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WO2006068011A1 - Tooth whitening composition and tooth whitening set - Google Patents

Tooth whitening composition and tooth whitening set Download PDF

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Publication number
WO2006068011A1
WO2006068011A1 PCT/JP2005/022918 JP2005022918W WO2006068011A1 WO 2006068011 A1 WO2006068011 A1 WO 2006068011A1 JP 2005022918 W JP2005022918 W JP 2005022918W WO 2006068011 A1 WO2006068011 A1 WO 2006068011A1
Authority
WO
WIPO (PCT)
Prior art keywords
tooth
composition
teeth
tooth whitening
sodium
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2005/022918
Other languages
French (fr)
Japanese (ja)
Inventor
Shimako Inoue
Akira Uchiyama
Ikuko Toki
Noriko Matsumoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lion Corp
Original Assignee
Lion Corp
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
Application filed by Lion Corp filed Critical Lion Corp
Priority to JP2006548869A priority Critical patent/JP4873155B2/en
Publication of WO2006068011A1 publication Critical patent/WO2006068011A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26Aluminium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/28Zirconium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29Titanium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/66Enzymes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426Polymers characterized by specific structures/properties characterized by the charge cationic

Definitions

  • the present invention relates to a tooth whitening composition and a tooth whitening set for making teeth whiter than the original color. More specifically, the present invention relates to a tooth whitening composition and a powder such as titanium dioxide applied or applied to a tooth. The present invention relates to a tooth whitening composition and a tooth whitening set which are fixed on the surface of a tooth for a certain period of time and make the teeth white by irregular reflection and exhibit a high whitening effect for a long time.
  • techniques for whitening teeth include (1) technology that removes coloring substances attached to the teeth and restores the whiteness of the original teeth, and (2) whitening the teeth even more than the original color.
  • technologies a physical removal method using a dentifrice or toothbrush and brushing with a polishing component contained in the dentifrice, a solubilizer such as polyethylene glycol or polyvinylpyrrolidone, an enzyme or a chelating agent Chemical methods such as decomposing colored materials are used, etc.
  • the method (2) is representative of bleaching using peroxides frequently used in Europe and the United States, and dental curing agents. Applying concealing agents or dental materials such as laminating wear have been used.
  • Such whitening techniques include shellac, vinyl acetate resin and acrylic resin coatings.
  • coating agents such as nail polish utilizing the forming ability (Japanese Patent Laid-Open No. 04-82821, Japanese Patent Laid-Open No. 05-58844, Japanese Patent Laid-Open No. 09-100215, Japanese Patent Laid-Open No. 09-20 2718, JP-A-09-151123), there was a problem with the rough feeling of use of the coating agent coated on the teeth.
  • the particle size of titanium oxide used in combination with a coating agent is preferably lOOnm or less (Japanese Patent Laid-Open No. 09-151123)
  • a titanium oxide tooth without a coating agent is disclosed. The adsorptive properties to water were not always sufficient.
  • the specific surface area of titanium oxide which is conventionally used as a pigment in dentifrices and the like, is 10 to
  • Japanese Patent Application Laid-Open No. 2003-183142 discloses a method for enhancing the adsorptivity to enamel by applying an activation treatment that increases the number of surface hydroxyl groups of a metal oxide, and a method for making the teeth whiter.
  • a composition is disclosed.
  • operability and safety because it is necessary to treat the metal oxide under high strength conditions as pretreatment.
  • an object of the present invention is a tooth whitening composition for making teeth whiter than the original color, and is applied or applied to the teeth, and a powder such as titanium dioxide is applied to the teeth for a certain period of time. Fixing to the surface, making the teeth white by diffuse reflection, and maintaining the powder on the tooth surface stably for a long time, greatly reducing color unevenness and peeling, and continuously exerting a high whitening effect It is to provide a tooth whitening composition and a tooth whitening set.
  • a whitening powder selected from titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, and dinoleconium oxide, a gel
  • pullulan as a chemical agent
  • a cationic polymer selected from lysozyme, cationic cellulose, and polylysine
  • the present invention provides:
  • a tooth whitening composition characterized by containing one or more selected from lysozyme, cationized cellulose, and polylysine.
  • the present invention provides a tooth whitening set comprising an application tool that is detachably attached to a tooth while holding the above-mentioned tooth whitening composition.
  • the applicable tool includes a tape, a sheet, a Finolem, a mouth tray, a mouthpiece, a sponge, an imprint material, a pack material, or a tooth cover molded into a dentition.
  • the metal oxide powder having excellent adsorptivity to teeth can diffusely reflect light on the tooth surface and appear whiter than the original color. It is possible to stably hold the powder on the tooth surface and continuously exert a high whitening effect.
  • Component (A) used in the tooth whitening composition of the present invention is a metal oxide selected from titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, and dinoleconium oxide, preferably dioxide dioxide. These are titanium, zinc oxide, aluminum oxide and zirconium oxide. One or more of these may be used, and a composite of these metal oxides may be used.
  • the metal oxide used in the present invention is not particularly limited in the presence or absence of surface treatment, but is preferably coated with silicon dioxide, alumina, or zirconium oxide for the purpose of suppressing the catalytic activity of the metal oxide. Used for.
  • the amount of the component (A) metal oxide used in the present invention is not particularly limited as long as a sufficient amount can be released from the tooth whitening composition to the tooth surface. 0.:! To 50% by mass, more preferably 0.5 to 20% by mass. When the blending amount is less than 0.1% by mass, a sufficient whitening effect cannot be obtained and exceeds 50% by mass. In some cases, depending on the application form to the tooth, the composition may be poorly usable.
  • the average particle diameter of the metal oxide used as the component (A) of the present invention is preferably 0.005 to 5 / im. Particularly preferred is 0.01-: l x m. If the average particle size is less than 0.005 zm, light cannot be sufficiently scattered, and the whitening effect may not be obtained. If the average particle size exceeds 5 x m, the whitening effect may not be sustained due to insufficient fixation to the teeth.
  • the average particle size is a value measured by a 50% particle size using a Microtrac particle size analyzer (Nikkiso Co., Ltd.).
  • the pullulan of component (B) used in the present invention is a high molecule in which maltotriose has 1-6 bonds, and has a weight average molecular weight of about 4 to 800,000. Of these, 100,000 to 500,000 are particularly preferred.
  • the weight average molecular weight of pullulan can be determined by gel permeation chromatography (GPC) using polyethylene oxide of known molecular weight as a standard substance and dimethylformamide with LiBr added as a solvent.
  • Punoreran is a polyacrylic acid or salt thereof, carboxyvinyl polymer, vinyl acetate, vinylpyrrolidone copolymer, cellulose derivatives such as sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinylpyrrolidone, polyvinyl alcohol, It can be used in combination with other water-soluble polymers such as xanthan gum, carrageenan, and alginate.
  • the blending amount of pullulan in the composition is preferably in the range of 0.:! To 20% by mass, particularly in the range of 0.3 to 15% by mass of the whole composition.
  • the weight average molecular weight of pullulan it is preferable to select the blending amount according to the molecular weight of pullulan, particularly 0.1 to 5% by weight is preferable when the weight average molecular weight is about 790,000, and more preferably 0.3 to 3% by weight. It is. In the case of a weight average molecular weight of about 400,000, 0 :! to 7% by mass is preferable, and more preferably 0.5 to 5% by mass. When the weight average molecular weight is about 200,000, 0.3 to 15% by mass is preferable, and more preferably 0.5 to 10% by mass. When the weight average molecular weight is about 47,000, 0.5 to 20% by mass is preferable, and 1 to 15% by mass is more preferable.
  • the preferred compounding amount for each weight average molecular weight is less than that, it is a metal oxide that reduces the adsorptivity and sustainability of the composition to the teeth even when combined with other water-soluble polymers. May not adhere to teeth for a long time.
  • the preferred blending amount in each weight average molecular weight In some cases, the viscosity of the product becomes high, and a sufficient amount of metal oxide cannot be adsorbed on the teeth.
  • the component (C) used in the present invention is one or more selected from lysozyme, cationized cellulose, and polylysine.
  • the lysozyme is preferably lysozyme chloride.
  • the amount of lysozyme is 0.1 to 10% by mass of the whole composition, and 0.5 to 5% by mass is more preferable.
  • the amount of lysozyme is less than 0.1% by mass, a metal oxide having a low adsorptivity and sustainability to the teeth may not be stably adsorbed on the teeth for a long time. If it exceeds 10% by mass, the bitterness unique to lysozyme becomes strong and the taste of the composition may deteriorate.
  • Cationized cellulose is composed of hydroxydimethylallyl ammonium chloride and
  • ⁇ 2-Hydroxy-1- (trimethylammonio) ⁇ propyl hydroxyethyl cellulose is preferably used.
  • a weight average molecular weight of about 300,000 to about 2 million is preferably used. If the weight average molecular weight is less than 300,000, the whitening effect may not be sustained due to insufficient fixation to the tooth, and if the weight average molecular weight is more than 2 million, the viscosity of the preparation increases and the operability is improved. It may be damaged.
  • the substitution degree of the cationic group is preferably 0.5 to 3% by mass as the nitrogen content.
  • the weight average molecular weight is a value determined by a gel permeation chromatograph (GPC) method using polyethylene glycol as a standard substance.
  • the nitrogen content is the value obtained by CHN organic element analysis.
  • Strength The blending amount of thiolated cellulose is preferably from 0.:! To 5% by mass of the whole composition, and more preferably from 0.5 to 3% by mass.
  • the compounding power of the cationized cellulose is less than 0.1% by mass, a metal oxide having a low adsorptivity and persistence to the tooth of the composition may not be stably adsorbed on the tooth for a long time.
  • the content exceeds 5% by mass, the viscosity of the composition becomes so high that a sufficient amount of metal oxide may not be adsorbed on the teeth.
  • polylysine polylysine alone, polylysine hydrochloride, polylysine hydride mouth bromide and the like can be used.
  • Polylysine having a number average molecular weight of 1,000 to 1,000,000 can be used, and 3,000 to 300,000 is particularly preferred. If the number average molecular weight is less than 100 0, the whitening effect may not be sustained due to insufficient fixation to the teeth. When the number average molecular weight force is greater than sioo million, the viscosity of the preparation increases, and the operability may be impaired.
  • the method for measuring the number average molecular weight is not particularly limited. For example, the number average molecular weight should be determined under the following conditions by the low-angle light scattering method (GPC-LALLS method) of gel permeation chromatography using polystyrene as a standard substance. Can do.
  • the blending amount of polylysine is preferably 0.01 to 20% by mass of the total composition, and more preferably 0.5 to 10% by mass.
  • the blending amount of polylysine is less than 0.01% by mass, a metal oxide having a low adsorptivity and persistence to the tooth may not be stably adsorbed on the tooth for a long time.
  • it exceeds 20% by mass the viscosity of the composition becomes high, and a sufficient amount of metal oxide may not be adsorbed on the teeth.
  • the tooth whitening composition of the present invention can further be applied to a tooth for a long time, and a gelling agent that prevents dissolution of the tooth whitening composition over the entire oral cavity according to its form. Can be blended.
  • the gelling agent used in the present invention is not particularly limited, but is polyacrylic acid or a salt thereof, a carboxyvinyl polymer, a vinyl acetate vinylpyrrolidone copolymer, carboxymethyl resorenolose sodium, hydroxye Cellulose derivatives such as chinorecenolose and hydroxypropenorescenellose, polyvinyl pyrrolidone, polybial alcohol, xanthan gum, carrageenan, and alginates are preferably used, and one or more selected from these are blended. obtain.
  • the blending amount of the gelling agent is preferably 0.1 to 10% by mass of the entire composition, and particularly preferably
  • the gelling agent may not be sufficiently dissolved, and the preparation may become non-uniform and may inhibit the preparation from adsorbing on the tooth surface.
  • the blending amount is less than 0.1% by mass, a feeling of strangeness such as stickiness in the mouth due to the dissolution of the gel may occur.
  • the tooth whitening composition of the present invention may further contain other components as necessary. You can.
  • anionic surfactants for the purpose of emulsification and dispersion, one or more of anionic surfactants, nonionic surfactants and zwitterionic surfactants can be used in combination.
  • anionic surfactants include sodium alkyl sulfates such as sodium lauryl sulfate, sodium myristyl sulfate and sodium cetyl sulfate, sodium N-acyl glutamate such as sodium N-lauroyl glutamate and sodium N-palmitoyl glutamate.
  • Nonionic surfactants include glycerin fatty acid esters such as monoglyceryl stearate and decaglyceryl laurate, sucrose fatty acid esters, maltose fatty acid esters, sugar fatty acid esters such as malatose fatty acid esters, maltitol fatty acid esters , Sugar alcohol fatty acid esters such as ratathitol fatty acid esters, polyoxyethylene polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, fatty acid ethanolamides such as myristic mono- or diethanolamide, sorbitan fatty acid esters , Polyoxyethylene higher alcohol ether, polyoxyethylene polyoxypropylene copolymer, polyoxyethylene polyoxypropylene fatty acid Ester, or the like is used.
  • glycerin fatty acid esters such as monoglyceryl stearate and decaglyceryl laurate
  • Zwitterionic surfactants include alkyl dimethylamino acetate betaines such as lauryl dimethylamino acetate betaine, ⁇ -lauryl diaminoethyl glycine, ⁇ ⁇ ⁇ ⁇ -alkyldiaminoethyl glycine such as ⁇ -myristyl diaminoethyl glycine, ⁇ - Alkinole ⁇ — Carboxymethylammonium betaine, 2-alkyl 1-hydroxyethylimidazoline sodium betaine, etc. are used.
  • alkyl dimethylamino acetate betaines such as lauryl dimethylamino acetate betaine, ⁇ -lauryl diaminoethyl glycine, ⁇ ⁇ ⁇ -alkyldiaminoethyl glycine such as ⁇ -myristyl diaminoethyl glycine, ⁇ - Alkinole
  • enzymes such as dextranase, mutanase, amylase, protease, superoxide dismutase, water-soluble polyphosphate such as potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate Salt, allantoin, dihydrocholestanol, glycyrrhizic acid, glycyrrhetinic acid, ⁇ -aminocaproic acid, tranexamic acid, bisabolol, isopropylmethylphenol, sodium chloride, trisan san, chlorhexidine salts, cetylpyridinium chloride, benzethonium chloride 1 or 2 or more of active ingredients such as herbal extracts such as benzalkcoumum chloride, ascorbic acid and its salts, tocopherol, ogon, obata, rosemary, chiioji, thyme, etc.
  • water-soluble polyphosphate such as potassium pyrophosphate, sodium tripolyphosphat
  • the composition for tooth whitening of the present invention further includes a fragrance such as vanitol, carvone, peppermint oil, and spearmint oil, a preservative such as benzoic acid and its sodium salt, parabens, red No. 3, red 104. No. 4, Yellow No. 4, Blue No. 1, Green No. 3, pigments or colorants such as titanium mica, petal, sweeteners such as saccharin and its sodium salt, stepioside, glycyrrhizin, aspartame and the like.
  • a fragrance such as vanitol, carvone, peppermint oil, and spearmint oil
  • a preservative such as benzoic acid and its sodium salt
  • parabens red No. 3, red 104. No. 4
  • Yellow No. 4 Blue No. 1, Green No. 3, pigments or colorants
  • titanium mica such as titanium mica, petal
  • sweeteners such as saccharin and its sodium salt
  • stepioside such as glycyrrhizin,
  • ⁇ of the tooth whitening composition is not particularly limited as long as it is within the range of safety in the oral cavity and the human body, but preferably the tooth whitening composition is diluted 10 times with purified water. ⁇ is 4 to 10 and more preferably ⁇ is 5.5 to 9. If it is less than ⁇ 4, there is a concern about decalcification depending on the application time. If it exceeds ⁇ , there is a concern about mucosal detachment when touching the gingiva.
  • acetic acid, hydrochloric acid, sulfuric acid, nitric acid, citrate, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium tamate, sodium hydrogen citrate, sodium phosphate, phosphoric acid Sodium hydrogen or the like can be combined.
  • the tooth whitening composition is prepared in a paste form, a gel form, a liquid form, or the like, and depending on the form, it should be applied together with an application tool dedicated to holding and fixing to a tooth.
  • the application tool for holding and fixing to the tooth used in combination with the tooth whitening composition of the present invention assists the reliable application and fixation of the tooth whitening composition to the tooth. Inhibiting elution of the tooth whitening composition in use on the gums, tongue and oral mucosa, preventing unpleasant use and preventing the induction of saliva, as well as intrusion, occlusion, chewing and other physical stimuli It is used for the purpose of preventing the dilution of the tooth whitening composition and the separation of the tooth force.
  • the material and shape of the tool are not particularly limited as long as the above object can be achieved, but tape, sheet, Finolem, mouth tray, mouthpiece, sponge, impression material made of water-insoluble raw material.
  • a tooth cover molded into a pack material or a dentition is preferably used.
  • the thickness of the above-mentioned application tool is preferably 0.01 to 5 mm, which does not give a sense of incongruity when worn on the oral cavity, and is particularly preferably 0.01 to 2 mm for tapes, sheets and films.
  • polyethylene, foamed polyethylene, polypropylene, foamed polypropylene, polyester, polyurethane which have excellent fit when applied to the oral cavity and enable the formulation to be applied for a long time by suppressing the generation of saliva. It is preferable to use one or more of rayon, pulp, cotton, silk, paper, polysaccharide film, metal foil, etc.
  • the poorly water-soluble Punoreran film is a film of Punoreran and is not included in the pullulan component (B).
  • the saliva produced in the mouth is made by forming the material on the side that contacts the oral mucosa and the tongue with a hydrophilic or highly absorbent material such as woven or non-woven fabric using rayon, pulp, cotton, silk, paper, etc. It is preferable because it absorbs and retains water and has excellent usability.
  • a water-impermeable film such as polyethylene, polypropylene, polyester, polyurethane, etc. on the side holding the tooth whitening composition, it is possible to prevent the tooth whitening composition from adsorbing and penetrating into the application tool. You can also.
  • trays or mouthpieces made of thermoplastic resins such as silicone rubber and natural rubber and thermoplastic resins such as butyl acetate resin, acrylic resin, and ethylene-butyl acetate copolymer have a high degree of freedom of deformation. It is easy to fit in the user's dentition and tooth type, and therefore has excellent adhesion and fixability, and is suitable for the purpose of applying a tooth whitening composition to a tooth for a longer time.
  • the number of times of application, time, etc. are appropriately selected, but usually 1 to 6 times a day, especially:! To 3 times, once:! To 10 minutes, especially:! To 3 minutes. .
  • the pressure was reduced to 4 kPa and mixed until the composition became uniform to prepare a tooth whitening composition.
  • the pH was measured with a pH meter (HM-26S, manufactured by Toa DKKEI Co., Ltd.) after 1 minute at 25 ° C when diluted 10 times with purified water, and adjusted to pH 5.5 to 9.0. As needed, it adjusted using sodium hydroxide or hydrochloric acid.
  • Heated polyethylene film low density polyethylene, thickness 10 zm, manufactured by Tosoh Corporation, product grade; 212
  • a three-layer nonwoven fabric sheet having a thickness of 0.5 mm was prepared by fusing.
  • a sheet coated with the composition shown in Table 1 by the above method is placed on the extracted human tooth whose color difference L * a * b * has been measured in advance, and left in a thermostat at 37 ° C for 3 minutes. Thereafter, the sheet was peeled off, the gel was gently wiped with a tissue, washed with water, and then transferred into artificial saliva. After immersion in artificial saliva for 3 hours, the color difference L * a * b * was measured to determine ⁇ . The color difference was measured with a spectrocolorimeter (Minolta Co., Ltd., CM_2022).
  • the composition of artificial saliva is as follows.
  • ⁇ * (2) ((L * 2-L * 0) 2 + (a * 2- -a O) + (b 2 ⁇ b 0))
  • L * 0, a * 0, b * 0 represent the initial L * a * b * values, and similarly L * l, a * l, b * l, L * 2, a * 2, b * 2 Are the L * aV value after whitening and the L * aV value after immersion in artificial saliva, respectively.
  • Whitening effect ⁇ : ⁇ * (1) is 7.0 or more
  • ⁇ : ⁇ * (1) is more than 5.0 and less than 7.0
  • ⁇ : ⁇ * (1) is 3.0 or more and less than 5.0
  • ⁇ * (2) is 6.0 or more ⁇ : ⁇ (2) is 4.0 or more and less than 6.0
  • ⁇ : ⁇ * (2) is 3.0 or more and less than 4.0
  • Foamed polyethylene sheet (Sekisui Chemical Co., Ltd. Borara XL_IF08008, 15 mm X 60 mm X) that covers the lips of the front teeth left 3 to right 3 with 2.g of tooth whitening composition 1.
  • a thickness of 800 zm was applied to the labial surface of the tooth.
  • Titanium dioxide 3.0% (Ishihara Sangyo Co., Ltd. Typeter CR-50, average particle size 0 ⁇ 25 ⁇ )
  • Pullulan (Hayashibara Corporation, PF-2, weight average molecular weight 200,000)
  • Polylysine (Chisso Corporation, polylysine powder, number average molecular weight 4400)
  • Titanium dioxide 4.0%
  • a polyethylene film (Toray Co., Ltd., soft PE, 10 mm x 15 mm x 25 ⁇ m thick) with one tooth each coated with 0.2 g of the following tooth whitening composition 3 in advance is colored. Affixed only to the teeth of interest.
  • the whitening effect was ⁇ , and the persistence of the whitening effect was ⁇ .
  • Zirconium oxide (Nippon Denko, N—PC, average particle size 0 ⁇ 02 / im) 0.5% Titanium dioxide 3.0
  • Example 14 Apply the following tooth whitening composition 4 with 1. Og brush to the left lip of the front teeth 3rd to 3rd right, and from the top polypropylene film (Toray Industries soft PP, 15mm X 60mm X thickness 100 zm) was affixed. When evaluated in the same manner as in the above Examples:! To 10 and Comparative Examples 1 to 4, the whitening effect was ⁇ , and the persistence of the whitening effect was ⁇ .
  • the mouthpiece made of ethylene butyl acetate resin was warmed and softened with hot water, and the mouthpiece fitted with each tooth shape was made by massaging.
  • the mouthpiece was filled with 1. Og of the following tooth whitening composition 5 and attached.
  • the whitening effect was ⁇ , and the persistence of the whitening effect was ⁇ .
  • Silicon dioxide 1.0% (Huber, trade name Zeodentl l 3, average particle size 5 ⁇ 0 / im)

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cosmetics (AREA)

Abstract

A tooth whitening composition characterized by containing: (A) one or two or more members selected from among titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide and zirconium oxide, (B) pullulan, and (C) one or two or more members selected from among lysozyme, cationized cellulose and polylysine. In the use of this composition, metal oxide powder excelling in adsorption onto the teeth performs diffuse reflection of light on the teeth surface to thereby cause the same to look whiter than the inherent color. In particular, such a high whitening effect can be persistently exerted by realizing stable retention of the powder on the teeth surface for a prolonged period of time.

Description

明 細 書  Specification

歯牙美白用組成物及び歯牙美白用セット  Tooth whitening composition and tooth whitening set

技術分野  Technical field

[0001] 本発明は、歯を元の色よりも白くみせるための歯牙美白用組成物及び歯牙美白用 セットに関し、更に詳述すると、歯牙に貼付又は塗布して、二酸化チタンなどの粉体 を一定時間歯の表面に固定し、乱反射によって歯を白く見せるものであって、高い白 色化効果を長時間持続的に発揮させる歯牙美白用組成物及び歯牙美白用セットに 関する。  [0001] The present invention relates to a tooth whitening composition and a tooth whitening set for making teeth whiter than the original color. More specifically, the present invention relates to a tooth whitening composition and a powder such as titanium dioxide applied or applied to a tooth. The present invention relates to a tooth whitening composition and a tooth whitening set which are fixed on the surface of a tooth for a certain period of time and make the teeth white by irregular reflection and exhibit a high whitening effect for a long time.

背景技術  Background art

[0002] 従来より、歯を白くするための技術は、(1)歯に付着した着色物質を取り除き、元の 歯の白さを取り戻す技術と、(2)歯を元の色より更に白くする技術に大別される。 (1) の方法としては、歯磨剤、歯ブラシを用い、歯磨剤に含まれる研磨成分でブラッシン グすることによる物理的な除去方法や、ポリエチレングリコール、ポリビニルピロリドン 等の可溶化剤、酵素、キレート剤等により着色物を分解する等の化学的な方法が用 レ、られ、(2)の方法としては、欧米で多用される過酸化物を使った漂白や、歯のマ二 キュア剤などに代表される隠蔽剤の塗布、あるいはラミネートべユア等の歯科材料が 使われてきた。  [0002] Conventionally, techniques for whitening teeth include (1) technology that removes coloring substances attached to the teeth and restores the whiteness of the original teeth, and (2) whitening the teeth even more than the original color. Broadly divided into technologies. As the method of (1), a physical removal method using a dentifrice or toothbrush and brushing with a polishing component contained in the dentifrice, a solubilizer such as polyethylene glycol or polyvinylpyrrolidone, an enzyme or a chelating agent Chemical methods such as decomposing colored materials are used, etc., and the method (2) is representative of bleaching using peroxides frequently used in Europe and the United States, and dental curing agents. Applying concealing agents or dental materials such as laminating wear have been used.

[0003] 近年、 口腔衛生意識と審美願望の向上を受けて、歯の美白に対するニーズは、 (1 )の「清掃」から(2)の「白色化」に移行しつつある。し力 ながら、過酸化物での漂白 は、歯肉の炎症、退縮のおそれがあり、専門知識のない消費者が勝手に使用するこ とは非常に危険である。一方、マニキュア等の塗布剤は、飲食等により剥離するため 持続性に欠ける。また、ラミネートべユアによる方法は、歯科医しか行うことができず、 し力、も健全な歯の表面を削る必要があり、患者が結果に対して不満足であっても、術 後元の歯に戻すことができない。  [0003] In recent years, with the improvement of oral hygiene awareness and desire for aesthetics, the need for whitening teeth is shifting from “cleaning” in (1) to “whitening” in (2). However, bleaching with peroxide can cause gingival irritation and regression, and it is extremely dangerous for consumers without expertise to use it without permission. On the other hand, nail polish and other coating agents are not sustainable because they are peeled off by eating and drinking. In addition, the laminating belay method can only be performed by a dentist, and it is necessary to sharpen the surface of the teeth with a sufficient force. Even if the patient is not satisfied with the results, the original tooth after surgery I can't go back to it.

[0004] 以上のことから、「白色化」の分野において、審美性が良ぐ且つ簡便で安全性が 高い、歯牙白色化技術の開発が望まれてきた。  In view of the above, in the field of “whitening”, it has been desired to develop a tooth whitening technique that has good aesthetics, is simple, and has high safety.

[0005] このような白色化技術として、シェラック、酢酸ビニル樹脂やアクリル系樹脂の被膜 形成能を活用したマニキュア等の塗布剤が提案されているが(特開平 04— 82821 号公報、特開平 05— 58844号公報、特開平 09— 100215号公報、特開平 09— 20 2718号公報、特開平 09— 151123号公報)、歯にコーティングされた被膜剤のザラ ザラした使用感に課題があった。また、被膜剤と併用して用レ、られる酸化チタンの粒 径は lOOnm以下が好ましいことが開示されているが(特開平 09— 151123号公報) 、被膜剤を併用しない場合の酸化チタンの歯牙への吸着性は必ずしも十分とは言え なかった。 [0005] Such whitening techniques include shellac, vinyl acetate resin and acrylic resin coatings. There have been proposed coating agents such as nail polish utilizing the forming ability (Japanese Patent Laid-Open No. 04-82821, Japanese Patent Laid-Open No. 05-58844, Japanese Patent Laid-Open No. 09-100215, Japanese Patent Laid-Open No. 09-20 2718, JP-A-09-151123), there was a problem with the rough feeling of use of the coating agent coated on the teeth. Further, although it has been disclosed that the particle size of titanium oxide used in combination with a coating agent is preferably lOOnm or less (Japanese Patent Laid-Open No. 09-151123), a titanium oxide tooth without a coating agent is disclosed. The adsorptive properties to water were not always sufficient.

[0006] 従来より歯磨剤等で一般的に顔料として用いられる酸化チタンの比表面積は 10〜  [0006] The specific surface area of titanium oxide, which is conventionally used as a pigment in dentifrices and the like, is 10 to

20m2Zgであるが、この範囲の比表面積を有する金属酸化物を被膜剤のような支持 体なしで歯牙に適用しても、歯牙への吸着性が低ぐ十分な白色化効果を発揮する ことができなかった。 Even if a metal oxide with a specific surface area in this range is 20m 2 Zg and applied to a tooth without a support such as a coating agent, it exhibits a sufficient whitening effect with low adsorptivity to the tooth. I couldn't.

[0007] 一方、特開 2003— 183142号公報には、金属酸化物の表面水酸基数を増加させ る活性化処理を施すことで、エナメル質への吸着性を高めて歯を白く見せる方法及 びその組成物が開示されている。し力しながら、前処理として金属酸化物を高アル力 リ条件で処理する必要があるため、操作性、安全性に課題があった。  [0007] On the other hand, Japanese Patent Application Laid-Open No. 2003-183142 discloses a method for enhancing the adsorptivity to enamel by applying an activation treatment that increases the number of surface hydroxyl groups of a metal oxide, and a method for making the teeth whiter. A composition is disclosed. However, there is a problem in operability and safety because it is necessary to treat the metal oxide under high strength conditions as pretreatment.

発明の開示  Disclosure of the invention

発明が解決しょうとする課題  Problems to be solved by the invention

[0008] 従って、本発明の目的は、歯を元の色よりも白くみせるための歯牙美白用組成物で あって、歯牙に貼付又は塗布して、二酸化チタンなどの粉体を一定時間歯の表面に 固定し、乱反射によって歯を白く見せ、且つ、長時間安定して粉体を歯面に保持す ることで色ムラや剥がれを大幅に低減して、高い白色化効果を持続的に発揮させる 歯牙美白用組成物及び歯牙美白用セットを提供することである。  [0008] Therefore, an object of the present invention is a tooth whitening composition for making teeth whiter than the original color, and is applied or applied to the teeth, and a powder such as titanium dioxide is applied to the teeth for a certain period of time. Fixing to the surface, making the teeth white by diffuse reflection, and maintaining the powder on the tooth surface stably for a long time, greatly reducing color unevenness and peeling, and continuously exerting a high whitening effect It is to provide a tooth whitening composition and a tooth whitening set.

課題を解決するための手段  Means for solving the problem

[0009] 本発明者らは上記課題を解決するために鋭意検討を重ねた結果、二酸化チタン、 二酸化ケイ素、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化ジノレコニゥムか ら選ばれる白色化粉体と、ゲル化剤としてのプルランと、リゾチーム、カチオンィヒセル ロース、ポリリジンから選ばれるカチオン性高分子を組み合わせることで、白色化粉 体を歯面に長時間安定して固定し、色ムラや剥がれを大幅に低減して、高い白色化 効果の持続性を与えることを見出し、本発明をなすに至った。 [0009] As a result of intensive studies to solve the above problems, the present inventors have found that a whitening powder selected from titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, and dinoleconium oxide, a gel By combining pullulan as a chemical agent with a cationic polymer selected from lysozyme, cationic cellulose, and polylysine, the whitening powder is stably fixed to the tooth surface for a long time, and color unevenness and peeling are greatly reduced. High whitening It has been found that the effect is sustained, and the present invention has been made.

[0010] 従って、本発明は、  [0010] Therefore, the present invention provides:

(A)二酸化チタン、二酸化ケイ素、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、 酸化ジノレコニゥムから選ばれる 1種又は 2種以上、  (A) one or more selected from titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, dinoleconium oxide,

(B)プルラン、  (B) Pullulan,

(C)リゾチーム、カチオン化セルロース、ポリリジンから選ばれる 1種又は 2種以上 を含有することを特徴とする歯牙美白用組成物を提供する。  (C) A tooth whitening composition characterized by containing one or more selected from lysozyme, cationized cellulose, and polylysine.

[0011] また、本発明は上記歯牙美白用組成物を保持した状態で、歯に着脱可能に装着さ れる適用用具とを備えたことを特徴とする歯牙美白用セットを提供する。この場合、適 用用具としては、テープ、シート、フイノレム、マウストレー、マウスピース、スポンジ、印 象材、パック材、又は歯列に成型した歯のカバーが挙げられる。  [0011] Further, the present invention provides a tooth whitening set comprising an application tool that is detachably attached to a tooth while holding the above-mentioned tooth whitening composition. In this case, the applicable tool includes a tape, a sheet, a Finolem, a mouth tray, a mouthpiece, a sponge, an imprint material, a pack material, or a tooth cover molded into a dentition.

発明の効果  The invention's effect

[0012] 本発明によれば、歯牙への吸着性に優れた金属酸化物粉体が歯の表面で光を乱 反射して本来の色よりも白く見せることができ、この場合、特に長時間安定して該粉 体を歯面に保持し、高い白色化効果を持続的に発揮させることができる。  [0012] According to the present invention, the metal oxide powder having excellent adsorptivity to teeth can diffusely reflect light on the tooth surface and appear whiter than the original color. It is possible to stably hold the powder on the tooth surface and continuously exert a high whitening effect.

発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION

[0013] 本発明の歯牙美白用組成物に用いられる (A)成分は、二酸化チタン、二酸化ケィ 素、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化ジノレコニゥムから選ばれる 金属酸化物であり、好ましくは二酸化チタン、酸化亜鉛、酸化アルミニウム、酸化ジル コニゥムであり、これらの 1種又は 2種以上が用いられ、これら金属酸化物の複合物で あってもよい。 [0013] Component (A) used in the tooth whitening composition of the present invention is a metal oxide selected from titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, and dinoleconium oxide, preferably dioxide dioxide. These are titanium, zinc oxide, aluminum oxide and zirconium oxide. One or more of these may be used, and a composite of these metal oxides may be used.

[0014] 本発明に用いられる金属酸化物は、表面処理の有無は特に制限されなレ、が、金属 酸化物の触媒活性を抑制する目的で二酸化ケイ素、アルミナ、酸化ジルコニウムで 被覆したものも好適に用いられる。  [0014] The metal oxide used in the present invention is not particularly limited in the presence or absence of surface treatment, but is preferably coated with silicon dioxide, alumina, or zirconium oxide for the purpose of suppressing the catalytic activity of the metal oxide. Used for.

[0015] 本発明に用いられる (A)成分の金属酸化物の配合量は、歯牙美白用組成物から 歯の表面に十分な量放出することができれば特に制限されないが、好ましくは組成 物全体の 0.:!〜 50質量%、更に好ましくは 0. 5〜20質量%である。配合量が 0. 1 質量%未満の場合には、十分な白色化効果を得ることができず、 50質量%を超える 場合には、歯牙への適用形態によっては使用性の悪い組成物になってしまう場合が ある。 [0015] The amount of the component (A) metal oxide used in the present invention is not particularly limited as long as a sufficient amount can be released from the tooth whitening composition to the tooth surface. 0.:! To 50% by mass, more preferably 0.5 to 20% by mass. When the blending amount is less than 0.1% by mass, a sufficient whitening effect cannot be obtained and exceeds 50% by mass. In some cases, depending on the application form to the tooth, the composition may be poorly usable.

[0016] 本発明の(A)成分として用いられる金属酸化物の平均粒子径は、 0. 005〜5 /i m が好ましい。特に好ましくは 0. 01〜: l x mである。平均粒子径が 0. 005 z m未満の 場合には十分に光を散乱することができず、白色化効果が得られない場合がある。 平均粒子径が 5 x mを超える場合には、歯牙への固定性が十分でなぐ白色化効果 が持続しないことがある。なお、本発明において、平均粒子径はマイクロトラック粒度 分析計(日機装 (株) )による 50%粒径の測定値である。  [0016] The average particle diameter of the metal oxide used as the component (A) of the present invention is preferably 0.005 to 5 / im. Particularly preferred is 0.01-: l x m. If the average particle size is less than 0.005 zm, light cannot be sufficiently scattered, and the whitening effect may not be obtained. If the average particle size exceeds 5 x m, the whitening effect may not be sustained due to insufficient fixation to the teeth. In the present invention, the average particle size is a value measured by a 50% particle size using a Microtrac particle size analyzer (Nikkiso Co., Ltd.).

[0017] 本発明に用いられる(B)成分のプルランは、マルトトリオースがひ 1—6結合した高 分子であり、重量平均分子量約 4〜80万のものが挙げられる。なかでも特に 10〜50 万のものが好適に使用される。なお、プルランの重量平均分子量は既知分子量のポ リエチレンオキサイドを標準物質とし、 LiBrを添カ卩したジメチルホルムアミドを溶媒とし た、ゲルパーミエーシヨンクロマトグラフ(GPC)法により求められる。プノレランは、ポリ アクリル酸又はその塩、カルボキシビ二ルポリマー、酢酸ビエル.ビエルピロリドン共重 合体、カルボキシメチルセルロースナトリウム、ヒドロキシェチルセルロース、ヒドロキシ プロピルセルロース等のセルロース誘導体、ポリビエルピロリドン、ポリビエルアルコー ノレ、キサンタンガム、カラギーナン、アルギン酸塩などの他の水溶性高分子と組み合 わせて使用できる。プルランの組成物中の配合量は、組成物全体の 0.:!〜 20質量 %の範囲、特に 0. 3〜: 15質量%の範囲が好ましい。この場合、プルランの分子量に 応じて配合量を選定することが好ましぐ特に、重量平均分子量約 79万の場合 0. 1 〜5質量%が好ましぐ更に好ましくは 0. 3〜3質量%である。重量平均分子量約 40 万の場合 0.:!〜 7質量%が好ましぐ更に好ましくは 0. 5〜5質量%である。重量平 均分子量約 20万の場合 0. 3〜: 15質量%が好ましぐ更に好ましくは 0. 5〜: 10質量 %である。重量平均分子量約 4. 7万の場合 0. 5〜20質量%が好ましぐ更に好まし くは 1〜: 15質量%である。プノレランの配合量力 各重量平均分子量における好まし い配合量に満たない場合には、他の水溶性高分子と組み合わせても、組成物の歯 牙への吸着性と持続性が低ぐ金属酸化物が歯に長時間安定して吸着できない場 合がある。また各重量平均分子量における好ましい配合量を超える場合には、組成 物の粘度が高くなり、十分な量の金属酸化物が歯に吸着できない場合がある。 [0017] The pullulan of component (B) used in the present invention is a high molecule in which maltotriose has 1-6 bonds, and has a weight average molecular weight of about 4 to 800,000. Of these, 100,000 to 500,000 are particularly preferred. The weight average molecular weight of pullulan can be determined by gel permeation chromatography (GPC) using polyethylene oxide of known molecular weight as a standard substance and dimethylformamide with LiBr added as a solvent. Punoreran is a polyacrylic acid or salt thereof, carboxyvinyl polymer, vinyl acetate, vinylpyrrolidone copolymer, cellulose derivatives such as sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinylpyrrolidone, polyvinyl alcohol, It can be used in combination with other water-soluble polymers such as xanthan gum, carrageenan, and alginate. The blending amount of pullulan in the composition is preferably in the range of 0.:! To 20% by mass, particularly in the range of 0.3 to 15% by mass of the whole composition. In this case, it is preferable to select the blending amount according to the molecular weight of pullulan, particularly 0.1 to 5% by weight is preferable when the weight average molecular weight is about 790,000, and more preferably 0.3 to 3% by weight. It is. In the case of a weight average molecular weight of about 400,000, 0 :! to 7% by mass is preferable, and more preferably 0.5 to 5% by mass. When the weight average molecular weight is about 200,000, 0.3 to 15% by mass is preferable, and more preferably 0.5 to 10% by mass. When the weight average molecular weight is about 47,000, 0.5 to 20% by mass is preferable, and 1 to 15% by mass is more preferable. Formulation power of Punoreran If the preferred compounding amount for each weight average molecular weight is less than that, it is a metal oxide that reduces the adsorptivity and sustainability of the composition to the teeth even when combined with other water-soluble polymers. May not adhere to teeth for a long time. In addition, when exceeding the preferred blending amount in each weight average molecular weight, In some cases, the viscosity of the product becomes high, and a sufficient amount of metal oxide cannot be adsorbed on the teeth.

[0018] 本発明に用いられる(C)成分は、リゾチーム、カチオン化セルロース、ポリリジンから 選ばれる 1種又は 2種以上である。  [0018] The component (C) used in the present invention is one or more selected from lysozyme, cationized cellulose, and polylysine.

[0019] リゾチームは塩化リゾチームが好適に用いられる。リゾチームの配合量は、組成物 全体の 0. 1〜: 10質量%が好ましぐ 0. 5〜5質量%が更に好ましレ、。リゾチームの配 合量が、 0. 1質量%未満の場合には、組成物の歯牙への吸着性と持続性が低ぐ金 属酸化物が歯に長時間安定して吸着できない場合がある。また 10質量%を超える 場合には、リゾチーム独特の苦味が強くなり、組成物の味が悪くなる場合がある。  [0019] The lysozyme is preferably lysozyme chloride. The amount of lysozyme is 0.1 to 10% by mass of the whole composition, and 0.5 to 5% by mass is more preferable. When the amount of lysozyme is less than 0.1% by mass, a metal oxide having a low adsorptivity and sustainability to the teeth may not be stably adsorbed on the teeth for a long time. If it exceeds 10% by mass, the bitterness unique to lysozyme becomes strong and the taste of the composition may deteriorate.

[0020] カチオン化セルロースはヒドロキシジメチルァリルアンモニゥムクロライドや塩化〇_  [0020] Cationized cellulose is composed of hydroxydimethylallyl ammonium chloride and

{ 2—ヒドロキシ一 3— (トリメチルアンモニォ) }プロピルヒドロキシェチルセルロースが 好適に用いられる。重量平均分子量は約 30万〜約 200万のものが好適に用いられ る。重量平均分子量が 30万より小さい場合、歯牙への固定性が十分でなぐ白色化 効果が持続しないことがあり、重量平均分子量が 200万より大きい場合は製剤の粘 度が高くなり、操作性が損なわれる場合がある。カチオン基の置換度は、窒素分とし て 0. 5〜3質量%が好適に用いられる。窒素分が 0. 5質量%未満の場合、歯牙への 固定性が十分でなぐ白色化効果が持続しないことがあり、窒素分が 3質量%を超え る場合は味が悪くなり、使用感が低下する場合がある。なお、重量平均分子量はポリ エチレングリコールを標準物質としたゲルパーミエーシヨンクロマトグラフ(GPC)法に より求めた値である。また、窒素分は CHN有機元素分析によって求めた値である。力 チオン化セルロースの配合量は、組成物全体の 0.:!〜 5質量%が好ましぐ 0. 5〜3 質量%が更に好ましい。カチオン化セルロースの配合量力 0. 1質量%未満の場合 には、組成物の歯牙への吸着性と持続性が低ぐ金属酸化物が歯に長時間安定し て吸着できない場合がある。また 5質量%を超える場合には、組成物の粘度が高くな り、十分な量の金属酸化物が歯に吸着できない場合がある。  {2-Hydroxy-1- (trimethylammonio)} propyl hydroxyethyl cellulose is preferably used. A weight average molecular weight of about 300,000 to about 2 million is preferably used. If the weight average molecular weight is less than 300,000, the whitening effect may not be sustained due to insufficient fixation to the tooth, and if the weight average molecular weight is more than 2 million, the viscosity of the preparation increases and the operability is improved. It may be damaged. The substitution degree of the cationic group is preferably 0.5 to 3% by mass as the nitrogen content. If the nitrogen content is less than 0.5% by mass, the whitening effect may not be sustained due to insufficient fixation to the teeth, and if the nitrogen content exceeds 3% by mass, the taste will deteriorate and the feeling of use will be reduced. May decrease. The weight average molecular weight is a value determined by a gel permeation chromatograph (GPC) method using polyethylene glycol as a standard substance. The nitrogen content is the value obtained by CHN organic element analysis. Strength The blending amount of thiolated cellulose is preferably from 0.:! To 5% by mass of the whole composition, and more preferably from 0.5 to 3% by mass. When the compounding power of the cationized cellulose is less than 0.1% by mass, a metal oxide having a low adsorptivity and persistence to the tooth of the composition may not be stably adsorbed on the tooth for a long time. On the other hand, when the content exceeds 5% by mass, the viscosity of the composition becomes so high that a sufficient amount of metal oxide may not be adsorbed on the teeth.

[0021] ポリリジンは、ポリリジン単独やポリリジン塩酸塩、ポリリジンハイド口ブロマイドなどの 塩を使用することができる。ポリリジンの数平均分子量は、 1000〜: 100万のものを用 レ、ることができ、特に 3000〜30万のものが好適に使用される。数平均分子量が 100 0より小さい場合、歯牙への固定性が十分でなぐ白色化効果が持続しないことがあ り、数平均分子量力 sioo万より大きい場合は製剤の粘度が高くなり、操作性が損なわ れる場合がある。なお、数平均分子量の測定法は特に限定されるものではないが、 例えばポリスチレンを標準物質としたゲルパーミエーシヨンクロマトグラフの低角度光 散乱法 (GPC— LALLS法)により以下の条件で求めることができる。 [0021] As polylysine, polylysine alone, polylysine hydrochloride, polylysine hydride mouth bromide and the like can be used. Polylysine having a number average molecular weight of 1,000 to 1,000,000 can be used, and 3,000 to 300,000 is particularly preferred. If the number average molecular weight is less than 100 0, the whitening effect may not be sustained due to insufficient fixation to the teeth. When the number average molecular weight force is greater than sioo million, the viscosity of the preparation increases, and the operability may be impaired. The method for measuring the number average molecular weight is not particularly limited. For example, the number average molecular weight should be determined under the following conditions by the low-angle light scattering method (GPC-LALLS method) of gel permeation chromatography using polystyrene as a standard substance. Can do.

カラム : Tosoh Biosep G5000 PW , 7. 8mm X 30cm  Column: Tosoh Biosep G5000 PW, 7.8mm X 30cm

XL  XL

移動層 :0. ImolZL リン酸ナトリウムバッファー(pH7. 0)  Moving bed: 0. ImolZL sodium phosphate buffer (pH 7.0)

流 量 :0. 5mL/min  Flow rate: 0.5mL / min

カラム温度: 40°C  Column temperature: 40 ° C

[0022] また、ポリリジンの配合量は組成物全体の 0. 01〜20質量%が好ましぐ 0. 5〜10 質量%が更に好ましい。ポリリジンの配合量が、 0. 01質量%未満の場合には、組成 物の歯牙への吸着性と持続性が低ぐ金属酸化物が歯に長時間安定して吸着でき ない場合がある。また 20質量%を超える場合には、組成物の粘度が高くなり、十分な 量の金属酸化物が歯に吸着できなレ、場合がある。  [0022] The blending amount of polylysine is preferably 0.01 to 20% by mass of the total composition, and more preferably 0.5 to 10% by mass. When the blending amount of polylysine is less than 0.01% by mass, a metal oxide having a low adsorptivity and persistence to the tooth may not be stably adsorbed on the tooth for a long time. On the other hand, if it exceeds 20% by mass, the viscosity of the composition becomes high, and a sufficient amount of metal oxide may not be adsorbed on the teeth.

[0023] 本発明の歯牙美白用組成物は、上記成分に加え、更に歯牙に長時間適用でき、 且つ歯牙美白用組成物の口腔全体への溶け出しを防ぐゲル化剤をその形態に応じ て配合することができる。  [0023] In addition to the above components, the tooth whitening composition of the present invention can further be applied to a tooth for a long time, and a gelling agent that prevents dissolution of the tooth whitening composition over the entire oral cavity according to its form. Can be blended.

[0024] 本発明に用いられるゲル化剤は特に制限されなレ、が、ポリアクリル酸又はその塩、 カルボキシビ二ルポリマー、酢酸ビニル'ビニルピロリドン共重合体、カルボキシメチ ノレセノレロースナトリウム、ヒドロキシェチノレセノレロース、ヒドロキシプロピノレセノレロース 等のセルロース誘導体、ポリビエルピロリドン、ポリビエルアルコール、キサンタンガム 、カラギーナン、アルギン酸塩が好適に用いられ、これらの中から選ばれる 1種又は 2 種以上を配合し得る。  [0024] The gelling agent used in the present invention is not particularly limited, but is polyacrylic acid or a salt thereof, a carboxyvinyl polymer, a vinyl acetate vinylpyrrolidone copolymer, carboxymethyl resorenolose sodium, hydroxye Cellulose derivatives such as chinorecenolose and hydroxypropenorescenellose, polyvinyl pyrrolidone, polybial alcohol, xanthan gum, carrageenan, and alginates are preferably used, and one or more selected from these are blended. obtain.

[0025] 上記ゲル化剤の配合量は、組成物全体の 0. 1〜: 10質量%が好適であり、特に 0.  [0025] The blending amount of the gelling agent is preferably 0.1 to 10% by mass of the entire composition, and particularly preferably

5〜5質量%が望ましい。配合量が 10質量%を超えるとゲル化剤が十分に溶けきら ず、製剤が不均一になるだけでなぐ製剤の歯面への吸着を阻害する場合がある。 配合量が 0. 1質量%未満の場合は、ゲルの溶け出しによる口中の粘つき等の違和 感が生じる場合がある。  5-5 mass% is desirable. If the compounding amount exceeds 10% by mass, the gelling agent may not be sufficiently dissolved, and the preparation may become non-uniform and may inhibit the preparation from adsorbing on the tooth surface. When the blending amount is less than 0.1% by mass, a feeling of strangeness such as stickiness in the mouth due to the dissolution of the gel may occur.

[0026] 本発明の歯牙美白用組成物には、更に必要に応じて適宜、他の成分を配合するこ とができる。 [0026] The tooth whitening composition of the present invention may further contain other components as necessary. You can.

例えば、乳化、分散などの目的で、界面活性剤として、ァニオン性界面活性剤、ノ 二オン性界面活性剤や両性イオン界面活性剤の 1種又は 2種以上を併用することが できる。  For example, for the purpose of emulsification and dispersion, one or more of anionic surfactants, nonionic surfactants and zwitterionic surfactants can be used in combination.

この場合、ァニオン性界面活性剤としては、ラウリル硫酸ナトリウム、ミリスチル硫酸 ナトリウム、セチル硫酸ナトリウムなどのアルキル硫酸ナトリウム、 N—ラウロイルグルタ ミン酸ナトリウム、 N—パルミトイルグルタミン酸ナトリウムなどの N—ァシルグルタミン 酸ナトリウム、 N—ラウロイルサルコシンナトリウム、 N—ミリストイルサルコシンナトリウ ムなどの N—ァシルサルコシンナトリウム、 N—ラウロイルメチルタウリンナトリウム、 N —ミリストイルメチルタウリンナトリウムなどの N—メチル _N_ァシルタウリンナトリウム 、 N—メチル一N—ァシルァラニンナトリウム、ラウリルベンゼンスルホン酸ナトリウム、 水素添加ココナツ脂肪酸モノグリセリドモノ硫酸ナトリウム、ラウリルスルホ酢酸ナトリウ ム、 α—ォレフインスルホン酸ナトリウム、ラウリル ΡΟΕ硫酸ナトリウム、ラウリノレ ΡΟΕ 酢酸ナトリウム、ラウリル ΡΟΕリン酸ナトリウム、ステアリル ΡΟΕリン酸ナトリウム等が用 いられる。  In this case, anionic surfactants include sodium alkyl sulfates such as sodium lauryl sulfate, sodium myristyl sulfate and sodium cetyl sulfate, sodium N-acyl glutamate such as sodium N-lauroyl glutamate and sodium N-palmitoyl glutamate. N-lauroyl sarcosine sodium, N-mysyl sarcosine sodium N-acyl sarcosine sodium, N-lauroyl methyl taurine sodium, N-myristoyl methyl taurine sodium N-methyl _N_acyl taurine sodium, N-methyl Mono N-acylalanine sodium, sodium lauryl benzene sulfonate, hydrogenated coconut fatty acid monoglyceride sodium monosulfate, sodium lauryl sulfoacetate, α-olefin Sodium sulfonate, sodium lauryl ΡΟΕ sulfate, Raurinore ΡΟΕ sodium acetate, sodium lauryl ΡΟΕ phosphate, stearyl ΡΟΕ sodium phosphate and the like are needed use.

[0027] ノニオン性界面活性剤としては、ステアリン酸モノグリセリル、ラウリン酸デカグリセリ ルなどのグリセリン脂肪酸エステル、ショ糖脂肪酸エステル、マルトース脂肪酸エステ ノレ、ラタトース脂肪酸エステルなどの糖脂肪酸エステル、マルチトール脂肪酸エステ ノレ、ラタチトール脂肪酸エステルなどの糖アルコール脂肪酸エステル、ポリオキシェ ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油等の ポリオキシエチレン脂肪酸エステル、ミリスチン酸モノ又はジエタノールアミドなどの脂 肪酸エタノールアミド、ソルビタン脂肪酸エステル、ポリオキシエチレン高級アルコー ノレエーテル、ポリオキシエチレンポリオキシプロピレン共重合体、ポリオキシエチレン ポリオキシプロピレン脂肪酸エステル等が用いられる。  [0027] Nonionic surfactants include glycerin fatty acid esters such as monoglyceryl stearate and decaglyceryl laurate, sucrose fatty acid esters, maltose fatty acid esters, sugar fatty acid esters such as malatose fatty acid esters, maltitol fatty acid esters , Sugar alcohol fatty acid esters such as ratathitol fatty acid esters, polyoxyethylene polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, fatty acid ethanolamides such as myristic mono- or diethanolamide, sorbitan fatty acid esters , Polyoxyethylene higher alcohol ether, polyoxyethylene polyoxypropylene copolymer, polyoxyethylene polyoxypropylene fatty acid Ester, or the like is used.

[0028] 両性イオン界面活性剤としては、ラウリルジメチルァミノ酢酸べタインなどのアルキ ルジメチルァミノ酢酸べタイン、 Ν—ラウリルジアミノエチルグリシン、 Ν—ミリスチルジ アミノエチルグリシンなどの Ν—アルキルジアミノエチルグリシン、 Ν—アルキノレ一 Ν— カルボキシメチルアンモニゥムベタイン、 2—アルキル 1ーヒドロキシェチルイミダゾ リンべタインナトリウム等が用いられる。 [0028] Zwitterionic surfactants include alkyl dimethylamino acetate betaines such as lauryl dimethylamino acetate betaine, Ν-lauryl diaminoethyl glycine, ア ル キ ル -alkyldiaminoethyl glycine such as Ν-myristyl diaminoethyl glycine, Ν- Alkinole Ν— Carboxymethylammonium betaine, 2-alkyl 1-hydroxyethylimidazoline sodium betaine, etc. are used.

[0029] 更に、本発明においては、有効成分として、デキストラナーゼ、ムタナーゼ、アミラー ゼ、プロテアーゼ、スーパーオキサイドデイスムターゼなどの酵素、ピロリン酸カリウム 、トリポリリン酸ナトリウム、メタリン酸ナトリウムなどの水溶性ポリリン酸塩、アラントイン、 ジヒドロコレスタノール、グリチルリチン酸類、グリチルレチン酸、 ε—アミノカプロン酸 、トラネキサム酸、ビサボロール、イソプロピルメチルフエノール、塩化ナトリウム、トリク 口サン、クロルへキシジン塩類、塩化セチルピリジニゥム、塩化べンゼトニゥム、塩化 ベンザルコユウム、ァスコルビン酸及びその塩類、トコフエロール、ォゥゴン、ォォバタ 、ローズマリー、チヨウジ、タイムなどの生薬抽出物等の有効成分の 1種又は 2種以上 を配合し得る。 [0029] Further, in the present invention, as an active ingredient, enzymes such as dextranase, mutanase, amylase, protease, superoxide dismutase, water-soluble polyphosphate such as potassium pyrophosphate, sodium tripolyphosphate, sodium metaphosphate Salt, allantoin, dihydrocholestanol, glycyrrhizic acid, glycyrrhetinic acid, ε-aminocaproic acid, tranexamic acid, bisabolol, isopropylmethylphenol, sodium chloride, trisan san, chlorhexidine salts, cetylpyridinium chloride, benzethonium chloride 1 or 2 or more of active ingredients such as herbal extracts such as benzalkcoumum chloride, ascorbic acid and its salts, tocopherol, ogon, obata, rosemary, chiioji, thyme, etc. The

[0030] 本発明の歯牙美白用組成物には、更に、ァネトール、カルボン、ペパーミント油、ス ペアミント油などの香料、安息香酸及びそのナトリウム塩、パラベン類などの防腐剤、 赤色 3号、赤色 104号、黄色 4号、青色 1号、緑色 3号、雲母チタン、弁柄などの色素 又は着色剤、サッカリン及びそのナトリウム塩、ステピオサイド、グリチルリチン、ァスパ ルテームなどの甘味剤等を配合し得る。  [0030] The composition for tooth whitening of the present invention further includes a fragrance such as vanitol, carvone, peppermint oil, and spearmint oil, a preservative such as benzoic acid and its sodium salt, parabens, red No. 3, red 104. No. 4, Yellow No. 4, Blue No. 1, Green No. 3, pigments or colorants such as titanium mica, petal, sweeteners such as saccharin and its sodium salt, stepioside, glycyrrhizin, aspartame and the like.

[0031] 歯牙美白用組成物の ρΗは、 口腔内及び人体に安全性上問題ない範囲であれば、 特に限定されるものではないが、望ましくは歯牙美白用組成物を精製水で 10倍希釈 した時の ρΗが 4〜: 10であり、更に望ましくは ρΗが 5. 5〜9である。 ρΗ4未満の場合 には適用時間によっては脱灰の懸念があり、 ρΗΙΟを超える場合には、歯肉に触れ た場合、粘膜剥離等の懸念がある。 pH調整剤として、酢酸、塩酸、硫酸、硝酸、クェ ン酸、リン酸、水酸化ナトリウム、水酸化カリウム、酢酸ナトリウム、炭酸ナトリウム、タエ ン酸ナトリウム、クェン酸水素ナトリウム、リン酸ナトリウム、リン酸水素ナトリウム等を配 合し得る。  [0031] ρΗ of the tooth whitening composition is not particularly limited as long as it is within the range of safety in the oral cavity and the human body, but preferably the tooth whitening composition is diluted 10 times with purified water. ΡΗ is 4 to 10 and more preferably ρΗ is 5.5 to 9. If it is less than ρΗ4, there is a concern about decalcification depending on the application time. If it exceeds ρΗΙΟ, there is a concern about mucosal detachment when touching the gingiva. As pH adjusters, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, citrate, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium tamate, sodium hydrogen citrate, sodium phosphate, phosphoric acid Sodium hydrogen or the like can be combined.

[0032] 上記歯牙美白用組成物は、ペースト状、ゲル状、液状等の形態に調製されるが、そ の形態に応じて、歯牙への保持'固定専用の適用用具と併せて適用することが好ま しいが、本発明の歯牙美白用組成物と併用して使用される歯牙への保持'固定専用 の適用用具は、歯牙美白用組成物の歯牙への確実な適用、固定を補助すると共に 、使用中の歯牙美白用組成物の歯肉、舌及び口腔粘膜への溶出を抑え、不快な使 用感ゃ唾液の誘発を防ぎ、更に唾液の侵入や咬合、咀嚼、その他物理的な刺激に よる歯牙美白用組成物の希釈や歯牙力 の離脱を防ぐ目的で使用される。用具の素 材及び形状については、上記目的を達成できるものであれば特に限定されないが、 水不溶†生の素材で作られたテープ、シート、フイノレム、マウストレー、マウスピース、ス ボンジ、印象材、パック材、又は歯列に成型した歯のカバーが好適に用いられる。 [0032] The tooth whitening composition is prepared in a paste form, a gel form, a liquid form, or the like, and depending on the form, it should be applied together with an application tool dedicated to holding and fixing to a tooth. Although it is preferable, the application tool for holding and fixing to the tooth used in combination with the tooth whitening composition of the present invention assists the reliable application and fixation of the tooth whitening composition to the tooth. Inhibiting elution of the tooth whitening composition in use on the gums, tongue and oral mucosa, preventing unpleasant use and preventing the induction of saliva, as well as intrusion, occlusion, chewing and other physical stimuli It is used for the purpose of preventing the dilution of the tooth whitening composition and the separation of the tooth force. The material and shape of the tool are not particularly limited as long as the above object can be achieved, but tape, sheet, Finolem, mouth tray, mouthpiece, sponge, impression material made of water-insoluble raw material. A tooth cover molded into a pack material or a dentition is preferably used.

[0033] 上記適用用具の厚みは、口腔着用時に違和感のない 0. 01〜5mmが好ましぐ特 にテープ、シート、フィルムについては、 0. 01〜2mmが望ましい。  [0033] The thickness of the above-mentioned application tool is preferably 0.01 to 5 mm, which does not give a sense of incongruity when worn on the oral cavity, and is particularly preferably 0.01 to 2 mm for tapes, sheets and films.

[0034] 上記用具の素材については、 口腔適用時のフィット感に優れ、唾液の発生を抑える ことで製剤の長時間適用を可能にするポリエチレン、発泡ポリエチレン、ポリプロピレ ン、発泡ポリプロピレン、ポリエステル、ポリウレタン、レーヨン、パルプ、綿、絹、紙、多 糖フィルム、金属箔等の 1種又は 2種以上を用いるのが好ましぐ特にポリエチレン、 発泡ポリエチレン、ポリプロピレン、発泡ポリプロピレン、ポリエステル、ポリウレタン、レ 一ヨン、水難溶性プルランフィルムが良レ、。水難溶性プノレランフィルムはプノレランをフ イルム化したもので、上記(B)成分のプルランには含まれない。更に、 口腔粘膜及び 舌と接する側の材質を親水性、吸水性の高い素材、例えばレーヨン、パルプ、綿、絹 、紙等を使った織布又は不織布で構成することにより、 口中で発生した唾液を吸収し 保持するため、使用感に優れており好ましい。この場合、歯牙美白用組成物を保持 する側には、ポリエチレン、ポリプロピレン、ポリエステル、ポリウレタン等の水不透過 性フィルムを組み合わせることで、歯牙美白用組成物の適用用具への吸着、浸透を 防ぐこともできる。  [0034] With regard to the materials of the above-mentioned devices, polyethylene, foamed polyethylene, polypropylene, foamed polypropylene, polyester, polyurethane, which have excellent fit when applied to the oral cavity and enable the formulation to be applied for a long time by suppressing the generation of saliva. It is preferable to use one or more of rayon, pulp, cotton, silk, paper, polysaccharide film, metal foil, etc. Especially polyethylene, foamed polyethylene, polypropylene, foamed polypropylene, polyester, polyurethane, rayon, Good water-insoluble pullulan film. The poorly water-soluble Punoreran film is a film of Punoreran and is not included in the pullulan component (B). Furthermore, the saliva produced in the mouth is made by forming the material on the side that contacts the oral mucosa and the tongue with a hydrophilic or highly absorbent material such as woven or non-woven fabric using rayon, pulp, cotton, silk, paper, etc. It is preferable because it absorbs and retains water and has excellent usability. In this case, by adhering a water-impermeable film such as polyethylene, polypropylene, polyester, polyurethane, etc. on the side holding the tooth whitening composition, it is possible to prevent the tooth whitening composition from adsorbing and penetrating into the application tool. You can also.

[0035] 一方、シリコーンゴム、天然ゴム等の可塑性樹脂及び酢酸ビュル樹脂、アクリル樹 脂、エチレン—酢酸ビュル共重合体等の熱可塑性樹脂からなるトレー又はマウスピ ースは、変形の自由度が高ぐ使用者の歯列、歯型にフィットさせやすいため、密着 性、固定性に優れており、より長時間の歯牙美白用組成物の歯牙への適用を目的と する場合に適している。  On the other hand, trays or mouthpieces made of thermoplastic resins such as silicone rubber and natural rubber and thermoplastic resins such as butyl acetate resin, acrylic resin, and ethylene-butyl acetate copolymer have a high degree of freedom of deformation. It is easy to fit in the user's dentition and tooth type, and therefore has excellent adhesion and fixability, and is suitable for the purpose of applying a tooth whitening composition to a tooth for a longer time.

[0036] 更に、粘度が低く歯牙への粘着性の弱いゲル組成物を併用する場合には、製剤を 含浸させたスポンジや、レーヨン、綿、パルプ等の吸水性樹脂を歯のカバー、トレー 等の内側に敷き詰め、これを咬み続けることで、適量のゲル組成物を歯牙に適用す ることちでさる。 [0036] Furthermore, when a gel composition having a low viscosity and a low adhesiveness to teeth is used in combination, a sponge impregnated with the preparation, or a water-absorbing resin such as rayon, cotton, pulp, etc., is used. It is possible to apply an appropriate amount of gel composition to the teeth by laying on the inside and keeping biting it.

[0037] なお、適用回数、時間等は適宜選定されるが、通常、 1日 1〜6回、特に:!〜 3回で 、 1回:!〜 10分、特に:!〜 3分である。  [0037] The number of times of application, time, etc. are appropriately selected, but usually 1 to 6 times a day, especially:! To 3 times, once:! To 10 minutes, especially:! To 3 minutes. .

実施例  Example

[0038] 以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記実 施例に制限されるものではない。なお、各例中の%はいずれも質量%である。また、 下記例で平均粒子径、重量平均分子量、数平均分子量、窒素分の測定は上述した 通りである。また、下記実施例及び比較例において、チッソ (株)製ポリリジン粉末を 用いた例がある力 S、これは 50%粉末であるので、その配合量は、純分換算したものを 示した。  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In addition, all% in each example is the mass%. In the following examples, the average particle diameter, weight average molecular weight, number average molecular weight, and nitrogen content are measured as described above. Further, in the following examples and comparative examples, there is an example using Chisso Co., Ltd. polylysine powder, which is 50% powder, and the blending amount is shown as a pure conversion.

製剤の調製  Formulation preparation

全原料を秤量し、ニーダ一に投入後、 4kPaまで減圧し、組成物が均一になるまで 混合して歯牙美白用組成物を調製した。なお、 pHは精製水で 10倍希釈した時の 25 °Cにおける 1分後の pHを pHメーター(東亜ディーケーケ一(株)製、 HM— 26S)で 測定し、 pH5. 5〜9. 0になるように必要に応じて水酸化ナトリウム又は塩酸を用いて 調整した。  After all the raw materials were weighed and put into a kneader, the pressure was reduced to 4 kPa and mixed until the composition became uniform to prepare a tooth whitening composition. In addition, the pH was measured with a pH meter (HM-26S, manufactured by Toa DKKEI Co., Ltd.) after 1 minute at 25 ° C when diluted 10 times with purified water, and adjusted to pH 5.5 to 9.0. As needed, it adjusted using sodium hydroxide or hydrochloric acid.

[0039] シートの作製 [0039] Fabrication of sheet

加熱したポリエチレンフィルム(低密度ポリエチレン、厚さ 10 z m、東ソー(株)製、 商品グレード; 212)を、ポリプロピレン不織布(ポリプロピレン 100%、スパンボンド、 目付 40g/m2、表面エンボス加工、出光石油化学 (株)製、商品グレード;出光 RN2 040)とレーヨン/ポリプロピレン不織布(レーヨン/ポリプロピレン = 70/30、スパン レース、 目付 40gZm2、シンヮ(株)製、商品グレード; 7140— 6)で挟んで熱融着さ せて厚さ 0. 5mmの 3層不織布シートを作製した。この 3層不織布シートのレーヨン Z ポリプロピレン不織布面側と、フェイシンダフイルム(ポリエチレンテレフタレート 100% 、片面シリコンコート、厚さ 50 μ ΐη、東レフイルム加工 (株)製、商品グレード;セラピー ル BK (S) # 50)のシリコンコート面の間に、トータルの厚みが lmmになるように展延 機 (花栄機械工業製、ロールサンドコーター)を用いて歯牙美白用組成物を塗膏した 。その後、上下顎の左右:!〜 3番の歯の唇面、舌面を覆える大きさ(60mm X 25mm )になるように歯牙美白用組成物を塗膏したシートを型抜きし、上下顎の歯列に貼付 可能なシートを作製した。 Heated polyethylene film (low density polyethylene, thickness 10 zm, manufactured by Tosoh Corporation, product grade; 212), polypropylene nonwoven fabric (100% polypropylene, spunbond, basis weight 40 g / m 2 , surface embossing, Idemitsu Petrochemical Product grade; Idemitsu RN2 040) and rayon / polypropylene nonwoven fabric (rayon / polypropylene = 70/30, spun lace, basis weight 40gZm 2 , product made by Shingo Co., Ltd., product grade; 7140-6) A three-layer nonwoven fabric sheet having a thickness of 0.5 mm was prepared by fusing. Rayon Z polypropylene nonwoven fabric side of this three-layer nonwoven fabric sheet and Faisin film (polyethylene terephthalate 100%, single-sided silicon coat, thickness 50 μΐη, manufactured by Toray Film Co., Ltd., product grade; Therapy BK (S) Tooth whitening composition was applied between the silicon coated surfaces of # 50) using a spreader (manufactured by Kaei Machinery Co., Ltd., roll sand coater) so that the total thickness was lmm. . Then, left and right of the upper and lower jaws:! ~ The tooth coated with a tooth whitening composition so that the size (60mm X 25mm) can cover the lip and tongue of the teeth of No. 3 A sheet that can be applied to the dentition was prepared.

[実施例:!〜 10、比較例:!〜 4]  [Example:! To 10, Comparative example:! To 4]

予め色差 L*a*b*を測定したヒト抜去歯の上に、表 1に示した組成物を上記の方法に より塗膏したシートをのせ、 37°C, 3分間恒温槽中に静置後、シートを剥がし、ゲルを ティッシュで軽く拭き取って水洗した後、人工唾液中に移した。人工唾液中に 3時間 浸漬後、色差 L*a*b*を測定して ΔΕを求めた。色差は分光測色計 (ミノルタ (株)製、 C M_ 2022)を用いて測定した。なお、人工唾液の組成は以下の通りである。  A sheet coated with the composition shown in Table 1 by the above method is placed on the extracted human tooth whose color difference L * a * b * has been measured in advance, and left in a thermostat at 37 ° C for 3 minutes. Thereafter, the sheet was peeled off, the gel was gently wiped with a tissue, washed with water, and then transferred into artificial saliva. After immersion in artificial saliva for 3 hours, the color difference L * a * b * was measured to determine ΔΕ. The color difference was measured with a spectrocolorimeter (Minolta Co., Ltd., CM_2022). The composition of artificial saliva is as follows.

塩ィ匕カルシウム '二水塩 0. 2205g  Salty Calcium 'Dihydrate 0, 2205g

ジン酉変二 !^力];クム 0.6805g  Jin Jin Henji! ^ Power]; Kum 0.6805g

塩ィ匕ナ卜リウム 5. 8440g  Salty natrium 5. 8440g

酢酸 6. Og  Acetic acid 6. Og

Na〇H(pH調整剤)  NaOH (pH adjuster)

A  A

計 1, OOOmL  Total 1, OOOmL

•白色化効果  • Whitening effect

2、 1/2  2, 1/2

△ E*(1) = ((L*1— L*0)2+(a*l_ -a O) +(b 1-b 0) ) △ E * (1) = ((L * 1— L * 0) 2 + (a * l_ -a O) + (b 1-b 0))

'白色化効果の持続性  'Durability of whitening effect

2ヽ 1/2  2 ヽ 1/2

ΔΕ*(2) = ((L*2-L*0)2+ (a*2- -a O) +(b 2— b 0) ) ΔΕ * (2) = ((L * 2-L * 0) 2 + (a * 2- -a O) + (b 2− b 0))

なお、 L*0、 a*0、 b*0は初期 L*a*b*値を表し、同様に L*l、 a*l、 b*l、 L*2、 a*2、 b*2 はそれぞれ白色化操作後の L*aV値、人工唾液浸漬後の L*aV値である。  L * 0, a * 0, b * 0 represent the initial L * a * b * values, and similarly L * l, a * l, b * l, L * 2, a * 2, b * 2 Are the L * aV value after whitening and the L * aV value after immersion in artificial saliva, respectively.

龍娜 Longan

白色化効果 ◎: ΔΕ*(1)が 7. 0以上  Whitening effect ◎: ΔΕ * (1) is 7.0 or more

〇: ΔΕ*(1)が 5. 0以上〜 7.0未満  ○: ΔΕ * (1) is more than 5.0 and less than 7.0

Δ: ΔΕ*(1)が 3. 0以上〜 5.0未満  Δ: ΔΕ * (1) is 3.0 or more and less than 5.0

X: ΔΕ*(1)が 3. 0未満  X: ΔΕ * (1) is less than 3.0

白色化効果の持続性 ◎: ΔΕ*(2)が 6.0以上 〇: ΔΕ (2)が 4.0以上〜 6.0未満 Persistence of whitening effect ◎: ΔΕ * (2) is 6.0 or more ◯: ΔΕ (2) is 4.0 or more and less than 6.0

Δ: ΔΕ*(2)が 3.0以上〜 4.0未満  Δ: ΔΕ * (2) is 3.0 or more and less than 4.0

x: ΔΕ*(2)が 3.0未満  x: ΔΕ * (2) is less than 3.0

結果を表 1に示す。  The results are shown in Table 1.

[表 1] [table 1]

Figure imgf000013_0001
Figure imgf000013_0001

[実施例 11]  [Example 11]

予め下記歯牙美白用組成物 1が 2. Og塗布された、前歯左 3番から右 3番の唇面を 覆える発泡ポリエチレン製シート (積水化学工業 (株)製ボラーラ XL_IF08008、 15 mm X 60mm X厚さ 800 zm)を歯牙の唇面に貼付した。前述の実施例:!〜 10、比 較例 1〜4と同様の方法により評価したところ白色化効果は◎、白色化効果の持続性 はつであった。  Foamed polyethylene sheet (Sekisui Chemical Co., Ltd. Borara XL_IF08008, 15 mm X 60 mm X) that covers the lips of the front teeth left 3 to right 3 with 2.g of tooth whitening composition 1. A thickness of 800 zm) was applied to the labial surface of the tooth. When evaluated in the same manner as in the above-mentioned Examples:! To 10 and Comparative Examples 1 to 4, the whitening effect was 、 and the whitening effect was sustained.

T 成, ペースト  T, paste

二酸化チタン 3.0% (石原産業 (株)タイペータ CR— 50、平均粒子径 0· 25 μ ΐη) プルラン((株)林原商事、 PF— 2、重量平均分子量 20万) Titanium dioxide 3.0% (Ishihara Sangyo Co., Ltd. Typeter CR-50, average particle size 0 · 25 μΐη) Pullulan (Hayashibara Corporation, PF-2, weight average molecular weight 200,000)

ポリリジン (チッソ (株)、ポリリジン粉末、数平均分子量 4400)  Polylysine (Chisso Corporation, polylysine powder, number average molecular weight 4400)

カルボキシメチルセルロースナトリウム 0. 5  Sodium carboxymethylcellulose 0.5

(ダイセル化学工業 (株)製、商品名 CMCダイセル— 1150)  (Product name: CMC Daicel — 1150, manufactured by Daicel Chemical Industries, Ltd.)

70ο/οソノレビ、卜一ノレ 30. 0 70 ο / ο Sonorevi, 卜 1 Nore 30. 0

プロピレングリコール 3. 0  Propylene glycol 3.0

サッカリンナトリウム 0. 2  Saccharin sodium 0.2

メチルパラベン 0. 1  Methylparaben 0.1

香料 1. 0  Fragrance 1.0

精製水 バランス  Purified water balance

計 100. 0%  Total 100. 0%

[実施例 12]  [Example 12]

予め下記歯牙美白用組成物 2が 2. Og塗布された、前歯左 3番から右 3番の唇面を 覆えるポリウレタンフィルム(シーダム(株)製、 DUS2124— CDB、 15mm X 60mm X厚さ 50 μ ΐη)を歯牙の唇面に貼付した。前述の実施例:!〜 10、比較例 1〜4と同様 の方法により評価したところ白色化効果は◎、白色化効果の持続性は〇であった。 歯牙姜白用組成物 2 (ゲル状)  2. Polyurethane film (made by Seadam Co., DUS2124-CDB, 15mm x 60mm x thickness 50) with the following tooth whitening composition 2 pre-coated with 2. Og and covering the lip of the left 3rd to right 3rd teeth μΐη) was affixed to the lip surface of the tooth. When evaluated in the same manner as in the above-mentioned Examples:! To 10 and Comparative Examples 1 to 4, the whitening effect was 、, and the persistence of the whitening effect was ◯. Tooth whitening composition 2 (gel)

二酸化チタン 4. 0%  Titanium dioxide 4.0%

(石原テクノ(株) TTO— 51 (A)、平均粒子径 0· 02 μ ΐη)  (Ishihara Techno Co., Ltd. TTO-51 (A), average particle size 0 · 02 μΐη)

プルラン(昭光通商 (株)、 P— 800、重量平均分子量 79万) 3· 0 カチオン化セノレロース 0. 3  Pullulan (Shokko Tsusho Co., Ltd., P-800, weight average molecular weight 790,000) 3 · 0 Cationized Senorelose 0.3

(日本 NSC (株)、窒素分 2%、重量平均分子量 30万)  (Japan NSC Co., Ltd., nitrogen content 2%, weight average molecular weight 300,000)

キサンタンガム 0. 2  Xanthan gum 0.2

(三栄源エフ 'エフ'アイ (株)製、商品名サンエース NXG_ S)  (Made by Saneigen F FF Eye Co., Ltd., trade name Sanace NXG_S)

ポリアクリル酸ナトリウム 0. 6  Sodium polyacrylate 0.6

(日本純薬 (株)製、商品名ァロンビス SS)  (Nippon Pure Chemicals Co., Ltd., trade name Aalunbis SS)

ブチルパラベン 0. 1 70ο/οソノレビ、卜一ノレ 23. 0 Butylparaben 0.1 70 ο / ο Sonorevi, 卜 1 Nore 23. 0

プロピレングリコール 5. 0  Propylene glycol 5.0

安息香酸ナトリウム 0. 2  Sodium benzoate 0.2

香料 1. 0  Fragrance 1.0

精製水 バランス  Purified water balance

計 100. 0%  Total 100. 0%

[実施例 13]  [Example 13]

予め下記歯牙美白用組成物 3が 0. 2g塗布された、歯 1本ずつの形をしたポリェチ レン製フィルム(東レ(株)製軟質 PE、 10mm X 15mm X厚さ 25 μ m)を色の気にな る歯だけに貼付した。前述の実施例:!〜 10、比較例 1〜4と同様の方法により評価し たところ白色化効果は◎、白色化効果の持続性は◎であった。  A polyethylene film (Toray Co., Ltd., soft PE, 10 mm x 15 mm x 25 μm thick) with one tooth each coated with 0.2 g of the following tooth whitening composition 3 in advance is colored. Affixed only to the teeth of interest. When evaluated in the same manner as in the above Examples:! To 10 and Comparative Examples 1 to 4, the whitening effect was ◎, and the persistence of the whitening effect was ◎.

T 成, )3 (ゲル状) T,) 3 (gel)

酸化ジルコニウム(日本電工、 N— PC、平均粒子径 0· 02 /i m) 0. 5% 二酸化チタン 3. 0  Zirconium oxide (Nippon Denko, N—PC, average particle size 0 · 02 / im) 0.5% Titanium dioxide 3.0

(石原テクノ(株) TTO— 51 (A)、平均粒子径 0· 02 μ ΐη)  (Ishihara Techno Co., Ltd. TTO-51 (A), average particle size 0 · 02 μΐη)

プルラン(昭光通商 (株)、 P— 400、重量平均分子量 40万) 5· 0 リゾチーム (和光純薬工業 (株)、リゾチーム、分子量 14400) 0. 1 ポリリジン (チッソ (株)、ポリリジン粉末、数平均分子量 4400) 1. 5  Pullulan (Shoko Tsusho Co., Ltd., P-400, weight average molecular weight 400,000) 5 · 0 Lysozyme (Wako Pure Chemical Industries, Ltd., lysozyme, molecular weight 14400) 0.1 Polylysine (Chisso Corporation, polylysine powder, number (Average molecular weight 4400) 1.5

グリセリン 15. 0  Glycerin 15.0

ポリオキシエチレン(60モル)硬化ヒマシ油 1. 0  Polyoxyethylene (60 mol) hydrogenated castor oil 1.0

キサンタンガム 0. 2  Xanthan gum 0.2

(三栄源エフ 'エフ'アイ (株)製、商品名サンエース NXG_ S)  (Made by Saneigen F FF Eye Co., Ltd., trade name Sanace NXG_S)

フッ化ナトリウム 0. 2  Sodium fluoride 0.2

香料 1. 0  Fragrance 1.0

サッカリンナトリウム 0. 1  Saccharin sodium 0.1

精製水 バランス  Purified water balance

計 100. 0%  Total 100. 0%

[実施例 14] 下記歯牙美白用組成物 4を 1. Og筆で前歯左 3番から右 3番の歯の唇面に塗布後 、上からポリプロピレン製フィルム(東レ(株)製軟質 PP、 15mm X 60mm X厚さ 100 z m)を貼付した。前述の実施例:!〜 10、比較例 1〜4と同様の方法により評価したと ころ白色化効果は◎、白色化効果の持続性は◎であった。 酸化アルミニウム 2. 0% [Example 14] Apply the following tooth whitening composition 4 with 1. Og brush to the left lip of the front teeth 3rd to 3rd right, and from the top polypropylene film (Toray Industries soft PP, 15mm X 60mm X thickness 100 zm) was affixed. When evaluated in the same manner as in the above Examples:! To 10 and Comparative Examples 1 to 4, the whitening effect was ◎, and the persistence of the whitening effect was ◎. Aluminum oxide 2.0%

(メラー社製、商品名:純アルミナ末、平均粒子径 0. 06 x m)  (Meller, trade name: pure alumina powder, average particle size 0.06 x m)

プルラン((株)林原商事、 PF_ 2、重量平均分子量 20万) 3. 0 カチオンィ匕セノレロース 1. 5  Pullulan (Hayashibara Corporation, PF_2, weight average molecular weight 200,000) 3.0 Cationic senorelose 1.5

(日本 NSC (株)、窒素分 2%、重量平均分子量 30万)  (Japan NSC Co., Ltd., nitrogen content 2%, weight average molecular weight 300,000)

カラギーナン 0. 1  Carrageenan 0.1

(三栄源エフ 'エフ'アイ (株)製、商品名ゲルリッチ No. 3)  (Product name: GELRICH No. 3 manufactured by San-Ei Gen F "F-I")

ポリオキシエチレン(60モル)硬化ヒマシ油 1. 0  Polyoxyethylene (60 mol) hydrogenated castor oil 1.0

安息香酸ナトリウム 0. 3  Sodium benzoate 0.3

メチルパラベン 0· 1  Methylparaben 0 · 1

クェン酸 0. 1  Quenic acid 0.1

クェン酸ナトリウム 0· 3  Sodium quenate 0 · 3

香料 0. 5  Fragrance 0.5

サッカリン 0· 02  Saccharin 0 · 02

精製水 バランス  Purified water balance

計 100. 0%  Total 100. 0%

[実施例 15]  [Example 15]

エチレンビュルアセテート樹脂製のマウスピースをお湯で温めて軟化させ、嚙んで 各自の歯型にフィットしたマウスピースを作製した。下記歯牙美白用組成物 5をマウス ピースに 1. Og充填し、装着した。前述の実施例:!〜 10、比較例 1〜4と同様の方法 により評価したところ白色化効果は◎、白色化効果の持続性は〇であった。  The mouthpiece made of ethylene butyl acetate resin was warmed and softened with hot water, and the mouthpiece fitted with each tooth shape was made by massaging. The mouthpiece was filled with 1. Og of the following tooth whitening composition 5 and attached. When evaluated by the same method as in the above-mentioned Examples:! To 10 and Comparative Examples 1 to 4, the whitening effect was ◎, and the persistence of the whitening effect was ◯.

T 成, )5 (ゲル状) T,) 5 (gel)

二酸化ケイ素 1. 0% (Huber社製、商品名 Zeodentl l 3、平均粒子径 5· 0 /i m) Silicon dioxide 1.0% (Huber, trade name Zeodentl l 3, average particle size 5 · 0 / im)

プルラン(昭光通商 (株)、 P— 50、重量平均分子量 4. 7万) 5. 0 ポリリジン 1. 2 Pullulan (Shoko Tsusho Co., Ltd., P-50, weight average molecular weight 47,000) 5.0 Polylysine 1.2

(和光純薬工業 (株)、ポリ Lリジン臭化水素酸塩、数平均分子量 30万以上) カルボキシメチルセルロースナトリウム 0. 3  (Wako Pure Chemical Industries, Ltd., poly L lysine hydrobromide, number average molecular weight of 300,000 or more) Sodium carboxymethylcellulose 0.3

(ダイセル化学工業 (株)製、商品名 CMCダイセル— 1150)  (Product name: CMC Daicel — 1150, manufactured by Daicel Chemical Industries, Ltd.)

力ラゲナン 0. 2 Force Lagenan 0.2

(三栄源エフ 'エフ'アイ (株)製、商品名ゲルリッチ No. 3)  (Product name: GELRICH No. 3 manufactured by San-Ei Gen F "F-I")

ソノレビット 20. 0 Sonorebit 20. 0

キシリット 10. 0 Xyrit 10.0

プロピレングリコール 3. 0 Propylene glycol 3.0

メチルパラベン 0. 05 Methylparaben 0. 05

香料 1. 0 Fragrance 1.0

サッカリンナトリウム 0. 15 Saccharin sodium 0.15

精製水 バランス Purified water balance

計 100. 0% Total 100. 0%

Claims

請求の範囲 The scope of the claims [1] (A)二酸化チタン、二酸化ケイ素、酸化亜鉛、酸化アルミニウム、酸化マグネシウム 、酸化ジノレコニゥムから選ばれる 1種又は 2種以上、  [1] (A) Titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, magnesium oxide, one or more selected from dinoleconium oxide, (B)プルラン、  (B) Pullulan, (C)リゾチーム、カチオン化セルロース、ポリリジンから選ばれる 1種又は 2種以上 を含有することを特徴とする歯牙美白用組成物。  (C) A composition for whitening teeth, comprising one or more selected from lysozyme, cationized cellulose, and polylysine. [2] 請求の範囲第 1項記載の歯牙美白用組成物と、この歯牙美白用組成物を保持する と共に、この歯牙美白用組成物を保持した状態で歯に着脱可能に装着される適用用 具とを備えたことを特徴とする歯牙美白用セット。  [2] The tooth whitening composition according to claim 1 and the application for holding the tooth whitening composition and detachably attaching to the tooth while holding the tooth whitening composition A set for teeth whitening characterized by comprising a tool. [3] 適用用具が、テープ、シート、フィルム、マウストレー、マウスピース、スポンジ、印象 材、パック材、又は歯列に成型した歯のカバーである請求の範囲第 2項記載の歯牙 美白用セット。 [3] The tooth whitening set according to claim 2, wherein the application tool is a tape, a sheet, a film, a mouth tray, a mouthpiece, a sponge, an impression material, a pack material, or a tooth cover molded into a dentition. .
PCT/JP2005/022918 2004-12-22 2005-12-14 Tooth whitening composition and tooth whitening set Ceased WO2006068011A1 (en)

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JP2008162936A (en) * 2006-12-28 2008-07-17 Lion Corp Tooth cosmetic pressure transfer seal
KR100870232B1 (en) 2006-12-07 2008-11-24 재단법인서울대학교산학협력재단 Teeth Whitening Functional Materials Delivery System
JP2010523526A (en) * 2007-04-05 2010-07-15 グラクソ グループ リミテッド New use
WO2010114638A1 (en) 2009-03-30 2010-10-07 E. I. Du Pont De Nemours And Company Peptide-based tooth whitening reagents
JP2012116768A (en) * 2010-11-29 2012-06-21 Kao Corp Liquid composition for oral cavity
US8475772B2 (en) 2003-09-08 2013-07-02 E I Du Pont De Nemours And Company Peptide-based oral care surface reagents for personal care
CN103421329A (en) * 2013-08-21 2013-12-04 华南理工大学 Preparation method for antimicrobial edible film material
WO2017172955A1 (en) 2016-03-29 2017-10-05 Safewhite, Inc. Polyelectrolyte dental adhesives for whitening teeth and teeth components
KR20220052899A (en) 2019-08-27 2022-04-28 라이온 가부시키가이샤 oral composition
CN116898741A (en) * 2023-08-18 2023-10-20 广州品硬生物科技有限公司 Gum repair toothpaste containing lysozyme and probiotics and preparation method thereof

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CN116898741A (en) * 2023-08-18 2023-10-20 广州品硬生物科技有限公司 Gum repair toothpaste containing lysozyme and probiotics and preparation method thereof

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