DE3942642B4 - Packaged oral care products with plaque-preventing properties - Google Patents

Abstract

A packaged mouthwash having an effective plaque preventing content of a substantially water-insoluble, non-cationic, antibacterial agent as dispensed packaged in a dispensing container having a solid polymeric material in contact with the oral care product, wherein the solid polymeric material is in the presence of the oral care product oral composition is compatible with the antibacterial agent and does not show excessive loss of antibacterial and antifouling property of the oral composition when stored in the container, characterized in that
the antibacterial agent is present in an amount of 0.02 to 1% by weight in the oral hygiene product,
the antibacterial agent is a halogenated diphenyl ether substituted with 1 to 3 hydroxyl radicals and 1 to 4 chlorine or bromine atoms, and
the solid polymeric material in contact with the oral composition in the container is polyfluoroethylene or polyvinyl chloride.

Description

The The invention relates to packaged oral care products containing plaque preventing properties, namely oral compositions that prevent the formation of dental plaque Bactericidal such as 2 ', 4,4'-trichloro-2-hydroxy-diphenyl ether (THDE) as an effective component against plaque, these being Composition in a container is packaged, which has a polymeric plastic material and in Contact with the oral composition stands, taking the plastic is compatible with the bactericide in the oral composition.

Although Numerous plastics have the plaque-preventing effect of antibacterial Reduce bactericides, it has been found that certain Plastics such as polyfluoroethylene and polyvinyl chloride are compatible with THDE.

It It was also stated that this no excessive impairment the antibacterial effect and the anti-inflammatory properties the oral composition when stored at room temperature or at elevated Cause temperatures.

It is well known that plaque the periodontal area adversely affected and as a precursor for tartar is seen. Dental plaque can attach to any area of a tooth including form the gingival margins, tarnishes the enamel, reinforces the Calculus formation and can lead to gingivitis. That's why oral compositions containing anti-plaque ingredients for the Dental hygiene essential.

It Although it is known that antimicrobial Means or microbicides in oral compositions the plaque prevent and in some cases especially effective in combination with other ingredients are. However, many such bactericides have disadvantages when used in oral compositions. For example, they tend cationic bactericides such as quaternary ammonium halides, the teeth to discolor; Furthermore, they are by anionic ingredients such as surfactants in the Oral care products inactivated.

In the DE 38 34 354 A1 there is described a packaged toothpaste in direct contact with a low or medium density polyethylene or polypropylene surface. The DE 37 01 123 A1 discloses a toothpaste that is packaged in direct contact with a polyolefin resin package surface. In the DE 36 28 359 A1 a packaged toothpaste is described which is in direct contact with a polyolefin surface of the package. In the three mentioned documents it is agreed that it is also possible to use antibacterial substances in the oral hygiene products, the following antibacterial substances being mentioned concretely:
N ¹ - (4-chlorobenzyl) -N ⁵ (2,4-dichlorobenzyl) biguanide;
p-chlorophenyl biguanide;
4-chlorobenzhydryl biguanide;
4-Chlorbenzhydrylguanylharnstoff;
N-3-Lauroxypropyl-N, ⁵ -chlorobenzyl biguanide;
1,6-Dichlorphenylbiguanidhexan;
1,6-bis (lethylhexylbiguanido) hexane;
1- (lauryldimethylammonium) -8- (p-chlorbenzyldimethylammonium) -octandichlorid;
5,6-dichloro-2-guanidinobenzimidazole;
N ¹ -p-chlorophenyl-N ⁵ -laurylbiguanide;
5-Amino-1,3-bis- (2-ethylhexyl) -5-methylhexahydropyrimidine
and their non-toxic acid addition salts

The specified in the three cited prior art documents Antibacterial substances are other than the antibacterial ones Means, which according to the present Invention can be used.

It was found in the essential water-insoluble halogenated and 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, however inactivated by non-ionic surfactants and by numerous plastics become.

Accordingly, it is an object of the present invention, antibacterial plaque preventing ingredients such as halogenated diphenyl ethers and in particular THDE and DDDE and similar zahnbelagver to provide obstructive ingredients for oral care products therein and to store and dispense these compositions in containers which do not lose an excessive amount of the activity of such bactericides on storage prior to use. In the previously known triclosan dentifrices, as dispensed from a dispensing container, the provision of triclosan is not sufficient to prevent plaque when these agents are used once or twice daily at a rate of 1.5 g / use when brushing usually be presented one minute. To be effective, the user should have a plaque reduction of at least 25% at least after three weeks compared to a control toothpaste used analogously for three weeks.

The most preferred bactericidal and plaque preventing component The present packaged oral care product is THDE, which Also known as triclosan, in accordance with US Patent 4,022,880 as a bactericide in combination anticalculus agent that provides zinc ions and according to DE-OS 35 32 860 in combination with a copper compound. 5 also disclose EU-A-0 161 898, 0 161 899 and 0 220 890 dentifrice with polyethylene glycol and an oily one Flavoring agent.

Dentifrice in the form of pastes, gels, powders, liquids, tablets, lozenges as well as in packaged form are well known, as well as liquid and tableted mouthwashes. Further, by dentists the most diverse dental treatment agents for hardening the teeth, for example in shape of fluoride solutions used. Such products are in deformable tubes, in dispensers with pump pressure or those with propellant gas, also in packets, Bottles, cans or other containers packaged. Although such deformable or compressible containers or Tubes earlier made of metal such as lead or aluminum and the bottles made of glass, there are recent container made of synthetic organic polymer plastics or laminates, containing such plastics. An effect between the oral compositions and the container materials for these is known as, for example, the reaction between toothpaste and Aluminum tubes, whereby to prevent such disturbing factors the containers either pretreated accordingly or other materials used were.

A Interaction between plastic packaging material on the one hand and plaque reducing properties of halogenated Diphenyl ether bactericides have not yet been suspected; it is also unexplored, to what extent bactericidal compounds in dentifrices be affected by contact with the existing plastic packaging can; In particular, it was unexplored whether certain plastics for such container a loss of the anticalculus effect of halogenated Can cause diphenyl ethers or that the Plaque preventing effect in contact with plastics through Reaction, absorption or otherwise impaired or by adding terpenes such as limonene or other flavorings can be inhibited.

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

The Task is solved prevent by a packaged oral care product with an effective plaque Content of a substantially water-insoluble, non-cationic, Delivered antibacterial agent packed in a dispensing container which is a solid polymeric material in contact with the oral hygiene product wherein the solid polymeric material is in the presence of the oral Composition compatible with the antibacterial agent is and no excessive loss of antibacterial and plaque-preventing property of the oral composition at Storage in the container shows, wherein the antibacterial agent in an amount of 0.02 to 1 wt.% Is present in the oral care product, the antibacterial Is a halogenated dephenyl ether containing from 1 to 3 hydroxyl radicals and 1 to 4 chlorine or bromine atoms is substituted, and the solid polymeric material that is in contact with the oral composition in the container is polyfluoroethylene or polyvinyl chloride. preferred Embodiments of Invention will become apparent from the dependent claims.

The packaged oral care product is usually a toothpaste, a dental gel or a mouthwash which are packaged in deformable tubes, pump containers or bottles which have no plastic parts which inhibit the plaque-preventing action of the bactericide, namely a halogenated diphenyl ether like triclosan, adversely affect.

in the Following, the invention will be explained in more detail in connection with drawings; show it:

1 a perspective view of a toothpaste tube with removed screw cap and a pressed onto a toothbrush strand toothpaste;

2 an enlarged partial section of a multi-layer wall of a crimp tube analog 1 ;

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

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

5 a view of a mouthwash bottle capped.

In the 1 illustrated plaque preventing toothpaste tube 11 consists of the deformable tube 13 taking the plaque preventing toothpaste 15 contains, from a use amount of 0.8 to 2 g on the brush 17 squeezed out. The tube 13 is opaque and is made of a synthetic polymeric plastic such as polyfluoroethylene or is coated as a laminate with such a material, which does not affect the anti-plaque effect of the toothpaste during storage.

Preferably, neither the Zahnpastatube nor their closure 19 nor any other part of the tube which may come into contact with the toothpaste, such as the gasket in the screw cap, a copolyester / polyether elastomer, or other plastic material which substantially reduces the plaque-reducing effect of the oral composition, itself 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.

The Parts made of a plastic that does not detoxify the teeth Effect adversely affected even in the absence of terpenes or other stabilizers in the toothpaste.

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 seal insert, not shown here for the tube closure 19 may also be of polyfluoroethylene so that all surfaces in contact with the toothpaste during storage are compatible with the halogenated diphenyl ether, namely the bactericidal component in the toothpaste, and do not cause excessive losses of the antiplatelet activity on storage.

The in 3 A toothpaste dispenser of Guala SpA, Italy, shown in US Pat. No. 4,776,496, has been shown to be a pump-like dispensing container for toothpaste. The donor 27 contains in the chamber 29 passing through the bottom wall 31 and a membrane 33 is formed, the toothpaste. By depressing the operating lever 35 the membrane moves 33 down and pushes toothpaste through the pipe 37 from the discharge opening 39 out. When the pressure on the operating lever 35 decreases, the released elastic membrane goes 33 returns to its original position and moves the line 37 and the lever 35 back to the starting position. At the same time, the floor becomes 31 pushed upwards by atmospheric pressure. The various parts of this dispenser that are in contact with the toothpaste are made of plastic that does not inactivate the bactericidal and plaque preventing halogenated diphenyl ether.

The in 4 shown bag or pillow 41 is a heat-sealed unit that is seamed on three sides 43 and 45 while the fourth page 47 only folded over 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.

5 shows an opaque bottle 49 with a cap 51 , Both the bottle and the here not shown seal insert in the screw cap are made of plastic, which with the THDE, so the plaque-preventing component in the mouthwash 53 is compatible in the bottle.

The packaged oral care products that instead of toothpaste as well Tooth gel or as a thick liquid can exist additionally still other dentifrice compositions such as dental hardeners, e.g. Fluorides and phosphates, bactericides, color solutions to indicate dental plaque or other suitable oral compositions as used by dentists become. It can also bottled under pressure or aerosol compositions are filled in pressure cans, the ones mentioned containing plaque preventing compounds, being used as a propellant mostly nitrogen is used.

Next the containers shown in the drawings can also be squeeze bottles, Capsules, pots, spongy carrier and a variety of types of mechanical dispensers can be used. As some of the antibacterial halogenated diphenyl ether are sensitive to light, it is appropriate in certain cases, these containers to produce a chemically or physically light-shielding material or with this coat or laminate, so that no plaque preventing compound inactivating radiation such as UV light can occur. Such containers are often opaque to one Inactivation of the anti-plaque component in the oral care products how to prevent toothpastes by actinic radiation.

The causes of inactivation of THDE and other essentially non-cationic bactericides with anti-plaque properties in oral care products are not yet fully elucidated, including whether it is a chemical reaction or physical absorption. Experiments with basic mouthwash compositions containing THDE show that on aging in dispensers at room temperature at 38 ° C and at 49 ° C over 12 weeks, significant losses occur in the range of more than 25% of the original concentration of THDE, if Mouthwash water is in contact with container walls or parts of low density polyethylenes, high density polyethylenes, polyethylene terephthalates, polypropylenes, polyamides (nylon - WZ), polyallomers and polymethylpentenes. To the same extent, high losses result when stored in containers whose inner walls or parts thereof are made of copolyester / polyether elastomers such as have heretofore been used as pumping membranes in the Guala dispensers. It has been found that polyfluoroethylenes such as polytetrafluoroethylene, polyvinyl chlorides, polycarbonates and polysulfones do not react with or absorb significant levels of THDE. On the other hand, polycarbonates and polysulfones are brittle and usually unsuitable for parts of dispensing containers. Polyvinyl chlorides give the oral care products such as toothpastes a foreign taste and are therefore usually not used as a container material, unless this taste is compatible with that of the Zahnpastaaromastoffes. Of all the possible polymeric plastics, polyfluoroethylene is particularly provided as a suitable material for the present containers or packages, which does not substantially reduce the anticalculus effect of the anticalculus agents; As already mentioned, stabilizing compounds may be added to the oral compositions for the antiplaque components, such as terpenes, preferably limonene, essential oils, often containing terpenes, and other flavoring agents having similar stabilizing properties; In this case one can reduce the loss of activity of the antiplaque agent when they are in contact with containers or container parts, which consist of the above-mentioned plastics, which otherwise cause a significant loss of zahnbelagver hindering effect. It is therefore not entirely dependent on polyfluoroethylene as a container material, provided that the oral composition also contains a stabilizing portion of a terpene or other suitable stabilizer. In the presence of such a stabilizer in the oral compositions or when polyfluoroethylene or polyvinylchloride is the only plastic in contact with the oral composition, the activity losses of the antiplatelet component are below 25% and preferably below 10%, even after a relatively high Storage temperature of eg 20 to 40 ° C for a storage period of a few weeks to a year or more. The most stable oral compositions are those which contain a stabilizing portion of terpene or other suitable stabilizer and which are in a container in which the parts in contact with the oral care product are made only of polyfluoroethylene or other non-reactive plastic. While terpenes and essential oils are the major stabilizers of the invention, other flavor components may also contribute to the stabilization of the plaque preventing components by either interfering with destabilizing reactions or inhibiting the absorption of halogenated diphenyl ether by plastic. It can be assumed purely theoretically that some components of the oral composition tend to solubilize the THDE and then retain it in the composition and inhibit or prevent migration into the plastic. On the other hand, it is theoretically also conceivable that such a solubilizing effect supports the migration of the solubilized THDE in the plastic. Although the terpenes and other stabilizers he If flavoring agents are desired, this is not necessary and the stabilizers can only be used for the purpose of stabilization.

Even though preferably the packaging according to the invention Interior walls, so walls in contact with the composition, made of a solid synthetic have organic polymeric plastic or with this material coated, can according to the invention Other solid and / or film-forming polymers may be used and independently of whether they are synthetic, organic or plastic. So it can Polyethylene glycols and oxypolyethylene glycols such as "Carbowax" varieties, e.g. Carbowax 4000 and Carbowax 6000 often as coating material in the dispensing containers for the described Compositions are used. As a coating are also inorganic Silicone polymers such as siloxane and non-synthetic organic film-forming Fabrics such as gums, e.g. Carrageenan, Tragacanth and Karayagum suitable. Further can solid polymeric substances such as cellulose and starch and derivatives of these as container material in contact with the antibacterial and plaque preventing components of the oral composition so packaged.

The numerous packaged compositions of the invention are mostly toothpastes, tooth gels and mouthwashes. The dentifrices consist essentially of three basic components, namely one Carrier, a polishing material and a surfactant. The antibacterial component, i.e. the halogenated diphenyl ether, is normally in the carrier material usually available 10 to 80 wt.% Of the dentifrice makes up, where the numbers refer to the total composition. The carrier is generally from 3 to 40% by weight of water and from about 7 to 77% by weight of humectant, such as Glycerol, sorbitol, propylene glycol or mixtures thereof, during 0.5 up to 10% by weight of a gelling agent such as sodium carboxymethylcellulose, Irish moss, iota carrageenan or hydroxyethyl cellulose or mixtures thereof can be. The polish in the dentifrice makes about 10 bsi 75% by weight in a tooth gel or a toothpaste and about 50 to 99% by weight in a tooth powder. Polishes are colloidal among others silica, precipitated silica, Sodium aluminum silicate, insoluble Sodium metaphosphate, hydrated alumina, calcined Alumina, dicalcium phosphate dihydrate, anhydrous dicalcium phosphate or calcium carbonate, optionally mixed together.

When Surfactants can anionic, nonionic, cationic and zwitterionic surfactants nonionic surfactants are often used because of their disadvantageous influences on the antibacterial compound e.g. THDE avoided; as well cationic and zwitterionic surfactants are often avoided because her teeth make stains or dark. Accordingly, anionic surfactants used as a cleansing component in the dentifrices, wherein 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 sulfonated surfactants partially or completely can be used as such. Other active ingredients are fluoride-providing compounds such as Sodium fluoride or sodium monofluorophosphate, which is used to cure the Teeth mostly is present in such amounts that the composition is 0.001 contains up to 1% fluorides. Other accessories like flavorings and sweeteners can in amounts of 0.1 to 10%. In addition, it is an advantage a polycarboxylate such as a polyvinyl methyl ether / maleic anhydride copolymer (PVM / MA) like "Gantrez" - WZ - in an amount of 0.5 to 5% by weight. Such polycarboxylate compounds increase the anti-tickle effect of the bactericide; the use of such Polycarboxylates in oral compositions are disclosed in U.S. Patent 4,627 977 described.

at mouthwashes is the vehicle preferably water and alcohol, with ethanol or isopropanol be preferred as alcohol. The liquid carrier makes up about 90 to 99% of the Composition of, wherein the alcohol content is 5 to 30%; further is propylene glycol in amounts of often 2 to 10% each based on the final product is available. The remaining components of this composition from 0.1 to 10% Flavorings, wetting agents, sweeteners, coloring agents, antiplaque agents and others additions be. In dentifrices and mouthwashes is the effective amount antibacterial plaque preventing compound in general in a range of 0.03 to 0.1% in mouthwashes and usually 0.25 to 0.5% in dentifrices. The proportion of THDE in toothpastes should not be higher than 0.8% and in mouthwashes not more than 0.2%, since otherwise at higher concentrations deafening feeling can adjust. The concentration of THDE should be the specified Minimum limits do not fall below as they are at lower concentrations against plaque are ineffective. Preferably, the to be delivered contain Compositions the antiplaque agent and THDE in the specified areas. If the initial concentration in the specified A loss up to 25% may be acceptable, and such from containers delivered compositions are within the scope of the present Invention.

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

Although in the present case essentially of dentifrices and mouthwashes Speech is, can also other oral compositions according to the invention such as Chewing gum similar proportions of the components, depending on the type of composition, being the liquid Products less, such as the mouthwashes and the thicker compounds how toothpastes can contain more such additives, and often together with special additives according to the purposes of the Composition. So can Compositions that have a cure the teeth fluorinated and phosphates such as sodium or potassium fluoride and sodium fluorophosphate in a range of 1 to 5% in dentifrices or mouthwashes contain. color solutions To display the plaque can be a corresponding color, preferably red, light in concentration from 0.001 to 0.1% in a mouthwash.

The Antibacterial agent is a non-cationic material insoluble in water or substantially water-insoluble is; it has a water solubility at 25 ° C less than 10 g / l and in some cases even less than 1 g or 0.1 g / l. Such compounds are soluble in the dentifrice carriers or dispersible, namely in straps which contain glycerol, sorbitol and / or propylene glycol and in end products with these; they are also in watery alcoholic Medium of mouthwash soluble or dispersible.

From The antibacterial compounds contain the halogenated diphenyl ether Bromine and / or chlorine, with chlorine being the preferred halogen. These Compounds are with 1 to 3 hydroxyl radicals and 1 to 4 halogen atoms substituted and preferably with 1 to 2 hydroxyl radicals and 2 or 3 halogen atoms, preferably 4 substituents, that is two on lie to each ring. Most suitable are 2,2'-dihydroxy-5,5'-dibromodiphenyl ether and 2 ', 4,4'-trichloro-2-hydroxy-diphenyl ether (THDE), which is particularly preferred.

The Terpenes, which are terpene hydrocarbons and oxygenated derivatives these are, for example, dl-limonene, menthol, Diterpenes, polyterpenes and their derivatives, many of which are find in a variety of essential oils and flavors. additionally for their property as stabilizer for halogenated diphenyl ethers to act, they impart the present oral compositions a desired one Aroma. Among the terpenes and their derivatives is limonene these properties are best balanced, although other terpenes, which do not serve as flavoring agents can also be used, as well other emulsifiable lipophilic essential oils and flavorings containing stabilizing components included.

The various plastics of the container or dispensing container or their parts are only briefly described, as their chemical nature and the extent of her Polymerization is well known; further details emerge from "Modern Plastics Encyclopedia, McGraw-Hill Inc., New York.

The Compositions according to the invention can have a fluorine source containing 25 to 5000 ppm fluoride ions in the oral cavity to disposal represents, preferably 300 to 2000 ppm and in particular 800 to 1500 ppm, where for for further details see U.S. Patent 4,627,977. The fluoride works primarily for hardening the teeth, but also serves to stabilize any existing anti-calculus Polyphosphates. Such polyphosphates are preferably mixtures from sodium and potassium pyrophosphate stabilized by Gantrez S-97 - TM the quantities given in US application 07/398 605 of August 25, 1989; and U.S. Patents 4,627,977 and 4,806 340 find.

The preparation of the described oral compositions is carried out in any known manner. Thus, for example, the THDE is dispersed and / or dissolved in a carrier portion of the dentifrice, wherein the terpene is present as a flavoring agent. To prepare a dentifrice, a carrier of glycerol, sorbitol and propylene glycol, gelling agents and suitable additives including Gantrez S-97 and triclosan is prepared, and the carrier and aqueous surfactant preferably sodium lauryl sulfate or a mixture thereof mixed with sodium methyl cocoyl taurate, followed by polishing with this premix is processed. Then flavorings, terpene, dissolved in ethanol, are added and the pH is adjusted. For the preparation of the mouthwash, the various components are only in the mixed alcoholic or aqueous-alcoholic phase and stirred until dissolved. A mixture of sodium lauryl sulfate (SLS) and sodium methyl cocoyl taurate in a ratio of 1: 4 to 4: 1 is preferably used as an anionic surfactant in mouthwash, it being possible to allow a desired lowering of the content of SLS by the taurate present.

At the Packing the oral composition into the dispensing container is it expedient one Contact of the composition with plastic parts made of polyester / polyether elastomers and it is further desired to have one contact each Composition that does not contain stabilizers such as terpene or terpene Contains aroma, in contact with plastic parts to bring that up as listed above as reactive with THDE and other such antibacterial and plaque preventing agents Connections are. In particular, the mentioned plastic parts in the storage containers or other containers, avoiding the supply lines, pumps and other equipment, with which the oral compositions have a significant amount of time long in touch come or even for a short time in contact with elevated temperatures.

Even when the packaged invention Compositions are made and a contact of this THDE or other halogenated diphenyl ethers or bactericides Compositions avoiding contact with the reactive plastics is avoided, it is still desirable to packaged compositions not the action of heat and expose light, otherwise the loss of anti-plaque Effectiveness is accelerated. Accordingly, the compositions of the invention preferably in opaque containers or dispensing container packaged and stored at temperatures in the range of 10 to 38 ° C; otherwise you can stored and used the packaged compositions in the usual way be, with the desired anti-fog properties are retained. Such effects could by laboratory tests and by observations on the teeth of Subjects taking the different packaged compositions and control preparations used, verified. Significant improvements in the anti-tarnish Effect of the packaged compositions according to the invention were observed in particular in comparison with control preparations in which the compositions were in packages that were reactive with halogenated diphenyl ether were and did not contain any stabilizer. improvements were also festgetellt if packaging with reactive plastic - not however, copolyester / polyether elastomers - with compositions used, which contain terpenes, with the comparators oral Contains compositions without terpenes and without flavorings.

In the following, the invention will be explained in more detail by way of examples, wherein all quantities are based on weight. Trademarks are identified by the suffix "WZ" Example 1 (with comparative experiments) ingredients weight Water, desalted 47.84 Sorbitol (70% aqueous solution) 20.00 Ethanol (95% aqueous solution) 12.50 glycerin 10.00 propylene glycol 7.00 Gantrez S-97 (13% solution) 1.92 Sodium hydroxide (50% aqueous solution) 0.12 sodium lauryl sulfate 0.25 Tauranol WSHP - WZ 0.20 aroma mixture 0.12 triclosan (Irgasan - WZ - DP 300 from Ciba-Geigy) 0.05 100.00

The mouthwash of the above composition was obtained by mixing the various ingredients in any order, but triclosan was first dissolved in a propylene glycol and ethanol mixture, followed by an aqueous solution of sorbitol, glycerol and anionic acid blended surfactant and the aroma mixture was finally added. The sodium hydroxide solution serves to neutralize the resulting acidic mixture to a pH of about 6.84 because it is desired that the product be neutral or near neutral.

The got mouthwash has an excellent cosmetic stability and a pleasant aroma. The flavorings and triclosan will be sufficient solved, being this solution attributable at least in part to the presence of tauranol WSHP is. If only 0.25% SLS is used as the anionic surfactant, Solubilization of flavors and triclosan is not sufficient. Although this solubilization is achieved by using more SLS up to the maximum allowed can increase this component in the mouthwash is usually 0.25% and Tauranol WSHP and SLS be used without difficulty in these proportions. This mouthwash water was in vitro on the bioavailability from Triclosan opposite a comparable mouthwash with a composition without tauranol WSHP tested and further, in another case, by half a nonionic surfactant (Pluronic F-127).

tries for determining uptake of triclosan by measuring triclosan absorption on hydroxyapatite discs coated with saliva, and by protein absorption with zones of inhibition was found that the Presence of mixed anionic surfactants a comparable bioavailability of triclosan, compared with the availability from the SLS only Composition. The availability is considerably larger at Compositions containing no nonionic surfactant compared with those containing as nonionic surfactant Pluronic F-127.

The Mouthwash according to example was elevated at Temperature of 41 ° C three weeks and five Aging weeks, giving a storage at room temperature of six Months or one year respectively. These aging tests were in dispensers or glass bottles, polyvinyl chloride and polyethylene terephthalate or in containers coated with these plastics. at no chemical analysis was found after aging of the mouthwash Triclosan losses in glass containers, however, marked triclosan losses in polyethylene terephthalate containers or polyvinyl chloride. However, they are at the present Composition well below the tolerable 25% of the starting concentration and can under 5 or 10% lie.

If instead of the aroma mixture dl-limonene in amounts of 0.1 or 0.2 and 0.4% is used In the packages described dentifrice according to the invention with better Stabilization obtained, and such stabilization is Also, if other terpenes of any other essential oils and Flavoring agents are present in appropriate amounts. Good results are also obtained when the container material or its coating from polymethylpentene, polyallomer, polypropylene, polyethylenes higher and low density and polyamides, though such materials do Absence of flavorings and their contained terpenes significant and excessive losses at the disposal standing triclosan from the mouthwash when stored in particular at elevated Show temperature.

Example 2 (with comparative experiments)

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

For this mouthwash, the availability of triclosan after three weeks of storage was examined in various dispensing containers made of or lined with different plastics. The experiments were carried out at room temperature at 38 ° C and at 49 ° C, the elevated storage temperatures corresponded to a longer storage time at room temperature of one year or more. Triclosan losses of more than 25% were found when the containers consisted of polymethylpentene, polyallomer, polypropylene, high and low density polyethylene and polyamides, with excessive losses for containers made of polypropylene, polyethylene and polyamides (nylon).

Container off Polyvinyl chloride, polycarbonate, polysulfone or polyfluoroethylene, such as polytetrafluoroethylene or coated with these materials container showed essentially no triclosan loss. The losses Triclosan from mouthwash in containers the above mentioned Kind as Polymethylpenten can be analogous Example 1 can be reduced by adding limonene to the composition, other terpenes or essential oils containing a content of these compounds, the proportion of terpenes preferably at least 0.1 and even better, higher, such as at 0.2 or 0.4%, based on the final product. In some cases also has the use of flavorings that are not appreciable quantities contained in terpenes, a positive effect although this effect, not as good as adding terpenes.

Example 3 (with comparative experiments)

A toothpaste of the following composition was prepared. ingredients weight propylene glycol 10.00 Iota-carrageenan 0.75 sodium fluoride 0.33 Sorbitol (70%) 30.00 sodium 0.30 Titanium dioxide 0.50 Sodium hydroxide (50% aqueous solution) 0.80 Water, desalted 27.71 Luviform - WZ - (35% solution) 4.76 Silica polishing agent (Zeodent 113) 20.00 Silica thickener (Sident 22S) 2.00 Sodium lauryl sulfate (94% active) 1.60 Aroma 0.95 triclosan 0.30 100.00

This conventionally prepared toothpaste was tested to examine the stability of triclosan, again using various plastics in the dispensing containers. Specifically, for the membranes in a pump dispenser according to 3 once used "Pibiflex - WZ - 46" from Inmont and secondly "Arnitel - WZ - 460" from AKZO. In each case, three samples of the respective plastics were investigated, each of which treated the three patterns with different mold release agents, 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 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 0 Master" - TM, which consists of 5% Oleoamide and 95% polypropylene was used.

To two weeks storage of the samples in contact with the toothpaste Room temperature at 38 ° C and at 49 ° C The toothpastes were isolated and the plastic samples with water washed and placed in methanol to absorb approximately during storage Triclosan. The methanolic washing liquids were recorded and examined chromatographically. It was determined, that essentially the same kind of absorption of triclosan at the different ones Membranes, although there are differences between them, which are also somewhat dependent on the release agent used, so are the results in all cases essentially the same. The copolyester / polyether elastomers absorb considerable Amounts of triclosan from toothpaste; these results will be approved, when copolyester / polyether elastomers as membrane or bellows material used in donation dispensers containing the toothpaste above but also other toothpaste according to the invention contain. It follows that it undesirable is copolyester / polyether elastomers in contact with the present Toothpastes or mouthwashes even if this is a flavoring material with terpenes up to contain at least 0.1% based on the toothpaste.

In a repeat of these experiments with Guala toothpaste dispensers with membranes from a Copolyester / polyether elastomers from "Arnitel" - TM - the losses of triclosan were excessively large. However, substituting other non-reactive plastics such as polyfluoroethylene for these plastics will improve triclosan activity within acceptable limits. Other plastic parts of such pump dispensers such as the polypropylene inner walls do not absorb excessive amounts of triclosan and do not substantially reduce the antiplaque effect of the toothpaste, presumably due to the presence of terpenes in the flavor of the subject toothpaste.

at Another attempt was the toothpaste made with polyethylene terephthalate and polyethylene coated tubes from at least ten subjects used twice a day Toothbrushes in the Over the course of a month. The plaque formation became after a month estimated. The results showed that the Toothpaste composition a significant plaque preventing effect has, as well as it with the mouthwash according to Examples 1 and 2 of the case was. It also showed that the Triclosan had not been noticeably inactivated and still in an effective antibacterial and plaque preventing amount was present in the toothpaste.

Example 4 (with comparative experiments)

A toothpaste of the following composition was prepared: 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 -) Silica thickener 20.00 (Sylodent 15 - WZ -) 3.00 flavorings 0.95 sodium lauryl sulfate 2.00 triclosan 0.30 100.00

It was a toothpaste of the above composition in a Guala pump dispenser packaged, whose membrane consisted of an Arnitel plastic. The toothpaste was further in laminated tubes with an inner layer of polyethylene terephthalate given.

The Toothpastes were stored for two, four and six weeks at 5 ° C and 25 ° C and 39 ° C, respectively. Subsequently The toothpastes were dispensed in an amount of about 1.5 a day and in weekly Distance of triclosan content detected in the delivered toothpaste.

Of the Triclosan loss was present in the Guala pump dispensers Dentifrice about 27%, which was beyond the 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 explained by the pumping membrane which is in contact with the toothpaste before delivery. This membrane consists of a copolyester / polyether elastomer, belongs So to the class of plastics, which are avoided as container material should. When the elastomeric membrane of copolyester / polyether from one of the above mentioned acceptable plastics, such as polyethylene terephthalate, becomes the triclosan stability elevated, and the delivered toothpaste is as a toothpaste preventing toothpaste effective and satisfactory.

gels behave similarly in such packages with respect to the triclosan stability after storage and delivery.

In similar tests, polyethylene terephthalate-lined tubes were examined, with only a slight loss of triclosan was found to be less than 5%, indicating that the presence of terpenes of 0.1% or more in the composition, including limonene in the flavoring agent or the flavoring agent itself, caused loss of triclosan or inactivation thereof prevented.

If Polyfluoroethylene coated tubes are used, there is one small loss of triclosan, even if the toothpaste composition contains no flavoring agent; that same is the case when polyvinyl chloride as the inner coating of the tube or when polysulfone or polycarbonate packaging parts with such Contact toothpastes. As already mentioned, these last three mentioned Plastics hardly used.

If the toothpaste is dispensed from the Guala dispensers and in the toothpaste formulation the Gantrez S-97 replaced by 4.76 parts Luviform (35%) and the Difference is compensated by desalinated water is not significant difference in triclosan stability.

at The above toothpaste is used as a polishing agent, a silica system and not alumina. When going as a polish on alumina, this reduces the above Difficulties with some plastics, but are still noticeable available. The presence of terpenes in the toothpastes to increase the triclosan also shows in similar Toothpaste compositions based on silicate-containing polishing agents.

Example 5 (only partially Inventive)

The Mouthwash and toothpastes from the previous examples can be found in their composition by ± 10% and ± 25% for the Various components are modified, provided that the then obtained Values not outside the otherwise specified areas are; it will be effective antibacterial and obtained antiplaque products, which in an effective anti-fouling Condition from the dispensing containers leak, provided that they consist of the compatible plastics. The products can also be modified by that one as tooth gels, oral gels, pastes, liquids, lollipops, Reformulated capsules and tablets. These modified products behave the same way by the triclosan or other halogenated Diphenyl ether or antibacterial antifraps sufficient stable in the presence of polyfluoroethylene, polyvinyl chloride, polycarbonate and polysulfone packaging or packaging parts are themselves if no flavoring agent and no terpene in the oral compositions is available; they are also stable in the presence of polyethylenes, Polypropylenes, polyethylene terephthalates, polyallomers, polyamides and polymethylpentenes, provided that a terpene such as limonene or a stabilizing flavor component is present in the composition is. As with the other toothpastes and mouthwashes mentioned above Copolyester / polyether and other elastomers due to excessive absorption and other adverse effects to triclosan unsuitable.

Example 6 (with comparative experiments)

It were toothpastes having the composition according to Example 3 and Example 4 prepared and after one month's storage at 30 ° C from tubes, which in one case coated with polyethylene and in the other case coated with polyethylene terephthalate, expressed on toothbrushes and although in strand amounts of 0.8 to 2.0 g, with 1 to 1.5 g being preferred has been. With a 1.5 g strand, the active triclosan content is in toothpaste at about four milligrams (with only 10% of triclosan has been inactivated). When the tubes are at a higher temperature for a longer time be stored or with a more destabilizing plastic in Contact can get the compositions only about 3 mg triclosan in a 1.5 g heavy strand available stand. So if the Zahnpastastrang on the brush is 1 g, so lie triclosan levels at about 2.7 mg and 2 mg, respectively. For toothpastes the 0.25 to 0.6% triclosan are found on the toothbrush 2.2 to 8 mg triclosan if triclosanin activation in one Range of 10 to 25%; they are around 9 mg if not Triclosan was inactivated.

The Toothpastes are generally used with strand quantities of 0.8 to 2 g on the brush used. If you go twice a day In the morning and in the evening one minute, the teeth with these toothpastes four Brushes for weeks, will significantly improve the anti-inflammatory effect clearly and in comparison with control toothpastes that no Triclosan included. Improving the anti-tickling effect is also recognizable when comparing non-flavored control toothpastes who does not contain terpene but triclosan in a toothpaste tube, which is coated with polyethylene and polyethylene terephthalate.

Claims (4)

A packaged mouthwash having an effective plaque preventing content of a substantially water-insoluble, non-cationic, antibacterial agent as dispensed packaged in a dispensing container having a solid polymeric material in contact with the oral care product, wherein the solid polymeric material is in the presence of the oral care product oral composition is compatible with the antibacterial agent and does not show excessive loss of antibacterial and antifouling property of the oral composition when stored in the container, characterized in that the antibacterial agent is present in an amount of 0.02 to 1% by weight in the oral hygiene product , the antibacterial agent is a halogenated diphenyl ether substituted with 1 to 3 hydroxyl radicals and 1 to 4 chlorine or bromine atoms, and the solid polymeric material in contact with the oral composition in the container, polyfluoroethylene or pol yvinyl chloride is. Packaged oral care product according to claim 1, characterized in that the halogenated diphenyl ether is a 2 ', 4,4'-trichloro-2-hydroxydiphenyl ether (THDE) is. Packaged oral care product according to claim 2, characterized characterized in that the oral hygiene product is a mouthwash which 0.03 to 0.1 wt.% THDE contains. Packaged oral care product according to claim 2, characterized that it is a toothpaste or a dental gel with a Content of 0.25 to 0.5 wt.%, Preferably 0.3 wt.% THDE and the container a deformable tube, a pump dispenser or a bag is.