DE3502830A1 - DENTISTRY COMPOSITION - Google Patents

Description

The invention relates to a color-stabilized dentifrice composition, those have a cinnamaldehyde or citral flavor which shows discoloration / yellowing on aging, and one containing trisubstituted double bonds Contains terpene or sesquiterpene or propylene glycol or dipropylene glycol, which significantly reduces discoloration and / or prevented, keeping the pH of the composition below 8.5 and preferably in the neutral or acidic range will. The dentifrice can be aqueous or anhydrous. The dentifrice must be free from oxidizing agents such as Hydrogen peroxide or salts containing hydrogen peroxide release, such as sodium perborate, peracids and peracid salts.

A large number of dentifrice compositions are known in the art known that together have a cinnamaldehyde or citral flavor and a terpene

as shown in U.S. Patents 3,867,557 and 3,928,560, according to those, oral compositions containing 0.0001 to 20% paramethoxycinnamaldehyde flavor in 100 Parts of orange oil are dissolved (Example VII), and 4% of the cinnamaldehyde is dissolved in 500 ml of ethyl alcohol and 10 ml of orange oil (Example XIII). It is known to be essential oils like orange oil contain terpenes. US Pat. No. 4,001,438 also discloses the use of flavor compositions, containing citral and orange terpenes (example B in column 10), in oral compositions. However, there is no indication in this group of patents of the discoloration or yellowing problems associated with the use of the Cinnamaldehyde flavor. These patents relate to other aspects of dentifrice compositions. The combination of a cinnamon aldehyde flavor and a Terpene is mentioned in passing in the general discussion of flavorings.

A large number of dentifrice compositions are known in the art known that contain the combination of a cinnamaldehyde or citral flavor and propylene glycol or dipropylene glycol, as in US Pat

867 557 and 3,928,560, according to which oral compositions-5

Settlements that contain 0.0001 to 20% paramethoxycinnamaldehyde flavor contained, to be dissolved in 100 parts of propylene glycol; U.S. Patent 4,132,771 and U.S. Patent 4,187,287, where describes a two-tone flavored toothpaste containing cinnamon flavor in a propylene glycol carrier; the US PS 4,242,323 which describes an oral anti-plaque composition which also includes propylene glycol as a liquid Carrier is used; and U.S. Patent 3,864,472 relating to a lemon-flavored clear mouthwash, the lemon oil, Contains cinnamaldehyde and glycerin or propylene glycol. Also the

"15

U.S. Patent 4,001,438 discloses flavor formulations which Citral and / or cinnamaldehyde as a component of a physically captured flavor composition Contained with an uncapped aroma oil, a suspending agent and preferably a small amount (0.5%)

20th

Propylene glycol, which increases product stability (column 6, lines 32 to 33), is used in admixture for oral compositions are suitable. However, there is no reference to the discoloration or yellowing problems in this group of patents due to the aging associated with the use of

25th

Cinnamaldehyde flavors are linked. These patents relate to other aspects of dentifrice formulations. The combination of cinnamon aldehyde flavor and propylene glycol is incidentally used in a general discussion of the

Flavors and typical humectants mentioned. 30th

35

From the prior art is also the shrinkage and / or the Decomposition of flavors or colors is known as shown in US Pat. No. 3,666,496, which is a poly (oxyethylene) -poly (oxypropylene) copolymer concerns that terpenic flavors such as orange oil are added to prevent the in 5

flavored foods or beverages to be used To prevent flavoring. U.S. Patent No. 4,305,928 relates to the addition of 0.05 to 5% phytic acid and / or benzoic acid as a chelating agent to prevent or reduce the fading of red or yellow with monazite or blue with Triarylmethylene dye colored optically clear toothpaste. U.S. Patent 3,957,964 relates to a dentifrice which contains encapsulated flavorings that include cinnamon oil or Contain orange oil and which are used during storage until the tooth cleaning agent is released for use by the basic

1 5

tooth cleaning agent (which contain propylene glycol can) remain separate, making the flavored dentifrice more stable and fresher in taste. In the However, there is no indication of the stabilization of cinnamaldehyde or citral taste by the patents mentioned

a specific group of terpenes or sesquiterpenes, which are characterized by a trisubstituted double bond, or by propylene glycol or dipropylene glycol.

In US Pat. No. 2,184,526, the instability against air oxidation of p-isopropyl-oi - methylhydrocinnamaldehyde is also known as Perfume ingredient described, whereby the aldehyde is converted into the corresponding acid, whereby the aldehyde odor gets destroyed. The addition of alcohols of the aromatic or terpene series stabilizes the aldehyde

on

against air oxidation by converting the aldehyde into a hemiacetal of alcohol is convicted.

35

U.S. Patent 3,671,630 relates to the use of several classes of terpenes as color stabilizers for aqueous halogenated ones phenolic germicidal compositions which discolor within a few hours when exposed to light. It will however stated that many terpenes such as limonene are ineffective. 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, is used as a color stabilizer for the flavor can be used as ineffective in stabilizing the germicidal composition specifically is excluded.

None of the above references disclose the use of any particular group of terpenes or sesquiterpenes in a dentifrice that is free from oxidizing agents and at an acidic or neutral pH and which contains cinnamaldehyde or citral flavor to prevent the flavor from changing color with aging.

It has surprisingly been found that the discoloration occurs in Reduces and / or prevents the aging of dentifrices flavored with cinnamaldehyde or citral can be made by adding (1) a terpene or Sesquiterpene, which is characterized by trisubstituted double bonds and consists of limonene, ocimen, caryophyllene and Clove sesquiterpenes, myrcene, derivatives of the terpenes and mixtures thereof or essential oils rich in these may be selected from, or from (2) propylene glycol or dipropylene glycol, or mixtures thereof. It is essential that the carrier suitable for dentifrice is free from Is oxidizing and is kept at an acidic or neutral pH to keep the terpenes and sesquiterpenes

can effectively fulfill their function.

Accordingly, the main object of the invention is to provide cinnamaldehyde or citral flavorings Dentifrice formulations that fail with aging

yellow or discolored.

The invention is to provide a color-stabilized Toothpaste or a mouthwash that tastes cinnamaldehyde or citral and an effective amount of one Color stabilizer, which is characterized by (1) trisubstituted double bonds and consists of limonene, 'ocimen, Caryophyllene and clove sesquiterpenes, myrcene and terpene derivatives thereof or selected from these rich essential oils or (2) propylene glycol or dipropylene glycol

or mixtures thereof.

The invention also relates to a color-stabilized, cinnamaldehyde or citral-containing dentifrice which is at a pH below 8.5 and preferably at a

neutral or acidic pH is maintained.

The invention also relates to an acidic or neutral, color stabilized, containing aldehyde flavor

Tooth cleaning agent that is free from oxidizing agents. 25th

Another subject of the invention is a color stabilized one white toothpaste or a mouthwash that contains cinnamaldehyde or citral flavoring.

Additional Subjects, Advantages, and Novelty of the Invention Features are set forth in part in the following description and in part become apparent to those skilled in the art will become apparent upon examination of the following or may be learned in the practice of the invention. The inventive

Moderate objects and advantages can be achieved through the means and combinations that are specifically pointed out in the claims will be realized and achieved.

To achieve the above and other goals, the contains

Tooth cleaning agent according to the invention, the increased stability against discoloration with aging, one that discolors with aging, selected from cinnamaldehyde and citral, a flavoring agent containing unsaturated aldehyde and, as a discoloration inhibitor (1), one trisubstituted by one

Double bonds marked terpene or sesquiterpene color stable isator, which is made from limonene, ocimen, caryophyllene and clove sesquiterpenes, myrcene, terpene derivatives of the same and Mixtures of the same or essential oils rich in these is selected in an amount of about 0.1 to 5% by weight or

(2) propylene glycol, dipropylene glycol and mixtures thereof, in a carrier suitable for dentifrice, which is free from oxidizing agents and at a pH value below 8.5 and preferably at an acidic to neutral pH of about 5

to 7.5 is held. 20th

In particular, the invention relates to a color-stabilized white toothpaste or a mouthwash which is free from Is oxidizing agents and has an acidic to neutral pH value, which is about 0.1 to 1% by weight of cinnamaldehyde or citral

flavor and (1) one or more terpenes or Sesquiterpenes that contain trisubstituted double bonds or (2) propylene glycol or dipropylene glycol as discoloration inhibitors, preferably in a ratio of 1: 1.

It has been found that the cinnamaldehyde or citral flavors decompose on aging to form conjugated unsaturated aldehydes (dienals). These dienals are responsible for the yellowing or discoloration that occurs in

Cinnamaldehyde or citral in white dentifrices 35

occurs, both with liquids and with creams (pastes).

The discoloration problem arises with commercially available toothpastes that use small amounts of cinnamaldehyde by coloring the goods, e.g. red, blue, light green etc. With white toothpastes, however, there is discoloration unacceptable due to a small amount of cinnamaldehyde.

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

- "1 3 ™

Autoxidation of cinnamaldehyde

10

CH - CH

(CA)

CH »CH -

Il

-O-OH = ± (O> - CH - CH - C - 0 - 0. "

15th

Slow

fast

- CHO

- CO ₂ H

- CO,

(Ο) - CH ₂ CHO

CA -H ₂ O

CH = CH - CH =

Il

C-CH

other dienals

The acid forms even when specimens in solid sealed bottles, the headspace of which has been purged with nitrogen. Cinnamaldehyde is low against Very sensitive amounts of oxygen. Since cinnamic acid is white, its formation takes place within a short time after exposure takes place, not responsible for the yellowing of the cinnamaldehyde. The intensity of the yellow color tends to decrease the duration of the exposure to oxygen than with the amount of oxygen, which indicates that with aging a more complex Oxidation takes place. In particular, the conjugated dienals formed are the intensely yellow components that are responsible for the Discoloration and yellowing of the cinnamaldehyde are responsible.

It has now been found that the discoloration of minor proportions Cinnamaldehyde (maximum about 1 wt.%) Is reduced when certain terpenes or sesquiterpenes are substituted with trx Double bonds are incorporated into the dentifrice composition, preferably in a weight ratio 1: 1. The terpenes include limonene (1), ocimen (2), caryophyllene (3), myrcene (4), terpene derivatives such as citronellyl acetate (5) and mixtures thereof.

(D X U) V θ) Vf * U). V (5) Si

25th

L ι 1 / v if λ

30th

Each one reduced in a ratio of 1: 1 to cinnamaldehyde clearly the discoloration of cinnamaldehyde with aging in a glass bottle. These compounds also reduce that Yellowing on aging in white toothpastes, as shown in Table IA, corresponding to a 40% reduction in Yellowing is caused. Natural products that contain these compounds can be used, such as Lime rich essential oils including citrus oils such as Orange oil, grapefruit oil and mandarin oil. Also clove sesquiterpenes act as color stabilizers.

Toothpaste yellowing was measured instrumentally on a Colorgard reflectometer. The data presented in the following tables are + ZIb values (yellow scale) and mean the increase in yellow compared to unflavoured and unaged 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 a ^ Tb value of 2 to 3 is the limit of _{what is acceptable, since a ^ Jb of 2 a} ] _ _{s is} just off-white and a ZIb of 4 is recognizable as a weak yellow tint.

\: " ^: -3-5Q2830

Table 1

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

Aging at 49 ° C; ^ Jb values

1.0% cinnamaldehyde (CA) 1.0% CA + 1.0% limonene 1.0% CA + 1.0% ociites 1.0% CA + 1.0% caryophyllene 3.2 1.0% CA + 1.0% citronellyl

acetate 3.6 4.2 5.4

B. Influence of pH

3 weeks 6 weeks 9 weeks 4.5 7.5 8.0 2.9 4.9 5.8 2.5 5.4 5.9 3.2 5.3 6.0

1.0% CA pH 5.0
(Citric acid) 4th , 25 5 , 5 5 ,1 1.0% CA pH 6.9-7.1
(Example 1) 4th , 5 7th , 5 8th , 0 1.0% CA pH 8.5
(NaHCO ₃ ) 7th , 5 10 , 5 11th , 2

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

Although lime is a mild flavor (similar to orange) is, contents above 1% are unsuitable and can be undesirable because the orange taste is the original Can change the taste of cinnamon.

The auto-oxidation of cinnamaldehyde is caused by the presence of the Group of terpenes and sesquiterpenes inhibited (interrupted). The formation of epoxycinnamaldehyde is prevented when limonene to which cinnamaldehyde is added. Preventing the formation of this epoxy also prevents the formation of the subsequent ones

Dienale. Analytical investigations have shown that limonene prefers cinnamaldehyde with percinnamic acid reacts to form 1,2-epoxylimones. 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 have sxe show greater reactivity with peracids than mono- or disubstituted double bonds. It is also to be expected that Cinnamaldehyde shows a lower reactivity towards electrophilic attack by peracids because of its double bond with

is substituted by an electron-withdrawing aldehyde group.

By preventing the formation of the dienals, the limonene significantly reduces yellowing. Other terpenes like eugenol are not effective in reducing yellowing.

The means of reducing the discoloration of cinnamaldehyde are

can also be used for other conjugated unsaturated aldehydes such as citral, (CH ₃ ) ₂ C = CHCH ₂ CH ₂ (CH ₃ ) = CHCHO. Citral is another flavor that is commonly found in teeth cleaning agents.

tel compositions is used.

The yellowing of a liquid mixture of cinnamaldehyde or citral with a terpene additive was both fresher
Production and measured after 24 hours of aging at 90 ⁰ C + 2 ° C with a Gardner color meter. 10 g samples were prepared from mixtures of the flavor and limonene in varying amounts and the following measurements were obtained:

Color measurement

Citaldehyde (%)

95
90
75
100
50

Limonene (% -)

10 25

0 50

fresh

4 1/4

4 1/4

4 1/4

4 1/2

3 3/4

aged

6 3/4

4 1/2

^ Average of 2 measurements

Citral (%)

100

50

100 50

1 1/3

(b)

3 2/3

(b)

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

Gitral alone (b) _? (b) ₇ ^ ₃ (b) _g

50:50 citral: limes (b). (b). 1/3 (b)

₁ Q The pH of the toothpaste is either acidic or weakly alkaline, with a pH of about 5 to 7.5 _f as shown in Table IB being preferred. The terpenes are not effective in reducing yellowing in a moderately alkaline medium. At pH = 8.5 or above, the anion of the peracid and is formed

^ ₅ 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 by slight

2Q proportions of cinnamaldehyde (maximum approx. 1% by weight) in the presence of Propylene glycol and / or dipropylene glycol is reduced. These materials are in a 1: 1 weight ratio to cinnamaldehyde Effectively prevents almost any yellowing during aging in glass. In toothpastes, however, they showed at levels from 1 to 5% only a slight reduction in yellowing by 1% cinnamaldehyde. However, since these glycols are odorless, it is possible to incorporate them in much larger quantities. The substitution of water or glycerine in teeth cleaning formulations propylene glycol or dipropylene glycol prevents the yellowing of cinnamaldehyde or citral containing flavorings. When a non-aqueous paste is formulated, pass the water through either of the two Glycols is replaced, then no discoloration is observed. Also by replacing the 22% glycerine in a toothpaste yellowing is significantly reduced by propylene glycol.

It is believed that the mechanism of the glycol effect Includes acetal and hemiacetal formation, Z complexation. The glycols are believed to be effective in that they complex the aldehydes through acetal formation. Because aldehydes in four different phases of the dienal formation mechanism

mus are involved (Figure I), affects the response the formation of dienals with the glycol lasts. Analysis of the aged 1: 1 CA / propylene glycol sample showed a notable formation of acetals in addition to 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 be increased must to make up for this loss.

The auto-oxidation of cinnamaldehyde is caused by the presence

Inhibited (interrupted) due to the propylene glycol Formation of glycol acetals, which form rapidly at room temperature and increase over time. This prevents the formation of the dienals, which are responsible for the yellowing in the

Aging are responsible. 20th

This agent for reducing the discoloration of cinnamaldehyde is also applicable to other conjugated unsaturated aldehydes such as citral, (CH ₃ J ₂ C = CHCH ₂ GH ₂ C (CH ₃ J = CHCHO. Citral

is another flavor that is commonly found in dental

cleaning compositions is used.

The yellowing of a liquid mixture of cinnamaldehyde with propylene glycol or dipropylene glycol was caused by a Gardner color meter measured both when fresh

manufactured material as well as after 24 hours of aging

in a vial at 90 ° C (I) as well as 48 hours at 50 ⁰ C (II) and initial winding-passing oxygen over the sample for 5 seconds. The samples were made from mixtures of cinnamaldehyde and the glycols, cinnamaldehyde

and glycerin "and cinnamaldehyde alone and the the following measurement results were obtained:

Citaldehyde (CA) 50/50 CA + glycerine 50/50 CA + propylene glycol

50/50 CA + dipropylene glycol

C.
Faro measurement aged fresh 11th
11 '
• _r 7 = 7 4th
3; 4th
? 7th : 8 »9 = 9 3 10

Cinnamaldehyde 50/50 CA / propylene glycol

4.5 3.5

7 4.5

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

It should be noted that the propylene glycol mixture is a little less dark than the dipropylene glycol mixture, however much lighter than the cinnamaldehyde alone.

It is important that the pH of the toothpaste is either 5
is 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 is formed and the epoxidation of cinnamaldehyde takes place via Michael addition.

This type of addition reaction can be triggered by propylene glycol 10

not be inhibited.

Toothpaste yellowing was measured using a Colorgard reflectometer. The information in the following tables are + Ah values (yellow scale) and mean the

Increase in yellow color compared to unflavoured

and unaged toothpaste used as a zero-b reference was taken. Measurements after 3, 6 and 9 weeks at 49 C should be approximations for 1 year, 2 years and 3 years Be room temperature. It is assumed that a ^ b value

from 2 to 3 is the limit of what is acceptable as one

of 2 as just off white and a ^ Jb of 4 as weak yellow tint is visible.

Table 2

Cinnamaldehyde discoloration in toothpaste (Example 1)

Influence of pH

Aging at 49 C: Z | b values

3 weeks 6 weeks 9 weeks

1% CA pH 5.0 citric acid

1% CA pH 6.9 to 7.1 (example 1)

T% CA pH 8.5 (NaHCO ₃ )

4.25

4.5
7.5

5.5

7.5
10.5

5.1

8.0 11.2

It is also important that the dentifrice is free from oxidizing agents such as hydrogen peroxide or Salts that release hydrogen peroxide such as sodium perborate, peracids, and peracid salts. The presence of oxidizing agents would be the preferred reaction of the terpene with the percinnamic acid in the formation of the 1,2-epoxylimony as well as interfere with the preferred reaction of the glycol with cinnamaldehyde in the formation of the glycol acetal. How nice with reference to the need for an acidic or neutral pH of the dentifrice suitable vehicle discussed, in the presence of the peracid anion, the epoxidation of cinnamaldehyde takes place via Michael addition ' away.

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 produced a very intense yellow. These differences were due to the different pH levels

assigned and also the presence of TiO ₀ :

20 ^Z

p_H

25 Example 1 6.9 to 7.1 0

Example 2 6.15 0.5%

Lowering the pH of Example 1 by adding

of either citric acid or phosphoric acid reduced 30

the yellowing (Table 1B). Increasing the pH to 8.5 by adding NaHCO ₃ significantly increased the yellowing. The addition of limonene had no effect on the reduction in yellowing in the NaHCO ₃ -BaSe (pH = 8.5).

- ■ 25 -; - "

/ These observations are carried out with the auto-oxidation mechanism consistent. The peracid anion is formed at a pH = 8.5 and the epoxidation proceeds faster by Michael addition. Limes and the other terpenes

and sesquiterpenes with trisubstituted double bonds 5

are not reactive towards nucleophilic addition and cannot trap the peroxide anion. Are peracids much weaker than the corresponding carboxylic acids. The pK value of percinnamic acid is estimated to be 7.5.

In a neutral base there are both free acids and the

Anion present. By lowering the pH

prevents the reaction based on the anion addition.

As noted by comparing Example 1 and Example 2, the presence of TiO ₀ provides both

visible and measurable reduction in yellowing. Based on a number of comparisons with and without TiO ₂ , a 4b reduction of 1.0 for 1% TiO ₂ and 0.5 for 0.5% TiO _{2 was} observed.

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

Yellowing in toothpastes containing various flavors containing cinnamaldehyde in the presence and absence of TiO ₂ .

Table 3 Flavor discoloration in toothpaste (Example 1)

History material

Citaldehyde (CA)

1% CA

1% CA + 1% limonene + 0.5%
TiO ₂ ? pH 5.6

Spice 10 (SIO) '

1% S10

1% S10 + 1% litnones + 0.5% TiO.

Weeks 6 weeks 9 weeks

7.5

2.9

4.2 2.3

8.0

4.5

4.6 2.6

Spice 12 (12S) '

1 week

0.8% 12S 1 2.7 4.0 4.6 0.8% 12S + 0.1% A. Limes I. 2.1 3.2 3.9

"it

Spice 12 (12S) '

1 week 3 weeks 6 weeks 9 weeks

0.8% 12S + 0.1% limonene + 1% TiO ₂

0.8%. 12S- + 0.5% limonene + 1%

0.8% 12S + 0.25% limonene 0.8% 12S + 0.5% TiO ₂

0.8% 12S + 0.1% limonene + 0.5% TiO ₂

0.8% 12S + 0.1% limonene +

° ' ^{5% Ti} ° _2i pH 5.2 (citric acid)

0.8% 12S + 0.25% limonene 0.5% TiO ₂

0.8% 12S + 0.25% limonene + 1% TiO ₂

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

Spice 10 (STO) ¹ 1% S10

1% S10 (glycerine replaced by propylene glycol)

1% S10 (glycerine replaced by propylene glycol) + 1%

0.9

0.7 'Spice 10 flavor contains 55% cinnamaldehyde

2.3

2.0 3.0 2.9

4.2 2.7

2.6

2.5 3.5 3.1

2.8 4.0

4.6

Spice 12 flavor contains 15% cinnamaldehyde

Other flavor compositions containing cinnamaldehyde include:

White Spice 1 - contains 20% cinnamaldehyde. White Spice 2 - contains 25% cinnamaldehyde. Spice-11 Flavor - contains 55% cinnamaldehyde.

The cinnamaldehyde flavor compositions can contain

100% supplemented with flavor components such as menthol, 10

Eugenol, peppermint, spearmint, clove, anethole, Methyl salicylate, vanillin and the like in various mixtures. Menthol and eugenol influence the yellowing the dental formulations do not.

By mixing the cinnamaldehyde with limonene or others

Terpenes, incorporation of TiO ₂ and lowering of the pH value can make high levels of cinnamaldehyde acceptable.

Mixing cinnamaldehyde with propylene glycol or dipropylene glycol, incorporating TiO ₂ and lowering the pH value can also make high levels of cinnamaldehyde acceptable. This can easily be done by replacing the glycerin or water with propylene glycol

is replaced in the teeth cleaning formulation.

The flavors with cinnamaldehyde, which generally constitutes at least about 5% of the total flavor, such as spice 10 or spice 12, discolor

in white toothpaste. When the toothpaste is colored green

then the yellowing is not visible.

In the case of Spice 10 flavor, the addition of 1% soda reduces

nen and 0.5% TiO ₀ the discoloration to just about

^Δ

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. 5

In the case of Spice 12 flavor, the yellowing exceeds the level expected due to the 15% cinnamaldehyde content. Interactions due to other components contribute to the discoloration. If this taste is required for a white paste, then by adding only 0.1% limonene and 1% TiO _2, a significant improvement in color is achieved with only a slight change in taste.

The dental base material used according to the invention can

in the form of a paste, cream or liquid mouthwash present and contain known ingredients that are common be used for dentifrices.

Toothpastes or creams can be based on aqueous or essentially

borrowed not based on aqueous systems. The former usually contain appreciable proportions of finely divided solid polishing agent, surface-active agent, gelling agent, Water and a certain amount of non-aqueous vehicles, e.g. glycerin, sorbitol, and they are opaque while

the latter types are often a clear gel or opaque

and a small amount of a visually clear, finely divided solid polishing agent, a larger amount of one non-aqueous vehicle comprising at least 10% of the formulation propylene glycol or dipropylene glycol alone

or mixed with other non-aqueous carriers such as Contains sorbitol or glycerin, a surfactant and a gelling agent in addition to one that is often present may contain a small amount of water.

The surfactant or detergent present in the dentifrice may in some cases be cationic or be amphoteric, but usually it is anionic or nonionic. Of these connections are

the anionic ones are most preferred. The anionic 5

Detergents or surfactants usually serve also as a foaming agent. As useful anionic Detergents can be named: Higher fatty acid monoglyceride monosulphates 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 dodecylbenzenesulfonate; higher olefin sulfonates such as sodium sulfonates of higher olefins, in which the olefin group has 12 to 21 carbon atoms having; higher alkyl potassium sulfoacetates; higher fatty acid

15th
esters of 1,2-dihydroxypropanesulfonates, magnesium salts; the essentially saturated higher aliphatic acylamides of the lower aliphatic aminocarboxylic acid alkali metal salts, such as those with 12 to 16 carbon atoms in the fatty acid residues, higher alkyl poly-

20th
lower alkoxy (10 to 100 alkoxy groups) sodium sulfates; higher fatty acid sodium and potassium soaps made from coconut oil, tallow, and the like. Most of the time the detergents are sulfated or sulfonated compounds. Examples of suitable anionic amides that can be used are N-Lau-

25th
royl sarcosine and disodium, potassium and ethanol ammonium 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

30th
material 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 include those of chains 35

Contain lower alkylene oxides, for example ethylene oxide, propylene oxide, in which 10 to 100 or more moles of the lower alkylene oxides are present. These materials include the block copolymers of ethylene oxide, propylene oxide, and propylene glycol sold as Pluronics; the alkylphenyl polyethoxyethanols sold as Igepale; mixed copolymers of ethylene oxide and propylene oxide sold as Ucon; and various other well known nonionic materials derived from fatty alcohols or acids and polyethylene oxide. The amphoteric or ampholytic agents include long chain (alkyl) amidoalkylene alkylamine derivatives such as "miranols", for example miranol C ₃ M; and cationic germicidal detergents such as diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, benzyldimethylstearylammonium chloride and tertiary

15th

arer amines with a higher fatty alkyl group and 2 polyoxyethylene groups, which are bound to the nitrogen of the same.

The detergents make up about 0.5 to 5% by weight and preferred

20th

wise up to 3% by weight of the teeth cleaning compositions

the end.

Toothpastes, toothpastes, and tooth powders usually contain it . Substantially water-insoluble polishing agents or

25th

Abrasives compatible with the formulation in amounts of from about 20 to 75% by weight of the total cream or Paste formulation and up to 95% of tooth powder. Suitable polishing agents include anhydrous dicalcium phosphate, Dicalcium phosphate dihydrate, tricalcium phosphate,

30th

insoluble sodium metaphosphate, crystalline silicon dioxide, colloidal silica, complex aluminosilicates, aluminum hydroxide (including alumina trihydrate or hydrated aluminum oxide), magnesium phosphate, magnesium carbonate, calcium carbonate, calcium pyrophosphate

35

- 32: -:. '■■' / ■■ ·,

phate, bentonite, talc, calcium silicate, calcium aluminate, Alumina, aluminum silicate and silica xerogels. Most of the polishes mentioned are above all useful for making opaque dentifrices, but some of them, like the colloidal silicon-5

dioxides, especially the disilica xerogels and the complex sodium aluminosilicates, can be used in the manufacture be used by clear dentifrices because their index of refraction is close to that of the rest of the dentifrice ingredients lies in a suitable carrier. 10

In the case of toothpaste or toothpaste formulations, the liquids and solids must necessarily be sized accordingly that a creamy mass of the desired consistency is formed, for example from a compressible

Aluminum tube is extrudable. Generally included the liquids in toothpastes are mainly water, glycerin, sorbitol, polyethylene glycol or propylene glycol 400 including suitable mixtures thereof. It is usually beneficial to have a mixture of water and

a humectant such as glycerin, sorbitol, or mixtures thereof. The total liquid content is generally from about 20 to 75 percent by weight of the formulation. It is preferred to also be a gelling agent in toothpastes to use like the natural and synthetic

rubber-like materials, e.g. Irish moss, gum tragacanth, sodium carboxymethyl cellulose, polyphenyl pyrolidone or strength. Irish moss and sodium carboxymethyl cellulose are particularly compatible and preferred gelling agents. The gum content is, usually up to about

10% and preferably about 0.3 to 5% by weight of the formulation. Fillers such as fumed silica and silica airgel can also be used, typically in amounts up to about 10% by weight as a supplement of the gelling agent. These colloidal silicas

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

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

Furthermore, various other materials can be incorporated into the dentifrice-suitable carrier. Examples are fluorine-containing compounds such as tin (II) fluoride, potassium tin (II) fluoride (SnF ₂ KP), sodium hexafluorostannate, tin (II) chlorofluoride, sodium fluorozirconate

and sodium monofluorophosphate. These materials that dissociate or release fluorine-containing ions in water, can in the dental carrier in an effective, but not toxic amount, usually in the range of about 0.1 to 5% by weight. Other additives include Preservatives such as sodium benzoate, chlorophyll compounds, Silicones, ammonium materials such as urea and diammonium phosphate, antibacterial agents such as benzethonium chloride and other quaternary antibacterial compounds, sweeteners like sodium saccharin, blue dyes,

additional flavorings like peppermint or green Mint and the like. These additives can be used in amounts that affect the properties and characteristics of the dentifrice according to the invention do not adversely affect. Every single component can be in minimal

Amounts up to a maximum of 5% by weight and preferably

• Up to 1% by weight of the formulation may be present.

The tooth cleaning agent according to the invention is by conventional methods of making toothpaste,

Toothpastes, mouthwashes and tooth powders. In particular, a toothpaste can be produced by forming a gel from carboxymethyl cellulose and water, adding the powdered materials and the humectant while mixing, then adding the polishing agent while mixing
medium and then add the surfactant and the flavoring together with the terpene or sesquiterpene 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 according to the invention to promote the Oral hygiene is the tooth cleaning agent according to the invention

regularly on 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 upset.

In the following the invention is illustrated by means of examples

explained in more detail, but it should be noted that the Invention is not limited to this. The compositions are made in the usual way and all Quantities and proportions mentioned here and in the claims

are, unless otherwise stated, refer to

the weight. The flavor-forming component is one Flavor composition containing cinnamaldehyde or citral, to which a terpene or sesquiterpene (Tables 4 to 7) or propylene glycol or dipropylene glycol are added

is as in the examples following the experiments

is described (Table 8).

Example 1

Tooth cleanses

AWAY

ingredients

Glycerin 22.00 22, ο Sodium monofluorophosphate 0.76 0.8 Sodium carboxymethyl cellulose 1.00 1.0 Tetranatriene pyrophosphate 0.25 0.2

AB ingredients%%

Sodium saccharin 0.20 0.2 Sodium ribenzoate 0.50 0.5 Deionized water 24.49 24.5 Dicalcium phosphate dihydrate 48.76 48.8 Flavor 0.84 0.8 Sodium lauryl sulfate 1.20 1.2

pH 6.9-7.1 6.9-7.1

Example 2 Toothpaste

ingredients

Glycerin 10.00 10.0 Sodium monofluorophosphate 0.76 0.8 Sodium carboxymethyl cellulose 1.10 IrI Sodium benzoate 0.50 0.5 Sodium saccharin 0.20 0.2 Sorbitol (70% solution) 17.00 17.0

AWAY

Ingredients % %

Dedonized water 22.19 22.2 Titanium dioxide 0.40 0.4 Insoluble Sodium metaphosphate 39.35 39.3 Hydrated alumina 1.00 1.0 Dicalcium phosphate anhydrous 5.00 5.0 Flavor 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 (PBG 12) 3.00

Dye 0.20

Sodium aluminosilicate

(Containing silicon dioxide

combined alumina) 18.00

Colloidal silica airgel 5.50

Flavor 0.65

Sodium Laurel Sulphate 1.20

Example 4 toothpaste

ingredients

Glycerin 25.00

Sodium carboxymethyl cellulose 1.40

Sodium ribenzoate 0.50

Sodium saccharin 0.20

Sodium monofluorophosphate 0.76

Deionized water 35.44

Titanium dioxide 0.40

Ingredients % ^

Alumina 10.00

Silica 24.00

Flavor 1.10

Sodium Lauryl Sulphate 1.20 pH 6.2 + 0.5

Example 5

Example 4 was reworked with the difference that the sodium lauryl sulfate increased to 1.5% and the water content has been set accordingly,

Example 6 mouthwash

ingredients

Ethyl alcohol glycerine polysorbate 80 '

2 Poloxamer 338 benzethonium chloride Flavor composition Deionized water

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

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

25 2

Polyethylene polyoxypropylene block polymer according to

Formula:.

HO (CH ₉ CH ₉ O) (-CH-CH ₂ O) (CH ^ O) H,

T2

χ ·

CH-

in which χ and ζ = 128 and y = 54.

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

Example 7 Tooth powder

AWAY

Ingredients % %

Magnesium Silicate Sodium Saccharin ° Flavor Dicalcium Phosphate Anhydrous Sodium Lauryl Sulphate

The flavor levels in tooth powders are generally bigger than in toothpastes.

7.00 7.0 0.15 0.2 2.50 2.5 88.35 88.3 2.00 2.0

Example 8
20th

Non-Aqueous Toothpaste Ingredients J ^

Propylene glycol 43.4

Klucel GF ¹ (Hercules) 1.5

Sodium saccharin 0.2

TiO ₂ 0.4

Dicalcium phosphate dihydrate 50.0

Peroxydiphosphate 3.0

Sodium Lauryl Sulphate 1.5 pH 6.4

• Hydroxypropyl cellulose - a propylene glycol ether of Cellulose.

Example 9 Non-aqueous toothpaste

ingredients

Propylene glycol. 22.0

Sodium nonofluorophosphate 0.8

Sodium carboxyin ethyl cellulose 1.0

Tetranatriuitpyrophosphate 0.2

Sodium saccharin 0.2

Sodium benzoate 0.5

Dicalcium phosphate dihydrate 48.8

Spice 10 0.9 Sodium Lauryl Sulphate 1.2

¹⁵ TiO ₂ 1.0

H ₂ O QS.

The following tables show discoloration results Aging at 49 ° C of the toothpastes from Example 1, if not otherwise stated, namely not flavored, containing cinnamaldehyde (CA) flavor alone and with certain terpenes or sesquiterpenes, which contain a tr! substituted double bond, or with propylene glycol or dipropylene glycol to prevent or reduce the discoloration caused by the cinnamaldehyde component caused.

The b values in the tables denote the yellowing of the toothpaste, which was measured on the Colorgard reflectometer, and the Δ b values denote the increase in yellowing compared to the unaged and unflavoured sample, which was the zero b reference.

Tabel

Investigation of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from Example 1A

Reference b ZIb

3 wb.

4 weeks b YIb Wo.
b Ab

Where.
b Ab

Where. 9 Wo b'4b b

Experiment I 0.5% CA

0.5% Ca + 0.5% limonene not flavored Experiment II 0.5% CA

0.5% CA + 0.5% eugenol

0.5% CA in Example 2A

0.5% CA + 0.5% eugenol in Ex. 2A

not flavored e.g. 2A

2.7

1.9 + 0.2

2.0 1.8 1.9 1.9

, 6 5.2 + 2.5
5.5 + 2.8 5, 7 + 3 , 9 , 2 5.2 + 2.5
5.6 + 2.9 6, 0 + 4 , 2 2.9 + 0.2 2, 7 + 0 , 9 4.6 + 2 , 9 4.9 + 3.1 6.2 + 4 7.6 + 5.8 3.3 + 1 3.7 + 1.9 3.8 + 1 4.3 + 2.5

6.6 + 4.8 6.6 + 4.8

6.7 + 4.9 6.9 + 5.1

2.9 + 1.1

5.7 + 3.8 6.4 + 4.5 '7.7 + 5.8 9.5 + 7.6'

Separation separation 4.8 + 2.9 5.6 + 3.7.

GO Ol O ro

OO

co

CD

reference

Experiment III 1% CA

1% CA + 1% limonene 1% CA + 2% limonene

not arcxnated

Experiment IV

1% CA

1% CA + 1% ocimen 1% CA + 2% ocimen 2% ocimen

not flavored

2.7

3 weeks 4 weeks 5 Wb.

b / | b b ZJb b.

6.6 + 3.9 7.6 + 5.4

4.9 + 2.2 5.4 + 3.2

4.5 + 1.8 4.8 + 2.6

2.1

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

7 weeks 9 wks.

b 4b b Ah b 4b

9.3 + 7.1 10.5 + 9

9.9 + 8.4

6.5 + 4.4 7.5 + 6

6.9 + 5.4

5.7 + 3.6 6.2 + 4.7 5.8 + 4.3

9.2 + 7.3 9.9 + 8.1

7.3 + 5.4 7.7 + 5.9 ■

7 +5.1 7.7 + 5.9

3.8 + 1.9 3.9 + 2.1

2.1 + 0.2 2 + 0.2

cn

OK)

co

CO O

Experiment V

1% eugenol

1% CA + 1% eugenol

0.5% CA + 0.5% eugenol

0.9% CA + 0.1% eugenol

1% spice 10

10% white spice # 1

not flavored

Table 5

Investigation of the discoloration of toothpaste aging in the toothpaste from Example 1A

'Reference

2 wb.
b Ab

3 where.

6.7 +4.8

4.1 +2.2 8.1 +6.2 5.9 +4
5 +3.1

4.8 +2.9

3> Ö +1.9

4 Wb.

6 weeks b Ab

9 Wb.

8.4 +6.5 9.6
10.2 +7.9
+8.5 4.5 +2.6 4; 3 +2.6 9.9 +8 10.7 +9 M. +6.2 8.9 +7.2 6.6 +4.7 7, 2 +5.5 6.3 +4.4 6.7
6.4 +5
+ 4 ^ 7 4.6 +2.7 5.0 +3.3
+ 3 * 4

Experiment VI

1% white spice # 2

not flavored

3.3 +1 _? 2 3.5 +1.7

2.1 0

+2.3 5.1 +3.2 CO + 0 ^ 5 cn 4.6 2 + O ₇ I. CD
| SJ 4th CX) 2.2 CO
CD

Reference b Ab

'2 Wb. B Ab

'3 Wb.

Wb.
b Ab

ι 6 wb.

b A b

'9 Wb. B Ab

Experiment VII

0.5? * CA + O, 5 #, eugenol

0 ^ 55 ^ · CA + 0.5 # eugenol + li » limonene

not arcsmatized

1 * 9

5.9 +4 4.7 +2.0

7.2 +5.3

+4.1 6

7.0 +6 7 +6 each

7 +5.2 7.5 + 5 ^ 7

Experiment VIII Ij4 white spice spice ίο

Spice IQ + Lime

seasoning
Limes

Limes

4.1 +1.9 4.0 +3.0 4.9 ⁺ 3% 1

+2.6

5.0 +4.2 5.6 40

4.9 +2.7 4.0 +3.2 5.2 +3.6

5.1 +3.5 0

5.4 +3.0 +0.2 2y3 +0.5

5.1 +3.5

5, ft +3.0 6 +4.4

5 +3 5.4 +3.0

5.3 +3.7

co cn

1.9 +0.3 cd ⁷ ro

OO

CO CD

Experiment IX

I ^ Ck + O.25V & Limonen 1 # CA + O * 5 # Limonen VjL CA + O.75 # Limonen VjL Ca + Vß> Limonen VjL Ca + 1.5 $ Limonen Γ / S CA + yjL Limonen V}> CA + 5 $ Limonene not aranatized Ij4 CA. * VjL caryophyllene

Experiment X

Example 4
Example 4

Tabel

Investigation of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from Example 1A

¹ reference b Ab

1.5

1 Wb.

4.5

3.3 +1.3 / 3 Wb.

Where.

(9 wks.b ab

7.2 +5.1 10.5 + β, 9 11.1 +9.2 I. , 6.1 +4 7.7 +6.1 β, 5 +6.6 < 3502830 5.9 + 3, β 6.9 +5.3 β, 3 +6.4 5.4 +3.3 6.9 +5.3 7.0 +5.9 5.3 +3.2 6.5 +4.9 7.9 +6 5.0 +2.9 6.6 +5.0 6.7 +4 »* 4, β +2.7 5.3 +3.7 6.2 +4.3 4.2 +2.1 5.0 +3.4 V + 3, β 5 »3 +3.2 6.9 +5.3 7.9 +6 Ι, β +0.3 Ι, β
Ι, β -0.2 1.6 +0.4 Ι, β +0.2
-0.1

Reference 1 wb. 2 wks. 3 weeks 6 weeks 9 weeks ^ bb Ab b_ Ab b Äb b £ J> * _

Example 1 A 2.3 2.6 + 0 ^ 3 ² j7

Example 1 A 2 ^ 5 +0.5 2 _? 3 +0.7 2.3

ι _A η -λ 1 «7 -0 · 3 ¹ J ⁵ " ⁰ ^

Example 2 not classified ^χ ν ^ ~ ^υ ί · '~ ⁷

Example 1 not flavored I.9 2.1 + 0.1 ■ · ■> "

Example 5 not flavored χ 5 -0.4 ¹ I ^ -0.1 * -f ~ >

XT

1% white spice 11 + 1% 2.9 +1.2 ^> 6 +2/9 5 ^ 3 + 3f7 5.5 + 3 * 6

Limones in Example 5 ^ g 2.9 +1.2 hf 5 +2 _? ß 5 ^ 2 + 3, ο 5 _? ^ + J ^ ■>

- _Of K CA 2.3 +0.1 3.1 +1.4 4.5 +2.9 6.1 +4.5 6.0 H, l

CD "" TO OO OO CD

Table 7

Investigation 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 / b b From b / Tb b Ab b Ab b Ab

Exp (; »Mment XII

1 ·; Ό cn in Ex. 1 α pH 4.9 3.1 +1.3 6.3 +4.5 7 * 4 +5.5 7.2 +4.0

IZCh in Ex, IA pH 6 _? -9 4 +2.2 7 +5.2 β, 9 +7 0.3 +5.9

Example 1A unflavoured pH 4.9 1.6 1.8

1.9 2.4

Example 1A not aranated pH 6.9 1.0 1 ^ 9 2.2, E.g. 2A not flavored ■ · • '

Experiment XIII .

2.9 +1.1 3.6 +1.9 4.9 +2.0

0 ü / ₀ spice 12 + 0.5 # ⁷ TiO ₂ + 0.156 limonene

Q HUo + u, J-7 »immune

O as above at pH 5.2 (citric acid) 4 ^ 9 + 3.1 5.3 + 3.6 6.1 + 4.0

g _as above at pH 5.1 / u po) 47 + 2-9 5 +3.3 CO

S ^v 3 4 ⁷ cn

O as above at pH 6.2 (HoPO. ) 4.4 +2, ο 4.9 + 3jZ ^

g as above for PH ₅ 3 (citric acid). 4 ^ 7 + 2.9 5 ^ 2 +3 _? 5 5.7

1% spice 10 + , 0 _? 5 # TiO ₂ + 2 _y 7 +0.9 3 _? Ö +2.1 4.2 +2.5 4.7

1% lithium ions ■■■ - 3.6 + 2.0

reference

λ κ

1 wb. 3 wb.

5 weeks

6 Wb.

A V> Λ Κ

9 wks. b Δ h__

as above for pH 5.2 as above for pH 5.1

(Citric acid) 2.6 + 0.0 3.5

Experiment XIV

1 # CA in Ex. 2 A I56 CA + 1 # Limonene in Ex. 2 A repeat sample Citral

Citral '+ $ 1 limes

CA + 0.5 '/ * TiO ₂ pH 5.6

CA + V / o limonene +0.55 »TiO ₂ pH 5.6

), ÖjS Gewürz 12 + 0.5 '/ S TiO ₂ pH 5.6

) · 0; ί Spice _ 12 + O * 1 $ S Limonene + ⁷ O, 5 # * fiO ₂ pH 5 _? "o 5.2 +3.5 4.2 +2.5 4.4 + 2j7 4.9 +3.2 3.7 +2.0

5.2 +3.5

4.1 +2.4

4.3 +2.7

4.2 +2.6

3.0 + 2.1

2.0 +1.0 3.7 +2 4 »3 +2.6

3.2 +1.6

as above for ipH 5, Ö (citric acid) 2 _? Ö +1 3.7 + 2.1 4.1 +2.4

as above at _pH ^ ₂ ( _H P ₀ ) 2., Ö +1 3.0 + 2 ^ 2 4.1 +2.4

4.6 +2.5 5.6 +2.5

+3.2

4 * 6

6.9 +4.7 7.1 +5.3 • * cn
CD
NJ 5.2 +3.0 5.0 +4.0 CO
CO
CD 5.2 +3.0 5, ö +4.0 5 ^ 4 +3.2 6.2 +4.4 4.3 +2.1 4.0 +3.0 6.9 +4.7 6.7 +4.9 +2.9 6.1 +4.5 5.2 +3.0, 5.7 +3.9 5.3 +3.1 5.9 + 4 * 1.

Table 8

Investigation of the discoloration of toothpaste aging at 49 ° C. of the toothpaste from Example 1A

1 week 3 weeks 6 weeks

b A b b A bb Ab

Experiment XV

1% CA in Ex. 7 2.3 + 0.3 3.8 + 1.8 5.1 + 3.4

1% CA + 1%
Limonene in Ex. 7 ¹ ' ^{7 + 0} 3.3 + 1.3 4.6 + 2.9

1% CA + 10% propylene glycol 4.0 + 1.8 5.0 + 3.0 7.1 + 5.4

1% CA + 36% propylene glycol. '

+ 63% dicalcium phosphate 2.0 + 0 1.8 + 0 sample had solidified. ']'>, ^

Experiment XVE

1% CA 5.1 + 3.2

1% CA + 1% propylene glycol 5.2 + 3.3

1% CA + 1% dipropylene

glycol 4.5 + 2.6

1% CA + 5% propylene

g! ycol 4.9 + 3.0 y, ι + _{bf3 b} , b + z, y _o

K) OO CO CZ)

12, 6th +10 , 4 10, + 6, 9, 6th + 7 , 4 8th + 4th 8th, 6th + 6 , 4 6, + 2, 8th, 3 9, 1 + 6 , 5 6, + 2, , 6 r7 , 0 r3 4th 7th 6th 9

6 weeks

b A ^ b

1% CA + 5% dipropylene

glycol 4.4 + 2.5 8.0 + 5.8 5.0 + 1.3

4th , 4 1 Where Λ b b 8th 3 , 0 Where Δ b H 1 ,8th 5 2 , 4 ,8th + 2, + 5 , 2 + 0 + 0

1% CA + 35% dipropylene glycol + 64% dicalcium phosphate 1.8 + 0 2.4 + 0.2 2.9 + 0

Experiment XVII

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% Φ '.. "

Propylene glycol + 1% unions 3.9 + 2.1 5.8 + 3.7 5.9 + 4.1 ~ t - "·

1% spice 10 + 5%

Propylene glycol + 1% TiO ₉ ? pH 5.1 2.4 + 0.6 3.9 + 1.8 - '

^Δ 2.7 + 0.9 3.7 +1.6

Experinent XVIII

0.9% spice 10 3.9 + 1.7 6.4 + 4.0 6.5 + 4.7, ','

0.9% spice 10 in example 8 3.3 + 1.1 4.7 + 2.3 4.5 + 2.7 '··''

CO Experiment XIX cn

0.9% spice in Ex. 8 I ^s -)

+ 1% TiO ₀ 2.8 + 0.7 2.7-0 - CO

¹ CO

Tables 4 to 7 inclusive relate to formulations containing various cinnamaldehyde and citral Contain flavors that yellow with aging, as well as the reduction of yellowing through additives of limonene and other terpenes and sesquiterpenes, which are characterized by trisubstituted double bonds are. Adjusting the pH to about 6 and adding TiO “reduces the yellowing of these flavored foods Formulations even further.

It should be noted that the above detailed Description is for illustrative purposes only and may vary within the scope of the invention are. The "summary" above is for the convenience of technical researchers only, and you are getting to the point the scope of the invention is of no importance.

Claims (1)

Dentifrice composition Claims Dentifrice composition with increased stability against discoloration with aging, characterized in that that it is an aldehyde flavoring selected from cinnamaldehyde and citral which changes color with aging and as discoloration inhibitor (1) at least one terpene or sesquiterpene containing trisubstituted double bonds in an amount of 0.1 to 5% by weight, or (2) Propylene glycol, dipropylene glycol, or a mixture the same in a suitable carrier for dentifrices, which is free from oxidizing agents and one has a pH below 8.5. Dentifrice according to Claim 1, characterized in that the discoloration inhibitor is at least one terpene or Sesquiterpene is. _ 2 - 3. Dentifrice according to claim 2, characterized in that the discoloration inhibitor from limonene, ocimen, caryophyllene and clove sesquiterpenes, myrcene, their terpene derivatives and mixtures thereof or from these range
essential oils is selected. 4. Dental care product according to claim 1, characterized in that that the discoloration inhibitor is propylene glycol, dipropylene glycol, or a mixture thereof. 5. dentifrice according to claim T, characterized in that the flavoring is about 0.1 to 1% by weight
Composition matters. 6. dentifrice according to claim 2, characterized in that the weight ratio of the aldehyde flavor to the terpene is 1: 1. ^y 7. Dental care product according to claim 4, characterized in that the discoloration inhibitor is about 10 to 45% by weight of the '"* Composition matters. 8. dentifrice according to claim 4, characterized in that the suitable carrier for dentifrice
is anhydrous toothpaste. 9. dentifrice composition according to claim 4, characterized
characterized in that the suitable for dentifrice
The carrier is a water-based toothpaste. Dentifrice according to claim 1, characterized in that it is used as a carrier suitable for dentifrice
with a pH of about 5 to 7.5. 11. Dental care product according to claim 10, characterized in that it is a white, color-stabilized carrier as the carrier
Contains toothpaste. 12. Dental care product according to claim 11, characterized in that it is used as an additional 0.5 to 1 wt.% Contains titanium dioxide. 13. Dental care product according to claim 10, characterized in that that the dentifrice is a white, color-stabilized Mouthwash is. 14. Dental care product according to claim 2, characterized in that it is present as a white-colored toothpaste and 1 Wt% cinnamaldehyde flavor and 1 wt% limonene color stabilizer contains. 15. 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 Ocimen- <* "color stabilizer. \ 16. Dental care product according to claim 2, characterized in that it is in the form of a white-colored toothpaste and 1 Contains% by weight cinnamaldehyde flavor and 1% by weight caryophyllene color stabilizer. 17. Dental care product according to claim 2, characterized in that it is in the form of a white toothpaste and 1% by weight Cinnamaldehyde flavor and 1% by weight citronellylace- ~ " Contains tat color stabilizer. 18. Dental care product according to claim 2, characterized in that it is present as a white-colored toothpaste and 1 wt.% Citral flavor and 1% by weight lime color stabilizer contains. 19. Dental care product according to claim 2, characterized in that that it is present as a white toothpaste and 1% by weight cinnamaldehyde flavor, 1% by weight limonene color stabilizer and additionally contains about 0.5 to 1% by weight of titanium dioxide. 20. Dental care product according to claim 13, characterized in that that it is from 0.1 to 0.5% by weight of a flavor composition containing cinnamaldehyde or citral contains. 21. Dental care product according to claim 2, characterized in that it is present as a white-colored toothpaste and 0.1 up to 1% by weight of a flavor composition containing cinnamaldehyde or citral and additionally about 0.5 Contains up to 1% by weight of titanium dioxide. 22. Dental care product according to claim 1, characterized in that it is present as a toothpaste that is about 20 to 75% Contains% by weight of a water-insoluble polishing agent. 23. Dentifrice according to claim 1, characterized in that it contains about 0.05 to 5% surfactant. 24. Dental care product according to claim 1, characterized in that it is present as a toothpaste »which has a liquid content comprises from about 20 to 75 percent by weight of the composition. 25. Dental care product according to claim 1, characterized in that net that it is available as a mouthwash that has a liquid content of about 90 to 98% by weight of the Has composition. 26. Dental care product according to claim 4, characterized in that that is present as a white toothpaste and 1% by weight of cinnamaldehyde flavor f, 22% by weight propylene glycol as a discoloration inhibitor and an additional 0.5 to 1% by weight Contains titanium dioxide. 27. Dental care product according to claim 4, characterized in that it is in the form of a white-colored toothpaste and 1% by weight Cinnamaldehyde flavor, 35 wt% dipropylene glycol as Discoloration inhibitor and an additional 0.5 to 1% by weight Contains titanium dioxide. 28. Dental care product according to claim 8, characterized in that that it contains 1% by weight cinnamaldehyde flavor and 43% by weight propylene glycol. 29. Dental care product according to claim 8, characterized in that that it is 1% cinnamaldehyde flavor, 22% propylene glycol and contains 1% titanium dioxide. 30. Dental care product according to claim 13, characterized in that that it is considered anhydrous and has 10 to 15% propylene glycol and 0.1 to 0.5% cinnamaldehyde.