CA1193550A - Visually clear coloured dentifrice - Google Patents
Visually clear coloured dentifriceInfo
- Publication number
- CA1193550A CA1193550A CA000416116A CA416116A CA1193550A CA 1193550 A CA1193550 A CA 1193550A CA 000416116 A CA000416116 A CA 000416116A CA 416116 A CA416116 A CA 416116A CA 1193550 A CA1193550 A CA 1193550A
- Authority
- CA
- Canada
- Prior art keywords
- dentifrice
- weight
- lake pigment
- lake
- liquid vehicle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- 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
- A61K8/26—Aluminium; Compounds thereof
-
- 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
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
Abstract
ABSTRACT
"VISUALLY CLEAR COLOURED DENTRIFRICE"
There is disclosed a visually clear coloured dentifrice comprising a liquid vehicle having a refractive index between about 1.36 and 1.47, up to about 10% by weight of a gelling agent, about 5-50% by weight of a polishing material having a refractive index similar to that of that of the said liquid vehicle, such that the said dentifrice is visually clear in appearance when the said polishing material is dispersed in the said liquid vehicle and about 0.004-1% by weight of a lake pigment insoluble in water and in the said liquid vehicle, the said lake pigment containing an inherently colourless substrate.
"VISUALLY CLEAR COLOURED DENTRIFRICE"
There is disclosed a visually clear coloured dentifrice comprising a liquid vehicle having a refractive index between about 1.36 and 1.47, up to about 10% by weight of a gelling agent, about 5-50% by weight of a polishing material having a refractive index similar to that of that of the said liquid vehicle, such that the said dentifrice is visually clear in appearance when the said polishing material is dispersed in the said liquid vehicle and about 0.004-1% by weight of a lake pigment insoluble in water and in the said liquid vehicle, the said lake pigment containing an inherently colourless substrate.
Description
33~
1.
"VISllALLY CLEAR COLOURE~:D DENTIF:RICE"
The presen-t invention rela~es to visually clear dentifrices.
Visually clear dentifrices have been marketed in recent years in view of their desirable aesthetic 5. aspect combined with their ability to provide desired hygenic and prophylactic eEfects to teeth and the oral cavity.
In visually clear dentifrices, it is necessary to select insoluble solid components with care since a lO. close match between the refractive index of a solid component and the refrac-tive index of the liquid vehicle is needed in order to provide clarity. For instance, a liquid vehicle mainly of glycerine and/or sorbitol with some water may be proportioned to have a refractive 15. index of abou-t 1.45 and a siliceous polishing material having a similar refractive index incorporated therein.
In order to increase their attractiveness, clear dentifrices have been dyed with water soluble dyes to make them red, yellow, orange, violet, blue, green or 20. other colours. Indeed in British Patent 1,289,323 a plurality of water-soluble dyes are used to make discreetly coloured portions of a clear dentifrice.
Ir.soluble pigment materials have been avoided, since it would have been expected that the match of refractive 25. i~dices needed for clarity between liquid and solid ingredients would be complicated by the presence of an undissolved, dispersed pigment.
It is an advantage of the present invention that, quite unexpectedly, the insoluble aluminium lake 30. pi~ments ar~ efEective and in fact, provide great ~, 355~3 ~.
stability in colouring visually clear dentifrices.
Other advantages will be apparent from consideration of the following disclosure.
In accordance with certaln of its aspects, this 5. invention relates to a visually clear coloured denti-frice comprising a liquid vehicle having a refractive index between about 1.36 and 1.47, up to about 10% by weight of a gelling agent, about 5-50% by weight of a polishing material having a refractive index similar 10. to that of that of the said liquid vehicle, such that the said dentifrice is visually clear in appearance to the extent of being transparent or translucent when the said polishing material is dispersed in the said liquid vehicle and about 0A004-1~ preferably 0.005 to 15. 0.04 and especially 0.01 to 0.04~ by weight of a lake pi~ment insoluble in water and in the said li~uid vehicle, the said lake pigment containing an inherently colourless substrate.
The dentifrice of the present invention contains 20. a liquid vehicle which generally comprises humectant and may include some water. The liquids are selected and if necessary, proportioned to have a refractive index between about 1.36 and 1.47. Refractive indices in khis range match xefractive indices of dentifrice 25. polishing agents such as sodium aluminosilicates (or silica containing combined alumina), described in British Patent Nos. 1,348,492 and 1,347,650 silica xerogels, described in British Patent Nos. 1,186,706 and 1,264,292, insoluble potassium metaphosphate and 30. water-soluble alkali metal phosphates described in 5~
3.
British Patent No. l,424 7 034 and synthetic amorphous silica as described in U.S. Patent Nos. 3,939,262 and 4,007,260.
The most commonly employed humectants for denti-5. frices are glycerine (refractive index of l.47) andsorbi~ol (refractive index of 1.45 in 70% solution).
Other humectants such as low molecular weight polyethy-lene glycols ( e.g. having an average molecular weight of about 400) and propylene glycol may also be 10. employed in a liquid vehicle having a proper refractive index.
Water may also form a portion of the liquid vehicle. Its refractive index is 1.33. When a polishing agent having a refractive index of about l.44-15. l.47 is used, it may be necessary to limit the amount of free water to up to about l0~ by weight of the dentifrice, e.g. about 3-5%; however, when polishing agents of lower refractive index, such as those described in British Patent No. l,424,034 and U.S.
20. Patent No. 3,939,262 and 4,007,260 are used, larger amounts of free water such as about 15% or more may be present. The expression "free water" refers to water which is not specifically associated with sorbitol or another dentirice component. The liquid vehicle 25. typically comprises at least about ~0~ by weight of the dentifrice, e.g. about 20-80~ preferably about 50-75%.
Polishing agents of the type which have refractive indices which can be closely matched with the refractive index of the liquid vehicle have been indicated above.
30. In general, sodium aluminosilicates and silica xerogels 4 ~33~
having refractive indices in the range of about 1~44 to 1.47 are employed and the liquid vehicle is proportioned to have a refractive index similar to that of the polishing agent, typically within about 0.01 unit and 5. preferably within about 0.005 unit or less. The polishing agent typically comprises about 5-50~ by weight, preferably about 10-30% and most preferably about 15-25%, of the dentifrice.
In addition to the liquid vehicle, the dentifrice 10. contains a solid vehicle portion of a gelling agent, possibly supplemented with a thickener to provide gel character to the dentifrice. Typical gelling agents are natural or synthetic gum or gum-like materials, e.g. Irish moss, gum tragacanth, alkali metal carboxy-15. methyl or carboxyethyl cellulose, hydroxyethyl cellu-lose, xanthan, polyvinyl pyrrolidone, starch, water-soluble hydxophilic colloidal carboxyvinyl polymers such as those sold under the trade names Carbopol 934 and Carbopol 940 (CARBOPOL is a Trade Mark) and 20. synthetic inorganic silicated clays such as those sold under the trade names Laponite CP and Laponite SP
(LAPONITE is a Trade Mark). These grades of Laponite have the formula ( BMs5~lLio~6H7 624) 0 6 Na~0 ~
25. The solid portion of the vehicle is typically present in ~n amount up to 10~ by weight of the dentifrice, preferably in the ranye from 0.5 to 5% by weight.
When employed, such grades of Laponite are preferably used in amounts in the range of from 1 to 5% by ~eight.
30. Synthet$c finely divided silicas such as those ~'355~
sold under the krade names Cab-O Sil M-5, Syloid 24, Syloid 266, Aerosll D200 and Zeosyl 200 and mixtures thereof may also be employed in amounts of from 0.5 to 20% by weight to promote thickening or gelling and to 5. improve the clarity of the dentifrice.
The lake pigment employed in the dentifrice contains an inherently colourless substrate. Typical desirable substrates are alumina, zirconia, and titanla, most preferably alumina~ These substrates 10. absorb the pigment onto their surfaces.
The Lakes are familiar to dye chemists. For instance, they are described in the Handbook of U.S.
Colourants for Foods, Drugs, and Cosmetics, D.M. Marmion, Wiley-Interscience P~lication, e.g. at pages 30-31, 15. 96, 106, and 170-172. Many are available from the Anstead Company (U.X.) and are described in this Company's Booklet. They are water-insoluble pigments formed by precipitation and extension of a soluble dye onto an insoluble base or substratum, such as alumina, 20. z:irconia, or titania. D & C colours and FD & C
colours may be used. Water-soluble dyes colour objects by absorption or attachment from their solution to the material which is coloured; lakes, differently, provide colour by dispersion in the medium which is coloured.
25. The success of lakes in coloured visually clear de~tifrices ln particularly unexpected since opacity is a yeneral property of lakes.
The following dyes are illustrated with typical approprlate s~strata therefor:
, .
.~93~:~5~
COLOUR
SUBSTRATE ~ r~l LY~s5Ur~ INDEX NUMBER
Alumi~ Ponceau 4R (red) 16255 Carmo.isine (red) 14720 Amaranth (red) 16185 5. Erythrosine (pink) 45430 Red 2 G (red) 18050 Tartrazine (yellow) 19140 Yellow 2G (yellow) 18965 Sunset Yellow (orange) 15985 10. Quinoline Yellow (yellow) 47005 Green S (green) 44090 Indi~o Carmine (blue) 73015 Patent Blue V (blue) 42051 Brilliant Blue FCF 42090 15. Titania D & C Red No. 19 45170 D ~ C Red No. 21 45380 D & C Red No. 27 45410 D & C Orange No. 5 4S370 Other pigmented lakes which may be used wi~h the 20. various substrata are:
COLOUR_INDEX NUM_ER
FD & C Red No. 2 Lake 16185 FD & C Red No. 3 Lake 45430 FD ~ C Red No. 40 Lake 16035 30. FD & C Yellow No. 5 Lake 19140 FD & C Yellow No. 6 Lake 15985 FD & C Blue No. 1 Lake 42090 FD & C Blue No. 2 Lake 73015 Dispersed Blue (Patent Blue V) Lake 12726 35. Dispersed Blue Lake 18010 5~
7.
Typically about 10-40~ of the lake is the water-soluble dye.
rrhe preferred lakes are on alumina with dispersed blues C.I. 12726 and 18010 being preferred. The lakes 5. are typically present in an amount of 0.011 to 0.04%
e.g. about 0.02%, when the red dyes are used in the alumina lake (depending on the dye content of the lake) and up to about 0.005 to 0.04% when ~he blue dyes or the green dyes are used in the alumina lake. Lakes of 10. other colours are also used in appropriate amounts (depending on the pure dye content of the lake) to provide desired colour depth.
It is preferred that the lake pigment is present in an amount not in excess of 0.035% by weight.
15. The quality or depth of the colour may be modified, if desired, by including a water-soluble dye such as those listed above, separate from the lake in the visually clear dentifrice.
The water-soluble dye should complement the colour 20. effect of the lake. For instance, Patent Blue V is desirable when used with an alumina lake such as dispersed Blue 12726 lake. Typically about 5 to 10 times as much lake is used over the amount of separate water-soluble dye.
25. Organic surface-active agents may be used in the compositions of the present invention to achieve increased prophylactic action, assist in achieving thorough and complete dispersion of the compositions of the present invention throughout the oral cavity, and 30. render the compositions of the present invention more ~3~)~g.~
8.
;
cosmetically acceptable. ~he organic surface-active material may be anionic, nonionic, ampholytic, or cationic in nature, and it is preferred to employ as the surface-active agent a detersive material which 5. imparts to the composition detersive and foaming propex~ies. Suitable types of such detergents include water-soluble salts of higher fatty acid monoglyceride monosulphates, such as the sodium salt of the monosul-phated monoglyceride of hydrogenated coconut oil fatty 10. higher alkyl sulphates, such as sodi~n lauryl sulphates, sodi~n C12 18 alkyl sulphate, alkyl aryl sulphonates~
such as sodi~n dodecyl benzene sulphonate, olefin sulphonates, such as sodium olefin sulphonate in which the olefin group contains 12-21 carbon atoms, higher alkyl sulphoacetates, higher fatty acid esters of 1,2-dihydroxy propane sulphonates, and the substantially saturated higher aliphatic acyl amides of lower alipha-tic amino carboxylic acid compounds, such as those having 12-16 carbons in the fatty acid alkyl or acyl 20. radicals~ Examples of the last mentioned amides are N-lauroyl sarcosine, and the sodium, potassi~un, and ethanolami~e salts of N-lauroyl, N-myristoyl or N~palmitoyl sarcosine, which should be substantially free from soap or similar higher fatty 25. acid material which tends to substantially reduce the effe~t of these compolmds. The use of these sarcosine compounds in dentifrice compositions of the present invention is particularly advantageous since these materials exhibit a prolonged and marked effect in the 30. inhibition of acid formation in the oral cavity due to 3S5~3 9.
carbohydrate breakdown in addition to exerting some reduction in the solubility of tooth enamel in acid solutions.
Other particularly suitable surface-active 5. materials i.nclude nonionic agents such as condensates of sorbitan monostearate with approximately 20 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide, condensates of propylene glycol ~"Pluronics") and amphoteric agents such as quaternized 10. imidazole derivatives, which are available under the trademark "Miranol" C2M. Cationic surface active germi.cides and antibacterial compounds such as di-isobutylphenoxyethyoxyethyl dimethyl benzyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, 15. tertiary amines having one fatty alkyl group (of from 12-18 carbon atoms) and two (poly) oxyethylene groups attached to the nitrogen (typically ~ontaining a total of from about 2 to 50 ethanoxy groups per molecule) and salts therec~f with acids, and compounds of the 20. structure (CH2CH2O) H / (CH2CH2O) H
R-N-c~I2cH2 cH2N - , (CH2CH2O)yH
25. where R represents a fatty alkyl group containing from abont 12 to 18 carbon atoms, and x, y and z total 3 or higher, as well as salts thereof with mineral or organic acids, may also be used. It is preferred to use from about 0.05 to 5% by weight of the foregoing 30. surface-active materials in the oral preparation of the present .invention.
~5 10 .
y suitable flavouring or sweetening materials may he employed in formulating a flavour for the compositions of the present invPntion. Examples of suitable ~lavouring constituents include the flavouring 5. oils, e.g. oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, as well as methylsalicylate. Suitable sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, perillartine and saccharine.
10. Suitably~ flavour and sweetening agents may together comprise from about 0.01 to 5% or more of the composi-tion of the present invention. Chloroform may also be used.
The compositions of the present invention may also 15. contain a fluorine-containing compound having a beneficial effect on the care and hygiene of the oral cavity, e.g. diminution of enamel solubility in acid and protection of the teeth against decay which do not substantially detract from the clarity of the denti-20. frice. Examples thereof include sodium fluoride,potassium fluoride and complex fluorides, particularly sodium monofluorophosphate. These materials, which dissociate or release fluorine-containing ions, suitably may be present in an effective but non~toxic 25. amount, usually within the range of about 0.01 to 1%
by weight of the water-soluble fluorine content thereof. Sodium fluoride and sodium monofluorophosphate are particularly preferred as well as mixtures thereof.
Various okher materials may be incorporated in the 30. oral preparations oE this invention. Examples thereof ~1~3q ~ 3 ll .
are colouring or whi~enlng agents or dyestuffs, preservatives, silicones, chlorophyll compounds, ammoniated mat~rials such as urea, diammoniumphosphate and mix~ures ~hereof, and other constituents. The 5. adjuvants are incorporated in the compositions of the present invention in amounts which do not substantially adversely affect the properties and characteristics desired and are selected and used in proper amounts depending upon the particular type of preparation 10. involved.
Antibacterial agents may also be employed in the oral preparations of the present invention in an amount of about 0.01-5~ by weight. Typical antibacterial agents include 15. Nl-(4-chlorobenzyl)-N5-(2,4-dichlorobenzyl biguanide;
p-chlorophenyl biguanide;
4-chloroben2hydryl biguanide;
4-chlorobenzhydrylguanylurea;
N-3-lauroxypropyl-N -p-chlorobenzylbiguanide;
20. 1,6-di-p-chlorophenylbiguanidohexane;
1,6-bis(2-ethylhexylbiguanido) hexane;
l-(lauryldimethylammonium)-8-(p-chlorobenzyl~
dimethylammonium) octane dichloride;
5,6-dichloro-2-guanidinobenzimidazole;
25. Nl p-chlorophenyl-N5-laurylbiguanide;
~5-amino-1,3-bi.s(2~ethylhexyl)-5-methylhexahydro pyrimidine;
and their non-toxic acid addition salts.
In the manufacture of dentifrices, it is conven~
30. tional to remove entrained air from the product by s~q~
12.
deaeration under vacuum typically at a late stage in the manufacture. If desired the dispersed, immobile air bubbles desirably can be permitted to remain as they can enhance the appearance of the dentifrice.
5. E~urthermore, air can be at least partially removed and reintroduced as subs~antially globular or spheroidal bubbles of say about 0.1-8mm, preferably about 0.5-5mm in size, well distributed in the gel at an average of at least one per cubic centimeter. Such air bubbles 10. may be placed in the gel by stirring it while intro-ducing air. Instead of air, bubbles of another gas, such as nitrogen or carbon dioxide, can be introduced in non-toxic quantity. In particular, carbon dioxide can provide an effervescent character to the dentifrice.
15. In theevent it is desired to have a minimum amount of air in the dentifrice of the present invention, the "Unimix" apparatus described in "Process Engineering"
Sept. 11, 1970, pages 81-85, is particularly efficacious for this purpose. In this apparatus a mixing tool can 20. be rotated in clockwise or counterclockwise manner, and the action of the mixing tool is followed by the action of a scraper blade to ensure that the working surface of the apparatus is scraped clean. Preferably, a plastic such as polytetrafluorethylene is used as 25. the scraper since it is compatible with the various ing~redients of the dentifrice. The positioning of the mixing tool and the scraper from a raised central column in the apparatus and the further presence of a hydraulically operated vacuum tight lid permits but 30. little air to enter the formulation during processing.
5(:~
13.
Thus, gelling agent and a portion of liquid including water and/or humec~ant can be efficiently blended in the Unimix apparatus. Then the remaining liquid can be separately blended with the polishing agent and 5. additional components (except for post-added components, such as flavouring oil) in the Unimix, and then the two dispersions blended together in the Unimix apparatus.
If desired, the small amount of air can be largely removed under the depressuri~ed conditions in the 10. apparatus. The apparatus can be used to blend ingredients at room temperature as well as at higher temperatures.
Furthermore, if desired, visible particles of dyes, pearlescent flakes or particles of insoluble salts of 15. antibacterial agents such as the monofluorophosphate salt or the disarcosinate salt of 1,6-di-p-chlorophenyl-biguanidoxhexane, as well as other particles, can be distributed in the dentifrice.
The dentiErices should have a pH practicable for 20. use. A slightly acid to slightly alkaline pH is preferred~ The dentifrices may be packaged in lined or unlined aluminium tubes, lined lead tubes, plastic tubes or aerosol or pump tubes.
The invention may be put into practice in various 25. ways and a number of specific embodiments will be described to i]lustrate the invention with reference to the accompanying Examples. All amounts are by weight ~mless otherwise indicated.
14.
EX~MPLES 1 to 4 Visually clear dentifrices were prepared and deaerated. The dentifrices had the following compositions:
5, ~ lA 2A 3A 4A
INGREDIENTS PARTS
Glyoerine 25.000 25.000 25.000 25.000 Sorbitol (70~ caq~us soln.) 44.053 44.484 45.984 44.405 Sodium Saccharine 0.170 0.170 0.170 0~170 10. Sodium Carbo~yl Cellulose 0.240 0.190 0.190 0.190 Dispersed Blue Al~
Lake (C.I. 12726) 0.011 0.011 0.011 Water-soluble E~ & C Blue Dye Blue Dye (1%) - - - 0.190 15. Sodium Fluoride 0.100 0.100 0.100 0.100 ZeO 49 (ex H~æ~) ~x~um Aluminosilicate (Silica Wi~l co~bined Alu~na) 17.000 17.000 17.000 17.000 Zeosyl 200 (Silica Thickener) 7.000 6.500 5.000 6.500 20. Sodium C12 18 ~kyl Sulphate 1.666 1.765 1.765 1.765 Flav~ur 1.000 1.000 1.000 1.000 Water 3-000 3.000 3.000 3.000 The blue colour of the visually clear dentifrices of Examples 1 to 3 remained stable longer upon storage 25. than did the blue colour of the visually clear denti-fri~e of Fxample 4 which was less deep and faded during storage.
EXAMPLES 2B and 2C
The colour of the visually clear dentifrice of 30. Example 2 was modified by varying the amount of lake to 15.
0.008 parts (Example 2B) and 0.013 parts (Example 2C), respectively, with corresponding adjustments o the amounts of Sorbitol ~70%).
EXAMPLES 5 to 7 5. Green lakes were used in amounts comparable to the blue lakes of Examples 1 to 3 with desirable colour and stability.
Red la}ces were used in amounts approximately 3 10. times greater than the amount of blue lake in Example 2 (approxØ033) with desirable colour and stabili~y.
r~QW~ t~ Z
Visually clear dentifrices were prepared and deaerated. The dentifrices had the following 15. compositions:
Example _ 10 11 12_ _ INGREDIENTS P~g~
Glycerine25.0000 25.0000 25.0000 25.0000 Sorbitol (70% ~ous SO~l.) 44.5910 44.5870 44.5790 44.4050 20. Sodium Saccharirle 0.1700 0.1700 0.1700 0.1700 Sodium C~*~xymethyl Cblluloæ 0.1900 0.1900 0.1900 0.1900 Di~sed Bl~e ~lu~ium L2ke (C.I. 12726) 0.0035 0.0070 0.0140 Ultramarine Blue pi~E~t 0.0005 0.0010 0.0020 25. Wa~Soluble FD & C
B~ue No. 1 (1%) - - ~ 0.1900 Sodium Mbnofluor~phosphate 0.7600 0.7600 0.7600 0.7600 ZeO 49 (ex. Huber) Sodium Al~nosilicate (Silica with oombirled Alumlna) 17.0000 17.0000 17.0000 17.0000 Zeosyl 200 (Silica Ihi~cener) 6~5000 6.5000 6.5000 6.5000 Sodium C12 18 Alkyl S~lphate 1.7650 1.7650 1.7650 1.7650 FlavDur 1.0000 1.0000 1.0000 1.0000 Water 3.0000 3.0000 3.0000 3.0000 ~L9~3~5~
16.
The blue colour of the visually clear dentifrices of Examples 9 to 11 remained stable longer upon storage than did the blue colour of the visually clear denti-frice of Example 12, which was less deep and faded 5. during storage.
1.
"VISllALLY CLEAR COLOURE~:D DENTIF:RICE"
The presen-t invention rela~es to visually clear dentifrices.
Visually clear dentifrices have been marketed in recent years in view of their desirable aesthetic 5. aspect combined with their ability to provide desired hygenic and prophylactic eEfects to teeth and the oral cavity.
In visually clear dentifrices, it is necessary to select insoluble solid components with care since a lO. close match between the refractive index of a solid component and the refrac-tive index of the liquid vehicle is needed in order to provide clarity. For instance, a liquid vehicle mainly of glycerine and/or sorbitol with some water may be proportioned to have a refractive 15. index of abou-t 1.45 and a siliceous polishing material having a similar refractive index incorporated therein.
In order to increase their attractiveness, clear dentifrices have been dyed with water soluble dyes to make them red, yellow, orange, violet, blue, green or 20. other colours. Indeed in British Patent 1,289,323 a plurality of water-soluble dyes are used to make discreetly coloured portions of a clear dentifrice.
Ir.soluble pigment materials have been avoided, since it would have been expected that the match of refractive 25. i~dices needed for clarity between liquid and solid ingredients would be complicated by the presence of an undissolved, dispersed pigment.
It is an advantage of the present invention that, quite unexpectedly, the insoluble aluminium lake 30. pi~ments ar~ efEective and in fact, provide great ~, 355~3 ~.
stability in colouring visually clear dentifrices.
Other advantages will be apparent from consideration of the following disclosure.
In accordance with certaln of its aspects, this 5. invention relates to a visually clear coloured denti-frice comprising a liquid vehicle having a refractive index between about 1.36 and 1.47, up to about 10% by weight of a gelling agent, about 5-50% by weight of a polishing material having a refractive index similar 10. to that of that of the said liquid vehicle, such that the said dentifrice is visually clear in appearance to the extent of being transparent or translucent when the said polishing material is dispersed in the said liquid vehicle and about 0A004-1~ preferably 0.005 to 15. 0.04 and especially 0.01 to 0.04~ by weight of a lake pi~ment insoluble in water and in the said li~uid vehicle, the said lake pigment containing an inherently colourless substrate.
The dentifrice of the present invention contains 20. a liquid vehicle which generally comprises humectant and may include some water. The liquids are selected and if necessary, proportioned to have a refractive index between about 1.36 and 1.47. Refractive indices in khis range match xefractive indices of dentifrice 25. polishing agents such as sodium aluminosilicates (or silica containing combined alumina), described in British Patent Nos. 1,348,492 and 1,347,650 silica xerogels, described in British Patent Nos. 1,186,706 and 1,264,292, insoluble potassium metaphosphate and 30. water-soluble alkali metal phosphates described in 5~
3.
British Patent No. l,424 7 034 and synthetic amorphous silica as described in U.S. Patent Nos. 3,939,262 and 4,007,260.
The most commonly employed humectants for denti-5. frices are glycerine (refractive index of l.47) andsorbi~ol (refractive index of 1.45 in 70% solution).
Other humectants such as low molecular weight polyethy-lene glycols ( e.g. having an average molecular weight of about 400) and propylene glycol may also be 10. employed in a liquid vehicle having a proper refractive index.
Water may also form a portion of the liquid vehicle. Its refractive index is 1.33. When a polishing agent having a refractive index of about l.44-15. l.47 is used, it may be necessary to limit the amount of free water to up to about l0~ by weight of the dentifrice, e.g. about 3-5%; however, when polishing agents of lower refractive index, such as those described in British Patent No. l,424,034 and U.S.
20. Patent No. 3,939,262 and 4,007,260 are used, larger amounts of free water such as about 15% or more may be present. The expression "free water" refers to water which is not specifically associated with sorbitol or another dentirice component. The liquid vehicle 25. typically comprises at least about ~0~ by weight of the dentifrice, e.g. about 20-80~ preferably about 50-75%.
Polishing agents of the type which have refractive indices which can be closely matched with the refractive index of the liquid vehicle have been indicated above.
30. In general, sodium aluminosilicates and silica xerogels 4 ~33~
having refractive indices in the range of about 1~44 to 1.47 are employed and the liquid vehicle is proportioned to have a refractive index similar to that of the polishing agent, typically within about 0.01 unit and 5. preferably within about 0.005 unit or less. The polishing agent typically comprises about 5-50~ by weight, preferably about 10-30% and most preferably about 15-25%, of the dentifrice.
In addition to the liquid vehicle, the dentifrice 10. contains a solid vehicle portion of a gelling agent, possibly supplemented with a thickener to provide gel character to the dentifrice. Typical gelling agents are natural or synthetic gum or gum-like materials, e.g. Irish moss, gum tragacanth, alkali metal carboxy-15. methyl or carboxyethyl cellulose, hydroxyethyl cellu-lose, xanthan, polyvinyl pyrrolidone, starch, water-soluble hydxophilic colloidal carboxyvinyl polymers such as those sold under the trade names Carbopol 934 and Carbopol 940 (CARBOPOL is a Trade Mark) and 20. synthetic inorganic silicated clays such as those sold under the trade names Laponite CP and Laponite SP
(LAPONITE is a Trade Mark). These grades of Laponite have the formula ( BMs5~lLio~6H7 624) 0 6 Na~0 ~
25. The solid portion of the vehicle is typically present in ~n amount up to 10~ by weight of the dentifrice, preferably in the ranye from 0.5 to 5% by weight.
When employed, such grades of Laponite are preferably used in amounts in the range of from 1 to 5% by ~eight.
30. Synthet$c finely divided silicas such as those ~'355~
sold under the krade names Cab-O Sil M-5, Syloid 24, Syloid 266, Aerosll D200 and Zeosyl 200 and mixtures thereof may also be employed in amounts of from 0.5 to 20% by weight to promote thickening or gelling and to 5. improve the clarity of the dentifrice.
The lake pigment employed in the dentifrice contains an inherently colourless substrate. Typical desirable substrates are alumina, zirconia, and titanla, most preferably alumina~ These substrates 10. absorb the pigment onto their surfaces.
The Lakes are familiar to dye chemists. For instance, they are described in the Handbook of U.S.
Colourants for Foods, Drugs, and Cosmetics, D.M. Marmion, Wiley-Interscience P~lication, e.g. at pages 30-31, 15. 96, 106, and 170-172. Many are available from the Anstead Company (U.X.) and are described in this Company's Booklet. They are water-insoluble pigments formed by precipitation and extension of a soluble dye onto an insoluble base or substratum, such as alumina, 20. z:irconia, or titania. D & C colours and FD & C
colours may be used. Water-soluble dyes colour objects by absorption or attachment from their solution to the material which is coloured; lakes, differently, provide colour by dispersion in the medium which is coloured.
25. The success of lakes in coloured visually clear de~tifrices ln particularly unexpected since opacity is a yeneral property of lakes.
The following dyes are illustrated with typical approprlate s~strata therefor:
, .
.~93~:~5~
COLOUR
SUBSTRATE ~ r~l LY~s5Ur~ INDEX NUMBER
Alumi~ Ponceau 4R (red) 16255 Carmo.isine (red) 14720 Amaranth (red) 16185 5. Erythrosine (pink) 45430 Red 2 G (red) 18050 Tartrazine (yellow) 19140 Yellow 2G (yellow) 18965 Sunset Yellow (orange) 15985 10. Quinoline Yellow (yellow) 47005 Green S (green) 44090 Indi~o Carmine (blue) 73015 Patent Blue V (blue) 42051 Brilliant Blue FCF 42090 15. Titania D & C Red No. 19 45170 D ~ C Red No. 21 45380 D & C Red No. 27 45410 D & C Orange No. 5 4S370 Other pigmented lakes which may be used wi~h the 20. various substrata are:
COLOUR_INDEX NUM_ER
FD & C Red No. 2 Lake 16185 FD & C Red No. 3 Lake 45430 FD ~ C Red No. 40 Lake 16035 30. FD & C Yellow No. 5 Lake 19140 FD & C Yellow No. 6 Lake 15985 FD & C Blue No. 1 Lake 42090 FD & C Blue No. 2 Lake 73015 Dispersed Blue (Patent Blue V) Lake 12726 35. Dispersed Blue Lake 18010 5~
7.
Typically about 10-40~ of the lake is the water-soluble dye.
rrhe preferred lakes are on alumina with dispersed blues C.I. 12726 and 18010 being preferred. The lakes 5. are typically present in an amount of 0.011 to 0.04%
e.g. about 0.02%, when the red dyes are used in the alumina lake (depending on the dye content of the lake) and up to about 0.005 to 0.04% when ~he blue dyes or the green dyes are used in the alumina lake. Lakes of 10. other colours are also used in appropriate amounts (depending on the pure dye content of the lake) to provide desired colour depth.
It is preferred that the lake pigment is present in an amount not in excess of 0.035% by weight.
15. The quality or depth of the colour may be modified, if desired, by including a water-soluble dye such as those listed above, separate from the lake in the visually clear dentifrice.
The water-soluble dye should complement the colour 20. effect of the lake. For instance, Patent Blue V is desirable when used with an alumina lake such as dispersed Blue 12726 lake. Typically about 5 to 10 times as much lake is used over the amount of separate water-soluble dye.
25. Organic surface-active agents may be used in the compositions of the present invention to achieve increased prophylactic action, assist in achieving thorough and complete dispersion of the compositions of the present invention throughout the oral cavity, and 30. render the compositions of the present invention more ~3~)~g.~
8.
;
cosmetically acceptable. ~he organic surface-active material may be anionic, nonionic, ampholytic, or cationic in nature, and it is preferred to employ as the surface-active agent a detersive material which 5. imparts to the composition detersive and foaming propex~ies. Suitable types of such detergents include water-soluble salts of higher fatty acid monoglyceride monosulphates, such as the sodium salt of the monosul-phated monoglyceride of hydrogenated coconut oil fatty 10. higher alkyl sulphates, such as sodi~n lauryl sulphates, sodi~n C12 18 alkyl sulphate, alkyl aryl sulphonates~
such as sodi~n dodecyl benzene sulphonate, olefin sulphonates, such as sodium olefin sulphonate in which the olefin group contains 12-21 carbon atoms, higher alkyl sulphoacetates, higher fatty acid esters of 1,2-dihydroxy propane sulphonates, and the substantially saturated higher aliphatic acyl amides of lower alipha-tic amino carboxylic acid compounds, such as those having 12-16 carbons in the fatty acid alkyl or acyl 20. radicals~ Examples of the last mentioned amides are N-lauroyl sarcosine, and the sodium, potassi~un, and ethanolami~e salts of N-lauroyl, N-myristoyl or N~palmitoyl sarcosine, which should be substantially free from soap or similar higher fatty 25. acid material which tends to substantially reduce the effe~t of these compolmds. The use of these sarcosine compounds in dentifrice compositions of the present invention is particularly advantageous since these materials exhibit a prolonged and marked effect in the 30. inhibition of acid formation in the oral cavity due to 3S5~3 9.
carbohydrate breakdown in addition to exerting some reduction in the solubility of tooth enamel in acid solutions.
Other particularly suitable surface-active 5. materials i.nclude nonionic agents such as condensates of sorbitan monostearate with approximately 20 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide, condensates of propylene glycol ~"Pluronics") and amphoteric agents such as quaternized 10. imidazole derivatives, which are available under the trademark "Miranol" C2M. Cationic surface active germi.cides and antibacterial compounds such as di-isobutylphenoxyethyoxyethyl dimethyl benzyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, 15. tertiary amines having one fatty alkyl group (of from 12-18 carbon atoms) and two (poly) oxyethylene groups attached to the nitrogen (typically ~ontaining a total of from about 2 to 50 ethanoxy groups per molecule) and salts therec~f with acids, and compounds of the 20. structure (CH2CH2O) H / (CH2CH2O) H
R-N-c~I2cH2 cH2N - , (CH2CH2O)yH
25. where R represents a fatty alkyl group containing from abont 12 to 18 carbon atoms, and x, y and z total 3 or higher, as well as salts thereof with mineral or organic acids, may also be used. It is preferred to use from about 0.05 to 5% by weight of the foregoing 30. surface-active materials in the oral preparation of the present .invention.
~5 10 .
y suitable flavouring or sweetening materials may he employed in formulating a flavour for the compositions of the present invPntion. Examples of suitable ~lavouring constituents include the flavouring 5. oils, e.g. oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange, as well as methylsalicylate. Suitable sweetening agents include sucrose, lactose, maltose, sorbitol, sodium cyclamate, perillartine and saccharine.
10. Suitably~ flavour and sweetening agents may together comprise from about 0.01 to 5% or more of the composi-tion of the present invention. Chloroform may also be used.
The compositions of the present invention may also 15. contain a fluorine-containing compound having a beneficial effect on the care and hygiene of the oral cavity, e.g. diminution of enamel solubility in acid and protection of the teeth against decay which do not substantially detract from the clarity of the denti-20. frice. Examples thereof include sodium fluoride,potassium fluoride and complex fluorides, particularly sodium monofluorophosphate. These materials, which dissociate or release fluorine-containing ions, suitably may be present in an effective but non~toxic 25. amount, usually within the range of about 0.01 to 1%
by weight of the water-soluble fluorine content thereof. Sodium fluoride and sodium monofluorophosphate are particularly preferred as well as mixtures thereof.
Various okher materials may be incorporated in the 30. oral preparations oE this invention. Examples thereof ~1~3q ~ 3 ll .
are colouring or whi~enlng agents or dyestuffs, preservatives, silicones, chlorophyll compounds, ammoniated mat~rials such as urea, diammoniumphosphate and mix~ures ~hereof, and other constituents. The 5. adjuvants are incorporated in the compositions of the present invention in amounts which do not substantially adversely affect the properties and characteristics desired and are selected and used in proper amounts depending upon the particular type of preparation 10. involved.
Antibacterial agents may also be employed in the oral preparations of the present invention in an amount of about 0.01-5~ by weight. Typical antibacterial agents include 15. Nl-(4-chlorobenzyl)-N5-(2,4-dichlorobenzyl biguanide;
p-chlorophenyl biguanide;
4-chloroben2hydryl biguanide;
4-chlorobenzhydrylguanylurea;
N-3-lauroxypropyl-N -p-chlorobenzylbiguanide;
20. 1,6-di-p-chlorophenylbiguanidohexane;
1,6-bis(2-ethylhexylbiguanido) hexane;
l-(lauryldimethylammonium)-8-(p-chlorobenzyl~
dimethylammonium) octane dichloride;
5,6-dichloro-2-guanidinobenzimidazole;
25. Nl p-chlorophenyl-N5-laurylbiguanide;
~5-amino-1,3-bi.s(2~ethylhexyl)-5-methylhexahydro pyrimidine;
and their non-toxic acid addition salts.
In the manufacture of dentifrices, it is conven~
30. tional to remove entrained air from the product by s~q~
12.
deaeration under vacuum typically at a late stage in the manufacture. If desired the dispersed, immobile air bubbles desirably can be permitted to remain as they can enhance the appearance of the dentifrice.
5. E~urthermore, air can be at least partially removed and reintroduced as subs~antially globular or spheroidal bubbles of say about 0.1-8mm, preferably about 0.5-5mm in size, well distributed in the gel at an average of at least one per cubic centimeter. Such air bubbles 10. may be placed in the gel by stirring it while intro-ducing air. Instead of air, bubbles of another gas, such as nitrogen or carbon dioxide, can be introduced in non-toxic quantity. In particular, carbon dioxide can provide an effervescent character to the dentifrice.
15. In theevent it is desired to have a minimum amount of air in the dentifrice of the present invention, the "Unimix" apparatus described in "Process Engineering"
Sept. 11, 1970, pages 81-85, is particularly efficacious for this purpose. In this apparatus a mixing tool can 20. be rotated in clockwise or counterclockwise manner, and the action of the mixing tool is followed by the action of a scraper blade to ensure that the working surface of the apparatus is scraped clean. Preferably, a plastic such as polytetrafluorethylene is used as 25. the scraper since it is compatible with the various ing~redients of the dentifrice. The positioning of the mixing tool and the scraper from a raised central column in the apparatus and the further presence of a hydraulically operated vacuum tight lid permits but 30. little air to enter the formulation during processing.
5(:~
13.
Thus, gelling agent and a portion of liquid including water and/or humec~ant can be efficiently blended in the Unimix apparatus. Then the remaining liquid can be separately blended with the polishing agent and 5. additional components (except for post-added components, such as flavouring oil) in the Unimix, and then the two dispersions blended together in the Unimix apparatus.
If desired, the small amount of air can be largely removed under the depressuri~ed conditions in the 10. apparatus. The apparatus can be used to blend ingredients at room temperature as well as at higher temperatures.
Furthermore, if desired, visible particles of dyes, pearlescent flakes or particles of insoluble salts of 15. antibacterial agents such as the monofluorophosphate salt or the disarcosinate salt of 1,6-di-p-chlorophenyl-biguanidoxhexane, as well as other particles, can be distributed in the dentifrice.
The dentiErices should have a pH practicable for 20. use. A slightly acid to slightly alkaline pH is preferred~ The dentifrices may be packaged in lined or unlined aluminium tubes, lined lead tubes, plastic tubes or aerosol or pump tubes.
The invention may be put into practice in various 25. ways and a number of specific embodiments will be described to i]lustrate the invention with reference to the accompanying Examples. All amounts are by weight ~mless otherwise indicated.
14.
EX~MPLES 1 to 4 Visually clear dentifrices were prepared and deaerated. The dentifrices had the following compositions:
5, ~ lA 2A 3A 4A
INGREDIENTS PARTS
Glyoerine 25.000 25.000 25.000 25.000 Sorbitol (70~ caq~us soln.) 44.053 44.484 45.984 44.405 Sodium Saccharine 0.170 0.170 0.170 0~170 10. Sodium Carbo~yl Cellulose 0.240 0.190 0.190 0.190 Dispersed Blue Al~
Lake (C.I. 12726) 0.011 0.011 0.011 Water-soluble E~ & C Blue Dye Blue Dye (1%) - - - 0.190 15. Sodium Fluoride 0.100 0.100 0.100 0.100 ZeO 49 (ex H~æ~) ~x~um Aluminosilicate (Silica Wi~l co~bined Alu~na) 17.000 17.000 17.000 17.000 Zeosyl 200 (Silica Thickener) 7.000 6.500 5.000 6.500 20. Sodium C12 18 ~kyl Sulphate 1.666 1.765 1.765 1.765 Flav~ur 1.000 1.000 1.000 1.000 Water 3-000 3.000 3.000 3.000 The blue colour of the visually clear dentifrices of Examples 1 to 3 remained stable longer upon storage 25. than did the blue colour of the visually clear denti-fri~e of Fxample 4 which was less deep and faded during storage.
EXAMPLES 2B and 2C
The colour of the visually clear dentifrice of 30. Example 2 was modified by varying the amount of lake to 15.
0.008 parts (Example 2B) and 0.013 parts (Example 2C), respectively, with corresponding adjustments o the amounts of Sorbitol ~70%).
EXAMPLES 5 to 7 5. Green lakes were used in amounts comparable to the blue lakes of Examples 1 to 3 with desirable colour and stability.
Red la}ces were used in amounts approximately 3 10. times greater than the amount of blue lake in Example 2 (approxØ033) with desirable colour and stabili~y.
r~QW~ t~ Z
Visually clear dentifrices were prepared and deaerated. The dentifrices had the following 15. compositions:
Example _ 10 11 12_ _ INGREDIENTS P~g~
Glycerine25.0000 25.0000 25.0000 25.0000 Sorbitol (70% ~ous SO~l.) 44.5910 44.5870 44.5790 44.4050 20. Sodium Saccharirle 0.1700 0.1700 0.1700 0.1700 Sodium C~*~xymethyl Cblluloæ 0.1900 0.1900 0.1900 0.1900 Di~sed Bl~e ~lu~ium L2ke (C.I. 12726) 0.0035 0.0070 0.0140 Ultramarine Blue pi~E~t 0.0005 0.0010 0.0020 25. Wa~Soluble FD & C
B~ue No. 1 (1%) - - ~ 0.1900 Sodium Mbnofluor~phosphate 0.7600 0.7600 0.7600 0.7600 ZeO 49 (ex. Huber) Sodium Al~nosilicate (Silica with oombirled Alumlna) 17.0000 17.0000 17.0000 17.0000 Zeosyl 200 (Silica Ihi~cener) 6~5000 6.5000 6.5000 6.5000 Sodium C12 18 Alkyl S~lphate 1.7650 1.7650 1.7650 1.7650 FlavDur 1.0000 1.0000 1.0000 1.0000 Water 3.0000 3.0000 3.0000 3.0000 ~L9~3~5~
16.
The blue colour of the visually clear dentifrices of Examples 9 to 11 remained stable longer upon storage than did the blue colour of the visually clear denti-frice of Example 12, which was less deep and faded 5. during storage.
Claims (8)
1. A visually clear coloured dentifrice comprising a liquid vehicle having a refractive index between about 1.36 and 1.47, up to about 10% by weight of a gelling agent, about 5-50% by weight of a polishing material having a refractive index similar to that of that of the said liquid vehicle, such that the said dentifrice is visually clear in appearance when the said polishing material is dispersed in the said liquid vehicle and about 0.004-1% by weight of a lake pigment insoluble in water and in the said liquid vehicle, the said lake pigment containing an inherently colourless substrate.
2. A dentifrice as claimed in Claim 1 in which the said substrate comprises alumina, zirconia, or titania or a mixture thereof.
3. A dentifrice as claimed in Claim 1 in which the said lake pigment has dispersed in it a blue dye and the said lake pigment is present in amount of about 0.005 - 0.04% by weight.
4. A dentifrice as claimed in Claim 3 in which the said lake pigment is Dispersed Blue Colour Index 12726.
5. A dentifrice as claimed in Claim 4 wherein Patent Blue V dye is present and the amount of the said lake pigment is about 5 to 10 times by weight greater than the amount of dye.
6. A dentifrice as claimed in Claim 1 in which a red dye is dispersed in the said lake pigment and the said lake pigment is present in amount of about 0.01 - 0.04% by weight.
7. A dentifrice as claimed in Claim 6 in which the lake pigment is present in an amount not in excess of 0.035% by weight.
8. A dentifrice as claimed in Claim 1 or Claim 2 in which a green dye is dispersed in the said lake pigment and the said lake pigment is present in amount of about 0.005 - 0.04% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08135326A GB2110083B (en) | 1981-11-24 | 1981-11-24 | Visually clear coloured dentifrice |
| GB8135326 | 1981-11-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1193550A true CA1193550A (en) | 1985-09-17 |
Family
ID=10526091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416116A Expired CA1193550A (en) | 1981-11-24 | 1982-11-23 | Visually clear coloured dentifrice |
Country Status (25)
| Country | Link |
|---|---|
| US (1) | US4444746A (en) |
| JP (1) | JPS58113119A (en) |
| AR (1) | AR231605A1 (en) |
| AT (1) | AT382311B (en) |
| AU (1) | AU549757B2 (en) |
| BE (1) | BE895119A (en) |
| BR (1) | BR8206762A (en) |
| CA (1) | CA1193550A (en) |
| CH (1) | CH651750A5 (en) |
| DE (1) | DE3242739A1 (en) |
| DK (1) | DK163796C (en) |
| ES (1) | ES517602A0 (en) |
| FR (1) | FR2516792B1 (en) |
| GB (1) | GB2110083B (en) |
| GR (1) | GR78380B (en) |
| HK (1) | HK47890A (en) |
| IT (1) | IT1157245B (en) |
| MX (1) | MX162785A (en) |
| NL (1) | NL8204581A (en) |
| NO (1) | NO157444C (en) |
| NZ (1) | NZ202540A (en) |
| PH (1) | PH18641A (en) |
| PT (1) | PT75883B (en) |
| SE (1) | SE453049B (en) |
| ZA (1) | ZA828527B (en) |
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| US20130129642A1 (en) * | 2010-08-06 | 2013-05-23 | Andrew Joiner | Oral care compositions |
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| US4240566A (en) * | 1979-09-17 | 1980-12-23 | Whirlco, Inc. | Captive mixing cap arrangement for multiple chamber container |
| US4368089A (en) * | 1981-09-30 | 1983-01-11 | Colgate-Palmolive Company | Method and apparatus for manufacturing dentifrice containing dispersed speckles |
| US4376762A (en) * | 1981-09-30 | 1983-03-15 | Colgate-Palmolive Company | Functional agglomerated speckles, dentifrices containing such speckles and methods for manufacturing such speckles and dentifrices containing them |
| US4376763A (en) * | 1981-09-30 | 1983-03-15 | Colgate-Palmolive Company | Functional agglomerated speckles, method for manufacture thereof and dentifrices containing such speckles |
-
1981
- 1981-11-24 GB GB08135326A patent/GB2110083B/en not_active Expired
-
1982
- 1982-11-17 NZ NZ202540A patent/NZ202540A/en unknown
- 1982-11-18 ZA ZA828527A patent/ZA828527B/en unknown
- 1982-11-18 GR GR69850A patent/GR78380B/el unknown
- 1982-11-18 DK DK513782A patent/DK163796C/en not_active IP Right Cessation
- 1982-11-19 DE DE19823242739 patent/DE3242739A1/en not_active Ceased
- 1982-11-19 JP JP57203525A patent/JPS58113119A/en active Granted
- 1982-11-23 CA CA000416116A patent/CA1193550A/en not_active Expired
- 1982-11-23 MX MX195299A patent/MX162785A/en unknown
- 1982-11-23 BR BR8206762A patent/BR8206762A/en not_active IP Right Cessation
- 1982-11-23 SE SE8206664A patent/SE453049B/en not_active IP Right Cessation
- 1982-11-23 IT IT49556/82A patent/IT1157245B/en active
- 1982-11-23 PT PT75883A patent/PT75883B/en not_active IP Right Cessation
- 1982-11-23 ES ES517602A patent/ES517602A0/en active Granted
- 1982-11-23 NO NO823922A patent/NO157444C/en unknown
- 1982-11-23 FR FR8219606A patent/FR2516792B1/en not_active Expired
- 1982-11-23 AT AT0425882A patent/AT382311B/en not_active IP Right Cessation
- 1982-11-23 PH PH28186A patent/PH18641A/en unknown
- 1982-11-24 CH CH6861/82A patent/CH651750A5/en not_active IP Right Cessation
- 1982-11-24 BE BE0/209550A patent/BE895119A/en not_active IP Right Cessation
- 1982-11-24 NL NL8204581A patent/NL8204581A/en not_active Application Discontinuation
- 1982-11-24 AR AR291398A patent/AR231605A1/en active
- 1982-11-24 AU AU90840/82A patent/AU549757B2/en not_active Ceased
- 1982-11-24 US US06/444,099 patent/US4444746A/en not_active Expired - Fee Related
-
1990
- 1990-06-21 HK HK478/90A patent/HK47890A/en unknown
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