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JP6693504B2 - Dentifrice composition - Google Patents

Dentifrice composition Download PDF

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JP6693504B2
JP6693504B2 JP2017502374A JP2017502374A JP6693504B2 JP 6693504 B2 JP6693504 B2 JP 6693504B2 JP 2017502374 A JP2017502374 A JP 2017502374A JP 2017502374 A JP2017502374 A JP 2017502374A JP 6693504 B2 JP6693504 B2 JP 6693504B2
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JPWO2016136719A1 (en
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誠 吉江
誠 吉江
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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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27Zinc; Compounds thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • 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

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

Description

本発明は、口臭抑制効果が優れ、かつ経時における製剤表面の肌荒れ、液分離が抑制され外観安定性が優れ、口臭の予防又は抑制に好適な水溶性金属塩含有の歯磨剤組成物に関する。   TECHNICAL FIELD The present invention relates to a dentifrice composition containing a water-soluble metal salt, which has an excellent effect of suppressing bad breath, is excellent in appearance stability by preventing roughening of the preparation surface over time and liquid separation, and is suitable for preventing or suppressing bad breath.

従来から、銅塩、亜鉛塩のような金属塩には口臭予防効果があるといわれており、口腔用組成物への応用に関する提案がなされている(特許文献1;特開平01−153622号公報)。しかし、上記金属塩を歯磨剤組成物に配合すると、リン酸水素カルシウム、炭酸カルシウム等の研磨剤との反応や吸着などによって、経時で口臭除去効果が十分発揮されないという欠点があり、研磨剤として改質水酸化アルミニウムを用いることによってメチルメルカプタンの消臭率が向上し、口臭防止効果を改善した技術が特許文献2(特開平02−311413号公報)に提案されている。   BACKGROUND ART Conventionally, metal salts such as copper salts and zinc salts are said to have a halitosis-preventing effect, and proposals for application to oral compositions have been made (Patent Document 1; JP-A No. 01-153622). ). However, when the above metal salt is blended in a dentifrice composition, there is a disadvantage that the effect of removing halitosis is not sufficiently exerted over time due to reaction or adsorption with an abrasive such as calcium hydrogen phosphate, calcium carbonate, etc. Patent Document 2 (Japanese Patent Laid-Open No. 02-311413) proposes a technique in which the deodorizing rate of methyl mercaptan is improved by using modified aluminum hydroxide and the effect of preventing bad breath is improved.

一方、オーラルケア分野において、ポリエチレングリコールは保湿剤又は粘稠剤として使用されている。しかし、分子量が10万以上の高重合ポリエチレングリコールを製剤に配合した例は少なく、液体歯磨剤の泡立ち性能の向上に使用した例(特許文献3:特表2006−506359号公報)や、歯牙の再石灰化促進効果に優れた歯磨剤に使用した例(特許文献4:特開2013−112613号公報)、高重合ポリエチレングリコールとアルキル硫酸塩と増粘性シリカとの配合によって、歯磨き時の起泡性や泡の持続性を改善した例(特許文献5:国際公開第2010/073975号)が開示されている程度である。   On the other hand, in the field of oral care, polyethylene glycol is used as a moisturizer or a thickener. However, there are few examples in which a highly polymerized polyethylene glycol having a molecular weight of 100,000 or more is blended in a preparation, and an example of using it for improving the foaming performance of a liquid dentifrice (Patent Document 3: Japanese Patent Publication No. 2006-506359) and teeth. Example used in a dentifrice having an excellent remineralization promoting effect (Patent Document 4: JP 2013-112613 A), foaming during tooth brushing by blending a highly polymerized polyethylene glycol, an alkyl sulfate and a thickening silica. It is only to the extent that an example (Patent Document 5: International Publication No. 2010/073975) in which the property and the persistence of foam are improved is disclosed.

特開平01−153622号公報Japanese Patent Laid-Open No. 01-153622 特開平02−311413号公報JP-A-02-311413 特表2006−506359号公報Japanese Patent Publication No. 2006-506359 特開2013−112613号公報JP, 2013-112613, A 国際公開第2010/073975号International Publication No. 2010/073975

しかしながら、上記金属塩を配合した歯磨剤組成物の口臭予防効果は十分とは言い難く、口臭抑制効果を向上し、口臭予防に更に有効に利用し得る製剤の開発が望まれた。   However, it is difficult to say that the dentifrice composition containing the above metal salt is effective in preventing halitosis, and it has been desired to develop a formulation that improves the halitosis-suppressing effect and can be more effectively used for halitosis prevention.

本発明は、上記事情に鑑みなされたもので、口臭抑制効果が優れ、かつ経時における製剤表面の肌荒れ、液分離が抑制され外観安定性が優れる水溶性金属塩含有の歯磨剤組成物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 provides a dentifrice composition containing a water-soluble metal salt, which has an excellent effect of suppressing bad breath, roughens the surface of the preparation over time, and suppresses liquid separation and has excellent appearance stability. The purpose is to

本発明者は、上記目的を達成するため鋭意検討を行った結果、(A)銅塩及び亜鉛塩から選ばれる水溶性金属塩を0.01〜1質量%と、(B)ブルックフィールド型粘度計で測定した25℃における5W/V%水溶液の粘度が10mPa・s以上であり、かつ前記粘度計で測定した25℃における2W/V%水溶液の粘度が800mPa・s以下である高重合ポリエチレングリコールを0.01〜0.5質量%とを併用して配合すると、口臭抑制効果が向上し、かつ経時における歯磨製剤表面の肌荒れ、液分離が抑制され良好な外観安定性を与えることができることを見出した。即ち、本発明によれば、(A)成分を含有する歯磨剤組成物に、(B)成分を適切に配合することによって、口臭抑制効果が高く、かつ外観安定性が優れる、口臭の予防又は抑制に好適な歯磨剤組成物が得られることを知見し、本発明をなすに至った。   The present inventors have conducted extensive studies to achieve the above object, and as a result, (A) a water-soluble metal salt selected from a copper salt and a zinc salt is 0.01 to 1% by mass, and (B) a Brookfield type viscosity. A highly polymerized polyethylene glycol having a viscosity of 5 W / V% aqueous solution at 25 ° C. measured by a viscometer of 10 mPa · s or more and a viscosity of 2 W / V% aqueous solution measured at 25 ° C. by a viscometer of 800 mPa · s or less. When used in combination with 0.01 to 0.5% by mass, the effect of suppressing bad breath is improved, and the surface of the dentifrice preparation is roughened over time, liquid separation is suppressed, and good appearance stability can be provided. I found it. That is, according to the present invention, by properly blending the component (B) with the dentifrice composition containing the component (A), the breath odor suppressing effect is high and the appearance stability is excellent. The inventors have found that a dentifrice composition suitable for suppression can be obtained, and have completed the present invention.

即ち、銅塩、亜鉛塩といった水溶性金属塩の口臭抑制効果は十分ではなく、また、高重合ポリエチレングリコールには口臭抑制効果が認められないにもかかわらず、本発明では、(A)成分に(B)成分を併用することによって、(A)成分由来の口臭抑制効果が向上し、かつ製剤外観が安定化する。この場合、歯磨剤組成物において、(A)成分に(B)成分を不適切量で併用すると、経時において製剤表面が肌荒れして歯磨剤のきめが悪くなり、液分離も発生し、外観安定性が低下するという課題が生じるが、(A)、(B)成分を適切に組み合わせると、意外にも、上記課題も解消して製剤外観が悪化することなく口臭抑制効果が高まり、口内から採取された口臭が十分に抑制されて認知されなくなる優れた口臭抑制効果を奏し、また、製剤外観が経時で安定化し、50℃で1ヶ月保存後に製剤表面がしわや粒状の凝集体によって肌荒れするのが抑えられ、滑らかでツヤのある表面を与えることも可能となり、歯磨剤のきめが良好となり、更には液分離を抑制することもできる。
なお、本発明において、(B)成分の高重合ポリエチレングリコールによって、(A)成分含有歯磨剤組成物の口臭抑制効果及び外観安定性が改善することは、歯磨剤組成物の粘稠剤、保湿剤としてのポリエチレングリコールの使用からは予測できない。
That is, the bad breath suppressing effect of water-soluble metal salts such as copper salts and zinc salts is not sufficient, and the high polymerized polyethylene glycol has no bad breath suppressing effect. By using the component (B) in combination, the effect of suppressing bad breath derived from the component (A) is improved, and the appearance of the preparation is stabilized. In this case, if the component (A) and the component (B) are used in an inappropriate amount in the dentifrice composition, the surface of the preparation becomes rough over time, the texture of the dentifrice deteriorates, liquid separation occurs, and the appearance is stable. However, surprisingly, when the components (A) and (B) are properly combined, the above-mentioned problems are solved and the oral malodor suppressing effect is enhanced without deteriorating the appearance of the preparation, and it is collected from the mouth. It exerts an excellent effect of suppressing bad breath that is sufficiently suppressed and is not perceived, and the appearance of the preparation is stabilized over time, and the surface of the preparation becomes rough due to wrinkles and granular aggregates after storage for 1 month at 50 ° C. It is also possible to provide a smooth and glossy surface, to improve the texture of the dentifrice, and to suppress liquid separation.
In the present invention, the fact that the highly polymerized polyethylene glycol as the component (B) improves the bad breath suppressing effect and appearance stability of the dentifrice composition containing the component (A) means that the thickener and the moisturizing agent of the dentifrice composition are used. It cannot be predicted from the use of polyethylene glycol as a drug.

従って、本発明は、下記の歯磨剤組成物を提供する。
〔1〕
(A)銅塩及び亜鉛塩から選ばれる1種又は2種以上の水溶性金属塩を0.01〜1質量%と、
(B)ブルックフィールド型粘度計で測定した25℃における5W/V%水溶液の粘度が30〜2,000mPa・sある高重合ポリエチレングリコールを0.01〜0.5質量%と
を含有し、(A)成分と(B)成分との配合量の割合を示す(A)/(B)が、質量比として0.1〜10であることを特徴とする歯磨剤組成物。
〔2〕
(A)成分の水溶性金属塩が、グルコン酸銅、クエン酸銅、硫酸銅、塩化銅、グルコン酸亜鉛、硫酸亜鉛及びクエン酸亜鉛から選ばれる1種又は2種以上である〔1〕に記載の歯磨剤組成物。
〔3〕
(A)成分の水溶性金属塩が、グルコン酸銅及び/又はクエン酸亜鉛である〔〕に記載の歯磨剤組成物。
〔4〕
(B)成分の高重合ポリエチレングリコールが、ブルックフィールド型粘度計で測定した25℃における5W/V%水溶液の粘度が55250mPa・sものである〔1〕、〔2〕又は〔3〕に記載の歯磨剤組成物。
〔5〕
(A)成分と(B)成分との配合量の割合を示す(A)/(B)が、質量比として0.5である〔1〕〜〔4〕のいずれかに記載の歯磨剤組成物。
〔6〕
更に、(C)アルギン酸プロピレングリコールエステルを0.01〜3質量%含有する〔1〕〜〔5〕のいずれかに記載の歯磨剤組成物。

練歯磨剤である〔1〕〜〔〕のいずれかに記載の歯磨剤組成物。
Therefore, the present invention provides the following dentifrice compositions.
[1]
(A) 0.01 to 1 mass% of one or more water-soluble metal salts selected from copper salts and zinc salts,
(B) 0.01 to 0.5 mass% of highly polymerized polyethylene glycol having a viscosity of a 5 W / V% aqueous solution of 30 to 2,000 mPa · s at 25 ° C. measured with a Brookfield viscometer , (a) component and (B) shows the percentage of the amount of component (a) / (B) is, dentifrice composition comprising 0.1 to 10 der Rukoto as a mass ratio.
[2]
The water-soluble metal salt of the component (A) is one or more selected from copper gluconate, copper citrate, copper sulfate, copper chloride, zinc gluconate, zinc sulfate and zinc citrate [1]. The dentifrice composition described.
[3]
The dentifrice composition according to [ 2 ], wherein the water-soluble metal salt of the component (A) is copper gluconate and / or zinc citrate.
[4]
(B) highly polymerized polyethylene glycol ingredients, Brook viscosity of 5W / V% aqueous solution at 25 ° C. as measured by field type viscometer is of 55 ~ 250 mPa · s [1], [2] or [3 ] The dentifrice composition of statement.
[5]
The toothpaste according to any one of [1] to [4], wherein (A) / (B), which represents the ratio of the blending amounts of the (A) component and the (B) component, is 0.5 to 2 as a mass ratio. Agent composition.
[6]
The dentifrice composition according to any one of [1] to [5], which further comprises (C) 0.01 to 3 mass% of propylene glycol alginate.
[ 7 ]
The dentifrice composition according to any one of [1] to [ 6 ], which is a toothpaste.

本発明によれば、口臭抑制効果が優れ、かつ経時における製剤表面の肌荒れ、液分離が抑制され外観安定性が優れ、口臭の予防又は抑制に好適に使用し得る水溶性金属塩含有の歯磨剤組成物を提供することができる。   According to the present invention, a dentifrice containing a water-soluble metal salt, which has an excellent halitosis-suppressing effect, and which has a rough surface of the preparation over time, has excellent appearance stability by suppressing liquid separation, and can be suitably used for preventing or suppressing halitosis. A composition can be provided.

以下、本発明について更に詳述する。本発明の歯磨剤組成物は、(A)銅塩及び亜鉛塩から選ばれる水溶性金属塩と、(B)ブルックフィールド型粘度計で測定した25℃における5W/V%水溶液の粘度が10mPa・s以上であり、かつ前記粘度計で測定した25℃における2W/V%水溶液の粘度が800mPa・s以下である高重合ポリエチレングリコールとを配合してなる。   Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention comprises (A) a water-soluble metal salt selected from a copper salt and a zinc salt, and (B) a 5 W / V% aqueous solution having a viscosity of 10 mPa · s at 25 ° C. measured by a Brookfield viscometer. and a highly polymerized polyethylene glycol having a viscosity of 2 W / V% aqueous solution of 800 mPa · s or less at 25 ° C. measured by the above viscometer.

(A)成分の水溶性金属塩は、水溶性の銅塩、亜鉛塩から選ばれる1種又は2種以上であり、例えばグルコン酸銅、クエン酸銅、硫酸銅、塩化銅、グルコン酸亜鉛、硫酸亜鉛、クエン酸亜鉛等が挙げられ、無水物だけでなく硫酸銅5水和物等の結晶水を含む水和物を用いることもできるが、中でもグルコン酸銅、クエン酸銅、クエン酸亜鉛、特にグルコン酸銅、クエン酸亜鉛が好ましい。   The water-soluble metal salt of component (A) is one or more selected from water-soluble copper salts and zinc salts, and examples thereof include copper gluconate, copper citrate, copper sulfate, copper chloride, zinc gluconate, Examples thereof include zinc sulfate and zinc citrate, and not only anhydrous but also hydrates containing crystal water such as copper sulfate pentahydrate can be used, but among them, copper gluconate, copper citrate, zinc citrate, etc. Especially, copper gluconate and zinc citrate are preferable.

上記水溶性金属塩の配合量は、口臭抑制の点から組成物全体の0.01〜1%(質量%、以下、同様。)であり、好ましくは0.01〜0.5%、より好ましくは0.05〜0.3%である。0.01%以上配合すると、十分な口臭抑制効果が得られる。1%以下であることが、経時で歯磨剤のきめが悪くなるのを防止するには好適である。
なお、上記配合量の範囲内において、(A)成分の水溶性銅塩の配合量は、銅として組成物全体の0.0014〜0.5%、特に0.007〜0.15%が好ましい。また、水溶性亜鉛塩の配合量は、亜鉛として組成物全体の0.0014〜0.5%、特に0.007〜0.15%が好ましい。
The content of the water-soluble metal salt is 0.01 to 1% (mass%, hereinafter, the same) of the entire composition from the viewpoint of suppressing bad breath, preferably 0.01 to 0.5%, and more preferably. Is 0.05 to 0.3%. When it is blended in an amount of 0.01% or more, a sufficient bad breath suppressing effect can be obtained. The content of 1% or less is suitable for preventing deterioration of the texture of the dentifrice over time.
In addition, within the range of the above blending amount, the blending amount of the water-soluble copper salt as the component (A) is preferably 0.0014 to 0.5%, and particularly preferably 0.007 to 0.15% of copper as the whole composition. .. The amount of the water-soluble zinc salt as zinc is preferably 0.0014 to 0.5%, and more preferably 0.007 to 0.15% of the total composition.

(B)成分の高重合ポリエチレングリコールは、エチレングリコールが重合した構造をもつ高分子化合物であり、ブルックフィールド型粘度計で測定した25℃における5W/V(質量/体積(容量))%水溶液の粘度が10mPa・s以上であり、かつ前記粘度計で測定した25℃における2W/V%水溶液の粘度が800mPa・s以下のものである。
5W/V%水溶液の粘度が20,000mPa・sを超える場合は、粘度測定が不能となるため、2W/V%水溶液における粘度を採用する。即ち、本発明において、高重合ポリエチレングリコールは、下記(1)又は(2)の粘度物性を有する。
(1)25℃における5W/V%水溶液の粘度が10〜20,000mPa・s
(2)(1)で粘度が20,000mPa・sを超える場合は、25℃における2W/V%水溶液の粘度が800mPa・s以下
本発明において、より好ましい高重合ポリエチレングリコールは、25℃における5W/V%水溶液の粘度が10〜18,000mPa・s、特に30〜10,000mPa・s、とりわけ55〜2,000mPa・s、更にとりわけ55〜250mPa・sのものである。
本発明では、(B)成分として粘度が上記特定範囲内である高重合ポリエチレングリコールを用いることで、(A)成分由来の口臭抑制効果が向上し、また、経時における製剤表面の肌荒れが改善し、液分離が抑制され、良好な外観安定性を与える。
上記5W/V%水溶液の粘度が10mPa・sに満たないと、歯磨剤のきめの改善効果が十分に得られず、上記2W/V%水溶液の粘度が800mPa・sを超えると、歯磨剤のきめが経時で低下する。
The highly polymerized polyethylene glycol as the component (B) is a polymer compound having a structure in which ethylene glycol is polymerized, and is a 5 W / V (mass / volume (volume))% aqueous solution at 25 ° C. measured by a Brookfield viscometer. The viscosity is 10 mPa · s or more, and the viscosity of a 2 W / V% aqueous solution at 25 ° C. measured by the viscometer is 800 mPa · s or less.
When the viscosity of the 5 W / V% aqueous solution exceeds 20,000 mPa · s, the viscosity cannot be measured, so the viscosity in the 2 W / V% aqueous solution is used. That is, in the present invention, the highly polymerized polyethylene glycol has the following viscosity physical properties (1) or (2).
(1) The viscosity of a 5 W / V% aqueous solution at 25 ° C is 10 to 20,000 mPa · s.
(2) When the viscosity exceeds 20,000 mPa · s in (1), the viscosity of a 2 W / V% aqueous solution at 25 ° C. is 800 mPa · s or less. In the present invention, more preferable highly polymerized polyethylene glycol is 5 W at 25 ° C. / V% aqueous solution has a viscosity of 10 to 18,000 mPa · s, particularly 30 to 10,000 mPa · s, especially 55 to 2,000 mPa · s, and especially 55 to 250 mPa · s.
In the present invention, by using a highly polymerized polyethylene glycol having a viscosity within the above specific range as the component (B), the effect of suppressing bad breath derived from the component (A) is improved, and the roughening of the preparation surface over time is improved. , Liquid separation is suppressed, and good appearance stability is provided.
If the viscosity of the 5 W / V% aqueous solution is less than 10 mPa · s, the effect of improving the texture of the dentifrice cannot be sufficiently obtained. If the viscosity of the 2 W / V% aqueous solution exceeds 800 mPa · s, The texture deteriorates over time.

(B)成分の高重合ポリエチレングリコールとしては下記に示す市販品を使用し得る。
・POLYOX WSR N−10
(ダウ・ケミカル社製、5W/V%水溶液の粘度:12〜50mPa・s、測定機器:ブルックフィールド RVT、ローターNo.1、回転数50rpm、測定温度25℃、測定時間0.5分)
・POLYOX WSR N−80
(ダウ・ケミカル社製、5W/V%水溶液の粘度:55〜115mPa・s、測定機器:ブルックフィールド RVT、ローターNo.1、回転数50rpm、測定温度25℃、測定時間0.5分)
・POLYOX WSR N−750
(ダウ・ケミカル社製、5W/V%水溶液の粘度:1,000〜1,200mPa・s、測定機器:ブルックフィールド RVF、ローターNo.2、回転数10rpm、測定温度25℃、測定時間1分)
・POLYOX WSR−205
(ダウ・ケミカル社製、5W/V%水溶液の粘度:4,500〜8,800mPa・s、測定機器:ブルックフィールド RVF、ローターNo.2、回転数2rpm、測定温度25℃、測定時間5分)
・POLYOX WSR−1105
(ダウ・ケミカル社製、5W/V%水溶液の粘度:8,800〜17,600mPa・s、測定機器:ブルックフィールド RVF、ローターNo.2、回転数2rpm、測定温度25℃、測定時間5分)
・POLYOX WSR N−12K
(ダウ・ケミカル社製、2W/V%水溶液の粘度:400〜800mPa・s、測定機器:ブルックフィールド RVF、ローターNo.1、回転数10rpm、測定温度25℃、測定時間1分)
As the highly polymerized polyethylene glycol as the component (B), the following commercial products can be used.
・ POLYOX WSR N-10
(Viscosity of 5 W / V% aqueous solution, manufactured by Dow Chemical Co., Ltd .: 12 to 50 mPa · s, measuring instrument: Brookfield RVT, rotor No. 1, rotation speed 50 rpm, measuring temperature 25 ° C., measuring time 0.5 minutes)
・ POLYOX WSR N-80
(Viscosity of 5 W / V% aqueous solution: 55 to 115 mPa · s, measuring instrument: Brookfield RVT, rotor No. 1, rotation speed 50 rpm, measuring temperature 25 ° C., measuring time 0.5 minutes) (manufactured by Dow Chemical Co., Ltd.)
・ POLYOX WSR N-750
(Manufactured by Dow Chemical Co., Ltd., viscosity of 5 W / V% aqueous solution: 1,000 to 1,200 mPa · s, measuring instrument: Brookfield RVF, rotor No. 2, rotation speed 10 rpm, measurement temperature 25 ° C., measurement time 1 minute )
・ POLYOX WSR-205
(Manufactured by Dow Chemical Co., Ltd., viscosity of 5 W / V% aqueous solution: 4,500 to 8,800 mPa · s, measuring instrument: Brookfield RVF, rotor No. 2, rotation speed 2 rpm, measuring temperature 25 ° C., measuring time 5 minutes )
・ POLYOX WSR-1105
(Manufactured by Dow Chemical Co., Ltd., viscosity of 5 W / V% aqueous solution: 8,800 to 17,600 mPa · s, measuring instrument: Brookfield RVF, rotor No. 2, rotation speed 2 rpm, measuring temperature 25 ° C., measuring time 5 minutes )
・ POLYOX WSR N-12K
(Manufactured by Dow Chemical Co., 2W / V% aqueous solution viscosity: 400 to 800 mPa · s, measuring instrument: Brookfield RVF, rotor No. 1, rotation speed 10 rpm, measuring temperature 25 ° C., measuring time 1 minute)

(B)成分の高重合ポリエチレングリコールの配合量は、組成物全体の0.01〜0.5%であり、好ましくは0.03〜0.2%、より好ましくは0.05〜0.1%である。配合量が0.01%に満たないと、十分な口臭抑制効果、歯磨剤のきめの改善効果が得られない。配合量が多すぎると、それ以上の効果向上が期待できない上に製剤の外観安定性が低下し、0.5%を超えると歯磨剤のきめを良好に維持できず、液分離を抑えることができない。   The amount of the highly polymerized polyethylene glycol as the component (B) is 0.01 to 0.5%, preferably 0.03 to 0.2%, and more preferably 0.05 to 0.1% of the total composition. %. If the blending amount is less than 0.01%, a sufficient breath odor suppressing effect and a dentifrice texture improving effect cannot be obtained. If the blending amount is too large, further improvement of the effect cannot be expected, and the appearance stability of the formulation will be deteriorated. If it exceeds 0.5%, the texture of the dentifrice cannot be maintained well and liquid separation can be suppressed. Can not.

本発明では、(A)成分と(B)成分とを適切比率で配合すると、口臭抑制効果がより優れ、外観安定性もより向上する。この場合、(A)成分と(B)成分との配合量の割合を示す(A)/(B)が質量比として0.02〜100が好ましく、より好ましくは0.1〜10,特に好ましくは0.5〜6、更に好ましくは0.5〜2である。(A)/(B)比が小さすぎると、口臭抑制効果が十分に得られない場合があり、大きすぎると、歯磨剤のきめが十分に改善しなかったり、液分離が十分に抑えられない場合がある。
なお、(A)/(B)の質量比が上記範囲内において、(A)成分の水溶性銅塩の銅としての配合量と(B)成分の配合量との割合を示す(A−1)/(B)は質量比として0.003〜50、特に0.07〜3が好ましい。また、(A)成分の水溶性亜鉛塩の亜鉛としての配合量と(B)成分の配合量との割合を示す(A−2)/(B)は質量比として0.003〜50、特に0.07〜3が好ましい。
In the present invention, when the component (A) and the component (B) are blended in an appropriate ratio, the breath odor suppressing effect is more excellent and the appearance stability is further improved. In this case, the mass ratio of (A) / (B), which represents the proportion of the components (A) and (B), is preferably 0.02 to 100, more preferably 0.1 to 10, and particularly preferably. Is 0.5 to 6, and more preferably 0.5 to 2. If the (A) / (B) ratio is too small, the effect of suppressing bad breath may not be sufficiently obtained, and if it is too large, the texture of the dentifrice may not be sufficiently improved or liquid separation may not be sufficiently suppressed. There are cases.
In addition, in the mass ratio of (A) / (B) within the above range, the ratio of the compounding amount of the water-soluble copper salt of the component (A) as copper and the compounding amount of the component (B) is shown (A-1). ) / (B) is preferably 0.003 to 50, particularly preferably 0.07 to 3 as a mass ratio. Further, (A-2) / (B) showing the ratio of the blending amount of the water-soluble zinc salt of the component (A) as zinc and the blending amount of the component (B) is 0.003 to 50 as a mass ratio, particularly 0.07-3 is preferable.

本発明の歯磨剤組成物に、更に、(C)アルギン酸プロピレングリコールエステルを配合すると、口臭抑制効果の持続性が向上し、(A)成分由来の金属味を抑制するため、好ましい。使用するアルギン酸プロピレングリコールエステルは、特に制限されないが、ブルックフィールド型粘度計による1%水溶液(20℃)の粘度が、10〜1,300mPa・s、特に10〜200mPa・sの範囲であることが好ましい。
(C)アルギン酸プロピレングリコールエステルの配合量は、組成物全体の0.01〜3%が好ましく、より好ましくは0.05〜3%である。前記範囲内で、口臭抑制持続効果が特に優れ、また、金属味が抑制され使用感も良好である。
また、(C)アルギン酸プロピレングリコールエステルに対する(A)成分の配合比率は質量比で0.01〜5であることが好ましい。
It is preferable to further add (C) propylene glycol alginate to the dentifrice composition of the present invention because the durability of the breath odor suppressing effect is improved and the metallic taste derived from the component (A) is suppressed. The propylene glycol alginate used is not particularly limited, but the viscosity of a 1% aqueous solution (20 ° C.) measured by a Brookfield viscometer is in the range of 10 to 1,300 mPa · s, particularly 10 to 200 mPa · s. preferable.
The blending amount of (C) propylene glycol alginate is preferably 0.01 to 3% of the total composition, and more preferably 0.05 to 3%. Within the above range, the effect of suppressing bad breath is particularly excellent, and the metallic taste is suppressed and the feeling of use is good.
Further, the mixing ratio of the component (A) to the propylene glycol alginate (C) is preferably 0.01 to 5 in mass ratio.

本発明の歯磨剤組成物は、練歯磨剤、液状歯磨剤等として、特に練歯磨剤として好適に調製される。また、その剤型に応じて、上記成分以外に通常使用される公知の成分を必要に応じ配合できる。例えば、研磨剤、粘稠剤、粘結剤、界面活性剤、甘味剤、防腐剤、着色剤、香料、上記以外の有効成分などを、本発明の効果を妨げない範囲で通常量で用いることができる。   The dentifrice composition of the present invention is preferably prepared as a toothpaste, a liquid dentifrice or the like, particularly as a toothpaste. In addition to the above-mentioned components, known components that are normally used can be blended as necessary depending on the dosage form. For example, an abrasive, a thickener, a binder, a surfactant, a sweetener, a preservative, a coloring agent, a fragrance, an active ingredient other than the above, and the like are used in a usual amount within a range that does not impair the effects of the present invention. You can

研磨剤としては、シリカゲル、沈降シリカ、アルミノシリケート、ジルコノシリケート等のシリカ系研磨剤、第二リン酸カルシウム等のリン酸カルシウム系研磨剤、水酸化アルミニウム、アルミナ、炭酸カルシウム、合成樹脂系研磨剤等が挙げられる。研磨剤の配合量は通常、5〜50%である。   Examples of the polishing agent include silica gel, precipitated silica, aluminosilicate, silica-based polishing agents such as zirconosilicate, calcium phosphate-based polishing agents such as dicalcium phosphate, aluminum hydroxide, alumina, calcium carbonate, and synthetic resin-based polishing agents. Be done. The content of the abrasive is usually 5 to 50%.

粘稠剤としては、ソルビット、キシリット、エリスリトール等の糖アルコール、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。これら粘稠剤の配合量は通常、5〜50%である。   Examples of the thickener include sugar alcohols such as sorbit, xylit and erythritol, and polyhydric alcohols such as glycerin and propylene glycol. The content of these thickeners is usually 5 to 50%.

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等のセルロース系誘導体、キサンタンガム等のガム類等が挙げられる。粘結剤の配合量は通常、0〜5%、特に0.1〜5%である。   Examples of the binder include cellulosic derivatives such as sodium carboxymethyl cellulose and gums such as xanthan gum. The content of the binder is usually 0 to 5%, especially 0.1 to 5%.

界面活性剤としては、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤、両性界面活性剤を配合できる。
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などが挙げられる。非イオン性界面活性剤としては、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ショ糖脂肪酸エステル等の糖アルコール脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル等の多価アルコール脂肪酸エステル、ポリオキシエチレンアルキルエーテル、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、脂肪酸アルカノールアミドなどが挙げられる。
カチオン性界面活性剤としては、アルキルアンモニウム型等が挙げられ、両性界面活性剤としては、ベタイン型、イミダゾリン型等が挙げられる。
界面活性剤の配合量は、組成全体の0.5〜5%が好ましい。
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be blended.
Examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate. As the nonionic surfactant, polyalcohol such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sugar alcohol fatty acid ester such as sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, etc. Examples thereof include alcohol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, and fatty acid alkanolamides.
Examples of the cationic surfactant include alkyl ammonium type and the like, and examples of the amphoteric surfactant include betaine type and imidazoline type.
The content of the surfactant is preferably 0.5 to 5% of the total composition.

甘味剤としては、サッカリンナトリウム等が挙げられる。防腐剤としては、メチルパラベン等のパラオキシ安息香酸エステル、安息香酸又はその塩等が挙げられる。着色剤としては、青色1号、黄色4号等が挙げられる。   Examples of the sweetener include saccharin sodium and the like. Examples of antiseptics include paraoxybenzoic acid esters such as methylparaben, benzoic acid or salts thereof, and the like. Examples of colorants include Blue No. 1 and Yellow No. 4.

香料としては、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。これら香料の配合量は通常、0.00001〜3%である。   As the fragrance, 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, chamomile oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, grapefruit oil, sweetie. Natural fragrances such as oil, citrus oil, iris concrete, absolute peppermint, absolute rose, and orange flower, and processing of these natural fragrances (pre-cut, post-cut, fractionation, liquid-liquid extraction, essence, powder) Fragrance, etc.) and menthol, Rubon, anethole, cineol, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramenthane- 3-carboxamide, pinene, octyl aldehyde, citral, pulegone, carbetyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethylmethylphenylglycidate, vanillin, undecalactone, Hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cyclotene, furfural, trimethylpyrazine, ethyl lactate, ethyl Single fragrances such as o-acetate, strawberry flavors, apple flavors, banana flavors, pineapple flavors, grape flavors, mango flavors, butter flavors, milk flavors, fruit mix flavors, tropical fruit flavors, etc. Known perfume materials used in can be used in combination. The compounding amount of these fragrances is usually 0.00001 to 3%.

有効成分としては、歯磨剤組成物に通常配合される公知のものを使用でき、例えばフッ化物、殺菌剤、抗炎症剤、酵素、植物抽出物、歯石防止剤、歯垢防止剤などを配合できる。具体的には、フッ化ナトリウム、モノフルオロリン酸ナトリウム等のフッ化物、イソプロピルメチルフェノール等の非イオン性殺菌剤、カチオン性殺菌剤、デキストラナーゼ等の酵素トラネキサム酸、イプシロンアミノカプロン酸、アラントイン等の抗炎症剤などが挙げられる。なお、上記有効成分は、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 ones usually added to dentifrice compositions can be used, and for example, fluoride, bactericide, anti-inflammatory agent, enzyme, plant extract, anticalculus agent, antiplaque agent, etc. can be added. .. Specifically, sodium fluoride, fluorides such as sodium monofluorophosphate, nonionic bactericides such as isopropylmethylphenol, cationic bactericides, enzymes tranexamic acid such as dextranase, epsilon aminocaproic acid, allantoin, etc. Anti-inflammatory agents of The above-mentioned active ingredients can be added in effective amounts within a range that does not impair the effects of the present invention.

以下、実施例及び比較例、処方例を示し、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。   Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples and prescription examples, but the present invention is not limited to the following Examples. In the following examples,% means 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(練歯磨)を常法によって調製し、下記方法で評価した。結果を表1〜3に併記した。
[Examples and Comparative Examples]
Dentifrice compositions (toothpaste) having the compositions shown in Tables 1 to 3 were prepared by a conventional method and evaluated by the following methods. The results are also shown in Tables 1 to 3.

(1)口臭抑制効果の評価方法
健常人で口臭を有し、かつ1ヶ月以内に抗生物質を服用していないボランティア5名を被験者とした。被験者には前日夜から試験当日まで口腔清掃と飲食を禁止した。口臭試験は、試験開始前と歯磨きして1時間経過後(試験後)の口臭をそれぞれテドラバッグに採取し、テドラバッグに採取した呼気1リットルの口臭強度を、専門評価者3名が下記の評点基準に従い判定した。
<口臭強度の評点基準>
0点:口臭は認められない
1点:わずかな口臭が認められる
2点:口臭が認められる
3点:著しい口臭が認められる
更に、下記式により、口臭改善度を求め、試験組成物の口臭抑制効果を下記基準で評価した。
<口臭改善度の算出式>
(口臭改善度)=(試験開始前の口臭強度平均値)−(試験後の口臭強度平均値)
なお、口臭強度平均値は、各群被験者の口臭強度を平均した値である。
<口臭抑制効果の評価基準>
◎:顕著な効果あり。口臭改善度が1.5点以上
○:効果あり。口臭改善度が1.0点以上1.5点未満
△:若干の効果あり。口臭改善度が0.5点以上1.0点未満
×:効果なし。口臭改善度が0.5点未満
(1) Evaluation Method of Halitosis Suppressing Effect Five volunteers were healthy volunteers who had halitosis and did not take antibiotics within one month. Subjects were prohibited from cleaning the mouth and eating and drinking from the night before to the day of the test. In the bad breath test, the bad breath before the start of the test and after 1 hour from brushing the teeth (after the test) were collected in a tedra bag, and the breath odor intensity of 1 liter of exhaled breath collected in the tedra bag was evaluated by the three expert evaluators as follows. It was determined according to.
<Rating criteria for bad breath intensity>
0 points: No bad breath 1 point: Slight halitosis 2 points: Halitosis 3 points: Significant halitosis Further, the degree of improvement of halitosis was calculated by the following formula, and the bad breath suppression of the test composition was suppressed. The effect was evaluated according to the following criteria.
<Calculation formula of bad breath improvement>
(Improved breath odor) = (Average breath odor intensity before test)-(Average breath odor intensity after test)
In addition, the bad breath intensity average value is a value obtained by averaging the bad breath intensity of the subjects in each group.
<Evaluation criteria for bad breath control effect>
A: There is a remarkable effect. Halitosis improvement rate is 1.5 points or more. ○: Effective. The degree of improvement in bad breath is 1.0 point or more and less than 1.5 point. Δ: There is some effect. Bad breath improvement degree is 0.5 point or more and less than 1.0 point x: No effect. Halitosis improvement is less than 0.5 point

(2)製剤表面の肌荒れのなさ(歯磨剤のきめ)の評価方法
50℃で1ヶ月保存後、歯磨剤組成物をチューブから歯ブラシに出した時の練の外観(製剤表面の肌荒れのなさ(歯磨剤のきめ))について、評価者3名が、下記の評点基準で判定した。
評点基準
5:しわが認められなく、更に滑らかでツヤがある
4:しわが認められない
3:しわがわずかに認められるが、品質的には問題ないレベルである
2:しわが認められるが、粒状の凝集体は認められない
1:しわや粒状の凝集がかなり認められる
3名の平均点を求め、歯磨剤のきめについて下記基準で評価した。
評価基準
◎:平均点が4.5点以上
○:平均点が3.0点以上4.5点未満
△:平均点が2.0点以上3.0点未満
×:平均点が2.0点未満
(2) Evaluation method of roughness of surface of preparation (texture of dentifrice) After storage at 50 ° C for 1 month, appearance of paste when toothpaste composition is taken out from tube to toothbrush (smoothness of surface of preparation ( Regarding the texture of the dentifrice)), three evaluators judged according to the following rating criteria.
Rating criteria 5: No wrinkles are observed, smoother and shiny 4: Wrinkles are not recognized 3: Wrinkles are slightly recognized, but there is no problem in quality 2: Wrinkles are recognized, No granular aggregates are observed 1: Wrinkles and granular aggregates are considerably observed The average score of 3 persons was obtained, and the texture of the dentifrice was evaluated according to the following criteria.
Evaluation Criteria ◎: Average score is 4.5 points or more ○: Average score is 3.0 points or more and less than 4.5 points Δ: Average score is 2.0 points or more and less than 3.0 points ×: Average score is 2.0 Less than a point

(3)液分離のなさの評価方法
50℃で1ヶ月保存後、歯磨剤組成物をチューブから歯ブラシに出した時の液分離について、評価者3名が、下記の評点基準で判定した。
評点基準
5:全く液の分離が認められない
4:口元にわずかな滲みが認められるが、全体的には問題ない
3:全体的にわずかな滲みが認められるが、品質的には問題ないレベル
である
2:全体に液の分離が認められる
1:歯ブラシから落ちるほどの激しい液分離が認められる
3名の平均点を求め、液分離のなさについて下記基準で評価した。
評価基準
◎:平均点が4.5点以上
○:平均点が3.0点以上4.5点未満
△:平均点が2.0点以上3.0点未満
×:平均点が2.0点未満
(3) Evaluation Method of No Liquid Separation After storage at 50 ° C. for one month, three evaluators evaluated the liquid separation when the dentifrice composition was taken out from the tube to the toothbrush according to the following rating criteria.
Rating criteria 5: No liquid separation is observed 4: Slight bleeding is observed in the mouth, but there is no overall problem 3: Slight bleeding is generally observed, but there is no problem in quality 2: Separation of liquid is observed throughout 1: 1: Liquid separation that is so severe as to fall from the toothbrush is observed An average point of 3 persons was obtained, and the lack of liquid separation was evaluated according to the following criteria.
Evaluation Criteria ◎: Average score is 4.5 points or more ○: Average score is 3.0 points or more and less than 4.5 points Δ: Average score is 2.0 points or more and less than 3.0 points ×: Average score is 2.0 Less than a point

使用原料の詳細を下記に示す。なお、高重合ポリエチレングリコールの粘度は、上記と同様に、ブルックフィールド型粘度計(ブルックフィールド RVT又はRVF)で測定した25℃における粘度である。また、同様の方法で測定したポリエチレングリコール#400の粘度は、(B)高重合ポリエチレングリコールの粘度に満たなかった。
(A)グルコン酸銅;関東化学(株)製、グルコン酸銅
(A)クエン酸亜鉛;関東化学(株)製、クエン酸亜鉛
(B)高重合ポリエチレングリコール;
POLYOX WSR N−80
(ダウ・ケミカル社製、5W/V%水溶液の粘度:85mPa・s(ロー
ターNo.1、回転数50rpm、測定時間0.5分))
POLYOX WSR N−10
(ダウ・ケミカル社製、5W/V%水溶液の粘度:35mPa・s(ロー
ターNo.1、回転数50rpm、測定時間0.5分))
POLYOX WSR N−750
(ダウ・ケミカル社製、5W/V%水溶液の粘度:1,100mPa・s
(ローターNo.2、回転数10rpm、測定時間1分))
POLYOX WSR N−12K
(ダウ・ケミカル社製、2W/V%水溶液の粘度:420mPa・s(ロ
ーターNo.1、回転数10rpm、測定時間1分))
ポリエチレングリコール#400
(三洋化成工業社製、医薬部外品原料規格2006記載の平均分子量380
〜420)
The details of the raw materials used are shown below. The viscosity of the highly polymerized polyethylene glycol is the viscosity at 25 ° C. measured by a Brookfield viscometer (Brookfield RVT or RVF) as in the above. Moreover, the viscosity of polyethylene glycol # 400 measured by the same method was less than the viscosity of (B) highly polymerized polyethylene glycol.
(A) Copper gluconate; manufactured by Kanto Chemical Co., Inc., copper gluconate (A) zinc citrate; manufactured by Kanto Chemical Co., Ltd., zinc citrate (B) highly polymerized polyethylene glycol;
POLYOX WSR N-80
(Viscosity of 5 W / V% aqueous solution manufactured by Dow Chemical Co .: 85 mPa · s (rotor No. 1, rotation speed 50 rpm, measurement time 0.5 minutes))
POLYOX WSR N-10
(Viscosity of 5 W / V% aqueous solution manufactured by Dow Chemical Co., Ltd .: 35 mPa · s (rotor No. 1, rotation speed 50 rpm, measurement time 0.5 minutes))
POLYOX WSR N-750
(Manufactured by Dow Chemical Company, viscosity of 5 W / V% aqueous solution: 1,100 mPa · s
(Rotor No. 2, rotation speed 10 rpm, measuring time 1 minute)
POLYOX WSR N-12K
(Viscosity of 2 W / V% aqueous solution manufactured by Dow Chemical Co., Ltd .: 420 mPa · s (rotor No. 1, rotation speed 10 rpm, measurement time 1 minute))
Polyethylene glycol # 400
(Sanyo Chemical Co., Ltd., quasi-drug raw material standard 2006 average molecular weight 380
~ 420)

Figure 0006693504
*;実施例5は参考例。
Figure 0006693504
*; Example 5 is a reference example.

Figure 0006693504
Figure 0006693504

Figure 0006693504
Figure 0006693504

次に、表4に示す組成の歯磨剤組成物(練歯磨)を上記と同様の原料を用いて常法によって調製し、同様の方法で評価した。また、口臭抑制効果の持続性(口臭抑制持続効果)、金属味抑制効果を下記方法で評価した。結果を表4に併記した。   Next, a dentifrice composition (toothpaste) having the composition shown in Table 4 was prepared by the usual method using the same raw materials as above, and evaluated by the same method. In addition, the persistence of the bad breath suppressing effect (bad breath suppressing effect) and the metallic taste suppressing effect were evaluated by the following methods. The results are also shown in Table 4.

(4)口臭抑制持続効果の評価方法
前記口臭抑制効果の評価方法に準じ、試験後として歯磨きして4時間経過後の口臭を採取して口臭強度を判定し、更に、同様にして口臭改善度を求め、口臭抑制効果を評価した。
(4) Method for evaluating the effect of suppressing bad breath The method for evaluating the effect of suppressing bad breath is based on the method for evaluating the effect of suppressing bad breath, and after the test, the bad breath after 4 hours has been collected and the bad breath intensity is determined, and the degree of improvement of bad breath is similarly determined. Then, the effect of suppressing bad breath was evaluated.

(5)金属味抑制効果の評価方法
被験者10名を用い、歯磨剤組成物約1gを歯ブラシにとり、3分間歯磨きを行った際の金属味について、金属味を全く感じないを4点、やや金属味を感じるを3点、金属味を感じるを2点、金属味を非常に感じるを1点として、判定した。
10名の平均点から以下の基準で、金属味の抑制効果を評価した。
金属味の抑制効果の評価基準:
◎:平均点が3.5点以上4.0点未満
○:平均点が3.0点以上3.5点未満
△:平均点が2.0点以上3.0点未満
×:平均点が1.0点以上2.0点未満
(5) Evaluation Method of Metallic Taste Suppressing Effect Using 10 test subjects, about 1 g of the dentifrice composition was placed on a toothbrush, and when the toothpaste was brushed for 3 minutes, the metallic taste was not felt at all 4 points, which was slightly metallic. The taste was judged as 3 points, the feeling of metallic taste was 2 points, and the feeling of very metallic taste was 1 point.
The effect of suppressing the metallic taste was evaluated based on the following criteria from the average of 10 persons.
Evaluation criteria for the effect of suppressing metallic taste:
⊚: Average score of 3.5 to less than 4.0 ○: Average score of 3.0 to less than 3.5 Δ: Average score of 2.0 to less than 3.0 x: Average score 1.0 points or more and less than 2.0 points

Figure 0006693504
*1:商品名「キミロイドBF」、(株)キミカ製、
1%水溶液(20℃)の粘度:20mPa・s(BL型粘度計、ロー
ターNo.1、回転数60rpm)
Figure 0006693504
* 1: Product name "Kimiloid BF", manufactured by Kimika Co., Ltd.
Viscosity of 1% aqueous solution (20 ° C): 20 mPa · s (BL type viscometer, rotor No. 1, rotation speed 60 rpm)

[処方例]
以下、処方例を表5に示す。処方例の歯磨剤組成物を上記と同様に調製し、同様に評価したところ、口臭抑制効果、歯磨剤のきめ、液分離のなさがいずれも◎であった。
[Prescription example]
Hereinafter, a prescription example is shown in Table 5. When the dentifrice composition of the formulation example was prepared in the same manner as above and evaluated in the same manner, the bad breath suppressing effect, the texture of the dentifrice, and the lack of liquid separation were all ⊚.

Figure 0006693504
Figure 0006693504

Claims (7)

(A)銅塩及び亜鉛塩から選ばれる1種又は2種以上の水溶性金属塩を0.01〜1質量%と、
(B)ブルックフィールド型粘度計で測定した25℃における5W/V%水溶液の粘度が30〜2,000mPa・sある高重合ポリエチレングリコールを0.01〜0.5質量%と
を含有し、(A)成分と(B)成分との配合量の割合を示す(A)/(B)が、質量比として0.1〜10であることを特徴とする歯磨剤組成物。
(A) 0.01 to 1 mass% of one or more water-soluble metal salts selected from copper salts and zinc salts,
(B) 0.01 to 0.5 mass% of highly polymerized polyethylene glycol having a viscosity of a 5 W / V% aqueous solution of 30 to 2,000 mPa · s at 25 ° C. measured with a Brookfield viscometer , (a) component and (B) shows the percentage of the amount of component (a) / (B) is, dentifrice composition comprising 0.1 to 10 der Rukoto as a mass ratio.
(A)成分の水溶性金属塩が、グルコン酸銅、クエン酸銅、硫酸銅、塩化銅、グルコン酸亜鉛、硫酸亜鉛及びクエン酸亜鉛から選ばれる1種又は2種以上である請求項1記載の歯磨剤組成物。   The water-soluble metal salt of component (A) is one or more selected from copper gluconate, copper citrate, copper sulfate, copper chloride, zinc gluconate, zinc sulfate and zinc citrate. Dentifrice composition. (A)成分の水溶性金属塩が、グルコン酸銅及び/又はクエン酸亜鉛である請求項記載の歯磨剤組成物。 The dentifrice composition according to claim 2 , wherein the water-soluble metal salt of the component (A) is copper gluconate and / or zinc citrate. (B)成分の高重合ポリエチレングリコールが、ブルックフィールド型粘度計で測定した25℃における5W/V%水溶液の粘度が55250mPa・sものである請求項1、2又は3記載の歯磨剤組成物。 (B) highly polymerized polyethylene glycol ingredients, toothpaste according to claim 1, wherein the viscosity of 5W / V% aqueous solution at 25 ° C. as measured by Brookfield viscometer is of 55 ~ 250 mPa · s Agent composition. (A)成分と(B)成分との配合量の割合を示す(A)/(B)が、質量比として0.5である請求項1〜4のいずれか1項記載の歯磨剤組成物。 (A) component and (B) shows the percentage of the amount of component (A) / (B) is, dentifrice according to any one of claims 1 to 4 is 0.5 to 2 as a mass ratio Composition. 更に、(C)アルギン酸プロピレングリコールエステルを0.01〜3質量%含有する請求項1〜5のいずれか1項記載の歯磨剤組成物。Further, the dentifrice composition according to any one of claims 1 to 5, further comprising 0.01 to 3% by mass of (C) propylene glycol alginate. 練歯磨剤である請求項1〜のいずれか1項記載の歯磨剤組成物。 Dentifrice composition according to any one of claims 1 to 6 is a toothpaste.
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