BE621490A - - Google Patents

Description

       

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  "Rdain * cleaning agents" *
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 This invention relates to an aen.t1tr1t containing a particular synthetic CO.-uf. cleaning agent and ionic agents to reduce tooth quality; the latter are constituted by escif; clucuMnt by: Loue fluorides or are ions a't <ill.'1 (: ux and fluoride.



  A satisfactory toothpaste should have a cosmetic effect on the teeth and the: aaâ.xrGeâ3r light colored emant a, JL1 should also have a functional effect on the teeth and the mouth, keeping them clean
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 and free of food debris, contributing sinai to, prevent tooth decay In order to achieve these two goals, it is necessary to brush your teeth with toothpaste containing a cleaning agent often called an abrasive. this cleaning agent is to aid in the removal of the very adherent film which, in many people, contains pigment in the dye in brown or yellow,

     

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 The cleaning aght should remove and film with minimum abrasion of the surrounding material. Usai! which covers a large part of the exposed aurfaaa of which this relatively hard and does not cover as much
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 of importance that the dentinet will tend more, which can be exposed by receding gums. The ideal cleaning agent is one which achieves maximum film removal with minimum dentin abrasion.



   In addition to the function devalued to a denture, to maintain the cleanliness of the mouth, it is in-
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 trtaaaat 1 \ '1 incorporate an agent acting specifically to reduce tooth decay. The work estimated by the discovery of the beneficial effect of fluoride in
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 aau food, or applied positively to dental has led to the denial to the point of toothpaste * containing fluorurea etannous. The effect of the atannous fluoride of a toothpaste of the appropriate formula in reducing 1. ' importance of caries, * been well 'tabl1. reported recently. concerning this effect have appeared in the scientific literature and are reproduced in a publication by
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 W..A. Jordan et .i.C.

   Peteraon in, 1 Ara. Dental tonoc .. 68, 42 18.5). It is believed that both the atannous ions and the fluoride ions help to prevent cavities.



  Some i.trit was also found for dentifricea containing other. inorganic fluorides than stannous fluoride and for organic fluorides, such
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 than the tydrofluorurea of ethanolactina.



   A problem recognized in the scientific literature and in patents is that of establishing the forma * le of a toothpaste in which the atannous fluoride or
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 the other ionic anti-caries agent will remain available for treatment in doubt rather than reacting with the cleaning agent. Important steps towards the solution of this problem have been fra # hias.

   Belgian patent ae 53.dDB

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 granted to William II, Nebergall dated March 3, 1859 and corresponding to British patent & * 74 S. 550 as well as a Canadian patent 573,522j indicates the improved compatibility of hot-treated calcium phosphates with fluorides, in toothpastes. The means for maintaining stannous ions in a condition making them available for reaction with teeth has been set forth in Belgian Patent No. 556,526 of March 11, 159 and the Canadian Patent Application No. 76,321 which indicates the use of a reservoir of stannous ions in the form of a slightly soluble compound.



   The preparation of a cleaning agent having a high cleaning to abrasion ratio has been discussed in
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 U.S. Patent No. 2,876,168 granted to lt.1ti ..: 33: 'og. and B.J, urabenttetter March 3, tle59, This patent shows the preparation and use of calcium pyrophoopbate has, yt.nt these properties
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 Although the progress described is eubttantlaland the opportunity still exists to improve the compatibility of the cleaning agent with ionic ingredients, such as atannamc ions and fluoride ions, and in the meantime maintain or improve the compatibility of the cleaning agent. cleaning report 1 abrasion.



   An object of this invention is to provide a
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 toothpaste in which a eubatantial amount of ions and rings and of fluoride ions do not react with the cleaning agent and therefore remain available for the treatment of the surface of the teeth during use. a further object is to provide a cleaning agent which is effective in removing dental films and which causes minimal abrasion of uentine,

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 These were thus produced in a toothpaste formula containing a highly crosslinked synthetic resin.

   polymerized, heat-cured, and substantially waterproof, which is formed into particles having a specified range of average diameters; this formula also includes a water-soluble source of fluoride * or ion * ions
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 fluorides and atannous.



  The use of synthetic resin in d8Q.41. t1rr 08. has been disclosed above and the prior art suggests a variety of thermoplastic resins. et thera!) ". curable, but does not disclose or suggest the type of particulate, highly polyneric retina used in its formulas provided herein.



   Resins suitable for use
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 in the prônent * invention are esseâtielle # entt crosslinked resins highly polymdristu8., thormod.u.rCi8.6ble, and essentially iupermeable to water, a resin thera. hardened s / sand solidifies 3ore, u'o.a lschauxi'a and can not sire remelted. This property arises from the formation of cross-links between the polymer chains during the chemical reaction which is promoted by heat or by chemical means. The polymer network. The resulting three-dimensional structure is the type of structure suitable for the buta of the invention.

   Certain plastics
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 th81'lliOdurciaaables ae softening at temperatures of about 1% * 0 * C are included in the taxwe "thermoset" used herein.



  The term "predominantly water-soluble" denotes resins which do not absorb adequate amounts of water, upon prolonged contact, such as water absorption for 24 hours. at 250 C, measured

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 according to the method of eaaai .w: I.K D, '/ O ... 67'l, is less than about 1%, The absorption dfoa, i conouit to a loJ11'l.men1;

   * t fa softens resin p, ur'ticul,: i. *, unwanted in a cleaning agent p iw Casein resins are examples of one type of thermoset pl ti <- that: L.8.bla which cannot be suitable, in ra1., One of the roof that it absorbs 1 * tau in a rôlative moorish-jiint, 4Xa'r <.1.Iea common types of réaintfa & yn1.hétitp ... thermosetting suitable for Stre employed in this invention, when. aisle are haatcmant polym.Ór1af .., 80n.'t the tiélaminant 100 resin. phenolics, urea., medirainea-urea4b cross-linked epoxides and trans-linked polyesters * 4, The last two types are generally less desireable. and some * resin4 of these types are examples of the class of thermoset 188ablea tesin which and soften.
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 to 1SO * <nvl] <on.



  The ruined theraoplaotiquetf which does not COllVie4- nout generally pa4 for this Invantion can Sire melted and roucklidifîdea in losing their property
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 original Their property., presumably a dura *
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 The lesser than gellau strength and stiffness of thermally hardened resins are such that they do not remove dental films effectively.

  pl.,. Common thermop14at.ique.e retinas are acrylic resins. laws of cof3uloaiques resins such as acetates and buty- rates, polyamides,!, 'olyét1 \ Ylà # .., polystyrenes and vinyls,
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 The highly polymerized synthetic resins
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 eeee to use C1an ,. this invention are also excepted that) posl1.bl. of fine-weight, mlecha42re and dïltàatu materials. m1'0 d'Vl'a1ant atre forttmitt pelyeKts <,

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 to present a content n1muD18n materials It * starting of low poioe maiieuialri "and a maximum of transverse bonding, The impures <'a of ta1blftl Molecular weight, canvas * than the monomer. e ,. other * starting materials, must read' Vi'W8s) cr * ... ta can react, living the. Stannous ions and the lona '., UOrur8..t.

   cause the, 1Q, already odor or ... undetectable veLU. The dilators which are u.t.i1.id. in the * pl & 4tîquen industry to conveniently <<ccrcreate> the volume of ayntbetic resin which should be <wit <Sa, due to their marked tendency to absorb or adulterate ingredients such as * that atannawc ions and / or fluorinated ions. iien exeofilee of
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 dilating materials usually used in practice
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 and which should be absent in the news. I1t11186e. in 1 * 8 components of this invention consist of flour, wood, cell sa, aobeste and mica.



  Laa resin. me14rnll'A8, the poly- m6riaetioa product of m4lam118 and formaldehyde are preferred *
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 commits cleaning agents, due to their excellent
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 physical property * and their comparison: .1b111 ti with the 1.ngr6d1ent. & loniquts, combined with an absence of a * color
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 and smell.
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  Phenolic and uric re Bina a, for example phenol-t'orm & lè4byde and urn foroalaéliyde Met
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 desirable from the point of view of physical properties and
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 compatibility. Most resins etc are d.1rt1c1 .. them to get cana a highly po1yma1'1ae state of color and all therefore desirable for the to1.:1011
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 of a white toothpaste.
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  The polyester or réI1.n, .. ld .. are the prodQ4t4 of resot4on O .., flintlC4 \ 10Q..n \ "these alcohols J) 01yI \ Ydr1qUl. And acids po] .yba.1quI .. To prepare

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 a thermoset, crosslinked, wheat polyester, a dihydric alcohol and a dibasic acid, one or more of which
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 the other or. both contain a double bond, are esterified, and the resulting unsaturated polyester then takes
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 cross-links by reaction with a # onocur * such as st.yrene..IJ Usually, a saturated aqueous alcohol, such as ethylene glycol, propylene .. glycol, 1,3- and 3. butylene glycol, di6t.hylà. ': Glycol and dipropylene glycol, with an unsaturated d3 aa.çra acid, such as maleic or lucid anhydride 1uw ..:. RiqJ.a.



  The polymerizable monomer can be styrene, vinyl toluene, alljrle phthalate. Lî: mel: ha <; methylate or cyanuraly ClEt 'r.riallyl, Cil .t .: 1se heat or a peroxide catalyst, alone or fine COn.'. 1 naiaol1, for
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 cause polymerization.
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  Epoxy resins are made by reacting epichlorobydrina with hydric cocpO3 <S po3, such as diphenol $ and; rctla. The resulting polymers prejunsnt C1as t.ranavoara ±! .Lu4 bonds to form thi r.aodtirci8sableat resins by direct rtSao1.ion between ClpOxyC1E1U groups, bond "(1 epoxy groups with aroUll.1t1quRr hydroxyls or.:,!) B .ït1 "ue8 art. trl \ Il8V4ir8ale link with agents. of tra1tt.Jt \ ': Ü .. through various radicals.

   The most common cross-linked agents are the primary and secondary amines p (\ l.; Rfo.o.c: n: .iQl) - nelleeg and d: nasic acids
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 or acid anhydrides.
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 The low olecular starting materials of the retdnes described above are polym.l :: S8. in pure co # racial practice tav :: 3.sva reactions by heat, with or without a catalyst ,. In pratips, we sometimes use pressure in wi taa te-qis que lu c :. their

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 during polymerization, ctana ctana the molding operation.

   The highest degree of polymerization of a real does not meet in molding practice that obtained when a resin is used in a coiling process involving high temperatures and high pressures.
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 applied for several minutes to the tool, the wetting of re-elected without the use of dilator. would not be in the face in commercial practice,
It has been found that the resins used as cleaning agents in the compositions of this invention
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 tion should Sire ex3,

  paste of dilator and be polymerized. teens in a 4-stage. The polymerization of the paint achieved in practice, the commercially processed resins, m3me without expanding, do not have the cleanability and the cony. Desired ionic tibllit for toothpastes containing fluorides. Commercial treatments do not cause the high degrees of transverse bonding,

   nor the reduction of materials
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 starting residuals at low weight which are ta * estiola to obtain these properties
The resinous cleaning agents used here should undergo heat curing, for
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 a period of time measured in heurang 4 of? temperature ranging from about 1000 Z 'to about 1800 C, in order to obtain the desired properties. Optimum temperatures vary with the resin, but should be sufficient to pro-
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 voquar the polymerization without sarboniuer this one.

   For example, the conditions cte pol, mdrx8ation at the pressure a-Uuoephér.Lque can range from me lieia% e to 100 - 120B C for polyesters, to 16 .. 2-1 -or to 150 - 165 * C 'for les ruins nyZamins Polymerization, ionic compatibility and effectiveness of don rinea Uuguenteil

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 ax even teipa as the harsh art lt treatment temperature.



  Increases in increased polymerization rate are obtained with higher temperatures! greater treatment than with longer treatment times. your treatment time is always substantially longer than the polymerization times recognized in commercial molding practice.
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 A certain degree of polymerization can Ztr. made with an acid and is especially useful for melanin-formaldehyde resins, urea-fermai-ddbyde resins and melamine-ur4e-tormalde resins, but additional heat polymerization is required.

   Acid polymerization is accomplished by adding an acid, usually a strong acid such as HNO4, to the starting material at low molecular weight in water. The polymerization is pushed to a temperature below the boiling point of the solution,
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 The high degree of hot polymerization known to obtain the resinous cleaning agents of this invention impart to the resins an extreme brittleness stiffness (low degree of impact resistance).



  Such a property would be undesirable in any of the conventional uses of resins, such as in the
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 molding; therefore, in these cases, a high degree of polymerization was avoided, - however, in 1
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 resinous cleaning of the present invention, brittleness is highly desirable, since it is apparently the basis of the remarkable cleaning ability of the resins as well as an indicator of the high degree of polish.
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 lymerization which causes an excellent ionic compatibility.



   Hot polymerization of resins from

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 should be carried out at an empératurs 1 during a tflt1; "sufficient to obtain a comparison; 1bil 'J' ionic slow * to the compatibility of an atamuux ion not less than about 30%, determined by the test one hour described
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 LaaBËHX below in Example 1. Comp.) 111t "is also an indicator of cleaning efficiency and fluoride ion cul patibility. Tanning compatibility is the most severe test of the fluoride ion. degree of polymerization, since when this compatibility is helpful, the latter properties are less so.



   11. And required that the resinous cleaning agent be in the form of a particle. If it has been prepared in bulk, it can be reduced to the desired particle size, as discussed in detail below, by
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 Conventional grinding processes can be used with ball hammer mills and tube mills to grind highly crosslinked resins.

   The final hot treatment can be followed by grinding and it is desirable to grind before the hot treatment, in order to decrease the time required to reach the high degree of heat.
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 Polymerization required the resin is in the form of particles having the particle size distribution. delirium. during final hot polymerization and if the desired particle size is not disturbed during singing. final rage, final grinding is not necessary.



   An indication of the types of thermo-resins
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 ourc1ssable. suitable for use in this invention has been given. As long as the renin meets the other stated requirements, i.e. be impermeable
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 to water, exhibit cross-links and be ther. mcdurc1saabltt the .x.aott component of the resin, as long as it is highly polymerized, has little effect on

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    acts as a compatible cleaning agent in the dentifrices of this invention.

   Commercially available materials in different stages of polymerization may be suitable by subjecting them to further polymerization as described above. Specific resins suitable for use in this invention and their mode of treatment are given in the following example *.



   The resinous cleaning agents are compo.
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 Larger particles tend to give a aabl4 feel in the mouth and stick between the teeth, it is desirable that the average diameter of the particles are essentially all smaller than microns. particles of cleaning agents re aituo between about 5 microns and about 40 adore and, '; the meadow.
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 ftfrence, between S and 80 m1Cro :: l8, seen * from a; fi't'1'14 "4; l1. ' optimal, ie preferably, no more than the * in P:!. (111: '1.0.



  Particles have a diameter less than one micron a.V1.Q .. few finer particles are relatively ineffective for cleaning teeth and the proportion of firm is
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 401 \ 0 limited. By particle 'is meant aggregates * as well as individual particles. One might assume that I.l8ule. particles * with edges * t with sharp corners cent & tftlcboeu to remove the dental film ,.



  However, it was found that coarse spherical culture. and aggregates thereof also serve as an effective cleaning agent. The .18UlGT.r '"of evoked particle;. Here was determined by micI'08oopiquee wear. Or using a caliber eyepiece.



  Fluorine is an essential component of the toothpastes of this invention, which may be provided by a component of any fluorine inof1 \: n:; it ', 1Zlu-

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 b181 .. in water, which gives fluoride ions on contact with water. The term “offensive compound” is understood to mean * a compound which is not: & .. n4a1rabl'W8: lt. toxic, so * - colored or whose use in a toothpaste does not
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 not encounter any other objections.

   Many water-soluble inorganic salts are useful sources.
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 properties of fluoride ions Among these, we can mention sodium and potassium fluorides which IOnt 4cono # 1 .....
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 than. and possess desirable properties *, Examples
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 other fluorides to -proprideg are 4 '.mollita fluoride, 1! YJium fluoride that is to say ln *' 3 palladium fluoride, 01 * 6t, -fau rua $ ferrous fluoride, lithijm fluoride and mixtures of cmtX-ci. Male cotsplexes containing fluorides tt soluble in water, such as tluoros1licatee that is to say Na2U'6J the fluorosirconatea, that is to say Naazrr6, IGZr'g! the t1uQI'Oa-qn.tlÎ1: ... o '..1:

  , .. ".. cu, r8 xsalb the fluoroboratea, that is to say Na'4, and the fluorotitanatea are also suitable for use in toothpastes of this kind.
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 invention. Mixtures of fluorides can also be used. Preferred water-soluble inorganic fluorides are those which also contain
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 stannous ions, as they belong to both the beneficial effects of fluoride and stanrux ions, examples of suitable stannous fluorides are stannous fluoride itself, mixed stannous halides, such as 6nCIr and ClF3 and fluoroatar. nitez, It also comes within the framework of this
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 invention to provide atannous ions from a compound
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 posed other than 'a fluor are. uses soluble stannous compound.

   

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 in water which may be suitable are thlolgimit and nitrates. An i: nnt ùoltiblt tin reservoir can be provided, as in the English patent na i.3 cited above, but it is not necessary due to the compatibility of the resinous Y4ge agent, it is not necessary. the fa.cxarurl ion does not need to be supplied to the inorganic sol ,. It can come from any organic fluoride soluble in water, at least which dissociates to give fluoride ions = eu on contact * with water. Fluoride ions * can also be called
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 worn by must organic bydrotluorure8. 1 * Suitable amine fluorides disclosed in Canadian Patent No. 6.D68 (P1rl.11p Jiutavorn.

   et Consort, c. July 1, M57) are the hydronuoride8, de mono- di and tr1Qtl'.anoL18. these compounds may also be cited as the corresponding ethanol ammonium fluorides, other useful organic ras fluors and α-hydrofluorides have been disclosed in a publication by H, Hublemann et al., of Helvetica Odontology * Acta> Vol. 10 no 2, page '3t 16?),
The essential ingredients of the toothpaste * of this invention can be combined into a number of cosmetically acceptable elm. They can for example be combined in the form of a pouar * or a paste.

   In formulating the finished toothpaste, it is desirable to employ only auxiliary agents.
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 which do not precipitate, combine or otherwise react with the biannous ions or the fluoride ions, thus reducing the advantage provided by the net agent.
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 compatible resinous toyage, Some loss of stannous io; * 8 is probably inevitable due to the oxida-
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 brand and slow hydrolysis .. tea pasta 4eJ1't.it'r1o'l oon1.:i.en.naat. of t1.Ib3. kill.

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 a humectant, a tIIOl.1elan1 ;. ua binder, a softener art a perfume, in addition to a f. \ t8nt. of cleaning. ijkion fluoride u3me. is ooupatible via the auxiliary * ingredient * of the toothpaste usually used therein.

   If the et.aM8WC ion is also present, these ingredients * must be: .. of prot'Ó1 "8tJ.CQ, to be chosen with great care, Glycerin and sorbitol are * hU! 1wctanta cota" patiblea with the .tann8 \ & x ion. Hanta of a non-ionic character are preferred because generally the most common are the hydroxyethyl cellulose and the high molecular weight poly4tb31ene oxide.

   Nonionic and cationic detergents are coffl- tiC.aa agents. Suitable nonionics include sugar monolurrte .. and alcohol clearing products ddeJ11qU6 with 1 - w moles of wave. of ettyltne, 1it) to the cut of aromatic oil * used conciundraant mont coccprt3blsa with the stannous ion naturally, have the i3
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 gredient is present in relatively small amount pure
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 compared to the atannous ion, its COmpat.1bi11 't-i is less healthy and we can enyi841g8r the use of: Lnr1ent ..
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 auxiliary * habit, Bide, stannous ions must Sire present * dana
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 toothpaste, like this 4 ra, e these in the form of a sheave. A preferred embodiment of this invention, they are used in an amount of about 10 ppm to about z ppm. about.

   The
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 about
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 preferred proportion is .0lppc h tCOO ppn. about,
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 since it is not necessary to provide an amount to react with the cleaning agent. The * Fluoride ions * are
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 present in a higher proportion as ppm so and..t- t, tir.11 '"the desire effect ** It'1 has little advantage to have more than 4000 ppm 4'lona flu01" U: rt1 present tto of prlf: jQ! the proportion of flueiuret will go from tito ppat approximately ²500 P18

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 about. Pane toothpaste, cleaning agent
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 will constitute "about 0% to about 00 of the composition.



  The proportion will preferably be e 30 i) about to. About 40% of the composition, or a tempting powder, higher proportions of cleaning agents are used and this can reach about 65%. typical humectants, softeners, binders, a4uàq- santa and perfume are illustrated in the 4l.11.e!
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 citiques,
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 He wanted Ole d * a 1ua-wer the pH C (t .3.a, paste in the optimal proportions ** indicated i ... prè8 "The 'acids chosen for 3.'; J; xa'e.nent dt pis. ton :. ctea strong acids or, preferably, due to weak acids, m. preferen- tially, they do not ôoiran-fe nas Sire <3e fona èq, ueat.1; oa.nta. el ': Lana s't 'f, U1r18UX. if the h, in must be taken into the cO';: OS3. tion.



  Examples of these weakened acids are: 4iaea sucéti. than. t chloroPI'oP1o, n1que. me Ionic, -roiuaque #: tumax, 4que # métl1Oxy .. & ceUque et pl'Op: ioI1J.que ..



  The pH of the brewing pastes of this invention is greater than about 3 years and less.



  PH values below 3 are not effective for oral 81Iloi and cause hydrolyno problems of some of the ingredients in the p'II as well as corrosion problems of the containers. metallic. When due. lona sttnnsux are present, the pH should preferably be less than 5.

   In the absence of a complexing agent stronger than the fluûrurea, the ion atanneus1. rushed under the hydrated tannous oxide taroli with more elevated fold dell. have worked \ 1na. such as # .elaillJ.lles, which posaeaent a natural alkalinity are euployi5eu eo.4na aìent ae cleanuac, the neutralization of the resins should n 'f: 1ffctlGr before associating them with the 6túl1l1.UX ions .. a balance t, HltriJ the properties deairéee by the cozlbc.:. c, teuz and. ' e'i'x Lac, is obtained in the pH gaorae pl. ± t: l'is, I ": l.a ':

  <.1't. 3rd in-

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 around 6. when stannous ions are absent. the preferred pH value is somewhat higher and ranges from about s 5 to about 7, it is necessary to ensure that the toothpaste does not attack the teeth
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 Lower values of the pure are safer in the presence of stannous iona than in their absence. Lower pHs are generally preferred to be. ions as m6t1 heavy tala that da inctiua ions are presenta Laya resins mentioned in this eX4alf \) are ceeentielleuent all dss rhinea impenneable8 to water, crosslinked, tberroodu.cio88blee strong gold, .4 * ment polymerized, suitable to be used in the toothpastes of this invention.

   These resins were obtained from their manufacturers
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 and pOlym: r.16t: t.lS more up to .. a High degree, The recor.u..ndat1ona of the manufacturers are generally followed, with regard to the teuipuraturea of po1ynubi.8ation and the proportions of the ingredients. However, a substantial additional period of heating was used to induce a high degree of polymerization.

   The treatment applied to each resin is shown in the table,
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 : 1.'01.11.18 the resins were tested to verify the pos. sensitivity of their use in toothpaste,
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 The compatibility of these reactions with fluoride is very high, that is to say that it produces only a very slow reaction of the fluoride ion with the resins and very little d '[ .orpt1on marked by it, in particular pa, rt: Or; paI'a: 1COn with calcium pyrophosphate, the preferred abrasive used so far with fluoride, The compatibility with the stannous ion varies somewhat and is shown in the table.

   These results were obtained
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 by forming a purticu resin whore tool: teb with a

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 EMI17.1
 solution this has stannal fluoride and measured as much of the tanning ion in solution after three periods of the test. The results were obtained on an ocellum established by mixing 10 g of resin in particles with 80 c! l of 0 solution. , 1 z, 3) 3iT3t ** temperature s: bi.az. * 4rès
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 one hour, a sample of the supernatant liquid was analyzed.
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 lysed for the stanous ion and the percentrgô fat calculated pure compared to that present at the origin. Use test and beaū, more severe blow which the existing conditions,. Has a pat * toothpaste, due to the dilution of the 94te and (the
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 the absence of non-aqueous ingredients *.

   A scale arbi-
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 milking used is the following t 0-30, poor j 40, 3'r pasah3.e, W - 90%; to good; and SO - 10C% pe% - elleat, Cal3i pyrophosphate (I examined in this so rigorous you rate it "poor although it is the preferred abrasive used iuj3qalî0l with tin.



  The ability of the resin to be cleaned was% J- ri: ri4 p-ir a ncrriial test described in the African patent.? 6 ... 68 cited above, the application 1 removes a film of lacquer from a block plastic. The results were obtained. reported on a scale of 1 to 10, in which a classic cleaning agent for toothpastes, calcium phosphate didrats, has 3.ats 5 and? .e calciua pyrophosphate: with high power n, ttayat has the dimension approximate esb to 9.
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  An estimate of the abrasion ability
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 compared to that of yrxap2..sp1-.at.e of calcium with strong cleaning power but with abrasive power this data. The lab aid to co-repair the abrasion ability of these powders is to measure the weight loss of a mechanically brushed lead strip, under standardized conditions, with resin powder.

   Ua e * .-

 <Desc / Clms Page number 18>

 
 EMI18.1
 8a1 realistic, hardworking hand, iwp: t.; I.quant. the mechanical broatiage of riC11oaotiviè tontine from untreated denta hmnainea such as q. described in US Patent 8.3Y6V168 above was used for certain samples where indicated. Instead of calculating a value
 EMI18.2
 d ', abraeior as was done in the cited reference. the mieragrams of dentin removed by ICO double yard ... with the cleaning agent of the test are simply compared with the same figure for a normal sample of
 EMI18.3
 Calcium pyrophosphate with a high cleaning to abrasion ratio.

   These values for Ion two samples indicated in the table and the thieves for control have the following t
 EMI18.4
 C9 1) 111 DX21TIn.



   << t * <. # ***. <- #### *. ### <* # XHt.



  ! té a: 1ne A 70 Maint B ti0 CAP07 1lS - 150-
 EMI18.5
 * other data relating to 1abrar.an of obtained obtained * on resinous cleaning agents suitable for use in this invention are
 EMI18.6
 sheave. eî-deanous. Wout are suitable for film removal and compatible with non-tan and fluoride ions, the starting materials are further identified in the accompanying table.
 EMI18.7
 



  Niem 1'ra1't8ment JJ1ameter Abraaion da dentine Commercial, particle and culcs Sample Cage Y3cro EchtúL1: .1Uon 31 'al 4Ot. Heating 4:30 p.m. (medium) ttO-HS 95-180 .. 1608C Pul-
 EMI18.8
 
<tb> Go-Sizer,
<tb>
<tb> sifted
<tb>
 
 EMI18.9
 Cymel 404S Chauffa 16H 30 ma '/ 81Ul8 ta 130 II. 160, rulv ....
 EMI18.10
 
<tb>



  Sizer
<tb>
<tb> Tanized
<tb>
 

 <Desc / Clms Page number 19>

 
 EMI19.1
 Rosimene Heated. 4:00 p.m. 30 (average) 40 115
 EMI19.2
 
<tb> 817 <SEP> 150 C, <SEP> Spray-
<tb>
<tb> Sizer, <SEP> siege
<tb>
 
 EMI19.3
 ceutl 404 R Heated to 10 (maximum) 10-20 115
 EMI19.4
 
<tb> 150 C, <SEP> the <SEP> trac-
<tb>
<tb> tion <SEP> Lower
<tb>
<tb> to <SEP> 10 <SEP> microns
<tb>
<tb> separate <SEP> elec-
<tb>
 
 EMI19.5
 trostatically.



   In the tests disclosed here, it was not convenient to reduce the particle size of the resins indicated as having an average particle diameter of 75 ner
 EMI19.6
 micron. for the ram'a / inside the limits which eliminate the oenaatï, 3n of sand, in the. mouth, '. However, the results of the compatibility tests are not
 EMI19.7
 factéa appreciably e.t, a good estimate of. cleaning and abrasion can be done, the data in the appended table cited in the title "properties of the finished resin" are provided.
 EMI19.8
 by the manufacturer, These data are usually obtained * #:

   by the AS3U Test process: p 89t for 2.1 6C180J'PUOn,. * at $ mas for hardness and D695 for co-pressure resistance, hence the cleaning efficiency should individual samples vary from "very poor" to -much better "than a conventional abrasive for toothpastes, the compatibility with fluoride and tin was remarkable and in most samples, the abra-
 EMI19.9
 Zion is lower than that of C "" "pyrophoephate, which is commonly chosen for its high cleaning to abrasion ratio, EXAMPLE 11.
 EMI19.10
 Ira brightening toothpaste was prepared:

   
 EMI19.11
 Fluoride from trit'hat.olatm1Onian. 1.7 (tom ppm k "O bas4 on the coaposi-
 EMI19.12
 
<tb> tion <SEP> -total)
<tb>
<tb> Saccharin <SEP> 0.12
<tb>
 

 <Desc / Clms Page number 20>

 
 EMI20.1
 
<tb> Sorbitol <SEP> 20
<tb>
<tb> Glycerina <SEP> 10
<tb>
 
 EMI20.2
 Coco monoglyedroisultoi * t * de
 EMI20.3
 
<tb> sodium <SEP> osai
<tb>
<tb> Coco <SEP> sulfate <SEP> of <SEP> sodium <SEP> 0.70
<tb>
 
 EMI20.4
 Melamine resin ...: rormaldéqd8 (specified below) 35 ydroj <yMttylcal3.ulose 116
 EMI20.5
 
<tb> perfume <SEP> 0.85
<tb>
<tb> <SEP> distilled water <SEP> solda
<tb>
 
 EMI20.6
 The viscosity of an 8% solution at ZOO C is * iG # 125 centipoieea, using Braokfield's # 8 spindle at 30 rpm.



   This paste, of good consistency, has a final pK of 6.52.



   The melamine formaldehyde resin used
 EMI20.7
 was Qymel 404E * The manufacturer's rogue powder was ground with dry glice in a âdikro-Pulv îx4r (typa (W); the part4cuIO4 that passed through a chipmunk in 32S mesh a were removed and cbau: f: d * 4 % for 16 baurte at 1600 C. The powder was again sprayed with the micro pulverizer. The average particle diameter was
 EMI20.8
 30 - 40 microns; monk of 10 14 of the powder were smaller than one micron, there was substantially no particle larger than bO microns.



   The resinous cleaning agent did not react with or absorb the fluoride ion strongly.



  The effectiveness of this toothpaste in reducing the attack of acids on the teeth in a biological environment was great. The toothpaste cleaning rating obtained in the standard test was 10.
 EMI20.9
 



  JD # UE l1. vL p 1 The following toothpaste was prepared and

 <Desc / Clms Page number 21>

 it was found that it had a desirable consistency and advantageous properties in use; in other words, the resinous cleaning agent did not give the sandy feel and was well suited to removing dental film.
 EMI21.1
 
<tb>
<tb>
 
 EMI21.2
 



  Fitioruro etaaneux (1070 ppm! R '3900 ppm Sa) 0.44 Saccharin 0.30 Mojmmyriatattt of sucroree 125
 EMI21.3
 
<tb> Perfume <SEP> 0.5
<tb>
<tb> Glycerin <SEP> 25
<tb>
 
 EMI21.4
 Hydroxy4ttylc <tlluloaa (see example II) St Résina melamina-fomaldébyûe (specified below) 37
 EMI21.5
 
<tb> Water <SEP> Balance
<tb>
 
 EMI21.6
 The 1'4, sÎU'b J11elamine-tomaldeb; yde wax prepared by the. faction of 3 mole. of formaldehyde per mole of melanin and the polymerization was carried out to a high degree of progress. The polymer was then acidified
 EMI21.7
 up to a ph. from - 6 --- and. the resulting solid treated for 16 hours at 75 C.

   The solid was then crushed into a
 EMI21.8
 Pulva-Sizer impact crusher (pulverizer) and heated during; hours at 11 Ce The resulting material) aprea grinding for three days in a ball mill,
 EMI21.9
 had an average particle tx .... stre of 10 microns; less than 10% were less than one micron and significantly
 EMI21.10
 no particle had a diameter greater than ± 0 ederona.



   The toothpaste was stored at room temperature and samples taken periodically diluted at 3 parts water to 1 part toothpaste and the available stannous tin was determined. The results obtained are given below.

 <Desc / Clms Page number 22>

 
 EMI22.1
 i'e # pa, a! 0! l't'1! t sn remaining
 EMI22.2
 
<tb> 10 <SEP> 55
<tb>
<tb>
<tb> 21 <SEP> 47
<tb>
<tb> 50 <SEP> 49
<tb>
 
 EMI22.3
 The tluoride ion does not undergo Iss (11UIl18ua.m; .. UQ does not leave at èl18p0n1bU'U during this t.emp8.

   This ..... 1.10r that it is continued for io days more is atQ.8.i severe than the 8s81 compatibility of the <! Ttinp <Nd * nt one hour described in the 'exem3.e Le, EXS.! PU5 IV.- The following toothpaste * fat pr-4.p #, sheave and one conatata that it had a good consistency.
 EMI22.4
 Stannous fluoride (1000 pipa bzz t 3OOo flat Sn) 0.40
 EMI22.5
 
<tb> Saccharin <SEP> 0.20
<tb>
<tb> Colorant <SEP> 1.7
<tb>
<tb> Part = <SEP> 0.5
<tb>
<tb> Glycerin <SEP> 24
<tb>
 
 EMI22.6
 Hydroxyet.l: \ YlaeUuloa8 (see x inpl 11) ài Resin roé1amine formalàéqyà8 (specified below) -t4 -
 EMI22.7
 
<tb> Water <SEP> boldo
<tb>
 
A solution of Regiment 817, a melamine-formaldehyde resin, was fixed to the acid by means of nitric aid at 60 C.

   The resulting solid was dried heated
 EMI22.8
 at 110. C for 16 bU1 then ground in a ball mill for 16 hours, The average particle diameter was 6.t 1 micron, Jls8811Uuo no particles had. a diameter greater than 10 micro = and the poumen targe in weight of particles less than one micron was tnt4rieur z 10 If U84 p4rtl4uzel oboirvdn ioui the = 0101- ddpî appears todüt itO * .1.rtn ephr1.qu ...

 <Desc / Clms Page number 23>

 
 EMI23.1
 



  The pbt of this toothpaste was. (the 3toe <, m toothpaste cleaned well, giving. in the normal test a cleaning rating of fi, S, The abrasive capacity
 EMI23.2
 the dough was sufficiently reduced,
 EMI23.3
 EXAMPLE V ... Renin 3? Q-1 was obtained from faoncant (Union Carbide Plasties C.) as a po \ 10. coarse, light buff which had been heat treated for 16 hours at 1100 C. It is a ree, iriphralde1, ytie modified by an amina. The powder was hardened with dry ice, pulverized in a Fulva..S1zer mill and sieved, 1 diameter da prti .., average was about 30 microns and it was essentially none. particle with a diameter of # rxaur # ho microns; less than 10 ? smaller spreading particles
 EMI23.4
 than a micron.
 EMI23.5
 



  The radioactive dentin abrasion report showed that the resinous particles swallowing abrasion approximately equal to that of calcium pyrophosphate. tira odds of $ 7 15 t'ut obtained in the rwttoyugti test, The resin l) hénol-ala.éde lXt) d: 1.t'i.a by a * wedge * proved to be highly costly with lea ions
 EMI23.6
 atannals of a toothpaste of the following composition.



  The resin is also compatible with fluoride.
 EMI23.7
 



  9'r Stannous fluoride (1000 para. Ï 3000 pou Sa + * 0.40. Perfume .50 Saccarine. C.



  Colourant I. '. Q0 droxyÓt1Vl cellulose (see example li.) 2.fez10 Glycerin ..8. CO Particles of phenol resin 1; 1cléhJae modified by a divine (material prpbr6 as above) 6.CO Water, '... "1 V..LA1 y7,

 <Desc / Clms Page number 24>

   Tin. remaining available after 5 days.
 EMI24.1
 next held them (i (.. c: r J: t.8 in example ill, fat found equal to 81% The tin remaining harsh * there Day. was 74%.



   Toothpastes whose formula con-
 EMI24.2
 holds the resinous cleaning agent described in the first paragraph of this example cleans the dental film effectively and maintains. available stannous ions and fluorides.
 EMI24.3
 
<tb>



  Property * <SEP> of <SEP> the <SEP> resin <SEP> ends
<tb>
 
 EMI24.4
 Brand & manufacturer J) t8, ript.ion du Absorption Hardness jhëaiateuscw product of water t: 5 *,, t (ockwe1J ,. at U4 hours compression FOra.tAWEIr1DZ. * KH /) Btti <i ..... .......... J. V P "L 17VV ..........



  1ttlsima.ne 817 Soluble powder Honaanto Cn9mical by atomization fla-
 EMI24.5
 
<tb> Company <SEP> bricked <SEP> following <SEP> on
<tb>
<tb>
<tb> proceed <SEP> described <SEP> in
<tb>
<tb> the <SEP> US <SEP> patent
<tb>
 
 EMI24.6
 '' 485.08 Uymel 404R Material, of soft7 aga American Cyanamid granular fJ, 3 'O, b; 6 11.0 ü8.i..7., Eü Cymel 06, Amer! Can Oyanamid C. Soluble powder tJ.2S PHErtOL- FORALDËHYD, Resin born 71 11arblett.e Corp. Retina to flow 4, ütt MCMSO '. 1 "Union Resin 1 <pheno11qujj) diaCarbiaa; Laotian paraaole ciana l'fire,
 EMI24.7
 
<tb> C <SEP> to <SEP> strong <SEP> content <SEP> in <SEP> t'or ..
<tb>
 
 EMI24.8
 n.adhyde, alkaline concieilsatioa agent,
 EMI24.9
 
<tb> type <SEP> disclosed <SEP> in <SEP> on
<tb>
 
 EMI24.10
 patent Lur.l.Jr1ce: in a.ieo.672 Resin B.

   Union 'riI: lél.or \ ylolph':. 1lOl in J.Q93 Carbide YlastiGe solu 1; .10.1. é.qi1UDe at t4,
 EMI24.11
 
<tb> C <SEP> retort <SEP> described <SEP> in <SEP> on
<tb>
<tb> bravet <SEP> African <SEP> n
<tb>
 
 EMI24.12
 3:, szsia.; I7
 EMI24.13
 
<tb> (Resin <SEP> A <SEP> and <SEP> resin <SEP> B <SEP> not <SEP> are <SEP> not <SEP> of
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> marks deposited)
<tb>
 
 EMI24.14
 U?, W ;, F ', I ,, i3ß: ï Y1 r a co n 360 will need Alliai n:; 60 P.hldr
 EMI24.15
 
<tb> Corp.
<tb>
 

 <Desc / Clms Page number 25>

 
 EMI25.1
 
<tb> '
<tb>
 
 EMI25.2
 Properties! S the finite hdaine W -wW rw, rml-a.W l, wrrwrmri, mw., R-w 'arque 4 manufacturer nieeeript, 3n of the product Absorption curity héaiataooa of water 2569 eockwell at a4 hours co - preaulon
 EMI25.3
 
<tb> kg / mm2
<tb>
 
 EMI25.4
 .u RU-Uu ... W.1.1 # -lo'Ola.! It.LUEHY'u;

  C # - rrT Will. | |. | , ... ¯ ¯ .- .. # .. - .l rt-A- J.cI "" l1 \ li ........ tJ. [1I ': Expert resin * "physical mixture of retell rntale iansanto aimane 817 and dUiF71: r.El11lical C. which is a powdery ta-
 EMI25.5
 
<tb> bricked <SEP> following <SEP> the <SEP> pro-
<tb>
<tb>
<tb> assigned <SEP> described <SEP> in <SEP> on
<tb>
<tb> US <SEP> patent <SEP> n
<tb>
 
 EMI25.6
 S! .48a.OS9, Mauf que
 EMI25.7
 
<tb> urea <SEP> replaces <SEP> the
<tb>
<tb> melamine.
<tb>
<tb>



  POLYESTERS <SEP> j
<tb>
 
 EMI25.8
 Balaotroa 6003 "Fluid Toine with 0.3 K1.10 16.17
 EMI25.9
 
<tb> Pittaburgh <SEP> flat * <SEP> 34 <SEP>% <SEP> of <SEP> styrene <SEP> M115 <SEP> @
<tb> Qlass <SEP> C.
<tb>



  Aropol <SEP> 7120 <SEP> Archer <SEP> Ré <SEP> eine <SEP> fluid <SEP> with <SEP>.
<tb>
 
 EMI25.10
 Janie3a llidland GO * 33% styrene
 EMI25.11
 
<tb> EPOXIDE
<tb>
<tb>
<tb> Reaiwold <SEP> n <SEP> 101 <SEP> Fluid <SEP> resin
<tb>
 
 EMI25.12
 Hww i1.6r Cy.



  Marked i're1tement. product diameter Cleaning Abrasion Compatt--
 EMI25.13
 
<tb> medium <SEP> ap- <SEP> bility
<tb>
<tb>
<tb>
<tb> proximate <SEP> with <SEP> Sa ** <SEP> @
<tb>
<tb>
<tb>
<tb> of the <SEP> parti-
<tb>
<tb>
<tb> culas
<tb>
 
 EMI25.14
 R1! J \ LD8 Heaimene Heat at, 15O * C; a0 it infériez- iâxcellen- 817 crushed in a Pulvs- rete (100%)
 EMI25.15
 
<tb> Sizer; <SEP> reheated <SEP> 16H
<tb> to <SEP> 150 <SEP> C; <SEP> sifted
<tb>
 
 EMI25.16
 Cymel 4C4R Ground in a crusher 75 6 Equals 3.xCel3 in <hammer heymorY3 .. te (100):

   Heat 11l to 165 ', sieve. 'Cymel 405 Heat 16H at .b0 C, 30 1 lower - Yssab7.a
 EMI25.17
 
<tb> crushed <SEP> in <SEP> a <SEP> Pulva- <SEP> re <SEP> (56)
<tb>
<tb> Si; er <SEP> reheated <SEP> 16H
<tb>
<tb> to <SEP> 150 <SEP> C, <SEP> sifted
<tb>
 

 <Desc / Clms Page number 26>

 
 EMI26.1
 The first brand of the Product = yen 1) iameter ap- lqe +, toyr, g4, Abrasion tb'.oimt raximative with the parti-
 EMI26.2
 
<tb> cules
<tb>
 
 EMI26.3
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯PUBSCL-POiJmS ######## - #############! heins .4daine and accelerated 76 y "Inferred i: 3coe.a.ec1 tor 342 mixda (10ego) rrrut'fr 4Fi at 100 C;

   
 EMI26.4
 
<tb> crushed <SEP> in <SEP> a <SEP> crusher
<tb>
 
 EMI26.5
 with hammer itaymondt chipmunk itdaine A Heats * one hour 160 * Ci crushed with pgace oache passable Pu2va-rixsr tatnlaél 30 (eu) Raias '4 Heated $ one hour at î, 44irieu- good 1600 crushed with re' (Ossaï laat aèohe radio * * - dlglao .. tir) pulvSir, ÛH.r11t1EAL = ir7.aekott 3 parts melan8ra 30 Fair Safe with 2 parts water; heat 16H 105 ° C;
 EMI26.6
 
<tb> crushed <SEP> with <SEP> from <SEP> the
<tb>
 
 EMI26.7
 aceha ice in a '., V \\ Raymond hammer mill; siege XIREE MEUÙOM VQMMLSiSlW32 xed,. with, HI dry ;, 90 g lower- rkxcelltn- 4b, autri for 16E (10clo) aN 3.10 * 0; ground with Pulva-Sizar rOUTE3TER3 ¯¯ #### 8 lectrott Heated 3H 4 16S-C; lis i féri u. cjUjJj <) C03 pulverized <m crusher.! ##. * # bzz BayOnd hammers; Heat Arapol for 3 hours at 1656 C;

   lis infër3s cat3.ls 7120 pulveritu grinder re * # aw * / a atarteaux raymond; entered R siw I4 Heated 211-156 C; 75 re 101 crushed in a crusher at 't7 jMrtMuRaysoTt &;
 EMI26.8
 
<tb> sifted
<tb>



    

Claims (1)

EMI27.1 -KNVSNDICATO Hf,. 1, - Toothpaste capable of removing plaque dental film * with minimum abrasion from exposed tooth surfaces and in which the cleaning agent is compatible with ionic ingredients, characterized in that he confidently increased by about 20% by weight EMI27.2 of a crosslinked, highly polymerized, thermosetting, substantially water-impermeable resin, preferring the particle size a having a diameter of EMI27.3 Average ranging from approximately b microns to <t0 microns approximately, essentially all of these particles having a diameter of less than about 0 microns and more than 10? about by weight of these particles having a diameter of less than 1 micron, and from about 25 ppm to * (> 00 ppa, about fluoride ions, supplied by a water soluble fluoride. 8. Toothpaste according to claim 1, EMI27.4 characterized in that the. synthetic resin is U.Wà rd4lus ûtlaui.Lna'a. ox plaJ.4 Gjitâ 8 3 - Itentifrice according to claim 1, characterized in that the soluble fluoride d <ne Il iau is a stannous salt. 4.- Toothpaste capable of removing plaque dental filas, with minimum abrasion of, * exposed tooth surfaces and in which the cleaning agent is compatible with ionic ingredients, EMI27.5 Characterized in that it contains from about 20% L to about 0% of a strong cross-linked resin: a ;; -t. polymdrj.- adee thermoo'urcisable, essentially captive to water, rraeni.anaoua the form of particles having in average diameter ... LGN4 of about & microns to about 20 cli-crona, <Desc / Clms Page number 28> substantially all of those particles having a diameter of less than about 50 microns and not more than EMI28.1 About 10 years. poiàr of those particles having a d1a # è. less than one micron, from about 25 pak to about e.500 ppm of fluoride ions, supplied by a water soluble salt. and water, the pH of this toothpaste ranging from about 4.5 to about 7. 5.- Toothpaste according to claim 4, characterized in that the synthetic resin is a EMI28.2 melamine resin1nA.fo: mwld'bVde. 6. Toothpaste capable of removing coated dental films, with minimum abrasion of the exposed areas of the tooth and in which the cleaning agent is compatible with the ionic ingredients, EMI28.3 characterized in that it confides from about to about 30% by weight of a crosslinked synthetic resin ** tOI ". J.1Aüab1e to water, appearing to fuzz the t01.rne of particles having an average diameter ranging from about 5 microns to about 20 microns, essentially all of these particles having a diameter less than about 50 microns and not more than about 10% by weight of those particles having a diameter of less than one micron, from about 25 ppm to about 2500 ppm of fluoride ions, supplied by EMI28.4 a salt soluble in water and from about 1000 ppm to about 100 ppm allutim H'.Rnnet.m, provided by a salt soluble in water, the pH of this p-za entitr1ce ranging from 3.5 to about 5 about. <Desc / Clms Page number 29> EMI29.1 '1. "" 1> 9'tte toothpaste S1,11Van1i la revef \ l1ica't.ion. and 'aéz.eâe n ce' que la n..yntq ... # ràaine melamine .. tO% 'll1a14'1Vo ..