DE3331650A1 - TOOTHPASTE - Google Patents

Description

description

Sodium carboxymethyl cellulose is used in toothpastes because of its ready availability and that in general satisfactory rheological properties which it imparts to toothpastes, usually as a gel-forming agent Means of choice used, especially when the toothpaste is manufactured and applied in temperate climates will. In tropical climates the cellulose can

- | 5 are subject to decomposition.

In toothpastes made with sodium carboxymethylcellulose of many quality grades, even at room temperature, _{r is} observed in particular when they are subjected to dynamic aging, i.e. when they are squeezed out of a tube twice a day over a period of 2 weeks to a length of 2 cm, which is normal use corresponds to a toothpaste that the toothpastes get a rough appearance, ie form soft lumps.

Even quality grades of sodium carboxymethyl cellulose that do not appear rough during dynamic aging cause, can lead to other rheological problems, e.g. obtained, "stand properties", so that the squeezed toothpaste quickly settles into a flat band or thickens over time.

It should be noted that a rough appearance occurs in the dynamic aging especially when the

Toothpaste contains a fluoride-producing compound and a calcium phosphate polishing agent. Minor problems occur when the fluorine is made up of sodium monofluorophosphate or a mixture of sodium monofluorophosphate and sodium fluoride is supplied and the polishing agent is a silica material. The problem becomes however easily visible when the fluorine is made up of sodium monofluorophosphate or a mixture of sodium monofluorophosphate and sodium fluoride in at least about 35 weight percent calcium phosphate, such as dicalcium phosphate Toothpaste containing polishing agents is provided.

Try to get over the roughening problem without encountering other problems, like bad ones "Stand properties" consisted of blending different grades of sodium carboxymethyl cellulose or in mixing sodium carboxymethyl cellulose with other gelling agents such as synthetic inorganic ones siliceous clays, e.g., of materials sold under the trademarks "Laponite" and "Veegum" are available, thickeners, such as silica thickeners from Huber under the trademark "Zeosyl", such as Zeosyl 200, Tixosil, such as Tixosil 33J from Rhone-Poulenc or the product "HDK N20" from the company Wacker and from liquid materials such as polyethylene glycol 600. These attempts were unsatisfactory.

3Q As an alternative gelling agent to sodium carboxymethyl cellulose Hydroxyethyl cellulose has been proposed and, in fact, one has hydroxyethyl celluloses such as Natrosol M used in commercially available toothpastes. Various grades of hydroxyethyl cellulose are, for example, in U.S. Patents 3,862,307

(Natrosol G) and 3 0 70 510 (Brookfield viscosity at 20 ° C 75 to 125 cP; 2% in water) and 4,022,881 (Natrosol 250 H, a highly viscous material). These are hydroxyethyl celluloses in general satisfactory, but can lead to expansion rheology in toothpastes due to visible "tail formation" (tail) when filling into containers and when squeezing out onto a toothbrush. For example is "Viscosity" is described in US Pat. No. 4,022,881 for toothpastes which, as a thickening agent, contain a Contains a mixture of 30% hydroxyethyl cellulose and 70% sodium carboxymethyl cellulose. One not tough Toothpaste with calcium carbonate as an abrasive and a mixture of 10% hydroxyethyl cellulose and 90% Sodium carboxymethyl cellulose as a thickening agent is also described there.

According to the invention, a mixture is used as the gel-forming agent which have little tendency to appear rough with age and others are desirable has rheological properties, such as good "stand", no "tailing" in an expressed Band of toothpaste and good shine of this band. The toothpaste can easily be made with this mixture without being compared to the production with sodium carboxymethyl cellulose as the only gel-forming agent significant modifications to the manufacturing process are necessary. The gel-forming material with which the sodium carboxymethyl cellulose is advantageous in particular Weight ratio mixed is hydroxyethyl cellulose. This material, although generally good, is not entirely satisfactory from a rheological standpoint when taken alone or in admixture with others Thickening or gelling materials such as sodium carboxymethyl cellulose is used. Indeed

show toothpastes that provide hydroxyethyl celluloses such as Natrosol 250 M, dicalcium phosphate and a fluorine Compound contain a "tailing" and / or low "stand" when using hydroxyethyl celluloses, such as Natrosol 250 M are present as the sole gelling agent or together with sodium carboxymethyl cellulose in a weight ratio of sodium carboxymethyl cellulose to hydroxyethyl cellulose (Natrosol 250 M and the like) of less than about 2: 3, e.g. of about 1:10 and 3: 7 can be used.

In the aforementioned U.S. Patent No. 4,022,881 a dentifrice described, which as a thickener 5 to 30% highly viscous hydroxyethyl cellulose, e.g. Natrosol 25 0 H and 70 to 95% sodium carboxymethyl cellulose to stabilize the sodium carboxymethyl cellulose contains against degradation. These proportions of e.g. 10: 1 and 7: 3 are not satisfactory, since, in contrast to the invention, they do not remove the surface roughness.

According to the invention a gel-forming system for a Toothpaste Provided That Remains Smooth With Dynamic Aging; and others generally desirable Has rheological properties.

A particular advantage of the toothpaste according to the invention is that it does not flow and has improved state, even if the hydroxyethyl cellulose in the gel-forming System predominates. This benefit can be particularly noticeable when the toothpaste is being bottled or out is expressed by a pressure differential or mechanically operated container or tube, especially when using hydrated alumina as a polishing agent.

The asserted benefits can be achieved with a gel-forming mixture of carboxymethyl cellulose and sodium Hydroxyethyl cellulose in a special weight ratio or, if the hydroxyethyl cellulose is highly viscous, can be achieved without sodium carboxymethyl cellulose.

Further advantages are evident in toothpastes that contain a source of fluorine, e.g. a binary fluorine supplying system of sodium monofluorophosphate and sodium fluoride, and a polishing agent including a calcium phosphate.

The invention encompasses toothpastes which comprise about 20 to 80% by weight of the toothpaste in the liquid phase of water

-) 5 and one or more humectants and about 0.5 To 5% by weight of the toothpaste contain gel-forming agent, the sodium carboxymethyl cellulose and hydroxyethyl cellulose in a mutual weight ratio of about 3: 2 to 2: 3. The ones given here Viscosities were measured using a Brookfield viscometer on a 2% strength aqueous solution at 25 ° C.

The toothpastes according to the invention can also contain a compound contain which provides at least about 100 ppm fluorine available, furthermore about 40 to 75 wt.% Of one a dentally acceptable non-toxic water-insoluble polishing agent with a calcium phosphate in one An amount of at least about 35% by weight of the toothpaste.

The gelling agent is in the toothpaste in an amount of about 0.5 to 5% by weight, preferably of about 0.8 to 2% by weight and in particular from about 0.9 to 1.1% by weight are present, the ratio being sodium carboxymethyl cellulose to hydroxyethyl cellulose about 3: 2 to 2: 3, typically 1: 1 and preferably less

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is less than 1: 1 to 2: 3, e.g. 49: 51, 9: 11 or 2: 3.

Sodium carboxymethyl cellulose is commercially available from Hercules available as CMC-7MXF and 7MXD, which are preferred for the purposes of the invention. The quality classes may have a degree of polymerization of about 500, which corresponds to a molecular weight of about 100,000 is equivalent to. The viscosity is medium to high, e.g., about 300 to 3000 cP or more, typically about 300 to 1200 cP and preferably about 300 to 500 cP (Brookfield, 2% at 25 ° C). CMC-7MXF contains approximately 0.7 sodium carboxymethyl groups per anhydroglucose unit.

The following table describes advantageous commercially available sodium carboxymethyl celluloses (CMC). In those cases where the viscosity is not using a Brookfield viscometer on a 2% aqueous Solution was measured at 25 ° C, this is indicated.

Tabel

Manufacturer Hercules

Wolff Walsrode

Ny ma Enka Il

Cros Uddeholm Hoechst

1% solution (Brookfield; 25 C)
Hoeppler viscometer (2%; 2 0 C)

CMC 7MXF viscosity - 500 7MFD 300 - 500 9M31F 300 - 1200 9M31XF 900 - 1200 12M31XF 900 - 1200 7MF 900 - 500 12M31PD 300 - 1200 7M8SXF 900 - 800 200 - 1200 700 - 80
- 120
- 120 50
80
60 - 900 700 - 800
- 260 500
120 Walocel CRT 1000
PA 07 Nymcel ZMF.
Akucell AC
Akucell AC .33
1642 *
1632 * Cellogen HP-SA Cekol MVEP
**
TVlose CB 200

Hydroxyethyl cellulose is commercially available from Hercules as Natrosol 250 M, which is used for the present invention Purposes is preferred.

The quality classes can have a degree of polymerization close to 75 0, which is a molecular weight of about 190,000. The viscosity is medium to high, e.g., about 3,000 to 12,000 cP or more, in typically about 3000 to 7000 cP and preferably about 4500 to 6500 cP (Brookfield, 2% at 25 ° C). if the viscosity not with a Brookfield viscometer

was measured on a 2% aqueous solution at 25 ° C., this is indicated.

The following table lists desirable commercially available hydroxyethyl celluloses (HEC):

Tabel

Manufacturer Hercules

HEC

BP-. Chemicals ir ti

Maximum

Natrosol 250M and MR
Natrosol 250 HR *

and 250 H *
Natrosol 250 HHR

and 250 HH
Cellobond 5000A

Cellobond 7000A
**

Tylose H 4000P

GYLES HlOOOOP

1% solution (Brookfield; 25 C)
Hoeppler viscometer (2%; 20 ° C)

Viscosity 4500 - 6500

1500-2500

3400 - 5000 4200 - 5600 6000 - 7000 3000 - 5000 7000 -12000

The sodium carboxymethyl cellulose and the hydroxyethyl cellulose can be mechanically mixed with one another, before being mixed with the liquid carrier of the toothpaste, or they can be separated with the liquid Phase are mixed.

The rheological advantages achieved according to the invention are evident when the toothpaste connects which contains at least about 100 ppm fluorine, typically about 100 to 10,000 ppm, and especially provides about 750 to 2000 ppm fluorine. To these connec-

fertilizers include sodium fluoride, tin (II) fluoride, potassium fluoride, Potassium tin (II) fluoride, sodium hexafluorostannate, tin (II) chlorofluoride and sodium monofluorophosphate. Sodium monofluorophosphate or a mixture of sodium monofluorophosphate is particularly typical of the invention and sodium fluoride. The rheological benefits are also striking when using a calcium phosphate Polishing agents, especially dicalcium phosphate, are used in an amount of at least about 35% by weight of the toothpaste will.

These toothpastes typically contain about 35 to 75 weight percent, preferably about 40 to 55 weight percent, of one dental acceptable water-insoluble polishing agent that

- | 5 consists essentially of a calcium phosphate such as dicalcium phosphate in its dihydrated or anhydrous form, or mixtures thereof in any one Ratio, tricalcium phosphate and calcium pyrophosphate is made. Most often, dicalcium phosphate is used, im generally called a dihydrate. Typically, dicalcium phosphate is the only polishing agent, but you can if so desired, smaller amounts, e.g., up to 5% by weight of the toothpaste and up to about 12% by weight of the total polishing agent on other dentally acceptable water-insoluble polishing agents that have the properties the formulation according to the invention, to require oral hygiene, do not significantly impair. Typical polishing agents are alumina, silicon dioxide, sodium aluminosilicate and others. A lesser amount of hydrated Aluminum oxide of e.g. about 1% also inhibits or even prevents the tendency of some toothpastes to settle in to separate or "bleed out" their tubes.

The toothpaste typically contains sodium monofluorophosphate or a mixture of sodium monofluorine

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phosphate and sodium fluoride in an amount that about 100 to 10,000 ppm fluorine, e.g., about 750 to 2000 ppm, and especially about 1400 to 2000, such as about 1400 to 1670 ppm fluorine are made available. A binary fluorine-supplying system made from sodium monofluorophosphate is advantageous and sodium fluoride, which is about 30 to 40% of the fluorine, e.g., about 30 to 35%, i.e. about 300 to 580 ppm, can be provided by the sodium fluoride.

The mixed system of gelling agents is particularly advantageous for toothpastes that provide a binary fluorine Contains system and dicalcium phosphate as a polishing agent, as in the British patent 20 68 727 A (application 79/43642) is described, to which reference is expressly made here. This is how in a typical toothpaste usually uses sodium monofluorophosphate in the binary system in an amount that it delivers about 700 to 109 0 ppm fluorine to the toothpaste, the total amount of fluorine being about 1000 to 1670 ppm and about 30 to 35 weight percent of the total fluorine is provided by the sodium fluoride (about 300 to 580 ppm) will. This corresponds to about 0.5 to 1.2% by weight of sodium monofluorophosphate and about 0.05 to 0.11% by weight Sodium fluoride. The toothpaste preferably contains about 1000 to 1500 ppm and in particular about 950 to 1000 ppm fluorine, which is provided by the sodium monofluorophosphate, and about 450 to 500 ppm, which the Sodium Fluoride supplies.

Sodium monofluorophosphate, Na ~ PO-.F, which is commercially available can vary considerably in purity. It can be used in any suitable purity provided the impurities do not significantly affect the desired properties.

In general, the purity is desirably at least 80%. To achieve the best results it should be at least 85% and preferably at least 90% by weight sodium monofluorophosphate, the Remainder consists primarily of manufacturing-derived impurities or by-products such as sodium fluoride and water soluble sodium phosphate salt. In other words, the sodium monofluorophosphate used should have a total fluoride content of over 12%, preferably of over 12.7%, a content of not more than 1.5% and preferably no more than 1.2% free sodium fluoride and a sodium monofluorophosphate content of at least 12%, preferably at least 12.1%, all calculated as fluoride.

As stated above, in the binary system, the sodium fluoride is a fluorine-containing component which separate from sodium monofluorophosphate. About 300 to 580 ppm fluorine are preferred from sodium fluoride delivered to the toothpaste.

The invention further encompasses toothpastes containing from about 20 to 75% of a polishing agent, at least of which about half consists of hydrated aluminum oxide, and a carrier comprising about 20 to 80%, based on the weight of the toothpaste, of the liquid phase Water and one or more humectants and about 0.5 to 5%, based on the weight of the toothpaste, a gelling agent consisting essentially of high viscosity range hydroxyethyl cellulose the average of which is at least about 24,000 cP as with a Brookfield viscometer at 2 0 ° C in a water: glycerine (1: 1.56) 'solution with a # 6 spindle at 20 rpm.

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In this, the gel-forming agent is according to the invention Toothpaste in an amount of from about 0.5 to 5% by weight, preferably from about 0.8 to 2% by weight and in particular from about 0.9 to 1.4% by weight. A typical hydroxyethyl cellulose effective for the purposes of the invention is Tylose H lOOOOP of Farbwerke Hoechst, Frankfurt / M., West Germany.

The invention also includes toothpastes that contain a binary

-10 Fluorine-supplying system made from a mixture of sodium monofluorophosphate and sodium fluoride, with about 30 to 40% by weight of the fluorine from the sodium fluoride in an amount of about 750 to 2000 ppm of the total ionic fluoride are provided, about 35 to 75% by weight of a polishing agent consisting essentially of a calcium phosphate and about 20 to 80%, based on the weight of the toothpaste, in the liquid phase of water, and one or more humectants as Carrier and about 0.5 to 5%, based on the weight of the toothpaste, of a gelling agent which is essentially consists of hydroxyethyl cellulose with a high viscosity range, the average of which is at least is about 24,000 cP, as with a Brookfield viscometer on a 2% water: glycerin (1: 1.56) solution at 20 ° C with a # 6 spindle at 20 rpm.

Binary fluorine-producing systems are described above. According to the invention, the gel-forming agent is contained in the toothpaste in an amount of about 0.5 to 5% by weight , preferably about 0.8 to 2% by weight and in particular about 0.9 to 1.1% by weight. Tylose H 100OOP is a typical hydroxyethyl cellulose which is effective for the purposes of the invention.

Tylose H IOOOOP and others useful in the present invention Hydroxyethyl celluloses have viscosities in a range that average at least about 24,000 cP is measured with a Brookfield viscometer at 20 ° C on a water glycerine (1: 1.56) solution with a # 6 spindle at 20 rpm. Values expressed in this way differ from those determined earlier in the description specified values. High viscosity hydroxyethyl celluloses used in the present invention are compiled in the table below.

Tabel

Manufacturer HEC viscosity

Hercules Natrosol 250 HR

and 250 H 17000-31000

¹¹ Natrosol 250 HHR

and 250 HH 37000-41000

Hoechst Tylose H IOOOOP 20000-30000
20th

Hydroxyethyl celluloses with a viscosity the average of which does not reach about 24,000 cP, such as Hercules 250 M and MR (average viscosity 15,500 cP) and Tylose H 4000P from Hoechst (viscosity up to 23,000 cP) do not lead to the desired rheological properties if they are the only gel-forming properties Funds are used.

When the toothpaste is about 20 to 75% by weight of a polishing agent contains at least about half of which consists of hydrated alumina, can, if desired, up to about half of the total buff from another dentally acceptable buff consist of silicon dioxide, dicalcium phosphate, calci-

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nated alumina, zirconium silicate, insoluble sodium methaphosphate i.a. Preferably about 40 to 55% abrasive is typically complete consists of hydrated alumina.

The hydrated alumina used preferably has a small particle size, ie at least about 85% of the particles are smaller than 20 µm, such as that classified as gibbsite (<k - alumina trihydrate) which η
will.

ΊΟ which is usually defined as Al-O ... 3H-0 or Al (OH) -

The ^ -alumina trihydrate can have a particle size in the range of about 2.6 to 10 µm. That of the

-15 Alcoa sold as C333 aL-aluminum oxide trihydrate consists of finely divided gibbsite and is particularly desirable. The average particle size of C333 alumina is about 7 to 9 µm (Coulter counter). It is obtained by finely grinding the aluminum oxide trihydrate sold by Alcoa as C333. Other hydrated aluminas that can be used are AF 260 and AF 230 from the British Aluminum Company and SH 100 from Rhone-Poulenc.

The toothpaste containing hydrated alumina is usually filled into containers from which they can be easily expressed, e.g. from a dispenser operated by a pressure differential or mechanically or from a lined or unlined aluminum or lead tube or a laminate tube. The rheological properties are special desirable if a mechanically operated dispenser of the type described in British Patent Application 2,070,695Λ Type is used, which on September 9th

τκ was published about 1981 and on the here express-

borrowed is referred to. This dispenser has a mouthpiece, a pull rod, a piston and a handle. service on. Dispensers operated by pressure differential can be of the aerosol or vacuum type.

^ * v

The hydrated alumina toothpaste may contain a compound that provides fluoride, or a binary fluorine supplying system as described above.

The calcium phosphate-containing toothpaste typically has about 35 to 75% by weight, preferably 40 to 55% by weight of a dentally acceptable water-insoluble polishing agent, which consists essentially of a calcium

- \ 5 phosphate, such as dicalcium phosphate in its dihydrated or anhydrous form or mixtures thereof in any ratio, tricalcium phosphate and calcium pyrophosphate. In particular, dicalcium phosphate is used, generally as a dihydrate. Dicalcium phosphate is typically the sole polishing agent, if desired, but minor amounts of, for example, up to 5% by weight of the toothpaste and up to about 12% by weight of the total polishing agent can consist of other dentally acceptable water-insoluble polishing agents which have the property of formulation according to the invention to promote oral hygiene do not significantly impair. Typical polishing agents are alumina, silica, sodium aluminosilicate, and others. A lower amount of hydrated alumina, say about 1%, also inhibits or even prevents the tendency of some toothpastes to separate or "bleed" in their tubes.

In the toothpaste formulations, the carrier consists of a liquid phase which, in such quantities, contains yellowish-yellow

the means is added that a squeezable creamy mass of the desired consistency is formed. In general The liquids in the toothpaste mainly contain water, glycerine, sorbitol and polyethylene glycol 400, propylene glycol, or the like, including suitable mixtures of these ingredients. Usually it is advantageous to use a mixture of water and a humectant or binding agent, such as glycerin or Use sorbitol. Typically around 10! up to 30% by weight of water and about 15 to 50% by weight of humectant used. Glycerine or sorbitol is preferably used. The total liquid content is generally about 20 to 80% by weight of the formulation.

Ί5 Any suitable surface active agent or surfactant can be incorporated into the toothpaste formulations. Such compatible materials are desirable
to give the toothpaste additional cleaning, foaming and antibacterial properties, depending on the specific type of surfactant selected. These surfactants are usually water soluble and can be anionic, nonionic, or cationic. Water-soluble synthetic organic surfactants other than soaps are usually preferred. Suitable surfactants are known and include, for example, the water-soluble salts of higher fatty acid monoglyceride monosulfates, for example sodium coconut fatty acid monoglyceride monosulfate, higher alkyl sulfates, for example sodium lauryl sulfate, alkylarylsulfonates, for example sodium dodecylbenzenesulfonate, higher fatty acid esters of 1,2-dihydroxypropanesulfonate and the like.

Other surfactants are essentially the same saturated higher aliphatic acylamides lower aliphatic aminocarboxylic acid compounds, e.g.

those with 12 to 16 carbon atoms in the acyl radical. Of the Amino acid content is generally derived from lower aliphatic saturated monoaminocarboxylic acids with about 2 up to 6 carbon atoms, usually the monocarboxylic acids. Suitable compounds are the fatty acid amides of Glycine, sarcosine, alanine, 3-aminopropanoic acid and valine with about 12 to 16 carbon atoms in the acyl residue. The N-Lauroyl-, -Myristoyl- and -PaI-mitoylsarcosidverbindungen are preferred, with which optimal effects ΊΟ can be achieved.

The amide compound can be used in the form of the free acid or, preferably, as a water-soluble salt, e.g. as alkali metal, ammonium, amine or alkylol

■ \ 5 amine salt. Specific examples are the sodium and potassium N-lauroyl, myristoyl and palmitoyl sarcosides, ammonium and ethanolamine N-lauroyl glycide and alanide. The term "aminocarboxylic acid compound", "sarcoside" and the like herein denotes compounds having a free carboxyl group or their water-soluble salts.

These materials are used in pure or substantially pure form. You should as far as how possible to be free of soap or similar higher fatty acid materials which would reduce the effectiveness of these compounds to decrease. In practice the amount of higher fatty acid materials is usually less than 15% by weight of the amide and is not sufficient to this

3Q adversely affect, and preferably amounts to its amount less than about 10% of the amide material.

In the toothpastes according to the invention, various. other materials can be incorporated. Examples of this are coloring or whitening substances, preservatives

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curing agents, stabilizers, Tctraiuil r i wmpyiopln-> sphat, Silicones, chlorophyll compounds and ammoniated materials such as urea, diaminonium phosphate and their mixtures. These auxiliaries are incorporated in such amounts that they have the desired properties of the toothpaste and are appropriately selected in conventional amounts and applied.

For some purposes it may be desirable to include in the invention Formulations to incorporate antibacterial agents. Typical antibacterial agents that come in quantities from about 0.01 to about 5%, preferably from about 0.05 to about 1.0%, of the weight of the dentifrice

- | 5 are:

N -4-chlorobenzyl) -N - (2,4-dichlorobenzyl) biguanide;

p-chlorophenyl biguanide;

4-chlorobenzylhydryl biguanide;
4-chlorobenzylhydrylguanylurea;

N-3-lauroxypropyl-N-p -chlorobenzyl biguanide;

1,6-di-p-chlorophenyl biguanide hexane;

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

N -p-chlorophenyl-N -lauryl biguanide;

5-amino-1,3-bis - (- ethylhexyl) -5-methylhexahydropyrimi-

din;

and their non-toxic acid addition salts.

The compositions of the invention can be used with anyone appropriate flavoring or sweetening agent flavor can be imparted. Examples of flavor components are flavor-imparting oils, e.g. the oils of spearmint, peppermint, wintergreen, sassafras, milking,

Sage, eucalyptus, marjoram, cinnamon, lemon and orange oils, as well as methyl salicylate. Suitable sweeteners include sucrose, lactose, maltose, sorbitol, sodium cyclamate, Sodium saccharine dipeptides according to US Pat. No. 3,939,261 and oxathiazine salts according to US Pat U.S. Patent 3,932,606. The amount of the flavors and sweeteners combined is appropriate about 0.01 to 0.5% or more of the formulation.

The toothpastes should have a pH value that is practical for use. A pH range of 5 to 9 is particularly desirable. When the polishing agent is hydrated alumina, the pH can range from 3 to Be 10.5. These pH values are to be understood in such a way that they were measured directly on the toothpastes. If desired, can be used to adjust the pH to generally 5.5 to 6.5 or, in the case of toothpastes, the hydrated Contain aluminum oxide, added to 4 to 7.5 substances, such as benzoic acid or citric acid will.

The toothpaste is usually supplied in a squeezable tube such as lined or unlined Aluminum or lead, or in general in laminate tubes and especially when the toothpaste is hydrated Contains aluminum oxide, filled in mechanically operated dispensers.

The following examples illustrate the invention. In them, all quantities are based on weight, unless otherwise stated.

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Examples 1-3

Mixture of gelling agents - calcium phosphate - simple and binary sources of fluorine

example 1

The following toothpastes are made in a conventional manner made using sodium carboxymethyl cellulose and hydroxyethyl cellulose, which are separately a -ΙΟ A premix of glycerine and water can be added. They are filled into tubes made of aluminum and subjected to dynamic aging by being carried out during 2 cm long strips of toothpaste twice on 5 days a week for 2 weeks.

Parts

AWAY

Glycerin 22.00 22.00

Sodium carboxymethyl cellulose

(Hercules 7MFD) 0.44 0.45

Hydroxyethyl cellulose

(Hercules Natrosol 250 M) 0.46 0.50

Dicalcium Phosphate Dihydrate 48.00 48.00 Sodium Lauryl Sulphate 1.50 1.50

Sodium saccharin 0.20 0.20

Sodium monofluorophosphate 0.76 0.76

Sodium fluoride 0.10 0.10

Flavor 0.90 0.90

deionized water

to fill up to 100.00 100.00

After two weeks of dynamic aging, the toothpaste surfaces were smooth and rheologically acceptable. The creams did not thin out when they were squeezed out of the tube and stood well on the toothbrushes.

Similar rheological properties are found in a The weight ratio of sodium carboxymethyl cellulose to hydroxyethyl cellulose of 3: 2 was observed.

If the formulations are modified so that the Weight ratio of the sodium carboxymethyl cellulose is greater than 3: 2 (7: 3 and 10: 1), the surface becomes rough during dynamic aging. If only sodium carboxymethyl cellulose is used as a gel-forming agent (0.90 parts), the surface can after Ending the two week dynamic aging will become lumpy.

If the ratio of sodium carboxymethyl cellulose to hydroxyethyl cellulose is below 2: 3, the toothpaste has stopped not good, but quickly settles into a flat band. Also towards the end of squeezing out the toothpaste strip Tail formation observed. This also occurs when the hydroxyethyl cellulose is the only one gel forming agent.

Example 2

Toothpaste A of Example 1 is modified in such a way that that 0.36 part of sodium carboxymethyl cellulose and 0.54 part of hydroxyethyl cellulose are used. The surface of the toothpaste is smooth, the toothpaste does not show any tailing and stands well.

Example 3

Toothpaste A of Example 1 is modified in such a way that that 0.45 parts of sodium carboxymethyl cellulose (Hercules 7MFD) and 0.45 parts of hydroxyethyl cellulose (Hercules 250 M) used. The surface is

smooth, the toothpaste shows no tail formation and stands well.

Similar desirable rheological properties were observed when the toothpaste A of Example 1 is modified in such a way that 0.50 part of sodium carboxymethyl cellulose (Hercules 7MF) and 0.50 part of hydroxyethyl cellulose (Hercules 250 MR) and 0.25 part of tetrasodium pyrophosphate used.

Similar properties as with the formulations of the Examples 1 to 3 are achieved using other grades of sodium carboxymethyl cellulose, e.g., Hercules 7MXF, Wolff Walsrode Walocel CRT 1000 PAA 107, Nyma Nymcel XMF. 33 and Enka Akucel AC 1632 and the hydroxyethyl cellulose can be used, e.g. Hercules Natrosol 250 HR and Natrosol 250 HHR as well as Hoechst Tylose H 4000P.

Effects analogous to those with the formulations of Examples 1 to 3 occur when 1.15 parts of sodium monofluorophosphate can be used and the sodium fluoride is omitted.

Example 4

Highly viscous hydroxyethyl cellulose-hydrated aluminum oxide-no fluoride and no binary fluorine sources

The following toothpastes are made in the usual manner. The toothpastes A and B are in mechanical powered dispenser bottled in accordance with UK Patent Application 2,070,695A. Toothpaste C is turned into a unlined aluminum tube and the tooth cromc D bottled in a lined aluminum tube.

% ige solution A. 00 B. Texle 00 20, 20th D. 00 23, 23, C. 23, Sorbitol, 70 - - - Glycerin

Hydroxyethyl cellulose

(Hercules Natrosol 250M) - 1.00

Hydroxyethyl cellulose (Hoechst Tylose H lOOOOP)

oC aluminum oxide trihydrate (Alcoa C333)

C _1n -C ₁ ο-alcohol sodium sulfate

Li. Xo
(100% AI)

Zinc sulfate .7H ₂ O

Aluminum sulfate .18H-O sodium saccharin methyl p-hydroxybenzoate Sodium monofluorophosphate Sodium fluoride Pyridylcarbinol Allantoin

Phosphoric acid flavor, 85% deionized water

to fill up to 100 100 100 100

l, Q0 52.00 1.30 1, 00 52.00 0.5 52.00 52, 00 0.5 - 1.5 1, 5 - - 0.48 - - 0.17. - 0, 78 0.17 0.08 0.20 0, 17th 0.08 0.76 0.08 - 0.76 0.10 - - 0.10 0.10 - - 0.10 0.15 - - 0.15 1.20 0.15 - 1.20 0.14 1.00 1, 20th 0.14 _ _

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During filling and pressing, the surfaces of toothpastes A, C and D are smooth and rheological desirable, while the toothpaste B melts during filling and squeezing out of the container. Similar Rheological properties like the toothpastes A, C and D are achieved when the Tylose H 100OOP in these Toothpastes are replaced by Natrosol 250 H and Natrosol 250 HH. Tailing occurs when the Toothpaste B (with Natrosol 250 M) is filled into a tube.

Example 5

High viscosity hydroxyethyl cellulose calcium phosphate binary 5 r'e fluorine sources

The following toothpaste is produced in a conventional manner and filled into an aluminum tube. While 2 weeks are expressed on 5 days of each week toothpaste strips twice a day.

Parts glycerin 22.00

Hydroxyethyl cellulose
Viscosity 20,000 to 30,000 cP
(Hoechst Tylose H lOOOOP) 1.00

Dicalcium phosphate dihydrate 48.00

Sodium Lauryl Sulphate 1.50

Sodium saccharin 0.2 0

Sodium monofluorophosphate 0.76

Sodium fluoride 0.10

Flavor 0.90 deionized water to make up to 100

The toothpaste does not dilute when it is pressed out and shows rheologically desirable properties.

The rheological properties are also desirable, if the Tylose H 100OOP is replaced by Natrosol 250 H or Natrosol 250 HH.

If the Tylose H 100OOP is replaced by hydroxyethyl cellulose with a lower viscosity, such as Natrosol 250 M (Hercules) or Tylose H 4000P, tail formation occurs when the toothpaste is squeezed out.

Claims (1)

Claims Toothpaste, characterized in that it, based on the weight of the toothpaste, about 2 0 to 80% of a liquid phase composed of water and one or more humectants and about 0.5 contains up to 5% of a gel-forming agent made from sodium carboxymethyl cellulose and hydroxyethyl cellulose, their weight ratio to one another is approximately 3: 2 to 2: 3. Toothpaste according to claim 1, characterized in that it contains sodium carboxy- contains methyl cellulose and hydroxyethyl cellulose in a weight ratio of 49:51 to 2: 3. 3. Toothpaste according to claim 1 and 2, characterized in that that it contains a link that provides at least about 100 ppm fluorine, furthermore about 40 to 75% by weight of a dental acceptable, water-insoluble polishing agent containing a calcium phosphate in an amount of at least Ί0 contains approximately 35% by weight of the toothpaste. 4. Toothpaste according to claim 3, characterized in that about 750 to 2000 ppm of ionic fluorine made available to a source of fluorine, -15 namely from sodium monofluorophosphate or a mixture From sodium monofluorophosphate and sodium fluoride, with about 30 to 40 wt.% Of the fluorine from Sodium fluoride can be supplied. 5. Toothpaste according to claim 4, characterized in that that it contains a mixture of sodium monofluorophosphate and sodium fluoride and of sodium fluoride about 30 to 35% by weight of the fluorine can be supplied. 6. Toothpaste according to claim 3, characterized in that it contains dicalcium phosphate as a polishing agent in an amount of about 40 to 50% by weight. 7. Toothpaste according to claim 5 and 6, characterized in that the with a Brookfield viscometer The viscosity of the sodium carboxymethyl cellulose measured at 25 ° C. on a 2% strength aqueous solution about 300 to 500 cP and that of the hydroxyethyl cellulose is about 4500 to 6500 cP. 8. Toothpaste, characterized in that it contains about 2 0 to 75 wt.% Of a polishing agent, of which at least about half consists of hydrated alumina and also about 20 to 80 wt. a liquid phase of water and one or more humectants and about 0.5 to 5% by weight of a gel-forming agent, which consists essentially of hydroxyethyl cellulose, of which with a Brookfield viscometer, spindle no. 6 at 20 rpm on a 2% strength by weight water: glycerine (1: 1.56) solution at 20 C measured viscosity is in a range whose average is at least is about 24,000 cps. 9. Toothpaste according to claim 8, characterized in that it contains about 40 to 55 wt.% <^ - aluminum oxide trihydrate contains as a polishing agent. 10. Toothpaste according to claim 8 and 9, characterized in that that they are in a dispenser operated by a pressure differential, a mechanically operated one Dispenser or filled into a tube. 11. Toothpaste according to claim 8 to 10, characterized in that the fluorine supplying compound in is present in an amount which will provide about 100 to 10,000 ppm fluorine. 12. Toothpaste according to claim 11, characterized in that the fluorine of sodium monofluorophosphate in is provided in an amount of about 750 to 2000 ppm. 13. Toothpaste according to claim 11, characterized in that about 75 0 to 2,000 ppm of fluorine from one -A- binary fluorine system from sodium monofluorophosphate and sodium fluoride, with about 30 to 40% by weight of the fluorine being provided by the sodium fluoride to be delivered. 14. Toothpaste according to claim 8 to 11 and 13, characterized in that it is zinc sulfate or aluminum sulfate Contains in an amount of about 0.05 to 1.5% by weight. 15. Toothpaste, characterized in that it is a binary fluorine system of sodium monofluorophosphate and contains sodium fluoride in an amount that provides about 750 to 2000 ppm ionic fluorine, -j5 where about 30 to 40% by weight of the fluorine is from the sodium fluoride Are made available, about 35 to 75 wt.% Of a polishing agent, which is essentially consists of calcium phosphate, about 20 to 80% by weight of a liquid phase of water, humectants or a mixture of these as a carrier and about 0.5 to 5% by weight of a gel-forming agent which is contained in the consists essentially of hydroxyethyl cellulose, whose spindle with a Brookfield viscometer No. 6 at 20 rpm on a 2% water: glycerine (1: 1.56) solution, viscosity measured at 20 ° C is in a range the average of which is at least about 24,000 cP. 16. Toothpaste according to claim 15, characterized in that the binary fluorine system is about 1400 to Provides 2000 ppm ionic fluorine. 17. Toothpaste according to claim 15 and 16, characterized in that it contains dicalcium phosphate as a polishing agent Contains in an amount of about 40 to 75% by weight. 18. Toothpaste according to claim 8 to 17, characterized in that the hydroxyethyl cellulose has a viscosity from about 17,000 to 31,000 cP, from about 37,000 to 41,000 cP, or from about 20,000 to 30,000 cP. 19. Toothpaste according to claim 18, characterized in that the hydroxyethyl cellulose has a viscosity from about 20,000 to 30,000 cps. 20. Toothpaste according to claim 1 to 19, characterized in that it contains the gel-forming agent in one Contains an amount of about 0.8 to 2% by weight.