DE2522042A1 - TOOTHPASTE - Google Patents

Description

(Addition to patent

(Patent application P 23 47 787.4))

In the patent (patent application P 23 47 787.4) is one

Toothpaste described as an abrasive to a greater extent sodium bicarbonate and to a lesser extent a water-insoluble one Contains abrasives that are compatible with the sodium bicarbonate in the toothpaste. It has now been found that advantageous toothpastes are obtained even if the abrasive is made from sodium bicarbonate to a lesser extent and consists largely of a water-insoluble abrasive that is compatible with the sodium bicarbonate. the Toothpastes according to the invention are suitable for filling into unlined aluminum tubes.

Sodium bicarbonate is used in many fields and is a common household item. In the past few years became its use in dentifrices, in particular Tooth powders suggested. It was generally, however

509850 / 09S8

not particularly received. Typical dentifrices that Toothpastes with a high content of toothpastes have been accepted by consumers in substantial quantities in recent years water-insoluble abrasives, such as dicalcium phosphate or other insoluble phosphates in an aqueous, the moisture reluctant carrier.

The development of a practical and effective toothpaste containing sodium bicarbonate, which is consumed by the consumer accepted poses a number of problems. One of the factors to be considered is the special chemical, physical and cosmetic properties of sodium bicarbonate when used as a component in toothpaste. For example, it is relatively water soluble and tends to release carbon dioxide in an aqueous system. It has an extremely salty taste, which is probably one of the more important factors in buying and using one specific product. Other factors in formulating a suitable product are overall cleaning efficiency The polishing power of the product, its stability and appearance, the special care with which it is made must, etc.

When formulating a dentifrice based on of precipitated calcium carbonate must be the intolerance of the

509850/0968

Calcium carbonate with acids and most fluoride salts should be considered. If a dentifrice both Thus, containing sodium bicarbonate as well as calcium carbonate, several problems must be considered. The foregoing are some of the many difficulties the invention overcomes.

Another feature of the invention relates to the filling of the toothpastes in non-lined aluminum tubes, which because of their relatively low cost and light weight are preferred. When toothpastes in unlined When aluminum containers are filled, the containers sometimes corrode and / or the toothpaste becomes unstable will.

The invention provides a toothpaste that can be filled into aluminum containers and is compatible with them and a backing which contains, dispersed or dissolved, about 20 to 60% abrasive, the Abrasives consist to a large extent of calcium carbonate and to a lesser extent of sodium bicarbonate. if in one embodiment of the invention, the toothpaste is filled in unlined aluminum tubes and the toothpaste also contains aluminum oxide as an abrasive it is advantageous if it contains about 0.05 to 0.25% silicate

5098 5 0/0968

dissolves or disperses them to the compatibility of the toothpaste to improve with the unlined aluminum container. The calcium carbonate also acts as a stabilizing agent for composition and retains active fluoride. Toothpastes containing calcium carbonate have in regard to tooth stain removal has an improved effectiveness.

The calcium carbonate can be used in the form of chalk. Chalk in the form of a powder with a particle size between 1 and 10 microns is preferred. It is also beneficial to use a calcium carbonate with a moderate apparent specificity Weight of for example about 0.7-0.9 to be used. If desired, calcium carbonate .with a higher apparent specific gravity of, for example, 1.19 to 1.29 can be used. The "apparent specific Weight "refers to the non-tamped specific gravity of the calcium carbonate. Calcium carbonate, in particular in the form of chalk, often contains magnesium carbonate as an impurity. Calcium carbonate, which contains only small amounts of magnesium carbonate of about 0.1 to 0.3%, for example, tends to reduce the durability of a fluoride-containing toothpaste to affect. The permanent toothpastes of the invention allow small amounts of contaminants, for example Magnesium carbonate in amounts less than about 1%.

509850/0968

Preferably, however, the magnesium carbonate should be about 0.1 to 0.5% based on the calcium carbonate, especially when fluoride is present.

The presence of magnesium carbonate impurities in calcium carbonate or chalk also affects the compatibility of the toothpaste with unclad aluminum surfaces. if Magnesium carbonate is present in an amount of at least about 0.1% of the total calcium carbonate will be beneficial between about 0.025 and 0.25% silicate is dissolved or dispersed in the toothpaste to make it compatible with not increase lined aluminum tanks.

According to the invention it has now become possible to use a sodium bicarbonate To make toothpaste containing, which can be filled into aluminum tubes, the hygienic conditions promotes in the oral cavity and meets consumer demands. This dentifrice has acceptable cleaning, Polishing and other desirable properties and thus a good effect on the parts of the dental system (the teeth and including their surrounding or adjacent areas, such as plaque, tartar, gums, mucous membranes, saliva, etc.) . In particular, it leaves the consumer with a desired fresh mouthfeel. The inventive Product can be formulated so that it is in storage

5098S0 / 0968

is stable without releasing significant amounts of carbon dioxide bubbles or unwanted segregation or other To be subject to reactions. When using certain amounts of bicarbonate it is possible, partly due to the im substantial homogeneous distribution of macroscopic crystalline bicarbonate particles in an otherwise smooth, continuous Carrier to manufacture and maintain granules of non-crystalline appearance.

It is an object of the invention to produce a toothpaste containing abrasives which is larger in size Part of water-insoluble abrasives or mixtures thereof and a smaller part of sodium bicarbonate. The abrasive can, for example, consist of a larger amount of calcium carbonate, which is preferably about 20 to 60% of the toothpaste and a smaller amount of sodium bicarbonate. As a water-insoluble abrasive, chalk, Silica, alumina, zirconium silicate, sodium aluminosilicate or another compatible silicate or carbonate that does not react with the bicarbonate can be used, or a mixture of two or more of these water-insoluble abrasives. The amount of the water-insoluble is advantageously Abrasive more than 20% and especially at least about 25% of the toothpaste, usually about 25 to 50% and even better about 25 to 35%.

509850/0968

Although the sodium bicarbonate particles compared to the most conventional abrasive particles used in toothpastes are relatively soft, they exert a mechanical cleaning effect on the teeth. For example can in a radioactive dentin grinding test (RDA) an approx. 50% Toothpaste containing sodium bicarbonate as the only abrasive has an RDA of about 100, while the Examination of the abrasive-free backing of this toothpaste showed an RDA value of only about 50.

The toothpastes according to the invention preferably contain 1 to about 25% and especially about 10 to 20% sodium bicarbonate. The particle size of the sodium bicarbonate particles can vary. It is preferably largely below 0.40 mm with a greater proportion by weight of over 0.01 mm. The carrier in which the sodium bicarbonate particles dispersed is preferably aqueous, its amount and nature being preferred however, selected so that the sodium bicarbonate is mainly in the undissolved solid state in the toothpaste is present. Of course, however, when you brush your teeth, the sodium bicarbonate particles will tend to settle in the To loosen saliva.

According to a preferred embodiment of the invention, there is the water-insoluble, larger amount of abrasive

B09850 / 096B

medium made of chalk. It has been found that this ingredient greatly improves the detergency of the sodium bicarbonate. In addition, the presence of the chalk appears to increase the resistance of the toothpaste to aging at elevated temperatures increase so that the tendency of the essential oils used as flavorings to deteriorate during aging at 43 or 49 ° C from the toothpaste, for example when the sodium bicarbonate particles are relatively large, and for example over 150 microns in diameter will.

The use of the water-insoluble abrasives such as chalk, silica, alumina, zirconium silicate and the like or a mixture of these results in a toothpaste containing sodium bicarbonate which, in addition to a lack of tendency to separate the flavor and gas formation during storage has improved cleaning power. In contrast to this can be achieved using conventional abrasives such as dicalcium phosphate or insoluble sodium metaphosphate in the Sodium bicarbonate toothpaste generates considerable amounts of gas even when stored for a short time (for example at 49 ° C), when the sodium bicarbonate is present in sufficient quantity.

The average particle size of the chalk is preferably less than 20 microns and more preferably less than 10 microns and

509850/0 9 68

25220A2

over 1 micron as previously stated. In Tables 1 and 2, the ranges of particle sizes and densities are various types of chalk that can be used according to the invention are indicated.

Table 1

Precipitated calcium carbonate particle size, diameter , etc.

Art 0-3 3-6 6-10 over 10 apparent
Density, g / ml easy 80% 14% 4% 2% 0.351-0.430 middle 67 17th 12th 4th 0.500-0.588 tight 55 21 16 8th 0.727-0.851 extra
tight 50 20th 20th 10 0.870-1.050

Obtained by microscopic counting.

u difficult Tabel 2 easy ,% 85.3 98.6 Particle size vertexization of the 66.4 precipitated calcium carbonate (USP) 96.8 extra light Weight under the 30.6 specified size, 85.7 98.8 14.9 Art .77.5 98.8 Diameter,, 7.3 middle 52.1 95.6 10.0 3.6 97.7 20.0 93.1 7.5 2.1 92.9 10.2 70.6 5.0 - 61.4 5.2 27.7 4.0 43.7 10.5 3.0 32.1 5.5 2.0 19.7 1.0 10.1 0.5 5.1

509850/0968

A particularly suitable aluminum oxide consists of flat ones Flakes of o ^ alumina crystals in disk or Platelet shape, with the flakes having a mean (weight) particle diameter of less than about 7 µ (for example about

2 to 7 / U). These flat crystals of alumina and a process for their production are Ia of the US patent 3 121 623. The dentifrice according to the invention are preferably substantially free of anhydrous alumina particles with diameters greater than or equal to 15 / U and a thickness of about 2, u. Although it is most beneficial is, alumina flakes with an average particle diameter of less than 5 µ (for example about 3 to 4, u) can also be used within the scope of the invention, aluminum oxide flakes with a larger diameter but one similar thickness may be used, for example alumina flake disclosed in the aforementioned U.S. patent

3,121,623, have mean diameters of 9, 12, or 15 or more microns, free of particles with a Diameters greater than 40 microns (preferably free of particles greater than about 20 microns in diameter) and im are substantially free of particles greater than about 3 microns thick. According to a preferred embodiment of the According to the invention, the α £ -alumina flakes are not coated and do not adhere to other particles of material. The invention also encompasses the use of other o ^ -aluminum oxides or

509850/0968

other abrasives with a Mohs hardness greater than 6 im Mixture with the QO ~ aluminum oxide flakes. For example can about half of the alumina flakes by powdered o £ -alumina with irregular shape and a medium one Particle size of about 3 to 4 microns can be replaced (with all of these irregular particles in their largest dimension are less than about 7 microns). Accordingly, the toothpaste can contain 3% of the flakes and 2% of the irregular particles contain.

A typical alkali or alkaline earth metal aluminosilicate consists of a complex with an index of refraction of about 1.45, a moisture content of about 5 to 20% (e.g. 10%), an alumina content of up to about 10% (e.g. 8%), a silica content of at least about 70%, a sodium oxide (or other alkali metal, or Alkaline earth metal oxide (e.g. calcium oxide) content of up to about 10% (e.g. 7%) and a particle size below 40 microns, preferably about 1 to 20 microns.

Examples of mixtures are mixtures of chalk and hydrated Aluminum oxide in, for example, equal proportions or in a ratio of about 25:75 or about 75:25.

The toothpaste may also contain a small amount of titanium dioxide powder, which when it is in the sodium bicarbonate toothpaste

509850/0968

is used, has a pronounced polishing effect on the teeth.

The titanium dioxide make the toothpaste in the toothpaste., In general, more than about 1% by weight O _r. The titanium dioxide can be incorporated into the toothpaste in amounts up to about 6.0, preferably from about 0.2 to 0.6% by weight. The particle size of the titanium dioxide is preferably about 0.1 to 1 micron.

The carrier for the toothpaste consists of a suitable liquid, which is preferably a thickening agent (for example a gelling agent). As previously indicated, the carrier is preferably aqueous, but the invention also includes the use of non-aqueous vehicles. Generally the liquid will contain a humectant or other viscous one material that is miscible with water, such as glycerine, sorbitol, polyethylene glycol, Mannitol or mixtures thereof. If water is present, it preferably makes up about 5 to 35% (for example about 10 to 30%) of the total carrier. Beneficial results (e.g. better taste) are achieved, if the proportion of water is relatively low, for example about 10 to 20% of the total toothpaste, for example when the water / glycerin ratio is in the range of about 0.4: 1 to 0.7: 1.

509850/0968

Gelling agents for toothpaste carriers are known. Often These are high polymer substances (for example rubber or other thickeners) that are in water or aqueous media are soluble or swellable. With sodium carboxymethyl cellulose excellent results will be obtained. Other suitable substances are gum tragacanth, Gum arabic, gum karaya, sodium alginate, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose,! Carrageenan and other polysaccharides, polyvinylpyrollidones or thickeners such as "Veegum" (a complex magnesium aluminum silicate). The amount of the thickener used according to the invention is preferably sufficient to give the mixture a pasty consistency, To give body and a non-sticky texture characteristic of conventional toothpastes or toothpastes is. As is known, these toothpastes can be cut from ordinary squeezable toothpaste tubes in sections of substantial thickness (for example of about 1 cm) that remain unchanged, their original thickness over a Substantially maintain a period of 1 minute or more and do not substantially penetrate the bristles of the toothbrush, if they lie on the ends of these bristles for a similar period of time, but preferably brushing or do not offer any significant resistance to a deformation, for example if you touch it lightly with your finger, and are little sticky, that is, they do not tend to have threads

509850/0968

pulling your finger away from the section. The amount of thickener is often in the range of about 0.5 to 2%, for example from about 0.8 to 1.5% of the toothpaste.

In the compositions according to the invention "is preferred an organic surfactant used to have prophylactic effects and careful dispersion the composition in the oral cavity as well as the cosmetic suitability and the cleaning and foam properties. These surfactants include water-soluble salts of higher alkyl sulfates such as sodium lauryl sulfate, or other suitable alkyl sulfates having 8 to 18 carbon atoms in the alkyl group; water-soluble salts of sulfonated Higher fatty acid monoglycerides such as sodium coconut monoglyceride sulfonate or other suitable sulfonated monoglycerides from fatty acids having 10 to 18 carbon atoms; Salts of amides of higher fatty acids (for example those with 12 to 16 carbon atoms) with lower aliphatic amino acids (for example taurine or sarcosine) or others Amino acids with 2 to 6 carbon atoms, such as sodium-N-methyl-N-palmitoyl tauride, Sodium-N-lauroyl-, -N-myristoyl- or -N-palmitoyl sarcosinate; water-soluble salts of esters such fatty acids with isethionic acid or with glycerol monosulphate, like the sodium salt of the monosulphated mono-

509850/0968

glyceride hydrogenated coconut oil fatty acids; water soluble
Salts of olefin sulfonates, for example alkene sulfonates
or hydroxyalkanesulfonates or mixtures thereof having 12 to 18 carbon atoms in the carbon chain of the molecule;
water soluble soaps of higher fatty acids, for example those having 12 to 18 carbon atoms such as coconut fatty acids. The cation of the salt can be, for example, sodium, which is preferred, potassium or mono-, di- or triethanolamine. It
Mixtures of surfactants can also be used. A particularly advantageous mixture, which gives high foaming power with little or no irritant effect, contains a higher alkyl sulfate and a higher fatty acid sarcosinate, for example in a ratio of about 1: 2 to 2: 1, such as about 1: 1,
wherein a higher fatty acid monoglyceride sulfonate may be present in place of all or part of the sarcosinate.

Other suitable surfactants are nonionics such as condensation products of sorbitan monostearate
with about 60 moles of ethylene oxide, condensation products of
Ethylene oxide with propylene oxide condensation products of propylene glycol (available under the trademark "Pluronics") and amphoteric agents, such as quaternized imidazole derivatives,
which are available under the trademark "Miranol", for example as Miranol C ₉ M. Cationic germicidal surfactants and antibacterial compounds can also be used

SQ9850 / G968

will. These compounds include di-isobutylphenoxyethoxy = ethyl-dimethylbenzyl-ammonium chloride, benzyl-dimethyl-stearylammonium chloride, tertiary amines with a fatty alkyl group
(with 12 to 18 carbon atoms) and two polyoxyethylene groups bonded to the nitrogen atom (which typically contain a total of about 2 to 50 ethyleneoxy groups per molecule) and their salts with acids and compounds of the general formula

(CH ₉ CH ₉ O) H ^ - (CHCHO) H

RN-CH ₀ CH ₀ CH ₀ N - * = (CH ₀ CH ₀ O) H

in which R is a fatty alkyl group with about 12 to 18 carbon atoms, x, y and ζ together mean 3 or a higher number, as well as their salts with mineral or organic acids. Preferably about 0.05 to 5% by weight of the above surface-active substances are used in the dental care products according to the invention Compounds, especially about 1 to 3%, for example about 1 1/2 to 2%.

Cationic antibacterial agents incorporated, for example:

509850/0968

N - (4-chlorobenzyl) -N - (2,4-dichlorobenzyl) biguanide; p-chlorophenyl biguanide; 4-chlorobenzyhydryl biguanide; 4-chlorobenzhydryl guanylurea; N-3-lauropropyl-N-p -chlorobenzyl biguanide;

1- (Lauryldimethylammonium) -8- (p -chlorobenzyldimethylammonium) -octane dichloride; 5,6-dichloro-2-guanidinobenzimidazole; N -p-chlorophenyl-N -lauryl biguanide;

5-Amino-1,3-bis (2-ethylhexyl) -5-methylhexahydropyrimidine-cetyl-pyridinium chloride

and their non-toxic acid addition salts, especially their fluorides and dihydrofluorides. 1,6-di- (p-chlorophenylbiguanidohexane) is particularly preferred. These agents can be used in amounts from about 0.01 to 5 percent by weight of the dentifrice be used.

All agents suitable for this purpose can be used as flavoring and sweetening agents. Examples are oils, like the oil of Spearmint, peppermint oil, wintergreen oil, sassafras oil, Clove oil, sage oil, eucalyptus oil, marjoram oil, cinnamon oil, lemon oil and orange oil as well as methyl salicylate. Suitable sweeteners are Lactose, maltose, sorbitol, sodium cyclamate, perillartin, Saccharin and ammoniated glycyrrhizin (for example its monoammonium salt). The flavors and sweeteners make

609850/0968

2522CH2

together expediently about 0.01 to 5% or more of the substances according to the invention Compositions from. Preferably the amount of the flavoring oil is more than 0.3%, for example 0.8 up to 1.2%.

A sweetener from the N ^ ohesperidin dihydrochalcone group can be used in equal amounts can be added.

The toothpaste can also contain an anti-caries agent containing fluoride. There are many water-soluble inorganic salts that are useful sources of fluoride ions. These include sodium, potassium, ammonium, manganese, and lithium, and amine fluorides. The monofluorophosphates are also useful and include Na ₄ P ₃ O ₉ F, K ₄ P ₃ O ₉ F, (NH ₄ ) P ₃ O ₉ F-, Na KP ₃ O ₉ F, (NH ₄ ) NaP ₃ O ₉ F and Li ₄ P ₃ O ₉ F. Likewise, water-soluble fluoride-containing salts such as fluorosilicate (i.e. Na ₂ SiFg), fluorozirconate (i.e. Na ₃ ZrFg), fluorostannite (i.e. KSnF ₃ ), fluoroborate (i.e. NaBF ₄ ), Fluorotitanate (i.e. NaTiF ₅ ) and fluorine manate (i.e. K “GeFg) can be used. The fluoride ion can also be supplied by an organic fluoride that supplies fluoride ions in water. Suitable organic compounds are mono-, di- and triethanolamine hydrofluoride. These compounds are present in an effective but non-toxic amount, usually in an amount that provides the dentifrice with about 0.01 to 1% by weight of the water

S09 8-5 0/0968

soluble fluorine content mediated. Sodium fluoride and sodium monofluorophosphate are the preferred compounds.

The dental care products according to the invention can also be used in various ways other materials are incorporated. Examples are dyes and whitening agents, preservatives, Silicones, chlorophyll compounds and their mixtures and other ingredients. These auxiliaries are added in quantities which do not significantly impair the desired properties, and will depend on the particular type of Preparation selected.

The following examples illustrate the invention. Unless otherwise stated, all proportions refer to them is on weight.

example 1

Toothpaste is made by mixing a gelling agent, in this case sodium carboxymethyl cellulose ("CMC") with glycerin and water (in the presence of a sweetener, sodium salt of saccharin, one Flavor and a preservative, sodium benzoate) Make a gel, add sodium bicarbonate, chalk and titanium dioxide powder to the gel and then add the mixture Vacuum degassed. The following were used: 10% sodium carbonate,

509850/0968

35% chalk, 0.4% titanium dioxide, 16.1% deionized water, 34.0% glycerin, 1.2% CMC, 2% of a solution of 35% sodium N-lauroyl sarcosinate in a mixture of 35% water and 30% glycerine, 0.98% sodium lauryl sulfate, 0.5% sodium benzoate, 0.2% sodium salt of saccharin and 0.9% flavor.

The sodium bicarbonate powder was U.S.P. grade and that the following particle size distribution, the percentages denoting the part accumulated on the specified sieve and the sieve sizes correspond to the US standard: sieve no. lane; # 70 sieve (210 micron sieve opening) 27%; Sieve no. (Screen opening 177 microns) 66.5%; # 100 sieve (sieve opening 149 microns) 92.5%; No. 170 sieve (88 micron sieve opening) 99%.

The chalk consisted of USP-precipitated calcium carbonate with a content of at least 98% CaCO ₃ and no more than 0.2% substances insoluble in dilute hydrochloric acid. Their particle size was such that over 99% passed through a US Standard No. 325 sieve (sieve opening 44 microns). The particles were primarily 1 to 10 microns in size with an average particle size of about 3 microns. A sand-free USP non-Fer-Al chalk with similar properties can also be used if the gelling agent and viscosity are adjusted accordingly.

509850/0968

²¹ "25220Λ2

The titanium dioxide consisted of a sand-free anatase powder, at least 99.0% of which passed through a US Standard No. 325 sieve (sieve opening 44 microns) and whose mean particle size diameter (measured on a Kahn sedimentation balance) was less than 1 micron. Microscopic measurements showed one average particle diameter of 0.3 microns.

The toothpaste had good cleaning and whiteness and aged in tests at -13.3 ⁰ C, 4.5 ⁰ C, 43 ° C and 49 ° C well. The toothpaste had a pleasant odor during brushing. Although the large particles of sodium bicarbonate are moderately palpable, they break easily into smaller particles under the pressure of the toothbrush and under the action of saliva.

Example 2

Example 1 is repeated with the difference that the proportion of chalk is reduced to 25% and the proportion of Sodium bicarbonate is increased to 20%.

Example 3

Example 1 is repeated with the difference that 5% of the chalk is replaced by 5% hydrated aluminum oxide will. The proportion of sodium bicarbonate remains the same. A mixture of essential oils, mainly used peppermint oil.

509850/0968

The hydrated alumina had the following particle size distribution and consisted of oi-alumina trihydrate:

28 to 40% finer than 5 microns

56 to 67% finer than 10 microns

85 to 93% finer than 20 milr λ

94 to 99% finer than 30 microns

Example 4

Example 3 is repeated with the difference that the 5% hydrated aluminum oxide is replaced by 5% zirconium silicate powder can be replaced with the following particle size distribution:

80% finer than 1.25 microns

90% finer than 1.77 microns

95% finer than 2.15 microns

99% finer than 2.50 microns

Example 5

Example 3 is repeated with the difference that instead of the 5% hydrated aluminum oxide, 5% finely powdered aluminum oxide Silica can be used. In addition, half of the sodium bicarbonate is replaced by a finer sodium bicarbonate replaced with the following particle size distribution (the percentages indicate the amount that is has accumulated on the specified sieve; the sieve sizes

509850/0968

speak the US standard): Sieve No. 45 (sieve opening 35O microns) Track; No. 100 sieve (sieve opening 149 microns) 0.5%; # 170 sieve (88 micron sieve opening) 20%; Sieve No. 200 (sieve opening 74 microns) 35%; # 325 sieve (44 micron sieve opening) 70%; No. 400 sieve (37 micron sieve opening) 80%.

The invention also encompasses the use of calcium pyrophosphate (for example in the B or) f "form or mixtures thereof in various proportions, for example in a ratio of about 1: 1, such as 53% B, 47% tf ") with an average particle size below about 20 microns, for example about 1 or 2 to 10 microns, for a portion of the water-insoluble abrasive in the toothpaste.

Another feature of the invention relates to the degassing of toothpastes containing sodium bicarbonate particles. It it has been found that if such toothpastes are subjected to a high vacuum, for example of over 660 ram Hg, the toothpaste Blisters form and expand, but not like conventional toothpastes with further vacuum treatment contracts to essentially its original volume, but continues to expand. It has now been established that produced an excellent vented product with good durability and desirable rheological properties can be achieved by using the sodium bicarbonate-containing dental

509850/0968

pasta subjected to a vacuum of at least 660 mm Hg, so that it expands to a volume that is at least 150% (e.g. about 200%) of its volume at atmospheric pressure is, and the high vacuum treatment stops when the expanded mixture begins to contract, its volume but still at least 150% of the volume at atmospheric pressure amounts to.

Example 6

This example illustrates the degassing treatment according to the invention. 18.3 parts of glycerol, 1.1 parts of sodium carboxymethyl cellulose, 0.5 part of sodium benzoate, 0.2 part of the sodium salt of saccharin and 15.4 parts of water are mixed at 43 to 46 C for 20 minutes and poured into a "vertical cylindrical Given a container that is equipped with a stirrer, in particular a double mixer, a number of against each other has rotating mixing rods mounted radially along its height. Then 25 parts of calcium carbonate (Chalk), 20 parts of sodium bicarbonate and 0.4 parts of titanium dioxide are added and it is slowly mixed, taking a vacuum of 699 mm Hg is applied. Then the stirring speed is increased. During this vacuum treatment that takes at least about 5 minutes, the batch expands to a volume that is about 2/3 greater than the volume before vacuum treatment. Then the volume decreases

509850/0968

some. The mixture is then brought to atmospheric pressure, 0.975 parts of sodium lauryl sulfate and 2 parts of one are added Solution of 35% sodium lauroyl sarcosnate in a water-glycerine (35% - 30%) mixture, creates a vacuum of 716 mm Hg and hold the mixture under vacuum for about 5 minutes while stirring. During this time, the volume of the Charge too and something off. It is only slightly larger than the volume observed during the previous vacuum treatment. That The mixture is then brought to atmospheric pressure. Then 15.1 parts of glycerol are added and the mixture is stirred in a vacuum of 711 mm Hg for about 5 minutes. During this treatment, the volume increases by more than 100% (i.e. it increases to more than 200% of the original volume) and then begins to decrease somewhat. After this The container is vented to atmosphere for 5 minutes. The volume of the mixture is then still around 75 to 100% larger than the volume immediately before the vacuum treatment. Then add some of the essential oils and stir then again using a vacuum of 724 mm Hg. Stirring is continued under this vacuum for about 12 minutes. Thereon the container is vented to the atmosphere. During these 12 minutes the mixture expands in a similar way as during the immediately preceding vacuum treatment. Before the mixture is vented to the atmosphere, there is expansion still visible.

509850/0968

It is advantageous to interrupt the vacuum treatment despite the possibly further expansion before the change in pH value (pH value of the vacuum-treated mixture minus pH of the non-vacuum-treated mixture) reaches a pH unit and preferably less, for example 1/2 unit. This prevents the sodium bicarbonate from decomposing and the formation of sodium carbonate during degassing.

According to a further embodiment of the invention, the Toothpaste can be prepared and degassed as follows:

The amount of glycerin given is added with stirring without use given by heat the carboxymethyl cellulose. It is mixed for two minutes, then the saccharin and the Sodium benzoate added. Mix for another minute. The specified amount of water is then the sodium lauryl sulfate and the flavorings added. The mixture is then stirred again for 15 minutes and mixed until the batch is ready for filling. The lid of the double mixer is closed and a vacuum of 711 mm Hg applied. The vacuum valve is then closed. At this point, half of the gel mixture is in place in the mixer. The mixer is then turned off, the vacuum released, and those corresponding to the formulation are used

509350/0968

Amounts of titanium dioxide and sodium N-lauroyl sarcosinate added, whereupon a vacuum of 711 mm Hg is applied and the vacuum sustains until the level of the cream drops. Then add the other half of the gel mixture and vent for 5 minutes long at 711 mm Hg. The mixer is turned off, the vacuum released, and the calcium carbonate and sodium bicarbonate are removed added. Vacuum is applied to this while mixing. Mixing is continued for 15 minutes under full vacuum. At with With the mixer running at a slower speed, the vacuum is released and the cream is then removed.

Example 7

This example illustrates the use of OL alumina flakes in toothpaste containing sodium bicarbonate.

For example, using the procedure of Example 1, the toothpaste is made from 10% sodium bicarbonate powder of the Example 1.30% chalk, 5% οό alumina flakes, 0.4% titanium dioxide of Example 1, 33.4% glycerin, 15.4% deionized water, 1.1% carboxymethyl cellulose (Hercules 7MF), 2% of a solution of 35% sodium N-lauroyl sarcosinate in a mixture of 35% water and 30% glycerine, 1% sodium lauryl sulfate, 1% Flavor (water-insoluble essential oils, for example a mixture of essential oils rich in peppermint oil), 0.5% Sodium benzoate and 0.2% of the sodium salt of saccharin.

509850/0968

The οί-alumina flakes have a medium (due by weight) particle diameter of about 4 microns with all particles having diameters of less than 10.1 microns, about 85 to 95% by weight diameter less than 6.0 microns and about 30 to 35% diameter less than 3.5 microns.

The properties of the toothpaste of this example are similar to those given in Example 1. It is very consistent with regard to the separation of the flavors.

Example 8

Example 7 is repeated with the difference that the toothpaste contains 0.22% sodium fluoride (the glycerol content is reduced accordingly by 0.22%). The toothpaste obtained has excellent aging properties including a very good resistance to the deposition of flavors on aging and a very good one good maintenance of the fluoride content. Like the toothpaste of Example 7, it exerts a high polishing effect on tooth enamel the end. Their re-polishing effect is 64%.

The re-polishing effect, expressed as a percentage, is determined by means of a test in which sections of human tooth enamel, on which flat matte areas have been applied, first polished, then matted with chalk and applied on top of 5000 reciprocal brush strokes with one

50985 0/0968

slurry of a toothpaste to be brushed. To determine A "Monsanto Tooth Reflectance Instrument" is used to ensure the mirror reflection of the surface after each treatment stage. turns. The matting of the surface is adjusted so that it is about 150 units (Monsanto Instrument) below that of the polished surface. The polishing ability of the dentifrice is expressed by the following equation:

^(SR 5OOO lines ~ ^SR matted

Re-polishing effect,% = SR,. , -SR ....

^J ' polished mattxert

where SR _Ί . . , SR .... and SR, - », ^ _o . . , the values for polished 'matted 5000 strokes

the specular reflection of the enamel surface after the initial one Represent polishing, matting with chalk, and brushing with the toothpaste slurry.

Example 9

Example 7 is repeated with the difference that the toothpaste contains 0.76% sodium monofluorophosphate (the glycerol content is reduced accordingly by 0.76%).

Example 10

Examples 7, 8 and 9 are repeated with the difference that the οό-aluminum oxide flakes have an average particle diameter of 5 microns, with substantially all of the particles being less than about 12 microns in diameter.

509850/0968

25220A2

Example 11

This example illustrates the use of unlined Aluminum tubes for various toothpastes containing sodium bicarbonate.

(a) A toothpaste is made, for example according to the method of Example 1, from 20% sodium bicarbonate powder of Example 1, 25% calcium carbonate of Example 1, 0.4% titanium dioxide of Example 1, 34.02% glycerin, 16.1% deionized water, 1.2% carboxymethyl cellulose (Hercules 7MF), 2% a solution of 35% sodium N-lauroyl sarcosinate in a mixture of 35% water and 30% glycerin, about 0.9% sodium lauryl sulfate, 0.9% flavoring substances (water-insoluble essential oils, for example a mixture of essential oils rich in peppermint oil), 0.5% sodium benzoate and 0.2% of the sodium salt of saccharin manufactured.

(b) Example 11a. is repeated with the difference that 0.5% very finely divided silicon dioxide (Cab-O-Sil) incorporated the amount of calcium carbonate is increased to 35% and the amount of sodium bicarbonate is decreased to 10%.

(c) Example 11b is repeated with the difference that the amount of sodium bicarbonate is changed accordingly of the other components is reduced to 5%.

509850/0988

(d) Example 11 is repeated four times with an additional different proportions of non-acidic dicalcium phosphate dihydrate can be used, namely 0.04%, 0.2% and 0.8% (based on based on the weight of the formulation excluding the phosphate); in the first case (0.04%) the titanium dioxide is omitted. The dicalcium phosphate dihydrate In terms of its purity, it corresponds to the requirements for dental care products and has an average Particle diameter of about 4 microns. Its pH (measured in a 20% slurry in water) is in the range from 9.3 to 9.9. When it comes into contact with water, it forms phosphate ions.

(e) Example 11a_ becomes with further incorporation of insoluble Sodium metaphosphate in an amount of 0.8% (based on the weight of the formulation without the phosphate) was repeated. The insoluble sodium metaphosphate is the same as for dentifrices requirements and has an average particle size of about 5 microns. Its pH (measured in a 20% slurry in water) is in the range from 5.3 to 6.3. When it comes into contact with water, it forms phosphate ions.

(f) Example 11a. is repeated with the difference that 5% finely divided silicon dioxide can be used instead of 5% calcium carbonate, another essential oil as a flavoring agent in an amount of 0.9% and the glycerine in an amount of 33.5%.

50985 0/0968

(g) Example 11a is repeated with the difference that 3% finely divided silicon dioxide instead of 3% calcium carbonate and the toothpaste contains 0.9% essential oil as a flavoring agent.

(h) Example 11a is repeated with the difference that 5% precipitated silicon dioxide instead of 5% calcium carbonate be used.

(i) Example 11a. is repeated with the difference that 5% anhydrous dicalcium phosphate can be used instead of 5% calcium carbonate. The toothpaste contains 0.9% essential Oils as flavorings. The anhydrous dicalcium phosphate consists of a fine non-acidic powder with the purity required for dental care products. Its pH (measured on a 20% slurry in water) is 7.6 to 7.8. When it comes into contact with water, it forms low concentrations of phosphate ions.

(j) Example 11a. is repeated with the difference that 5% zirconium silicate of Example 4 instead of 5% calcium carbonate (with less change in the proportion and type of Flavor) can be used.

(k) Example 11a is repeated with the difference that 5% β-calcium pyrophosphate instead of 5% calcium carbonate

509850/0968

can be used. The calcium pyrophosphate consists of a fine powder with the purity required for dental care products. Its pH (measured on a 20% slurry, in water) is 5.2 to 5.3.

Each of the above toothpastes was placed in a tube of uncoated high purity aluminum (99.7% aluminum or more pure) and aged. During the aging at 49 ° C., the tube filled with the toothpaste 11a swelled, or a foamy product film was found in contact with the inner aluminum wall of the tube. For those with toothpastes 11b, £, d, ί. ' g_, h_, i_, j. ^{un <^]} S filled tubes were not observed this phenomena. These toothpastes show essentially no tendency to react with the wall of the toothpaste tube.

The finely divided silicon dioxide (compare Example 11b) is, for example, in Encyclopedia of Chemical Technology, Kirk-Othmer, 2nd edition, Volume 18, pages 62 and 67, described. The invention encompasses the use of this finely divided silica in toothpastes containing sodium bicarbonate, which are filled into and from unlined aluminum tubes the compatible water-insoluble abrasive (such as calcium carbonate) is omitted. Also within the scope of the invention the use of very finely dispersed or dissolved silicon dioxide in other forms, for example as alkali metal

509850/0968

25220A2

silicate, such as sodium silicate, for example as hydrated sodium silicate in flake form with the ratio Na ₃ OrSiO ₉ . H "0 of about 1: 2 - 3.2: 5, or in the form of sodium silicate solutions (water glass), for example those in which the Na ~ O: SiO" ratio is at least about 1: 2, or of sodium silicate formed in situ in the toothpaste, or from colloidal silica or precipitated silica (see Encyclopedia of Chemical Technology, Kirk-Othmer, 2nd Edition, Volume 18, pages 63 and 66-67) or other silicate.

The dicalcium phosphate dihydrate of Example 11d is a commercially available stabilized material with the purity required for dentifrices. A process for the preparation of such a dicalcium phosphate dihydrate and its stabilization is described in US Pat. No. 3,169,096; see also "Cosmetic Science", Volume 1, 1972 (Wiley Interscience) by Balsam and Sagarin, pages 477 to 479. One typical analysis of the dicalcium phosphate dihydrate indicates a water-soluble material content of 0.18% (its percentage of water-solubles, expressed as P ₃ O _5, is 0.11%). A typical stabilizer level is a mixture of about 1 to 2% sodium calcium pyrophosphate and a minor amount, for example about 0.4% pyrophosphoric acid.

509850/0968

The insoluble sodium metaphosphate of Example 11 is a commercially available material of dentifrice grade. Its production and its properties are in the already cited reference "Cosmetic Science "on pages 480 to 481 and in" Phosphorus and Its Compounds "by Van Wazer, Volume 2, 1961 (Interscience), Pages 1652 to 1653 described.

The anhydrous dicalcium phosphate of Example 11i_ and the Calcium pyrophosphate of Example 11k with dentifrice grade are also commercially available, see "Phosphorus and Its Compounds", page 1651 and "Cosmetic Science", Pages 479 to 480.

Example 12

Example 11a is repeated with the difference that the toothpaste additionally contains anhydrous disodium phosphate (as water-soluble powder incorporated) in an amount of (a) 0.05% and (b) 0.01%, and the amount of water in the Toothpaste is set to 100% accordingly. In any case, swell as they age in unlined aluminum tubes (as in Example 11) the filled toothpaste tubes do not or develop gas and (after aging for 9 weeks at 49 C) the inner wall of the tubes was gold-colored. The color of the The tube containing toothpaste 12b was very light.

509850/0983

search for the inner wall of the unlined aluminum tubes containing the toothpaste 11d (again after 9 weeks Aging at 49 C) it was found that this was dark (if the toothpastes were 0.8% or 0.4% dicalcium phosphate dihydrate contained) or gold colored (if the tubes contained 0.04% and 0.2% dicalcium phosphate dihydrate). Investigating the Inner wall of the non-lined aluminum tubes containing the toothpaste 11k showed that they were after 3 and 6 weeks Aging at 49 C was golden in color and dark after aging for 9 weeks. It is believed that those containing the dicalcium phosphate dihydrate (or toothpastes that form with aging) small amounts of dissolved phosphate ions (for example orthophosphate and / or pyrophosphate), which acts on the aluminum wall, or on the aluminum oxide layer - on this wall, and forms a protective layer on it. The amount of dissolved phosphate ion present in the preferred composition is sufficient to prevent the gas formation reaction between the alkaline toothpaste and the aluminum wall of the tube, but the amount of the phosphate or acidic component is insufficient to cause a gas-forming reaction (e.g. swelling or bursting of the tube) between the ingredients of the toothpaste. The inclination the last-mentioned reaction can of course be investigated by converting the composition into a suitable one lined aluminum tube (the walls of which are accordingly

50985 0/0968

2522G42

are essentially inert above the composition) and ages for several weeks (for example 9 weeks) at elevated temperature (for example 49 C).

The storage of other types of toothpastes in unlined aluminum tubes is disclosed in U.S. Patents 3,662,066 and 3 678 155 as well as in the Austrian patent specification 267. As is well known, toothpaste tubes that come from consist of relatively thin, flexible aluminum, to squeeze the toothpaste out of the opening of the tube and deform.

Example 13

This example illustrates the use of olefin sulfonate surfactants in those containing sodium bicarbonate Toothpaste. These olefin sulfonates perform when brushing teeth, although the medium (containing saliva and sodium bicarbonate Toothpaste) contains a relatively high concentration of dissolved electrolyte, resulting in very good foam formation.

(a) The formulation of the toothpaste is the same as in Example 10, with the difference that instead of the sarcosinate solution, about 0.7% of a sodium olefin sulfonate is used and the amount of water is increased to about 16.6%.

609850/0968

(b) The formulation of the toothpaste is the same as in Example 10, with the difference that instead of the sodium lauryl sulfate and the sarcosinate solution, about 1.7% of one Sodium olefin sulfonate can be used and the amount of water is increased to about 16.5%.

The olefin sulfonate used in Example 13 consists of a reaction product of SO-. and an olefin mixture (such as is obtained, for example, from cracking paraffin wax) and contains approximately equal amounts of C _1t -f C., -, C ₁₇ - and C.o "" oils. The average chain length is about 16 1/2 carbon atoms. Other olefin sulfonate surfactants can also be used in the toothpaste containing sodium bicarbonate. The olefin sulfonates are known compounds in the detergent field. In general, they contain long chain alkenyl sulfonates or long chain hydroxyalkanesulfonates (the hydroxyl group being on a carbon atom that is not directly bonded to a carbon atom bearing the SO, group). Usually the olefin sulfonate detergent will contain a mixture of varying amounts of these two types of compounds, often together with long chain disulfonates or sulfate sulfonates. Such olefin sulfonates are for example in US Patents 2,061,618, 3,409,637, 3,332,880, 3,420,875, 3,428,654, 3,506,580, British Patent 1,139,158 and in "Fette-Seifen-paint",

50985 0/09 6 8

Volume 72, No. 4, pages 247-253 (1970). It is stated there that the olefin sulfonates are prepared from straight-chain o ^ -olefins, internal olefins, olefins in which the unsaturation is present as a vinylidene side chain (for example dimers of C £ olefins) etc. or, more often, from mixtures of these compounds may be, the olefin usually constituting the main component. The sulfonation is usually carried out with sulfur trioxide under low partial pressure, for example with SO ₂ , which is highly diluted with an inert gas such as air or nitrogen, or with SO 3 under vacuum. This reaction generally leads to an alkenyl sulfonic acid, often together with a sultone. The acidic material obtained is then generally made alkaline and treated to open the sultone ring to form a hydroxyalkanesulfonate and alkenylsulfonate. The number of carbon atoms in the olefin is usually in the range from 10 to 25, more often in the range from 12 to 20. Suitable mixtures are, for example, those consisting mainly of C ₁₉ , C ₁ and C ₁ olefins and one Have an average of about 14 carbon atoms, or mixtures of mainly C ₁ -, C ₁ , - and C _{1 Q-} 01efins with an average of

I4 Ib Io

about 16 carbon atoms. The preferred olefin sulfonates are the sodium salts, in the context of the invention, however, other water-soluble salts, for example ammonium or Potassium salts can be used.

509850/0968

The sodium bicarbonate used in the examples is a product obtained by precipitation from solution (For example, by treating a sodium carbonate solution with carbon dioxide to precipitate the bicarbonate), below Drying, treatment with carbon dioxide gas and sieving to the desired particle size (generally without substantial Reduction or pulverization) was obtained.

These particles generally consist of monoclinic crystals or tablets or conglomerates of these crystals (for example, twin crystals), with some protruding spike-like parts of generally rhombohedral shape with many re-entrant angles, see FIG. 1 for a photomicrograph of that used in Example 1 FIG. 2 shows crystals and FIG. 2 shows a view of these crystals with an electron microscope. Fig. 3 illustrates a Figure 6 is a photomicrograph of the crystals used in Example 2.

The toothpastes of the above examples do not foam, that is, develop when diluted with water they do not have carbon dioxide bubbles.

The toothpastes according to the invention have an alkaline pH value, generally in the range from about 8.5 to 10.0, usually from about 9.3 to 9.9.

509850/0968

The dentin abrasion with the toothpastes according to the invention can with the aid of that described by Grabenstetter et al in "Journal of Dental Research", Volume 37, page 1060 (1958) radioactive technology in the modification according to Stookey and coworkers in "Journal of Dental Research", Volume 47, page 524 (July-August 1968).

509350/0968

Claims (30)

Claims Toothpaste containing sodium bicarbonate as an abrasive according to patent (patent application P 23 47 787.4), characterized in that it is used as an abrasive (1) a smaller proportion of sodium bicarbonate and (2) a Contains a larger proportion of water-insoluble abrasive that is compatible with the bicarbonate. 2. Toothpaste according to claim 1, characterized in that the insoluble abrasive consists of silica, alumina, silicates or carbonates and at least makes up about 20% by weight of the toothpaste. 3. Toothpaste according to claim 1 and 2, characterized in that the sodium bicarbonate is about 1 to 25% by weight of the toothpaste matters. 4. Toothpaste according to claim 1 to 3, characterized in that the insoluble abrasive is about 20 to 50% by weight Toothpaste. 5. Toothpaste according to claim 1 to 4, characterized in that the total abrasive content is about 25 to 60% of the 50 9 8 50/0968 Toothpaste and is dispersed in an aqueous, moisture-retaining medium. 6. Toothpaste according to claim 1 to 5, characterized in that the insoluble abrasive consists of calcium carbonate. 7. Toothpaste according to claim 6, characterized in that
the calcium carbonate consists of precipitated calcium carbonate, has a density of about 0.7 to 0.9 g / cm and about 99% passes through a sieve with a pore opening of 44 microns. 8. Toothpaste according to claim 1 to 5, characterized in that the insoluble abrasive consists of flat o ^ aluminum oxide flakes consists. 9. Toothpaste according to claim 1 to 8, characterized in that the aqueous medium of water-glycerol in the ratio from about 0.4: 1 to 0.7: 1. 10. Toothpaste according to claim 1 to 9, characterized in that it is a water-soluble polymeric gel-forming agent and a water-insoluble essential oil as a flavoring agent
contains in an amount of about 0.5 to 1.5%. 509850/0968 11. Toothpaste according to claim 10, characterized in that it contains sodium carboxymethyl cellulose as a gel-forming agent. 12. Toothpaste according to claim 1 to 11, characterized in that it contains a compatible surface-active agent. 13. Toothpaste according to claim 1 to 12, characterized in that that the sodium bicarbonate largely has a particle size greater than about 150 microns and a diameter less than about 0.4 mm. 14. Toothpaste according to claim 13, characterized in that the greater part by weight of the sodium bicarbonate is a Has particle size greater than about 0.01 mm in diameter. 15. Toothpaste according to claim 1 to 14, characterized in that that it additionally contains about 0.2 to about 6.0% by weight of titanium dioxide. 16. Toothpaste according to claim 15, characterized in that the titanium dioxide consists of a sand-free anatase powder, at least 99.0% of which is a sieve with a pore opening of 44 microns happened. 509850/0968 17. Toothpaste according to claim 1 to 16, characterized in that that it also contains sodium fluoride. 18. Toothpaste according to claim 1 to 16, characterized in that that it also contains sodium monofluorophosphate. 19. Toothpaste according to claim 1 to 18, characterized in that it also contains sodium lauryl sulfate and a surface-active one contains higher fatty acid sarcosinate. 20. Toothpaste according to claim 1 to 18, characterized in that that it additionally contains sodium lauryl sulfate and a surface-active higher olefin sulfonate. 21. Toothpaste according to claim 1 to 18, characterized in that it also contains a higher surface-active olefin sulfonate contains. 22. Toothpaste according to claim 1 for filling in not
lined aluminum tubes, characterized in that
that it is dissolved or dispersed in the aqueous vehicle
Contains silicon dioxide. 23. Toothpaste according to claim 22, characterized in that
they are very finely divided silicon dioxide or sodium silicate
contains. 509850/0968 24. Toothpaste according to claim 22, characterized in that it additionally contains anhydrous dicalcium phosphate. 25. Toothpaste according to claim 22, characterized in that it additionally contains calcium pyrophosphate. 26. Toothpaste according to claim 22, characterized in that it additionally contains zirconium silicate. 27. Toothpaste according to claim 22, characterized in that it contains phosphate ions in an amount that causes gas formation on the aluminum wall of the tube. 28. Toothpaste according to claim 27, characterized in that it contains calcium carbonate and dicalcium phosphate dihydrate, 29. Toothpaste according to claim 27, characterized in that it contains calcium carbonate and insoluble sodium metaphosphate contains. 30. Toothpaste according to claim 27, characterized in that it contains calcium carbonate and a water-soluble phosphate. sch: kö 503850/0968