FR2508312A1 - TOOTHPASTE - Google Patents

Abstract

THE INVENTION CONCERNS TOOTHPASTS WHICH CONTAIN A NON-IONIC SURFACTANT AGENT CONSISTING OF A COPOLYMER OF POLYOXYETHYLENE AND POLYOXYPROPYLENE AND A XANTHANE-TYPE GELLING AGENT; FOAM AND ORAL SENSATION ARE IMPROVED BY POLY (ETHYLENE OXIDE); POLY (ETHYLENE OXIDE) AND A SILICEOUS POLISHING MATERIAL PRODUCE A FLOCCULATED POLISHING MATERIAL WHICH IMPROVES STAIN REMOVAL WITHOUT INCREASING DENTINE ABRASION; MALTITOL IS A DESIRABLE HUMECTANT WHICH PROVIDES A CLEAR TOOTHPASTE CONTAINING, AS A POLISHING AGENT, A COMPLEX ALKALINAL METAL ALUMINOSILICATE.

Description

The invention relates to a foaming toothpaste and in particular a

  toothpaste in which the surfactant

used is of nonionic nature.

  Foam is a desirable feature of toothpaste because it spreads the toothpaste into the bucket cavity.

  wedge while brushing teeth, which promotes comfort

  tact between the toothpaste and the tooth surface and creates a

characteristic mouth sensation.

  The foam, in particular a high viscosity foam

  apparent site (having body) is generally obtained by

  the use of an anionic surfactant Typically

  pikes, other surfactants, particularly nonionic surfactants, do not foam as well as anionic surfactants Of the many anionic surfactants only a few have been used industrially in toothpastes; most

  commonly used being sodium lauryl sulfate.

  Anionic surfactants can cause

  some moderate side effects that some people use

  teurs may find it somewhat undesirable For example

  some users may experience moderate irritation

  temporary opening of the oral cavity, moderate bitterness,

  partial desquamation of the oral mucosa or a reaction

  unpleasant taste when they drink or eat citrus fruit for a short time afterwards, in case they use a toothpaste containing a surfactant

anionic tif -

  Although it is known that surface-active properties

  These can be imparted to a toothpaste by a tender agent.

  nonionic surfactant, such an agent has not usually been used because foaming does not occur without the addition of a

anionic surfactant.

  One of the advantages of the invention is that a toothpaste which is easy to extrude from a tube of toothpaste, which contains a nonionic surfactant and a specific binding agent, which makes it possible to obtain a foam which is stable at

  high apparent viscosity desirable.

  Another advantage of the invention is that the denti-

  the frice used is sweet without the presence of a sweetening additive being necessary and non-irritating, and that it does not tend to cause the user to have a peeling of the oral mucosa or an undesirable taste reaction to

citrus after use.

  Other advantages of the invention will emerge from the

description which follows.

  According to some of its aspects, the invention relates

  a toothpaste comprising about 20 to 80% by weight of a

  liquid humectant, about 0.5 to 7% by weight of gum

  xanthan and about 1 to 10% by weight of a surfactant

  tif which is a polyoxyethylene nonionic block copolymer

  polyoxypropylene Preferably, up to about 5% by weight

  a resinous poly (ethylene oxide) are also present.

  The nonionic surfactant used in the invention

  vention is a block copolymer containing polyoxyethylene

  lene and polyoxypropylene These block copolymers are supplied: by Wyandotte Chemicals Corporation under the trademark "Pluronic" They can be liquid, pasty or solid and are generally defined chemically by the molecular weight of the hydrophobic fragment of polyoxypropylene

  and the weight percentage of the hydrophilic fragment of polyo-

  xyethylene The following block copolymers are supplied by Wyandotte: Nature no. of fragment Molecular weight Pluronic physical hydrophilic of fragment:; ______ hydrophobic L 121 liquid 10 4000 L 101 liquid 10 3250 L 81 liquid 10 2250 L 61 liquid 10 1750 L 31 liquid 10 950 NO of Pluronic L 122

L 92

  L 72 L 52 L 42 Physical nature liquid liquid liquid liquid liquid / O of hydrophilic fragment Molecular weight of hydrophobic fragment

-P 123

P 103

  L 63 L 43 P 104 P 94 P 84 L 64 L 44 P 105 P 85 P 75 P 65 L 35 F 127 F 87 F 77 F 108 F 98 F 88 F 68 F 38 paste liquid liquid paste

dough -

  paste liquid liquid paste paste paste liquid paste solid solid solid solid solid solid solid solid solid The preferred nonionic block copolymers are solid materials (or in flakes) and very particularly preferred are Pluronic F 108 (80 Fo of polyethylene; molecular weight of polyoxypropylene: 3,250) and F 87 (70% polyoxyethylene; molecular weight of polyoxypropylene: 2,250) The nonionic surfactant is used in the

  toothpaste at a rate of about 1 to 10% by weight and preferably

  rate of about 2 to 5 d and better about 3 ri.

  The binding or gelling agent consisting of xanthan or xanthan and resinous poly (ethylene oxide) cooperates with the nonionic surfactant to produce a stable foam with high apparent viscosity (although the only agent

  present non-ionic surfactant) and the characteristics

  desirable mouth sensation of toothpaste Xanthan gum, at the indicated concentrations, provides

  a stable foam with high apparent viscosity In addition,

  In another aspect of the invention, the characteristics of mouth sensation can be modified as described by

  the addition of a resinous poly (ethylene oxide) The dentifri-

  this has a desirable viscosity allowing its extrusion of a

  tube of toothpaste in the form of a cord.

  Resinous poly (ethylene oxide) has been described as

  me gelling agent or binder for toothpaste in the patent

  US 2 991 229 Its presence softens the texture of toothpaste.

  The poly (ethylene oxide) used in the invention

  are colorless, water-soluble solid resins.

  They seem to form homogeneous systems in water in all

  your proportions although the relatively high molecular weight ethylene oxide polymers simply swell by adding small amounts of water when adding

  larger amounts of water, the polymers dissolve

  wind Aqueous solutions are viscous, viscosity

  increasing with the concentration of the polymer in the solution

  tion and reduced viscosity of the polymer The polymers o-

  ethylene oxide used in the invention have a weakness

  ble variation of the melting point when the reduced viscosity

250 831 2

  increases (it is an indication of the increase in molecular weight) and the melting point, measured by the change in stiffness as a function of temperature, has been found to be around 65 2 "C in the range reduced viscosities of between about 1.0 and about 10 and above.

  These polymers, on X-ray examination, have a structure

  crystalline structure similar to that of polyethylene The time

  crystallization temperature, determined by measuring the

  fall in the cooling curve, is around 55 OC.

  To facilitate understanding of the invention, di-

  towards terms will be defined First of all it should be noted that the term "poly (ethylene oxide)" used in the present

  description and claims designated polymers o-

  ethylene xyde which have a reduced viscosity in aceto-

  nitrile of at least 0.5 and up to 75 and over.

  Unless otherwise indicated, the term "viscosity

  pick "used here denotes the value obtained by dividing

  the specific viscosity by the concentration of the polymer o-

  ethylene oxide in the solution, the concentration being

  measured in grams of polymer per 100 ml of solvent at a given temperature, and is considered a measure of

  molecular weight The specific viscosity is obtained in di-

  targeting the difference between the viscosity of the solution and the

  viscosity of the solvent by the viscosity of the solvent

  Reduced sites indicated here are measured at the concentration

  0.2 gram of poly (ethylene oxide) in 100 millili-

  very acetonitrile at 30 OC (unless otherwise indicated).

  Granular poly (ethylene oxide) results from the suspension polymerization of a stirred reaction mixture

  comprising ethylene oxide in contact with a catalyst

  polymerization thereof and in the presence of a diluent

  inert organic, for example heptane, in which the oxy-

  of ethylene is soluble and poly (ethylene oxide) obtains

  naked is insoluble The granular poly (ethylene oxide) thus produced is obtained in the form of solid particles finely

  divided like fine sand Unlike poly (oxy-

  of ethylene) granular resulting from the polymerization

  suspension, obtained by mass or solid polymerization

  lution a polymer which is essentially in the form of a homogeneous mass conforming to the shape of the reactor or which, after elimination of the organic medium, for example by mechanical extrusion by means for example of a Marshall Mill (under vacuum

  and at slightly higher temperatures), with the appearance of

  sheets or sheets This polymer can then be transformed

  in particles, for example in cubes or the like.

  The term "granular" applies to the size of the par-

  ethylene oxide polymer particles prepared by poly-

  suspended merization A granular product is a pro-

  free flowing material consisting of particles passing on average through a sieve of 4.00 mm mesh opening When

  poly (ethylene oxide) is present up to

  about 5% of the weight of the toothpaste and preferably about

0.1 to 1.5%.

  Xanthan gum is a fermentation product prepared by the action of bacteria of the genus Xanthomonas on carbohydrates Four species of Xanthomonas, X. campetris, X phaseoli, X malvocearum, and X carotae are reported in the literature as the producers most effective gum Although the exact chemical structure has not been determined, it is generally accepted that gum

  xanthan is a heteropolysaccharide having a molecular weight

  several million milk It contains D-glucose,

  D-mannose and D-glucuronic acid in the molai-

  re 2.8 / 3 / 2.0 The molecule contains 4.7% acetyl and

  about 3% o of pyruvate You can find the configuration chi-

  developed nique proposed in McNeely and Kang, Industrial

  Gums, ed R L Whistler, CH XXI, 2 nd edition, New York 1973.

  We will find the modes of culture, isolation and purification.

  cation of xanthan gum in Manufacturing Chemist, May 1960, pages 206-208 (including the indication on page 33 208 of the possible use of the gums described here for

prepare toothpaste).

25083 1 2

  The use of special qualities of xan gum

  thane as described in US Patent 4,263,399 is within the scope of the invention A quality described in US Patent 4,263,399 is a xanthan gum in which up to about 1.6% of the carboxy radicals are attached to calcium and the remaining carboxy radicals are attached to sodium, potassium or a

  mixture of sodium and potassium or other different cations

calcium rents.

  The gelling agent of xanthan type is present at

  about 0.5 to 7% of the weight of the toothpaste and pre-

ference of about 1.5 to 3%.

  As the surfactant used in the invention is of nonionic nature, the moderate bitterness generally

  produced by an anionic surfactant is not felt

  tied by the users Therefore the sweetening agents

  rants that are often added to toothpaste at least in part to remove bitterness, are less necessary in

  the toothpaste of the invention compared to the prior art

  In fact, you can easily get a flavor

  creates sufficient satisfaction due to the slightly sweetening character of many of the commonly used humectants

  in toothpaste compositions These humectants are pre-

  smells in the liquid phase of toothpaste, typically

  with water Typical humectants include sorbi-

  tol (in the form of a 70% aqueous solution), glycerin,

  maltitol, xylitol, polyethylene glycol 400 and po-

  lyethylene glycol 600 The liquid phase represents approximately to 80% of the weight of the toothpaste, preferably approximately 30 to 60%, the proportion of water (when it is present) being typically at most approximately 60% and the proportion of humectant typically being about 20 to 60% On

  note that maltitol is described as an ingredient of den-

  tifrice in the patents published JA 73/10241 and 65/15120.

  The liquid vehicle and the gelling agent as well as the other components of the toothpaste are dosed to form

  a cream or gel with the desired consistency which can

250 831 2

  be extruded from an aerosol container or from a pump container or from a collapsible tube (for example made of aluminum,

  lead or plastic) The toothpaste contains

  typical lesson a polishing agent suitable for dental use

  be quiet which is generally essentially insoluble in water and which belongs to the type commonly used in

dental creams.

  Typical examples of polishing agents are dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide and

  including hydrated alumina, calcined ltalumine, silica col-

  loïdal, magnesium carbonate, calcium carbonate, calcium pyrophosphate, bentonite etc including their suitable mixtures When used, it is preferred to use

  water-insoluble phosphates as a polishing agent

  ge and more particularly sodium metaphosphate insoluble

  luble and / or a calcium phosphate such as phosphate di-

  calcium dihydrate in dental creams When using

  reads clear or opacified gels, a polishing agent consisting of colloidal silica, such as those sold under the brand Syloid such as Syloid 72 and Syloid 74 or under

  Santocel brand such as Santocel 100 and aluminosilica-

  Synthetic complex alkali metal or alumina containing combined silica may be particularly useful When using the polishing agent, its content is

  generally about 10 to 75% o by weight in a den-

  silence and about 5 to 50% by weight in a clear or opacified gel. According to another of its aspects, the invention provides a toothpaste containing a siliceous polishing material such as those indicated in the preceding paragraph and poly (oxide

  ethylene) as previously described.

  From the considerations of the prior art

  re, as described in US Pat. No. 3,020,230 which indicates the

  coagulation or flocculation of a siliceous material in pre-

  resinous poly (ethylene oxide) to precipitate it out

  from a liquid suspension, the dentifri-

  these would not have led to the use of siliceous materials.

  ses in a toothpaste containing poly (ethylene oxide) resinous In fact in the patent US 2 991 229, the polishing agents or the abrasives described in a toothpaste

  containing poly (ethylene oxide) are "tri-

  calcium, dicalcium phosphate and calcium carbonate

  and the like ", but not siliceous materials.

  One of the advantages of this aspect of the invention is to provide a toothpaste whose stain removal power

  is improved and whose cosmetic rheology and characteristics

  Dentin abrasion statistics are acceptable.

  Another advantage is that you get foaming

  desirable by incorporating a poly- block copolymer

  oxyethylene-polyoxypropylene and xanthan in toothpaste

this.

  Other advantages will emerge from the description

following.

  According to these aspects, the invention relates to a toothpaste comprising approximately 20 to 80% by weight of a liquid humectant vehicle, approximately 5 to 50% by weight of a polishing material.

  siliceous and about 0.05 to 5% o by weight of a poly (summer oxide

  thylene) resinous, said toothpaste containing flocculated particles of said siliceous polishing agent in the presence of said

poly (ethylene oxide).

  As previously indicated, in particular with regard to a clear or opacified gel, the content of the siliceous polishing agent is in the range of 5 to 50% of the

  weight of the toothpaste and preferably from 10 to 30%, for example-

  10 to 25% ple Such a polishing agent is an aluminum

  complex alkali metal silicate having a refractive index

  1.44 to 1.47 and containing at least 70 GB of silica, up to

  only 10% alumina, such as about 0.1-10%, for example

  about 0.1 to 3% o, preferably at most about 20% moisture

  said for example about 0.5 to 10% and up to about 10 o

  of alkali metal oxide Typically, the size of the

250 831 2

  particles of this material does not exceed about 40 Fm and

  preferably between 1 and 4 Pm The moisture content

  preferred density measured by calcination at 1000 C is 5 to IX and the typical alkali metal oxide content is 5% to 10% Generally the polishing agent has a low bulk density of at most 0.2 g / cm, for example

  from 0.07 to 0.2 g / cm 3 Another suitable type of polishing agent

  sage is a porous amorphous silicic anhydride having a size

  the average of the particles preferably less than 20 μm and greater than 1 AM, a specific surface of at least

  m / g, preferably at least 300 m / g and a mass vo-

  apparent light of at least 0.15 g / cm, preferably at least 0.30 g / cm, such as a dehydrated silica hydrogel

  (i.e. a xerogel) preferably having the density

  usual well-known or intermediate density

  Examples of such polishing agents

  of amorphous silicic anhydride are "t Syloid 63", "Sy-

  loid 72 "and t'Syloid 74" (Syloid is a trademark) which are described in "The Davison Family of Syloid Silicas"

  published by their manufacturer, Grace, Davison Chemical Company.

  Monsanto's "Santocel 100" (Santocel is a brand of fa-

  brick) is also a suitable dental abrasive The "Sy-

  loid 72 "has an average particle size of about 4 pim,

  a specific surface of approximately 340 m / g and a density

  apparent mica of approximately 1.77 g / cm 3 For the "Syloid 63" the corresponding values are approximately 9 mm, approximately 675 m / g

  and about 0.4 g / cm 3 A quality of "Santocel 100" has an over-

  specific surface of approximately 239 m / g and a specific gravity

  relative of about 0.24 g / cm These silica anhydrides absorb

  phes can be used individually or in mixtures.

  As previously indicated, poly (ethylene oxide) represents approximately 0.05 to 5% of the weight of the toothpaste and

preferably about 0.1 1.5%.

  In toothpaste, the siliceous polishing agent

  flocculates in situ in the presence of poly (ethylene oxide).

  flocculated ticles can typically agglomerate between

250 831 2

  if they and the particles have apparent sizes up to about 250 Fm or more, typically about 44 to

  177 one; in other terms, flocculated particles do not

  typically feels through a sieve of 0.180 mm mesh size and is retained by a sieve of 0.045 mm mesh size.

  Despite the presence of flocculated particles, the den-

  tifrice is easy to compose so that it has a desirable rheological appearance and texture without a "lumpy" appearance

  unwanted or sensation, 'sandy'.

  The liquid vehicle of the toothpaste according to this aspect of the invention can be as previously indicated and the components of the toothpaste are also dosed to form a cream or gel of desired consistency which can be extruded from an aerosol container or a pump container or a

  collapsible tube (e.g., aluminum, lead, or ma-

plastic).

  In addition to resinous poly (ethylene oxide), other

  gelling agents or binders such as carboxymethylcellulo-

  get sodium, Irish moss, xanthan and the like

  may be present at about 0.5 to 7%

  xanthan fère The total content of gelling agents or binding agents of the toothpaste can be approximately 0.1 to 12% by weight. The toothpaste according to this aspect of the invention can

* contain an anionic, nonionic, active surfactant

  ionic or amphoteric to increase the prophylactic effect,

  favor the complete dispersion of the compositions in the

  oral health and improve the cosmetic quality of these

positions.

  A preferred surfactant is the dry copolymer

  nonionic quencé containing polyoxyethylene and poly-

  oxypropylene previously described.

  Other nonionic surfactants which may be employed include condensate of monostearate.

  sorbitan and about 20 moles of ethylene oxide Les a-

*

  amphoteric gents include imidazole derivatives quater-

  products supplied under the brand name "Miranol", such as Miranol C 2 M. Suitable types of non-ionic detergents are

  the water-soluble salts of monoglycerol monosulfates

  higher fatty acids such as the sodium salt of the monoglyceride monosulfate of the fatty acids of coconut oil

  hydrogenated, higher alkyl sulfates such as lauryl-

  sodium sulfate, alkylarylsulfonates, such as dode-

  sodium cylbenzenesulfonate, olefinesulfonates, such

  than a sodium olefin sulfonate whose olefin fragment contains

  holds 12 to 21 carbon atoms, the higher alkyl sulfoacetates

  laughing, the higher fatty acid esters of 1,2-aciihydrox Cy-

  propane sulfonates and higher aliphatic acylamides

  essentially saturated with alipha- amino-carboxylic acids

  lower ticks such as those having 12 to 16 carbon atoms in fatty acid and alkyl or acyl radicals, and the like Examples of the last amides mentioned are N-lauroyl sarcosine and the sodium, potassium and tethanolamine salts N-lauroyl, N-myristoyl or Npalmitoyl sarcosine which may be practically devoid of soap or

  similar materials of a higher fatty acid type which

  tooth to greatly reduce the effect of these compounds The use of these sarcosine derivatives in the toothpaste compositions of the invention is particularly advantageous because these materials

  have a clear and prolonged effect of inhibiting the formation of a-

  cide in the oral cavity as a result of the breakdown of carbohydrates, in addition to the fact that they decrease to some extent the solubility of dental enamel in

acid solutions.

  It is also possible to use cationic germicidal and antibacterial surfactant compounds such as diisobutylphenoxyethoxyethyl-dimethyl-benzyl-ammonium chloride,

  benzyl-dimethyl-stearyl ammonium chloride, amnines ter-

  tiaries having a fatty alkyl radical (from 12 to 18 carbon atoms) and two (poly) oxyethylene radicals attached to nitrogen (typically containing in total approximately 2 to 50 radicals

2508312.

  ethanoxy per molecule) and their gels formed with acids, and the compounds of formula (CH 2 CH 2) z H (CH 2 CH 2 O) H

  R-N-CH 2 CH 2 CH 2 N (CH 2 CH 2 O) H

  in which R represents a fatty alkyl radical containing approximately 12 to 18 carbon atoms, and the total of x, y and z is 3 or more, as well as their salts formed with mineral or organic acids It is preferred to use approximately 0.05 to Ho by weight of the previous surfactants in the

present toothpaste.

  According to another of these aspects, the invention provides a toothpaste whose humectant is maltitol and the material

  polishing agent is a complex alkali metal aluminosilicate.

This toothpaste is crystal clear.

  In recent years, toothpaste has been developed

  these clear which contain a cleaning agent or

  dental smoothing These cleaning or polishing agents den-

  generally have a siliceous nature and refractive indices of approximately 1.44 to 1.47 The use of these materials has made it possible to prepare toothpastes in which the refractive index of the liquid vehicle corresponds to that of the agent Typically this has been achieved by the use of glycerin and / or sorbitol as humectants

  in the liquid vehicle because the glycerin has a refractive index

  fraction of 1.473 and sorbitol (70% aqueous solution) of 1.460 However, since water has a refractive index of 1.333, only a very small amount of formulation water (i.e. water not combined with other components such as sorbitol) can be used without greatly reducing

  refractive index and cause a decrease or a dis-

appearance of clarity.

  We tried to develop toothpaste

25083 1 2

  clear with less glycerin and / or sorbitol Par

  example: (1) in US Pat. No. 3,842,167, a mal-

  todextrin as a non-humectant component of the liquid phase

  to reduce the amount of glycerin and / or sorbitol ne-

  cessaire; (2) in US patent 3,927,202, various

  Non-siliceous phosphate-type polishing agents which

  put to modify the range of refractive indices of the

  liquid hicle; (3) in US Pat. No. 4,007,260 we use

  as a silica polishing agent having a refractive index

fraction of about 1.410 to 1.440.

  One of the advantages of this aspect of the invention is that

  provide a clear toothpaste in which the vehicle liquidates

  of consists of a humectant having a refractive index of about 1.48 (for example from about 1.4750 to about

1.4849) and water.

  Another advantage is that one can use a quantity of free water greater than that previously used

  in clear toothpaste containing a polishing agent

  ge consisting of an alkali metal aluminosilicate having a refractive index of about 1.44 to about 1.47 and a humectant having a refractive index of about 1.48 La

  amount of water is not so high as to cause des-

  dry undesirable toothpaste due to immediate evaporation

  bearing water in particular as a result of the presence of maltitol Other advantages will emerge from the description

following.

  According to these aspects, the invention relates to a dentifri-

  this clear containing a vehicle comprising approximately 0.5 to 101%, by weight of a solid portion of gelling agent and approximately 50 to 94.5% by weight of a liquid portion comprising (a) a

  humectant in which maltitol having a refractive index

  tion of about 1.48 is present as a single or main com-

  posing other than the water of said liquid vehicle and (b) water

  in an amount such that said liquid vehicle has an indi-

  that of refraction between approximately 1.44 and approximately 1.47, said clear toothpaste also containing approximately 5 to 50%

  by weight of a polishing agent consisting of an aluminosili-

  complex alkali metal cate having a refractive index

  between about 1.44 and about 1.47.

  The liquid portion of the vehicle represents approximately 50 to 94.5% of the weight of the clear toothpaste, preferably

  about 55 to 80 5 It contains a humectant which is

  killed entirely or mainly (i.e. more than

  about 50%) of maltitol Maltitol is essentially a

  glycosyl sorbitol, i.e. 4-O-e-D-glucopyrannosyl-

  D-glucitol, corresponding to the structural formula:

CH 2 OH

H jh CH 8 p.m.

Ho HO-CH.

H_ _ _ _ _ _ _ O

H HO HC-OH

I HO-CH

H-2 OH

  It is prepared by hydrogenation of maltose In an essentially pure form, it is a glassy solid. It dissolves easily in small amounts of water and it is found that its solutions containing at least about 73% of maltitol and

  at most about 27 a of water have refractive indexes of

  approximately 1.48, (i.e. approximately 1.4750 to 1.4849)

  add it to a toothpaste with water added separately

  Recently having a refractive index of about 1.333, the

  liquid bed can be adjusted to obtain an in-

  refractive dice of approximately 1.44 to approximately 1.48 Typically, approximately 5 to 25% by weight of water makes it possible to obtain

  such a refractive index, the small amounts of water pro-

  combining a high refractive index (Dar example around 1.47) and the high quantities of water (for example around 15 to 23 S) producing

  a low refractive index (for example close to 1.44).

  Preferably the refractive index of the liquid vehicle is

25083-1 2

  from about 1.44 to 1.47 and it is obtained with about 5 to 10% in hairs of formulation water The water portion of the toothpaste is water which is separated and not associated with the water used

to dissolve the humectant.

  The required purity of maltitol is not such that it

  must be the carbohydrate polyol derived from the mal-

  tose pure Commercial maltitol consists of maltitol

  with small amounts of polyalcohols of glucidic character

  dique derived from maltotriose, maltotetrose, and por-

  related low molecular weight maltodextrins

  corn syrup and with minimal amounts of D-sorbitol.

  So a commercially available "hydrogenated starch hydrolyzate"

  boasting a high maltose corn syrup can be

  used in the practice of the invention.

  The use of maltitol has been recommended in denti-

  but not as the primary moisturizer for limp toothpaste

  pides containing a polishing agent.

  In this regard, see "Caries Research", vol.

  14 number 2, (1980) pages 67-74, Rundegren et al (on ob-

  serve that maltitol does not contribute to demineralization); "Shigakcu '", Vol 60, number 6 (1973), pages 760-765, Matsuo

  (we observe that maltitol is not fermented by Strepto-

  coccus salivarius, S); "Acta Odont Scand", Vol 37, number-

  ro 2, (1979) pages 103-115, Birkhed et al and "Caries Re-

  search ", Vol 12, number 3 (1978), pages 128-136, Birkhed (ob-

  served on the plate); "Acta Odont Scand" '

  Vol 35 number 5 (1977) pages 257-263, Edwardsson et al (ob-

  servations made on oral bacteria); and the patent

  Japanese published JA 73 10241 (describing maltitol as a

  In addition, maltitol can be one of the components of a variety of sorbitol known as

  "non-crystallizable sorbitol" which can be used as humus

  mectant for toothpaste However, the high sorbitol content of the non-crystallizable sorbitol is such that a refractive index of approximately 1.48 is not obtained, which

  reduces the possibility of varying the composition of the vehicle

-17

  cule consisting of water and humectant compared to the invention.

  It will also be noted that fatty acid esters of maltitol and other polyalcohols of a carbohydrate nature are described as flavor components of a toothpaste in the patent.

GB 2,038,182.

  If desired, the liquid carrier of the clear toothpaste of the invention may contain a small amount (i.e., less than about 50%) of a humectant in addition to maltitol or even a non-humectant component of vehicle

  liquid such as maltodextrin Moisturizers can be used

  such as those previously indicated, for example the

  glycerin, sorbitol (typically a solution of sor-

  70% bitol), polyethylene glycol 400, polyethylene-

  glycol 600 and the like Preferably maltitol represents

  te more than about 50% of the weight of the portion other than water of the liquid vehicle and preferably about 65 to 100% of

  maltitol is typically supplied as a solution.

  73-85% and among these suppliers are Al-

  drich Chemical Companys Merck and Co Inc, Imperial Chemicals

  Industries, Pfizer Inc, Lonza, Roquette Frères, and Hayashi-

bara Chemical Laboratories.

  The solid portion of the vehicle is a gelling agent as previously indicated, for example natural and synthetic gums and gummy materials such as Irish moss, an alkali metal derivative (for example sodium) of carboxymethylcellulose and xanthan as well that gum

  tragacanth, hydroxymethylcarboxymethylcellulose, polyvi-

  nylpyrrolidone, starch, guar, sodium alginate, hydrophilic colloidal carboxyvinyl polymers such as

  those sold under the Carbopol 934 and 940 brand, and the argi-

  synthetic silicate minerals such as those sold

  due under the brand Laponite CP and Laponite SP These qualities of Laponite correspond to the formula (Si 8 lg 5.1 Lio 6 H 7, 6024) -0.6

  Na + 6 The solid portion of the vehicle is typically pre-

  smells at a rate of at most about 10% of the weight of the toothpaste and preferably about 0.25 to 5% When using qualities of Laponite, their concentration is typically

from about 1 to 5% by weight.

  The alkali metal aluminosilicate salt

  plex is as described above It is alkaline in nature, in particular a sodium salt, and it promotes effectively

  oral hygiene It is an amorphous powder whose particles

  when incorporated into the vehicle, they become practical

hardly invisible.

  The alumina content of the aluminosilicate is therefore

  typical lesson of about 0.1 to 3% by weight and preferably about 1% It is desirable that the refractive index

  aluminosilicate does not deviate more than about 0.005 units

  t, especially about 0.001 unit, of that of the vehicle

what.

  As noted, the polishing agent represents

  typical lesson about 5 to 50 5 of the weight of the tooth composition

  frice and preferably about 10 to 30% of this weight.

  The alkali metal aluminosilicate salt

  plex seems to contain silica and alumina bound in-

  be them by Al-O-Si bonds as described by Temele

  in "Chemistry od the Surface and the Activity of Alumina-

  Silica Cracking Catalyst "', Discussions of the Faraday Society, N 8, pages 270-279 (1950) and in particular page 273, figure 1,

  curve 3, the interaction between the ions of silica and a-

  luminium being detected by potentiometry We can cite com-

  other documents describing this type of complex Mblilliken et al "The Chemical Characteristics and Structures of Cracking Catalystst, Discussion of the Faraday Society, N 8, pages 279-290 (1950) and in particular the sentence between pages 284 and 285 Ces complexes differ significantly from the gel

  silica as described by Plank and call "Differences Bet-

  ween Silica and Silica-Alumina Gels I Pactors Affecting the Porous Structure of These Gels, 'Journal of Colloid Science, 2, pages 399-412 (1947) and Plank, "Differences Between Silica

  and Silica-Alumina Gels II A Proposed Mechanism for the Ge-

  lation and Syneresis of These Gels, "Journal of Colloid Scien-

  ce 2, pages 413-427, (1947) o the formation of the Ai-O-Si bond is described on pages 419-422 The aluminosilicate can

  It is described as silica containing alumina combi-

  born. As previously indicated, the use of maltitol in toothpastes has been described in Japanese patents

  published JA 15120/65 and 73/10241 The first does not indicate a-

  gent of polishing siliceous and the second mentions the silicic anhydride like polishing agent However, it was noted that when one uses silicic anhydride such as xerogel of colloidal silica supplied by Grace Davison under the name of Syloid 74, in a clear toothpaste containing maltitol, the toothpaste quickly takes on a dull appearance and

  -dries when exposed to air to form an opaque product

  cified hardened When the complex aluminosilicate of the invention is used, the toothpaste practically retains its appearance

  limpid desirable and its rheology.

  Organic surfactants can be used

  used in the compositions corresponding to this aspect of the invention to increase the prophylactic effect, promote

  the complete dispersion of the compositions in the oral cavity

  and improve the cosmetic quality of these compositions. The organic surfactant material can be of anionic nature,

  non-ionic, ampholytic or cationic as previously mentioned

  diqué and it is desirable to use as surfactant

  tif a detergent material which gives the composition of

  detergent and foaming properties.

  Can be used in the toothpastes described herein a compound providing fluorine and an alkali metal The compounds

  providing fluorine and an alkali metal include fluo-

  sodium rure, stannous fluoride, standard chlorofluoride

  stannous potassium fluoride (Sn F 2- F),

  lithium fluoride, ammonium fluoride and fluoru-

  complex res such as potassium fluorozirconate, he-

  sodium xafluorostannate and metal monofluorophosphates

  tal alkaline These compounds have a beneficial effect on the care and hygiene of the oral cavity, for example by reducing the solubility of enamel in acids and by protecting

  teeth against cavities and they allow for retention

  satisfactory fluoride soluble in toothpaste of the

  In particular, the retention rate of the monofluorophosphate ion in the form of fluoride is very high with

  alkali metal monofluorophosphates The com-

  laid fluoride in an amount providing an effective amount

  non-toxic fluoride ion to toothpaste, typically

  about 0.01 to 1 5 by weight and preferably about 0.1 5 of fluorine Sodium fluoride A is therefore typically used

  about 0.02 A 2 7 by weight and preferably about

  0.2% ron and sodium monofluorophosphate, Na 2 PO 3 F, due to

  bran from about 0.1 to 7.6% by weight, preferably about

0.76%.

  Alkali metal monofluorophosphates which can be used include sodium monofluorophosphate, lithium monofluorophosphate, sodium monofluorophosphate

  potassium and ammonium monofluorophosphate The pre-

  feré is sodium monofluorophosphate, Na 2 PO 3 F whose

  Purity of commercial forms can vary widely.

  It can be used with any suitable purity under

  provided that the impurities practically do not alter the pro-

  desired properties In general, it is desirable that pure-

  be at least about 80% to get the best

  results, it is desirable that the content of monofluorophos-

  sodium phate is at least 85% and preferably at least 90 I by weight, the remainder consisting mainly of impurities or manufacturing by-products such as sodium fluoride, a sodium phosphate soluble in water and the like In other words, monofluorophosphate

  sodium used must have a total fluoride content of

  about 12%, preferably about 12.7 X; a content of

  free sodium fluoride not exceeding 1.5 to and preferably

  rence not exceeding 1.2 S; and a monofluoro- content

  sodium phosphate of at least 12 5% and preferably at least

  12.1 o, all these contents being expressed as fluorine.

  Other monofluorophosphate salts which are

  can use in the invention include monofluoro-

  polyphosphates such as Na 4 P 3 09 F, K 4 P 309 F, (NH) 4 P 3 09 F, Na 3 KP 309 F, (N 4) 3 Na P 30 09 F and Li 4 P 309 F. We can , to give a flavor to the compositions of the invention, use suitable weapons or sweeteners

  Examples of flavoring constituents suitable

  properties include aromatic essences such as, for example, spearmint, peppermint 6 th, wintergreen, sassafras, cloves, sage, eucalyptus, marjoram, cinnamon, lemon and orange as well as methylyl salicylate Suitable sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, perillartin and saccharin De

  appropriately, flavoring agents and tedulcora-

  tion can together represent about 0.01% to 5% or more of the compositions of the invention. Chloroform can also be used. The sweetening agents are less necessary in the absence of anionic surfactants because the agents

  anionic surfactants impart a slight bitterness to the den-

  scent. Antibacterial agents can be used in

* the toothpaste described at a rate of approximately 0.01 to 5% by weight.

  Typical antibacterial agents include: M- (4-chlorobenzyl) -N 5 (2,4-dichlorobenzyl) biguanide; p-chloroph 6 nylbiguanide; 4chlorobenzhydrylbiguanide; 4-chlorobenzhydrylguanylurea; N-3lauroxypropyl-N -p-chlorobenzylbiguanide; 1,6-di-pchlorophenylbiguanidohexane; 1,6-bis (2-ethylhexylbiguanido) hexane;

  1- (lauryldimethylammonium) -8- (p-chlorobenzyl) dichloride

  dimethylammonium) octane; 5,6-dichloro-2-guanidinobenzimidazole; N p-chlorophenyl-1 \ -laurylbiguanide; 5-amino-1,3-bis (2-ethylhexyl) -5methlylhexahydropyrimidine;

  and their addition salts with non-toxic acids.

  Various other materials can be incorporated into the pre-

  examples of the invention Examples are coloring or bleaching agents or dyes, preservatives,

  silicones, chlorophyll compounds, ammoniated materials such as

  urea, diammonium phosphate and their mixtures

  and other constituents Additives are incorporated into the pre-

  present compositions in amounts having practically no deleterious effects on properties and characteristics

  desired and chosen and used in appropriate quantities

  required according to the particular type of preparation envisaged.

  One can also use finely divided synthetic pyrogenic silica 13 such as those sold under the brands Cab-O-Sil M-5, Syloid 244, Syloid 266 and

  Aerosil D-200 at a rate of about 1 to 5 5 by weight for favori-

  ser thickening or gelation of the toothpaste described.

  Toothpastes must have a p H suitable for use

  ploi A moderately acid to alkali p Hli is prepared.

  The following examples illustrate the nature of the denti-

  of the invention without in any way limiting it All

  quantities are expressed by weight, unless otherwise indicated

  res. E) EIPLES 1 and 2 The following opacified toothpaste gels are prepared:

EXAMPLES

1 2

  Glycerin 10.0 10.0 laltitol 15.0 15.0 Sodium aluminosilicate (silica combined with about 1 'c of alumina) Zeo 49 B (Huber) 18.0 18 O

1 2

  Pluronic F-10 G (block copolymer) 3.0 Sodium lauryl sulfate 1.0 Xanthan 2.0 2.0 Polyox WSR 301 0.2 0.2 Sodium monofluorophosphate 0.76 0.76 Titanium dioxide 0.4 0 , 4 Weak aroma of menthol 0.5 Aroma of peppermint essence 0.5 Saccharin sodium 0.2 Coloring solution (1) 0.05 0.05 Water Q So Po 100 QSP 100

  The toothpaste of Example 1 which contains lauryl-

  sodium sulfate has a desirable foaming character The den-

  the scent of example 2 also forms a very good stable foam with high apparent viscosity although anionic surfactants are not used. The foam remains in the whole of the oral cavity with an oral sensation.

  advantageous when brushing teeth with toothpaste.

  In addition, it has no bitter note although a weak ar 6 me

  menthol is present and that no 6 dulco- has been added

  rant Toothpastes have a natural structure and appearance

  re fine and homogeneous, effectively remove stains and have an acceptable dentin abrasion character They

  contain flocculated particles of aluminum aluminosilicate

  dium. Similar good results are obtained when the xanthan of Example 2 is replaced by the low xanthan

  calcium content of Example 1 of US Patent 4,263,399.

  Similar foam and feel are obtained when replacing Pluronic F-108 with other copolymers

  polyethylene and polyoxypropylene blocks in particular

bind the Pluronic F-87.

  The Polyox WSR-301 is supplied by Union Carbide Corp. in the form of water-soluble poly (ethylene oxide) resin granules having a molecular weight of approximately 4,000 and a Brookfiel viscosity of 1,650 3,850 c P (1650 3850 x 10-3 Pa s) ( 25 C, rod 1, speed 2 rpm) in water at 1% by weight Similarly, a similar foam and feeling is obtained when the Polyox WSR-301 is replaced by other poly (oxide) resins water soluble ethylene) supplied by Union Carbide Corp such as Polyox

  WSR-N-80, WSR-N-750, WSR-N-3000, WSR-205 and WISR-1105 to differ-

annuities concentrations.

  The silica with combined alumina indicated in the examples is supplied by J M Huber, Corp de Havre de

  Grace, Maryland, as Zeo 49 (A or B).

EXAMPLES 3 to 6

  The following limpid (3 and 4) and opacified (5 and 6) toothpaste gels are prepared:

EXAMPLES 3-6

3 4 5

  Glycerin Sorbitol Maltitol (Active) Sodium aluminosilicate (silica combined with alumina) Pluronic F-108 Pluronic F 87 Xanthane Polyox WSR301 Sodium monofluorophosphate Titanium dioxide Weak menthol flavor Coloring solution (1 5) Water Exer toothpastes, O 16.0 16.0 22.0 3.0 1.5 0.2.0 0.0 18.0 3.0 2.0 0.2.0 0.0 18.0 0.0 2.0 0.2

0.76 0.76 0.76

_ 0.4

0.5 0.5 0.5

0.05 0.05 0.05

Q.S P Q S P Q S.

100 100

  mples 3 and 4 are, 0 18.0 2.0 0.2 0, 76 0.4 0.5 0.05

P Q S P

crystal clear

  and those of examples 5 and 6 are clouded They have a structure

  homogeneous texture The four toothpastes form a very good

  stable foam with high apparent viscosity, that of the

  frice of example 5 being the most consistent and the teeth

  tips of examples 3 and 4-coming next The toothpaste of

  Example 6 forms a larger amount of foam.

  All foams create a good mouth feel all over your mouth while brushing your teeth.

  no bitter note Toothpaste effectively eliminates

  this stains and their abrasion of dentin is acceptable.

  They contain flocculated particles of aluminosilicate

sodium.

  EXAMPLES 7 11 l The following toothpastes are prepared: Active maltitol Sodium aluminosilicate (silica combined with alumina) Calcined alumina Pluronic F-108 Xanthane Polyox WSR-301

WSR-1105

WSR-N-750

  Sodium monofluorophosphate Titanium dioxide Ar 8 me weak menthol

7 8

.0 30.0

  12.0.0 3.0 2.0 0.2 12.0 3.0 3.0 2.0 0.2

EXAMPLES 7-11

9 10

.0 30.0

  12.0, 0 3.0 2.0 1.0 0.76 0.4 0.5 QS P 0.76 0.4 0.5 QS P 0.76 0.4 0.5 18, 0, 0 3.0 1.7 0.2 0.76 0.4 0.5

Q.S P Q S P O Q S P.

100 100

  The toothpastes of examples 7 to 11 have a high detergent efficiency and produce a good stable foam with high apparent viscosity They have a homogeneous structure, the toothpastes of examples 7, 10 and 11 containing Polyox WSR-301 having the best texture All form a foam producing a good sensation throughout the mouth during, 0 2.0 2.0 3.0 2.0 0.2 0.76 0.4 0.5 __

250 8 3 1 2

  brushing teeth They have no bitter note They eli-

  effectively stain stains and their abrasion of

  dentin is acceptable They contain loose particles

  sodium aluminosilicate abutments.

EXAMPLES 12 to 15

  The following toothpastes are prepared:

EXAMPLES 12-15

  Glycerin Sorbitol Maltitol (active) Dicalcium phosphate dihydrate Anhydrous dicalcium phosphate Calcined alumina Pluronic F-108 Xanthan Polyol WSR-301 Sodium monofluorophosphate Titanium dioxide Weak menthol flavor Water, 0, 0, 0, O, 0, 0, O, 0 , 0, O, 0 O, 0

.0 30.0 15.0 15.0

  , O 3.0 2.0 0.76 0.4 0.5 QS P 3.0 2.0 0.2 0.76 0.4 0.5 QS P 3.0 2.0 0.2 0, 76 0.4 0.5 QS PO, 0 3.0 2.0 0.2 0.76 0.4 0.5 QS P The toothpastes of Examples 12 to 15 produced a good, stable foam with high apparent viscosity.

  examples 13 to 15 (which contain Polyox) have a structure

  particularly fine, homogeneous texture All form a foam

  producing a pleasant sensation in the entire bou-

  che while brushing teeth Although we do not use

  no sweetener, toothpaste has a fairly sweet flavor.

EXAMPLES 16 to 17

  The following opacified toothpaste gels are prepared:

250 831 2

PARTS

  Maltitol 40.00 Sodium aluminosilicate (silica containing approximately 1% combined alumina Zeo 49 B-Huber) 18.00 Pluronic F-108 (block copolymer 5) 3.00 Xanthan 1.70 Polyox WSR 301 (Union Carbide) 0 , 20 Titanium dioxide 0.40 Ar 8 me 0.50 Saccharin sodium 0.20 Deionized water QSP 100, 00 18.00 3.00 1.70 0.40 0.50 0.20

Q.S P 100

  The two toothpastes produce a stable foam with high apparent viscosity with a good mouth feel; the mouth feel of toothpaste 16 is particularly satisfactory.

  When comparing the 6 t elimination capacity

  dental and abrasion of dentin, the toothpaste of Example 16 containing Polyox removes stains better with

  less dentine abrasion than toothpaste from e-

  xample 17 without Polyox In the toothpaste of example 17,

  flocculated particles of aluminosilicate are formed in situ.

  The results are as follows: Abrasion Elimination of

stains (%) dentin (techni-

__ that radioactive)

TOOTHPASTE

16

  17- In the stain removal test, we attack

  6 sections of human dental mail with chlorhy- acid

  0.1 N dric for 2 minutes, rinsed with water, then moistened with a dilute solution of stannous fluoride,

  wiped and finally exposed to a stream of sulfhy-

  gas gas which forms a brown deposit of stannous sulphide.

  We measure the importance of the coloring of the surface with a

  Gardner On Automatic Differential Colorimeter

  following the surface with a mechanical brushing machine for

  500 back and forth with a suspension of toothpaste and one me-

  on residual stains with colorimôtre Finally

  completely remove stains with pumice stone

  keep silent and measure the reflection power of the surface The power to remove stains from a toothpaste is expressed by the following equation: percentage of removal (Rd 500 back and forth R initial) 10 stains = Rdponcé -Rd initial

  o Rdinitial, Rd 500 back and forth, and Rdponcé, are respective-

  the measured reflection factors of stained surfaces

  initials, after brushing with 500 back and forth and after eli-

  removal of residual coloring by sanding.

  Dentin abrasion values were ob-

  held using a radioactive technique described in the lit-

  Stookey, C K and Muhler, J C, J Dental Research 47

524-538 (1968).

EXAMPLE 18

We prepare the following toothpaste

toothpaste from example 10.

Maltitol (solution 75)

  Sodium aluminosilicate (silica containing

  approximately 1% combined alumina) Zeo 49 B Huber Calcined alumina Pluronic F-108 Xanthane Titanium Dioxide Arônae 35 Sodium saccharin and compared to

PARTS

  , 0 (30.00 active) 18.00, 00 3.00 1.70 0.40 0.50 O, 10 QSP 100 deionized water The toothpastes of Examples 10 and 18 produce a stable foam - with high apparent viscosity with a good mouth feeling; the mouth feel of toothpaste 10 is particularly satisfactory. The results below of the stain removal and abrasion tests of dentin (radioactive technique) obtained with the toothpastes of Examples 10 and 18 show

  the superiority of the toothpaste of Example 10 containing the Po-

  lyox which removes stains better with abrasion of the

similar dentin.

  TOOTHPASTE Stain removal Dentine abrasion (%) (radioactive ________________ technique)

65 47

18 44 41

  EXAMPLES 19 and 20 The following toothpastes are prepared:

PARTIES

19 20

  Maltitol (80%) 59.0 59.0 Deionized water 10.74 10.74 Sodium monofluorophosphate 0.76 0.76 Sodium saccharin 0.25 0.25 Sodium carboxymethylcellulose 0.35 0.35 Polyethylene glycol (Carbowax 600) 3 .0 3.0

  Silica xerogel (Syloid 74) 18 00 -

Sodium aluminosilicate -

  (silica containing about 1 s of combined dalumine) Zeo 49 B-Huber 18.0 Sodium lauryl sulfate 1.2 1.2 Aroma 1.2 1.2

  The Syloid 74 refractive index in the denti-

  frice from example 19 and Zeo 49 B in the toothpaste of e-

  example 20 does not differ by more than about 0.005 units from

  that of the liquid vehicle of each toothpaste.

  Each toothpaste is bright and clear at the start However after a week at normal temperature

  naire, the toothpaste of example 19 which contains a xerogel

  silica, looks dull and when left ex-

  when placed in the air, it takes an opaque whitish coloration and becomes quite hard Under the same conditions, the toothpaste of Example 20 remains shiny and limpid and continues to

  have desirable flow characteristics.

EMEIPLES 21 23

  The following clear toothpastes are prepared in which the refractive index of the polishing agent does not

  not differ by more than 0.005 unit from that of the vehicle li-

what.

  Maltitol (73 5) 62.0 Maltitol (80%) Deionized water 7.24 Sodium monofluorophosphate 0.76 Sodium saccharin 0.25 Sodium benzoate 0.50 Sodium carboxymethylcellulose 0.35

Xanthane -

  Polyethylene glycol (Carbowax 600) 3.00 Sodium aluminosilicate (silica containing approximately 1 5 'combined dtalumine) Zéo 49 A 18.00 in example 21 and Zeo 49 B in examples 22 and 23 Huber) Thickening silica (Syloid 244) 5.50 Sodium lauryl sulfate 1.20 Flavor 1.20

PARTS

  O, 0 16.6 0.76 0.24 48.0 22.6 0.76 0.24 0.4 1.4

.00 20.00

1.20 0.80 1.20 0 80

R EVEN D I C A T I O NS

  1 Toothpaste characterized in that it comprises

  about 20 to 80% c by weight of a liquid humectant v 6, about 0.5 to 7% by weight of xanthan gum and about 1 to 10% by weight of a surfactant, said tensile agent surfactant being a nonionic surfactant consisting

  of a polyoxyethylene-polyoxypropylene block copolymer.

  2 Toothpaste according to claim 1, charac-

  dried in that resinous poly (ethylene oxide) is present

  in an amount of about 0.1 to 5% by weight.

  3 Toothpaste according to claim 1 or 2, charac-

  terized in that the block copolymer is a solid material.

  4 Toothpaste according to claim 3 e characterized in that the solid block copolymer contains approximately 80%

  by weight of polyoxyethylene and the molecular weight of polyo-

  xypropylene is about 3,250 or about 70% polyoxy-

  ethylene and the molecular weight of polyoxypropylene is about

approximately 2,250.

  Toothpaste according to claim 2, characterized in that approximately 1.5 to 3% by weight of xanthan and approximately 0.1 to 1.5% by weight of said resinous poly (ethylene oxide)

are here.

  6 Toothpaste according to claim 1 or -2, charac-

  characterized in that the liquid humectant vehicle includes

  glycerin, sorbitol, maltitol or a mixture thereof.

  7 Toothpaste according to claim 6, characterized

  in that maltitol is present as a humectant, the dentitol

  frice contains about 5 to 50% by weight of a polishing agent

  sage consisting of a complex alkali metal aluminosilicate

and the toothpaste is crystal clear.

  8 Toothpaste according to claim 2, characterized in that it contains approximately 5 to 50 5% by weight of a material

siliceous polishing.

  9 Toothpaste according to claim 8, characterized

  in that the siliceous polishing material is an aluminum-

  complex alkali metal silicate.

  Toothpaste characterized in that it comprises approximately 20 ′ O @ O% by weight of a liquid humectant vehicle,

  about 5 x 50 'by weight of a polishing material

  and about 0.05 to 5 <3 by weight of a resinous poly (ethylene oxide), said toothpaste containing flocculated particles 6 es formed by the siliceous polishing material in

  presence of poly (ethylene oxide).

  11 Toothpaste according to claim 10, character-

  ris 6 in that the resinous poly (ethylene oxide 11) has a

  cosity r 6 of at least 0.5 as measured at the concentration

  0.2 g of poly (ethylene oxide) in 100 millili-

very acetonitrile at 30 C.

  12 Toothpaste according to claim 11, character-

  laughed in that the resinous poly (o 3 cyde) is present

  in an amount of about 0.1 to 1.5% by weight.

  13 Toothpaste according to claim 10, character-

  laughed in that the siliceous polishing material is an aluminum

  complex alkaline m 6 tal minosilicate having a refractive index

fraction from 1.44 to 1.47.

  14 Toothpaste according to claim 13, caract 6-

  laughed in that the alkali metal aluminosilicate is an alu-

  sodium minosilicate in which silica is combined 6 e

with about 0.1 to 3% alumina.

  15 Toothpaste according to claim 10, character-

  that the flocculated particles have an apparent size

rent about 44 to 177) M.

  16 Toothpaste according to claim 10, caract 6-

  laughed at that maltitol is present as a humectant.

  17 Toothpaste characterized 6 in what it contains

  a vehicle comprising approximately 0.5 to 10% by weight of a

  solid gelling agent and about 50 to 94.5% by weight of a liquid portion comprising (a) a humectant in which maltitol having an index of r 6 fraction of about 1.48 is present as the sole or main component other than the water of said

  liquid vehicle and (b) of Mau in a quantity 6 such that the

  dice of refraction of said liquid vehicle is between

  about 1.44 and about 1.47, said toothpaste containing also

  about 5 to 50% by weight of a polishing agent

  made from a complex alkali metal aluminosilicate having a refractive index of between about 1.44 and about

1.47 and being clear.

  18 Toothpaste according to claim 17, character-

  laughed in that maltitol is present as a solution

  tion containing at least about 73% by weight of mal-

titol.

* 19 Toothpaste according to claim 18, character-

  laughed in that maltitol is present as a solution

  tion containing approximately 73 to 85% by weight of maltitol.

  Toothpaste according to claim 19, character-

  laughed in that the maltitol solution represents approximately 65 to 100 I of the weight of the portion other than water of the liquid vehicle and the portion of water of the liquid vehicle represents

  about 5 to 25% of the weight of the toothpaste, the water from said

  tion of water that is not associated with a humectant.

  21 Toothpaste according to claim 17, character-

  laughed in that the alkali metal aluminosilicate is an alu-

sodium minosilicate.

  22 Toothpaste according to claim 21, -character-

  laughed in that the sodium aluminosilicate contains about

  0.1 to 3% alumina in combination with silica.

  23 Toothpaste according to claim 22, character-

  laughed in that 1 sodium taluminosilicate contains about

  1% alumina in combination with silica.

  24 limpid toothpaste according to claim 17,

  characterized in that the refractive index of aluminosili-

  sodium cate does not differ by more than 0.005 unit from that of the liquid vehicle