CA2031121A1 - Denture stabilizer - Google Patents
Denture stabilizerInfo
- Publication number
- CA2031121A1 CA2031121A1 CA 2031121 CA2031121A CA2031121A1 CA 2031121 A1 CA2031121 A1 CA 2031121A1 CA 2031121 CA2031121 CA 2031121 CA 2031121 A CA2031121 A CA 2031121A CA 2031121 A1 CA2031121 A1 CA 2031121A1
- Authority
- CA
- Canada
- Prior art keywords
- adhesive composition
- denture adhesive
- weight
- percent
- total weight
- 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
- 239000003381 stabilizer Substances 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 117
- 230000001070 adhesive effect Effects 0.000 claims abstract description 112
- 239000000853 adhesive Substances 0.000 claims abstract description 111
- 125000002091 cationic group Chemical group 0.000 claims abstract description 35
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 27
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 27
- 239000011976 maleic acid Substances 0.000 claims abstract description 27
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims abstract description 27
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 27
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 26
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 26
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 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 abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000006071 cream Substances 0.000 claims description 31
- -1 halogen ion Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 239000002480 mineral oil Substances 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 235000010446 mineral oil Nutrition 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 239000004264 Petrolatum Substances 0.000 claims description 9
- 229940066842 petrolatum Drugs 0.000 claims description 9
- 235000019271 petrolatum Nutrition 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 231100000252 nontoxic Toxicity 0.000 claims description 5
- 230000003000 nontoxic effect Effects 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 4
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 4
- 239000000546 pharmaceutical excipient Substances 0.000 claims 4
- 239000000843 powder Substances 0.000 abstract description 14
- 238000009472 formulation Methods 0.000 description 29
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 22
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 22
- 239000004615 ingredient Substances 0.000 description 17
- 239000001525 mentha piperita l. herb oil Substances 0.000 description 11
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 11
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 11
- 229960002216 methylparaben Drugs 0.000 description 11
- 235000019477 peppermint oil Nutrition 0.000 description 11
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 11
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 description 11
- 229960003415 propylparaben Drugs 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 229920002367 Polyisobutene Polymers 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000001464 adherent effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001206 natural gum Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 210000000214 mouth Anatomy 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012956 testing procedure Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920000569 Gum karaya Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 101000654316 Centruroides limpidus Beta-toxin Cll2 Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000015125 Sterculia urens Nutrition 0.000 description 1
- 240000001058 Sterculia urens Species 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 description 1
- 239000000305 astragalus gummifer gum Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000231 karaya gum Substances 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- IHBKAGRPNRKYAO-UHFFFAOYSA-M methyl sulfate;trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound COS([O-])(=O)=O.CC(=C)C(=O)OCC[N+](C)(C)C IHBKAGRPNRKYAO-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Landscapes
- Dental Preparations (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improved anhydrous denture adhesive composition is prepared to contain a mixture of a cationic acrylamide polymer, sodium carboxymethylcellulose and a mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid). The composition may be formulated as a powder or anhydrous paste, which when applied to dentures and exposed to moisture, develops superior adhesive properties. Suitable cationic acrylamide polymers include a copolymer of acrylamide and Beta-acryloyloxyethyltrimethyl-ammonium chloride, or a copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate.
An improved anhydrous denture adhesive composition is prepared to contain a mixture of a cationic acrylamide polymer, sodium carboxymethylcellulose and a mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid). The composition may be formulated as a powder or anhydrous paste, which when applied to dentures and exposed to moisture, develops superior adhesive properties. Suitable cationic acrylamide polymers include a copolymer of acrylamide and Beta-acryloyloxyethyltrimethyl-ammonium chloride, or a copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate.
Description
P7283SOl/9 IMPROVE~D DENTrURB 8$ABII~IZBR
B~CKGROUND OF TH}~ INVENTION
1. Field of the Invention This invention relates to denture adhesives or stabilizers, and particularly to an improved anhydrous denture adhesive composition.
B~CKGROUND OF TH}~ INVENTION
1. Field of the Invention This invention relates to denture adhesives or stabilizers, and particularly to an improved anhydrous denture adhesive composition.
2. Description of the Prior Art Traditionally, adherent powders used to secure dentures within the mouth were prepared from such materials as finely powdered natural gums, i.e., karaya, acacia or tragacanth gum. These materials have the particular property of swelling to many times their original volume upon the addition of water to form a gelatinous or mucilaginous mass.
Denture adhesive powders may be a combination of one or more natural gums, generally flavored with pleasant tasting volatile oils. Many other additives may also be included, such as antiseptics, stabilizers, bactericides, special deodorants, plasticizing agents, fillers, coloring agents, and the like.
Cream forms of the denture adherent, prepared from finely ground particles of the natural gums dispersed in a cream base, are also available and may be used instead of the powder compositions. In any event, when wet with water, the natural gum in either the cream or powder formulation, expands to become a viscous gel which acts as a cushion and an adherent between the denture plate and the gum tissue.
While these relatively simple formulations are effective in securing dentures within the oral cavity for a short period of time, generally more than one application of adhesive per day is necessary. This is, at best, inconvenient and therefore, most undesirable.
In recent years, there have been numerous improvements in the above-described simple denture adhesive formulations.
For example, in U.S. Patent No. 3,003,988, a water insoluble, water-sensitized copolymer is disclosed as the adhesive or stabilizing component of a denture composition.
P7283sol/s ~ 2 More particularly, this patent discloses mixed, partial salts of copolymers of maleic anhydride with lower alkyl-vinyl-ethers, and partial esters of these salts, as the adhesive material. For example, the calcium-sodium partial salts of a partial isopropyl ester of methyl vinyl ether/maleic anhydride copolymer is said to provide a superior denture adhesive.
Another improvement over conventional denture adhesives is claimed in U.S. Patent No. 3,511,791, which teaches that copolymers of acrylamide and acrylic acid or homopolymers of acrylamide can form the principle adhesive component in a denture adherent to provide sustained adherence in use without swelling. Whenever a homopolymer of acrylamide, which is nonionic in character, is used, gum karaya is added to the formulation in order to provide a synergistic improvement in gel strength and adhesiveness.
U.S. Patent No. 3,736,274 discloses a denture adhesive containing three essential ingredients: a maleic anhydride and/or acid copolymer (with a lower alkyl vinyl ether), a polymeric N-vinyl lactam, and sodium carboxymethyl cellulose, preferably incorporated into a diluent such as petrolatum and/or mineral oil.
U.S. Patent No. 3,919,357 provides anhydrous powders and creams useful in cosmetic and drug products such as denture adhesive powders, prepared from an anionic/cationic adhesive co~bination, toqether with a powdered polyethylene or powdered polypropylene polymer. Example I shows the formulation of a denture adhesive powder which includes poly (methyl vinyl ether/maleic acid) and a copolymer of 85% by weight acrylamide with 15% by weight Beta-methacryloyloxyethyltrimethyl ammonium methyl sulfate, as well as powder polyethylene having an average molecular weight of 2000 and havinq a particle size such that 99.5% of the polyethylene powder passes through a 60 mesh screen.
U.S. Patent No. 4,393,080 discloses an adhesive composition which may include sodium carboxymethylcellulose P7283SOl/9 2 ~ ~ ~ 1 2 1 as well as sodium, calcium poly (methyl vinyl ether/maleic acid), as illustrated in Examples 4, 6, 10, 18 and 19.
U.S. Patent No. 4,514,528 is directed to a hydrophilic denture adhesive which consists of an admixture of mixed, partial salts of lower alkyl vinyl ether-maleic anhydride-type copolymers with either sodium carboxymethylcellulose or poly (ethylene oxide) homopolymer or both in a hydrophilic vehicle.
While all of the above denture adhesives provide some improvement over simple formulations containing only finely powdered natural gums, it is generally recognized that no one product has yet been developed which can accommodate, over a long period of time, the many variations in temperatures, pH and mechanical agitation which are quite normal in the oral cavity.
It has now been found that the denture adhesive of this invention will provide superior adherent properties over prolonged periods of time and under unusually varied conditions, without the disadvantages characteristic of previously known products.
SVMMARY OF ~HE INVENTION
An anhydrous denture adhesive composition exhibiting superior performance as a denture stabilizer comprises a mixture of a cationic acrylamide polymer, sodium carboxymethylcellulose, and a mixed, calcium/sodium partial salt of poly tmethyl vinyl ether/maleic acid) in an optional petrolatum-like vehicle. The invention also involves a method for preparing these novel denture stabilizers.
DESCRIPTION OF THE INVENTION
Applicant has unexpectedly discovered a denture adhesive composition comprising a substantially anhydrous mixture of:
~ a) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a cationic acrylamide polymer having the formula:
Denture adhesive powders may be a combination of one or more natural gums, generally flavored with pleasant tasting volatile oils. Many other additives may also be included, such as antiseptics, stabilizers, bactericides, special deodorants, plasticizing agents, fillers, coloring agents, and the like.
Cream forms of the denture adherent, prepared from finely ground particles of the natural gums dispersed in a cream base, are also available and may be used instead of the powder compositions. In any event, when wet with water, the natural gum in either the cream or powder formulation, expands to become a viscous gel which acts as a cushion and an adherent between the denture plate and the gum tissue.
While these relatively simple formulations are effective in securing dentures within the oral cavity for a short period of time, generally more than one application of adhesive per day is necessary. This is, at best, inconvenient and therefore, most undesirable.
In recent years, there have been numerous improvements in the above-described simple denture adhesive formulations.
For example, in U.S. Patent No. 3,003,988, a water insoluble, water-sensitized copolymer is disclosed as the adhesive or stabilizing component of a denture composition.
P7283sol/s ~ 2 More particularly, this patent discloses mixed, partial salts of copolymers of maleic anhydride with lower alkyl-vinyl-ethers, and partial esters of these salts, as the adhesive material. For example, the calcium-sodium partial salts of a partial isopropyl ester of methyl vinyl ether/maleic anhydride copolymer is said to provide a superior denture adhesive.
Another improvement over conventional denture adhesives is claimed in U.S. Patent No. 3,511,791, which teaches that copolymers of acrylamide and acrylic acid or homopolymers of acrylamide can form the principle adhesive component in a denture adherent to provide sustained adherence in use without swelling. Whenever a homopolymer of acrylamide, which is nonionic in character, is used, gum karaya is added to the formulation in order to provide a synergistic improvement in gel strength and adhesiveness.
U.S. Patent No. 3,736,274 discloses a denture adhesive containing three essential ingredients: a maleic anhydride and/or acid copolymer (with a lower alkyl vinyl ether), a polymeric N-vinyl lactam, and sodium carboxymethyl cellulose, preferably incorporated into a diluent such as petrolatum and/or mineral oil.
U.S. Patent No. 3,919,357 provides anhydrous powders and creams useful in cosmetic and drug products such as denture adhesive powders, prepared from an anionic/cationic adhesive co~bination, toqether with a powdered polyethylene or powdered polypropylene polymer. Example I shows the formulation of a denture adhesive powder which includes poly (methyl vinyl ether/maleic acid) and a copolymer of 85% by weight acrylamide with 15% by weight Beta-methacryloyloxyethyltrimethyl ammonium methyl sulfate, as well as powder polyethylene having an average molecular weight of 2000 and havinq a particle size such that 99.5% of the polyethylene powder passes through a 60 mesh screen.
U.S. Patent No. 4,393,080 discloses an adhesive composition which may include sodium carboxymethylcellulose P7283SOl/9 2 ~ ~ ~ 1 2 1 as well as sodium, calcium poly (methyl vinyl ether/maleic acid), as illustrated in Examples 4, 6, 10, 18 and 19.
U.S. Patent No. 4,514,528 is directed to a hydrophilic denture adhesive which consists of an admixture of mixed, partial salts of lower alkyl vinyl ether-maleic anhydride-type copolymers with either sodium carboxymethylcellulose or poly (ethylene oxide) homopolymer or both in a hydrophilic vehicle.
While all of the above denture adhesives provide some improvement over simple formulations containing only finely powdered natural gums, it is generally recognized that no one product has yet been developed which can accommodate, over a long period of time, the many variations in temperatures, pH and mechanical agitation which are quite normal in the oral cavity.
It has now been found that the denture adhesive of this invention will provide superior adherent properties over prolonged periods of time and under unusually varied conditions, without the disadvantages characteristic of previously known products.
SVMMARY OF ~HE INVENTION
An anhydrous denture adhesive composition exhibiting superior performance as a denture stabilizer comprises a mixture of a cationic acrylamide polymer, sodium carboxymethylcellulose, and a mixed, calcium/sodium partial salt of poly tmethyl vinyl ether/maleic acid) in an optional petrolatum-like vehicle. The invention also involves a method for preparing these novel denture stabilizers.
DESCRIPTION OF THE INVENTION
Applicant has unexpectedly discovered a denture adhesive composition comprising a substantially anhydrous mixture of:
~ a) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a cationic acrylamide polymer having the formula:
- 3 -P7283SOl/9 2 ~ 2 ~
--F CH CIIO ¦_ Cll 2 - C
J H C O
C~2 CH ~ C 13 L
N
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N is an integer between 5-20, inclusive.
(b) from about 10 to about 43 percent by weight, based on the total weight of the denture adhesive composition, of sodium carboxymethylcellulose: and (c) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a mixed, calcium/sodium partial salt of poly (methyl vinyl ether/maleic acid).
The denture adhesive compositions formed in accordance with the above-listed combination yield a product which provides surprising good performance as a denture stabilizer. Specifically, denture adhesives of the present invention require fewer applications per day, exhibit increased holding power and time of holding, and provide greater consumer confidence of product function.
The invention comprises a unique combination of three essential components, namely a specific cationic acrylamide polymer, sodium carboxymethylcellulose and a mixed salt of poly (methyl vinyl ether/maleic acid). In the absence of P7283SOl/9 any of these components from the formulations of this invention, compositions may be prepared which do not exhibit the enhanced effect achieved from this combination.
Suitable cationic acrylamide polymers of the invention have the general formula:
[ N2 c T ~ l2 _~ ~
CH~.-- N --Cll~
~ N
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N is an integer between 5-20, inclusive. Halogen ion is understood to mean any one of the electronegative elements in Group VII~ of~the Periodic Table, namely fluorine, chlorine, bromine, iodine or astatine.
Particularly preferred species of cationic acrylamide polymers include the copolymers of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate, and preferably comprises a copolymer of acrylamide and Beta-acryloyloxyethyltrimethylammonium chloride. The latter, preferred, cationic acrylamide polymer is commercially available under the trademark E-l911Rx (American Cyanamid). The copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and P7283SOl/9 2 ~ 3 1 1 2 ~
dimethyl sulfate is commercially available under the trademark Polytec 7M (SNF Floerger).
Sodium carboxymethylcellulose, which i8 the second component in the inventive formulations is a synthetic gum derived from cellulose, and generally comprises an anionic, water-soluble, long chain polymer. The preferred sodium carboxymethylcellulose utilized in the present invention is commercially available from Hercules Incorporated under the trademark CMC 7HXF.
The mixed, partial salts of poly(methyl vinyl ether/maleic acid) employed in the present invention are preferably the mixed salts of calcium and sodium which are commercially available under the trademark Gantrez MS955 (General Aniline and Film Corp.).
The three essential components utilized in the present denture adhesive composition physically interact to form a two adhesive system which surprisinqly outperforms either adhesive system taken individually. The first adhesive system is based on an anionic/cationic interaction between sodium carboxymethylcellulose and the cationic acrylamide polymer. The second adhesive system comprises the mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid). When these two systems are combined according to the present invention, a denture adhesive composition providing surprising performance as a denture stabilizer is provided.
In a preferred embodiment of the invention, the cationic acrylamide polymer is present in amounts of from about 8% to about 27~ by weight, based on the total weight of the denture adhesive composition; sodium carboxymethylcellulose i8 present in amounts of from about 15~ to about 43~ by weight, based on the total weight of the denture adhesive composition; and the mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid) is present in amounts of ~rom about 10% to about 27% by weight, based on the total weight of the denture adhesive composition.
The denture adhesive compositions of this invention maybe formulated to contain the cationic acrylam~de polymer, sodium carboxymethylcellulose, and mixed, calcium/sodium partial salts of poly(methyl vinyl ether/maleic acid) in either powder or paste form. In the powder formulation, the components are admixed with conventional flavors and colorants, together with other non-essential ingredients such as non-toxic anti-caking agents (silica, magnesium stearate, talcum powder or the like). The mixture of ingredients is thoroughly agitated or stirred to yield a generally homogenous intermixing of all components. In the past formulations, the cationic acrylamide polymer, sodium carboxymethylcellulose, and mixed, calcium/sodium partial salts of poly(methyl vinyl ether/maleic acid) are admixed with petrolatum, mineral, animal or vegetable oils, and the like, along with flavors, colorants and certain commonly used preservatives and fillers.
A particularly preferred paste or cream formulation is prepared by utilizing as the cream or paste base, the product of U.S. Patent No. 3,215,599. The cream or paste base of this patent is characterized as a mixture of white petroleum oil with a minor amount of a polyethylene wax having an average molecular weight of 1,000 to 20,000. This product is described as having emollient properties, useful in the formulation of medicaments where absorption of the medicaments by the skin is of paramount importance. Denture adhesive creams formulated with this petroleum oil/polyethylene wax blend as the paste or cream base display unusually good stability, extrudability and product appearance.
The method for preparing the denture adhesive compositions according to the present invention, whether formulated as a powder or paste, employs conventional types of mixing equipment which are known in the art for blending, heating and cooling solids and liguids.
P7283So1/g ~ 3 ~
Whether formulated as a powder or paste, the denture adhesive mixture of this invention, when applied to dentures and exposed to moisture, hydrates to form an adhesive compo~ition which exhibits unexpectedly superior characteristics in comparison with denture adhesives of the prior art.
The following examples are given to illustrate the invention, but are not deemed to be limiting thereof. All percentages given throughout the specification are based on the weight of the final denture adhesive composition unless otherwise indicated.
P7283SOl/
EXAMP~ 1 Preparation of Denture Adhesive Cream A dsnture ~dhesive cream is prepared from the following ingredients:
Percent Inqredients w~W
Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 24.2 Sodium carboxymethylcellulose23.42 Cationic acrylamide polymer 12.1 Peppermint Oil O.10 Methyl Paraben 0.05 Propyl Paraben O.10 Color 0.03Q
100 . 000 A. Weigh Polyethylene, Polyisobutylene and Mineral Oil into a pot (Polyisobutylene is added as a 40% w/w concentrate in the Mineral Oil) and mix to form a homogenous mixture while raising the temperature to 90-95 C. Check to assure complete solution of the wax. With continued mixing, cool to at least 45 C.
B. Add Peppermint Oil, Methyl Paraben and Propyl Paraben to the mixture from Step A and continue mixing again until a homogenous blend is obtained.
C. Preblend the mixed partial salt of poly(methyl vinyl ether/maleic acid), sodium carboxymethylcellulose, cationic acrylamide polymer and color; add to the above mixtùre with continued mixing. After about 5 minutes scrape down as needed. Reduce pressure to about 28-29 inches vacuum and mix for about 5-10 additional minutes. The product is removed and stored for use.
This formulation was subjected to panel testing using the formulations of this Example with multiple panelists.
The panelists were requested to use the denture adhesive according to the following instructions:
1. Thoroughly brush away any remaining adhesive and _ g _ P7283SOl/9 dry dentures. 2. Apply three short strips evenly as shown.
Keep strips away from edges. Use only the amount necessary.
A few trials should indicate the proper amount and best placement of strips for your individual needs. 3. Press dentures firmly in place and hold for 20 seconds while cream sets.
The panelists were then requested to rate the denture adhesive for the following:
a) number of applications per day, b) firmness of hold (7=excellent to l=totally unusable), c) duration of hold (in hours), d) confidence of hold (l=very certain dentures would not hold, to 5=very certain dentures would hold), and e) usage intent (l=definitely would not use, to 5=definitely would use).
The results are set forth in Table I, along with the results of Example 4.
The formulation of Example 1 was then subjected to a second panel study according to the above-described testing procedure, in which the panelists were requested to rate the denture adhesive against the adhesive of a Comparative Example A. The formulation of Comparative Example A
contained only two of the three essential components of the invention (cationic acrylamide polymer, sodium carboxymethylcellulose).
The results of the second panel study are set forth in Table II.
As evidenced by the data of Table II, the formulation o~ Example 1 performed significantly better than the formulation of Comparative Example A, with respect to holding power (firmness), duration of hold, confidence of hold and usage intent.
P7283sol/s 2 ~ 2 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared according to the procedure of Example 1, using the following ingredients:
Percent Ingredients w~w Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 12.259 Sodium carboxymethylcellulose 25.00 Cationic acrylamide polymer 22.461 Peppermint Oil O.10 Methyl Paraben 0.05 Propyl Paraben O.lo Color 0-030 100. 000 The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
, P7283SO1/9 2~121 Preparation of a Denture Adhesive Cream A denture adhesive cream i~ prepared according to the procedure of Example l, using the following ingredients:
Percent Ingredients w/w Polyethylene 4.0 Polyisobutylene 4.0 Mineral Oil 32.0 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 18.00 Sodium carboxymethylcellulose 29.72 Cationic acrylamide polymer 12.0 Peppermint Oil O.10 Methyl Paraben 0.05 Propyl Paraben O.lo Color 0.030 100. ooo The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage int-nt when used by d-nture w-ar-rs.
`
~ ,-P7283sol/s 2 ~3 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared according to the procedure of Example 1, using the following ingredients:
Percent Inaredients w/w Polyethylene 4.0 Polyisobutylene 4.0 Mineral Oil 32.0 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 12.00 Sodium carboxymethylcellulose 35.72 Cationic acrylamide polymer 12.0 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0.030 100.000 The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
P7283SOl/9 2 ~ ~ 1 1 2 ~
EXAMPLE S
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared according to the procedure of Example 1, using the following ingredients:
Percent Ingredients w/w Polyethylene 2.80 Polyisobutylene 1.75 Mineral Oil 30.45 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 24.20 Sodium carboxymethylcellulose 28.438 Cationic acrylamide polymer 12.1 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0.012 100. 000 The formulation of this Example was subjected to panel testing, following the testing procedure of Example 1. The panelists were requested to rate the denture adhesive against a commercially available product A.
The results are set forth in Table III.
As illustrated therein, this adhesive formulation performed particularly well with respect to number of applications required per day and performed satisfactorily with regard to firmness, duration of hold, confidence and usage.
P7283S01/9 ~i~ 3 ~ 1 2 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared from the following ingredients:
Percent Ingredlents w/w Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 24.2 Sodium carboxymethylcellulose 23.355 Cationic acrylamide polymer 12.1 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0-035 Titanium Dioxide 0.060 100 . 000 Follow the procedures of steps A and B, as described in Example 1.
C. Preblend mixed partial salt of poly(methyl vinyl ether/maleic acid), sodium carboxymethylcellulose, cationic acrylamide polymer, color and titanium dioxide, mixing this preblend with the above mixture until a homogenous product is obtained. After about 5 minutes scrape down as needed.
Reduce pressure to about 28-29 inches vacuum and mix for about 5-10 additional minutes.
The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
P7283S01/9 2 ~ ~ ~ 1 2 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared from the following ingredients:
Percent Ingredient w/w Petrolatum 23.00 Mineral Oil 17 . 00 Cationic acrylamide polymer - 12.1 Sodium carboxymethylcellulose23.436 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 24.20 Peppermint Oil 0.10 Methyl Paraben o.OS
Propyl Paraben 0.10 Color 0.014 100. 000 A. Weigh Petrolatum and Mineral Oil into a Versamix pot. Mix with the anchor set to 75 until uniform.
B. Add Peppermint Oil, Methyl Paraben and Propyl Paraben with continued mixin~.
C. Preblend cationic acrylamide polymer, sodium carboxymethylcellulose, mixed partial salt of poly(methyl vinyl ether/maleic acid) and color by mixing in with the above mixture. After about 5 minutes scrape down as needed. Reduce pressure to about 28-29 inches vacuum and mix for about 5-10 additional minutes.
The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
P7283SOl/9 ~ I 2~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared from the following ingredients:
Percent Inaredien~ w~w Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 24.2 Sodium carboxymethylcellulose23.436 Cationic acrylamide polymer 12.1 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0.014 100. 00 Follow the procedures of steps A and B, as described in Example 1.
C. Preblend mixed partial salt of poly(methyl vinyl ether/maleic acid), sodium carboxymethylcellulose, cationic acrylamide polymer and color, mixing in the above mixture.
After about 5 minutes scrape down as needed. Reduce pressure to about 28-29" vacuum and mix for about 5-lO
additional minutes.
The cationic acrylamide polymer utilized in this formulation, unlike those of Examples 1-7, was a copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate.
The formulation of this Example was subjected to panel testing, following the testing procedure of Example 1.
The results are set forth in Table IV which shows a sati~factory number of applications, good firmness and confidence during use.
COMPA~ATIVE EXAMPLE A
Preparation of a Denture Adhesive Cream A denture adhesive creams is prepared according to the procedure of Example 7 from the following ingredients:
Percent Ingredient w~w Petrolatum 21.9848 Mineral Oil 19.9848 Silica 1.4812 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 29.6256 Sodium carboxymethylcellulose24.6880 Polyethylene oxide 1.9751 Peppermint Oil 0.0772 Methyl Paraben 0.0493 Propyl Paraben 0.0987 Color 0~0353 100. 0000 The formulation of this Example contains only two of the three essential components utilized in the invention.
As discussed above, and shown by the panel study results of Table II, the inventive formulation of Example 1 performed significantly better than that of Comparative Example A with respect to holding power (firmness), duration of hold, confidence of hold and usage intent.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and - scope of the invention and all such modifications are intended to be included within the scope of the following claims.
P7283S0l/9 TABLE I
ATTRIBUTE R~TINGS ~
~ENTURE CREAM ADHESIVE PANELISTS
Example Example l 4 #APPLICATIONS l.82 l.86 FIRMNESS 5.l9 4,99 DURATION l0.ll 9.23 CONFIDENCE 3.75 3.52 USAGE 3.86 3.67 P7283sol/~ S ~ 2 1 TABLE II
MEAN AT$RIBUT~ RATINGS ~Y
DENTURE CREAM ADH~SIVE PANELISTS
Example 1 Comparative Example A
#APPLICATIONS 1.95 2.075 FIRMNESS 5.27 4.61 DURATION 9.86 8.23 CONFIDENCE 3.82 3.22 USAGE 3.89 3.33 P7283SOl/9 ~ ~ 3 TABLE III
MEAN ATTRIBUTE RATINGS BY
DENTURE CREAM ADHESIVE PANELISTS
Example 5 #APPLICATIONS 1.54 FIRMNESS 5.42 DURATION 11.38 CONFIDENCE 4.08 USAGE 4.13 ~1 12~
ABLE I_ ~a_ ATT~IBUTE RATINGS BY
DENTURE CREAM ADHESIVE PANELISTS
E~ample 8 #APPLICATIONS 1.84 FIRMNESS 5.32 DURATION 12.66 CONFIDENCE 4.58 USAGE 4.26
--F CH CIIO ¦_ Cll 2 - C
J H C O
C~2 CH ~ C 13 L
N
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N is an integer between 5-20, inclusive.
(b) from about 10 to about 43 percent by weight, based on the total weight of the denture adhesive composition, of sodium carboxymethylcellulose: and (c) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a mixed, calcium/sodium partial salt of poly (methyl vinyl ether/maleic acid).
The denture adhesive compositions formed in accordance with the above-listed combination yield a product which provides surprising good performance as a denture stabilizer. Specifically, denture adhesives of the present invention require fewer applications per day, exhibit increased holding power and time of holding, and provide greater consumer confidence of product function.
The invention comprises a unique combination of three essential components, namely a specific cationic acrylamide polymer, sodium carboxymethylcellulose and a mixed salt of poly (methyl vinyl ether/maleic acid). In the absence of P7283SOl/9 any of these components from the formulations of this invention, compositions may be prepared which do not exhibit the enhanced effect achieved from this combination.
Suitable cationic acrylamide polymers of the invention have the general formula:
[ N2 c T ~ l2 _~ ~
CH~.-- N --Cll~
~ N
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N is an integer between 5-20, inclusive. Halogen ion is understood to mean any one of the electronegative elements in Group VII~ of~the Periodic Table, namely fluorine, chlorine, bromine, iodine or astatine.
Particularly preferred species of cationic acrylamide polymers include the copolymers of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate, and preferably comprises a copolymer of acrylamide and Beta-acryloyloxyethyltrimethylammonium chloride. The latter, preferred, cationic acrylamide polymer is commercially available under the trademark E-l911Rx (American Cyanamid). The copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and P7283SOl/9 2 ~ 3 1 1 2 ~
dimethyl sulfate is commercially available under the trademark Polytec 7M (SNF Floerger).
Sodium carboxymethylcellulose, which i8 the second component in the inventive formulations is a synthetic gum derived from cellulose, and generally comprises an anionic, water-soluble, long chain polymer. The preferred sodium carboxymethylcellulose utilized in the present invention is commercially available from Hercules Incorporated under the trademark CMC 7HXF.
The mixed, partial salts of poly(methyl vinyl ether/maleic acid) employed in the present invention are preferably the mixed salts of calcium and sodium which are commercially available under the trademark Gantrez MS955 (General Aniline and Film Corp.).
The three essential components utilized in the present denture adhesive composition physically interact to form a two adhesive system which surprisinqly outperforms either adhesive system taken individually. The first adhesive system is based on an anionic/cationic interaction between sodium carboxymethylcellulose and the cationic acrylamide polymer. The second adhesive system comprises the mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid). When these two systems are combined according to the present invention, a denture adhesive composition providing surprising performance as a denture stabilizer is provided.
In a preferred embodiment of the invention, the cationic acrylamide polymer is present in amounts of from about 8% to about 27~ by weight, based on the total weight of the denture adhesive composition; sodium carboxymethylcellulose i8 present in amounts of from about 15~ to about 43~ by weight, based on the total weight of the denture adhesive composition; and the mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid) is present in amounts of ~rom about 10% to about 27% by weight, based on the total weight of the denture adhesive composition.
The denture adhesive compositions of this invention maybe formulated to contain the cationic acrylam~de polymer, sodium carboxymethylcellulose, and mixed, calcium/sodium partial salts of poly(methyl vinyl ether/maleic acid) in either powder or paste form. In the powder formulation, the components are admixed with conventional flavors and colorants, together with other non-essential ingredients such as non-toxic anti-caking agents (silica, magnesium stearate, talcum powder or the like). The mixture of ingredients is thoroughly agitated or stirred to yield a generally homogenous intermixing of all components. In the past formulations, the cationic acrylamide polymer, sodium carboxymethylcellulose, and mixed, calcium/sodium partial salts of poly(methyl vinyl ether/maleic acid) are admixed with petrolatum, mineral, animal or vegetable oils, and the like, along with flavors, colorants and certain commonly used preservatives and fillers.
A particularly preferred paste or cream formulation is prepared by utilizing as the cream or paste base, the product of U.S. Patent No. 3,215,599. The cream or paste base of this patent is characterized as a mixture of white petroleum oil with a minor amount of a polyethylene wax having an average molecular weight of 1,000 to 20,000. This product is described as having emollient properties, useful in the formulation of medicaments where absorption of the medicaments by the skin is of paramount importance. Denture adhesive creams formulated with this petroleum oil/polyethylene wax blend as the paste or cream base display unusually good stability, extrudability and product appearance.
The method for preparing the denture adhesive compositions according to the present invention, whether formulated as a powder or paste, employs conventional types of mixing equipment which are known in the art for blending, heating and cooling solids and liguids.
P7283So1/g ~ 3 ~
Whether formulated as a powder or paste, the denture adhesive mixture of this invention, when applied to dentures and exposed to moisture, hydrates to form an adhesive compo~ition which exhibits unexpectedly superior characteristics in comparison with denture adhesives of the prior art.
The following examples are given to illustrate the invention, but are not deemed to be limiting thereof. All percentages given throughout the specification are based on the weight of the final denture adhesive composition unless otherwise indicated.
P7283SOl/
EXAMP~ 1 Preparation of Denture Adhesive Cream A dsnture ~dhesive cream is prepared from the following ingredients:
Percent Inqredients w~W
Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 24.2 Sodium carboxymethylcellulose23.42 Cationic acrylamide polymer 12.1 Peppermint Oil O.10 Methyl Paraben 0.05 Propyl Paraben O.10 Color 0.03Q
100 . 000 A. Weigh Polyethylene, Polyisobutylene and Mineral Oil into a pot (Polyisobutylene is added as a 40% w/w concentrate in the Mineral Oil) and mix to form a homogenous mixture while raising the temperature to 90-95 C. Check to assure complete solution of the wax. With continued mixing, cool to at least 45 C.
B. Add Peppermint Oil, Methyl Paraben and Propyl Paraben to the mixture from Step A and continue mixing again until a homogenous blend is obtained.
C. Preblend the mixed partial salt of poly(methyl vinyl ether/maleic acid), sodium carboxymethylcellulose, cationic acrylamide polymer and color; add to the above mixtùre with continued mixing. After about 5 minutes scrape down as needed. Reduce pressure to about 28-29 inches vacuum and mix for about 5-10 additional minutes. The product is removed and stored for use.
This formulation was subjected to panel testing using the formulations of this Example with multiple panelists.
The panelists were requested to use the denture adhesive according to the following instructions:
1. Thoroughly brush away any remaining adhesive and _ g _ P7283SOl/9 dry dentures. 2. Apply three short strips evenly as shown.
Keep strips away from edges. Use only the amount necessary.
A few trials should indicate the proper amount and best placement of strips for your individual needs. 3. Press dentures firmly in place and hold for 20 seconds while cream sets.
The panelists were then requested to rate the denture adhesive for the following:
a) number of applications per day, b) firmness of hold (7=excellent to l=totally unusable), c) duration of hold (in hours), d) confidence of hold (l=very certain dentures would not hold, to 5=very certain dentures would hold), and e) usage intent (l=definitely would not use, to 5=definitely would use).
The results are set forth in Table I, along with the results of Example 4.
The formulation of Example 1 was then subjected to a second panel study according to the above-described testing procedure, in which the panelists were requested to rate the denture adhesive against the adhesive of a Comparative Example A. The formulation of Comparative Example A
contained only two of the three essential components of the invention (cationic acrylamide polymer, sodium carboxymethylcellulose).
The results of the second panel study are set forth in Table II.
As evidenced by the data of Table II, the formulation o~ Example 1 performed significantly better than the formulation of Comparative Example A, with respect to holding power (firmness), duration of hold, confidence of hold and usage intent.
P7283sol/s 2 ~ 2 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared according to the procedure of Example 1, using the following ingredients:
Percent Ingredients w~w Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 12.259 Sodium carboxymethylcellulose 25.00 Cationic acrylamide polymer 22.461 Peppermint Oil O.10 Methyl Paraben 0.05 Propyl Paraben O.lo Color 0-030 100. 000 The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
, P7283SO1/9 2~121 Preparation of a Denture Adhesive Cream A denture adhesive cream i~ prepared according to the procedure of Example l, using the following ingredients:
Percent Ingredients w/w Polyethylene 4.0 Polyisobutylene 4.0 Mineral Oil 32.0 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 18.00 Sodium carboxymethylcellulose 29.72 Cationic acrylamide polymer 12.0 Peppermint Oil O.10 Methyl Paraben 0.05 Propyl Paraben O.lo Color 0.030 100. ooo The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage int-nt when used by d-nture w-ar-rs.
`
~ ,-P7283sol/s 2 ~3 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared according to the procedure of Example 1, using the following ingredients:
Percent Inaredients w/w Polyethylene 4.0 Polyisobutylene 4.0 Mineral Oil 32.0 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 12.00 Sodium carboxymethylcellulose 35.72 Cationic acrylamide polymer 12.0 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0.030 100.000 The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
P7283SOl/9 2 ~ ~ 1 1 2 ~
EXAMPLE S
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared according to the procedure of Example 1, using the following ingredients:
Percent Ingredients w/w Polyethylene 2.80 Polyisobutylene 1.75 Mineral Oil 30.45 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 24.20 Sodium carboxymethylcellulose 28.438 Cationic acrylamide polymer 12.1 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0.012 100. 000 The formulation of this Example was subjected to panel testing, following the testing procedure of Example 1. The panelists were requested to rate the denture adhesive against a commercially available product A.
The results are set forth in Table III.
As illustrated therein, this adhesive formulation performed particularly well with respect to number of applications required per day and performed satisfactorily with regard to firmness, duration of hold, confidence and usage.
P7283S01/9 ~i~ 3 ~ 1 2 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared from the following ingredients:
Percent Ingredlents w/w Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 24.2 Sodium carboxymethylcellulose 23.355 Cationic acrylamide polymer 12.1 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0-035 Titanium Dioxide 0.060 100 . 000 Follow the procedures of steps A and B, as described in Example 1.
C. Preblend mixed partial salt of poly(methyl vinyl ether/maleic acid), sodium carboxymethylcellulose, cationic acrylamide polymer, color and titanium dioxide, mixing this preblend with the above mixture until a homogenous product is obtained. After about 5 minutes scrape down as needed.
Reduce pressure to about 28-29 inches vacuum and mix for about 5-10 additional minutes.
The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
P7283S01/9 2 ~ ~ ~ 1 2 ~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared from the following ingredients:
Percent Ingredient w/w Petrolatum 23.00 Mineral Oil 17 . 00 Cationic acrylamide polymer - 12.1 Sodium carboxymethylcellulose23.436 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 24.20 Peppermint Oil 0.10 Methyl Paraben o.OS
Propyl Paraben 0.10 Color 0.014 100. 000 A. Weigh Petrolatum and Mineral Oil into a Versamix pot. Mix with the anchor set to 75 until uniform.
B. Add Peppermint Oil, Methyl Paraben and Propyl Paraben with continued mixin~.
C. Preblend cationic acrylamide polymer, sodium carboxymethylcellulose, mixed partial salt of poly(methyl vinyl ether/maleic acid) and color by mixing in with the above mixture. After about 5 minutes scrape down as needed. Reduce pressure to about 28-29 inches vacuum and mix for about 5-10 additional minutes.
The formulation of this Example would exhibit good firmness, duration of hold, confidence of hold and usage intent when used by denture wearers.
P7283SOl/9 ~ I 2~
Preparation of a Denture Adhesive Cream A denture adhesive cream is prepared from the following ingredients:
Percent Inaredien~ w~w Polyethylene 5.2 Polyisobutylene 4.0 Mineral Oil 30.8 Mixed partial salt of poly(methyl vinyl ether/maleic acid) 24.2 Sodium carboxymethylcellulose23.436 Cationic acrylamide polymer 12.1 Peppermint Oil 0.10 Methyl Paraben 0.05 Propyl Paraben 0.10 Color 0.014 100. 00 Follow the procedures of steps A and B, as described in Example 1.
C. Preblend mixed partial salt of poly(methyl vinyl ether/maleic acid), sodium carboxymethylcellulose, cationic acrylamide polymer and color, mixing in the above mixture.
After about 5 minutes scrape down as needed. Reduce pressure to about 28-29" vacuum and mix for about 5-lO
additional minutes.
The cationic acrylamide polymer utilized in this formulation, unlike those of Examples 1-7, was a copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate.
The formulation of this Example was subjected to panel testing, following the testing procedure of Example 1.
The results are set forth in Table IV which shows a sati~factory number of applications, good firmness and confidence during use.
COMPA~ATIVE EXAMPLE A
Preparation of a Denture Adhesive Cream A denture adhesive creams is prepared according to the procedure of Example 7 from the following ingredients:
Percent Ingredient w~w Petrolatum 21.9848 Mineral Oil 19.9848 Silica 1.4812 Mixed partial salt of poly (methyl vinyl ether/maleic acid) 29.6256 Sodium carboxymethylcellulose24.6880 Polyethylene oxide 1.9751 Peppermint Oil 0.0772 Methyl Paraben 0.0493 Propyl Paraben 0.0987 Color 0~0353 100. 0000 The formulation of this Example contains only two of the three essential components utilized in the invention.
As discussed above, and shown by the panel study results of Table II, the inventive formulation of Example 1 performed significantly better than that of Comparative Example A with respect to holding power (firmness), duration of hold, confidence of hold and usage intent.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and - scope of the invention and all such modifications are intended to be included within the scope of the following claims.
P7283S0l/9 TABLE I
ATTRIBUTE R~TINGS ~
~ENTURE CREAM ADHESIVE PANELISTS
Example Example l 4 #APPLICATIONS l.82 l.86 FIRMNESS 5.l9 4,99 DURATION l0.ll 9.23 CONFIDENCE 3.75 3.52 USAGE 3.86 3.67 P7283sol/~ S ~ 2 1 TABLE II
MEAN AT$RIBUT~ RATINGS ~Y
DENTURE CREAM ADH~SIVE PANELISTS
Example 1 Comparative Example A
#APPLICATIONS 1.95 2.075 FIRMNESS 5.27 4.61 DURATION 9.86 8.23 CONFIDENCE 3.82 3.22 USAGE 3.89 3.33 P7283SOl/9 ~ ~ 3 TABLE III
MEAN ATTRIBUTE RATINGS BY
DENTURE CREAM ADHESIVE PANELISTS
Example 5 #APPLICATIONS 1.54 FIRMNESS 5.42 DURATION 11.38 CONFIDENCE 4.08 USAGE 4.13 ~1 12~
ABLE I_ ~a_ ATT~IBUTE RATINGS BY
DENTURE CREAM ADHESIVE PANELISTS
E~ample 8 #APPLICATIONS 1.84 FIRMNESS 5.32 DURATION 12.66 CONFIDENCE 4.58 USAGE 4.26
Claims (21)
1. A denture adhesive composition comprising a substantially anhydrous mixture of:
a) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a cationic acrylamide polymer having the formula:
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X- comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N
is an integer between 5-20, inclusive;
(b) from about 10 to about 43 percent by weight, based on the total weight of the denture adhesive composition, of sodium carboxymethylcellulose; and (c) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid).
a) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a cationic acrylamide polymer having the formula:
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X- comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N
is an integer between 5-20, inclusive;
(b) from about 10 to about 43 percent by weight, based on the total weight of the denture adhesive composition, of sodium carboxymethylcellulose; and (c) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid).
2. The denture adhesive composition of claim 1, wherein said cationic acrylamide polymer comprises a copolymer of acrylamide and Beta -acryloyloxyethyltrimethylammonium chloride.
3. The denture adhesive composition of claim 2, further including from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of at least one cream base material selected from the group consisting of petrolatum, natural and synthetic oils.
4. The denture adhesive composition of claim 2, further including from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of a cream base material which is a combination of mineral oil with a minor amount of a polyethylene wax having an average molecular weight of 1,000 to 20,000.
5. The denture adhesive composition of claim 2, further including from about 10 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of non-toxic, powdered, excipient materials.
6. The denture adhesive composition of claim 1, wherein said cationic acrylamide polymer comprises a copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate.
7. The denture adhesive composition of claim 6, further including from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of at least one cream base material selected from the group consisting of petrolatum, natural and synthetic oils.
8. The denture adhesive composition of claim 6, further including from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of a cream base material which is a combination of mineral oil with a minor amount of a polyethylene wax having an average molecular weight of 1,000 to 20,000.
9. The denture adhesive composition of claim 6, further including from about 10 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of non-toxic, powdered, excipient materials.
10. The denture adhesive composition of claim 1, wherein said cationic acrylamide polymer is present in amounts of from about 8 to about 27 percent by weight, based on the total weight of the denture adhesive composition.
11. The denture adhesive composition of claim 1, wherein said sodium carboxymethylcellulose is present in amounts of from about 15 to about 43 percent by weight, based on the total weight of the denture adhesive composition.
12. The denture adhesive composition of claim 1, wherein said mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid) is present in amounts of from about 10 to about 27 percent by weight, based on the total weight of the denture adhesive composition.
13. A method for preparing a denture adhesive composition comprising:
a) preparing a mixture of:
i) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a cationic acrylamide polymer having the formula:
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X- comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N is an integer between 5-20, inclusive;
ii) from about lo to about 43 percent by weight, based on the total weight of the denture adhesive composition, of sodium carboxymethylcellulose; and iii) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid);
b) forming a denture adhesive composition including said mixture; and c) recovering said denture adhesive composition.
a) preparing a mixture of:
i) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a cationic acrylamide polymer having the formula:
wherein R comprises hydrogen or a lower alkyl having from 1 to 6 carbon atoms; X- comprises an anion selected from the group consisting of a halogen ion, perchlorate ion, hydrogen sulfate ion, methyl sulfate ion and mixtures thereof; M is an integer between 80-95, inclusive; and N is an integer between 5-20, inclusive;
ii) from about lo to about 43 percent by weight, based on the total weight of the denture adhesive composition, of sodium carboxymethylcellulose; and iii) from about 8 to about 30 percent by weight, based on the total weight of the denture adhesive composition, of a mixed, calcium/sodium partial salt of poly(methyl vinyl ether/maleic acid);
b) forming a denture adhesive composition including said mixture; and c) recovering said denture adhesive composition.
14. The method of claim 13, wherein said cationic acrylamide polymer comprises a copolymer of acrylamide and Beta - acryloyloxyethyltrimethylammonium chloride.
15. The method of claim 14, wherein said denture adhesive composition further includes from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of at least one cream base material selected from the group consisting of petrolatum, natural and synthetic oils.
16. The method of claim 14, wherein said denture adhesive composition further includes from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of a cream base material which is a combination of mineral oil with a minor amount of a polyethylene wax having an average molecular weight of 1,000 to 20,000.
17. The method of claim 14, wherein said denture adhesive composition further includes from about 10 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of non-toxic, powdered, excipient materials.
18. The method of claim 13, wherein said cationic acrylamide polymer comprises a copolymer of acrylamide and the reaction product of dimethylaminoethyl methacrylate and dimethyl sulfate.
19. The method of claim 18, wherein said denture adhesive composition further includes from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of at least one cream base material selected from the group consisting of petrolatum, natural and synthetic oils.
20. The method of claim 18, wherein said denture adhesive composition further includes from about 30 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of a cream base material which is a combination of mineral oil with a minor amount of a polyethylene wax having an average molecular weight of 1,000 to 20,000.
21. The method of claim 18, wherein said denture adhesive composition further includes from about 10 to about 75 percent by weight, based on the total weight of the denture adhesive composition, of non-toxic, powdered, excipient materials.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US44529189A | 1989-12-01 | 1989-12-01 | |
US445,291 | 1989-12-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2031121A1 true CA2031121A1 (en) | 1991-06-02 |
Family
ID=23768342
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2031121 Abandoned CA2031121A1 (en) | 1989-12-01 | 1990-11-29 | Denture stabilizer |
Country Status (2)
Country | Link |
---|---|
CA (1) | CA2031121A1 (en) |
IT (1) | IT1242171B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6491896B1 (en) | 2001-03-19 | 2002-12-10 | The Proctor & Gamble Company | Polybutene containing denture cleanser compositions |
US6500406B1 (en) | 2001-03-19 | 2002-12-31 | The Procter & Gamble Company | Denture care compositions and kits |
-
1990
- 1990-11-27 IT IT48526A patent/IT1242171B/en active IP Right Grant
- 1990-11-29 CA CA 2031121 patent/CA2031121A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6491896B1 (en) | 2001-03-19 | 2002-12-10 | The Proctor & Gamble Company | Polybutene containing denture cleanser compositions |
US6500406B1 (en) | 2001-03-19 | 2002-12-31 | The Procter & Gamble Company | Denture care compositions and kits |
Also Published As
Publication number | Publication date |
---|---|
IT9048526A1 (en) | 1992-05-27 |
IT1242171B (en) | 1994-02-16 |
IT9048526A0 (en) | 1990-11-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3926870A (en) | Denture adhesive preparation containing an anionic protein material | |
US5024701A (en) | Denture adhesive composition | |
US5093387A (en) | Denture adhesive | |
US5006571A (en) | Denture adhesive composition | |
US5001170A (en) | Denture stabilizer | |
CA2197189C (en) | Denture adhesive composition | |
US5011868A (en) | Denture stabilizer | |
AU747492B2 (en) | Denture adhesive comprising a polymeric activator and methods of preparing the same | |
US3868340A (en) | Denture adhesive preparation | |
US3833518A (en) | Denture adhesive preparation | |
US3868432A (en) | Denture adhesive preparation | |
JPH11511365A (en) | Improved denture fixative | |
US3511791A (en) | Denture adherent preparation | |
US4608088A (en) | Denture adherent powder | |
EP0141489B1 (en) | Denture adhesive composition | |
CA2396353C (en) | Denture adhesive compositions comprising a polymeric activator | |
US3868339A (en) | Denture adhesive preparation | |
CA2031121A1 (en) | Denture stabilizer | |
EP0140486B1 (en) | Denture adhesive composition | |
US3868260A (en) | Denture adhesive preparation | |
US3878135A (en) | Denture adhesive preparation containing an anionic protein material | |
US3868259A (en) | Denture adhesive preparation | |
AU775742B2 (en) | Denture adhesive | |
CA2032824A1 (en) | Denture adhesive | |
CA2027178A1 (en) | Denture adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Dead |