+

WO1996019191A1 - Compositions d'hygiene buccale - Google Patents

Compositions d'hygiene buccale Download PDF

Info

Publication number
WO1996019191A1
WO1996019191A1 PCT/US1995/016051 US9516051W WO9619191A1 WO 1996019191 A1 WO1996019191 A1 WO 1996019191A1 US 9516051 W US9516051 W US 9516051W WO 9619191 A1 WO9619191 A1 WO 9619191A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
weight
dimethicone copolyol
alkoxy
sodium
Prior art date
Application number
PCT/US1995/016051
Other languages
English (en)
Inventor
Iain Allan Hughes
Elizabeth Mary Ryan
Christopher David White
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to HU9800690A priority Critical patent/HU220794B1/hu
Priority to EP95943738A priority patent/EP0793478A4/fr
Priority to KR1019970704212A priority patent/KR100246832B1/ko
Priority to CA002208364A priority patent/CA2208364C/fr
Priority to PL95320866A priority patent/PL320866A1/xx
Priority to AU45140/96A priority patent/AU4514096A/en
Priority to US08/860,060 priority patent/US5827505A/en
Priority to CZ19971886A priority patent/CZ292313B6/cs
Priority to SK828-97A priority patent/SK82897A3/sk
Priority to BR9510307A priority patent/BR9510307A/pt
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP8519857A priority patent/JPH10511349A/ja
Publication of WO1996019191A1 publication Critical patent/WO1996019191A1/fr
Priority to MXPA/A/1997/004721A priority patent/MXPA97004721A/xx

Links

Classifications

    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • 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
    • A61K8/22—Peroxides; Oxygen; Ozone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P1/00—Drugs for disorders of the alimentary tract or the digestive system
    • A61P1/02—Stomatological preparations, e.g. drugs for caries, aphtae, periodontitis
    • 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
    • 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
    • A61Q11/02—Preparations for deodorising, bleaching or disinfecting dentures
    • 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
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/22—Gas releasing
    • A61K2800/222—Effervescent

Definitions

  • the present invention relates to oral compositions such as toothpastes, toothpowders, liquid dentifrices, mouthwashes, denture cleansers, chewing gums, candies and the like.
  • oral compositions having enhanced antiplaque activity together with excellent cleansing performance, physical characteristics, and in-use performance characteristics.
  • Plaque is initiated when bacteria adhered to pellicle form a proteinaceous film on the surface of teeth.
  • the adherent bacteria metabolize dietary constituents and reproduce and aggregate to form the tenacious deposit known as plaque.
  • Plaque generally consists of bacteria, bacterial end products such as polysaccharides, inorganic salts and salivary proteins. Plaque bacteria ferment dietary carbohydrates to organic acids which demineralize enamel resulting in tooth decay.
  • Calculus is essentially plaque that has been mineralized with calcium phosphates salts. As calculus matures and hardens, it tends to stain noticeably due to adsorption of dietary chromagens. In addition to their unattractive appearance, calculus deposits at the gum line are a contributing source of gingivitis and periodontal disease. Besides the hygienic and health problems resulting from plaque, research has shown that the primary source of bad breath is the retention and subsequent degradation of dead cellular material sloughed off continuously by the normal, healthy mouth.
  • Modern dental hygiene and denture preparations typically contain antiplaque and/or antitartar agents, as well as antimicrobial agents and flavorants.
  • Antimicrobial action could affect plaque formation by either reducing the number of bacteria in the mouth/dentures or by killing those bacteria trapped in the film to prevent further growth and metabolism.
  • Flavorants may alleviate the problem of bad breath via a deodorizing action.
  • Some antimicrobial agents, e.g. menthol may, also serve as breath deodorizers.
  • the efficacy of antimicrobial agents depends largely on their intraoral/denture retention, particularly their retention on the surface of the teeth or dentures where plaque is formed.
  • a typical disadvantage of known dental preparations is that only a relatively short time during which the teeth are being cleaned or the mouth is being rinsed is available for antimicrobial agents in the preparations to take effect.
  • the problem is compounded by the fact that dentifrice preparations are used infrequently: most are used once or, perhaps, twice daily. Consequently, the long time period between brushings for a majority of the population provides optimum plaque forming conditions.
  • GB-A- 689,679 discloses a mouthwash containing an organopolysiloxane for preventing adhesion of, or for removing tars, stains, tartar and food particles from the teeth.
  • the mouthwash may include antiseptic compounds, such as thymol, and flavoring and perfuming agents.
  • US-A-2,806,814 discloses dental preparations including, in combination, a higher aliphatic acyl amide of an amino carboxylic acid compound as an active and a silicone compound.
  • silicone compounds have been proposed for prevention of adhesion or to facilitate the removal of tars, stains, tartar and the like from teeth.
  • the silicone compound is said to act as a synergist in improving the antibacterial and acid inhibiting activity of the active ingredient.
  • Dimethyl polysiloxanes are said to be particularly effective. Flavoring oils and/or menthol may be included.
  • US-A-3624120 discloses quaternary ammonium salts of cyclic siloxane polymers for use as cationic surfactants, bactericides and as anticariogenic agents.
  • the present invention provides oral compositions having improved efficacy on plaque, mucilaginous and bacterial deposits and which at the same time provides excellent cleansing performance, physical characteristics, and in-use performance characteristics.
  • the invention further provides oral compositions containing a lipophilic compound such as a flavorant, physiological cooling agent or antimicrobial, and which has improved substantivity, impact and/or efficacy on teeth and dentures.
  • a lipophilic compound such as a flavorant, physiological cooling agent or antimicrobial
  • an oral composition in the form of a toothpaste, powder, liquid dentifrice, mouthwash, denture cleanser, chewing gum or candy comprising one or more oral composition components selected from abrasives, binders, humectants, surfactants, fluoride ion sources, anti-calculus agents and sweeteners and additionally comprising a dimethicone copolyol selected from alky I- and alkoxy-dimethicone copolyols having the formula (I):
  • X is selected from hydrogen, alkyl, alkoxy and acyl groups having from about 1 to about 16 carbon atoms
  • Y is selected from alkyl and alkoxy groups having from about 8 to about 22 carbon atoms
  • n is from about 0 to about 200
  • m is from about 1 to about 40
  • q is from about 1 to about 100
  • the molecular weight of the residue (C2H4 ⁇ -) ⁇ (C3H- ⁇ O- )yX is from about 50 to about 2000, preferably from about 250 to about 1000 and x and y are such that the weight ratio of oxyethylene:oxypropylene is from about 100:0 to about 0:100, preferably from about 100:0 to about 20:80.
  • an oral composition in the form of a toothpaste, powder, liquid dentifrice, mouthwash, denture cleanser, chewing gum or candy comprising a lipophilic compound selected from flavorants, physiological cooling agents and antimicrobial compounds and a dimethicone copolyol selected from alakyl- and alkoxy-dimethicone copolyols having the formula (I).
  • compositions of the invention thus comprise a dimethicone copolyol antiplaque agent while preferred compositions additionally comprise a lipophilic compound and/or one or more oral composition components selected from abrasives, binders, humectants, surfactants, fluoride ion sources, anti-calculus agents and sweeteners Each of these will be discussed in turn.
  • the dimethicone copolyol is selected from alkyl- and alkoxy-dimethicone copolyols having the formula (I):
  • X is selected from hydrogen, alkyl, alkoxy and acyl groups having from about 1 to about 16 carbon atoms
  • Y is selected from alkyl and alkoxy groups having from about 8 to about 22 carbon atoms
  • n is from about 0 to about 200
  • m is from about 1 to about 40
  • q is from about 1 to about 100
  • the molecular weight of the residue (C2H4 ⁇ -) x (C3H6 ⁇ - )yX is from about 50 to about 2000, preferably from about 250 to about 1000 and x and y are such that the weight ratio of oxyethylene:oxypropylene is from about 100:0 to about 0:100, preferably from about 100:0 to about 20:80.
  • the dimethicone copolyol is selected from Cj2 to C20 alkyl dimethicone copolyols and mixtures thereof. Highly preferred is cetyl dimethicone copolyol marketed under the Trade Name Abil EM90.
  • the dimethicone copolyol is generally present in a level of from about 0.01 % to about 25%, preferably from about 0.1 % to about 5%, more preferably from about 0.5% to about 1.5% by weight.
  • the oral compositions of the invention preferably also include a lipophilic compound.
  • lipophilic compounds suitable for use herein are oil-like materials which are soluble or solubilisable in the dimethicone copolyol, preferably at a level of at least about 1 %, more preferably at least about 5% by weight at 25°C.
  • Preferred lipophilic compounds are selected from flavorants, physiological cooling agents and antimicrobial compounds.
  • the dimethicone copolyol acts to enhance the substantivity of the lipophilic compound to teeth and/or dentures, thereby providing enhanced and/or sustained flavor impact and antimicrobial efficacy.
  • Lipophilic flavorants suitable for use herein comprise one or more flavor components selected from wintergreen oil, oregano oil, bay leaf oil, peppermint oil, spearmint oil, clove oil, sage oil, sassafras oil, lemon oil, orange oil, anise oil, benzaldehyde, bitter almond oil, camphor, cedar leaf oil, marjoram oil, citronella oil, lavendar oil, mustard oil, pine oil, pine needle oil, rosemary oil, thyme oil, cinnamon leaf oil, and mixtures thereof.
  • Lipophilic antimicrobial compounds suitable for use herein include thymol, menthol, triclosan, 4-hexylresorcinol, phenol, eucalyptol, benzoic acid, benzoyl peroxide, butyl paraben, methyl paraben, propyl paraben, salicylamides, and mixtures thereof.
  • Physiological cooling agent suitable for use herein include carboxamides, menthane esters and menthane ethers, and mixtures thereof.
  • Suitable menthane ethers for use herein are selected from those with the formula:
  • R5 is an optionally hydroxy substituted aliphatic radical containing up to 25 carbon atoms, preferably up to 5 carbon atoms, and where X is hydrogen or hydroxy, such as those commercially available under the trade name Takasago, from Takasago International Corporation.
  • a particularly preferred cooling agent for use in the compositions of the present invention is Takasago 10 [3-1-menthoxy propan-l,2-diol (MPD)].
  • MPD is a monoglycerin derivative of 1-menthol and has excellent cooling activity.
  • compositions in the form of toothpastes, denture cleansing liquids and pastes and the like will generally comprise a binder or thickening agent.
  • Binders suitable for use herein include carboxyvinyl polymers, carrrageenan, hydroxyethyl cellulose and water soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose.
  • Natural gums such as gum karaya, xanthan gum, gum arabic, and gum tragacanth can also be used.
  • Colloidal magnesium aluminum silicate or finely divided silica can be used as part of the thickening agent to further improve texture.
  • Binders/thickening agents can be used in an amount from about 0.1 % to about 5.0%, preferably from about 0.1 to about 1 % by weight of the total composition.
  • humectant material in a toothpaste to keep the composition from hardening upon exposure to air.
  • Certain humectants can also impart a desirable sweetness to toothpaste compositions.
  • Liquid dentifrice and mouth washes can also contain a quantity of humectant.
  • Suitable humectants include glycerin, sorbitol, xylitol, polyethylene glycols, propylene glycol, other edible polyhydric alcohols, and mixtures thereof. When present, humectants generally represent from about 10% to about 70%, by weight of the compositions of the invention.
  • liquid dentifrices and denture cleansers in liquid or paste form will generally comprise an abrasive polishing material.
  • the abrasive polishing material contemplated for use herein can be any material which does not excessively abrade dentin or denture acrylic.
  • silicas including xerogels, hydrogels, aerogels and precipitates, calcium and magnesium carbonates, calcium ortho-, pyro- meta- and polyphosphates such as dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, and calcium polymetaphosphate, insoluble sodium polymetaphosphate, alumina and hydrates thereof such as alpha alumina trihydrate, aluminosilicates such as calcined aluminium silicate and aluminium silicate, magnesium and zirconium silicates such as magnesium trisilicate and thermosetting polymerised resins such as particulate condensation products of urea and formaldehyde, polymethylmethacrylate, powdered polyethylene and others such as disclosed in US- A-3, 070,510, December 25, 1962 Mixtures of abrasives can also be used.
  • the abrasive polishing materials generally have an average particle size of from about 0.1 to about 30 microns, preferably from about 5 to 15 microns
  • Silica dental abrasives of various types offer exceptional dental cleaning and polishing performance without unduly abrading tooth enamel or dentin.
  • the silica abrasive can be precipitated silica or silica gels such as the silica xerogels described in Pader et al., US-A-3,538,230, issued March 2, 1970 and DiGiulio, US-A-3,862,307, June 21, 1975, for example silica xerogels marketed under the tradename "Syloid" by W. R. Grace & Company, Davison Chemical Division.
  • Suitable precipitated silica materials include those marketed by the J. M. Huber Corporation under the tradename, "Zeodent", particularly the silica carrying the designation "Zeodent 119". These silica abrasives are described in US- A-4,340,583, July 29, 1982.
  • the abrasive is generally present in dentifrice formulations of the invention at a level of from about 10% to about 70%, preferably from about 15% to about 25% by weight.
  • compositions can also contain surfactants.
  • Suitable surfactants are those which are reasonably stable and foam throughout a wide pH range, including non-soap anionic, nonionic, cationic, zwitterionic and amphoteric organic synthetic detergents. Many of these suitable agents are disclosed by Gieske et al. in US-A-4,051,234, September 27, 1977.
  • Suitable surfactants include alkyl sulfates; condensation products of ethylene oxide with fatty acids, fatty alcohols, fatty amides, polyhydric alcohols (e.g. sorbitan monostearate, sorbitan oleate), all y 1 phenols (e.g. Tergitol) and polypropyleneoxide or polyoxybutylene (e.g.
  • amine oxides such as dimethyl cocamine oxide, dimethyl lauryl amine oxide and cocoalkyldimethyl amine oxide (Aromox); polysorbates such as Tween 40 and Tween 80 (Hercules); sorbitan stearates, sorbitan monoaleate, etc; sarcosinates such as sodium cocoylsarcosinate, sodium lauroyl sarcosinate (Hamposyl-95 ex W. R.
  • cationic surfactants such as cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, di-isobutyl phenoxy ethoxy ethyl-dimethyl benzyl ammonium chloride and coconut alkyl trimethyl ammonium nitrate
  • a soluble fluoride ion source can also be incorporated in the present compositions.
  • the soluble fluoride ion source is used in amounts sufficient to provide from about 50 to about 3500 ppm of the fluoride ion.
  • Preferred fluorides are sodium fluoride, stannous fluoride, indium fluoride, zinc ammonium fluoride, tin ammonium fluoride, calcium fluoride and sodium monofluorophosphate.
  • Norris et al., US-A- 2,946,735, issued July 26, 1960 and Widder et al., US-A-3,678,154, issued July 18, 1972 disclose such salts as well as others.
  • compositions can also include an anti-calculus agent.
  • Suitable anti-calculus agents include the di- and tetra-alkali metal pyrophosphates as set out in EP-A-097476.
  • Specific salts include tetra alkali metal pyrophosphate, dialkali metal diacid pyrophosphate, trialkali metal monoacid pyrophosphate and mixtures thereof, wherein the alkali metals are sodium or potassium.
  • the salts are useful in both their hydrated and unhydrated forms.
  • the amount of pyrophosphate salt useful in these compositions is any effective amount and is generally enough to provide in composition at least 1.0% P2O7- , preferably from about 1.5% to about 10%, more preferably from about 3% to about 6% by weight of composition.
  • the pyrophosphate salts are described in more detail in Kirk & Othmer, Encyclopedia of Chemical Technology. Second Edition, Volume 15, Interscience Publishers (1968).
  • Zinc salts are disclosed in US-A-4, 100,269, US-A-4,416,867, US-A-4,425,325 and US- A-4,339,432.
  • a preferred agent of the zinc variety is zinc citrate.
  • Zinc compounds can be present in amounts sufficient to provide from about 0.01 % to about 4%, preferably from about 0.05% to about 1 % by weight of zinc ion.
  • Suitable anti-calculus agents include the synthetic anionic polymers (including polyacrylates and copolymers of maleic anhydride or acid and methyl vinyl ether (eg Gantrez) as described in US-A-4,627,977, polyamino propane sulfonic acid, polyphosphates (eg tripolyphosphate, hexametaphosphate), diphosphonates (eg EHDP, AHP), polypeptides (eg polyaspartic and polyglutamic acids), and mixtures thereof.
  • synthetic anionic polymers including polyacrylates and copolymers of maleic anhydride or acid and methyl vinyl ether (eg Gantrez) as described in US-A-4,627,977, polyamino propane sulfonic acid, polyphosphates (eg tripolyphosphate, hexametaphosphate), diphosphonates (eg EHDP, AHP), polypeptides (eg polyaspartic and polyglutamic acids), and mixtures thereof
  • Sweetening agents which can be used include aspartame, acesulfame, saccharin, dextrose, levulose and sodium cyclamate. Sweetening agents are generally used at levels of from about 0.005% to about 2% by weight of composition.
  • water-soluble antibacterial agents such as chlorhexidine digluconate, quaternary ammonium antibacterial compounds and water-soluble sources of certain metal ions such as zinc, copper, silver and stannous (e.g., zinc, copper and stannous chloride, and silver nitrate); pigments such as titanium dioxide; orally acceptable dyes/colorants such asFD&C Blue #1 , FD&C Yellow #10, FD&C Red #40; antioxidants, vitamins such as vitamin C and E, other antiplaque agents such as stannous salts, copper salts, strontium salts and magnesium salts; pH adjusting agents, anticaries agents such as urea, calcium glycerophosphate, sodium trimetaphosphate, plant extracts, desensitizing agents for sensitive teeth such as potassium nitrate and potassium citrate, and mixtures thereof.
  • water-soluble antibacterial agents such as chlorhexidine digluconate, quaternary ammonium antibacterial compounds and water-soluble sources of certain metal ions such as zinc,
  • mouthwashes comprise a water/alcohol solution, flavor, humectant, sweetener, sudsing agent, and colorant as described above.
  • Mouthwashes can include ethanol at a level of from 0 to 60%, preferably from 5 to 30% by weight.
  • Denture cleanser compositions of the invention can additionally include one or more bleaching agents, organic peroxyacid precursors, effervescence generators, chelating agents, etc
  • the bleaching agent takes the form of an inorganic persalt and can be selected from any of the well-known bleaching agents known for use in denture cleansers such as the alkali metal and ammonium persulfates, perborates, percarbonates and perphosphates and the alkali metal and alkaline earth metal peroxides.
  • suitable bleaching agents include potassium, ammonium, sodium and lithium persulfates and perborate mono- and tetrahydrates, sodium pyrophosphate peroxyhydrate and magnesium, calcium, strontium and zinc peroxides.
  • the alkali metal persulfates, perborates and mixtures thereof are prefered for use herein, highly preferred being the alkali metal perborates. Indeed, it is a feature of the invention that the tablet compositions herein will provide excellent antimicrobial activity even in the absence of alkali metal persulfates.
  • the amount of bleaching agent in the total composition is generally from about 5 to about 70% preferably from about 10% to about 50%.
  • the overall persulfate:perborate ratio is suitably from about 5:1 to about 1 :5, more especially from about 2:1 to about 1:2.
  • the denture cleansing compositions can also incorporate an effervescence generator, ie a material which in the presence of water releases carbon dioxide or oxygen with effervescence.
  • the effervescence generator can be selected from generators which are effective under acid, neutral or alkaline pH conditions, but preferably it consists of a combination of a generator which is effective or most effective under acid or neutral pH conditions and a generator which is effective or most effective under alkaline pH conditions.
  • Effervescence generators which are effective under acid or neutral pH conditions include a combination of at least one alkali metal carbonate or bicarbonate, such as sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, potassium carbonate, potassium bicarbonate, or mixtures thereof, in admixture with at least one non-toxic, physiologically-acceptable organic acid, such as tartaric, fumaric, citric, malic, maleic, gluconic, succinic, salicylic, adipic or sulphamic acid, sodium fumarate, sodium or potassium acid phosphates, betaine hydrochloride or mixtures thereof. Of these, malic acid is preferred.
  • Effervescence generators which are effective under alkaline pH conditions include persalts such as alkali and alkaline earth metal peroxoborates as well as perborates, persulphates, percarbonates, perphosphates and mixtures thereof as previously described, for example, a mixture of an alkali metal perborate (anhydrous, mono- or tetrahydrate) with a monopersulphate such as Caroat R marketed by E I du Point de Nemours Co. and which is a 2: 1 : 1 mixture of monopersulphate, potassium sulphate and potassium bisulphate and which has an active oxygen content of about 4.5% .
  • persalts such as alkali and alkaline earth metal peroxoborates as well as perborates, persulphates, percarbonates, perphosphates and mixtures thereof as previously described, for example, a mixture of an alkali metal perborate (anhydrous, mono- or tetrahydrate) with a monopersulphate such as Caroat R
  • the effervescence generator takes the form of a solid base material which in the presence of water releases carbon dioxide or oxygen with effervescence.
  • the solid base material incorporates a (bi)carbonate/acid effervescent couple optionally in combination with a perborate/persulphate oxygen effervescence generator.
  • the combination of generators is valuable for achieving optimum dissolution characteristics and pH conditions for achieving optimum cleaning and antimicrobial activity.
  • the (bi)carbonate components generally comprise from about 5% to about 65% , preferably from about 25% to 55% of the total composition; the acid components generally comprise from about 5% to about 50%, preferably from about 10% to about 30% of the total composition.
  • the denture cleansing compositions of the invention can be supplemented by other .known components of such formulations.
  • An especially preferred additional component is an organic peroxyacid precursor, which in general terms can be defined as a compound having a titre of at least 1.5ml of 0.1 N sodium thiosulfate in the following peracid formation test.
  • test solution is prepared by dissolving the following materials in 1000 mis distilled water:
  • the mixture obtained by addition of the activator is vigorously stirred and maintained at 60°C. After 5 minutes from addition, a 100 ml portion of the solution is withdrawn and immediately pipetted onto a mixture of 250 g cracked ice and 15 ml glacial acetic acid. Potassium iodide (0.4 g) is then added and the liberated iodine is immediately titrated with 0.1 N sodium thiosulphate with starch as indicator until the first disappearance of the blue colour. The amount of sodium thiosulphate solution used in ml is the titre of the bleach activator.
  • the organic peracid precursors are typically compounds containing one or more acyl groups, which are susceptible to perhydrolysis.
  • the preferred activators are those of the N-acyl or O-acyl compound type containing a acyl radical R-CO wherein R is a hydrocarbon or substituted hydrocarbon group having preferably from about 1 to about 20 carbon atoms.
  • suitable peracid precursors include:
  • N,N - diacetylaniline and N-acetylphthalimide a) N,N - diacetylaniline and N-acetylphthalimide; b) N-acylhydantoins, such as
  • Examples of compounds of this type include phenyl acetate, sodium acetoxy benzene sulphonate, trichloroethylacetate, sorbitol hexaacetate, fructose pentaacetate, p- nitrobenzaldehyde diacetate, isopropeneyl acetate, acetyl aceto hydroxamic acid, and acetyl salicylic acid.
  • esters of a phenol or substituted phenol with an alpha-chlorinated lower aliphatic carboxylic acid such as chloroacetylphenol and chloroacetylsalicylic acid, as disclosed in US-A-3,130,165.
  • Preferred compounds of this type are those wherein: a) Ac is R3-CO and R3 is a linear or branched alkyl group containing from 6 to 20, preferably 6 to 12, more preferably 7 to 9 carbon atoms and wherein the longest linear all yl chain extending from and including the carbonyl carbon contains from 5 to 18, preferably 5 to 10 carbon atoms, R3 optionally being substituted (preferably alpha to the carbonyl moiety) by Cl, Br, OCH3 or OC2H5.
  • this class of material examples include sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate, sodium 3,5,5-trimethyIhexanoyloxybenzoate, sodium 2- ethylhexanoyl oxybenzenesulfonate, sodium nonanoyl oxybenzene sulfonate and sodium octanoyl oxybenezenesulfonate, the acyloxy group in each instance preferably being p-substituted;
  • R3(AO) m XA wherein R3 is a linear or branched alkyl or alkylaryl group containing from 6 to 20, preferably from 6 to 15 carbon atoms in the alkyl moiety, R5 being optionally substituted by Cl, Br, OCH3, or OC2H5, AO is oxyethylene or oxypropylene, m is from 0 to 100, X is O, NR4 or CO-NR4, and A is CO, CO-CO, R6-CO, CO-R ⁇ -CO, or CO-NR4-R6-CO wherein R4 is C1-C4 alkyl and R6 is alkylene, alkenylene, arylene or alkarylene containing from 1 to 8 carbon atoms in the alkylene or alkenylene moiety.
  • m is preferably from 0 to 10
  • R3 is preferably Cg- C12, more preferably C ⁇ -Cio alkyl when m is zero and C9- C15 when m is non-zero.
  • the leaving group L is as defined above.
  • Optionally substituted anhydrides of benzoic or phthalic acid for example, benzoic anhydride, m-chlorobenzoic anhydride and phthalic anhydride.
  • the level of peroxyacid bleach precursor by weight of the total composition is preferably from about 0.1 % to about 10%, more preferably from about 0.5% to about 5% and is generally added in the form of a bleach precursor agglomerate.
  • the bleach precursor agglomerates preferred for use herein generally comprise a binder or agglomerating agent in a level of from about 5% to about 40%, more especially from about 10% to about 30% by weight thereof.
  • Suitable agglomerating agents include polyvinylpyrrolidone, poly (oxyethylene) of molecular weight 20,000 to 500,000, polyethyleneglycols of molecular weight of from about 1000 to about 50,000, Carbowax having a molecular weight of from 4000 to 20,000, nonionic surfactants, fatty acids, sodium carboxymethyl cellulose, gelatin, fatty alcohols, phosphates and polyphosphates, clays, aluminosilicates and polymeric polycarboxylates.
  • polyethyleneglycols are highly preferred, especially those having molecular weight of from about 1,000 to about 30,000, preferably 2000 to about 10,000.
  • bleach precursor agglomerates which comprise from about 10% to about 75%, preferably from about 20% to about 60% by weight thereof of peroxyacid bleach precursor, from about 5% to about 60% preferably from about 5% to about 50%, more preferably from about 10% to about 40% of a (bi) carbonate/acid effervescent couple, from about 0% to about 20% of a peroxoboroate, and from about 5% to about 40%, preferably from about 10% to about 30% of an agglomerating agent.
  • the final bleach precursor granules desirably have an average particle size of from about 500 to about 1500, preferably from about 500 to about 1 ,000 wm, this being valuable from the viewpoint of optimum dissolution performance and aesthetics.
  • the level of bleach precursor agglomerates is preferably from about 1 % to about 20%, more preferably from about 5% to about 15% by weight of composition.
  • the denture cleansing compositions of the invention can be in paste, tablet, granular or powder form, although tablet-form compositions are highly preferred herein.
  • Compositions in tablet form can be single or multiple layered tablets.
  • Denture cleansing compositions of the invention can be supplemented by other usual components of such formulations, especially surfactants, chelating agents, enzymes, flavorants, physiological cooling agents, antimicrobial compounds, dyestuffs, sweeteners, tablet binders and fillers, foam depressants such as dimethylpolysiloxanes, foam stabilizers such as the fatty acid sugar esters, preservatives, lubricants such as talc, magnesium stearate, finely divided amorphous pyrogenic silicas, etc.
  • the free moisture content of the final composition is desirably less than about 1 % and especially less than about 0.5%.
  • Tablet binders and fillers suitable for use herein include polyvinylpyrrolidone, poly (oxyethylene) of molecular weight 20,000 to 500,000, polyethyleneglycols of molecular weight of from about 1000 to about 50,000, Carbowax having a molecular weight of from 4000 to 20,000, nonionic surfactants, fatty acids, sodium carboxymethyl cellulose, gelatin, fatty alcohols, clays, polymeric polycarboxylates, sodium carbonate, calcium carbonate, calcium hydroxide, magnesium oxide, magnesium hydroxide carbonate, sodium sulfate, proteins, cellulose ethers, cellulose esters, poly vinyl alcohol, alginic acid esters, vegetable fatty materials of a pseudocolloidal character.
  • polyethyleneglycols are highly preferred, especially those having molecular weight of from about 1 ,000 to about 30,000, preferably from about 12,000 to about 30,000.
  • the surface active agent used in the denture cleansing compositions of the invention can be selected from the many available that are compatible with the other ingredients of the denture cleanser, both in the dry state and in solution. Such materials are believed to improve the effectiveness of the other ingredients of the composition by aiding their penetration into the interdental surfaces. Also, these materials aid in the removal of food debris attached to the teeth.
  • a dry powder or granular anionic surface active agent such as sodium lauryl sulfate, sodium N-lauroylsarcosinate, sodium lauryl sulfoacetate or dioctyl sodium sulfosuccinate or ricinoleyl sodium sulfosuccinate, may, for example, be included in the composition and preferably the surface active agent comprises between 0.5 and 4 percent of the composition.
  • Suitable cationic, non-ionic and ampholytic surface active agents include, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide, condensation products of alkylene oxides such as ethylene or propylene oxide with fatty alcohols, phenols, fatty amines or fatty acid alkanolamides, the fatty acid alkanolamides themselves, esters of long-chained (Cg-C22) atty acids with polyalcohols or sugars, for example glycerylmonostearate or saccharosemonolaurate or sorbitolpolyoxyethylenemono-or di-stearate, betaines, sulphobetaines or long-chain alkylaminocarboxylic acids.
  • quaternary ammonium compounds such as cetyltrimethylammonium bromide
  • condensation products of alkylene oxides such as ethylene or propylene oxide with fatty alcohols, phenols, fatty amines or fatty acid
  • Chelating agents beneficially aid cleaning and bleach stability by keeping metal ions, such as calcium, magnesium, and heavy metal cations in solution.
  • suitable chelating agents include sodium tripolyphosphate, sodium acid pyrophosphate, tetrasodium pyrophosphate, aminopolycarboxylates such as nitrilotriacetic acid and ethylenediamine tetracetic acid and salts thereof, and polyphosphonates and aminopolyphosphonates such as hydroxyethanediphosphonic acid, ethylenediamine tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and salts thereof.
  • the chelating agent selected is not critical except that it must be compatible with the other ingredients of the denture cleanser when in the dry state and in aqueous solution.
  • the chelating agent comprises between 0.1 and 60 percent by weight of the composition and preferably between 0.5 and 30 percent.
  • Phosphonic acid chelating agents preferably comprise from about 0.1 to about 1 percent, preferably from about 0.1 % to about 0.5% by weight of composition.
  • Enzymes suitable for use herein are exemplified by proteases, alkalases, amylases, lipases, dextranases, mutanases, glucanases etc.
  • the following are representative denture cleansing tablets according to the invention.
  • the percentages are by weight of the total tablet.
  • the tablets are made by compressing a mixture of the granulated components in a punch and dye tabletting press at a pressure of about 10 ⁇ kPa.
  • the denture cleansing tablets of Examples I to V display improved antiplaque, cleansing and anti-bacterial activity together with excellent cohesion and other physical and in-use performance characteristics.
  • the following are representative toothpaste/denture cleansing pastes according to the invention.
  • the percentages are by weight of total composition.
  • Titanium Dioxide 0.7 0.5 0.6
  • the toothpastes/denture cleansing pastes of Examples VI to VIII display improved antiplaque, flavor impact and anti-bacterial activity together with excellent cleansing characteristics.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Engineering & Computer Science (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

Composition d'hygiène buccale sous forme de pâte dentifrice, de poudre, de dentifrice liquide, de solution de rinçage, de produit de nettoyage dentaire, de gomme à mâcher ou de bonbon comprenant un ou plusieurs constituants de ladite composition sélectionnés à partir d'abrasifs, de liants, d'humectants, de tensioactifs, de sources d'ions fluorurés, d'agents anti-plaque et d'édulcorants et comprenant, de plus, un diméthicone polyol.
PCT/US1995/016051 1994-12-22 1995-12-12 Compositions d'hygiene buccale WO1996019191A1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
SK828-97A SK82897A3 (en) 1994-12-22 1995-12-12 Oral compositions
KR1019970704212A KR100246832B1 (ko) 1994-12-22 1995-12-12 구강용 조성물
CA002208364A CA2208364C (fr) 1994-12-22 1995-12-12 Compositions d'hygiene buccale
PL95320866A PL320866A1 (en) 1994-12-22 1995-12-12 Oral compositions
AU45140/96A AU4514096A (en) 1994-12-22 1995-12-12 Oral compositions
HU9800690A HU220794B1 (hu) 1994-12-22 1995-12-12 Dimetikont tartalmazó szájápoló készítmény és alkalmazása
CZ19971886A CZ292313B6 (cs) 1994-12-22 1995-12-12 Orální prostředky
US08/860,060 US5827505A (en) 1994-12-22 1995-12-12 Oral compositions
BR9510307A BR9510307A (pt) 1994-12-22 1995-12-12 Composições orais
EP95943738A EP0793478A4 (fr) 1994-12-22 1995-12-12 Compositions d'hygiene buccale
JP8519857A JPH10511349A (ja) 1994-12-22 1995-12-12 口腔用組成物
MXPA/A/1997/004721A MXPA97004721A (en) 1994-12-22 1997-06-23 Ora compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9425941.3 1994-12-22
GBGB9425941.3A GB9425941D0 (en) 1994-12-22 1994-12-22 Oral composition

Publications (1)

Publication Number Publication Date
WO1996019191A1 true WO1996019191A1 (fr) 1996-06-27

Family

ID=10766396

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/016051 WO1996019191A1 (fr) 1994-12-22 1995-12-12 Compositions d'hygiene buccale

Country Status (15)

Country Link
EP (1) EP0793478A4 (fr)
JP (1) JPH10511349A (fr)
KR (1) KR100246832B1 (fr)
CN (1) CN1088578C (fr)
AU (1) AU4514096A (fr)
BR (1) BR9510307A (fr)
CA (1) CA2208364C (fr)
CZ (1) CZ292313B6 (fr)
GB (1) GB9425941D0 (fr)
HU (1) HU220794B1 (fr)
PL (1) PL320866A1 (fr)
RU (1) RU2163480C2 (fr)
SK (1) SK82897A3 (fr)
TR (1) TR199501645A2 (fr)
WO (1) WO1996019191A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19646985A1 (de) * 1996-11-14 1998-06-04 Michael Dr Weichsel Geschmacksverbesserung bei Zahnregulierungsapparaten
WO1998031298A1 (fr) 1997-01-16 1998-07-23 The Procter & Gamble Company Procede pour le traitement des protheses dentaires
US6294154B1 (en) 1994-12-22 2001-09-25 Procter And Gamble Company Oral compositions containing dimethicone copolyols
US6648983B1 (en) * 1998-11-10 2003-11-18 The Procter & Gamble Company Process of cleaning enamel surfaces
US6685921B2 (en) 2000-10-25 2004-02-03 The Procter & Gamble Company Dental care compositions
WO2005058185A1 (fr) 2003-12-11 2005-06-30 Koninklijke Philips Electronics, N.V. Systeme de pompage pour une composition a administration par voie orale
KR100478211B1 (ko) * 1997-10-01 2005-08-11 애경산업(주) 미백치약조성물
US7364761B2 (en) 1997-09-18 2008-04-29 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents and method of preparing
AU2006265330B2 (en) * 2005-06-30 2012-11-01 Glaxo Group Limited Oral composition comprising dimethicone copolyol
WO2015065835A1 (fr) 2013-10-28 2015-05-07 The Procter & Gamble Company Ajout à une phase avancée de modificateur de rhéologie
WO2019032795A1 (fr) 2017-08-09 2019-02-14 The Procter & Gamble Company Aptamères pour compositions de soin buccal

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112012001716B1 (pt) * 2009-07-27 2017-06-20 Dow Global Technologies Llc Antimicrobial synergistic composition, and, method for inhibiting microbial growth in a medium.
TW201607894A (zh) * 2014-08-22 2016-03-01 穗曄實業股份有限公司 具有臭味淨化功能的水性溶液
CN107519026B (zh) * 2017-10-10 2020-08-04 广州立白企业集团有限公司 一种具有去渍及清新口气的牙粉及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5078988A (en) * 1988-11-28 1992-01-07 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Dentrifrices including modified aminoalkyl silicones

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1034782A (en) * 1962-01-24 1966-07-06 Union Carbide Corp Organosilicon compositions
US4950479A (en) * 1986-11-06 1990-08-21 Hill Ira D Method of interrupting the formation of plaque
US5078998A (en) * 1985-08-02 1992-01-07 Bevan Michael J Hybrid ligand directed to activation of cytotoxic effector T lymphocytes and target associated antigen
US5032387A (en) * 1986-11-06 1991-07-16 Princeton Pharmaceutical Inc. Dental and oral hygiene preparations
US5284648A (en) * 1989-03-17 1994-02-08 White Robert D Alcohol-free, oral rinse and pre-rinse emulsions method of prepration and method of use
US5162378A (en) * 1990-04-20 1992-11-10 Revlon Consumer Products Corporation Silicone containing water-in-oil microemulsions having increased salt content
FR2701845B1 (fr) * 1993-02-23 1995-04-07 Oreal Emulsion eau-dans-huile à usage cosmétique ou pharmaceutique.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5078988A (en) * 1988-11-28 1992-01-07 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Dentrifrices including modified aminoalkyl silicones

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts Service (C A S); 1 January 1994 (1994-01-01), PASTOUR V, POUGET F, FODOR P: "WATER IN OIL EMULSIONS FOR COSMETIC OR PHARMACEUTICAL USE", XP008054721, Database accession no. 212641B *
See also references of EP0793478A4 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294154B1 (en) 1994-12-22 2001-09-25 Procter And Gamble Company Oral compositions containing dimethicone copolyols
DE19646985A1 (de) * 1996-11-14 1998-06-04 Michael Dr Weichsel Geschmacksverbesserung bei Zahnregulierungsapparaten
WO1998031298A1 (fr) 1997-01-16 1998-07-23 The Procter & Gamble Company Procede pour le traitement des protheses dentaires
US7364761B2 (en) 1997-09-18 2008-04-29 Wm. Wrigley Jr. Company Chewing gum containing physiological cooling agents and method of preparing
KR100478211B1 (ko) * 1997-10-01 2005-08-11 애경산업(주) 미백치약조성물
US6648983B1 (en) * 1998-11-10 2003-11-18 The Procter & Gamble Company Process of cleaning enamel surfaces
US6685921B2 (en) 2000-10-25 2004-02-03 The Procter & Gamble Company Dental care compositions
WO2005058185A1 (fr) 2003-12-11 2005-06-30 Koninklijke Philips Electronics, N.V. Systeme de pompage pour une composition a administration par voie orale
US8287203B2 (en) 2003-12-11 2012-10-16 Koninklijke Philips Electronics N.V. Pumping system for an oral composition
AU2006265330B2 (en) * 2005-06-30 2012-11-01 Glaxo Group Limited Oral composition comprising dimethicone copolyol
WO2015065835A1 (fr) 2013-10-28 2015-05-07 The Procter & Gamble Company Ajout à une phase avancée de modificateur de rhéologie
WO2015065836A1 (fr) 2013-10-28 2015-05-07 The Procter & Gamble Company Procede de preparation d'une composition de soins personnels au moyen de modificateurs rheologiques compactes
WO2019032795A1 (fr) 2017-08-09 2019-02-14 The Procter & Gamble Company Aptamères pour compositions de soin buccal
WO2019032811A1 (fr) 2017-08-09 2019-02-14 The Procter & Gamble Company Aptamères pour compositions de produits de consommation

Also Published As

Publication number Publication date
CZ292313B6 (cs) 2003-09-17
MX9704721A (es) 1997-10-31
PL320866A1 (en) 1997-11-10
CZ188697A3 (en) 1997-11-12
TR199501645A3 (fr) 1996-07-21
CA2208364C (fr) 2001-11-06
BR9510307A (pt) 1997-11-11
CN1088578C (zh) 2002-08-07
EP0793478A4 (fr) 2005-10-12
JPH10511349A (ja) 1998-11-04
EP0793478A1 (fr) 1997-09-10
TR199501645A2 (tr) 1996-07-21
RU2163480C2 (ru) 2001-02-27
SK82897A3 (en) 1998-01-14
CN1170348A (zh) 1998-01-14
HU220794B1 (hu) 2002-05-28
CA2208364A1 (fr) 1996-06-27
KR100246832B1 (ko) 2000-04-01
AU4514096A (en) 1996-07-10
GB9425941D0 (en) 1995-02-22
HUT77713A (hu) 1998-07-28

Similar Documents

Publication Publication Date Title
US5827505A (en) Oral compositions
US6004538A (en) Oral compositions
CA2226160C (fr) Compositions a usage buccal
WO1996019193A1 (fr) Compositions a usage oral
CA2208364C (fr) Compositions d'hygiene buccale
US6193958B1 (en) Oral compositions
CA2208442C (fr) Compositions orales contenant des copolyalcools de dimethicone
US6294154B1 (en) Oral compositions containing dimethicone copolyols
EP0822806B1 (fr) Compositions orales
EP0793477A1 (fr) Compositions a usage oral
AU727373B2 (en) Oral compositions
AU4476499A (en) Oral compositions
MXPA97004721A (en) Ora compositions
MXPA97004663A (en) Ora compositions

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 95196900.5

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 300406

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: PV1997-1886

Country of ref document: CZ

ENP Entry into the national phase

Ref document number: 2208364

Country of ref document: CA

Ref document number: 2208364

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 82897

Country of ref document: SK

Ref document number: 1019970704212

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: PA/a/1997/004721

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1995943738

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1199700648

Country of ref document: VN

WWP Wipo information: published in national office

Ref document number: 1995943738

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 08860060

Country of ref document: US

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: PV1997-1886

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1019970704212

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1019970704212

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: PV1997-1886

Country of ref document: CZ

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载