DK163276B - DENTAL DETAILS WITH GELING AGENT MIXTURE - Google Patents
DENTAL DETAILS WITH GELING AGENT MIXTURE Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/042—Gels
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/20—Halogens; Compounds thereof
- A61K8/21—Fluorides; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
- A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
- A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/594—Mixtures of polymers
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Description
iin
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Den foreliggende opfindelse angår et tandplejemiddel med ønskværdige rheologiske egenskaber, der er hensigtsmæssige for effektiv påfyldning af en mekanisk betjent eller ved trykforskel virkende tandpiejemiddeldispenser og til eks-5 trusion deraf.The present invention relates to a dentifrice having desirable rheological properties suitable for effective filling of a mechanically operated or pressure differential toothpaste dispenser and for extrusion thereof.
Et tandplejemiddel erkendes generelt ved dets cremeagtige konsistens eller gelkonsistens og kan almindeligvis omtales som en dentalcreme, en tandpasta eller i nogle tilfælde en 1,0 klar eller uigennemsigtig geltandpasta. Det kan i virkeligheden karakteriseres som værende halvfast, idet det f.eks. er i det væsentlige fast, når det er placeret på en tandbørstes børstehår, og i det væsentlige flydende, såsom under fremstilling, under omrøring og påfyldning på en beholder, 15 eller når det udsættes for tryk til ekstrusion af tandplejemidlet fra dets beholder.A dentifrice is generally recognized by its creamy or gel consistency and can generally be referred to as a dental cream, a toothpaste or in some cases a 1.0 clear or opaque gel toothpaste. It can in fact be characterized as being semi-solid, being is substantially solid when placed on the bristles of a toothbrush, and substantially liquid, such as during manufacture, during stirring and filling on a container, or when subjected to pressure to extricate the dentifrice from its container.
Tandplejemidlers cremeagtige konsistens bibringes typisk ved hjælp af et gelerende middel eller et bindemiddel. Tidligere 20 har geldannende midler primært været valgt med henblik på opnåelse af let spredning af tandplejemidlet i mundhulen.The creamy consistency of dentifrices is typically imparted by a gelling agent or binder. In the past 20, gelling agents have been selected primarily for the purpose of achieving easy spreading of the dentifrice into the oral cavity.
Mange geleringsmidler, såsom cellulosematerialer, polysaccha-rider fra tang eller alger, gummiarter og lerarter opfylder dette kriterium. Nogle geleringsmidler forårsager imidlertid, 25 selv om de generelt er ønskelige til tandplejemidler emballeret i fleksible tuber, ulemper, når tandplejemidlerne emballeres i mekanisk betjente eller ved trykforskel virkende dispensere.Many gelling agents such as cellulose materials, polysaccharides from seaweed or algae, gums and clays meet this criterion. However, some gelling agents, although generally desirable for dentifrices packaged in flexible tubes, cause disadvantages when the dentifrices are packaged in mechanically operated or pressure differential dispensers.
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Tandplejemidler indeholdende konventionelle poleremidler, såsom a-aluminiumoxidtrihydrat, og konventionelle geleringsmidler, såsom natriumcarboxymethylcellulose eller hydroxyethyl-cellulose eller blandinger deraf, kan på ønskelig måde fyldes på fleksible tuber eller mekanisk betjente eller ved trykfor-35 ....Dental care agents containing conventional polishing agents such as α-alumina trihydrate and conventional gelling agents such as sodium carboxymethyl cellulose or hydroxyethyl cellulose or mixtures thereof may be desirably loaded onto flexible tubes or mechanically operated or pressurized.
skel virkende dispensere og ekstruderes derfra. Nar imidlertid tandplejemidlet indeholder mange aktive bestanddele, kan vanskeligheder forekomme ved forsøg på at fylde et tandplejemiddel på en mekanisk betjent eller ved trykforskel virkende 2distinguish active dispensers and extrude from there. However, when the dentifrice contains many active ingredients, difficulties may occur when attempting to fill a dentifrice on a mechanically operated or pressure differential acting 2
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dispenser, og/eller ved forsøg på at ekstrudere det derfra.dispenser, and / or by attempting to extrude it therefrom.
Især kan lækage fra åbninger i dispenserne forekomme under fyldning eller forsendelse, og produktet kan være vanskeligt at udpresse i rheologisk acceptabel stribeform.In particular, leaks from openings in the dispensers may occur during filling or shipping, and the product may be difficult to extrude in rheologically acceptable strip form.
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Tandplejemidler, som er fortykkede eller har tendens til at blive fortykkede, kan i stigende grad blive vanskelige for en forbruger at presse ud af en tandpiejemiddeltube i løbet af et tidsrum. Med andre ord kan forbrugeren være nødt til at forøge tryk-10 ket på en tandpiejemiddeltube indeholdende et sådant tandplejemiddel i løbet af brugstiden med henblik på at blødgøre eller gøre den halvfaste tandpiejemiddelmasse flydende for at udpresse den. Dette har ikke været noget større problem hidtil, eftersom sammensætninger kan indstilles til anvendelse af 15 mindre geleringsmiddel med henblik på at ramme en balance, hvor tandplejemidlet ikke er for blødt ved anvendelsens begyndelse og for tykt ved afslutningen, og i hvert tilfælde har forbrugere let indstillet sig på at udøve det tryk, der er nødvendigt til at presse den ønskede mængde tandplejemid-del ud på en tandbørstes børstehår.Dental care products that are thickened or tend to thicken can become increasingly difficult for a consumer to squeeze out of a dental care tube over a period of time. In other words, the consumer may need to increase the pressure on a dentifrice tube containing such a dentifrice during use to soften or liquefy the semi-solid dentifrice mass to extrude it. This has not been a major problem so far, since compositions can be adjusted to use less gelling agent to strike a balance where the dentifrice is not too soft at the beginning of application and too thick at the end, and in each case consumers have readily adjusted. Be sure to apply the pressure needed to squeeze the desired amount of dentifrice onto a toothbrush's bristles.
Tandplejemidler, som er tyndtflydende ved udpresning fra en tube, har også været accepteret under brug, hvis de størkner til mere fast form på tandpastabørstehår i løbet af nogle 25 få sekunder. Typen af geleringsmiddel kunne således varieres i vidt omfang til tandplejemidler emballeret i tuber. Således har Københavns Pectinfabrik A/S i Lille Skensved, Danmark, som er et datterselskab af Hercules Inc., Wilmington, Delaware, U.S.A., foreslået sit produkt "Genuvisco" type 0819, en iota-30 carrageenan (i-carrageenan), som et muligt fortykkelsesmiddel til tandpasta. I-carrageenan, som kan fås fra Marine Colloids Division af FMC Corporation i Springfield, New Jersey, som "Viscarin" TP-5, har også været foreslået til eventuelle tandpastaer i forbindelse med tandpasta indeholdende dicalcium-35 phosphat eller silica. I-carrageenan har endvidere været omtalt som en fortykkelseskomponent sammen med k-carrageenan og alka-limetalalginat til et tandplejemiddel indeholdende galactan- 3Toothpaste, which is thin-fluid by squeezing from a tube, has also been accepted during use if it solidifies to a more solid form on toothpaste bristles within a few 25 seconds. Thus, the type of gelling agent could be widely varied for dentifrices packaged in tubes. Thus, Copenhagen Pectinfabrik A / S in Lille Skensved, Denmark, which is a subsidiary of Hercules Inc., Wilmington, Delaware, USA, has proposed its product "Genuvisco" type 0819, an iota-30 carrageenan (i-carrageenan), as a possible thickening agent for toothpaste. I-carrageenan, which is available from the Marine Colloids Division of the FMC Corporation in Springfield, New Jersey, as "Viscarin" TP-5, has also been suggested for any toothpastes associated with toothpaste containing dicalcium phosphate or silica. In addition, I-carrageenan has been referred to as a thickening component together with k-carrageenan and alkali metal alginate for a dentifrice containing galactan-3.
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galactose i japansk offentliggørelsesskrift nr. 56 115711, der blev publiseret den 11. september 1981, af Lion Dentifrice Ltd.Galactose in Japanese Patent Publication No. 56,115,117, published September 11, 1981, by Lion Dentifrice Ltd.
5 Ved anvendelse af en tandpiejemiddeldispenser, der betjenes mekanisk eller ved trykforskel, kan konventionel teknik til formindskelse af tandplejemidlets fortykkelse undertiden ikke være fuldt tilfredsstillende sammenlignet med et tandplejemiddel fyldt på en fleksibel tube, eftersom tandplejemidlet, 10 når en dispenser anvendes, skal være relativt tyndt under fyldning, men genvinder sin konsistens og forbliver således under tidsrum for forsendelse, lagring og anvendelse. Med andre ord genvinder tandplejemidlet efter fyldning den konsistens, det havde forud for den udøvede forskydningskraft for 15 at gøre det flydende under påfyldningen. Konventionelle geleringsmidler, såsom natriumcarboxymethylcellulose, hydroxyethyl-cellulose eller blandinger deraf, kan på ønskelig måde anvendes til tandplejemidler indeholdende a-aluminiumoxidtrihydrat som poleremiddel, der skal fyldes på en dispenser. Når imid- 20 lertid et sådant tandplejemiddel indeholder mange kilder for aktive bestanddele, såsom mindst to kilder for fluor, et des-ensitiviserende middel, såsom allantoin (C^Hg^O^) og et vaso-dilatormiddel, såsom pyridylcarbinol 255 When using a dentifrice dispenser which is operated mechanically or by pressure difference, conventional techniques for reducing the thickening of the dentifrice may sometimes not be fully satisfactory when compared with a dentifrice filled on a flexible tube, since the dentifrice, when a dispenser is used, must be relatively thin. during filling, but regains its consistency and thus remains during shipping, storage and use periods. In other words, after filling, the dentifrice regains the consistency it had prior to the exerted shear force to make it fluid during filling. Conventional gelling agents such as sodium carboxymethyl cellulose, hydroxyethyl cellulose or mixtures thereof may be desirably used for dentifrices containing α-alumina trihydrate as a polishing agent to be loaded onto a dispenser. However, when such a dentifrice contains many sources of active ingredients such as at least two sources of fluorine, a desensitizing agent such as allantoin (C CH HgO₂) and a vasodilator such as pyridylcarbinol
N )-CH -OHN) -CH -OH
\=/ 2 30 optræder der vanskeligheder, når tandplejemidlet fyldes på en mekanisk betjent eller ved trykforskel fungerende dispenser. Især kan tandplejemiddel sive gennem rummet mellem en stang og et stempel, som især benyttes i en mekanisk betjent 35 dispenser, og lækage finder sted ved dispenseråbninger. Den fra en mekanisk betjent eller ved trykforskel virkende dispenser udpressede tandpiejemiddelstribe kan endvidere være uregelmæssig og ikke-kontinuerlig. Eftersom det er særligt 4\ = / 2 30 Difficulties occur when the dentifrice is loaded on a mechanically operated or pressure differential dispenser. In particular, dentifrice may seep through the space between a rod and a piston, which is particularly used in a mechanically operated dispenser, and leakage occurs at dispenser openings. Furthermore, the toothpaste strip extruded from a mechanically operated or pressure differential dispenser may be irregular and non-continuous. Since it is particularly 4
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ønskeligt at fremstille et tandplejemiddel indeholdende a-alu-miniumoxidtrihydrat-poleremiddel, der indeholder flere aktive stoffer, såsom de ovenfor omtalte, som følge af problemer med sådanne materialers forenelighed med poleremidlet, var et alter-5 nativt geleringssystem nødvendigt.desirable to prepare a dentifrice containing α-alumina trihydrate polishing agent containing several active substances such as those mentioned above, due to problems with the compatibility of such materials with the polishing agent, an alternative gelling system was necessary.
Pra engelsk offentliggørelsesskrift nr. 2.070.695 kendes en dispenser, der er velegnet til dispensering af pastaagtigt materiale, såsom tandpasta, men offentliggørelsesskriftet nævner intet om sammensætningen af til brug i dispenseren egnede tandplejemidler.English Publication No. 2,070,695 discloses a dispenser suitable for dispensing paste-like material, such as toothpaste, but the disclosure does not mention anything about the composition of dentifrices suitable for use in the dispenser.
10 Blandt alternative typer geleringsmidler tilvejebringer en blanding af et cellulose-geleringsmiddel og i-carrageenan helt uventet en fortrinlig geleringsmiddelblanding, når den anvendes i et tandplejemiddel indeholdende α-aluminiumoxidtrihydrat og flere aktive bestanddele, når tandplejemidlet er beregnet på påfyldning på og 15 udpresning fra en mekanisk drevet eller ved trykforskel virkende dispenser. Det er bemærkelsesværdigt, at xanthan ikke tidligere har været forligeligt med cellulose-geleringsmidler, eftersom det kan indeholde cellulaseAmong alternative types of gelling agents, a mixture of a cellulose gelling agent and i-carrageenan unexpectedly provides an excellent gelling agent mixture when used in a dentifrice containing α-alumina trihydrate and several active ingredients when the dentifrice is intended for filling and pressing from a mechanically driven or differential pressure dispenser. It is noteworthy that xanthan has not previously been compatible with cellulose gelling agents since it may contain cellulase
Det er en fordel ved den foreliggende opfindelse, at der tilveje-20 bringes et tandplejemiddel, som let kan fyldes på og udpresses fra en mekanisk betjent eller ved trykforskel virkende tandpiejemiddel-dispenser.It is an advantage of the present invention to provide a dentifrice which can be readily filled and extruded from a mechanically operated or pressure differential actuator dispenser.
Andre fordele vil fremgå af den følgende beskrivelse.Other advantages will be apparent from the following description.
Opfindelsen angår et tandplejemiddel, som egner sig til dosering 25 med en mekanisk eller trykpåvirket dispenser, omfattende ca. 20 - ca. 8C vægt% af en vandig befugtningsmiddelblanding,ca. 0,1 - ca. 0,5 vægt% ringsmiddelblanding, ca. 20 - ca. 75 vægt% α-aluminiumoxidtrihydrat som poleremiddel, natriumfluorid og natriummonofluorphosphat i en mængde til opnåelse af ca. 300 til ca. 10.000 ppm fluor-, ca. 0,05 - ca. 0,5 vægt% 30 allantoin som desensibiliseringsmiddelca. 0,05 - ca. 0,5 vægt% pyri-dylcarbinol som karudvidende middel.The invention relates to a dentifrice suitable for dosing 25 with a mechanical or pressure-controlled dispenser, comprising approx. 20 - approx. 8% by weight of an aqueous wetting agent mixture, approx. 0.1 - approx. 0.5% by weight of the solvent mixture, approx. 20 - approx. 75% by weight of α-alumina trihydrate as a polishing agent, sodium fluoride and sodium monofluorophosphate in an amount to obtain approx. 300 to approx. 10,000 ppm fluorine, approx. 0.05 - approx. 0.5% by weight of allantoin as a desensitizer. 0.05 - approx. 0.5 wt% pyridylcarbinol as a vasodilator.
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Tandplejemidlet ifølge opfindelsen er kendetegnet ved, at nævnte geleringsmiddelblanding er en blanding af enten et cellu-losegeleringsmiddel eller xanthan med i-carrageenan i et vægtforhold mellem cellulosegeleringsmiddel eller xanthan og i-car-5 rageenan fra ca. 5:1 til ca. 1:5.The dentifrice according to the invention is characterized in that said gelling agent mixture is a mixture of either a cellulose gelling agent or xanthan with i-carrageenan in a weight ratio of cellulose gelling agent or xanthan to i-carrageenan from ca. 5: 1 to approx. 1: 5.
I tandpiejemiddelsammensætningen omfatter den dentale bærer en flydende fase tilsat geleringsmidlet til dannelse af en ekstruderbar cremeagtig masse med ønskelig konsistens. Den flydende fase i tandplejemidlet vil omfatte hovedsagelig vand 10 og befugtningsmiddel, såsom polyoler, inklusive glycerol, sorbitol, maltitol, xylitol, polyethylenglycol med lav molekylvægt (f.eks. 400 eller 600), propylenglycol eller lignende, inklusive egnede blandinger deraf. Det er sædvanligvis fordelagtigt som den flydende fase at anvende vand og et be-15 fugtningsmiddel, såsom glycerol, sorbitol eller polyethylenglycol, typisk i mængder på ca. 10 - ca. 55 væg€% vand og ca.In the toothpaste composition, the dental carrier comprises a liquid phase added to the gelling agent to form an extrudable creamy mass of desirable consistency. The liquid phase of the dentifrice will comprise mainly water 10 and wetting agent such as polyols, including glycerol, sorbitol, maltitol, xylitol, low molecular weight polyethylene (e.g. 400 or 600), propylene glycol or the like, including suitable mixtures thereof. It is usually advantageous as the liquid phase to use water and a wetting agent, such as glycerol, sorbitol or polyethylene glycol, typically in amounts of about 5%. 10 - approx. 55 wall €% water and approx.
20 - ca. 50 vægt% befugtningsmiddel.20 - approx. 50 wt% wetting agent.
Tandplejemidlet indeholder a-aluminiumoxidtrihydrat-polere-mid-del i mængder på ca. 20 - ca. 75 vaegt%. . a-aluminiumoxidtrihydrat 20 fremstilles typisk ved Bayer-processen og anvendes som partikler med en størrelse under ca. 40 mikron, fortrinsvis ca.3 -ca. 20 mikron. Andre poleremidler kan være inkorporeret, såsom uopløseligt natriummetaphosphat, dicalciumphosphat, calcine-ret aluminiumoxid, silica eller calciumcarbonat i mindre masng-25 de i forhold til a-aluminiumoxidtrihydrat.The dentifrice contains α-alumina trihydrate polishing agent in amounts of approx. 20 - approx. 75% by weight. . α-alumina trihydrate 20 is typically produced by the Bayer process and used as particles having a size below about 40 microns, preferably about 3-ca. 20 microns. Other polishing agents may be incorporated, such as insoluble sodium metaphosphate, dicalcium phosphate, calcined alumina, silica or calcium carbonate in lesser mass relative to α-alumina trihydrate.
Geleringsmiddelblandingen er ifølge opfindelsen til stede i tandplejemidlet i en mængde på ca. 0,1 - ca. 5 vægt%. Den indeholder enten et cellulose-geleringsmiddel eller xanthan blandet ired i-carrageenan, hvor vægtforholdet mellem cellulose-geleringsmidlet eller xanthan og nævnte i-carrageenan er fra ca. 5:1 til ca. 1:5, fortrinsvis fra ca. 1:1 til ca. 1:3, og den samlede mængde geleringsmiddelblanding er fortrinsvis ca. 0,2 - ca. 3 vægt%.The gelling composition according to the invention is present in the dentifrice in an amount of approx. 0.1 - approx. 5% by weight. It contains either a cellulose gelling agent or xanthan mixed with i-carrageenan, wherein the weight ratio of the cellulose gelling agent or xanthan to said i-carrageenan is from ca. 5: 1 to approx. 1: 5, preferably from ca. 1: 1 to approx. The total amount of gelling agent mixture is preferably about 1: 3. 0.2 - approx. 3% by weight.
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Som nævnt ovenfor er iota-carragenan kommercielt tilgængeligt som "Genuvisco" type 0819 og "Viscarin" TP-5 og har været anbefalet til anvendelse i en tandpasta. En sådan anvendelse i en tandpasta blev beskrevet i japansk offentliggørelses-5 skrift nr. 56 115711 af Lion Dentifrice Limited, hvori i-carragenan omtales som en mulig komponent i et geleringssystem sammen med k-carragenan og alkalimetalalginat. I US patentskrift nr. 4.353.890 er i-carragenan omtalt som et alternativ til k-carragenan som tandpastageleringsmiddel, hvor 10 tandpastaen udsættes for mikrobølgestråling til formindskelse af carragenans tendens generelt til at blive tynd under fremstilling. Carragenanen kan være det eneste geleringsmiddel eller være blandet med andre geleringsmidler. Ifølge den foreliggende opfindelse behøver tandplejemidlet inde-15 holdende i-carragenan til påfyldning på en mekanisk betjent eller ved trykforskel virkende dispenser ikke mikrobølgestråling.As mentioned above, iota-carrageenan is commercially available as "Genuvisco" type 0819 and "Viscarin" TP-5 and has been recommended for use in a toothpaste. Such use in a toothpaste was described in Japanese Publication No. 56,115,117 by Lion Dentifrice Limited, wherein i-carrageenan is referred to as a possible component of a gelling system together with k-carrageenan and alkali metal alginate. In U.S. Patent No. 4,353,890, i-carrageenan is referred to as an alternative to k-carrageenan as a toothpaste gelling agent, wherein the toothpaste is subjected to microwave radiation to reduce the tendency of carrageenan to become thin during manufacture. The carrageenan may be the only gelling agent or may be mixed with other gelling agents. According to the present invention, the dentifrice containing i-carrageenan for loading on a mechanically operated or pressure differential dispenser does not need microwave radiation.
Den ovenfor generelt omtalte kendte teknik angiver ikke, at geleringssystemer af cellulose-geleringsmiddel og i-carrage-20 nan kan tilvejebringe tandplejemidler indeholdende a-alumi- niumoxidtrihydrat-poleremiddel og mange aktive bestanddele med de nødvendige egenskaber til effektiv påfyldning på en mekanisk betjent eller ved trykforskel virkende dispenser og til udpresning derfra.The above-mentioned prior art does not indicate that cellulose gelling and i-carrageenan gelation systems can provide dentifrices containing α-alumina trihydrate polishing agent and many active ingredients with the necessary properties for effective loading on a mechanically operated or pressure differential acting dispenser and for extortion therefrom.
25 Det er værd at bemærke, at OS patentskrift nr. 4.029.760 omhandler et oralt middel, hvori i-carragenin er anført som et antitandkødsbetændelsesmiddel i forhold til andre carrageni-ner. Carrageniner er meget depolymeriserede derivater af carragenaner. Carragenaner viser sig ikke at tilvejebringe 30 en antitandkødsbetændelsesvirkning.It is worth noting that U.S. Patent No. 4,029,760 discloses an oral agent wherein i-carrageenin is listed as an anti-gum inflammatory agent in comparison to other carrageenans. Carragenins are highly depolymerized derivatives of carrageenans. Carrageenans are found not to provide an antitumor effect.
Tandplejemidler fremstilles sædvanligvis ved en kold proces, f.eks. ved ca. 25°C, eller ved en varm proces, f.eks. ved ca. 60°C. I-carragenan kan anvendes ved enten kold proces- 7Dental care products are usually produced by a cold process, e.g. at about. 25 ° C, or in a hot process, e.g. at about. 60 ° C. I-carrageenan can be used in either cold process 7
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teknik eller varm procesteknik. Eftersom xanthan fremstilles med kold oparbejdning, kan det, når det anvendes, let blandes med i-carragenan og inkorporeres sammen dermed i tandplejemidlet ved kold oparbejdning. Xanthan kan kun anven-5 des ved varm oparbejdning.engineering or hot process engineering. Since xanthan is made with cold work up, when used, it can easily be mixed with i-carrageenan and thus incorporated together into the dentifrice during cold work up. Xanthan can only be used for hot work-up.
Fysiske egenskaber af "Genuvisco" type 0819 i-carragenan er anført nedenfor: 1. Viskositet af 0/30% opløsning af "Genuvisco" type 0819 i magert opløsningsmiddel fremstillet under anvendelse af 10 en varm proces (60°C):Physical properties of "Genuvisco" type 0819 i-carrageenan are listed below: 1. Viscosity of 0/30% solution of "Genuvisco" type 0819 in lean solvent prepared using a hot process (60 ° C):
Viskositet = 110 + 17 cp ved 32 omdrejninger pr. minut Viskositet = 70 jr 11 cp ved 64 omdrejninger pr. minutViscosity = 110 + 17 cp at 32 rpm. minute Viscosity = 70 yr 11 cp at 64 rpm minute
Viskositet = 45 + 1 cp ved 128 omdrejninger pr. minut målt på HAAKE Rotovisco RV3 ved 25°C.Viscosity = 45 + 1 cp at 128 rpm. minutes measured on HAAKE Rotovisco RV3 at 25 ° C.
15 2. Viskositet af 0,30% opløsning af "Genuvisco" type 0819 i magert opløsningsmiddel fremstillet ved anvendelse af en kold proces (25°C):2. Viscosity of 0.30% solution of "Genuvisco" type 0819 in lean solvent prepared using a cold process (25 ° C):
Viskositet = 85 + 60 cp målt på Brookfield Viscometer LVT ved 25°C.Viscosity = 85 + 60 cp measured on Brookfield Viscometer LVT at 25 ° C.
20 Viskositet = 85 jt- 13 cp ved 32 omdrejninger pr. minut.20 Viscosity = 85 µt-13 cp at 32 rpm. minute.
Viskositet = 55 + 8 cp ved 64 omdrejninger pr. minut.Viscosity = 55 + 8 cp at 64 rpm. minute.
Viskositet = 37 + 6 cp ved 128 omdrejninger pr. minut.Viscosity = 37 + 6 cp at 128 rpm. minute.
Målt på HAAKE Rotovisco RV3 ved 25°C.Measured on HAAKE Rotovisco RV3 at 25 ° C.
Det magre opløsningsmiddel, der af fabrikanten af "Genu-25 visco" 0819 blev benyttet til viskositetsbestemmelser, inde holder 220 g glycerol (100%), 4,20 g tetranatriumpyrophos-phatdecahydrat, 7,60 g natriummonofluorphosphat, 2,00 g na-triumsaccharinat og 260,30 g destilleret vand.The lean solvent used by the manufacturer of "Genuvisco" 0819 for viscosity determinations contains 220 g of glycerol (100%), 4.20 g of tetrasodium pyrophosphate decahydrate, 7.60 g of sodium monofluorophosphate, 2.00 g of sodium phosphate. triaccharinate and 260.30 g of distilled water.
3. Partikelstørrelse: Mindre end 1% gummi på 0,075 mm 30 , .3. Particle size: Less than 1% rubber of 0.075 mm 30,.
forsøgssigte (DIN 80, 200 UStest screen (DIN 80, 200 US)
mesh).mesh).
88
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4. Fugtighedsindhold: Mindre end 12%.4. Moisture content: Less than 12%.
5. pH: 8,5 + 1,5 i 0,51 opløsning i destilleret vand ved 25°C.5. pH: 8.5 + 1.5 in 0.51 solution in distilled water at 25 ° C.
6. Farve: Hvid til creme.6. Color: White to cream.
5 "Viscarin" TP-5 i-carragenan har følgende fysiske egenskaber:5 "Viscarine" TP-5 i-carrageenan has the following physical properties:
Farve Lysebrun til brunColor Light brown to brown
Partikelstørrelse: mere end 95,0% gennem en USParticle size: more than 95.0% through a US
standardsigte, 250 nm (serie 10 nr. 60).standard sieve, 250 nm (Series 10 # 60).
Fugtighed: maksimum 12,0% (Cenco MoistureHumidity: maximum 12.0% (Cenco Moisture
Balance).Balance).
pH: 7,0 til 9,5, 1,5% opløsning, 3 0°C.pH: 7.0 to 9.5, 1.5% solution, 30 ° C.
15 Typiske ønskelige cellulose-geleringsmidler indbefatter al-kalimetalcarboxymethylcellulose, hydroxymethylcellulose og hydroxypropylcellulose. Natriumcarboxymethylcellulose foretrækkes. Det blandede gelsystem er til stede i en mængde på ca. 0,1 - ca. 5 vægt% af tandplejemidlet, og vægtforholdet mellem 20 cellulose-geleringsmiddel og i-carragenan er fra ca. 5:1 til ca. 1:5, fortrinsvis ca. 1:1 til ca. It3 og mest foretrukket 1:1. Et typisk foretrukket tandplejemiddel kan således indeholde ca. 0,9 - ca. 1,2% geleringsmiddel i"alt, omfattende"ca. 0,3 - ca. 0,9% af hver af komponenterne cellulose-geleringsmiddel 25 og i-carragenan, idet vægtforholdet imellem de to komponenter er fra ca. 1:1 til ca. 1:3.Typical desirable cellulose gelling agents include alkali metal carboxymethyl cellulose, hydroxymethyl cellulose and hydroxypropyl cellulose. Sodium carboxymethyl cellulose is preferred. The mixed gel system is present in an amount of approx. 0.1 - approx. 5% by weight of the dentifrice, and the weight ratio of 20 cellulose gelling agent to i-carrageenan is from approx. 5: 1 to approx. 1: 5, preferably approx. 1: 1 to approx. It3 and most preferably 1: 1. Thus, a typical preferred dentifrice may contain about. 0.9 - approx. 1.2% gelling agent in "all-inclusive" approx. 0.3 - approx. 0.9% of each of the components cellulose gelling agent 25 and i-carrageenan, the weight ratio of the two components being from about 1: 1 to approx. 1: 3.
Det er værd at bemærke, at kvaliteter af natriumcarboxymethylcellulose, som kan anvendes, indbefatter følgende: 9It is worth noting that grades of sodium carboxymethyl cellulose that can be used include the following:
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o TABEL I.o TABLE I.
LEVERANDØR CMC KVALITET VISKOSITETSUPPLIER CMC QUALITY VISCOSITY
5 Hercules * 7MXF 300-5005 Hercules * 7MXF 300-500
Hercules 7MFD 300-500Hercules 7MFD 300-500
Hercules 9M31F 900-1200Hercules 9M31F 900-1200
Hercules 9M31XF 900-1200Hercules 9M31XF 900-1200
Hercules 12M31XF 900-1200 10 Hercules 7MF 300-500Hercules 12M31XF 900-1200 10 Hercules 7MF 300-500
Hercules 12M31PD 900-1200Hercules 12M31PD 900-1200
Hercules 7M8SXF 200-800Hercules 7M8SXF 200-800
Wolff Walsrode "Walocel" CRTWolff Walsrode "Walocel" CRT
1000 PA 07 700-1200 15 Nyma "Nymcel" ZMF.3f- 50-801000 PA 07 700-1200 15 Nyma "Nymcel" ZMF.3f- 50-80
Enka "Akucell" AC 164^ 80 -120Enka "Akucell" AC 164 ^ 80 -120
Enka "Akucell" AC 1632* 60 -120Enka "Akucell" AC 1632 * 60 -120
Cros "Cellogen" HP-SA 700-900Cros "Cellogen" HP-SA 700-900
Uddeholm "Cekol" MVEP 500-800 20 —Uddeholm "Cekol" MVEP 500-800 20 -
Hoechst "Tylose" CB 200** 120-260 x 1% opløsning (Brookfield; 25°C) ** Hoeppler Viscometer (2%; 20°C).Hoechst "Tylose" CB 200 ** 120-260 x 1% solution (Brookfield; 25 ° C) ** Hoeppler Viscometer (2%; 20 ° C).
2525
Yderligere kvaliteter af hydroxyethylcellulose, der kan anvendes, indbefatter følgende: 30 35 10Additional grades of hydroxyethyl cellulose that may be used include the following:
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o TABEL II.o TABLE II.
LEVERANDØR HEC KVALITET VISKOSITETSUPPLIER HEC QUALITY VISCOSITY
5 Hercules "Natrosol" 250M og MR 4500-65005 Hercules "Natrosol" 250M and MR 4500-6500
Hercules "Natrosol" 250 HRX 1500-2500Hercules "Natrosol" 250 HRX 1500-2500
og 250HXand 250HX
Hercules "Natrosol" 250 HHR* 3400-5000Hercules "Natrosol" 250 HHR * 3400-5000
og 250 HHand 250 HH
10 BP Chemicals Cellobond 5000 A 4200-5600 BP Chemicals Cellobond 7000 A 6000-700010 BP Chemicals Cellobond 5000 A 4200-5600 BP Chemicals Cellobond 7000 A 6000-7000
Hoechst "Tylose" H 4000 P5® 3000-5000Hoechst "Tylose" H 4000 P5® 3000-5000
Hoechst "Tylose" H 10000 P55* 7000-12000 15 s 1% opløsning (Brookfield; 25°C).Hoechst "Tylose" H 10000 P55 * 7000-12000 15 s 1% solution (Brookfield; 25 ° C).
534 Hoeppler Viscometer (2%; 25°C).534 Hoeppler Viscometer (2%; 25 ° C).
I-carragenanen og cellulose-geleringsmidlet kan blandes sammen mekanisk forud for blanding med den dentale cremegrund- 20 masses flydende fase eller kan separat blandes med den flydende fase, enten ved varm oparbejdningsteknik (typisk ca. 60°C) eller ved kold oparbejdningsteknik (typisk ca. 25°C).The i-carrageenan and cellulose gelling agent may be mixed mechanically prior to mixing with the liquid phase of the dental cream base or may be mixed separately with the liquid phase, either by hot work-up technique (typically about 60 ° C) or by cold work-up technique (typically about 25 ° C).
Xanthangummi er et fermenteringsprodukt dannet ved indvirk- 25 ning af bakterier af slægten Xanthomonas på kulhydrater. Fire arter af Xanthomonas, nemlig X campetris, x phaseoli, X malvocearum og X carotae/er i litteraturen omtalt som værende de mest effektive gummiproducenter. Selv om den nøjagtige kemiske formel ikke er fastlagt, er den generelt accepteret 30 som værende et heteropolysaccharid med en molekylvægt på flere millioner. Den indeholder D-glucose, D-mannose og D-glucuronsyre i molforholdet 2,8:3:2,0. Molekylet indeholder 4,7% acetyl- og ca. 3% pyruvat-molekyldele. Den foreslåede kemiske formelkonfiguration kan findes i McNeelly og Kang, Industri- 35 al Gums, udgivet af R.L. Whistler, CH XXI, 2. udgave, New York, 1973. Proceduren til dyrkning, isolation og rensning af xanthangummi findes også i denne publikation. Yderligere beskrivelse af xanthangummi findes i Manufacturing Chemist,Xanthan gum is a fermentation product formed by the action of bacteria of the genus Xanthomonas on carbohydrates. Four species of Xanthomonas, namely X campetris, x phaseoli, X malvocearum and X carotae /, have been referred to in the literature as being the most effective rubber producers. Although the exact chemical formula has not been determined, it is generally accepted as a heteropolysaccharide having a molecular weight of several million. It contains D-glucose, D-mannose and D-glucuronic acid in the molar ratio 2.8: 3: 2.0. The molecule contains 4.7% acetyl and approx. 3% pyruvate molecule parts. The proposed chemical formula configuration can be found in McNeelly and Kang, Industrial Gums, published by R.L. Whistler, CH XXI, 2nd edition, New York, 1973. The procedure for cultivating, isolating and purifying xanthan gum is also found in this publication. Further description of xanthan gum can be found in the Manufacturing Chemist,
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maj 1960, side 206-208 (inklusive omtalen på side 208 af 0 eventuel anvendelse af deri beskrevne gummiarter til sammensætning af pastaer.May 1960, pages 206-208 (including the discussion on page 208 of 0 possible use of gums described therein for the composition of pastes.
I-carragenanen og xanthanen kan sammenblandes mekanisk forud for blanding med den dentale cremegrundmasses flydende fase 5 eller kan separat blandes med den flydende fase ved anvendelse af kold procesteknik (typisk ca. 25°C).The i-carrageenan and xanthan may be mechanically mixed prior to mixing with the liquid phase 5 of the dental cream base or may be separately mixed with the liquid phase using cold process technique (typically about 25 ° C).
Tandplejemidlet emballeres i en beholder, hvorfra det let kan ekstruderes eller udpresses, såsom en ved trykforskel 10 virkende eller mekanisk betjent dispenser for dentalcreme.The dentifrice is packaged in a container from which it can be easily extruded or extruded, such as a pressure differential or mechanically operated dispenser for dental cream.
De rheologiske egenskaber er overordentlig ønskelige, når der anvendes en mekanisk betjent dispenseringsbeholder af den type, der er beskrevet i britisk offentliggørelsesskrift nr. 2.070.695A, offentliggjort 9. september 1981.The rheological properties are extremely desirable when using a mechanically operated dispensing vessel of the type described in British Patent Specification No. 2,070,695A published September 9, 1981.
1515
Denne dispenseringsbeholder omfatter et dispenserende mundstykke, et spændeorgan, en central stang, et stempel og et manuelt betjeningsorgan.This dispensing container comprises a dispensing nozzle, a clamping means, a central rod, a piston and a manual actuator.
2020
Ved trykforskel virkende dispenseringsbeholdere kan være af aerosol- eller vakuumtypen. Egnede ved trykforskel virkende dispensere indbefatter sådanne omfattende en sammeklappelig produkt-indeholdende pose, der er placeret i en stiv beholder, som indeholder et drivfluidum. I sådanne dispenserings-25 beholdere tillader betjening af ventilen kun frigivelse af produktet, idet drivfluidumet er adskilt fra produktet af den fluidumuigennemtrængelige pose. Dispensere af denne type er beskrevet i US patentskrifterne nr. 3.828.977 og nr. 3.838.976. Disse dispensere er de såkaldte "Sepro"-dispen- 30 sere. De såkaldte "Exxel"-beholdere anvender også tryk.Pressure differential acting dispensing vessels may be of the aerosol or vacuum type. Suitable pressure differential dispensers include such comprising a collapsible product-containing bag located in a rigid container containing a propellant fluid. In such dispensing containers, operation of the valve only permits release of the product, the drive fluid being separated from the product by the fluid impermeable bag. Dispensers of this type are described in U.S. Patent Nos. 3,828,977 and 3,838,976. These dispensers are the so-called "Sepro" dispensers. The so-called "Exxel" containers also apply pressure.
Endnu en type dispenser er barriere-stempelbeholderen, der er beskrevet i US patentskrift nr. 4.171.757. En sådan beholder har en ventil, et produkt-indeholdende rum og et i 35 det væsentlige fluidumtæt barrierestempel, der adskiller drivfluidumet fra det indeholdte produkt (den såkaldte "Dia- 12Another type of dispenser is the barrier plunger described in U.S. Patent No. 4,171,757. Such a container has a valve, a product-containing compartment, and a substantially fluid-tight barrier piston separating the drive fluid from the contained product (the so-called
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0 mond"-beholder).0 mouth "container).
Tandpiejemidlet indeholder som aktive midler en blanding af natriumfluorid og natriummonofluorphosphat til opnåelse af ca. 300 - ca. 10000 ppm fluor, f.éks. ca. 750 - ca. 2000 ppm, .og især c 3 1400-2000 ppm, såsom ca. 1400 - ca. 1670 ppn.Et binært fluoridsy stem af natriummonofluorphosphat og natriumfluorid benyttes fordelagtigt, hvori ca. 30 - ca. 40% af fluormængden (f.eks. ca. 30 - ca.35%) tilvejebringes ved hjælp af natriumfluorid.The toothpaste agent contains as active agents a mixture of sodium fluoride and sodium monofluorophosphate to give approx. 300 - approx. 10000 ppm fluorine, e.g. ca. 750 - approx. 2000 ppm, and especially c 3 1400-2000 ppm, such as approx. 1400 - approx. A binary fluoride system of sodium monofluorophosphate and sodium fluoride is advantageously used, wherein approx. 30 - approx. About 40% of the fluorine amount (e.g., about 30 - about 35%) is provided by sodium fluoride.
10 Natriummonofluorphosphat, Na2PC>3F, kan som kommercielt til gængeligt variere betydeligt i renhed. Det kan anvendes i enhver passende renhed, forudsat at eventuelle urenheder ikke på væsentlig måde påvirker de ønskede egenskaber. Generelt er det ønskeligt, at renheden er mindst 80%. Til op-15 nåelse af de bedste resultater, bør den være mindst 85%, og fortrinsvis er mindst 90 vægt% natriummonofluorphosphat, i-det resten primært er urenheder eller biprodukter fra fremstillingen, såsom natriumfluorid og vandopløseligt natrium-phosphatsalt. Udtrykt på anden måde, bør den benyttede na- 20 tnummonofluorphosphatkvalitet have et samlet fluoridindhold over 12%, fortrinsvis over 12,7%, fordelt på et indhold på højst 1 1/2%, fortrinsvis ikke mere end 1,2% hidrørende fra frit natriumfluorid, og et indhold af fluorid på mindst 12%, fortrinsvis mindst 12,1% hidrørende fra natriummonofluorphosphat.Sodium monofluorophosphate, Na2PC> 3F, as commercially available, can vary widely in purity. It can be used in any suitable purity, provided that any impurities do not significantly affect the desired properties. In general, it is desirable that the purity is at least 80%. For best results, it should be at least 85% and preferably at least 90% by weight sodium monofluorophosphate, the remainder being primarily impurities or by-products of the preparation such as sodium fluoride and water-soluble sodium phosphate salt. In other words, the sodium monofluorophosphate grade used should have a total fluoride content above 12%, preferably above 12.7%, distributed at a content of not more than 1 1/2%, preferably no more than 1.2% derived from free sodium fluoride, and a fluoride content of at least 12%, preferably at least 12.1%, derived from sodium monofluorophosphate.
2525
Som ovenfor anført er natriumfluorid i den binære blanding en separat fluorholdig komponent i forhold til natriummonofluorphosphat. Ca. 225 - ca. 800 ppm fluor tilvejebringes fortrinsvis i den dentale creme ved hjælp af natriumfluorid.As stated above, sodium fluoride in the binary mixture is a separate fluorine-containing component relative to sodium monofluorophosphate. Ca. 225 - approx. 800 ppm fluorine is preferably provided in the dental cream by means of sodium fluoride.
3030
Yderligere aktivt middel tilvejebringes i tandplejemidlet ved tilstedeværelsen af ca. 0,05 - ca. 0,5 vægt%, fortrinsvis ca.Additional active agent is provided in the dentifrice in the presence of ca. 0.05 - approx. 0.5% by weight, preferably approx.
0,08 - ca. 0,2% allantoin-desensiti.viserende middel. Et sådant middel bekæmper sensitivitet af læderet periodontalt væv og fremmer dets heling. Allantoin kan fås fra ABM Industrial Products Ltd., Woodley, Stockport, Cheshire, England.0.08 - approx. 0.2% allantoin desensitizer. Such an agent combats the sensitivity of the leather periodontal tissue and promotes its healing. Allantoin is available from ABM Industrial Products Ltd., Woodley, Stockport, Cheshire, England.
3535
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13 0 Pyridylcarbinol, der benyttes som aktivt middel i en mængde på ca, 0,05 - ca. 0,5 vægt%, fortrinsvis ca. 0,08 - ca. 0,2%, giver tandplejemidlet en karudvidende virkning.Pyridylcarbinol used as an active agent in an amount of about 0.05 to ca. 0.5% by weight, preferably approx. 0.08 - approx. 0.2%, the dentifrice has a vasodilating effect.
Når der anvendes et tandplejemiddel ifølge opfindelsen inde-5 holdende a-aluminiumtrihydrat-poleremiddel, det binære fluorid-system, allantoin-desensitiviserende middel, pyridylcarbinol-vasodilatormiddel og gelsystemet som ovenfor beskrevet, foregår fyldning og udpresning under anvendelse af mekanisk betjente eller ved trykforskel virkende dispensere effektivt og rheolo- 10 gisk ønskeligt.When using a dentifrice of the invention containing α-aluminum trihydrate polishing agent, binary fluoride system, allantoin desensitizing agent, pyridylcarbinol vasodilator agent and gel system as described above, filling and squeezing takes place using mechanically operated or pressure differential dispensing effectively and rheologically desirable.
Fyldning foretages ved hjælp af konventionel teknik. Når f.eks. en mekanisk betjent dispenser af den i britisk offentliggørelsesskrift nr. 2.070.695A beskrevne type anven-15 des, presses en forudbestemt mængde af tandplejemidlet gennem en dyse til fyldning af dispenseren, som er åben ved sin bund, og som indeholder en central stang. Et stempel med en diameter svarende til dispenserens indre diameter og med et centralt hul til at muliggøre indføring af den centrale 20 stang deri, skydes på plads. Dispenseren lukkes derpå med en bundplade.Filling is done by conventional technique. For example, when a mechanically operated dispenser of the type described in British Patent Specification No. 2,070,695A is used, a predetermined amount of the dentifrice is pressed through a nozzle to fill the dispenser which is open at its bottom and containing a central rod. A piston having a diameter corresponding to the inner diameter of the dispenser and having a central hole to allow insertion of the central 20 rod therein is slid into place. The dispenser is then closed with a base plate.
Ethvert egnet overfladeaktivt eller rensende materiale kan inkorporeres i tandplejemidlerne. Sådanne dermed forenelige 25 materialer er ønskelige til opnåelse af yderligere rensende, skummende og antibakterielle egenskaber, afhængigt af den specifikke type overfladeaktivt materiale, og de vælges i overensstemmelse hermed. Disse detergenter er sædvanligvis vandopløselige forbindelser, og de kan være anioniske, 30 ikke-ioniske eller kationiske i opbygning. Det foretrækkes sædvanligvis at anvende de vandopløselige, ikke-sæbe detergenter eller syntetiske organiske detergenter. Egnede rensende materialer kendes og indbefatter f.eks. de vandopløselige salte af højere fedtsyremonoglycerid-monosulfatdeter-35 gent (f.eks. natriumkokosnødfedtsyremonoglycerid-monosul-fat), højere alkylsulfat (f.eks. natriumlaurylsulfat), al-kylarylsulfonat (f.eks. natriumdodecylbenzensulfonat og 14Any suitable surfactant or cleanser can be incorporated into the dentifrices. Such compatible materials are desirable for obtaining additional cleansing, foaming and antibacterial properties, depending on the specific type of surfactant, and are selected accordingly. These detergents are usually water-soluble compounds and can be anionic, nonionic or cationic in structure. It is usually preferred to use the water-soluble, non-soap detergents or synthetic organic detergents. Suitable cleaning materials are known and include e.g. the water-soluble salts of higher fatty acid monoglyceride monosulfate detergent (e.g., sodium coconut fatty acid monoglyceride monosulfate), higher alkyl sulfate (e.g., sodium lauryl sulfate), alkylarylsulfonate (e.g., sodium dodecylbenzenesulfonate) and 14
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0 højere fedtsyreestere af 1,2-dihydroxypropansulfonat) og lignende.0 higher fatty acid esters of 1,2-dihydroxypropane sulfonate) and the like.
Yderligere overfladeaktive midler indbefatter de i det væsentlige mættede højere alifatiske acylamider af lavere ali-5 fatiske aminocarboxylsyreforbindelser, såsom de, der har 12 til 16 carbonatomer i acylgruppen. Aminosyredelen er generelt afledt af de lavere alifatiske mættede monoaminocarb-oxylsyrer med 2 til 6 carbonatomer, sædvanligvis mono-: carboxylsyreforbindelserne. Egnede forbindelser er fedtsyre-10 amiderne af glycerol, sarcosin, alanin, 3-aminopropionsyre og val in med 12 til 16 carbonatomer i acylgruppen. Det foretrækkes imidlertid at anvende N-lauroyl-, myristoyl- og palmitoylsarcosidforbindelserne til opnåelse af optimale virkninger.Additional surfactants include those substantially saturated higher aliphatic acyl amides of lower aliphatic aminocarboxylic acid compounds such as those having 12 to 16 carbon atoms in the acyl group. The amino acid moiety is generally derived from the lower aliphatic saturated monoaminocarboxylic acids of 2 to 6 carbon atoms, usually the mono-: carboxylic acid compounds. Suitable compounds are the fatty acid amides of glycerol, sarcosine, alanine, 3-aminopropionic acid and val with 12 to 16 carbon atoms in the acyl group. However, it is preferred to use the N-lauroyl, myristoyl and palmitoyl sarcoside compounds to obtain optimal effects.
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Amidforbindelserne kan anvendes i form af den frie syre eller fortrinsvis som de vandopløselige salte deraf, såsom alkalimetal-, ammonium-, amin- og alkylolaminsaltene. Specifikke eksempler derpå er natrium- og kalium-N-lauroyl-, my- 20 ristoyl- og palmitoylsarcosider, ammonium- og ethanolamin-N-lauroylglycid og alanin. For letheds skyld refererer henvisning til "aminocarboxylsyreforbindelse", "sarcosid" og lignende til sådanne forbindelser med en fri carboxylsyregruppe hos de vandopløselige carboxylatsalte.The amide compounds can be used in the form of the free acid or preferably as the water-soluble salts thereof, such as the alkali metal, ammonium, amine and alkylolamine salts. Specific examples thereof are sodium and potassium N-lauroyl, myristoyl and palmitoyl sarcosides, ammonium and ethanolamine N-lauroyl glycide and alanine. For ease, reference to "aminocarboxylic acid compound", "sarcoside" and the like refers to such compounds having a free carboxylic acid group of the water-soluble carboxylate salts.
25 Sådanne materialer anvendes i ren eller hovedsagelig ren form. De bør være så fri som praktisk muligt for sæbe eller lignende højere fedtsyremateriale, der har tendens til at formindske aktiviteten af disse forbindelser. I praksis er 30 mængden af sådanne højere fedtsyrematerialer sædvanligvis mindre end 15 vægt% af amidet og utilstrækkelig til i væsentlig grad at påvirke det uheldigt, og fortrinsvis mindre end 10% af nævnte amidmateriale.Such materials are used in pure or mostly pure form. They should be as free as practicable for soap or similar higher fatty acid material which tends to decrease the activity of these compounds. In practice, the amount of such higher fatty acid materials is usually less than 15% by weight of the amide and insufficient to substantially adversely affect it, and preferably less than 10% of said amide material.
Forskellige andre materialer kan inkorporeres i tandplejemidlet ifølge opfindelsen. Eksempler herpå er farvende eller hvidhedsfrembringende midler, præserveringsmidler, såsom me- 35 15Various other materials can be incorporated into the dentifrice of the invention. Examples of these are coloring or whiteness agents, preservatives such as 15
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0 thyl-p-hydroxybenzoat, stabilisatorer, tetranatriumpyrophos-phat, siliconer, chlorophyllforbindelser og ammoniakafledte materialer, såsom urinstof, diammoniumphosphat og blandinger deraf. Disse hjælpestoffer inkorporeres i de omhandlede midler i en mængde, der ikke i væsentlig grad på uheldig måde 5 påvirker de ønskede egenskaber og karakteristika, og de vælges hensigtsmæssigt og anvendes i konventionelle mængder.0 thyl p-hydroxybenzoate, stabilizers, tetrasodium pyrophosphate, silicones, chlorophyll compounds and ammonia-derived materials such as urea, diammonium phosphate and mixtures thereof. These adjuvants are incorporated in the present compositions in an amount which does not substantially adversely affect the desired properties and characteristics, and they are suitably selected and used in conventional amounts.
Til nogle formål kan det være ønskeligt at inkorporere anti-r bakterielle midler i midlerne ifølge opfindelsen. Typiske 10 antibakterielle midler, der kan anvendes i mængder fra ca.For some purposes, it may be desirable to incorporate anti-bacterial agents into the agents of the invention. Typical antibacterial agents which can be used in amounts from about
0,01 vægt% til ca. 5 vægt%, fortrinsvis fra ca. 0,05 til ca.0.01% by weight to approx. 5% by weight, preferably from ca. 0.05 to approx.
1,0 vægt% af tandplejemidlet, indbefatter: N^-4(chlorbenzyl)—N^—(2,4-dichlorbenzyl)biguanid; 15 p-chlorphenylbiguanid; 4-chlorbenzhydrylguanid; 4- chlorbenzhydrylguanylurinstof; N-3-lauroxypropyl-N^-p-chlorbenzylbiguanid; 1.6- di-p-chlorbenzylbiguanid; 20 1-(lauryldimethylammonium)-8-(p-chlorbenzyld imethylammo-nium)octandichlorid; 5.6- dichlor-2-guanidinobenzimidazol? N^-p-chlorphenyl-N^-laurylbiguanid; 5- amino-l,3-bis-(2-ethylhexyl)-5-methylhexahydropyrimi-25 din; og ikke-toksiske syreadditionssalte deraf.1.0% by weight of the dentifrice includes: N 1 -4 (chlorobenzyl) - N 2 - (2,4-dichlorobenzyl) biguanide; P-chlorophenyl biguanide; 4-chlorbenzhydrylguanid; 4-chlorobenzhydryl guanylurea; N-3-lauroxypropyl-N @ ^ -p-chlorobenzylbiguanide; 1,6-di-p-chlorobenzylbiguanide; 1- (lauryldimethylammonium) -8- (p-chlorobenzyl imethylammonium) octane dichloride; 5.6- dichloro-2-guanidinobenzimidazole? N ^ -p-chlorophenyl-N ^ -laurylbiguanid; 5- amino-1,3-bis- (2-ethylhexyl) -5-methylhexahydropyrimidine; and non-toxic acid addition salts thereof.
Hvilke som helst egnede aromatiserende eller sødende materialer kan anvendes til sammensætning af en aroma til midlerne ifølge den foreliggende opfindelse. Eksempler på egnede aro-mabestanddele indbefatter de aromatiserende olier, f.eks. grøn mynteolie, pebermynteolie, vintergrøntolie, sassafras-olie, krydderneliikeolie, salvieolie, eucalyptusolie, meri-anolie, kanelolie, citronolie og orangeolie samt methylsa- licylat. Egnede sødemidler indbefatter sucrose, lactose, maltose, sorbitol, natriumcyklamat, natriumsaccharin-dipep-tider ifølge US patentskrift nr. 3.939.261 og oxathiazinsal- 35 16Any suitable flavoring or sweetening materials may be used to formulate an aroma for the agents of the present invention. Examples of suitable aroma ingredients include the aromatizing oils, e.g. green mint oil, peppermint oil, winter vegetable oil, sassafras oil, clove oil, sage oil, eucalyptus oil, merry oil, cinnamon oil, lemon oil and orange oil as well as methyl salicylate. Suitable sweeteners include sucrose, lactose, maltose, sorbitol, sodium cyclamate, sodium saccharin dipeptides according to U.S. Patent No. 3,939,261 and oxathiazine salt 16
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te ifølge US patentskrift nr. 3.932.606. Egnede aromatise-rende og sødende midler kan tilsammen udgøre fra ca. 0,01 til ca. 5% eller mere af midlet.tea according to US Patent No. 3,932,606. Suitable aromatizing and sweetening agents may together comprise from ca. 0.01 to approx. 5% or more of the agent.
5 Tandplejemidlerne bør have en pH-værdi, der er praktisk til anvendelse. Et pH-interval fra 3 til 10,5 er særligt ønskeligt. Med henvisningen til pH-værdien menes pH-bestemmelsen direkte på tandplejemidlet. Om ønsket kan sådanne materialer som benzoesyre eller citronsyre tilsættes til indstilling af 10 pH-værdien til f.eks. 4 til 8,5.5 The dentifrices should have a pH value that is convenient for use. A pH range from 3 to 10.5 is particularly desirable. By the reference to the pH value is meant the pH determination directly on the dentifrice. If desired, such materials as benzoic acid or citric acid may be added to adjust the pH to e.g. 4 to 8.5.
De følgende eksempler illustrerer yderligere naturen af den foreliggende opfindelse. Alle mængder af de forskellige bestanddele er vægtmængder, med mindre andet er anført.The following examples further illustrate the nature of the present invention. All amounts of the various constituents are by weight unless otherwise stated.
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Eksempel 1.Example 1.
Følgende tandplejemiddel fremstilles ved konventionel stue- 20 temperatur-koldproces og fyldes på den mekanisk betjente dispenser, som er beskrevet i britisk offentliggørelsesskrift nr. 2.070.695A.The following dentifrice is prepared by conventional room temperature cold process and loaded onto the mechanically operated dispenser described in British Patent Specification No. 2,070,695A.
Dele 25 -Parts 25 -
Sorbitol (70%) 23,000Sorbitol (70%) 23,000
Natriumsaccharin 0,170 I-carragenan ("Genuvisco" 0819) 0,500Sodium saccharin 0.170 I-carrageenan ("Genuvisco" 0819) 0.500
Natriumcarboxymethylcellulose (7MFD) 0,500Sodium carboxymethyl cellulose (7MFD) 0.500
Methyl-p-hydroxybenzoat 0,080 30Methyl p-hydroxybenzoate 0.080
Allantoin 0,150Allantoin 0.150
Natriumfluorid 0,100Sodium fluoride 0.100
Natriummonofluorphosphat 0,760Sodium monofluorophosphate 0.760
Pyridylcarbinol 0,100 a-aluminiumoxidtrihydrat ("Alcoa" 0333) 51,000 35Pyridylcarbinol 0.100 α-alumina trihydrate ("Alcoa" 0333) 51,000
Benzoesyre 0,140Benzoic Acid 0.140
Natriumlaurylsulfat 1,667Sodium lauryl sulfate 1.667
Titaniumdioxid 0,500Titanium dioxide 0.500
Aromastof 1,200Flavor 1,200
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Tandplejemidlet fyldes effektivt på dispenseren og undergår ikke lækage under lagring ved 43°C i mere end 1 måned. Det udpresses godt fra dispenseren efter 1 måneds lagring ved 43°C.The dentifrice effectively fills the dispenser and does not undergo leakage during storage at 43 ° C for more than 1 month. It is extruded well from the dispenser after 1 month of storage at 43 ° C.
55
Lignende tilfredsstillende resultater opnås, når tandplejemidlet modificeres til at indeholde 0,55 dele af hver af komponenterne i-carragenan og natriumcarboxymethylcellulose i et tilfælde og 0,45 dele af hver af komponenterne i-carra-10 genan og natriumcarboxymethylcellulose i et andet tilfælde under tilsvarende indstilling af vandindholdet. I virkeligheden iagttages fravær af lækage samt god ekstruderbarhed eller udpresselighed efter lagring ved 43°C i 3 måneder for disse tandplejemidler.Similar satisfactory results are obtained when the dentifrice is modified to contain 0.55 parts of each of the components i-carrageenan and sodium carboxymethyl cellulose in one case and 0.45 parts of each of the components i-carrageenan and sodium carboxymethyl cellulose in another case under the corresponding setting the water content. In fact, absence of leakage as well as good extrudability or extrudability is observed after storage at 43 ° C for 3 months for these dental care products.
1515
Der iagttages også tilfredsstillende resultater, når hvert af de tre ovenfor beskrevne tandplejemidler modificeres til at indeholde 50,000 dele a-aluminiumoxidtrihydrat i ét sæt af disse tandplejemidler og 52,000 dele a-aluminiumoxidtri- 20 hydrat i et andet sæt af de tre tandplejemidler under tilsvarende indstilling af vandindholdet.Satisfactory results are also observed when each of the three dentifrices described above is modified to contain 50,000 parts of α-alumina trihydrate in one set of these dentifrices and 52,000 parts of α-alumina trihydrate in another set of the three dentifrices under the corresponding setting of the water content.
Eksempel 2.Example 2.
25 Følgende tandplejemiddel fremstilles ved koldprocessen og fyldes på den samme dispenser som i eksempel 1.The following dentifrice is prepared by the cold process and filled with the same dispenser as in Example 1.
30 35 1830 35 18
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DeleParts
Sorbitol (70%) 23,000Sorbitol (70%) 23,000
Natriumsaccharin 0,170 I-carragenan ("Genuvisco" 0819) 0,666 5 Natriumcarboxymethylcellulose (7MFD) 0,334Sodium Saccharin 0.170 I-Carrageenan ("Genuvisco" 0819) 0.666 Sodium Carboxymethyl Cellulose (7MFD) 0.334
Methyl-p-hydroxybenzoat 0,080Methyl p-hydroxybenzoate 0.080
Allantoin 0,150Allantoin 0.150
Natriumfluorid 0,100Sodium fluoride 0.100
Natriummonofluorphosphat 0,760 10 Pyridylcarbinol 0,100 α-aluminiumoxidtrihydrat ("Alcoa" 0333) 51,500Sodium monofluorophosphate 0.760 Pyridylcarbinol 0.100 α-alumina trihydrate ("Alcoa" 0333) 51,500
Benzoesyre 0,140Benzoic Acid 0.140
Natriumlaurylsulfat 1,667Sodium lauryl sulfate 1.667
Titaniumdioxid 0,500 15 Aroma 1,200Titanium dioxide 0.500 Aroma 1,200
Deioniseret vand 19,633Deionized water 19,633
Tandplejemidlet fyldes effektivt på dispenseren og undergår ikke lækage samt ekstruderes godt fra dispenseren efter lag- 20 ring i 1 måned ved 43 C.The dentifrice effectively fills the dispenser and does not undergo leakage and extrude well from the dispenser after storage for 1 month at 43 ° C.
Lignende ønskelige virkninger opnås, når tandplejemidlerne ifølge eksemplerne fyldes på en ved trykforskel virkende dispenser.Similar desirable effects are achieved when the dentifrices of the examples are filled with a pressure differential dispenser.
25 Når natriumcarboxymethylcellulose anvendes som det eneste geleringsmiddel, indtræder dårlig ekstrusion. Når hydroxy-ethylcellulose anvendes som det eneste geleringsmiddel, optræder lækage. Når imidlertid hydroxyethylcellulose blandes 30 med i-carragenan, opnås ønskelig fyldning og ekstrusion. Eksempel 3.When sodium carboxymethyl cellulose is used as the only gelling agent, poor extrusion occurs. When hydroxyethyl cellulose is used as the only gelling agent, leakage occurs. However, when hydroxyethyl cellulose is mixed with i-carrageenan, desirable filling and extrusion are obtained. Example 3
Følgende tandplejemiddel fremstilles ved konventionel stue-35 temperatur-koldproces og fyldes på den mekanisk betjente dispenser omhandlet i britisk offentliggørelsesskrift nr. 2.070.695A.The following dentifrice is prepared by conventional room-temperature-cold process and loaded onto the mechanically operated dispenser disclosed in British Patent Specification No. 2,070,695A.
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19 0 Dele19 0 Parts
Sorbitol (70%) 23,000Sorbitol (70%) 23,000
Natriumsaccharin 0,170 I-carragenan ("Genuvisco" 0819) 0,500Sodium saccharin 0.170 I-carrageenan ("Genuvisco" 0819) 0.500
Xanthan ("Keltrol") 0,500 5Xanthan ("Keltrol") 0.500 5
Methyl-p-hydroxybenzoat 0,080Methyl p-hydroxybenzoate 0.080
Allantoin 0,150Allantoin 0.150
Natriumfluorid 0,100Sodium fluoride 0.100
Natriummonofluorphosphat 0,760Sodium monofluorophosphate 0.760
Pyridylcarbinol 0,100 10 a-aluminiumoxidtrihydrat ("Alcoa" C—333) 51,000Pyridylcarbinol 0.100 α-alumina trihydrate ("Alcoa" C-333) 51,000
Benzoesyre 0,140Benzoic Acid 0.140
Natriumlaurylsulfat 1,667Sodium lauryl sulfate 1.667
Titaniumdioxid 0,500Titanium dioxide 0.500
Aroma 1,200 15Aroma 1,200 15
Deioniseret vand 20,133Deionized water 20,133
Tandplejemidlet fyldes effektivt på dispenseren og undergår ikke lækage under lagring ved 43°C i mere end 1 måned. Det ekstruderer godt fra dispenseren efter 1 måneds lagring ved 20 n 43°C.The dentifrice effectively fills the dispenser and does not undergo leakage during storage at 43 ° C for more than 1 month. It extrudes well from the dispenser after 1 month of storage at 20 n 43 ° C.
Lignende tilfredsstillende resultater opnås, når tandplejemidlet modificeres til at indeholde 0,55 dele af hver af komponenterne i-carragenan og xanthan i ét tilfælde og 0,45 25 dele af hver af komponenterne i-carragenan og xanthan i et andet tilfælde, idet der foretages tilsvarende indstilling af vandindholdet. I virkeligheden iagttages fravær af lækage samt god ekstruderbarhed efter lagring ved 43°C i 3 måneder af tandplejemidlet indeholdende 0,45 dele af hver af kompo-30 nenterne xanthan og i-carragenan.Similar satisfactory results are obtained when the dentifrice is modified to contain 0.55 parts of each of the components i-carrageenan and xanthan in one case and 0.45 parts of each of the components i-carrageenan and xanthan in another case, corresponding setting of water content. In fact, absence of leakage as well as good extrudability after storage at 43 ° C is observed for 3 months by the dentifrice containing 0.45 parts of each of the components xanthan and i-carrageenan.
Der iagttages også tilfredsstillende resultater, når hver af de tre ovenfor beskrevne tandplejemidler modificeres til at indeholde 50,000 dele α-aluminiumoxidtrihydrat i ét sæt afSatisfactory results are also observed when each of the three dentifrices described above is modified to contain 50,000 parts of α-alumina trihydrate in one set of
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disse tandplejemidler og 52,000 dele a-aluminiumoxidtrihydrat i et andet sæt af de tre tandplejemidler, idet der foretages tilsvarende indstilling af vandindholdet.these dentifrices and 52,000 parts of α-alumina trihydrate in a second set of the three dentifrices, adjusting the water content accordingly.
2020
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Phosphorsyre kan anvendes i stedet for benzoesyre med lignende resultater.Phosphoric acid can be used instead of benzoic acid with similar results.
Eksempel 4.Example 4
5 Følgende tandplejemiddel fremstilles ved koldprocessen og fyldes på den samme dispenser som i eksempel 3.5 The following dentifrice is made by the cold process and filled with the same dispenser as in Example 3.
Dele 10Parts 10
Sorbitol (70%) 23,000Sorbitol (70%) 23,000
Natriumsaccharin 0,170 I-carragenan ("Genuvisco" 0819) 0,750Sodium Saccharin 0.170 I-Carrageenan ("Genuvisco" 0819) 0.750
Xanthan ("Keltrol") 0,250 15Xanthan ("Keltrol") 0.250 15
Methyl-p-hydroxyenzoat 0,080Methyl p-hydroxyenzoate 0.080
Allantoin 0,150Allantoin 0.150
Natriumfluorid 0,100Sodium fluoride 0.100
Natriummonofluorphosphat 0,760Sodium monofluorophosphate 0.760
Pyridylcarbinol 0,100 20 a-aluminiumtrihydrat ("Alcoa" C-333) 51,000Pyridylcarbinol 0.100 α-aluminum trihydrate ("Alcoa" C-333) 51,000
Benzoesyre 0,140Benzoic Acid 0.140
Natriumlaurylsulfat 1,667Sodium lauryl sulfate 1.667
Titaniumdioxid 0,500Titanium dioxide 0.500
Aroma 1,200 25Aroma 1,200 25
Deioniseret vand 20,133Deionized water 20,133
Tandplejemidlet fyldes effektivt på dispenseren og undergår ikke lækage samt ekstruderer godt fra dispenseren efter lagring i 3 måneder ved 43°C.The dentifrice effectively fills the dispenser and does not undergo leakage and extrudes well from the dispenser after storage for 3 months at 43 ° C.
3030
Lignende ønskelige resultater opnås med 50,000 dele a-alumi- niumoxidtrihydrat. Hver variant tilvejebringer også lignende resultater med et gelsystem indeholdende (a) 0,825 dele i- carragenan og 0,275 dele xanthan og (b) 0,675 dele i-carra-35 genan og 0,225 dele xanthan.Similar desirable results are obtained with 50,000 parts of α-alumina trihydrate. Each variant also provides similar results with a gel system containing (a) 0.825 parts of i-carrageenan and 0.275 parts of xanthan and (b) 0.675 parts of i-carrageenan and 0.225 parts of xanthan.
Lignende ønskelige virkninger opnås, når tandplejemidlerne ifølge eksemplerne fyldes på en ved trykforskel virkendeSimilar desirable effects are achieved when the dentifrices of the examples are filled with a pressure differential acting
Claims (7)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/564,966 US4529584A (en) | 1983-12-23 | 1983-12-23 | Dentifrice composition |
US56496683 | 1983-12-23 | ||
US56496783 | 1983-12-23 | ||
US06/564,967 US4529585A (en) | 1983-12-23 | 1983-12-23 | Dentrifrice preparation |
Publications (4)
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DK604584D0 DK604584D0 (en) | 1984-12-17 |
DK604584A DK604584A (en) | 1985-06-24 |
DK163276B true DK163276B (en) | 1992-02-17 |
DK163276C DK163276C (en) | 1992-07-13 |
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Application Number | Title | Priority Date | Filing Date |
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DK604584A DK163276C (en) | 1983-12-23 | 1984-12-17 | DENTAL DETAILS WITH GELING AGENT MIXTURE |
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JP (1) | JPS6122008A (en) |
KR (1) | KR920004817B1 (en) |
AT (1) | AT388291B (en) |
BE (1) | BE901363A (en) |
BR (1) | BR8406681A (en) |
CH (1) | CH660961A5 (en) |
DE (1) | DE3445772A1 (en) |
DK (1) | DK163276C (en) |
ES (1) | ES8605980A1 (en) |
FI (1) | FI77982C (en) |
FR (1) | FR2556963B1 (en) |
GB (1) | GB2152371B (en) |
GR (1) | GR82566B (en) |
HK (1) | HK61191A (en) |
IN (1) | IN160752B (en) |
IT (1) | IT1178302B (en) |
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NL (1) | NL8403894A (en) |
NO (1) | NO164514C (en) |
NZ (1) | NZ210616A (en) |
PT (1) | PT79702B (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4701319A (en) * | 1984-09-14 | 1987-10-20 | The Procter & Gamble Company | Toothpaste compositions |
JPS6341345A (en) * | 1986-08-06 | 1988-02-22 | Koyo Autom Mach Co Ltd | Rotary drum structure |
AT387715B (en) * | 1987-05-04 | 1989-03-10 | Blendax Werke Schneider Co | TOOTHPASTE |
JPH085921B2 (en) * | 1987-11-12 | 1996-01-24 | 三菱レイヨン株式会社 | Modified iota carrageenan and toothpaste using the same |
GB8803329D0 (en) * | 1988-02-12 | 1988-03-09 | Alcan Int Ltd | Alumina hydrates |
GB8803328D0 (en) * | 1988-02-12 | 1988-03-09 | Alcan Int Ltd | Alumina hydrates |
GB2372213B (en) * | 2000-11-17 | 2003-07-16 | Icebella Enterpises Ltd | Applicator and stimulator device |
JP6288840B2 (en) * | 2013-04-30 | 2018-03-07 | ライオン株式会社 | Cleaning agent for clothing |
ES2523066B2 (en) * | 2014-09-26 | 2015-06-09 | Suavizantes Y Plastificantes Bituminosos, S.L. | FORMULATION OF A PRODUCT FOR COSMETIC USE AND PERSONAL HYGIENE AND ITS MANUFACTURING PROCESS |
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Publication number | Priority date | Publication date | Assignee | Title |
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GB1372382A (en) * | 1971-02-05 | 1974-10-30 | Unilever Ltd | Toothpastes |
US4002732A (en) * | 1973-08-03 | 1977-01-11 | Colgate-Palmolive Company | Speckle particle for dentifrice |
DE2409756A1 (en) * | 1974-03-01 | 1975-09-11 | Blendax Werke Schneider Co | Toothpastes and powders contg. abrasive plastics particles - with addn. of urea to prevent discoloration |
FR2263753B1 (en) * | 1974-03-12 | 1978-07-21 | Roeck Yannick De | |
JPS53133642A (en) * | 1977-04-23 | 1978-11-21 | Sunstar Inc | Tooth paste composition |
US4353890A (en) * | 1979-10-24 | 1982-10-12 | Colgate-Palmolive Company | Stabilization of carrageenan-containing toothpaste |
JPS56147709A (en) * | 1980-04-18 | 1981-11-16 | Lion Corp | Tooth paste composition |
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1984
- 1984-12-05 SE SE8406152A patent/SE461012B/en not_active IP Right Cessation
- 1984-12-10 MX MX203665A patent/MX162744A/en unknown
- 1984-12-10 IN IN922/DEL/84A patent/IN160752B/en unknown
- 1984-12-14 DE DE19843445772 patent/DE3445772A1/en not_active Withdrawn
- 1984-12-17 DK DK604584A patent/DK163276C/en active
- 1984-12-17 FR FR8419284A patent/FR2556963B1/en not_active Expired
- 1984-12-18 NZ NZ210616A patent/NZ210616A/en unknown
- 1984-12-18 FI FI844994A patent/FI77982C/en not_active IP Right Cessation
- 1984-12-18 PT PT79702A patent/PT79702B/en unknown
- 1984-12-19 IT IT49317/84A patent/IT1178302B/en active
- 1984-12-19 LU LU85691A patent/LU85691A1/en unknown
- 1984-12-19 AT AT0401984A patent/AT388291B/en not_active IP Right Cessation
- 1984-12-21 GB GB08432393A patent/GB2152371B/en not_active Expired
- 1984-12-21 GR GR82566A patent/GR82566B/en unknown
- 1984-12-21 CH CH6146/84A patent/CH660961A5/en not_active IP Right Cessation
- 1984-12-21 NO NO845198A patent/NO164514C/en unknown
- 1984-12-21 BE BE0/214222A patent/BE901363A/en not_active IP Right Cessation
- 1984-12-21 BR BR8406681A patent/BR8406681A/en unknown
- 1984-12-21 ES ES538937A patent/ES8605980A1/en not_active Expired
- 1984-12-21 NL NL8403894A patent/NL8403894A/en not_active Application Discontinuation
- 1984-12-22 KR KR1019840008263A patent/KR920004817B1/en not_active IP Right Cessation
- 1984-12-24 JP JP59272721A patent/JPS6122008A/en active Granted
-
1991
- 1991-07-10 SG SG54991A patent/SG54991G/en unknown
- 1991-08-08 HK HK611/91A patent/HK61191A/en unknown
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