AT390369B - Dental care composition - Google Patents

Abstract

The invention relates to dental care compositions with increased stability to discoloration on ageing, which contain a cinnamaldehyde flavouring and propylene glycol, dipropylene glycol and mixtures thereof in a vehicle which is suitable for dental care compositions and is free of oxidizing agents such as peracids and salts thereof, and is kept at a pH below 8.5 and preferably acidic to weakly alkaline (pH = 5 to 7.5).

Description

No. 390 369

The invention relates to a white or colorless dentifrice composition, which is in the form of a toothpaste or mouthwash, with increased stability against discoloration during aging, which contains an aging discolouring cinnamon aldehyde flavor in an amount of 0.1 to 1% by weight Dentifrice suitable carrier, which is free of oxidizing agents and has a pH below 8.5, and which according to the invention contains propylene glycol, dipropylene glycol or a mixture thereof in an amount of 10 to 45% by weight of the composition.

A large number of dentifrice compositions are known in the art which contain the combination of a cinnamaldehyde or citral flavor and propylene glycol or dipropylene glycol, as shown in U.S. Patents 3,867,557 and 3,928,560, according to which oral compositions are 0 Contain, 0001 to 20% paramethoxycinnamaldehyde flavoring agent to be dissolved in 100 parts of propylene glycol; U.S. Patent Nos. 4,132,771 and 4,187,287, which describe a two-tone flavored toothpaste containing cinnamon flavor in a propylene glycol vehicle; U.S. Patent 4,242,323 which describes a plaque inhibiting oral composition for which propylene glycol is also used as the liquid carrier; and U.S. Patent 3,864,472 which relates to a clear lemon flavored mouthwash containing lemon oil, cinnamon aldehyde and glycerin or propylene glycol. U.S. Patent No. 4,001,438 also discloses flavor formulations containing citral and / or cinnamaldehyde as a component of a physically captured flavor composition comprising an unlocked flavor oil, a suspending agent, and preferably a small amount (0.5%) of propylene glycol, which Product stability increased (column 6, lines 32 to 33), is mixed, which are suitable for oral compositions. However, in this group of patents, there is no evidence of the discoloration or yellowing problems due to aging associated with the use of cinnamaldehyde flavors. These patents concern other aspects of dentifrice formulations. The combination of cinnamaldehyde flavor and propylene glycol is mentioned casually in a general discussion of flavors and typical humectants.

Also known in the art is the shrinkage and / or degradation of flavor or color, as shown in U.S. Patent 3,666,496, which relates to a poly (oxyethylene) -poly (oxypropylene) copolymer containing terpene-containing flavors How orange oil is added to prevent degradation of the flavor to be used in flavored foods or beverages. US Pat. No. 4,305,928 relates to the addition of 0.05 to 5% phytic acid and / or benzoic acid as a chelating agent to prevent or reduce the fading of red or yellow with monazite, or blue, optically clear toothpaste colored with triarylmethylene dye. U.S. Patent 3,957,964 relates to a dentifrice that contains encapsulated flavors that contain cinnamon oil or orange oil and that remain separated from the dentifrice base (which may contain propylene glycol) during use until the dentifrice is released for use, thereby making the flavored dentifrice more stable and fresher in taste However, there is no indication in the patents mentioned of the stabilization of cinnamaldehyde or citral taste by propylene glycol or dipropylene glycol.

US Pat. No. 2,184,526 also describes the instability against air oxidation of p-isopropyl-alpha-methylhydrocinnamaldehyde as a perfume component, the aldehyde being converted into the corresponding acid, which destroys the aldehyde odor. The addition of alcohols of the aromatic or of the terpene series stabilizes the aldehyde against atmospheric oxidation by converting the aldehyde into a hemiacetal of the alcohol.

None of the above references disclose the use of propylene glycol or dipropylene glycol in a dentifrice-free, oxidant-free, acidic or neutral pH, containing cinnamaldehyde flavor to prevent the color of the flavor from aging.

It has surprisingly been found that the discoloration in the age of tooth cleaning agents which are flavored with cinnamaldehyde can be reduced and / or prevented by the addition of propylene glycol or dipropylene glycol or mixtures thereof.

Accordingly, the primary object of the invention is to provide dentifrice formulations containing cinnamaldehyde flavor which do not become yellow or discolored upon aging.

The object of the invention is to provide a white or colorless dentifrice composition, which is present as a toothpaste or mouthwash, with increased stability against discoloration during aging, which contains a cinnamaldehyde flavoring discoloring in an amount of 0.1 to 1 wt. -% in a carrier suitable for dentifrices, which is free from oxidizing agents and has a pH below 8.5, and which is characterized in that it contains 10 to 45 propylene glycol, dipropylene glycol or a mixture thereof as a discoloration inhibitor % By weight of the composition contains.

It has been found that the cinnamaldehyde flavors decompose with the formation of conjugated unsaturated aldehydes (dienals). These dienals are responsible for the yellowing or discoloration that occurs with cinnamaldehyde in white dentifrices, both in liquids and in creams (pastes).

For commercial toothpastes that use small amounts of cinnamaldehyde, the -2-

No. 390 369

Discoloration problem due to coloring the goods, e.g. B. red, blue, light green, etc. bypassed. With white toothpastes, however, the discoloration due to a small amount of cinnamaldehyde is unacceptable.

The autoxidation of cinnamaldehyde (CA) works according to the following mechanism:

Autoxidation of cinnamaldehyde

0 "

ch " -sch - co2h

CH2CH0

CA-h2o and other Dienale ._ ^

rJy - CH * CH - CH * C - CH

The acid builds up even when samples are kept in tightly closed bottles, the head space of which has been flushed with nitrogen. Cinnamaldehyde is very sensitive to small amounts of oxygen. Because cinnamic acid is white, its formation, which occurs within a short time after exposure, is not responsible for the yellowing of the cinnamon aldehyde. The intensity of the yellow color increases with the duration of the exposure to oxygen rather than with the amount of oxygen, which indicates that a more complex oxidation takes place with aging. The conjugated dienals in particular are the intensely yellow components which are responsible for the discoloration and yellowing of the cinnamaldehyde.

It has now been found that the discoloration is reduced by small amounts of cinnamaldehyde (maximum about 1% by weight) in the presence of propylene glycol and / or dipropylene glycol. These materials are effective in a 1: 1 weight ratio of cinnamaldehyde to prevent almost any yellowing from aging in glass. However, in toothpastes they showed only a slight reduction in yellowing by 1% cinnamaldehyde at levels of 1 to 5%. However, since these glycols are odorless, it is possible to use them in much higher amounts.

No. 390 369 to be incorporated. The substitution of water or glycerin in tooth cleaning formulations with propylene glycol or dipropylene glycol prevents the yellowing of flavorings containing cinnamaldehyde. If a non-aqueous paste is formulated by replacing the water with one of the two glycols, no discoloration is observed. Yellowing is also significantly reduced by replacing the 22% glycerol in a toothpaste with propylene glycol.

The mechanism of the glycol effect is believed to include acetal and hemiacetal formation / complexation. The glycols are believed to be effective by complexing the aldehydes through acetal formation. Since aldehydes are involved in four different phases of the dienal formation mechanism (Figure I), the reaction with the glycol has a lasting influence on the dienal formation. Analysis of the aged 1: 1 CA / propylene glycol sample showed significant acetal formation along with some hemiacetal. This reversible reaction has the problem that part of the cinnamaldehyde is consumed. In practice, this means that the amount of cinnamaldehyde may need to be increased to compensate for this loss.

The auto-oxidation of cinnamaldehyde is inhibited (interrupted) by the presence of propylene glycol due to the formation of glycol acetals, which form rapidly at room temperature and increase with time. This prevents the formation of the dienals that are responsible for yellowing as they age.

The yellowing of a liquid mixture of cinnamaldehyde with propylene glycol or dipropylene glycol was measured with a Gardner colorimeter, both with freshly made material and after 24 hours of aging in an ampoule at 90 ° C (I) and 48 hours at 50 ° C ( II) and initially passing oxygen over the samples for 5 seconds. The samples were prepared from mixtures of cinnamaldehyde and the glycols, cinnamaldehyde and glycerin and cinnamaldehyde alone, and the following measurement results were obtained:

I.

Color measurement fresh geaHeri cinnamaldehyde (CA) 4 11 50/50 CA + glycerin 3; 4 11 '50/50 CA + propylene glycol 3 7; 7 = 50/50 CA + dipropylene glycol 3 I 10; 8th; 9 cinnamaldehyde 4.5 7 50/50 CA ^ opylene glycol 3.5 4.5

Gylcerin and CA formed two phases. The glycerol phase (bottom) remained watery white while the top phase from CA turned dark.

It should be noted that the propylene glycol mixture was slightly less dark than the dipropylene glycol mixture, but was considerably lighter than the cinnamaldehyde alone.

It is important that the pH of the toothpaste be either acidic or neutral, with a pH of about 5 to 7.5 being preferred, as shown in Table I. At pH = 8.5 or higher, the peracid anion is formed and the epoxidation of the cinnamaldehyde proceeds via Michael addition. This type of addition reaction cannot be inhibited by propylene glycol.

The toothpaste yellowing was measured using a Colorgard reflection meter. The information in the following tables are + Ab values (yellow scale) and mean the increase in yellowing compared to non-flavored and non-aged toothpaste, which was taken as a zero-b reference. Measurements after 3, 6 and 9 weeks at 49 ° C are approximations for 1 year, 2 years and 3 years at room temperature. An Ab value of 2 to 3 is believed to be the acceptable range, since an Ab of 2 is visible as off-white, and an Ab of 4 is seen as a faint yellow tint

Table I

Cinnamon disc discoloration in toothpaste <Ex. Γ)

Influence of pH aging at 49 ° C: Ab values 3 weeks 6 weeks 9 weeks 1% CA pH 5.0 citric acid 4.25 5.5 5.1 1% CA pH 6.9 to 7.1 (example 1) 4.5 7.5 8.0 1% CApH8.5 (NaHC03) 7.5 10.5 11.2 -4-

No. 390 369

It is also important that the dentifrice be free of oxidizing agents such as hydrogen peroxide or salts that give off hydrogen peroxide such as sodium perborate, peracids and peracid salts. The presence of oxidizing agents would interfere with the preferred reaction of the glycol with cinnamaldehyde in the formation of the glycol acetate. As already discussed with reference to the need for an acidic or neutral pH of the carrier suitable for dentifrices, the epoxidation of the cinnamaldehyde takes place via Michael addition in the presence of the peracid anion.

Experiments with various dental bases showed that the discoloration of the cinnamaldehyde in Example 2 was approximately half that in Example 1. The discoloration in a bicarbonate base gave a very intense yellow. These differences were assigned to the different pH values and also to the presence of Ti02:

CiL 1% Example 1 6.9 to 7.1 0 Example 2 6.15 0.5%

Lowering the pH of Example 1 by adding either citric acid or phosphoric acid reduced yellowing (Table I). Increasing the pH to 8.5 by adding NaHCOß significantly increased the yellowing.

These observations are consistent with the autoxidation mechanism performed. The peracid anion is formed at pH = 8.5 and the epoxidation proceeds more quickly through Michael addition. Peracids are much weaker than the corresponding cafbonic acids. The pKa value of percinnamic acid is estimated at 7.5. In a neutral base both free acid and the anion are present. The reaction based on anion addition is prevented by lowering the pH

As found in the comparison of Example 1 and Example 2, the presence of TiO 2 provides both a visible and measurable reduction in yellowing. Based on a number of comparisons with and without Ti02, an Ab reduction of 1.0 for 1% Ti02 and 0.5 for 0.5% Ti02 was observed

An additive which may be desirable and which supports the reduction of cinnamaldehyde yellowing in dental formulations is titanium dioxide (TiO 2) in small amounts of about 0.5 to 1% by weight. Table II shows the effectiveness of propylene glycol in reducing yellowing in toothpastes containing various cinnamaldehyde-containing flavors in the presence and in the absence of TiO 2.

Flavor discoloration in toothpaste (Bsn Tables JI Flavor Zimtaldehvd (CA) 3 weeks 6 weeks 9 weeks 1% CA 4.5 7.5 8.0 1% CA + 35% dipropylene glycol or propylene glycol + 64% dicalcium phosphate dihydrate spice 10 CSIOV 1% SI0 0 , 2 3.0 4.2 4.6 1% S10 (glycerin replaced by propylene glycol) 2.3 2.7 m 1% S10 (glycerin replaced by propylene glycol) + 1% Ti02 0.7 - - 'Spice contains 10 flavorings 55% cinnamaldehyde

Other flavor compositions containing cinnamaldehyde include:

White Spice 1 - contains 20% cinnamaldehyde.

White Spice 2 · contains 25% cinnamaldehyde.

Spice-11 flavor - contains 55% cinnamaldehyde.

Gewfliz-12 flavor - contains 15% cinnamaldehyde.

The cinnamon aldehyde flavor compositions can be supplemented to 100% with flavor components such as menthol, eugenol, peppermint, spearmint, clove, anethole, -5-

No. 390 369

Methyl salicylate, vanillin and the like in various mixtures. Menthol and eugenol do not affect the yellowing of the dental formulations

By mixing cinnamaldehyde with propylene glycol or dipropylene glycol, incorporating TiC> 2 and lowering the pH, high levels of cinnamaldehyde can be acceptable. This can easily be accomplished by replacing the glycerin or water with propylene glycol in the dentifrice formulation.

The flavorings with cinnamon aldehyde, which generally makes up at least about 5% of the total flavor, such as spice 10 or spice 12, change color in white toothpaste. If the toothpaste is colored green, then the yellowing is not visible.

The dental base material used according to the invention can be in the form of a paste, cream or a liquid mouthwash and contain known ingredients which are usually used for tooth cleaning agents.

Toothpastes or creams can be based on aqueous or essentially non-aqueous systems. The former usually contain significant proportions of finely divided solid polishing agent, surfactant, gelling agent, water and a certain amount of non-aqueous carrier, e.g. Gylcerin, sorbitol, and they are opaque, while the latter types are often a clear gel or opaque and a low level of a visually clear, finely divided, solid polishing agent, a greater proportion of a non-aqueous vehicle, which is at least 10% of the formulation from propylene glycol or dipropylene glycol alone or mixed with other non-aqueous carriers, such as sorbitol or glycerol, may contain a surface-active agent and a gelling agent in addition to a small amount of water which is often present.

The surfactant or detergent present in the dentifrice can be cationic or amphoteric in some cases, but is usually anionic or nonionic. Of these compounds, the anionic ones are most preferred. The anionic detergents or surfactants normally also serve as foaming agents. Suitable anionic detergents which may be mentioned are: higher fatty acid monoglyceride monosulfates, such as disodium salts of the monosulfated monoglycerides of hydrogenated coconut oil fatty acid; higher alkyl sulfates such as sodium lauryl sulfate; higher alkyl aryl sulfonates such as linear sodium dodecyl benzene sulfonate; higher olefin sulfonates such as sodium sulfonates of higher olefins in which the olefin group has 12 to 21 carbon atoms; higher alkyl potassium sulfoacetates; higher fatty acid esters of 1,2-dihydroxypropane sulfonates, magnesium salts; the substantially saturated higher aliphatic acylamides of the lower aliphatic aminocarboxylic acid alkali metal salts such as those having 12 to 16 carbon atoms in the fatty acid residues, higher alkyl poly lower alkoxy (10 to 100 alkoxy groups) sodium sulfates; higher fatty acid sodium and potassium soaps from coconut oil, tallow and the like. The detergents are mostly sulfated or sulfonated compounds. Examples of suitable anionic amides that can be used are N-lauroyl sarcosine and disodium, potassium and ethanolamine salts of N-lauroyl, N-myristoyl and N-palmitoyl sarcosine. In the above description, &quot; higher &quot; Chain lengths of 12 to 22 carbon atoms, preferably 12 to 18 carbon atoms and most preferably 12 to 16 carbon atoms. The term &quot; low &quot; means 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms and most preferably 2 carbon atoms.

The nonionic detergents include those containing chains of lower alkylene oxides, e.g. B. ethylene oxide, propylene oxide in which 10 to 100 or more moles of the lower alkylene oxides are present. These materials include the block copolymers of ethylene oxide, propylene oxide and propylene glycol, sold as Pluronics; the alkylphenyl polyethoxyethanols sold as Igepale; mixed copolymers of ethylene oxide and propylene oxide, which are sold as Ucon; and various other well known nonionic materials derived from fatty alcohols or acids and polyethylene oxide. The amphoteric or ampholytic agents include long chain (alkyl) amidoalkylene alkylamine derivatives such as &quot; miranols &quot;, e.g. B. Miranol C2M; and cationic germicidal detergents such as diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, benzyldimethylstearylammonium chloride and tertiary amines having a higher fatty alkyl group and 2 polyoxyethylene groups attached to the nitrogen thereof.

The detergents make up about 0.5 to 5% by weight and preferably up to 3% by weight of the tooth cleaning compositions.

Toothpastes, toothpastes and toothpowder typically contain essentially water-insoluble polishing or abrasive agents that are compatible with the formulation in amounts of about 20 to 75 percent by weight of the total cream or paste formulation and up to 95% of the tooth powder. Suitable polishing agents include anhydrous dicalcium phosphate, dicalcium phosphate dihydrate, tricalcium phosphate, insoluble sodium metaphosphate, crystalline silica, colloidal silica, complex aluminosilicates, aluminum hydroxide (including alumina trihydrate or hydrated alumina), magnesium phosphate, magnesium carbonate, calcium carbonate, calcium pyrophosphate, bentonite, talc, calcium silicate, calcium aluminate, alumina, aluminum silicate and silica xeiogels. Most of the polishing agents mentioned are particularly useful for the production of opaque -6-

No. 390 369

Dentifrices, but some of them, such as the colloidal silicas, particularly the disoxidant xerogels and the complex sodium aluminosilicates, can be used in the manufacture of clear dentifrices because their refractive index is close to that of the rest of the dentifrice ingredients in a suitable carrier. 5 In the case of toothpaste or toothpaste formulations, the liquids and the solids must necessarily be dimensioned such that a creamy mass of the desired consistency is formed, which, for. B. is extrudable from a compressible aluminum tube. In general, the liquids in toothpastes mainly contain water, glycerin, sorbitol, polyethylene glycol or propylene glycol 400, including suitable mixtures thereof. It is usually advantageous to use a mixture of water and a humectant such as glycerin, sorbitol or mixtures thereof. The total liquid content is generally about 20 to 75% by weight of the formulation. It is preferred to also use a gelling agent in toothpastes, such as the natural and synthetic rubber-like materials, e.g. B. Irish moss, gum tragacanth, sodium carboxymethyl cellulose, polyphenyl pyrolidone or starch. Irish moss and sodium carboxymethyl cellulose are particularly compatible and preferred gelling agents. The gum content 15 is normally up to about 10% by weight and preferably about 0.3 to 5% by weight of the formulation. Fillers such as pyrogenic silica and silica airgel can also be used, typically in amounts up to about 10% by weight to supplement the gelling agent. These colloidal silicon dioxide aerogels, which include Syloids 244 and 266 and Aerosil, and the fumed silicas sold as Cäb-O-Sil can be used as gelling and thickening agents. 20 The liquid carrier in a mouthwash (mouthwash) normally comprises ethyl alcohol, glycerin, sorbitol, water and mixtures thereof in an amount of about 90 to 98% by weight total liquid content.

Various other materials can also be incorporated into the carrier suitable for dentifrices. Examples of these are fluorine-containing compounds, such as tin (H) fluoride, potassium tin (II) fluoride (SnFjKP), 25 sodium hexafluorostannate, stannous chlorofluoride, sodium fluorozirconate and sodium monofluorophosphate. These materials that dissociate or release fluorine-containing ions in water can be present in the dental support in an effective but non-toxic amount, usually in the range of about 0.1 to 5 percent by weight. Other additives include preservatives such as sodium benzoate. Chlorophyll compounds, silicones, ammonium materials such as urea and diammonium phosphate, antibacterial agents such as benzethonium chloride and other quaternary antibacterial compounds, sweeteners such as sodium saccharin, blue colorants, additional flavors such as peppermint or spearmint and the like. These additives can be used in amounts which do not adversely affect the properties and features of the tooth cleaning agent according to the invention. Each individual ingredient can be present in minimal amounts up to a maximum of 5% by weight and preferably up to 1% by weight of the formulation. 35 The tooth cleaning agent according to the invention is produced by conventional methods for the production of toothpastes, toothpastes, mouthwashes and tooth powders. In particular, a toothpaste can be made by forming a gel of carboxymethyl cellulose and water or non-aqueous humectant, including propylene glycol or dipropylene glycol, with mixing the powdered materials and, if desired, additional humectant, then with mixing the polishing agent and then the surfactant and the Flavor is added and the mixture obtained is filled into tubes. The flavor composition is preferably mixed with the propylene glycol or dipropylene glycol color stabilizer prior to addition to the mixture

In the inventive application for promoting oral hygiene, the tooth cleaning agent according to the invention is regularly applied to the enamel by brushing the teeth for 30 to 90 seconds 45 at least once a day and / or rinsing the teeth with a mouthwash once a day

The invention is explained in more detail below with the aid of examples, but it should be pointed out that the invention is not limited to these. The compositions are made in the usual manner and all amounts and proportions herein and in the claims are by weight unless otherwise stated. The flavor-forming component is a flavor composition containing cinnamaldehyde, to which propylene glycol or dipropylene glycol is added, as described in the examples following the experiments (Table ΙΠ).

Example 1 55 ingredients toothpaste% 60 glycerin sodium monofluorophosphate sodium carboxymethyl cellulose tetrasodium pyrophosphate 22.0 0.8 1.0 0.2 -7-

No. 390 369

Ingredients B &amp;

Sodium saccharinate 0.2

Sodium benzoate 0.5

Deionized water 24.5

Dicalcium phosphate dihydrate 48.8

Flavor 0.8

Sodium lauryl sulfate 1.2 pH 6.9-7.1

Example 2 toothpaste ingredients SI glycerin 10.0 sodium monofluorophosphate 0.8 sodium carboxymethyl cellulose U sodium benzoate 0.5 sodium saccharinate 0.2 sorbitol (70% solution) 17.0 B ingredients% deionized water 22.2 titanium dioxide 0.4 insol. Sodium metaphosphate 39.3 Hydrated aluminum oxide 1.0 Anhydrous dicalcium phosphate 5.0 Flavor 1.0 Sodium lauryl sulfate 1.5 6.15 pH

Example 3

Non-water ripe cream.

ingredients

Propylene glycol 43.4

Klucel GF (Hercules) 1.5

Sodium saccharinate 0.2

Ti02 0.4

Dicalcium phosphate dihydrate 50, Q

Peroxydiphosphate 3.0

Sodium lauryl sulfate 1.5 pH 6.4 'hydroxypropyl cellulose - a propylene glycol ether of cellulose. -8th-

No. 390 369

Example 4 Aqueous toothpaste

ingredients

Propylene glycol

Sodium monofluoiphosphate

Sodium carboxymethyl cellulose

Tetrasodium pyrophosphate

Sodium saccharinate

Sodium benzoate

Dicalcium phosphate dihydrate

Spice 10

Sodium lauryl sulfate ΤϊΟλ h2o%. 22.0 0.8 1.0 0.2 0.2 0.5 48.8 0.9 1.2 1.0 Q.S.

Example 5 Mouthwash

Ingredients 15 - 30 10 - 15 2 - 3 0 - 0.5 0 - 0.075 0.1 - 0.5 rest

Ethyl alcohol glycerin polysorbate 80 ’

Poloxamer 338 ^ Benzethonium Chloride Flavor Composition Deionized Water 'A mixture of oleate esters of sorbitol and sorbital anhydrides consisting of the monoester condensed with approximately 20 moles of ethylene oxide. ^ Polyethylene polyoxypropylene block polymer according to the formula: H0 (CH2CH20) x (-CH-CH20) y (CH2CH20) zH,

I ch3 in the x and z = 128 and y = 54.

The flavor levels in mouthwash are generally lower than in a toothpaste.

Example 6

Tooth powder

Ingredients %.

Magnesium silicate 7.0

Sodium saccharinate 0.2

Flavor 2.5

Dicalcium phosphate anhydrous 88.3

Sodium lauryl sulfate 2.0

The flavors in tooth powders are generally larger than in toothpastes.

The following table shows discoloration results after aging at 49 ° C. of the toothpastes from Example 1, unless stated otherwise, and in fact not flavored, containing cinnamaldehyde (CA) flavoring alone and -9-

No. 390 369 with propylene glycol or dipropylene glycol to prevent or reduce the discoloration caused by the cinnamaldehyde ingredient. The b-values in the table indicate the yellowing of the toothpaste measured on the color gel reflectance meter, and the Ab-values indicate the increase in yellowing compared to the unaged and 5 non-flavored sample, which was the zero b reference. Table ΙΠ 10 Investigations of the discoloration of toothpaste Aging at 49 ° C of the toothpaste from Example 1A lWo 3 Wo 6 Wo h_Lh b Ah b Ab 15 ExDerimentI 1% CA in Ex. 7 2.3 + 0.3 3.8 + 1, 8 5.1 + 3.4 1% CA +1% 20 limonene in Ex. 7 1.7 + 0 3.3 +1.3 4.6 + 2.9 1% CA +10% propylene glycol 4.0 + 1.8 5.0 + 3.0 7.1 + 5.4 1% CA + 36% propylene glycol Sample was solidified 25 + 63% dicalcium phosphate 2.0 + 0 1.8 + 0 exoiment 1% CA 5.1 + 3.2 12.6 + 10.4 10.6 + 6.7 30 1% CA + 1% propylene glycol 5.2 + 3.3 9.6 + 7.4 8.0 + 4.3 1% CA + 1 % Dipropylene glycol 4.5 + 2.6 8.6 + 6.4 6.4 + 2.7 35 1% CA + 5% propylene- 8.3 6.6 + 2.9 glycol 4.9 + 3 , 9.1 + 6.5 1% CA + 5% dipropylene- 5.0 + 1.3 40 glycol 4.4 + 2.5 8.0 + 5.8 1% CA + 35% dipropylene glycol + 64% dicalcium phosphate 1.8 + 0 2.4 + 0.2 2.9 + 0 45 ExDerimentin 1% spice 10 3.9 + 2.1 5.7 + 3.6 5.7 + 3.9 3.9 + 2.1 5.8 + 3.7 5.6 + 3.8 50 1% spice 10 + 5% propylene glycol 3.7 +1.9 5.5 + 3.4 5.8 + 4.0 1% spice 10 + 5% 55 propylene glycol + 1% limonene 3.9 + 2.1 5.8 + 3.7 5.9 + 4.1 1% spice 10 + 5 % Propylene glycol + 1% TiOj; pH 5.1 2.4 + 0.6 3.9 + 1.8. 2.7 + 0.9 3.7 + 1.6 - -10-

Claims (1)

No. 390 369 (continuation of table ΙΠ) 1 week h_ 3 week b_ 6 week b_ Experiment IV 3.9 + 1.7 6.4 + 4.0 6.5 + 4.7 3.3 + 1.1 4, 7 + 2.3 4.5 + 2.7 2.8 + 0.7 2.7 - 0 0.9% spice 10 0.9% spice 10 in Ex. 8 Experiment V 0.9% spice in Ex. 8 +1% Ti02 Table m relates to formulations which contain various cinnamaldehyde-containing flavorings which yellow with aging, and the reduction in yellowing by adding propylene glycol and dipropylene glycol or by using these glycols as the sole humectant according to Examples 3 and and 4 in large quantities. Adjusting the pH to about 6 and adding Ti02 further reduces the yellowing of this flavor-containing formulation. It is to be understood that the above detailed description is illustrative only and that variations are possible within the scope of the invention. The above &quot; summary &quot; is for the convenience of technical researchers only, and is of no importance in the scope of the invention. PATENT CLAIM White or colorless dentifrice composition, available as a toothpaste or mouthwash, with increased stability against discoloration during aging, which contains an aging discolouring cinnamon aldehyde flavor in an amount of 0.1 to 1% by weight in a carrier suitable for dentifrices , which is free from oxidizing agents and has a pH below 8.5, characterized in that it contains propylene glycol, dipropylene glycol or a mixture thereof in an amount of 10 to 45% by weight of the composition as a discoloration inhibitor. -11-