FR2559387A1 - TOOTHPASTE CONTAINING COLOR STABILIZERS - Google Patents

Abstract

THE INVENTION RELATES TO A TOOTHPASTE HAVING IMPROVED STABILITY AGAINST COLOR ALTERATION DURING AGING. THIS TOOTHPASTE INCLUDES AN UNSATURE ALDEHYDE TYPE FLAVOR, CHOSEN FROM CINNAMIC ALDEHYDE AND CITRAL, WHICH IS SENSITIVE TO A COLOR ALTERATION DURING AGING, AND ABOUT 0.1 TO 5 BY WEIGHT OF AT LEAST ONE TERPERENEP OR SESQUITANT DOUBLE TRISUBSTITUTED BINDINGS AS COLOR ALTERATION INHIBITORS, OR PROPYLENE-GLYCOL, DIPROPYLENE-GLYCOL OR THEIR MIXTURE, IN A DENTAL VEHICLE FREE OF OXIDIZING AGENTS AND WITH A LESS THAN 8.5 PHERIS.

Description

The present invention relates to a composition of

  color-stabilized dentifrice comprising a cinnamal aldehyde

  namic or citral as a flavoring agent that is subject to

  discolouration and yellowing in the old age.

  and a trisubstituted double bond terpene or sesquiterpene or propylene glycol or dipropylene glycol

  which significantly reduces and / or prevents alteration of

  and whose pH is kept below 8.5 and below

  at a neutral pH to acid. The toothpaste may be aqueous or anhydrous. It must be free from oxidizing agents such as

  hydrogen peroxide, or salts releasing hydrogen peroxide

  such as sodium perborate, peracids and

salts of peracids.

  The prior art abounds in dental formulations comprising the combination of a cinnamal aldehyde or citral flavoring agent and a terpene, as described in US Pat.

  U.S. patents N 3 867 557 and N 3 928 560 in the-

  which oral compositions containing 0.0001 to 20% of

  ramethoxycinnamaldehyde as a flavoring agent, are dissolved in 100 parts of orange essence (Example VII)

  and or 4 of the cinnamaldehyde are dissolved in 500 ml of

  cool ethyl and 10 ml of orange essence (Example XIII).

  Essential oils such as orange essence are

  known to contain terpenes. The U.S. Patent

  No. 4,001,438 also discloses flavoring formulations containing citral and orange terpenes (Example B,

  column 10) for use in oral compositions. How-

  In this series of patents, there is no mention of

  the problem of discolouration or yellowing associated with

  the use of cinnamic aldehyde as an aro-

  matisant. These patents concern different aspects of the

  toothpaste mulations. The description of the combination

  cinnamic aldehyde as a flavoring agent and a terpene

  does not fall within a general description of flavoring agents.

  The prior art abounds in dental formulations

  comprising the combination of cinnamic aldehyde or

  tral as a flavoring agent and propylene glycol or

  dipropylene glycol, as described in U.S. patents.

  Nos. 3,867,557 and 3,928,560, in which oral compositions containing 0.0001 to 20% of paramethoxycinnamaldehyde as a flavoring agent are dissolved in 100 parts of propylene glycol; U.S. patents N 4 132 771 and N 4 187 287 in which a two-flavored toothpaste

  tints, containing cinnamon aroma uses a vehicle

  the propylene glycol type liquid; the U.S. Patent

  No. 4,242,323 in which an oral composition inhibiting the

  plate, containing aromatic essence of cinnamon,

  also reads propylene glycol as a liquid vehicle; and the U.S. Patent. No. 3,864,472 to a lemon-flavored, clear, mouth wash solution containing lemon essence, cinnamaldehyde, and glycerine or propylene glycol. The patent of

  USA. No. 4,001,438 also discloses aromatic formulations

  compositions comprising citral and / or cinnamic aldehyde

  as a component in a flavoring composition

  trapped which is mixed with an aromatic gasoline

  non-enclosed health, a suspending agent and, preferably, a small amount (0.5%) of propylene glycol

  which improves the stability of the product (column 6, lines 32-

  33), useful in oral compositions. However, this group

  Many patents do not mention the problem of discoloration or yellowing due to aging associated with the use of cinnamic aldehyde as a flavoring agent. These patents concern different aspects of the formulations of

  toothpastes. The description of the combination of aldehyde

  as flavoring and propylene glycol is

  general description of flavoring agents and agents

typical humectants.

  The prior art also mentions the

  dyeing and / or degradation of aro-

  matting agents or dyes, as described in the US Pat.

  USA. No. 3,666,496 in which a poly (oxy) copolymer

  ethylene) -poly (oxypropylene) is added to flavoring agents

  tents containing terpenes such as orange oil

  in order to avoid an alteration of the flavoring agent

  to be used in flavored foods or drinks.

  The U.S. Patent No. 4,305,928 discloses the addition of 0.05 to 5% of phytic acid and / or benzoic acid as

  chelating agent in order to prevent or reduce the

  color treatment of a toothpaste of transparent appearance, colored with red or yellow monoazo coloring agents or with triarylmethylene blue. The U.S. Patent No. 3,957,964 discloses a toothpaste containing an encapsulated flavoring agent, which

  includes cinnamon or orange essence and is now

  naked from the toothpaste base (which may include propylene glycol) during storage until released

  at the moment of use of the toothpaste, so as to obtain

  a more stable flavored toothpaste with a cooler taste.

  However, these patents do not mention the

  stabilization of the flavoring agent cinnamal aldehyde

  or citral with a specific group of terpenes or sesquiterpenes, characterized by a double

  trisubstituted or with propylene glycol or dipropylene

  glycol. The U.S. Patent N 2 184 526 also demonstrated the instability with respect to the air oxidation of pisopropyl-c-methylhydrocinnamic aldehyde

  fragrance ingredient, according to which the aldehyde is trans-

  formed in the corresponding acid, thus destroying the o-

  aldehyde. The addition of alcohols from the aromatic series

  tic or terpene stabilizes the aldehyde vis-à-vis the oxy-

  air by transforming the aldehyde into a semi-acetal

tal of said alcohol.

  The U.S. Patent No. 3,671,630 describes the use of

  multiple classes of terpenes as color stabilizers of aqueous halogenated compositions of phenolic germicides whose color is altered in a few hours of exposure to light. However, many terpenes

  such as limonene have been described as being ineffective.

  Halogenated phenolic germicidal compounds can not

  cinnamal aldehyde or citral, which are aldehyde

  unsaturated, as flavoring agents. In addition,

  that limonene, which is one of the terpenes used

  especially as a color stabilizer for an aroma agent

  matisant, is particularly excluded because it is inefficient

  ficient to stabilize the germicidal composition.

  No aforementioned reference of the prior art

  describes the use of a specific group of terpenes or sesquiterpenes in a toothpaste, free of oxidizing agents

  and maintained at an acidic or neutral pH, containing as aromatic

  cinnamic aldehyde or citral, in order to reduce

  discoloration of said flavoring agent during aging

ment.

  It has been unexpectedly discovered that the alteration

  coloring when aging denture products

  flavored with cinnamaldehyde or citral could be reduced and / or avoided by the addition, (1)

  terpene or sesquiterpene characterized by

  trisubstituted linkages that can be chosen in the

  group consisting of limonene and essential oils

  limonene, ocimene, caryophyllene and sesqui-

  terpenes of clove, myrcene, derivatives of said terpenes and mixtures thereof, or (2) propylene glycol or dipropylene glycol or a mixture thereof. It is essential that the dental vehicle is free of oxidizing agents and maintained at an acid to neutral pH so that said terpenes and

  sesquiterpenes act effectively.

  Therefore, the present invention is primarily

  purpose of providing toothpaste formulations

  containing cinnamic aldehyde or citral as the aromatic agent

  matting, which do not turn yellow and do not suffer

  discolouration as you age.

  Another object of the present invention is to provide

  a dental cream or wash solution

  che, whose color is stabilized, comprising a flavoring

  cinnamal aldehyde or citral and a quantity of

  characterized by (1) having trisubstituted double bonds and is selected from the group consisting of limonene and

  essential oils rich in limonene, ocimene, karyo-

  phyllene and sesquiterpenes clove, myrcene

  and their terpene derivatives or (2) by the fact that it is

  if between propylene glycol, dipropylene glycol or their mixtures

  Another object of the present invention is to provide

  a toothpaste containing cinnamic aldehyde or stabilized color citral, maintained at a pH below

  8.5, and preferably at a neutral pH to acid.

  Another object of the present invention is to provide

  a stabilized color acid or neutral toothpaste

  holding a flavoring agent of the aldehyde type which is free

oxidizing agents.

  Another object of the present invention is

  to provide a white dental cream or rinse solution

  mouth with a stabilized color, containing

  cinnamic dehyde or citral as a flavoring agent.

  Other goals, benefits and features of

  the invention will emerge in part from the description which will

  follow, and in part will be obvious to the specialist at

seen from the following.

  To achieve the above goals as well as

  according to the present invention, as described, the new

  toothpaste caliper of the present invention which exhibits improved stability against color discoloration

  during aging, comprises a flavoring agent containing

  an unsaturated aldehyde selected from the group consisting of cinnamaldehyde and citral, which is susceptible to discoloration upon aging, and about 0.1 to 5%

  by weight (1) of a terpene or sesquiterpene as a stabilizer

  reading of color, characterized by double bonds -

  trisubstituted and preferably selected from the

  carrying limonene and limonene-rich essential oils, ocimene, caryophyllene and clove sesquiterpenes, myrcene, their terpene derivatives, and mixtures thereof or (2) propylene glycol, dipropylene glycol or their mixtures, in a dental vehicle free of oxidizing agents and maintained at a pH below 8.5 and,

  preferably at an acid to neutral pH of about 5-7.5.

  More particularly, the present invention relates to

  a white, stabilized, colorless toothpaste or mouth rinse, with no oxidizing agents and an acid to neutral pH of about

  0.1 to 1% by weight of cinnamaldehyde or citral,

  flavoring agent, and (1) one or more terpenes or

  quiterpenes with trisubstituted double bonds or (2) propylene glycol or dipropylene glycol, as

  color alteration inhibitor, preferably in a ratio of

wearing 1: 1.

  It has been found that cinnamaldehyde or

  are used as flavoring agents to decompose when

  aging by forming unsaturated aldehyde conjugates

  fords (dienals). These dienals are responsible for yellowing

  or the discolouration that occurs when

  cinnamic dehyde or citral are incorporated in the pro-

  white dental products that include liquids or

creams (pasta).

  In commercial dental creams using

  low levels of cinnamal aldehyde, we have circumvented the

  blemish the color, eg red, blue, light green, etc. However, in white dental creams, the discoloration caused

  a small proportion of cinnamaldehyde is unacceptable.

table.

  The auto-oxidation of cinnamal aldehyde (CA) is

fectue according to the following mechanism:

255,938?

  Autooxidation of cinnamic aldehyde CH a CH-CH (AcJ)

17 CH-OH CH CH - C - OH

AC AC

slow fast

X - CH'-CHO

CH - CH-- CO2H

CO2

, '- CH2CHO

  AC -H20 C - C - C - c - C and other dinls (> CH H - CH C - CH and other dienals Acid is formed even when the samples are

  kept in hermetically sealed bottles, the

  free upper space having been swept by nitrogen. The

  Namaldehyde is clearly sensitive to low levels of

  xygen. Since cinnamic acid is white, its strength is

  tion, which takes place in a short period of time after the ex-

  position, is not responsible for the yellowing of cinnamal-

  dehyde. The intensity of the yellow color increases with the

  exposure to oxygen, rather than the amount of oxygen

  xygen, indicating that more complex oxidation occurs during aging. In particular, there is training

  of conjugated dienals which are the intense yellow components

  responsible for the discolouration and yellowing of

cinnamic aldehyde.

  It has now been discovered that an alteration engenders

  dreaded by low levels of cinnamal aldehyde (a maximum

  about 1% by weight) is reduced when certain terpenes

  or sesquiterpenes with trisubs-

  are incorporated in the toothpaste composition,

  preferably at a weight ratio of 1: 1. These terpenes

  take limonene (1), ocimene (2), caryophyllene (3), myrcene (4), terpene derivatives such as acetate

  citronellyl (5), and mixtures thereof.

> (> <>

  (1) t (2) t (3) (4) O (I) Each, taken individually in proportion to 1: 1 with cinnamaldehyde, significantly reduces the discoloration of cinnamaldehyde during aging. These compounds also reduce yellowing when aged in a white dental cream, as shown in Table 1A, which results in a 40% reduction in yellowing. , for example, limonene-rich essential oils, of which

  citrus essences such as orange, pum-

  plumousse, tangérine and mandarin. Clove sesquiterpenes are also effective stabilizers

of color.

  The yellowing of the dental cream is measured

  instrumentally on Colorgard's reflectometer. The re-

  The results given in the following tables are the + Ab (yellow scale) values and represent the increase in yellowness compared to unflavoured and non-flavored dental cream.

  aged who is considered a witness to zero b. The readings

  at 3 weeks, 6 and 9 weeks at 49 C are considered to correspond approximately to

  observed after 1 year, 2 years and 3 years at room temperature.

  ature. It is estimated approximately that an Ab value of 2 to 3 is within the marginal acceptability range, an Ab value of 2 is visually a slightly dirty white, and an Ab value of 4 represents a slightly light color.

yellow tan.

TABLE 1

  Altered color of cinnamic aldehyde in a

dental cream (Example 1) -

  A. Effect of chemicals with double bonds

  trisubstituted sounds. Aging at 49 C; Values Ab 3 weeks 6 weeks 9 weeks 1.0% cinnamic aldehyde (CA) 4.5 7.5 8.0 1.0% AC + 1.0% limonene 2.9 4.9 5.8 1.0% AC + 1.0% ocimene 2.5 5.4 5.9 1.0% AC + 1.0% caryophyllene3.2 5.3 6.0 1.0% AC + 1.0% citronellyl acetate 3.6 4.2 5.4 B. pH effect 1.0% AC pH 5.0 (citric acid) 4.25 5.5 5.1 1.0 % AC pH 6.9 to 7.1 (Example 1) 4.5 7, 8.0 8.0 1.0% AC pH 8.5 (NaHCO3) 7.5 10.5 11.2 The reduction is improved with the increase in the amount of terpene, as indicated with limonene on

the attached figure.

  In the figure, the abscissa

  limonene added and on the ordinate the degree of yellowing

  ab Ab of a dental cream with 1 Z of cinnamaldehyde.

  Curve A represents the effect of maintaining the product

  3 weeks at 49 C and curve B the effect of maintaining

  of the product for 6 weeks at 49 C.

FIGURE

i, '' '' 'l l it

* .... _...

I.- .. -N.:I

_________: ..... F ...

I, '.

:, ___ - i t.- -

  I .................................

"..-

_ _ _ _ _ _ _ rff

___'- t; --- i--

...

at.. -; .

t559387

  Although limonene is a mild flavoring agent (analogous

  orange), rates higher than 1% may be

  impractical and may be undesirable because the aroma of o-

  range can alter the original aroma of cinnamon.

  The autooxidation of cinnamaldehyde is inhibited (interrupted) by the presence of this group of terpenes

  and sesquiterpenes. The formation of epoxy-cinnabar aldehyde

  is prevented when limonene is added to alde-

  cinnamic hyde. Avoiding the formation of this epoxy-

  also prevents the formation of subsequent dienals.

  It has been shown by analytical studies that limonene preferentially reacts with cinnamic aldehyde with percinnamic acid to form 1,2-epoxy-limonene. We

  think that the other terpenes (2, 3, 4 and 5) form epochs

  analogous xyds because of the trisubstituted double bond.

  Trisubstituted double bonds are known to present

  ter greater reactivity with peracids than

  mono- or disubstituted double bonds. In addition, aldehyde

* cinnamic suggests that it presents a less reactive

  against an electrophilic attack of peracids because its

  double bond is substituted with an aldehyde group

  electron generator. Thus, by preventing the formation of

  nals, limonene significantly reduces yellowing. On au

  terpenes such as eugenol are ineffective in reducing

yellowing.

  The means for reducing discoloration of cinnamaldehyde is also applicable to other unsaturated conjugated aldehydes such as citral

  (CH3) 2C = CHCH2CH2C (CH3) = CHCHO. Citral is another flavoring

  commonly used in toothpaste compositions.

  these. Yellowing of a liquid mixture of aldehyde

  cinnamic or citral with a terpene additive is measured

  with the Gardner colorimeter when fresh

  prepared and after aging for 24 hours at 90 C 2 C.

  10 gram samples of the mixtures of

  Aromatizing and lions in various quantities, and the following readings are read: Readings on Colorimetric cinnamic aldehyde (Z) Limonene (Z) Fresh Aged

95 5 4 1 7

Zr

10 4 1 6 3/4

25 4 - 5

  100 0 (a) 4 l (a) 8 50 (a) 3 3/4 (a) 4 (a) Average of 2 readings Citral (Z) 0 (b) 1 1/3 (b) 3 2/3 O 100 (b) l 50 (b) 1 (b) 2 (b) Average of 3 readings Citral alone and the 50:50 mixture of citral and limonene are further aged for: 4 days 6 days ll days Citral alone (b) 7 (b) 7 1/3 (b) 9 2/3 Citral; Limonene at 50:50 (b) 4 (b) 4 1/3 (b) The pH of the dental cream is either acidic. only slightly alkaline, preferably from about 5 to

  7.5 as shown in Table lB. Terpenes are inefficient

  to reduce yellowing in a moderate environment.

  alkaline At pH 8.5 or higher, the peracid anion is

  form and epoxidation of cinnamal aldehyde is

  kills by addition of Michael. This type of addition reaction

  can not be interrupted by limonene.

  It has also been discovered that an alteration

  color produced by low levels of aldehyde

  Namec (a maximum of about 1% by weight) is reduced in the presence of propylene glycol and / or dipropylene glycol. These materials in a ratio of 1: 1 by weight with the aldehyde

  effectively prevent almost all the yellows

  during aging in the glass. However, in dental creams at levels of 1-5%, they do not offer

  a slight reduction in yellowing from 1% of

  cinnamic dehyde. Since these glycols are odorless, it is convenient to incorporate them in much larger proportions. Substitution of water or glycerine in dental formulations with propylene glycol or dipropylene glycol effectively prevents yellowing of flavoring agents containing cinnamaldehyde or citral. When a non-aqueous pulp is formulated by replacing the water with either glycol, no discoloration is observed. Similarly, the replacement of

  22% glycerine in a dental cream with propylene

  glycol significantly reduces yellowing.

  The mechanism of the glycol effect is assumed to be im-

  ploid formation / complexation of acetal and hemi-acetal.

  Glycols are believed to be effective by complexing aldehydes by acetal formation. Since the

  aldehydes are involved in four different phases of the -

  mechanism of formation of dienals (see reactions above),

  the reaction with glycol can significantly disturb the

  neration of dienals. An analysis of the aged sample

  1: 1 ratio of CA / propylene glycol reveals a valuable formation

  bead of acetal with a little hemi-acetal. This reaction

  versible poses the problem of consuming a certain amount of cinnamal aldehyde. In practice, the quantity

  cinnamal aldehyde may need to be increased to

think this loss.

  The autooxidation of cinnamaldehyde is

  (interrupted) by the presence of propylene glycol in

  because of the formation of glycol-acetals which are formed quickly.

  at room temperature and increase with time.

  This prevents the formation of the dienals who are responsible

  yellowing during aging.

  This means of reducing the discolouration of

  Cinnamic dehyde is also applicable to other aldehyde

  Conjugated insoluble hydes such as citral, (CH3) 2C = CHCH2-

  CH2C (CH3) = CHCHO. Citral is another flavoring agent

  commonly used in toothpaste compositions.

  Yellowing of a liquid mixture of cinnamaldehyde with propylene glycol or dipropylene glycol is measured with a Gardner colorimeter, freshly prepared and after aging for 24 hours in a 90 C flask (I), and also at 50 C for 48 hours (II), and passing oxygen on the samples

  initially for 5 seconds. Samples are pre-

  prepared with mixtures of cinnamaldehyde and said glycan

  collars, cinnamic aldehyde and glycerin and aldehyde

  cinnamic itself and the following readings are

  : Readings on Fresh Colorimetric Aged Cinnamic aldehyde (AC) 4 ll AC + Glycerin (50/50) 3; 4,111 AC + Propylene glycol (50/50) 37; 7 = 7 AC + Dipropylene glycol (50/50) 3 10; 8; 9 = 9 II Cinnamic aldehyde 4.5 7 A / Propylene glycol (50/50) 3.5 4.5 Glycerine and AC form two phases. The glycerin phase (lower) remains the white color of

  water, while the upper phase of AC darkens.

  Note that the propylene glycol mixture is slightly less dark than the dipropylene glycol mixture, but considerably lighter than the cinnamaldehyde alone. It is essential that the pH of the dental cream be acidic or. neutral, preferably about 5-7.5, as shown in Table 2. At pH 8.5 or higher, the peracid anion

  is formed and the epoxidation of cinnamal aldehyde is

  killed by the addition of Michael. This type of addiction reaction

  can not be interrupted by propylene glycol.

  The yellowing of the dental cream is measured

  instrumentally on a Colorgard reflectometer. The results

  States shown in the following tables, are + Ab values (yellow scale) and represent the increase in yellow compared to an unflavoured and unaged aged cream which is taken as reference with b equals zero. The

  readings at 3, 6 and 9 weeks at 49 C are considered

  as approximately corresponding to what we observe

  after 1 year, 2 years and 3 years, at room temperature

  ature. It is estimated approximately that a Lb value of 2 to 3 is within the marginal acceptability range, that a value of b of 2 has a slightly dirty white appearance, and that an Ab value of 4 corresponds to a slightly yellow color. tan.

TABLE 2

  Altered color of cinnamaldehyde in dental cream (Example 1) Influence of pH Aging at 49 C: Ab values 3 weeks 6 weeks 9 weeks 1% AC pH 5.0 (citric acid) 4.25 5, 5.1 5.1% AC pH 6.9 to 7.1 45 75 8.0

(Example 1)

  1 Z of AC pH 8.5 (NaHCO3) 7.5 10.5 11.2 It is also essential that the toothpaste be free from oxidizing agents such as hydrogen peroxide or

  salts releasing hydrogen peroxide such as

  sodium spleen, peracids and peracid salts. The presence of these oxidizing agents could interfere with the preferential reaction of terpene with percinnamic acid during

  1,2-epoxy-limonene formation and the pre-reaction

  ferrificial glycol with cinnamaldehyde during the formation of glycol-acetals. As described with reference to

  the need to maintain an acidic to neutral pH in the vehi-

  the presence of the peracid anion leads to

  poxidation of cinnamaldehyde by the addition of Michael.

  Tests carried out with various dental bases

  show that the discoloration of cinnamic aldehyde in Example 2 is approximately half that of

  Example 1. Similarly, discolouration

  in a bicarbonate base gives a very intense yellow

  is. These differences are identified as being due to

  differences in pH and also to the presence of TiO2 as

  dique: pH TiO2 Example 1 6.9 to 7.1 0 Example 2 6.15 0.5% Lowering the pH in Example 1 by addition

  citric acid or phosphoric acid, it reduces the

  (Table lB). By increasing the pH to 8.5 by the ad-

  NaHCO3, jaundice is significantly increased.

  is lying. Note that the addition of limonene has no reducing effect of yellowing in the NaHCO3 type base (pH 8.5).

  These remarks confirm the mechanism of auto-oxydation

  mentioned. The peracid anion is formed at a pH of 8.5 and epoxidation occurs more rapidly by addition

  from Michael. Limonene and other terpenes and sesquiter-

  with trisubstituted olefins do not react

  nucleophilic addition and thus can not eliminate

  the peroxide anion. The peracids are substantially lower than the corresponding carboxylic acid. The pKa of percinnamic acid is estimated to be 7.5. In a neutral base, free acid and anion are present. By lowering the pH, reactions caused by addition of anion are prevented. As indicated by comparing Example 1 with the Example

  ple 2, the presence of TiO2 ensures a decrease in the yellowing

  both visually and instrumentally. On the basis of a number of comparisons made with and without TiO2, there is a decrease Ab of 1.0 with 1% of

TiO2 and 0.5 with 0.5% TiO2.

  An optional advantageous additive that promotes the reduction of yellowing of cinnamaldehyde in dental formulations is titanium dioxide (TiO 2) in

  secondary amounts of about 0.5 to 1% by weight. The Your-

  Bleau 3 shows the effectiveness of limonene and propylene-gly-

  collar to reduce yellowing in dental creams having a plurality of flavoring agents containing aldehyde

  cinnamic in the presence and absence of TiO2.

TABLE 3

  Alteration of the color of the flavoring agent in a dental cream (Example 1) Flavoring agent Cinnamic aldehyde (AC) 3 weeks 6 weeks 9 weeks 1 Z of AC 4.5 7.5 8.0 1 Z of AC + 1 Z limonene + 0.5% TiO2; pH 5.6 2.4 2.9 4.5 "Spice 10" (SlO) 10 1% SiO 3.0 4.2 4.6 1% S1O + 1% Limonene + 0.5% TiO2 1.9 2.3 2.6 "Spice 12" (12s) 2 1 week 0.8% of 12S 1 2.7 4.0 4.6 0.8% of 12S + 0.1% of limonene 2, 1 3.2 3.9 255ss9387 "Spice 12" (12S) 2 1 week 3 weeks 6 weeks 9 weeks 0.8% of 12S + 0.1% of Limonene + 1% of TiO2 1.1 2.3 2 , 6 0.8% 12S + 0.5% Limonene + 1% TiO2 - 0.7 2.0 2.5 0.8% 125 + 0.25% Limonene 0.9 2.0 3 , 0 3.5 0.8% 12S + 0.5% TiO2 - 1.5 2.9 3.1 0.8% 125 + 0.1% Limonene + 0.5% TiO2 - 1 5 - 2.8 0.8% 12S + 0.1% Limonene + 0.5% TiO; pH 5.2 (citric acid) - 3.1 - 4.0 0.8% of 12S + 0.25% of Limonene +

0.5% TiO2 - 1.5 -

  0.8% of 12S + 0.25% of Limonene + 1% of TiO2 - 1.0O

1% AC + 35% dipropylene

  glycol or propylene glycol + 64% dicalcium phosphate

0.2 - dihydrate

  "Spice 10" (SlO) 1 1% S10 3.0 4.2 4.6 1% SiO (Glycerin replaced by

Propylene Glycol) 2.3 2.7 -

  1% SO10 (Glycerin replaced by

  Propylene Glycol) + 1% TiO2 0.7 -

  1The flavoring agent "Spice 10" contains 55% cinnamic aldehyde

  2The flavoring agent "Spice 12" contains 15% cinnamic aldehyde.

  Other flavoring compositions containing

cinnamic dehyde include

  White Spice 1 "- contains 20% cinnamic aldehyde.

  "White Spice 2" contains 25% cinnamic aldehyde

  The flavoring agent "Spice 11" contains 55% of

cinnamic dehyde.

  The flavoring compositions based on cinnamaldehyde can be supplemented to 100% with flavoring components such as menthol, eugenol, peppermint,

255,938?

  spearmint, clove, anethole, methyl salicylate, vanillin and the like in various mixtures. The

  menthol and eugenol are not involved in jaundice.

dental formulations.

  By mixing cinnamaldehyde with the limo

  or other terpenes, incorporating TiO2 and reducing

  At pH, high levels of cinnamaldehyde can be

be acceptable.

  By mixing cinnamaldehyde with propylene

  ethylene glycol or dipropylene glycol, by incorporating TiO2 and reducing the pH, high levels of cinnamaldehyde may also be acceptable. This can be achieved

  easily by replacing glycerine or water with propylene

  ethylene glycol, in the formulation of toothpaste.

  Flavoring agents containing cinnamic aldehyde, generally in a proportion of at least about one percent of the total flavoring agent, such as "Spice 10" or "Spice 12", cause the cream to turn white. If the dental cream is colored green, the yellowing is not

visually obvious.

  With the flavoring agent "Spice 10", the addition of 1% limonene and 0.5% TiO 2 reduces discoloration in a barely acceptable range. This addition

  modifies the initial aroma but is useful for obtaining aroma

  my like. In this case, one could prefer 1 Z of TiO2 and the use of caryophyllene (a spicy flavoring)

with limonene.

  With the "Spice 12" flavoring, the degree of yellowing

  significantly exceeds the foreseeable one with the 15%

  Cinnamic aldehyde. Interactions due to other

  posers contribute to the alteration of the color. If this

  matting is necessary for a white paste, the addition of only 0, 1% limonene and 1% TiO2 would ensure significant color improvements and a modification

only slight of the aroma.

  The dental base used in the present invention

  may be in the form of a paste, a cream or a soap

  mouth washing solution comprising ingredients

  naked, commonly used in the field of toothpastes.

  Paste or cream dentifrices can be based on aque systems. or substantially non-aqueous. The

  aqueous systems usually contain significant proportions

  carriers of finely divided solid polishing agent, a surfactant, a gelling agent, water and a non-aqueous vehicle, for example glycerol, sorbitol, and is opaque, whereas substantially non-aqueous systems are often form of a transparent or opaque gel containing

  a secondary proportion of a solid polishing agent

  ticular, transparent to the eye, a greater proportion of non-aqueous vehicle, which can constitute-at least 10%

  of the formulation of propylene glycol or dipropylene

  glycol alone or in admixture with other non-aqueous liquid vehicles such as sorbitol or glycerin, a surfactant and a gelling agent, often with

a secondary proportion of water.

  The surfactant, or detergent, present in the dentifrice can sometimes be cationic or amphoteric,

  but it is usually anionic or nonionic. Among these-

  compounds, the anionic compounds are those which are

  re. Anionic detergents or surfactants are also generally used as foaming agents. Among the useful anionic detergents, monosulphates of monoglycerides of higher fatty acids such as salts may be mentioned.

  of monosulphated monoglycerides of oil fatty acid

  hydrogenated coconut; higher alkyl sulphates such as sodium lauryl sulphate; higher alkyl arylsulfonates such as sodium linear dodecyl benzene sulfonate, olefin sulfonates

  such as higher olefin sodium sulphonate

  in which the olefinic group contains 12 to 21 atoms

  carbon mon; alkyl potassium sulfoacetates

  superior; higher fatty acid esters of 1,2-dihydric

255,938?

  droxypropane sulfonates, a magnesium salt; acyl amines

  higher aliphatics substantially saturated with

  alkaline metals of aliphatic aminocarboxylic acids

  such as those having 12 to 16 carbon atoms in the fatty acyl radicals, sodium sulfates (higher alkyl lower polyalkoxy) (10 to 100 alkoxy groups); sodium and potassium soaps of higher fatty acids

  of coconut oil and tallow, and the like. As we have

  Most often labeled, detergents are sulphated or sulphonated compounds. Examples of useful anionic amides which can be used are N-lauroyl-sarcosine and sodium, potassium and ethanolamine salts of N-lauroyl-,

  N-myristoyl- and N-palmitoyl-sarcosines. In the descriptions

  above, the term "higher" refers to chain lengths of 12 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 to 16 carbon atoms.

  carbon. The term "lower" means 2 to 4 carbon atoms.

  ne, preferably 2 or 3 carbon atoms and, better still,

two carbon atoms.

  Nonionic detergents include those

  chains of lower alkylene oxide, for example ethylene oxide, propylene oxide, in which

  there are 10 to 100 moles or more of lower alkylene oxide. By-

  Among these materials are the block copolymers of

  ethylene oxide, propylene oxide and propylene glycol,

  sold under the designation "Pluronic"; alkylphenyl

  polyethoxy ethanols sold under the designation "Igepal";

  mixed copolymers of ethylene oxide and

  pylene, sold under the designation "Ucon"; and various

  very well known nonionic compounds derived from alcohols and fatty acids and from polyethylene oxide. The agents

  amphoteric or ampholytic agents include (alkyl) amido

  alkylene alkylated long chain amines, such as "Mira-

  such as Miranol C2M and the detergents

  cationic cides such as diisobutylphenox-

  ethoxyethyl dimethyl benzyl ammonium chloride; benzyl chloride

  dimethyl-stearyl-ammonium; tertiary amines

  both a higher fatty alkyl group and two polyoxy-

  ethylene fixed to their nitrogen atom.

  The detergents comprise about 0.5 to 5%, and preferably up to 3% by weight of the dentifrice composition. Toothpastes, dental creams and

  Dental powders commonly contain polishing agents

  wise or abrasives substantially insoluble in water that

  are compatible with the formulation, in

  viron 20-75% by weight of the total formulation of the cream

  or dough and up to 95% in the case of dentine powders.

  frices. Suitable polishing agents include

  anhydrous dicalcium phosphate, dicalcium dihydrogen phosphate

  tricalcium phosphate, insoluble sodium metaphosphate, crystalline silica, colloidal silica,

  complex aluminosilicates, aluminum hydroxide (including

  alumina trihydrate or hydrated alumina), phosphorus

  magnesium phate, magnesium carbonate, calcium carbonate, calcium pyrophosphate, bentonite, talc, calcium silicate, calcium aluminate, oxide

  of aluminum, aluminum silicate and xerogels of

  contention. Most of the polishing agents mentioned are very

  useful in the preparation of opaque dentifrices, but

  some of them, for example colloidal silicas, in particular silica xerogels, and aluminosilicates

  sodium complexes, can be used in the manufacture of

  Transparent dentifrices, because their refractive index is close to that of other constants

  toothpaste in a suitable vehicle.

  In toothpaste or dental cream formulations,

  toothpaste, liquids and solids must

  be proportionate to form a creamy mass of

  desired consistency which is, for example, extrudable at

  shot of a folding aluminum tube. In general, liquid

  dental cream contains mainly water, glycerine, sorbitol, polyethylene glycol or

  propylene glycol 400, including their appropriate mixtures.

  It is generally advantageous to use a mixture of water and a humectant such as glycerin, or sorbitol or mixtures thereof. The total liquid content is usually

  20 to 75% by weight of the formulation. It is preferable

  also use a gelling agent in dental creams, for example synthetic and natural gum-like materials, such as Irish moss,

  gum tragacanth, sodium carboxymethylcellulose, poly-

  vinylpyrrolidone or starch. Irish moss and

  sodium carboxymethylcellulose are particularly

  and are the preferred gelling agents. The gum content is generally around 10% maximum,

  and preferably from about 0.3 to 5% by weight of the

  lation. It is also possible to use loads such as

  pyrogenic silica and a silica airgel, for example in

* proportions up to about 10% by weight in order to complete

  ter the gelling agent. These colloidal silica aerogels which include "Syloids" 244 and 266 and "Aerosil" and pyrogenic silica sold under the designation "Cab-O-Sil"

  can be used as gelling and thickening agents

  sants. The liquid vehicle in the form of a mouth wash solution generally comprises ethyl alcohol, glycerine, sorbitol, water and mixtures thereof in a proportion of about 90 to 98% by weight of

the total liquid content.

  Various other materials may also be incorporated into the dental vehicle. Examples are

  fluorinated compounds such as stannous fluoride, fluorine

  potassium stanneaux (SnF2KP), sodium hexafluorostannate and stannous chlorofluoride, sodium fluorozirconate and

  sodium monofluorophosphate. These matters, which dissociate or liberate

  fluoride-containing ions in water may be present in

  the dental vehicle in an effective, but non-toxic,

  generally between about 0.1 and 5% by weight. Other additives include preservatives such as sodium benzoate, compo. chlorophyllates, silicones, ammoniated materials such as urea and diammonium phosphate, antibacterial agents such as benzethonium chloride and other antibacterial compounds.

  quaternary products, sweeteners such as sodium salt,

  dium saccharin, blue dyes, flavoring

  such as peppermint or green mint

  te, etc. These additives can be used in quantities

  which do not adversely affect the properties and characteristics

  characteristics of the toothpaste according to the present invention. Cha-

  constituent may be present in minimum quantities

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

  up to 1% by weight of the formulation.

  The toothpaste of the present invention is prepared

  by conventional methods of making toothpaste

  this, dental creams, bouillon rinsing solutions

  che and toothpaste powder. More particularly, a toothpaste may be prepared by forming a gel with

  carboxymethylcellulose and water, adding

  powder and humectant, and then add

  mixing the polishing agent and then the surfactant

  tif and flavoring at the same time as the color stabilizer which is the terpene or sesquiterpene, and by tubeing the final mixture. The flavoring composition is preferably mixed with the color stabilizer which

  is terpene or sesquiterpene before addition to the

  lange. In the practice of the present invention intended. to promote oral hygiene, the toothpaste according to the present invention is applied regularly to the dental enamel by brushing the teeth for 30 to 90 seconds at least once a day and / or rinsing the teeth with a

  washing solution once a day.

  The following examples illustrate the invention without limiting it. The compositions are prepared in the usual manner and all the quantities and proportions mentioned here

  and in the appended claims are expressed by weight

  unless otherwise specified. The aromatic ingredient is

  a flavoring composition containing cinnamic aldehyde

  or citral to which a terpene or sesquiterpene (Tables 4 to 7) or propylene glycol or dipropylene glycol is added, as described in the tests according to the examples

(Table 8).

EXAMPLE 1

Dental cream

A B

  Ingredients% Glycerin 22.00 22.0 Sodium monofluorophosphate 0.76 0.88 Sodium carboxymethylcellulose 1.00 1.0 Tetrasodium pyrophosphate 0.25 0.2 Sodium salt of saccharin 0.20 0.2 Sodium benzoate 0.50 0.5 Deionized water 24.49 24.5 Dicalcium phosphate dehydrated 48.76 48.8 Flavoring agent 0.84 0.8 Sodium lauryl sulfate 1.20 1.2 pH 6.9- 7.1 6, 9 to 7.1

EXAMPLE 2

  AB dental cream Ingredients% Z Glycerine 10.00 10.0 Sodium monofluorophosphate 0.76 0.8 Sodium carboxymethylcellulose 1, 10 1.1 Sodium benzoate 0.50 0.5 Sodium salt of 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 Hydrated alumina 1.00 1.0 Phosphate dicalcium anhydrous 5.00 5.0 Flavoring agent 1.00 1, O Sodium Lauryl Sulfate 1.50 1.5 pH 6.15

EXAMPLE 3

  Gel dental cream Ingredients% Deionized water 3.00 Sodium salt of saccharin 0.30 Sodium monofluorophosphate 0.76 Glycerin 25.00 Sodium carboxymethylcellulose 0.35 Sodium benzoate 0.50 Titanium dioxide 0.01 Sorbitol (70% solution) 41.53 "Carbowax 600" (PEG 12) 3.00 0.20 Sodium alumino-silicate dye (silica containing combined alumina) 18.00 Colloidal silica aerogel 5.50 Flavoring agent 0 , 65 Sodium Lauryl Sulfate 1.20

EXAMPLE 4

  Toothpaste Ingredients% Glycerin 25.00 Sodium carboxymethylcellulose 1.40 Sodium benzoate 0.50 Sodium salt of saccharin 0.20 Sodium monofluorophosphate 0.76 Deionized water 35.44 Titanium dioxide 0.40 Aluminum oxide 10 , 00 Silica 24.00 Flavoring agent 1.10 Sodium Lauryl Sulfate 1.20 pH 6.2 0.5

EXAMPLE 5

  Example 4 is repeated with the difference that

  to 1.5% the amount of sodium lauryl sulphate and that

  the water content is adjusted accordingly.

EXAMPLE 6

  Mouth wash Ingredients% Ethyl alcohol Glycerine 10 - 15 Polysorbate 80 1 2- 3 Poloxamer 3382 O - 0.5 Benzethonium chloride O - 0.075 Flavoring composition 0.1- 0.5 Deionized water the remainder

  1A mixture of sorbitol oleates and sorbitol anhydrides

  tal, consisting of the condensed monoester with about 20

moles of ethylene oxide.

  2The polyoxyethylene-polyoxypropylene block polymer which has the formula: HO (CH 2 CH 2 O) x (-CH-CH 2 O) y (CH 2 CH 2 O) zH, CH 3

  where x and z = 128, and y = 54.

  The levels of flavoring in a washing solution

  mouth are usually lower than those used

in a dental cream.

EXAMPLE 7

Dental powder

A B

  Ingredients% Magnesium Silicate 7.00 7.0 Sodium Saccharin 0.15 0.2 Flavoring 2.50 2.5 Dicalcium Phosphate Anhydrous 88, 35 88.3 Sodium Lauryl Sulfate 2.00 2.0 flavoring level in dental powders

  are generally higher than those used in

my teeth.

EXAMPLE 8

  Non-aqueous dental cream Ingredients% Propylene Glycol 43.4 "Klucel GF" 11 (Hercules) 1.5 Sodium salt of saccharin 0.2 TiO2 0.4 Dicalcium phosphate dihydrate 50.0 Peroxydiphosphate 3.0 Sodium Lauryl Sulfate 1 PH 6.4 Hydroxypropyl cellulose - propylene glycol ether of cellulose.

EXAMPLE 9

  Aqueous tooth cream Ingredients% Propylene Glycol 22.0 Sodium monofluorophosphate 0.8 Sodium carboxymethylcellulose 1.0 Tertrasodium pyrophosphate 0.2 Sodium salt of saccharin 0.2 Sodium benzoate 0.5 Dicalcium phosphate dihydrate 48.8 "Spice 10 "o, 9 Sodium Lauryl Sulfate 1.2 TiO2 1.0

H20 Q.S.

  The following tables show the results of discoloration on aging at 49 ° C

  dental creams of Example 1 unless otherwise specified

  milking, both aroma-free and aldehyde-containing

  cinnamic (AC) itself as a flavoring agent and with

  special bolts or sesquiterpenes containing a double

  trisubstituted linkage or propylene glycol or dipropyl

  glycol to prevent or reduce the alteration of

  color caused by the ingredient cinnamon aldehyde

nomic.

  The values b of the tables represent the yellows

  of the dental cream measured on the reflectometer

  Colorgard and the value Ab represents the increase in

  compared to an unaged sample without

aroma which is the witness at b = o.

TABLE 4

  Dental Crème Alteration Studies 49 C Aging in the Dental Cream of Example 1A Control 3 weeks 4 weeks 5 weeks, 6 weeks 7 weeks 9 weeks b Ab Ab Ab Ab Ab Ab Ab Ab Ab Test I 0.5% AC 5.2 + 2.5 5.7 + 3.9 6.6 + 4.8

, 5 +2.8 6.6 +4.8

  0.5% AC + 0.5% 5.2 +2.5 6.0 +4.2 6.7 +4.9 Limonene 5.6 +2.9 6.9 +5, 1 Without flavoring 2.7 2.9 +0.2 2.7 +0.9 2.9 +1.1 Trial II 0.5% of AC 1.9 +0.2 4.6 +2.6 4.9 + 3.1 5.7 + 3.8 6.4 + 4.5 0.5% AC + 0.5% Eugenol 6.2 + 4.2 7.6 + 5.8 7.7 +5 , 9.55 + 7.6 0.6% AC in Example 2A 3.3 +1.7 + 1.9 separation separation 0.5% AC + 0.5% Eugenol in 'Example 2A 3, 8 +1.9 4.3 +2.5 4.8 +2.9 5.6 +3.7

Example 2A

without flavoring 2.0 1.8 o

1.9 1.9 -

  TABLE 4 (continued) Witness 3 weeks 4 weeks 5 weeks 6 weeks 7 weeks 9 weeks Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab

TEST III

  1% AC 6.6 +3.9 7.6 + 5.4 9.3 +7.1 10.5 +9

9.9 +8.4

  1% AC + 1% Limonene 4.9 +2.2 5.4 +3.2 6.5 +4.4 7.5 +6

6.9 +5.4

  1% AC + 2% Limonene 4.5 +1.8 4.8 +2.6 5.7 +3.6 6.2 +4.7

, 8 +4.3

Without flavoring 2.7 O0

TEST IV

  1% AC 5,7 +3,6 9,2 +7,3 9,9 +8,1 1% AC + 1 Z Ocimene 4,6 +2,5 7, 3 +5,4 7 , 7 +5.9 i% AC + 2% Ocimene 5.1 +3 7 +5.1 7.7 +5.9 2% Ocimene 3 +0.9 3.8 +1.9 3.9 +2.1 Flavor-free 2.1 2.1 2.1 + 0.2 2 + 0.2 Co

TABLE 5

  49 C Aging in the Dental Cream of Example 1A 2 weeks 3 weeks 4 weeks 6 weeks 9 weeks Ab Ab Ab Ab Ab Ab Ab Ab

TEST V

  1% AC 6.7 +4.8 8.4 + 6.5 9.6 + 7.9

, 2 +8.5

  1% Eugenol 4.1 +2.2 4.5 +2.6 4.3 +2.6 1% AC + 1% Eugenol 8.1 +6, 2 9.9 +8 10, 7 +9 0.5% AC + 0.5% Eugenol 5.9 +4 8.1 +6.2 8.9 +7.2 0, 9% AC + 0.1% Eugenol 5 +3.1 6.6 +4.7 7.2 +5.5 1% Spice 10 4.8 +2, 9 6.3 +4.4 6.7 +5

6.4 +4.7

  % of "White Spice" N l 3.8 +1.9 4.6 +2.7 5.0 +3.3

, 1 +3,4

  No flavoring 1.9 TEST VI ua Co 1% of "White Spice N 2 3.3 + 1.2 3, 5 +1.7 4.6 +2.9 5.1 +3.2 -4

4 +2.3

  Flavor-free 2.1 2.1 0 2.2 +0.5 2 +0.1 TABLE 5 (continued) Control 2 weeks 3 weeks 4 weeks 6 weeks 9 weeks b a b b Ab b b b to b b b b to b

TEST VII

  0.5% of AC + 0.5% 5.9 +4 7.2 +5.3 7.8 +6 of Eugenol 6.9 +5.0 7.8 +6 0.5% of AC + 0.5% 4.7 +2.8 6 +4.1 7 +5.2 Eugenol + 1% of 6 +4.1 7.5 +5.7 Limonene No flavoring 1.9

TEST VIII

  1% of "White Spice" N I 4.1 +1.9 4.8 +3.0 5.1 +3.5

4.9 + 3.1

  1% of "Spice 10" 5.6 +3.4 5.8 +4.2 5.8 +3.8

, 6 +4.0 6 +4.4

  1% of "Spice 10" + 1% of Limonene 4.9 +2.7 4.8 +3.2 5 +3

, 2 +3.6 5.4 +3.8

  1% "Spice I1" + 1% Limonene 4.8, 2.6 5.1 +3.5 5.3 +3.7, 4 + 3.8 one us 1% Limonene 2.4 +0 , 2 2.3 +0.5 1.9 +0.3 d co

TABLE 6

  Aging at 49 ° C in the dental crM of Example 1A Control 1 week 2 weeks 3 weeks 6 weeks 9 weeks b b & b b, b b b b b b Ab Test i 1% of. AC 45 +2.5 7.2 t5.1 10.5 * 8.9 11.1 +9.2% of AC4 0.25% of Limon 6t1 +4 7.7.6.1 8.5.6.6 1% of AX 0.5% of L1onane 5.9 * 3.8 6.9 +5, 3 8.3.6s4 Ideac 0.75% of Liznke 5.4 * 3.3 6.9 +5.3 7.8 +5.9] % Ace 1 'Limine 5.3 * 3.2 6.5 * 499 7.9 t6].) A> 1.5% Limonene 5.0 t2s9 6.6 + 590 6.7 +4.8 lde AC 3% of Lionane 4g8,2,7 5s3 +3,7 6,2 +4,3 of AXO5%. Limnene 4.2 t2.1 5O0 +3.4 597 +3.8 Without arganizer 2 1 1% AC + 1% caryophyllene 3.3 * 1.3 593 t3.2 6.9 +593 79 +6 Test Example 4 1.5 1, 8.0.3 1.8 2.1 +0.4 2.1 +0.2 Sample 4 1.8 -0.2 1.6 1.8 -0l u Co te * 4 0119c18 + 11966Z + l 16t + tT * OA - [the r6zoap -, 5c 'C4 8'S9'C + Z'4aZv + 5s z'T 6'z 6'l S aTdoexat smp ORQUOqW op 9'C4 S5 Le4SC + 6I z 91r + '' z 4 TT! ldr *, 42op% T re) r t6u! ## EQU0000 ## ## EQU0000 ## ## EQU1 ## '' '' '' '' '' • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • •

TABLE 7

  Aged at 49 ° C. in the dental cream of Example 1A Control 1 week 3 weeks 5 weeks 6 weeks 9 weeks bbb b b b b Qb b, Ab., A b b

E-SSAI I

  1% of AC from example 1 pH 4.9 3.1 tl13 6.3 +4.5 7.4 +5.5 702 + 4.8 LUdc AC of example 1A pH 6.9 4 2, 2 7 +592 S, 9 +7 8.3.519 Ex. 1A without arcmatizer pH 4.9 1.6 1B 1.9 2.4 Ex. 1JA without armnatising pH 6.9 1.8 1.9 292 Ex. 2A without arnMatisant 1.6

ESSA. II !!

  O.8.deSpoC + 0.5% of 299 + lj1 3t6 +1.9 4.9 + 2Sl Toi2. above 5.2 Pm (citric acid) 499 * 3.1 5 $ 3 +3.6 6.1 * 4.0 Above pU 591 (ll3PO4) 4? 7 f2.9 5 +3.3 Above pHI 6.2 (H3PO4) 4.4.2.6 419 +3.2 Above pH 58 (citric acid) 4.7 +2.9 5.2 +3.5 5> 7 +3 , 6 1% of Spioel. 0.5% TiO2 + 2p7 + 0J9 3.8.291 4 $ 2 +295 497 + 2y6 1% Limonene 396 + 2O0 co s .. 1 week control. weeks5 weeks 6 weeks 9 weeks t ..... hh A h At, h.Ah h Ab abb4b bb bAh Ab Above $ 5.2 acid 296.or8 35 * 1.99 390.291 496 * 205 citriqu4 Above depli 51 (H PO) 2.8.1.0 37 2 43 * 2, 6 516 +25 3 .. g27 + 2s Above depi 5.8 (citric acid) 2.8 +1 397 + 291 41 +2, 4 593 +392 Above 6.2 (13P04) 4.8 +1 34.8 2.2 4.1 +294 496 + 2.5

TEST XIV 1% of AC of Example 2A 5.2.3.5 6.9 * 4.7 7.1 +.53 binds AC 1% of Limnene

  in ex-example 2A 492.2.5 5.2.3.0 5.8 +4.0 one sample 44 27 52 30 58 40 W 4% 14.29.7 592,: 3t, 00 4 C 1% of citral 499 +3. ) 2 5,4 * 3,2 692 +4, 4 1% citral + 1% Limonene 3t7.2.0 4.3 * 2.1 498. + 30 1% dcbA, + 0.5 02 fold 5 ) 6,592 +3,5 6,9.4.7 6,7,419 _deI. 1DF. 4monne.09,5% 4,1 +2,4 5,1 2s, 9 6,1 + 4 $ 5 of Tio2 pl 5,6 096 '; ke s8pic 12 + 0,5'eTiJ.02 493.2,7 5, 2.3Y0 5,7 '3t9 fold 5,6 r> 098taice U * _ O 1% Litnia 4.2.2,6 5,3 * 3,1 5f9 * 4,1 o

39 2559387

TABLEA.U 8

  Studies of discoloration of dental breasts Aging at 49 in the dental cream of Example lB 1 week 3 weeks 6 seaines

TEST XV

  2 of AC in the example 82.3 + 0i3 3.8, +1 5.1 * 3 4 I X in the eighth

1.7 + 0 3.3 +1.3 1.6 +299

  UldebC + 10% Propylinm Olycol 4O0.1,8 540 +30 791.594% + 36% Proprl * nc Glycol + 6% phosphate - 8, dioxolecoe O 198 + o Solidified sample

XVT TEST

  1% of AC 591 + 392 12.6 + 10 * 4 109, +66.7 1% i G o 2 + 33 9% 6 s + s3 pylias Glycol 592 +393 9.6 + 7j, 4 8.0, 4.3 rT + 6J6 660+ e6 a + r0 / + 66 (9Z + CZ oda ToDTm I t 6 $ SL "t 8" "t" z 64s ST & bOd w,% + .OT aoTds.itt 04, To tG ir + G6G 6 T + L '/. ToD.x TAeimmd op% S + OT GoTdS ap li C + 9f 4C + /? Gg OT otdds + t IA lX vss' O * 6 & {Z {O + "z O + it1, bTO' Tcp 9iutdsoqd ep% I9 + Tot 66Z' At 949 9o '+ X * 6 0S + 6'4r po ct auel & bZe% S + ov Rp kT Tooe L4t. #F {9 & 9 + e' 94OZ 9 {{Uer T 1 OOLTO -. uqTMocT op%! + av dp Om'lml '' C tt -UTdl GP% Sv- qO qTdSGp CK o0 If '-, eLo Z6 tcTlu te, Su, OT, oTddN "O 0 XIX xi% as L'. CZ Li't tt C'ó 6 OTdkoeXt on: p o0 '-TdS 6 * 0O L / 4r O'9 Oi4 / 9 T4 66C.oT oTdS o 0 rr r'9 - enq 4 q _ ^ ___ q 's' q CIA ivs

- 42

  Tables 4 to 7 inclusive describe formulations

  containing various flavoring agents containing cinnamal aldehyde

  and decreasing yellowing by the addition of limonene or other terpenes and sesquiterpenes characterized by trisubstituted double bonds. Adjusting the pH to about 6 and the addition of TiO2 further reduces the yellowing of

  these formulations containing a flavoring.

Claims (24)

R E V E N D I C A T I 0 N S   1 - Toothpaste having improved stability to   against an alteration of color during aging   characterized in that it comprises an unsaturated aldehyde flavoring agent, selected from cinnamaldehyde and citral, which is susceptible to discoloration upon aging, and about 0.1 to 5% by weight of (1 ) to   least one terpene or sesquiterpene containing double bonds   trisubstituted substances, such as color distortion inhibitor, or (2) propylene glycol, dipropylene glycol or a mixture thereof, in a dental vehicle free of agents   oxidizing agents and having a pH below 8.5.   2 - Toothpaste according to claim 1, characterized   rised in that the color change inhibitor is at   least said terpene or sesquiterpene.   3 - A toothpaste according to claim 2, characterized in that the color alteration inhibitor is chosen from   group consisting of limonene and essential oils   limonene, ocimene, caryophyllene and sesquiterpenes of clove, myrcene, terpene derivatives thereof, and their mixtures.   4 - Dent: according to claim 1, characterized in that the color alteration inhibitor is said   propylene glycol, dipropylene glycol, or mixtures thereof.   5 - Toothpaste according to claim 1, characterized   in that said flavoring constitutes about 0.1 to 1% by weight of the composition.   6 - Toothpaste according to claim 2, characterized   in that the weight ratio of said flavoring aldehyde at terpene is 1: 1.   7 - Toothpaste according to claim 4, characterized   in that the color distortion inhibitor   about 10 to 45% by weight of the composition.   8 - Toothpaste according to claim 4, characterized   in that the dental vehicle is an anhydrous dental cream.   9 - Toothpaste according to claim 4, characterized   in that the dental vehicle is an aqueous dental cream.   Toothpaste according to claim 1, characterized   rised in that the toothpaste is a dental vehicle having a pH of about 5 to 7.5.   11. The toothpaste according to claim 10, characterized   in that the toothpaste is a stabilized dental cream white color.   12 - A toothpaste according to claim 11, characterized   in addition to containing approximately 0.5 to 1% weight of titanium dioxide.   13 - Toothpaste according to claim 10, characterized   rised in that the toothpaste is a washing solution of   the mouth stabilized, white color.   14 - Toothpaste according to claim 2, characterized   it is in the form of a white dental cream and contains 1% of cinnamal aldehyde as   flavoring agent and 1% limonene as color stabilizer.   15 - Toothpaste according to claim 2, characterized   rised in that it is in the form of a dental cream of   their white and contains 1% cinnamic aldehyde as   flavoring agent and 1% ocimene as color stabilizer.   16 - Toothpaste according to claim 2, characterized   it is in the form of a dental cream of   white and contains 1% cinnamic aldehyde as aro-   matting and 1% of caryophyllene as a their.   17 - Toothpaste according to claim 2, characterized   it is in the form of a dental cream of   their white and contains 1% cinnamic aldehyde and 1%   of citronellyl acetate as color stabilizer.   18 - Toothpaste according to claim 2, characterized   it is in the form of a dental cream of   their white and contains 1 Z of citral as a flavoring and   1% limonene as color stabilizer.   19 - Toothpaste according to claim 2, characterized   rised in that it is in the form of colored dental cream   white and contains 1% cinnamic aldehyde as aromatic   and 1% of limonene as a color stabilizer and, in addition, about 0.5 to 1% by weight of titanium dioxide.   Toothpaste according to claim 13, characterized   in that it contains 0.1 to 0.5% by weight of a compound   flavoring containing cinnamic aldehyde or citral.   O 21 - Toothpaste according to claim 2, characterized   rised in that it is in the form of colored dental cream   white and contains 0.1 to 1% by weight of an aromatic composition.   containing cinnamic aldehyde or citral and,   in addition, about 0.5 to 1% by weight of titanium dioxide.   22 - Toothpaste according to claim 1, characterized   rised in that it is in the form of a dental cream con-   approximately 20 to 75% by weight of an internal polishing agent soluble in water.   23 - Toothpaste according to claim 1, characterized   in that it contains about 0.05 to 5% of surfactant.   24 - Toothpaste according to claim 1, characterized   in that it is in the form of a dental cream containing   a liquid in a proportion of about 20 to 75% by weight of the composition.   25 - Toothpaste according to claim 1, characterized   is in the form of a mouth wash solution having a liquid content of about 90 to 98% by weight of the composition.   26 - Toothpaste according to claim 4, characterized   rised in that it is in the form of colored dental cream   white and contains 1% cinnamic aldehyde as aromatic   and 22% of propylene glycol as an inhibitor of   color and, in addition, about 0.5 to 1% by weight of titanium dioxide.   27 - Toothpaste according to Claim 4, characterized   in that it is in the form of white-colored dental cream   and contains 1% cinnamic aldehyde as a flavoring and 35% dipropylene glycol as a color change inhibitor and, in addition, about 0.5 to 1% by weight of titanium dioxide. 28 - Anhydrous toothpaste according to claim 8, characterized in that it contains 1% of cinnamaldehyde   as flavoring and 43% propylene glycol.   29 - Anhydrous toothpaste according to claim 8, characterized in that it contains 1% of cinnamaldehyde   as flavoring and 22% propylene glycol and 1% titanium oxide.   Toothpaste according to claim 13, characterized   rised in that it is anhydrous and contains 10 to 15% propylene   ethylene glycol and 0.1 to 0.5% cinnamic aldehyde.