WO1997000665A1

WO1997000665A1 - Liquid tooth-cleaning agents

Info

Publication number: WO1997000665A1
Application number: PCT/EP1996/002568
Authority: WO
Inventors: Peter Wülknitz; Amerigo Pastura; Hans Laska; Klaus Schumann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1995-06-22
Filing date: 1996-06-14
Publication date: 1997-01-09
Also published as: DE19522750A1

Abstract

The invention pertains to liquid tooth-cleaning agents containing sodium hydrogen carbonate as a polishing component in quantities of 1-60 wt.%, as well as water-soluble binders and moisturisers, and having a viscosity of 2-50 P.s (at 20 °C). In order to ensure advantageous flow characteristics, a combination of hydroxypropyl guar and polyvinyl pyrrolidone is used as the binder. Water-insoluble polishing agents, preferably silicic acid, are preferably also included.

Description

"Liquid tooth cleaning products"

The invention relates to liquid tooth cleaning agents with a Ge content of polishing components, humectants and water-soluble binders, which can be removed from a flexible container in the form of drops and slowly penetrate the bristles when applied to a toothbrush without running off the toothbrush.

Liquid dentifrices have been known for a long time. A particular problem, however, is the production of storage-stable liquid preparations with a content of polishing bodies which, when stored for a prolonged period of time, neither show a settling of the polishing component on the floor nor a sharp increase in viscosity which makes it difficult to dispense from a flexible container. The viscosity of such liquid tooth cleaning agents is preferably in a range from 2 to 50 Pa * s (20 ° C.), measured with a rotary viscometer.

Liquid tooth cleaning agents of this type are known, for example, from US Pat. No. 5,178,869 and from WO 94/01080. Sodium bicarbonate (so-called baking soda) has been known as a polishing component in dentifrices for many years. For example, DE-A-2347787 proposes toothpastes which contain sodium hydrogen carbonate together with smaller amounts of conventional polishing components. Liquid tooth cleaning agents were already known from EP-A-0517319, but they only contained smaller amounts of dissolved sodium hydrogen carbonate in addition to chalk as polishing bodies. However, it has proven to be very difficult to produce liquid tooth cleaning agents with higher proportions of undissolved sodium bicarbonate, since the sodium bicarbonate dissolved in the aqueous phase up to the saturation limit interacts with the water-soluble polymeric binders required for viscosity adjustment and either leads to a slimy, stringy structure or to a strong increase in viscosity, to gelation, to phase separation or to sedimentation.

It was therefore the task of developing tooth cleaning agents with a higher proportion of finely divided sodium hydrogen carbonate as a plaque-neutralizing polishing component in the form of a still flowable preparation which can be poured out from a storage container, or from a flexible dispenser bottle by light pressure in the form of Drop can be removed. It has surprisingly been found that this object can be achieved if a special combination is used as the water-soluble polymeric binder.

The invention relates to a liquid dentifrice containing polishing components, humectants and water-soluble polymeric binders, characterized in that an alkali hydrogen carbonate is contained as the polishing component and a combination of a nonionic guar derivative and a polyvinylpyrrolidone is contained as the water-soluble polymeric binder. A liquid tooth cleaning agent should be understood to be a preparation whose viscosity at 20 ° C. is in the range from 2 to 60 Pa * s, measured, for example, in a Brookfield Synchro Lectric RVF rotary viscometer.

The tooth cleaning agents according to the invention remain flowable even after prolonged storage, the polishing components do not settle and the flow behavior is very advantageous for use from a flexible dispensing container with a narrow opening, since the product is easy to remove and in the form of viscous drops has the toothbrush brought.

Sodium bicarbonate or a mixture of sodium and potassium bicarbonate is preferably used as the alkali bicarbonate. Potassium hydrogen carbonate causes a higher viscosity of the system than sodium bicarbonate. It has been shown that a mixture of sodium and potassium hydrogen carbonate in the weight ratio NaHC03: KHCO3 = 100: (5-30) achieves a particularly high viscosity even with a relatively low binder content. The addition of potassium bicarbonate also improves the salty taste.

The alkali hydrogen carbonate is preferably used as a fine, anhydrous powder of commercial quality and with a particle size which is predominantly in the range from 0.001 to 0.4 mm. The fine particle size of the hydrogen carbonate also has a favorable effect on the viscosity. The sodium hydrogen carbonate should therefore preferably have at least 90% by weight of a grain size below 0.16 mm. Although the sodium bicarbonate particles are relatively soft compared to other polishing components, they have a good mechanical cleaning action on the tooth surface. The alkali metal hydrogen carbonate can be present in an amount of 1 to 50% by weight in the liquid tooth cleaning agents according to the invention. to To improve the polishing effect, water-insoluble polishing components may also be present, for example silica polishing agents customary for dentifrices or aluminum hydroxide, calcium phosphates, polymetaphosphate, chalk or sodium aluminum silicate.

The dentifrices according to the invention preferably contain a combination of 5 to 25% by weight of alkali metal bicarbonate and 1 to 20% by weight of silica polishing agents. Suitable silicic acid polishing agents are gel silicas and precipitated silicas.

As a nonionic guar derivative, an etherification of the guar gum with alkylene oxides, e.g. hydroxyalkyl guar obtained with ethylene oxide or propylene oxide can be used. Such guar derivatives are indeed very good thickeners for aqueous preparations, when used in the liquid tooth cleaning agents according to the invention as the sole water-soluble binder they also lead to stable preparations, the viscosity behavior of which is, however, characterized by low fluidity and strong threading due to high structural viscosity . Surprisingly, it was found that this effect is avoided by using polyvinylpyrrolidone as the second water-soluble binder.

Suitable hydroxyalkyl guar is preferably hydroxypropyl guar, which is obtainable by adding propylene oxide to guar gum and is commercially available, for example, as Jaguar ( ^R ) HP-8 (degree of substitution 0.3-0.5).

The commercially available products with K values from 30 to 90 and average molecular weights from 40,000 to 700,000, which are commercially available as Luviskol ( ^R ) K30 or Luviskol ( ^R ) K90, are suitable as polyvinylpyrrolidone. Liquid tooth cleaning agents according to the invention preferably contain a combination of

0.1-2% by weight of hydroxypropyl guar and 0.1-5% by weight of polyvinylpyrrolidone.

In addition to these obligatory binders, other known inorganic and organic thickeners can also be present in the tooth cleaning agents according to the invention. Particularly fine thickening silicas, e.g. Silicas obtained by pyrolysis (type Aerosil), and layered silicates are used. Other organic polymers are e.g. natural vegetable gums, swelling starch, water-soluble starch and cellulose derivatives, e.g. Carboxymethyl cellulose or hydroxyl ethyl starch. Biopolymers such as Xanthan gum or succino-glycane are suitable as further thickeners. The proportion of the further organic thickeners is preferably less than 0.5% by weight of the composition.

Polyols with 2 to 6 carbon atoms and 2 to 6 hydroxyl groups or polyalkylene glycols are suitable as humectants. Suitable polyols are glycerol, sorbitol, 1,2-propylene glycol, polyethylene glycol and polypropylene glycol as well as ethylene oxide-propylene oxide block polymers and mixtures of these substances. Liquid polyethylene glycols with molecular weights up to 800 are particularly suitable as polyethylene glycols. If sorbitol is used as a humectant, a particularly pure quality free of reducing sugars and disaccharides must be used in order to prevent disruptive discoloration or elimination.

The tooth cleaning agents according to the invention preferably contain glycerol, polyethylene glycol or a mixture of these substances in an amount of 30 to 80% by weight. Water and optionally smaller amounts of ethanol or isopropanol may be present as further carrier components. The water content is preferably below 25% by weight, the ethanol content should remain below 10% by weight.

In addition, the dentifrices according to the invention may contain the usual auxiliaries and additives, e.g.

surfactants, e.g. Anionic surfactants in the form of their alkali metal or ammonium salts such as sodium lauryl sulfate or sodium lauryl ether sulfate, acyl sarcosinates, acyl isethionates, acyl (methyl) taurides or ether carboxylates, amphoteric and zwitterionic surfactants such as e.g. Cocoamphoglycinate or cocoamido propyl betaine, amine oxide surfactants, nonionic surfactants such as e.g. Fatty alcohol polyglycol ether, fatty acid (mono) glycerides and their oxethylates or fatty acid oxethylates or alkyl (oligo) glucosides.

Flavors and plant extracts such as Peppermint oil, spearmint oil, eucalyptus oil, anise oil, fennel oil, caraway oil, menthyl acetate, cinnamon aldehyde, vanilla, thymol or flavorings with strawberry, raspberry, pineapple, apple, orange or kiwi flavor

Sweeteners such as Na saccharinate, K-acesulfame, cyclamate, aspartame and others

water-soluble fluorine compounds such as e.g. Sodium fluoride, monofluorophosphate, tin fluoride, amine fluoride,

pH adjusting agents such as mono-, di- and trialkali metal phosphates, citric acid / Na citrate, lactic acid / Na lactate, Anti-tartar active ingredients, e.g. di- and polyphosphonates (e.g. 2-hydroxyethane-2,2-diphosphonate) or polyphosphates (e.g. tetrasodium pyrophosphate, pentasodium triphosphate)

antimicrobial substances such as Triclosan, biguanides (such as chlorhexidine) and other quaternary ammonium compounds,

Dyes, pigments and opacifiers (e.g. titanium dioxide, zinc oxide).

The liquid dentifrices according to the invention preferably contain

5 - 25% by weight sodium bicarbonate 1 - 20% by weight silica polishing agent 0.2 - 1% by weight hydroxypropyl guar 1 - 3% by weight polyvinylpyrrolidone 30 - 80% by weight glycerin or polyethylene glycol or one Mix of both 5 - 25 wt .-% water, ethanol or mixtures thereof as well

1 - 10% by weight of additives from the group of surface-active substances, aromas, sweeteners, fluorine compounds and their mixtures.

The liquid dentifrices according to the invention are produced, for example, in such a way that the polishing components are dispersed in the greater part of the humectants, the binders are dispersed in the remaining humectants (and, if present, are brought into solution with part of the water) and then the po Body dispersion with the binder dispersion and with the solution of the surfactants, the fluorine compounds and the sweeteners in Water or its dispersion in polyol and with a solution of the aromatic oil, an emulsifier and possibly ethanol is combined and mixed.

The following examples are intended to explain the subject of the invention in more detail:

B e i s p i e l e

Liquid tooth cleaning agents were produced according to the following recipe examples:

1 2 3 4 VI V2

NaHCÜ3 finely powdered ¹ ) 6.0 10.0 20.0 20.0 20.0 20.0

Silica (Sident (R) l2 SPLS) 12.0 12.0 12.0 12.0 12.0 12.0

Titanium dioxide 0.5 0.5 0.5 0.5 0.5 0.5

Glycerin (86% in H2O) 45.0 50.0 40.0 40.0 40.0 40.0

Polyethylene glycol (MW: 400) 8.0 8.0 8.0 8.0 8.0 8.0

Na saccharinate 0.2 0.2 0.2 0.2 0.2 0.2

Na fluoride 0.231 0.231 0.231 0.231 0.231 0.231

Jaguar ( ^R ) HP8 0.4 0.4 0.45 0.3 0.45 -

Luviskol ( ^R ) K30 2.0 2.0 1.5 2.0 - 2.0

Carbopol 980 0.1 - - - - -

Keltrol F - - - - - 0.2

Texapon K 1296 1.5 1.5 1.5 1.5 1.5 1.5

Tego Betain BL 215 ³ ) 0.6 0.6 0.6 0.6 0.6 0.6

Tagat S 0.5 0.5 0.5 0.5 0.5 0.5

Aromatic oil 0.8 0.8 0.8 0.8 0.8 0.8

Ethanol 5.0 5.0 5.0 5.0 5.0 5.0

Water ad 100 ad 100 ad 100 ad 100 ad 100 ad 100

Viscosity (20 ° C) Pa-s 11.4 7.4 4.7 0.75 Solid Solid Continuation of examples

5 6 7 8

NaHCÜ3 finely powdered) 20 18 20 18

KHCO3 finely powdered ² ) - 2 - 2

Silica (Sident ( ^R ) l2 SPLS) 12 12 12 12

Titanium dioxide 0.5 0.5 0.5 0.5

Glycerin (86% in H2O) 34.4 34.4 34.4 34.4

Polyethylene glycol (MW: 400) 8 8 8 8

Na saccharinate 0.2 0.2 0.2 0.2

Na fluoride 0.231 0.231 0.231 0.231

Jaguar ( ^R ) HP60 0.15 0.15 0.3 0.3

Luviskol ( ^R ) K30 1.5 1.5 1.5 1.5

Keltrol F

Texapon K 1296 1.5 1.5 1.5 1.5

Tego Betain BL 215 ³ ) 0.6 0.6 0.6 0.6

Tagat S 0.5 0.5 0.5 0.5

Aroma oil 0.8 0.8 0.8 0.8

Ethanol 5 5 5 5

Water ad 100 ad 100 ad 100 ad 100

Viscosity (20 ° C) Pa-s after 1 hour 12 34 8 56

!) Grain spectrum:> 0.2 mm: 0.3%, 0.2-0.16 mm: 7%, 0.16-0.063 mm: 83%,> 0.063 mm: 10%

2) Grain spectrum:> 0.7 mm: 2%,> 0.5 mm: max. 20%,> 0.25 mm: max. 80%,> 0.1 mm: 97%

3) 30% solution in H2O The following commercial products were used to prepare the examples:

Jaguar HP-8: hydroxypropyl guar obtained by hydroxypropylation (addition of propylene oxide to guar gum (degree of substitution 0.35 to 0.45)

Jaguar HP-60: as above, degree of substitution: 0.6

Luviskol K30: poly-N-vinylpyrrolidone (-2), molecular weight approx.40,000, K value (1%) 30 + 4

Carbopol 980: polyaeric acid, cross-linked; Acid number 700 - 750

Keltrol F: xanthan gum (food-grade)

Texapon K 1296: sodium lauryl sulfate

Tego-Betain BL 215: Cocoamidopropyl-betaine (1-Ci2-i8-Alcylamido-3-dimethylaminopropane-3-carboxymethylbetaine), 30% by weight (NaCl: 5% by weight) in water

Tagat S: polyoxyethylene (20) glycerol monostearate

The dentifrices were produced using the following procedure:

The polishing components (NaHC03, KHCO3, silicas) and TiO2 were mixed with glycerin to a homogeneous slurry. The water-soluble binders (PVP, hydroxypropyl guar) were mixed with the polyethylene glycol and swollen in part of the water with vigorous stirring. The surfactants (Texapon K 1296, Tego-Betain), saccharin-Na and NaF were dissolved in the remaining water. The aromatic oil and the Emulsifier (Tagat S) was dissolved in ethanol. Finally, the surfactant solution, the binder solution and the aroma oil solution were successively mixed into the polishing paste and the mixture was deaerated.

The viscosity measurement was carried out with a Brookfield Synchro Lectric, RVF, rotary viscometer using spindle No. 3 at 4 RPM.

Comparative approaches VI and V2 were not flowable.

Claims

claims

1. Liquid dentifrices containing polishing components, humectants and water-soluble binders, characterized in that an alkali hydrogen carbonate and a water-soluble polymeric binder contain a combination of a nonionic guar derivative and a polyvinylpyrrolidone.

2. Liquid tooth cleaning agent according to claim 1, characterized gekenn¬ characterized in that the viscosity at 20 ° C in the range of 2 to 60 Pa ^« s, measured in a rotary viscometer, is.

3. Liquid tooth cleaning agent according to claim 1 or 2, characterized in that the alkali hydrogen carbonate is contained in an amount of 1 to 50 wt .-%.

4. Liquid tooth cleaning agent according to one of claims 1 to 3, characterized in that a combination of as a binder

0.1-2% by weight of hydroxypropyl guar and 0.1-5% by weight of polyvinylpyrrolidone

is included.

5. Liquid tooth cleaning agent according to one of claims 1 to 4, characterized in that silica are contained as additional polishing components in an amount of 1 to f.0 wt .-%.

6. Liquid dentifrice according to one of claims 1 to 5, characterized in that glycerin, polyethylene glycol or mixtures of these substances are contained in an amount of 30 to 80 wt .-% as humectant.

7. Liquid tooth cleaning agent according to one of claims 1 to 6, characterized in that a sodium bicarbonate or a mixture of sodium and potassium bicarbonate, preferably in the weight ratio NaHC03: KHCO3 * 100: (5-30) is contained as alkali bicarbonate.

8. Liquid tooth cleaning agent according to one of claims 1 to 7, characterized by a content of

5 - 25% by weight alkali hydrogen carbonate

1 - 20 wt .-% silica polishing agents 0.2 - 1 wt .-% hydroxypropyl guar

1-3% by weight of polyvinylpyrrolidone 30-80% by weight of glycerin or polyethylene glycol or a mixture of both

5 - 25 wt .-% water, ethanol or their mixtures as well

1-10% by weight of additives from the group of surface-active substances, aromas, sweeteners and fluorine compounds.