WO2000030597A1 - Striped toothpastes - Google Patents

Abstract

The invention relates to a toothpaste composition consisting of at least two separate, plastically flowing components which can be squeezed out of a container together in the form of parallel, concentric or striped strands and which contain a polishing agent in an aqueous support containing moisturisers and tensides. At least one of the components contains coloured pigments. Compositions of this type are especially stable in relation to colour migration in the boundary phase when they contain water-insoluble iron oxide pigments from the group of the pigment red 101 and the pigment yellow 42 or organic red pigments from the group of the pigment red 4.5 or 181 or a mixture thereof, in a sufficient quantity for colouring. One of the components is preferably colourless or pigmented white.

Description

 "Striped toothpastes"

The invention relates to a toothpaste composition consisting of at least two separate, plastically flowing components which are filled in a container and can be squeezed out of this together in the form of parallel, concentric or striped strands, at least one of the components being colored, water-insoluble pigments, preferably of contains yellow to red color direction.

Striped toothpastes are known. For example, EP 0 331 617 AI describes a striped toothpaste, the strip component of which is a clear gel with organic pigments from the group β-carotene and chlorophyllin. From DE 38 41 775 AI a striped toothpaste was known, the strip component of which has a lower yield point than the carrier component. EP 0 661 041 AI describes a striped toothpaste, the strip component of which has a significantly higher viscosity than the carrier component.

One problem that always arises in the development of multi-colored, striped toothpastes is the bleeding of the dyes from the colored component, which is caused by a gradual transition of the dye taking place at the phase boundary between the colored and the undyed or differently colored phase. This problem does not only exist when using soluble dyes, many products are also unsuitable for pigment dyes because they either do not produce brilliant colors or because they are incompatible with certain toothpaste ingredients or also tend to bleed out in certain formulations. This applies in particular to the area of yellow and red color pigments, most of which are unsuitable for coloring toothpastes. It also applies increasingly to toothpaste formulations whose strip phase and carrier phase do not differ significantly in composition or theological behavior.

It was therefore the task of finding suitable colorants for toothpastes which contain polishing agents in an aqueous carrier containing humectants and surfactants, which allow a part of the paste to be colored in such a way that after filling the colored and uncolored component into a container, as is customary for striped pastes, have them squeezed out in the form of parallel strands which show no transition of the color into the carrier mass at the phase boundary.

This object was achieved according to the invention by a toothpaste composition consisting of at least two separate, plastically flowing components which are filled in a container and can be pressed out of this in the form of parallel, concentric or striped strands, and the polishing agents in an aqueous carrier with a content contain humectants and surfactants, at least one of the components containing colored, water-insoluble iron oxide pigments or organic red pigments from the group Pigment Red 4, 5 and 181 or a mixture thereof in an amount sufficient for coloring.

Such toothpastes are particularly attractive to the user, especially since the known devices and containers for dispensing striped toothpastes are very versatile due to the corresponding design of the outlet opening of the containers and the number, size and shape of the openings through which the components emerge from the container enable aesthetic design of the product line.

Information on the infestation of such toothpaste containers and the design of the outlet openings of tubes can be found in numerous patent publications, for example in GB 813 514 B, US 2,789,731 A, US 2,935,231 A, DE 11 124 47 A, DE 11 859 81 C, DE 12 141 41 C, DE 37 41 087 AI and DE 38 41 775 AI. The toothpaste composition according to the invention can be composed of two, three or even four separate, plastically flowing components, of which at least one, but optionally also two, three or all, contain colored pigments. If more than one of the components is pigmented in color, pigments of different color directions are preferably used in the pigmented components. However, a colorless component can also be colored white with white pigments, for example with titanium dioxide or zinc oxide, and in this way create very appealing contrasts. Another very attractive possibility is to formulate one of the components as a clear gel and to store strips of pigmented paste in this clear gel matrix.

The essence of the present invention, however, lies in the selection of suitable pigments, in particular yellow and red pigments, which make it possible to achieve beautiful orange to vermilion colorations which do not pass into the adjacent component even in long storage times.

According to the invention, iron oxide pigments are primarily suitable for this. Such pigments are available in a wide range of colors from various manufacturers. They belong to the dyes of Color Index No. 77491 and 77492 and are iron oxide powders with different oxidation levels and hydration. The following commercial products have proven to be particularly suitable:

Pigment Red 101 (C.I. 77491):

- Sicovit Rot 30 E 172 (BASF AG.)

- CG. 140 Red and CG. 165 Red Iron Oxide (Whittaker, Clark & Daniels)

- CG. 375 Orange Iron Oxide (Whittaker, Clark & Daniels)

- CG. 325 Orange Iron Oxide (Whittaker, Clark & Daniels)

- Soft-Tex Russet C33-7775 (Sun Chemical)

- Russet C33-128 (Sun Chemical)

- Russet C33-8075 (Sun Chemical) - Blue Russet C33-5138 (Sun Chemical)

- Russet C33215 (Sun Chemical)

Pigment Yellow 42 (C.I. 77492):

- CG. 425 Yellow Iron Oxide (Whittaker, Clark & Daniels)

- CG. 490 Yellow Iron Oxide (Whittaker, Clark & Daniels)

- Cogilor Ocher 90076 (Ellis & Everard)

- Soft-Tex Cosmetic Yellow C33-7720 (Sun Chemical)

- Soft-Tex Yellow C33-7773

- Yellow C33-8073 (Sun Chemical)

- Yellow C33210 (Sun Chemical)

Pigment Red 4 (C.I. 12085):

Cosmenyl Red R (Clariant)

Pigment Red 5 (C.I. 12490):

Cosmenyl Carmin FB 1 (Clariant)

Pigment Red 181 (C.I. 73360):

Rosa Para Cosmetica RC 01 (Clariant).

The toothpaste according to the invention preferably consists of two components, one of which contains colored iron oxide pigments from the group Pigment Red 101 and Pigment Yellow 42 or organic red pigments from the group Pigment Red 4, 5 or 181 or a mixture thereof and the other colorless or is white pigmented.

The colored pigmented component represents the strip paste and the colorless or white pigmented paste serves as a matrix or carrier paste. Orange stripes are particularly preferred, which are achieved by the pigmented component containing a combination of red pigments and a yellow pigment, which together create an orange color. Such pigment combinations of pigment red 101 and pigment yellow 42 are also available as commercial products, for example

Tan C33-130 (Sun Chemical) Tan C33-107 (Sun Chemical) Orange C33-120 (Sun Chemical) Orange C33-123 (Sun Chemical).

A sufficient intensity of the pigmentation is usually already achieved when the colored component contains the pigments in an amount of 0.001-0.1% by weight.

The components of the toothpaste composition according to the invention can have different compositions, e.g. the carrier component can be a clear, colorless or colored gel and the strip component can be a conventional opaque but colored pigmented toothpaste. However, the strip component can also be produced by producing a clear gel and pigmenting it accordingly. However, the components preferably have largely the same composition except for the pigments or any dyes additionally present.

The toothpaste composition according to the invention can in principle contain as polishing agent all of the abrasive components customary for toothpastes, but especially those which do not contain calcium ions.

Polishing agent components which are preferably suitable are therefore silicas, aluminum hydroxide, aluminum oxide, sodium aluminum silicates, organic polymers or mixtures of such friction bodies.

Calcium-containing polishing components such as chalk, calcium pyrophosphate, dicalcium phosphate dihydrate can, however, be present in amounts of up to 5% by weight. The total content of polishing agents is preferably in the range of 5-50% by weight of the dentifrice.

Toothpastes and liquid tooth cleaning agents which contain silicas as the polishing agent are particularly preferred. Suitable silicas are e.g. Gel silicas, hydrogel silicas and precipitated silicas. Gel silicas are produced by reacting sodium silicate solutions with strong, aqueous mineral acids to form a hydrosol, aging to the hydrogel, washing and drying. If drying is carried out under gentle conditions to a water content of 15 to 35% by weight, the so-called hydrogel silicas are obtained, such as those e.g. are known from US 4,153,680. Drying to water contents below 15% by weight results in an irreversible shrinkage of the previously loose structure of the hydrogel to form the dense structure of the so-called xerogel. Such xerogel silicas are e.g. in US 3,538,230.

A second, preferably suitable group of silicic acid polishing agents are the precipitated silicas. These are obtained by precipitating silica from dilute alkali silicate solutions by adding strong acids under conditions in which the aggregation to the sol and gel cannot occur. Suitable processes for the preparation of precipitated silicas are described, for example, in DE-OS 25 22 486 and in DE-OS 31 14 493. A precipitated silica prepared according to DE-OS 31 14 493 with a BET surface area of 15-110 m ² / g and a particle size of 0.5-20 μm is particularly suitable, with at least 80% by weight of the primary particles being below 5 μm should, and a viscosity in 30% glycerol water (1: 1) dispersion of 30 - 60 Pa.s (20 ° C) in an amount of 10 - 20 wt .-% of the toothpaste. Particularly suitable precipitated silicas of this type have rounded corners and edges and are under the tradename ^® Sident 12 DS (DEGUSSA).

Other precipitated silicas of this type are Sident 8 (DEGUSSA) and Sorbosil AC 39 (Crosfield Chemicals). These silicas are characterized by a lower thickening effect and a somewhat higher average particle size of 8-14 μm a specific surface of 40 - 75 m ² / g (according to BET). In order to obtain a sufficient viscosity of the toothpastes, in addition to the precipitated silicas mentioned, even finer particles, so-called thickening silicas with a BET surface area of 150-250 m ² / g, are added, for example the commercial products Sipernat 22 LS or Sipernat 320 DS.

As a further polishing agent component, e.g. Alumina in the form of weakly calcined alumina containing γ- and α-alumina in an amount of about 1 - 5 wt .-%. Such a suitable aluminum oxide is available under the trade name "Polishing clay P10 finest" (Giulini Chemie).

As a fluorine compound, the toothpaste compositions according to the invention can e.g. Contain sodium fluoride, zinc fluoride, tin (II) fluoride, amine fluoride or sodium monofluorophosphate. An amount of 100-1500 ppm fluorine should preferably be contained in the form of the compounds mentioned.

Glycerin, sorbitol, xylitol, propylene glycol, polyethylene glycol or mixtures of these substances can be used as humectants.

Natural and synthetic water-soluble polymers such as carrageenan, tragacanth, guar, cellulose and their non-ionic derivatives such as hydroxyethyl cellulose or methyl hydroxypropyl cellulose are used as binders and consistency regulators. Agar-agar, xanthan gum, pectins, water-soluble carboxyvinyl polymers (eg Carbopol ^® types), polyvinyl alcohol, polyvinylpyrrolidone and higher molecular weight polyethylene glycols (with molecular weights of 10 ³ - 10 ⁶ D) are also suitable as binders and thickeners.

Preferred toothpaste compositions according to the invention contain 10-30% by weight of silica polishing agent, 30-60% by weight of humectant and 0.1-2% by weight of a binder in both components. In addition to the compulsory components mentioned, the toothpaste compositions according to the invention can contain further auxiliaries and additives known per se. Particularly preferred additional components are non-cationic, bactericidal components, panthenol or salts of pantothenic acid and vitamins, in particular vitamin A (retinol) or its derivatives.

Suitable non-cationic, bactericidal components are e.g. Phenols, resorcinols, bisphenols, salicylanilides and their halogenated derivatives, halogenated carbanilides and p-hydroxybenzoic acid esters. Particularly preferred antimicrobial components are halogenated diphenyl ethers, e.g. 2,4-dichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro-2'-hydroxydiphenyl ether, 2,4,4 '-tribromo-2'-hydroxydiphenyl ether and 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan). They are preferably used in amounts of 0.01-1% by weight in the dentifrices according to the invention. Triclosan is particularly preferably used in an amount of 0.01-0.3% by weight.

D-panthenol [D - (+) - 2,4-dihydroxy-N- (3-hydroxypropyl) -3,3-dimethyl-butyramide] shows a biological activity corresponding to pantothenic acid. Pantothenic acid (R - (+) - N - (2,4-dihydroxy-3,3-dimethylbutyryl-ß-alanine) is a precursor in the biosynthesis of coenzyme A and is included in the vitamin B complex (B ₃ ) "These substances are known to promote wound healing and have a beneficial effect on the skin. Therefore, they have also been described occasionally in toothpastes. The toothpaste compositions according to the invention preferably contain 0.05-5% by weight panthenol or a." Salt of pantothenic acid.

Retinol (3,7-dimethyl-9- (2,6,6-trimethyl-l-cyclohexenyl) -2,4,6,8-nonatetraen-l-ol is the international free name for vitamin A, instead of retinol one of its derivatives with a similar biological effect, for example an ester or retinoic acid (tretinoin), one of its salts or its esters can also be used .. A retinol ester, in particular a fatty acid ester of a fatty acid having 12-22 C atoms, is preferably used retinol palmitate is preferably suitable, when using a retinol ester, for example retinol palmitate with an activity of 1.7 10 ⁶ IU per g Amount of 0.001 to 0.1 wt .-% preferred. When using other retinol derivatives, it is recommended to use an amount corresponding to a concentration of 10 ³ to 10 ⁶ IU (international units) per 100 g.

In addition to polishing agents, humectants and binders, preferred toothpaste compositions according to the present invention preferably contain in at least one of the components:

0.01-1% by weight of a halogenated diphenyl ether

0.05 - 5 wt .-% panthenol or a salt of pantothenic acid and

0.001-0.1% by weight of a retinol ester, preferably retinol palmitate.

In addition to the compulsory components mentioned, the toothpaste compositions according to the invention can contain further auxiliaries and additives known per se. An additive that has long been known as a toothpaste component is particularly effective in the dentifrices according to the invention: calcium glycerophosphate, the calcium salt of glycerol-1-phosphoric acid or glycerol-2-phosphoric acid or of the enantiomers of glycerol-1-phosphoric acid Glycerin-3-phosphoric acid - or a mixture of these acids. The compound has a remineralizing effect in dentifrices because it provides both calcium and phosphate ions. Calcium glycerophosphate is preferably used in amounts of 0.01-1% by weight in the dentifrices according to the invention. Overall, the tooth cleaning agents according to the invention can contain customary auxiliaries and additives in amounts of up to 10% by weight.

The toothpastes according to the invention can be improved in their organoleptic properties, for example, by adding aromatic oils and sweeteners. All the natural and synthetic aromas customary for oral and dental care products can be used as aroma oils. Natural aromas can be contained both in the form of the natural essential oils isolated from drugs and in the individual components isolated therefrom. Suitable flavors are, for example, peppermint oil, spearmint oil, eucalyptus oil, anise oil, fennel oil, caraway oil, menthyl acetate, cinnamaldehyde, anethole, vanillin, thymol and mixtures of these components.

Suitable sweeteners are e.g. Saccharin sodium, sodium cyclamate, sucrose, lactose, maltose, fructose.

Other common auxiliaries and additives for toothpastes are:

Surface-active substances, preferably anionic, zwitterionic, amphoteric, nonionic surfactants or a combination of several different surfactants, solvents and solubilizers, e.g. lower monohydric or polyhydric alcohols or ethers, e.g. Ethanol, 1, 2-propylene glycol, diethylene glycol or butyl glycol glycol dyes

- buffer substances, e.g. primary, secondary or tertiary alkali phosphates or citric acid / Na citrate

- other wound healing or anti-inflammatory substances, e.g. Allantoin, urea, azulene, chamomile active ingredients, acetylsalicylic acid derivatives or rhodanide

- other vitamins such as Ascorbic acid, biotin, tocopherol or rutin

- mineral salts such as Manganese, zinc or magnesium salts.

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

Two basic toothpastes were produced according to recipes A and B and each 30% by weight of this was colored with pigment dyes (according to recipe AP and BP).

The following products were used:

Sident 8 SPLS: Amorphous synthetic silica

Specific surface area (BET): 60 m ² / g (DEGUSSA AG)

Sident 22 S: precipitated silica

Specific surface area (BET): 190 m ² / g

(DEGUSSA AG)

Sipernat 320 DS: precipitated silica

Specific surface area (BET): 170 m ² / g

(DEGUSSA AG)

Cekol 500 T: carboxy methyl cellulose, sodium salt

Degree of substitution: 0.6 - 0.75

(Nordmann-Rassmann)

Mineral salts: mixture of MgSO ₄ 7H ₂ O (20 parts by weight) ZnSO ₄ 7H ₂ O (8 parts by weight) and MnSO ₄ H ₂ O (1 part by weight)

Soft-Tex Yellow: iron oxide, average particle size 0.02 - 0.25 μm (Sun Chemical) Cosmenyl Rot R: 40% preparation (H ₂ O / glycerin) of Pigment Red 4 (CI 12085)

Components A and AP or B and BP were filled in a strip dispenser tube according to DE-A 21 41 436. After 4 weeks of storage, the toothpastes could be removed as striped paste strands and a sharp phase boundary (without bleeding).

Claims

claims 1. Toothpaste composition, consisting of at least two separate, plastically flowing components, which are filled in a container and can be pressed together in the form of parallel, concentric or striped strands and contain the polishing agents in an aqueous carrier containing humectants and surfactants , characterized in that at least one of the components contains colored, water-insoluble iron oxide pigments from the group pigment red 101 and pigment yellow 42 or organic red pigments from the group pigment red 4, 5 or 181 or a mixture thereof in an amount sufficient for coloring. 2. Toothpaste composition according to claim 1, characterized in that it consists of two components, of which one colored iron oxide pigments from the group pigment red 101 and pigment yellow 42 or red pigments from the group pigment red 4, 5 or 181 or one mixture of which contains and the other is colorless or white pigmented. 3. Toothpaste composition according to one of claims 1 or 2, characterized in that the components have largely the same composition except for the pigments or dyes. 4. toothpaste composition according to any one of claims 1-3, characterized in that the pigments are contained in the colored component in an amount of 0.001 - 0.1 wt .-%. 5. toothpaste composition according to any one of claims 1-4, characterized in that the colored component contains red and yellow pigments which together cause an intense orange color of the component. 6. Toothpaste composition according to one of claims 1-5, characterized in that the components 10-30 wt .-% silica polish, 30-60 wt .-% humectant and 0.1-2 wt .-% of a binder contain. 7. toothpaste composition according to any one of claims 1-6, characterized in that at least one of the components 0.01-1% by weight of a halogenated diphenyl ether 0.05 - 5 wt .-% panthenol or a salt of pantothenic acid and Contains 0.001-0.1% by weight of a retinol ester.