CA1193549A - Stable dentifrice containing acidic siliceous polishing agent - Google Patents
Stable dentifrice containing acidic siliceous polishing agentInfo
- Publication number
- CA1193549A CA1193549A CA000415864A CA415864A CA1193549A CA 1193549 A CA1193549 A CA 1193549A CA 000415864 A CA000415864 A CA 000415864A CA 415864 A CA415864 A CA 415864A CA 1193549 A CA1193549 A CA 1193549A
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- Prior art keywords
- dentifrice
- weight
- polishing agent
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- amount
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/55—Phosphorus compounds
- A61K8/556—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
- A61K2800/526—Corrosion inhibitors
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT
STABLE DENTIFRICE CONTAINING ACIDIC SILICEOUS
POLISHING AGENT
There is disclosed a dentifrice formulation which is stable in the sense of not producing gassing as evidenced by visually discernable distention over a period of 168 days at 43°C in an unlined aluminium tube.
The formulation comprises an aqueous dentally acceptable oral vehicle at least 27.5% by weight of the dentifrice comprising water and dispersed in the said oral vehicle from 10 to 40% by weight of the dentifrice of a neutral siliceous polishing agent having a stirred slurry pH (as herein defined) in the range from 5 to less than 6.5, and a stabilizing amount of monofluorophosphate ion, the dentifrice having a stirred slurry pH in the range from 5.5 to 8.
STABLE DENTIFRICE CONTAINING ACIDIC SILICEOUS
POLISHING AGENT
There is disclosed a dentifrice formulation which is stable in the sense of not producing gassing as evidenced by visually discernable distention over a period of 168 days at 43°C in an unlined aluminium tube.
The formulation comprises an aqueous dentally acceptable oral vehicle at least 27.5% by weight of the dentifrice comprising water and dispersed in the said oral vehicle from 10 to 40% by weight of the dentifrice of a neutral siliceous polishing agent having a stirred slurry pH (as herein defined) in the range from 5 to less than 6.5, and a stabilizing amount of monofluorophosphate ion, the dentifrice having a stirred slurry pH in the range from 5.5 to 8.
Description
1. 2301-1189 STABLE DENTIFRICE CONTAINING ACIDIC SILICEOUS
POLISHING AGENT
This invention relates to a stable dentifrice and in particular to a dentifrice which can be used in an unlined aluminium tube.
According to the present invention a stable dentifrice comprises an aqueous dentally acceptable oral vehicleJ at least 27.5% and typically 30 to 60%, preferably 40 to 55% for example about 45% by weight of the dentifrice comprising water and dis-persed in the said oral vehicle from 10 to 40%, preferably 10 to 30% and especially 15 to 25% by weight of the dentifrice of an acidic siliceous e.g. alkali metal aluminosilicateJ polishing agent characterised as having a stirred slurry pH ~as defined herein) in the range from 5 to less than 6.5 preEerably 5 to 6.4 e.g. 5.1, 5.2, 5.3 or 5.4 to 6.3, 6.2, 6.1 or 6.0 especially 5.5 to 6.0 particularly 5.7 to 5.9, and a stabilizing amount of mono-fluorophosphate ion, the dentifrice having a stirred slurry pH in the range 5.5 to 8, preferably 6.5 to 7.5, and especially 6.7 to 7.3, optionally a non-toxic amount of at least 0.2% by weight of the dentifrice of chloroform, and desirably, at least when chloro-form is present~ Erom 0.05 to 5% by weight oE the dentifrice of a stabilizing allionlc phosphatc cstcr mixture, the said mixture com-prising monocster oE the Eormula:
( 2 4)n 1 --OM
0~1 alld diester of tlle formula:
o R~OC2H4)nO - I (C2H4 )n OM
I.R. 577F-B Br. 8134926 ~ 3~
wherein R is an alkyl group of 10 to 20 carbon atoms; n is a number from 1 to 6; and M is hydrogen, alkali metal or ammonium. The stabili~ing anionic phosphate ester mixture reduces or prevents corrosion ;n the presence of chloroform and stabilises the dentifrice.
The pH measurement of solids as slurries may be liable to variation depending on how the slurry is made up and we thus prefer to define the technique used for pH measurement herein.
The pH values both for the alkali metal (preferably,sodium) a,lumino silicate (SAS) and the dentifrice formulation were measured on KENT ~lodel No. 7060 pH meter using an ORION combination electrode calibrated at pH
9.2 ~ 0.1 at 20C using British Drug Houses borate buffer and at pH
7.0 * 0.1 at 20 C using BDH phosphate buffer.
~ 20% aqueous slurry iII distilled water of the test material was then made up and stirred for 10 minutes using a magnetic stirrer prior to determination of the pH at 20 C. ~ pll measured this way will be referred to herein as a stirred slurry pH.
It is an advantage of this invention that a stable dentifrice containing siliceous polishing agent is provided.
The stability with which the present invention is concerned is the substantial absence of gas generating reactions between the components oE the dentifrice and the aluminium surface of an unlined aluminium tube as shown by the absence of visually d:iscernable distension of the closed toothpaste tube containing the dentifrice when the said tube has been held at ~3C for 168 clclys.
The invention also extends to an unlined a]uminium tube filled with a stable dentiEr:Lce in accordance with the present invention.
The stab:[lising mono-fluorophosphate ion may be provided by any appropriate compound thereof but a particularly convenient compound is sodium monofluorophosphate.
This may be used in any amount having the necessary defined ~a~ 3 stabilising ef~ect on the particular embodiment of the dentlfrice according to the invention but amounts providing at least 0.01% mono-fluorophosphate ion are prudently used and ~or greater certainty at least 0.05% or at least 0.075, or 0.09%, should be used. Sodium monofluorophosphate will provide such amounts of the monofluorophosphate ion when present in amounts of 0.076, 0.38, 0.57, or 0.68% respectively. Use o:E 0.7 to 0.8% of sodium - 2a -35~
monofluoro~hosphate has been found particularly effec-tive and thus a preferxed proportion thereof is at least 0.7%. Hisher amo~nts are not precluded bu. an upper limit of 7~6% will usually not be exceeded.
5~ The polishing material employed in the present invention is an acidic siliceous material which may contain a small amount e.g. up to about 10~ or somewhat more o~ alumina interbonded in the silica lattice. It can be further characte~ised 25 being synthetic and 10. amorphous and as having a rerractive index between about,l.4 and 1.5.
II desireG, othe~ ?olishins agents which a5 indi-vidual components do not contribute substantially to instability or corrosi~ity with an unlined aluminium 15. surface may also be present. Such additional polishing ager.ts include dicalci~m phosphate dihydrate and anhydrous dicalcium phos?hate as well as tricalcium phosphate)calcium pyrophosphate and calcined alumina.
~hen"an additio~al polishing agent is present, the 2C. amount o ,olishing material in the dentifrice mav amount to up to about 75% by weight preferably 30 to 55% of the dentifrice.
When chloro~orm is present in the formulation it is employed in a non-toxic amount which is effective 25. to provide flavour to the dentifrice. However since chloroform in combination with the siliceous polishing agent results in instabllity and corrosion in the presence of an unlined aluminium surface an appropriate stabilizin~ amount of an anionic phosphate ester' 30. mixture is also incorporated in such chloroform ~9~59~9 ~.
containina ^ormulations. The chloroform may be present in an amount as low as about 0.2~ bv weight of the dentifrice and as high as 8~ by weight or more. An amount of chloroform in the range of 0.5 to 3.5% by 5. weight is preferred. It is noted that in view o the toxic properties of large amounts of chloroform some countries have or are establishing l~gal limits on the maximum amount o_ chloroform which can be used in products such as dentifrices, providing a safety margin 10. by not a?proaching the toxic threshold too closely.
However/ even ~iven such legal maxima, the e.fect o_ the stzbilizing phos?.~ate ester can be observed when non-toxic amoun's such 2S 8~, 5~, 3.5~, 0.5% or 0.2%
by weisht o-^ chloro^orm are present.
15. The anionic phosphate esters are mixtures of mono and di-esters ol the formulas set forth above. Suit-able esters are available from MoDo Kemi AXtiebolaget, formerly Berol Aktiebolaget, o Sweden under the name BERO~ (BEROL is a t~ade mar};) anc may include an 20. anionic triester moieLy too, as well 2S some non~ionic ~ortion. BEROL 729 has alkyl chain lengths of 16 to 18 carbon atoms and contains series of 4 ethylene oxide units. ~EROL 729 is generally used in neu~ralised or partizlly neutralised form.
25. ~urther anio~ic phosphate esters which may be used in acid or neutralised forms axe BEROL 525 which contains alkyl groups of 10 to 18 carbon atoms and series of 5 ethylene oxide units and BEROL 513 which also con~ains alkyl groups of 16 to 18 carbon atoms.
30. However, BEROI, 525, is also preferred in neutralised or 5~
5.
partially neutraliseà form. ~urther BEROL anionic phosphate esters are available 2s-BEROL 521, BEROL 724 and BEROL 733. The weignt ratio of monoester to diester may vary, typically from about 1:10 to 10:1.
5. When the acid forms of the 2nionic phosphate ester surface active agents are neutralised or partially - neutralised, alkali metal, preferably sodium, or ammonium ca,ions are present.
Desirably the s~irred slurry pH OL the completed 10. den,ifrice is in the range LrOm 6.5 to 8, prefer~bly 6.; to 7.5.
The preferred anio~ic phospha,e ester is BE~OL 513.
The anionic phosphate ester, when present, is 1;. used in an amount up to about 5~ by weight e~fective to stabilize the denti rice in an unlined aluminium tube. This amount can be as little asabout 0.05% znd would depend, at least in part on the amounts of chloro orm and siliceous polishing agent presen,. For 20. instance ~ith about 3.5% chloroform, it would be des rable to employ about 1.5~ c~ the anionic ~hosphate ester. A typical ester content would be in the range o 0.1 to 2% by weight, preferably 0.5 to 1.5%, of the dentifrice.
25. Besides stabilizing the dentifrice the anionic phosphate ester also provides sur~ace active proper-ties. Such surface active properties are described in British Patent Specific2tions 1475251 and 1475252.
The dentifrice as mentioned above contains a high 30. proport.ion of a liauiQ vehicle which ma~ comDrise water, in amount of at least 2705~ by ~ight Or the pre-paration. The liquid vehicle may-~dditionally or alternatively comprise humectants such 25 glycerine, but unlike c~nventional high liquid vehicle dentifrices 5. can dispense with such humectants as sorbitol solution or propylene glycol. A mixture of water and clycerine is particularly a~vantageous.
Tne solid portion OL the vehicle o_ the dentifrice is a gellin~ agent or binder such as hydroxyethyl cellulose or ~vdroxypropyl cellulose, Irisr, moss, sum 15. tr2~ac2nth, sodi~m carboxymethyl cellulose, polyvinvl pyrrolidone, xan,han, stzrch or water-soluble hyaro-philic colloidal carboxyvinyl pol~ers such as those sold as C~BOPOL 93~ and 9-~0 (CARBO~OL is a trade mark).
The dentifrices will include an organic surface 20. ac,ive agent which can be replaced by the anionic phosphate ester stabilizing agent if such is present, or retained. Such additional agent may be znionic, nonIonic, cationic or ampholytic in nature, an~ it is preferred to employ as the surface active agent a 25. detexsive material which imparts to the dentifxice detersive and foaming properties. Suitable types of such detergents are wa~er~soluble salts of higher (i.e.
having at least 12 carbon atoms) fatty acid monogly-ceride monosulphates, such as the sodium salt o~ the 30. monosulphated monoglyceriAe OL hydrogenated coconut 35~
7.
oil ~atty acids, hisher alkyl sulphates, such as sodium lauryl sulphate, alkyl aryl sulphonates, such 25 sodium dodecyl benzene sulphonate, olef.in sulpnonates, such as a s~dium olefin sulphonate in which the olefin 5. group contains 12-21 ca~bon atoms, higher alkyl sulpho-acetates, higher fatt~T acid esters of 1,2-dihydroxy propane sulphona.es, and the substantially saturated hig~er aliphatic acyl amides of lower (i.e. having not mo_e than ~ carbon atoms) alipha~ic amino carboxylic 10. acid`com?ou~.ds, such as those ha~!ing 12 to 1~ carbons in the fatty acid, alXyl or acvl radicals. Example~ o~
the last mentionec a~.,ides are ~-lauroyl sarcosine, and ,he sodium, potassium and ethanolamine salts of ~-lauroyl, ~-myristoyl or ~-palmitoyl sarcosine, which 15. should be substantially free from soap or similar higher fa~ty acid materi21 which tends to substantially reduce the effect of these compounds. The use o~ these sarcosine compounds in denti_rices is particularly advantageous since these materials exhibit a prolonged 20. znc ~,arkec efIect in the inhibition of acid form2tion in the oral cavity due .o the carbohydrates breakdown in addition to exerting some reduction in the solubili-ty of tooth enamel in acid solutions.
Other particularly suitable surface-active 25. materials include nonionic agents such as condensates of sorbitan monostearate with approximately 60 moles of ethylene oxide, condensates of ethylene oxide with propylene glycol ("Pluronics"--PLURONIC is a Trade Mark) and amphoteric agents such as quaternised imidazole 30. derivatives, which are avaiiable under the trade mark 3~
8.
MIRANOL such as ~lIR~OL C2M. Cationic surface active germicides and anti~bacterial com~ounds such as di-isobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, tertiary amines havins one ~atty alkyl group 5. (of from 12-1~3 carbon atoms) and two (poly)oxyethylen~
groups attached to the nitrogen (typically containing a to.al o' Lrom 20 to 50 ethanoxy groups per molecule) and salts thereo with acids, and compounds of the s.ructure 10 . ( CH2CH20) zH / ( CH2Cn20) ~H
N-'-H2 C~^2 CH2~\
(Cr;2CH2O)~.H
wherein R is a ~atty alkyl group typicaîly containino from 12 to 18 carbon atoms, and x, y and z total 3 or 15. higher, 2s well as sal~s thereo' with mineral or organic acids, may also be used.
The total amount of surface active agent, including the anionic phospha.e ester, if present, typically does not exceed about 5~.
In cer~n fo~ of this lnvention, in addition to the source of mono-fluoroPho~te ion, a fluori ~ P~idinq co~und is pre ~ t in ~ oral preparation. These o~ounds may be s~ghtly soluble in water or may be ~ly water~soluble. They are d~racterised by their abilit~ to release fluori~e ia~ in water and by substantial freedom from reaction with ~kher a ~ounds of the oral preparation. Amang these materials are organic amine flu~rides such as cetylamine hydrofluoride and bis Ohy~ro~yethyl) - aminopropyl-N--hydroxy-ethyl-octadecyl-amine dihydrofluoride or inorganic fluoride salts, such as suitabls alkali metal, aIkaline earth metal, and heavy metal salts, for example, sodium fluoride, potassium fluoride, 35~
9.
ammonium fluoride, a copper fluoride, such as cuprous fluoride, zinc fluoride, a tin fluoride such as stannous fluoride, or stannous chlorofluoride, sodium fluorosilicate, ammonium fluoro-silicate, sodium fluorozirconate, aluminium mono and di-fluoro-phosphate, and fluorinated sodium calcium pyrophosphate. Alkali metal and tin fluorides are preferred. A mixture of so~ium fluoride and sodium monofluorophosphate is also highly desirable.
The amount of the fluorine-providing compound is depen-dent to some extent upon the type of compound, its solubility, and the type of oral preparation, but it must be a non-toxic amount.
It is considered that an amount of such compound which releases a maximum of 1% by weight of fluoride ion, based on the weight of the preparation, is satisfactory. Any suitable minimum amount of such compound may be used, but it is preferable to employ suffic-ient compound to release from 0.005% to 1%, most preferably about 0.1%, by weight of fluoride ion. Typically, in the cases of alkali metal fluoride and stannous fluoride, this component is present in an amoullt up to 2% by weight, based on the weight of the prepara-tion, and preferably in the range oE from 0.05% to 1%.
Antibacterial agents may also be present, typically ill an amount of 0.01-5% by weight. Typical antibacterial agents in-cludc Nl - (~-chlorobenzyl) - N5 - (2,~-dichlorobenzyl) biguanide;
p - chlorophetlylbiguani.de;
~ - clllorobellzhydrylbiguanide;
s~
10 .
4 - chloro~er,zhydrylsuanylurea;
N ~ 3 - lauxoxypropyl - N5 - p - chlorobenzylbiguanide;
1,6 ~ di p ~ chlorophenylbiguanidohexane;
~chlorhexidine);
5. 1,6 - ~is(2 - ethylhexylbiguanido)hexane;
1 - (lauryldimethylammonium) - 8 - (p-chlorobenzyldi-methyla~monium~ octane dichloride;
5,6 - dichloro - 2 - guanidinobenzimidazole;
~ - p - chlorophenyl - ~ - laurylbiguanide;
10. 5 - amino - 1,3 - bis (2 - ethylhe~vl) - 5 -meth~lhexah~aro ~yr midine;
and their non-toxic aci~ ad~ition salts.
Various other m~ter als may be incorporabed in th~
oral preparations o this invention as adjuvants.
15. Exa~ples are colouring or whitening agents, preserva-tives, silicones, chlorophyll compounds, and ammoniated material such as urea, diammonium phosphate, and mixtures thereof.
These adjuvants, where present, are incorporated 20. in the preparations in amounts which do not substan-tially adversely affect ~he properties and character-; istics desired. Whitening agents such as titanium dioxide or zinc oxide, typically in amount of 0.2 to 1% by weight provide a particularly fine cosmetic 25. appearance to the dentifrice.
The dentifrice will usually contain flavouringand/or sweetening material, in addition to any chloro-form which may be employed. Examples of suitable flavouring constitutents are flavouring oils, e.g.
~0. oils of spearmint, peppermint, wintergreen, sassafras, \
~Lgl.~S~
ll .
clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, and me~hylsalicylate. Sui-table sweetening agents include sucrose, lactose, maltoses, sorbitol, sodium cyclamate, perillartine and sacchzrin. Suitably 5. fla~our and sweetening agents may together comprise ~rom 0.01% to S~ or more of the preparation.
The denti~rice is typically prepared by dispersing the polishing material (and when chloroform is to be present the phosphate ester) in the dental vehicle and 10. other components, (except for the chloroform) and then subjecting the mix.ure to deaeration after which any chloroform ~hich is to be incorporated may be intro-duced in a close~ vacu~-" system.
The centifrice is then placed in an aluminium 15. tube.
Due to the compositions stability to aluminium, the inner surface of the aluminium tube need not be provided with a lining and thus the tubes can be.
unlined aluminium tubes.
20. However the stability OL the composition is o benefit even when lined tubes are to be used because in this case gassing of such ~ubes in which the lining may be defective or damaged in use so as to expose the aluminium sur~ace is avoided. Also the invention 25. permits the use of its chloroform containing embodi~
ments in tubes which,although lined,use linings which can be penetrated by chloroform or its breakdown products.
The invention may be put into practice in ~arious ways and one specific embodiment will be described to illustrate the invention with reference to the accompanying Example.
All amounts and proportions given in this specification are by weight unless otherwise indicated.
EXAMPLE
The dentifrice formulation given in Table 1 below was prepared in conventional manner by mixing the ingredients together and allowing them to gel with the water for 15 minutes at ~5 to 50 C after which the gelled blend was mixed to adequately disperse the powders.
The Table gives the composition and initial properties of the dentifrice Eormulation.
35~
13.
The following points should be noted about th~
data in Table 1.
Note 1 __ The sodium carboxymethyl cellulosè is grade 7 MF.
Note 2 The % soluble fluoride value given is the ~avarage of two readings) X 102, i.e. a figure of 10 in Table 1 .means an average fluoride content of 0.10.
Note 3 _ _ The pH for the dentifrice was measured immediately after the dentifrice had been made up.
The dentifrice formulations given in the Table is filled in conventional mann~r into unlined aluminium tubes.
iL:1935~
_ .
COl~PONENT AMOUNl Glycerine : 25 . 00 Sodium Carboxymethyl Cellulose - ( 1) : 1. 00 Titanium Dioxide : 0.40 Sodium Saccharin : 0.18 Sodium Mono-fluorophosphate : 0.76 ~soluble fluoride (2) ~ 10. 7 Water : 42016 Sodium Aluminosilicate (SAS) : 24.00 SAS Type o Dentolex 644 pH of SAS : 5.8 Sodium Lauryl Sulphate : 1.50 Water 4.00 Flavour : 1.00 pH of dentifrice - (3) : 6.6 ~9~
15.
The dentifrice formulation of the Example aged well in the unlined aluminium tubes over a three month period at 43C, and though it contained some hard lumps throughout this period and suffered some yellowing at the end, there was no gassing.
This lumpiness is thought to be due to some oversize particles being present in the Dentolex 644 SAS
material used and it may be that this problem could be overcome by sieving of this SAS material.
Dentolex 644 may be obtained from Zeofinn YI of Hainina, Finland and the manufacturers describe it as having the following characteristics:
Chemical Composition : Sodium Silico Aluminate Primary Particle Diameter : 0.016 microns Moisture Loss : Not more than 7%
on heating to 105C
~or 2 hours.
Density : 2.0 g/cm3 at 25C
Bulk Density : 30n Rg/m3 as packed Oil Absorption : 170 ml oil/lOOg Refractive Index : 1.47 at 20c
POLISHING AGENT
This invention relates to a stable dentifrice and in particular to a dentifrice which can be used in an unlined aluminium tube.
According to the present invention a stable dentifrice comprises an aqueous dentally acceptable oral vehicleJ at least 27.5% and typically 30 to 60%, preferably 40 to 55% for example about 45% by weight of the dentifrice comprising water and dis-persed in the said oral vehicle from 10 to 40%, preferably 10 to 30% and especially 15 to 25% by weight of the dentifrice of an acidic siliceous e.g. alkali metal aluminosilicateJ polishing agent characterised as having a stirred slurry pH ~as defined herein) in the range from 5 to less than 6.5 preEerably 5 to 6.4 e.g. 5.1, 5.2, 5.3 or 5.4 to 6.3, 6.2, 6.1 or 6.0 especially 5.5 to 6.0 particularly 5.7 to 5.9, and a stabilizing amount of mono-fluorophosphate ion, the dentifrice having a stirred slurry pH in the range 5.5 to 8, preferably 6.5 to 7.5, and especially 6.7 to 7.3, optionally a non-toxic amount of at least 0.2% by weight of the dentifrice of chloroform, and desirably, at least when chloro-form is present~ Erom 0.05 to 5% by weight oE the dentifrice of a stabilizing allionlc phosphatc cstcr mixture, the said mixture com-prising monocster oE the Eormula:
( 2 4)n 1 --OM
0~1 alld diester of tlle formula:
o R~OC2H4)nO - I (C2H4 )n OM
I.R. 577F-B Br. 8134926 ~ 3~
wherein R is an alkyl group of 10 to 20 carbon atoms; n is a number from 1 to 6; and M is hydrogen, alkali metal or ammonium. The stabili~ing anionic phosphate ester mixture reduces or prevents corrosion ;n the presence of chloroform and stabilises the dentifrice.
The pH measurement of solids as slurries may be liable to variation depending on how the slurry is made up and we thus prefer to define the technique used for pH measurement herein.
The pH values both for the alkali metal (preferably,sodium) a,lumino silicate (SAS) and the dentifrice formulation were measured on KENT ~lodel No. 7060 pH meter using an ORION combination electrode calibrated at pH
9.2 ~ 0.1 at 20C using British Drug Houses borate buffer and at pH
7.0 * 0.1 at 20 C using BDH phosphate buffer.
~ 20% aqueous slurry iII distilled water of the test material was then made up and stirred for 10 minutes using a magnetic stirrer prior to determination of the pH at 20 C. ~ pll measured this way will be referred to herein as a stirred slurry pH.
It is an advantage of this invention that a stable dentifrice containing siliceous polishing agent is provided.
The stability with which the present invention is concerned is the substantial absence of gas generating reactions between the components oE the dentifrice and the aluminium surface of an unlined aluminium tube as shown by the absence of visually d:iscernable distension of the closed toothpaste tube containing the dentifrice when the said tube has been held at ~3C for 168 clclys.
The invention also extends to an unlined a]uminium tube filled with a stable dentiEr:Lce in accordance with the present invention.
The stab:[lising mono-fluorophosphate ion may be provided by any appropriate compound thereof but a particularly convenient compound is sodium monofluorophosphate.
This may be used in any amount having the necessary defined ~a~ 3 stabilising ef~ect on the particular embodiment of the dentlfrice according to the invention but amounts providing at least 0.01% mono-fluorophosphate ion are prudently used and ~or greater certainty at least 0.05% or at least 0.075, or 0.09%, should be used. Sodium monofluorophosphate will provide such amounts of the monofluorophosphate ion when present in amounts of 0.076, 0.38, 0.57, or 0.68% respectively. Use o:E 0.7 to 0.8% of sodium - 2a -35~
monofluoro~hosphate has been found particularly effec-tive and thus a preferxed proportion thereof is at least 0.7%. Hisher amo~nts are not precluded bu. an upper limit of 7~6% will usually not be exceeded.
5~ The polishing material employed in the present invention is an acidic siliceous material which may contain a small amount e.g. up to about 10~ or somewhat more o~ alumina interbonded in the silica lattice. It can be further characte~ised 25 being synthetic and 10. amorphous and as having a rerractive index between about,l.4 and 1.5.
II desireG, othe~ ?olishins agents which a5 indi-vidual components do not contribute substantially to instability or corrosi~ity with an unlined aluminium 15. surface may also be present. Such additional polishing ager.ts include dicalci~m phosphate dihydrate and anhydrous dicalcium phos?hate as well as tricalcium phosphate)calcium pyrophosphate and calcined alumina.
~hen"an additio~al polishing agent is present, the 2C. amount o ,olishing material in the dentifrice mav amount to up to about 75% by weight preferably 30 to 55% of the dentifrice.
When chloro~orm is present in the formulation it is employed in a non-toxic amount which is effective 25. to provide flavour to the dentifrice. However since chloroform in combination with the siliceous polishing agent results in instabllity and corrosion in the presence of an unlined aluminium surface an appropriate stabilizin~ amount of an anionic phosphate ester' 30. mixture is also incorporated in such chloroform ~9~59~9 ~.
containina ^ormulations. The chloroform may be present in an amount as low as about 0.2~ bv weight of the dentifrice and as high as 8~ by weight or more. An amount of chloroform in the range of 0.5 to 3.5% by 5. weight is preferred. It is noted that in view o the toxic properties of large amounts of chloroform some countries have or are establishing l~gal limits on the maximum amount o_ chloroform which can be used in products such as dentifrices, providing a safety margin 10. by not a?proaching the toxic threshold too closely.
However/ even ~iven such legal maxima, the e.fect o_ the stzbilizing phos?.~ate ester can be observed when non-toxic amoun's such 2S 8~, 5~, 3.5~, 0.5% or 0.2%
by weisht o-^ chloro^orm are present.
15. The anionic phosphate esters are mixtures of mono and di-esters ol the formulas set forth above. Suit-able esters are available from MoDo Kemi AXtiebolaget, formerly Berol Aktiebolaget, o Sweden under the name BERO~ (BEROL is a t~ade mar};) anc may include an 20. anionic triester moieLy too, as well 2S some non~ionic ~ortion. BEROL 729 has alkyl chain lengths of 16 to 18 carbon atoms and contains series of 4 ethylene oxide units. ~EROL 729 is generally used in neu~ralised or partizlly neutralised form.
25. ~urther anio~ic phosphate esters which may be used in acid or neutralised forms axe BEROL 525 which contains alkyl groups of 10 to 18 carbon atoms and series of 5 ethylene oxide units and BEROL 513 which also con~ains alkyl groups of 16 to 18 carbon atoms.
30. However, BEROI, 525, is also preferred in neutralised or 5~
5.
partially neutraliseà form. ~urther BEROL anionic phosphate esters are available 2s-BEROL 521, BEROL 724 and BEROL 733. The weignt ratio of monoester to diester may vary, typically from about 1:10 to 10:1.
5. When the acid forms of the 2nionic phosphate ester surface active agents are neutralised or partially - neutralised, alkali metal, preferably sodium, or ammonium ca,ions are present.
Desirably the s~irred slurry pH OL the completed 10. den,ifrice is in the range LrOm 6.5 to 8, prefer~bly 6.; to 7.5.
The preferred anio~ic phospha,e ester is BE~OL 513.
The anionic phosphate ester, when present, is 1;. used in an amount up to about 5~ by weight e~fective to stabilize the denti rice in an unlined aluminium tube. This amount can be as little asabout 0.05% znd would depend, at least in part on the amounts of chloro orm and siliceous polishing agent presen,. For 20. instance ~ith about 3.5% chloroform, it would be des rable to employ about 1.5~ c~ the anionic ~hosphate ester. A typical ester content would be in the range o 0.1 to 2% by weight, preferably 0.5 to 1.5%, of the dentifrice.
25. Besides stabilizing the dentifrice the anionic phosphate ester also provides sur~ace active proper-ties. Such surface active properties are described in British Patent Specific2tions 1475251 and 1475252.
The dentifrice as mentioned above contains a high 30. proport.ion of a liauiQ vehicle which ma~ comDrise water, in amount of at least 2705~ by ~ight Or the pre-paration. The liquid vehicle may-~dditionally or alternatively comprise humectants such 25 glycerine, but unlike c~nventional high liquid vehicle dentifrices 5. can dispense with such humectants as sorbitol solution or propylene glycol. A mixture of water and clycerine is particularly a~vantageous.
Tne solid portion OL the vehicle o_ the dentifrice is a gellin~ agent or binder such as hydroxyethyl cellulose or ~vdroxypropyl cellulose, Irisr, moss, sum 15. tr2~ac2nth, sodi~m carboxymethyl cellulose, polyvinvl pyrrolidone, xan,han, stzrch or water-soluble hyaro-philic colloidal carboxyvinyl pol~ers such as those sold as C~BOPOL 93~ and 9-~0 (CARBO~OL is a trade mark).
The dentifrices will include an organic surface 20. ac,ive agent which can be replaced by the anionic phosphate ester stabilizing agent if such is present, or retained. Such additional agent may be znionic, nonIonic, cationic or ampholytic in nature, an~ it is preferred to employ as the surface active agent a 25. detexsive material which imparts to the dentifxice detersive and foaming properties. Suitable types of such detergents are wa~er~soluble salts of higher (i.e.
having at least 12 carbon atoms) fatty acid monogly-ceride monosulphates, such as the sodium salt o~ the 30. monosulphated monoglyceriAe OL hydrogenated coconut 35~
7.
oil ~atty acids, hisher alkyl sulphates, such as sodium lauryl sulphate, alkyl aryl sulphonates, such 25 sodium dodecyl benzene sulphonate, olef.in sulpnonates, such as a s~dium olefin sulphonate in which the olefin 5. group contains 12-21 ca~bon atoms, higher alkyl sulpho-acetates, higher fatt~T acid esters of 1,2-dihydroxy propane sulphona.es, and the substantially saturated hig~er aliphatic acyl amides of lower (i.e. having not mo_e than ~ carbon atoms) alipha~ic amino carboxylic 10. acid`com?ou~.ds, such as those ha~!ing 12 to 1~ carbons in the fatty acid, alXyl or acvl radicals. Example~ o~
the last mentionec a~.,ides are ~-lauroyl sarcosine, and ,he sodium, potassium and ethanolamine salts of ~-lauroyl, ~-myristoyl or ~-palmitoyl sarcosine, which 15. should be substantially free from soap or similar higher fa~ty acid materi21 which tends to substantially reduce the effect of these compounds. The use o~ these sarcosine compounds in denti_rices is particularly advantageous since these materials exhibit a prolonged 20. znc ~,arkec efIect in the inhibition of acid form2tion in the oral cavity due .o the carbohydrates breakdown in addition to exerting some reduction in the solubili-ty of tooth enamel in acid solutions.
Other particularly suitable surface-active 25. materials include nonionic agents such as condensates of sorbitan monostearate with approximately 60 moles of ethylene oxide, condensates of ethylene oxide with propylene glycol ("Pluronics"--PLURONIC is a Trade Mark) and amphoteric agents such as quaternised imidazole 30. derivatives, which are avaiiable under the trade mark 3~
8.
MIRANOL such as ~lIR~OL C2M. Cationic surface active germicides and anti~bacterial com~ounds such as di-isobutylphenoxyethoxyethyl dimethyl benzyl ammonium chloride, tertiary amines havins one ~atty alkyl group 5. (of from 12-1~3 carbon atoms) and two (poly)oxyethylen~
groups attached to the nitrogen (typically containing a to.al o' Lrom 20 to 50 ethanoxy groups per molecule) and salts thereo with acids, and compounds of the s.ructure 10 . ( CH2CH20) zH / ( CH2Cn20) ~H
N-'-H2 C~^2 CH2~\
(Cr;2CH2O)~.H
wherein R is a ~atty alkyl group typicaîly containino from 12 to 18 carbon atoms, and x, y and z total 3 or 15. higher, 2s well as sal~s thereo' with mineral or organic acids, may also be used.
The total amount of surface active agent, including the anionic phospha.e ester, if present, typically does not exceed about 5~.
In cer~n fo~ of this lnvention, in addition to the source of mono-fluoroPho~te ion, a fluori ~ P~idinq co~und is pre ~ t in ~ oral preparation. These o~ounds may be s~ghtly soluble in water or may be ~ly water~soluble. They are d~racterised by their abilit~ to release fluori~e ia~ in water and by substantial freedom from reaction with ~kher a ~ounds of the oral preparation. Amang these materials are organic amine flu~rides such as cetylamine hydrofluoride and bis Ohy~ro~yethyl) - aminopropyl-N--hydroxy-ethyl-octadecyl-amine dihydrofluoride or inorganic fluoride salts, such as suitabls alkali metal, aIkaline earth metal, and heavy metal salts, for example, sodium fluoride, potassium fluoride, 35~
9.
ammonium fluoride, a copper fluoride, such as cuprous fluoride, zinc fluoride, a tin fluoride such as stannous fluoride, or stannous chlorofluoride, sodium fluorosilicate, ammonium fluoro-silicate, sodium fluorozirconate, aluminium mono and di-fluoro-phosphate, and fluorinated sodium calcium pyrophosphate. Alkali metal and tin fluorides are preferred. A mixture of so~ium fluoride and sodium monofluorophosphate is also highly desirable.
The amount of the fluorine-providing compound is depen-dent to some extent upon the type of compound, its solubility, and the type of oral preparation, but it must be a non-toxic amount.
It is considered that an amount of such compound which releases a maximum of 1% by weight of fluoride ion, based on the weight of the preparation, is satisfactory. Any suitable minimum amount of such compound may be used, but it is preferable to employ suffic-ient compound to release from 0.005% to 1%, most preferably about 0.1%, by weight of fluoride ion. Typically, in the cases of alkali metal fluoride and stannous fluoride, this component is present in an amoullt up to 2% by weight, based on the weight of the prepara-tion, and preferably in the range oE from 0.05% to 1%.
Antibacterial agents may also be present, typically ill an amount of 0.01-5% by weight. Typical antibacterial agents in-cludc Nl - (~-chlorobenzyl) - N5 - (2,~-dichlorobenzyl) biguanide;
p - chlorophetlylbiguani.de;
~ - clllorobellzhydrylbiguanide;
s~
10 .
4 - chloro~er,zhydrylsuanylurea;
N ~ 3 - lauxoxypropyl - N5 - p - chlorobenzylbiguanide;
1,6 ~ di p ~ chlorophenylbiguanidohexane;
~chlorhexidine);
5. 1,6 - ~is(2 - ethylhexylbiguanido)hexane;
1 - (lauryldimethylammonium) - 8 - (p-chlorobenzyldi-methyla~monium~ octane dichloride;
5,6 - dichloro - 2 - guanidinobenzimidazole;
~ - p - chlorophenyl - ~ - laurylbiguanide;
10. 5 - amino - 1,3 - bis (2 - ethylhe~vl) - 5 -meth~lhexah~aro ~yr midine;
and their non-toxic aci~ ad~ition salts.
Various other m~ter als may be incorporabed in th~
oral preparations o this invention as adjuvants.
15. Exa~ples are colouring or whitening agents, preserva-tives, silicones, chlorophyll compounds, and ammoniated material such as urea, diammonium phosphate, and mixtures thereof.
These adjuvants, where present, are incorporated 20. in the preparations in amounts which do not substan-tially adversely affect ~he properties and character-; istics desired. Whitening agents such as titanium dioxide or zinc oxide, typically in amount of 0.2 to 1% by weight provide a particularly fine cosmetic 25. appearance to the dentifrice.
The dentifrice will usually contain flavouringand/or sweetening material, in addition to any chloro-form which may be employed. Examples of suitable flavouring constitutents are flavouring oils, e.g.
~0. oils of spearmint, peppermint, wintergreen, sassafras, \
~Lgl.~S~
ll .
clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, and me~hylsalicylate. Sui-table sweetening agents include sucrose, lactose, maltoses, sorbitol, sodium cyclamate, perillartine and sacchzrin. Suitably 5. fla~our and sweetening agents may together comprise ~rom 0.01% to S~ or more of the preparation.
The denti~rice is typically prepared by dispersing the polishing material (and when chloroform is to be present the phosphate ester) in the dental vehicle and 10. other components, (except for the chloroform) and then subjecting the mix.ure to deaeration after which any chloroform ~hich is to be incorporated may be intro-duced in a close~ vacu~-" system.
The centifrice is then placed in an aluminium 15. tube.
Due to the compositions stability to aluminium, the inner surface of the aluminium tube need not be provided with a lining and thus the tubes can be.
unlined aluminium tubes.
20. However the stability OL the composition is o benefit even when lined tubes are to be used because in this case gassing of such ~ubes in which the lining may be defective or damaged in use so as to expose the aluminium sur~ace is avoided. Also the invention 25. permits the use of its chloroform containing embodi~
ments in tubes which,although lined,use linings which can be penetrated by chloroform or its breakdown products.
The invention may be put into practice in ~arious ways and one specific embodiment will be described to illustrate the invention with reference to the accompanying Example.
All amounts and proportions given in this specification are by weight unless otherwise indicated.
EXAMPLE
The dentifrice formulation given in Table 1 below was prepared in conventional manner by mixing the ingredients together and allowing them to gel with the water for 15 minutes at ~5 to 50 C after which the gelled blend was mixed to adequately disperse the powders.
The Table gives the composition and initial properties of the dentifrice Eormulation.
35~
13.
The following points should be noted about th~
data in Table 1.
Note 1 __ The sodium carboxymethyl cellulosè is grade 7 MF.
Note 2 The % soluble fluoride value given is the ~avarage of two readings) X 102, i.e. a figure of 10 in Table 1 .means an average fluoride content of 0.10.
Note 3 _ _ The pH for the dentifrice was measured immediately after the dentifrice had been made up.
The dentifrice formulations given in the Table is filled in conventional mann~r into unlined aluminium tubes.
iL:1935~
_ .
COl~PONENT AMOUNl Glycerine : 25 . 00 Sodium Carboxymethyl Cellulose - ( 1) : 1. 00 Titanium Dioxide : 0.40 Sodium Saccharin : 0.18 Sodium Mono-fluorophosphate : 0.76 ~soluble fluoride (2) ~ 10. 7 Water : 42016 Sodium Aluminosilicate (SAS) : 24.00 SAS Type o Dentolex 644 pH of SAS : 5.8 Sodium Lauryl Sulphate : 1.50 Water 4.00 Flavour : 1.00 pH of dentifrice - (3) : 6.6 ~9~
15.
The dentifrice formulation of the Example aged well in the unlined aluminium tubes over a three month period at 43C, and though it contained some hard lumps throughout this period and suffered some yellowing at the end, there was no gassing.
This lumpiness is thought to be due to some oversize particles being present in the Dentolex 644 SAS
material used and it may be that this problem could be overcome by sieving of this SAS material.
Dentolex 644 may be obtained from Zeofinn YI of Hainina, Finland and the manufacturers describe it as having the following characteristics:
Chemical Composition : Sodium Silico Aluminate Primary Particle Diameter : 0.016 microns Moisture Loss : Not more than 7%
on heating to 105C
~or 2 hours.
Density : 2.0 g/cm3 at 25C
Bulk Density : 30n Rg/m3 as packed Oil Absorption : 170 ml oil/lOOg Refractive Index : 1.47 at 20c
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS;
1. A stable dentifrice comprising an aqueous dentally acceptable oral vehicle, water in an amount of at least 27.5% by weight of the dentifrice, from 10 to 40% by weight of the dentifrice of an acidic siliceous polishing agent dispersed in the oral vehicle and having a stirred slurry pH in the range from 5.0 to less than 6.5, and a stabilizing amount of mono-fluorophosphate ion, the dentifrice having a stirred slurry pH in the range from 5.5 to 8.
2. A stable dentifrice as claimed in claim 1 also comprising a non toxic amount of at least 0.2% by weight of the dentifrice of chloroform and from 0.05 to 5% by weight of the dentifrice of a stabilizing anionic phosphate ester mixture, said mixture comprising monoester of the formula:
and diester of the formula:
wherein R is an alkyl group of 10 to 20 carbon atoms; n is a number from 1 to 6; and M is hydrogen, alkali metal or ammonium.
and diester of the formula:
wherein R is an alkyl group of 10 to 20 carbon atoms; n is a number from 1 to 6; and M is hydrogen, alkali metal or ammonium.
3. A dentifrice as claimed in claim 2 in which the chloroform is present in an amount in the range from 0.5 to 3.5% by weight of the dentifrice.
4. A dentifrice as claimed in claim 3, in which the chloroform is present in an amount of about 0.5% by weight of the dentifrice.
5. A dentifrice as claimed in any of claims 2 to 4, in which the R
group in the anionic phosphate ester mixture contains 16 to 18 carbon atoms and the weight ratio of monoester to diester is from about 1:10 to 10:1.
group in the anionic phosphate ester mixture contains 16 to 18 carbon atoms and the weight ratio of monoester to diester is from about 1:10 to 10:1.
6. A dentifrice as claimed in claim 1 in which the dentifrice comprises at least 30% by weight of water.
7. A dentifrice as claimed in claim 6 in which the dentifrice comprises 35 to 60% by weight of water.
8. A dentifrice as claimed in claim 7 in which the dentifrice comprises 40 to 55% by weight of water.
9. A dentifrice as claimed in claim 1 in which the siliceous polishing agent is an alkali metal aluminosilicate.
10. A dentifrice as claimed in claim 1 in which the siliceous polishing agent comprises 10 to 30% by weight of the dentifrice.
11. A dentifrice as claimed in claim 10 in which the siliceous polishing agent comprises 15 to 25% by weight of the dentifrice.
12. A dentifrice as claimed in claim 1 in which the stirred slurry pH of the siliceous polishing agent is in the range 5.0 to 6.4.
13. A dentifrice as claimed in claim 12 in which the stirred slurry pH of the siliceous polishing agent is in the range 5.5 to 6Ø
14. A dentifrice as claimed in claim 1 comprising at least 0.01% of mono-fluorophosphate ion.
15. A dentifrice as claimed in claim 14 comprising at least 0.05%
of mono-fluorophosphate ion.
of mono-fluorophosphate ion.
16. A dentifrice as claimed in claim 15 comprising at least 0.09% of mono-fluorophosphate ion.
17. A dentifrice comprising 35% to 50% by weight water, 0% to 30%
by weight glycerine, 15 to 25% of an alkali metal aluminosilicate polishing agent having a stirred slurry pH in the range 5.0 to 6.4, at least 0.5% by weight of alkali metal mono-fluorophosphate, calcined alumina in an amount in the range 0% to 15% by weight and one or more organic surface active agents in an amount not in excess of 5% by weight, the dentifrice having a stirred slurry pH in the range 5.5 to 8.
by weight glycerine, 15 to 25% of an alkali metal aluminosilicate polishing agent having a stirred slurry pH in the range 5.0 to 6.4, at least 0.5% by weight of alkali metal mono-fluorophosphate, calcined alumina in an amount in the range 0% to 15% by weight and one or more organic surface active agents in an amount not in excess of 5% by weight, the dentifrice having a stirred slurry pH in the range 5.5 to 8.
18. A packaged dentifrice comprising an unlined aluminium tube and contained therein a dentifrice as claimed in claim 1 or 17 in contact with the aluminium surface of the unlined aluminium tube.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8134926 | 1981-11-19 | ||
| GB08134926A GB2109683B (en) | 1981-11-19 | 1981-11-19 | Stable dentifrice |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1193549A true CA1193549A (en) | 1985-09-17 |
Family
ID=10526008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000415864A Expired CA1193549A (en) | 1981-11-19 | 1982-11-18 | Stable dentifrice containing acidic siliceous polishing agent |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS58126807A (en) |
| AT (1) | AT388868B (en) |
| AU (1) | AU556739B2 (en) |
| BE (1) | BE895054A (en) |
| BR (1) | BR8206655A (en) |
| CA (1) | CA1193549A (en) |
| CH (1) | CH650670A5 (en) |
| DE (1) | DE3241654A1 (en) |
| DK (1) | DK502182A (en) |
| ES (1) | ES517458A0 (en) |
| FR (1) | FR2516382B1 (en) |
| GB (1) | GB2109683B (en) |
| GR (1) | GR77040B (en) |
| IT (1) | IT1158028B (en) |
| NL (1) | NL8204516A (en) |
| NZ (1) | NZ202428A (en) |
| PH (1) | PH18522A (en) |
| SE (1) | SE8206565L (en) |
| ZA (1) | ZA828114B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4425324A (en) * | 1981-05-11 | 1984-01-10 | Colgate-Palmolive Company | Hazed toothpaste |
| JP3025567B2 (en) * | 1991-12-16 | 2000-03-27 | 花王株式会社 | Oral composition |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3538230A (en) * | 1966-12-05 | 1970-11-03 | Lever Brothers Ltd | Oral compositions containing silica xerogels as cleaning and polishing agents |
| GB1277585A (en) * | 1968-10-29 | 1972-06-14 | Unilever Ltd | Toothpastes |
| FR2107827B1 (en) * | 1970-09-21 | 1976-06-04 | Colgate Palmolive Co | |
| GB1365296A (en) * | 1970-10-30 | 1974-08-29 | Unilever Ltd | Dentifrice compositions |
| US3862307A (en) * | 1973-04-09 | 1975-01-21 | Procter & Gamble | Dentifrices containing a cationic therapeutic agent and improved silica abrasive |
| GB1476633A (en) * | 1973-10-03 | 1977-06-16 | Unilever Ltd | Dentifrice composition |
| US4007260A (en) * | 1974-01-21 | 1977-02-08 | Monsanto Company | Dentifrices |
| US4075317A (en) * | 1974-04-29 | 1978-02-21 | Colgate-Palmolive Company | Dental cream composition |
| US4191742A (en) * | 1974-05-22 | 1980-03-04 | J. M. Huber Corporation | Amorphous precipitated siliceous pigments and methods for their production |
| US4144321A (en) * | 1974-10-31 | 1979-03-13 | J. M. Huber Corporation | Amorphous precipitated siliceous pigments and methods for their production |
| US4122160A (en) * | 1974-10-31 | 1978-10-24 | J. M. Huber Corporation | Toothpaste compositions containing improved amorphous precipitated silicas |
| GB1475251A (en) * | 1975-01-15 | 1977-06-01 | Colgate Palmolive Co | Oral preparations |
| GB1587176A (en) * | 1976-09-15 | 1981-04-01 | Huber Corp J M | Abrasive compositions for incorporation in a toothpaste and methods for their production |
| AT358180B (en) * | 1977-12-21 | 1980-08-25 | Blendax Werke Schneider Co | TOOTHPASTE |
| DE2757290A1 (en) * | 1977-12-22 | 1979-07-05 | Blendax Werke Schneider Co | TOOTHPASTE |
| GB1594878A (en) * | 1978-05-19 | 1981-08-05 | Colgate Palmolive Co | Dentifrices |
| GB1587980A (en) * | 1978-05-30 | 1981-04-15 | Colgate Palmolive Co | Dentifrices |
| US4349533A (en) * | 1979-08-20 | 1982-09-14 | Pq Corporation | Toothpaste containing pH-adjusted zeolite |
-
1981
- 1981-11-19 GB GB08134926A patent/GB2109683B/en not_active Expired
-
1982
- 1982-11-04 ZA ZA828114A patent/ZA828114B/en unknown
- 1982-11-08 NZ NZ202428A patent/NZ202428A/en unknown
- 1982-11-11 DK DK502182A patent/DK502182A/en not_active Application Discontinuation
- 1982-11-11 DE DE19823241654 patent/DE3241654A1/en not_active Withdrawn
- 1982-11-16 PH PH28144A patent/PH18522A/en unknown
- 1982-11-16 AT AT0416782A patent/AT388868B/en not_active IP Right Cessation
- 1982-11-18 ES ES517458A patent/ES517458A0/en active Granted
- 1982-11-18 BR BR8206655A patent/BR8206655A/en unknown
- 1982-11-18 CA CA000415864A patent/CA1193549A/en not_active Expired
- 1982-11-18 GR GR69849A patent/GR77040B/el unknown
- 1982-11-18 BE BE0/209504A patent/BE895054A/en not_active IP Right Cessation
- 1982-11-18 IT IT49524/82A patent/IT1158028B/en active
- 1982-11-18 FR FR8219322A patent/FR2516382B1/en not_active Expired
- 1982-11-18 SE SE8206565A patent/SE8206565L/en unknown
- 1982-11-19 JP JP57203524A patent/JPS58126807A/en active Pending
- 1982-11-19 CH CH6755/82A patent/CH650670A5/en not_active IP Right Cessation
- 1982-11-19 AU AU90742/82A patent/AU556739B2/en not_active Ceased
- 1982-11-19 NL NL8204516A patent/NL8204516A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NZ202428A (en) | 1985-10-11 |
| FR2516382B1 (en) | 1986-04-11 |
| BR8206655A (en) | 1983-10-04 |
| ES8401847A1 (en) | 1984-01-01 |
| IT8249524A0 (en) | 1982-11-18 |
| IT1158028B (en) | 1987-02-18 |
| CH650670A5 (en) | 1985-08-15 |
| DE3241654A1 (en) | 1983-05-26 |
| ZA828114B (en) | 1984-06-27 |
| PH18522A (en) | 1985-08-02 |
| AU556739B2 (en) | 1986-11-20 |
| ES517458A0 (en) | 1984-01-01 |
| GR77040B (en) | 1984-09-04 |
| JPS58126807A (en) | 1983-07-28 |
| DK502182A (en) | 1983-05-20 |
| NL8204516A (en) | 1983-06-16 |
| GB2109683A (en) | 1983-06-08 |
| GB2109683B (en) | 1985-09-11 |
| ATA416782A (en) | 1989-02-15 |
| AT388868B (en) | 1989-09-11 |
| FR2516382A1 (en) | 1983-05-20 |
| SE8206565L (en) | 1983-05-20 |
| SE8206565D0 (en) | 1982-11-18 |
| AU9074282A (en) | 1983-05-26 |
| BE895054A (en) | 1983-05-18 |
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