DE2131943A1 - Dentifrice - Google Patents

Description

The invention relates to dentifrices and, more particularly, to a transparent toothpaste in which in small Amounts of iridescent tinsel are dispersed. The toothpaste according to the invention besitat possesses a unique one shimmering appearance very good properties as a dentifrice such as improved stain removal on the teeth.

The transparent toothpastes known per se generally contain a gel or a carrier as a carrier eremige mass with such a consistency that it can simply be removed from a deformable tube such as. B. an aluminum or lead tube, can be pushed out.

The carrier, usually a gel, usually contains liquids and solids. Generally exist the liquid substances from water and / or - a humectant such as glycerine, sorbitol, propylene glycol or polyethylene glycol 400 or mixtures thereof. A mixture is generally advantageous

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applied from water and one or two humectants. The total content of liquids is generally at 20-90 percent by weight of the carrier. The preferred humectants are glycerin and sorbitol. Typically the carrier contains from 0 to 80 percent by weight glycerin, around 20-80 percent by weight sorbitol and • around 20-80 percent by weight water.

The solid content of the carrier is a gelling agent, like natural and artificial rubber and rubber-like materials such as Irish moss, tragacanth, alkali metal salts (e.g. lithium, potassium or sodium) of carboxymethyl cellulose, hydroxymethyl-carboxyethyl cellulose, polyvinylpyrrolidone, starch, water-soluble '' Carboxyvinyl hydrophilic colloidal polymers, which are classified under the Trade names Carbopol 934 and 940 are available, hydroxyethyl cellulose, karaya gum, acacia gums, agar agar, Rubbers, Laponite CP or SP, two under this trade name from Laporte Industries, Ltd. manufactured synthetic inorganic complex silicate clays, pectin or inorganic thickeners such as colloidal silica such as the synthetic very fine silica of the trademarks Cab-O-Sil M5, Syloid 244, Syloid 266 and Aerosil D200. The solids content of the carrier is generally in amounts up to 10 percent by weight and preferably around 0.5-5 percent by weight of the toothpaste.

The composition of transparent, gel-like 109884/1876

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Toothpastes and the conditions necessary for transparency are well known. One knows, for example, that the presence of flavors insoluble in this system reduces the transparency and that appropriate changes Changes, e.g. emulsification, also increase the transparency to increase the solubility of such flavors.

The transparent toothpaste preferably also contains a dentifrice. The type and proportion of cleaning agent should be sized so that the transparency of the toothpaste is not destroyed. A particularly good one usable material is a porous, amorphous silicon dioxide with an average particle size of approximately 1-65 microns, a surface area of about 200-450 m / g and a bulk density of about 0.15-0.3Og / cm Such an amorphous silica contains little water, usually around $ 5 or less, and is therefore often called considered a dehydrated silica gel. The preferred Amorphous silica polishing agents used are Syloid 72 and Syloid 74, which are included in "The Davison Family of Syloid Silicas" by the manufacturer Grace, Davison Chemical Co. to be discribed. Santocel 100 from Monsanto is also a good polishing agent. Syloid 72 has an average particle size of about 4 microns, a surface area of about 340 m / g, and a bulk density of about

■ z

0.177 g / cm, Syloid 74 has an average particle size of

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8 microns, a surface area of about 321 m / g and a. Bulk density of about 0.6 g / cm, a sample of Santocel .100 has an average particle size of about 46-64 microns, a surface area of about 239 m / g and a bulk density of about 0.24 g / cm. These amorphous silicas can be used individually or in mixtures, generally they are used in amounts of about $ 5-50, and preferably $ 10-20, of the toothpaste. The maximum particle size of the preferred amorphous silicon dioxide polishing agents should desirably be below the tactile limit, and thus less than 75 microns. Of course, other cleaning agents can also be used, in particular those whose refractive index is similar to that of the wearer.

Another popular polishing agent is a complex sodium aluminum silicate with a refractive index of approximately 1.44-1.47, a Si / Al molar ratio of approximately 7: 1, a 20 percent by weight moisture content and about 10 percent by weight sodium dioxide content. This material generally has a Particle size of about 35 and preferably 1-20 microns. The preferred moisture content is around 10 - 20 percent by weight, determined by drying to constant weight at 105 ^° C., and the sodium dioxide content is around 5 - 10 percent by weight. This material usually has a loose bulk density.

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te of about 0.2 g / cm and preferably from 0.07-0.12 g / cm ⁵ .

The transparent toothpaste can also contain surfactants, e.g. to achieve better prophylaxis, to effect a thorough and complete distribution of the toothpaste in the oral cavity or the invention To make toothpastes more cosmetically appealing. An anionic, nonionic, amphoteric or cationic surfactant are used, preferably a surfactant that the Toothpaste gives heat and foam properties. These include the water-soluble salts of the higher fatty acid monoglyceride monosulfates such as the sodium salt of the monoglyceride monosulphate of hydrogenated coconut oil fatty acids, higher Alkyl sulfates such as sodium lauryl sulfate, alkyl aryl sulfonates such as sodium dodecyl benzenesulfonaf, higher alkyl sulfoacetates, higher fatty acid esters of 1,2-hydroxypropanesulfonates, the higher saturated aliphatic acylamides of lower aliphatic aminocarboxylic acid compounds with " 12 to 16 carbon atoms in the fatty acid or in the alkyl or acyl radical and other compounds. Examples of such Amides are N-lauro yl-sarcosine and the sodium, potassium or Ethanolamine salts of N-lauro 'yl- or N-myristoyl- or N-palmitoyl sarcosine, which is completely different from soap or similar higher fatty acid compounds should be free, as these reduce the effect of the sarcosines. The use of sarcosins in toothpastes is

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particularly favorable, since these compounds have a prolonged and noticeable prevention of acid formation in the Oral cavity during carbohydrate breakdown and, in addition, a lower solubility of the tooth enamel in acid solutions cause.

Other suitable compounds are the nonionic surfactants such as the condensation products of Sorbifc tan monostearate with about 60 mol of ethylene oxide, condensation products of ethylene oxide with propylene oxide-propylene glycol condensation products ("Pluronics") and amphoteric. ^e re! surfactants such as quaternized imidazole derivatives, which are available under the trade name "Miranol". Cationic surface-active germicides and bactericides can also be used, for example di-isobutyl-phenoxyethoxyethyl-dimethyl-benzyl-ammonium chloride, benzyl-dimethylstearyl-ammonium chloride, or tertiary amines with a higher alkyl group (about 12-18 carbon atoms) and two polyoxyethylene groups on nitrogen (mostly with a total content of 2-50 ethanoxy groups per molecule) and the salts of such amine compounds or compounds with the structural formula

(CH ₂ CH ₂ O) ₂ H ^^^^ (CH ₂ CH ₂ O) _x H

R-Jt-CH ₂ CH ₂ CH ₂ IT t ^ T ^ "^ (CH ₂ CH ₂ O) _y H

in which R is a higher alkyl group with about 12 to 18 carbon atoms and x, y and ζ are an integer from 3 or greater mean, as well as the salts of the compounds with inorganic or organic acids. Usually the total

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content of surfactants 0.05-5 percent by weight and preferably by 1-3 percent by weight, based on the dentifrice.

Various other compounds can also be added to the agent according to the invention, such as white or dyes, protective substances, silicones, chlorophyll compounds, nitrogen compounds such as urea, diammonium phosphate or their mixtures or other compounds.These auxiliaries are usually incorporated into the toothpaste in amounts of up to 5 $.

The toothpaste can also contain antibacterial substances in amounts of approximately 0.01 to 59 °. Examples for this are the guanidines, biguanides and amines such as:

W - (4-chlorobenzyl) -N -2,4- (dichlorobenzyl) biguanide; p-chlorophenyl biguanide;
4-chlorobenzhydryl biguanide;

4-chlorobenzhydryl guanylcarbamide;

5
N-3-lauroxypropyl-N -p-chlorobenzyl-biguanide; 1,6-di-p-chlorophenyl-biguanido-hexane; i-CLauryl-dimethylammonium (i-S-ip-chlorbenzyl-dimethylammonium) octane dichloride;

5,6-dichloro-2-guanidino-benzimidazole;

1 5

N -p-chlorophenyl-N -lauryl-biguanid j 5-Amino-1,3-bis (2aethylhexyl) -5-methyl-hexahydropyrimidinj

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and their non-toxic salts,

In addition, substances which promote taste, sweetness and saliva flow can be added to the agent according to the invention. Examples of flavorings are essential oils v / ie the essential oils of spearmint, peppermint, Gaultheria, Sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon and orange or sodium methyl salicylate; Sweeteners include cane sugar, lactose, maltose, sorbitol, sodium cyclamate and saccharin. Flavor and sweetener together can amount to about $ 0.01 to 2 or more of the agent according to the invention, and chloroform can also be added to modify the taste.

Furthermore, the agent according to the invention can contain fluorine compounds which, as is known, bring about a lower acid solubility of the tooth enamel and a protection of the teeth against caries. Suitable for this are, for example, sodium fluoride, tin-fluoride, potassium fluoride, potassium-sinnfluoride (SnFg'KP), hatri \ un-hexafluorostannate, tin-2-chlorostannate, tin-H-chlorofluoride, sodium fluorozirconate and F & trium-monofluorophosphate. These compounds give off fluorine ions to water and should be contained in effective but non-toxic amounts, usually in amounts of around 0.01-1 percent by weight based on the water-soluble fluorine content «

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The iridescent tinsel according to the invention are usually contained in amounts of up to $ 5, preferably less than $ 3, based on the weight of the transparent toothpaste. A particularly useful product consists of the iridescent lining of mother-of-pearl, a natural excretion on the inner surfaces of oyster shells of non-toxic CaCO. ,, These mother-of-pearl tinsel reflect the light of different wavelengths of the spectrum and their incorporation into a transparent toothpaste (e.g. usually in quantities around 1 , $ 5 to $ 3> preferably $ 2, i.e. $ 1.75 to $ 2.25) results in a multicolored, iridescent effect in the transparent, intact gel and thus a

man
very nice play of colors. If ^ the toothpaste according to the invention from one of the common toothpaste tubes on the toothbrush, the mostly about 4-8 mm wide pressed out piece of toothpaste appears clear with light-reflecting glittering points when the toothpaste is moved on the brush, appear, based on the eye of the Observer, always new points, and the color of these points changes.

Particularly good results were obtained with selected mother-of-pearl tinsel from a 100-mesh sieve (U.S. standard, corresponds to a particle size of around 139 microns) were retained, but a 30-mesh screen (corresponding to a particle size of approximately 590 microns) passed, so that the majority larger than Was 200 microns.

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The mother-of-pearl tinsel can be produced by rubbing oyster shells and mechanical separation, e.g. Flotation of the mother-of-pearl tinsel obtained from the starting material. Most of these tinsel are flat, rounded, less than 50 microns (usually 10-40 microns) thick and oval in top view and consist of numerous thin ones parallel layers, the width of which is 2-3 to less than 1 micron.

Other iridescent tinsel consists of thin, transparent mica coated with titanium dioxide. A pattern of this type of tinsel has a TiO _? - Contains around Mfof an average width of less than one micron (e.g. 0.7 micron), the largest dimension of most flakes is less than 100 microns (e.g. between 15 to 40 microns) and the refractive index of the mica layer is 1.58 and that of the TiO ₂ - Shift is 2.3. When these tinsel are incorporated into a transparent toothpaste in amounts of about $ 0.1 to $ 0.3, and preferably $ 0.25, the toothpaste squeezed out of the tube appears to be glittery too, and there are the individual reflective and iridescent dots are very small and very close together, they give an opaque pearl-like sheen.

Another, but not so desirable, type of tinsel is mica with a layer of another Material, namely BiOCl, whose refractive index differs from that

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the glimmer is different.

By changing the amount or by using mixtures of the different types of flakes, different types can be created Achieve effects.

In addition, it was surprisingly found that the presence of the iridescent tinsel not only represents a unique aesthetic enrichment, but also a noticeable improvement of the dentifrice B. in terms of removing stains from teeth means.

The transparent toothpaste can be produced in a manner known per se by dispersing a gelling agent such as sodium carboxymethyl cellulose or Carbopol 934 and - if desired - a preservative such as sodium benzoate in a humectant such as glycerol and / or glycerol water. After adding another humectant and water such as an aqueous? 0 £ ig6fc Jer1 & t (3 & iÖauö £ kUhl Mt ßlk & wm aof

40-65 ⁰ G * usually 50 ^ö c, ztir form a phloem, a FREEZE gels or oil-eae heated AnBoiiltiBßend is added to the cleaning agent and, if desired, a surfactant such as EB-Katrium iaurylsulfat. The Misehuttg was then cooled and, if desired, flavored and sweetened «

The iridescent tinsel is then

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ORJGfNAL INSPECTED

Lets little exercise incorporated, do a collapse of the gel. The toothpaste is then carefully deaerated, e.g. in a vacuum, and filled into tubes.

It is common in the manufacture of toothpastes to vent the air incorporated into the product to be removed under vacuum as late as possible in the manufacturing process. In the tooth cleaning agent according to the invention it was found that the dispersed air bubbles in a clear gel of corresponding viscosity can improve the appearance and can therefore be left in the gel. On the other hand, the air can also be replaced by another gas in non-toxic quantities such as nitrogen or carbon dioxide will. Carbon dioxide in particular can give the dentifrice a tingly taste.

In the event that all or part of the air is removed from the tooth cleaning agent according to the invention is the one in "Process Engineering" September 1J> "Unimix" apparatus described in 1970, pp. 81-85, is particularly suitable. A mixer rotates in this machine clockwise or in the opposite direction, and this movement is followed by a scraping knife so that the inner The surface of the container is always scraped clean. Tolytetrafluoroethane is preferably used for the scraper knife, dac with the various components dei3 Dental cleaning Ginittel is compatible. . "The attachment dee

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Mixing device and scraper knife on an elevated central column in the apparatus and the existing possibility of applying a vacuum, require that very little Air is incorporated during manufacture. So you get the gelling agent and some of the water first and / or the cleaning agent solution in the "Unimix" machine, and the remaining liquid together with the cleaning agent and the other auxiliary materials (apart from the components such as essential oils, which are added later are processed separately in the "Unimix" and then mix the two mixtures in the "Unimix". The small portion of incorporated air can be removed under reduced pressure if required, as can the components in room or higher temperatures can be processed.

The following examples are intended to explain the invention in more detail. Unless otherwise stated, refer to all quantities by weight and sieve sizes specified are in accordance with U.S. Default.

example 1

A transparent toothpaste of the following composition is made:

Glycerin $ 25, aqueous sorbitol solution $ 40, sodium carboxy- & ethyl cellulose $ 0.35, colloidal silica (bulk density 0.11 g / cm ³ ) $ 3.5, syloid $ 74 $ 18, sodium lauryl sulfate $ 3, water $ 6, $ 1 watery blue color

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solution, preservatives, flavorings

This clear toothpaste comes with $ 2 mother-of-pearl tinsel of the described size (retained by a 100-mesh sieve and not retained by a 40-mesh sieve) mechanically mixed. This transparent glitter toothpaste was based on its ability to stain to remove from human tooth enamel, tested.

In this test, parts of human tooth enamel were etched with 0.1ΪΓ HCl for 2 minutes, rinsed with water, moistened with a dilute tin H fluoride solution, shaken dry and then exposed to hydrogen sulfide gas, whereby a brown precipitate of tin sulfide formed. The amount of precipitation on the surface is then determined using a Gardner automatic color comparator. The surface is then brushed 3000 times in both directions with a slurry of the toothpaste on a mechanical brush and the remaining stains are evaluated with the device. Finally, the stains are completely removed by treatment with dental pumice stone and the reflection of the surface treated in this way is measured. The stain removing effect of a dentifrice is expressed by equation 1: 'm · ν ι ( ^R d 3000 brush movements - ^R d beginning) Equation 1 : · ** π - ■ ~ - ^u κ

d pumice coated - d beginning percent stain removal,

1Q $ 88A / 1876

τ? τ? τ?

where d beginning, d 3000 brush movements and d pumice finely treated the reflection values of the initially spotted surface, treated with 3000 brush movements and after removing the remaining stains by treating with pumice stone.

The toothpaste of the invention has been found to be 34% more effective than a corresponding toothpaste was without mother-of-pearl tinsel.

Example 2

Example 1 was repeated with the exception that instead of the mother-of-pearl tinsel 0.255 ° the one previously described mica flakes coated with titanium dioxide were used. This was an opaque toothpaste obtained with a pearl-like shimmer, which has a similar stain-removing effect as that of Example 1 showed.

Example 3

Example 1 was repeated with the exception that o.25 $ titanium dioxide-coated mica flakes with as largest dimensions around 50 - 80 microns were used,

According to the invention, a clear, transparent toothpaste is used as a matrix in which the flakes are dispersed v / earth. Mostly the transparency of the matrix is like this great that you can go through an 8 mm thick sample of toothpaste

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can easily read normal print such as newspaper print. But of course the flakes can also be added to a somewhat more cloudy or, less desirable, a more or less opaque matrix, and larger amounts of the flakes such as ΙΟ ', ί 15 $ or more can be used to achieve the iridescent or glittering effect will. In a non-translucent matrix, the well-known cleaning agents such as Al ₃ O '3H ₂ O, Ca ₂ HPO.'2H ₂ O, chalk, etc., can be used

Refractive index differs considerably from that of the matrix, to be used. Furthermore, it is within the scope of the invention the iridescent tinsel in tooth cleaning agents other than toothpastes, π «13, toothpaste powders or toothpaste tablets, to incorporate,

Pearl consists of prismatic pseudohexagonalem aragonite (CaCO ^ with -Brechungsindex 1.6809), in which the long crystallographic axes at right angles with the plane h of the leaflets form that are stisammengehalten by Conchiolin, a horn-like organic secretion.

The iridescent materials that are preferred for use have parallel layers less than 1 micron wide, which, through refraction of light, produce interference colors. The refractive indices of the materials s: hid. generally from the index of refraction of the tranrpa'eni cn matrix

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different, the refractive index of the latter "is e.g. in a preferred composition about 1.4 - 1.5.

Example 4

The transparent toothpaste of the following composition is made with the $ 2 pearl tinsel described Mixed size:

Components lot Glycerin 15th Sorbitol ($ 70) 45 Sodium carboxymethyl cellulose 0.7 Syloid 244 5 Sodium aluminum silicate 16 Sodium lauryl sulfate 2 Sodium benzoate 0.5 Sodium saccharine 0.2 dye 0.2 "Flavor 1 chloroform 2.5 water 3

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Claims (8)

Claims 1 «Tooth cleaning agent with a content of iridescent or pearl-like, shimmering flakes, 2. Tooth cleaning agent according to claim 1, characterized in that said flake plates are dispersed in a toothpaste. 3. Tooth cleaning agent according to claim 2 with fc a salary of around 0.1-5 $ of the said in a transparent Toothpaste dispersed flakes. 4. Tooth cleaning agent according to claims 1-3 with a content of non-toxic iridescent or pearl-like shimmering flakes with a smaller one Particle size as 590 microns. 5 «Tooth cleaning agent according to claim 3 with a content of mother-of-pearl flakes with a particle size less than 590 microns. 6. Tooth cleaning agent according to claim 5, characterized in that the concentration of the mother-of-pearl flakes around $ 1.5-3 and that a 4-8mm thick sample of this dentifrice was translucent with visible refractive glittering dots is. 7. Tooth cleaning agent according to claim 3 and 4 with a content of iridescent coated mica platelets chen. 8. Tooth cleaning agent according to claim 7, characterized in that the mica platelets with titanium dioxide 109884/1876 tierchielrfcet are. 9 · Tooth cleaning agent according to claim 8 with a content of titanium dioxide-related mica flakes with a particle size below 100 microns in amounts of 0.1-0.3 $ »characterized in that a 4 - 8 mm
thick sample of this detergent has a non-translucent pearl-like appearance. 109834/1876 BATH ORIGINAL