DE3942642A1 - PACKED ORAL PRODUCTS WITH DENTAL RETAINING PROPERTIES - Google Patents

Abstract

A dentifrice or a liquid mouthwash, containing a substantially water insoluble non-cationic plaque-inhibiting antibacterial agent, such as triclosan, is packaged in a dispensing container or bottle of a solid polymeric material, such as polyfluoroethylene, which is compatible with the antibacterial agent so that loss of anti-plaque agent on storage is avoided. Alternatively, other polymers may be employed as container, which normally would cause excessive losses of anti-plaque agent but such action is countered by the presence of a terpene, e.g. limonene, as a stabilizer in the oral composition.

Description

The invention relates to packaged oral care products with the Plaque-preventing properties, namely oral composition which prevents the formation of dental plaque Bactericide such as 2 ', 4,4'-trichloro-2-hydroxy-diphenyl ether (THDE) as an effective component against dental plaque, these being Composition is packaged in a container, the one polymeric plastic material and in contact with the oral composition is, the plastic with the Bactericide in the oral composition is compatible.

Although many plastics prevent the plaque Effect of antibacterial agents or bactericides ver It has been found that certain plastics such as Polyfluoroethylene and polyvinyl chloride are compatible with THDE.  

It has also been found that these are not excessive Impairment of the antibacterial effect and the plaque inhibiting properties of the oral composition during storage effect at room temperature or at elevated temperatures. Even when in contact with the antibacterial compound standing plastic parts of the container of such Plastic material, which is not complete in itself Compatible with the bactericide can be tolerability be increased by the oral composition or the oral care product a stabilizing share of Stabilizer for the bactericidal compound added, such as a Terpene, e.g. Limes or a natural or synthetic essential oil, which is used as a flavoring in oral is present. Such a stabilizer is in sufficient quantity so that the oral composition in the packaged form or in the donor, an effective, plaque preventing composition represents what purpose of the present invention. Furthermore, the invention comprises a Method in which oral surfaces containing oral care products in Contact, which is an effective part of a plaque preventing ingredient included. The invention further relates to a toothbrush having on its bristles a effective proportion of a toothpaste with dental plaque preventing Contains properties.

It is well known that plaque is the periodontal area negatively affected and considered as a precursor for tartar becomes. Dental plaque can attach itself to any area of a tooth Finally, the gingival margins form, clouding the Enamel, intensifies calculus formation and can be used for Cause gingivitis. For this reason, oral compositions Contains a content of plaque preventing components for the Dental hygiene essential.

Although it is known that antimicrobial agents or microbicides in oral compositions prevent the plaque and in  some cases especially in combination with other ingredients are particularly effective. Have many such bactericides but disadvantages when used in oral compositions. For example, cationic bactericides tend to be quaternary Ammonium halides to discolor the teeth; furthermore by anionic ingredients such as surfactants in the oral care inactivated.

It has been found that substantially water-insoluble halogenated and usually hydroxylated diphenyl ethers such as 2 ', 4, 4'-trichloro-2'-hydroxydiphenyl ether, which is referred to as THDE or triclosan and 2, 2'-dihydroxy-5, 5 ' - dibromodiphenyl ether (DDDE) are very effective antiplaque bactericides but are inactivated by non-ionic surfactants and by numerous plastics.

Accordingly, it is an object of the present invention, antibak terial plaque preventing components such as halogenated Diphenyl ethers and in particular THDE and DDDE and the like Anti - plaque ingredients for oral care products in to provide such and these compositions in containers store and give away from them, these being none before use excessive proportion of the activity of such bactericides Lose storage. Contain in the previously known Triclosan dentifrices as delivered from a dispensing container is not the provision of triclosan sufficient to prevent dental plaque when using these agents or twice a day at a rate of 1.5 g / use at Brushing teeth of usually one minute will be presented. Around to be effective at least after three weeks at Users set a plaque reduction of at least 25%, and in comparison to a three weeks analogously used Control toothpaste.

The most preferred bactericidal and plaque preventive Component of the present packaged oral care products  THDE, which is also known as Triclosan, according to US-PS 40 22 880 as a bactericide in combination with a tartar preventing agent which provides zinc ions and according to DE-OS 35 32 860 in combination with a copper compound. Further disclose EU-A-01 61 898, 01 61 899 and 02 20 890 dentifrice agent with polyethylene glycol and an oily flavoring agent.

Dentifrices in the form of pastes, gels, powders, liquid th, tablets, lozenges and in packaged form generally known, as well as liquid and tableted mouthwash. Furthermore, dentists use a variety of dental treatments agent for hardening the teeth, for example in the form of fluoride solutions used. Such products are in malleable Tubes, in dispensers with pump pressure or those with propellant, further abge in parcels, bottles, cans or other containers abge grabs. Although such deformable or compressible Containers or tubes formerly made of metal such as lead or aluminum are made and the bottles were made of glass, there are Recently, containers of synthetic organic polymer art or laminates containing such plastics. An effect between the oral compositions and the Container materials for these are known, such as the Reaction between toothpaste and aluminum tubes, wherein the Preventing such disturbing factors the container either pretreated accordingly or other materials used were.

An interaction between plastic packaging material on the one hand and the plaque reducing properties of halogenated Diphenyletherbakteriziden is not yet been suspected; it is also unexplored to what extent bactericidal Compounds in dentifrices by contact with the Plastic existing packaging may be affected; In particular, it was unexplored whether certain plastics for such containers a loss of tartar Can cause effect of halogenated diphenyl ethers or  that the plaque-preventing effect in contact with plastic by reaction, absorption or otherwise impaired or by the addition of terpenes such as limonene or others Flavored can be inhibited.

Object of the present invention is an oral hygiene product to propose, which is an effective plaque preventing amount a substantially water-insoluble non-cationic contains antibacterial component in a dispensing container which is a solid polymeric material such as For example, plastic and in contact with the Oral care product stands, wherein the polymeric material with the Bactericide in the presence of the oral care product with the polymeric Material is compatible and no loss in antibakteriel len and plaque preventing properties during storage of the Dispensing container, at e.g. Temperatures in the range of 20 to 40 ° C over the course of several weeks and up to a year or more suffers.

The packaged oral care product is usually a toothpaste, a dental gel or a mouthwash, which in deformable tubes, Pumped containers or bottles that are not plastic have parts that the plaque preventing effect of Bactericidal, preferably that of a halogenated diphenyl ether like triclosan, adversely affect or those in the tooth Care products contain a component which such adverse effects between bactericide and plastic parts of the container.

In the following, the invention in conjunction with drawings be explained in more detail; it shows

Fig. 1 is a perspective view of a toothpaste tube with screw cap removed and squeezed to a toothbrush toothpaste strand;

Figure 2 is an enlarged fragmentary section of a multi-layer wall of a collapsible tube analogous to FIG. 1.

Figure 3 is a vertical section through a pump-like dispensing container for receiving and dispensing toothpaste or tooth gel.

Fig. 4 is a side view of a heat-sealed bag containing a disposable portion of toothpaste and

Fig. 5 is a view of a mouthwash bottle, which is closed with a cap.

The antiplaque toothpaste tube 11 shown in FIG. 1 consists of the deformable tube 13 , which contains the plaque-preventing toothpaste 15 , from which a use amount of 0.8 to 2 g is squeezed out onto the brush 17 . The tube 13 is opaque and consists of a synthetic polymeric plastic such as polyfluoroethylene or is coated as a laminate with such a material, which does not affect the dental plaque preventing effect of the toothpaste during storage. Alternatively, the tube 13 may be made of a plastic or be covered with a plastic layer, which adversely affects the zahnbelaghin end effect of the toothpaste, by reducing the Zahnbelagindernden effect of Bak terizids or halogenated diphenyl ether, which is as zahnbe lag hindering component in the toothpaste ; In this case, the adverse effect on the plaque-preventing effect is prevented by the presence of a stabilizing agent in the dental care agent, which may be a terpene such as limonene or another effective flavoring component. Preferably, neither the toothpaste tube nor its closure 19, nor any other part of the tube that may come into contact with the toothpaste, such as the gasket in the screw cap, made of a copolyester / polyether elastomers or of any other plastic material that the zahnbelaghindernde effect of the oral composition, even in the presence of a stabilizer for the plaque preventing component. Further, it is desirable to avoid the presence of other elastomers such as isobutadiene, polychloroprene, butadiene rubber and nitrile rubber, which could react with or absorb THDE. Preferably, the parts are made of a plastic which does not adversely affect the antiplatelet effect, even in the absence of terpenes or other stabilizing agents in the toothpaste; however, other destabilizing plastics can be used if such a stabilizer is present in the toothpaste and counteracts the interfering action of the plastic (except that elastomeric copolyesters / polyethers and other detrimental elastomers are preferably avoided).

Fig. 2 shows a laminate of a polyfluoroethylene film 21 , an aluminum foil 23 and a polyethylene layer 25 , wherein the polyfluoroethylene lies on the inside of the tube wall where it is in contact with the toothpaste. The sealing insert for the tube closure 19 , not shown here may also be made of polyfluoroethylene, so that all during storage in contact with the toothpaste surfaces with the halogenated diphenyl ether, namely the bactericidal component in the toothpaste are compatible and no excessive loss of zahnbelaghindernden effectiveness Cause storage. The inner wall 21 of the laminate may also be made of polyethylene or other suitable polymer.

The pump-like dispensing container for toothpaste shown in Fig. 3 is a trained according to US-PS 47 76 496 toothpaste dispenser Guala SpA, Italy. The dispenser 27 contains in the chamber 29 , which is formed by the bottom wall 31 and a diaphragm 33 , the toothpaste. By depressing the operating lever 35 , the diaphragm 33 moves down and pushes toothpaste through the conduit 37 out of the discharge opening 39 . When the pressure on the operating lever 35 decreases, the released ela tical membrane 33 goes back to its original position and moves the line 37 and the lever 35 back to the Ausgangspo position. At the same time, the bottom 31 is pushed upwards by atmospheric pressure. The various parts of this dispenser that are in contact with the toothpaste are preferably made of plastic that does not inactivate the bactericidal and plaque preventing halogenated diphenyl ether. However, if it is inconvenient to use plastics which have the required physical properties for the various parts in contact and are still compatible with the dental antiperspirant component, other plastics can be used, provided that the toothpaste or the dental gel stabilizing substance such as limonene or other effective terpene or aroma components. However, it is best not to use copolyester / polyether elastomers, and in particular, not to make the pump membrane 33 from this material, which is particularly effective against THDE in such compositions.

The bag or pad 41 shown in Fig. 4 is a heat-sealed unit having seal seams 43 and 45 on three sides, while the fourth side 47 is folded over only and does not need to be welded. In the sealed bag is the oral hygiene product such as a toothpaste, and the inner surface of this bag is made of a plastic which prevents excessive loss of the antiplatelet effect of the bactericidal compound in the oral hygiene product.

As with the other antiplaque containers can be used laminates whose plasticin layer does not adversely affect the bactericide; if However, the plastic such an adverse effect on the Bactericide, this may be due to the presence of a  suitable stabilizer in the oral composition be acted, which preferably also serves as a flavoring.

Fig. 5 shows an opaque bottle 49 with a cap 51 . Both the bottle and the Dichtungssein not shown position in the screw cap are made of plastic, which is compatible with the THDE, so the plaque-preventing component in the mouthwash 53 in the bottle; If, as in the above-mentioned examples, a "reactive" plastic material is used for the interior of the bottle or the gasket of the screw cap, a suitable stabilizer should be present in the mouthwash to prevent excessive loss of the antiperspirant effect of the THDE or other halogenated Prevent diphenyl ether.

The packaged oral care products instead of toothpaste too as a tooth gel or as a thick liquid, can add Lich still contain other dental treatment compositions such as Tooth hardener, e.g. Fluorides and phosphates, bactericides, dye solutions conditions for the display of dental plaque or other suitable oral Compositions as used by dentists. It can also be filled under pressure or aerosol Zusammenset be filled in pressurized cans containing the mentioned plaque containing preventive compounds, being mostly used as propellant Nitrogen is used, provided that in contact with the content reaching plastic parts of a material which is the dental antifoulant property of the dental plaque preventing agent in the packaged toothpastes or others Oral care products are not unduly affected.

In addition to the reproduced in the drawings containers also squeeze bottles, capsules, pots, spongy carriers and the most diverse types of mechanical dispensers be used. Because some of the antibacterial ones halogenated diphenyl ethers are photosensitive, it is in certain cases, these containers from a chemical  or physically light-shielding material or to coat or laminate with this, so that no plaque preventing compound inactivating radiation such as For example, UV light can occur. Such containers are often opaque to inactivation of the plaque-reducing Kom component in the oral care products such as toothpastes by actinic To prevent radiation.

The causes of inactivation of THDE and others in the essential non-cationic bactericides with dental plaque Other properties of oral care products are not quite there yet clarified including the cause, whether it is a chemical Reaction or physical absorption. Try with basic mouthwash compositions containing THDE show that when aged in dispensers at room temperature at 38 ° C and at 49 ° C over a period of 12 weeks Losses in the range of more than 25% of the original concentration tion to THDE occur when the mouthwash water with container walls or parts of low-density polyethylene, polyethy high density polyethylene terephthalates, polypropylenes, Polyamides (nylon - WZ), polyallomers and polymethylpentenes in contact. In equal measure, high losses result, when stored in containers, their internal walls or Parts of these consist of copolyester / polyether elastomers, as previously used as pumping membranes in the Guala dispensers have been. It has been found that polyfluoroethylenes such Polytetrafluoroethylene, polyvinyl chlorides, polycarbonates and Polysulfones do not react with significant proportions of THDE or absorb them. On the other hand, polycarbonates and polysul fone brittle and mostly unsuitable for parts of dispensing containers. Polyvinyl chlorides mediate the oral care products such as toothpastes a foreign taste and are therefore usually as Behälterma not used, unless this taste with that of the dentifrice matrial is compatible. From all possible polymeric plastics polyfluoroethylene is particularly as a suitable material for the present container or  Packages provided which the tartar preventing Effect of anticalculus agents not essential reduced; As already mentioned, one can take the oral together stabilizing compounds for the dental obstacle the components such as terpenes, preferably limonene, essential oils that often contain terpenes and other flavorings with similar stabilizing properties; Here you can the loss of activity of the plaque-preventing agents decrease when in contact with containers or containers are made of the above-mentioned plastics otherwise there is a significant loss of dental plaque cause hindering effect. So you're not from Polyfluor ethylene as a container material, provided that the oral composition nor a stabilizing portion of a Contains terpene or another suitable stabilizer. at Presence of such a stabilizer in the oral Compositions or when polyfluoroethylene or polyvinyl chloride rid, polycarbonate or polysulfone is the only plastic that are in contact with the oral composition, are the Loss of activity of the anti-inflammatory component below 25% and preferably below 10%, even after a ratio moderately high storage temperature of e.g. 20 to 40 ° C at a Storage time from a few weeks to a year or more. The Most stable oral compositions are those containing a stabilizing proportion of terpene or other suitable Stabilizers contained and are in a container, at the parts coming into contact with the oral hygiene product only made of polyfluoroethylene or another non-reactive Plastic exist. Although terpenes and essential oils the may be primary stabilizers according to the invention, also other flavor components to stabilize the plaque ver hindering components by either destabili interfering transformations or the absorption of halogenated Inhibit diphenyl ether by plastic. It can be pure theore be assumed that some components of the oral Composition tend to solubilize the THDE and  then hold this in the composition and a Abwande inhibit or prevent tion in the plastic. on the other hand In theory, it is also conceivable that such a solubilization the migration of the solubilized THDE into the Plastic supports. Although the terpenes and others Stabilizers are desirable flavorings, this is not necessary, and the stabilizers can only for the purpose of Stabilization can be used.

Although preferably the packaging of the invention inside walls, ie walls in contact with the composition, from one solid synthetic organic polymer plastic or have coated with this material, according to the invention also other solid and / or film-forming polymers are used, and regardless of whether they are synthetic, organic or are plastic. It can therefore polyethylene glycols and Oxypoly ethylene glycols such as "Carbowax" varieties, e.g. Carbowax 4000 and Carbowax 6000 often as a coating material in the dispensing container Tern be used for the compositions described. As a coating, inorganic silicone polymers such as Siloxane and non-synthetic organic film-forming substances like gums, e.g. Carrageenan, Tragacanth and Karayagum suitable. Furthermore, solid polymeric substances such as cellulose and starch and Derivatives of these as container material in contact with the antibak terial and plaque preventing components of such packaged oral composition can be used.

The numerous prepackaged compositions of the invention are mostly toothpastes, tooth gels and mouthwashes. The dental care means consist essentially of three basic components, namely a carrier, a polishing material and a surfactant. The antibacterial component, for example the halogenated Diphenyl ether, is normally present in the carrier material, which is usually 10 to 80% by weight of the dentifrice, where the numbers are based on the total composition Respectively. The carrier is generally from 3 to 40 wt .-%  Water and about 7 to 77% by weight of humectants such as glycerol, Sorbitol, propylene glycol or mixtures thereof, while 0.5 to 10% by weight of a gelling agent such as sodium carboxymethylcellulose, Irish moss, iota carrageenan or hydroxyethyl cellulose or Mixtures of these can be. The polish in the dentifrice makes about 10 to 75 wt .-% in a tooth gel or a toothpaste from and about 50 to 99 wt .-% in a tooth powder. polish include colloidal silica, precipitated silica, Sodium aluminum silicate, insoluble sodium metaphosphate, hydrated alumina, calcined alumina, Dicalcium phosphate dihydrate, anhydrous dicalcium phosphate or Calcium carbonate, optionally in mixture with each other.

As surfactants, anionic, nonionic, cationic and zwitterionic surfactants are used, often without ionic surfactants because of their adverse effects on the antibacterial compound, e.g. THDE, to be avoided; as well cationic and zwitterionic surfactants are often avoided because they make their teeth spotty or dark. Consequently, be anionic surfactants as a cleaning component in the dental care used, with sodium lauryl sulfate and other higher Alkyl sulfates having 10 to 18 carbon atoms in the alkyl radical are preferred, although other known sulfated and partially or completely as sulfonated surfactants can be used. Other active ingredients are fluoride supplying compounds such as sodium fluoride or sodium monofluor Phosphate, which is used to harden the teeth usually in such quantities it is present that the composition 0.001 to 1% fluorides contains. Other additives such as flavorings and sweeteners can in amounts of 0.1 to 10%. In addition, it is from Advantage, a polycarboxylate such as a polyvinyl methyl ether / maleic acid anhydride copolymer (PVM / MA) such as "Gantrez" - WZ -k in one Use amount of 0.5 to 5 wt .-%. Such polycarboxylate compounds increase the anti-itch effect of Bak terizids; the use of such polycarboxylates in oral Compositions are described in US-PS 46 27 977.  

In mouthwashes, the vehicle is preferably water and Alcohol, with ethanol or isopropanol being preferred as the alcohol become. The liquid carrier makes up about 90 to 99% of the total from which the alcohol content is 5 to 30%; further is propylene glycol in amounts of often 2 to 10% in each case present on the final product. The remaining components of this Composition of 0.1 to 10% may contain flavoring agents, wetting agents, Sweeteners, coloring agents, antiplaque agents and other other additions. For dentifrices and Mouthwash is the effective amount of antibacterial plaque preventing compound generally in one area from 0.02 to 0.2% and preferably in a range of 0.03 to 0.1% in mouthwashes and usually 0.25 to 1% and preferably at 0.25 to 0.5 or 0.6% in dentifrices. The Proportion of THDE in toothpastes should not exceed 0.8% and in Mouthwashes are not more than 0.2%, otherwise at higher concentrations can set a numbing sensation. The concentration of THDE should be within the specified minimum limits do not fall short as they are at lower concentrations against plaque are ineffective. Preferably, the contain Compositions to be delivered to the antiplatelet and THDE in the specified ranges. If the initial concentration within the specified ranges, a loss of up to 25% may be acceptable, and those dispensed from containers together settlements are within the scope of the present invention.

To packaged oral compositions in containers from a to stabilize the bactericide "reactive" plastic, 0.01 to 2% by weight of terpenes or stabilizers may be oral Compositions are added and preferably 0.05 to 1% and especially 0.1 to 0.5%. Such stabilizers can be present in a suitable flavoring for the toothpaste and may optionally contain at least 5% by weight of the flavor fes, preferably at least 10%, in particular 25% and best make up at least 50% of the flavor.  

Although in the present case essentially of dental care There is also talk of oral and oral fluids Compositions according to the invention such as chewing gum contain similar proportions of the components, depending on the type the composition, wherein the liquid products less, such as e.g. the mouthwashes and the thicker compounds like Toothpastes may contain more such additives, often together with special additives according to the purposes of use the composition. So can compositions that have a Curing the teeth are still fluorides and phosphates such as sodium or potassium fluoride and sodium fluorophosphate in one Range of 1 to 5% in dentifrices or mouthwashes contain. Color solutions for displaying the plaque may be a corresponding color, preferably red, light in a Konzentra tion of 0.001 to 0.1% in a mouthwash.

The antibacterial agent is a non-cationic material which is water insoluble or substantially water insoluble is; it has a water solubility at 25 ° C of less than 10 g / l and in some cases even less than 1 g or 0.1 g / l. Such compounds are in the dentifrice carriers soluble or dispersible, namely in carriers the glycerol, Sorbitol and / or propylene glycol and in end products with this; they are also in the aqueous alcoholic medium of Mouthwashes soluble or dispersible.

Of the antibacterial compounds contain the halogenated Diphenyl ether generally bromine and / or chlorine, wherein chlorine preferred is halogen. These compounds are preferably with Substituted from 1 to 3 hydroxyl radicals and 1 to 4 halogen atoms and preferably with 1 to 2 hydroxyl radicals and 2 or 3 halogen atoms, preferably 4 substituents, ie two at each Ring lie. Most suitable are 2, 2'-dihydroxy-5, 5'-dibromo diphenyl ether and 2 ', 4, 4'-trichloro-2-hydroxy-diphenyl ether (THDE), which is particularly preferred. The halogenated diphenol ethers may also be replaced by halogenated phenolic, non-cat  ionic and substantially water-insoluble antibacterial plaque preventing compounds are replaced, as in the US application 07/3 98 566 of 25 August 1989 are listed.

The terpenes, which are terpene hydrocarbons and oxygenated Derivatives of these are included, for example, dl- Limonene, menthol, diterpenes, polyterpenes and their derivatives, of which are many in the most different essential oils and Find flavors. In addition to their property as Stabilizer for halogenated diphenyl ether act to mediate they are a desired one for the present oral compositions Aroma. Among the terpenes and their derivatives is limonene in terms of these properties, the best balanced, though other terpenes that do not serve as flavorings, too can be used, as well as other emulsifiable lipophilic essential oils and flavors that are the stabilizing Components included.

The different plastics of the container or dispensing container or parts thereof are only briefly described as their chemical nature and the extent of their polymerization is well known; Further Details emerge from "Modern Plastics Encyclopedia", McGraw-Hill Inc., New York.

The compositions according to the invention may have a fluorine delivery agent providing 25 to 5000 ppm fluoride ion in the oral cavity, preferably 300 to 2000 ppm and especially 800 to 1500 ppm, reference being made to US Pat. No. 4,627,977 for further details. The fluoride acts primarily to harden the teeth, but also serves to stabilize any existing anti-calculus polyphosphates. Such polyphosphates are preferably mixtures of sodium and potassium pyrophosphate, by Gantrez S-97 - WZ - are stabilized, where the amounts given in U.S. Application 07/3 98,605 of August 25, 1989 and in the US-PS 46 27 977 and US-PS 48 06 340 find.

The preparation of the described oral compositions takes place in any known manner. So is the example THDE dispersed in a carrier portion of the dentifrice and / or dissolved, wherein the terpene is present as a flavoring agent. To prepare a dentifrice, a carrier is made Glycerin, sorbitol and propylene glycol, gelling agents and suitable Additives including Gantrez S-97 and Triclosan, and the carrier and the aqueous surfactant are preferably sodium lauryl sulfate or a mixture of this with sodium methylcocoyl taurate mixed, whereupon the polish with this Premix is processed. Subsequently, flavorings, Terpene dissolved in ethanol was added and the pH adjusted. For the preparation of the mouthwash, the various Components only in the alcoholic or aqueous-alcoholic Phase mixed and stirred until dissolved. A mix of Sodium lauryl sulfate (SLS) and Natriummethylcocoyltaurat in one Ratio of 1: 4 to 4: 1 is preferably as anionic Surfactant used in the mouthwash, passing through the existing Taurate made a desired lowering of the content of SLS possible can.

When packaging the oral composition in the dispensing container it is appropriate to contact the composition with art to avoid polyester / polyether elastomers and it is further desirable to have one contact of each composition, not a stabilizer such as terpene or terpene-flavored contains, to contact with plastic parts, which like listed above as being reactive with THDE and other suchi antibacterial and plaque preventing compounds are. In particular, the mentioned plastic parts in the Storage containers or other containers, the supply lines, pumps and other equipment with which the oral compositions for a considerable time in contact come or even briefly at elevated temperatures in Get in touch.  

Even if the packaged compositions of the invention are prepared and contact of these THDE or other halogenated diphenyl ether or bactericidal compositions is avoided while avoiding contact with the reactive plastics, it is still desirable not to expose the packaged compositions to the action of heat and light otherwise the loss of antifraud effectiveness is accelerated. Accordingly, the compositions of the invention are preferably packaged in opaque containers or dispensing containers and stored at temperatures in the range of 10 to 38 ° C; otherwise, the packaged compositions may be stored and used in a conventional manner while retaining the desired anti-foaming properties. Such effects could be verified by laboratory tests and observations on the teeth of subjects using the various packaged compositions and control preparations. Significant improvements in the antifraud effect of the packaged compositions according to the invention were observed, particularly in comparison with control preparations in which the compositions were in packages reactive with halogenated diphenyl ether and which contained no stabilizing agent. Improvements have also been noted when using packages of reactive plastic , but not copolyester / polyether elastomers , with compositions containing terpenes, the comparators containing oral compositions without terpenes and no flavoring.

In the following, the invention is based on examples closer be explained, all quantities are by weight Respectively.

example 1

Mouthwash of the above composition was mixed by mixing the various components in any order but triclosan is first in a propylene glycol and ethanol mixture was dissolved, whereupon it with a aqueous solution of sorbitol, glycerin and anionic surfactant mixed and the aroma mixture was finally added. The  Sodium hydroxide solution is used to neutralize the obtained acidic mixture to a pH of about 6.84, as it is it is desirable that the product is neutral or nearly neutral.

The mouthwash obtained has an excellent cosmetic Stability and a pleasant aroma. The flavors and the Triclosan are sufficiently dissolved, with this solution minde partly due to the presence of tauranol WSHP is. If only 0.25% SLS is used as the anionic surfactant, is not the solubilization of flavorings and triclosan sufficient. Although this solubilization by use from more SLS to the maximum permitted limit this component in the mouthwash mostly at 0.25% and tauranol WSHP and SLS can be used without difficulty in these proportions be used. This mouthwash water was in vitro on the Bioavailability of triclosan versus a comparable Mouthwash with a composition without Tauranol WSHP tested and, in another case, by half in one case nonionic surfactant (Pluronic F-127).

Experiments to determine the uptake of triclosan by measurement of triclosan absorption on hydroxyapatite disks, which were treated with Saliva were coated, and by protein absorption with Inhibition zones it was found that the presence of the mixed anionic surfactants a comparable bioavailable Triclosan results compared to availability the composition containing only SLS. The availability is significantly larger in compositions that are not nonionic Contain surfactant compared with those considered non-ionic Tenside Pluronic F-127 included.

The mouthwash according to Example was at elevated temperature of 41 ° C for three weeks and five weeks aged, resulting in storage Room temperature of six months or one year. These aging tests were in dispensing containers or bottles made of glass, polyvinyl chloride and polyethylene terephthalate or  performed in containers coated with these plastics. Chemical analysis revealed aging of the mouthwash no triclosan losses in glass containers, but noticeable Triclosan losses in polyethylene terephthalate or made of polyvinyl chloride. However, they are at the present Composition well below the tolerable 25% of Initial concentration and may be below 5 or 10%.

If, instead of the aroma mixture dl-limonene in amounts of 0.1 or 0.2 and 0.4%, can be in the described Packaging dentifrice according to the invention with better Stabilization obtained, and such stabilization Also exists when other terpenes eat from any other essential oils and flavoring agents in appropriate quantities are. Good results are also obtained when the container ma material or its coating of polymethylpentene, polyallomer, Polypropylene, high and low density polyethylenes and Polyamides, although such materials in the absence of flavors and the terpenes contained therein and excessive losses of available triclosan from the Mouthwash when stored, especially at elevated temperature demonstrate.  

example 2

A mouthwash of the following composition was prepared:

ingredients weight Water, desalted 84.42 Ethanol (95%) 10.00 propylene glycol 5.00 sodium lauryl sulfate 0.50 triclosan 0.06 sodium  0.02 100.00

With this mouthwash, the availability of triclosan diminished three weeks storage in different dispensing containers, which consisted of different plastics or with these lined. The experiments were carried out at room temperature at 38 ° C and at 49 ° C, the elevated storage temperatures of a longer storage time at room temperature of one year or more corresponded. Triclosan losses of more than 25% were determined when the containers are made of polymethylpentene, polyallomer, Polypropylene, high and low density polyethylene and off Polyamides persisted, causing excessive losses to containers Polypropylene, polyethylene and polyamides (nylon) were.

Container made of polyvinyl chloride, polycarbonate, polysulfone or Polyfluoroethylene, such as polytetrafluoroethylene or with these Materials coated containers showed essentially no Triclosanverlust. The losses of triclosan from mouthwash in Containers of the type mentioned above, such as polymethylpentene be reduced analogously to Example 1, that one of the Containing limonene, other terpenes or essential oils added to a content of these compounds, wherein the proportion of  Terpenes preferably at least 0.1 and even better, higher was, for example, at 0.2 or 0.4%, based on the Final product. In some cases, the use of Aromastof which contain no appreciable amounts of terpenes, one positive effect although this effect is not as good as Addition of terpenes is.

example 3

A toothpaste of the following composition was prepared provides.

This conventionally prepared toothpaste was tested to examine the stability of triclosan, again using various plastics in the dispensing containers. More specifically, for the membranes in a pump dispenser according to FIG. 3, once "Pibiflex - WZ - 46" from Inmont and secondly "Arnitel - WZ - 460" from AKZO were used. In each case, three samples of the respective plastics were examined, of which the three samples were treated with different mold release agents, respectively, to determine whether the nature of the release agent is relevant in terms of triclosan stability in contact with plastics during storage. The release agent used was once a product "Silicone Master" - WZ -, which consisted of 5% silicone oil and 95% polypropylene, on the other hand "Silicone Master" with an addition of silicone oil and "Armid O Master" - WZ -, which was made from 5 % Oleoamide and 95% polypropylene was used.

After two weeks storage of the samples in contact with the toothpaste at room temperature at 38 ° C and at 49 ° C, the toothpastes were isolated and the plastic samples washed with water and in Placed methanol to about recorded during storage Triclosan. The methanolic washing liquids were recorded and examined chromatographically. It was found that essentially the same type of absorption of triclosan takes place at the different membranes, although there are differences between these, they are also something of depend on the used release agent, the results are in essentially the same in all cases. The copolyester / polyether Elastomers absorb significant levels of triclosan the toothpaste; These results are confirmed when one Copolyester / polyether elastomers as membrane or bellows material used in donation dispensers containing the toothpaste indicated above but also contain other toothpaste according to the invention. from that it follows that it is undesirable copolyester / polyether elastomers in contact with the present toothpastes or mouthwashes too even if this is a flavoring material with terpenes up to contain at least 0.1% based on the toothpaste.  

Repeat these trials with Guala toothpastes Dispenser with membranes of a copolyester / polyether elastomers from "Arnitel" - WZ - the losses at Triclosan were excessive large. But if instead of these plastics other for non-reactive plastics such as polyfluor exchanges ethylene, the triclosan activity is within improved acceptable limits. Other plastic parts of such Pump dispensers such as the polypropylene inner walls absorb Do not use excessive amounts of Triclosan and reduce the tooth area Lagverhindernde effect of toothpaste is not essential, namely presumably due to the presence of terpenes in the flavor substance of the toothpaste in question.

In another trial, the toothpaste was made with Polyethy lenterephthalate and polyethylene coated tubes of minde at least ten subjects, twice a day Toothbrushes in the course of a month. The plaque formation was estimated after one month. The results showed that the Toothpaste composition a significant plaque preventing Has effect, as well as it with the mouthwash according to Examples 1 and 2 was the case. It was also shown that triclosan not noticeably inactivated and still in one effective antibacterial and plaque preventing amount in the toothpaste was present.  

example 4

A toothpaste of the following composition was prepared provides:

ingredients weight glycerin 7.00 propylene glycol 3.00 Iota-carrageenan 0.75 Sorbitol (70%) 30.00 sodium 0.30 sodium fluoride 0.33 Titanium dioxide 0.50 Gantrez S-97 -WZ- (13% solution) 15.00 desalinated water 16.07 Sodium hydroxide (50% aqueous solution) 0.80 Silicic Acid Remedy (Zeodent 113 -WZ-) 20.00 Silica thickener (Sylodent 15 -WZ-) 3.00 flavorings 0.95 sodium lauryl sulfate 2.00 triclosan  0.30 100.00

There was a toothpaste of the above composition in one Guala pump dispenser, whose membrane is made of an Arnitel Plastic passed. The toothpaste was further laminated in Tubes with an inner layer of polyethylene terephthalate given. The toothpastes were kept at 5 ° C for two, four and six weeks, respectively or stored at 25 ° C and 39 ° C. Then the toothpastes were added delivered in an amount of about 1.5 per day and in weekly Distance of triclosan content in the delivered toothpaste detected.  

The triclosan loss was those in the Guala pump donor existing dentifrice about 27%, which is beyond tolerance limit and is objectionable. The loss is independent of the storage temperature or the storage time constant, which is due to the Absorption of triclosan can be explained by the pumping membrane can be in contact with the toothpaste before delivery. This membrane consists of a copolyester / polyether elastomers ren, therefore, belongs to the class of plastics, which as Container material should be avoided. If you look at the elastomers Copolyester / polyether membrane of any of the above acceptable plastics, such as polyethylene terephthalate lat, the triclosan stability is increased, and the delivered Toothpaste is effective as a plaque-preventing toothpaste and satisfactory.

Tooth gels behave similarly in such packages in terms of triclosan stability after storage and delivery.

In similar tests were lined with polyethylene terephthalate Dete tubes examined, with only a small loss of Triclosan, less than 5% was found, what indicated that the presence of terpenes of 0.1% or more in the composition including limonene in the flavoring agent or the flavoring agent itself a loss of triclosan or a Inactivation of the same prevented.

If polyfluoroethylene coated tubes are used There is a small loss of triclosan, even if the toothpaste composition contains no flavoring agent; the same is the one Case when polyvinyl chloride as inner coating of the tube or when polysulfone or polycarbonate packaging parts with such Contact toothpastes. As already mentioned, find these last mentioned three plastics barely application.

When the toothpaste is dispensed from the Guala dispensers and in Toothpaste formulation the Gantrez S-97 by 4.76 parts  Luviform (35%) replaced and the difference due to desalted Water is balanced, no significant difference in of triclosan stability.

In the above toothpaste, the polishing agent is a silica system used and not alumina. When you put on as a polish Alumina passes, so reduce the above Difficulties with some plastics, but are still noticeable available. The presence of terpenes in the toothpastes Increasing the triclosan stability is also evident in similar ones Toothpaste compositions based on silicate-containing polishing tel.

Example 5

The mouthwash and toothpastes from the previous examples can in their composition by ± 10% and ± 25% for the Various components are modified, provided that the values then obtained are not outside the otherwise specified Ranges lie; It will be effective antibacterial and tooth lagverindernde products obtained in an effective belagver prevent leakage from the dispensing containers, if they consist of compatible plastics. The products can also be modified by being used as tooth gels, oral gels, pastes, liquids, lollipops, and capsules Reformulated tablets. These modified products behave equals itself by the triclosan or other halogenated Diphenyl ethers or antibacterial antifraps sufficiently stable in the presence of polyfluoroethylene, polyvinyl chloride, polycarbonate and polysulfone packaging or Packaging parts are, even if no flavoring agent and no Terpene is present in the oral compositions; you are also stable in the presence of polyethylenes, polypropylenes, Polyethylene terephthalates, polyallomers, polyamides and Polymethylpentenes, provided that a terpene like limonene  or a stabilizing flavor component in the composition is available. As with the other toothpastes mentioned above and Mouthwashes are copolyesters / polyethers and other elastomers because of excessive absorption and other detrimental Effects against triclosan unsuitable.

Example 6

There were toothpastes with the composition of Example 3 and Example 4 prepared and after one month's storage at 30 ° C. from tubes, which in one case are coated with polyethylene and in the other case were coated with polyethylene terephthalate Toothbrushes, in strand quantities of 0.8 to 2.0 g, with 1 to 1.5 g being preferred. At a strand of 1.5 g, the active Triclosangehalt in toothpaste is about four milligrams (with only 10% of the triclosan inactivated is). If the tubes are stored for a longer time at a higher temperature be or in with a more destabilizing plastic Contact, the compositions can only about 3 mg Triclosan in a 1.5 g strand are available. So if the Zahnpastastrang on the brush is 1 g, so the triclosan levels are about 2.7 mg and 2 mg, respectively. at Toothpastes containing 0.25 to 0.6% triclosan can be found Toothbrush 2.2 to 8 mg triclosan if triclosaninac in a range of 10 to 25%; they are enclosed about 9 mg if no triclosan was inactivated.

The toothpastes are generally used with strand amounts of 0.8 to 2 g used on the brush. If you go twice a day in the morning and in the evening one minute, the teeth with these toothpastes four Brushing for weeks will be a significant improvement Tooth plaque-reducing effect significantly, in comparison with Control toothpastes that do not contain Triclosan. The verbs The effect of the anti-inflammatory effect is also recognizable when to take non-flavored control toothpastes for comparison,  that contain no terpene but triclosan in a toothpaste tube, which is coated with polyethylene and polyethylene terephthalate.  

LIST OF REFERENCE NUMBERS

11 toothpaste tube
13 tubes
15 toothpaste
17 brush
19 tube closure
21 polyfluoroethylene film
23 aluminum foil
25 polyethylene layer
27 donors
29 chamber
31 bottom wall
33 membrane
35 operating lever
37 line
39 discharge opening
41 pillows
43 and 45 sail seams
47 Fourth page
49 Opaque bottle
51 cap
53 mouthwash

Claims (20)

1. Packaged oral hygiene product with an effective dental plaque preventing content of a substantially water-insoluble non-cationic antibacterial agent in the delivered Condition, which is packaged in a dispensing container, which a solid polymeric material in contact with the oral care having the solid polymeric material in Presence of the oral composition compatible with the antibacterial agent is and no excessive loss of antibacterial and anti-fouling property of oral composition when stored in the container. 2. Packaged oral care product according to claim 1, characterized characterized in that the solid polymeric material used in Contact with the oral composition stands, a firm one synthetic organic polymeric plastic material. 3. Packaged oral care product according to claim 2, characterized characterized in that it is a toothpaste, a gel or a liquid toothpaste, a liquid mouthwash or a paste, is a gel or liquid dental treatment agent, wherein the antibacterial agent is a halogenated one Diphenyl ether, and the container is a deformable Dispensing tube, a pump dispenser, a pressurized Dispensing container or bag for toothpaste, dental gel or pastel or gel dentifrices or a Bottle or other container for a liquid tooth pasta, mouthwash or dentifrice. 4. Packaged oral care product according to claim 3, characterized characterized in that the antibacterial agent is a haloge nierter diphenyl ether, with 1 to 3 hydroxyl radicals and 1 to 4 chlorine or bromine atoms is substituted.   5. Packaged oral care product according to claim 4, characterized characterized in that it is a toothpaste, a dental gel or a Mouthwash is and that the antibacterial halogenated Diphenyl ether with 1 or 2 hydroxyl groups and 2 or 3 Chlorine or bromine atoms substituted diphenyl ether is and that the container of a deformable tube, a pump penspender or bag for toothpaste or dental gel or a bottle or dispensing container for the liquid Mouthwash exists. 6. Packaged oral care product according to claim 5, characterized characterized in that the halogenated diphenyl ether a 2 ', 4, 4'-trichloro-2-hydroxydiphenyl ether (THDE), which in in an amount of 0.02 to 1 wt .-% is present. 7. Packaged oral care product according to claim 6, characterized characterized in that the oral hygiene product is a mouthwash, which contains 0.03 to 0.1 wt .-% of THDE and wherein the solid polymeric material that is in contact with the oral Composition is located in the container, polyfluoroethylene len or polyvinyl chloride. 8. Packaged oral care product according to claim 6, characterized draws that it is a toothpaste or a tooth gel which From 0.25 to 0.5% by weight of THDE in a deformable tube, a Pump dispenser or a bag included and that the solid polymeric material in contact with the oral composition in the container is polyfluoroethylene or polyvinyl chloride. 9. Packaged oral care product according to claim 6, characterized indicates that the toothpaste or the tooth gel is about 0.3% by weight THDE contains and the container a deformable tube or a Pump dispenser is. 10. Packaged oral hygiene product according to claim 8, characterized records that the container is a deformable tube, in which  the inner surface is in contact with the oral composition stands, and consists of polyfluoroethylene. 11. Packaged oral hygiene product according to claim 6, characterized characterized in that the solid polymeric material is in contact with the oral composition of a synthetic organic non-elastomeric plastic material. 12. Packaged oral care product according to claim 1, characterized records that it is a stabilizing component of a terpene or a flavoring agent containing the antibacterial Stabili in the presence of the solid polymeric material Siert. 13. Packaged oral care product according to claim 7, characterized draws that it is a liquid mouthwash, which one stabilizing portion of a terpene or a flavoring agent containing the THDE in the presence of a synthetic organic non-elastomeric polymeric plastic material stabilized in contact with the oral composition. 14. Packaged oral care product according to claim 8, characterized draws that it is a toothpaste that has a stabilizing Contains a quantity of a terpene or flavoring agent, which contains the THDE in the presence of synthetic organic non- elastomeric polymeric plastic material in contact with the stabilized oral composition. 15. Packaged oral care product according to claim 14, characterized characterized in that the content of stabilizing terpenes and / or flavorings in the toothpaste in the range of 0.01 is up to 2 wt .-% and that the plastic material selected is from the group consisting of polyethylenes, polypropyls NEN, polymethylpentenes, polyallomers, polyamides, poly fluoroethylenes, polyvinyl chlorides, polycarbonates and Polysulfones.   16. Packaged oral care product according to claim 16, characterized characterized in that the content of stabilizing terpenes and / or flavorings in the mouthwash in a range of 0.01 to 2 wt .-% and that the plastic material is selected from the group consisting of polyethylene, Polypropylene, polymethylpentene, polyallomers, polyamides, Polyfluorethylenes, polyvinyl chlorides, polycarbonates and Polysulfones. 17. Packaged oral care product according to claim 12, characterized characterized in that the terpene content of the composition stabilizing agent is a component of the flavoring agents and in an amount of 0.01 to 2%. 18. Packaged oral care product according to claim 17, characterized characterized in that the terpene is a limonene. 19. Packaged oral hygiene product according to claim 1 or 11, characterized in that it contains 0.5 to 4% by weight of polyvinylmethyl contains ether / maleic anhydride copolymer. 20. Packaged oral care product according to claim 1 to 20, characterized characterized in that it is packaged in an opaque container is.