WO2017022829A1 - Agent for preventing adhesion of dental plaque and stains, and composition for oral use comprising same - Google Patents

Agent for preventing adhesion of dental plaque and stains, and composition for oral use comprising same Download PDF

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Publication number
WO2017022829A1
WO2017022829A1 PCT/JP2016/072957 JP2016072957W WO2017022829A1 WO 2017022829 A1 WO2017022829 A1 WO 2017022829A1 JP 2016072957 W JP2016072957 W JP 2016072957W WO 2017022829 A1 WO2017022829 A1 WO 2017022829A1
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structural unit
group
meth
dental plaque
hydrogen atom
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PCT/JP2016/072957
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French (fr)
Japanese (ja)
Inventor
俊輔 櫻井
幸治 宮本
佳久 島村
山本　宣之
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日油株式会社
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Priority to JP2017533124A priority Critical patent/JP6819592B2/en
Publication of WO2017022829A1 publication Critical patent/WO2017022829A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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

Definitions

  • the present invention relates to a dental plaque / stain adhesion inhibitor containing a polymer component, and more particularly to an oral composition containing a copolymer.
  • Non-patent Document 1 Non-patent Document 1
  • Non-patent Document 1 Non-patent Document 1
  • Non-Patent Document 2 Non-Patent Document 2
  • the mechanism of pigment deposition on the tooth surface is not necessarily considered. Is not clear.
  • MPC 2-methacryloyloxyethyl phosphorylcholine
  • Patent Document 3 As oral care agents using MPC, a method relating to prevention of dryness and stimulation in the oral cavity (Patent Document 3) and a method relating to prevention of microorganism adhesion in the oral cavity (Patent Document 4) are disclosed.
  • Non-Patent Document 3 Non-Patent Document 4
  • Patent Document 4 Although it was thought that it was possible to prevent dental plaque adhesion in the oral cavity by using MPC, It has not been verified, and its method and effect are unknown. Moreover, the method and effect regarding prevention and suppression of the deposition of the stain in the oral cavity using MPC were not known at all.
  • Patent Document 1 and Patent Document 2 cannot prevent the adhesion / deposition of dental plaque / stain sufficiently, the dental that can prevent or suppress the adhesion / deposition of dental plaque / stain on the tooth surface.
  • the plaque / stain adhesion inhibitor and the oral composition containing the same have not yet been satisfactory.
  • an object of the present invention is to provide a dental plaque / stain adhesion inhibitor capable of preventing or suppressing adhesion / deposition of dental plaque / stain and an oral composition containing the same.
  • the present inventors have found that a copolymer having a specific proportion of a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine and a specific structural unit different from the structural unit.
  • the polymer By using the polymer as a dental plaque / stain adhesion preventive agent, the inventors have found out that the above problems can be solved and have completed the present invention.
  • the present invention is as follows. 1. A weight average molecular weight of 10,000 to 5,000,000, A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%, Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer A dental plaque / stain adhesion-preventing agent comprising a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3).
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 4 to 18 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X ⁇ represents a halogen ion
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 2.
  • the structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine
  • the structural unit (B2) is a structural unit based on 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride.
  • the structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine
  • the structural unit (B1) is a structural unit based on stearyl methacrylate
  • the structural unit (B3) is N, N-dimethylaminopropyl. 2.
  • the dental plaque / stain adhesion preventer according to item 1 which is a structural unit based on acrylamide. 6).
  • An oral composition containing 0.001 to 5.0 w / v% of the dental plaque / stain adhesion inhibitor described in 1 to 5 above and 3.0 to 99.9 w / v% of water. 7).
  • a dental plaque / stain adhesion prevention method comprising the following steps: A weight average molecular weight of 10,000 to 5,000,000, A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%, Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer
  • Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1)
  • Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer
  • (meth) acrylamide monomer Dental plaque / stain adhesion inhibitor containing a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3),
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 4 to 18 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X ⁇ represents a halogen ion
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a weight average molecular weight of 10,000 to 5,000,000 A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%, Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 4 to 18 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X ⁇ represents a halogen ion or
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 10.
  • a weight average molecular weight of 10,000 to 5,000,000 A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%, Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 4 to 18 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X ⁇ represents a halogen ion or
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the dental plaque / stain adhesion preventive agent and oral composition containing the dental plaque / stain of the present invention can prevent or suppress the adhesion / deposition of dental plaque / stain on the tooth surface. Useful.
  • the dental plaque / stain adhesion-preventing agent of the present invention includes ⁇ a structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine, a structural unit (B1) based on an alkyl group-containing (meth) acrylic monomer, A structural unit (B2) based on a quaternary ammonium group-containing (meth) acrylic monomer and at least one structural unit selected from the group consisting of a structural unit (B3) based on a (meth) acrylamide monomer Containing copolymer ⁇ .
  • the structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine is more specifically represented by the following formula (A), and is obtained by polymerization of a monomer represented by the formula (A ′). .
  • R 1 may be either a hydrogen atom or a methyl group, but is preferably a methyl group.
  • the copolymer used for this invention can express the effect which prevents adhesion of a dental plaque and a stain by having a structural unit (A) in a molecular chain.
  • the content of the structural unit (A) in the copolymer used in the present invention is 10 to 90 mol%. If the content is less than 10 mol%, the dental plaque / stain adhesion preventing effect cannot be expected. If the content is more than 90 mol%, the adsorptive properties on the tooth surface are poor due to the super hydrophilicity of the MPC segment. The effect cannot be expected.
  • Preferable examples of 2- (meth) acryloyloxyethyl phosphorylcholine include 2-methacryloyloxyethyl phosphorylcholine.
  • (meth) acryl means acryl or methacryl (methacryl)
  • (meth) acryloyl means acryloyl or methacryloyl (methacryloyl)
  • (meth) acrylate Acrylate or methacrylate (methacrylate).
  • the structural unit (B1) based on the alkyl group-containing (meth) acrylic monomer is more specifically represented by the following formula (B1), and by polymerization of the monomer represented by the formula (B1 ′). can get.
  • the copolymer used for this invention can improve the adsorptivity to the tooth surface of a copolymer more by having a structural unit (B1) in a molecular chain.
  • R 2 may be either a hydrogen atom or a methyl group, but is preferably a methyl group.
  • R 3 may be any linear or branched alkyl group having 4 to 18 carbon atoms.
  • the linear alkyl group having 4 to 18 carbon atoms include n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, Examples thereof include n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.
  • Examples of the branched alkyl group having 4 to 18 carbon atoms include t-butyl group, isobutyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, and isoundecyl group.
  • alkyl group-containing (meth) acrylic monomer examples include butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. It is done.
  • R 4 may be either a hydrogen atom or a methyl group, but is preferably a methyl group.
  • R 5 , R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear, branched or cyclic.
  • R 5 , R 6 and R 7 methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group Group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
  • R 5 , R 6 and R 7 are preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and more preferably a methyl group.
  • Examples of X ⁇ include halogen ions such as fluorine ion, bromine ion and chlorine ion (chloride ion), and acid residues such as sulfate ion and methyl sulfate ion. Preferably, it is a halogen ion.
  • halogen ions such as fluorine ion, bromine ion and chlorine ion (chloride ion
  • acid residues such as sulfate ion and methyl sulfate ion.
  • it is a halogen ion.
  • 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride is preferable.
  • the structural unit (B3) based on the (meth) acrylamide monomer is represented by the following formula (B3), and is obtained by polymerization of the monomer represented by the formula (B3 ′).
  • the copolymer used in the present invention has the structural unit (B3) in the molecular chain, the copolymer can have a high molecular weight, and the adhesion of the copolymer to the tooth surface can be further increased.
  • R 8 may be a hydrogen atom or a methyl group, but is preferably a hydrogen atom.
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic.
  • R 9 and R 10 are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group, and more preferably a methyl group.
  • N, N-dimethylaminopropyl (meth) acrylamide and the like are preferred examples of (meth) acrylamide monomers. Is mentioned.
  • the copolymer used in the present invention has at least one structural unit selected from the group consisting of (B1), (B2) and (B3) in the molecular chain.
  • the copolymer used in the present invention may have only one structural unit selected from the group consisting of (B1), (B2) and (B3) in the molecular chain, (B1), Two structural units selected from the group consisting of (B2) and (B3) (for example, a combination of (B1) and (B2), a combination of (B2) and (B3), and a combination of (B3) and (B1) ) Or all the structural units of (B1), (B2) and (B3).
  • the copolymer used in the present invention has the structural units (B1) to (B3) in the molecular chain, thereby increasing the adsorptivity and adhesion to the tooth surface of the copolymer. Furthermore, by having not only (B1) to (B3) but also the structural unit (A) in the same polymer chain, the copolymer used in the present invention has a dental plaque stain having adsorptivity to the tooth surface. It becomes an adhesion preventing agent.
  • the content of structural units (B1) to (B3) in the copolymer used in the present invention is 10 to 90 mol%, preferably 10 to 80 mol%, more Preferably, it is 10 to 70 mol%. If the content is less than 10 mol%, the hydrophilicity of the copolymer becomes high, the adsorptivity to the tooth surface becomes poor, and the dental plaque / stain adhesion preventing effect may not be expected, and the content is 90 mol%. If it is more, the solubility in water is lowered, and it may be difficult to produce an oral composition.
  • Preferred examples of the combination of the structural unit (A) and the structural units (B1) to (B3) contained in the molecular chain of the copolymer used in the present invention are the dental plaque / stain adhesion preventing effect and the copolymer. From the viewpoint of adsorptivity and adhesion to the tooth surface, the following combinations are exemplified.
  • the copolymer used in the present invention may contain a structural unit other than the structural unit (A) and the structural units (B1) to (B3).
  • the structural unit (A) and the structural unit (B1) ), (B2), and (B3) one, two, or three constituent units.
  • the copolymer used in the present invention includes an MPC polymer (1) obtained by polymerization according to the method of JP-A-11-035605, an MPC polymer (2) obtained by polymerization according to the method of JP-A 2004-196868, MPC polymer (3) obtained by polymerization according to the method of 2004-196868, MPC polymer (4) obtained by polymerization according to the method of JP2004-189678 and MPC obtained by polymerization according to the method of JP2013-018749 Polymer (5) can be used.
  • the weight average molecular weight of the copolymer used in the present invention is 10,000 to 5,000,000, preferably 20,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the adsorptivity to the tooth surface is reduced, and the dental plaque / stain adhesion preventing effect cannot be expected. If the weight average molecular weight is more than 5,000,000, the viscosity increases rapidly. It may be difficult to produce a composition for oral cavity.
  • the amount of the copolymer contained in the dental plaque / stain adhesion inhibitor of the present invention or the oral composition containing the inhibitor is such that the copolymer is added to the inhibitor or the entire composition in an amount of 0. 0. 001 to 5.0 w / v%. If the blending amount is less than 0.001 w / v%, the dental plaque / stain adhesion preventing effect may not be obtained, and even if the blending amount is 5.0 w / v% or more, the effect commensurate with the addition amount Cannot be obtained.
  • the concentration of the dental plaque / stain adhesion inhibitor of the present invention or the oral composition containing the inhibitor is more preferably 0.01 to 5.0 W / V%, still more preferably 0. 0.05-5.0 W / V%.
  • (C) group used in the present invention is saccharin, saccharin sodium, glycerin, sucralose, xylitol, maltitol, stevioside, aspartame.
  • group (C) By adding the components of group (C), dental plaque and stain on the tooth surface are more difficult to adhere and deposit, and further, dental plaque and stain once attached and deposited on the tooth surface are more likely to fall off.
  • the content of the group (C) of the present invention is usually 0.001 to 10.0 w / v%. From the viewpoint of further enhancing the effect of preventing dental plaque / stain adhesion, 0.002 to 10.0 w / v% is preferable, and 0.003 to 8.0 w / v% is more preferable.
  • the dental plaque / stain adhesion preventive agent of the present invention or the oral composition containing the inhibitor is a buffer that can be generally used for oral compositions as needed in addition to the copolymer and the (C) group component.
  • An agent, a wetting agent, a drug, a surfactant, an antiseptic and bactericide, a binder, a fragrance, an organic acid, an antioxidant, a stabilizer, a metal sequestering agent, a solvent, and the like can be blended.
  • Citric acid Citric acid, phosphoric acid, malic acid, gluconic acid, and these salts are mentioned, It is desirable to be used at 0.001 w / v%-3.0 w / v%.
  • wetting agent examples include polyhydric alcohols such as propylene glycol, butylene glycol, pentylene glycol, dipropylene glycol, polyethylene glycol, mannitol, and erythritol, and are used at 1.0 w / v% to 50.0 w / v%. It is desirable.
  • the drug is not particularly limited, but sodium azulenesulfonate, epsilon-aminocaproic acid, allantoin, allantochlorohydroxyaluminum, allantoinhydroxyaluminum, epidihydroxycholesterine, dihydrocholesterol, sodium chloride, potassium nitrate, aluminum lactate, zinc chloride, glycyrrhizin Acids and salts thereof, ⁇ -glycyrrhizic acid, isopropylmethylphenol, cetylpyridinium chloride, depotassium chloride, benzalkonium chloride, benzethonium chloride, alkyldiaminoethylglycine hydrochloride, chlorhexidine hydrochloride, chlorhexidine gluconate, triclosan, 1,8-cineole, Ascorbic acid and its salts, pyridoxine hydrochloride, dl- ⁇ -tocopherol acetate, nicotinic acid
  • the surfactant is not particularly limited, and examples thereof include polyoxyethylene hydrogenated castor oil, sorbitan fatty acid ethylene adduct, polyglycerin fatty acid ester, acylamino acid salt, fatty acid aminopropyl betaine, fatty acid amide betaine, and particularly polyoxyethylene. It is preferable to use hydrogenated castor oil and sorbitan fatty acid ethylene adduct at 0.05 w / v% to 2.0 w / v%.
  • the antiseptic disinfectant is not particularly limited, and examples thereof include polyhexanide hydrochloride, hinokitiol, benzoic acid and salts thereof, and parabens, and the usual blending amount is 0.01 w / v% to 1.0 w / v%.
  • the binder is not particularly limited, but cellulose-based thickening agents such as pullulan, gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hyaluronic acid and its salt, chondroitin sulfate and its salt And polysaccharides such as alginic acid and salts thereof, duran gum, xanthan gum and the like.
  • cellulose-based thickening agents such as pullulan, gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hyaluronic acid and its salt, chondroitin sulfate and its salt And polysaccharides such as alginic acid and salts thereof, duran gum, xanthan gum and the like.
  • fragrance peppermint oil, spearmint oil, anise oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander Oil, mandarin oil, lime oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil , Grapefruit oil, sweetie oil, cocoon oil, Iris concrete, absolute peppermint, absolute rose, orange flower, and other natural fragrances, and processing of these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction) Essence, powdered fragrance, etc.) , And l-menthol, carvone, anethole, cineol, methyl salicylate, synamic aldehyde, etc.
  • the stabilizer is not particularly limited, and examples thereof include sodium sulfite, sodium pyrosulfite, sodium hydrogen sulfite, butylhydroxytoluene, propyl gallate, and butylhydroxyaryl.
  • 1-hydroxyethane-1,1-diphosphonic acid 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, edetate tetra
  • disodium edetate trisodium edetate
  • edetate tetra examples include sodium, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate, and the like.
  • water and ethanol can be mentioned.
  • the dental plaque / stain adhesion preventing agent of the present invention is preferably used as a composition for oral cavity, and the following can be exemplified. That is, toothpaste, liquid toothpaste, mouthwash, mouthwash, oral refreshing agent and the like.
  • toothpaste, liquid toothpaste, mouthwash, and mouthwash are preferable.
  • the dental plaque / stain adhesion preventive agent of the present invention is preferably applied to human teeth as a toothpaste, liquid toothpaste, mouthwash or mouthwash, etc. Can also be applied.
  • the present invention is also directed to a dental plaque / stain adhesion prevention method including the following steps.
  • a weight average molecular weight of 10,000 to 5,000,000 A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%, Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer
  • Dental plaque / stain adhesion inhibitor containing a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3), or an oral composition containing the inhibitor Is administered to the oral cavity of mammals including humans.
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 4 to 18 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X ⁇ represents a halogen ion
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the method for preventing dental plaque / stain adhesion of the present invention is not particularly limited.
  • 5 to 50 mL of oral dental composition (liquid toothpaste) containing the dental plaque / stain adhesion preventing agent of the present invention is used for 1 day. 1-10 times, 1-8 times, 1-6 times, 1-4 times, 1-3 times (preferably morning, noon, evening) Is possible.
  • an oral composition (toothpaste) containing 0.01 to 2 g per day containing the dental plaque / stain adhesion preventive agent of the present invention is used in an amount of 1 to 2 per day. Brushing is possible 10 times, 1 to 8, 1 to 6, 1 to 4, 1 to 3 times (preferably morning, noon, evening).
  • the subject of the dental plaque / stain adhesion prevention method is not particularly limited, but is intended for mammals including humans.
  • the mammal including the said human is equipped with a removable denture or dental material
  • the removed denture or dental material can also be targeted.
  • a denture or dental material is added 1 to 10 times, 1 to 8 times, 1 to 6 times, 1 to 4 times, 1 to 4 times a day in a solution of the dental plaque / stain adhesion inhibitor of the present invention dissolved in water or ethanol.
  • Examples of the immersion are 1 to 3 times, 30 seconds or more per time.
  • the present invention has a weight average molecular weight of 10,000 to 5,000,000, A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%, Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer A dental plaque / stain adhesion-preventing copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3) is also targeted.
  • a structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol% Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on qua
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 4 to 18 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X ⁇ represents a halogen ion
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the present invention has a weight average molecular weight of 10,000 to 5,000,000, A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%, Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer.
  • a structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol% Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer
  • R 1 represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkyl group having 4 to 18 carbon atoms.
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • X ⁇ represents a halogen ion
  • R 8 represents a hydrogen atom or a methyl group
  • R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • MPC polymer (1) 2-methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer (copolymerization composition ratio (molar ratio) 80/20, weight average molecular weight: 600,000), Examples of JP-A No. 11-035605 It was obtained by carrying out the polymerization by the method described.
  • MPC polymer (2) 2-methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer (copolymerization composition ratio (molar ratio) 30/70, weight average molecular weight: 142,000), Examples of JP-A 2004-196868 It was obtained by carrying out the polymerization by the method described.
  • MPC polymer (3) 2-methacryloyloxyethyl phosphorylcholine / stearyl methacrylate copolymer [copolymerization composition (molar ratio) 33/67, weight average molecular weight: 164,000], described in Examples of JP-A-2004-196868 It was obtained by carrying out polymerization by the method.
  • MPC polymer (4) 2-methacryloyloxyethyl phosphorylcholine / 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride copolymer [copolymerization composition (molar ratio) 70/30, weight average molecular weight: 450,000] The polymerization was carried out by the method described in Examples of JP-A-2004-189678.
  • MPC polymer (5) 2-methacryloyloxyethyl phosphorylcholine / N, N-dimethylaminopropylacrylamide / stearyl methacrylate copolymer [copolymerization composition (molar ratio) 90/2/8, weight average molecular weight: 820,000] And obtained by polymerization according to the method described in Examples of JP2013-018749A.
  • Homopolymer (B1) butyl methacrylate polymer [weight average molecular weight: 180,000], purchased from Wako Pure Chemical Industries, Ltd. (product name: poly (n-butyl methacrylate)) for testing It was.
  • N N-dimethylacrylamide polymer [number average molecular weight: 10,000], purchased from Sigma-Aldrich Japan (product name: Poly (N, N-dimethylacylamide), DDMAT terminated) for testing It was.
  • Example 1 To about 80 g of purified water, 0.001 g of MPC polymer (1) was added and stirred. Thereafter, purified water was added thereto so that the total amount was 100 mL, thereby producing the oral composition of the present invention.
  • Examples 2 to 11 An oral composition of the present invention was produced according to the same procedure as in Example 1 except that the components of the types and amounts shown in Table 1 were used.
  • Example 1 An oral composition different from the oral composition of the present invention was produced according to the same procedure as in Example 1 except that the types and amounts of components shown in Table 2 were used.
  • ⁇ Coffee dirt adhesion suppression evaluation> The stain adhering to the tooth surface was defined as being only derived from coffee, and the evaluation of the suppression of adhesion of coffee stains was performed according to the following procedure. (1) 40 mg of hydroxyapatite powder was weighed into a centrifuge tube, 1 mL of Example 1 was added and allowed to stand for 10 minutes. (2) Further, 1 mL of coffee was added and allowed to stand for 10 minutes. (3) Thereafter, the supernatant is filtered out and measured for transmittance (% T) at 550 nm using an ultraviolet-visible absorptiometer (V-560, manufactured by JASCO Corporation). 2) was used to calculate the coffee stain adhesion inhibition rate (%). In addition, when carrying out the coffee dirt adhesion inhibition evaluation, a test was conducted under conditions using purified water instead of Example 1, and this was used as a control.
  • Example 2 For Example 2 to Example 11, Comparative Example 1 to Comparative Example 9, and the control, the coffee stain adhesion inhibition rate was calculated according to procedures (1) to (3). Tables 1 and 2 show the coffee dirt adhesion inhibition rate.
  • Example 1 the protein stain adhesion inhibition rate was 10.2%. As the blending concentration of MPC polymer (1) increased, the protein stain adhesion inhibition rate improved, and the highest protein stain adhesion inhibition rate in Example 7 was 40.1%. This effect was observed not only for the MPC polymer (1), but also for the MPC polymer (2), MPC polymer (3), MPC polymer (4) and MPC polymer (5). It was 27.3 to 28.1%. On the other hand, the protein stain adhesion inhibition rate of the comparative example was remarkably low at 2.4 to 5.8%. In Comparative Example 7 and Comparative Example 9, the test was not possible because the polymerized polymer was insoluble (* indicated by “-” in the table).
  • Example 1 the coffee stain adhesion inhibition rate was 20.9%. As with the protein stain adhesion inhibition rate, the coffee stain adhesion inhibition rate improved as the blending concentration of MPC polymer (1) increased, and the highest inhibition rate in Example 7 was 78.9%. there were. Similar to the protein stain adhesion inhibitory effect, the coffee stain adhesion inhibitory effect was also observed for MPC polymer (2), MPC polymer (3), MPC polymer (4) and MPC polymer (5), and the inhibition rate was 50. It was 7 to 53.7%. In the comparative example, the coffee stain adhesion inhibition rate was remarkably low at 5.3 to 10.4%. Similar to the protein stain adhesion inhibition rate, the coffee stain adhesion inhibition rate was not able to be performed for Comparative Example 7 and Comparative Example 9 because the polymerized polymer was insoluble (* indicated by “-” in the table). ).
  • Example 12 To about 80 g of purified water, 0.001 g of MPC polymer (1) was added and stirred. Then, saccharin sodium 0.006 g, glycerin 3.0 g, polyglyceryl myristate 0.25 g, sorbitol solution (70%) 1.0 g, ethanol 4.0 g, citric acid 0.01 g, trisodium citrate 0.05 g Then, 0.05 g of ethyl paraoxybenzoate and 0.5 g of fragrance were added and stirred, and purified water was added so that the total amount became 100 mL to produce a liquid toothpaste which is an oral composition of the present invention.
  • Example 13 to 20 A liquid toothpaste, which is a composition for oral cavity of the present invention, was produced according to the same procedure as in Example 12 except that the types and amounts of components shown in Table 3 were used.
  • Example 10 to 18 and Control A liquid toothpaste, which is a composition for oral cavity different from the composition for oral cavity of the present invention, was produced according to the same procedure as in Example 12 except that the components of the types and amounts shown in Table 4 were used.
  • Example 12 which is the obtained composition for liquid oral cavity (liquid toothpaste), the mouth was soaked with 10 mL for 20 seconds, and the feeling when the tooth surface immediately after spitting was touched with the tongue was evaluated according to the following criteria. Evaluation is performed by a specialized panelist, and the evaluation results are shown in Tables 3 and 4.
  • C The tooth surface is not smooth and the cleaning effect is poor.
  • D The tooth surface is sharp.
  • the Examples 13 to 20 and Comparative Examples 10 to 18 and the control were also evaluated for the feel of the tooth surface after use, and the results are shown in Tables 3 and 4.
  • Example 13 For Example 13 to Example 20, Comparative Example 10 to Comparative Example 18, and the control, the protein stain adhesion inhibition rate was calculated according to procedures (1) to (4). Table 3 and Table 4 show the protein dirt adhesion inhibition rate.
  • Example 12 the protein stain adhesion inhibition rate was 15.1%, and the protein stain adhesion inhibition rate tended to improve as the blending concentration of MPC polymer (1) increased.
  • the highest value in Example 16 was 33. It was 5%.
  • This protein stain adhesion inhibitory effect was also observed for MPC polymer (2), MPC polymer (3), MPC polymer (4) and MPC polymer (5), and the protein stain adhesion inhibition rate was 20.0 to 28.8. %Met.
  • the protein stain adhesion inhibition rate of the comparative example was 3.8 to 7.7%. Since Comparative Example 16 and Comparative Example 18 were insoluble in the composition, they could not be tested (* denoted by “-” in the table).
  • Example 21 to Example 25 In addition to the liquid toothpaste, toothpastes shown in Table 5 were produced, and the tooth surface feel after use and protein stain adhesion inhibition rate (%) were evaluated. As a result, as for the toothpaste, the feel of the tooth surface after use was good as in the case of the liquid toothpaste, and all were evaluated as A. In addition, the protein stain adhesion inhibition rate was 15.3 to 15.5%, indicating a good result.
  • the dental plaque / stain adhesion preventive agent of the present invention showed the effect of preventing the adhesion and deposition of stains and pigments on the tooth surface derived from foods. These effects were also effective when used in oral compositions such as liquid toothpaste and toothpaste, and showed a good feeling of use and suppression of plaque formation. Furthermore, from these results, it was confirmed that the dental plaque / stain adhesion preventing method using the dental plaque / stain adhesion preventing agent of the present invention also has an effect of preventing the adhesion / deposition of dental plaque / stain.
  • the excellent effects of the dental plaque / stain adhesion preventive agent of the present invention, the composition for oral cavity containing the same and the dental plaque / stain adhesion preventing method are such that the copolymer molecules used in the present invention are adsorbed on the tooth surface itself or the pellicle. Thus, it is presumed that it is expressed by inhibiting adsorption of components produced by bacteria and pigments.
  • a dental plaque / stain adhesion inhibitor capable of preventing or suppressing adhesion / deposition of dental plaque / stain, a composition for oral cavity containing the same, and a method for preventing dental plaque / stain adhesion.

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Abstract

Provided are: an agent for preventing adhesion of dental plaque and stains, said agent enabling the prevention or suppression of the adhesion and deposit of dental plaque and stains; and a composition for oral use comprising the same.　Specifically provided are an agent for preventing the adhesion of dental plaque and stains, and a composition for oral use comprising the same, said agent for preventing the adhesion of dental plaque and stains comprising a copolymer including: 10-90mol% of structural unit (A) having a weight average molecular weight of 10,000-5,000,000 and based on 2-(meth)acryloyloxyethyl phosphorylcholine; and 90-10mol% of at least one structural unit selected from the group consisting of a structural unit (B1) based on an alkyl group-containing (meth)acrylic monomer, a structural unit (B2) based on a quaternary ammonium group-containing (meth)acrylic monomer, and a structural unit (B3) based on a (meth)acrylamide monomer.

Description

デンタルプラーク・ステイン付着防止剤およびこれを含有する口腔用組成物Dental plaque / stain adhesion inhibitor and oral composition containing the same
　本発明は、高分子成分を含有するデンタルプラーク・ステイン付着防止剤に関し、より詳しくは共重合体を含有する口腔用組成物に関する。
　本出願は、参照によりここに援用されるところの日本出願特願2015-155442号優先権を請求する。 The present invention relates to a dental plaque / stain adhesion inhibitor containing a polymer component, and more particularly to an oral composition containing a copolymer.
This application claims the priority of Japanese Patent Application No. 2015-155442, which is incorporated herein by reference.
　従来から、健康で白い歯は美の象徴とされており、医学分野でも審美歯科領域が発達するなど、美しい歯の維持には大きなニーズがある。美しい歯を維持するには歯科医院の治療を受けることが出来るものの、治療に時間を要することや通院が必要となることから、より簡便な方法として自宅で行いたいというニーズが強い。 Traditionally, healthy white teeth have been regarded as a symbol of beauty, and there is a great need for maintaining beautiful teeth, such as the development of aesthetic dentistry in the medical field. To maintain beautiful teeth, you can receive treatment from a dental clinic, but because treatment takes time and requires hospital visits, there is a strong need to do it at home as a simpler method.
　このため、健康で白い歯を保ち続けることを目的とした練り歯磨きや液体ハミガキといったオーラルケア剤が数多く開発・販売されている。歯の白さを妨げる原因としては、食品、タバコやコーヒーなどによる汚れ（デンタルプラーク）や色素（ステイン）が歯面に付着・沈着することで発生することによる（非特許文献１）と考えられている。 For this reason, many oral care agents such as toothpaste and liquid toothpaste have been developed and sold for the purpose of maintaining healthy white teeth. The cause of hindrance to teeth whiteness is considered to be caused by the deposition (stains) of food, tobacco, coffee, etc. (dental plaque) or pigment (stain) on the tooth surface (Non-Patent Document 1). ing.
　デンタルプラークの形成は、ペリクルと呼ばれる唾液中に含まれる糖タンパク質が歯面へと付着、さらに歯面に付着したペリクルに細菌が付着することから始まる。付着した細菌は、多糖類を産生し、歯面に堆積することでデンタルプラークとなることが知られている（非特許文献１）。 Dental plaque formation starts when glycoproteins contained in saliva, called pellicle, adhere to the tooth surface, and bacteria attach to the pellicle attached to the tooth surface. It is known that the attached bacteria produce a polysaccharide and become dental plaque by depositing on the tooth surface (Non-patent Document 1).
　ステインの形成は、一般的には、ペリクルが関与して歯面へコーヒー、お茶やタバコのヤニなどが吸着することが原因である（非特許文献１）と理解されている。しかし、歯のエナメル質に含まれる微量元素が、コーヒーなどの色素と関与して着色する可能性も指摘されており（非特許文献２）、必ずしも歯面への色素の沈着の作用機序については明らかとなっていないのが現状である。 It is understood that the formation of stain is generally caused by the pellicle being involved and adsorbing coffee, tea, cigarettes, etc. on the tooth surface (Non-patent Document 1). However, it has also been pointed out that trace elements contained in tooth enamel may be colored by being involved with pigments such as coffee (Non-Patent Document 2), and the mechanism of pigment deposition on the tooth surface is not necessarily considered. Is not clear.
　このため、作用機序が十分に明らかとなっていないものの、デンタルプラークやステインの付着・沈着を防止する方法について多くの研究開発がされている。これまでにピロリン酸塩などを配合することで歯面への汚れの付着を防止する方法（特許文献１）や、Ｎ－アシルアミノ酸とピロリン酸とを併用することで歯面への汚れの付着を防止する方法（特許文献２）等が開示されているものの、いずれもその歯面へのデンタルプラーク付着防止効果は、不十分であって満足できるものではなかった。このため歯面へのデンタルプラーク・ステインの付着・沈着を防止、抑制効果を併せ持つオーラルケア剤の開発が切望されていた。 For this reason, although the mechanism of action has not been fully clarified, much research and development has been conducted on methods for preventing adhesion and deposition of dental plaque and stain. The method of preventing adhesion of dirt to the tooth surface by adding pyrophosphate, etc. (Patent Document 1), and the adhesion of dirt to the tooth surface by using N-acylamino acid and pyrophosphate together Although the method (patent document 2) etc. which prevent this are disclosed, the dental plaque adhesion preventing effect on the tooth surface is insufficient and is not satisfactory. For this reason, the development of an oral care agent that prevents adhesion and deposition of dental plaque and stain on the tooth surface and has an inhibitory effect has been eagerly desired.
　一方、２－メタクリロイルオキシエチルホスホリルコリン（以下、「ＭＰＣ」という）は、高い生体適合性、抗タンパク質吸着能および高い親水性を有する化合物として知られている（非特許文献３、非特許文献４）。ＭＰＣを用いたオーラルケア剤として、口腔内の乾燥防止や刺激緩和に関する方法（特許文献３）、口腔内の微生物付着防止に関する方法（特許文献４）が開示されている。これまでの研究（非特許文献３、非特許文献４）や開発（特許文献４）から、ＭＰＣを用いることで口腔内のデンタルプラーク付着を防止することは可能であると考えられていたものの、実証はなされておらず、その方法や効果については知られていない状況であった。また、ＭＰＣを用いた口腔内のステインの沈着の防止や抑制に関する方法や効果は全く知られていない状況であった。 On the other hand, 2-methacryloyloxyethyl phosphorylcholine (hereinafter referred to as “MPC”) is known as a compound having high biocompatibility, antiprotein adsorption ability and high hydrophilicity (Non-patent Documents 3 and 4). . As oral care agents using MPC, a method relating to prevention of dryness and stimulation in the oral cavity (Patent Document 3) and a method relating to prevention of microorganism adhesion in the oral cavity (Patent Document 4) are disclosed. From previous research (Non-Patent Document 3, Non-Patent Document 4) and development (Patent Document 4), although it was thought that it was possible to prevent dental plaque adhesion in the oral cavity by using MPC, It has not been verified, and its method and effect are unknown. Moreover, the method and effect regarding prevention and suppression of the deposition of the stain in the oral cavity using MPC were not known at all.
　これより、従来の技術（特許文献１、特許文献２）では十分なデンタルプラーク・ステインの付着・沈着を防止できないために、歯面へのデンタルプラーク・ステインの付着・沈着を防止または抑制できるデンタルプラーク・ステイン付着防止剤およびこれを含有する口腔用組成物は、いまだ満足のいくものが得られていない状況であった。 As a result, since the conventional techniques (Patent Document 1 and Patent Document 2) cannot prevent the adhesion / deposition of dental plaque / stain sufficiently, the dental that can prevent or suppress the adhesion / deposition of dental plaque / stain on the tooth surface. The plaque / stain adhesion inhibitor and the oral composition containing the same have not yet been satisfactory.
特開平９－１２４３８号公報JP-A-9-12438 ＷＯ２０１３／１８３７４８号公報WO2013 / 183748 特開２００６－２７３７６７号公報JP 2006-273767 A 特開２０１１－１５３１０１号公報JP 2011-153101 A
　上記の通り、本発明の課題は、デンタルプラーク・ステインの付着・沈着を防止または抑制できるデンタルプラーク・ステイン付着防止剤およびこれを含有する口腔用組成物を提供することである。 As described above, an object of the present invention is to provide a dental plaque / stain adhesion inhibitor capable of preventing or suppressing adhesion / deposition of dental plaque / stain and an oral composition containing the same.
　本発明者らは、上記課題を解決するために鋭意検討を行った結果、２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位と、これとは異なる特定の構成単位とを特定割合で有する共重合体を、デンタルプラーク・ステイン付着防止剤として用いることで、上記の課題を解決することの知見を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a copolymer having a specific proportion of a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine and a specific structural unit different from the structural unit. By using the polymer as a dental plaque / stain adhesion preventive agent, the inventors have found out that the above problems can be solved and have completed the present invention.
　すなわち、本発明は以下の通りである。
　１．重量平均分子量１０，０００～５，０００，０００であり、
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
　を含有する共重合体を含有するデンタルプラーク・ステイン付着防止剤。
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
 （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。）
　２．構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ１）がブチルメタクリレートに基づく構成単位である、前項１に記載のデンタルプラーク・ステイン付着防止剤。
　３．構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ１）がステアリルメタクリレートに基づく構成単位である、前項１に記載のデンタルプラーク・ステイン付着防止剤。
　４．構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ２）が２－ヒドロキシ－３－メタクリロイルオキシプロピルトリメチルアンモニウムクロライドに基づく構成単位である、前項１に記載のデンタルプラーク・ステイン付着防止剤。
　５．構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ１）がステアリルメタクリレートに基づく構成単位であり、構成単位（Ｂ３）がＮ，Ｎ－ジメチルアミノプロピルアクリルアミドに基づく構成単位である、前項１に記載のデンタルプラーク・ステイン付着防止剤。
　６．前記の１～５に記載のデンタルプラーク・ステイン付着防止剤を０．００１～５．０ｗ／ｖ％と、水３．０～９９．９ｗ／ｖ％とを含有する口腔用組成物。
　７．さらに、サッカリン、サッカリンナトリウム、グリセリン、スクラロース、キシリトール、マルチトール、ステビオサイド、アスパルテームからなる群（Ｃ）より選ばれる少なくとも１種の成分を含有する前記６に記載の口腔用組成物。
　８．以下の工程を含む、デンタルプラーク・ステイン付着防止方法、
　重量平均分子量１０，０００～５，０００，０００であり、
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
　を含有する共重合体を含有するデンタルプラーク・ステイン付着防止剤又は該防止剤を含有する口腔用組成物を、ヒトを含む哺乳類の口腔に投与する工程。
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。）
　９．重量平均分子量１０，０００～５，０００，０００であり、
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
　を含有するデンタルプラーク・ステイン付着防止用共重合体。
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
 （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。）
　１０．重量平均分子量１０，０００～５，０００，０００であり、
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
　を含有する共重合体をデンタルプラーク・ステイン付着防止剤の製造としての使用。
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
 （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。） That is, the present invention is as follows.
1. A weight average molecular weight of 10,000 to 5,000,000,
A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer A dental plaque / stain adhesion-preventing agent comprising a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
 (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
2. 2. The dental plaque / stain adhesion-preventing agent according to item 1, wherein the structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, and the structural unit (B1) is a structural unit based on butyl methacrylate.
3. 2. The dental plaque / stain adhesion inhibitor according to item 1, wherein the structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, and the structural unit (B1) is a structural unit based on stearyl methacrylate.
4). In the item 1, the structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, and the structural unit (B2) is a structural unit based on 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride. The dental plaque / stain adhesion preventer described.
5). The structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, the structural unit (B1) is a structural unit based on stearyl methacrylate, and the structural unit (B3) is N, N-dimethylaminopropyl. 2. The dental plaque / stain adhesion preventer according to item 1, which is a structural unit based on acrylamide.
6). An oral composition containing 0.001 to 5.0 w / v% of the dental plaque / stain adhesion inhibitor described in 1 to 5 above and 3.0 to 99.9 w / v% of water.
7). The oral composition according to 6 above, further comprising at least one component selected from the group (C) consisting of saccharin, sodium saccharin, glycerin, sucralose, xylitol, maltitol, stevioside, and aspartame.
8). A dental plaque / stain adhesion prevention method comprising the following steps:
A weight average molecular weight of 10,000 to 5,000,000,
A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer Dental plaque / stain adhesion inhibitor containing a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3), or an oral composition containing the inhibitor Is administered to the oral cavity of mammals including humans.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
9. A weight average molecular weight of 10,000 to 5,000,000,
A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer A dental plaque / stain adhesion-preventing copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
 (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
10. A weight average molecular weight of 10,000 to 5,000,000,
A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer Use of a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3) as a dental plaque / stain adhesion inhibitor.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
 (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
　本発明のデンタルプラーク・ステイン付着防止剤およびこれを含有する口腔用組成物は、歯面へのデンタルプラーク・ステインの付着・沈着を防止または抑制することができるため、歯の美観・健康維持に有用である。 The dental plaque / stain adhesion preventive agent and oral composition containing the dental plaque / stain of the present invention can prevent or suppress the adhesion / deposition of dental plaque / stain on the tooth surface. Useful.
　以下、本発明をさらに詳細に説明する。
　本発明のデンタルプラーク・ステイン付着防止剤は、｛２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）と、アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位とを含有する共重合体｝を含有する。 Hereinafter, the present invention will be described in more detail.
The dental plaque / stain adhesion-preventing agent of the present invention includes {a structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine, a structural unit (B1) based on an alkyl group-containing (meth) acrylic monomer, A structural unit (B2) based on a quaternary ammonium group-containing (meth) acrylic monomer and at least one structural unit selected from the group consisting of a structural unit (B3) based on a (meth) acrylamide monomer Containing copolymer}.
＜２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）＞
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）は、より具体的には下記の式（Ａ）で表され、式（Ａ'）で表される単量体の重合によって得られる。 <Constitutional unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine>
The structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine is more specifically represented by the following formula (A), and is obtained by polymerization of a monomer represented by the formula (A ′). .
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
 　式（Ａ）および式（Ａ'）において、Ｒ１は水素原子もしくはメチル基のいずれでも良いが、好ましくはメチル基である。
　本発明に用いる共重合体は、分子鎖中に構成単位（Ａ）を有することによって、デンタルプラークやステインの付着を防止する効果を発現することが出来る。
Figure JPOXMLDOC01-appb-C000022
 In Formula (A) and Formula (A ′), R 1 may be either a hydrogen atom or a methyl group, but is preferably a methyl group.
The copolymer used for this invention can express the effect which prevents adhesion of a dental plaque and a stain by having a structural unit (A) in a molecular chain.
　本発明に用いる共重合体中の構成単位（Ａ）の含有量は、１０～９０モル％である。含有量が１０モル％未満であるとデンタルプラーク・ステイン付着防止効果が期待出来ず、含有量が９０モル％より多いと、ＭＰＣセグメントの有する超親水性のために歯面への吸着性に乏しくなり効果が望めなくなる。
　２－（メタ）アクリロイルオキシエチルホスホリルコリンの好適な例として、２－メタクリロイルオキシエチルホスホリルコリンが挙げられる。
　なお、本発明において「（メタ）アクリル」は、アクリルまたはメタアクリル（メタクリル）を意味し、「（メタ）アクリロイル」は、アクリロイルまたはメタアクリロイル（メタクリロイル）を意味し、「（メタ）アクリレート」は、アクリレートまたはメタアクリレート（メタクリレート）を意味する。 The content of the structural unit (A) in the copolymer used in the present invention is 10 to 90 mol%. If the content is less than 10 mol%, the dental plaque / stain adhesion preventing effect cannot be expected. If the content is more than 90 mol%, the adsorptive properties on the tooth surface are poor due to the super hydrophilicity of the MPC segment. The effect cannot be expected.
Preferable examples of 2- (meth) acryloyloxyethyl phosphorylcholine include 2-methacryloyloxyethyl phosphorylcholine.
In the present invention, “(meth) acryl” means acryl or methacryl (methacryl), “(meth) acryloyl” means acryloyl or methacryloyl (methacryloyl), and “(meth) acrylate” , Acrylate or methacrylate (methacrylate).
＜アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）＞
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）は、より具体的には下記の式（Ｂ１）で表され、式（Ｂ１'）で表される単量体の重合によって得られる。
　本発明に用いる共重合体は、分子鎖中に構成単位（Ｂ１）を有することによって、共重合体の歯面への吸着性をより高めることが出来る。 <Constitutional unit (B1) based on alkyl group-containing (meth) acrylic monomer>
The structural unit (B1) based on the alkyl group-containing (meth) acrylic monomer is more specifically represented by the following formula (B1), and by polymerization of the monomer represented by the formula (B1 ′). can get.
The copolymer used for this invention can improve the adsorptivity to the tooth surface of a copolymer more by having a structural unit (B1) in a molecular chain.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（Ｂ１）および式（Ｂ１'）において、Ｒ２は水素原子もしくはメチル基のいずれでも良いが、好ましくはメチル基である。Ｒ３は炭素数４～１８の直鎖状または分岐状のアルキル基のいずれでも良い。
　具体的には、炭素数４～１８の直鎖状のアルキル基としては、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンダデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基が挙げられる。炭素数４～１８の分岐状のアルキル基としては、ｔ－ブチル基、イソブチル基、イソペンチル基、ｔ－ペンチル基、ネオペンチル基、イソヘキシル基、イソヘプチル基、イソオクチル基、イソノニル基、イソデシル基、イソウンデシル基、イソドデシル基、イソトリデシル基、イソテトラデシル基、イソペンタデシル基、イソヘキサデシル基、イソヘプタデシル基、イソオクタデシル基が挙げられる。
　共重合体の歯面への吸着性の観点から、ｎ－ブチル基、ｎ－ドデシル基、ｎ－オクタデシル基が好ましい。 In Formula (B1) and Formula (B1 ′), R 2 may be either a hydrogen atom or a methyl group, but is preferably a methyl group. R 3 may be any linear or branched alkyl group having 4 to 18 carbon atoms.
Specifically, examples of the linear alkyl group having 4 to 18 carbon atoms include n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, Examples thereof include n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Examples of the branched alkyl group having 4 to 18 carbon atoms include t-butyl group, isobutyl group, isopentyl group, t-pentyl group, neopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, and isoundecyl group. , Isododecyl group, isotridecyl group, isotetradecyl group, isopentadecyl group, isohexadecyl group, isoheptadecyl group and isooctadecyl group.
From the viewpoint of adsorptivity to the tooth surface of the copolymer, n-butyl group, n-dodecyl group, and n-octadecyl group are preferable.
　構成単位（Ｂ１）を満たす構造を有していれば、共重合体の歯面への吸着性を損なうことが無いため、いずれでも用いることができるが、共重合体の歯面への吸着性をより高める観点から、アルキル基含有（メタ）アクリル系単量体の好適な例として、ブチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレートが挙げられる。 As long as it has a structure satisfying the structural unit (B1), it does not impair the adsorptivity of the copolymer to the tooth surface, and any of these can be used. From the viewpoint of further improving the viscosity, preferred examples of the alkyl group-containing (meth) acrylic monomer include butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. It is done.
＜４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）＞
　４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）は、より具体的には下記の式（Ｂ２）で表され、式（Ｂ２'）で表される単量体の重合によって得られる。
　本発明に用いる共重合体は、分子鎖中に構成単位（Ｂ２）を有することによって、共重合体の歯面への吸着性をより高めることが出来る。 <Structural Unit (B2) Based on Quaternary Ammonium Group-Containing (Meth) acrylic Monomer>
More specifically, the structural unit (B2) based on the quaternary ammonium group-containing (meth) acrylic monomer is represented by the following formula (B2), which is a monomer represented by the formula (B2 ′). Obtained by polymerization.
The copolymer used for this invention can improve the adsorptivity to the tooth surface of a copolymer more by having a structural unit (B2) in a molecular chain.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（Ｂ２）および式（Ｂ２'）において、Ｒ４は水素原子もしくはメチル基のいずれでも良いが、好ましくはメチル基である。Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、アルキル基は直鎖状、分岐状および環状のいずれであっても良い。 In formula (B2) and formula (B2 ′), R 4 may be either a hydrogen atom or a methyl group, but is preferably a methyl group. R 5 , R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear, branched or cyclic.
　具体的には、Ｒ５、Ｒ６およびＲ７としてメチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｎ－ヘキシル基、イソヘキシル基、ｎ－ヘプチル基、イソヘプチル基、ｎ－オクチル基、イソオクチル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基などが挙げられる。
　Ｒ５、Ｒ６およびＲ７として好ましくはメチル基、エチル基、プロピル基、イソプロピル基であり、より好ましくはメチル基である。 Specifically, as R 5 , R 6 and R 7 , methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group Group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
R 5 , R 6 and R 7 are preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and more preferably a methyl group.
　Ｘ－としては、例えば、フッ素イオン、臭素イオン、塩素イオン（クロライドイオン）などのハロゲンイオン、硫酸イオン、メチル硫酸イオンなどの酸残基が挙げられる。好ましくは、ハロゲンイオンである。
　共重合体の歯面への吸着性をより高める観点から、４級アンモニウム基含有（メタ）アクリル系単量体の好適な例として、２－ヒドロキシ－３－（メタ）アクリロイルオキシプロピルトリメチルアンモニウムクロライドなどが挙げられる。 Examples of X − include halogen ions such as fluorine ion, bromine ion and chlorine ion (chloride ion), and acid residues such as sulfate ion and methyl sulfate ion. Preferably, it is a halogen ion.
As a suitable example of a quaternary ammonium group-containing (meth) acrylic monomer from the viewpoint of further enhancing the adsorptivity of the copolymer to the tooth surface, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride is preferable. Etc.
＜（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）＞
　（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）は、より具体的には下記の式（Ｂ３）で表され、式（Ｂ３'）で表される単量体の重合によって得られる。
　本発明に用いる共重合体は、分子鎖中に構成単位（Ｂ３）を有することによって、共重合体を高分子量化し、共重合体の歯面への密着性をより高めることが出来る。 <Structural Unit (B3) Based on (Meth) acrylamide Monomer>
More specifically, the structural unit (B3) based on the (meth) acrylamide monomer is represented by the following formula (B3), and is obtained by polymerization of the monomer represented by the formula (B3 ′).
When the copolymer used in the present invention has the structural unit (B3) in the molecular chain, the copolymer can have a high molecular weight, and the adhesion of the copolymer to the tooth surface can be further increased.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（Ｂ３）および式（Ｂ３'）において、Ｒ８は水素原子もしくはメチル基のいずれでも良いが、好ましくは水素原子である。Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示し、アルキル基は直鎖状、分岐状および環状のいずれであっても良い。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｎ－ヘキシル基、イソヘキシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基などが挙げられる。
　Ｒ９およびＲ１０として好ましくは、水素原子、メチル基、エチル基、プロピル基もしくはイソプロピル基であり、より好ましくはメチル基である。
　共重合体を高分子量化し、共重合体の歯面への密着性をより高める観点から、（メタ）アクリルアミド系単量体の好適な例として、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド等が挙げられる。 In formula (B3) and formula (B3 ′), R 8 may be a hydrogen atom or a methyl group, but is preferably a hydrogen atom. R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
R 9 and R 10 are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group, and more preferably a methyl group.
From the viewpoint of increasing the molecular weight of the copolymer and further improving the adhesion of the copolymer to the tooth surface, N, N-dimethylaminopropyl (meth) acrylamide and the like are preferred examples of (meth) acrylamide monomers. Is mentioned.
　本発明に用いる共重合体は、分子鎖中に（Ｂ１）、（Ｂ２）および（Ｂ３）からなる群から選択される少なくとも１つの構成単位を有する。本発明に用いる共重合体は、分子鎖中に（Ｂ１）、（Ｂ２）および（Ｂ３）からなる群から選択されるいずれか１つの構成単位のみを有していてもよく、（Ｂ１）、（Ｂ２）および（Ｂ３）からなる群から選択される２つの構成単位（例えば、（Ｂ１）および（Ｂ２）の組み合わせ、（Ｂ２）および（Ｂ３）の組み合わせ、（Ｂ３）および（Ｂ１）の組み合わせ）を有していてもよく、（Ｂ１）、（Ｂ２）および（Ｂ３）の全ての構成単位を有していても良い。 The copolymer used in the present invention has at least one structural unit selected from the group consisting of (B1), (B2) and (B3) in the molecular chain. The copolymer used in the present invention may have only one structural unit selected from the group consisting of (B1), (B2) and (B3) in the molecular chain, (B1), Two structural units selected from the group consisting of (B2) and (B3) (for example, a combination of (B1) and (B2), a combination of (B2) and (B3), and a combination of (B3) and (B1) ) Or all the structural units of (B1), (B2) and (B3).
　本発明に用いる共重合体は、分子鎖中に構成単位（Ｂ１）～（Ｂ３）を有することによって、共重合体の歯面への吸着性、密着性が高くなる。さらに（Ｂ１）～（Ｂ３）だけでなく、構成単位（Ａ）をも同一高分子鎖中に有することによって、本発明に用いる共重合体は、歯面への吸着性を有するデンタルプラーク・ステイン付着防止剤となる。本発明に用いる共重合体中の構成単位（Ｂ１）～（Ｂ３）の含有量｛（Ｂ１）～（Ｂ３）のうち１つの構成単位のみを含有する場合は当該構成単位の含有量、（Ｂ１）～（Ｂ３）のうち２つまたは３つの構成単位を含有する場合は、それらの構成単位の含有量の合計｝は１０～９０モル％であり、好ましくは１０～８０モル％であり、より好ましくは１０～７０モル％である。含有量が１０モル％未満であると共重合体の親水性が高くなり、歯面への吸着性に乏しくなり、デンタルプラーク・ステイン付着防止効果が望めなくなる恐れがあり、含有量が９０モル％より多いと水への溶解性が低下し、口腔用組成物を製することが困難となる恐れがある。 The copolymer used in the present invention has the structural units (B1) to (B3) in the molecular chain, thereby increasing the adsorptivity and adhesion to the tooth surface of the copolymer. Furthermore, by having not only (B1) to (B3) but also the structural unit (A) in the same polymer chain, the copolymer used in the present invention has a dental plaque stain having adsorptivity to the tooth surface. It becomes an adhesion preventing agent. Content of structural units (B1) to (B3) in the copolymer used in the present invention {when only one structural unit is contained among (B1) to (B3), the content of the structural unit (B1 ) To (B3) containing two or three constituent units, the total content of these constituent units} is 10 to 90 mol%, preferably 10 to 80 mol%, more Preferably, it is 10 to 70 mol%. If the content is less than 10 mol%, the hydrophilicity of the copolymer becomes high, the adsorptivity to the tooth surface becomes poor, and the dental plaque / stain adhesion preventing effect may not be expected, and the content is 90 mol%. If it is more, the solubility in water is lowered, and it may be difficult to produce an oral composition.
　本発明に用いる共重合体の分子鎖中に含まれる、構成単位（Ａ）と構成単位（Ｂ１）～（Ｂ３）の組み合わせの好適な例は、デンタルプラーク・ステイン付着防止効果と共重合体の歯面への吸着性・密着性の観点から、以下の組み合わせが挙げられる。
　２－（メタ）アクリロイルオキシエチルホスホリルコリン（Ａ）およびブチル（メタ）アクリレート（Ｂ１）；
　２－（メタ）アクリロイルオキシエチルホスホリルコリン（Ａ）およびステアリル（メタ）アクリレート（Ｂ１）；
　２－（メタ）アクリロイルオキシエチルホスホリルコリン（Ａ）および２－ヒドロキシ－３－（メタ）アクリロイルオキシプロピルトリメチルアンモニウムクロライド（Ｂ２）；ならびに、
　２－（メタ）アクリロイルオキシエチルホスホリルコリン（Ａ）、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド（Ｂ３）およびステアリル（メタ）アクリレート（Ｂ１）。 Preferred examples of the combination of the structural unit (A) and the structural units (B1) to (B3) contained in the molecular chain of the copolymer used in the present invention are the dental plaque / stain adhesion preventing effect and the copolymer. From the viewpoint of adsorptivity and adhesion to the tooth surface, the following combinations are exemplified.
2- (meth) acryloyloxyethyl phosphorylcholine (A) and butyl (meth) acrylate (B1);
2- (meth) acryloyloxyethyl phosphorylcholine (A) and stearyl (meth) acrylate (B1);
2- (meth) acryloyloxyethyl phosphorylcholine (A) and 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride (B2); and
2- (meth) acryloyloxyethyl phosphorylcholine (A), N, N-dimethylaminopropyl (meth) acrylamide (B3) and stearyl (meth) acrylate (B1).
　本発明に用いる共重合体は、構成単位（Ａ）および構成単位（Ｂ１）～（Ｂ３）以外の構成単位を含んでいても良いが、好ましくは、構成単位（Ａ）および、構成単位（Ｂ１）、（Ｂ２）並びに（Ｂ３）からなる群より選択される１つ、２つまたは３つの構成単位からなる。 The copolymer used in the present invention may contain a structural unit other than the structural unit (A) and the structural units (B1) to (B3). Preferably, the structural unit (A) and the structural unit (B1) ), (B2), and (B3), one, two, or three constituent units.
　本発明に用いられる共重合体は、特開平１１－０３５６０５の方法に従って重合を行い得たＭＰＣポリマー（１）、特開２００４－１９６８６８の方法に従って重合を行い得たＭＰＣポリマー（２）、特開２００４－１９６８６８の方法に従って重合を行い得たＭＰＣポリマー（３）、特開２００４－１８９６７８の方法に従って重合を行い得たＭＰＣポリマー（４）および特開２０１３－０１８７４９の方法に従って重合を行い得たＭＰＣポリマー（５）を用いることが出来る。 The copolymer used in the present invention includes an MPC polymer (1) obtained by polymerization according to the method of JP-A-11-035605, an MPC polymer (2) obtained by polymerization according to the method of JP-A 2004-196868, MPC polymer (3) obtained by polymerization according to the method of 2004-196868, MPC polymer (4) obtained by polymerization according to the method of JP2004-189678 and MPC obtained by polymerization according to the method of JP2013-018749 Polymer (5) can be used.
　本発明に用いる共重合体の重量平均分子量は１０，０００～５，０００，０００であり、好ましくは、２０，０００～１，０００，０００である。重量平均分子量が１０，０００未満であると歯面への吸着性が低下し、デンタルプラーク・ステイン付着防止効果が望めなくなり、重量平均分子量が５，０００，０００より大きいと粘度が急激に上昇し、口腔用組成物を製することが困難となる恐れがある。 The weight average molecular weight of the copolymer used in the present invention is 10,000 to 5,000,000, preferably 20,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the adsorptivity to the tooth surface is reduced, and the dental plaque / stain adhesion preventing effect cannot be expected. If the weight average molecular weight is more than 5,000,000, the viscosity increases rapidly. It may be difficult to produce a composition for oral cavity.
　本発明のデンタルプラーク・ステイン付着防止剤または該防止剤を含有する口腔用組成物に含有する前記共重合体の配合量は、当該共重合体を防止剤または組成物全体に対して、０．００１～５．０ｗ／ｖ％である。配合量が０．００１ｗ／ｖ％未満であると、デンタルプラーク・ステイン付着防止効果が得られない恐れがあり、配合量が５．０ｗ／ｖ％以上であっても、添加量に見合った効果が得られない。
　加えて、本発明のデンタルプラーク・ステイン付着防止剤または該防止剤を含有する口腔用組成物の濃度は、より好ましくは、０．０１～５．０ Ｗ／Ｖ％であり、さらに好ましくは０．０５～５．０ Ｗ／Ｖ％である。 The amount of the copolymer contained in the dental plaque / stain adhesion inhibitor of the present invention or the oral composition containing the inhibitor is such that the copolymer is added to the inhibitor or the entire composition in an amount of 0. 0. 001 to 5.0 w / v%. If the blending amount is less than 0.001 w / v%, the dental plaque / stain adhesion preventing effect may not be obtained, and even if the blending amount is 5.0 w / v% or more, the effect commensurate with the addition amount Cannot be obtained.
In addition, the concentration of the dental plaque / stain adhesion inhibitor of the present invention or the oral composition containing the inhibitor is more preferably 0.01 to 5.0 W / V%, still more preferably 0. 0.05-5.0 W / V%.
　本発明に用いる（Ｃ）群としては、サッカリン、サッカリンナトリウム、グリセリン、スクラロース、キシリトール、マルチトール、ステビオサイド、アスパルテームである。これら（Ｃ）群の成分を添加することで歯面へのデンタルプラークやステインがより付着・沈着しにくくなるとともに、さらに、一度歯面へ付着・沈着したデンタルプラークやステインが落ち易くなる。本発明の（Ｃ）群の含有量は、通常、０．００１～１０．０ｗ／ｖ％であれば良い。よりデンタルプラーク・ステイン付着防止効果を高める観点から、０．００２～１０．０ｗ／ｖ％が好ましく、さらに好ましくは、０．００３～８．０ｗ／ｖ％である。 (C) group used in the present invention is saccharin, saccharin sodium, glycerin, sucralose, xylitol, maltitol, stevioside, aspartame. By adding the components of group (C), dental plaque and stain on the tooth surface are more difficult to adhere and deposit, and further, dental plaque and stain once attached and deposited on the tooth surface are more likely to fall off. The content of the group (C) of the present invention is usually 0.001 to 10.0 w / v%. From the viewpoint of further enhancing the effect of preventing dental plaque / stain adhesion, 0.002 to 10.0 w / v% is preferable, and 0.003 to 8.0 w / v% is more preferable.
　さらに、本発明のデンタルプラーク・ステイン付着防止剤または該防止剤を含有する口腔用組成物は、共重合体や（Ｃ）群成分以外にも必要に応じて一般に口腔用組成物に使用できる緩衝剤、湿潤剤、薬剤、界面活性剤、防腐殺菌剤、粘結剤、香料、有機酸、酸化防止剤、安定剤、金属封鎖剤、溶剤等を配合することができる。
　緩衝剤としては特に限定されないが、クエン酸、リン酸、リンゴ酸、グルコン酸およびこれらの塩が挙げられ、０．００１ｗ／ｖ％～３．０ｗ／ｖ％で使用されることが望ましい。 Furthermore, the dental plaque / stain adhesion preventive agent of the present invention or the oral composition containing the inhibitor is a buffer that can be generally used for oral compositions as needed in addition to the copolymer and the (C) group component. An agent, a wetting agent, a drug, a surfactant, an antiseptic and bactericide, a binder, a fragrance, an organic acid, an antioxidant, a stabilizer, a metal sequestering agent, a solvent, and the like can be blended.
Although it does not specifically limit as a buffering agent, Citric acid, phosphoric acid, malic acid, gluconic acid, and these salts are mentioned, It is desirable to be used at 0.001 w / v%-3.0 w / v%.
　湿潤剤は、プロピレングリコール、ブチレングリコール、ペンチレングリコール、ジプロピレングリコール、ポリエチレングリコール、マンニトール、エリスリトールなどの多価アルコールが挙げられ、１．０ｗ／ｖ％～５０．０ｗ／ｖ％で使用されることが望ましい。
　薬剤としては、特に限定されないが、アズレンスルホン酸ナトリウム、イプシロン－アミノカプロン酸、アラントイン、アラントインクロルヒドロキシアルミニウム、アラントインヒドロキシアルミニウム、エピジヒドロキシコレステリン、ジヒドロコレステロール、塩化ナトリウム、硝酸カリウム、乳酸アルミニウム、塩化亜鉛、グリチルリチン酸およびその塩、β－グリチルリチン酸、イソプロピルメチルフェノール、塩化セチルピリジニウム、塩化デカリウム、塩化ベンザルコニウム、塩化ベンゼトニウム、塩酸アルキルジアミノエチルグリシン、塩酸クロルヘキシジン、グルコン酸クロルヘキシジン、トリクロサン、１、８－シネオール、アスコルビン酸およびその塩、塩酸ピリドキシン、酢酸ｄｌ－α－トコフェロール、ニコチン酸ｄｌ－α－トコフェロール、ゼオライト、ピロリン酸二水素二ナトリウム、ピロリン酸ナトリウム、リン酸１水素ナトリウム、リン酸三ナトリウム、ポリリン酸ナトリウム、フッ化ナトリウム、モノフルオロリン酸ナトリウム、ポリエチレングリコール、ポリビニルピロリドン、ポビドンヨード、塩化リゾチーム、銅クロロフィリンナトリウム、ヒノキチオール、ポリオキシエチレンラウリルエーテル（８～１０Ｅ．Ｏ．）、ラウロイルサルコシンナトリウム、トラネキサム酸、サリチル酸メチル、ｌ－メントールなどが挙げられる。 Examples of the wetting agent include polyhydric alcohols such as propylene glycol, butylene glycol, pentylene glycol, dipropylene glycol, polyethylene glycol, mannitol, and erythritol, and are used at 1.0 w / v% to 50.0 w / v%. It is desirable.
The drug is not particularly limited, but sodium azulenesulfonate, epsilon-aminocaproic acid, allantoin, allantochlorohydroxyaluminum, allantoinhydroxyaluminum, epidihydroxycholesterine, dihydrocholesterol, sodium chloride, potassium nitrate, aluminum lactate, zinc chloride, glycyrrhizin Acids and salts thereof, β-glycyrrhizic acid, isopropylmethylphenol, cetylpyridinium chloride, depotassium chloride, benzalkonium chloride, benzethonium chloride, alkyldiaminoethylglycine hydrochloride, chlorhexidine hydrochloride, chlorhexidine gluconate, triclosan, 1,8-cineole, Ascorbic acid and its salts, pyridoxine hydrochloride, dl-α-tocopherol acetate, nicotinic acid dl-α-tocopherol, zeolite, disodium dihydrogen pyrophosphate, sodium pyrophosphate, sodium monohydrogen phosphate, trisodium phosphate, sodium polyphosphate, sodium fluoride, sodium monofluorophosphate, polyethylene glycol, polyvinylpyrrolidone, Examples thereof include povidone iodine, lysozyme chloride, copper chlorophyllin sodium, hinokitiol, polyoxyethylene lauryl ether (8 to 10 EO), lauroyl sarcosine sodium, tranexamic acid, methyl salicylate, and l-menthol.
　界面活性剤としては特に限定はされないが、ポリオキシエチレン硬化ヒマシ油、ソルビタン脂肪酸エチレン付加物、ポリグリセリン脂肪酸エステル、アシルアミノ酸塩、脂肪酸アミノプロピルベタイン、脂肪酸アミドベタインなどが挙げられ、特にポリオキシエチレン硬化ヒマシ油、ソルビタン脂肪酸エチレン付加物を０．０５ｗ／ｖ％～２．０ｗ／ｖ％で使用されることが好ましい。 The surfactant is not particularly limited, and examples thereof include polyoxyethylene hydrogenated castor oil, sorbitan fatty acid ethylene adduct, polyglycerin fatty acid ester, acylamino acid salt, fatty acid aminopropyl betaine, fatty acid amide betaine, and particularly polyoxyethylene. It is preferable to use hydrogenated castor oil and sorbitan fatty acid ethylene adduct at 0.05 w / v% to 2.0 w / v%.
　防腐殺菌剤としては特に限定はされないが、塩酸ポリヘキサニド、ヒノキチオール、安息香酸およびこの塩、パラベン類などが挙げられ、通常配合量は０．０１ｗ／ｖ％～１．０ｗ／ｖ％である。 The antiseptic disinfectant is not particularly limited, and examples thereof include polyhexanide hydrochloride, hinokitiol, benzoic acid and salts thereof, and parabens, and the usual blending amount is 0.01 w / v% to 1.0 w / v%.
　粘結剤としては特に限定はされないが、プルラン、ゼラチン、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルセルロースなどのセルロース系粘稠化剤、ヒアルロン酸およびその塩、コンドロイチン硫酸およびその塩、アルギン酸およびその塩、ジュランガム、キサンタンガムなどのような多糖類などが挙げられる。 The binder is not particularly limited, but cellulose-based thickening agents such as pullulan, gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hyaluronic acid and its salt, chondroitin sulfate and its salt And polysaccharides such as alginic acid and salts thereof, duran gum, xanthan gum and the like.
　香料としては特に限定はされないが、ペパーミント油、スペアミント油、アニス油、ユーカリ油、ウィンターグリーン油、カシア油、クローブ油、タイム油、セージ油、レモン油、オレンジ油、ハッカ油、カルダモン油、コリアンダー油、マンダリン油、ライム油、ラベンダー油、ローズマリー油、ローレル油、カモミル油、キャラウェイ油、マジョラム油、ベイ油、レモングラス油、オリガナム油、パインニードル油、ネロリ油、ローズ油、ジャスミン油、グレープフルーツ油、スウィーティー油、柚油、イリスコンクリート、アブソリュートペパーミント、アブソリュートローズ、オレンジフラワー等の天然香料、およびこれら天然香料の加工処理（前溜部カット、後溜部カット、分留、液液抽出、エッセンス化、粉末香料化等）した香料、および、ｌ－メントール、カルボン、アネトール、シネオール、サリチル酸メチル、シンナミックアルデヒド、オイゲノール、３－ｌ－メントキシプロパン－１、２－ジオール、チモール、リナロール、リナリールアセテート、リモネン、メントン、メンチルアセテート、Ｎ－置換－パラメンタン－３－カルボキサミド、ピネン、オクチルアルデヒド、シトラール、プレゴン、カルビールアセテート、アニスアルデヒド、エチルアセテート、エチルブチレート、アリルシクロヘキサンプロピオネート、メチルアンスラニレート、エチルメチルフェニルグリシデート、バニリン、ウンデカラクトン、ヘキサナール、ブタノール、イソアミルアルコール、ヘキセノール、ジメチルサルファイド、シクロテン、フルフラール、トリメチルピラジン、エチルラクテート、エチルチオアセテート等の単品香料、さらに、ストロベリーフレーバー、アップルフレーバー、バナナフレーバー、パイナップルフレーバー、グレープフレーバー、マンゴーフレーバー、バターフレーバー、ミルクフレーバー、フルーツミックスフレーバー、トロピカルフルーツフレーバー等の調合香料などが挙げられ、０．００１ｗ／ｖ％～１．０ｗ／ｖ％で使用されることが望ましい。
　有機酸としては特に限定はされないが、リンゴ酸、クエン酸、酒石酸、アスコルビン酸などが挙げられる。
　酸化防止剤としては特に限定はされないが、ビタミンＥ、ビタミンＣ、茶抽出物、ローズマリー抽出物などが挙げられる。
　安定剤としては特に限定はされないが、亜硫酸ナトリウム、ピロ亜硫酸ナトリウム、亜硫酸水素ナトリウム、ブチルヒドロキシトルエン、没食子酸プロピル、ブチルヒドロキシアリール等が挙げられる。 Although it is not particularly limited as a fragrance, peppermint oil, spearmint oil, anise oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander Oil, mandarin oil, lime oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil , Grapefruit oil, sweetie oil, cocoon oil, Iris concrete, absolute peppermint, absolute rose, orange flower, and other natural fragrances, and processing of these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction) Essence, powdered fragrance, etc.) , And l-menthol, carvone, anethole, cineol, methyl salicylate, synamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate , N-substituted-paramentane-3-carboxamide, pinene, octyl aldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate , Vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine , Ethyl lactate, ethyl thioacetate, etc. And is preferably used at 0.001 w / v% to 1.0 w / v%.
Although it does not specifically limit as an organic acid, Malic acid, a citric acid, tartaric acid, ascorbic acid etc. are mentioned.
Although it does not specifically limit as antioxidant, A vitamin E, vitamin C, a tea extract, a rosemary extract etc. are mentioned.
The stabilizer is not particularly limited, and examples thereof include sodium sulfite, sodium pyrosulfite, sodium hydrogen sulfite, butylhydroxytoluene, propyl gallate, and butylhydroxyaryl.
　金属封鎖剤として特に限定はされないが、１－ヒドロキシエタン－１，１－ジフォスホン酸、１－ヒドロキシエタン－１，１－ジフォスホン酸四ナトリウム塩、エデト酸二ナトリウム、エデト酸三ナトリウム、エデト酸四ナトリウム、クエン酸ナトリウム、ポリリン酸ナトリウム、メタリン酸ナトリウム、グルコン酸、リン酸、クエン酸、アスコルビン酸、コハク酸、エデト酸、エチレンジアミンヒドロキシエチル三酢酸３ナトリウム等を挙げることが出来る。
　溶剤として特に限定はされないが、水、エタノールを挙げることができる。 Although it does not specifically limit as a metal sequestering agent, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, edetate tetra Examples include sodium, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate, and the like.
Although it does not specifically limit as a solvent, Water and ethanol can be mentioned.
　本発明のデンタルプラーク・ステイン付着防止剤の具体的な製品形態としては、口腔用組成物として使用することが好ましく、次のようなものを例示することが出来る。すなわち、練り歯磨き、液体ハミガキ、洗口液、含そう薬、口腔清涼化剤などが挙げられる。口腔用組成物としては、中でも、練り歯磨き、液体ハミガキ、洗口液、含そう薬とすることが好ましい。
　本発明のデンタルプラーク・ステイン付着防止剤は、練り歯磨き、液体ハミガキ、洗口液や含そう薬等として、ヒトの歯へ適用してその効果を発現させることが好ましいが、義歯や歯科材料へも適用することが出来る。 As a specific product form of the dental plaque / stain adhesion preventing agent of the present invention, it is preferably used as a composition for oral cavity, and the following can be exemplified. That is, toothpaste, liquid toothpaste, mouthwash, mouthwash, oral refreshing agent and the like. As the composition for oral cavity, toothpaste, liquid toothpaste, mouthwash, and mouthwash are preferable.
The dental plaque / stain adhesion preventive agent of the present invention is preferably applied to human teeth as a toothpaste, liquid toothpaste, mouthwash or mouthwash, etc. Can also be applied.
　本発明は、以下の工程を含む、デンタルプラーク・ステイン付着防止方法も対象とする。
　重量平均分子量１０，０００～５，０００，０００であり、
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
　を含有する共重合体を含有するデンタルプラーク・ステイン付着防止剤又は該防止剤を含有する口腔用組成物を、ヒトを含む哺乳類の口腔に投与する工程。
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
 （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。） The present invention is also directed to a dental plaque / stain adhesion prevention method including the following steps.
A weight average molecular weight of 10,000 to 5,000,000,
A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer Dental plaque / stain adhesion inhibitor containing a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3), or an oral composition containing the inhibitor Is administered to the oral cavity of mammals including humans.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
 (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
　本発明のデンタルプラーク・ステイン付着防止方法は、特に限定されないが、例えば、本発明のデンタルプラーク・ステイン付着防止剤を含有する口腔用組成物（液体ハミガキ）１回あたり５～５０ ｍＬを１日あたり１～１０回、１～８回、１～６回、１～４回、１～３回（好ましくは、朝、昼、晩）、１回あたり５秒以上口に含み含そうすることが可能である。
　また、別の態様では、例えば、本発明のデンタルプラーク・ステイン付着防止剤を含有する口腔用組成物（練り歯磨き剤）１回あたり０．０１～２ ｇを使用して、１日あたり１～１０回、１～８回、１～６回、１～４回、１～３回（好ましくは、朝、昼、晩）、ブラッシングすることが可能である。
　デンタルプラーク・ステイン付着防止方法の対象は、特に限定されないが、ヒトを含む哺乳類を対象とする。なお、前記ヒトを含む哺乳類が、取外し可能な義歯又は歯科材料を装着している場合、取り外した状態の義歯又は歯科材料も対象とすることができる。
　例えば、本発明のデンタルプラーク・ステイン付着防止剤を水やエタノール等に溶解した溶液に、義歯又は歯科材料を、１日あたり１～１０回、１～８回、１～６回、１～４回、１～３回、１回あたり３０秒以上浸漬することを例示することができる。 The method for preventing dental plaque / stain adhesion of the present invention is not particularly limited. For example, 5 to 50 mL of oral dental composition (liquid toothpaste) containing the dental plaque / stain adhesion preventing agent of the present invention is used for 1 day. 1-10 times, 1-8 times, 1-6 times, 1-4 times, 1-3 times (preferably morning, noon, evening) Is possible.
In another embodiment, for example, an oral composition (toothpaste) containing 0.01 to 2 g per day containing the dental plaque / stain adhesion preventive agent of the present invention is used in an amount of 1 to 2 per day. Brushing is possible 10 times, 1 to 8, 1 to 6, 1 to 4, 1 to 3 times (preferably morning, noon, evening).
The subject of the dental plaque / stain adhesion prevention method is not particularly limited, but is intended for mammals including humans. In addition, when the mammal including the said human is equipped with a removable denture or dental material, the removed denture or dental material can also be targeted.
For example, a denture or dental material is added 1 to 10 times, 1 to 8 times, 1 to 6 times, 1 to 4 times, 1 to 4 times a day in a solution of the dental plaque / stain adhesion inhibitor of the present invention dissolved in water or ethanol. Examples of the immersion are 1 to 3 times, 30 seconds or more per time.
　本発明は、重量平均分子量１０，０００～５，０００，０００であり、
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
　を含有するデンタルプラーク・ステイン付着防止用共重合体も対象とする。
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
 （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。） The present invention has a weight average molecular weight of 10,000 to 5,000,000,
A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer A dental plaque / stain adhesion-preventing copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3) is also targeted.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
 (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
　本発明は、重量平均分子量１０，０００～５，０００，０００であり、
　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
　を含有する共重合体をデンタルプラーク・ステイン付着防止剤の製造としての使用も対象とする。
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
 （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。） The present invention has a weight average molecular weight of 10,000 to 5,000,000,
A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer The use of a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3) as a dental plaque / stain adhesion inhibitor is also an object.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
 (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
　以下、本発明について実施例および比較例により、本発明のデンタルプラーク・ステイン付着防止剤、該防止剤を含む口腔用組成物およびデンタルプラーク・ステイン付着防止方法の効果を具体的に説明する。なお、本実施例および比較例に用いた共重合および重合体は、次の通りである。
　ＭＰＣポリマー（１）：　２－メタクリロイルオキシエチルホスホリルコリン・ブチルメタクリレート共重合体〔共重合組成比（モル比）８０／２０、重量平均分子量：６００，０００〕であり、特開平１１－０３５６０５の実施例記載の方法によって重合を行って得られた。
　ＭＰＣポリマー（２）：　２－メタクリロイルオキシエチルホスホリルコリン・ブチルメタクリレート共重合体〔共重合組成比（モル比）３０／７０、重量平均分子量：１４２，０００〕であり、特開２００４－１９６８６８の実施例記載の方法によって重合を行って得られた。
　ＭＰＣポリマー（３）：　２－メタクリロイルオキシエチルホスホリルコリン・ステアリルメタクリレート共重合体〔共重合組成（モル比）３３／６７、重量平均分子量：１６４，０００〕であり、特開２００４－１９６８６８の実施例記載の方法によって重合を行って得られた。
　ＭＰＣポリマー（４）：　２－メタクリロイルオキシエチルホスホリルコリン・２－ヒドロキシ－３－メタクリロイルオキシプロピルトリメチルアンモニウムクロライド共重合体〔共重合組成（モル比）７０／３０、重量平均分子量：４５０，０００〕であり、特開２００４－１８９６７８の実施例記載の方法によって重合を行って得られた。
　ＭＰＣポリマー（５）：　２－メタクリロイルオキシエチルホスホリルコリン・Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミド・ステアリルメタクリレート共重合体〔共重合組成（モル比）９０／２／８、重量平均分子量：８２０，０００〕であり、特開２０１３－０１８７４９の実施例記載の方法によって重合を行って得られた。
　ホモポリマー（Ａ）：　２－メタクリロイルオキシエチルホスホリルコリンの重合体〔重量平均分子量：２００，０００〕であり、特開平８－３３３４２１の実施例記載の方法によって重合を行って得られた。
　ホモポリマー（Ｂ１）：ブチルメタクリレートの重合体〔重量平均分子量：１８０，０００〕であり、和光純薬工業（株）（製品名：ポリ（メタクリル酸ｎ－ブチル））より購入して試験に用いた。
　ホモポリマー（Ｂ２）：　２－ヒドロキシ－３－メタクリロイルオキシプロピルトリメチルアンモニウムクロライドの重合体〔重量平均分子量：３００，０００〕であり、特開平８－２５８４０３の実施例記載の方法によって重合を行って得られた。
　ホモポリマー：　Ｎ，Ｎ－ジメチルアクリルアミドの重合体〔数平均分子量：１０，０００〕であり、シグマアルドリッチジャパン（製品名：Ｐｏｌｙ（Ｎ，Ｎ－ｄｉｍｅｔｈｙｌａｃｒｙｌａｍｉｄｅ）、ＤＤＭＡＴ　ｔｅｒｍｉｎａｔｅｄ）より購入して試験に用いた。 Hereinafter, the effects of the dental plaque / stain adhesion preventing agent, the oral composition containing the inhibitor and the dental plaque / stain adhesion preventing method of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. The copolymers and polymers used in the examples and comparative examples are as follows.
MPC polymer (1): 2-methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer (copolymerization composition ratio (molar ratio) 80/20, weight average molecular weight: 600,000), Examples of JP-A No. 11-035605 It was obtained by carrying out the polymerization by the method described.
MPC polymer (2): 2-methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer (copolymerization composition ratio (molar ratio) 30/70, weight average molecular weight: 142,000), Examples of JP-A 2004-196868 It was obtained by carrying out the polymerization by the method described.
MPC polymer (3): 2-methacryloyloxyethyl phosphorylcholine / stearyl methacrylate copolymer [copolymerization composition (molar ratio) 33/67, weight average molecular weight: 164,000], described in Examples of JP-A-2004-196868 It was obtained by carrying out polymerization by the method.
MPC polymer (4): 2-methacryloyloxyethyl phosphorylcholine / 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride copolymer [copolymerization composition (molar ratio) 70/30, weight average molecular weight: 450,000] The polymerization was carried out by the method described in Examples of JP-A-2004-189678.
MPC polymer (5): 2-methacryloyloxyethyl phosphorylcholine / N, N-dimethylaminopropylacrylamide / stearyl methacrylate copolymer [copolymerization composition (molar ratio) 90/2/8, weight average molecular weight: 820,000] And obtained by polymerization according to the method described in Examples of JP2013-018749A.
Homopolymer (A): 2-methacryloyloxyethyl phosphorylcholine polymer [weight average molecular weight: 200,000], which was obtained by polymerization according to the method described in Examples of JP-A-8-333421.
Homopolymer (B1): butyl methacrylate polymer [weight average molecular weight: 180,000], purchased from Wako Pure Chemical Industries, Ltd. (product name: poly (n-butyl methacrylate)) for testing It was.
Homopolymer (B2): 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride polymer [weight average molecular weight: 300,000], obtained by polymerization according to the method described in Examples of JP-A-8-258403 It was.
Homopolymer: N, N-dimethylacrylamide polymer [number average molecular weight: 10,000], purchased from Sigma-Aldrich Japan (product name: Poly (N, N-dimethylacylamide), DDMAT terminated) for testing It was.
［実施例１］
　精製水約８０ｇにＭＰＣポリマー（１）０．００１ｇを加え、攪拌した。この後、これに全量１００ｍＬとなるように精製水を加えて本発明の口腔用組成物を製造した。
［実施例２～実施例１１］
　表１に示す種類および量の成分を使用した以外は、実施例１と同様の手順に従って本発明の口腔用組成物を製造した。
［比較例１～比較例９および対照］
　表２に示す種類および量の成分を使用した以外は、実施例１と同様の手順に従って本発明の口腔用組成物とは異なる口腔用組成物を製造した。 [Example 1]
To about 80 g of purified water, 0.001 g of MPC polymer (1) was added and stirred. Thereafter, purified water was added thereto so that the total amount was 100 mL, thereby producing the oral composition of the present invention.
[Examples 2 to 11]
An oral composition of the present invention was produced according to the same procedure as in Example 1 except that the components of the types and amounts shown in Table 1 were used.
[Comparative Examples 1 to 9 and Control]
An oral composition different from the oral composition of the present invention was produced according to the same procedure as in Example 1 except that the types and amounts of components shown in Table 2 were used.
＜タンパク汚れ付着抑制評価＞
　歯面に付着するデンタルプラークをタンパク汚れと定義して、以下の手順に従ってタンパク汚れ付着抑制評価を行った。
（１）ハイドロキシアパタイト粉５０ｍｇと精製水５ｍＬとを混合し、懸濁液を調製した。
（２）この懸濁液７５μＬを取り出し、エッペンドルフチューブへ入れ、遠心分離操作（３０００ｒｐｍ、５分間）により上澄みを取り除いた。
（３）実施例１を１ｍＬ加え、２分間攪拌した。
（４）遠心分離操作（３０００ｒｐｍ、５分間）により上澄みを取り除き、精製水１ｍＬを加え混合した（この操作を「洗浄操作」という）。
（５）再度、洗浄操作を行った。
（６）遠心分離操作（３０００ｒｐｍ、５分間）により上澄みを取り除き、アルブミン溶液（アルブミン濃度：３ｍｇ／ｍＬ）７５μＬを加え、９０分間静置した。
（７）洗浄操作を２回繰返し、１Ｎ塩酸１００μＬおよび０．１ｍｏｌ／Ｌリン酸緩衝液、ｐＨ８．０　１ｍＬを加えて攪拌した後、この液４００μＬを取り出しフルオレスカミンのアセトン溶液（フルオレスカミン濃度：０．３ｍｇ／ｍＬ）１５０μＬと混合した。
（８）（７）の液を９６ウェルプレートへ２００μＬ入れ、プレートリーダー（Ｓｐｅｃｔｒａ　Ｍａｘ　Ｍ３、Ｍｏｌｅｃｕｌａｒ　Ｄｅｖｉｃｅｓ社製）を用いて蛍光強度（励起波長：３６０ｎｍ、蛍光波長：４６０ｎｍ）を測定し、下記の式（１）を用いてタンパク汚れ付着抑制率（％）を算出した。
　なお、タンパク汚れ付着抑制評価実施に際して、実施例１の代わりに精製水を用いた条件で試験を行い、これを対照とした。 <Evaluation for suppressing protein contamination>
Dental plaque adhering to the tooth surface was defined as protein stain, and protein stain adhesion inhibition evaluation was performed according to the following procedure.
(1) 50 mg of hydroxyapatite powder and 5 mL of purified water were mixed to prepare a suspension.
(2) 75 μL of this suspension was taken out, put into an Eppendorf tube, and the supernatant was removed by centrifugation (3000 rpm, 5 minutes).
(3) 1 mL of Example 1 was added and stirred for 2 minutes.
(4) The supernatant was removed by centrifugation (3000 rpm, 5 minutes), and 1 mL of purified water was added and mixed (this operation is referred to as “washing operation”).
(5) The washing operation was performed again.
(6) The supernatant was removed by centrifugation (3000 rpm, 5 minutes), 75 μL of albumin solution (albumin concentration: 3 mg / mL) was added, and the mixture was allowed to stand for 90 minutes.
(7) The washing operation was repeated twice, and 100 μL of 1N hydrochloric acid and 1 mL of 0.1 mol / L phosphate buffer, pH 8.0 were added and stirred, and then 400 μL of this solution was taken out and an acetone solution of fluorescamine (fluorescamine) Concentration: 0.3 mg / mL) was mixed with 150 μL.
(8) 200 μL of the solution of (7) is put into a 96-well plate, and the fluorescence intensity (excitation wavelength: 360 nm, fluorescence wavelength: 460 nm) is measured using a plate reader (Spectra Max M3, manufactured by Molecular Devices). The protein soil adhesion inhibition rate (%) was calculated using the formula (1).
In conducting the protein stain adhesion inhibition evaluation, a test was conducted under the condition using purified water instead of Example 1, and this was used as a control.
　｛タンパク汚れ付着抑制率（％）｝＝｛（対照の蛍光強度）－（実施例１の蛍光強度）｝／（対照の蛍光強度）×１００・・・式（１） {Protein contamination inhibition rate (%)} = {(fluorescence intensity of control) − (fluorescence intensity of Example 1)} / (fluorescence intensity of control) × 100 (1)
　実施例２～実施例１１、比較例１～比較例９および対照についても手順（１）～（８）によりタンパク汚れ付着抑制率を算出した。タンパク汚れ付着抑制率を表１および表２に示す。 For Examples 2 to 11 and Comparative Examples 1 to 9 and the control, the protein stain adhesion inhibition rate was calculated by procedures (1) to (8). Tables 1 and 2 show protein stain adhesion inhibition rates.
＜コーヒー汚れ付着抑制評価＞
　歯面に付着するステインを、コーヒー由来のもののみであると定義して、以下の手順に従ってコーヒー汚れ付着抑制評価を行った。
（１）遠心管へハイドロキシアパタイト粉４０ｍｇを量り、実施例１を１ｍＬ加えて１０分間静置した。
（２）さらにコーヒーを１ｍＬ加えて１０分間静置した。
（３）この後、上澄み液をろ過して取り出し、紫外可視吸光光度計（Ｖ－５６０、日本分光（株）製）を用いて５５０ｎｍにおける透過率（％Ｔ）を測定し、下記の式（２）を用いてコーヒー汚れ付着抑制率（％）を算出した。
　なお、コーヒー汚れ付着抑制評価の実施に際して、実施例１の代わりに精製水を用いた条件で試験を行い、これを対照とした。 <Coffee dirt adhesion suppression evaluation>
The stain adhering to the tooth surface was defined as being only derived from coffee, and the evaluation of the suppression of adhesion of coffee stains was performed according to the following procedure.
(1) 40 mg of hydroxyapatite powder was weighed into a centrifuge tube, 1 mL of Example 1 was added and allowed to stand for 10 minutes.
(2) Further, 1 mL of coffee was added and allowed to stand for 10 minutes.
(3) Thereafter, the supernatant is filtered out and measured for transmittance (% T) at 550 nm using an ultraviolet-visible absorptiometer (V-560, manufactured by JASCO Corporation). 2) was used to calculate the coffee stain adhesion inhibition rate (%).
In addition, when carrying out the coffee dirt adhesion inhibition evaluation, a test was conducted under conditions using purified water instead of Example 1, and this was used as a control.
　｛コーヒー汚れ付着抑制率（％）｝＝｛（実施例１の透過率）－（対照の透過率）｝／｛（コーヒー１／２希釈液の透過率）－（対照の透過率）｝×１００・・・式（２） {Coffee dirt adhesion inhibition rate (%)} = {(Transmittance of Example 1) − (Transmittance of control)} / {(Transmittance of coffee 1/2 dilution) − (Transmittance of control)} × 100 ... Formula (2)
　実施例２～実施例１１、比較例１～比較例９および対照についても手順（１）～（３）によりコーヒー汚れ付着抑制率を算出した。コーヒー汚れ付着抑制率を表１および表２に示す。 For Example 2 to Example 11, Comparative Example 1 to Comparative Example 9, and the control, the coffee stain adhesion inhibition rate was calculated according to procedures (1) to (3). Tables 1 and 2 show the coffee dirt adhesion inhibition rate.
　実施例１ではタンパク汚れ付着抑制率は１０．２％であった。ＭＰＣポリマー（１）の配合濃度が上昇するに従って、タンパク汚れ付着抑制率は向上し、実施例７において最も高いタンパク汚れ付着抑制率４０．１％を示した。この効果はＭＰＣポリマー（１）だけではなく、ＭＰＣポリマー（２）、ＭＰＣポリマー（３）、ＭＰＣポリマー（４）およびＭＰＣポリマー（５）についてもタンパク汚れ付着抑制効果が見られ、その抑制率は２７．３～２８．１％であった。一方、比較例のタンパク汚れ付着抑制率は２．４～５．８％と著しく低い結果であった。また、比較例７および比較例９については、重合したポリマーが不溶のため試験実施不可能であった（＊表中には「－」で記載）。 In Example 1, the protein stain adhesion inhibition rate was 10.2%. As the blending concentration of MPC polymer (1) increased, the protein stain adhesion inhibition rate improved, and the highest protein stain adhesion inhibition rate in Example 7 was 40.1%. This effect was observed not only for the MPC polymer (1), but also for the MPC polymer (2), MPC polymer (3), MPC polymer (4) and MPC polymer (5). It was 27.3 to 28.1%. On the other hand, the protein stain adhesion inhibition rate of the comparative example was remarkably low at 2.4 to 5.8%. In Comparative Example 7 and Comparative Example 9, the test was not possible because the polymerized polymer was insoluble (* indicated by “-” in the table).
　コーヒー汚れ付着抑制率に関し、実施例１において２０．９％であった。コーヒー汚れ付着抑制率についてもタンパク汚れ付着抑制率と同様、ＭＰＣポリマー（１）の配合濃度が上昇するに従って、コーヒー汚れ付着抑制率が向上し、実施例７において最も高い抑制率７８．９％であった。コーヒー汚れ付着抑制効果についても、タンパク汚れ付着抑制効果と同様に、ＭＰＣポリマー（２）、ＭＰＣポリマー（３）、ＭＰＣポリマー（４）およびＭＰＣポリマー（５）についても見られ、その抑制率は５０．７～５３．７％であった。比較例のコーヒー汚れ付着抑制率は、５．３～１０．４％と著しく低い結果であった。コーヒー汚れ付着抑制率は、タンパク汚れ付着抑制率と同様に、比較例７および比較例９について、重合したポリマーが不溶のため試験実施不可能であった（＊表中には「－」で記載）。 In Example 1, the coffee stain adhesion inhibition rate was 20.9%. As with the protein stain adhesion inhibition rate, the coffee stain adhesion inhibition rate improved as the blending concentration of MPC polymer (1) increased, and the highest inhibition rate in Example 7 was 78.9%. there were. Similar to the protein stain adhesion inhibitory effect, the coffee stain adhesion inhibitory effect was also observed for MPC polymer (2), MPC polymer (3), MPC polymer (4) and MPC polymer (5), and the inhibition rate was 50. It was 7 to 53.7%. In the comparative example, the coffee stain adhesion inhibition rate was remarkably low at 5.3 to 10.4%. Similar to the protein stain adhesion inhibition rate, the coffee stain adhesion inhibition rate was not able to be performed for Comparative Example 7 and Comparative Example 9 because the polymerized polymer was insoluble (* indicated by “-” in the table). ).
［実施例１２］
　精製水約８０ｇにＭＰＣポリマー（１）０．００１ｇを加え、攪拌した。この後、順次、サッカリンナトリウム０．００６ｇ、グリセリン３．０ｇ、ミリスチン酸ポリグリセリル０．２５ｇ、ソルビトール液（７０％）１．０ｇ、エタノール４．０ｇ、クエン酸０．０１ｇ、クエン酸三ナトリウム０．０５ｇ、パラオキシ安息香酸エチル０．０５ｇおよび香料０．５ｇを加え攪拌し、全量１００ｍＬとなるように精製水を加えて本発明の口腔用組成物である液体ハミガキを製造した。
［実施例１３～実施例２０］
　表３に示す種類および量の成分を使用した以外は、実施例１２と同様の手順に従って本発明の口腔用組成物である液体ハミガキを製造した。
［比較例１０～比較例１８および対照］
　表４に示す種類および量の成分を使用した以外は、実施例１２と同様の手順に従って、本発明の口腔用組成物とは異なる口腔用組成物である液体ハミガキを製造した。 [Example 12]
To about 80 g of purified water, 0.001 g of MPC polymer (1) was added and stirred. Then, saccharin sodium 0.006 g, glycerin 3.0 g, polyglyceryl myristate 0.25 g, sorbitol solution (70%) 1.0 g, ethanol 4.0 g, citric acid 0.01 g, trisodium citrate 0.05 g Then, 0.05 g of ethyl paraoxybenzoate and 0.5 g of fragrance were added and stirred, and purified water was added so that the total amount became 100 mL to produce a liquid toothpaste which is an oral composition of the present invention.
[Examples 13 to 20]
A liquid toothpaste, which is a composition for oral cavity of the present invention, was produced according to the same procedure as in Example 12 except that the types and amounts of components shown in Table 3 were used.
[Comparative Examples 10 to 18 and Control]
A liquid toothpaste, which is a composition for oral cavity different from the composition for oral cavity of the present invention, was produced according to the same procedure as in Example 12 except that the components of the types and amounts shown in Table 4 were used.
＜使用後の歯面の感触＞
　得られた液体口腔用組成物（液体ハミガキ）である実施例１２について１０ｍＬで口腔内を２０秒間含そうし、吐き出した直後の歯面を舌で触ったときの感触を下記基準に従って評価した。評価は専門パネラーが行い、その評価結果を表３および表４に示す。
　　Ａ：歯面がなめらかな感触であり、清掃実効感が高い
　　Ｂ：歯面がややきしむが、清掃実効感はある
　　Ｃ：歯面がなめらかでなく、清掃実効感に乏しい
　　Ｄ：歯面がギシギシする
　実施例１３～実施例２０、比較例１０～比較例１８および対照についても使用後の歯面の感触について評価を行い、その結果を表３および表４に示す。 <Feeling of tooth surface after use>
About Example 12 which is the obtained composition for liquid oral cavity (liquid toothpaste), the mouth was soaked with 10 mL for 20 seconds, and the feeling when the tooth surface immediately after spitting was touched with the tongue was evaluated according to the following criteria. Evaluation is performed by a specialized panelist, and the evaluation results are shown in Tables 3 and 4.
A: The tooth surface is smooth and the cleaning feeling is high. B: The tooth surface is slightly squeezed, but there is a cleaning effect. C: The tooth surface is not smooth and the cleaning effect is poor. D: The tooth surface is sharp. The Examples 13 to 20 and Comparative Examples 10 to 18 and the control were also evaluated for the feel of the tooth surface after use, and the results are shown in Tables 3 and 4.
＜タンパク汚れ付着抑制評価（口腔内）＞
　以下の手順に従ってタンパク汚れ付着抑制評価（口腔内）を行った。
（１）あらかじめデンタルプラークがゼロになるまで歯をブラッシングした。
（２）実施例１２の液体ハミガキ１０ｍＬを用いて３０秒間うがいをし、再度、２分間ブラッシングした。
（３）この後、ブラッシング、洗口液による洗浄を行わずに８時間生活をした。
（４）８時間後に歯に付着した歯垢量を測定した。実施例１２の液体ハミガキの歯垢量は３名のパネラーの合計量とし、下記の式（３）を用いてタンパク汚れ付着抑制率（％）を算出した。
　なお、デンタルプラークがゼロになるまでの歯のブラッシングを行うのみで、実施例１２の液体ハミガキによるブラッシングを行っていない場合の歯垢量を対照とした。  <Evaluation of protein dirt adhesion inhibition (in the oral cavity)>
In accordance with the following procedure, protein dirt adhesion suppression evaluation (in the oral cavity) was performed.
(1) The teeth were brushed in advance until the dental plaque was zero.
(2) Gargle with 30 mL of the liquid toothpaste of Example 12 for 30 seconds and brush again for 2 minutes.
(3) After this, she lived for 8 hours without brushing and washing with mouthwash.
(4) The amount of plaque adhered to the teeth after 8 hours was measured. The plaque amount of the liquid toothpaste of Example 12 was the total amount of the three panelists, and the protein stain adhesion inhibition rate (%) was calculated using the following formula (3).
Note that the amount of plaque when only brushing the teeth until the dental plaque was zero and not brushing with the liquid toothpaste of Example 12 was used as a control.
　｛タンパク汚れ付着抑制率（％）｝＝｛（対照の歯垢量）－（実施例１２の歯垢量）｝／（対照の歯垢量）×１００・・・式（３） {Protein dirt adhesion inhibition rate (%)} = {(control plaque amount) − (plaque plaque amount of Example 12)} / (control plaque amount) × 100 (3)
　実施例１３～実施例２０、比較例１０～比較例１８および対照についても手順（１）～（４）によりタンパク汚れ付着抑制率を算出した。タンパク汚れ付着抑制率を表３および表４に示す。 For Example 13 to Example 20, Comparative Example 10 to Comparative Example 18, and the control, the protein stain adhesion inhibition rate was calculated according to procedures (1) to (4). Table 3 and Table 4 show the protein dirt adhesion inhibition rate.
　実施例１２ではタンパク汚れ付着抑制率は１５．１％であり、ＭＰＣポリマー（１）の配合濃度が上昇するに従って、タンパク汚れ付着抑制率も向上する傾向を示し、実施例１６で最も高い値３３．５％となった。このタンパク汚れ付着抑制効果は、ＭＰＣポリマー（２）、ＭＰＣポリマー（３）、ＭＰＣポリマー（４）およびＭＰＣポリマー（５）についても見られ、そのタンパク汚れ付着抑制率は２０．０～２８．８％であった。一方、比較例のタンパク汚れ付着抑制率は３．８～７．７％となった。比較例１６および比較例１８については、組成物に対して不溶であったため試験実施不可能であった（＊表中には「－」で記載）。 In Example 12, the protein stain adhesion inhibition rate was 15.1%, and the protein stain adhesion inhibition rate tended to improve as the blending concentration of MPC polymer (1) increased. The highest value in Example 16 was 33. It was 5%. This protein stain adhesion inhibitory effect was also observed for MPC polymer (2), MPC polymer (3), MPC polymer (4) and MPC polymer (5), and the protein stain adhesion inhibition rate was 20.0 to 28.8. %Met. On the other hand, the protein stain adhesion inhibition rate of the comparative example was 3.8 to 7.7%. Since Comparative Example 16 and Comparative Example 18 were insoluble in the composition, they could not be tested (* denoted by “-” in the table).
　使用後の歯面の感触に関し、実施例では全てＡ評価となったが、比較例での評価は、比較例１０～比較例１５についてＣ評価であり、比較例１７および対照についてはＤ評価であった。比較例１６および比較例１８については、組成物に対して不溶であったため試験実施不可能であった（＊表中には「－」で記載）。 Regarding the feel of the tooth surface after use, all evaluations were evaluated as A in the examples, but the evaluations in the comparative examples were C evaluations for the comparative examples 10 to 15 and D evaluations for the comparative example 17 and the control. there were. Since Comparative Example 16 and Comparative Example 18 were insoluble in the composition, they could not be tested (* denoted by “-” in the table).
［実施例２１～実施例２５］
　液体ハミガキ以外にも、表５に示す練り歯磨き剤を製造し、使用後の歯面の感触およびタンパク汚れ付着抑制率（％）に関する評価を実施した。
　その結果、練り歯磨き剤については、液体ハミガキと同様に、使用後の歯面の感触は良好で全てＡ評価であった。さらに、タンパク汚れ付着抑制率も１５．３～１５．５％と良好な結果を示した。 [Example 21 to Example 25]
In addition to the liquid toothpaste, toothpastes shown in Table 5 were produced, and the tooth surface feel after use and protein stain adhesion inhibition rate (%) were evaluated.
As a result, as for the toothpaste, the feel of the tooth surface after use was good as in the case of the liquid toothpaste, and all were evaluated as A. In addition, the protein stain adhesion inhibition rate was 15.3 to 15.5%, indicating a good result.
　以上より、本発明のデンタルプラーク・ステイン付着防止剤は食品等に由来する汚れ、色素の歯面への付着・沈着の防止効果を示した。また、これらの効果は液体ハミガキや練り歯磨き剤といった口腔用組成物とした際にも有効で、良好な使用感と歯垢形成抑制を示した。さらに、これらの結果から、本発明のデンタルプラーク・ステイン付着防止剤を使用したデンタルプラーク・ステイン付着防止方法についても、デンタルプラーク・ステインの付着・沈着の防止効果を有することを確認できた。本発明のデンタルプラーク・ステイン付着防止剤、これを含有する口腔用組成物およびデンタルプラーク・ステイン付着防止方法の優れた効果は、本発明に用いる共重合体分子が歯面自体やペリクルへと吸着することで、細菌の生産する成分や、色素の吸着を阻害することで発現されるものと推測される。 As described above, the dental plaque / stain adhesion preventive agent of the present invention showed the effect of preventing the adhesion and deposition of stains and pigments on the tooth surface derived from foods. These effects were also effective when used in oral compositions such as liquid toothpaste and toothpaste, and showed a good feeling of use and suppression of plaque formation. Furthermore, from these results, it was confirmed that the dental plaque / stain adhesion preventing method using the dental plaque / stain adhesion preventing agent of the present invention also has an effect of preventing the adhesion / deposition of dental plaque / stain. The excellent effects of the dental plaque / stain adhesion preventive agent of the present invention, the composition for oral cavity containing the same and the dental plaque / stain adhesion preventing method are such that the copolymer molecules used in the present invention are adsorbed on the tooth surface itself or the pellicle. Thus, it is presumed that it is expressed by inhibiting adsorption of components produced by bacteria and pigments.
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
　デンタルプラーク・ステインの付着・沈着を防止または抑制できるデンタルプラーク・ステイン付着防止剤、これを含有する口腔用組成物およびデンタルプラーク・ステイン付着防止方法を提供することができる。 It is possible to provide a dental plaque / stain adhesion inhibitor capable of preventing or suppressing adhesion / deposition of dental plaque / stain, a composition for oral cavity containing the same, and a method for preventing dental plaque / stain adhesion.

Claims (7)

  1. 　重量平均分子量１０，０００～５，０００，０００であり、
    　２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位（Ａ）１０～９０モル％と、
    　アルキル基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ１）、４級アンモニウム基含有（メタ）アクリル系単量体に基づく構成単位（Ｂ２）および（メタ）アクリルアミド系単量体に基づく構成単位（Ｂ３）からなる群から選ばれる少なくとも１種の構成単位９０～１０モル％と
    　を含有する共重合体を含有するデンタルプラーク・ステイン付着防止剤。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
     （式（Ａ）中、Ｒ１は水素原子またはメチル基を示す。式（Ｂ１）中、Ｒ２は水素原子またはメチル基を示し、Ｒ３は炭素数４～１８のアルキル基を示す。式（Ｂ２）中、Ｒ４は水素原子またはメチル基を示し、Ｒ５、Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示し、Ｘ－はハロゲンイオンもしくは酸残基を示す。式（Ｂ３）中、Ｒ８は水素原子またはメチル基を示し、Ｒ９およびＲ１０は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を示す。）
    A weight average molecular weight of 10,000 to 5,000,000,
    A structural unit (A) based on 2- (meth) acryloyloxyethyl phosphorylcholine (A) of 10 to 90 mol%,
    Structural unit (B1) based on alkyl group-containing (meth) acrylic monomer (B1), Structural unit (B2) based on quaternary ammonium group-containing (meth) acrylic monomer, and (meth) acrylamide monomer A dental plaque / stain adhesion-preventing agent comprising a copolymer containing 90 to 10 mol% of at least one structural unit selected from the group consisting of the structural unit (B3).
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
     (In the formula (A), R 1 represents a hydrogen atom or a methyl group. In the formula (B1), R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 4 to 18 carbon atoms. In (B2), R 4 represents a hydrogen atom or a methyl group, R 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X − represents a halogen ion or In the formula (B3), R 8 represents a hydrogen atom or a methyl group, and R 9 and R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  2. 　構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ１）がブチルメタクリレートに基づく構成単位である、請求項１に記載のデンタルプラーク・ステイン付着防止剤。
    The dental plaque / stain adhesion preventing agent according to claim 1, wherein the structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, and the structural unit (B1) is a structural unit based on butyl methacrylate. .
  3. 　構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ１）がステアリルメタクリレートに基づく構成単位である、請求項１に記載のデンタルプラーク・ステイン付着防止剤。
    The dental plaque / stain adhesion preventing agent according to claim 1, wherein the structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, and the structural unit (B1) is a structural unit based on stearyl methacrylate. .
  4. 　構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ２）が２－ヒドロキシ－３－メタクリロイルオキシプロピルトリメチルアンモニウムクロライドに基づく構成単位である、請求項１に記載のデンタルプラーク・ステイン付着防止剤。
    The structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, and the structural unit (B2) is a structural unit based on 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride. Dental plaque / stain adhesion preventive agent according to 1.
  5. 　構成単位（Ａ）が２－（メタ）アクリロイルオキシエチルホスホリルコリンに基づく構成単位であり、構成単位（Ｂ１）がステアリルメタクリレートに基づく構成単位であり、構成単位（Ｂ３）がＮ，Ｎ－ジメチルアミノプロピルアクリルアミドに基づく構成単位である、請求項１に記載のデンタルプラーク・ステイン付着防止剤。
    The structural unit (A) is a structural unit based on 2- (meth) acryloyloxyethyl phosphorylcholine, the structural unit (B1) is a structural unit based on stearyl methacrylate, and the structural unit (B3) is N, N-dimethylaminopropyl. The dental plaque / stain adhesion inhibitor according to claim 1, which is a structural unit based on acrylamide.
  6. 　請求項１～５のいずれか１に記載のデンタルプラーク・ステイン付着防止剤を０．００１～５．０ｗ／ｖ％と、水３．０～９９．９ｗ／ｖ％とを含有する口腔用組成物。
    An oral composition comprising 0.001 to 5.0 w / v% of dental plaque / stain adhesion inhibitor according to any one of claims 1 to 5 and 3.0 to 99.9 w / v% of water object.
  7. 　さらに、サッカリン、サッカリンナトリウム、グリセリン、スクラロース、キシリトール、マルチトール、ステビオサイド、アスパルテームからなる群（Ｃ）より選ばれる少なくとも１種の成分を含有する請求項６に記載の口腔用組成物。 The oral composition according to claim 6, further comprising at least one component selected from the group (C) consisting of saccharin, saccharin sodium, glycerin, sucralose, xylitol, maltitol, stevioside, and aspartame.
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JP2018052914A (en) * 2016-09-23 2018-04-05 小林製薬株式会社 Composition for oral cavity
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JP2016037455A (en) * 2014-08-06 2016-03-22 アース製薬株式会社 Stain adhesion inhibitor and oral composition
JP2018052914A (en) * 2016-09-23 2018-04-05 小林製薬株式会社 Composition for oral cavity
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