JP2014139162A - Dentifrice composition and teeth dentinal tubule blocking agent - Google Patents

Dentifrice composition and teeth dentinal tubule blocking agent Download PDF

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JP2014139162A
JP2014139162A JP2013257919A JP2013257919A JP2014139162A JP 2014139162 A JP2014139162 A JP 2014139162A JP 2013257919 A JP2013257919 A JP 2013257919A JP 2013257919 A JP2013257919 A JP 2013257919A JP 2014139162 A JP2014139162 A JP 2014139162A
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dentinal tubule
dentifrice composition
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oil
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JP6206153B2 (en
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Noriko Matsumoto
典子 松本
Kenta Suzuki
健太 鈴木
Masahito Arai
将人 荒井
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Lion Corp
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20Halogens; Compounds thereof
    • A61K8/21Fluorides; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/24Phosphorous; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26Aluminium; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365Hydroxycarboxylic acids; Ketocarboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Birds (AREA)
  • Epidemiology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Emergency Medicine (AREA)
  • Cosmetics (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a dentifrice composition and a teeth dentinal tubule blocking agent which improve ability of dentinal tubule blocking, stably maintain high dentinal tubule blocking effect after storage, and contain aluminium lactate effective for the prevention of hyperesthesia.SOLUTION: A dentifrice composition comprises: (A) sodium monofluorophosphate; (B) sodium dihydrogen phosphate; and (C) aluminium lactate, and the mass ratio of ((A) component+(B) component)/(C) component) is 0.10 to 1.0. The dentifrice composition also comprises (D) coconut oil fatty acid amidopropyl betaine. A teeth dentinal tubule blocking agent comprises the (A), (B) and (C) components, and the mass ratio of ((A) component+(B) component)/(C) component) is 0.10 to 1.0. The teeth dentinal tubule blocking agent also comprises the (D) component.

Description

本発明は、象牙細管の開口部を封鎖、狭窄する象牙細管封鎖能が向上し、高い象牙細管封鎖効果が保存後も安定に維持され、知覚過敏症の予防に有効な乳酸アルミニウム含有の歯磨剤組成物及び歯牙の象牙細管封鎖剤に関する。   The present invention relates to an aluminum lactate-containing dentifrice that improves the ability of dentinal tubules to seal and constrict the opening of dentinal tubules, maintains a high dentinal tubule sealing effect even after storage, and is effective in preventing hypersensitivity The present invention relates to a composition and a dental dentinal tubule sealant.

知覚過敏症は、象牙質の露出によって、種々の外来刺激により非常に不快な痛みが一過性に生じるものであり、この知覚過敏症の痛みを緩和、除去し、あるいは予防するには、象牙細管の開口部を封鎖、狭窄することによって刺激の伝達を抑制、阻止することが有効である。   Hypersensitivity is a very unpleasant pain caused by various external stimuli due to exposure of dentin. To alleviate, eliminate, or prevent this hypersensitive pain, ivory It is effective to suppress and prevent the transmission of stimulation by blocking and constricting the opening of the capillary tube.

乳酸アルミニウムは、象牙細管の開口部を封鎖、狭窄する作用を有し、この乳酸アルミニウムを口腔用組成物に配合して象牙質知覚過敏症を予防する技術は多く提案されている。乳酸アルミニウムとリン酸化合物を含有し、知覚過敏を予防する技術は知られている。特許文献1(特開平7−165550号公報)には、乳酸アルミニウム等の象牙細管狭窄閉鎖有効成分とリン酸化合物を口腔用組成物に配合することで象牙細管を狭窄又は閉鎖する効果を向上できることが提案されている。特許文献2(特開昭61−155314号公報)には、乳酸アルミニウム化合物が安定配合され象牙質知覚過敏症予防、治療に好適に使用し得る口腔用組成物として、実施例3には乳酸アルミニウム、リン酸水素二ナトリウム、モノフルオロリン酸ナトリウムが配合された練歯磨、実施例6には乳酸アルミニウム、リン酸水素二ナトリウムが配合された練歯磨が開示されている。
また、乳酸アルミニウムとフッ化物とを配合し組成物のpHが特定範囲であることで象牙質知覚過敏抑制効果が向上した口腔用組成物が、特許文献3(特許第3152467号公報)に提案されている。
これら特許文献1〜3は、処置後の象牙細管狭窄又閉鎖効果の向上であり、保存後の象牙細管封鎖効果について言及されていない。
Aluminum lactate has the effect of blocking and constricting the opening of the dentinal tubule, and many techniques for preventing hypersensitivity of dentin by blending this aluminum lactate into the oral composition have been proposed. A technique that contains aluminum lactate and a phosphate compound to prevent hypersensitivity is known. Patent Document 1 (Japanese Patent Application Laid-Open No. 7-165550) discloses that the effect of stenosis or closure of dentinal tubules can be improved by blending an oral composition with a dentinal tubule stenosis closure active ingredient such as aluminum lactate. Has been proposed. Patent Document 2 (Japanese Patent Application Laid-Open No. 61-155314) discloses a composition for oral cavity which can be suitably used for the prevention and treatment of dentin hypersensitivity by stably containing an aluminum lactate compound. A toothpaste containing disodium hydrogen phosphate and sodium monofluorophosphate, and Example 6 discloses a toothpaste containing aluminum lactate and disodium hydrogen phosphate.
In addition, a composition for oral cavity in which the effect of suppressing hypersensitivity to dentin is improved by blending aluminum lactate and fluoride and the pH of the composition is in a specific range is proposed in Patent Document 3 (Patent No. 3152467). ing.
These Patent Documents 1 to 3 are improvements in dentinal tubule stenosis or closure effect after treatment, and no mention is made of the dentinal tubule sealing effect after storage.

特開平7−165550号公報Japanese Patent Laid-Open No. 7-165550 特開昭61−155314号公報JP 61-155314 A 特許第3152467号公報Japanese Patent No. 3152467

しかしながら、乳酸アルミニウム含有の歯磨剤組成物においては、象牙細管の開口部を封鎖、狭窄する象牙細管封鎖能は未だ改善の余地があり、特に経時での象牙細管封鎖能に課題があり、また、乳酸アルミニウムを比較的多く配合してその有効性を高めると安定性や味に問題が生じることがあった。従って、乳酸アルミニウム含有の歯磨剤組成物の経時での象牙細管封鎖能の向上が課題となっていた。   However, in an aluminum lactate-containing dentifrice composition, there is still room for improvement in the ability of dentinal tubules to seal and constrict the opening of the dentinal tubules, and in particular, there is a problem in the ability to seal dentinal tubules over time, When a relatively large amount of aluminum lactate is added to increase its effectiveness, problems may arise in stability and taste. Therefore, the improvement of the dentinal tubule sealing ability over time of the dentifrice composition containing aluminum lactate has been a problem.

本発明は、上記事情に鑑みなされたもので、象牙細管封鎖能が向上し、高い象牙細管封鎖効果が保存後も安定に維持され、知覚過敏症の予防に有効な乳酸アルミニウム含有の歯磨剤組成物及び歯牙の象牙細管封鎖剤を提供することを目的とする。   The present invention has been made in view of the above circumstances, and has an aluminum lactate-containing dentifrice composition that improves dentinal tubule sealing ability, maintains a high dentinal tubule sealing effect even after storage, and is effective in preventing hypersensitivity. It is an object of the present invention to provide a dentinal tubule sealant for objects and teeth.

本発明者らは、上記目的を達成するため鋭意検討を行った結果、(A)モノフルオロリン酸ナトリウム、(B)リン酸二水素ナトリウム及び(C)乳酸アルミニウムを配合し、(A)成分及び(B)成分の合計配合量が(C)成分の配合量に対して適切割合であることにより、歯牙の象牙細管の開口部を封鎖、狭窄する象牙細管封鎖能が向上し、象牙細管封鎖効果が優れると共に高い象牙細管封鎖効果が長期保存後も安定に維持されることを知見した。また、更に(D)ヤシ油脂肪酸アミドプロピルベタインを配合すると、乳酸アルミニウムに由来する嫌味が改善することを知見した。   As a result of intensive studies to achieve the above object, the present inventors formulated (A) sodium monofluorophosphate, (B) sodium dihydrogen phosphate and (C) aluminum lactate, and (A) component And the total compounding quantity of (B) component is an appropriate ratio with respect to the compounding quantity of (C) component, the dentinal tubule sealing ability which seals and narrows the opening part of a dental dentinal tubule improves, and dentinal tubule sealing It was found that the effect was excellent and the high dentinal tubule sealing effect was maintained stably after long-term storage. Furthermore, it was found that when (D) coconut oil fatty acid amidopropyl betaine is further blended, the unpleasant taste derived from aluminum lactate is improved.

本発明では、乳酸アルミニウム、モノフルオロリン酸ナトリウム、リン酸二水素ナトリウムを適切に組み合わせることによって、象牙細管封鎖能が格段に向上し、後述の実施例に示すように液の通過性抑制率80%以上、特に90%以上という象牙細管封鎖効果を奏し、このような高い象牙細管封鎖効果が40℃という高温で、6ヶ月保存後に低下することなく安定に維持される。この場合、モノフルオロリン酸ナトリウムとリン酸二水素ナトリウムとを組み合わせることで意外にも両成分が特異的に作用し、象牙細管封鎖能を経時で安定に維持できるものであり、モノフルオロリン酸ナトリウム又はリン酸二水素ナトリウムの単独配合ではなし得ない上記格別の作用効果を与えることができる。また、上記のような経時での象牙細管封鎖能の向上は、正リン酸のナトリウム塩に属するリン酸水素二ナトリウム、リン酸三ナトリウムでは付与し得ないものであり、リン酸二水素ナトリウムの特異的な作用によるものである。   In the present invention, by properly combining aluminum lactate, sodium monofluorophosphate, and sodium dihydrogen phosphate, the ability to seal dentinal tubules is remarkably improved, and as shown in the examples described later, the liquid permeability control rate 80 % Or more, particularly 90% or more of the dentinal tubule-sealing effect, and such a high dentinal tubule-sealing effect is stably maintained at a high temperature of 40 ° C. without decreasing after storage for 6 months. In this case, by combining sodium monofluorophosphate and sodium dihydrogen phosphate, both components unexpectedly act specifically and can maintain the dentinal tubule sealing ability stably over time. It is possible to give the above-mentioned special effects that cannot be achieved with sodium or sodium dihydrogen phosphate alone. Moreover, the improvement of the dentinal tubule sealing ability over time as described above cannot be imparted with disodium hydrogen phosphate and trisodium phosphate belonging to the sodium salt of orthophosphoric acid. This is due to a specific action.

また更に、本発明においては、(D)ヤシ油脂肪酸アミドプロピルベタインを配合することで、(A)、(B)、(C)成分を併用した系における乳酸アルミニウムのえぐみ、金属味に由来する独特の嫌味を抑制し使用感を向上できる。   Furthermore, in the present invention, (D) by adding palm oil fatty acid amidopropyl betaine, it is derived from the excretion of aluminum lactate and metallic taste in a system in which components (A), (B), and (C) are used in combination. You can improve the feeling of use by suppressing the unique taste.

従って、本発明は、下記の歯磨剤組成物及び歯牙の象牙細管封鎖剤を提供する。
〔1〕
(A)モノフルオロリン酸ナトリウム、(B)リン酸二水素ナトリウム及び(C)乳酸アルミニウムを含有し、((A)成分+(B)成分)/(C)成分が質量比として0.10〜1.0であることを特徴とする歯磨剤組成物。
〔2〕
(A)成分を0.3〜1質量%、(B)成分を0.01〜0.2質量%、(C)成分を1〜5質量%含有する〔1〕に記載の歯磨剤組成物。
〔3〕
更に、(D)ヤシ油脂肪酸アミドプロピルベタインを含有する〔1〕又は〔2〕に記載の歯磨剤組成物。
〔4〕
(D)成分を0.1〜2質量%含有する〔3〕に記載の歯磨剤組成物。
〔5〕
知覚過敏用である〔1〕〜〔4〕のいずれかに記載の歯磨剤組成物。
〔6〕
(A)モノフルオロリン酸ナトリウム、(B)リン酸二水素ナトリウム及び(C)乳酸アルミニウムとからなり、((A)成分+(B)成分)/(C)成分が質量比として0.10〜1.0である歯牙の象牙細管封鎖剤。
〔7〕
更に、(D)ヤシ油脂肪酸アミドプロピルベタインを含む〔6〕に記載の歯牙の象牙細管封鎖剤。
Accordingly, the present invention provides the following dentifrice composition and tooth dentinal tubule sealant.
[1]
(A) Sodium monofluorophosphate, (B) Sodium dihydrogen phosphate and (C) Aluminum lactate, ((A) component + (B) component) / (C) component is 0.10 as a mass ratio. The dentifrice composition characterized by being -1.0.
[2]
The dentifrice composition according to [1], containing 0.3 to 1% by mass of component (A), 0.01 to 0.2% by mass of component (B), and 1 to 5% by mass of component (C). .
[3]
The dentifrice composition according to [1] or [2], further comprising (D) a palm oil fatty acid amidopropyl betaine.
[4]
(D) Dentifrice composition as described in [3] which contains 0.1-2 mass% of components.
[5]
The dentifrice composition according to any one of [1] to [4], which is for hypersensitivity.
[6]
(A) Sodium monofluorophosphate, (B) Sodium dihydrogen phosphate, and (C) Aluminum lactate, where ((A) component + (B) component) / (C) component is 0.10 as a mass ratio. -1.0 dental dentinal tubule sealant.
[7]
Furthermore, the tooth dentinal tubule sealant according to [6], further comprising (D) a palm oil fatty acid amidopropyl betaine.

本発明によれば、象牙細管封鎖能が向上し、象牙細管封鎖効果が優れると共に高い象牙細管封鎖効果が長期保存後も安定に維持され、知覚過敏症の予防に有効な乳酸アルミニウム含有の歯磨剤組成物及び歯牙の象牙細管封鎖剤を提供できる。   According to the present invention, the dentin tubule sealing ability is improved, the dentinal tubule sealing effect is excellent, and the high dentinal tubule sealing effect is stably maintained even after long-term storage, and is an aluminum lactate-containing dentifrice effective in preventing hypersensitivity A composition and a dental dentinal tubule sealant can be provided.

以下、本発明につき更に詳述する。本発明の歯磨剤組成物は、(A)モノフルオロリン酸ナトリウム、(B)リン酸二水素ナトリウム、及び(C)乳酸アルミニウムを含有し、これら成分の配合割合が特定範囲であることを特徴とする。   The present invention will be described in further detail below. The dentifrice composition of the present invention contains (A) sodium monofluorophosphate, (B) sodium dihydrogen phosphate, and (C) aluminum lactate, and the blending ratio of these components is in a specific range. And

(A)モノフルオロリン酸ナトリウムは、例えばローディア日華(株)製のものなど市販品を使用することができる。
モノフルオロリン酸ナトリウムの配合量は、組成物全体の0.3〜1%(質量%、以下同様。)が好ましく、より好ましくは0.6〜1.0%である。配合量が多いほど象牙細管封鎖能は高まり、0.3%以上であると象牙細管封鎖効果を十分に得ることができるが、1%以下であることが、経時での象牙細管封鎖効果を十分に得るのに好適である。
(A) As sodium monofluorophosphate, commercially available products such as those manufactured by Rhodia Nikka Co., Ltd. can be used.
The blending amount of sodium monofluorophosphate is preferably 0.3 to 1% (mass%, the same applies hereinafter) of the whole composition, more preferably 0.6 to 1.0%. The amount of dentinal tubule sealing increases as the blending amount increases, and if it is 0.3% or more, the dentinal tubule sealing effect can be sufficiently obtained, but if it is 1% or less, the dentinal tubule sealing effect over time is sufficient. It is suitable for obtaining.

(B)成分はリン酸二水素ナトリウムであり、太平化学産業(株)製の市販品を用いることができる。なお、(B)成分のリン酸二水素ナトリウムの代わりに、リン酸水素二ナトリウムやリン酸三ナトリウムを用いても、経時での象牙細管封鎖効果が向上せず本発明の目的は達成されない。   The component (B) is sodium dihydrogen phosphate, and a commercial product manufactured by Taihei Chemical Industry Co., Ltd. can be used. Even if disodium hydrogen phosphate or trisodium phosphate is used in place of the component (B) sodium dihydrogen phosphate, the effect of sealing the dentinal tubule over time is not improved and the object of the present invention is not achieved.

リン酸二水素ナトリウムの配合量は、組成物全体の0.01〜0.2%が好ましい。配合量が0.01%以上であると、象牙細管封鎖効果を十分に得ることができ、0.2%以下であることが、経時での象牙細管封鎖効果を十分に得るのに好適である。   The blending amount of sodium dihydrogen phosphate is preferably 0.01 to 0.2% of the entire composition. When the blending amount is 0.01% or more, the dentinal tubule sealing effect can be sufficiently obtained, and when it is 0.2% or less, it is suitable for sufficiently obtaining the dentinal tubule sealing effect over time. .

(C)乳酸アルミニウムは、市販品を使用でき、例えば武蔵野化学(株)製のものを用いることができる。
乳酸アルミニウムの配合量は、組成物全体の1〜5%が好ましく、より好ましくは2〜5%である。配合量が上記範囲内であることが象牙細管封鎖能の向上にはより好適である。配合量が1%より少なかったり、5%より多いと、象牙細管封鎖能を十分に向上できない場合がある。
(C) The aluminum lactate can use a commercial item, for example, the thing made by Musashino Chemical Co., Ltd. can be used.
The blending amount of aluminum lactate is preferably 1 to 5%, more preferably 2 to 5% of the entire composition. It is more suitable for the improvement of dentinal tubule sealing ability that a compounding quantity exists in the said range. If the blending amount is less than 1% or more than 5%, the dentinal tubule sealing ability may not be sufficiently improved.

本発明においては、(A)、(B)、(C)成分の配合比率を示す((A)成分+(B)成分)/(C)成分が特定範囲であることが効果発現に重要であり、特定比率であることで三成分が特異的に作用し、特に経時での象牙細管封鎖能が向上する。((A)成分+(B)成分)/(C)成分は、質量比として0.10〜1.0であり、好ましくは0.2〜1.0、より好ましくは0.3〜0.6、更に好ましくは0.3〜0.5である。配合比率が0.10より少ない、又は1.0より大きいと、象牙細管封鎖能が向上せず経時での象牙細管封鎖効果が得られない。   In the present invention, it is important for the effect expression that (A) component + (B) component) / (C) component indicating the blending ratio of components (A), (B), (C) is in a specific range. Yes, the specific ratio of the three components acts specifically, and the dentinal tubule sealing ability with time is improved. ((A) component + (B) component) / (C) component is 0.10-1.0 as mass ratio, Preferably it is 0.2-1.0, More preferably, it is 0.3-0. 6, More preferably, it is 0.3-0.5. If the blending ratio is less than 0.10 or greater than 1.0, the dentinal tubule sealing ability is not improved and the dentinal tubule sealing effect over time cannot be obtained.

本発明組成物は、更に(D)ヤシ油脂肪酸アミドプロピルベタインを配合することが好ましく、これにより嫌味を改善できる。
ヤシ油脂肪酸アミドプロピルベタインは、ラウリン酸、ミリスチン酸、パルミチン酸といった飽和脂肪酸を含むヤシ油脂肪酸を原料としたアミドプロピルベタインである。例えばデグッサ社製のTEGO Betain CK OK(30%水溶液)、花王(株)製アンヒトール55AB(30%水溶液)などの市販品が挙げられ、これら市販品を使用できる。ヤシ油脂肪酸アミドプロピルベタインの代わりに、ヤシ油脂肪酸以外を原料としたアミドプロピルベタイン、例えばラウリル酸アミドプロピルベタイン等を用いても、苦味が生じて嫌味を改善できない。
The composition of the present invention preferably further contains (D) coconut oil fatty acid amide propyl betaine, and this can improve taste.
Coconut oil fatty acid amidopropyl betaine is amidopropyl betaine made from coconut oil fatty acid containing saturated fatty acids such as lauric acid, myristic acid and palmitic acid. For example, commercially available products such as TEGO Betaine CK OK (30% aqueous solution) manufactured by Degussa Co., Ltd. and Anhitol 55AB (30% aqueous solution) manufactured by Kao Corporation can be used, and these commercially available products can be used. In place of coconut oil fatty acid amide propyl betaine, even when amide propyl betaine other than coconut oil fatty acid is used as a raw material, for example, lauric acid amide propyl betaine or the like, bitterness is produced, and taste amelioration cannot be improved.

ヤシ油脂肪酸アミドプロピルベタインを配合する場合、その配合量は、純分換算で組成物全体の0.1〜2%が好ましく、より好ましくは0.1〜1%である。配合量が0.1%以上であると、えぐみが解消し味の改善効果を与えることができ、2%以下であると、ヤシ油脂肪酸アミドプロピルベタイン由来の苦味が生じるのを抑えることができる。   When the coconut oil fatty acid amidopropyl betaine is blended, the blending amount is preferably 0.1 to 2%, more preferably 0.1 to 1% of the total composition in terms of pure content. If the blending amount is 0.1% or more, the sashimi is eliminated and the effect of improving the taste can be given. If the blending amount is 2% or less, the occurrence of the bitterness derived from the coconut oil fatty acid amidopropyl betaine can be suppressed. it can.

本発明の歯磨剤組成物は、練歯磨剤、液状歯磨剤、液体歯磨剤、潤製歯磨剤等として調製される。また、上記成分に加えて、剤型に応じた公知成分を本発明の効果を妨げない範囲で必要に応じて配合できる。例えば、練歯磨剤では研磨剤、粘稠剤、粘結剤、界面活性剤、更に必要により香料、甘味料、着色剤、防腐剤、有効成分などを配合できる。   The dentifrice composition of the present invention is prepared as a toothpaste, a liquid dentifrice, a liquid dentifrice, a moisturizing dentifrice or the like. Moreover, in addition to the said component, the well-known component according to a dosage form can be mix | blended as needed in the range which does not prevent the effect of this invention. For example, toothpastes can contain abrasives, thickeners, binders, surfactants, and if necessary, flavorings, sweeteners, colorants, preservatives, active ingredients, and the like.

研磨剤としては、シリカゲル、沈降シリカ等のシリカ系研磨剤、第2リン酸カルシウム2水和物及び無水和物、第3リン酸カルシウム、第4リン酸カルシウム等のリン酸カルシウム系研磨剤、ピロリン酸カルシウム、炭酸カルシウム、水酸化アルミニウム、アルミナ、合成樹脂系研磨剤などが挙げられる。研磨剤の配合量は、組成物全体の0〜40%、特に2〜30%が好ましい。   Examples of the abrasive include silica-based abrasives such as silica gel and precipitated silica, dicalcium phosphate dihydrate and anhydrous, calcium phosphate-based abrasives such as tertiary calcium phosphate and tetrabasic calcium phosphate, calcium pyrophosphate, calcium carbonate, hydroxylated Examples thereof include aluminum, alumina, and synthetic resin abrasive. The blending amount of the abrasive is preferably 0 to 40%, particularly preferably 2 to 30% of the entire composition.

粘稠剤としては、ソルビット、キシリット等の糖アルコール、グリセリン、プロピレングリコール等の多価アルコールが挙げられる。これらの配合量は通常、5〜50%、特に20〜40%である。   Examples of the thickener include sugar alcohols such as sorbit and xylit, and polyhydric alcohols such as glycerin and propylene glycol. These compounding amounts are usually 5 to 50%, particularly 20 to 40%.

粘結剤としては、カルボキシメチルセルロースナトリウム、メチルセルロース、ヒドロキシプロピルセルロース等のセルロース誘導体、キサンタンガム、アラビアガム等のガム類、アルギン酸誘導体、カラゲナン、ポリビニルアルコール、ポリアクリル酸ナトリウム、カルボキシビニルポリマー、ポリビニルピロリドンなどの有機粘結剤、ゲル化性シリカ、ゲル化性アルミニウムシリカ等の無機粘結剤が挙げられる。配合量は通常0.1〜10%である。   Examples of the binder include cellulose derivatives such as sodium carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose, gums such as xanthan gum and gum arabic, alginic acid derivatives, carrageenan, polyvinyl alcohol, sodium polyacrylate, carboxyvinyl polymer, and polyvinylpyrrolidone. Examples thereof include inorganic binders such as organic binders, gelling silica, and gelling aluminum silica. The amount is usually 0.1 to 10%.

界面活性剤としては、歯磨剤組成物に通常用いられるものであればよく、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤等を配合できるが、ラウリル硫酸ナトリウムを好適に配合できる。
アニオン性界面活性剤としては、ラウリル硫酸ナトリウム等のアルキル硫酸塩、N−ラウロイルサルコシンナトリウム、N−ミリストイルサルコシンナトリウム等のN−アシルサルコシン酸塩、ドデシルベンゼンスルホン酸ナトリウム、水素添加ココナッツ脂肪酸モノグリセリドモノ硫酸ナトリウム、ラウリルスルホ酢酸ナトリウム、N−パルミトイルグルタミン酸ナトリウム等のN−アシルグルタミン酸塩、N−メチル−N−アシルタウリンナトリウム、N−メチル−N−アシルアラニンナトリウム、α−オレフィンスルホン酸ナトリウムなどが挙げられる。
As the surfactant, any surfactant usually used in dentifrice compositions may be used, and anionic surfactants, nonionic surfactants, cationic surfactants and the like can be blended, but sodium lauryl sulfate is suitably blended. it can.
Anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, N-acyl sarcosine salts such as sodium N-lauroyl sarcosine, sodium N-myristoyl sarcosine, sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid monoglyceride monosulfate Examples include sodium, sodium lauryl sulfoacetate, N-acyl glutamate such as sodium N-palmitoyl glutamate, sodium N-methyl-N-acyl taurate, sodium N-methyl-N-acylalanine, sodium α-olefin sulfonate, etc. .

ノニオン性界面活性剤としては、ショ糖脂肪酸エステル、マルトース脂肪酸エステル、ラクトース脂肪酸エステル等の糖脂肪酸エステル、マルチトール脂肪酸エステル、ラクチトール脂肪酸エステル等の糖アルコール脂肪酸エステル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、モノラウリン酸ヘキサグリセリル、モノミリスチン酸ヘキサグリセリル、モノラウリン酸デカグリセリル、モノミリスチン酸デカグリセリル等のポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノステアレート等のポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油等のポリオキシエチレン脂肪酸エステル、ポリオキシエチレンラウリルエーテル等のポリオキシエチレン高級アルコールエーテル、ラウリン酸ジエタノールアミド等の脂肪酸アルカノールアミド、ポリオキシエチレンポリオキシプロピレン共重合体、ポリオキシエチレンポリオキシプロピレン脂肪酸エステルが挙げられる。
カチオン性界面活性剤としては、アルキルアンモニウム、アルキルベンジルアンモニウム塩等が挙げられる。
界面活性剤、特にラウリル硫酸ナトリウムの配合量は、通常0.1〜5.0%である。
Nonionic surfactants include sugar fatty acid esters such as sucrose fatty acid ester, maltose fatty acid ester and lactose fatty acid ester, sugar alcohol fatty acid esters such as maltitol fatty acid ester and lactitol fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, monolaurin Polyglycerin fatty acid esters such as hexaglyceryl acid, hexaglyceryl monomyristate, decaglyceryl monolaurate, decaglyceryl monomyristate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate Polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, and polyoxyethylene lauryl ether Polyoxyethylene higher alcohol ethers, fatty acid alkanolamides, such as lauric acid diethanolamide, polyoxyethylene polyoxypropylene copolymer, polyoxyethylene polyoxypropylene fatty acid esters.
Examples of the cationic surfactant include alkyl ammonium and alkyl benzyl ammonium salts.
The compounding quantity of surfactant, especially sodium lauryl sulfate is 0.1 to 5.0% normally.

香料としては、通常用いられる周知の香料を適宜配合することができる。具体的には、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、及び、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、及び、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、更に、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等、歯磨剤組成物に用いられる公知の香料素材を組み合わせて使用することができる。   As a fragrance | flavor, the well-known fragrance | flavor used normally can be mix | blended suitably. Specifically, peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen 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, Sweet 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 conversion) Fragrance, powdered fragrance, etc.) and menthol, Rubon, Anethole, Cineol, Methyl salicylate, Synamic aldehyde, Eugenol, 3-1-Mentoxypropane-1,2-diol, Thymol, Linalol, Linarel acetate, Limonene, Menthone, Menthyl acetate, N-Substituted paramenthane 3-carboxamide, pinene, octyl aldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, Hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, ethyl Single-flavored ingredients such as o-acetate, as well as fragrances such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, and dentifrice composition It can be used in combination with known perfume materials used in the above.

甘味料としては、サッカリンナトリウム、ステビオサイド、パラメトキシシンナミックアルデヒド、ネオヘスペリジルヒドロカルコン、ペリラルチン等が挙げられる。
着色剤としては、青色1号、黄色4号、二酸化チタン等が挙げられ、防腐剤としては、メチルパラベン、エチルパラベン等のパラオキシ安息香酸エステル、安息香酸ナトリウム等の安息香酸又はその塩などが挙げられる。
Examples of the sweetener include saccharin sodium, stevioside, paramethoxycinnamic aldehyde, neohesperidyl hydrochalcone, and perilartin.
Examples of the colorant include Blue No. 1, Yellow No. 4, titanium dioxide, and the like. Examples of the preservative include paraoxybenzoic acid esters such as methylparaben and ethylparaben, benzoic acid such as sodium benzoate, and salts thereof. .

有効成分としては、モノフルオロリン酸ナトリウム、乳酸アルミニウム以外の通常配合される公知の成分を配合できる。例えば、イソプロピルメチルフェノール等の非イオン性殺菌剤、塩化セチルピリジニウム、塩化ベンザルコニウム、塩化ベンゼトニウム等のカチオン性殺菌剤、トラネキサム酸、イプシロンアミノカプロン酸、アラントイン、グリチルレチン酸、グリチルリチン酸などの抗炎症剤、デキストラナーゼ、ムタナーゼ、アミラーゼ、プロテアーゼ、リゾチーム等の酵素、フッ化ナトリウム等のフッ化物、正リン酸のカリウム塩等の水溶性リン酸化合物、グルコン酸銅、銅クロロフィリンナトリウム等の銅化合物、塩化ナトリウム、硝酸カリウム、塩化亜鉛、クエン酸亜鉛、塩化ストロンチウムなどの無機塩類、アスコルビン酸、酢酸トコフェロール等のビタミン類、クロロフィル、トウキ軟エキス、タイム、オウゴン、チョウジ、ハマメリス等の植物抽出物、歯石防止剤、歯垢防止剤などが挙げられる。これら有効成分は、本発明の効果を妨げない範囲で有効量配合することができる。   As the active ingredient, known ingredients other than sodium monofluorophosphate and aluminum lactate can be blended. For example, nonionic fungicides such as isopropylmethylphenol, cationic fungicides such as cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, anti-inflammatory agents such as tranexamic acid, epsilon aminocaproic acid, allantoin, glycyrrhetinic acid, glycyrrhizic acid , Enzymes such as dextranase, mutanase, amylase, protease, lysozyme, fluorides such as sodium fluoride, water-soluble phosphate compounds such as potassium salt of orthophosphate, copper compounds such as copper gluconate, copper chlorophyllin sodium, Inorganic salts such as sodium chloride, potassium nitrate, zinc chloride, zinc citrate, and strontium chloride, vitamins such as ascorbic acid and tocopherol acetate, chlorophyll, soft bean extract, thyme, ogon, clove, hamamelis, etc. Things extract, anti-tartar agents and antiplaque agents. These active ingredients can be blended in an effective amount as long as the effects of the present invention are not hindered.

以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記の例において%は特に断らない限りいずれも質量%を示す。   EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “%” means “% by mass” unless otherwise specified.

[実施例、比較例]
表1〜3に示す組成の歯磨剤組成物を常法により調製し、下記方法で評価した。結果を表1〜3に示す。
[Examples and Comparative Examples]
Dentifrice compositions having the compositions shown in Tables 1 to 3 were prepared by conventional methods and evaluated by the following methods. The results are shown in Tables 1-3.

<象牙細管封鎖能の評価>
Pashleyらの方法(J.Dent.Res.57,187−193,1987)に準じ、象牙細管の液の通過性を計測し、各歯磨剤組成物による象牙細管の封鎖の程度を評価した。
ヒトの歯根から象牙質ブロックを切り出し、耐水研磨紙#2000で研磨を行って標本を作製し、サンプルとした。歯磨剤組成物3gと1mM相当のCaCl2及び3mM相当のKH2PO4を含むpH7.0の人工唾液6gとを混合して3倍希釈液とし、遠心分離して得た上澄を処置液とした。なお、3倍希釈は、歯磨き時に歯磨剤組成物が唾液によって希釈されることを想定したことによる。この処置液にサンプルを1分間浸漬し、蒸留水で濯いだ後、上記人工唾液中に37℃で12時間浸漬した。同様の操作を1日2回行い、この一連の操作を合計5日間繰り返した。最終日サンプルを蒸留水でよく濯ぎ、乾燥後、サンプルを固定し一定圧下で生理食塩水を流し、サンプルを通過する単位時間当たりの生理食塩水の量を測定して、処置液で処置前の通過量に対する、各実施例及び比較例の通過性抑制率を算出した(下記式(1))。各例(実施例、比較例)とも、評価はn=3で行い、その平均値を採用した。

Figure 2014139162
<Evaluation of ivory tubule sealing ability>
According to the method of Pashley et al. (J. Dent. Res. 57, 187-193, 1987), the permeability of the dentinal tubule was measured, and the degree of occlusion of the dentinal tubule by each dentifrice composition was evaluated.
A dentin block was cut out from a human tooth root and polished with water-resistant abrasive paper # 2000 to prepare a sample, which was used as a sample. 3 g of the dentifrice composition and 6 g of artificial saliva of pH 7.0 containing 1 mM of CaCl 2 and 3 mM of KH 2 PO 4 were mixed to obtain a 3-fold dilution, and the supernatant obtained by centrifugation was treated liquid. It was. The 3-fold dilution is based on the assumption that the dentifrice composition is diluted with saliva during brushing. The sample was immersed in this treatment solution for 1 minute, rinsed with distilled water, and then immersed in the artificial saliva at 37 ° C. for 12 hours. The same operation was performed twice a day, and this series of operations was repeated for a total of 5 days. Rinse the sample thoroughly with distilled water on the last day, and after drying, fix the sample, flush saline under constant pressure, measure the amount of saline per unit time passing through the sample, and treat with the treatment solution before treatment The permeability suppression rate of each Example and the comparative example with respect to the passage amount was calculated (the following formula (1)). In each example (Example, Comparative Example), the evaluation was performed with n = 3, and the average value was adopted.
Figure 2014139162

得られた通過性抑制率の平均値から、下記基準により各例の象牙細管封鎖の程度を判断して象牙細管封鎖能を評価した。○以上のものを合格とした。
評価基準;
◎:通過性抑制率が90%以上である
○:通過性抑制率が80%以上90%未満である
△:通過性抑制率が60%以上80%未満である
×:通過性抑制率が60%未満である
The degree of dentinal tubule sealing of each example was judged from the average value of the obtained permeability inhibition rate according to the following criteria, and dentinal tubule sealing ability was evaluated. ○ The above was considered acceptable.
Evaluation criteria;
A: The permeability inhibition rate is 90% or more. O: The permeability inhibition rate is 80% or more and less than 90%. Δ: The permeability inhibition rate is 60% or more and less than 80%. X: The permeability inhibition rate is 60. Less than%

<経時での象牙細管封鎖能の評価>
経時での象牙細管封鎖能は、40℃で6ヶ月保存した後の歯磨剤組成物を用いて上記象牙細管封鎖能の評価と同様にして操作、算出し、同様の評価基準によって経時での象牙細管封鎖能を評価した。
<Evaluation of dentinal tubule sealing ability over time>
The dentinal tubule sealing ability over time was operated and calculated in the same manner as the evaluation of the dentinal tubule sealing ability using the dentifrice composition after being stored at 40 ° C. for 6 months. Capillary blocking ability was evaluated.

更に、表2の実施例については、嫌味について下記方法で評価した。
<嫌味のなさの評価>
歯磨剤組成物約1gを市販品歯ブラシにのせて3分間ブラッシングを行い、使用中に感じた嫌味のなさを、以下の評点に従って判定して下記評価基準によって評価した(n=10)。
評点
4点:嫌味が全くない
3点:嫌味がほとんどない
2点:嫌味がややある
1点:嫌味がある
評価基準
◎:3.5点以上4.0点以下
○:3.0点以上3.5点未満
△:2.0点以上3.0点未満
×:2.0点未満
Furthermore, about the Example of Table 2, it evaluated by the following method about unpleasant taste.
<Evaluation of bad taste>
About 1 g of the dentifrice composition was placed on a commercially available toothbrush and brushed for 3 minutes. The unpleasant taste felt during use was determined according to the following rating and evaluated according to the following evaluation criteria (n = 10).
Rating 4 points: No disgusting 3 points: Little disgusting 2 points: Some disgusting 1 point: Disgusting Evaluation criteria ◎: 3.5 points or more 4.0 points or less ○: 3.0 points or more 3 Less than 5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

使用原料の詳細は下記の通りである。
(A)モノフルオロリン酸ナトリウム;ローディア日華(株)製
(B)リン酸二水素ナトリウム;太平化学産業(株)製
(C)乳酸アルミニウム;武蔵野化学(株)製
フッ化ナトリウム;ステラケミファ(株)製
リン酸水素二ナトリウム;太平化学産業(株)製
リン酸三ナトリウム;太平化学産業(株)製
Details of the raw materials used are as follows.
(A) Sodium monofluorophosphate; Rhodia Nikka Co., Ltd. (B) Sodium dihydrogen phosphate; Taihei Chemical Industry Co., Ltd. (C) Aluminum lactate; Musashino Chemicals Co., Ltd. sodium fluoride; Stellachemifa Disodium hydrogen phosphate manufactured by Taihei Chemical Industrial Co., Ltd. Trisodium phosphate manufactured by Taihei Chemical Industrial Co., Ltd.

Figure 2014139162
Figure 2014139162

Figure 2014139162
Figure 2014139162

Figure 2014139162
*:比較品との比率
Figure 2014139162
*: Ratio to comparison product

Claims (7)

(A)モノフルオロリン酸ナトリウム、(B)リン酸二水素ナトリウム及び(C)乳酸アルミニウムを含有し、((A)成分+(B)成分)/(C)成分が質量比として0.10〜1.0であることを特徴とする歯磨剤組成物。   (A) Sodium monofluorophosphate, (B) Sodium dihydrogen phosphate and (C) Aluminum lactate, ((A) component + (B) component) / (C) component is 0.10 as a mass ratio. The dentifrice composition characterized by being -1.0. (A)成分を0.3〜1質量%、(B)成分を0.01〜0.2質量%、(C)成分を1〜5質量%含有する請求項1記載の歯磨剤組成物。   The dentifrice composition of Claim 1 which contains (A) component 0.3-1 mass%, (B) component 0.01-0.2 mass%, and (C) component 1-5 mass%. 更に、(D)ヤシ油脂肪酸アミドプロピルベタインを含有する請求項1又は2記載の歯磨剤組成物。   The dentifrice composition according to claim 1 or 2, further comprising (D) a coconut oil fatty acid amidopropyl betaine. (D)成分を0.1〜2質量%含有する請求項3記載の歯磨剤組成物。   The dentifrice composition of Claim 3 which contains 0.1-2 mass% of (D) component. 知覚過敏用である請求項1乃至4のいずれか1項記載の歯磨剤組成物。   The dentifrice composition according to any one of claims 1 to 4, which is used for hypersensitivity. (A)モノフルオロリン酸ナトリウム、(B)リン酸二水素ナトリウム及び(C)乳酸アルミニウムとからなり、((A)成分+(B)成分)/(C)成分が質量比として0.10〜1.0である歯牙の象牙細管封鎖剤。   (A) Sodium monofluorophosphate, (B) Sodium dihydrogen phosphate, and (C) Aluminum lactate, where ((A) component + (B) component) / (C) component is 0.10 as a mass ratio. -1.0 dental dentinal tubule sealant. 更に、(D)ヤシ油脂肪酸アミドプロピルベタインを含む請求項6記載の歯牙の象牙細管封鎖剤。   The tooth dentinal tubule sealant according to claim 6, further comprising (D) a palm oil fatty acid amidopropyl betaine.
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JP2021031447A (en) * 2019-08-27 2021-03-01 ライオン株式会社 Composition for oral cavity

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JPS6136212A (en) * 1984-07-26 1986-02-20 Lion Corp Composition for oral cavity application
JP2006182705A (en) * 2004-12-28 2006-07-13 Lion Corp Article to be put on tooth and method for supplying oral cavity care substance
JP2010143842A (en) * 2008-12-18 2010-07-01 Lion Corp Dentifrice composition
JP2012056868A (en) * 2010-09-08 2012-03-22 Lion Corp Dentifrice composition

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JPS6136212A (en) * 1984-07-26 1986-02-20 Lion Corp Composition for oral cavity application
JP2006182705A (en) * 2004-12-28 2006-07-13 Lion Corp Article to be put on tooth and method for supplying oral cavity care substance
JP2010143842A (en) * 2008-12-18 2010-07-01 Lion Corp Dentifrice composition
JP2012056868A (en) * 2010-09-08 2012-03-22 Lion Corp Dentifrice composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021031447A (en) * 2019-08-27 2021-03-01 ライオン株式会社 Composition for oral cavity
JP7400266B2 (en) 2019-08-27 2023-12-19 ライオン株式会社 Oral composition

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