-10-21 | 1998-12-01 | No Touch North America | Lustering and protecting agent for rubber, vinyl, and the like |
ES2410371T3 (en) * | 1996-12-13 | 2013-07-01 | Dsg International Limited | Compositions of highly absorbent composite material, absorbent sheets provided with the compositions and process for the production thereof |
AU3561697A (en) * | 1997-06-24 | 1999-01-04 | Sca Molnlycke Ab | Absorbent polymer material based on renewable starting materials |
US6083211A (en) * | 1998-03-13 | 2000-07-04 | The Procter & Gamble Company | High suction polymeric foam materials |
US6013589A (en) * | 1998-03-13 | 2000-01-11 | The Procter & Gamble Company | Absorbent materials for distributing aqueous liquids |
US6160028A (en) * | 1998-07-17 | 2000-12-12 | The Procter & Gamble Company | Flame retardant microporous polymeric foams |
US6245697B1 (en) | 1998-11-12 | 2001-06-12 | The Procter & Gamble Company | Flexible mat for absorbing liquids comprising polymeric foam materials |
US6794557B1 (en) | 1999-07-16 | 2004-09-21 | Associated Hygienic Products Llc | Disposable absorbent article employing an absorbent composite and method of making the same |
WO2002060971A1 (en) * | 2001-01-31 | 2002-08-08 | Seikagaku Corporation | Crosslinked polysaccharide sponge |
DE10125599A1 (en) * | 2001-05-25 | 2002-11-28 | Stockhausen Chem Fab Gmbh | Super-absorbent polymer powder for use in e.g. diapers, packaging and soil improvers, obtained by pre-swelling polycarboxy-polysaccharide in water and then drying and surface-crosslinking resulting hydrogel |
AU2003213459A1 (en) * | 2002-03-14 | 2003-09-22 | Nippon Shinyaku Co., Ltd | External medicine for wounds |
US20040087564A1 (en) * | 2002-10-31 | 2004-05-06 | Wright D. Craig | Delivery composition and method |
EP1559315A1 (en) * | 2004-01-28 | 2005-08-03 | Stephen Marshall | Sorbent additive and composition |
US20060246186A1 (en) * | 2005-04-28 | 2006-11-02 | Nowak Michael J | Polycarboxylated polymer, method of making, method of use, and superabsorbent compositions including the same |
CA2621732A1 (en) * | 2005-05-18 | 2006-11-23 | Merlita Acquisition Corporation | Goggles with removable frame and methods of making and using the same |
WO2008037082A1 (en) * | 2006-09-25 | 2008-04-03 | Archer-Daniels-Midland Company | Superabsorbent surface-treated carboxyalkylated polysaccharides and process for producing same |
US7625463B2 (en) | 2006-10-02 | 2009-12-01 | Weyerhaeuser Nr Company | Methods for the preparation of fibrous superabsorbent composite containing cellulose |
US20080082065A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Mixed polymer superabsorbent fibers containing cellulose |
US7645806B2 (en) * | 2006-10-02 | 2010-01-12 | Weyerhaeuser Nr Company | Methods for the preparation of superabsorbent particles containing carboxyalkyl cellulose |
US7785710B2 (en) | 2006-10-02 | 2010-08-31 | Weyerhaeuser Nr Company | Superabsorbent particles containing carboxyalkyl cellulose and temporary metal crosslinks |
US20080079188A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of mixed polymer superabsorbent fibers |
US20080081165A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Fibrous superabsorbent composite containing cellulose |
US20080078514A1 (en) * | 2006-10-02 | 2008-04-03 | Weyerhaeuser Co. | Methods for the preparation of cellulose fibers having superabsorbent particles adhered thereto |
US7717995B2 (en) * | 2006-10-02 | 2010-05-18 | Weyerhaeuser Nr Company | Methods for the preparation of mixed polymer superabsorbent fibers containing cellulose |
FR2917292B1 (en) * | 2007-06-18 | 2014-06-13 | Centre Nat Rech Scient | USE OF A HEMOGLOBIN FOR THE PREPARATION OF DRESSINGS, AND DRESSINGS THUS PREPARED |
US7591891B2 (en) * | 2007-06-25 | 2009-09-22 | Weyerhaeuser Nr Company | Fibrous blend and methods of preparation |
US7749317B2 (en) | 2007-06-25 | 2010-07-06 | Weyerhaeuser Nr Company | Fibrous blend and method of making |
JP5680817B2 (en) * | 2008-03-31 | 2015-03-04 | ユニ・チャーム株式会社 | Absorber that forms crosslinks upon absorption |
US8084391B2 (en) * | 2008-06-30 | 2011-12-27 | Weyerhaeuser Nr Company | Fibers having biodegradable superabsorbent particles attached thereto |
US7833384B2 (en) * | 2008-06-30 | 2010-11-16 | Weyerhaeuser Nr Company | Method for making fiber having biodegradable superabsorbent particles attached thereto |
US7959762B2 (en) * | 2008-06-30 | 2011-06-14 | Weyerhaeuser Nr Company | Method for making biodegradable superabsorbent particles |
US20090325797A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles |
US8101543B2 (en) * | 2008-06-30 | 2012-01-24 | Weyerhaeuser Nr Company | Biodegradable superabsorbent particles |
US20090326180A1 (en) * | 2008-06-30 | 2009-12-31 | Weyerhaeuser Co. | Biodegradable Superabsorbent Particles Containing Cellulose Fiber |
US8641869B2 (en) * | 2008-06-30 | 2014-02-04 | Weyerhaeuser Nr Company | Method for making biodegradable superabsorbent particles |
WO2010096742A2 (en) * | 2009-02-20 | 2010-08-26 | Archer Daniels Midland Company | Acidic gas permeated carboxyalkyl starch particles, extrudates, and process for making the same |
GB2492171A (en) * | 2011-06-24 | 2012-12-26 | Sca Hygiene Prod Ab | Sanitary articles comprising biodegradable plastic and Bacillus spores |
CN103240065B (en) * | 2013-05-03 | 2015-06-03 | 大连理工大学 | Elastic hydrophobic material and synthetic method as well as application thereof |
EP3263141A4 (en) * | 2015-02-27 | 2018-10-24 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Medical material and anti-adhesion material |
EP3263142A4 (en) * | 2015-02-27 | 2018-10-24 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Medical/cosmetic material and adhesion preventing material |
WO2016136885A1 (en) * | 2015-02-27 | 2016-09-01 | 大日精化工業株式会社 | Method for manufacturing medical material, medical material, and anti-adhesion material |
US20210290452A1 (en) * | 2020-03-20 | 2021-09-23 | Tethis, Inc. | Systems and methods for treating an article including a biodegradable superabsorbent material |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3741894A (en) * | 1967-06-15 | 1973-06-26 | Exxon Production Research Co | Chemically modified organic polymers |
US4160063A (en) * | 1973-11-16 | 1979-07-03 | Shell Oil Company | Method for preventing the adherence of oil to surfaces |
US4090013A (en) * | 1975-03-07 | 1978-05-16 | National Starch And Chemical Corp. | Absorbent composition of matter |
GB1453279A (en) * | 1975-03-07 | 1976-10-20 | Johnson & Son Inc S C | Solid air freshener gels |
NZ191703A (en) * | 1978-10-05 | 1981-12-15 | Unilever Ltd | Absorbent material surface treated with aliphatic hydrocarbon or nonionic derivative thereof |
SU779473A1 (en) * | 1978-12-21 | 1980-11-15 | Центральный научно-исследовательский институт бумаги | Paper pulp production method |
CA1152483A (en) * | 1979-04-23 | 1983-08-23 | John H.C. Windust | Absorbent materials |
JPS56155203A (en) * | 1980-04-30 | 1981-12-01 | Kuraray Co Ltd | Production of carboxyl group-containing polymer material |
US4454055A (en) * | 1980-08-25 | 1984-06-12 | National Starch And Chemical Corporation | Absorbent composition of matter, process for preparing same and article prepared therefrom |
US4486335A (en) * | 1982-08-30 | 1984-12-04 | Hercules Incorporated | Carboxymethyl hydroxyethyl cellulose composition |
US4610678A (en) * | 1983-06-24 | 1986-09-09 | Weisman Paul T | High-density absorbent structures |
US4548847A (en) * | 1984-01-09 | 1985-10-22 | Kimberly-Clark Corporation | Delayed-swelling absorbent systems |
JPS60226832A (en) * | 1984-04-02 | 1985-11-12 | Daicel Chem Ind Ltd | Separating agent containing polysaccharide fatty acid ester |
JPS63152667A (en) * | 1986-08-22 | 1988-06-25 | Kao Corp | Water-absorptive resin with high stability |
DE8712723U1 (en) * | 1986-12-08 | 1987-12-17 | Hanfspinnerei Steen & Co Gmbh, 2000 Hamburg, De | |
US4826880B1 (en) * | 1987-09-21 | 2000-04-25 | Johnson & Johnson Inc | Immobilizing particulate absorbents by conversion to hydrates |
FR2620914B1 (en) * | 1987-09-25 | 1991-11-08 | Oreal | SHEET MATERIAL FOR PERFORMING SKIN OR HAIR TREATMENT, METHOD FOR MANUFACTURING SAME, AND ARTICLES MADE THEREOF |
US4959341A (en) * | 1989-03-09 | 1990-09-25 | Micro Vesicular Systems, Inc. | Biodegradable superabsorbing sponge |
US4952550A (en) * | 1989-03-09 | 1990-08-28 | Micro Vesicular Systems, Inc. | Particulate absorbent material |
US4944734A (en) * | 1989-03-09 | 1990-07-31 | Micro Vesicular Systems, Inc. | Biodegradable incontinence device with embedded granules |
-
1989
- 1989-03-09 US US07/320,944 patent/US4959341A/en not_active Expired - Lifetime
-
1990
- 1990-03-08 JP JP2504607A patent/JPH0720547B2/en not_active Expired - Lifetime
- 1990-03-08 BR BR909007212A patent/BR9007212A/en not_active Application Discontinuation
- 1990-03-08 KR KR1019900702416A patent/KR920700020A/en not_active Application Discontinuation
- 1990-03-08 CA CA002049054A patent/CA2049054A1/en not_active Abandoned
- 1990-03-08 EP EP90904542A patent/EP0462178B1/en not_active Expired - Lifetime
- 1990-03-08 WO PCT/US1990/001275 patent/WO1990010426A1/en not_active Application Discontinuation
- 1990-03-08 CA CA002049055A patent/CA2049055C/en not_active Expired - Fee Related
- 1990-03-08 BR BR909007210A patent/BR9007210A/en not_active Application Discontinuation
- 1990-03-08 AU AU52841/90A patent/AU627014B2/en not_active Ceased
- 1990-03-08 WO PCT/US1990/001049 patent/WO1990010495A1/en active IP Right Grant
- 1990-03-08 JP JP2505069A patent/JP2651952B2/en not_active Expired - Lifetime
- 1990-03-08 DE DE90904542T patent/DE69003810T2/en not_active Expired - Fee Related
- 1990-03-08 EP EP90905032A patent/EP0593421A1/en not_active Withdrawn
- 1990-03-08 AU AU52676/90A patent/AU624695B2/en not_active Ceased
- 1990-03-09 ZA ZA901853A patent/ZA901853B/en unknown
- 1990-03-13 ZA ZA901923A patent/ZA901923B/en unknown
Also Published As
Publication number | Publication date |
---|---|
JPH0720547B2 (en) | 1995-03-08 |
EP0462178A1 (en) | 1991-12-27 |
AU627014B2 (en) | 1992-08-13 |
JP2651952B2 (en) | 1997-09-10 |
JPH04504978A (en) | 1992-09-03 |
ZA901923B (en) | 1991-05-29 |
DE69003810D1 (en) | 1993-11-11 |
JPH04504969A (en) | 1992-09-03 |
WO1990010495A1 (en) | 1990-09-20 |
EP0593421A1 (en) | 1994-04-27 |
EP0462178B1 (en) | 1993-10-06 |
BR9007210A (en) | 1992-02-18 |
BR9007212A (en) | 1992-03-24 |
DE69003810T2 (en) | 1994-05-05 |
AU624695B2 (en) | 1992-06-18 |
ZA901853B (en) | 1991-08-28 |
EP0462178A4 (en) | 1992-06-03 |
KR920700020A (en) | 1992-02-19 |
CA2049054A1 (en) | 1990-09-10 |
AU5284190A (en) | 1990-10-09 |
AU5267690A (en) | 1990-10-09 |
US4959341A (en) | 1990-09-25 |
WO1990010426A1 (en) | 1990-09-20 |
CA2049055A1 (en) | 1990-09-10 |
EP0593421A4 (en) | 1993-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2049055C (en) | Biodegradable superabsorbing sponge | |
KR100331905B1 (en) | Flushable Compositions | |
CA2088033C (en) | Water dispersible towelette impregnated with non-aqueous lotion formulations | |
KR100257366B1 (en) | Method for reducing malodor in absorbent products and products formed thereby | |
DE60109026T2 (en) | PERMANENT WATERBANDABLE HIGH ABSORPTION FIBERS | |
KR100385270B1 (en) | Premoistened, Flushable, Disposable and Biodegradable Wet Wipes | |
US5417977A (en) | Method of producing an absorbent composition | |
EP1518567B1 (en) | Absorbent articles comprising fluid acquisition zones with coated superabsorbent particles | |
DE69924605T2 (en) | ABSORBENT STRUCTURE WITH IMPROVED ABSORPTION CHARACTERISTICS | |
AU722114C (en) | Absorbent composite and disposable absorbent garment comprising same | |
DE60320255T2 (en) | Absorbent articles containing superabsorbent polymer particles having a non-covalently bonded coating | |
SA93130361B1 (en) | absorbent structure | |
CZ265094A3 (en) | Absorption body for an absorption article | |
EP0800455B1 (en) | A water-flushable film | |
MXPA06012307A (en) | Absorbent composition having multiple surface treatments. | |
SK279288B6 (en) | Absorbent structure for absorbing body fluids | |
WO1995000183A1 (en) | Absorbent articles containing superabsorbent material which has a delayed activation time | |
EP0461484A2 (en) | Multi-layered sheet | |
CA2019557A1 (en) | Cosmetic article | |
RU2624510C2 (en) | Improved personal care product | |
KR20040070245A (en) | Microphase Separated Superabsorbent Compositions and Method for Making | |
MXPA05006138A (en) | Low evaporative superabsorbent products and methods for utilizing the same. | |
CA1124951A (en) | Disposable absorbent structure having a surfactant treated intermediate layer | |
CA2472863A1 (en) | Absorbent article including in situ cover | |
CA2313003C (en) | Absorbent articles having liquid shrinkable breathable backsheets |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |