CH668359A5 - DENTISTRY COMPOSITION. - Google Patents

Description

DESCRIPTION 55 The invention relates to a color-stabilized dentifrice composition which contains a cinnamaldehyde or citral flavor which shows discoloration / yellowing on aging, and a trisubstituted double bond-containing terpene or sesquiterpene or propylene glycol 60 or dipropylene glycol or a mixture thereof which significantly reduces the discoloration and / or prevented, the pH of the composition being kept below 8.5 and preferably in the neutral or acidic range. The dentifrice can be aqueous or anhydrous 65. The dentifrice must be free from oxidizing agents such as hydrogen peroxide or salts that release hydrogen peroxide such as sodium perborate, peracids and peracid salts.

A large number of dentifrice compositions are known from the prior art which together contain a cinnamaldehyde or citral flavor and a terpene as shown in U.S. Patents 3,867,557 and 3,928,560, according to which oral compositions are 0.0001 to Contain 20% paramethoxycinnamaldehyde flavoring agent, be dissolved in 100 parts of orange oil (Example VII), and 4% of the cinnamaldehyde be dissolved in 500 ml of ethyl alcohol and 10 ml of orange oil (Example XIII). Essential oils such as orange oil are known to contain terpenes. US Pat. No. 4,001,438 also discloses the use of flavoring compositions containing citral and orange genpenes (Example B in column 10) in oral compositions. In this group of patents, however, there is no indication of the discoloration or yellowing problems associated with the use of the cinnamaldehyde flavor. These patents concern other aspects of dentifrice compositions. The combination of cinnamaldehyde flavor and a terpene is mentioned casually in the general discussion of flavorings.

A large number of dentifrice compositions are known from the prior art which contain the combination of a cinnamaldehyde or citral flavor and propylene glycol or dipropylene glycol, as shown in US Pat. Nos. 3,867,557 and 3,928,560, according to which oral compositions which are 0 Contain, 0001 to 20% para-methoxycinnamaldehyde 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 carrier; 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 flavors or colors, as shown in U.S. Patent 3,666,496, which relates to a poly (oxyethylene) -poly (oxypropylene) copolymer which terpene-containing flavors such as orange oil is added to prevent decomposition 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 toothpaste colored with monazite or blue 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 is in storage until released

668 359

Dentifrices for use remain separate from the dentifrice base (which may contain propylene glycol), making the flavored dentifrice more stable and fresher in taste. In the patents mentioned, however, there is no indication of the stabilization of cinnamaldehyde or citral taste by a certain group of terpenes or sesquiterpenes, which are characterized by a trisubstituted double bond, or by propylene glycol or dipropylene glycol.

US Pat. No. 2,184,526 also describes the instability against atmospheric oxidation of p-isopropyl-a-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 the terpene series stabilizes the aldehyde against atmospheric oxidation by converting the aldehyde into a hemiacetal of the alcohol.

US Pat. No. 3,671,630 relates to the use of several classes of terpenes as color stabilizers for aqueous halogenated phenolic germicidal compositions which change color under the influence of light within a few hours. However, it is stated that many terpenes such as limonene are not effective. The halogenated phenolic germicidal compounds cannot be equated with the cinnamaldehyde or citral flavors, which are unsaturated aldehydes. It should also be noted that limonene, which is one of the terpenes used as color stabilizers for the flavor, is specifically excluded as ineffective in stabilizing the germicidal composition.

None of the above references disclose the use of a particular group of terpenes or sesquiterpenes in a dentifrice free of oxidizing agents and kept at acidic or neutral pH and containing cinnamaldehyde or citral flavor to prevent the discoloration of the flavor Aging.

It has surprisingly been found that the discoloration during the aging of tooth cleaning agents which are flavored with cinnamaldehyde or citral reduces and /

or can be prevented by the addition of (1) a terpene or sesquiterpene, which is characterized by trisubstituted double bonds and selected from limonene, ocmen, caryophyllene and carnation quiterpenes, myrcene, derivatives of the terpenes and mixtures thereof or essential oils rich in these can, or of (2) propylene glycol or dipropylene glycol or mixtures thereof. It is essential that the carrier suitable for dentifrices is free from oxidizing agents and is kept at an acidic or neutral pH so that the terpenes and sesquiterpenes can function effectively.

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

The object of the invention is to provide a dentifrice composition with increased stability against discoloration during aging, which is characterized in that it contains an aldehyde flavor which changes color with aging and is selected from cinnamaldehyde and citral and contains at least one trisubstituted double bond as a discoloration inhibitor (1) or sesquiterpene in an amount of 0.1 to 5% by weight, or (2) propylene glycol, dipropylene glycol or a mixture thereof in a dental vehicle suitable for dentifrices which is free of

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Is oxidizing agents and has a pH below 8.5.

The dentifrice according to the invention preferably has a neutral or acidic pH.

In preferred embodiments, the dentifrice according to the invention is in the form of a toothpaste or mouthwash.

Additional objects, advantages and new features according to the invention are explained in part in the following description and in another part will become clear to the person skilled in the art when examining the following or can be experienced in the practice of the invention. The objects and advantages according to the invention can be achieved and achieved by the means and combinations to which particular reference is made in the claims.

In order to achieve the above and other objectives, the tooth cleaning agent according to the invention, which has increased stability against discoloration during aging, contains a flavoring discoloring agent selected from cinnamaldehyde and citral and containing an unsaturated aldehyde and as a discoloration inhibitor (1) trisubstituted double bonds labeled terpene or sesquiterpene color stabilizer, for example is selected from limonene, ocimen, caryophyllene and carnation quiterpenes, myrcene, terpene derivatives thereof and mixtures thereof or essential oils rich in these, in an amount of 0.1 to 5% by weight or (2) propylene glycol, dipropylene glycol and mixtures thereof, in one Dental vehicle suitable for dentifrices, which is free of oxidizing agents and is kept at a pH below 8.5 and preferably at an acidic to neutral pH of 5 to 7.5.

s In a preferred embodiment, the invention relates to a color-stabilized white toothpaste or a mouthwash which is free from oxidizing agents and has an acidic to neutral pH value which contains 0.1 to 1% by weight of cinnamaldehyde or citral flavoring and (1) one or Several terpenes or sesquiterpenes containing trisubstituted double bonds or (2) propylene glycol or dipropylene glycol as a discoloration inhibitor, preferably in a ratio of 1: 1.

It has been found that the cinnamaldehyde or Ci-i5 tral flavors decompose with the formation of conjugated unsaturated aldehydes (dienals). These dienals are responsible for the yellowing or discoloration that occurs with cinnamaldehyde or citral in white dentifrices, both in liquids and in creams (pastes).

In the case of commercially available toothpastes in which small amounts of cinnamaldehyde are used, the discoloration problem is solved by coloring the goods, e.g. 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

<S> "CH e CH - CH (CA)

0

II

1

CH »CH - C - 0 - OH CA

Lanqsanr

0

H

CH «CH - C - 0 - 0"

CA / fast

I.

Clf '-' tH - CH0

CH - CH - C02H

j-co2

© -

chgcho ca -h2o

CH »CH - CH * C - CH and other dienals

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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. Since cinnamic acid is white, its formation, which takes place 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 intense

(1)

(2) \

1.0% cinnamaldehyde (CA) 4.5 1.0% CA + 1.0% limonene 2.9 1.0% CA + 1.0% ocimen 2.5 1.0% CA + 1.0% caryo -phylls 3.2

1.0% CA + 1.0% Citronel

3.6

7.5 4.9 5.4

5.3

4.2

8.0

5.8

5.9

5.4 5.4

lylacetate

B. Influence of pH

1.0% CA pH 5.0 (citric acid) 1.0% CA pH 6.9-7.1 (example 1) 1.0% CA pH 8.5 (NaHCOj)

The reduction is improved by increasing the amount of terpene. FIG. 1 shows the effect of the addition of limonene on the discoloration of a toothpaste which contains 1% by weight of cinnamaldehyde.

4.25

5.5

5.1

4.5

7.5

8.0

7.5

10.5

11.2

yellow components that are responsible for the discoloration and yellowing of cinnamaldehyde.

It has now been found that the discoloration of small amounts of cinnamaldehyde (maximum about 1% by weight) is reduced 5 when certain terpenes or sesquiterpenes with tri-substituted double bonds are incorporated in the dentifrice composition, preferably in a weight ratio of 1: 1. The terpenes preferably include limonene (1), ocimene (2), caryophyllene (3), myr-lo cene (4), terpene derivatives such as citronellyl acetate (5) and mixtures thereof.

(3)

(4)

*

(L-öAc

(') a'

Each one in a ratio of 1: 1 to cinnamaldehyde significantly reduces the discoloration of cinnamaldehyde as it ages in a glass bottle. These compounds also reduce yellowing on aging in white toothpastes, as shown in Table 1A, which results in a 40% reduction in yellowing. Natural products containing these compounds can be used, such as essential oils rich in lemon, including citrus oils such as orange oil, grapefruit oil and mandarin oil. Clove sesquiterpenes also act as color stabilizers.

The toothpaste yellowing was measured instrumentally on a Colorgard reflection meter. The data presented in the following tables are + Ab values (yellow scale) and mean the increase in yellow compared to non-flavored and non-aged toothpaste, which was taken as the zero-b reference. Measurements after 3.6 and 9 weeks at 49 ° C should correspond to approximately 1 year, 2 years and 3 years at room temperature. It is approximately assumed that an Ab value of 2 to 3 is the limit of what is acceptable, since an Ab of 2 can be recognized as just off-white and an Ab of 4 as a weak yellow tint.

Table 1

Cinnamaldehyde discoloration in toothpaste (Ex. 1) A. Influence of chemicals with trisubstituted double bonds

Aging at 49 ° C; Ab values 3 weeks 6 weeks 9 weeks

35

Although lime is a mild flavor (orange-like), levels above 1% are unsuitable and may be undesirable because the orange taste can alter the original cinnamon taste.

The auto-oxidation of cinnamaldehyde is inhibited (interrupted) by the presence of the group of terpenes and sesquiterpenes. The formation of epoxy cinnamaldehyde 25 is prevented if limonene is added to the cinnamaldehyde. The prevention of the formation of this epoxide also prevents the formation of the subsequent dienals. It was shown by analytical studies that limonene reacts preferentially with cinnamaldehyde with percinnamic acid to form 1,2-epoxyimones. It can be assumed that the other terpenes (2, 3, 4 and 5) form similar epoxides due to the substituted double bond. Trisubstituted double bonds are known to show greater reactivity with peracids than mono- or disubstituted double bonds. Furthermore, it is expected that cinnamaldehyde shows a lower reactivity towards electrophilic attack by peracids because its double bond is substituted with an electron-withdrawing aldehyde group. By preventing the formation of the Dienale re-40, limonene significantly reduces yellowing. Other terpenes such as eugenol are not effective in reducing yellowing.

The agents for reducing the discoloration of cinnamaldehyde can also be used for other conjugated unsaturated aldehydes such as citral, (CH3) 2C = CHCH2CH2 (CH3) = CHCHO. Citral is another flavoring agent that is commonly used in dentifrice compositions.

The yellowing of a liquid mixture of cinnamaldehyde or citral with a terpene additive was measured with a Gardner colorimeter both after fresh production and after 24 hours aging at 90 ° C + 2 ° C. 10 g samples were made from mixtures of the flavor and 55 limes in different amounts and the following measurements were obtained:

45

Cinnamaldehyde 60 (%)

Lime (%)

Color measurement freshly aged

95 90 75 65 100 50

5 10 25 0 50

41/4 41/4 41/4 4 1/2 3 3/4

7

63/4 5

(a) g

W 4 1/2

W average of 2 measurements

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6

Color measurement

Citral (%) freshly aged limes

(%)

100 0 M1 1/3 (b) 3 2/3

0 100 Wl

50 50 (b) 1 (b) 2

® Average of 3 measurements

The citral alone and the 50:50 mixture of citral and limes were aged even further:

4 days 6 days 11 days

Citral alone (b) 71/3 <b> 9 2/3

50: 50 Citral: Lime <b> 4 ^ 41/3 W 5

The pH of the toothpaste is either acidic or slightly alkaline, with a pH of about 5 to 7.5 as shown in Table IB being preferred. The terpenes are not effective in reducing the yellowing in moderately alkaline medium. At pH = 8.5 or above, the anion of peracid is formed and the epoxidation of cinnamaldehyde proceeds through Michael addition. This type of addition reaction cannot be inhibited by limonene.

It has now also 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 weight ratio of 1: 1 to 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 incorporate them in much higher amounts. The substitution of water or glycerin in tooth cleaning formulations with propylene glycol or dipropylene glycol prevents the yellowing of flavorings containing cinnamaldehyde or citral. If a non-aqueous paste is formulated by replacing the water with one of the two glycols, then no discoloration is observed. Yellowing is also significantly reduced by replacing the 22% glycerol in a toothpaste with propylene glycol.

The mechanism of the glycolef 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 (FIG. 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 over time. This prevents the formation of the dienals that are responsible for yellowing as they age.

This agent for reducing the discoloration of cinnamaldehyde is also applicable to other conjugated unsaturated aldehydes such as citral, (CH3) 2C = CHCH2CH2C (CH3) = CHCHO. Citral is another flavoring agent that is commonly used in tooth cleaning compositions.

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 tjlycerin and cinnamaldehyde alone and the following measurement results were obtained:

I.

Color measurement freshly aged

Cinnamaldehyde (CA) 4 11

50/50 CA + glycerin 3; 4 11 '

50/50 CA + propylene glycol 3 7; 7 = 7

50/50 CA + dipropylene glycol 3 10; 8th; 9 = 9

II

Cinnamaldehyde 4.5 7

50/50 CA / propylene glycol 3.5 4.5

'Glycerin and CA formed two phases. The glycerin phase (bottom) remained watery white, while the upper phase from CA became dark.

It should be noted that the propylene glycol mixture was slightly less dark than the dipropylene glycol mixture, but was much 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 2. At pH = 8.5 or higher, the peracid anion forms 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 Color-Gard 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. It is assumed that an Ab value of 2 to 3 is the limit of what is acceptable, since an Ab of 2 is visible as just broken white and an Ab of 4 as a weak yellow tint.

Table 2

Cinnamaldehyde discoloration in toothpaste (Ex. 1)

Influence of pH aging at 49 ° C: Ab values

3 weeks 6 weeks 9 weeks

1% CA pH 5.0 lemons

acid

4.25

5.5

5.1

1% CA pH 6.9 to 7.1

(Example 1)

4.5

7.5

8.0

1% CA pH 8.5 (NaHCOs)

7.5

10.5

11.2

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It is also important that the dentifrice is 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 terpene with the percinnamic acid in the formation of the 1,2-epoxylimony as well as the preferred reaction of the glycol with cinnamaldehyde in the formation of the glycol acetal. 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 different 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 TÌO2:

pH

TiCh

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 1B). Increasing the pH to 8.5 by adding NaHC03 significantly increased the yellowing. The addition of limonene had no effect on the reduction in yellowing in the NaHŒ> 3 base (pH = 8.5).

7 668359

These observations are consistent with the mechanism of external oxidation. The peracid anion is formed at pH = 8.5 and the epoxidation proceeds more quickly through Michael addition. Limonene and the other 5 terpenes and sesquiterpenes with trisubstituted double bonds are not reactive towards nucleophilic addition and cannot intercept the peroxide anion. Peracids are much weaker than the corresponding carboxylic acids. The pKa of percinnamic acid is estimated to be 7.5 ge-10. Both free acid and anion are present in a neutral base. Lowering the pH prevents the reaction based on anion addition.

As was found in the comparison of Example 1 and Example 2, the presence of TÌO2 provides both a visible and measurable reduction in yellowing. On the basis of a number of comparisons with and without Ti02, an Ab reduction of 1.0 for 1% TÌO2 and of 0.5 for 2o 0.5% TÌO2 was observed.

An additive which may be desirable and which supports the reduction of cinnamaldehyde yellowing in dental formulations is titanium dioxide (TÌO2) in small amounts of about 0.5 to 1% by weight. Table 3 shows the effectiveness of limonene and propylene glycol in reducing the yellowing in toothpastes which contain various flavorings containing cinnamaldehyde in the presence and in the absence of TiO 2.

Table 3

Flavor discoloration in toothpaste (Ex. 1)

Flavoring

1 week

3 weeks

6 weeks

9 weeks

Cinnamaldehyde (CA)

r / oCA.

1% CA + 1% limonene + 0.5% TÌO2; pH 5.6

Spice 10 (S10) '

1% S10

1% S10 + 1% limonene + 0.5% Ti02

Spice 12 (12S) 2 0.8% 12S

0.8% 12S + 0.1% lime

0.8% 12S + 0.1% limonene + 1% TÌO2

0.8% 12S + 0.5% limonene + 1% TÌO2

0.8% 12S + 0.25% lime

0.8% 12S + 0.5% Ti02

0.8% 12S + 0.1% lime

+ 0.5% Ti02

0.8% 12S + 0.1% limonene + 0.5% TÌO2;

pH 5.2 (citric acid)

0.8% 12S + 0.25% limonene + 0.5% TÌO2

0.8% 12S + 0.25% lime

+ 1% TiOz

1% CA + 35% dipropylene glycol or propylene glycol + 64% dicalcium phosphate dihydrate

Spice 10 (S10) 1 1% S10

1% S10 (glycerin replaced by propylene glycol)

1% S10 (glycerin replaced by propylene glycol) + 1% Ti02

0.9

4.5 2.4

3.0 1.9

2.7 2.1 1.1 0.7

2.0 1.5

1.5

3.1 1.5

1.0

0.2

3.0 2.3 0.7

7.5 2.9

4.2

2.3

4.0

3.2

2.3 2.0 3.0 2.9

4.2 2.7

8.0

4.5

4.6 2.6

4.6 3.9 2.6 2.5 3.5

3.1

2.8 4.0

4.6

'' Spice 10 flavor contains 55% cinnamaldehyde 2Spice 12 flavor contains 15% cinnamaldehyde

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Other flavor compositions containing cinnamaldehyde include:

White Spice 1 - contains 20% cinnamon aldehyde.

White Spice 2 - contains 25% cinnamaldehyde.

Spice-11 flavor - contains 55% cinnamaldehyde.

The cinnamon aldehyde flavor compositions can be supplemented to 100% with flavor components such as menthol, eugenol, peppermint, spearmint, clove, anethole, methyl salicylate, vanillin and the like in various mixtures. Menthol and eugenol do not affect the yellowing of the dental formulations.

Mixing the cinnamaldehyde with limonene or other terpenes, incorporating Ti02 and lowering the pH can make high levels of cinnamaldehyde acceptable.

Mixing cinnamaldehyde with propylene glycol or dipropylene glycol, incorporating Ti02 and lowering the pH can also make high levels of cinnamaldehyde acceptable. This can easily be accomplished by replacing the glycerin or water with propylene glycol in the tooth cleaning formulation.

The flavorings with cinnamaldehyde, which generally makes up at least 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.

In the case of spice 10 flavor, the addition of 1% limonene and 0.5% Ti02 reduces the discoloration to a barely acceptable level. This addition changes the original taste, but it should be useful to achieve similar tastes. In this case, 1% TiO 2 and the use of caryophyllene (a spicy taste) in addition to limonene may be preferred.

With spice 12 flavor, the yellowing exceeds the expected level due to the 15% cinnamaldehyde content. Interactions due to other components contribute to the discoloration. If this taste is required for a white paste, the addition of only 0.1% limonene and 1% Ti02 results in a significant color improvement with only a slight change in taste.

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

Toothpastes or creams can be based on aqueous or essentially non-aqueous systems. The former usually contain significant amounts of finely divided solid polish, surfactant, gelling agent, water and some non-aqueous dental vehicle, e.g. Glycerin, sorbitol, and they are opaque, while the latter types are often a clear gel or opaque and a small proportion of a visually clear fine-particle solid polishing agent, a larger proportion of a non-aqueous dental vehicle, which is at least 10% of the formulation Propylene glycol or dipropylene glycol alone or mixed with other non-aqueous carriers such as sorbitol or glycerin, may contain a surface-active agent and a gelling agent in addition to an often present small amount of water.

The surfactant or detergent optionally present in the dentifrice may be cationic or amphoteric in some cases, but is usually anionic or nonionic. Of these compounds, the anionic are most preferred. The anionic detergents or surfactants normally also serve as foaming agents. Useful 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 higher olefin sodium sulfonates in which the olefin group has 12 to 21 carbon atoms; higher alkyl potassium sulfate; 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, "higher" means chain lengths of 12 to 22 carbon atoms, preferably 12 to 18 carbon atoms and most preferably 12 to 16 carbon atoms. The term "lower" means 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms and most preferably 2 carbon atoms.

The nonionic detergents usually include those containing chains of lower alkylene oxides, e.g. Ethylene oxide, propylene oxide in which 10 to 100 or more moles of the lower alkylene oxides are present. These materials include, in particular, the block copolymers of ethylene oxide, propylene oxide and propylene glycol, which are sold as Plu-ronics; 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) amidoalkylenealkylamine derivatives such as "Miranols", e.g. Miranol C2M; and cationic germicidal detergents such as diisobutylphen-oxyethoxyethyldimethylbenzylammonium chloride, benzyldimethylstearylammonium chloride and tertiary amines with a higher fatty alkyl group and 2 polyoxyethylene groups attached to the nitrogen thereof.

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

Toothpastes, toothpastes and toothpowder usually contain essentially water-insoluble polishing or abrasive agents which are compatible with the formulation in amounts of 20 to 75% 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, Tricalci-umphosphat, insoluble sodium metaphosphate, crystalline silica, colloidal silica, complex Alumi-nosilikate, aluminum (including aluminum oxidtrihydrat or hydrated alumina), magnesium phosphate, magnesium carbonate, calcium carbonate, Cal-ciumpyrophosphat, bentonite, talc , Calcium silicate, calcium aluminate, aluminum oxide, aluminum silicate and silicon dioxide xerogels. Most of the abrasives mentioned are particularly useful for the manufacture of opaque dentifrices, but some of them, such as the colloidal silicas, especially the disilicas,

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668359

Rogele and the complex sodium aluminosilicates can be used in the manufacture of clear dentifrices because their refractive index is close to that of the remaining dentifrice ingredients in a suitable carrier. s

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 e.g. can be extruded from a compressible aluminum tube. In general 10 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. Irish moss, 20 gum tragacanth, sodium carboxymethyl cellulose, polyphenyl pyrrolidone or starch. Irish moss and sodium carboxymethyl cellulose are particularly compatible and preferred gelling agents. The gum content is normally up to about 10% by weight and preferably about 0.3 to 25

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 silica aerogels, which include Syloids 244 and 266 and 30 Aerosil, and the fumed silicas sold as Cab-O-Sil can be used as gelling and thickening agents.

The liquid vehicle in a mouthwash (mouthwash) normally comprises ethyl alcohol, glycerin, sorbitol, water and mixtures thereof in an amount of 90 to 98% by weight total liquid content.

Various other materials can also be incorporated into the carrier suitable for dentifrices. Examples include fluorine-containing compounds such as 40 tin (II) fluoride, potassium tin (II) fluoride (SnF2KP), sodium hexafluorostannate, tin (II) chlorofluoride, sodium fluorozirconate and sodium monofluorophosphate. These materials that dissociate or release fluorine-containing ions in water can be present in the dental carrier in an effective but not toxic amount, usually in the range of 0.1 to 5 percent by weight. Other additives include e.g. Preservatives such as sodium benzoate, chlorophyll compounds, silicones, ammonium materials such as urea and diammonium phosphate, antibacterial agents such as benzonium chloride and other quaternary antibacterial compounds, sweeteners such as sodium saccharin, blue colorants, additional flavorings 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. 60

The tooth cleaning agent according to the invention can be produced by conventional methods for producing toothpastes, toothpastes, mouthwashes and tooth powders. In particular, a toothpaste can be made by forming a gel of carboxymethyl cellulose and 65 water, adding the powdered materials and the humectant while mixing, then adding the polishing agent and then the surfactant and flavor together with the terpene or sesquiter pen color stabilizer and pour the resulting mixture into a tube. The flavor composition is preferably mixed with the terpene or sesquiterpene color stabilizer prior to addition to the mixture.

When used to promote oral hygiene, the tooth cleaning agent according to the invention is usually applied regularly to the enamel by brushing the teeth for 30 to 90 seconds 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 mentioned herein and in the claims are by weight unless otherwise specified. The flavor-forming component is a flavor composition containing cinnamaldehyde or citral, to which a terpene or sesquiterpene (Tables 4 to 7) or propylene glycol or dipropylene glycol is added, as described in the examples following the experiments (Table 8).

Example 1 Toothpaste

A

B

ingredients

%

%

Glycerin

22.00

22.0

Sodium monofluorophosphate

0.76

0.8

Sodium carboxymethyl cellulose

1.00

1.0

Tetrasodium pyrophosphate

0.25

0.2

A

B

ingredients

%

%

Sodium saccharin

0.20

0.2

Sodium benzoate

0.50

0.5

Deionized water

24.49

24.5

Dicalcium phosphate dihydrate

48.76

48.8

Flavoring

0.84

0.8

Sodium lauryl sulfate

1.20

1.2

pH

6.9-7.1

6.9-7.1

Example 2

toothpaste

A

B

ingredients

%

%

Glycerin

10.00

10.0

Sodium monofluorophosphate

0.76

0.8

Sodium carboxymethyl cellulose

1.10

1.1

Sodium benzoate

0.50

0.5

Sodium saccharin

0.20

0.2

Sorbitol (70% solution)

17.00

17.0

A

B

ingredients

%

%

Deionized water

22.19

22.2

Titanium dioxide

0.40

0.4

Unsolvable Sodium metaphosphate

39.35

39.3

668359

10th

A

B

ingredients

%

%

Hydrated alumina

1.00

1.0

Anhydrous dicalcium phosphate

5.00

5.0

Flavoring

1.00

1.0

Sodium lauryl sulfate

1.50

1.5

6.15 pH

Example 3

Gel toothpaste

ingredients

%

Deionized water

3.00

Sodium saccharin

0.30

Sodium monofluorophosphate

0.76

Glycerin

25.00

Sodium carboxymethyl cellulose

0.35

Sodium benzoate

0.50

Titanium dioxide

0.01

ingredients

%

Sorbitol (70% solution)

41.53

Carbowax 600 (PEG 12)

3.00

dye

0.20

Sodium aluminosilicate (silicon

combined containing dioxide

Aluminum oxide)

18.00

Colloidal silica airgel

5.50

Flavoring

0.65

Sodium lauryl sulfate

1.20

Example 4

toothpaste

ingredients

%

Glycerin

25.00

Sodium carboxymethyl cellulose

1.40

Sodium benzoate

0.50

Sodium saccharin

0.20

Sodium monofluorophosphate

0.76

Deionized water

35.44

Titanium dioxide

0.40

ingredients

%

Alumina

10.00

Silicon dioxide

24.00

Flavoring

1.10

Sodium lauryl sulfate

1.20

pH 6.2 ± 0.5

Example 6 Mouthwash

ingredients

%

Ethyl alcohol glycerin polysorbate 80 '

Pòloxamer 3382 io benzethonium chloride

Flavor composition Deionized water

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

A mixture of oleate esters of sorbitol and sorbital anhydride consisting of the monoester condensed with approximately 20 moles of ethylene oxide.

2 polyethylene polyoxypropylene block polymer according to the formula:

20th

H0 (CH2CH20) (- CH-CH20) (CH2CH20) H,

x y ^

CH-,

25th

in which x and z = 128 and y = 54.

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

30th

35

Example 7 Tooth powder

A

B

ingredients

%

%

Magnesium silicate

7.00

7.0

Sodium saccharin

0.15

0.2

Flavoring

2.50

2.5

Dicalcium phosphate anhydrous

88.35

88.3

Sodium lauryl sulfate

2.00

2.0

45

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

50

55

Example 8 Non-aqueous toothpaste

ingredients

%

Example 5

Example 4 was followed up with the difference that the sodium lauryl sulfate was increased to 1.5% and the water content was adjusted accordingly.

Propylene glycol so Klucel GF1 (Hercules) sodium saccharin Ti02

Dicalcium phosphate dihydrate peroxydiphosphate 65 sodium lauryl sulfate pH 6.4

43.4 1.5 0.2 0.4 50.0 3.0 1.5

1 hydroxypropyl cellulose - a propylene glycol ether of cellulose.

11

668359

Example 9 Aqueous toothpaste

ingredients

%

Propylene glycol

22.0

Sodium monofluorophosphate

0.8

Sodium carboxymethyl cellulose

0.1

Tetrasodium pyrophosphate

0.2

Sodium saccharin

0.2

Sodium benzoate

0.5

Dicalcium phosphate dihydrate

48.8

Spice 10

0.9

Sodium lauryl sulfate

1.2

Ti02

1.0

h2o

Q.S.

The following tables show discoloration results after aging at 49 ° C. of the toothpastes from Example 1, unless stated otherwise, and not flavored, containing cinnamaldehyde (CA) flavoring alone and with certain terpenes or sesquiterpenes which contain a trisubstituted double bond or with propylene glycol or dipropylene glycol to prevent or reduce the discoloration caused by the cinnamaldehyde ingredient.

The b-values in the tables indicate the yellowing of the toothpaste measured on the color guard reflectance meter, and the Ab-values indicate the increase in yellowing over the unaged and non-flavored sample, which was the zero b reference.

Table 4

Examination of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from example 1A

Reference b Ab

3 weeks b From

4 weeks b From

5 weeks b From

6 weeks b From

7 weeks b From

9 weeks b From

Experiment I 0.5% CA

0.5% CA + 0.5%

Limonene not flavored 2.7

Experiment II

0.5% CA 1.9 + 0.2

0.5% CA + 0.5% eugenol 0.5% CA in Example 2A 0.5% CA + 0.5% eugenol in Example 2A

not flavored Ex. 2A

2.0 1.9

1.8

1.9

Experiment III 1% CA

1% CA + 1% lime

1% CA + 2% limonene not flavored 2.7 0

Experiment IV 1% CA

1% CA + 1% Ocimen 1% CA + 2% Ocimen 2% Ocimen not flavored 2.1

4.6 + 2.6

6.2 + 4.2

3.3 + 1

6.6 + 3.9 7.6 + 5.4 4.9 + 2.2 5.4 + 3.2 4.5 + 1.8 4.8 + 2.6

5.7 + 3.6 4.6 + 2.5 5.1 + 3 3 +0.9 2.1

5.2 + 2.5

5.5 + 2.8 5.2 + 2.5

5.6 + 2.9 2.9 + 0.2

4.9 + 3.1

7.6 + 5.8

3.7 + 1.9

3.8 + 1.9 4.3 + 2.5

5.7 + 3.9 6.0 + 4.2 2.7 + 0.9

5.7 + 3.8 7.7 + 5.8 separation

9.3 + 7.1 6.5 + 4.4 5.7 + 3.6

9.2 + 7.3

7.3 + 5.4 7 +5.1 3.8 + 1.9 2.1 + 0.2

6.6 + 4.8

6.6 + 4.8

6.7 + 4.9 6.9 + 5.1 2.9 + 1.1

6.4 + 4.5

9.5 + 7.6 separation

4.8 + 2.9 5.6 + 3.7

10.5 + 9 9.9 + 8.4 7.5 + 6 6.9 + 5.4 6.2 + 4.7 5.8 + 4.3

9.9 + 8.1 7.7 + 5.9 7.7 + 5.9 3.9 + 2.1 2 +0.2

Table 5

Examination of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from example 1A

Reference b Ab

2 weeks b From

3 weeks b From

4 weeks b From

6 weeks b From

9 weeks b From

Experiment V 1% CA

1% eugenol

1% CA + 1% eugenol

6.7 + 4.8

4.1 + 2.2 8.1 + 6.2

8.4 + 6.5

4.5 + 2.6 9.9 + 8

9.6 + 7.9 10.2 + 8.5 4.3 + 2.6 10.7 + 9

668 359

12

Table 5 (continued)

reference

2 weeks

3 weeks

4 weeks

6 weeks

9 weeks

b Ab b Ab b Ab b Ab b Ab b Ab

0.5% CA + 0.5% eugenol

5.9 + 4

8.1 + 6.2

8.9 + 7.2

0.9% CA + 0.1% eugenol

5 +3.1

6.6 + 4.7

7.2 + 5.5

1% spice 10

4.8 + 2.9

6.3 + 4.4

6.7 + 5

6.4 + 4.7

10% white spice # 1

3.8 + 1.9

4.6 + 2.7

5.0 + 3.3

5.1 + 3.4

not flavored

1.9

Experiment VI

1% white spice # 2

3.3 + 1.2

3.5 + 1.7

4.6 + 2.9

5.1 + 3.2

4 +2.3

not flavored

2.1

2.1 0

2.2 + 0.5

2 +0.1

Experiment VII

0.5% CA + 0.5% eugenol

5.9 + 4

7.2 + 5.3

7.8 + 6

6.9 + 5.0

7.8 + 6

0.5% CA + 0.5% eugenol

4.7 + 2.8

6 +4.1

7 +5.2

+ 1% lime

6 + 4.1

7.5 + 5.7

not flavored

1.9

Experiment VIII

1% white spice # 1

4.1 + 1.9

4.8 + 3.0

5.1 + 3.5

4.9 + 3.1

1% spice 10

5.6 + 3.4

5.8 + 4.2

5.8 + 3.8

5.6 + 4.0

6 +4.4

1% spice 10 + 1% lime

4.9 + 2.7

4.8 + 3.2

5 +3

5.2 + 3.6

5.4 + 3.8

1% spice 11 + 1% lime

4.8 + 2.6

5.1 + 3.5

5.3 + 3.7

5.4 + 3.8

1% lime

2.4 + 0.2

2.3 + 0.5

1.9 + 0.3

Table 6

Examination of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from example 1A

Reference 1 week. 2 weeks 3 weeks 6 weeks 9 weeks

b Ab b Ab b Ab b Ab b Ab b Ab

Experiment IX 1% CA

1% CA + 0.25% Limonen 1% CA + 0.5% Limonen 1% CA + 0.75% Limonen 1% CA + 1% Limonen 1% CA + 1.5% Limonen 1% CA + 3% Limonen 1% CA + 5% Limonen not flavored 1% CA + 1% caryophyllene

Experiment X Example 4 Example 4 Example 1A Example 1A

Example 2 not flavored Example 1 not flavored Example 5 not flavored

2.1

1.5 2.3

1.6 - 0.3 1.9

1.5 - 0.4

4.5 + 2.5

3.3 + 1.3

1.8 + 0.3 2.6 + 0.3

7.2 + 5.1

6.1 +4 5.9 + 3.8 5.4 + 3.3

5.3 + 3.2 5.0 + 2.9 4.8 + 2.7

4.2 + 2.1

1.8

1.8 - 0.2

2.5 + 0.5 1.7 - 0.3 2.1 + 0.1

1.9 - 0.1

10.5 + 8.9 7.7 + 6.1 6.9 + 5.3 6.9 + 5.3

6.5 + 4.9

6.6 4 * 5.0 5.3 + 3.7 5.0 + 3.4

2.1 + 0.4

1.6

2.7 + 1 2.3 + 0.7

11.1 +9.2 8.5 + 6.6 8.3 + 6.4

7.8 + 5.9

7.9 + 6 6.7 + 4.8 6.2 + 4.3 5.7 + 3.8

5.3 + 3.2 6.9 + 5.3 7.9 + 6

2.1 + 0.2

1.8 - 0.1 3.0 + 1.1 2.3 + 0.4 1.5 - 0.4

1.9

1.8 - 0.1

Experiment XI

1% white spice 11 + 1% limes 2.9 + 1.2 4.6 + 2.9 5.3 + 3.7 5.5 + 3.6

in Example 5 1.9 2.9 + 1.2 4.5 + 2.8 5.2 + 3.6 5.4 + 3.5

0.5% CA 2.3 + 0.1 3.1 + 1.4 4.5 + 2.9 6.1 + 4.5 6.0 + 4.1

13 668 359

Table 7

Examination of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from example 1A

reference

1 week

3 weeks

5 weeks

6 weeks

9 weeks

b Ab b Ab b Ab b A

b Ab b Ab

Experiment XII

1% CA in Ex.1A pH 4.9

3.1 + 1.3

6.3 + 4.5

7.4 + 5.5

7.2 + 4.8

1% CA in Ex.1A pH 6.9

4 +2.2

7 +5.2

8.9 + 7

8.3 + 5.9

Example 1A not flavored pH 4.9

1.6

1.8

1.9

2.4

Example 1A not flavored pH 6.9

1.8

1.9

2.2

Example 2A not flavored

1.6

Experiment XIII

0.8% spice 12 + 0.5% Ti02

+ 0.1% lime

2.9 + 1.1

3.6 + 1.9

4.9 + 2.8

as above at pH 5.2 (citric acid)

4.9 + 3.1

5.3 + 3.6

6.1 + 4.0

as above at pH 5.1 (H3PO4)

4.7 + 2.9

5 +3.3

as above at pH 6.2 (H3PO4)

4.4 + 2.6

4.9 + 3.2

as above at pH 5.8 (citric acid)

4.7 + 2.9

5.2 + 3.5

5.7 + 3.6

1% spice 10 + 0.5% TÌO2

2.7 + 0.9

3.8 + 2.1

4.2 + 2.5

4.7 + 2.6

+ 1% lime

3.6 + 2.0

as above at pH 5.2 (citric acid)

2.6 + 0.8

3.5 + 1.9

3.8 + 2.1

4.6 + 2.5

as above at pH 5.1 (H3PO4)

2.8 + 1.0

3.7 + 2

4.3 + 2.6

5.6 + 2.5

3.2 + 1.6

as above at pH 5.8 (citric acid)

2.8 + 1

3.7 + 2.1

4.1 + 2.4

5.3 + 3.2

as above at pH 6.2 (H3PO4)

2.8 + 1

3.8 + 2.2

4.1 + 2.4

4.6 + 2.5

Experiment XIV

1% CA in Ex. 2A

5.2 + 3.5

6.9 + 4.7

7.1 + 5.3

1% CA + 1% limonene in Example 2A

4.2 + 2.5

5.2 + 3.0

5.8 + 4.0

Repeat test

4.4 + 2.7

5.2 + 3.0

5.8 + 4.0

1% citral

4.9 + 3.2

5.4 + 3.2

6.2 + 4.4

1% citral + 1% lime

3.7 + 2.0

4.3 + 2.1

4.8 + 3.0

1% CA + 0.5% Ti02pH 5.6

5.2 + 3.5

6.9 + 4.7

6.7 + 4.9

1% CA + 1% limonene + 0.5% Ti02

pH 5.6

4.1 + 2.4

5.1 + 2.9

6.1 + 4.5

0.8% spice 12 + 0.5% TiOz

pH 5.6

4.3 + 2.7

5.2 + 3.0.

5.7 + 3.9

0.8% spice 12 + 0.1% lime

+ 0.5% Ti02 pH 5.6

4.2 + 2.6

5.3 + 3.1

5.9 + 4.1

Table 8

Examination of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from example 1A

1 week b Ab

3 weeks b Ab

6 weeks b Ab

Experiment XV

1% CA in Example 8

2.3 + 0.3

3.8 +

1.8

5.1 + 3.4

1% Ca + 1% limonene in Example 8

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

2.0 + 0

1.8 +

0

Sample was

+ 63% dicalcium phosphate

stiffens

Experiment XVI

1% CA

5.1 + 3.2

12 +

10.4

10.6 + 6.7

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

1% CA + 5% propylene glycol

4.9 + 3.0

8.3

6.6 + 2.9

9.1 +

6.5

1% CA + 5% dipropylene glycol

4.4 + 2.5

8.0 +

5.8

5.0 + 1.3

1% CA + 35% dipropylene glycol

+ 64% dicalcium phosphate

1.8 + 0

2.4 +

0.2

2.9 + 0

668359

14

Table 8 (continued)

1 Wo 3 Wo 6 Wo b Ab b Ab b Ab

XVTI experiment

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

1% spice 10 + 5% propylene glycol

3.7 + 1.9

5.5 +

3.4

5.8 + 4.0

1% spice 10 + 5% propylene glycol + 1% limonene

3.9 + 2.1

5.8 +

3.7

5.9 + 4.1

1% spice 10 + 5% propylene glycol + 1% TÌO2;

2.4 + 0.6

3.9 +

1.8

-

pH 5.1

2.7 + 0.9

3.7 +

1.6

-

Experiment XVIII

-

0.9% spice 10

3.9 + 1.7

6.4 +

4.0

6.5 + 4.7

0.9% spice 10 in example 9

3.3 + 1.1

4.7 +

2.3

4.5 + 2.7

Experiment XIX

0.9% spice in Ex. 9 + 1% TÌO2

2.8 + 0.7

2.7-

0

-

Tables 4 to 7, inclusive, relate to formulations containing various cinnamaldehyde and citral-containing flavors that yellow with aging, and the reduction in yellowing by adding limonene and other terpenes and sesquiterpenes, which are characterized by trisubstituted double bonds. Adjusting the pH to about 6 and adding TÌO2 further reduces the yellowing of these flavor-containing formulations.

It is noted that the above detailed description is for illustration only and that variations are possible within the scope of the invention. The above "summary" is for the convenience of technical researchers only and is of no importance in the scope of the invention.

35

40

45

50

60

65

S

1 sheet of drawings

Claims (26)

668359 PATENT CLAIMS 1. A dentifrice composition with increased stability against discoloration during aging, characterized in that it contains an aldehyde flavoring discolored from aging from cinnamaldehyde and citral and as a discoloration inhibitor (1) contains terpene or sesquiterpene containing at least one trisubstituted double bond , 1 to 5% by weight, or (2) propylene glycol, dipropylene glycol or a mixture thereof in a dental vehicle suitable for dentifrices, which is free from oxidizing agents and has a pH below 8.5. 2. Dental care product according to claim 1, characterized in that the discoloration inhibitor is at least one terpene or sesquiterpene. 3. Dentifrice according to claim 2, characterized in that the discoloration inhibitor is selected from limonene, oci-men, caryophylls and clove quiterpenes, myrcene, their terpene derivatives and mixtures thereof or from essential oils rich in these. 4. Dental care product according to claim 1, characterized in that the discoloration inhibitor is propylene glycol, dipropylene glycol or a mixture thereof. 5. Dentifrice according to claim 1, characterized in that the flavor O! makes up 1% by weight of the composition. 6. Dentifrice according to claim 2, characterized in that the weight ratio of the aldehyde flavor to the terpene is 1: 1. 7. Dentifrice according to claim 4, characterized in that the discoloration inhibitor makes up 10 to 45% by weight of the composition. 8. Dental care product according to claim 4, characterized in that the dental base material suitable for the dental care product is an anhydrous toothpaste. 9. Dentifrice according to claim 4, characterized in that the dental base material suitable for the dentifrice is a water-containing toothpaste. 10. Dental care product according to claim 1, characterized in that the dental vehicle suitable for the dental care product has a pH of 5 to 7.5. 11. Dental care product according to claim 10, characterized in that it contains a white, color-stabilized toothpaste as the dental base material. 12. Dental care product according to claim 11, characterized in that it additionally contains 0.5 to 1% by weight of titanium dioxide. 13. Dentifrice according to claim 10, characterized in that the dentifrice is a white, color-stabilized mouthwash. 14. Dental care product according to claim 2, characterized in that it is in the form of a white-colored toothpaste and contains 1% by weight of cinnamaldehyde flavor and 1% by weight of lime color stabilizer. 15. Dental care product according to claim 2, characterized in that it comprises a white toothpaste and contains 1% by weight of cinnamaldehyde flavor and 1% by weight of ocimen color stabilizer. 16. Dental care composition according to claim 2, characterized in that it is in the form of a white toothpaste and contains 1% by weight of cinnamaldehyde flavor and 1% by weight of caryophyllene color stabilizer. 17. Dental care product according to claim 2, characterized in that it is present as a white-colored toothpaste and Contains 1% by weight of cinnamaldehyde flavor and 1% by weight of citro-nelly acetate color stabilizer. 18. Dentifrice according to claim 2, characterized in that it is in the form of a white toothpaste and contains 1% by weight citral flavor and 1% by weight lime color stabilizer. 19. Dentifrice according to claim 2, characterized in that it is in the form of a white toothpaste and contains 1% by weight cinnamaldehyde flavor, 1% by weight lime color stabilizer and additionally 0.5 to 1% by weight titanium dioxide. 20. Dentifrice according to claim 13, characterized in that it contains 0.1 to 0.5% by weight of a flavor Contains io substance composition that has cinnamaldehyde or citral. 21. Dental care product according to claim 2, characterized in that it is in the form of a white toothpaste and contains 0.1 to 1% by weight of a cinnamaldehyde or citral. i5 tendency flavor composition and additionally contains 0.5 to 1 wt.% Titanium dioxide. 22. Dental care product according to claim 1, characterized in that it is present as a toothpaste that 20 to Contains 75% by weight of a water-insoluble polishing agent. 23 23. Dentifrice according to claim 1, characterized in that it contains 0.05 to 5% surfactant. 24. Dental care product according to claim 1, characterized in that it is in the form of a toothpaste which has a liquid content of 20 to 75% by weight of the composition. 25 points. 25. Dentifrice according to claim 1, characterized in that it is in the form of a mouthwash which has a liquid content of 90 to 98% by weight of the composition. 26. Dental care composition according to claim 4, characterized in that it is in the form of a white toothpaste and contains 1% by weight of cinnamon aldehyde flavor, 22% by weight of propylene glycol as an anti-discoloration compound and additionally 0.5 to 1% by weight of titanium dioxide. 35 27. Dentifrice according to claim 4, characterized in that it is in the form of a white toothpaste and contains 1% by weight of cinnamaldehyde flavor, 35% by weight of dipropylene glycol as an anti-discoloration and additionally 0.5 to 1% by weight of titanium dioxide. 40 28. Dental care product according to claim 8, characterized in that it contains 1% by weight of cinnamaldehyde flavor and 43% by weight of propylene glycol. 29. Dentifrice according to claim 8, characterized in that it contains 1% cinnamaldehyde flavor, 22% Contains 45 propylene glycol and 1% titanium dioxide. 30. Dental care product according to claim 13, characterized in that it is anhydrous and contains 10 to 15% propylene glycol and 0.1 to 0.5% cinnamaldehyde. 50