CA2220095C - Silica abrasive compositions - Google Patents
Silica abrasive compositions Download PDFInfo
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- CA2220095C CA2220095C CA002220095A CA2220095A CA2220095C CA 2220095 C CA2220095 C CA 2220095C CA 002220095 A CA002220095 A CA 002220095A CA 2220095 A CA2220095 A CA 2220095A CA 2220095 C CA2220095 C CA 2220095C
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- abrasive
- precipitated silica
- ratio
- silica
- abrasion
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
Abstract
Oral compositions, such as oral gels and toothpastes, containing a novel abrasive.
Description
W 0'36134595 P~r~IUS~6~060~2 S~ICA ABR~SIVE COMPOSmONS
TECHNICAL FIELD
~i This il~ion relates to de"li~,ce compositions CQ~ SlICh as toulh~ le~ which provide improved oral c1 ~ni~
BACKGROUND OF 1~ lNVENTION
S~ r--~iCA'lly produced p~ ecl silicas play an i~ JO~ role as an di~nl in many of today's toothpaste fo,,~ ;t)n~ In ~ ition to theil ~P~nir~
10 ability, they are also relatively safe, n-mto~ , and co...p~ lc with other tooLllya~le ingredients, incllldin~ glycclill, sorbitol (or xylitol), ~ L~ninp agents, dc~lt~r enls c:oloring and fragrance materials and, optionally, fluoride co.~ co.nyo ;l;c-n-~
Synthetic y~-';p;~ erl silicas are p,cpared by a~ ;7~ lk~line silicate solutions with acids, stirring and then filtering out the pfc~ip;l~e~l silica. The 15 r~sultin~ prec;~ dte is next washed, dried and co....n;..-~ted to desired size. When -~a ing synthetic pre~ .iL~ed silicas, the objective is to obtain silicas which provide ",~h,~l c~ P with minim~l damage to oral tissue. Dental research~l, are contim-~lly concc,..ed with identifying p-~ te(i silicas mf-etin~ these objectives.
FY~rnrles of p,c-~;p;l;1~ed silicas include U.S. Patent 4.122~161 to Wason, October 24, 1978, U.S. Patents 4~992~251 and 5.035~879 to ~Idcroft et al., February 12, 1991 and July 30, 1991 respectively, U.S. Patent 5~098~695 to Newton et al.,March 24, 1992, and U.S Patent 5~279~815 to Wason et al., January 18, 1994.
Moreover, various colllbilldlions of silicas have also been described in the art.
Siilica combinations iinvolving compositions of di~cling particle sizes and specific sui-face areas are disclosed in U.S. Patent 3~S77~521 to Karlheinz Scheller et al., May 4, 1971 and U.S. Patent 4~618~488 to Maeyama et al., October 21, 1986, res~e~ ely. Similarly, U.S. Patents 5.110.574 to Reinhardt et al., May S, 1992 closPS colllbilul~; thi lrf-nPr and polishing silicas to forl-n silica compositions having oil absorption values of at least 200. Further ~,c~n,~les of silica combinations include U~S Patent 5~124~143 to Muhlemann, June 23, 1992 and U.S Patent 4~632~826 to Ploger et aL, December 30, 1986.
In spite of the many disclosures relating to compositions for oral cleanir~r and~ntipl~llue activity, there is still a need for additional compositions providing improved pelLicle cle~nin~ with minim~l abrasion The present inventor has 3~; discovered abrasive compositions COIllplisillg silicas having particles of differing hardness values provide improved dental cleaning with minim~1 abrasion Accordin~, it is the object of the present i"~,e.-lion to provide p,ec~ a~e(l silica CO~pOa;~;QIl~ e~ ;"P improved pellicle e~ P will~uul a co~l~O~o~ 9.
,.,."~ase in dentin or enamel ~l~a;On. Another object of the present invention is to provide an e~t~ rc; method for the prevention or removal tooth stains. A further5 object ofthe present invention is to provide an effective method for the p,t;~ ion or removal of plaque. These and other objects will beco,.lc readily appa~ from the r,loSllre which follows.
SUMMARY QF 1~ INVEN~ION
The present invention relates to p,~.i~ d silica abrasive composition, 10 CC~ l iaing.
a.) a pleC;IJil~le~ silica, COlllpliSil~g particles wl,er~;" said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. < 7);
ii.) an F.inlehnPr hardness of from about 0.8 to about 2.5 for abrasive to brass screen and from about S to about below 8 for abrasive to polyester screen;
iii.) an oil abso-~Lion of from 95 mltlOO gm to about 13S
ml/100 gm; and iv.) a ra~lioac~ive dentin abrasion of from about 25 to about below 80;
and b.) a preci~ilaled silica, comprising particles wherein said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. c 7);
ii.) an FinlrhnPr hardness of from about 3 to about 8 for abrasive to brass screen and from 8 to about 11 for abrasive to polyester screen;
iii.) an oil absorption of from about 70 mltlOO grn to about below 9S mltlOO gm; and iv) a r~ioactive dentin abrasion of from 80 to about 200 ,reil at least about 70% of all of said particles have a ~i~m~oter of below about 20 microns and wherein the pellicle rlf~nin~ ratio is from about 90 to about 135 and the r~-iioactive dentin abrasion is from about 60 to about 100 with a pellicle c~ nin~
ratiotra~ioactive dentin abrasion ratio of from about 1.25 to about 1.75 and wherein the ratio of the silica in a.) to the silica in b.) is from about 90:10 to about 40:60, respectively.
W0 !,~6/34595 PC'r~US96~06012 All levels and ratios are by weight of the total col..posilion, unless oth~;l vv..,e ;.,c1i,~ ,1 PCR and RDA values are Imi~lec~ ition~lly, all ~ 7~r,-llel1ls are made at 25~C unless oll,." wi~e s~ ed The pH of the present herein des~;.il,ed col.,po~;l;on~ range from about 4 to about 9.5, with the p,erc,,,ed pH being from about 6.5 to about 9.0 and the mostrell~d pH being 7.0 to about 8.5, as ~lle&~ td in a 5% aqueous slurIy.
DETAILED DESCRIPTION OF TE~ INVEN~ION
The ~ as well as optional co,ll,volle~ of the co..~pos.~;on~ of the present invention are described in the following paragraphs.
1 0 Abrasive The pr~ ed silicas used to form the silica compositions of the present ul~ ion can be chara~;t~ ed as either Low Structure or Medium Structure si1icas in accoldance with the d~finitions set forth in the J. Soc. Cosmet. Chem. 29., 497-521 I~August, 1978), and Pigment Handbook: Volume 1, Plope.Lies and Ecorlomics, ,Second Fr1ition~ Edited by Peter A. Lewis, John Wiley & Sons, Inc., 198~, p. 139-15~ and are p,~,rt;l~bly chara~;Ltl~ed as synthetic hydrated a"l,ull,hous silicas, also Icnown as silicon dioxides or SiO2. Further, these silicas may be chara~;Lel~ed as hsving a BET surface area in the range of 50 to 250 m2tg.
These co,.ll-o."llons are further chara~iLe"~Ged as having a median average particle size ranging from about 5 microns to about 11 Illicl'ons with at lea ,t 70% of the paLrticle size distribution being less than 20 microns. The average palticle size (mean value and median or 50%) is measured using a Microtrac II apparatus, Leedsand Northrup. Specifi~ y, a laser beam is projected through a Ll~u~sp..-~nL cellwhich co..l;~ c a stream of moving particles suspended in a liquid. Lights ra~ys which 25 s;trilce the particles are scalL~,led through angles which are inversely propoltiona~ to their sizes. The photodetector array measures the quantity of light at several pred~le~...;..~d angles. Electrical signals propolLonal to the measured light ~ux ~alues are then p,ucessed by a microcomputer system to form a multi-channel histogram ofthe particle size distribution.
The yre~ fd silicas used to form the co-,.posilions of the present illvention are further di~,~ d by means of their ~ ue~ re Einlehner l.aldness values, P~ io~rtive Dentin Abrasion (RDA) values and oil absorption values Fin1~hn.or ha~dness values are measured using an ~inl~hner At-1000 Abrader to measure the so~nes~ of the silicas in the following l"~m~.. A Fourdrinier ~,vire 35 sereen is weighed and exposed to the action of a 10% aqueous silica suspension for a clertain length of time. The amount of abrasion is then determined as milligrams weight lost of the Fouldli fier wire screen per 100,000 revo1~ltionc Brass F.inl~hn-~r ~13E) and Polyester Finl~hn~r (PE) results are e,~ ,sed in milligrams.
The RDA values are dc~ ed accorLlg to the method set forth by II~,~llen, Journal of Dental Research, July-August 1976, pp. 563-573, and descl;l,cd in the Wason U.S. Patents 4.340.583. 4~420.312 and 4.421.527. which ~ul~lic~;c)n and patents are illcOl,uolal~d herein by l~r~cllcc.
The p(~ pi~ted silica co..-posiLions of the present invention may be c,l~a-,Ltli~cd as having oil absol~.Lion values of less than 200cctlOOg. Oil absorption values are lll~;a~ul~d using the ASTM rub-out method D281. Surface area is 10 de~ ed by the BET nitrogen adso.l.Lion method of Brunaur et al., J. Am. Chem.Soc., 60, 309 (1938). To measure bl;gl.~ cs, fine powder materials that are pressed into a smooth surfaced pellet are evaluated using a Technid,vne B-;~ n~te~ S-5tBC.
This ill~L.u...~.lL has a dual beam optical system where the sample is ill~ ed at a angle of 45~, and the rPflected light viewed at 0~. It co~ s to TAPPI test mrthsric T452 and T646, and ASTM Standard D985. A series of filters direct to reflected light of desired wavçlPngthe to a photocell where it is converted to an output voltage. This signal is amplified and then processed by an internal microcomputer for display and printout.
~lec;~iLaLion of the silicas of the present invention is accnmpliched in 20 accoldance with the general methods desclil,ed, for eY~mrl~, in prior U.S. Pate.lls.
3.893.840~ issued July 8, 1975, to Wason; 3.988.162. issued October 26, 1976, toWason, 4.067~746. issued January 10, 1978, to Wason; and 4.340,583. issued July 29, 1982, to Wason; all of which are herein incorporated by lc;rerence.
In one step ofthe process, a first pleci,uilaLed silica suspension is plt;p~ed by 25 varying ~ ,iLaLion reaction parameters in a manner, ordinarily, res~-lting inplt;r;~ cl silicas having BE values in the range of from about 0.8 mg to about 2.5 mg and PE values in the range of about 5 mg to about below 8 mg, an RDA ranging from about 25 to about 80, and an oil absorption of from 95ml/100gm to about 135ml/100gm. Reaction parameters which afrect the characteristics of the res .lt~nt 30 silica incl~lde the rate at which the various react~ntc are added; the levels of concentration of the various re~cPntc; the reaction pH; the reaction temperature or the rate at which electrolytes are added.
In another step of the ~ ;on process, a second preci~.iL~led silica ~us~)en~ion is similarly plepaled varying reaction pararneters in a manner, ordinarily, 35 resulting in precipitated silicas having BE values in the range of from about 3 mg to about 8 mg and PE values in the range of 8 mg to about 11 mg, an RDA ranging WO 9l6134595 5 PC'r~lJSS'6J~6012 from about 81 to about 200, and an oil abso~l,liol- of from about 70mll'100gm toabout below 95ml/100gm.
Th~i~ler, the t~,vo ~ eci silica suspensions can be co...kil~f~
the pH to about 5Ø The co~ il,aL;on suspension is filtered and then wa~shed with S water to remove salts from the filter cake. The filter cake is dried, prer~l~bly by coll~ n~l spray d~ging to produce a l~reç;~ d silica co~ about 3% to 10% lllo;alule. The pr~ ed silica co...h;~ ;on is milled to a particle size in wllich 70% of the particle size ~ ibulion is below 20 Illicrons. Alle-llaLiv~l~, the silicas can be co",l),l~ed prior to ulcollJol~lion into de"li~;ce coll,l,o~;l;ons.
In ~d~liti~ to the above described essf~nti~l colllpon~ Ls, the dentifrice compositions of the present invention can contain a variety of optional df ntifrjce ingredients some of which are described below. Optional ingredients in~lude, forexarnple, but are not lirnited to, adhesives, sudsing agents, fiavoring agents, s~ t~ agents, ~d~lition~l ~ntirl~ e agents, abrasives, and coloring agents.
These and other optional componenl~ are further described in U S. Patent s~004~597.
April 2, 1991 to Majeti; U.S. Patent 4.885.155. Dec~mh~ ~i, 1989 to Parran, Jr. et al.; U.S. Patent 3.959.458. May Z5, 1976 to Agricola et al. and U.S. Patent 3.937.807. Febn~ary 10, 1976 to ~tof~l~, all being incorporated herein by re~rence.
The Pellicle Cleaning Ratio (PCR) of the inventive silica CO~ si laLion, which is a mea~u,e,llc;,l~ ofthe cle~ning characteristics of a dentifrice, ranges from 90 to 135 and preferably from 100 to 130 for the p.e~i~,iLaLed silica colllbil.aLion of the invention. The P~riio~ctive Dentin Abrasion (RDA) of the inventive silicas, which is a lll~ult;lllelll of the abrasiveness of the pl~ ed silica col..bil.a~iorl when inco.~cs.aLed into a dentifrice, ranges from 60 to 10, p.t;re-ably from 80 to 90.
The PCR (Pellicle Cleaning Ratio) cle~ning values are detel.. uned by a slightly modified version of the PCR test described in "In Vitro Removal of Stain With Dentifrice", G. K. Stookey, T.A. Burkhard and B. R. Schemerhorn, J. Dental Research, 61, 1236-9, 1982. Cleaning is ~csessed in vitro by use of the modifiedpellicle cle~ning ratio test. This test is id~ntic~l to that described by Stookey et al.
30 with the following modific~tions: (1) a clear artificial pellicle film is applied to bovine ¢hiips prior to application of the stained filn~ (2) solution heating is used rather than ~radiative heating during film application, (3) the number of brush strokes is reduced ltO 200 strokes and (4) the slurry conce--Ll~Lion is 1 part dentifrice to 3 parts w.lter.
The pl ~ciplL~Led silica compositions of the present invention, when 3~i iincorporated into a dentifrice composition further provide an improved PCEVRDA
Iratio. The PCRJRDA ratio is used to determine the relative ratio of cle.ming and abrasion characteristics of a dentifrice formulation. Comrnercially available dentifrice CA 02220095 l997-lO-3l fc~ lulaLions ~,n~.~lty have a PCR/RDA ratio in the range of 0.5 to below 1Ø The ;P;I ~led silicas used in the co~ o~;~ iO~c of the present invention provide PCR to RDA ratios to dentifrice rul~ ;onc of greater than 1, usually in the range of 1.25 to 1.75, but more ~Icrc~bly in the range 1.6 to 1.75.
The abrasive, in the form of a pre~ ed silica compositionc of the present i"~_.,lion, when illcol~ul~lc~ into the compositions dc3~,il,ed herein, is present at a L
level of from about 6% to about 70%, prtre,~bly from about 15% to about 35%
when the dt-,Lir,icc is a tooll.p~le Higher levels, as high as 95%, may be used if the c~",l,osilion is a too~ ùwder.
OPTIONAL COMPONENTS
Pharm~ce~-tically Acceptable Carner The carrier for the co,~lpon~llLs of the present compositions is optional and can be any dentifrice vehicle suitable for use in the oral cavity. Such carriers include the usual co.~lponclll~ of too~ les, tooth powders, prophylaxis pastes, lo,~-ges, gums and the like and are more fully described helcina[lel. Toothr~ctes are the plcrt:llcd ~lClllS.
Surf~ct~ntc-One of the plcr~llcd optional agents of the present invention is a surfactant, ~,fc~ably one sPlected from the group consi~li,lg of sa,~;o~ P surf~t~ntc isethionate surf~ct~nts and taurate surf~ct~nts Pre~ d for use herein are alkatimetat or ammonium satts ofthese surf~ct~ntc Most p.crc-led herein are the sodiumand potassium salts of the following: lauroyl sarcosin~t~, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinale and oteoyl s~cosinate.
This surfactant can be present in the compositions of the present invention from about 0.1% to about 2.5%, preferably from about 0.3~/O to about 2.5% and most preferably from about 0.5% to about 2.0% by weight of the total composition.
Other suitable co--.patible surf~ntc can optionally be used along with the sarcosin~te surfactant in the compositions of the present invention. Suitable optional surf~ct~nts are desclibcd more fully in U S Patent 3.959.458. May 25, 1976 to Agricola et al.; U.S. Patent 3.937.807. February 10, 1976 to ~ e; and US
Patent 4.0~1.234. Sep~elllbcl 27, 1988 to Gieske et al. These patents are incorpo-rated herein by lefelcllcc.
P~if~lled anionic surf~ct~ntc useful herein include the water-soluble salts of al-kyl suLfates having from 10 to 18 carbon atoms in the alkyl radical and the water-soluble salts of sulfonated monoglycerides of fatty acids having from 10 to 18 carbon atoms. Sodium lauryl sulfate and sodium coconut monoglyceride sulfonates are WO 96134595 7 PC'r~US96~06012 , ' of anionic ;.~. r~ of this type. ~lui~s of anionic sll~f~n~c can also be lltili7ç,1 F~fc~l~,d ç~tion;c~ surf~çt~nts useful in the present invention can be broadly defined as derivatives of ~lirh~tic qualc--l~y ~ .. compounds having ane long 5 alkyl chain con~ g from about 8 to 18 carbon atoms such as lauryl LILUICLI1Y1~.... chloride; cetyl pyridinium chloride; cetyl Ll.,n~ ol~ium bromide; di-is-o~u~ h~ llyl-dimcllly~ .~y~ chloride; coconut all~yl~lL~ lyla~
1 nitrite; cetyl pyridinium fluoride; etc. Pr~Çc,lcd compounds are the quater-nary ~-....-O~ -.. fluorides descl~ed in U.S Patent 3.535.421. October 20, 1970, to Briner et al., herein incorporated by ~cfcl~_nce, where said ~luaLclllaly a~.. ol~
fll~ori(l~s have dele~enL propcllies. Certain cationic surf~çt~ntc can also act as gerrnicides in the compositiorlc ~~ic. losed herein. C~fionic surf~ nts such as chlor-hPY~inP" although suitable for use in the current invention, are not prcrc,~ ~d due to their capacitv to stain the oral cavity's hard tissues. Persons skilled in t'he art are 15 aware of this possibility and should incol,uo-ale c,ationic surf~çt~nt~ only with this l;...;l~l;ol- in mind.
~ cÇclled nonionic surf~ct~ntc that can be used in the compositions of the present invention can be broadly defined as compounds produced by the co~ Pnc~
tion of alkylene oxide groups (hydrophilic in nature) with an organic Lydlol~hDb'~
20 co,llpou..d which may be aliphatic or alkylal~ alic in nature. Examples of suitable nonionic surf~ct~nts include the Pluronics, polyethylene oxide con~enc~tçs of alkyl phenols, products derived from the condçnc~tion of ethylene oxide with the.reaction product of propylene oxide and ethylene ~ mine, ethylene oxide con~ienc~tes of ~liph~tic alcohols, long chain tertiary amine oxides, long chain tertiary ]phosphinP
25 oxides, long chain dialkyl sl~ifoxid~os and Il~ALulcs of such materials.
Prcrcllcd zwitterionic synthetic surfactants useful in the present invention can'be broadly described as derivatives of aliphatic quaternary ammonium, phos-phomillm, and sulfonium compounds, in which the ~lirh~tic radicals can b~e straight ch~in or branched, and wherein one of the aliphatic su!QstitU~ntc col~ s ~om about 30 8 to 18 carbon atoms and one collL~ns an aniornic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosph~te or phosphonate.
Plcrc~lcd betaine surf~ nts are disclosed in U.S. Patent 5,180,577 to ]?olefka ~et al., issued January l9, 1993. Typical alkyl dimethyl beL~ es include decyl betaine lor 2-(N-decyl-N,N-dimethylammonio) acetate, coco betaine or 2-(N-coc-N, N-35 dimethyl ammonio) acetate, myristyl betaine, paln~ityl betaine, lauryl betaine, cetyl'betaine, cetyl betaine, stearyl betaine, etc The amidobetaines are exemrlified by eoco~midoethyl betaine, coco~midopropyl betaine, lauramidopropyl betaine and the CA 0222009~ lgg7-lo-3l wo 96/34595 8 PCT/USg6/06012 like. The b~L~.es of choice are pr.,fe.ably the cocoamidopropyl betaine and, more ,r~,.d~ly, the laul~l~ido propyl betaine.
Ch~ agents:
Another p,~re"td optional agent is a ~h~l~tin~ agent s~ (ed from the group 5 eon~ of tartaric acid and ph~rm~cel~tic~lly-~cGc;~ ble salts thereof, citric acid and alkali metal citrates and l~Llllcs thereof. Ch~l%~ agents are able to complex calcium found in the cell walls of the bacteria. Ch~ agents can also disruptplaque by removing c~lCium from the e~lei~lm bridges which help hold this biomass intact. However, it is possible to use a ch~ agent which has an afflnity for 10 calcium that is too high. This results in tooth cle~ ,-alization and is COllllaly to the objects and ;.~ ;ol-~ ofthe present invention.
So-li--m and potassium citrate are the p.~;r~"~d alkali metal citrates, with sodium citrate being the most prc;rt..cd. Also p-cr~ d is a citric acid/alkali metal citrate cG-.LillaLion. Pl~relled herein are alkali metal salts of tartaric acid. Most 15~l~r~ d for use herein are tiicodium tartrate, dipotassium tartrate, sodium potassium tartrate, sodium hydlo~,el1 tartrate and potassium hydrogen tartrate. The amounts of agent suitable for use in the present invention are about 0.1% to about 2.5%, prerelably from about 0.5% to about 2.5% and more p,er~lably from about 1.0% to about 2.5%. The tartaric acid salt ~.hPI~tin~ agent can be used alone or in 20colllbi~lalion with other optional ch~ ting agents.
Other optional ~h.ol~ting agents can be used. Preferably these rhPI~ting agents have a calcium binding consL~rlL of about 101 to 105 provide improved ~le~nin~ with reduced plaque and c~lc~ c formation.
Another group of agents suitable for use as çh~l~tin~ agents in the present 25invention are the soluble pyrophosphates. The pyrophosph~te salts used in the present compositions can be any of the alkali metal pyrophosphate salts. Specific salts include tetra alkali metal pyrophosphate, dialkali metal diacid pyrophosphate, trialkali metal monoacid pyrophosphate and mixtures thereof, wherein the allcalimetals are preferably sodium or pOpcsillm The salts are useful in both their hy-30drated and unl-~d.~Led forms. An effective amount of pyrophosphate salt useful in the present composition is generally enough to provide at least 1.0% pyrophosphate ion, preferably from about 1.5% to about 6%, more preferably from about 3.5% to ahout 6% of such ions. It is to be appl c:~iaLed that the level of pyrophosphate ions is that capable of being provided to the composition (i.e., the theoretical amount at an 35applup~iate pH) and that pyrophosphate forms other than P207~ (e.g., (HP207-3)) may be present when a final product pH is established.
W0~36134595 9 PCT~US.~6~06012 The p~ hG;,~ salts are des~;,;l,ed in more detail in Kirk & Ot~ner, Encv-pe~lia of Ch-rnir~l Technolog;sr~ Second Fr~itior, Volume 15, LILc~ie;l~ec Publish ers (1968), iluoll.GIaLcd herein by Icrcl~ence.
Still another po~;l,lc group of ~ agents suitable for use in 1he present 5 invention are the anionic polymeric polyc~bu~ylal.es. Such materials are ~well known in the art, being employed in the form of their iiee acids or partially or pr~rt;~ably fu21y neutralized water soluble alkali metal (e.g. po~ ;ul,l and p,crc~bly sodium) or A~ salts. Plcf~ d are 1:4 to 4:1 copolymers of maleic anhydride or acid with another poly",c.;~le ethylenically u"saLu,aLed ,..n nn ~ , plcrelaT~ly methyl vinyl ether (~ ho~clllylene) having a molecul~ weight (M.W.) of about 30,000 to about 1,000,000. These copolymers are availabl~ for ~ ple as Gantre~z ,AN 139 (M.W. 500,000), AN 119 (M.W. 250,000) and pler~lably S-97 P1...,..
Grade (M.W. 70,000), of GAF ~h~mir~lc Coll ol~Lion.
Other operative polymeric polycarboxylates include those such as the 1:1 copolymers of malelc anhydride with ethyl acrylate, hydl o~yt;lllyl meth~r,r~late, N-vi-nyl-2-pyrolli~onP or ethylene, the latter being a~ailable for example as MOI~CAIIIQ
EMANo. 1103, M.W. 10,000 and EMA Grade 61, and 1:1 copolymers oi.'acrylic acid with methyl or hydlu~yt;Lllyl mçth~rrylate~ methyl or ethyl acrylate, isobutyl v2nyl ether or N-vinyl-2-pyrrolidone.
Additional operative polymeric polyca,lJ~rlates are disclosed in U.S Patent 4.138~477. February 6, 1979 to Gaffar and U.S. Patent 4.183.914. January 15, 1980 to Gaffar et al. both patents are incorporated herein by ~~;r~lellce, and include co-polymers of maleic anhydride with styrene, isobutylene or ethyl vinyl ether, poly-acrylic, polyitaconic and polymaleic acids, and sulf~acrylic oligomers of M W. as low as 1,000 available as Uniroyal ND-2.
Flavoring agents can also be added to dentifi~ce compositions. Suitable fiavor-ing agents include oil of W~hlLt;l~ en~ oil of peppe2mint, oil of spearmint, oil of sds ,aG~s, and oil of clove. SweetPning agents which can be used include ~p~ L~ne, ~cPs~llf~mP saccharin, dextrose, levulose and sodium cycl~m~te Flavoring and ~weet~ -p agents are generally used in dentifrices at levels of from about 0.005% to about 2% by weight.
It is comrnon to have a water-soluble fluoricie compound present in del1tifricesand other oral compositions in an arnount sr-ffiri~nt to give a fluori,de ion conr~ ion in the composition at 25~Ç, and/or when it is used of from about 0.0025% to about 5.0% by weight, preferably frorn about 0.005% to about 2.0% by wleight, to provide additional anticaries effectiveness. A wide variety of fluor~de ion-yielding materials can be employed as sources of soluble fluoride in the present .p~ n~ F~.... l.les of suitable fl--oritle ion-yielding m~tPriAlc are found in U.S.
Patent No. 3.535~421. October 20, 1970 to Briner et al. and U.S. Patent No.
TECHNICAL FIELD
~i This il~ion relates to de"li~,ce compositions CQ~ SlICh as toulh~ le~ which provide improved oral c1 ~ni~
BACKGROUND OF 1~ lNVENTION
S~ r--~iCA'lly produced p~ ecl silicas play an i~ JO~ role as an di~nl in many of today's toothpaste fo,,~ ;t)n~ In ~ ition to theil ~P~nir~
10 ability, they are also relatively safe, n-mto~ , and co...p~ lc with other tooLllya~le ingredients, incllldin~ glycclill, sorbitol (or xylitol), ~ L~ninp agents, dc~lt~r enls c:oloring and fragrance materials and, optionally, fluoride co.~ co.nyo ;l;c-n-~
Synthetic y~-';p;~ erl silicas are p,cpared by a~ ;7~ lk~line silicate solutions with acids, stirring and then filtering out the pfc~ip;l~e~l silica. The 15 r~sultin~ prec;~ dte is next washed, dried and co....n;..-~ted to desired size. When -~a ing synthetic pre~ .iL~ed silicas, the objective is to obtain silicas which provide ",~h,~l c~ P with minim~l damage to oral tissue. Dental research~l, are contim-~lly concc,..ed with identifying p-~ te(i silicas mf-etin~ these objectives.
FY~rnrles of p,c-~;p;l;1~ed silicas include U.S. Patent 4.122~161 to Wason, October 24, 1978, U.S. Patents 4~992~251 and 5.035~879 to ~Idcroft et al., February 12, 1991 and July 30, 1991 respectively, U.S. Patent 5~098~695 to Newton et al.,March 24, 1992, and U.S Patent 5~279~815 to Wason et al., January 18, 1994.
Moreover, various colllbilldlions of silicas have also been described in the art.
Siilica combinations iinvolving compositions of di~cling particle sizes and specific sui-face areas are disclosed in U.S. Patent 3~S77~521 to Karlheinz Scheller et al., May 4, 1971 and U.S. Patent 4~618~488 to Maeyama et al., October 21, 1986, res~e~ ely. Similarly, U.S. Patents 5.110.574 to Reinhardt et al., May S, 1992 closPS colllbilul~; thi lrf-nPr and polishing silicas to forl-n silica compositions having oil absorption values of at least 200. Further ~,c~n,~les of silica combinations include U~S Patent 5~124~143 to Muhlemann, June 23, 1992 and U.S Patent 4~632~826 to Ploger et aL, December 30, 1986.
In spite of the many disclosures relating to compositions for oral cleanir~r and~ntipl~llue activity, there is still a need for additional compositions providing improved pelLicle cle~nin~ with minim~l abrasion The present inventor has 3~; discovered abrasive compositions COIllplisillg silicas having particles of differing hardness values provide improved dental cleaning with minim~1 abrasion Accordin~, it is the object of the present i"~,e.-lion to provide p,ec~ a~e(l silica CO~pOa;~;QIl~ e~ ;"P improved pellicle e~ P will~uul a co~l~O~o~ 9.
,.,."~ase in dentin or enamel ~l~a;On. Another object of the present invention is to provide an e~t~ rc; method for the prevention or removal tooth stains. A further5 object ofthe present invention is to provide an effective method for the p,t;~ ion or removal of plaque. These and other objects will beco,.lc readily appa~ from the r,loSllre which follows.
SUMMARY QF 1~ INVEN~ION
The present invention relates to p,~.i~ d silica abrasive composition, 10 CC~ l iaing.
a.) a pleC;IJil~le~ silica, COlllpliSil~g particles wl,er~;" said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. < 7);
ii.) an F.inlehnPr hardness of from about 0.8 to about 2.5 for abrasive to brass screen and from about S to about below 8 for abrasive to polyester screen;
iii.) an oil abso-~Lion of from 95 mltlOO gm to about 13S
ml/100 gm; and iv.) a ra~lioac~ive dentin abrasion of from about 25 to about below 80;
and b.) a preci~ilaled silica, comprising particles wherein said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. c 7);
ii.) an FinlrhnPr hardness of from about 3 to about 8 for abrasive to brass screen and from 8 to about 11 for abrasive to polyester screen;
iii.) an oil absorption of from about 70 mltlOO grn to about below 9S mltlOO gm; and iv) a r~ioactive dentin abrasion of from 80 to about 200 ,reil at least about 70% of all of said particles have a ~i~m~oter of below about 20 microns and wherein the pellicle rlf~nin~ ratio is from about 90 to about 135 and the r~-iioactive dentin abrasion is from about 60 to about 100 with a pellicle c~ nin~
ratiotra~ioactive dentin abrasion ratio of from about 1.25 to about 1.75 and wherein the ratio of the silica in a.) to the silica in b.) is from about 90:10 to about 40:60, respectively.
W0 !,~6/34595 PC'r~US96~06012 All levels and ratios are by weight of the total col..posilion, unless oth~;l vv..,e ;.,c1i,~ ,1 PCR and RDA values are Imi~lec~ ition~lly, all ~ 7~r,-llel1ls are made at 25~C unless oll,." wi~e s~ ed The pH of the present herein des~;.il,ed col.,po~;l;on~ range from about 4 to about 9.5, with the p,erc,,,ed pH being from about 6.5 to about 9.0 and the mostrell~d pH being 7.0 to about 8.5, as ~lle&~ td in a 5% aqueous slurIy.
DETAILED DESCRIPTION OF TE~ INVEN~ION
The ~ as well as optional co,ll,volle~ of the co..~pos.~;on~ of the present invention are described in the following paragraphs.
1 0 Abrasive The pr~ ed silicas used to form the silica compositions of the present ul~ ion can be chara~;t~ ed as either Low Structure or Medium Structure si1icas in accoldance with the d~finitions set forth in the J. Soc. Cosmet. Chem. 29., 497-521 I~August, 1978), and Pigment Handbook: Volume 1, Plope.Lies and Ecorlomics, ,Second Fr1ition~ Edited by Peter A. Lewis, John Wiley & Sons, Inc., 198~, p. 139-15~ and are p,~,rt;l~bly chara~;Ltl~ed as synthetic hydrated a"l,ull,hous silicas, also Icnown as silicon dioxides or SiO2. Further, these silicas may be chara~;Lel~ed as hsving a BET surface area in the range of 50 to 250 m2tg.
These co,.ll-o."llons are further chara~iLe"~Ged as having a median average particle size ranging from about 5 microns to about 11 Illicl'ons with at lea ,t 70% of the paLrticle size distribution being less than 20 microns. The average palticle size (mean value and median or 50%) is measured using a Microtrac II apparatus, Leedsand Northrup. Specifi~ y, a laser beam is projected through a Ll~u~sp..-~nL cellwhich co..l;~ c a stream of moving particles suspended in a liquid. Lights ra~ys which 25 s;trilce the particles are scalL~,led through angles which are inversely propoltiona~ to their sizes. The photodetector array measures the quantity of light at several pred~le~...;..~d angles. Electrical signals propolLonal to the measured light ~ux ~alues are then p,ucessed by a microcomputer system to form a multi-channel histogram ofthe particle size distribution.
The yre~ fd silicas used to form the co-,.posilions of the present illvention are further di~,~ d by means of their ~ ue~ re Einlehner l.aldness values, P~ io~rtive Dentin Abrasion (RDA) values and oil absorption values Fin1~hn.or ha~dness values are measured using an ~inl~hner At-1000 Abrader to measure the so~nes~ of the silicas in the following l"~m~.. A Fourdrinier ~,vire 35 sereen is weighed and exposed to the action of a 10% aqueous silica suspension for a clertain length of time. The amount of abrasion is then determined as milligrams weight lost of the Fouldli fier wire screen per 100,000 revo1~ltionc Brass F.inl~hn-~r ~13E) and Polyester Finl~hn~r (PE) results are e,~ ,sed in milligrams.
The RDA values are dc~ ed accorLlg to the method set forth by II~,~llen, Journal of Dental Research, July-August 1976, pp. 563-573, and descl;l,cd in the Wason U.S. Patents 4.340.583. 4~420.312 and 4.421.527. which ~ul~lic~;c)n and patents are illcOl,uolal~d herein by l~r~cllcc.
The p(~ pi~ted silica co..-posiLions of the present invention may be c,l~a-,Ltli~cd as having oil absol~.Lion values of less than 200cctlOOg. Oil absorption values are lll~;a~ul~d using the ASTM rub-out method D281. Surface area is 10 de~ ed by the BET nitrogen adso.l.Lion method of Brunaur et al., J. Am. Chem.Soc., 60, 309 (1938). To measure bl;gl.~ cs, fine powder materials that are pressed into a smooth surfaced pellet are evaluated using a Technid,vne B-;~ n~te~ S-5tBC.
This ill~L.u...~.lL has a dual beam optical system where the sample is ill~ ed at a angle of 45~, and the rPflected light viewed at 0~. It co~ s to TAPPI test mrthsric T452 and T646, and ASTM Standard D985. A series of filters direct to reflected light of desired wavçlPngthe to a photocell where it is converted to an output voltage. This signal is amplified and then processed by an internal microcomputer for display and printout.
~lec;~iLaLion of the silicas of the present invention is accnmpliched in 20 accoldance with the general methods desclil,ed, for eY~mrl~, in prior U.S. Pate.lls.
3.893.840~ issued July 8, 1975, to Wason; 3.988.162. issued October 26, 1976, toWason, 4.067~746. issued January 10, 1978, to Wason; and 4.340,583. issued July 29, 1982, to Wason; all of which are herein incorporated by lc;rerence.
In one step ofthe process, a first pleci,uilaLed silica suspension is plt;p~ed by 25 varying ~ ,iLaLion reaction parameters in a manner, ordinarily, res~-lting inplt;r;~ cl silicas having BE values in the range of from about 0.8 mg to about 2.5 mg and PE values in the range of about 5 mg to about below 8 mg, an RDA ranging from about 25 to about 80, and an oil absorption of from 95ml/100gm to about 135ml/100gm. Reaction parameters which afrect the characteristics of the res .lt~nt 30 silica incl~lde the rate at which the various react~ntc are added; the levels of concentration of the various re~cPntc; the reaction pH; the reaction temperature or the rate at which electrolytes are added.
In another step of the ~ ;on process, a second preci~.iL~led silica ~us~)en~ion is similarly plepaled varying reaction pararneters in a manner, ordinarily, 35 resulting in precipitated silicas having BE values in the range of from about 3 mg to about 8 mg and PE values in the range of 8 mg to about 11 mg, an RDA ranging WO 9l6134595 5 PC'r~lJSS'6J~6012 from about 81 to about 200, and an oil abso~l,liol- of from about 70mll'100gm toabout below 95ml/100gm.
Th~i~ler, the t~,vo ~ eci silica suspensions can be co...kil~f~
the pH to about 5Ø The co~ il,aL;on suspension is filtered and then wa~shed with S water to remove salts from the filter cake. The filter cake is dried, prer~l~bly by coll~ n~l spray d~ging to produce a l~reç;~ d silica co~ about 3% to 10% lllo;alule. The pr~ ed silica co...h;~ ;on is milled to a particle size in wllich 70% of the particle size ~ ibulion is below 20 Illicrons. Alle-llaLiv~l~, the silicas can be co",l),l~ed prior to ulcollJol~lion into de"li~;ce coll,l,o~;l;ons.
In ~d~liti~ to the above described essf~nti~l colllpon~ Ls, the dentifrice compositions of the present invention can contain a variety of optional df ntifrjce ingredients some of which are described below. Optional ingredients in~lude, forexarnple, but are not lirnited to, adhesives, sudsing agents, fiavoring agents, s~ t~ agents, ~d~lition~l ~ntirl~ e agents, abrasives, and coloring agents.
These and other optional componenl~ are further described in U S. Patent s~004~597.
April 2, 1991 to Majeti; U.S. Patent 4.885.155. Dec~mh~ ~i, 1989 to Parran, Jr. et al.; U.S. Patent 3.959.458. May Z5, 1976 to Agricola et al. and U.S. Patent 3.937.807. Febn~ary 10, 1976 to ~tof~l~, all being incorporated herein by re~rence.
The Pellicle Cleaning Ratio (PCR) of the inventive silica CO~ si laLion, which is a mea~u,e,llc;,l~ ofthe cle~ning characteristics of a dentifrice, ranges from 90 to 135 and preferably from 100 to 130 for the p.e~i~,iLaLed silica colllbil.aLion of the invention. The P~riio~ctive Dentin Abrasion (RDA) of the inventive silicas, which is a lll~ult;lllelll of the abrasiveness of the pl~ ed silica col..bil.a~iorl when inco.~cs.aLed into a dentifrice, ranges from 60 to 10, p.t;re-ably from 80 to 90.
The PCR (Pellicle Cleaning Ratio) cle~ning values are detel.. uned by a slightly modified version of the PCR test described in "In Vitro Removal of Stain With Dentifrice", G. K. Stookey, T.A. Burkhard and B. R. Schemerhorn, J. Dental Research, 61, 1236-9, 1982. Cleaning is ~csessed in vitro by use of the modifiedpellicle cle~ning ratio test. This test is id~ntic~l to that described by Stookey et al.
30 with the following modific~tions: (1) a clear artificial pellicle film is applied to bovine ¢hiips prior to application of the stained filn~ (2) solution heating is used rather than ~radiative heating during film application, (3) the number of brush strokes is reduced ltO 200 strokes and (4) the slurry conce--Ll~Lion is 1 part dentifrice to 3 parts w.lter.
The pl ~ciplL~Led silica compositions of the present invention, when 3~i iincorporated into a dentifrice composition further provide an improved PCEVRDA
Iratio. The PCRJRDA ratio is used to determine the relative ratio of cle.ming and abrasion characteristics of a dentifrice formulation. Comrnercially available dentifrice CA 02220095 l997-lO-3l fc~ lulaLions ~,n~.~lty have a PCR/RDA ratio in the range of 0.5 to below 1Ø The ;P;I ~led silicas used in the co~ o~;~ iO~c of the present invention provide PCR to RDA ratios to dentifrice rul~ ;onc of greater than 1, usually in the range of 1.25 to 1.75, but more ~Icrc~bly in the range 1.6 to 1.75.
The abrasive, in the form of a pre~ ed silica compositionc of the present i"~_.,lion, when illcol~ul~lc~ into the compositions dc3~,il,ed herein, is present at a L
level of from about 6% to about 70%, prtre,~bly from about 15% to about 35%
when the dt-,Lir,icc is a tooll.p~le Higher levels, as high as 95%, may be used if the c~",l,osilion is a too~ ùwder.
OPTIONAL COMPONENTS
Pharm~ce~-tically Acceptable Carner The carrier for the co,~lpon~llLs of the present compositions is optional and can be any dentifrice vehicle suitable for use in the oral cavity. Such carriers include the usual co.~lponclll~ of too~ les, tooth powders, prophylaxis pastes, lo,~-ges, gums and the like and are more fully described helcina[lel. Toothr~ctes are the plcrt:llcd ~lClllS.
Surf~ct~ntc-One of the plcr~llcd optional agents of the present invention is a surfactant, ~,fc~ably one sPlected from the group consi~li,lg of sa,~;o~ P surf~t~ntc isethionate surf~ct~nts and taurate surf~ct~nts Pre~ d for use herein are alkatimetat or ammonium satts ofthese surf~ct~ntc Most p.crc-led herein are the sodiumand potassium salts of the following: lauroyl sarcosin~t~, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinale and oteoyl s~cosinate.
This surfactant can be present in the compositions of the present invention from about 0.1% to about 2.5%, preferably from about 0.3~/O to about 2.5% and most preferably from about 0.5% to about 2.0% by weight of the total composition.
Other suitable co--.patible surf~ntc can optionally be used along with the sarcosin~te surfactant in the compositions of the present invention. Suitable optional surf~ct~nts are desclibcd more fully in U S Patent 3.959.458. May 25, 1976 to Agricola et al.; U.S. Patent 3.937.807. February 10, 1976 to ~ e; and US
Patent 4.0~1.234. Sep~elllbcl 27, 1988 to Gieske et al. These patents are incorpo-rated herein by lefelcllcc.
P~if~lled anionic surf~ct~ntc useful herein include the water-soluble salts of al-kyl suLfates having from 10 to 18 carbon atoms in the alkyl radical and the water-soluble salts of sulfonated monoglycerides of fatty acids having from 10 to 18 carbon atoms. Sodium lauryl sulfate and sodium coconut monoglyceride sulfonates are WO 96134595 7 PC'r~US96~06012 , ' of anionic ;.~. r~ of this type. ~lui~s of anionic sll~f~n~c can also be lltili7ç,1 F~fc~l~,d ç~tion;c~ surf~çt~nts useful in the present invention can be broadly defined as derivatives of ~lirh~tic qualc--l~y ~ .. compounds having ane long 5 alkyl chain con~ g from about 8 to 18 carbon atoms such as lauryl LILUICLI1Y1~.... chloride; cetyl pyridinium chloride; cetyl Ll.,n~ ol~ium bromide; di-is-o~u~ h~ llyl-dimcllly~ .~y~ chloride; coconut all~yl~lL~ lyla~
1 nitrite; cetyl pyridinium fluoride; etc. Pr~Çc,lcd compounds are the quater-nary ~-....-O~ -.. fluorides descl~ed in U.S Patent 3.535.421. October 20, 1970, to Briner et al., herein incorporated by ~cfcl~_nce, where said ~luaLclllaly a~.. ol~
fll~ori(l~s have dele~enL propcllies. Certain cationic surf~çt~ntc can also act as gerrnicides in the compositiorlc ~~ic. losed herein. C~fionic surf~ nts such as chlor-hPY~inP" although suitable for use in the current invention, are not prcrc,~ ~d due to their capacitv to stain the oral cavity's hard tissues. Persons skilled in t'he art are 15 aware of this possibility and should incol,uo-ale c,ationic surf~çt~nt~ only with this l;...;l~l;ol- in mind.
~ cÇclled nonionic surf~ct~ntc that can be used in the compositions of the present invention can be broadly defined as compounds produced by the co~ Pnc~
tion of alkylene oxide groups (hydrophilic in nature) with an organic Lydlol~hDb'~
20 co,llpou..d which may be aliphatic or alkylal~ alic in nature. Examples of suitable nonionic surf~ct~nts include the Pluronics, polyethylene oxide con~enc~tçs of alkyl phenols, products derived from the condçnc~tion of ethylene oxide with the.reaction product of propylene oxide and ethylene ~ mine, ethylene oxide con~ienc~tes of ~liph~tic alcohols, long chain tertiary amine oxides, long chain tertiary ]phosphinP
25 oxides, long chain dialkyl sl~ifoxid~os and Il~ALulcs of such materials.
Prcrcllcd zwitterionic synthetic surfactants useful in the present invention can'be broadly described as derivatives of aliphatic quaternary ammonium, phos-phomillm, and sulfonium compounds, in which the ~lirh~tic radicals can b~e straight ch~in or branched, and wherein one of the aliphatic su!QstitU~ntc col~ s ~om about 30 8 to 18 carbon atoms and one collL~ns an aniornic water-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosph~te or phosphonate.
Plcrc~lcd betaine surf~ nts are disclosed in U.S. Patent 5,180,577 to ]?olefka ~et al., issued January l9, 1993. Typical alkyl dimethyl beL~ es include decyl betaine lor 2-(N-decyl-N,N-dimethylammonio) acetate, coco betaine or 2-(N-coc-N, N-35 dimethyl ammonio) acetate, myristyl betaine, paln~ityl betaine, lauryl betaine, cetyl'betaine, cetyl betaine, stearyl betaine, etc The amidobetaines are exemrlified by eoco~midoethyl betaine, coco~midopropyl betaine, lauramidopropyl betaine and the CA 0222009~ lgg7-lo-3l wo 96/34595 8 PCT/USg6/06012 like. The b~L~.es of choice are pr.,fe.ably the cocoamidopropyl betaine and, more ,r~,.d~ly, the laul~l~ido propyl betaine.
Ch~ agents:
Another p,~re"td optional agent is a ~h~l~tin~ agent s~ (ed from the group 5 eon~ of tartaric acid and ph~rm~cel~tic~lly-~cGc;~ ble salts thereof, citric acid and alkali metal citrates and l~Llllcs thereof. Ch~l%~ agents are able to complex calcium found in the cell walls of the bacteria. Ch~ agents can also disruptplaque by removing c~lCium from the e~lei~lm bridges which help hold this biomass intact. However, it is possible to use a ch~ agent which has an afflnity for 10 calcium that is too high. This results in tooth cle~ ,-alization and is COllllaly to the objects and ;.~ ;ol-~ ofthe present invention.
So-li--m and potassium citrate are the p.~;r~"~d alkali metal citrates, with sodium citrate being the most prc;rt..cd. Also p-cr~ d is a citric acid/alkali metal citrate cG-.LillaLion. Pl~relled herein are alkali metal salts of tartaric acid. Most 15~l~r~ d for use herein are tiicodium tartrate, dipotassium tartrate, sodium potassium tartrate, sodium hydlo~,el1 tartrate and potassium hydrogen tartrate. The amounts of agent suitable for use in the present invention are about 0.1% to about 2.5%, prerelably from about 0.5% to about 2.5% and more p,er~lably from about 1.0% to about 2.5%. The tartaric acid salt ~.hPI~tin~ agent can be used alone or in 20colllbi~lalion with other optional ch~ ting agents.
Other optional ~h.ol~ting agents can be used. Preferably these rhPI~ting agents have a calcium binding consL~rlL of about 101 to 105 provide improved ~le~nin~ with reduced plaque and c~lc~ c formation.
Another group of agents suitable for use as çh~l~tin~ agents in the present 25invention are the soluble pyrophosphates. The pyrophosph~te salts used in the present compositions can be any of the alkali metal pyrophosphate salts. Specific salts include tetra alkali metal pyrophosphate, dialkali metal diacid pyrophosphate, trialkali metal monoacid pyrophosphate and mixtures thereof, wherein the allcalimetals are preferably sodium or pOpcsillm The salts are useful in both their hy-30drated and unl-~d.~Led forms. An effective amount of pyrophosphate salt useful in the present composition is generally enough to provide at least 1.0% pyrophosphate ion, preferably from about 1.5% to about 6%, more preferably from about 3.5% to ahout 6% of such ions. It is to be appl c:~iaLed that the level of pyrophosphate ions is that capable of being provided to the composition (i.e., the theoretical amount at an 35applup~iate pH) and that pyrophosphate forms other than P207~ (e.g., (HP207-3)) may be present when a final product pH is established.
W0~36134595 9 PCT~US.~6~06012 The p~ hG;,~ salts are des~;,;l,ed in more detail in Kirk & Ot~ner, Encv-pe~lia of Ch-rnir~l Technolog;sr~ Second Fr~itior, Volume 15, LILc~ie;l~ec Publish ers (1968), iluoll.GIaLcd herein by Icrcl~ence.
Still another po~;l,lc group of ~ agents suitable for use in 1he present 5 invention are the anionic polymeric polyc~bu~ylal.es. Such materials are ~well known in the art, being employed in the form of their iiee acids or partially or pr~rt;~ably fu21y neutralized water soluble alkali metal (e.g. po~ ;ul,l and p,crc~bly sodium) or A~ salts. Plcf~ d are 1:4 to 4:1 copolymers of maleic anhydride or acid with another poly",c.;~le ethylenically u"saLu,aLed ,..n nn ~ , plcrelaT~ly methyl vinyl ether (~ ho~clllylene) having a molecul~ weight (M.W.) of about 30,000 to about 1,000,000. These copolymers are availabl~ for ~ ple as Gantre~z ,AN 139 (M.W. 500,000), AN 119 (M.W. 250,000) and pler~lably S-97 P1...,..
Grade (M.W. 70,000), of GAF ~h~mir~lc Coll ol~Lion.
Other operative polymeric polycarboxylates include those such as the 1:1 copolymers of malelc anhydride with ethyl acrylate, hydl o~yt;lllyl meth~r,r~late, N-vi-nyl-2-pyrolli~onP or ethylene, the latter being a~ailable for example as MOI~CAIIIQ
EMANo. 1103, M.W. 10,000 and EMA Grade 61, and 1:1 copolymers oi.'acrylic acid with methyl or hydlu~yt;Lllyl mçth~rrylate~ methyl or ethyl acrylate, isobutyl v2nyl ether or N-vinyl-2-pyrrolidone.
Additional operative polymeric polyca,lJ~rlates are disclosed in U.S Patent 4.138~477. February 6, 1979 to Gaffar and U.S. Patent 4.183.914. January 15, 1980 to Gaffar et al. both patents are incorporated herein by ~~;r~lellce, and include co-polymers of maleic anhydride with styrene, isobutylene or ethyl vinyl ether, poly-acrylic, polyitaconic and polymaleic acids, and sulf~acrylic oligomers of M W. as low as 1,000 available as Uniroyal ND-2.
Flavoring agents can also be added to dentifi~ce compositions. Suitable fiavor-ing agents include oil of W~hlLt;l~ en~ oil of peppe2mint, oil of spearmint, oil of sds ,aG~s, and oil of clove. SweetPning agents which can be used include ~p~ L~ne, ~cPs~llf~mP saccharin, dextrose, levulose and sodium cycl~m~te Flavoring and ~weet~ -p agents are generally used in dentifrices at levels of from about 0.005% to about 2% by weight.
It is comrnon to have a water-soluble fluoricie compound present in del1tifricesand other oral compositions in an arnount sr-ffiri~nt to give a fluori,de ion conr~ ion in the composition at 25~Ç, and/or when it is used of from about 0.0025% to about 5.0% by weight, preferably frorn about 0.005% to about 2.0% by wleight, to provide additional anticaries effectiveness. A wide variety of fluor~de ion-yielding materials can be employed as sources of soluble fluoride in the present .p~ n~ F~.... l.les of suitable fl--oritle ion-yielding m~tPriAlc are found in U.S.
Patent No. 3.535~421. October 20, 1970 to Briner et al. and U.S. Patent No.
3.678.154. July 18, 1972 to W~dder et al., both being i~lcGll,olaled herein by refer-ence. Represe.llali.,re fiuoride ion sources include: stannous f1uoride, sodium fluo-5 ride, pot~cci~m fluoride, sodium mnnofllloro~ os~h,.~e and many others. StAnnollc fllloride and sodium fluoride are particularly prere..~d, as well as n~lLIles thereo~
Water is also present in the toc,ll~pa~ of this i~ ioll. Water employed in the pl~p~Lion of comm~rcially suitable tooll.pA~les should pl~;re;la~ly be ~Pioni7Pcl and free of organic impurities. Water generally CGl.l~l;ses from about 10% to 50%;
1 0 preferably from about 20% to 40%, by weight of the tooLl,pasLe col"pos;l ;O~c herein.
These ~,-uu"ls ûf water include the free water which is added plus that which isintroduced with other materials such as with sorbitol.
In p,ep~i,lg toothp~ctec it is nP~cpsc~ry to add some thirlfPning material to provide a desirable concictPnry P,ere:"ed thi~lrPning agents are c~buAy~inyl 15 polymers, carra~e~n~n~ hydroxethyl cPlllllose and water soluble salts of celllllose ethers such as sodium ca,l UAY"~CLI~YI cPll~lose and sodium c~l~uAy~t;LLyl hy-d~uA~;Lhyl CPlllllOSP~ Natural gums such as gum karaya, x~ n gun, gum arabic, and gum tr~p~r~nth can also be used. Thirl~Pning agents in an amount from 0.5% to 5.0% by weight of the total composition can be used.
It is also desirable to include some h-- .. P~ material in a toothpaste to keep it from hardening. Suitable hllmPct~ntc include glycelin, sorbitol, and other edible polyhydric alcohols at a level offrom about 15% to about 70%.
Also desirable for inrlllcion in the compositions of the present invention are other stannous salts such as stannous pyrophosphate and stannous ~ r,orl~te and A.~ . ub;als such as quaternary amrnonium salts, such as cetyl pyridinium chloride and tetradecylethyl py~idinium chloride, bis-biquanide salts, copper biS~Iy-,h~àl~, nonionic anti microbial salts and flavor oils. Such agents are disclosed in U.S. Patent No. 2,946,725, July 26, 1960, to Norris et al. and U.S. Patent No. 4,051,234, S~lc~ber 27, 1977 to Gieske et al., incol},olaled herein by r~;rc;l~nce. Other optional colllpone"ls include buffering agents, bicarbonates, peroxides, nitrate salts such as sodium and potassium nitrate. These agents, if present, are inrhlded at levels offrom about 0.01% to about 30%.
Other useful carriers include biphasic dentifrice forrnulations such as those ~Iic~,losed in U.S. Patents 5,213,790, issued May 23, 1993, 5,145,666, issued Se~ ",ber 8, 1992, and 5,281,410 issued January 25, 1994 all to Lukacovic et al.and in U. S. Patents 4,849,213 and 4,528,180 to Schaeffer the disclosures of which are incorporated by reference herein.
WO '36/34595 1 1 PCTJ',USg6/061~12 S~;t:lt'~e 1O7P~ and c,l.~ gum COIII~are ,l~ se(1 in U.S. Patent I~o. 4,083,955, April 11, 1978 to G. ~ et al., illc~ laled herein by refer-e.
EXAMPLES
5The following ~ lf-s further des."il,e and d~ O~ ale pl~Ec~l~d em-bo~ ~,1 c within the scope of the present invention. The eY~mpl~ s are gi~ren solely fDr illu~Llal;oll, and are not to be coraLllled as 1;... l;.l;9l~ of this invention as many v~ c thereof are possible wi~ u~ dcph~ Lillg from its spirit and scope.
Example I
10A dentifrice composition of the present invention CUIII~IS the following com-ponents as des_lil,ed below.
Coml)~ ~ t W~t %
Sorbitol 70% soln 24.200 RO Water 24.757 Glycerin 7.000 C~bO~IIICLI1~YI Cellulosel 0.500 PEG 6 4.000 Sodium Fluoride 0.243 So~ m ~S~ e 0. 130 Monosodium Phosph~te 0.415 Trisodium Phosph~te 0.395 Sodium Tartrate 1.000 TiO2 O.SOO
Silica2 35 ooo Sodium Lauroyl Sarco~ le (95% active)1.060 Flavor 0.800 1 Supplied by Aqualon CGIIII)~IY.
2The l~rc.;i~iLated silica ill~edienL possesses the following characteristics: APS
M[ean Value = 8.5 microns; oil absorption = 103cc/lOOg; BE = 1.6; PE = 7~ PCR=
lt)6; RDA= 67.
The jacket temperature of a mixing tank is set to about 150~F (65~C) to about 160~F (71~C). The h~.. s,;l~.. lc and water are added to the rnixing tanlc and ap,itation is started. When the temperature reaches applu~llately 120~F (50~C) fluolide, sweetening agents, buffering agents, chelant, coloring agents and l~it~nillm 35 dioxide are added. Thic~ninP~ agents are added to the abrasive and the resulting rnixture is added to the rnixing tar~c with }iigh agitation. The surfactant is add~ed to th,e comb;llalion and rnixing is continlled The tank is cooled to 120~F (50''C) and W096/34595 12 PCTrUS96/06012 the ilavoring agents are added. Mixing is contin-~e~l for appru~ ely S ...;~
The ,~ 8 co...po~;l.on will have a pH of about 7.
F.Y~-Tlrle II
A denti~ice co,..po~ilion of the present invention co~ e the following com-5 pone..lj as des~i-ibed below.
Com.~ nt Wgt %
Sorbitol 70% so~ 29.810 RO Water 24.757 Glycerin 7.000 CarbO~Y.I~tLI.~I Ce11~10Sel 0.750 PEG 6 4.000 Sodium Fluoride - 0.243 Sodium Saccharine 0.130 Monosodium PhnSPh~te 0.415 Tri~o~ m Phosphate 0.395 TiO2 0-500 Silica2 30.000 Sodium Lauryl Sulfate 1.200 Flavor 0.800 1 Supplied by Aqualon Co--,pal-y.
2The p-~ d silica ingredient possesses the following characteristics: APS
Mean Value = 8.5 microns; oil absorption = 103CC/100g; BE = 1.6; PE = 7; PCR =
106; RDA= 67.
Example m A gum composition of the present invention co~ c the following com-pon~nls as described below.
Component Weight %
Gum Base 30.000 30 parts E~Le-~U---45 parts Coumorone Resin 15 parts D~y Latex Silical 10.00 Sugar 40.000 Corn Syrup 18.175 Sodium Lauroyl Sarcosinate 0.075 Sodium Tartrate 0.250 W~ 9l6/~4595 13 PC~n7Sg6~0~0~2 Flavor 1.500 ]The ~ç~~ ed silica L,~.,.l;~ G~e,~ ~ the following char~ cl;cc APS
l~ean Value = 8.5; oil absol~lion = lOlcc/lOOg; BE = 1.9; PE = 7.2.
.
5 WEAT IS CLAL!.IED IS:
Water is also present in the toc,ll~pa~ of this i~ ioll. Water employed in the pl~p~Lion of comm~rcially suitable tooll.pA~les should pl~;re;la~ly be ~Pioni7Pcl and free of organic impurities. Water generally CGl.l~l;ses from about 10% to 50%;
1 0 preferably from about 20% to 40%, by weight of the tooLl,pasLe col"pos;l ;O~c herein.
These ~,-uu"ls ûf water include the free water which is added plus that which isintroduced with other materials such as with sorbitol.
In p,ep~i,lg toothp~ctec it is nP~cpsc~ry to add some thirlfPning material to provide a desirable concictPnry P,ere:"ed thi~lrPning agents are c~buAy~inyl 15 polymers, carra~e~n~n~ hydroxethyl cPlllllose and water soluble salts of celllllose ethers such as sodium ca,l UAY"~CLI~YI cPll~lose and sodium c~l~uAy~t;LLyl hy-d~uA~;Lhyl CPlllllOSP~ Natural gums such as gum karaya, x~ n gun, gum arabic, and gum tr~p~r~nth can also be used. Thirl~Pning agents in an amount from 0.5% to 5.0% by weight of the total composition can be used.
It is also desirable to include some h-- .. P~ material in a toothpaste to keep it from hardening. Suitable hllmPct~ntc include glycelin, sorbitol, and other edible polyhydric alcohols at a level offrom about 15% to about 70%.
Also desirable for inrlllcion in the compositions of the present invention are other stannous salts such as stannous pyrophosphate and stannous ~ r,orl~te and A.~ . ub;als such as quaternary amrnonium salts, such as cetyl pyridinium chloride and tetradecylethyl py~idinium chloride, bis-biquanide salts, copper biS~Iy-,h~àl~, nonionic anti microbial salts and flavor oils. Such agents are disclosed in U.S. Patent No. 2,946,725, July 26, 1960, to Norris et al. and U.S. Patent No. 4,051,234, S~lc~ber 27, 1977 to Gieske et al., incol},olaled herein by r~;rc;l~nce. Other optional colllpone"ls include buffering agents, bicarbonates, peroxides, nitrate salts such as sodium and potassium nitrate. These agents, if present, are inrhlded at levels offrom about 0.01% to about 30%.
Other useful carriers include biphasic dentifrice forrnulations such as those ~Iic~,losed in U.S. Patents 5,213,790, issued May 23, 1993, 5,145,666, issued Se~ ",ber 8, 1992, and 5,281,410 issued January 25, 1994 all to Lukacovic et al.and in U. S. Patents 4,849,213 and 4,528,180 to Schaeffer the disclosures of which are incorporated by reference herein.
WO '36/34595 1 1 PCTJ',USg6/061~12 S~;t:lt'~e 1O7P~ and c,l.~ gum COIII~are ,l~ se(1 in U.S. Patent I~o. 4,083,955, April 11, 1978 to G. ~ et al., illc~ laled herein by refer-e.
EXAMPLES
5The following ~ lf-s further des."il,e and d~ O~ ale pl~Ec~l~d em-bo~ ~,1 c within the scope of the present invention. The eY~mpl~ s are gi~ren solely fDr illu~Llal;oll, and are not to be coraLllled as 1;... l;.l;9l~ of this invention as many v~ c thereof are possible wi~ u~ dcph~ Lillg from its spirit and scope.
Example I
10A dentifrice composition of the present invention CUIII~IS the following com-ponents as des_lil,ed below.
Coml)~ ~ t W~t %
Sorbitol 70% soln 24.200 RO Water 24.757 Glycerin 7.000 C~bO~IIICLI1~YI Cellulosel 0.500 PEG 6 4.000 Sodium Fluoride 0.243 So~ m ~S~ e 0. 130 Monosodium Phosph~te 0.415 Trisodium Phosph~te 0.395 Sodium Tartrate 1.000 TiO2 O.SOO
Silica2 35 ooo Sodium Lauroyl Sarco~ le (95% active)1.060 Flavor 0.800 1 Supplied by Aqualon CGIIII)~IY.
2The l~rc.;i~iLated silica ill~edienL possesses the following characteristics: APS
M[ean Value = 8.5 microns; oil absorption = 103cc/lOOg; BE = 1.6; PE = 7~ PCR=
lt)6; RDA= 67.
The jacket temperature of a mixing tank is set to about 150~F (65~C) to about 160~F (71~C). The h~.. s,;l~.. lc and water are added to the rnixing tanlc and ap,itation is started. When the temperature reaches applu~llately 120~F (50~C) fluolide, sweetening agents, buffering agents, chelant, coloring agents and l~it~nillm 35 dioxide are added. Thic~ninP~ agents are added to the abrasive and the resulting rnixture is added to the rnixing tar~c with }iigh agitation. The surfactant is add~ed to th,e comb;llalion and rnixing is continlled The tank is cooled to 120~F (50''C) and W096/34595 12 PCTrUS96/06012 the ilavoring agents are added. Mixing is contin-~e~l for appru~ ely S ...;~
The ,~ 8 co...po~;l.on will have a pH of about 7.
F.Y~-Tlrle II
A denti~ice co,..po~ilion of the present invention co~ e the following com-5 pone..lj as des~i-ibed below.
Com.~ nt Wgt %
Sorbitol 70% so~ 29.810 RO Water 24.757 Glycerin 7.000 CarbO~Y.I~tLI.~I Ce11~10Sel 0.750 PEG 6 4.000 Sodium Fluoride - 0.243 Sodium Saccharine 0.130 Monosodium PhnSPh~te 0.415 Tri~o~ m Phosphate 0.395 TiO2 0-500 Silica2 30.000 Sodium Lauryl Sulfate 1.200 Flavor 0.800 1 Supplied by Aqualon Co--,pal-y.
2The p-~ d silica ingredient possesses the following characteristics: APS
Mean Value = 8.5 microns; oil absorption = 103CC/100g; BE = 1.6; PE = 7; PCR =
106; RDA= 67.
Example m A gum composition of the present invention co~ c the following com-pon~nls as described below.
Component Weight %
Gum Base 30.000 30 parts E~Le-~U---45 parts Coumorone Resin 15 parts D~y Latex Silical 10.00 Sugar 40.000 Corn Syrup 18.175 Sodium Lauroyl Sarcosinate 0.075 Sodium Tartrate 0.250 W~ 9l6/~4595 13 PC~n7Sg6~0~0~2 Flavor 1.500 ]The ~ç~~ ed silica L,~.,.l;~ G~e,~ ~ the following char~ cl;cc APS
l~ean Value = 8.5; oil absol~lion = lOlcc/lOOg; BE = 1.9; PE = 7.2.
.
5 WEAT IS CLAL!.IED IS:
Claims (10)
1. A precipitated silica abrasive composition, comprising:
a.) a precipitated silica, comprising particles wherein said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. < 9);
ii.) an Einlehner hardness of from about 0.8 to about 2.5 for abrasive to brass screen and from about 5 to about below 8 for abrasive to polyester screen;
iii.) an oil absorption of from 95 ml/100 gm to about 135 ml/100 gm; and iv.) a radioactive dentin abrasion of from about 25 to about below 80;
and b.) a precipitated silica, comprising particles wherein said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. < 9);
ii.) an Einlehner hardness of from about 3 to about 8 for abrasive to brass screen and from 8 to about 11 for abrasive to polyester screen;
iii.) an oil absorption of from about 70 ml/100. gm to about below 95 ml/100 gm; and iv) a radioactive dentin abrasion of from 80 to about wherein at least about 70% of all of said particles have a diameter of below about 25 microns and wherein the pellicle cleaning ratio is from about 90 to about 135 and the radioactive dentin abrasion is from about 60 to about 100 with a pellicle cleaning ratio/radioactive dentin abrasion ratio of from about 1.25 to about 1.75 and wherein the ratio of the silica in a.) to the silica in b.) is from about 90:10 to about 40:60, respectively.
a.) a precipitated silica, comprising particles wherein said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. < 9);
ii.) an Einlehner hardness of from about 0.8 to about 2.5 for abrasive to brass screen and from about 5 to about below 8 for abrasive to polyester screen;
iii.) an oil absorption of from 95 ml/100 gm to about 135 ml/100 gm; and iv.) a radioactive dentin abrasion of from about 25 to about below 80;
and b.) a precipitated silica, comprising particles wherein said particles have:
i.) a mean particle size of from about 5 to about 11 microns (s.d. < 9);
ii.) an Einlehner hardness of from about 3 to about 8 for abrasive to brass screen and from 8 to about 11 for abrasive to polyester screen;
iii.) an oil absorption of from about 70 ml/100. gm to about below 95 ml/100 gm; and iv) a radioactive dentin abrasion of from 80 to about wherein at least about 70% of all of said particles have a diameter of below about 25 microns and wherein the pellicle cleaning ratio is from about 90 to about 135 and the radioactive dentin abrasion is from about 60 to about 100 with a pellicle cleaning ratio/radioactive dentin abrasion ratio of from about 1.25 to about 1.75 and wherein the ratio of the silica in a.) to the silica in b.) is from about 90:10 to about 40:60, respectively.
2. A precipitated silica abrasive composition according to Claim 1, wherein the pellicle cleaning ratio is from about 90 to about 135, the radioactive enamel abrasion is from about 2.5 to about 5 and wherein the pellicle cleaning ratio/radioactive enamel abrasion ratio of said precipitated silica abrasive composition is greater than about 30.
3. A precipitated silica abrasive according to Claim 2, wherein the ratio of said silicas is from about 80: 20 to about 35: 65.
4. A precipitated silica abrasive according to Claim 3, wherein the pellicle cleaning ratio is from about 110 to about 135.
5. A precipitated silica abrasive according to Claim 4, wherein the radioactive dentin abrasion is from about 65 to about 85.
6. A precipitated silica abrasive according to Claim 5, wherein the pellicle cleaning ratio/radioactive dentin abrasion ratio of said abrasive is from about 1.60 to about 1.75.
7. A precipitated silica abrasive according to Claim 6, wherein the radioactive enamel abrasion is from about 2.5 to about 3.5.
8. A precipitated silica abrasive according to Claim 7, wherein the pellicle cleaning ratio/radioactive enamel abrasion ratio of said abrasive is from about 35 to about 44.
9. A precipitated silica abrasive according to Claim 8, wherein the radioactive dentin abrasion of the silica in a.) is from about 35 to 80.
10). A precipitated silica abrasive according to Claim 9, wherein the radioactive dentin abrasion of the silica in b.) is from about 110 to about 200.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43269595A | 1995-05-02 | 1995-05-02 | |
| US08/432,695 | 1995-05-02 | ||
| US08/593,175 US5676932A (en) | 1995-05-02 | 1996-02-01 | Silica abrasive compositions |
| US08/593,175 | 1996-02-01 | ||
| PCT/US1996/006012 WO1996034595A1 (en) | 1995-05-02 | 1996-04-29 | Silica abrasive compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2220095A1 CA2220095A1 (en) | 1996-11-07 |
| CA2220095C true CA2220095C (en) | 2001-08-07 |
Family
ID=27029605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002220095A Expired - Lifetime CA2220095C (en) | 1995-05-02 | 1996-04-29 | Silica abrasive compositions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5676932A (en) |
| EP (1) | EP0831761B2 (en) |
| JP (1) | JPH10511684A (en) |
| AT (1) | ATE200471T1 (en) |
| CA (1) | CA2220095C (en) |
| DE (1) | DE69612496T3 (en) |
| WO (1) | WO1996034595A1 (en) |
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| US5004597A (en) * | 1987-09-14 | 1991-04-02 | The Procter & Gamble Company | Oral compositions comprising stannous flouride and stannous gluconate |
| GB8721644D0 (en) * | 1987-09-15 | 1987-10-21 | Unilever Plc | Silicas |
| US5225177A (en) * | 1990-01-19 | 1993-07-06 | J. M. Huber Corporation | Dentifrice abrasives and compositions |
| WO1992002454A1 (en) * | 1990-08-06 | 1992-02-20 | Joseph Crosfield & Sons Limited | Silicas |
| US5213790A (en) * | 1991-10-23 | 1993-05-25 | The Procter & Gamble Co. | Methods of reducing plaque and gingivitis with reduced staining |
| US5281410A (en) * | 1991-10-23 | 1994-01-25 | The Proctor & Gamble Company | Methods of reducing plaque and gingivitis with reduced staining |
| ATE142170T1 (en) † | 1992-10-28 | 1996-09-15 | Crosfield Joseph & Sons | SILICIC ACIDS |
| US5603920A (en) * | 1994-09-26 | 1997-02-18 | The Proctor & Gamble Company | Dentifrice compositions |
| US6290933B1 (en) † | 2000-05-09 | 2001-09-18 | Colgate-Palmolive Company | High cleaning dentifrice |
-
1996
- 1996-02-01 US US08/593,175 patent/US5676932A/en not_active Expired - Lifetime
- 1996-04-29 WO PCT/US1996/006012 patent/WO1996034595A1/en active IP Right Grant
- 1996-04-29 JP JP8533426A patent/JPH10511684A/en active Pending
- 1996-04-29 AT AT96913273T patent/ATE200471T1/en not_active IP Right Cessation
- 1996-04-29 DE DE69612496T patent/DE69612496T3/en not_active Expired - Lifetime
- 1996-04-29 CA CA002220095A patent/CA2220095C/en not_active Expired - Lifetime
- 1996-04-29 EP EP96913273A patent/EP0831761B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69612496T2 (en) | 2001-11-08 |
| DE69612496D1 (en) | 2001-05-17 |
| EP0831761B1 (en) | 2001-04-11 |
| JPH10511684A (en) | 1998-11-10 |
| US5676932A (en) | 1997-10-14 |
| EP0831761A4 (en) | 1999-02-03 |
| DE69612496T3 (en) | 2005-05-19 |
| ATE200471T1 (en) | 2001-04-15 |
| EP0831761B2 (en) | 2004-09-08 |
| EP0831761A1 (en) | 1998-04-01 |
| CA2220095A1 (en) | 1996-11-07 |
| WO1996034595A1 (en) | 1996-11-07 |
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| EEER | Examination request | ||
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