FR2516382A1 - STABLE TOOTHPASTE CONTAINING SILICAOUS ACID POLISHING AGENT - Google Patents

Abstract

THE OBJECT OF THE INVENTION IS A TOOTHPASTE COMPOSITION WHICH IS STABLE IN THE SENSE THAT IT DOES NOT PRODUCE GAS FORMATION AS EVIDENCE BY VISUALLY DISCERNABLE DILATION DURING A TIME LAP OF 168 DAYS AT 43C IN AN ALUMINUM TUBE WITHOUT COATING. THE COMPOSITION INCLUDES AN AQUEOUS VEHICLE FOR USE IN THE MOUTH AND TOOTHPASTE, THE TOOTHPASTE INCLUDING AT LEAST 27.5 BY WEIGHT OF WATER AND, DISPERSED IN THESE VEHICLE, FROM 10 TO 40 BASED ON THE WEIGHT OF THE TOOTHPASTE OF A POLISHING AGENT ACIDIC SILICEOUS HAVING, IN THE FORM OF A SHAKED SUSPENSION, A PH OF 5 TO LESS THAN 6.5, AS WELL AS A STABILIZING QUANTITY OF MONOFLUOROPHOSPHATE ION, THE TOOTHPASTE HAVING, IN THE FORM OF A SHAKING SUSPENSION, A PH OF 5 , 5 A 8.

Description

The present invention relates to a stable toothpaste and, in

  particular, to a toothpaste that can be used in

  an uncoated aluminum tube.

  In accordance with the present invention, a stable toothpaste comprises a vehicle for oral use acceptable in toothpastes, at least 27.5% and especially 30 to%, preferably 40 to 55% and for example about 45% of the weight of the toothpaste being water and, dispersed in said vehicle, from 10 to 40%, preferably from 10 to 30% and most preferably from 15 to 25% relative to the weight of the dentifrice of a siliceous polishing agent For example an aluminosilicate alkali metal acid), characterized in that it has a pH of from 0.5 to less than 6.5, preferably 5.3 or 5.4 to 6.3, 6.2, 6.1 or 6.0, especially 5.5 to 6.0 and particularly 5.7 to 5.9,

  as well as a stabilizing amount of monofluoropiosphate ions, the den-

  tifrice having, in the form of a stirred suspension, a pH of 5.5 to 8,

  preferably from 6.5 to 7.5 and especially from 6.7 to 7.3,

  a nontoxic amount of chloroform accounting for at least 0.2% of the toothpaste weight and desirably at least

  when chloroform is present, from 0.05 to 5%

  the weight of the dentifrice of a stabilizing mixture of

  anionic phosphoric ters, said mixture comprising a monoester having the formula:

O

  I R (OC 2 H 4) n OP OM OM and a diester corresponding to the formula: OM

  R represents a C 10 to C 20 alkyl group, N represents

  a number from 1 to 6, and M representing a hydrogen atom

  The stabilizing mixture of anionic phosphates reduces or prevents corrosion in the presence of chloroform and stabilizes the toothpaste. It is an advantage of the present invention that a stable toothpaste containing a

siliceous polishing.

  The stability of the present invention is the virtually total absence of gas generating reactions between the dentifrice components and the aluminum surface of an uncoated aluminum tube, absence

  highlighted by the lack of visual dilation

  the discernable tube of closed toothpaste

  toothpaste, when the tube was kept at 430 C

for 168 days.

  The invention also relates to an aluminum tube without

  coating filled with a stable toothpaste according to the present

the invention.

  The stabilizing mono-fluorophosphate ions can be provided by any suitable compound, but sodium monofluorophosphate is a suitable compound

Especially.

  It can be used in any proportion

  the necessary stabilizing effect defined on the way in which

  Particularly contemplated use of the dentifrice according to the invention, but proportions providing at least 0.01% of mono-fluorophosphate ions are carefully used and, for greater safety, at least 0.05% must be used.

  or at least 0.075 or 0.09% The sodium monofluorophosphate

  dium provides these proportions of monofluorophosphate ions when present in respective proportions of 0.076, 0.38, 0.57 or 0.68% The use of 0.7 to 0.8% of

  sodium monofluorophosphate has been shown to be particularly

  effective, and that is how it is best to

  at least 0.7%.

  to use higher proportions, but usually an upper limit will not be exceeded

7.6% -

  The polishing material used according to the present invention is an acidic siliceous material which can contain a small amount, for example about 10% or more, of alumina bound to the interior of the silica network. in addition, as being synthetic and amorphous and having a refractive index

from about 1.4 to 1.5.

  If desired, may also be present

  other polishing agents which, considered individually

  do not contribute significantly to instability or corrosivity in the presence of an aluminum surface without

  These additional polishing agents include

  dicalcium phosphate dihydrate and dihydrogen phosphate

  anhydrous calcium, as well as tricalcium phosphate, calcium pyrophosphate and calcined alumina. When an additional polishing agent is present, the proportion of polishing material in the toothpaste may be up to about 75% and preferably from

at 55% of the weight of the toothpaste.

  When chloroform is present in the composition it is used in a non-toxic, effective proportion

  to flavor toothpaste However, like chlorine

  in combination with the siliceous polishing agent results in instability and corrosion phenomena in the presence of an uncoated aluminum surface,

  appropriate stabilizing proportion of a mixture of phos-

  anionic phates is also incorporated into these compounds.

  Chloroform may be present in a proportion as little as 0.2% of the weight of the dentifrice and as high as 8% or more, by weight A weight proportion of chloroform of 0.5 to 3.5% It is worth noting that, because of

  toxic properties of significant proportions of chloro-

  Some countries have imposed or are in the process of imposing

  legal limits on the maximum quantity of chloro-

  form that can be used in products such as toothpastes, providing a margin of safety by not approaching the toxicity threshold too closely. However, even with these

  maxima, one can observe the effect of phosphate phosphate

  biliser when non-toxic weight proportions

  of chloroform of 8%, 5%, 3.5%, 0.5% or 0.2% are present.

  Anionic phosphoric esters are mixtures

  mono and di-esters corresponding to the above formulas.

  Suitable esters are provided by Mo Do Kemi Aktiebo-

  laget, formerly Berol Aktiebolaget, of Sweden, under the name BEROL (BEROL is a trademark) and may also include an anionic triester moiety, as well as

  that a little BEROL 729 nonionic fragment has long

  chain of 16 to 18 carbon atoms and contains series of 4 ethylene oxide units of a

  In general, BEROL 729 is used in a neutral form.

seized or partially neutralized.

  As other anionic phosphoric esters which can be used under

  acid or neutralized form, mention may be made of BEROL 525 which

  holds C 10 to C 18 alkyl groups and series of 5

  ethylene oxide units, and BEROL 513 which also contains

  However, BEROL 525 is also preferable in neutralized or partially neutralized form. Other BEROL type anionic phosphoric esters are available under the names BEROL 621, BEROL 724 and BEROL 733. The weight ratio of monoester

  to diester can vary, especially from about 1/10 to 10/1.

  When the acidic forms of surfactants

  anionic phosphoric esters are neutralized or partially

  If neutralized, metal cations are present

  alkali, preferably sodium or ammonium cations.

  It is desirable that the p H toothpaste completed,

  measured on a shaking suspension, from 6.5 to 8, of

from 6.5 to 7.5.

  The preferred phosphoric ester is a product

provided as BEROL 513.

  The anionic phosphoric ester, when present, is used in a weight proportion of up to about 5%, effective for stabilizing the dentifrice in an uncoated aluminum tube. This proportion can be as low as about 0.05% and depends, at least in part, on the proportions of chloroform and polishing / agent present For example, with about 3.5% chloroform, it is desirable to use about 1.5%

  anionic phosphoric ester

  The ester content is about 0.1 to 2% by weight, and preferably

  from 0.5 to 1.5% based on the weight of the toothpaste.

  In addition to stabilizing the toothpaste, the phospho-

  Anionic activity also confers tensio-

  These surfactant properties are described in

  thebrilliant Britains 1475251 and 1475252.

  The above toothpaste contains a high proportion of a liquid vehicle which may comprise water, in one

  proportion representing at least 27,5% of the weight of the pre-

  The vehicle can additionally or instead of water include humectants such as glycerin, but, unlike conventional dentifrices high content of liquid vehicle, can dispense humectants such as a solution of sorbitol or propylene glycol A mix

  water and glycerine is particularly advantageous.

  The solid part of the toothpaste carrier is a gelling or binding agent such as hydroxyethyl cellulose or hydroxypropyl cellulose, Irish moss, gum

  tragacanth, sodium carboxymethyl cellulose, polyvinyl

  nyl pyrrolidone, xanthan, starch or water-soluble hydrophilic colloidal carboxyvinyl polymers such as those provided under the names CARBOPOL 934 and 940

  (CARBOPOL is a trademark).

  Toothpastes comprise an organic surfactant that can be replaced by the stabilizing agent

  of the anionic phosphoric ester type optionally used

  This additional agent may be of

  anionic, nonionic, cationic or ampholytic, and it is preferable to use as a surfactant a detergent material which imparts detergent and foaming properties to the dentifrice.

  detergents, water-soluble salts of monosulphonate

  higher fatty acid monoglycerides (ie

  ie containing at least 12 carbon atoms) such as the sodium salt of monosulphated monoglyceride

  hydrogenated coconut oil; higher alkyl sulphates

  like sodium lauryl sulphate; alkoylarylsul-

  fonates such as sodium dodecylbenzene sulfonate; olefin sulfonates such as sodium olefin sulfonate wherein the olefinic group contains from 12 to 21 carbon atoms; higher alkyl sulfoacetates;

  higher fatty acid esters of 1,2-dihydroxypropa

  sulphonates; as well as the higher aliphatic acylamides

  almost saturated with amino acid compounds

  lower aliphatic boxylics (that is to say,

  not more than 4 carbon atoms), such as those containing from 12 to 16 carbon atoms in the fatty acid, alkyl or acyl radicals. Examples of the last amides mentioned include N-lauroyl sarcosine, as well as sodium and potassium salts. and ethanolamine of Nlauroyl, N-myristoyl or N-palmitoyl sarcosine, which should be substantially completely free of soap or other similar higher fatty acid material which tends to substantially reduce the effect of these compounds. of these

  sarcosine compounds in toothpastes is particularly

  advantageously because these materials exert a prolonged and clear effect of inhibition of acid formation in the oral cavity due to the decomposition of hydrates

  in addition to reducing the amount of

  bility of dental enamel in acidic solutions.

  Other particularly suitable surfactant materials include nonionic agents such as

  condensates of sorbitan monostearate with approximately 60

  ethylene oxide condensates, ethylene oxide condensates with propylene glycol ("Pluronics" PLURONIC being a trademark) as well as amphoteric agents such as quaternized imidazole derivatives supplied under the brand name

  MIRANOL, such as MIRANOL C 2 M can also be

  use germicides and antibacterial compounds

  cationic surfactants such as diisobutyl chloride

  phenoxyethoxyethyl dimethyl benzyl ammonium, tertiary amines containing a (C 12 to C 18) fatty alkyl group

  and two (poly) oxyethylene groups attached to nitrogen (

  typically in total from 20 to 50 ethanoxy groups per molecule) as well as their salts with acids, and that compounds of structure: (CH 2 CH 2 O) z H CH 2 CH 2 O) XH

R N CH 2 CH 2 N

2 2

Y CH 2 CH 2 O) H

  wherein R represents a fatty alkyl group typically containing from 12 to 18 carbon atoms, and x y and z represent in total 3 or more, and their salts with

inorganic or organic acids.

  The total amount of surfactant, including the optionally present anionic phosphoric ester,

  must, in a representative manner, not exceed approximately 5%.

  According to certain embodiments of the invention, in addition to the source of monofluorophosphate ions, a compound

  fluoride supplier is present in the preparation.

  These compounds may be slightly or wholly hydrophilic

  They are characterized by their liberating power

  fluoride ions in water and a practical absence

  total reaction with other

  the preparation for oral use. Among these compounds,

  will have organic amine fluorides such as fluorhy-

  cetylamine dichloride and bis (hydroxyl) dihydro

  ethyl) -aminopropyl-N-hydroxy-ethyl-octadecylamine, or inorganic fluorides such as suitable salts of alkali metals, alkaline earth metals and heavy metals such as, for example, sodium fluoride, potassium fluoride, ammonium fluoride; a copper fluoride

  like cuprous fluoride; zinc fluoride; a fluorescent

  of tin as stannous fluoride or chlorofluorocarbon

  stannous fiber; sodium fluorosilicate, fluorosilicate

  Ammonium carbonate, sodium fluorozirconate, ammonium mono and difluorophosphate, and fluorinated sodium and calcium pyrophosphate Alkali metal and tin fluorides are preferable A mixture of sodium fluoride and sodium monofluorophosphate is preferable also

very desirable.

  The proportion of fluorine supplier compound depends

  in some measure of the type of compound, its solubility

  and the type of the preparation for oral use, but it must be a non-toxic proportion.

  quantity of this compound which liberates at most 1% of fluorescent ions

  the weight of the preparation is satisfactory.

  Any appropriate minimum proportion may be used

  of this compound, but it is preferable to use sufficient compound to release 0.005 to 1%, and most preferably 0.1% by weight representative fluoride ion, in the case of an alkali metal fluoride and stannous fluoride, this component is present in a proportion which can represent up to 2% of the weight of the preparation and, preferably, in a proportion of 0.05

at 1%.

  Antibacterial agents may also be present

  representative in a proportion by weight

  from 0.01 to 5% As representative examples of anti-

  Bacteria, Nl- (4-chlorobenzyl) -N 5- (2,4-di-

  chlorobenzyl) biguanide; p-chlorophenylbiguanide; 4chlorobenzhydrylbiguanide; 4-chlorobenzhydrylguanyl urea; N-3-Lauroxypropyl-N 5-p-chlorobenzylbiguanide; 1,6-di-pchlorophenylbiguanidohexane (chlorhexidine); 1,6-bis (2-ethylhexylbiguanido) hexane; dichloride

  1- (lauryldiméthylammonium) -8- (p-chlorobenzyldiméthylammo-

  nium) octane; 5,6-dichloro-2-guanidinobenzimidazole;

  Nl-p-chlorophenyl-N 5-laurylbiguanide; 5-amino-1,3-

  bis (2-ethylhexyl) -5-methylhexahydro pyrimidine; as well as

  their addition salts with non-toxic acids.

  Various other substances can be incorporated

  as adjuvants in the following oral preparations:

  As examples, mention may be made of dyestuffs

  bleaching agents, preservatives, silicones

  cones, chlorophyll compounds and

  these ammonia such as urea, diammonium phosphate and

their mixtures.

  These adjuvants, when present, are incor-

  pores in the preparations in proportions which do not

  do not significantly affect the properties and characteristics

  desired whitening agents, such as titanium dioxide or zinc oxide, used in particular

  in a proportion by weight of 0.2 to 1%, confer on the den-

  tifrice a particularly good cosmetic appearance.

  The toothpaste usually contains an aromatic

  and / or sweetener, in addition to any chloroform

  To be used as examples of aromatic constituents,

  suitable species include flavoring essences such as mint, mint, peppermint,

  wintergreen, sassafras, cloves, sage, eucalyptus

  tus, marjoram, cinnamon, lemon and orange, as well as

  Methyl salicylate Examples of suitable sweetening agents are sucrose, lacto,

  maltoses, sorbitol, sodium cyclamate, peril-

  lartine and saccharin Suitably, flavoring and sweetening agents may represent together

  from 0.01 to 5% or more of the preparation.

  In a representative way, the toothpaste is prepared in

  dispersing the polishing material (and, when chlorine

  roform must be present, the phosphoric ester) in the dentifrice vehicle and the other constituents (except chloroform) and then deaerating the mixture, after which any chloroform to be incorporated can be introduced into a

closed vacuum system.

  The toothpaste is then introduced into an aluminum tube. Due to the stability of the composition with respect to aluminum, the inner surface of the aluminum tube does not need to be coated and thus the

  tubes can be uncoated aluminum tubes.

  However, the stability of the composition is advantageous.

  even when using tubes with a coating

  because, in this case, the formation of gases in tubes of this type in which the coating may be defective or damaged in use and expose the aluminum surface is avoided.

  the use of the compositions according to the invention

  chloroform in tubes which, although coated, use coatings that can be penetrated

  chloroform or its decomposition products.

  The invention can be realized in various ways and a particular embodiment will be described in

  the following non-limiting example, given as an illustration

of the invention.

  Unless otherwise indicated, the quantities and proportions

are expressed in weight.

EXAMPLE

  The toothpaste composition shown in Table 1

  The bottom is prepared in a conventional manner by mixing the ingredients and allowing them to gel with water for minutes at a temperature of 45 to 500 ° C., after which the

  gelled mixture is mixed in order to disperse the

adequately.

  The table shows the composition and properties

  initials of the toothpaste composition.

  The measurement of the solids content in the form of suspensions may vary according to the suspension preparation method, and this is why the Applicant prefers to define the technique used here for the measurement of the H.sub.2H. for sodium aluminosilicate (SAS) than for dentifrice compositions were measured on a KENT Model No. 7060 meter using an ORION combined electrode calibrated at pH 9.2 + 0.1 at 200 ° C. using a borate buffer British Drug Houses (BDH)

  and at pH 7.0 ± 0.1 at 200 ° C using a phosphate buffer.

BDH phate.

  A 20% aqueous suspension is then prepared in the distilled water of the test product and stirred for 10 minutes.

  minutes with a magnetic stirrer before deter-

  p H at 20 ° C A p H measured in this way is said

here p H of the stirred suspension.

  1 l The following points should be noted with regard to the indications in Table I: Note 1 Sodium carboxymethylcellulose is of grade 7 MF Note 2 The percentage of soluble fluoride indicated is (the average value of two readings) x 102, that is -to say

  that a value of 10 in Table I indicates an average

only 0.10 fluoride.

  Note 3 The p H toothpaste is measured immediately after the

preparation of the toothpaste.

  The toothpaste composition indicated in the table is conventionally introduced into aluminum tubes

without coating.

TABLE I

QUANTITY CONSTITUENTS

  Glycerine 25.00 Sodium carboxymethylcellulose (1) 1.00 Titanium dioxide 0.40 Sodium saccharin 0.18 Sodium monofluorophosphate 0.76 Percent soluble fluorine (2) 10.7 Water 42.16 Sodium aluminosilicate (SAS) 24 , 00 Product of SAS type Dentolex 644 pH SAS 5.8 Sodium Lauryl Sulfate 1.50 Water 4.00 Flavoring Agent 1.00 p H toothpaste (3) 6.6 The toothpaste composition of the example ages well in uncoated aluminum tubes, during

  a period of three months at 43 C and, although it does

  hold a few hard pieces throughout this time and have a little yellowing at the end, there is

no gas formation.

16382

  It is believed that the formation of these lumps or lumps is due to the presence of some excessively large particles in the Dentolex 644 (SAS product) used and this problem may be solved by passing this SAS product through the sieve. Dentolex 644 can be obtained from Zeofinn Oy in Hainina, Finland, and the manufacturer describes it as having the following characteristics: Chemical composition: Sodium silicoaluminate Primary particle diameter: 0.016 micron Moisture loss: not more than 7% by heating Density Bulk density Oil absorption Refractive index up to 1050 ° C for 2 hours: 2.0 g / cm 3 at 25 ° C: 300 kg / m 3 as packaged: 170 ml oil / 100 g

1.47 to 200 C

Claims (14)

  Stable toothpaste, comprising an aqueous vehicle for oral use acceptable in toothpastes, 27.5% at   the weight of the toothpaste being water, and,   in said oral vehicle, 10 to 40% by weight of the dentifrice of an acidic siliceous polishing agent having, in the form of a stirred suspension, a pH of from 5 to less than 6.5, and a stabilizing proportion; of monofluorophosphate ions, the toothpaste having, in the form of   stirred suspension, a pH of 5.5 to 8.   Stable toothpaste according to Claim 1, characterized in that it also comprises a non-toxic proportion of chloroform representing at least 0.2% of the weight of the dentifrice and from 0.05 to 5%, relative to the weight   toothpaste, a stabilizing mixture of phospho-   anionic mixture, said mixture comprising a monoester corresponding to the formula: ## STR2 ## OM   and a diester corresponding to the formula: II R (OC 2 H 4) O -P O (C 2 H 40) n R 2 4 N 1 (2 4) n OM   R represents a C 10 to C 20 alkyl group, N represents   a number from 1 to 6, and M representing a hydrogen atom   drogen, an alkali metal or ammonium.   Toothpaste according to Claim 2, characterized in that the chloroform is present in a proportion   representing 0.5 to 3.5% of the weight of the toothpaste.   Dentifrice according to Claim 3, characterized in that chloroform is present in a proportion   representing about 0.5% of the weight of the toothpaste.   Toothpaste according to any one of the claims   2 to 4, characterized in that the group R in the   Anionic phosphoric acid mixture contains from 16 to 18 carbon atoms and the weight ratio of monoester 16382   to diester is about 1/10 to 10/1.   6 Toothpaste according to any one of the claims   1 to 5, characterized in that the toothpaste contains at least 30% water, by weight.   Toothpaste according to Claim 6, characterized in that the dentifrice contains from 35 to 60% of water, by weight. 8 dentifrice according to claim 7, characterized in that the toothpaste contains from 40 to 55% of water, weight.   9.Dentifrice according to any one of the claims   1 to 8, characterized in that the polishing agent   siliceous is an alkali metal aluminosilicate.   Toothpaste according to any of the claims   cations 1 to 9, characterized in that the polishing agent   silica represents 10 to 30% of the weight of the toothpaste.   Dentifrice according to Claim 10, characterized in that the siliceous polishing agent is 15 at 25% of the weight of the toothpaste.   12 Toothpaste according to any of the claims   1 to 11, characterized in that the siliceous polishing agent exhibits, as a stirred suspension, a pH of 5.0 at 6.4.   13 A toothpaste according to claim 12, characterized   in that the siliceous polishing agent has   as a stirred suspension, a pH of 5.5 to 6.0.   14 Toothpaste according to any of the claims   cations 1 to 13, characterized in that it contains at least 0.01% monofluorophosphate ions.   Toothpaste according to claim 14, characterized   in that it contains at least 0,05% of monofluoro- phosphate.   Toothpaste according to claim 15, characterized   in that it contains at least 0,09% of monofluoro- phosphate.   A toothpaste comprising, by weight, from 35 to 50% water, from 0 to 30% glycerine, from 15 to 25% of an alkali metal aluminosilicate polishing agent having, in the form of a stirred suspension, a from 5.0 to 6.4, at least 0.5% alkali metal monofluorophosphate, from 0 to 15% calcined alumina, and one or more   organic surfactants in an amount not greater than   than 5%, toothpaste having, in the form of suspension agitated, a pH of 5.5 to 8.   18 Packaged toothpaste, comprising an uncoated aluminum tube and contained therein a   toothpaste according to any one of claims 1   at 17, in contact with the aluminum surface of the aluminum tube minium without coating.