DE2437698A1 - ORAL CARE PRODUCTS - Google Patents

Description

IICHTSANWALTE

DR. JUR. DIFL-CHEM. WALTER BEI - 2. Aug. Wf ti

ALFRED HO-PPENER. '-

DP. JüR. Ci ¹¹ L-CHtM. H.-J. WOLfP

DR. JUR. HOUSE CHR. AX

6 * 3 FRANKHJRTAM MAIN- HÖCHST

Our no. 19 414

The Procter & Gamble Company Cincinneti, Ohio, V.St'.A.

Oral care products

The present invention relates to oral care products, among which Products are understood that, with normal use, remain in the oral cavity for a long time and in such a way that they are practical come into contact with all tooth surfaces but are not intentionally ingested. These products include e.g. toothpastes, mouthwashes, pastes for prophylaxis and topical solutions. ■

The peroxyacids according to the invention are known and have been described, for example, in US Pat. No. 5,075,921, in "Organic Peroxides", Ed. (1970) John Wiley & Sons, Inc., and in BE-PS 779599 described. - ".

It has been found that certain specific organic peroxy acids of the type described below in oral care products

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Can be used for the treatment of the oral cavity and in particular teeth to reduce staining or discoloration, e.g. on the teeth. These blanks can be natural appearing stains act as they are caused e.g. by coffee, tea, breath and food, or around Stains * caused by antibacterial agents, in particular those of the type described in BE-PS 801703.

It is surprising that these special organic peroxy acids Against stains and discoloration are so effective, while most other organic peracids, other organic percompounds as well as inorganic per-compounds remain relatively ineffective, if not elevated temperatures and / or longer Exposure times are used.

The invention relates to oral care products that reduce the extent of Effectively reduce stains on stained or discolored teeth. These agents contain an effective amount of a bleaching agent Compound consisting of (1) alkyl diperoxy acids with alkylene groups with 5-11 carbon atoms including substituted alkyl diperoxy acids, e.g. those with up to 2 substituents from chlorine, fluorine, nitro, trifluoromethyl, trimethylammonium, Carboxy or acetyl groups per methylene group, or (2) Aryl peroxy acids of the formula

VV-

C-O-OH

wherein at least one X is a substituent with a Hammett digma constant equal to or greater than +0.2 and η a number from 1-? represent. Groups with Hammett sigma constants greater than +0.2 are strongly electron withdrawing and increase the reactivity of the peroxy acid group. tile substituents in either meta- or para-position. The Hammett Sigma

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PAD ORIGINAL

Constants are from Jaffe, Chemical Reviews, 53, 191 (1953). has been described.

Examples of substituents X are chlorine, m-fluorine, the nitro, Trifluoromethyl, trimethylammonium, cyano, carboxy, percarboxy and acetyl group. X can also be iodine, bromine, an amino or amide group, but such are reactive groups expediently not present, since they "coincide with the peroxy group or groups can react, thereby reducing the stability and effectiveness of the compound.

In general, the aromatic peroxy acids are preferred, because they are more effective. Furthermore, in accordance with the Teaching of US-PS 3075921 those substituted peroxybenzoic acids preferred whose melting point is not lower than 50 ° C, since these acids are more permanent. In general, preference is given to those substituted peroxybenzoic acids which have substituents have higher positive Hammett sigma constant. Several groups can also be present «- It is advisable to avoid substituents, which react with the peroxygen. Lying quaternaries If groups are present as substituents, the anion is preferably compatible with the peroxygen and makes the connection water soluble or dispersible in water. Suitable anions are, for example, the fluoride, nitrate, sulfate and methyl sulfate fatanion. In the case of the alkyl diperoxy acids, preference is given to the unsubstituted ones Alkyl diperoxy acids.

The mode of action of the organic peroxyacids is not known. Similar organic peroxygen compounds are not useful for preventing and / or removing ..stains such as the special peroxy acids provided according to the invention. Bs it was found that the peroxyacids provided according to the invention inhibit the calcification of the stains, so that their Removal is facilitated by mechanical means. The inventiveii intended organic peroxyacids are antibacterial agents. Antibacterial agents inhibit the growth of tartar and contribute to the containment of tooth decay, gingivitis and the

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BATH ORIGINAL

compensate by controlling the bacterial population in the mouth.

Preferably, of course, the substituents should be such Be that the resulting organic peroxyacid is non-toxic in use. Artificial teeth can, however taken out of the mouth} treated and then cleaned, so that contact with toxic material is avoided.

The method according to the invention relates to the treatment of stained teeth with an aqueous oral care product which contains an effective amount of an organic peroxy acid in the form of an alkyl diperoxy acid with alkylene groups with 5-11 carbon atoms or a substituted alkyl diperoxy acid, for example with up to two »<- , Nitro, trifluoromethyl, trimethylammonium, carboxy or acetyl substituents per methylene group, or an aryl peroxy acid of the formula

- C - 0 - OH

wherein at least one substituent X is a Hammett sigma constant equal to or greater than +0.2 and η represent a number from 1-3.

The inventive compositions preferably contain from about 2 to about 50, particularly about 5 to about 35% of the organic peroxyacid in tfall of concentrates, and about 0.01 to about 5, and preferably about 0.05 to about 0.5 ^c / <> the organic peroxyacid when used to treat stained teeth.

The concentrates can be aqueous or anhydrous. BoIQ en never be stored for a long time and they contain a reactive Material, non-corroding products are often preferred. The means according to the invention know the usual components

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components of toothpastes, tooth powders, mouthwashes, prophylactic pastes and the like, which are described in more detail below will; Usually, however, the other components are limited to substances that do not have reactive "bodies" such as amino, amide, hydroxyl groups, iodine, bromine or sulfhydryl groups or contain double bonds, imino groups or thioether bonds, if the product is to be stored for a longer period of time. Agents with such reactive components can, however are manufactured when they are intended for direct use, for example when the consumer has them through simultaneous extrusion of two separate mixtures prepared. A mouthwash concentrate represents a preferred embodiment of the invention, since it, in contrast to toothpastes, there are fewer components that can react with the peroxyacid. Toothpastes usually contain abrasives, Foaming agents, binders, humectants, flavorings and sweeteners. Most of these substances cannot work together with oxidizing agents are stored. Toothpastes according to the invention are therefore usually made up of two separate components Containers or chambers exist which are combined with one another just before use.

Abrasives usually only turn into dilute media directly added before use, as numerous abrasives make the peroxy acids unstable. To the abrasives include e.g. Dicaleiumorthophoaphat, Calciumcarbonat, Calciumpyrophoaphat in betar-Phase ^ that e.g. according to the US-PS 3 112 247 can be made -particulate thermosetting polymerized resins such as those described in U.S. Patent 3,070,510 Type (e.g. melamine, phenol, urea, melamine-urea, Melamine-formaldehyde, urea-formaldehyde, melamine-urea-formaldehyde resins, crosslinked epoxies and crosslinked polyesters), alumina, silicic acid xerogels of those described in BE-PS 796 532 Art and other phosphate and silicate abrasives like; z.H. insoluble sodium metaphoaphate. Also mixtures of abrasives can be used. The total amount of abrasive in a toothpaste according to the invention can be 0.5 to 95 percent by weight turn off. Preferably toothpastes contain about 20 "

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up to about 60% by weight abrasives. The particle size of the The abrasive is preferably between about 1 and about 30 microns.

Suitable foaming agents are those which are sufficiently stable and which form foam within a broad pH range, preferably soap-free anionic organic synthetic detergents which are relatively non-reactive with the peroxyacids provided according to the invention. Examples of suitable foaming agents are water-soluble salts of alkyl sulfates with 10 to 18 carbon atoms in the alkyl radical, for example sodium lauryl sulfate. Another, somewhat more reactive detergents are water-soluble salts of sulfonated monoglycerides of fatty acids wi-t 10 to 18 carbon atoms, for example Natriummonoglyceridsulfa ^ e, salts of GQ Og fatty acid amides of i'fiurins such as sodium N-methyl-N-palmitoyl tauride; Salts of Ό ^ -Cj ₈ fatty acid esters of inethionic acid, and essentially saturated aliphatic acylamides of saturated monoamine carboxylic acids. with 2 to 6 carbon atoms, the acyl radical of which has 12 to 16 carbon atoms, such as sodium N-lauroyl sarcoside. Creirische made from 2 or more foaming agents can also be used. Other suitable foaming agents are nonionic, cationic, zwitterionic and amphoteric, non-soap organic synthetic detergents.

Nonionic synthetic detergents for use in the invention Oral care products should not be stored in concentrated products with the intended for prolonged storage Peroxy acids are present if they have reactive hydroxyl groups contain. Non-ionic synthetic detergents can be referred to as compounds produced by condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound that is aliphatic or alkylaromatic can be formed. The length of the hydrophilic or polyoxyalkylene itest that condenses with the hydrophobic group can easily be set so that one can get a water-soluble compound with any desired balance

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BATH ORIGINAL

between hydrophilic and hydrophobic elements.

For example, a known class of nonionic synthetic detergents is marketed under the trade name "Pluronic". These compounds are produced by the condensation of ethylene oxide with a hydrophobic base, the latter being formed by the condensation of propylene oxide with propylene glycol. The hydrophobic part of the molecule, which is of course insoluble in water, has a molecular weight of about 1500 to about 1800. The addition of polyoxyethylene residues to this hydrophobic part increases the overall water solubility of the molecule and the liquid character of the product is retained up to Achievement of a polyoxyethylene content of about 50 ⁰ Jo of the total weight of the condensation products.

Other suitable non-ionic synthetic detergents include:

1o The polyethylene oxide condensates of alkylphenols, e.g. the Condensation products from alkylphenols with straight or branched alkyl groups with about 6 to 12 carbon atoms Chain and ethylene oxide, wherein the ethylene oxide is present in amounts of 10 to 60 mol per MoüUlkylphenol. the Alkyl substituents in such compounds can, for example, consist of polymerized propylene, diisobutylene ", or esm exist.

2. Detergents made by condensation of ethylene oxide with arise from the reaction product of propylene oxide and ethylenediamine and the composition in terms of the Compensation between hydrophobic and hydrophilic elements can be varied. For example connections with about 40 to 80 weight ^ polyoxyethylene units and oneir. Molecular weight from about 5,000 to about 11,000, which can be obtained by reacting ethylene oxide groups with a hydrophobic base, which in turn is the reaction product of ethylenediamine and excess propylene oxide, "with the base having a molecular weight of the order of 2500

5 0 9809 / 10A 8 _ ■

. *.,; _..-., -. BAD QRIGfNAL

up to 3000 * suitable.

3. Condensation products of aliphatic alcohols with 8 to 18 Carbon atoms in a straight or branched chain and ethylene oxide, e.g. a coconut alcohol-ethylene oxide condensate with 10 to 30 moles of ethylene oxide per mole of coconut alcohol, with the coconut alcohol fraction has 10 to 14 carbon atoms having.

The following nonionic synthetic detergents are in the form of amine oxides and phosphine oxides, if any have no hydroxyl groups, compatible with the peroxy acids:

4. Long-chain tertiary amine oxides of the general formula

H ₁ RpR ^ N »0 where R- is an alkyl, alkenyl or monohydric

hydroxyalkyl radical with about 8 to about 18 carbon atoms and 0 to about 10 ethylene oxide units and 0 to 1 glyceryl units and Rp and R, 1 to about 3 carbon atoms and 0 to about 1 hydroxyl group and, for example, from methyl, ethyl, propyl, hydroxyethyl - or hydroxypropyl residues. The arrow in the above formula indicates a semi-polar bond. Examples of amine oxides suitable according to the invention are: dimethyldodeoylamine oxide, oleyl di (2-hydroxyethyl) amine oxide, dimethyl octylamine oxide, dimethyl decylamine oxide, dimethyltetradecylamine oxide, 3 _f 6,9-trioxaheptadecyl-diethylamine oxide, di (2-hydrideyl) -oxydylamine 2-D # deeaxyethyldimethylamine oxide, 3-dodecexy-2-hydroxypropyl-di (3-hydroxypropyl) amine oxide, dimethyl-hexadecylamine oxide.

5. L _a ngkettige tertiary Phosphinexyde of the general formula RR ¹ R ¹¹ P> 0 wherein R contains an alkyl, alkenyl, "the mono hydroxyalkyl re st having 8 to 18 carbon atoms in chain length and 0 to about 10 ethylene oxide units and 0 to 1 Represents glyceryl unit and R ¹ and R ″ denote alkyl or monohydroxyalkyl groups with 1 to 3 carbon atoms. The arrow in turn denotes a semipolar bond.

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Games of suitable phosphine oxides: Are:

Dodecyl dimethylphosphine oxide,

Tetradecyl dimethylphosphine oxide,

i'etradecyl-methyl-ethylphosphine oxide, 3,6, g-l'rioxaoctadecyl-dimethylphosphine oxide, Cetyl dimethylphosphine oxide,

3-dodecoxy-2-hydroxypropyl ~ di (2-hydroxyethyl) phosphine oxide, Stearyl dimethylphosphine oxide,

Oetyl-ethyl-propylphosphine oxide,

Oleyl diethylphosphine oxide,

Dodecyl diethylphosphine oxide, ■

Tetradecyl diethylphosphine oxide,

Dodecyl dipropylphosphine oxide,

Dodecyl di (hydroxymethyl) phosphine oxide, Uodecyl-di (2-hydroxyethyl) phosphine oxide, l'etradecyl-methyl-2-hydroxypropylphoaphine oxide, üleyl-dimethylphosphine oxide,

2-hydroxydodecyl dimethylphosphine oxide.

6. Long-chain dialkyl sulfoxides with a short-chain alkyl or hydroxyalkyl radical having 1 to about 3 carbon atoms (usually methyl) and a long hydrophobic chain comprising an alkyl, alkenyl, hydroxyalkyl or ketoalkylreat with about 8 to about 20 carbon atoms, 0 to · about 10 ethylene oxide residues and 0 to 1 grlyceryl residue. Examples of such connections are:

Octadecyl diethyl sulfoxide, 2-ketotridecyl mettiyl sulfoxide, 3,6,9-trioxaoctadecyl-2-hydroxyethyl sulfoxide, Dodecyl methyl sulfoxide,

Oleyl 3-hydroxypropyl sulfoxide,

Tetradecyl methyl sulfoxide,

3-methoxytridecyl-methyl-sulfoxide,

3-Hydroxytridecyl-methyl-sulfoxide,

3-Hydroxy-4-dodecoxybutyl-methyl-sulfoxide.

The zwitterionic synthetic ones suitable according to the invention Detergents can generally be more aliphatic as derivatives

509809/1048

quaternary ammonium, phosphonium and sulphonium verb ⁵ η describe in which the aliphatic radicals can be straight-chain or branched and in which one of the aliphatic substituents has about 8 to 18 carbon atoms and 'one of the substituents is an aiionic water-solubilizing group, z. B. has a carboxyl, sulfonot, sulfate, phosphorus or phosphonate group. If these detergents do not contain hydroxyl groups, they are usually compatible with the peroxyacids. A general formula of these compounds is:

H ² _ γ ( ⁺ ) ~ CH ₂ - R ⁴ - Z ^

ο
wherein R is an alkyl, alkenyl or hydroxyalkyl radical with about 8 to 18 carbon atoms, ü to about 10 ethylene oxide units and 0 to 1 glyceryl unit, Y is nitrogen, phosphorus or sulfur, R is an alkyl or monohydroxyalkyl radical with 1 to about 3 carbon atoms, χ the The number 1 when Y is a sulfur atom and the number 2 when Y is a nitrogen or phosphorus atom is R eirmalkylene or hydroxyalkylene radical having 1 to about 4 carbon atoms and Z is a carboxylate, sulfonate, sulfate, phosphonate or phosphate radical. Examples of such connections are:

4- [N, N-M (2 / hydroxyethyl) -N-octadecylammonium] butane-1-carboxylate; 5- £ S-3-hydroxypropyl-S-hexadecylsulfonioJ-3-hydroxypentan-i-

Sulfate;
3- [p, P-diethyl-P-3,6,9-trioxatetradecoxylphosphonio] -2-hydroxy-

propane-1-pho sphat;
3- [N, N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonioJ propane-1-phosphonate;

3 - <(N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate; 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-1-

sulfonate;
4- [N, N-di (2-hydroxyethyl) -N- (2-hydroxydodecyl) ammonium butane-1-carboxylate;

$ 09809/1048

^ - [_S-ethyl-3 - (? - dodecoxy-2-hydroxypropyl) sulfoniej-propane-1-phosphate;

3- [~ P, P-dimethyl-P-dodecylphosphoniej-propane-i-phosphonate; and

5-fN,? T-bi (3-hydroxypropyl) -N-hexadecylammoniol -2-hydroxy- pentane-1-suliate.

Those which can be used in the oral care products according to the invention cationic synthetic detergents can be used as jjuaternary Ammonium compounds with a long alkyl chain with about S can be denoted up to about 18 carbon atoms; It deals are compounds such as lauryl trimethylammonium chloride; Cetyl pyridinium chloride; Oetyl-trimethylammonium bromide; Diisobutylphenoxyethoxyethyl-dimethylbenzylammonium chloride; Coconut trimethylammonium nitrite; Oetyl pyridinium fluoride and the same. The quaternary ammonium fluorides according to US Pat. No. 3,535,421, the detergent action, are particularly preferred own. Of hydroxyl groups and reactive nitrogenous ones Cationic detergents free of groups and bonds are usually compatible with the peroxyacids.

Synthetic amphoteric which can be used in the compositions according to the invention Detergents can be referred to as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be straight-chain or branched and in which one of the aliphatic substituents is about 8 to about Has 13 carbon atoms, and one of the substituents an anionic water-solubilizing group, e.g. one Carboxyl, sulfonate, sulfate, phosphate or phosphonate group owns. Examples of compounds of this type are sodium 3-dodecylaminopropionate, Sodium dodecylaminopropanaulphonate, dodecyl-ß-alanine, N-alkyl-taurine., For example those according to Dodecylamine reaction products available in U.S. Patent 2,653,072 and sodium isethionate, N-higher-alkyl-aapartic acids, e.g. according to US Pat. No. 2,438,091, and also those available on the market under the trade name "Miranol" and products described in U.S. Patent 2,528,378.

509809 / 10A8 BAD ORIGINAL

Dtr foaming agent can be used in toothpastes according to the invention in Amounts τοη 0.5 to 1o and preferably from 1 to 5 weight ^, based on the total mixture.

In the mixtures according to the invention, a water-soluble Fluoride compound are incorporated in an amount that has a fluoride concentration of about 0.0025 to about 5, and preferably from about 0.005 to about 2.0 ^ results, with an additional anti-caries effect is achieved. Suitable sources of fluoride ions are given in the examples. Preferred fluorides are sodium, indium and tin (H) -fluoride, such as sodium monofluorophosphate. Suitable Fluorides are also mentioned in U.S. Patent 3,535,421.

In the present description, all parts, percentages and proportions relate to the weight, if any nothing else is said.

To make toothpastes, you need a thickener add so that the desired consistency is achieved. However, all thickeners react with the exception of the polymeric polyether compounds, e.g. polyethylene or polypropylene oxide (Molecular weight ^ uO up to 1,000,000), which with alkyl or acyl groups of 1 to about 18 carbon atoms are capped are, with the peroxy acids used according to the invention. If the peroxy acids are formulated separately, they are used as Thickeners, preferably hydroxyethyl cellulose and water-soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl-hydroxyethyl cellulose <, also natural gums such as karaya gum, gum arabic and tragacanth can be used. To further improve the structure, colloidal magnesium aluminum silicate or finely divided Apply silica as part of the thickener. The thickeners are used in amounts of 0.5 to 5.0% by weight used throughout the mixture.

A humectant is expediently incorporated into a toothpaste, to prevent becoming_hard. Suitable moisture

5098ÖS / 1 (HS

Glycerine, oorbitol and other edible polyhydric alcohols are used. The humectant can constitute up to about 36 percent by weight of the toothpaste. On the other hand, the agent can also contain up to about 36 % of a paraffin oil.

Suitable flavors are wintergreen oil, peppermint oil, Spearmint oil, sassafras oil, and clove oil. Suitable sweeteners are saccharin, dextrose, levulose and sodium cyclamate.

According to a preferred embodiment, the organic Peroxyacid formulated in a mixture, which consists essentially of an inert organic, because of its high reactivity or inorganic diluent, which due to its limited reactivity with the oxidizing material was chosen. The main function of the inert material is to act as a carrier for the peroxyacid and others Additions in the appropriate concentrations within a single mixture to which water is added can form an agent for treating the oral cavity, or as part of a two-component agent, wherein one component can be aqueous and the other can be anhydrous. The two components can be mixed together to form the z Treatment suitable agent.

The organic diluent can be a liquid or a be soft wax, it is preferably a liquid. In the present description, the term "saturated" is used Compounds with both aryl radicals. understood as saturated alkyl radicals. "Polytxyalkylenes" are ethoxylated and propoxylated Understand products.

The organic diluent is expediently a non-ionic synthetic detergent which is ethoxylated and nonionic and capped by an alkyl or acyl group to eliminate the reactive hydroxyl groups. Another class of these detergents has semipolar properties. Preferred classes of non-ionic synthetic detergents are as follows:

509-809 / 1048

1. The nonionic synthetic detergents known under the trade name "Pluronic" are produced by condensation obtained from ethylene oxide with a hydrophobic base, in turn by condensation of Propylen'xid with Pro.

'pylene glycol is formed, whereupon by alkylation (C ₁ -Cq) or acylation (Cp-O.ojL the molecule is "capped" with the formation of ether or ester groups. The hydrophobic part of the molecule, which is of course insoluble in water has a molecular weight of about 1500 to 1800. The addition of the polyethylene radicals to this hydrophobic component increases the water solubility of the molecule as a whole, and the liquid character of the product is maintained until the polyoxyethylene content is about 50> the total weight of the condensation product.

2. The polyethylene oxide condensates of alkylphenols, that is to say the condensation products of alkylphenols with alkyl groups with about 6 to 12 carbon atoms in straight or branched configuration and ethylene oxide, in which the ethylene oxide is present in amounts of 5 to 2% per mole of alkylphenol

the

is present. The condensates are "capped" as in Group 1 above. The alkyl substituents in These compounds can e.g. from polti.merisierteii. Propylene, Diisobutylene, octene or nonene exist.

3. Non-ionic synthetic detergents obtained by the condensation of ethylene oxide with the reaction product of propylene oxide and ethylene diamine. The condensates are "capped" like the group 1 compounds. For example, compounds have proven to be satisfactory which have about W to about 80 percent by weight of polyoxyethylene and a molecular weight of about 5000 to about 11000 and are obtained by reacting ethylene oxide groups with a hydrophobic base, which consists of the reaction product of ethylene diamine and excess propylene oxide, the Base has a molecular weight of the order of 2500 to 3000.

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BATH ORIGINAL

A. Condensation products from aliphatic alcohols with 8 to 22 carbon atoms in the straight © of the branched chain and Ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate with ^ to 40 moles of ethylene oxide per mole of coconut alcohol, w - coconut alcohol has 10 to 14 carbon atoms.

Further preferred organic diluents are, for example, coconut fatty acid, lauric acid, cetyl acid, acylate esters from fatty acid pTupppr with ? up to about 18 carbon atoms and 1 to 3 carboys, groups and alcohol residues with 2 to about 18 carbon atoms and. 1 bi "about 6 Hydroxy 1 fjruppoη, mineral oils with a viscosity at 2 ^, Q ⁰ C of about 50 to about 700 Saybolt seconds Purol (SSF) and saturated triglycerides of C 1-4 fatty acids.

Particularly preferred organic diluents are the diesters of propylene glycol and triester of glycerin.

Inorganic diluents include alkaline earth and alhalimetal sulfates. These diluents are recommended especially with diisoperoxyphthalic acid, which can be dangerous without such a diluent.

Suitable gene flavorings for use in concentrates are "unsaturated" esters such as ethyl butyrate, kethyl acetate and benzyl acetate, saturated ketones such as IV.ethylamyl ketone, menthone and Eucal.vptol.

Example 1

Aqueous fillings with about O ₁ ? Percentage by weight of the following organic peroxyacids are prepared and used for the treatment of naturally stained teeth, with the results also given results:-6hloroperoxybenzoic acid: aur ^ pez.ii chnete. Stain removal; Diperisophthalic acid: very good flccion removal; Diperoxyadipic acid: good stain removal; Mperazelaic acid: good 1 ^ 3 corner removal; Dipersebacic acid: sufficient removal of plectones; p-Nitroperoxybenzoic acid: excellent pleclrene removal; and m-trifluoro

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■ ethylperexybenzoic acid: very good stain removal.

Example 2

The following perexy acid concentrates are used alone and together with the toothpastes and mouthwashes of BE-PS 801 703, furthermore together with an oral care product, which contains a bis-biguanide effective against tartar, caries and gingiritis, eg chlorhexidine, whereby one dilutes aqueous treatment mixtures by dilution with water to a concentration of 0.2 to 0.6 ° / o obtained. These mixtures are then applied to stained teeth to remove the stains and prevent them from forming.

p -chloroperoxybenzoic acid Triacetin

6 rest

m-chloroperbenzoic acid Mineral oil (SSF-60)

8 rest

Diperisophthalic acid
Methyl acetate and methylene (1: 1) sodium alkyl (C ₁₀ -C ₁₂ ) sulfate

Diethyl ether of polyethylene glycol (Mol.gew. 1000)

2 4

rest

Diperoxyadipic acid

5 09 809 / 10A8 BAD ORIGINAL

Potassium rfolyethoxyl. (4) coconut fatty alcohol sulfate

JV; et hy Il au rat

rest

Diperazelaic acid Dimethyldodecylphoaphine oxide

Diacetyl polyethylene oxide (mol.wt. 800)

8 1

Heat

Mperseba an acid Natriuniicokoanuii ^ alkyl sulfate Coconut alkyl dimethylamine oxide Magnesium sulfate sodium sulfate

■ 12

23 rest

p-nitroperoxyhenzoic acid m-trifluoromethylperoxybenzoic acid

Coconut alkylbenzyl dimethylammonium chloride

Ethyl butyrate, benzyl acetate, methyl amyl ketone and eucalyptol (1: 2: 1: 3) Triacetin

Diethyl ether of polyethylene oxide (mol. Wt. 1200) methyl butyl ether 4 2

4 45

40 rest

509809 / 1CU8

m-T rifluo rme thyl-p-ni t rope roxybenzoic acid

Cetyl pyridinium sulfate Saccharin

Anethole

Methyl salicylate methyl laurate Triacetin

j,

1.5

0.9

0.6

0.6

10

rest

ill

ρ- (trimethylammonium sulfate) peroxybenzoic acid

Calcium sulfate

4th
rest

ill

in-Chl * rpe ro xy benzoic acid Barium sulfate

5
rest

example J>

Dentures were kept over night in an aqueous solution containing 0.2 $> 1,6-di (Np-chloro-phenyldiguanido) -hexane-digluconate "(chlorhexidine) and worn for days until a brown discoloration had formed. these bits were then be'handelt for three minutes at room temperature with aqueous solutions welohe 0.2 ° / o Diperisophtalsäure and 0.2 "/> Diperadipinsäure contained and had been buffered with phosphate buffer at pH about 7.5. The brown coloration had practically completely disappeared after this treatment.

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J ¹ IEC. "-. S were generated, one porous Porielfcnplatten INDEC successively in a solution containing chlorhexidine and in a Kqffeelös'.nf immersed until a brown color develops h-d · The slopes were then-lived with 0.2? dipped in aqueous solutions of the following peroxy acids with the results given: TT-chloroperoxybenzoic acid: excellent; diperisophthalic acid: α usre excels; jiperadipimic acid: very good.

uin the above concentrates. can also be used in a ratio of about 3 * 1 to about 3: 1 with conventional Llundwänsern and toothpastes, whereby an intermediate concentration is obtained, which can be diluted with Hainer in a ratio of 1: 1 to 1: 3 under HiId- .n _e : e-'iea wä.inrigeh mouth treatment agent, which removes and / or prevents stains when applied to tooth surfaces. "■" .-.

5 0 9 8 0 9/1048

BAD ORlGiNAl.

Claims (9)

Claims m \ Oral care products, characterized by the content of a effective amount of a bleaching agent (A) alkyldiperoxy acid with an alkylene radical with 5 to 11 carbon atoms, (B) a substituted alkyldiperoxy acid with up to 2 chlorine, fluorine, nitro, trifluoromethyl, trimethylammonium, carboxy or acetyl substituents per methylene group, and / or (C) an aryl peroxy acid of the formula: where X is a substituent with a Hammet sigma constant equal to or greater than +0.2 and η is a number from 1 to represent. 2. Means according to claim 1 in the form of a concentrate, characterized from about 2 to about 50% of the organic peroxy acid. 3 · concentrate according to claim 2, characterized in that it essentially ordered from the peroxyacid and an inert diluent. 4 · concentrate according to claim 3 »characterized in that the inert diluent consists of calcium, sodium, potassium, magnesium or barium sulfate. 5. Composition according to claim 1, characterized in that it contains an unsubstituted alkyldiperoxy acid as the peroxy acid. 509809/1048 6. Composition according to claim 1, characterized in that it contains an aryl peroxy acid as the peroxy acid. 7. Composition according to claim 1 in the form of a dilute aqueous mixture containing about 0.01 to about 5 I »of the peroxy acid. 8. A method for treating stained teeth, characterized in that that the teeth are treated with an agent according to claim. 9. The method according to claim 8, characterized in that one by salts of 1,6-di (N-p-chlorophenyldiguanido) hexane stained teeth treated. For (The Procter & Gamble Company
Gincinneti, Ohio, V.St.A.) (Lawyer) 509809/10 48