DE2613500A1 - ORAL CARE PRODUCTS AND METHODS TO PREVENT TEETH DISOLUTION - Google Patents

Description

Lawyers 2 March 9, 1976

OR. .JUR. DlPL-CHEM. WALTER BEIL
ALFRED HOEPPCNER
OR. JUR. DIi ¹ L-CHe-Vl. H.-J. WOLFF
DR. JUR. HANS CHk. AX

FRANKFURTAM MAIN-HüCHSf ADElONSTRASSt 58

Our no. 20 432 Ec / Fb

The Procter & Gamble Company Cincinnati, Ohio, V.St.A.

Oral care products and methods of preventing tooth discoloration

The invention relates to oral care products, such as dentifrices, mouthwashes and the like, which promote formation prevent or delay discoloration on teeth. These funds contain as an effective ingredient for prevention or delaying discoloration using a chelating agent, that is able to bind iron or iron and manganese ions in a chelate complex, but that no calcium removed from the teeth.

The appearance of discoloration on the teeth is a common occurrence. The degree of discoloration is individual different and depends on various factors, such as diet or smoking. Even if to combat good oral hygiene, especially brushing and cleaning with the help of silk threads (flossing) To some extent effective, tooth discoloration is still a serious problem for many people Problem even when good oral hygiene is used.

ORIGINAL INSPECTED

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BE-PS 818735 proposes the use of certain organic peroxy acids as bleaching agents in oral care products , for example dentifrices, in order to reduce discoloration. However, because of the chemical reactivity of these materials, formulation of persistent mixtures requires either a substantial departure from the types of ingredients commonly used in oral care products or the bleaching ingredient must be kept separate from the rest of the mixture until just prior to use.

Of certain bis-biguanide antibacterial agents known to be effective in reducing plaque on teeth, they have been found to exacerbate tooth discoloration beyond what is naturally occurring. To the To reduce discoloration caused by these agents, the use of chelating agents has been suggested, which form soluble or insoluble salts with these antibacterial agents, compare e.g. BE-PSs 801 703 and 811 878 as well as the French patent application 2281107

It has now been found that for the "natural" discoloration of teeth, i.e. the discoloration that occurs as a result contact of the teeth with common food and drink occurs, primarily the ferric ion (Fe ^)

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responsible for. The manganese ion (Mn) was also found that it contributes significantly to the discoloration, with the contribution of the manganese ions to the discoloration of the teeth, however, is slightly lower than that of the iron ions, since the manganese is in the substances normally associated with the Teeth come into contact, occurs in smaller quantities. These ions occur in saliva, in drinking water and in many Food and beverages in trace amounts. They appear to be in the membrane film, plaque and tartar, that accumulate on the teeth, including where they are

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if necessary, add other materials such as tannins and phenolic compounds, which are commonly found in many foods and beverages, e.g. in spinach, coffee and tea, can be found, can react with the formation of colored products.

In accordance with the present invention, it has been found that discoloration of teeth can be prevented or delayed without removing calcium from the teeth by contacting the teeth with an oral care agent which is a carrier suitable for use in the oral cavity and about 0.04 to about 8 % of a discoloration preventing agent selected from (A) metal chelating agents having a persistence constant K ₁ for Pe ^ ⁺ equal to or greater than 9 and a persistence constant K ₁ for calcium of 7.5 or less, or (B) calcium chelates of Metal chelating agents, the chelating agents having a resistance constant K- for calcium of greater than 7.5 and a resistance constant K ₁ for Fe which is greater than the resistance constant K. for calcium. These metal chelating agents or calcium chelates effectively chelate iron present in the membrane film or in the plaque or tartar on the teeth without chelating calcium off the surface of the teeth.

The discoloration-preventing agents of type (A) preferably additionally have a resistance constant K ₁ for

Mn of 7.0 and above, and preventing the discoloration Type (B) agents also have a resistance con-

2 +

constant K ₁ for Mn, which is greater than its constant K ₁ for calcium. This preferred discoloration

preventive agents prevent discoloration caused by Mn and caused by Fe.

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The present invention provides oral care products that prevent discoloration from forming on the Effectively prevent teeth. The term "oral care products" used here is intended to denote all types of products which in normal use are retained in the oral cavity for so long and in such a way that practically all of them Touching tooth surfaces that are not intentionally ingested as such. These products include e.g. Dentifrices, mouthwashes, lozenges or lozenges (lozenges), prophylactic pastes and solutions for topical treatment. Food and drinks, of course, only It does not include remaining in the mouth for a relatively short time before digestion. In the broadest sense, includes the term "oral care products" also includes tooth cleaning products, which are not used as such in the mouth, but which are used to clean devices that are used in the Mouth.

The effective discoloration preventing agents of the present invention are metal chelating agents. in the For the purposes of the present invention, the term "ketal chelating agent" means an organic compound which forms a coordination compound with a metal ion, xforin the metal ion to two or more atoms of one or several molecules of the organic compound is bound in such a way that one or more heterocyclic rings with the Ketallion can be formed as part of each ring. Metal chelating agents, which are suitable for use in accordance with the present invention are those which have useful constants of persistence for iron (and preferably also for manganese), so that they form complexes with these metals form, but do not react to such an extent with the calcium that is present in the teeth to form complexes, that they cause damage. As far as the terms "iron" and "manganese" are used here, it is understood to mean ~

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even that they ^{concern the Fe ^ +} and Mn ions. Persistence constant is a measure of the ability of the metal chelating agent to form persistent complexes with a particular metal ion. The higher the persistence constant, the greater its ability to form a persistent complex. Specifically, the discoloration preventing agent of type (A) according to the present invention are Metallchelatbxldungsinittel with a resistance constant K for iron of 9.0 or more (preferably greater than 10.0) and a resistance constant K ₁ for calcium of 7.5 or below. All resistance constants given here relate to resistance in water at 25 ° C ₃ unless otherwise stated. The discoloration preventing agents of type (B) are calcium chelates of chelating agents which have a resistance constant K ₁ for calcium of more than 7.5 and a resistance constant K- for iron which is greater (preferably at least 0.5 units greater) than the resistance constant K- is for calcium. The type (B) chelating agents are strong chelating agents for calcium, but since they are used in the form of the calcium chelate, they do not remove calcium from the teeth, and since their constant K ₁ (i.e. affinity) is greater for iron than for calcium, replaces them the iron removes the calcium in these chelates, so that in this way the discoloration of the teeth is prevented. Preferably, the discoloration preventing agents of the present invention are effective against iron and manganese. Therefore, the preferred discoloration preventing agents of the present invention are (A) metal chelating agents having a resistance constant K ₁ for iron equal to or greater than 9.0 (preferably greater than 10.0), a resistance constant K ₁ for manganese of 7.0 or more (preferably greater than 9.0) and a persistence constant K- for

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Calcium of 7.5 or below or (B) calcium helates of chelating agents having a resistance constant K ₁ for calcium greater than 7.5 and resistance constants K-for iron and manganese both greater (preferably at least 0.5 units greater) than that Constant constant K- for calcium are.

There are very many metal chelating agents that can Meet criteria for use in the agents according to the invention. The following lists are only Examples include many other metal chelating agents supplemented by those skilled in the art which also meet the above criteria and therefore fall within the scope of the present invention.

Table I. Type (A) discoloration preventing agents

Resistance constant K-

Chelating agent Fe ³⁺ Mn ² * Ca ²⁺

Kojic acid 9.2 9.8 2.5

Ethylenediamine diacetic acid 16.9 7.7 4.6 4,5-dihydroxy-m-benzene-

sulfonic acid 13.3 8.6 5.8

Maltol r ^ y 10.0 rJ 9.0 ^ 17.0

Ethylenediamine-Ν, Ν, Ν ¹ , R ¹ , -

tetra- (methanephosphonic acid) ρ ^ ΙΟ, Ο ■ 9.7 6.0 N, N, N ¹ , N ^f -Tetra (phosphono-

methyl) -cyclohexane-1,2-diamine 23.3 8.4 5.4 N, N ^t -Ethylenedi- (oC-o-hydroxy-

phenyl) glycine ^ 33.0-7.2

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Table II
Type (B) discoloration preventing agents

Persistence constant K of the chelating agent

Chelate Fe ^ ⁺ Mn ²⁺ Ca ²⁺ Caleium-dihydrogen-ethylene-
diamine tetra acetate 24.2 13.9 10.7 Calcium-hydrogen-nitrilotri-
acetate 8.2 7.7 7.7 Calcium-hydrogen-N '- (2-hydroxy-
ethyl) -ethylenediamine-N, N, N »-
triacetate 19.8 10.7 8.1 Calcium-dihydrogen-trans-
cyclohexane-1,2-diamine
N, N, N ¹ , N'-tetra acetate 27.5 16.7 12.5 Calcium trihydrogen diethylene
triamine-N, N _a N ^f , N ^ff , N '' - penta-
acetate 28.6 15.13 9.9 Calcium-hydrogen-N- (o-hydroxy-
cyclohexyD-ethylenediamine-
N, N ¹ , N'-triacetate 21.4 9.3 Cälcium-Ν, Ν ^f -äthylenendi-Z ¹ N-
(2-pyridyl-methyl) -glycine 7 28.8 12.7 7.9

The water-soluble pharmaceutically acceptable salts of the above metal chelating agents and calcium chelates can also be used. Examples of such salts are the alkali metal (e.g. sodium and potassium), ammonium and ammonium salts substituted by lower alkyl and hydroxyalkyl groups (e.g. mono-, di- and trialkylammonium salts and mono-, di- and trialkanolammonium salts, each with 1 to 3 Carbon atoms in the alkyl group, such as the mono-, di- and triethylammonium salts and the mono-, di- and triethanolammonium salts). The term "water-soluble" used here means a solubility in water / water of at least 0.04 % at 25 ° C. Examples of special salts

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are dipotassium ethylenediamine diacetate and calcium diammonium ethylenediamine tetraacetate.

A preferred group of discoloration preventing agents for use for the present invention are kojic acid, Maltol, ethylenediamine diacetic acid and calcium dihydrogen ethylenediamine tetraacetate and their water-soluble, pharmaceutically acceptable salts.

The pH of the oral care compositions of the invention should preferably be in the range of about 4.5 to about 9 0 ₃ of about 5.5 to about 7.5. The agents according to the invention preferably contain considerable amounts of water, for example about 15 to about 90 %, but they can also be dry (for example in the form of tooth powders), in which case the specified pH equals the pH value of 10% by weight Mixture of the agent according to the invention in v / ater. All percentages given here are based on weight, unless otherwise stated.

The method of the present invention for preventing discoloration of the teeth consists in contacting the teeth with an effective amount of the discoloration preventive agent consisting of a metal chelating agent or a calcium chelate as defined above. The amount of the discoloration preventing agent which causes an effective preventing or retarding the discoloration is at least 0.01 _s, preferably about 0.01 g to about 0.8 g, more preferably about 0.05 g to about 0.6 (solids basis) which are taken up into the oral cavity per use, the material taken up into the oral cavity preferably being moved in the mouth in such a way that it touches as wide an area of the tooth surface as possible. There should be a contact time of at least about 10 seconds and preferably at least about 20 seconds between

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the discoloration-preventing agent and the tooth surfaces. Preferably the discoloration. Preventive agents in an aqueous liquid or paste-like carrier distributed before, if it is on the Teeth is used, but dry forms (e.g. tooth powder) can also be used, which causes discoloration preventive agents dissolve in saliva to form an aqueous system. Generally there are two uses per day an excellent fight against discoloration of the teeth. Amounts above 0.8 g per application can be used, but in general such large amounts increase the degree of discoloration control achieved not essential.

The discoloration preventing agent can be used in any type of carrier suitable for use in the oral cavity, be applied to the teeth. The carrier plus the discoloration preventing agent make up the oral care products the invention. The carrier can consist of water.

The preferred mode of application of the oral care products according to the invention however, it consists in using the discoloration preventive agent in the form of an oral care product, e.g. toothpaste, mouthwash, chewing gum or lozenge or candy on your teeth applies. In the particularly preferred embodiment of the invention, the discoloration preventing agent is in the form of a dentifrice is used as this type of application is particularly effective at tearing up plaque and thus the The accessibility of the discoloration preventing agent to the iron and manganese embedded in the plaque is improved. Mouthwashes and chewing gum supplements are also preferred.

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Favored, but not as preferred as dentifrices.

Dentifrices contain an abrasive and buffing material and typically also contain foaming agents, flavorings and sweeteners. Toothpastes usually also contain humectants, binders and water. The dentifrices according to the invention contain about 0.5 to about 95 % abrasive and at least about O ₃ 25 %, preferably about 1 to about 5 % and in particular about 2 to about 4 % of the discoloration preventing agent according to the present invention. (All percentages are by weight unless otherwise noted.)

Any abrasive and polishing material that does not excessively damage the dentin can be used in the dentifrices rubs off. These include e.g. calcium carbonate, ■ dicalcium orthophosphate dihydrate, Calcium pyrophosphate, calcium polymethaphosphate, insoluble sodium polymethaphosphate and Resin-like scouring materials, such as finely divided condensation products of urea and formaldehyde and the resins described in US Pat. No. 3,070,510. The abrasives generally have a particle size of from about 0.1 to about 10 microns in diameter.

The total amount of abrasive in the dentifrices according to the invention can be 0.5 to 95% by weight _3, based on the dentifrice. Toothpastes preferably contain about 6 to about 60 % and tooth powder contain about 20 to about 95 % abrasives.

Dentifrices usually contain surfactants (also known as foaming agents). Surfactants suitable for use in the invention Dentifrices are suitable are those that

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result in a considerable amount of foam and otherwise are suitable for use in the oral cavity. Suitable foaming agents are those that spread over a wide area are reasonably stable in the pH range. Preferred are anionic organic synthetic detergents other than soaps are.

Examples of such agents are water-soluble salts of alkyl sulfates with 10 to 18 carbon atoms in the alkyl radical (e.g. sodium lauryl sulfate); water-soluble salts of sulfonated monoglycerides of fatty acids (e.g. sodium coconut monoglyceride sulfonate); Salts of fatty acid amides of taurine with 10 to 18 carbon atoms in the fatty acid residue, such as e.g., sodium N-methyl-N-palmitoyl-taurine; Salts of fatty acid esters of isethionic acid with 10 to 18 carbon atoms in the fatty acid residue; as well as essentially saturated ones aliphatic acylamides of saturated monoaminocarboxylic acids with 2 to 6 carbon atoms, the acyl radical of which is 12 to Contains 16 carbon atoms, such as sodium N-lauroyl sarcoside. Mixtures of two or more foaming agents can also be used.

The foaming agent can be used in amounts of about 0.5 to about 5.0 % ₃ based on the dentifrice.

Suitable flavorings for use in the dentifrices according to the invention are, for example, a distillate from the American wintergreen, gaultheria procumbens, (wintergreen oil), which consists of methyl salicylate, peppermint oil, sassafras oil (synthetic) and anisole. The flavoring agents should be present in the inventive dentifrices in an amount of 0.01 to 2 O _3%.

π Q R /,? / 1

The sweeteners that can be used in the dentifrices according to the invention include, for example, saccharin, dextrose and levulose. The sweeteners can be used in amounts from about 0.05 to about 2.0 % .

Toothpastes preferably contain thickeners such as hydroxyethyl cellulose and water-soluble salts of cellulose ethers, including sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose, or natural gums such as karaya gum, gum arabic, colloidal magnesium aluminum silicate (Veegum) and gum tragacanth. Colloidal magnesium aluminum silicate or one-part silicon dioxide can also be used as part of the thickener to improve the texture of the product. Thickeners can be used in amounts of 0.1 to 5.0 % _3, based on the composition of the toothpaste.

A humectant is preferably also incorporated into a toothpaste. Suitable agents for this purpose include glycerine, sorbitol and other edible polyhydric alcohols or mixtures thereof. These substances can make up about 1 % to about% of toothpaste. In addition to the above typical ingredients of a toothpaste, water usually constitutes the remainder of the toothpaste. Water can usually be present in a toothpaste in amounts up to about 50 % .

Mouthwashes generally contain a solution in water / ethyl alcohol and can optionally contain other ingredients such as e.g., flavorings, sweeteners and humectants such as those described above for dentifrices. The alcohol gives the mouthwash an antibacterial effect. Optional mouthwashes can also be used

contain foaming agents, such as the foaming agents listed above for dentifrices. Humectants, such as glycerine and sorbitol, cause the mouth to feel moist. Cationic antibacterial agents are sometimes incorporated into mouthwashes (or dentifrices) in amounts of from about 0.01 to about 2.0 percent . If so, the foaming agent used is preferably a nonionic foaming agent such as an ethylene oxide condensate of a fatty alcohol, alkylphenol or fatty acid sorbitan star, rather than an anionic foaming agent. Examples of nonionic foam-forming agents are the condensation product of 10 moles of ethylene oxide with 1 mole of lauryl alcohol, the condensation product of 15 moles of ethylene oxide with 1 mole of nonylphenol and the condensation product of 20 moles of ethylene oxide with 1 mole of sorbitan monooleate.

In general, the mouthwashes contain at least about 0.04 % and preferably about 0.5 to about 1.5 % of the discoloration preventing agents used according to the invention, 5 to 60 % ethyl alcohol, 0 to 20 % (preferably 5 to 20 %) glycerol or other Humectant, 0 to 2 % (preferably 0.1 to 2 %) foaming agent, 0 to 0.5 % (preferably 0.05 to 0.5 %) sweetener such as saccharin, and 0 to 0.3 % (preferably 0 .05 to 0.3 %) flavorings, with the remainder being water.

Chewing gum preparations contain a gum base and flavorings such as those listed above for the dentifrices. The flavoring agents are present in amounts of 0.01 to about 2.0 % ₃ based on the finished chewing gum preparation. Chewing gum preparations contain at least 0.25 %, preferably about 1 to about 5 % and in particular about 2 to about 4 % of the discoloration-preventing agents used according to the invention. The gum base is a chewable plastic

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cal rubber material, such as natural rubber, balata, polyvinyl acetate, ester gununi, coumarone resin and paraffin wax. The gum base is mostly made from a mixture of 2 or more plastic gum materials in order to achieve a preferred degree of plasticity for chewing. Corn syrup is optionally added as a plasticizer and binder for the chewing gum preparation, and sugar is optionally added as a filler and sweetener. A typical chewing gum preparation of the present invention contains 15 to 30 % gum base, 15 to 20 % corn syrup, 50 to 65 % sugar, 0.05 to 1.5 % flavoring, and about 2 to about 4 % of the anti-stain agent.

Lozenges and sweets (lozenges) contain a hard sugar base and one or more flavorings. The flavors are present in amounts from 0.01 to 2.0 % . Lozenges contain at least about 0.25 %, preferably about 1 to about 5 % and in particular about 2 to about 1% of the discoloration preventing agent. The lozenges can optionally contain various other substances. A typical lozenge preparation of the present invention is a hard sugar preparation consisting of a hard, sugar base containing 0.05 to 1.5 % flavoring and about 1 to about 5 % of the discoloration preventing agent. The hard sugar base is a solidified solution of amorphous sugar, generally formed from a sugar solution that has been boiled at high temperatures to remove almost all of the moisture. The flavoring and anti-staining agent are added before the moisture is removed. The flavorings that have already been listed above for the dentifrices are also exemplary of the flavorings that are suitable for use in the lozenge preparations.

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When the discoloration preventive agents of the present invention are formulated into an oral care product, the amount incorporated into the oral care product should be sufficient to provide at least 0.01 g of the discoloration preventive agent per application of the oral care product. Therefore, in dentifrices, where the amount of product used per application is about 1 to ¹ J g, the amount of discoloration preventing agent should be at least about 0.25 %, preferably about 1 to about %, and especially about 2 to about ¹ I % . In mouthwashes, the amount of the agent per application is about 10 to about 25 g, so that the amount of discoloration preventing agent in the mouthwash is at least 0.04 % _3, preferably about 0.5 to about 1.5 % and in particular about 0.75% should be around 1.25 % .

The amount of a chewing gum preparation or a candy preparation for one application is typically about 2 to about 5 gj so that the amount of the discoloration preventing agent in the chewing gum preparation or lozenge preparation is at least about 0.25 %, preferably about 1 to about 5 % and especially about 2 to should be about M % .

In general, the oral care compositions of the present invention should contain from about 1% to about 5% of the discoloration preventive agent.

The oral care compositions of the present invention can also contain therapeutic substances for use in the oral cavity, such as e.g. anticaries agents (e.g. water-soluble fluorides such as sodium fluoride and stannous fluoride) and agents against tartar, such as trisodium-ethane-l-hydroxy-l, l-diphosphonate., contain.

6098 /, 3 / 10Ί7

The following examples illustrate the invention. Example I.

This example illustrates the effectiveness of the invention Oral care products to prevent or delay discoloration of teeth.

The artificial teeth were each circulated overnight at 37 ° C. in 3 ml of human saliva which had previously been centrifuged to remove the pests. In this way, a natural membrane film was formed on the teeth. The teeth were then immersed for 1 minute in 5 ml of an aqueous ferric chloride solution with a pH of 2.0, rinsed in water and for one minute in 5 ml of water or in 5 ml of aqueous treatment solutions of ethylenediamine -diacetic acid (EDDA) immersed in concentrations of 2 % and 0.1 % and with a pH of ^ 1 5; _S were prepared at each concentration 0 7jO and 9, wherein the pH values were adjusted as needed with 2N sodium hydroxide or glacial acetic acid. The teeth were then immersed for one minute in 5 ml of a coffee-tea solution which had been prepared by dissolving 20 g of soluble coffee powder (Folgerst instant) and 2 g of soluble tea powder (Liptons ^ instant) and centrifuging for 20 minutes. The teeth were then rinsed again in water.

Two teeth were used per treatment. After the last rinse, the teeth were visually marked on one of O (none Discoloration) to an 8 (severe discoloration) scale. The results are in the table below together. The degree of discoloration for each treatment is an average of the ratings for the two teeth.

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- 17 Table III

Treatment evaluation

Water 6.0

0.1 / 1 EDDA, pH 4.5 4.0

0.1 % EDDA, pH 7.0 4.0

0.1 Ji EDDA, pH 9.0 5.0

2.0 % EDDA, pH 4.5-2.5

2.0 % EDDA, pH 7.0 1.0

2.0 % EDDA, pH 9.0 0.5

Similar results were obtained when calcium dihydrogen-ethylenediamine-tetraacetic acid was used instead of EDDA in this experiment or maltol were used.

Example II

A toothpaste was made from the following ingredients:

Part of parts by weight

Sorbitol (70 pound solution) 20.00

Sodium saccharin 0.21

colloidal magnesium aluminum silicate

(Veegum) 0.40

Dicalcium orthophosphate dihydrate 30.00

Flavor 1.00

Sodium carboxymethyl

cellulose 1.30

Glycerin 10.00

Disodium ethylenediamine

diacetate '6.00 (plague

fabrics)

Sodium Lauryl Sulphate 1.50

distilled water remainder

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When this toothpaste is used in the usual manner, it is effective in preventing the formation of discoloration on teeth and to remove discoloration that is already on the teeth.

Example III

There has been made a mouthwash in accordance with the present invention made from the following components:

Component parts by weight

Ethyl alcohol (95 % in water) 12.00

Cetyl pyridinium chloride 0.10

Polyoxyethylene (20) sorbitan monooleate

(Tween 80) 0.12

Sodium hydroxide (10 % in v / water) x 0.02

Sodium saccharin 0.055

Flavor 0.16

Maltol 1.0

Dye 0.50

Sorbitol (70 % in water) 12.00

Water rest on

When this preparation is used in the usual way to rinse the oral cavity, it is effective for prevention the formation of discoloration of the teeth and the removal of discoloration that is already on the teeth. Practically the same results are obtained if instead of maltol in the above preparation kojic acid, the disodium salt of ethylenediamine diacetic acid or calcium disodium ethylenediamine tetraacetate be used.

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- 19 Example IV .

A chewing gum preparation according to the present invention was made from made of the following components:

component 6.40 Parts by weight Rubber base 9.60 21.30 Ester rubber 3.20 Coumarone resin 2.10 Nature chews school
(Dry latex rubber) Paraffin wax
(Fp = 82 ° C) sugar 58.45 Corn Syrup (Baume 45) 17.20 Flavor 1.05 Kojic acid 2.00 (plague
fabrics)

If this chewing gum preparation is chewed in the usual manner, it will provide an effective treatment for prevention and removal of tooth decay.

Example V

A lozenge preparation according to the present invention was made from the following ingredients:

Component parts by weight

Hard sugar base 97.75

Flavor 0.25

Calcium disodium ethylenediamine

tetraacetate 2.00

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When allowed to dissolve in the mouth in the usual way ₃ , this preparation is effective in preventing plaque from growing on teeth.

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Claims (12)

- 21 patent claims: Oral care product for preventing discoloration of teeth, characterized in that it contains a carrier and at least about 0.04 % of a discoloration preventing agent selected from (A) metal chelating agents with a resistance constant K ₁ for iron of 9 * 0 or above and a resistance constant K ₁ for calcium of 7.5 or below and their water-soluble, pharmaceutically acceptable salts and (B) calcium chelates of metal chelating agents with a resistance constant K ₁ for calcium above 7 _S 5 and a resistance constant K ₁ for iron which is greater than that Resistance constant K ₁ for calcium, and contains its water-soluble, pharmaceutically acceptable salts. 2. Agent according to claim 1, characterized in that the discoloration-preventing agents of type A from metal _{chelating agents with a resistance constant K 1} for iron of 10.0 or above or the discoloration-preventing agents of type B from calcium chelates of chelating agents with a resistance constant K. ₁ for iron, which is at least 0.5 units greater than the resistance constant K ₁ for calcium. 3. Agent according to claim 2, characterized in that it is a discoloration preventing agent of type A fithylenediamine-diacetic acid, 4,5-dihydroxy-m-benzenedisulfonic acid, maltol, ethylenediamine-Ν, Ν, Ν ¹ , N'-tetra- ( methanephosphonic acid), N, N, N ^f , N'-tetra- (phosphonomethyl) _{-cyclohexane-1,2-diamine, N 9} N ¹ -ethylenedi- (cc-o-hydroxypheny1) -glycine, calcium-dihydrogen-ethylenediamine- tetraacetate, calcium hydrogen nitrilotriacetate, calcium hydrogen N '- (2-hydroxyethyl) ethylenediamine-N, N, N'-triacetate, calcium dihydrogen-trans-cyclohexane-1,2- 609843/1037 diamine-Ν, Ν, Ν ¹ , N'-tetraacetate, calcium-trihydrogen-diethylenetriarain-K ^T , N, N ^f , N ¹ ', N''-pentaeaetat, calcium-hydrogen-N- (ohydroxycyclohexyl) -ethylenediamine- N, N ^T , N'-triacetate, calcium-NjN ^l -äthylenedi- / K- (2-pyridylmethyl) -glycine7 and / or a water-soluble, pharmaceutically acceptable salt of one of these compounds. 4. Composition according to claim 1, characterized in that there is a discoloration preventing agent selected from (A) metal chelating agents with a resistance constant K ₁ for iron equal to or greater than 9.0, a resistance constant K ^ for manganese of 7.0 or above and a resistance constant K., for calcium of 7.5 or below and their water-soluble, pharmaceutically acceptable salts and (B) the calcium chelates of chelating agents with a resistance constant K ^ for calcium above 7.5 and resistance constants K ^ for iron and manganese , both of which are greater than the constant K ^ for calcium, and contain their water-soluble, pharmaceutically acceptable salts. 5. Agent according to claim 4, characterized in that it is a type A discoloration preventing agent, a chelating agent with a constant K-, for Iron above 10.0, a constant K ^ for Manganese above 9.0 and a resistance constant K ^ for Calcium of 7.5 or below or, as a discoloration preventing agent of type B, a calcium chelate of a metal chelating agent with a resistance constant K ^ for calcium above 7.5 and a resistance constant K ^ for Iron and manganese, which are at least 0.5 units greater than the resistance constant K ^ for calcium. 609843Λ1037 6. Agent according to claim 5, characterized in that it is a discoloration preventing agent M, 5-dihydroxy-mbenzenesulfonic acid, N, N, N ¹ , N'-tetra- (phosphonomethyl) -cyclohexanol ^ - diamine, N, N'- ethylenedi- (c <Lo-hydroxyphenyl) -gylcine, calcium-dihydrogen-ethylenediamine-tetraacetate, calcium-hydrogen-N '- (2-hydroxyäthy1) -ethylenediamine-N, N, N'-triacetate, calcium-dihydrogen-trans-cyclohexan 1,2-diamine-N, N, N ', N * - tetraacetate, calcium-t-rihydrogen-diethylenetriamine-Ν, Ν, N ¹ , N'', - N''- pentaacetate, calcium-N, N' -äthylenendi-ZN- (2-pyridylmethyl) -glycine7 and / or a water-soluble, pharmaceutically acceptable salt of one of these compounds. 7. Means according to claim!, Characterized in that it is as Anti-discolouration agent kojic acid, maltol, ethylenediamine-diacetic acid, Calcium dihydrogen ethylenediamine tetraacetate and / or a water-soluble, pharmaceutically acceptable one Salt contains one of these compounds. 8. Agent according to one of claims 1 to 7 in the form of a dentifrice, characterized in that it contains about 0.5 to about 95 % of a dentifrice abrasive and at least about 0.25 % of the discoloration preventing agent. 9. Composition according to claim 8, characterized in that it contains about 1 to about 5 % of the discoloration preventing agent. 10. Agent according to one of claims 1 to 7 in the form of a mouthwash, characterized in that it contains about 5 to about 60 % ethyl alcohol, 0 to about 20 % of a humectant, 0 to about 2 % of a foaming agent, 0 to about 0.5 % of a sweetener, 0 to about 0.3 % of a flavor R 0 9 8 h -] I 1 oil 7 .Ί. - F · ■ - 2k - substance and at least about 0.04 % of the discoloration preventing agent, with the remainder being water. 11. Composition according to claim 10, characterized in that it contains about 0.5 to about 1.5 % of the discoloration preventing agent. 12. Composition according to one of claims 1 to 7 in the form of a chewing gum preparation, characterized in that it contains about 15 to about 30% of a gum base, about 15 to about 20 % corn syrup, about 50 to about 65 % sugar, about 0.05 to contains about 1.5 % flavoring and at least about 0.25 % discoloration preventing agent. 13. Agent according to claim 12, characterized in that it contains about 1 to about 5 % of the discoloration preventing agent. l4 ^:. Agent according to one of Claims 1 to 7 in the form of lozenges, characterized in that it contains a hard sugar base, about 0.01 to about 2.0 % flavoring substances and at least about 0.25 % of the discoloration-preventing agent. 15. Agent according to claim 14, characterized in that it contains about 1 to about 5 % of the discoloration preventing agent. l6. Method for preventing or delaying discoloration of the teeth, characterized in that the Brings teeth into contact with an effective amount of an anti-staining agent in the form of an oral 6098 4 3/1037 - 25 care agent according to one of claims 1 to 15 is present. For: The Procter & Gamble Company Cincinnati, Ohio, V.St.A. Lawyer ORIGINAL INSPECTED 609843/1037