Note: Descriptions are shown in the official language in which they were submitted.
WO 92/109~8 2 ~ $ ~ PCT/US91/09467
DENTURE STABILIZING COMPOSI
- TECHNICAL FIELD
This invention relates to improvements in adhesives, in par-
ticular improved denture adhesives.
BACKGROUND OF THE INVENTI~ON~
o Ordinary remoYable dentures,:dental plates, and the like, com-
prise.teeth msunted in a suitable plate or base~ Dentures function as
a substitute for missing teeth and serve as a replacement for all or a
portion of the teeth ordinarily found in the oral :cavity. Although
dentures generally are skillfully prepared, often they do not fit
perfectly. Moreover, no matter how satisfactory at first, after a
period of time the fit of the denture becomes~lovse and i~perfect due
to natural shrinkage and changes in the gums, mucous tissues, and the
like. Loose and imperfectly fittPd dentures usually are corrected and
stabilized by the use of a denture stabilizer. Denture stabilizers
are used to fill the interstices between the dentures and the gums or
tissues. Prior to placement of the denture in the oral cavity, a
denture stabilizer is:applied to the denture-plate surface which, for
` a~~perfect fitj should-uniformly contact~the' gums a~d-mucous t;ssues.
The denture stabilizer is formulated not only for its adherent proper-
25.~-ties; but:also~to provide.~a.cushion or gasket.between the denture and
- . .. .the:gums.or tissues, .thereby positioning the denture`securely in the . oral cavity.~
; ' Requirements'i and icharacteristics .~for ~a satisfactory denture
stabil king composition~are~many,and are dictated.by~numerous factors.
Desirably, one daily~application of~such~a composition should fùnction
al)as an effectiYe means for.~.insulating" cu'shioning,!and `securely posi-
~ tioning ithe :denture.nn The~composition:should-lretain.its. characteris-
'` t ks.~and 'properties~ in.~the.~typical.npowder c.and.. crea~ nforms during .
' ,`; o~o~storage~under~Ya~ious climaticiconditions,~such.as~h'igh..temperature and
35lohumidity;7be~readily~.and.easily~capable~0f,~application to'..the dênture
`surface'; not be'irritating.or~unco~fortable'~to the user; be:safe and
nontoxi'c';?lhave: no~'disagreeable odor or: color;.have.no~.ùnpalatable
; . ?~n~:taste;`-.optiona11y~ provide antisPptic andigermicidal properties for
: ` :
: "
.. ., . - ,
... .. .. . - . . , , , ,. ,.. , ., . ~, .. -
WO 92/11~9~8 ~ PCT/lJS91/09467
~,~9S ~ -2- t'~
preventing or inhibiting the growth of organisms ordinari1y found in
the mouth; and function as an agent for prevention of putrefaction or
malodorous decomposition of foods or secretions lodging beneath or
adjacent to the denture. The stabilizing material must be capable of
imbibing water and saliva and swell;ng, so as to fill the interstices
between the denture and the gum or mucous tissues. ~he stabilizer
should not attack or damage the denture, as by caus;ng a crazing of
the denture-plate material. Additionally, the stabil ker should be
stable to bacteria, molds and enzyme systems found in the oral cavity,
o and ~ave a pH that is nonirritat1ng to the oral mucosa, generally
5-8.5, preferably a pH around neutrality. The mechanical strength of
the stabilizing mass, be it gel or colloid, formed by imbibition of
water should be great enough to securely maintain the position of the
denture.under normal use, and not so great as to make denture removal
l5 difficult when desired, or as to damage or inaure the gums, tissues or
denture upon removal.
. There has been a considerable effort made over many years to
develop improved denture adhesives. Both synthetic and natural
polymers and gums have been used singly, in combination, and in
20 combination with various additives.
,. ,., European Patent 64,672 to ~habhar and Schmidt, published November
,- ,; 17, 1982, relates .to a hydrophilic. denture. adhesive containing an
adhesive"polymeric~..fraction comprising'~carboxymethylcellulose (CMC)
~; and polyethylene oxide in a hydrophilic vehicle.
- 25 ~,j ,European Patent.Application 140,486 to A.J. Desmaris, filed.July: -t,31,- 19841relates to denture adhesive.compositions containing a hydro~
phobically modified water-solubl'e polymer, alone,or admixed with an
` .L~ `n alkal.i,,metal salt,'.of.:,CMC.- nHydrophobically:-~modified hydroxyalkyl
`. CJ~ cel,l~loses,~land,~:cupolymers of,~ethylenet,oxide~.and :long chain epoxy-
;~.,s30~ alkanes are preferred.for~ use in the compositions.~
~e~U.S:~Patent~4l280,936..to Dhabhar', Heyd ;? and Schm~dt jGi ssued July
~ J~ 28j~1981,,relatesitonimproved,denture.adhesives contain~ng a specifiedo~ o ~.~atio of~,!CMC~and polyethylene oxide,iin,a mineral,~oil base. .~
, . .
~,r~ n U.S.~ Patento4,474,902',.to:lDhabhar. and;Schmidt,.:issued.October 2,
35, -1984jtrelates ~o,~mproved denture~.adhesives~;containing,.karaya~gum:in a
~ .,hydrophilic,,vehicle'.',i;S~e also U.S."~.Patentt4,514,528, issued,April 30,
, : sl'~l985irland :U.S.:.Patent 4,518,72lj,?issued~May 21,,,~,1985~to~these same
-- inventors, relating,~; respectively, .to improved~identure adhesives
.
.
,
.
`: . . ,
w o 92/~09~8 2 ~ 9 ~ ~ ~ 8 PCT/VS91/09467
f: -3-
c~ntaining adhesive polymeric fractions consisting of admixtures of
partial salts of lower alkylvinyl ether maleic anhydride-type
copolymers with CMC or polyethylene oxide, as well as denture ad-
hesives containing CMC and polyethylene oxide. See also U.S. Patent
4,522,956, issued June 11, 1985 to Dhabhar and Schmidt relating to
improved denture adhesives containing polyethylene oxide as the snle
adhesive component in a hydrophilic vehicle comprising certain poly-
ethylene glycols.
Other denture adhesives are described in ~.S. Patents 4,530,942,
issued July 23, 1989; ~,542,168, issued September 17, 1985; and
4,569,955, issued February 11, 1986.
U.SO Patent 4,529,748 to H.G.P. Wienecke, issued July 16, 1985,
relates to dental prosthesis adhesives formed from f;lm-forming
substances such as various cellulose derivatives, acrylate polymers,
methacrylate polymers, and other film-providing substances.
U.S. Patent 4,138,477 to Gaffar, issued February 6, 197g dis-
closes oral compositions to control mouth odor containing zinc-polymer
combinations formed from zinc reacted with an anionic polymer contain-
ing carboxylic, sulfonic and/or phosphonic acid radicals.
U.S. Patent 3,003,988, to D.P. Germann et al., issued October 10,
1961, describes certain water-sensitized, but water-insoluble, materi-
als for stabil king dent~res which are synthetic, hydrophilic, col-
loidal materials comprising mixed~partial salts and esters~ of lower
alkyl (1 to 4 carbons) vinyl ether-:maleic anhydride-type copolymers~
: 25 said mixed partial salts.and esters containing both divalent calcium
. and monovalent alka7i (i.e., sodium, potassium and ammonium) cations.
U.S.~ Patent -4,758,630- to Shah et r al., issued:July. l9, 1988
relates to zinc and strontium partial.salts of lower alkyl (Cl to C~)
vinyl ether-maleic.acid.!copolymèrs,- wherein said zinc and strontium
30 cations are "unmixed"~with any other cations or ester functions in the
copolymeric`salt, thelremaining initlal carboxyl groups being unreact-
ed. These iower alkyl vinyl ether-maleic acid copolymers are referred
r ~ iaj~,7 to3here~nafter,by~the abbreviated ,term:"AVE/MA copolymer" and the
i)i~ o methyl - vinyl..~ether-maleic-~i~acid ioopolyill3eri:1-as-~~."M71E/MA ~;copolymer".
~r, ~ n35 e~Fur`ther~t EuropeanrPatent~Application 396~411~rto Holevat3and Gounaris
:J r i~published`November 7~?1990~ discloses~mixed partlal MVE/MA:copolymer
?~ ~s a l t s . ~ 6" ~ r ~ . ' ., , , , ~ `: 1 ;``
., . - ~ -
. . . ~ ~ .
.. . . ~ . . ~. i . .
. ~ ~ ... . .
- . : . , .. ~ : . . .
, .. . . .. .
WO 92/10988 ~ ~ PCI/US91/09467
It is known~ therefore, that combinations of mixed and unmixed
partial salts of lower alkyl vinyl ether-maleic anhydride-type co-
polymers are useful as denture adhesive compositions.
Yet, the search continues for denture stabilizers that will
5 provide the above-described characteristics and, importantly, will
maintain the secure fit of the denture over prolonged periods (10-14
hours) without the need for reapplication.
In accordance with the present invention, improved adhesive and
other characteristics are obtained in a denture stabilizing composi-
tion by using specific acids and partial salt(s) of a lower alkyl
~ vinyl ether-maleic acid copolymer with a speci~ied bulk density and
specific surface area.
It is an object of the present invention to provide improved
denture stabilizers which are easy to manufacture and thtt will be
stable over prolonged periods in the oral cavity, yet will allow easy
removal of the denture on demand.
It is a further object to provide such stabilizers using toxico-
logically-acceptable, palatable materials.
It is another object herein to provide stab;lizers that perform
well in the presence of moisture, particularly in the presence of body
fluids such as saliva, perspiration an~ blood.
: These.and..other objects are secured by .the present invention, in
, the manner-disclosed hereinafter.~
~ . SUMMARY OF THE INVENTION ..
; 25 ~. -; The .present .invent;on encompasses adhesives and stabili~er
. -.. ~ compositions .!;comprising: a lower. alkyl vinyl ether-maleic acid
.- copolymer.cons;sting essentially of the repeated struc~ural unit:
j " ~ ; c~ ..~ . OR ~ ...
t r~ t~ ~:3!1" ~ ~ CH~ -CH---ICH-.~-CH :r : ` .
3i0 2r~ ? ~ i' S ' .~ J ~ O~I.c3~lC=O ;
- ' ~ rc ~ ;i i ~ ? ., .' ~ n
wherein,R represents.a C, .to.C4 alkyl radical, n .is.ian-integer greater
.I 3t~ rOnithan~one irepresenting.c!jthe :.numberiof...repeated occurrences of said
5~l structural unit,.in:~a~molecule..of,said~copolymer:.and n :is.:large enough
".e!l.ito`~1characterize said copolymer as.having a~specific~.viscosity larger
than 1.2, the specific viscosity being determined in~methyl ethyl
ketone at 25'C and wherein said copolymer has a bulk density o~ ~rom
.
.
.
.
W O 92/10988 ~ ~ 9 ~ PCT/US91/09467
-5~
about 0.3 to about 1.2 grams per cubic centimQter and a specific
surface area of from about 0.5 to about 2.5 square meters pen ~ram.
Preferably these copoly~ers are part;al salts (mixed or unmixed,
preferably mixed), said partial salts containing from about 10% to
about 40% free acid, and as the cationic salt function, from about
0.1% to about 85% of the total initial carboxyl groups reacted with
one or more of a cationic salt function selected from the group
consisting of z;nc cations, strontium cat;ons, sodium cations, calcium
cations, magnesium cations, potassium cations and a~monium cations and
o mixtures thereof and wherein said copolymer has a bulk density of from
about 0.3 to about 1.2 grams per cubic centimeter and a spec;fic
surface area o~ from about 0.5 to about 2.5 square meters per gram.
Also d;sclosed are denture stabilizing compos;tions compr;s;ng a safe
and adhesively effective amount of two or more denture adhesive
components wherein one of said denture adhesive components is either
the copolymer or the mixed partial salt(s) of~the present invention.
Bulk densities are measured according to ASTM method B-52 (02.05).
- Preferably these copolymers or mixed partial salts are used along
w;th a water-sens;tized polymeric mater;al selected from the group
consisting of natural gums, synthet;c polymers, saccharide der;va-
tivesj cellulose derivatives, and mixtures thereof.
All percentages and ratios used here;n relating to the neutral;-
'" `zation of'the` salts of ! the''present'''invention are based`upon thestoichio~etric percent of the catior1ls' present in the salt. All
percentages and ratiosi used herein are `by weight, unlessi otherwise
~ specified.. ~ - ' ' ' '`
';DETAILED'DESCRIPTION OF THE_INVENTION ~
The 'present invention~ encompasses ~~stabilizer~compositions com-
' i prising: 'a~lowèrJalkyl'vinyl;ether-maleic'iacid copolymer consisting
~30 essentially of`the 'repeated structural unit~ ?
l ~ Ji~ OR~ ` ;
" r;.", ";; , : ,; ; ----CH2~ `ci~ CH---CH - -
'; :'C~ ;J? ~ ;. : t,, .~. j ~ ,'.?;~ O=cii` C~O ~ (I)
2~ t~ , ~ ''r HO- '~OH'~ ; ~
35 ~ ~ J~li`r 9~Si~ n -~ ?: . . .
'?~ 1 wherein R represents a:C1'to C4 alkyl radical,-n is an integer greater~ than'one representing' the nu~ber'''`of 'repeated 'occurrences~ of said
`i ~; 'structural unit in a moleculé of said copolymer and n is large enough
. ' .`
- , , , , , , ~ ~
WO 92/10988 ~ PCI/US91/09467
tD characterize said copolymer as having a specific viscosity larger
than 1.2, the specific viscosity being determined in methyl ethyl
ketone at 25 C and wherein said copo1ymer has a bulk density of from
about 0.3 to about 1.2 grams per cubic centimeter and a specific
5 surface area of from about 0.5 to about 2.5 square meters per gram.
Preferably these copolymers are partial salts, said partial salts
containing from about 10% to about 40% free acid, and as the cationic
salt function from about O.lYo to about 85% of the total initial
carboxyl groups reacted with one or more of a cationic salt function
selected fro~ the ~roup consisting of zinc cakions, strontium cations,
sodiurn cations, calcium cations, magnesium cations, potassium cations
and ammonium cations and mixtures thereof and wherein said copolymer
has a bulk density of from about 0.3 to about 1.2 grams per cubic
centimeter and a specific surface area of from about 0.5 to about 2.5
square meters per gram.
Preferably the partial salts ~preferably mixed) comprise from
about 0.1% to about 85% of one or more of the above mentiDned cations
in the following levels: from about 0.1% to about 65%, more pre-
ferably from about 2% to about 45%, and most preferably from about
2.5% to about 30% zinc or strontium cations (preferably zinc), and
from about 10% -to about 75%, more preferably from about 20% to about
.65%, and most preferably from about 40% to~about 65% calcium cations,
- from about 0.1%:to about 25%, andimore preferably from about-0.1% to
about 20% sodiu~ cations and from about 10% to about 40%, most pre-
25 ~ferably.from about 20% to about 35~ free acid.
The subject polymeric salts are advantageously prepared by theinteraction.of the AVE/MA copolymer (I) with the optional cationic
lca kium,"~sodium~ ,ammonium ,and ~eitheri.zinc .or1strontium compounds
, - .^:lhaving~,a.,functional-group:.typical,of reactants~ of carboxylic acid,
such as, for example, tthej hydroxide,,t~acetate,, carbonate, halide,
lactate, etc.~ in an aqueous medium. In a preferred embodiment, the
oxide of z~nc and the hydroxide~of~.calctum and sodium are utilized.
Since ~inc hydroxidej is not commercially available, its use as a
reàctant is readily and more economically accomplished by employing an
: 35 aqueous slurry of particul~te zinc oxide which, although practically
insoluble in Iwater, provides ~hydration ?to~.zinc hydroxide~ on the
~par~iculate .surface.3.Calcium and sodium~jhydroxides as well,,as stron-
: :tium hydroxide, on the other hand,-are available in either crystalline
,
. .
. . .
.
- .
,
.
. .
WO 92/10988 PCr/lJS91/09467
~ 209~8~ _7_
or powder form and are soluble in about 50 parts water. Aqueous
solutions of strontium oxide, however, which form the hydroxide when
treated with water ~caution: heat evolution), may also be used.
Strontium oarbonate may also be used.
Anions that form tox;c, ;rritating or contamlnating by-products
should be avo;ded, or special precautions and trPat~ent provided to
assure the removal and absence of such by-products from the polymeric
salt end-product. The part;cular compound used should be substantial-
ly pure to assure obtaining a substantially pure, substantially
off-white polymeric salt end-product.
The lower alkyl vinyl ether maleic acid (AVE/MA) copolymers (I)
are readily obtained by copolymerizing a lower alkyl vinyl ether
monomer, such as methyl vinyl ether, ethyl vinyl ether, divinyl ether,
propyl vinyl either and'isobutyl vinyl ether, with maleic anhydride to
yield. the corresponding lower alkyl vinyl ether-maleic anhydride
; copolymer which is readily hydrolyzable to the acid copolymer (I).
Both anhydride and acid forms are also available from commercial
suppliers. For example, the GAF Corporation, Wayne, New Jersey,
provides both the polymeric free ac1d form (I) and the corresponding
anhydride form under its "GANTREZ" trademark as the "GANTKEZ S Series"
and "GANTREZ AN Series", respectively. In the former acid series, the
6ANTRE2 S 97 (M.W.~50,000) ..is particularly suitable, and, in the
.latter anhydride series, the GANTREZ'AN-149 (M.W.350,000), the GANTREZ :~
AN-169 (M.W.=67,000)~and the GANTREZ AN-179 (M.W.=80,000) copolymers
are particularly suitable.-. Said acid ~nd anhydride forms of AVE/MA
opolymers, having an average:molecular weight of from about 50,000 to
; ';about 80,000 (as measured by membrane osmometry in 2-butanone 1-10
grams~1000 ml solution), are also characterized by having~the previ-
ously.described~:specific..viscosity.parameter.of,more than 1.2. When
30r~the-anhydrlde~.copolymer,dissol~es:in water,.the anhydride linkage is
q cleaved.so that:~th~ highlyi;polar,;polymeric free,~acid ,-(I).:is formed.
`. ..Accordingly,.ithe~ anhydride;form',~ which ;is~relatively~less.iexpensive
';than the.~a'cid.~orm,~,imay''be used as a~convenient and.cheaper.precursor
for.'the~acid.~-Elevateditemperatures;may.'be~iadvantageously employed to
,'d.s~35 ~ enhan^ce the.rate o'f.anhydr.ide-to-acid hydrolysis. .) on~ w~
In g'eneral, the'.lower alkyl~vinyl ether-malei'c:.acid"copolymer
~or its corresponding anhydride,` is'added to water.-preheated to
.~ about 70-80-C with vigorous stirring to 'form a homcgeneous mixture.
:
!
.. . . . . . . . . . . .
' . " ' . ' . ' ' , ,: .
. , ., ~ ' . ' ' ~ : . : ''
~ ~ ' ' ' . . . ', ' ~ ,
wo 92/10988 Pcr/ussl/os467
~ ~ 9 ~
If the anhydride precursor is utilized, it is reoommended that the
aqueous mixture be further heated to abuut 90-C with stirring to
ensure comp1ete hydrolysis of the anhydride to the acid form. Heating
is then discontinued although mixing is continued until the batch
turns clear with a simultaneous decrease in viscosity (about 65-75C).
In a preferred embodiment, an aqueous solution of the ca~ionic zinc or
strontium salt . forming compound, or, for example9 an aqueous
dispersion of particulate zinc oxide is combined with ca kium hy-
droxide in the form of a slurry, in an amount sufficienit to provide
o the desired zinc and calcium oationic conten$ desired in the
~ end-product, is separately prepared at ambient temperature and slowly
added to the hot polymeric acid solution with continuous vigorous
mixing so as to prevent localized precipitation of the cationic
polymeric salt. After the calcium and zinc have reacted, an aqueous
solution of sodium hydroxide is added slowly, in the amount sufficient
to provide the cation sodium content desired in the end-produot.
;. After addition is complete, mixing is continued to ensure that all the
salt forming compounds are reacted with the copolymer.
Alternatively for this preferred embodiment, an aqueous solution
containing the zinc and calcium source is preheated to 70-80-C with
: vigorous stirring.to form a homogeneous slurry. The lower alkyl vinyl
ether-maleic acid copolymer:~I) or its corresponding'anhydride is then
added:,to the slurry while:'further heating to 90-C,:and stirring to
. - ensure complete hydrolysis. : Alternatively, `the AYE/MA copolymer,
:25 calciu~, and strontium zinc oxide powders are slurried-in water at 25-
'.m :~.and subsequently heated .to sn-c - 9o C for reaction to occur. Upon
completion of this: reaction step an aqueous solution of~sodium hy-
~ 'droxide.is slowly,added.. ~ . ,tis ,;.~
il'3i.,~ The~.zinc ~or.~.strontium),;:,calciumi~ and'rsodium oations in the~i ~30.,~,resultant.mixed partial salt~of~AVE/MAicopolymer~should.belsuf~icient
,r,r.~ to'give,:a..neutr'al kation~ranging.from.about:lO~O to about.75%; prefera-
bly....from`about'20%.to about 65%,}and:most..preferably.from.about 40% to
lo~$!Jo~ about:65%~calcium,~,and~rom~about 0.1%.lto.,about~65%,~jtpreferably from
!~J ~3~a,~.about.2%;.to-about345%il~and most~preferably~'fromrabout-~.2.-5% to about
35 30% zinc or.strontiumj! and;from ~aboutrØ1~ to~-about ~25%,i~preferably ' .-
.i^n~ ;n~afrom;0.1% fto about 20% sodium, resulting in a:salt .containing frees~ acid in.the range~of from ~about 10%~to ~.about 40~, preferably from
:;' !'^~`;~ about 20% to about 35Z. ~
WO 9~/10988 PCr/US9t/09467
f ~ 2098~8 9
The reaction batch is then dried using drum dryers maintalned at
80-100 PSIG with hot steam to evaporate the water con~ent and recover
the polymeric salt with a high specific surface area, in the flake
form.
5The resulting flakes are subjected to milling and screening to
yield the desired physical properties to provide satisfactory denture
stabilizing properties while maintaining the desired high specific
surface areas. These surface areas can be obtained by any appropriate
micronizing technique, preferably air jet milling or pin/disk or
0 hammer milling as described in Remi.nqton's Pharmaceu~ical _Sciences
(16th edition) pp. 1535-1539, incorporated by references herein.
Said salts are friable so that appropriate particle size and bulk
density can be obtained. For best results, drum dried particles
should be milled to a preferred bulk density of about 0.3 to about 1.2
15more preferably about 0.6 to about 1.2 and most preferably about O . 7
to about 1.2 grams per cubic centimeter while maintaining a specific
surface area of about d.5 to about 2.57 more preferably about 0.6 to
about 2.5, and most preferably about 0.7 to about 2.0 square meters
per gram. 2round particles should be capable oF passage through a
20140- to 200-mesh sieve (U.S.B.S. series) and preferably are less than
0.3 millimeters in their largest dimension.
: The subject acid copolymers and their respective salts have
exceptional adhesive qualities when contacted with water or saliva
such that they,are extremely useful as denture adhesive materials in
denture stabilizing.icompositions. For such use the salt in particu-
: late.~orm is preferably characterized by a particle size of at least
- .. minus 14~-mesh U.S.B.S. sieve; a bulk density greater than 0.3 gram..''~7 .~ per cubic,centimeter `and preferably higher. then 0.6: gram~per cubic
n.~ o ~ centimeter; and~a pH between 3 and::8 and preferably~between~5 and 7.5,
..30...;the: pH being -determined. on a..one percent by ~weight :dispersion in
w~ter., .~lF!r~ 7i ~ .' .,!;'U.! !,~7 .i .~
,Each of the,subject::copolymer:salts ~ay be utilized,in effective
'"5'.'- adhesive-~:amounts, preferably ~at .least 25çipercent~.by weight, as the
...e .^, ,sole-adhesive~component;or as a co-adhesive in joint.usàge with other
Jr.,. 35:.sactive:;adhesive components~in denture~stabilizing~cbmpositions.~`:
:~;j..i , i~, ..;It ~is,preferred ~that-~said .copolymern.salt be .used.~along with a
:co-adhesive: in~:`denture :stabilizing~,oompositions.77.-~Preferably, the
'G~-~ - co-adhesive:-is a polymeric material selected ~rom the group cons;sting
.
.
:,: .: . .
WO 92J10988 PCI/US91/09467
~39~48~ -lo- f
of natural gums, synthetic polymers, saccharide derivatives, cellulose
derivatives, and mixtures thereof. In general, from about 15 to about
70 percent, based on the total weight of the composition, of said
mixed calcium/sodium/zinc or strontium salt is present.
Preferred co-adhesives include a water-soluble hydrophil;o
colloid or polymer having the particular property of swelling upon
exposure to moisture to form a mucilaginous mass. Such adhesive
materials include both natura1 gums and synthetic polymeric yums and,
among those commonly employed in denture stabilizing compositions and lo whic~ are also suitable herein co-adhesive action with the subject
mixea AVE/MA copolymer salts, there may be mentioned, for example,
karaya gum, gelatin, algin, sodium alginate, tragacanth, methylcPllu-
lose, acrylamide polymers~ ethylene oxide polymers, polyvinylpyrroli-
done, cationic polyarylamide polymers and, as the most preferred,
sodium carboxymethylcellulose and mixed partial salts of poly(vinyl
methylether-maleic acid) copolymer.
Accordingly, a preferred aspect of the.subject invention provides
adhesives and denture stabilizing compositions having as a stabilizing
component an effectiYe adhesive amount of a lower alkyl vinyl
20 ether-maleic acid copolymer consisting essentially of the repeated
structural unit:
. . .. . , ~. . OR
'~r ''!' i` .1' '' '~'- ''' "''''~'''~ '~ CH~ H---CH---CH -
~
. - . .. O=C C=O ~ (I
25 .... .- :. :.. :.HO~ OH
3; .) ~ .~ . n
.. wherein.R represents a Cl to C~- alkyl radical, n is an integer greater
ar ,~ Jw~ than? one representing ~the .number~of repeated :occurrences o~ said
; i; ~.n~ structural unit~in a;molecule of said.copolymer.and n is ~large enough
3o~1to!characterize said copolymer as having::a:.specif:ic viscosity larger
than 1.2, the specific viscosity being determined in imethyl ethyl
.:,i~ .. `'~ ketone at.25'C and wherein.. said .copolymer. has a bulk density of from
n~ about 0.3ito about: 1.2.-.grams.per cubic centimeter ,and .a specific
':;'it~ 1!.. ;surface.area of from:.about 0.5 to about 2.5~square-meters~per gram.
35.~ )r:~ ~Preferably.these.~.copolymers are-;partial salts,hsaid.partial:salts
I.J"" ?ncontaining from,about~10%~.to:about:40% free?~acid, and as the cationic
1 ... ~salt function fromaabout -Ø1% to about 85% of~;the ;total initial
- : - . carboxyl groups reacted w~th~:one or more of a cationic salt function
.
` ,
. . ~ '
~, ' ' ' ,
WO ~2/10988 PCT/US91/09467
2~9~8~
selected from the group consisting of zinc cations, strontium cations,
sodium cations, calcium cations, magnesium cations, potassium cations
and ammonium cations and mixtures thereof and wherein said copolymer
has a bulk density of from about 0.3 to about 1.2 grams per cubic
centimeter and a specific surface ar~a of from about 0.5 to aboùt 2.5
square meters per gram.
Another preferred aspect of this invention provides a denture
stabilizing composition comprising a safe and adhesively effective
amount of at least two denture adhesive components, wherein one of
said denture adhesive components is the acid or partial salt of a
lower alkyl vinyl ether-maleic acid copolymer described above.
Preferably the co-adhesive is as described above.
The compositions of the present invention can optionally include
from about 0.01% to about 5% of one or more components which provide
the user with sensory, including flavor, benefits. Suitable compo-
nents include menthol, menthyl lactate, peppermint oil, spearmint oil,
peppermint oil, leaf alcohol, as well as those paramenthane carboxy-
amides flavoring agents available from ~ilkinson-Sword (such as WS-3)
which are described in U.S. Patent 4,136,163 to Watson et al., issued
January 23, 1979 which is incorporated by reference herein.
The compositions of the present invention are manufaetured in an
art-recogni~ed manner known to those skilled in the art, such as in a
powder,!cream,~ointment, liquid, paste, water or ~fil~. The compo-
~ ; sitions of the present invention are preferably manufactured with drum25 ~dried AYE/MA;copolymers or their salts that are milled using appro-
~- priate micronization techniques such as fluid energy or air jet or
: hammer milling of drum driedimixed partial salts of AVE/MA copolymer.
.;~s ~/oSuitable examples of such,formulations are~disclosed in U.S. Patent
;,;-~;4,518,7~ ;issued Mayi21,j1985 and U.S. Patent 4,514,528, issued April
~30 , 30,~1985,~both to Dhabhar et~al;.and both of~which are hereby incor-
porated by reference herein. ." n~
~ ;c Preferably,.these~compositions contain !from~about 10% to about
.eliSJ~ 70%;of. one~or.imore ointment^bases. ~Prefèràbly,Othis-baselis mineral
,S~oil or petrolatum, howeYer polyethylene glycol,;paraffin,~;glycerin and
mixtures thereof~are ~alsoliluseful;~lMost~lpreferred:is~a~mixture of
mineral oil and petrolatum.
It is to be recognized that the adhesive salts of the present
invention can be used for a wide variety of general adhesive uses
~- , - .. . . . :
.. . . . . .
..... , . . ~ .. . ... .
.
. ' .' '. . ' ' ~ ' ', . ~ . ' ~ :
w o 92J10988 ~ PCT/~Ssl/09467
~3~ -12- ~
including, but not limited to, pharmaceutical uses (e.g., oral drug
delivery and topical bandages); and aqueous adhesives ~e.g., where
adhesiveness in the presence of water is required~.
The following non-limiting examples illustrate embodiments of the
subject invention wherein both essential and optional ingredients are
combined. It is to be understood that these examples are for illus-
trative purposes only and are not to be construed as limiting the
scope of the invention thereto.
f ExamPle I
o Intu a reaction vessel equipped with a high speed stirrer and
~ containing 94 parts (4.7 kg) of purified water heated to 85~C, is
slowly added 6 parts (390 grams~ methyl vinyl ether-maleic anhydride
copolymer to the reaction vessel over a 15 minute periodO Temperature
and mixing remain constant for 60 minutes after 15 minutes, the
resulting adhesive polymeric dispersion is characterized by an in-
crease in viscosity, and a decrease and stabilization of reaction pH
which is a dispersion of'said material in water, said.material con-
sisting of acid form of methyl vinyl ether~maleic acid copolymer.
The resultant solution of the methyl vinyl ether-maleic acid
~MVE/MA) copolymer is then dried using a drum dryer maintained at
80-100 PSIG with hot steam to evaporate the water content and recover
the polymeric salt with a high specific surface~area,.in flake form.
The thus~.obtained dried~.acid form of the~MVE/MAIcopolymer is then
~..ground using an air jet or hammer mill to a.bulk density of about 0.7
to about 1.1 grams per. cubic.centimeter.while.maintaining a.specific
~ . surface area~afiabout 0.7.to about 1.5.square.meters per gram. This
; .. copolymer is then screened through a 140-mesh sieve an~ then.ithrough a
,,J "j..! .200 mesh:sieve..~U.S.B.S.~:sieveiseries). The~powder~has'!a pH..~of about
.2.5 for:a.one percent solution in water.~ ' This part kular copolymer
30 ~.will1be~referred'to hereinafter:iby~the abbreviatedlterm,:racid form of
MVE~MA copolymer". ..I~ ?n '~ lS;:-'.3' ',U :.'~ '' 1;`!
.".`The,product,.when:iused..iin conjunction:~with conventional denture
.'..;:~ni~l adhesivesr.and. appl.ied-i~to wet-~dentures~with~;;normal~.usage,;.provides
:~s ;ii n;.denture~stabilizing 'characterist-ics superior."to.those~obtained by the
.~ .35.~. ~particular..conventlonal ~denture:-.adhesive itself..
s I~t`,~i,"; bj'.
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.
.
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wo 92/lrig88 PCI/US91/09467
!'` 2~98~ 13-
Example II
Into a reaction vessel equipped with a high speed stirrer and
cDntaining 92.1 parts (1.842 kg) of purified water heated to 85C, is
slowly added calcium hydroxide 1.9 parts (37.9 grams), and sodium
hydroxide 0.3 parts (5.8 grams). After addition is complete, the
temperature of the slurry is kept constant with high speed mixing.
While keeping heat and mixing constailt add 5.71 parts (114 grams) of
methyl vinyl ether-maleic anhydride copolymer to the reaction vessel
containing the alkali dispersion over a 15 minute period. Temperature
and mixing remain constant for 60 minutes. A~ter 15 minutes the
resulting adhesive polymeric dispersion is characterized by an in-
crease in viscosity, and a decrease and stabilizatinn of the reaction
pH which is a dispersion of said material in water, said material
consisting of mixed partial calcium sodium salt of methyl vinyl ether-
maleic acid copolymer.
The resultant solution of the calcium sodlum salt of methyl vinyl
ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer
maintained at 80-100 PSIG with hot steam to evaporate the water
content and recover the polymeric salt with a high specific sur~ace
area, in flake form. The thus obtained dried calcium sodium MVE/MA
copolymer salt is then ground using an air jet or hammer mill to a
bulk density of about 0.7 to about 1.1 grams per cubic centimeter
' while maintainlng' a specific surface area of?labout 0.7 to~about 1.5
square meters per-gram. This copolymer is then screened through a
-25 140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve
: series). The powder has a pH of about 6.5 for a one percent solution
in water. Analysis of the salt 1indicates about 70.0 percent neutrali-
zation~with~icalcium,~-10.0 'percent 'neutralized-withrsodium with 20%
n remaining`'carbo'xyl groups.~ This''~particular :salt will ~be re~erred to
~30i~hereinafte`r~by;the abbreviated `term',~ n70% Ca/10% Na partial;;salt of
MVE/MA copolymer".
''S"~ OThe ! product,~wheniused~iniconjunctionlwith conventional denture
~i~adhesives '~and~applied tou wet dentures'with unormal -usage,o-provides
t ~! denturé~stabilizing ! characteristics superior 7to those obtaiiriéd by the
~^ 35 particular conve'nt~ioiial~dent'ure~adhesiYe'itself.!7~ t~
. . .
'~ '
... . . , . ...... .. -.. - . ,., ,,.,, , . ~, . ,. , . .,,,- . .. . . . .. . . .
,: . . . -. . ~, . . .
WO 9,./10988 PCr/US91/09467
l4-
ExamPle ~I~
Into a reaction vessel equipped with a high speed stirrer and
containing 92.4 parts (4.6 kg) of purified water heated to 85-C, is
slowly added 0.53 parts ~26.3 grams) of zinc oxide and calcium hy-
5droxide 1.30 parts (64.6 grams). After ~ddition is complete, the
temperature of the slurry is kept constant with high speed mixing.
While keeping heat and mixing constant add 5.76 parts (288 grams) of
methyl vinyl ether-maleic anhydride copolymer to the reaction vessel
containing the alkali dispersion over a 15 minute period. Temperature
o and mixing remain constant for 60 minutes.~ After-15 minutes the
resulting adhesive polymeric dispersion is characterized by an in-
crease in viscosity, and a decrease and stabilization of the reaction
pH ~hich is a dispersion of said material in water, said material
consisting of mixed partial calcium zinc salt of methyl vinyl ether-
maleic acid copolymer.
The resultant solution of the calcium zinc salt of methyl vinyl
; ,ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer
maintained at 80-100 PSIG with hot steam to evaporate the water
content and recover the polymeric salt with a high specific surface
area, in flake form. The thus obtained dried calcium zinc MVE/MA
copolymer salt is then ground using an air jet or hammer mill to a
,bulk density ,of about,0.7 to about 1.1 grams per cubic centimeter
,while ~aintaining` a speci~ic~surface area of:about 0.7" to' about 1.5
, square ~meters per gram. This copolymer is then screened ,through a
140-mesh sieve and then through a 200 mesh sieve (U.S.B.S. sieve
, ~,series)., The powder,has a pH of about 5.4 for,a one percent solution
in water,.~ Analysis,of ~he salt indicates about 47.5 percent neutrali-
;zation,jwith calciumj1~17.5 percentineutral,ized .iwith.i zinc,,with 35%
0~ remainingicarboxyl groups.~,This,particular sal,t will be;referred to
~r~3 30;~hereinafter, by lthe abbreviated term, ,"47.5% ,Ca/17.5%JZnipartial saltof MVE/MA copolymer". .' "~3:';',''`::~ 1:a ~
Thelproduct,,,when used,dn conjunction with conventional denture
o,;~ "adhesives :and~applied ~to,wet dentures:,~with,~normal Ausagetihprovides
,denture,,stabilizing characteristics,~super~ior~,~o those obtained by the
pa'rticular conventional~,denture adheslve,jitself `~0! ~
.~
., , .: ~, .: ' ` ` '
: ~ `' ` . ' ` , : ' , : ,: .
: ` ' ` : ' . ::: ' '. : , .,
WV 92t1~988 PCI/US91/09467
f~: 2(~ 15-
ExamDle_IV
Into a react1On vessel equipped with a high speed stirrer and
containing 84.7 parts (7.6 kg) of purified water heated to 85~'C, is
slowly added. 0.2 parts (1~3 grams) of zinc oxide and calcium hy-
droxide 0.92 parts (82.7 grams). After addition is complete, the
temperature of the slurry is kept constant with high speed mixing.
While keeping heat and mixing constant add 3.9 parts (348 grams~ of
methyl vinyl ether-maleic anhydride copolymer to the reaction vessel
containing the alkali dispersion over a 15 minute period. At about 15
minutes the resulting adhesive polymeric dispersion is characterized
by an increase in viscosity, and a decrease and stabilization of the
reaction pH which is a dispersion of said material in water, said
material consisting of mixed partial ealcium zinc salt of methyl vinyl
ether-maleic acid copolymer. Temperature and mixing remain constant
for 60 minutes. Next, 890 grams of a 1% solution of sodium hydroxide
is slowly added over a 30 minute period and the reaction is allowed to
gu to completion as indicated by the stabilization of the reaction pH.
The resultant solution of the calcium zinc salt of methyl vinyl
ether-maleic acid ~MVE/MA) copolymer is then dried using a drum dryer
maintained at ~0-100 PSIG with hot steam to evaporate the water
-' content and recover the polymeric salt with a high specific surface
area, in flake form. The thus obtained dried calcium zinc MVE/MA
copolymer salt~isltheniground using an air jet or h'ammer `mill to a
bulk density of about 0.7 to about 1.1 grams per oubic centimeter
-while 'ma'intaining a specific sur~ace area of about'0.7 to about 1.5
square meters per ~ram. ;This-copolymer is then screened through a
~; 140-mesh sieve and the`n through a 200 ~esh sieve ~'(U.S.B.'S. sieve
series)~ ~The~powder has~a pH~ofiabout`5.7-~for:a one percent solution
in3water.;~ Analysis~-o~the''salt~would indicate about;50 percent of
30~ the~c`a'rboxyl grou'ps neutralized`~'with`;cal'c`ium`, 9.'9'percent ne`utràlized
u~with ~zinc;andr'5% ;neutrallzed ~w'ith sodium~with"35%~carboxyl groups
i~` rema~ining unreacted.'' Thisiparticular salt will-be`~`referred to here-
' } ~ h ~ inafter by t~e-~abbreviat`ëdqterm, `"50% Ca/9.`9% Zn/ 5% Na'`partial salt
of MVE/MA copolymer". "'~ ;i3~
~tl!S35~1 ~Et~ ThevprOduct~ whèn~used':in''conjunction with~'conYentional denture
'.' -.t'`J ~ adhesives~and~'applied ~;to'~wet dentures~ with;normal``~usage,~ provides
t~ "denture stabilizing'characteris,tics,~superior to'those obtàined by the
particular conventionalidenture adhesive'its`el~
'
- ,. . . .. . : .. . ...
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- . . ..
- . . , . - . .
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. .
.
. . . . . . . . .
WO 92/109~8 PCr/US91/09~67
Into a reaction vessel equipped with a high speed stirrer and
containing 85.1 parts (7.7 kg) of purified water heated to 85-C, is
slowly added 0.1 parts (9 grams) of zinc oxide and calcium hydroxide
5 1.1 parts (98.9 grams). After addition is complete, the temperature
of the slurry is kept constant with high speed mixlng. While keeping
heat and mixing constant add 3.9 parts (347.2 grams) of methyl vinyl
ether-maleic anhydride copolymer to the reaction vessel containing the
alkali dispersion over a 15 minute period. At about 15 minutes the
res,ulting adhesive polymeric dispersion is characterized by an in-
crease in viscosity, and a decrease iand stabilization of the reaction
pH of the dispersion of said material in water, said material con-
sisting of mixed partial calcium zinc salt of methyl vinyl ether-
maleic acid copolymer. Temperature and mixing remain constant for 60
minutes. Next, 890 grams of a 1% solution of sodium hydroxide is
slowly added over a 30 minute per~od and the reaction is allowed to go
to completion as indicated by stabilization of the reaction pH. I
The resultant solution o~ the calcium zinc salt of methyl vinyl ,
ether-maleic acid (MVE/MA) copolymer is then dried using a drum dryer
maintained at 80-100 PSI6 with hot steam to evaporate the water
content and recover ~he polymeric salt with a high specific surface
area,~,in flake form. The thus obtained dried;calcium zinc MVE/MA
: copolymer salt.is.then ground using an air,jet or hammer mill to a
, bulk density of about 0.7~to about 1.1 grams per ~cubic centimeter
,,, 25, whi,le maintaining a~specific surface areaiof about 0.7 to about 1.5
~square ~meters per gram. ,Thisicopolymer is- then~ screened through a
,~ ,, ,"140-mesh ,sieve, and then ,through a 200 mesh sieve ,~(U.S.B.S. sieve
,~S~Jj,lJj3~series). .~The,powder has,aipH,of,,about,6.0,fpr,~a one percent solution
,,)",,in ;water.;,," Analys,is ofljthe ~salt ~would,~"indicate about~,.6090 of the
30;~carboxyl!~groups ,ne,utr,alized,~with~calcium,,~5%,neutralized,with-zinc,
.ll)," iiand,35% neutral,ized,j,with, sodium~;with,,30X,of;~,the~carboxyl ~groups re-
maining,unreacted.,l~This,jparticular saltl,wil,l,~,be,, referred to here-
j;,lna,fte,r, by t~hq' abbreviated~term,i"60% Ca/5%,~7n/5% Na partial salt of '
MVE/MA copolymer". '~rJ~ r~ 3..~
,"~,,35~ "~,~he,product, when,i,used~",in,jconjunction with~,conventional denture '
,: 3,' r~ro~ ~1 adhe$i,yes;,,andyapplied ,to,,wet dentures,~withsnor~al-,~,usage; provides
,dentur,e stabilizing characteristics~superior~to those obtained by the
particular conventional denture adhesive itself. , - l -
, . . . -. . . .
, . . ..... .. . . . .
- . . - .: : , . . .
- . , . ::
. . ~
W~ 92/10988 PCI/US9t/09467
8 _17
Example VI
The procedure of Example I ;s repeated except that the follow;ng
amounts of reactants are employed: 3.9 parts t77.3 grams) of the
anhydride copolymer, 94.9 parts (1.9 kg) purified water; and 0.2 parts
(3.99 grams) of zinc oxide; 0.2 parts (3.99 grams) of sodium hydroxide
and 3.83 parts (16.5 grams) calcium hydroxide.
The resultant powder would have a bulk density of about 0.7 to
about 1.1 grams per cubic centimeter and a specific surface area of
about 0.7 to about 1.5 square meters per gram. Analysis of the salt
o indicates about 45 percent calcium neutralization of the total initial
carboxyl groups in the copolymer salt molecule; 9.9 percent neutrali-
zation with zinc and 10% neutralization with sodium will be referred
to hereinafter by the abbreviated term "45% calcium/9.9% zinc/10%
sodium partial salt of MVE/MA copolymer". -
ExamPle VII
By following the general procedure of Example V, except that an
appropriate amounts of zinc oxide, calcium hydroxide and sodium
hydroxide are utilized to provide the tabulated substitutions, the
following calcium/zinc/sodium salts of MVE/MA copolymer are obtained:
Sodium Calcium Zinc
0 60 5
- 5 55 5
i; lC ~ 60~5 ;~ '' '' 2.5
- 65 2.5 `
- - 40 ~ ` ` 9.9
,: 20 40 -- 9.9 -
5 ; ~ 5~ - 9.9
~Each of the indicated MVE/MA copolywer salts,~ which would have,
CCfor'the minus 140-mesh U.S.B.S. sieve powder, a bulk density greater
than 0.5 grams per cubic centimeter, while maintaining a specific
~.surface area greater than 0.6 ~square'meters"/per:~gram and provides
markedly beneficial~'denture st'abilizing charaetèristics.~ Each of the
indicated salts may be abbreviated by the percent~of,calcium/percent Z
~`of~zinc~percent sodium~neût`ralization as done in'Examples I through Y.
~,35IJ!3~ - ~ Example VIII ' '-'-
Thé MVE/MA copolymeric anhydride-to-acid hydrolysis procedure
outlined in Example Y ls repeated. To a vessel containing 8.5 kg of
purified water heated to 85~ is added 16.5 grams of strontium hy-
,
.. . .
- . ' -
WO 92/10988 ~ PC~/US91/09~67
- 18-
droxide octahydrate. With vigorous mixing~ 99.4 grams of calcium
hydroxide is slowly added. After addition is complete, the tempera-
ture of the slurry is kept constant with high speed mixing. While
maintaining the heat and constant mixing, 34.9 grams of methyl vinyl
ether-maleic anhydride copolymer are added to the reaction vessel
containing the alkali dispersion over a 20 minute period. This
produces a mixed partial calcium strontium salt of methyl vinyl
ether-maleic acid copolymer.
Example IX
lo Denture stabilizing powder compositions are prepared by blending
together the following:
% w/w
A B
A. Karaya gum 53 53
Sodium carboxymethylcellulose 16 16
Sodium borate 7 7
47.5% Ca/17.5% Zn mixed partial salt of MVE/MA
copolymer 24 --
60% Ca/5% Zn/5% Na partial salt of MVE/Ma copolymer -- 24
20100 1~0
B. Sodium alginate 55 55
Sodium carboxymethylcellulose 10 10
Polyvinylpyrrolidone ~average M.W.=90,000) 15 15
65% Oa/10% Zn mixed partial salt of PVM/MA
copolymer 20 ~-
60.5% Ca/2.5% Zn/ 10% Na partial salt of MVE/MA
-; " ~ -copolymer : ` -- 20; ~ , ` 100 100
`. C , ~ j; Sodium carboxymethyloellulose , 50 - 50
;; 70% Ca/10% Na mixed partial salt of MVE/MA
copolymer~ .; '' : n ' ~ 50 30
50% Zn unmixed partial salt of MVE/MA copolymer -- 20
'' 'j ' "~ OO '100
.-
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WO 9Z/1098~ PCl/US91/09467
Q~8'~88 -19-
D. Gantrez S-97 acid copolymer 60 30
Sodium carboxymethylcellulose 40 40
70YO Ca/10/O Na mixed partial salt of MVE/MA
copolymer -- 30
lû~ lO0
: Said free acid MVE/MA copolymer, and the indicated mixed or
unmixed partial salts of MVE/MA eopolymer which would have for the
minus 140-mesh U.S.B.S. sieve powder, a bulk density greater than 0.5
grams per cubic centimeter while maintaining a specific surface area
greater than 0.6 square meters per gram.
In use, the above powders (typically 0.1-1 9) are placed on a
premoistened denture, allowed to hydrate briefly, and the denture is
inserted in the mouth and pressed into place, all in the manner of
denture adhesives well-known in the art.
ExamDle X
Liquid-type denture stabilizing compositions are prepared by
mixing together the following:
% w/w
A B
; 20 Mineral oil, heavy 44-9 43-9
Petrolatum 3.0 3.0
Colloidal silica - 1.5 1.5
. -Sodium carboxymethylcellulose . ~ 30.5 30.5
Menthol -0.1 0.1
47.5% Ca/17.5% Zn mixed partial salt of MVE/MA copolymer 20.0
55% Ca/5% Zn/10% Na mixed~partiàl s~lt of MVE/MA
. copolymer ~ - 20.0
.. . .. . . 1 00 . 0 1 00 . 0
In use, the above l~quids (typically 0.1-1 9) are placed on a
premoistened denkure, allowed to hydrate briefly, and the denture is
inserted in the mouth and pressed into place, all in the manner of
denture adhesives well-known in the art.
~ .
'
. : : '
~ . ~ , ' . .. .
.
w,~ 92J1~)988 P~/U' ,91/~9467
~,9~ 20-
Cream-type denture stabilizing compositions are prepared by
mixing together the following:
% w/,~
e B
Mineral oil, heavy 24.82424.824 24.824
Sodium carboxymethylcellulose 22.00022.000 22.00,r~
Petrolatum 19.01619.016 19.016
Silicon -d,ioxide, colloidal 1.100 1.100 1.100
0 Colorant (oil so,luble red, color
~ dispersion) 0.060 0.060 0.060
47.5%Ca/17'.5%Zn, mixed partial salt
of MVE/'MA copolymer 33.000
55.0%Ca/5%Zn/10%Na mixed partial
salt of MVE/MA copolymer ~ 33.000 ----
7,'~% Ca/10% Na partial mixed salt of MYE/MA
copolymer ---- ---- 16.500
50% Zn unmixed partial salt of MVE/MA,
copolymer ---- ---- 16.500
Said free acid MVE/MA cop,olymer, and the indi,^ated mixed or
unmixed part-,al salts of MVE/MA copolymer which would have ~or the
minus 140-mesh U.S.B.S. sieve powder, a bulk density greater than 0.5
?.`; :'grams per cubic centimeter while maintaini,n,g'~'a specific sùr~face area
greater than 0.6 square meters per gram.
; 25 ~ ~. In~use, the above creams ~typ kally-0.1-2 g) are placed on a
premoistened denture, allowed to hydrate briefly, and the denture is
; ~in$erted in the mouth and pressed into place, all in the `manner of
id,enture adhesives well-known in the art.
3. i7ih 3i~ii.J
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WHAT IS CLAIMED IS:
, . . . . . . .
.
