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WO2008063188A2 - Betaine with calcium and/or strontium antiperspirants - Google Patents

Betaine with calcium and/or strontium antiperspirants Download PDF

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Publication number
WO2008063188A2
WO2008063188A2 PCT/US2006/060512 US2006060512W WO2008063188A2 WO 2008063188 A2 WO2008063188 A2 WO 2008063188A2 US 2006060512 W US2006060512 W US 2006060512W WO 2008063188 A2 WO2008063188 A2 WO 2008063188A2
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WO
WIPO (PCT)
Prior art keywords
band
weight
calcium
solution
antiperspirant
Prior art date
Application number
PCT/US2006/060512
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French (fr)
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WO2008063188A3 (en
Inventor
Zijun Li
Mark Rerek
Original Assignee
Reheis, Inc.
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Publication date
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Priority to PCT/US2006/060512 priority Critical patent/WO2008063188A2/en
Publication of WO2008063188A2 publication Critical patent/WO2008063188A2/en
Publication of WO2008063188A3 publication Critical patent/WO2008063188A3/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • 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
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof

Definitions

  • This invention relates to novel basic aluminium chlorides and basic aluminum chloride/zirconyl hydroxy .chloride antiperspiran compositions that have a particularr molecular stes d ⁇ $tHbu&Qa in the presets of bstaine ( ⁇ iis ⁇ hjlglycme) m eombmatios with g c&t ⁇ m and/or strontium compound, to processes for the prepasration of the antiperspirant compositionand to consumer acceptable antiperspirant vehicles such as aerosols, gels, rool-on, sticks and soft solids cmit ⁇ mng such ariHpetspfra ⁇ cotxipo ⁇ itions.
  • Basic aluminium halides partricularly chlorides and their use as effecitve antiperspirant compounds are well known.
  • Basic aluminium halides are complex structures made up of mixtures of polymeric and monomeric species of varioussizes and molecular structures depending upon their Al halide ratin,m together: with varying amountosf bound or coordinated water.
  • Ii is a challenge to ⁇ c ⁇ ru ⁇ ntealfy prepare enhanced Qf ⁇ kf&y aluminum aad akmmum-xuco ⁇ i ⁇ j ⁇ amiperspii-a ⁇ t selves at hsgjh con ⁇ s ⁇ jratio ⁇ s Of aluminum.
  • Th&*etemicm time M which these pss&s ⁇ ppestr, the?/ ⁇ rsi>lpliom ⁇ and ibcir rs$pectivie peak ai r «;a«, ⁇ it? the ftmcUos of fehe CAlmtr ⁇ ( ⁇ « • co ' hincfB g ) imtl ⁇ r ⁇ >fejJe pJ ⁇ se m& ⁇ .
  • lhe peak 4 corresponding to ke «0.7, io ⁇ Band. ⁇ lf, to that of peak 3 correspondjng t(i 1 ⁇ 0.5, i.c, Bm ⁇ H, L ⁇ at tei 2;1 asd ⁇ t le ⁇ et 30%, artd pitsfe ⁇ bly af.leasf $0%, of the m ⁇ ⁇ Imdinmx ⁇ s pxv& ⁇ $& within rhe j ⁇ alcs coir ⁇ tidmg m peak ⁇ 4 aj ⁇ d 3 (Sands HI un ⁇ H) (Column 2, Uass 60 ⁇ - ⁇ l), TJie resuhi ⁇ g practa c ⁇ csi ⁇ s Icw ⁇ r j? ⁇ oiecu1 ⁇ f wdght polymers t ⁇ in ⁇ «ase ⁇ ffic ⁇ cy, hwt sutfifess by fcaviag a winter ⁇
  • P ⁇ ak 4 should b ⁇ ve # l&i ⁇ t 53% of ⁇ lwrsi fturn species t ⁇ meet the requir ⁇ rttenis ⁇ a) of peak 4 to peak 3 $xz& ra ⁇ of at. least 2; I and (b) $u ⁇ & ⁇ ?f peaks 48fid 3 areas £ ⁇
  • That process comprises reacting pn aluminum conipoimd of tho fo ⁇ k; AI 8 XW ⁇ ltardtt X 5* Cl, Br.
  • ⁇ ,S, Patent No.4, ⁇ 44, ⁇ 33 of i ⁇ W ⁇ xi discloses a process for the manufacture of basic aiuminuni chbricte solutions vntth 1,5% to 13% by weight, having an aluminum chi ⁇ ride wdsx ratio in the range ⁇ f L7 to 2,2:1 ⁇ nd which- has Band IH fraction of a ⁇ lsssr 20% and ⁇ trjiug .he ifiital BAC solution.to ⁇ rvehydrated powder terving 8ftr ⁇ J ⁇ IJ fraciiofi ofsf least 20 ⁇ ?.
  • Th ⁇ ⁇ zmt lacks my ⁇ i sd ⁇ sttre or teachmg of u proaiss for Obtaining t ⁇ so de$5t$d high ⁇ itm ⁇ III e ⁇ meiai m concentrated BAC soluttcafcs as dw& th« $re$ttt& iirvemi ⁇ m.
  • IJt shouM also b « noted cb ⁇ jt these materials ait regatxied ss not FDA Aotipej ⁇ pirssRt Mono ⁇ ph £ ⁇ pro ⁇ ' ⁇ d actiyss s»4 tlieMora, ⁇ vo «ldbe unsccop ⁇ le for uso »$ antiper ⁇ piratii cotnposHio ⁇ * in ih ⁇ United State*.
  • the isevarsibility ⁇ f tk& heat &c ⁇ iv ⁇ ttiori process invents ⁇ he «e [aw an activated pi'O ⁇ uci ⁇ from being uss ⁇ d M geis or em ⁇ bion roll-r ⁇ s as tlie i-eUvcs muse remain in ⁇ tq ⁇ eotis solution ibr these types of prodMctx.
  • T ⁇ ir ⁇ ett?ylg?yc ⁇ ne (bet ⁇ ine) is " not an amino aoitl Tri «3ttthy%1.
  • yd «e has a quartcstia ⁇ mlr ⁇ g ⁇ i group ⁇ ar c ⁇ m) ⁇ f.&c ⁇ i ⁇ s a hydix>gfct5.
  • the ncsxnal ifcmi of ⁇ JIC mmjxnmd is as as iateraaJ.
  • the mveiftioft escarspassas a method for the addition o ⁇ bctaioe to previous ⁇ tuc ⁇ v&fed ulumimatn d ⁇ cttohy ⁇ to] s ⁇ )hiti ⁇ sis.follQwsd by- drying us skscribsd n ⁇ gteat detail h&t ⁇ i ⁇ below.
  • BAC soMtions,2i concsetraiKiss of from abct ⁇ * 8% by wssght to abw-t 20% by weight may fee mixed with betaine and a. caleiiflu a ⁇ dA>r **iwnt»um saJt.
  • the aium]mum ⁇ in.r ⁇ i ⁇ m-lJ ⁇ tai ⁇ ls;m ⁇ »/sf ⁇ »aaum salt solutions of eahsiiced efficacy can 1>e pffep ⁇ -evi by blending a zifcosi ⁇ ra salt s ⁇ tjon with m actrveted »iumii «im- betasn ⁇ -ca ⁇ cium ⁇ trontiian Salt solution i ⁇ iade abov « ro s ⁇ &t ⁇ m ⁇ i/Zr mtio oCsbcsut 2 to &bo!& 1.0 and a MKi ratio of aixwt 0.9 to ⁇ uoat 10.
  • Fig. 2 is ite O-SBC- B ⁇ iC of «n alumi ⁇ i ⁇ im-i?Itco ⁇ iitim- ⁇ 3CLB gai[ with beiiairse
  • Fig- 3 is ih « ⁇ Al NMR of ⁇ i ⁇ iumi n ⁇ int-zl ⁇ cQtuum-cMDta ssii powder w ⁇ h betaine imd caid ⁇ m sa)t prepuft ⁇ l ⁇ ccoix ⁇ ng to fe i ⁇ ve ⁇ i ⁇ n.
  • [0D34J Rg, 4 is the 27 Al A ⁇ ME of an ⁇ iminum ⁇ ?hc ⁇ >m ⁇ m- ⁇ cu ⁇ salt s ⁇ hitifm witl ⁇ bef ⁇ jne aRdcaldum Sftl ⁇ pr ⁇ »r ⁇ d according U>tht mv&Xi&on.
  • FIg.5 is the ICP-SEC-HPLC of an alimiinuns-xjticoiiium-octa ssJt solution with betaine and stro-adum salt ptt ⁇ aitsd decoding to tkt mv&ntHpn.
  • [0056J Th preso ⁇ r iaveatfo ⁇ h directed to the [S ⁇ epar ⁇ io ⁇ of approved, eat ⁇ ee4 efficicy aluminum «md. alttitcnum-ziicorriam an&pe ⁇ pita ⁇ t sol* comp ⁇ $iti ⁇ J3$ comprising betaine atsd a calcium or strontium gait or s* eofobi ⁇ atf ori erf calcium " ml str ⁇ aiiam sslts ⁇ herein lhc antipcrapiiatat has an .HPLC Bmd JE ⁇ o II area ratio ⁇ f at lease 0.5. "The basic ai ⁇ mi ⁇ uro salts of these o ⁇ r ⁇ po&itioss h ⁇ vo fee fonjit ⁇ ia:
  • X is Cl " . Bf, V or Np 3 " . a is fram-about 1 to about 2, with b ⁇ ic & ⁇ Dj «i ⁇ i ⁇ tn (shlodd ⁇ sohitiofc ihemoM ptdemdi.
  • U is ptisfmibie to have aBAC jsolmion with a ⁇ amjniuu io chlor ⁇ «k r« ⁇ io of about 12, Xn about 2.0 ajid i ⁇ ost pi ⁇ rdbiy ltom ⁇ boat 1.4 to about i ,8 depending on the type of p ⁇ lcium snd/or s ⁇ "o ⁇ tjwm compoiiRtl «s «d iti &e aciivaticMn ⁇ i JR.
  • wai «r soluble caJcium and/ orr ⁇ miu ⁇ saJ ⁇ > for example CaCV2HiO are use ⁇ in Process (2), & longer ped ⁇ d of t ⁇ .& requited to form the &cti va ⁇ ei slumiA ⁇ m species.
  • a high concsmration of EBhC Band ⁇ (>1O&) is fyfmtd when the AI/Ct ratio is dose to, or above, i :91 and tfee solution -readily gels.
  • mkfm% ⁇ tte ⁇ eof Typi ⁇ ;a ⁇ msol ⁇ bte, alkaline calcium tees I ⁇ d ⁇ dc caiciunrcMjo ⁇ afe, calciuTli bydfous.jdi ⁇ , calcium oxisb and mixtures thereof.
  • Preferred warer soiubk »tronHr «m-sa?ts incliid ⁇ stitKjfium chloride, st ⁇ Witilsm t>itt «ce, stitaifium bmmjd ⁇ ? strontiuns ⁇ Urate, strotiduin ibrmate, sfixmdura.
  • ftc ⁇ ai ⁇ stratum ascorbate strontittm iactaLeandfisixtases thereof. Typical f ⁇ so ⁇ ubl ⁇ , aikalfee * ⁇ it)fttiur ⁇ bases . ' mciude stmMwm c ⁇ rbcmafe, stnmdum hy ⁇ mn ⁇ e, suoBttuin at ⁇ a &n ⁇ muctuits th ⁇ reofv
  • -wha ⁇ au b is a numr ⁇ cai nuraber ⁇ x»» O to i X
  • X is (T , Br " faced T or NOf , wids vbl ⁇ s ⁇ d ⁇ > being the most pfct ' erred, lite zircomutis hyckoxychb ⁇ de (Z ⁇ IQ s ⁇ ?I«Ji «i ca ⁇ ' be prepared by ⁇ fce t ⁇ tctton of tek ⁇ c ⁇ niur ⁇ carbonate with hydrocblcwic auid or xlrconyl chk»cide at efevaied temperataro for a conaln pesriod of time.
  • Ir is$ ⁇ les ⁇ ? ⁇ ble *o have ZHC sok ⁇ ioas w*U ⁇ Cl/ ⁇ Jr ir ⁇ tio of ' *t least 1, preferably of ai Je ⁇ s ⁇ L4> snsl ⁇ s « ⁇ praltoably of ai lesst l.S,
  • ⁇ a re ⁇ s ⁇ lfaait solutions comprise fxxm alKHJt .15% • «» ' ak> ⁇ t 60% by weight ⁇ f a a j rco ⁇ lum-akm ⁇ ti ⁇ ra- chtorohydnii ⁇ -benbie $a?t, ⁇ wefinably ⁇ bcntt 30% t ⁇ ti» ⁇ S ( MK : by weight, ab ⁇ ut ' O.29& to. about 10% by smgjM. ⁇ f: ⁇ alcjam/sfexjcttiujrn $ai ⁇ .
  • ftlamimim-zirco ⁇ mn salt isoli ⁇ ions thus prepared h ⁇ ve a M/C;I ratio Df about 1 so af ⁇ ut 2» Prof ⁇ «bly the ⁇ tymroom-'jM iromu ⁇ i ssits aix; teirs and ⁇ cu ⁇ s» ⁇ % %vi ⁇ h M ⁇ CJ " ⁇ k> of abour 1 to> L4 ⁇ iost pitfeced
  • a polyh ⁇ dric alcohol such $& propylene glycol
  • Spray ⁇ kymg is the mo& preferred method Furthermore, the x ⁇ iutkms ⁇ an ' ht dried, into different densities and different shapes, such as Iwaadhsgh density i ⁇ hs ⁇ ie»i panicles io suit for die vaiiety appHcati ⁇ is in Ih ⁇ formulations like soft $ ⁇ . ⁇ $ and fow residue
  • Il ⁇ mifiti ve ⁇ reo of one or ⁇ i ⁇ rs peafe iss determined m order to chatftderlz ⁇ the d ⁇ «tHbuttcm. ⁇ f polymeric species in aiumfctu ⁇ ; complexes ft> ⁇ r «xi» H « al ⁇ rnsipittR a ⁇ wl yiiraiaam-y.ircojaium &nti ⁇ r ⁇ pr» ⁇ tf ss ⁇ n co ⁇ )£ai. ⁇ l ⁇ g bstain ⁇ aii ⁇ lca ' lcji-tn/8tro33ljy.ix3 sails accon&ng to the present inves ⁇ doa have SBC- HPLC Band Iff m Band Il area ratio Oi *t least 0.5 4 preferably at least 0,7, ⁇ ?sd ir ⁇ a prcl ⁇ ab ⁇ y a ⁇ leawt 0.9, Af least 70% of the total
  • H ⁇ e sc ⁇ a ⁇ t ⁇ i species am scot ro the UCP iastead of ⁇ tractive ⁇ & ⁇ ex (RX) det ⁇ eior as is regular HPLC, F ⁇ or Io the an&iy&i&v tbs column ⁇ yas conditiosed ⁇ >y f ⁇ peated.iajcc ⁇ o».s of ⁇ 10% alumlmr ⁇ -zirccr ⁇ iiTi Lemichi ⁇ r ⁇ hytirex gycinfc eolation ⁇ ti) xha atsa of Band I iscommiit
  • E?tai ⁇ ffllc 8 JP ⁇ mrion o ⁇ A-Br ⁇ i ⁇ um-l-tetatiie-C&i ⁇ um and Al» ⁇ aim.r»"Bet ⁇ a ⁇ e ⁇ S ⁇ r ⁇ nf ⁇ um Soluir ⁇ r ⁇ from B&t&irx 3 ⁇ O

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Abstract

Aluminum and aluminum-zirconium antiperspirant compositions comprising basic aluminum chlorides that have a particular molecular size distribution defined by having an SEC-HPLC Band III/II ratio of at least 0.5, having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having SEC-HPLC Band I content no more than 5% and containing betaine (trimethylglycine), calcium and/or strontium are disclosed. Also disclosed are the methods of making these compositions and the use thereof in consumer acceptable antiperspirant vehicles such as aerosols, gels, roll-on, sticks and soft solids.

Description

BETAINE WITH CALCIUM AND/OR STRONTIUM ANTIPERSPIRANTS
HELD OF THE INVENTION
[8081 j This invention relates to novel basic aluminium chlorides and basic aluminum chloride/zirconyl hydroxy .chloride antiperspiran compositions that have a particularr molecular stes dύ$tHbu&Qa in the presets of bstaine (αiisαhjlglycme) m eombmatios with g c&tøαm and/or strontium compound,, to processes for the prepasration of the antiperspirant compositionand to consumer acceptable antiperspirant vehicles such as aerosols, gels, rool-on, sticks and soft solids cmit^mng such ariHpetspfra^ cotxipoκitions.
BACKGROUND OF. TiW. CMVBNTION
[0002] Basic aliminium halides partricularly chlorides and their use as effecitve antiperspirant compounds are well known. Basic aluminium halides are complex structures made up of mixtures of polymeric and monomeric species of varioussizes and molecular structures depending upon their Al halide ratin,m together: with varying amountosf bound or coordinated water. The basie ^uminum corøpo^βds ^K "eRerally repn&euted by the eir»p3yk?»J forsimla:
wherεin Y is O, Br or f mά Q < x < 6 a«d n is »bn«t D.S to 4. ϊt should be undcr^lood that th« above f<5πnul« is ^mpliβ'ed bccau&i* it- is mi^Jckfd to include basic alymintmt halrdcs conlaiαiπg cϋCHxima!£cf or boi^id molecules Df water as well as basic aluminum haltcle poCym^1 coxn^ext^ and unittures of ti& abovo.
[0δϋ3I The in vziήan also coϊitrinpkies aqueous ^mMiAWn κircs)mum a«tip^'spiranι itctivei coiaprkmii hmc almmvm chhύύøs of the-form&la:
AJaCOHipiKijCU
whftre ώ i«s a number frυm about i.2 to 2.0, Mt&\ aix>m 5% to 40% bγ wei'gM having an SEC- EΑC Bshtl III to Sartc..11 arøΛ ratio of 4« le&w 0.5 i««l a ztrcotuum coϊnprjrød of tl^e tbnnwb: 2.T(XORhCh
tea about 15% to -10% hy weight ^fierejn b is a jiύmixrieail number from O &> J aad c 35 &ι Irøsi
L
|0004] Ii is a challenge to βcσruκntealfy prepare enhanced Qfϊkf&y aluminum aad akmmum-xucoπiυj^ amiperspii-aπt selves at hsgjh conαsήjratioβs Of aluminum. Effkaey snhaneeasem is oftes achieved by ehangsag the jnαiecular weight distrihaticra of lbe basic alumiiKUfc compounds 2rø?n a krger &> a smaller iaotec8te"wdght tϋstϋbmit^, These tUfforeaccs in moiecdar wdghj <&arife««ύm are often «xpr«ssed by v&fst&ncz m the various aiumimiTO persks ϊiiat can be idmtiβed when the salt & anaiyv&ci by siϊ» excbstόts dircmtsrog/δplty <SHC?) tvpicaily run by hi^i peϊfomi»>c* liquid ehmπnstøgϊ&ph.y (HPlXT). A iscjitable dτrm»i-t#graρhfc technique ϊs.ca:pξib!t?of tesolviτ5g thp major Trabecular weigh* sepwcsits in BAC imo ai .least fow dbtsi^ct paaks labeled B&nά I (<yr peak X 4t $&&k 2), Bδ«d ϊϊ <pesk 3), Band ϊlϊ (pessk 4) asrd.Band. IV (peak 5). Th&*etemicm time M which these pss&s ^ppestr, the?/ τ<rsi>lpliom§ and ibcir rs$pectivie peak air«;a«, ύit? the ftmcUos of fehe CAlmtrα (<«• co'hincfBg) imtl ιrκ>fejJe pJωse m&ά. lii gzmxύ, onbftTK'Ed esfficΛcy sails have been desejrfbed as having either c^hsnced WLC Band HI car peak 4 coxitsni or Bmd Ul (tmαk 4) to Bsnd il (peak 3} latiδβ df at least 0.5. It in impcataήt to noδs ih&i geϊ«5mliyf Bonds I, O^ UI mά ΪV of øn«? system c^rraspc^d respectively io pe^lc$ I & 2, 3,4 and .5 of the oilier sysiero, as described abesyø.
[0005] Jn accc^røcc; 'vvf ώ: rh& i avesuioti we h&vc ώszύvweά that s»pcπo:r eϊ?hsϊ.ϊc«rf
'efficacy ώft* shouM Ijtaye α«ix« esd^loB <?koxn^«fca|jhy SECΗ^X Band røto Bead JGF UΪΪ?& raøo of ai least 0>5, At kaat 70% of ?he total SEC-HPLC band conϊcm sb<?uJ«l be c(.m&\xvxi vstihitt B&wϊ 0 arid Bami ϊB.-jjr^ferably 80%. These £aτb&πcxkU&!t$.havs a βaitd ffi.-coπtent of si i««sfc 2^,. ήτ4 pf«!jfe?at)3y aϊ teas; 30%,_of the UΛSI sl««.τinam contained in all the peaks a$ αseasured by $%%k area. In cωitn^r* convcntional u«ϋ-eπha«ced antφer8piraϊ\t. salts have Band 10 content of the. range of about JOS vvd Band HI Io Band II «r&* rado feyts a'boαr O.iό to 0.2 or lesjs. Nb mom than 5% of the SEC-HPLC bjsidl corsεeitf skoαldbe io Band I which is sfgsffkantly iow<ϊr Btm^. ^ content ttøm in αόrivenuonai* ijoa-xϊcδ vated aπt^^»rfiτiL salts. Baad :i;V content should bø c^oai 30^>> prøfδra&y about t$%. [0006]l Aciivatioa of &Svn.riratm ^xperapiπ-m actives h Mnrn&iy achieved (h.to®$\ dilution of* søiicetitfiHed basic tάQmmm<Mϊ≠Φi (BAC) solution* panicsJ-tfly aluminum cfcfori&vfek; (ACIT) solution, followed &y h&aϋαg at elevated temperaJ&fea, This pεocm h described in UK. Patent Application OB 2,048,229 A of Ftøgeήtkl which diβclose» thai dϋutixqs ACIX solution with water to s&ibieve αsrøsoftatSon of &t least 5% .by weight, prafstabiy 1.5% sx?d inore. preferably 10% by weight or irkweraad agtøg fhe solution at a superstore above 5OX mύ Mow 200^C nssαlcs in the formation of an optimal group df comple&es άc£m&ά m Af mά usually predentin ainaunts frøm shout lϋ% ti> 30% by weight in the rέ^lll^ ACH solarion. Results obtained accosting so thrtf rsffoeeηce comprised concetτtx»riαm between .1.0% an<i 25% (page 2, line 3 of iMt &femnc&). However, the relatively dilute ACH solutions descdbed m GB 2^048,229 A are. outsak ilis p^aicai ^c<φe of the ptessm in veetioa.
[0007} US, Patent No, 43.59,456 of Gosling, ct si, discloses .hat basic βhuxtinum kaiides obtained by ccπvrø&øaa! mettexis cα« be furth«κ- br«άeα dosv» from higb Bκ>kcαiar wejghr poiyrruirg by diluting concentπitεd solutions Jh««of to lower aqueous coπcrøδraliorui {iily.mi«um cpnoεαm-adon of iϋ% to 35% by -weighi) and. he^Uug δt § s©#iperaime of 5(.}°C .o 1400C for a period of iiiϊve sufficient to' provide a B^d HI percent aJuminura vdue of ^t lam 2d%. No disclosure js αmtaised ?heα4iri co^cemir.g thc.distribrøfion ø^ mά αf any sig.«JHcόnώe siulbutabk io, alttmimi?!? specie* in Bands csύivr INm Ba^JB. No^bIe also in ϊfca? pfitear dkclosrø-e erf the S3gi*jficaxκe of the differing p]trø&# ^r^^terg thai compose the present invention.
.A method similar rø tlm of U.S. Pa.tenrMo.4^359^45.^ is d«5cάbddiπ U.S. Patent No, 4,775,528 of CalMan, et βiM for obtatøiHgόahaneed alumtr.υm. wϊ?h Z^oruum aπripeapiraftt active, AkfcYarmm chbrohydrate aobtioa is ^cliv^ed by dilutes to sbowf 2% to 2(I5?> by wei|f«i antil the ratio of the δcight or! lhe peak 4 corresponding to ke«0.7, io^ Band.ϊlf, to that of peak 3 correspondjng t(i 1^^0.5, i.c, Bmύ H, L^ at tei 2;1 asd ^t leαet 30%, artd pitsfe^bly af.leasf $0%, of the mϊύ ^Imdinmx \s pxv&<$& within rhe j^alcs coirøφύtidmg m peakβ 4 ajϊd 3 (Sands HI unά H) (Column 2, Uass 60<-δl), TJie resuhiπg practa cαπcsiπs Icwβr j?ιoiecu1ήf wdght polymers tø inα«ase ^fficβcy, hwt sutfifess by fcaviag a winter ρolydl$ρar$ity. Tm <mlφenψlrrm{ competition coπφιi$cs ?iiχ:<n\yi hydroxy chloride solatia and m. ammo &<ήά Ui provide a« atomic ratio of AbZr lτom 6Λ tø hL The aircmy! hydaaxy c&Ioracfe δόlulion camsrniBg an βdiπα &άά nmy he Bucket before, daring or af&r Ife&he&i frft-tmβst to obtain thε crøεtbmetf βnhεcnceύ ύmnϊMxωfzh&ύtά&w %ύi\$&ts,ρitwι ifccϋvs. These is oerøige or specification delineated far ύmtήwstn spodcs in peaks i md 2 aad ρc$k 5. Pόak 4 should bβve # l&iδt 53% of ølwrsi fturn species tø meet the requirørttenis <a) of peak 4 to peak 3 $xz& raϋø of at. least 2; I and (b) $uι& <?f peaks 48fid 3 areas £α |je S0% of the total aluminum pjτδem: withirr a)! tbδ peaks.
iθθ6^j US . Patent Ma.4,81&,512 of Mftskariffn 4'3sc:ioses a prqc&& fϋr preparing δ«^aτtced efficacy alaraiflon^ chfαn^hydrafe pivxiuct cosiafnifsg fiOJU sboot 77% tα aboδϊ δS9t> of an aϊumitiumdilαmhydratemoiecukr species hsv.i«j a fe value of eqαa] &> abi>ι*t Dv4 (Baad IH species) ccnκψri.mng hβ&mg. an aqueous &3te?ioπ of ^bcstS^ aluminuiiti chicsOh^i^e at $ teitϊper&Utf'€ of ϊxwn abom ifO^C to -atoϊf i32<JC for a peticsd of BΌTB about 30 jiύtuϊ?e$ rø shorn three rtϊoa&s to produce a rescfbs product wά spv&y (kym' g the teactkm ixrodiict. in this rsfercmsε, tiic eøect of tl\o eαøcenεraiiCHi øf alarainum cMotohydrate* <a series oC 5/6 ba.^lc ^tϊmirt«m db3rødκs were pisjpared zaagxngin concentr^Jon from 5% io 25% by weight) solution, tfie time of hea&ng w& ^he tempεratirø of hc&tiEg os tliε 4is^^5o?i of various mo!ecιi!-U' specks of alυmϊ«ajτt am described, llie results disclosed .in C/^. Patent No.4^δlS,5i2 demor&δr&e thaVa.t'higher coπ.ceiβ.lmti«π$ (25% or higher) the percent of lower moiecalar Band IH and Bund IV sfrødes attained is very- low (ksέ rh»« 20% end -5% respec{iy«iy) de$pik ≤gisig δJ m ft!$v^e4 ^nipeireiture for trørø ihm 3 oκraths. Su.d3 cαmposiβ.όm mά pnxfcss pjn^nu'tcru of UΛS, PaumtNo, 4*818,51.2 aπs dearly oiiteiclc ύt% rmjp of the improved aappo&Mons cduemplaled by th& pressrvt invention.
[fcCttO] P.S „ PjrteβfNc.4,850,446 of Abtaiya discloses a process for pfepadπg an-
€Jihanced aaϋperspiriani which is charsclcrixcd b^ ste exclusion, chtorafti^gr^ph c6?re6pondi»g to Band US <?f th^ ^andtird HAC solufckm »nd a Band IO percent alirøMmπi vafάe.of »1 lesst 40%. That process comprises reacting pn aluminum conipoimd of tho foπ∞k; AI8XW ^ltardtt X 5* Cl, Br. F.I, SO4 aaii NO>, TΪ IS 1 or 2 δnd in is 1 or 3, wjih alαmi«iim insial in a?i scpsoas .rø$41t«β %t a teis»p«mtoι:β between SϊfC and 1930C sntil a roήo of &hinύxmm 5» mm of 0,50- 2,5; ^ is obUH*w<i aγκl rea>veri-Rg ?5Ϊ« ?iε««fea«t pj.od«ict witfeout βlevared tetnpώraiure aging. 'XTie product composition diffejr$.ϊ& characterised by Hl5LC as well as the αppiit^S. process &vr$ from
[001 Ij U\$. Piirøύ'Nα.4^7 i .525 of Gkrvarniielfo discloses a process which wppHses beating m water, *t a temperature front about 5G°C to about UK)0C tti&tøijtwmntetsl preferably in ιh.e tan of pellets or -powder, vdth &π BX halogeti-eαrtfahύng co.rajκ)«β4 whefeifi X iβ chlorine,, bromine or x<xfciπ& Thώ antøαni of water xmεd is sudi ^u ?o feαw coocβϊitMioπ of tfø& ptvlymer m percent by weight m ώeririg& fmm abcaii ^s% to about 35%, pasferabiy frcau sώoot 35% to about 25%, artd .røαre pteferabl y fmm ab^ut 17% to abmil 22% by weight The reaction ten^pcwtttttβs a« ptcfcndbfy m ϋ\e*ruιg& ftom about 95*?C to -about- I0O*C sjsci shoαki not be zhvmά so as to create influx conditions ItKI^ olthe aluminum contaiaing polymas are found mBaπ^s ΪI8 KII and !!V aM Band M coBtams at tern 20% of ihe. total nϋuπujjum ^ymers. The resulting |Fo4uct rs dcsαibod s& h&ving narrow pαlydisj^rsity whcm the batch conctmtradon f&Os witbra Ω% -22% and røetd Io chloride atomic ratio t!o&δ nor exceed 2.D0; L The μrødαώ of the '52^ psteKt- differs from that of thζ UiS. 4^59«.45δ a«d U.S. 4,775,528 patents in thai $b *525 pstciei claims zero alirmxnum spcdes m Band L ft J5 Rot*worthy That in contrast ?r> the prssen. inven6θftt fione of ώiεsc lfej»έ ψεάsm άmάςm&, U»*cbes or suggests the pø|>-ffaϋoa csf effective composition* «t ACH concentmicMis ahow 35%, Ndiϊher do %^y di»closc ι5ic povi&icm of sl&hte soiut.iθ£ts at ariy conc≤?ιtration>
[0912] ϋ,S, PaϊeJit No, 4,900,534 of Iβwa^i disctfi&es a p.u>cess.tør the direct prcfmsetlon of ^uiκi«uϊxi zircoifήum hatohystoti^ of enhanced eMcacy having sjze-^xdiϊsjoπ chram^to^ph of- which the Bmd BJ -proportion k at least 20%. The? process p^ametrø &aύ praduct dliyactevfcgmion disclosed in tha? pamu, however, differ signifieaMij? from lh«5C of the ptcsenfc
lWi3>] ϋ ,S, Patent No.4,^44,^33 of iΛWϊβxi discloses a process for the manufacture of basic aiuminuni chbricte solutions vntth 1,5% to 13% by weight, having an aluminum chiαride wdsx ratio in the range αf L7 to 2,2:1 εnd which- has Band IH fraction of aϊ lsssr 20% and εtrjiug .he ifiital BAC solution.to ^rvehydrated powder terving 8ftrκJ ΪIJ fraciiofi ofsf least 20^?. Th^ ψϋzmt lacks my ύi sdøsttre or teachmg of u proaiss for Obtaining tϊso de$5t$d high ϊitmά III eαmeiai m concentrated BAC soluttcafcs as dw& th« $re$ttt& iirvemi<m.
[00141 US. Pfiββat No.5,356,(509 of Gi.ovaraii.dk) tenches a. moύific&tHMi of the dksct pjtxfectfioft of s&ftv#f.eri alumipuifc chloride ggdvcs tbrqugfc reacting AlC]>6HχO with ahπmnum metal at 5Q0C * 100*0 affording « solution of S&-25% by weight of the desired product, The pkriac* hm 1CX>% of Λe δluramδm ύoateatln' Bands IL IH, and IV. with at least 25%irt BfttKi WL U.S. PBβeπl'No. 5,358.^94 of Giovaiweilo έe&dies a aέmύlsr naetbocl whenrin HQ.ι» fcfeS8(i.in |>iace- of AICI361Ϊ2U> ΛUkjugh these pocesses uvoiii die initial produόtiør* of a ROft-etϊhsjrøjd BAC solution,, both :rø££hod$ result m sol^oπs- of lovv^- total &$ds wad ba^e less Bsnd BI activated alιim«u«ti species in their higher solids examples than the r^aircmeRtccmiemplaceU by the
[øα.15] VS. Ftøent K^- 5,202,115, 5^9$5?29, and 5?6265827 of Ban-, et at, digejose antipsn-xpirimi active compositiom compϊisϊag basic aluminum material lining ?h<≥ e?ιψrutjcδ1 formula Ab(OM)^Xs wherø 0.5 S a < 5 RIUJ X is a αmvMcm complex oxo a»ion of lutrøgcα or A univalent c!<?mpl<5K oκ.o røkrø of ahalogeti (forexaιγφlε> NQ5" , ClOV" , CiO^ jmd IDs"). Th? px-oduέts are cbawiciesdbfed by chsxfiϊiήto^mphy peaks ∞tTBspoπdin^; to psjak 3 and peak 4 of the $s;κe exclusion. BPLC chrot«aϊogcam with a ρεsk4 (Band JB) relative- area of. pi im>l 25% and peak-3 (Band U) rel^fi vώ area oC Ie^ ihaτ.ι 60%, the sum of the rdatlve peak: 3 tmd pcak= 4 (Band II Mid Ba?.d .TIO si^ bemg at te$st 50^5 a»d peak 1 less ti>an 10% {chn)ajatograpfek pealu% slutiag a? shorter τ«te«Hon.tfin$iA ilisn. pcώk 3 con-ss|3QjidiJigto peaks 1 snd 2), Tho prølucis are partjculady diftscted to basiu akiBiniiiT. sBfiperspiraftt materials &$d3hϋttg-ft ai«v'ate.>t complex WL&&(άκaι of nitrogen, or halogen and spedficaFly ditee&d selectivdy away ftrøi chlαride, Accdπ&ngiy, tf» cotnpc«fti;oro» of ?he«e i?aC£tU$ differ trots liiose- coatrøφiaf«d ϊm the prøs<^ι mveniκ>β. IJt shouM also b« noted cb<jt these materials ait regatxied ss not FDA Aotipej^pirssRt Mono^δph £φpro\'βd actiyss s»4 tlieMora, \vo«ldbe unsccop^le for uso »$ antiperΛpiratii cotnposHioπ* in ihβ United State*.
|M1<?| It is to be aoted that.5b≥. anUpe^^imnt ccunpositlon of ifsc above references, ones pnκluosd by lieat tmaijaerst foio^ed hy αxiihig m room t&ropemture. the activalϋ«l; lowet molecular weight solutions dsscήbed ift ihese xefαtaices rrnisi be drigd to powcki's quickly due to tbs rapid ΪQU of activation- gained ϊiiϊcrdgh the heat treating. The isevarsibility ώf tk& heat &cϊivϊttiori process invents ιhe«e [aw an activated pi'O^uci^ from being ussέd M geis or emδbion roll-røs as tlie i-eUvcs muse remain in ξtqμeotis solution ibr these types of prodMctx.
[0OiT] Oilaaro anά stnonilum s«8s hav« been, reported to stabilix* HPLC Baud IU/13 ratio oJ' aluminum or akimiπujis-zircoπisEπ «otaι5ons ift the presence of as armao ^aM such ^s g(yci?ie. FOT e^δxβple, U.S. Pateat Ho. 6,042,St^ ofSheR describes a method of siablli^ug art aqueou* $t>kiuon of etthanued eTJficacy «kmimwϊ5-ziκonium aatiperspimni salt, cώϊtdiπiπg an sffeeim* a^sjotmi trf a water sotøhfe caldam sah and βs effective (uτκ>«βt of a water soiubk amino Ωcidj against nψid degrsdαHoβ of IiPLC p?^ 4 (Bmtsά JIl) to peak 3 iβsmύ U) rglio of Uϊe ssait* Howcv«3\ high coπorøirstioπ dufflflnuni salt so3ut«M« with high peak 4/3 ratio sfs^lized by caldαm m lte piese^ce ot ^iino acM sαch as glycine ai© not stabk, i»., the sduUcsvs ge. qu5ckly at RT. Tlterefoii&j the έhdkrøge (in. soliutm petition) rsra&ins to bo^ actsva^ ssd- maintain, i«-> s&hiHfcc, the ajrttv^tion in higher coτ*c«Mtrasic*8 st>iutiθftδ of atamans t?ased δτι?ipempirimt Λdivos, Hi^i eoneenm_rk>n& of ihe iRitipcrspirøβi active i& cte&irable to provide ∑brmuiaii<κ5 βttidδ^cy in mtipempmtit products.
[08J8] U.S. Patent Pufciiej&iosi ϊ*α. 2004/D091436 Al of Ll, et at* <Msclo«es aluminum and aluittim.mt-ϊi' s^onium αfitsperspiraπtsofenhsnccd eHfeaoyco.ttt5ai»tt3sg strontium arid δn amino add suck as glycine with slabie BVW Bmxd Ul1Il ir&fios. Beit, agωa, s«ch Jkigfe aJurømyrϊi coπorøitraUoB sølαiioαs, ^ described io U>S. 2004/0091436 Ai, are prone to gøilimg upon sending.
[βOl^'i K si w«M bv m*x.i thai U h s.dlial!røge to achieve activaiiαii of alrømum antipe^pirani (%?ιxtpo&it!oi}S <a£ greater chloride contem, n&tnely duj«inus» sesqmchlorkiev Aluminαm sesquichloride- compositions mx>ixηm& aluminum to chloride atomic ra»os oi" i.8 Ui 1.2. Activation through- entoced B^ud ffi csoπtent is more 4£fScu5t at lower aKiminum %o Chloride ratios. WbOe U.S. P&efU. Ko> 6,902,724- of Parekh describes fe cotiψQsitiofn c<?stairang oj>_ima3 moiecαiai" weight mat^isil, it is nesesssry to msuatam a metal to chlorids ratio of b&κve«n 12 to zhvxit 1.5, pi^ferably bstv.-^eft I..3 to .1-4, δtid a $oMtiw solids eϋβ«ϋit maintained ■within a relatively narrow range of abo ut 30% to about 40% anhydrous weight percent 'and Size Exclusion Chromatography Test Bansl -with a Band I percent, aluminium value of less than 5, a Band 11 value about 20-60% a Band III value between about jϋ$> snά 35% and a. Band FV vglα« b&iwtεή 15 to 50. I'he jrøseftt iftveftdoiϊ ^ovϊ^es a solution hi improved ϊnoiecuϊsr w^igbt, greater Band Bl conceai at higter solids- and a αnnpositύx* whose solubility sjs^ility is .røβiπtaiήed.
[M^l Various "PUbIi^aIiCnSs diaseribe alumimira and δ1uminαm~2iiϊ»E?ι?m antjps«$pmmts ooatainhtg betaiβe. Betaine. al-so idsntiiisd as ϋimeihylglyciπe, ≤rtκlics ciadvativ^ iϊvJadjng rbe moαohyrirais ^^ Hydrt-κά>iDridc solids. Tϊirøett?ylg?ycιne (betδine) is" not an amino aoitl Tri«3ttthy%1.yd«e has a quartcstia^ mlrøg^i group φar c^m)θf.&cϊiιs a hydix>gfct5. tan dornor ot acceptor in ptoses of ^? «mi«o gr(?up. The ncsxnal ifcmi of ΪJIC mmjxnmd is as as iateraaJ. salt, or zwiierion, of ^composition (CH^St1TCHsCX)O" , As such, it ka$ Vary diflerent chcmi&try froήi glycine. S^^v^oM tvccut p«bϊk«tio?)S J>» bss»i«Q ars sαnsBiadzod hdow.
il>ft21J WO 20O4/O26295A2- Λsϊaies to the ιιs& of zwittedonlc comp<x»i'ci» and 3 jjfeir deπvjrii ws as prαtecϋβg: βgesils of skin, b^r.&R<i ft<ύi$. The xwitteni^c co^povmds tncliidle beuthtes. SiiaiJarfiiJngff mdliKle WO 2θ£W0J59325 Ait BP'ϊϋαsS53 Bl, O S.200^ΛJIO?833 Ai βndir.S, 2004/0198998 AL Ikssopmpestiea of betaήae aiβ ύot part oftiύs iavemiofi*
{;<|022} WO 2004/08932SAl describes a giyciaa-fufce tUumiuum and/or zirconium beiaine
SaJi where beraiuie ia med as eiihw fha .monofrwk-ac or- rhe h>τdrochIOB4e d&rivstivu 1WbSt & rømbssr Of <gfferesU .meihods wv disclosed in lbe IUcraiui^ for making antlpo^niiat/beiTii»e ψilι&, none <ifthB known methods describes a process to scύvvώ bmt- aluminum chloride In (he presence of betaκ*e. The mveiftioft escarspassas a method for the addition o^bctaioe to previous^ tucήv&fed ulumimatn dύcttohyύto] sι)hiti<sis.follQwsd by- drying us skscribsd n^ gteat detail h&tφiή below.
SUMMARY ortmiNvmiw®
101133} Th$ piδs^it invent joδ r^ids^ in dig discovery dmt s» aluminum salt soUttiαn (rf pwttailaf -nsAteCBlar weigln asβttϋβisd with caliaaoed'effioa^ having IiPlC Bmxi WU rMw of at least 0,5, prefcraWy XL least Q.7 mύ most jSrcfetably -Qt least OS wifh an SEC-EtPLC Band IH to Bond U area of tit least 7(1% off be total area ami tan SECHBPLC Band! coμtaμ of DO more ftuui 5% is obttrised Through the h&tt treatment of bigb solids basic njteminuura JcWθtruhy<trAtc (RAC) solution (and including altemati røly such OAC sαjjujtrøas tit cαπiføacHtin wiib * jdrcϋniura compound) ra (He ptr∞eace øfbetehe aad a cakivm mύfor støαntissi salt;
CO(KMi Atxwdirtøly, β iR rø objeΛ<){tte pa^
«0irøcy stable baύc alutninom batidc ΛoUpetπφitam (a terra which iϋChkkss aluiicriπum-zjfcooiimi andpenppiπαu) acdvw which cwn be.produced ccomimicaU^ as cit&cr »oMόn«; or solids.
[00S25] Il is another objcd of ύte p«;setu «iveation to provide basic ahJnumm halicle antJpcπtpiirDtH? <vf tfiia kύ«J with «*»rantiJ-i]y ςaluractd rebllvβ eJffcaey and rυ pπαvlcte ^ethocte of forming stick mMcrialΛ vsiihouet thσ xπtή for ϊ=πt«uifactu/it>g <ttøps pravjα&dy tliϋlighc to be heccssaryi e.g., heating diluted solutions of akeucly mamtfajsturcd bssic j^uminuni KaHdc* attii^ terapet^wtw mά /or pressure conditions
[0828} It is α ftuthβr object aflhe presαnf iav«nti<m.to isrovicfc th.5 formation of oπbaπced efficacy basic aluminum halidc sόioiions that bavt high cxractaωi-atjons thcr^iy minimizing spray drying cost,
10(127] Iri* y« aδoϊherobjrø<?f tfrø prc^ composition* having αrhttneed &iti|)er^>in»icy an4-skin friemdliaβss.
[0028] It is another object of this invcnϋόϋ tu provide u process {or the preparation and
$tabill2^dθft of concέiutittieϋ BAC uml nluminum Jrijcooium soJ>Uiθβ$ xvith high Jf-CPIX B«id Oϊ/U ratio with excellent ptvy&tøl a»d ehεmlrøϋ s^NJity thnt can be used rø cnbftaced efficacy gel and etenalslou anUpticspirtiαt pnxlacre.
[90291 Sp^dOcidly, ihό act) «^(cd «ύϋΛiinura<AlcuJτ^^γjntiiiJ»-T«iftJRe salts sere prepared by (1) bocuing α BAC sylution of nboαl 10% Io vbtm-5Q% by wtigx hu'vπαg aϋ Alurainum to chloricte rήiio of about .1.2 to about 2.0 in the pπsώnue ofbctain© *nd acnlciura arni/w str ooilam salt Bt a tcrapcr<αuxc of at !ca?t 4O0C and preferably higher, for a ponod of timc svliϊoentxo >pnάά the desired leveK of ώcilv«ttott; (2) ieactkg Al metaJ w Jih AlCl5 er HCl aquέøu* βoJufiϋn ύi the presence of be&ύn« and ft βύά&ύi &&Vør'strøi3tiπ.r& salt at higher tetnp»ratyrsg> AJϊt&maiiYs} yt the diluted Mttd heated. BAC soMtions,2i concsetraiKiss of from abctø* 8% by wssght to abw-t 20% by weight may fee mixed with betaine and a. caleiiflu aήdA>r **iwnt»um saJt.
£003$] The aium]mum^in.røiυm-lJβtai^<κls;mϊ»/sfκ»aaum salt solutions of eahsiiced efficacy can 1>e pffep^-evi by blending a zifcosiαra salt sσϊαtjon with m actrveted »iumii«im- betasnώ-caϊcium^trontiian Salt solution iϊiade abov« ro sϊϊ&tύ m Λi/Zr mtio oCsbcsut 2 to &bo!& 1.0 and a MKi ratio of aixwt 0.9 to ^uoat 10. ?mfejmb)[y the ^Ujmltiusft-z-πionimβ-te^Λe" caicjurn/strortlium ssK solutions is a lelrø or ocia sa!t wI^)M/ChaiJO of alkmt ! ϊύ abtHil L4- havjiϊg a bet8iR€/?ir<?omum ^o of about- i to a1χ->ϋt 2, p^fes-ably «boχd L the ac(ivslΦ<i. alujTunura a^id slums ?ium-23r<>DMum-J>BtaiB<>calc!iirn/siroTicl«in sail $o^r.ion» €^a bϋ mc4. as ύ »r to he dried to powders far the. use ΪΆ ae^5soϊ, soft saiid, creaiΩ* roll-cιτ, gel, stick foπnυMøji^ as
BRIEF DESCRIPTION OF THE FIGURES
[0031] • FJ^ 1 5$ ?!ie. ICP-SEC^HPLC of an fLiuiuinam«be^iinc!-<;^lciαm wit soiuitcm prepared according Co the mv^ntϊon,
C&032] Fig. 2 is ite O-SBC- BΨiC of «n alumiιi\im-i?Itcoτiitim-<3CLB gai[ with beiiairse
4nd c^iάiif^ §j.lt.$dlϋtioj3 prepared acαwdiag to the Hiventlόs,
TV
[603(3] Fig- 3 is ih« ~ Al NMR of ^i αiumi n\int-zlτcQtuum-cMDta ssii powder wάh betaine imd caidαm sa)t prepuft^l ^ccoixϋng to fe iδveβϊiαn.
[0D34J Rg, 4 is the 27Al A^ME of an ύ\iminum~?hc<>mύm-αcuϊ salt sαhitifm witlϊ beføjne aRdcaldum Sftlϊ prϊψ»rβd according U>tht mv&Xi&on.
FIg.5 is the ICP-SEC-HPLC of an alimiinuns-xjticoiiium-octa ssJt solution with betaine and stro-adum salt pttφaitsd decoding to tkt mv&ntHpn. DETAILED INSCRIPTION OF TBB INVENTION
[0056J Th« presoπr iaveatfoπ h directed to the [Sεeparøεioβ of approved, eatøee4 efficicy aluminum «md. alttitcnum-ziicorriam an&pe^pitaαt sol* compα$itiθJ3$ comprising betaine atsd a calcium or strontium gait or s* eofobiπatf ori erf calcium" ml strαaiiam sslts ^herein lhc antipcrapiiatat has an .HPLC Bmd JE \o II area ratio øf at lease 0.5. "The basic aiαmiπuro salts of these oørøpo&itioss hαvo fee fonjitτia:
wherein X is Cl" . Bf, V or Np3 " . a is fram-about 1 to about 2, with bδδic &ΪDj«iβiιtn (shloddβ sohitiofc ihemoM ptdemdi. U is ptisfmibie to have aBAC jsolmion with aϊamjniuu io chlorϊ«k r«ϊio of about 12, Xn about 2.0 ajid i^ost pi^εrdbiy ltom ώboat 1.4 to about i ,8 depending on the type of pζlcium snd/or sϋ"oπtjwm compoiiRtl «s«d iti &e aciivaticMn^ i JR.4 a watsr «oh.ιb)e s&it each as calcium smd/or sα'Oinvium chloride αr insoluble, ^jghly.alkaϋne b^e mch as calcium oxide or sironduii.5 hydrøxide *>r blends thereof. When fee water soluble calcimt^ aad/orsiϊDπtium salt is utied, BAC so.li.Ute wiib higher AlC) iSftJo such as Iwm about 1.6 to ^out 1.8 is p-πsfenrad, which gives maximum ac.tivstj.on o? the al5.τrmsurø species, IΛ,. less Band 1, preTembly ϊess than 5%, as^ Mgh«r Band'IϊI/TI raϋx> of at bssi 0,7» \V3MJO strong aLlvJtlifie calcium aad/or stκ«ntium ecjmpouRife ai'e used, BAC solutions wsth lower Al/CI mύ<y* sycb as fromabotr*t L2 to about lt6 are prd^πed.
C^0371 According to Process (1 > o/ ike preseat Utven^on,. the BAC solutaons arc xniλeti wiϋ? av^iβf »>i»W»CAJciaϊa and/Or ϋtsoαtiota $alrt preferably calcium «πd/or.Sf».ontiαm chlc«ide> mά betαi?ϊe tbon .heβtød fw« afeout 4001C to about «sfiωx anfil an BPLC Band 13FB cαrio of at leastθ.5 is achieved This process is most preferred since it quickly forms activated almmaum species thai arvs stable in thes» soJiuiom, WTrøa ACIl soϊvfrtoπ (Al/CI « jl .9-2.1 ) is used, higher ]-H*LC Bάsd i is formed &ιxl the aciS vated specie ars not stable at blotter ccmcentrations. A pj«ferred method for Process <2).ύrvo1ves-ieact.ng AJ powder with AlC)3 <w KCX), in Hie. presence of Sxsrøtøe and a. strosgly Alkβϋfie t^$e βudt as €aO or SrCOH), or a bteαri thereof for example. Ai lower Al/CI raϋm such »$ about U, 8« ac&vsted aluminum solution 5» formed . dwceUy with an HRLC Band IWU rmio of above OJ4. When beiaiae end's. wai«r soluble caJcium and/ orrømiuϊπ saJε> for example CaCV2HiO, are useά in Process (2), & longer pedαd of tπή©.& requited to form the &cti vaεεei slumiAυm species. A high concsmration of EBhC Band ϊ (>1O&) is fyfmtd when the AI/Ct ratio is dose to, or above, i :91 and tfee solution -readily gels. At AI/CI" -ratios of b» than I A the" solutiαa has «B HPLC Band IU aft* of le*s Cbαo 20^- or the HFIJC Band IlI/II mdo « less ilisn ϋ.$. However, tte soimior? Basd XIFII ratio hϋ-cøraes grø»teτ.( ύvm &S upon agiag.
[0939] 11«s ai untjnttm artiiperspafani solυtkm «il the picstsai \nvm\iύs\ dOSftpdses about
10% k> sbαirf 50% by wstght of basic aluκaiπojn ohlorobjdi'atø salt, pnefsrabi y about MY& Io about 45% by weigh*; abotit i.% ro jώcβji 15% by vrøgM bctaiπc, ^cfcj-ably about.2% to ifboivϊ 8% by wdght sad about 0^2% tø aboui i.i^ by weigfei Ca mά/βι Sr compooπd, «sd prøferatøy about Q.5>% ω about S^ by Wrø^t Ca and/or Sr compound Typical water soluble ca!ciu#* sate Include c^iϋiuπi cMonde, caidum lUtrase, caleium brømide, calcium citrό^e, caldum foπnafe, cβfcium aootste, caiciam ^€Oitw-te, c^ldtisn *uifaJe, calcium lactate mά. mkfm%κ tte^eof: Typiς;a^ msolαbte, alkaline calcium tees Iβdδdc caiciunrcMjoπafe, calciuTli bydfous.jdiϊ, calcium oxisb and mixtures thereof. Preferred warer soiubk »tronHr«m-sa?ts incliidβ stitKjfium chloride, stϊWitilsm t>itt«ce, stitaifium bmmjd≥? strontiuns εUrate, strotiduin ibrmate, sfixmdura. ftc^ai^ stratum ascorbate, strontittm iactaLeandfisixtases thereof. Typical fϋsoϊublβ, aikalfee *{it)fttiurø bases .'mciude stmMwm c^rbcmafe, stnmdum hyάmnάe, suoBttuin atάύa &nά muctuits thβreofv
[003^J According Co ftp -prog*.** igyenfion it has ho&n discovered th&l bigh concenlration of aluMtium-bβtaiije-csleiuin mάtof stttxtiiam solutions of enhanced efficacy mt very stable with iespect t» boch cc«tt|so*jtl(«t (HPLC.Band. ϊϊl/Ji ratio) and viscosity. This is m- clear oouitϊasr to itccoiYcspcHiiiiβg solutions cojstdmng aτniκo ndύs., such as glydiie, {in place of be&ijtø), vvbfch gel πφϊdly αi RT,
[0840} It has alsp been found djaf rhe aiuitiinis^-bstaiiis-cdciuas μi4/or stroi5duπ_ δθlot^oι?8 of erthancttd efficacy pjxjpsrrøl by the pi'ocξsjs afloat ijeatmenfef ACK ( Al/O « J ,9- 2.1) tioiuϊton (such as 46.8% by weight) wiih CaO^ asd be.aans restdts. in a tøy solution wiih : large Ba/ui L Tn αmlrasl; dear solutions "wsih HFLC B»τκi J of Uses than 5% «ht .foτ.?n««I frαiu higher concentration soktfksss of Φ&ή 48.4%- by weight of BAC wύk AVO ratio d about L75 when hε&t ireated wifch C&€b.aiui be&ifie. Mαreov^ iybeu biεπdijπg these two* solutions røfh a aiτcrø.um solution* the nssuiriag 2ifxoβi\Hrι-B.AC-b5t«iπ&»<:?ι!c3.a«]/δlB>Bti»m sαtøto, as ϋϊlαstrated by Eκampb-3 herein below, has « higher BsM BM ratio ihm for the 7i«x«5i«ϊR- ΛCH-betalβe-ca!c|ut«Λjtvom.iαyn $o!i-doD.
[004.1] The BAC SϋiutsOtt cer$- be prepaid directly, ϊ.t,y ^acting dυxn inuπi powder wl(h
AJCI',! or tKff aqyeoas solute «t βlβvs^βd terftpcrattirij osr ituSrediy , i .e,, mixing ACB with AlCI3 or HCi
I0042] Zh recmiurø com^ancfe useful in the .praseist invernicai Imve the fbtrnα Ja;
-whaαau b is a numrøcai nuraber ήx»» O to i X X is (T , Br" „ T or NOf , wids vbl<sϊdϋ> being the most pfct'erred, lite zircomutis hyckoxychbπde (ZϊIQ s<?I«Ji«i caα'be prepared by εfce tβtctton of tek ώcαniurø carbonate with hydrocblcwic auid or xlrconyl chk»cide at efevaied temperataro for a conaln pesriod of time. Ir is$ <lesϊ?έble *o have ZHC sokύioas w*Uι Cl/ϋJr irøtio of '*t least 1, preferably of ai Jeκsι L4> snsl κκs«ϊ praltoably of ai lesst l.S,
$0431 The ai«tninuni-^rc<πiium-l^2itιs-caldum/strofαtiuιn salts πm prepared by mi sJBg ώe actSvtfi&d BAC-'betahiβ-calciϊui^βlTORtium sotαtions wjih «. IMC solution.. t)\a re^sαlfaait solutions comprise fxxm alKHJt .15% •«»' ak>¥t 60% by weight ϋf a ajrcoαlum-akm^tiϋra- chtorohydnii^-benbie $a?t, {wefinably δbcntt 30% tα ti»αι S(MK:by weight, abσut'O.29& to. about 10% by smgjM.βf: ^alcjam/sfexjcttiujrn $aiι. prefrøbly »hcful 0.5% to about f>% by wdgbt The ftlamimim-zirco^mn salt isoliήions thus prepared hδve a M/C;I ratio Df about 1 so aføut 2» Prof<^«bly the αtymroom-'jM iromuπi ssits aix; teirs and ύcu\ s»\% %viιh M^CJ "ι^k> of abour 1 to> L4 Λiost pitfeced
{0044J A polyh^dric alcohol, such $& propylene glycol, may be itidudδd in ilie alaminujr» or 3iiMrøftuτa-zitcλmiu«vbfeiaifli^oaLdμni.%ln_}nιJu?β solafioois, which bM the. effect ot! røhsncmg tha-stδbOitv of th& corrssponumg zcύutions, especially vMi respect to i!M)lti<B to felling. [0045] Hie aiuimaum mά ϊ 'ύutMmmjSzciimvm solutions cόnfainiβjg calciuj^strøntiuni sails mdbe&røsc&r. be dried to powders. hy<*n.y &p£r»p.riafce rpeisns, iocJiudiBg fx&>ix&-άtyhi$ &nά vacuum drymg. Spray <kymg is the mo& preferred method Furthermore, the xαiutkms ^an 'ht dried, into different densities and different shapes, such as Iwaadhsgh density iφhsτie»i panicles io suit for die vaiiety appHcatiσϊis in Ihε formulations like soft $φ.ά$ and fow residue
[004^3 The cbaructc«κaiiθjθ <?£ akirύπum and aircoimtm spocies it* aUιmiBt.m»zirccβni»in- b^αiuc-calciiim/^rot^iufiiaπ^pej^irαπt sails are cietercfi.fted by the blowing mόfexls:
SBC-HPLC
[W47j Thφ de§n«r of the ^αly»iefiκatiDα o/ alurniti^im cmϊϊpiexes is <ktentixtt$4 by S?2e
Exclusion Gwmatøgraphy (SEC) βpCTi^ed vias High Pcifαrmance ϋqaicl Oimnifitogrt^ CHFLC) iπstπuneπt In this teεhmqu?, the hi^Lcsi moiecu^ vtelghc Ai species ai» cMcά fmi and ^f6 dssigttated as Band I or ethsnxiie called peaks 1 and 2, Bond H (or peak.3) aud Band Hl (or pesK 4) am due to ifrtειτn«βaβ mulecoliu- weight Al complexes, B$nd IV or pς$k 5 i* dm to rhe lowest .molecutΛr weight Ai cosrspte^es, mcl«dlng mc.moj7K?r« sπtd timers. Ilϊδ mifiti ve ήreo of one or πiαrs peafe iss determined m order to chatftderlz^ the dϊ«tHbuttcm.αf polymeric species in aiumfctuπ; complexes ft>αr«xi» H« al^rnsipittR aτwl yiiraiaam-y.ircojaium &ntiμrøpr»ιtf ssύn coτ)£ai.βlβg bstainδ aii<lca'lcji-tn/8tro33ljy.ix3 sails accon&ng to the present invesϊdoa have SBC- HPLC Band Iff m Band Il area ratio Oi *t least 0.54 preferably at least 0,7, ^?sd irκκa prcl^ab^y a^ leawt 0.9, Af least 70% of the total SEC4SPlX::ban&cou&m:*b;ø&-td be ctmialned witiim Band H aM B<«5<1 OL proferabl.y δβ%. Tbese «nbaneed salts htrve a Band 01 easterns si l«»sf 20%, and preferably at 1»?LS130%, of the tα&sl alm^itium cofU^ήeci in a1? the peaks «? ms&swreci by peak, area.- No more than 5% erf the S8CΗPI.C band content should b© contained m B^nd ϊ, Band [Y content should be aboui 30%, p&£et&b\y ihωii 7L)<fr.
i.^84^] A Pάmesphw Cl cdύnm (25Q?A.6mm) from P?ie«ara«uie)c i^ Mtd ft> αtaϋn a
SEC-HP2«C Chrom^ϊ^rΛm, Each sample is dissolved m deiori^^d water io fortri s 2% try weight A? solution. Hjaoh Sample is filtered dnough- a <K45μβϊi»i' QKd thωπmύgi'eφhzά vAthin 15 røhiutes mμig ≤ O.OlN βitjie ^eid sαlueios m the i«obiie phase m. a flow rate αf 1 ml/minute. Nuclear Magnetic Resonance Spectroscopy
[0049] -27AI Nuclear Magnetic Resonance (NMR) is utilized to identify the structures of different aluminεrm species in t&c actj.vat»d atoiπum*zjroc?nium sπJipesrspirrøt sails of enhanced efficacy. The smiperspirsαt salt ΠJ δøh&iøtt forna is mώ&airsd&s is and die powder is dissolve in deis&d&ted water ΪO fαmi a 10% by weight solution just before? th» measurement, Dsn& were coJlcGtsd usiag h. Vari'an trsova 4<K) insmuneiu a! 104.2 MHz.
Inductively Cguyfød Plasma Spectnascopv (ICFY SECrHPLC
j^OOSft] The present inversion empiovs JCF-SBC-HFLC anafcysite io cbaxacεeπze the
<Kstaib«rk>« of &!umi(?um, itkconivitft øaάeaicfunVstfOβtium species. 'Itie si∞ exclusitjn column operated by HFLC. ba& bee« med fosepanxte the a)u««i?αm artd yii^røtira polymers by ≤ia». H^e sc^a^tøi species am scot ro the UCP iastead of α tractive ύ&ϋex (RX) detόeior as is regular HPLC, Fπor Io the an&iy&i&v tbs column \yas conditiosed }>y fέpeated.iajccϋo».s of ^ 10% alumlmrø-zirccrøϊiiTi Lemichiαrøhytirex gycinfc eolation ^ωti) xha atsa of Band I iscommiit
[(HJSi] "llse iβvettticffi vsril! be farthsa- illu^jtftεd by the folbwlti'g Exsslitpies. 'hi ttie
.Ejum^es, parts are by weight untex othcχ-^rb?e specified.
Example I: Direcr Preparaficta of Alaraj«urø-Caldum-Bet.»i«e Solution «αd the Compari^tss- with AIuminusΛ-CfebJυni^iivcJfte S^luLicm
[θ«52] .1 740 parts of AlCb <32°δe) and 1500 pari$ of water wsre rnrxed and healed m «
4-ϋ«sr beaker. I4ρa«s of CaO (Akfridi, 9S% parity) wsa &άk,ά and the mix-in: w^ heated' Sommuoasiy ancil a: clear solution was formed. Following was ilie gradual atkϋtion of 15^ pajtts of M powder (Afoϋδ). Water was added during ih≤ eftfire reaction to maintain ύc reaction temfK-ttmire &nύ the volυrae of die α»Λcac>a.τaixrutts. 115 pvβis of be&ine anhydrous (Aich Chemicals IMC.) vs'as introduced $st the end of.ttie reaction aad ^ic fim\ jwlinlon wa» filtered to giye acle«r cotorlcss a1umsϊ?uπ)'be?toinc-<^lc.iuiπ salt-sol8tk)n. [0053]i Ji . A ύitάtøv reaction was e&rried out ©^e^pf 75 pans of gtydsfe was addsd at the eiκt of tfee mcjioft. The slumitiui^-^yciae-calciuin salt solution was a clear β«id after the fiUxatjøn &nά the results, are listed & follows:
Table I
Experiment % % % % %
Number- Al €( Ca belfiim ^iycinic Fresh 6MOΛRT GMQWpC
J
1.99 6.7* 0,42 - 1)3 0,S 0J5b
Figure imgf000018_0001
ϊM 6i5S 0.43 237 1.0 a
Note: a: galϊeϋ w\Mn a week a? RT,; b: viscosity » 5 cps
B*.ampfe 2: Coxa^aπsøπ of Al umkrum-Betaine-Caldiiin and Al umiimm-Olycine-Calduns Scjlαdons Made by the Heat Tπjiitmem of Basic Aiumkύm ChJoήde Soli^otis
W$4} 954 parfe-of BAC solm^n (12J%AI> 9.l%Ci4 Al/Cl ndβ of 1.75), - 135 pans. «f
CaCfe'jπfeO^CRβbβr, 2?k2%Ca) antd 78 puns of betaiπe anhydrous (Afch Chtmeak, te,} were s^flsxed for 2 hoars. The dew-*»κl stable BAC-betamu-^αkJum safe $o)sUon has an HPLCΕkmd IMΪ mtiD of about.1.3 »fter mixing σvsrøϊight
[0C^5] In. a timitar expeάaustϋ, 318 fmt& of tiie same BAC .sotøβαn wa? tβf!αxe4 wϊih 45 pans of CaC!2'2!I≥O cpyslals aβji J7 pasts of glycine far 2 bαura. A hαay solution was ftxmed^ which turπsci creamy ovcrmght mi gelled in kss ύim k w«^
Eliysdfei' Cαmpar&i-m of Alanucuui^deuifi^OIicloio S^It Soliifions Made from BAC ancJ ACH Solutions
(6O5<>3 i. 3.18 parts of BAC xohifrøα (12J.%Alf 9Λ%dt Al/Cl xatio of L75)f 35 parts of
OCh'3$hO anil 15 parts of bc*sijiiic-wer& nefluxed for 2 hours-Co form solution 3. 0057] ii 329.parts of ACH solution (11..7%A1, 8%C1 A1/C1 ratio of 1.92), 35 parts of
CsO^H2O and 15 parts of glycine were refluxed for 2 hours to form a bazy solution.4; the results are listed below:
Table II
% % % % %
Nmnbβr A) Ca glycήie Bend I BajiαUrø
I 10.46 2.6 4i)δ 0 3,2 0,37 ii 10. J 6 ZS 0 12.5
Figure imgf000019_0001
[0058] It has been observed that when a solution of ZrOC1 was mixed with the resulting solution from Experiment i, the HPLC Band III/II ratio increased to about 1.1. In contrast, when a solution of ZrOC12 was mixed with the resulting saolution from Experiment Solution ii, a bazy solution with a lower HPLC Band III/II ratio of 0.77 was formed, demonstrating that betaine Is. superrior to glycine in therse antiperspirant eompositions and processes.
Example 4: Aluminium-Betaine-Calcium Solutions Prepared at Different Concentration of Calcium Salt and Betaine
|0059] Several aluminium-betaione-calcium solutions were made through the heat treatment of a BAC solution (12.1%AI, 9, 1%C1 Al/Q ratio of 1,75) with different amounts of calcium chloride dihydrate and betaine.
Table III
Espedmeπt % % %■ HPLC
Muraber Al .Ca Band '.!IHf*
i 3,15 6.7 130 a 3,26" 3.5 1.10 in 2.59 41 0.74 iv 10.60 J.87 5.5 <m
Note: * HPLG were preformed the next clay after 5k: pseparaiiesu
IiKMO] AD, rrøulj.rng solutions of Bxpsήπrcnfa i~iv are stsble witb rispøet to iNjth HPLC
Baϊid. WIl sali» sad sα&lkvn viactw-ty. The ICP-! SEC-KPLE of aliiMinuai-bd^me-calcήim &aϊt
Solution i is ? It was subsøqiiejiily spray άήeύ prøvtdϊ&g m off.-whiis jm*ά$j;-
Example 5: ,\luisIπrøj-Ojkium-Btjiδ\ιιe Soluiiuss Prepared ihrcwgb Direct Process
Aiumi3iam-heϊair3.©-cai£4κm
Sdus&otts wejie prφared by mixing aqucfjus AΪC b (320Be) w& CsCl2-SH2O and bεtainα..M powder w&s-gmdαaOy added at higher tcmperaruπέ, ' ϊhz rai50iτre« vrøre'δliesied. after were finished liiε results are listed . ii table IV-.
likpsriitfent Band πim
Number AI Aim Cs betaine fresh/IMQ fi»sfa/lMO i. .9,1.9 3,05 2,05 3.08 30JW2.Q &.99/Ϊ36 ii IM -2.54 $#< IA3/3.O4 iϋ. %n 131 gel/1 r^D
Iv 9,62 1.92 141 3.65 gel/4 dap
V SW8 1.72 2.37 3.27 0/0 0,55/0.90 v£ L72 2.54 5.S0 0/0 O.T7/I.99 vϋ r.32 233 XU ■ 0/0 036/0.7.1 mm J .3ft 2,56 5,1.2 0/0 0«2βrøΛ4
Figure imgf000020_0001
[0062]j HPLC ά&ι& indlcaiB that ih& &lumiftum-bes&fte'Cs_.ie3um. sotetsoas nsade φto«^i ife« direct process (Process 2), afcMgher Al/Qiaibs such as- i.0 and higher, con&in mo∞ pdymerøed. ahtmitϊUjΩ jφeciss as indk&ted by the pmsfcncφ of a greater aatooum. oJ? Born! X The sote'cms srøs also less stabie, sad can gd at altamπϊim concentrations cf above 9%, At Al/Cf rafios of !«ss th^ii J-4, the 1.CPLC B«JKI ΪM! ratios of tfø frcsli s<?huiόns ate -usually beiow 0.5 b«{ b«<x>rne higher OΪΪ ugmg. AJambirm-betiai^e-^alcmin xdirtions fbismed at Al/CI ratio of about L.7 by the dii^cr process show «o evid^iee of poι>tϊ?eϊiz-3d alumltium specϊδs φ% Band t) and coa&m aetivaiccl δl»jτϋ^m spec?ies with jrespscc to higher Band IMf ratios of feeder tfeaa ϋ5y Q$$ccMly upon &φιg. The dϊ?eoi!ϊ3xχ:e&s forms depolymmxe^ arκl a.Qt?va?eil alurnaaasn species i?U5re slowly compat^d $o those of ths soluiioiis tr^de through the isdif ect heat«sεtiv^fi(m pfocess. HFLC B&xtά UUIl mύύ feecϋm<ι«» higher with higher toncenitations of be&rtee.
^^31 ϊx hax be«« observed thsf sub^qutHrt refluxmg deactivates ifte alαmjuαm-bβiak^- calciwi $oluUon& made by &τtct proce$δ » shown for solutions? vi and.viii. These v/ere aged for r.w« wedα ar mom tempemtom. tbea κ?0uxert foj-two hours.- Tbe Bami ilUlt ratios <^'op|ie4 6.1OnI US to i.23 in Bxahψlevi and from 0,63 to &30 i« Kxpsrios^it vili.
Sample 6? Preparation of Al.ut«ij?um-Zlrconiiiiai-Caidam-B^tai«e AntJpej^^iratU Salts
[0064] h Υϊkmυ$\ indirect pxQxv&il)
[0065 Se^ral dummyra*aijκroϊiium4se^!»es~c&Mm"R octa sslt soMioπs wen? prepare*! by jr?i?dπg aiu?τiiπuϊn»tøamc»ca!duπι sσlaOans ?sscle fey in<Sroct heat iruatuierK {>fcκ>6«s with 2rOCh sohitk>n$ ϊn.«ithe-εesute ar& listølin Tabk V, Table V
Experimen t % % ϊtand %
Nu.rnher AUZr M/P A.S. Ca lil/il Baud IV
i 8.35 r.3? 33.3 2,54 2.70 0.6 16.5 it 8.35 l\37 33,3 2.08 3.27 LO 24,9
$ 8.35 O7 33,3 JJ50 4.40 Li 19.6 iv 8.35 U37 33,3 2.54 3.43 1.6 26.7
Figure imgf000022_0001
(WKS) T&ε ICP^SEC-HFLC of «olutrcHi i hi shown in Rg. 2 a*ιd lhe z:?AI NME spectrum of the spray dried powfcr & s^wn trs Kg. 3»
$067ij An siumi.ninn-bet8«i«rcnlcj\i»\ solution was prbp&f ed by ϊ«?J!liϊχmg y BAC solution h#viRg ALCl ratio of i .3H with CaCI≤2H30 mά beiaiπe for two IiOrø. ZJOCI2 ^oMon WJIS a4dcfl to ths ϊ^bove soUmon to form an. ali^nαπvzάrcαRrαήvbet^niJ-calcairii octa salt soJu&rø mύs A.VZr ratio of S.35 ana M/tll ratio of J .i. The wsltttfon has an wihydt»u» solids eoniuit of 34.4% with an JIPLC B^πd i ofleβs lbjm."2% and Band HWΪTjflrø of 1,24, The 27AJ NMR is shown in Hg. 4.
!0&$J fi. "βuwgh direct process (2)
[0^69] The «ήur(»wus»-bβlidβe-calciυi» solution was |Sitφa«©d toWgli the direct reaction of Al powder iviϊh AiCl$ J«|ueous soktjrø in ilώ pt^sence of CaO and bβtaiac at «ler4ied tempe^acere. ZrOCIa solution was »sitfet! to αw^ όft akjminusi-z{rcom«m--heta?]ac-tαleiι.iτπ ocia SS^t swϊuϊiOH with AIrZr. fiaio of <S.S ^iil MO ratio of i I with anhydrous 3<ήϊά content of 29 J %, Sidϊkήtm. ZεGdi solution was fiddsd. to iri&lte aa ttemϊ mi?n-2lrc<mium-bcta3?3e-cakiurπ iefra saU solution with AS/ZJrmrto of 4.1 and MKa Mo of 1.0 and arihydκxt» solid ccwtent of 2SJ2%. The oct» salt sokttkm te SsH% Oa«d [ with Band HKIΪ fatio of 1.91 , v-ihile the iets^ salt sohϊtsoβ has. 22-1% Band } with Band ffl/H mάo of 1.87. I^ferre^ d«mjτjam-2iiκ:<?»«i»i^>^ai»c*caJdι*ra ϋcm-soiϋison am ώosc with ϊlPLCBand I of Ie^ $&n .10%.. [0070] A hsήø φmήtxϋm chloride soiatioα em.taiκiag strαntmm was fmz prqj§r©d- ss follows: 407 parts of AK3.? (32?Bb) WM isKsed Vuh 443 pam .of water and hsaε&d.62 puts of SJXOH)2I-H2O (NOAHv32%Sr} were added aid the mixture was costfriuou&ly heated imtii a cksr solution was formed, 88 patls <5f Λl powder wto sddcd attd &eiϊasϊ $d»t»<>R ftke&ά to give » BAC solution conUidng sttontiam KUM %Al« 9. ϊ 8%C1 arid 1.9%SrJ.. The B AC-sircsuium •$oløτit>n was mθ«x»d with bfiiaioe for 5^α hours, ^ben xtύwύ wilfe ZrOCi^ solution to .fora .s? alamiflumr7Jπ»iήmΩ-beεaine-$tϊθi?tmai tetrajδak -sohϊtu^ϊ having a jWC'i ratio df about L2 ϊm<l beJajm^Zr ratio of about 1 iL The ICP-SEC-HPLC of the duminum^ncomum-strontium- b«tøir.«« solβHon h shown in Pig. $.
E?tai\ffllc 8: JPπ^mrion o^ A-Brøiαum-l-tetatiie-C&iάum and Al»ϊaim.r»"BetιaΛe~S{rønfϊum Soluirør^ from B&t&irx 3^O
imi] 458 parts of AOI solutions (1O.^%AI, 7i%Cl, AI/CI rsϋ« of L92).40 parts of betaϊtte HCi powdsaa were neftαxed (J) "with 14 parts «f CaO or (H) or with W parta of Sr(OH)2 {Aidricb, 95% imriiy), reepociively, &τιd the js-saliβntsofeuons wsre .fiheyed".
Tahfc VT
% %. 1!FIuC
Number- Ai q Λl/Ci Cft Sr
i 9.33 S, 18 1.40 0.87 6.24 D.S5
H 9.26 » 1.76 0.52
Figure imgf000023_0001
C00721 It wOl be undei^tood shatthepresmi invention Ls susceptible &> ix«merous changes and mo$ Rcatiom 2$ apparent xo ihoso δkH^d jn the act Aocordin^y, the pt^sηt invention .roay be embodied in cώer specific foyrøs wjthpitt deφartitigffoin fhe spirit of essential atftibuteβ of the invcnUCKi <JJscIos«i hemm a^xd reference should be τmdc to ihe appeϊ><fe<l c!»m\s. rά^vst thmi io th& foregoing specif ?<;atk>rs& &s iflrfic4tujg die $eøpe of th&iβveβ«c*u

Claims

1. An aqueous antiperspirant active solution comprising the reaction product of
i) a basic aluminium chloride(BAC), having the empirical formula
AJ2(OHV8Ci4
where a is a number from about 12 to 2.0. in amounts of from about 10 to 50% by
ii) betaine(trimehtylglycine) .in amounts of from about 2% to 15% by wight; and
i«) a racial ion selected from calcium, strontium and mixtures thereof in amounts of from about of 0.2% to 6% by weight ; and
having an SEC-HPLC Band III to Band Il arera ratio of at least 0,5, having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having. SBC-HPLC Band I content of no more than 5%.
2, The aantiperspirant active solution of claim I wherein a is fcom 1.4 to 1.8.
3. The antiperspirant active solution of claim 1 wherein the BAC is from about 30 to 50% by weight
4. The antiperspirant active solution of claim 1 wherein the SBC-BPLC Band III. to Band II area ratio is at least 0.7.
5. The antiperspirtant active solution of claim 1 whwerein betaine is present inamounts of from about 4% to 10% by weight
6. The antiperspirant active solution of claim 1 wherein a calcium is present in amounts of from about 1% to 2,5% by weight
7. Th& aHvipessiJitfetot active solution of cUdm 1 whcreia the calcium h seteded/fto∞ the group oαruasiiβg cff calcioin chloride, ealcmm niirate, calcium bjrorøcte, calcium dims, c&teium"forrø»te, ealdum acetate, calcium assαtbsle, calcium. kGiute,.calciu.m.carbon^e. calcium sulfate <?alaura hydroxide, calcfemi cαicfe aral tb& mbw&re, thareoi
8.. The an_i£εrssκranf active soJinlαs of cleάm S wheissn a s_mn&ms is present in
9; The afltijtøftφiraϊU active δotutrø <f claim J ^IsoKin th« $fronJ?iim Ls sdsptsd from the gro^j ccjrjsistiήg of sfrocvtium chloride, stratitiuπi nitmtε, stroπtiαm bit)n.tsdeH strøntiuin oitrattsCstrcαirium formate, stcaisiam acώtMβ, ^Ticmtium escosbm*, siTOnTium ϊact^e, «ικmCiu!o carijonatε, strontkim sulfate strcrøtiαro hydroxide, sm>u.iam oxide mά &s mlxtm« thereof,
10. AB ήtttiptsrspirant prwdcr oN«ύτed by spray drying the solutioft of almm 1 ,
"11i . A method of making ύι» mύpea ψir&m active solxxtio^ of claim I comprising reacting a basic alurninilna salt, betaiis^ and A «alt selected frøtjj ibose-«f calcium, s£ro«tium and mixtures ύmedt by a prtieess selected fmm
(11 heating 'i solution tsx>m «lκ3«r 10% to alx^sfc 50*% l?y vvci^it of'« h&sic βlumifium salt, of UiC empirical foφuljs
AWQE-kAi whβmϊjβ a is fτoφ abottt 1.2 to £0t frøm ^røui 2% to 15^ by weight of be&issvaud 5sdκ selected from ttiose of cMcάnn, &rotuiufø and mlxmrg« thereof lh)m'aboιιt of 03% to 15% by weight at a -ffimpei-atTaxft^f mxro 40ΛC ft? about reflux for a period of iim<≥ ftαm about I hour to tshorn 7 days;-
(2) reacting Sr(OH)^ wjtli AZCh or HCl aqueous solution, adding beiainβ, tlsόή itacfiiBg with A? powder frotτ> ∑ibwt 5O0C tp abmn influx for a pedαd of tinae from xtbαut 1 hύisr to about 24 hours id aftόrd a f*i>a! jtoiotton JWMΛ about .1056 to ώboυέ 50% by wdght elf A basic alimiinuni salt of rhe erriprtrc^ϊ fomiuk wkttfclπ a js hoψ atei Ll to 23, from about 2% ip I0#- by weight of betam?., mά 0.5- 2.5% by weight #£ stroφmrø;
(3) reacting CaO with AlCij or IfCI aqueous solution, adding betaips, Ikrc reacting with. Al £røwφ? from αφut 50sC to about influx for a peti©st of tir^ from «k?«t I hmr *t> about. 24 hoois. io afford aftnii soluttøi item-about 10% to about 50% hy weight ύf a bs«jc alsmittair.
/U1 (QB)UCk
whβrøa a is jfrøjπ about 1.2 to 2-0 , frøm δixrαt 2% ύ> 10% by we^ht of be£&ff*t, ^nd D.2- L5% by weight of e^duiR; aot^
(4) reaαing Ai ρ<w4cr with AiC^ or HO i\qυ»oas sciiutloπ m the pj??ssϊjjv«? .of frøsrt alx)ϋt 2% to 15% by v<aghi ύi' h&ήat, imd & <xMxm\ mά/ov. stmtirimri salt from about of 0.2% to 15% by xvdghi fmm.iabutst 5(fC to sbcsϋffefluK fϋr a pedod of time fwm. about 1 bam- to < 'ώmι.24 hiκm h affatή a ^iulios from sbour iϋ% to υbovi 50%- by w«άglit ϋt ^ ba.^0 aium-ttun? ,sftli of the empirical feiφulα
whsrøia a ?§; Iroφ «jknιt L2 to 2*0;
fosuiting in ihe said ϋotmioji hswi^ aβ SEC-BPLC Band 111 to Bmά &pw& τnύo of αf. least a5, having SBC-HPLC Band ΪI3 plύ* B«ad 11 area of >t ]e&?ε 70% irf ϊϊie total a∑ea and. having SEC-HPIXU B&røl 1 crø?KΛt: no mo«5-th'«m 51^-
12, The mjptliod of dims .11 vvksrem tho alummum to cbioiride atcmjcc ratio (j| lh$ resulting.8AC sό1utioi> $s from 1.4 ta LS .
13. Tfce-meφϋd-of clsha 11 wherøύa tfø? iesulring solution compdse^ fetaiq xboiϊf 30% 105()% by wdghϊ BAC1
14. The method of εkim 1 i wlrøiisin the SBC-HPLC Band HI to Band JX arsa ratio Ig- stf. teas! ϋ.t,
J 5. The π?$tlød of claim U. v«'taein bet&in© is pr esentt m amcrønis of about 4% to !0<& by weighs.
.1.6. The wtlϊød of ctaita I i wtøreάa the heating, in the process <$).&.cmκfejct<wϊ at refiαx for at teml 2 Kmm.
17, The met|b4 of claim 11 wherein calcium in ifcs soktioα of processes Q) mά (4) is present in ansoums of froiti aboui 1% io 25% by wejght.
1 δ. ltie method .of dύϋm \. I whezάxk m ih& p?ocs*s«x o/ { 1.) and' (4) the sWturce of cslcύim is si?ks&?d from the group corø&ing'σf ssicium chϊtmik., cslci«m mtjate, cMduia biOmύie* c^?d«irt citrøte» cslαaxϊi fom^ϋ, a&lciu∑n ^etate, ct&ckvxt astxwrbal^ caLiasm Iac&is>
.19. '{"he n>etiod of ebiπa I J whsrda k iiie Sύfedϋ«§ «f ( 1). mά (4). the $troatiϊim is present m amounts of aβoov J .5%- so 3% by wdght
2d, TbiR xπc^feod of claim 11 wherein ifee source of strontium m procs:«s (I) tmά process (4) h select iϊmi the group Ci>a>1t«J.αg oϊ &tQi\wtn chtøide^ sέtontium niirate, stfόfiiium bromide, gttdwium ciϊr^e, sι?tmϋ«m Formate, strøβtiuπi arotaie, stϊoπdiπή ascort>sie> strontium lϋctate-, ^ro«tl'u«-)s sαll'ύtε STKΪ the mixture tirø≤ot
2L The mettwά of chim 11 wher^ic .1 % to 2% by weight of stomtia«ι t« prcaear in the r«^«jf.τng sf?!uU<?π oζpπκe*s (2),
2i 'fhe π^od of claim 11 whemtø ffie source of sirontium rn ^ocess (2) is selected f rOm δtrt>t$tiuγrj. oarbonntfe, sl«røimm ϊrydtx>xicte and \kt mixture iheimή.
23, The. mcifiod of daiϊjn 1.1 wBe^sift 0.4% to 1% hy wfή$\l oiOύύwn ss present in the resulting ^iaϊiort «£ JJJW^SSS (3)-
.
24. The method of claim 11 wherein the source of calcium in process (.3} is. selected from calcium hydroxide, calcium carbonate, calcium oxide and the mixture thereof.
.
25. The method of claim 11, wherein the final solution is dried to a powder.
.
26. An aqueous aluminium-zirconium antiperspirant active solution comprising the reaction product of;
(A)
i) a basic aluminum chloride (B AC), having the empirical formula
Al2(OgI)6-^I1I
where a is a number from about 1.2 to 2.0, in amounts of from about 10 to 50% by weight;
ii) beέaUtfs (iri«κalsyigl^!iϊ>e) in amounts of from about 2% to 1.5% by weight; and
iii) a metal ion selected from calcium, slmsatium and mixtures thereof in amounts of from about of 0.2% to 6% by wciglit;
having an SEC-HPLC Band III to Band II area ratio of at least 0,5,, having SBC-HFLC Band III plus Band II area of at least 70% of the total area and having SEC-HPL Band I content of no more than 5%;
(B) ffrom about 15% to about 40% by weight a zirconium compound of the 'formula
ZτO(OE4 αβ
wherein b is a numerical numberffrom 0 to 1 and c isd at least 1; and rthe resulting solution having from about 15 to 10% by weight betaine (trimethylglycine) and from about of 0.290 to' 5% by weight of a metal selected from calcium, strontium and
27, The antiperspirant active solution of claim.26 wherein the c for thezirconium compound is at. least 1-4,
28. The antiperspirant active solution of claim 26 wherein the betaione to zirconium molar ratio is between about 0.5 and 2.
29. The antioperpsirantt active solution of .claim 26 wherein the betaine to zirconium molar ratio is about 1.
30. The antiperspirant active solution of claim 26 wherein the MC1 ratio is from about 0.9 to about 1.7 whereM=A1+Zr.
31. The antiperspirant active solution of claim 26 wherein the M/Ci ratio is betweenabout 1 to 1.4.
32. The antiperspirant active solution of claim 26 wherein the A1/Zr ratio is 'between about 2 to about 10,
33. The antiperspirant actiuve solution of claim 26 wherein the A1-Zr composition is a
34. The antiperspirant active solution of claim 26 whereinthe A1-Zr composition is a
35. The antiperspirant active solution of claim 26 having an SEC-HPOLC Band III to Band II area ratio of at least 0.7.
36. The antioperspirant active solution of claim 26 wherein the final solution is dried to a powder.
37. A method of making an aqueous aluminium-zirconium antiperspirant active solution comprising reacting;
(A) the reaction product of: i) a basic aluminum chloride (BAC), having the empirical formula
where a is a number from about 1.2 to 2.0, in amounts of from about 10 to 50% by weight;
ii) betaine (trimethylglycine) in amounts of from about 2% to, 15% by weight and;
i ii) a meuil calcium ion selected from strontium and mixtures thereof in amounts of from about of 0.2% to 6% by weight;
having an SEC-HPLC Band III to Band II area ratio of at least 0.5 having SEC-HPLC Band III plus Band II area of at least 70% of the total area and having SEC-HPLC Band I content t»f «o 5.BOT (htin 5.%.;
(B) from about 15% to about 40% by weight a zirconium compound of formula
wherein b is a numerical number from 0 to 1 and c is at least 1; and
the resulting solution having from about 1% to 10% by weight betaine (trimethylglycine) and from about of 0.2% to 5% by weight of a metal, selected from calcium, sirontium and
38. A topical antiperspirant composition in the form of a pump apray, roll-on, lotion, cream, or gel comprising an antiperspirant.compositions according to claim 1
39. A topical antiperspirant composition in the form of a pump spray, roll-on, lotion, cream, or gel comprising an antiperspiran.compositions according to claim 2
40. A topical antiperspirant composition in theform of an aerosol, roll-on or stick comprising an antiperspirant compopsitions according to claim 10 41 Atopical antiperspirant composition in the form of a stick or roll-on comprising aτι antiperspirant compositions according to claim 36.
PCT/US2006/060512 2006-11-03 2006-11-03 Betaine with calcium and/or strontium antiperspirants WO2008063188A2 (en)

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