CA2192180A1 - Denture stabilizing compositions - Google Patents
Denture stabilizing compositionsInfo
- Publication number
- CA2192180A1 CA2192180A1 CA002192180A CA2192180A CA2192180A1 CA 2192180 A1 CA2192180 A1 CA 2192180A1 CA 002192180 A CA002192180 A CA 002192180A CA 2192180 A CA2192180 A CA 2192180A CA 2192180 A1 CA2192180 A1 CA 2192180A1
- Authority
- CA
- Canada
- Prior art keywords
- zinc
- copolymer
- composition according
- vinyl ether
- strontium
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 230000000087 stabilizing effect Effects 0.000 title description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 239000000853 adhesive Substances 0.000 claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract 6
- 239000011701 zinc Substances 0.000 claims description 33
- 229910052725 zinc Inorganic materials 0.000 claims description 33
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052712 strontium Inorganic materials 0.000 claims description 24
- -1 strontium cations Chemical class 0.000 claims description 20
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 125000002091 cationic group Chemical group 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 150000001719 carbohydrate derivatives Chemical class 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229920001206 natural gum Polymers 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- 239000011777 magnesium Substances 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- 229920001059 synthetic polymer Polymers 0.000 claims 2
- 239000003981 vehicle Substances 0.000 claims 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 29
- 239000002253 acid Substances 0.000 description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 15
- 150000008064 anhydrides Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 7
- 239000004264 Petrolatum Substances 0.000 description 6
- 229940066842 petrolatum Drugs 0.000 description 6
- 235000019271 petrolatum Nutrition 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 101100114828 Drosophila melanogaster Orai gene Proteins 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 244000202285 Acrocomia mexicana Species 0.000 description 2
- 235000003625 Acrocomia mexicana Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 1
- BPMMHGIISLRQDW-ODZAUARKSA-N (z)-but-2-enedioic acid;ethenoxyethene Chemical compound C=COC=C.OC(=O)\C=C/C(O)=O BPMMHGIISLRQDW-ODZAUARKSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- MFLCLMHBOLWTHH-UHFFFAOYSA-N Panial Natural products COc1ccc2C=CC(=O)Oc2c1C(O)C=C(/C)C=O MFLCLMHBOLWTHH-UHFFFAOYSA-N 0.000 description 1
- 241000934878 Sterculia Species 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 239000000231 karaya gum Substances 0.000 description 1
- 229940039371 karaya gum Drugs 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001525 mentha piperita l. herb oil Substances 0.000 description 1
- 239000001683 mentha spicata herb oil Substances 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000002103 osmometry Methods 0.000 description 1
- 235000019477 peppermint oil Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019721 spearmint oil Nutrition 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000010487 tragacanth Nutrition 0.000 description 1
- 239000000196 tragacanth Substances 0.000 description 1
- 229940116362 tragacanth Drugs 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N vinyl ethyl ether Natural products CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
- A61K6/35—Preparations for stabilising dentures in the mouth
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Dental Preparations (AREA)
Abstract
The subject invention encompasses adhesive compositions comprising unmixed partial salts of a lower alkyl vinyl ether-maleic acid copolymer and polyethylene glycol having an average molecular weight of above about 100 and equal to or below about 600.
Description
wo ss/3343~ 2 1 9 2 1 8 0 PCTIUS95107280 DENTURE STABILIZING COIviPOSITIONS
s BAI'.K('~OUND
Ordinary removable dentures, dentai plates and the like, comprise teeth mounted in a suitabie plate or base. Aithough dentures generally are skillfully 0 prepared, often they do not fit perfectly. Moreover, no matter how ~a~i~r~ u,y at first, afier a period of time the fit of the denture becomes loose and imperfect due to natural shrinkage and changes in the gums, mucous tissues, and the like. Loose and imperfectly fitted dentures usually are corrected and stabilized by the use of a denture stabiiizer. Denture stabilizers are used to fiii the interstices between the dentures and 15 the gums or tissues. Prior to placement of the denture in the orai cavity, a denture stabiiizer is appiied to the denture-plate surface which, for a perfect fit, should uniformiy contact the gums and mucous tissues. The denture stabiiizer is formulated not oniy for its adherent properties, but aiso to provide a cushion or gasket between the denture and the gums or tissues, thereby positioning the denture securely in the 20 orai cavity.
Severai d fi~ that commoniy exist with denture stabiiizing or adhesive -- are phaæ æparation, the need for more than one application of the adhesive per day and oozing of the adhesive from under the dental plate. Oozing is particularly I ' ' ' because of the resuiting unpleasant taste, unpleasant 2s mouthfeel, and loss of adhesive from under the dentai plate.
C~lnci~l~r~hl~ effort has been made over the years to develop improved denture adhesive , Both synthetic and naturai polymers and gums have been uæd singiy, in ' , and in ~ ' with various adhesives in an attempt to lesæn the ' " noted above. However, the need still exists for 30 improved denture stabiiizing ~ - which offer a secure hold, are ~
pleasing to the user, which ooze less than currently available products, and which are easy to clean from the mouth and/or denture.
It has been discovered, in accordance with the present invention, that a denture stabiiizer can be formulated having excellent adhesive quality while oozing 35 less and providing pleasing aesthetics to the user. The invention adhesive r '- may aiso be effectively used as a wound dressing, ulld~ d~el adhesive, bio-adhesive, and/or as a delivery vehicle for other actives.
woss/3343~ 2 1 92 l 80 PCT/US9~/07280 It is an object of the present invention to provide a denture stabilizing which effectively holds dentures in place for prolonged periods of time yet allows for easy removal of the denture on demand. It is also an object of the invention to provide an improved denture stabilizing cu~ which oozes less s than currently avaiiable stabilizers and is ' '1~ pleasing to the user. It is a further ûbject that the hydrophilic nature of the invention ~,u~ o~;Liu.~s will provide adhesive ~ that are easier to clean from the mouth and/or denture than currently available products.
These and other objects of the present invention will become readily apparent 0 from the detailed description which follows.
SUMMA~Y OF THE INVENTION
The present invention . ....~ adhesive ..(. ~ , a) from about I û% to about 8û% of an unmixed partial sait of a lower aiicyl vinyl ether-maieic acid copolymer consisting essentiaily of the repeated structural unit:
_ ~
I R
--CH2 ~:H--CH--f H--O=C C--O
~O OH n wherein R represents a Cl to C4 aiicyl radicai, n is an integer greater than oneq,.~ ~ the number of repeated O~,~,ul~ .. of the structural unit in a molecule of the copolymer and n is iarge enough to ~,llo a~,L~il;.._ the copolymer as having a 20 specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 2~C, and wherein the partiai sait contains a cationic salt function of from about û.1% to about 6û~/. zinc or strontium cations, ofthe totai initiai carboxyl groups reacted; and b) from about 20% to about 90% of ~vl~ , glycol having an average molecuiar weight above about lû0 and eciuai to or below about 60û.
DI~T~TFn DESC~ ON OF THE INVENTION
The adhesive . . of the present invention comprise lower alicyl vinyl ether-maieic acid copolymers consisting of unmixed zinc or strontium salts, and ~c,l~_Lh,l~...c giycol . ru~ giycol having an average molecular weight of about 4ûû iS most preferred for use in the present invention ~ l.c~ The present, . may be formulated âS creams, pastes, powders, liquids, W095/33434 21 921 80 PCT/US95/0728n ointments, and lotions. A detailed deseription of essential and optional ~ u~ vuof the present invention is given beiow.
s Lower Aiijyl Vinyl Ether-Maleie Aeid Covolymer Saits The present adhesive ~ eomprise an unmixed partial salt of a lower aikyl vinyl ether-maieie acid ("AVE/MA") eopolymer eonsisting essentially of the repeated structurai unit:
(I) fR
--CH2--CH--CH--fH--O=C C=o I
:~O OH
- n wherein R represents a Cl to C4 aiicyl radieal, n is an integer greater than one.~.. _ the number of repeated oc~,u.,~ of the struetural unit in a molecule of the eopolymer and n is large enough to .~ the eopolymer as having a speeiffc viscosity larger than 1.2, the speciffc viscosity being determined in methyl ethyl ketone at 25C, and wherein the partiai saits eontain a cationic salt function of from about û. 1% to about 60% zinc (preferred) or strontium cations, preferably from about 10% to about 60%, and most preferably from about 2û% to about 50%, of the totai initiai earboxyl groups reaeted.
The term "unmixed eopolymer saits" as used herein refers to zinc and strontium partiai saits of lower aiicyl vinyl ether-maieic acid CU~Vlr~ wherein the zinc or strontium eations are unmixed with any other ester funetions or r..,...~...l;.
eations on the same eopolymer, the remaining earboxyl groups being unreacted.
The term "mixed eopolymer saits" as used herein refers to zine and/or strontium partiai saits of lower aikyl vinyl ether-maieic acid ~,u~.ul~ wherein the zinc and strontium are mixeo on the same eopolymer with each other, or with other ester funetions or ' ' eations selected from the group consisting of caleium, sodium, _ , potassium, ~ , and mixtures thereo It is preferred that the present ~ further comprise from about 0.1% to about 75% of one or more mixed partial salts of lower alicyl vinyl ether-maieic acid copolymers wherein the partiai saits eontain a eationie salt funetion selected from the group eonsisting of eaieium, sodium, _ , potassium, wo ss/33434 2 1 9 2 1 8 ~ Pcr/uss~/07280 ammonium, zinc, strontium, and mixtures thereo Most preferred are mixed copolymer salts containing zinc, calcium, or sodium cations, or mixtures thereof.
Zinc cations may be present at a level of from about 0.1% to about 65%, preferably from about 10% to about 45%, and most preferably rom about 15% to about 30%, s of the total initial carboxyl groups reacted. Calcium ions may be present at a level of from about 10% to about 75%, preferably from about 25% to about 60%, and most preferably from about 40% to about 60%, of the total initial carboxyl groups reacted.
Sodium cations may be present at a level of from about 1% to about 20%, preferably from about 1% to about 15%, and most preferably from about 1% to about 10%, of o the total initial carboxyl groups reacted.
The subject polymeric salts are ad~,r l ~3, u ~l~ prepared by the interaction ofthe AVEIMA copolymer (I) with cationic zinc or strontium ~ having a functional group typical of reactants of a carboxylic acid, such as, for example, the hydroxide, acetate, halide, lactate, etc. in an aqueous medium. In a preferred 5 L ' t, mixed AVE/MA copol5~mer salts are prepared by the interaction of the AVEIMA copolymer (I) with cationic calcium, sodium, lg , potassium, zinc, strontium (and mixtures thereofl , ' having a functional group as specifed above for cationic zinc or strontium ~ r ~' In a preferred mixed AVE/MA copolymer e L- ' t, the oxide of zinc and the hydroxide of ~o calcium are utilized.
Since zinc hydroxide is not uun~ c~ "S, available, its use as a reactant is readily and more 'lS. e ,' ' ' by employing an aqueous slurry of particular zinc oxide which, although practically irlsoluble in water, provides hydration to zinc hydroxide on the particulate surface. Strontium hydroxide, on the 2s otber hand, is available in either crystalline or powder form and is soluble in about 50 parts water. Aqu~ous solutions of strontium oxide, however, which forms the hydroxide when treated with water (caution: heat evolution), may also be used.
Anions that form toxic, irritating or, ~, by-products should be avoided, or special ~ liu.... and treatment provided to assure the removal and 30 absence of such by-produhs from the polymeric salt end-produh The particular compound used should be ' '1~ pure to assure obtaining a ' '~S pure, '~ off-white polymeric salt end-produh~
The lower alxyl vinyl ether maleic acid ~AVE/MA) co~ are readily obtained by ~,upul~ a lower alkyl vinyl ether monomer, such as methyl vinyl 35 ether, ethyl vinyl ether, divinyl ether, propyl vinyl ether and isobutyl vinyl ether, with maleic anhydride to yield the ,u-,~ r '- ~, lower alkyl vinyl ether-maleic anhydride copolymer which is readily l~ ul~Lablc tû the acid copolymer (I). Both anhydride .. ....
wo ssl33434 2 1 q ~ 1 8 0 PCT/US9S/07280 and acid forms are also available from commercial suppliers. For example, the GAF
Corporation, Wayne, N.J. provides both the polyrneric free acid form (I) and theLUllL_r " _ anhydride form under its "GANTREZ" trademark as the "GANTREZ
S Series" and "GANTREZ AN Series", l~ .Li~ . In the forrner acid series, the s GANTREZ S-97 (M. W. TM 5û,00û) is particularly suitable, and, in the latter anhydride series, the GANTREZ AN-149 (M. W. = 50,000) the GANTREZ AN-169 (M. W = 67,000) and the GANTREZ AN-179 (M. W. = 80,000) cu~ùlyll~ are particularly suitable. The acid and anhydride forrns of AVE/MA .,u~.ul~....,.~, having an average molecular weight of from about 50,000 to about 80,000 (as measured byo membrane osmometry in 2-butanone 1-10 grarns/1000 ml solution), are also by having the previously described specific viscosity parameter of more than 1.2. When the anhydride copolymer dissolves in water, the anhydride linkage is cleaved so that the highly polar, polymeric free acid (I) is forrned. Accordingly, the anhydride form, which is relatively less expensive than the acid form, may be used as a convenient and cheaper precursor for the acid. Elevated le~ LLIlct may be a i v - ~ O. .r . ~l y employed to enhance the rate of ', J. i~c to-acid hydrolysis.
In general, the lower alkyl vinyl ether-maleic acid copolymer (I), or its cullL-r ' _ anhydride, is added to water preheated to about 70-80C. with vigorous stirring to form a l~.,. h.-~ru~ mixture. If the anhydride precursor isutilized, it is . ~.. \ l ~l that the aqueous mixture be further heated to about 90 C. with stirring to ensure complete hydrolysis of the anhydride to the acid form.
Heating is then ~' l aithough mixing is continued untii the batch turns clear with a ' decrease in viscosity (about 65-75C.). An aqueous solution of the cationic zinc or strontium sait forming compound, or, for example, an aqueous 25 dispersion of particulate zinc oxide in the form of a slurry, in an amount sufficient to provide the desire cationic content desired in the end-product, is separately prepared at arnbient i , I; and slowly added to the hot polyrneric acid solution with continuous vigorous mixing so as to prevent locaiized IJlC~.;,Ll;LdL;L.~ of the cationic polyrneric sait. After addition is complete, mixing is continued to ensure that all the 30 sait forming compound is rcacted with the copolymer.
, an aqueous soiution containing the zinc or strontium source is preheated to 70-80C. with vigorous stirring to forrn a 1, ~. u~ slurry. The lower aikyl vinyl ether-maieic acid copolymer (I) or its ~OIl~_r ~' _ anhydride is then added to the slurry while further heating to 90C. and stirring tû ensure 35 complete hydrolysis.
The reaction batch is then dried such as by shallow drying trays in a convection oven maintained at about 70C. with hot air circulation to evaporate the WO 95/3343~1 2 1 9 2 1 8 0 PCT/US95107280 water content and recover the polymeric salt product in dry form. Altematively, the reaction batch is then transferred to 5 drum dryers maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt in the flake fomm.
s The resulting flakes may be subjected to milling and screening to yield thedesired physical properties to provide satisfactory denture stabilizing properties.
The salts are ~iable so that ~Iyyl~y~;at~, particle size and bulk density can be obtained. For best results, particles should be capable of passage through a 140- to 200-mesh sieve (U.S.B.S. series) and preferably are less than 0.74 millimeter in their 0 largest dimension.
The subject zinc or strontium AVE/MA copolymer salts have exceptional adhesive qualities when contacted with water or saliva such that they are extremely useful as denture adhesive materials in denture stabilizing ~ c For such use the salt in particulate fomm is preferably cl.~..~.,i.,.i,.~,~ by a particle size of at least 5 minus 140-mesh U.S.B.S. sieve; a bulk density greater than 0.3 gram per cubic centimeter and preferably higher than 0.6 gram per cubic centimeter; and a pH
between 3 and 7.0, the pH being detemlined on a one percent by weight dispersion in water.
The subject zinc or strontium AVE/MA copolymer salts may be utilized in 20 effective adhesive amounts, preferably at least 20 percent by weight, as the sole adhesive component or as a co-adhesive in joint usage with other active adhesive - r ' in denture stabilizing . Preferably, the unmixed zinc or strontium AVE/MA copolymer salts may be utilized with mixed AVEIMA copolymer salts containing cations such as calcium, sodium, magnPcil~m potassium, r - -2Jr zinc, strontium, and mixtures thereo r~5~-lh~ - Glycol The invention .~ also comprise pGl.~lh/l~ glycol. In general, yO1~ ,,~ glycols are polymers with the general fommula (OCH2CH2)nOH, where n is greater than or equal to 4. The pul.~..h,!~ glycols are designated by a number 30 that represents the average molecular weight ~Merck Index. Tenth Edition, No. 7441, 1983]
The present , comprise p~ . glycol having an average molecular weight above about 100 and equal to or below about 600. Preferred is p~ glycol having an average molecular weight of equal to or greater than 3s about 300 and equal to or below about 600. rul~,.l./l, .. , glycol having an average molecular weight of about 400 is most preferred. The -y.Jl~.,lhjl~,..e glycols suitable -wo ss/33434 2 1 9 2 1 8 0 PCTIUS95107280 for use in the present inYention are well known and ~ available, such as those marketed by Union Carbide Corporation under the trademark "Carbowax".
The level of pol~ hJ ' giycol that is useful in the present invention is based on ' ~' 'I"'`'I;fJ''` containing AVE/MA copolymer saits ..l, -,- .Irl;~d by a particle size s of at least minus 140-mesh U.S.B.S. sieve. Therefore, P~JI~ hYI~ ; glycol having an average molecular weight above about 100 and equal to or below about 600 is present at a level of from about 20% to about 90%, preferably from about 30/0 to about 80%, and most preferably from about 35% to sbout 75%, by weight of the invention ' Optional ,; . , . ~
The present invention , may also include a safe and adhesively effective amount of a co-adhesive. The term "safe and adhesively effective amount"
as used herein means an amount sufficient to provide adherence of a denture or dental prosthesis to the orai cavity.
Preferred co-adhesives include a water-soluble hydrophilic colloid or polymer having the property of swelling upon exposure to moisture to form a mass. Such adhesive materiais include natural gums, synthetic polymeric gums, adhesive materiais commoniy employed in denture stabilizing ~ ,- and compatible with the subject AVE~A copolymer salts, synthetic poiymers, saccharide derivatives, cellulose derivatives, and mixtures thereo Examples of such materiais include karaya gum, guar gum, gdatin, algin, sodium alginate, tragacanth, h,' " ' , acrylamide polymers, ethylene oxide polymers, pul~
cationic ~fJI~ ~' ' ' polymers, ~bu~ ' ~ II,ulù~e, sodium .~i,uA~....,I~.~l~,eiiui~se and mixed partiai saits of poly(vinyl methyl-ether maleate).
25 Sodium ~ " ' is most preferred for use in the present invention. In generai, the co-adhesives may be present at a level of from about 5% to about 70%
by weight of the ~ .
Other suitable optionai ingredients include colorants; preservatives such as methyl and propyl parabens; thickeners such as silicon dioxide, and pfJI.~
30 giycol having an average molecular weight of 8000; and vehicles such as liquid , petrolatum, minerai oil, and giycerin. Preferred are ~JIJ~ l.., glycol having an average molecular weight of 8000, minerai oil, and petrolatum. Colorants, ..,I va~ , thickeners, and vehicles may be present at levels of from about 0% to about 20%, by weight of the c~
The , - of the present invention may optionally include from about 0.01% to about 5% of one or more c , which provide the user with sensory, including flavor, benefits. Suitable r include natural or artificial w095/3343.1 21/~2180 r~u~
sweetening agents, menthol, methyl lactate, ~ , oil, peppermint oil, spearmint oil, leaf alcohol, as well as coolants 3~ ,.u~,~u.G-1,2-diol and ~.~ ' c~ u~_ ' agents such as N-ethyl-p ' -3-~ bu~ idc which is described in U.S. Patent 4,136,163 to Watson et. al., which is i~.~,ul~o~cd 5 by reference herein in its entirety.
The ~ . of the present invention are ~ ur~ ulcJ in an art-recognized manner icnown to those sicilled in the art, such as powder, cream, ointment, liquid, or paste r".. l ~; Suitable examples of such r.... ~ ;.. are disclosed in U.S. Patent 4,518,721, issued May 21, 1985, and U.S. Patent 4,514,528, o issued April 30, 1985, both to Dhabar et ai., and both ;..vu.~u-~c~ by reference herein in their entirety.
The foliowing l~o,~ l ~ examples ii~ustrate ...~l~v~ of the subject invention wherein both essentiai and optionai ingredients are combined. These examples are given solely for the purpose of illustration and are not to be construed 5as limiting the scope of the invention F.XAMpi.F I
Inyredients. Weight %
17.5% Zinc unmixed partiai sait of AVEIMA copolymer(a) 33.0 ~orul~_L~.,!c.. ~, Glycol 400 40.5 Sodium Gubu~ yl~,ellulu ~ 17.3 Petrolatum 8.0 ru~ ......... c Glycol gO00 1.2 (a) AVE/MA copolymer salt having about 17.5% ' with zinc.
2s FXA.~PLE 11 ~ Weight %
20.0% Strontium unmixed partiai salt of AVE/MA copolymer(a) 10.0 47.5% Caicium/17.5% Zinc mixed partial salt of AVE/MA copolymer(b) 28.1 rUl~ ,J!~ . Glycol 40û 39.0 Sodium C.u~v~ ' ,1~1h.1~se 12.1 Petrolatum 10.0 Minerai Oii 0.8 (a) AVE/MA copolymer sait having about 20% : ' with strontium.
(b) AVE/MA copolymer sait having about 47.5% ' with caicium and about 17.5% 1 ' with zinc.
s BAI'.K('~OUND
Ordinary removable dentures, dentai plates and the like, comprise teeth mounted in a suitabie plate or base. Aithough dentures generally are skillfully 0 prepared, often they do not fit perfectly. Moreover, no matter how ~a~i~r~ u,y at first, afier a period of time the fit of the denture becomes loose and imperfect due to natural shrinkage and changes in the gums, mucous tissues, and the like. Loose and imperfectly fitted dentures usually are corrected and stabilized by the use of a denture stabiiizer. Denture stabilizers are used to fiii the interstices between the dentures and 15 the gums or tissues. Prior to placement of the denture in the orai cavity, a denture stabiiizer is appiied to the denture-plate surface which, for a perfect fit, should uniformiy contact the gums and mucous tissues. The denture stabiiizer is formulated not oniy for its adherent properties, but aiso to provide a cushion or gasket between the denture and the gums or tissues, thereby positioning the denture securely in the 20 orai cavity.
Severai d fi~ that commoniy exist with denture stabiiizing or adhesive -- are phaæ æparation, the need for more than one application of the adhesive per day and oozing of the adhesive from under the dental plate. Oozing is particularly I ' ' ' because of the resuiting unpleasant taste, unpleasant 2s mouthfeel, and loss of adhesive from under the dentai plate.
C~lnci~l~r~hl~ effort has been made over the years to develop improved denture adhesive , Both synthetic and naturai polymers and gums have been uæd singiy, in ' , and in ~ ' with various adhesives in an attempt to lesæn the ' " noted above. However, the need still exists for 30 improved denture stabiiizing ~ - which offer a secure hold, are ~
pleasing to the user, which ooze less than currently available products, and which are easy to clean from the mouth and/or denture.
It has been discovered, in accordance with the present invention, that a denture stabiiizer can be formulated having excellent adhesive quality while oozing 35 less and providing pleasing aesthetics to the user. The invention adhesive r '- may aiso be effectively used as a wound dressing, ulld~ d~el adhesive, bio-adhesive, and/or as a delivery vehicle for other actives.
woss/3343~ 2 1 92 l 80 PCT/US9~/07280 It is an object of the present invention to provide a denture stabilizing which effectively holds dentures in place for prolonged periods of time yet allows for easy removal of the denture on demand. It is also an object of the invention to provide an improved denture stabilizing cu~ which oozes less s than currently avaiiable stabilizers and is ' '1~ pleasing to the user. It is a further ûbject that the hydrophilic nature of the invention ~,u~ o~;Liu.~s will provide adhesive ~ that are easier to clean from the mouth and/or denture than currently available products.
These and other objects of the present invention will become readily apparent 0 from the detailed description which follows.
SUMMA~Y OF THE INVENTION
The present invention . ....~ adhesive ..(. ~ , a) from about I û% to about 8û% of an unmixed partial sait of a lower aiicyl vinyl ether-maieic acid copolymer consisting essentiaily of the repeated structural unit:
_ ~
I R
--CH2 ~:H--CH--f H--O=C C--O
~O OH n wherein R represents a Cl to C4 aiicyl radicai, n is an integer greater than oneq,.~ ~ the number of repeated O~,~,ul~ .. of the structural unit in a molecule of the copolymer and n is iarge enough to ~,llo a~,L~il;.._ the copolymer as having a 20 specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 2~C, and wherein the partiai sait contains a cationic salt function of from about û.1% to about 6û~/. zinc or strontium cations, ofthe totai initiai carboxyl groups reacted; and b) from about 20% to about 90% of ~vl~ , glycol having an average molecuiar weight above about lû0 and eciuai to or below about 60û.
DI~T~TFn DESC~ ON OF THE INVENTION
The adhesive . . of the present invention comprise lower alicyl vinyl ether-maieic acid copolymers consisting of unmixed zinc or strontium salts, and ~c,l~_Lh,l~...c giycol . ru~ giycol having an average molecular weight of about 4ûû iS most preferred for use in the present invention ~ l.c~ The present, . may be formulated âS creams, pastes, powders, liquids, W095/33434 21 921 80 PCT/US95/0728n ointments, and lotions. A detailed deseription of essential and optional ~ u~ vuof the present invention is given beiow.
s Lower Aiijyl Vinyl Ether-Maleie Aeid Covolymer Saits The present adhesive ~ eomprise an unmixed partial salt of a lower aikyl vinyl ether-maieie acid ("AVE/MA") eopolymer eonsisting essentially of the repeated structurai unit:
(I) fR
--CH2--CH--CH--fH--O=C C=o I
:~O OH
- n wherein R represents a Cl to C4 aiicyl radieal, n is an integer greater than one.~.. _ the number of repeated oc~,u.,~ of the struetural unit in a molecule of the eopolymer and n is large enough to .~ the eopolymer as having a speeiffc viscosity larger than 1.2, the speciffc viscosity being determined in methyl ethyl ketone at 25C, and wherein the partiai saits eontain a cationic salt function of from about û. 1% to about 60% zinc (preferred) or strontium cations, preferably from about 10% to about 60%, and most preferably from about 2û% to about 50%, of the totai initiai earboxyl groups reaeted.
The term "unmixed eopolymer saits" as used herein refers to zinc and strontium partiai saits of lower aiicyl vinyl ether-maieic acid CU~Vlr~ wherein the zinc or strontium eations are unmixed with any other ester funetions or r..,...~...l;.
eations on the same eopolymer, the remaining earboxyl groups being unreacted.
The term "mixed eopolymer saits" as used herein refers to zine and/or strontium partiai saits of lower aikyl vinyl ether-maieic acid ~,u~.ul~ wherein the zinc and strontium are mixeo on the same eopolymer with each other, or with other ester funetions or ' ' eations selected from the group consisting of caleium, sodium, _ , potassium, ~ , and mixtures thereo It is preferred that the present ~ further comprise from about 0.1% to about 75% of one or more mixed partial salts of lower alicyl vinyl ether-maieic acid copolymers wherein the partiai saits eontain a eationie salt funetion selected from the group eonsisting of eaieium, sodium, _ , potassium, wo ss/33434 2 1 9 2 1 8 ~ Pcr/uss~/07280 ammonium, zinc, strontium, and mixtures thereo Most preferred are mixed copolymer salts containing zinc, calcium, or sodium cations, or mixtures thereof.
Zinc cations may be present at a level of from about 0.1% to about 65%, preferably from about 10% to about 45%, and most preferably rom about 15% to about 30%, s of the total initial carboxyl groups reacted. Calcium ions may be present at a level of from about 10% to about 75%, preferably from about 25% to about 60%, and most preferably from about 40% to about 60%, of the total initial carboxyl groups reacted.
Sodium cations may be present at a level of from about 1% to about 20%, preferably from about 1% to about 15%, and most preferably from about 1% to about 10%, of o the total initial carboxyl groups reacted.
The subject polymeric salts are ad~,r l ~3, u ~l~ prepared by the interaction ofthe AVEIMA copolymer (I) with cationic zinc or strontium ~ having a functional group typical of reactants of a carboxylic acid, such as, for example, the hydroxide, acetate, halide, lactate, etc. in an aqueous medium. In a preferred 5 L ' t, mixed AVE/MA copol5~mer salts are prepared by the interaction of the AVEIMA copolymer (I) with cationic calcium, sodium, lg , potassium, zinc, strontium (and mixtures thereofl , ' having a functional group as specifed above for cationic zinc or strontium ~ r ~' In a preferred mixed AVE/MA copolymer e L- ' t, the oxide of zinc and the hydroxide of ~o calcium are utilized.
Since zinc hydroxide is not uun~ c~ "S, available, its use as a reactant is readily and more 'lS. e ,' ' ' by employing an aqueous slurry of particular zinc oxide which, although practically irlsoluble in water, provides hydration to zinc hydroxide on the particulate surface. Strontium hydroxide, on the 2s otber hand, is available in either crystalline or powder form and is soluble in about 50 parts water. Aqu~ous solutions of strontium oxide, however, which forms the hydroxide when treated with water (caution: heat evolution), may also be used.
Anions that form toxic, irritating or, ~, by-products should be avoided, or special ~ liu.... and treatment provided to assure the removal and 30 absence of such by-produhs from the polymeric salt end-produh The particular compound used should be ' '1~ pure to assure obtaining a ' '~S pure, '~ off-white polymeric salt end-produh~
The lower alxyl vinyl ether maleic acid ~AVE/MA) co~ are readily obtained by ~,upul~ a lower alkyl vinyl ether monomer, such as methyl vinyl 35 ether, ethyl vinyl ether, divinyl ether, propyl vinyl ether and isobutyl vinyl ether, with maleic anhydride to yield the ,u-,~ r '- ~, lower alkyl vinyl ether-maleic anhydride copolymer which is readily l~ ul~Lablc tû the acid copolymer (I). Both anhydride .. ....
wo ssl33434 2 1 q ~ 1 8 0 PCT/US9S/07280 and acid forms are also available from commercial suppliers. For example, the GAF
Corporation, Wayne, N.J. provides both the polyrneric free acid form (I) and theLUllL_r " _ anhydride form under its "GANTREZ" trademark as the "GANTREZ
S Series" and "GANTREZ AN Series", l~ .Li~ . In the forrner acid series, the s GANTREZ S-97 (M. W. TM 5û,00û) is particularly suitable, and, in the latter anhydride series, the GANTREZ AN-149 (M. W. = 50,000) the GANTREZ AN-169 (M. W = 67,000) and the GANTREZ AN-179 (M. W. = 80,000) cu~ùlyll~ are particularly suitable. The acid and anhydride forrns of AVE/MA .,u~.ul~....,.~, having an average molecular weight of from about 50,000 to about 80,000 (as measured byo membrane osmometry in 2-butanone 1-10 grarns/1000 ml solution), are also by having the previously described specific viscosity parameter of more than 1.2. When the anhydride copolymer dissolves in water, the anhydride linkage is cleaved so that the highly polar, polymeric free acid (I) is forrned. Accordingly, the anhydride form, which is relatively less expensive than the acid form, may be used as a convenient and cheaper precursor for the acid. Elevated le~ LLIlct may be a i v - ~ O. .r . ~l y employed to enhance the rate of ', J. i~c to-acid hydrolysis.
In general, the lower alkyl vinyl ether-maleic acid copolymer (I), or its cullL-r ' _ anhydride, is added to water preheated to about 70-80C. with vigorous stirring to form a l~.,. h.-~ru~ mixture. If the anhydride precursor isutilized, it is . ~.. \ l ~l that the aqueous mixture be further heated to about 90 C. with stirring to ensure complete hydrolysis of the anhydride to the acid form.
Heating is then ~' l aithough mixing is continued untii the batch turns clear with a ' decrease in viscosity (about 65-75C.). An aqueous solution of the cationic zinc or strontium sait forming compound, or, for example, an aqueous 25 dispersion of particulate zinc oxide in the form of a slurry, in an amount sufficient to provide the desire cationic content desired in the end-product, is separately prepared at arnbient i , I; and slowly added to the hot polyrneric acid solution with continuous vigorous mixing so as to prevent locaiized IJlC~.;,Ll;LdL;L.~ of the cationic polyrneric sait. After addition is complete, mixing is continued to ensure that all the 30 sait forming compound is rcacted with the copolymer.
, an aqueous soiution containing the zinc or strontium source is preheated to 70-80C. with vigorous stirring to forrn a 1, ~. u~ slurry. The lower aikyl vinyl ether-maieic acid copolymer (I) or its ~OIl~_r ~' _ anhydride is then added to the slurry while further heating to 90C. and stirring tû ensure 35 complete hydrolysis.
The reaction batch is then dried such as by shallow drying trays in a convection oven maintained at about 70C. with hot air circulation to evaporate the WO 95/3343~1 2 1 9 2 1 8 0 PCT/US95107280 water content and recover the polymeric salt product in dry form. Altematively, the reaction batch is then transferred to 5 drum dryers maintained at 80-100 PSIG with hot steam to evaporate the water content and recover the polymeric salt in the flake fomm.
s The resulting flakes may be subjected to milling and screening to yield thedesired physical properties to provide satisfactory denture stabilizing properties.
The salts are ~iable so that ~Iyyl~y~;at~, particle size and bulk density can be obtained. For best results, particles should be capable of passage through a 140- to 200-mesh sieve (U.S.B.S. series) and preferably are less than 0.74 millimeter in their 0 largest dimension.
The subject zinc or strontium AVE/MA copolymer salts have exceptional adhesive qualities when contacted with water or saliva such that they are extremely useful as denture adhesive materials in denture stabilizing ~ c For such use the salt in particulate fomm is preferably cl.~..~.,i.,.i,.~,~ by a particle size of at least 5 minus 140-mesh U.S.B.S. sieve; a bulk density greater than 0.3 gram per cubic centimeter and preferably higher than 0.6 gram per cubic centimeter; and a pH
between 3 and 7.0, the pH being detemlined on a one percent by weight dispersion in water.
The subject zinc or strontium AVE/MA copolymer salts may be utilized in 20 effective adhesive amounts, preferably at least 20 percent by weight, as the sole adhesive component or as a co-adhesive in joint usage with other active adhesive - r ' in denture stabilizing . Preferably, the unmixed zinc or strontium AVE/MA copolymer salts may be utilized with mixed AVEIMA copolymer salts containing cations such as calcium, sodium, magnPcil~m potassium, r - -2Jr zinc, strontium, and mixtures thereo r~5~-lh~ - Glycol The invention .~ also comprise pGl.~lh/l~ glycol. In general, yO1~ ,,~ glycols are polymers with the general fommula (OCH2CH2)nOH, where n is greater than or equal to 4. The pul.~..h,!~ glycols are designated by a number 30 that represents the average molecular weight ~Merck Index. Tenth Edition, No. 7441, 1983]
The present , comprise p~ . glycol having an average molecular weight above about 100 and equal to or below about 600. Preferred is p~ glycol having an average molecular weight of equal to or greater than 3s about 300 and equal to or below about 600. rul~,.l./l, .. , glycol having an average molecular weight of about 400 is most preferred. The -y.Jl~.,lhjl~,..e glycols suitable -wo ss/33434 2 1 9 2 1 8 0 PCTIUS95107280 for use in the present inYention are well known and ~ available, such as those marketed by Union Carbide Corporation under the trademark "Carbowax".
The level of pol~ hJ ' giycol that is useful in the present invention is based on ' ~' 'I"'`'I;fJ''` containing AVE/MA copolymer saits ..l, -,- .Irl;~d by a particle size s of at least minus 140-mesh U.S.B.S. sieve. Therefore, P~JI~ hYI~ ; glycol having an average molecular weight above about 100 and equal to or below about 600 is present at a level of from about 20% to about 90%, preferably from about 30/0 to about 80%, and most preferably from about 35% to sbout 75%, by weight of the invention ' Optional ,; . , . ~
The present invention , may also include a safe and adhesively effective amount of a co-adhesive. The term "safe and adhesively effective amount"
as used herein means an amount sufficient to provide adherence of a denture or dental prosthesis to the orai cavity.
Preferred co-adhesives include a water-soluble hydrophilic colloid or polymer having the property of swelling upon exposure to moisture to form a mass. Such adhesive materiais include natural gums, synthetic polymeric gums, adhesive materiais commoniy employed in denture stabilizing ~ ,- and compatible with the subject AVE~A copolymer salts, synthetic poiymers, saccharide derivatives, cellulose derivatives, and mixtures thereo Examples of such materiais include karaya gum, guar gum, gdatin, algin, sodium alginate, tragacanth, h,' " ' , acrylamide polymers, ethylene oxide polymers, pul~
cationic ~fJI~ ~' ' ' polymers, ~bu~ ' ~ II,ulù~e, sodium .~i,uA~....,I~.~l~,eiiui~se and mixed partiai saits of poly(vinyl methyl-ether maleate).
25 Sodium ~ " ' is most preferred for use in the present invention. In generai, the co-adhesives may be present at a level of from about 5% to about 70%
by weight of the ~ .
Other suitable optionai ingredients include colorants; preservatives such as methyl and propyl parabens; thickeners such as silicon dioxide, and pfJI.~
30 giycol having an average molecular weight of 8000; and vehicles such as liquid , petrolatum, minerai oil, and giycerin. Preferred are ~JIJ~ l.., glycol having an average molecular weight of 8000, minerai oil, and petrolatum. Colorants, ..,I va~ , thickeners, and vehicles may be present at levels of from about 0% to about 20%, by weight of the c~
The , - of the present invention may optionally include from about 0.01% to about 5% of one or more c , which provide the user with sensory, including flavor, benefits. Suitable r include natural or artificial w095/3343.1 21/~2180 r~u~
sweetening agents, menthol, methyl lactate, ~ , oil, peppermint oil, spearmint oil, leaf alcohol, as well as coolants 3~ ,.u~,~u.G-1,2-diol and ~.~ ' c~ u~_ ' agents such as N-ethyl-p ' -3-~ bu~ idc which is described in U.S. Patent 4,136,163 to Watson et. al., which is i~.~,ul~o~cd 5 by reference herein in its entirety.
The ~ . of the present invention are ~ ur~ ulcJ in an art-recognized manner icnown to those sicilled in the art, such as powder, cream, ointment, liquid, or paste r".. l ~; Suitable examples of such r.... ~ ;.. are disclosed in U.S. Patent 4,518,721, issued May 21, 1985, and U.S. Patent 4,514,528, o issued April 30, 1985, both to Dhabar et ai., and both ;..vu.~u-~c~ by reference herein in their entirety.
The foliowing l~o,~ l ~ examples ii~ustrate ...~l~v~ of the subject invention wherein both essentiai and optionai ingredients are combined. These examples are given solely for the purpose of illustration and are not to be construed 5as limiting the scope of the invention F.XAMpi.F I
Inyredients. Weight %
17.5% Zinc unmixed partiai sait of AVEIMA copolymer(a) 33.0 ~orul~_L~.,!c.. ~, Glycol 400 40.5 Sodium Gubu~ yl~,ellulu ~ 17.3 Petrolatum 8.0 ru~ ......... c Glycol gO00 1.2 (a) AVE/MA copolymer salt having about 17.5% ' with zinc.
2s FXA.~PLE 11 ~ Weight %
20.0% Strontium unmixed partiai salt of AVE/MA copolymer(a) 10.0 47.5% Caicium/17.5% Zinc mixed partial salt of AVE/MA copolymer(b) 28.1 rUl~ ,J!~ . Glycol 40û 39.0 Sodium C.u~v~ ' ,1~1h.1~se 12.1 Petrolatum 10.0 Minerai Oii 0.8 (a) AVE/MA copolymer sait having about 20% : ' with strontium.
(b) AVE/MA copolymer sait having about 47.5% ' with caicium and about 17.5% 1 ' with zinc.
2 1 9 2 1 ~3 0 PCTIUS95/07280 EXAMPLE III
Wei~ht %
25% Zinc unmixed partial salt of AVEIMA copolymer(a) 11.9 s 65% Calcium panial salt of AVE/MA copolymer (b) 24.1 rul~Lh,~ Glycol 400 42.2 Sodium COIbu~y~ h.~,dl~uL~se 12.8 Petrolatum 8.0 o rU~ h.~,.. , Glycol 8000 1.0 (a) AVE/MA copolymer salt having about 25% ' with zinc.
(b) AVEJMA copolymer salt having about 65% . _~. ' with calcium.
Examples l-m are prepared as follows. Combine P~IJ~,.I,J~ glycol 400, petrolatum, (and mineral oil if present) and heat to SS-65C until liquid. Add sodium 15 hu~u~.. ~.h,1~ " ' , pul~,.l.. ,l~.. ~ glycol 8000, and AVE/MA copolymer salts.
Stir until well mixed. Cool to room i . ~.
Wei~ht %
25% Zinc unmixed partial salt of AVEIMA copolymer(a) 11.9 s 65% Calcium panial salt of AVE/MA copolymer (b) 24.1 rul~Lh,~ Glycol 400 42.2 Sodium COIbu~y~ h.~,dl~uL~se 12.8 Petrolatum 8.0 o rU~ h.~,.. , Glycol 8000 1.0 (a) AVE/MA copolymer salt having about 25% ' with zinc.
(b) AVEJMA copolymer salt having about 65% . _~. ' with calcium.
Examples l-m are prepared as follows. Combine P~IJ~,.I,J~ glycol 400, petrolatum, (and mineral oil if present) and heat to SS-65C until liquid. Add sodium 15 hu~u~.. ~.h,1~ " ' , pul~,.l.. ,l~.. ~ glycol 8000, and AVE/MA copolymer salts.
Stir until well mixed. Cool to room i . ~.
Claims (14)
1. An adhesive composition comprising:
a) from 10% to 80% of an unmixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of the structural unit in a molecule of the copolymer and n is large enough to characterize the copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25C, and wherein the partial salts contain a cationic salt function of from 0.1% to 60% zinc or strontium cations, of the initial carboxyl groups reacted; and b) from 20% to 90% of polyethylene glycol having an average molecular weight above 100 and equal to or below 600.
a) from 10% to 80% of an unmixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of the structural unit in a molecule of the copolymer and n is large enough to characterize the copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25C, and wherein the partial salts contain a cationic salt function of from 0.1% to 60% zinc or strontium cations, of the initial carboxyl groups reacted; and b) from 20% to 90% of polyethylene glycol having an average molecular weight above 100 and equal to or below 600.
2. The composition according to Claim 1 further comprising from 0.1% to 75%
of one or more mixed partial salts of lower alkyl vinyl ether-maleic acid copolymers wherein the partial salts contain a cationic salt function selected from the group consisting of calcium, sodium, magnesium, potassium, ammonium, zinc, strontium, and mixtures thereof.
of one or more mixed partial salts of lower alkyl vinyl ether-maleic acid copolymers wherein the partial salts contain a cationic salt function selected from the group consisting of calcium, sodium, magnesium, potassium, ammonium, zinc, strontium, and mixtures thereof.
3. The composition according to Claim 2 comprising from 20% to 90% of polyethylene glycol having an average molecular weight of equal to or greater than 300 and equal to or below 600.
4. An adhesive composition comprising:
a) from 20% to 70% of an unmixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of the structural unit in a molecule of the copolymer and n is large enough to characterize the copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25C, and wherein the partial salts contain a cationic salt function of from 0.1% to 60% zinc or strontium cations, of the total initial carboxyl groups reacted; and b) from 30% to 80% of polyethylene glycol having an average molecular weight above 100 and equal to or below 600.
a) from 20% to 70% of an unmixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of the structural unit in a molecule of the copolymer and n is large enough to characterize the copolymer as having a specific viscosity larger than 1.2, the specific viscosity being determined in methyl ethyl ketone at 25C, and wherein the partial salts contain a cationic salt function of from 0.1% to 60% zinc or strontium cations, of the total initial carboxyl groups reacted; and b) from 30% to 80% of polyethylene glycol having an average molecular weight above 100 and equal to or below 600.
5. The composition according to Claim 4 further comprising from 0.1% to 75%
of one or more mixed partial salts of lower alkyl vinyl ether-maleic acid copolymers wherein the partial salts contain a cationic salt function selected from the group consisting of calcium, sodium, magnesium, potassium, ammonium, zinc, strontium, and mixtures thereof.
of one or more mixed partial salts of lower alkyl vinyl ether-maleic acid copolymers wherein the partial salts contain a cationic salt function selected from the group consisting of calcium, sodium, magnesium, potassium, ammonium, zinc, strontium, and mixtures thereof.
6. The composition according to Claim 5 comprising from 30% to 80% of polyethylene glycol having an average molecular weight of equal to or greater than 300 and equal to or below 600.
7. The composition according to Claim 6 wherein (a) is zinc.
8. The composition according to Claim 7 further comprising optional components selected from the group consisting of colorants, preservatives, thickeners, vehicles, and mixtures thereof.
9. The composition according to Claim 8 further comprising a safe and adhesively effective amount of a co-adhesive selected from the group consisting of natural gums, synthetic polymeric gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof.
10. An adhesive composition comprising:
a) from 25% to 65% of an unmixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of the structural unit in a molecule of the copolymer and n is large enough to characterize the copolymer as having a specific viscosity larger than 1.2, the specifc viscosity being determined in methyl ethyl ketone at 25C, and wherein the partial salts contain a cationic salt function of from 10% to 60% zinc or strontium cations, of the total initial carboxyl groups reacted;
b) a mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer wherein the partial salt contains a cationic salt function of from 0.1% to 65% zinc or strontium cations, and from 10% to 75% calcium cations, of the total initial carboxyl groups reacted; and c) from 35% to 75% of polyethylene glycol having an average molecular weight of 400.
a) from 25% to 65% of an unmixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer consisting essentially of the repeated structural unit:
(I) wherein R represents a C1 to C4 alkyl radical, n is an integer greater than one representing the number of repeated occurrences of the structural unit in a molecule of the copolymer and n is large enough to characterize the copolymer as having a specific viscosity larger than 1.2, the specifc viscosity being determined in methyl ethyl ketone at 25C, and wherein the partial salts contain a cationic salt function of from 10% to 60% zinc or strontium cations, of the total initial carboxyl groups reacted;
b) a mixed partial salt of a lower alkyl vinyl ether-maleic acid copolymer wherein the partial salt contains a cationic salt function of from 0.1% to 65% zinc or strontium cations, and from 10% to 75% calcium cations, of the total initial carboxyl groups reacted; and c) from 35% to 75% of polyethylene glycol having an average molecular weight of 400.
11. The composition according to Claim 10 wherein (a) is zinc.
12. The composition according to Claim 11 further comprising optional components selected from the group consisting of colorants, preservatives, thickeners, vehicles, and mixtures thereof.
13. The composition according to Claim 12 further comprising a safe and adhesively effective amount of a co-adhesive selected from the group consisting of natural gums, synthetic polymeric gums, synthetic polymers, saccharide derivatives, cellulose derivatives, and mixtures thereof.
14. The composition according to Claim 13 wherein the mixed partial salt further comprises a cationic salt function of from 1% to 20% sodium cations.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25761294A | 1994-06-09 | 1994-06-09 | |
US257,612 | 1994-06-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2192180A1 true CA2192180A1 (en) | 1995-12-14 |
Family
ID=22976999
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002192180A Abandoned CA2192180A1 (en) | 1994-06-09 | 1995-06-07 | Denture stabilizing compositions |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0764012A1 (en) |
JP (1) | JPH10501242A (en) |
AU (1) | AU2700695A (en) |
CA (1) | CA2192180A1 (en) |
WO (1) | WO1995033434A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5696181A (en) * | 1995-09-22 | 1997-12-09 | The Block Drug Company, Inc. | Denture fixative |
US5985312A (en) * | 1996-01-26 | 1999-11-16 | Brown University Research Foundation | Methods and compositions for enhancing the bioadhesive properties of polymers |
US6368586B1 (en) | 1996-01-26 | 2002-04-09 | Brown University Research Foundation | Methods and compositions for enhancing the bioadhesive properties of polymers |
WO1998043595A1 (en) * | 1997-03-27 | 1998-10-08 | The Procter & Gamble Company | Denture stabilizing compositions |
JP3957195B2 (en) * | 2001-01-24 | 2007-08-15 | ブライトスマイル プロフェッショナル インク. | Topical oral care composition |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4514528A (en) * | 1983-02-16 | 1985-04-30 | Richardson-Vicks Inc. | Hydrophilic denture adhesive |
US4758630A (en) * | 1986-10-27 | 1988-07-19 | Richardson-Vicks Inc. | Denture stabilizing zinc and strontium salts of ave/ma copolymer |
-
1995
- 1995-06-07 WO PCT/US1995/007280 patent/WO1995033434A1/en not_active Application Discontinuation
- 1995-06-07 JP JP8501304A patent/JPH10501242A/en active Pending
- 1995-06-07 EP EP95922258A patent/EP0764012A1/en not_active Withdrawn
- 1995-06-07 AU AU27006/95A patent/AU2700695A/en not_active Abandoned
- 1995-06-07 CA CA002192180A patent/CA2192180A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
WO1995033434A1 (en) | 1995-12-14 |
AU2700695A (en) | 1996-01-04 |
EP0764012A1 (en) | 1997-03-26 |
JPH10501242A (en) | 1998-02-03 |
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