NL8500359A - STABILIZING CINNAMONALDEHYDE-CONTAINING FLAVORS WITH TERPENES AND SESQUITERPENES AND PROPYLENE GLYCOL AND DIPROPYLENE GLYCOL IN THE USE THEREOF IN TENTICLE COMPOSITIONS. - Google Patents

Description

VO 7024

Stabilizing cinnamon aldehyde-containing flavors with terpenes and sesquiterpenes and propylene glycol and dipropylene glycol when used in dentifrice compositions.

This invention relates to a dentifrice composition, the color of which is stabilized, and which contains a cinnamaldehyde or citral based flavor discolored / discolored upon aging, and a terpene or sesquiterpene with a triple substituted double bond or propylene glycol or dipropylene glycol, which significantly reduces and / or prevents discoloration, and wherein the pH of said composition is kept below 8.5 and preferably at a neutral or acidic pH. The dentifrice can be water-based or anhydrous. The dentifrice must be free of oxidizing agents, such as hydrogen peroxide or salts, which release hydrogen peroxide, such as sodium perborate, peracids and salts of peracids.

The prior art is full of dentif formulations containing the combination of a cinnamic aldehyde or citral based flavoring agent and a terpene, as shown in U.S. Pat. Nos. 3,867,557 and 3,928,560, which disclose oral compositions containing 0.0001 - 20% paramethoxy-cinnamic aldehyde as a flavoring agent, the flavoring being dissolved in 100 parts of orange oil (example VII), and 4% of the cinnamic aldehyde being 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. U.S. Patent No. 4,001,438 also discloses flavoring formulations containing citral and orange terpenes (Example B in column 10), which formulations are for use in oral compositions. However, this group of patents does not recognize the problem of discoloration or yellowing associated with the use of the cinnamaldehyde as a flavoring agent. These patents relate to other aspects of dentifrice formulations. The description of the combination of a cinnamaldehyde based flavoring agent and a terpene is an addition to a general discussion of flavoring agents.

Also, the prior art is full of dentifrice formulations 8500359 2 containing a combination of a cinnamaldehyde or central based flavoring agent and propylene glycol or dipropylene glycol, as also shown in the aforementioned U.S. Patents 3,867,557 and 3,928 .560, which discloses oral compositions containing 5,0001-20% paramethoxy-cinnamaldehyde as a flavoring agent, which is dissolved in 100 parts of propylene glycol; in addition, U.S. Patent 4,132,771 and U.S. Patent 4,187,287, which discloses a two-flavored "tone" dentifrice containing cinnamon flavor, contained in a propylene glycol-based medium. U.S. Patent No. 4,242,323, which discloses an oral composition for inhibiting plaque, which composition contains cinnamon oil as a flavoring agent and also uses propylene glycol as the liquid medium; and U.S. Patent 3,864,472, which relates to a lemon flavored clear mouthwash containing citron oil, cinnamaldehyde and glycerol or propylene glycol. US Pat. No. 4,001,438 also discloses flavoring formulations containing citral and / or cinnamaldehyde as a component in a composition which physically traps flavor and which is mixed with an unclosed flavor oil, a suspending agent and preferably a small amount (0.5%) of propylene glycol, which improves product stability (column 6, lines 32 - 33), which formulations can be used in oral compositions. However, this group of patents does not recognize the aging-related discoloration or yellowing problem associated with the use of cinnamaldehyde as the flavoring agent. These patents relate to other aspects of dentifrice formulations. The description of the combination of a cinnamaldehyde based flavoring agent and propylene glycol is incidental to a general discussion of flavors and typical humectants.

Furthermore, the prior art has also recognized the fading and / or deterioration of flavors or dyes, such as is shown in U.S. Patent 3,666,496, according to which patent patents terpene-containing flavors, such as orange oil, to prevent of the deterioration of the flavoring poly (oxyethylene) poly (oxypropylene) copolymer to be used in flavored foods or drinks is added. According to U.S. Patent 4,305,928, 8,500,359 s 3 0.05 - 5% phytic acid and / or benzoic acid is added as a chelating agent to prevent color fading of visually clear dentifrice stained with red or yellow monazo or blue triarylmethylene dye, or to decrease. U.S. Patent 3,957,964 discloses a dentifrice containing encapsulated flavor, including cinnamon or orange oil, and which flavor is kept separate from the dentifrice (which may also contain propylene glycol) during storage until they are released when the dentifrice is used, thereby providing a more stable and fresher flavored dentifrice. However, the aforementioned patents do not mention the stabilization of the cinnamaldehyde or citral flavoring using a specific group of terpenes or sesqui terpenes, which are characterized by a trisubstituted double bond, or using propylene glycol or dipropylene glycol .

According to U.S. Patent 2,184,526, instability to air oxidation of p-isopropyl-α-methylhydro-cinnamaldehyde as a fragrance ingredient is also recognized, whereby the aldehyde is converted to the corresponding acid while destroying the aldehyde odor. The addition of alcohols of the aromatic series or terpene series stabilizes the aldehyde against air oxidation by converting the aldehyde into a hemi-acetal of said alcohol.

U.S. Patent 3,671,630 discloses the use of a variety of classes of terpenes as color stabilizers for aqueous germicidal compositions based on halogenated phenols, which discolor compositions within hours of exposure to light. However, many terpenes, such as limonene, have been reported to be ineffective. The germicidal compounds based on halogenated phenols cannot be equated with the flavors based on cinnamaldehyde or citral, which are unsaturated aldehydes.

In addition, it is stated that limonene, one of the terpenes, which are specifically used as a color stabilizer for the flavoring agent, is specifically excluded as being unworkable in stabilizing the germicidal composition.

The prior art cited above does not disclose the use of a specific group of terpenes or sesquiterpenes in a dentifrice that is free of oxidizing agents and maintained at an acidic or neutral pH and further contains cinnamic aldehyde or citral as a flavoring agent for the purpose of reducing discoloration of said flavoring agent upon aging.

Surprisingly, it has been found that the aging discoloration of dentifrice products flavored with cinnam aldehyde or citral can be reduced and / or prevented by the addition of (1) a trisubstituted double bond characterized terpene or sesquiterpene, which may be selected from the group of limonene and essential oils, which are rich in limonene, oci-10 meen, caryophyllene and clove sesquiterpenes, myrcene, derivatives of said terpenes and mixtures thereof or (2) propylene glycol or dipropylene glycol or mixtures thereof . It is essential that the dental medium be free of oxidizing agents and kept at an acidic to neutral pH for said terpenes and sesqui terpenes to function effectively.

Accordingly, the main object of this invention is to provide dentifrice formulations containing a cinnamaldehyde or citral flavoring that does not turn yellow or discolour with age.

Another object of this invention is to provide a dental cream or mouthwash, the color of which is stabilized and which contains cinnamic aldehyde or citral as a flavoring, as well as an effective amount of a color stabilizer, which is characterized by (1) triple substituted double bonds, selected from the group of limonene and essential oils, which are rich in limonene, ocimene, caryophyllene and clove sesquiterpenes, myrcene and terpene derivatives thereof, or in that (2) the stabilizer is propylene glycol or dipropylene glycol or a mixture thereof is.

Yet another object of this invention is to provide a dentifrice containing cinnamic aldehyde or citral, the color of which has been stabilized and which is maintained at a pH below 8.5 and preferably at a neutral or acidic pH.

Another object of this invention is to provide an acidic or neutral dentifrice which is free from oxidizing agents and contains as flavoring an aldehyde, the color of which has stabilized.

• 8500359 5

Yet another object of this invention is to provide a white dental cream or mouthwash, the color of which is stabilized and which contains cinnamon aldehyde or citral as a flavoring.

Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following, or may be known by the practice of the invention. The objects and advantages of the invention can be realized and achieved by means of the auxiliaries and combinations indicated in particular in the appended claims.

To achieve the aforementioned and other objects of the present invention, as embodied and broadly described herein, the novel dentifrice of this invention, which has improved stability against aging discoloration, contains a flavoring agent containing an unsaturated aldehyde and is selected from the group of cinnamaldehyde and citral, which is subject to aging discoloration, and about 0.1-5% by weight of (1) a color stabilizer based on terpene or sesquiterpene, which is characterized by triple substituted double bonds and which is preferably selected from the group of limonene and essential oils rich in limonene, ocimene, caryophyllene and clove sequiteres, myrcene, terpene derivatives thereof and mixtures thereof or (2) propylene glycol, dipropylene glycol and mixtures thereof, in a dental medium, free of oxidizing agents and at a pH below 8.5 and preferably at a and maintained at an acidic to neutral pH of about 5-7.5.

More particularly, this invention relates to a white dental cream or mouthwash, the color of which is stabilized and free of oxidizing agents and which has an acidic to neutral pH and about 0.1-1% by weight of cinnamaldehyde or citral as a flavoring agent and (1) one or more terpenes or sesquiterpenes with triply substituted double bonds or (2) propylene glycol or dipropylene glycol as the discoloration inhibitor, preferably in a 1: 1 ratio.

It was found that the cinnamic aldehyde or citral flavoring decomposed upon aging to form deconjugated unsaturated aldehydes (dienes). These servants are responsible

mm Λ Λ ^ Γ A

6 verbatim for, the yellowing or discoloration, which is visible with cinnamaldehyde or citral in white dental products, including liquids or Creams (pastes).

In commercially available dental creams, in which low levels of cinnamaldehyde have been used, the discoloration problem is to deal with by coloring the product, for example, red, blue, light green, etc. In white dental creams, however, the discoloration results from a low cinnamaldehyde level. , unacceptable.

Coxic aldehyde (KA) autooxidation proceeds according to the attached mechanism.

Even when samples are stored in tightly sealed bottles with the headspace purged with nitrogen, the acid is formed. Cinnamaldehyde is very sensitive to small amounts of oxygen. Since cinnamic acid is white, its formation, which occurs within a short time after exposure, is not responsible for the yellowing of cinnamic aldehyde. The intensity of the yellow color increases with the oxygen exposure time rather than with the amount of oxygen, indicating that more complex oxidation occurs during aging. More particularly, the formation of conjugated dienals provides the intensely yellow components responsible for the discoloration and yellowing of the cinnamaldehyde.

It has now been found that discoloration at low cinnamaldehyde levels (a maximum of about 1 wt%) is reduced when certain terpenes or sesquiterpenes with three-Z-substituted double bonds are included in the dentifrice composition, preferably in a weight ratio of 1: 1. The terpenes include limonene (formula 1), ocimene (formula 2), caryophyllene (formula 3), myrcene (4), terpene derivatives such as citronellyl acetate (formula 5) and mixtures thereof.

At 1: 1 cinnamic aldehyde ratios, when aging in a glass bottle, each of the aforementioned terpene representatives individually effected a significant reduction in cinnamon aldehyde discoloration. These compounds also reduced yellowing in white tame cream upon aging, as shown in Table 1A, which produces a 40% yellowing reduction. Natural products containing these compounds may be used, such as essential oils, which are rich in limonene and include citrus oils such as orange, grapefruit, tangerine and mandarin oils. Clove sesquiterpenes are also effective color stabilizers.

The yellowing of dental cream was measured instrumentally with the Colorgard reflectometer. The data listed in the following tables are + Ab values (yellow scale) and represent the increase in yellow color over unflavored and unaged aging cream taken as a zero-b control . Readings taken at 3 weeks, 6 weeks and 9 weeks at 49 ° C are thought to be approximately equal to those at 1 year, 2 years and 3 years at ambient temperature. Approximately, an Ab value of 2 to 3 is the region of marginal acceptability, since an Ab of 2 is visually light off-white and an Ab of 4 corresponds to a light tan color.

15 TABLE 1

Cinnamaldehyde discoloration in dental cream (Example I) A. Influence of chemical compounds with triply substituted double bonds

Aging at 49 ° C; db values 20 3 weeks 6 weeks 9 weeks 1.0% cinnamaldehyde (KA) 4.5 7.5 8.0 1.0% KA + 1.0% limonene 2.9 4.9 5.8 1.0 % KA + 1.0% ocimene 2.5 5.4 5.9 1.0% KA + 1.0% caryophyllene 3.2 5.3 6.0 25 1.0% KA + 1.0% citronelly acetate 3 , 6 4.2 5.4

B. Influence of the pH

1.0% KA pH 5.0 (citric acid) 4.25 5.5 5.1 1.0% KA pH 6.9 to 7.1 (Example I). 4.5 7.5 8.0 1.0% KA pH 8.5 (NhHC03) 7.5 10.5 11.2 30 The reduction is improved with increasing amount of terpene, as shown for limonene in the accompanying graph (figure 2).

Although limonene is a mild flavor (orangey), higher levels than 1% would be impractical and may be undesirable because the orange flavor could change the original cinnamon flavor.

The autoxidation of cinnamaldehyde is inhibited (interrupted) by the presence of this group of terpenes and sesqui-5 terpenes. Formation of epoxy-cinnamaldehyde is prevented when limonene is added to cinnamaldehyde. Preventing the formation of this epoxide also prevents the formation of the later dienalen. Analytical studies have shown that the limonene reacts preferentially with cinnamic acid over cinnamaldehyde to form 1,2-epoxy-limonene. The other terpenes (of formulas 2, 3, 4 and 5) are believed to form similar epoxides by virtue of the trisubstituted double bond. Trisubstituted double bonds are known to have greater reactivity to peracids than mono- or disubstituted double bonds.

Furthermore, cinnamaldehyde would be expected to have a lower reactivity to electrophilic attack of peracids because its double bond is substituted with an electron-withdrawing aldehyde group. Thus, by preventing the formation of the dienals, limonene significantly reduces yellowing. Other terpenes, such as eugenol, are ineffective in reducing yellowing.

The cinnamon aldehyde discoloration agent also applies to other conjugated unsaturated aldehydes, such as citral, (CH 2) (CH 3) = CHCHO. Citral is another flavoring agent commonly used in dentifrice compositions.

Yellowing of a liquid mixture of cinnamaldehyde or citral with a terpene addition was measured with the Gardner tintometer both when the mixture was freshly prepared and after aging at 90 ° C ± 2 ° for 24 hours. 10 g samples of flavoring and limonene mixtures were prepared and the following readings were reported.

_Tintometer_

Cinnamaldehyde (%) Limonene (%) Fresh Aged 95 5 4i 7 35 90 10 4 * 6 3/4 75 25 4i 5 100 0 (a) 4 * (a) 8 50 50 ia) 3 3/4 (a) 4 $ 9

Note to table ·; · (Continued) ^ Average of 2 readings • Tintometer_

Citral (%) - Ljmonene (%). Fresh Outdated 5 100 0 ö>)! 1/3 (b) 3 2/3 0 100 (b) 1 50 50 (b) l (b) 2 / h \ v Average of 3 readings

In addition, the citral alone and the 50:50 mixture of citral and limonene were aged for: 4 days 6 days 11 days citral alone (b) 7 (b) 7 * / 3 (b) 9 2/3 citral: limonene ( 50:50) ^ 4 ^ 4 * / 3 ^ 5

The pH of the dental cream is either acidic or only slightly alkaline, preferably the pH is about 5-7.5, as shown in Table 1B. in moderate alkaline environment, the terpenes are ineffective at reducing yellowing. At a pH of 8.5 or above the peracid anion is formed, while Michael addition proceeds epoxidation of cinnamaldehyde. This type of addition reaction cannot be intercepted by limonene.

It has also been found to reduce discoloration resulting from low levels of cinnamon aldehyde (a maximum of about 1% by weight) in the presence of propylene glycol and / or dipropylene glycol. These materials are effective with cinnamon aldehyde in a 1: 1 weight ratio in preventing nearly all yellowing when aging in glass. In dental cream, however, at levels of 1-5%, they showed only a slight reduction in yellowing, resulting from 1% cinnamaldehyde. Since these glycols are odorless, it is practical to absorb them in larger quantities. The replacement of water or glycerol in dental formulations with propylene glycol or dipropylene glycol is effective in preventing the yellowing of flavors containing cinnamaldehyde or citral. When a non-aqueous paste is formulated by replacing the water with any of the glycols, no discoloration is observed. Also, by replacing the 22% glycerol with propylene glycol in a dental cream, 8500359 10, yellowing is significantly reduced.

The mechanism of the glycol effect is believed to involve acetal and hemiacetal formation / complexation.

5. The glycols are believed to be effective by complexing the aldehydes via acetal formation. Since aldehydes are involved in four different phases of the dienal formation mechanism (Fig. 1), the reaction with glycol will significantly interfere with dienal formation. Analysis of the aged cinnamaldehyde / propylene glycol (1:; 1) sample showed significant language formation with the formation of a little hemi-acetal. This reversible reaction has the problem that the cinnamaldehyde is consumed a little less. In practice, the amount of cinnamaldehyde may need to be increased to make up for this loss.

The autoxidation of cinnamaldehyde is inhibited (interrupted) by the presence of propylene glycol due to the formation of glycol acetals, which takes place rapidly at ambient temperature and the amount of which increases with time. This prevents the formation of the dienals, which are responsible for the yellowing upon aging.

This cinnamon aldehyde reduction agent also applies to other conjugated unsaturated aldehydes, such as citral, (CHi) = CHCHO. Citral is another flavoring agent commonly used in dentifrice compositions. Yellowing of a liquid mixture of cinnamic aldehyde with propylene glycol or dipropylene glycol was measured with the Gardner tintometer both when the mixture was freshly prepared and after aging in a vial at 90 ° C for 24 hours (I) and also after 48 hours was aged at 50 ° C (II), and oxygen was initially passed over the samples for 5 seconds. The samples were prepared from mixtures of cinnamaldehyde and said glycole, cinnamaldehyde and glycerol and cinnamaldehyde as such, reporting the following readings: 8500359 11 I Tintometer

Freshly Outdated

Cinnamaldehyde (KA) 4 11 50/50 KA + glycerol 3; 4 'v / 11 ^ ^ 5 50/50 KA + propylene glycol 3 7, 7 = 7 50/50 KA + dipropylene glycol 3 10; 8; 9 = 9

II

Cinnamaldehyde 4.5 7 50/50 KA / propylene glycol 3.5 4.5 ^ Glycerol and KA formed two layers. The glycerol layer (bottom) remained. water-white, while the top layer of KA darkened.

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

It is essential that the pH of the dental cream is either acidic or neutral, preferably has a pH of about 5 - 7.5 as shown in Table 2. At a pH of 8.5 or higher, the peracid anion is formed and the epoxidation of cinnamaldehyde proceeds by Michael addition. This type of addition reaction cannot be intercepted by propylene glycol 20.

Yellowing of dental cream was measured instrumentally with the Colorgard reflectometer. The data reported in the following tables are + Ab values (yellow scale) and represent the increase in yellow over unflavored and unaged dental cream, taken as a zero-b control. The readings at 3, 6 and 9 weeks at 49 ° C are thought to approximately correspond to aging at 1 year, 2 years and 3 years at ambient temperature. A Δ b value of 2 to 3 roughly corresponds to the range of marginal acceptability, since a Δ b of 2 is visually slightly off-white, while a 30 Δ b of 4 means a light yellow-brown color.

8500359 12 TABLE 2

Cinnamaldehyde discoloration in dental cream (Example I)

Influence of the pH

Aging at 49 ° C = db values 5 3 weeks 6 weeks 9 weeks 1% KA pH 5.0 (citric acid) 4.25 5.5 5.1 1% KA pH 6.9 to 7.1 4.5 5 .5 8.0 1% KA pH 8.5 (Nè £ E03) 7.5 10.5 11.2

It is also essential that the dentifrice is free from oxidizing agents, such as hydrogen peroxide or salts, which release hydrogen peroxide, such as sodium perborate, peracids and peracid salts. The presence of said oxidizing agents would interfere with the preferentially progressive reaction of the terpene with the perkinic acid to form the 1,2-epoxylimonene, as well as the preferential reaction of the glycol with cinnamaldehyde to form the glycol acetals. As discussed with respect to the necessity of maintaining an acidic to neutral pH in the dental medium, the presence of the peracid anion triggers epoxidation of cinnamaldehyde by Michael addition.

Experiments with several dental bases showed that cinnamon aldehyde discoloration according to example II was about half that of example 1. Also discoloration in a hydrogen carbonate base gave a very intensive yellow color. These differences were found to be due to pH differences and also the presence of TiO2 as shown in the table below: pH TiO2

Example I 6.9 to 7.1.0

Example II 6.15 0.5%

By lowering the pH in Example I through the addition of either citric acid or phosphoric acid, the yellowing was reduced (Table 1B). Increasing the pH to 8.5 by the addition of NaHCO 2 significantly increased the yellowing. It should be noted that the addition of limonene had no effect on the reduction of the yellowing in the NaHCO2 base (pH 8/5).

- · ”Λ Λ T r A

13

These observations are compatible with the largely indicated auto-oxidation mechanism. The peracid anion is formed at a pH of 8.5, while epoxidation proceeds more quickly by Michael addition. Limonene and other terpenes and sesguiterpenes with a trisubstituted olefin structure are not reactive with respect to nucleophilic addition and thus cannot clear the peroxide anion. Peroxides are considerably weaker than the corresponding carboxylic acid. The pKa of perkinic acid is estimated at 7.5. In a neutral base, both free acid and anion would be present. Lowering the pH would prevent the reactions that would occur as a result of the anion addition.

As noted with respect to the comparison of Example I with Example II, the presence of TiO2 provides a yellowing reduction both visually and instrumentally. Based on a number of comparisons with and without TiO ^, a Δ b reduction of 1.0 with 1% Ti * ^ and a Δ b reduction of 0.5 with 0.5% T1O2 is observed.

An optional additive that may contribute to the reduction of cinnamaldehyde yellowing in dental formulations is titanium dioxide (TiCl 2) in small amounts of about 0.5-1 wt%. Table III shows the effectiveness of limonene and of propylene glycol in reducing yellowing in dental creams containing various cinnamaldehyde-containing flavors in the presence and absence of TiO2.

25 TABLE 3

Flavor discoloration in dental cream (Example I)

Flavoring

Cinnamaldehyde (KA) 3 weeks 6 weeks 9 weeks 1% KA 4.5 7.5 8.0 30 1% KA + 1% limonene + 0.5%

TiO2; pH 5.6 2.4 2.9 4.5

Spice 10 (S'10) * ^ 1% S 10 3.0 4.2 4.6 1% S 10 + 1% limonene + 0.5% TiC ^ 1.9 2.3 2.6 35 Spice 12 ( 12 S) 2) 1 week 0.8% 12S 1 2.7 4.0 4.6 0.8% 12S + 0.1% limonene 1 2.1 3.2 .3.9 oRnnufl 2) 14 TABLE 3 (Continuation)

Spice 12 (12S) 1 week 3 weeks. 6 weeks 9 weeks 0.8% 12S + 0.1% lumen + 1% TiO 2 - 1.1 2.3 2.6 0.8% 12S + 0.5% lumen 5 + 1% TiO 2 - 0.7 2.0 2.5 0.8% 12S + 0.25% lx-monene 0.9 2.0 3.0 3.5 0.8% 12S + 0.5% TiO2 - 1.5 2 , 9 3.1 0.8% 12S + 0.1% Limene + 0.5% TiO 2 - 1.5 - 2.8 0.8% 12S + 0.1% Limene + 0.5% TiO2; pH 5.2 (citric acid) - 3.1 - 4.0 0.8% 12S + 0.25% limene + 0.5% TiO 2 - 1.5 - - 0.8% 12S + 0.25 % limonene + 1% TiO2 - 1.0 1% KA + 35% dipropylene glycol or propylene-2Q glycol + 64% dicalcium phosphate dihydrate 0.2 - -

Spice 10 (S10) '1) 1% S10 3.0 4.2 4.6 1% S10 (glycerol replaced by propylene glycol) 2.3 2.7 1% S10 (glycerol replaced by propylene glycol) + 1% TiO2 0 , 7 - -

Flavor "Spice 10" contains 55% cinnamaldehyde.

2)

Flavor "Spice 12" contains 15% cinnamaldehyde.

30 Other flavoring compositions containing cinnamic aldehyde include:

White Spice 1, which contains 20% cinnamon aldehyde,

White Spice-2, which contains 25% cinnamon aldehyde,

Flavoring Spice 11, which contains 55% cinnamon aldehyde.

The cinnamon aldehyde flavoring compositions can be supplemented up to 100% with flavoring components such as menthol, eugenol, peppermint, deer mint, cloves, anethole, methyl salicylate, vanillin and the like in various mixtures. Menthol and eugenol are not involved in the yellowing of the dental formulations.

By mixing cinnamic aldehyde with limonene or terminal terpenes, incorporating TiO4 and lowering the pH, high levels of cinnamic aldehyde may be acceptable.

By mixing cinnamon aldehyde with propylene glycol or dipropylene glycol, incorporating TiO2 and lowering the pH, high levels of cinnamon aldehyde may also be acceptable. This can be easily accomplished by replacing the glycerol or water with propylene glycol in the dentifrice formulation.

The flavors with cinnamic aldehyde, generally in an amount of at least about 5% of the full flavor, such as Spice 10 or Spice 12, discolour in a white dental cream. If the dental cream is colored green, yellowing is not visually apparent.

The Spice 10 as a flavoring reduced the addition of 1% limonene and 0.5% TiO2 discoloration to a marginally acceptable range. This addition modifies the original flavor, but may be useful in creating similar flavors. In this case, the use of 1% TiO2 and the use of caryophyllene (one spice flavor) with limonene may be preferable.

The Spice 12 as a flavoring agent is the degree of yellowing higher than that expected on the basis of the cauial aldehyde content of 15%. Interactions due to other components contribute to the discoloration. If this flavor is required for a white paste, the addition of only 0.1% limonene and 1% TiO 2 would produce significant color improvements and only a slight change in taste.

The dental base used in the present invention may be in the form of a paste, cream or liquid mouthwash incorporating known ingredients commonly employed in the dentifrice art.

Dentifrices in the form of paste or cream may be based on aqueous or substantially non-aqueous systems.

The former will usually include significant amounts of finely divided solid polishing agent, surfactant, gelling agent, water and some non-aqueous medium, for example, glyce 8500359

roll, sorbitol, and are opaque, while those of the latter I

said type are often in the form of a clear gel or opaque

are visual and a small amount of a visually clear, from very I.

small individual solid particles existing polishing agent, a larger I.

5 amount of a non-aqueous medium containing at least 10% of the I.

formulation to propylene glycol or dipropylene glycol alone or mixed I.

with other non-aqueous liquid media, such as sorbitol or glycerol, I.

a surfactant and a gelling agent, wherein I

a small amount of water is usually present.

The surfactant, or detergent, present in the dentifrice can sometimes be cationic or amphoteric, but usually it will be anionic or nonionic. Of these compounds, the anionic representatives are most preferred. The anionic detergents or surfactants usually also serve as foaming agents. Among the suitable anionic detergents may be mentioned: the higher fatty acid monoglyceride monosulfates, such as the sodium 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 the sodium salt of linear dodecyl-20 benzenesulfonic acid; higher olefin sulfonates, such as the sodium salt, a higher olefin sulfonic acid in which the olefin group contains from 12 to 21 carbon atoms, high alkyl potassium sulfoacetates; high fatty acid esters of 1,2-dihydroxypropane sulfonates, magnesium salt; the substantially saturated high aliphatic acylamides of low aliphatic aminocarboxylic acid alkali metal salts, such as those having 12 to 16 carbon atoms in the fatty acyl radicals, high alkyl poly low alkoxy (with 10 to 100 alkoxy growth pon sodium sulfates; high fatty acid sodium and potassium soaps and coconut oil and tallow, and the like. As noted, the detergents are very often sulfated or sulfonated compounds. Examples of useful suitable anionic amides are N-lauroyl sarcosine and the sodium, potassium and ethanolamine salts of N-lauroyl, N-myristoyl and N-palmitoyl sarcosines. In the above descriptions, the term "high" refers to chain lengths of 12 to 22 carbon atoms, preferably 12 to 18 carbon atoms, especially 12 to 16 carbon-35 atoms. "Low" means 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, especially 2 carbon atoms.

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17

The nonionic detergents include those containing chains of lower alkylene oxide, for example ethylene oxide, propylene oxide, which are present in an amount of 10 to 100 or more moles of lower alkylene oxide. Such materials include the 5 block copolymers of ethylene oxide, propylene oxide and propylene glycol, which are commercially available as Pluronics®. the alkyl-phenyl-polyetho-ethanols, which are commercially available as lepals; mixed copolymers of ethylene oxide and propylene oxide available commercially as Ucons; and several other known nonionic compounds derived from fatty alcohols or acids and polyethylene oxide. The amphoteric or ampholytic agents include long (alkyl) chain amido-alkylene-alkylated amine derivatives, such as "Miranols," for example, Miranol C1M; and cationic germicidal detergents, such as diisobutyl-phenoxyethoxyethyl-dimethyl-benzyl-ammonium chloride; benzyl-15 dimethyl stearyl ammonium chloride; and tertiary amines with a high fatty alkyl group and two polyoxyethylene groups bonded to its nitrogen atom.

The detergents make up about 0.5-5% and preferably up to 3% by weight of the dentifrice composition.

Toothpastes, dental creams and tooth powders usually contain polishes or abrasives which are substantially water insoluble and compatible with the formulation in amounts of about 20-75% by weight of the total cream or paste formulation and up to 95 % in dental powders. Suitable polishes include anhydrous dicalcium phosphate, dicalcium phosphate dihydrate, tricalcium phosphate, insoluble sodium metaphosphate, crystalline silicon dioxide, colloidal silicon dioxide, complex aluminum silicates, aluminum hydroxide or hydroxide hydroxide (including magnesium hydroxide) magnesium carbonate, calcium carbonate, calcium pyrophosphate, bentonite, talc, calcium silicate, calcium aluminate, aluminum oxide, aluminum silicate and silica-based xerogels. Most of the aforementioned polishes are very useful in the preparation of opaque dentifrices, but some of them, such as the colloidal silicon dioxide, in particular the silica-based zerogels, and complex sodium-aluminum silicates, can be used in the manufacture of clear dentifrices used at 85 0 0 3.59 18 trough: their refractive indices are approximately equal to those of the rest of the dentifrice components in an appropriate medium.

In dental cream or toothpaste-dentifrice formulations, the liquids and solids must necessarily be present in such amounts that a creamy mass of desired consistency is formed, which can be extruded, for example, from a collapsible aluminum tube. Generally, the liquids contained in the dental cream will mainly comprise water, glycerol, sorbitol, polyethylene glycol or propylene glycol 400, including suitable mixtures thereof. It is usually advantageous to use a mixture of both water and a wetting agent, such as glycerol, or sorbitol or mixtures thereof. The total liquid content will generally be about 20-75% by weight of the formulation. Preferably, a gelling agent is also used in the dental creams, such as the natural and synthetic gum-like materials, for example Irish moss, tragacanth, sodium carboxymethyl cellulose, polyvinylpyrrolidone or starch. Irish moss and sodium carboxymethyl cellulose are particularly compatible and are the preferred gelling agents. The gum content usually corresponds to an amount of up to about 10% by weight and preferably about 3-5% by weight of the formulation. Fillers such as fumed silica and silica airgel can also be used, usually in amounts of up to about 10% by weight to supplement the gelling agent. These colloidal silicon dioxide aerogels, including Syloids 244 and 266 and 25 Aerosil, and the pyrogenic silica, which is commercially available as Cab-O-Sil, can be used as a gelling agent and thickener.

The mouthwash liquid madium usually comprises ethyl alcohol, glycerol, sorbitol, water and mixtures thereof, in an amount of about 90-98% by weight of the total liquid content.

Several other substances can also be included in the dental medium. Examples thereof are fluorine-containing compounds, such as stannous fluoride, potassium stannous fluoride (ShP2KP), sodium hexafluorostannate, stannous chlorofluoride, sodium fluorosirconate and sodium monofluorophosphate. These substances, which dissociate in water or release 8500359 19 fluorine-containing ions, may be present in the dental medium in an effective but non-toxic amount, usually within the range of about 0.1-5% by weight. Other additives include preservatives such as sodium benzoate, chlorophyll compounds, silicone, ammonia-derived substances such as urea and diammonium phosphate, antibacterial agents such as benzethonium chloride and other quaternary antibacterial compounds, sweeteners such as sodium saccharin, blue dyes, additional flavors, such as peppermint and deer mint and the like. These additives can be used in amounts that do not adversely affect the properties and characteristics of the dentifrice of the present invention. Each component can be present in minimal amounts from up to a maximum of 5% by weight and preferably at most 1% by weight of the formulation.

The dentifrice of this invention is prepared by conventional methods of making toothpaste, dental creams, mouthwashes and powdered teeth. More particularly, a toothpaste can be prepared by gel forming with carboxymethylcellulose and water, adding thereto the powders and wetting agent, followed by the addition of the polishing agent and then the surfactant and the flavoring , together with the terpene or sesquiterpene color stabilizer, and place the final mixture in a tube. Preferably, the flavoring composition is mixed with the terpene or sesqui terpene color stabilizer before being added to the mixture.

In the practice of this invention, to promote oral hygiene, the dentifrice of this invention is normally applied to the enamel by brushing the teeth for 30 - 90 seconds at least once a day and / or with a rinse mouthwash once a day.

Detailed description of the invention

The following examples serve to illustrate the nature of the present invention, but it will be understood that the invention is not limited thereto. The compositions are prepared in the usual manner and all amounts stated herein and in the appended claims 8500359 are amounts by weight unless otherwise indicated. The flavoring ingredient is a cinnamic aldehyde or citral containing flavoring composition, to which is added a terpene or sesqui terpene (Tables 4 through 7) or propylene glycol or dipropylene glycol (Table 8), as described in the experiments, which follow the examples.

Example I

Dental cream

A B

10 Ingredients _%

Glycerol 22.00 22.0

Sodium monofluorophosphate 0.76 0.8

Sodium carboxymethyl cellulose 1.00 1.0

Tetra sodium pyrophosphate 0.25 0.2 15 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

Flavor 0.84 0.8 20 Sodium lauryl sulfate 1.20 1.2 pH 6.9 - 7.1 6.9 - 7.1

Example II

Tooth cream

A B

25 Ingredients%

Glycerol 10.00, 10.0

Sodium monofluorophosphate 0.76 0.8

Sodium carboxymethyl cellulose 1.10 1.1

Sodium benzoate 0.50 0.5 30 Sodium saccharin 0.20 0.2

Sorbitol (70% solution) 17.00 17.0

Deionized water 22.19 22.2

Titanium dioxide 0.40 0.4

Insoluble sodium metaphosphate 39.35 39.3 35 Hydrated aluminum oxide 1.00 1.0

Anhydrous dicalcium phosphate 5.00 5.0 8500 359 21 (Vevrvol'g) Dental cream

A B

Ingredients% _

Flavor 1.00 1.0 5 Sodium lauryl sulfate 1.50 1.5

6.15 pH

Example III

Ge 1-tooth cream

Ingredients "% _ 10 Deionized water 3.00

Sodium saccharin 0.30

Sodium monofluorophosphate 0.76

Glycerol 25.00

Sodium carboxymethyl cellulose 0.35 15 Sodium benzoate 0.50

Titanium dioxide 0.01

Sorbitol (70% solution) 41.53

Carbowax 600 (PÈG 12) 3.00

Colorant 0.20 20 Sodium aluminum silicate (silicon dioxide containing combined aluminum oxide) 18.00

Airgel of colloidal silicon dioxide 5.50

Flavor 0.65 25 Sodium lauryl sulfate 1.20

Example IV

Toothpaste

Ingredients% _

Glycerol 25.00 30 Sodium carboxymethyl cellulose 1.40

Sodium benzoate 0.50

Sodium saccharin 0.20

Sodium monofluorophosphate 0.76

Deionized water 35.44 35 Titanium dioxide 0.40

Aluminum oxide 10.00 8500359 22 (Continued) Toothpaste

Ingredients% __

Silicon dioxide 24.00

Flavoring 1.10 5 Sodium lauryl sulfate 1.20 pH 6.2 ± 0.5

Example V

. Example IV was repeated, except that the amount of sodium lauryl sulfate was increased to 1.5% and the water content was adjusted accordingly.

Example VI

Mouthwash

Ingredients _%

Ethyl alcohol 15-30 15 Glycerol 10-15

Polysorbate 80 * ^ 2-3

Poloxamer 3382 ^ 0-0.5

Benzethonium chloride 0 - 0.075

Flavor composition 0.1-0.5. Deionized water the remainder. A mixture of oleate esters of sorbitol and sorbital anhydrides consisting of the monoester condensed with about 20 moles of ethylene oxide.

; 2)

The polyoxyethylene-polyoxypropylene block polymer, corresponding to the formula: ho (ch2ch2o) χ (-ch-ch2o) (ch2ch2o) zh, iH3 where x and z = 128 and y - 54.

The flavoring levels in mouthwash are generally lower than in dental cream.

P 5 f) n 7 c Λ 23

Example VII

Tooth powder

A B

Ingredients%% 5 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 10 The flavoring levels in dental powders are generally higher than in dental creams.

Example VIII

Anhydrous dental cream

Ingredients 15 Propylene glycol 43.4 JClucel (Hercules) 1.5

Sodium saccharin 0.2

TiO2 0.4

Dicalcium phosphate dihydrate 50.0 20 Peroxy diphosphate 3.0

Sodium lauryl sulfate 1.5 pH 6.4

Hydroxypropyl cellulose - a propylene glycol ether of cellulose. Example IX-Aqueous dental cream

Ingredients jfc

Propylene glycol 22.0

Sodium monofluorophosphate 0.8

Sodium carboxymethyl cellulose 1.0 30 Tetra sodium pyrophosphate 0.2

Sodium saccharin 0.2

Sodium benzoate 0.5

Dicalcium phosphate dihydrate 48.8

Spice 10 0.9 35 Sodium Lauryl Sulphate 1.2 8500359 24 (Continued) Anhydrous Tooth Cream

Ingredients jfc

TiO2 1.0 H2 O q.s.

The following tables show the discoloration results obtained upon aging of the dental cream according to Example I at 49 ° C, unless otherwise indicated, the dental creams having both no flavoring and cinnamaldehyde (KA) flavoring as such and with specific terpenes or sesqui terpenes containing a triple substituted double bond or used with propylene glycol or dipropylene glycol to prevent or reduce discoloration caused by the cinnamaldehyde ingredient.

The b values in the tables represent the tooth cream yellowing, as measured by the Colorgard reflec-15 tometer, while the Δ b value represents the increase in yellowing over the unaged sample without flavoring, which is used as the zero-b control.

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35

Tables 4 to 7 concern formulations with a variety of flavorings containing cinnamaldehyde and citral, which yellow upon aging, as well as the reduction of said yellowing by the addition of limonene and other terpenes and sesqui terpenes, which characterized by triple substituted double bonds. The adjustment of the pH to about 6 and the addition of Tit ^ further reduce the yellowing of these flavor-containing formulations.

BAD ORIGINAL

8500359

Claims (27)

The dentifrice of claim 1, wherein the discoloration inhibitor is said at least one terpene or sesqui terpene. The dentifrice of claim 1 or 2, wherein the staining inhibitor is selected from the group of limonene and essential oils rich in limonene, ocimene, caryophyllene, and clove sesquiterpenes, myrcene, terpene derivatives thereof, and mixtures thereof. The dentifrice of claim 1, wherein the discoloration inhibitor is said propylene glycol, dipropylene glycol or mixture thereof. A dentifrice according to any one of the preceding claims, wherein said flavor comprises about 0.1-1% by weight of the formulation. The dentifrice of claim 2 or 3, wherein the amount of said aldehyde flavor to terpene corresponds to a weight ratio of 1 s 1. The dentifrice of claim 4, wherein the discoloration inhibitor constitutes about 10-45% by weight of the formulation. The dentifrice of claim 4, wherein the dental medium is an anhydrous dental cream. The dental cream according to claim 4, wherein the dental medium is an aqueous dental cream. The dentifrice of any one of the preceding claims, wherein the dentifrice contains a dental medium, the pH of which is approximately BADOYiM. The dentifrice according to claim 10, wherein the dentifrice is 35 85 0 0 3 59. . J is a white tooth cream, the color of which has stabilized. The dentifrice of claim 11, additionally containing about 0.5-1% by weight of titanium dioxide. The dentifrice of claim 10, wherein the dentifrice 5 is a white mouthwash, the color of which has stabilized. The dentifrice of claim 2, consisting of a white color dental cream containing 1% cinnamaldehyde as a flavoring agent and 1% limonene as a color stabilizer. 15. A dental cream according to claim 2, consisting of a dental cream of a white color and containing 1% cinnamaldehyde as a flavoring agent and 1% ocimene as a color stabilizer. Dental cream according to claim 2, consisting of a dental cream of a white color and containing 1% cinnamaldehyde as a flavoring agent and 1% caryophyllene as a color stabilizer. A dental cream according to claim 2, consisting of a dental cream of a white color and containing 1% cinnamaldehyde as a flavoring agent and 1% citronellyl acetate as a color stabilizer. 1 A dental cream according to claim 2, consisting of a dental cream of a white color and containing 1% citral as a flavoring agent and 1% 20 limonene as a color stabilizer. A dental cream according to claim 2, consisting of a dental cream of a white color and containing 1% cinnamaldehyde as a flavoring agent and 1% limonene as a color stabilizer and additionally about 0.5-1% by weight titanium dioxide. A mouthwash according to claim 13 containing 0.1 to 0.5% by weight of a flavoring composition containing cinnamaldehyde or citral. A dental cream according to claim 2, consisting of a dental cream of a white color and containing 0.1-1 wt.% Of a flavoring composition containing cinnamaldehyde or citral and additionally about 0.5-130 wt.% Titanium dioxide. A dentifrice according to claim 1 in the form of a dental cream containing about 20-75% by weight of a water-insoluble polishing agent. A dentifrice according to claim 1, which contains about 0.05 - 35% surfactant. BAD OHGINAL A dentifrice according to claim 1 in the form of a. . ! dental cream, which contains a liquid content of about 20-75% by weight of the composition. 25. A dentifrice according to claim 1 in the form of a mouthwash containing a liquid content of about 90-98% by weight of the composition. A dental cream according to claim 4f consisting of a dental cream of a white color and containing 1% cinnamaldehyde as a flavoring agent and 22% propylene glycol as a discoloration inhibitor and additionally about 0.5-1% by weight titanium dioxide. A dental cream according to claim 4, consisting of a dental cream of a white color and containing 1% cinnamaldehyde as a flavoring agent and 35% dipropylene glycol as a discoloration inhibitor and additionally about 0.5-1% by weight titanium dioxide. An anhydrous dental cream according to claim 8 containing 1% cinnamon-15 aldehyde as a flavoring and 43% propylene glycol. An anhydrous dental cream according to claim 8, containing 1% cinnamic aldehyde as a flavoring and 22% propylene glycol and 1% titanium dioxide. 30. Mouthwash according to claim 13, which is anhydrous and contains 10-15% propylene glycol and 0.1-0.5% cinnamaldehyde. BATH QFUGIJSAL 8500359