JP3820402B2 - Oral composition and gum - Google Patents

Oral composition and gum Download PDF

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JP3820402B2
JP3820402B2 JP2003371917A JP2003371917A JP3820402B2 JP 3820402 B2 JP3820402 B2 JP 3820402B2 JP 2003371917 A JP2003371917 A JP 2003371917A JP 2003371917 A JP2003371917 A JP 2003371917A JP 3820402 B2 JP3820402 B2 JP 3820402B2
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teeth
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potassium
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和彦 加藤
光義 柏木
義徳 村上
愛行 室井
学 外村
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Kao Corp
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本発明は、歯に適用するときに、歯のエナメル質層内に光散乱層が形成され、内因性による歯着色層を遮蔽することができる口腔用組成物及びガム(口腔用組成物及びガムを以下において「歯美白用組成物」という)に関する。   When the present invention is applied to a tooth, a light scattering layer is formed in the enamel layer of the tooth, and an oral composition and gum capable of shielding the intrinsic tooth coloring layer (oral composition and gum). Is hereinafter referred to as a “tooth whitening composition”).

歯の着色は、歯石や歯垢、喫煙、又はコーヒー若しくはお茶等の習慣的飲食等により歯面に着色物が付着する外因性着色と、加齢等によって象牙質が着色してくるため透明度の高いエナメル質を通してその色が見える場合や、エナメル質形成期にテトラサイクリン等の薬剤の使用によりエナメル質自体が着色した場合等の内因性着色に依存する。そこで、歯を根本的に白くするためには、外因性着色のみならず内因性着色にも対応する必要がある。   Tooth coloring is exogenous coloring where coloring matter adheres to the tooth surface due to tartar, plaque, smoking, or customary eating and drinking such as coffee or tea, etc., and dentin is colored due to aging etc. It depends on intrinsic coloring such as when the color is visible through high enamel, or when the enamel itself is colored by the use of a drug such as tetracycline during the enamel formation stage. Therefore, in order to fundamentally whiten the teeth, it is necessary to deal with not only exogenous coloring but also intrinsic coloring.

従来、歯を白くするための手段としては、種々の物理的又は化学的方法が報告されている。物理的方法としては研磨除去による他に、n−ブチルエーテルやブチルブチレート等を用いて着色物を除去する方法(特許文献1、特許文献2)、或いは、セラミックベニヤ等を用い歯を被覆して色調を改善する方法がある。化学的方法としては、ヒドロキシアパタイトを配合した口腔用組成物により再石灰化を促進する方法(特許文献3、特許文献4)、過酸化物を用いて酸化漂白する方法(特許文献5)、過酸化物に自己硬化性リン酸カルシウム化合物及びフッ素化合物等を配合した歯美白組成物を用いる方法(特許文献6)、液状化リン酸カルシウム系化合物を含有する口腔用組成物によりエナメル質の再石灰化を促進する方法(特許文献7)等が知られている。   Conventionally, various physical or chemical methods have been reported as means for whitening teeth. As a physical method, in addition to removal by polishing, a method of removing a colored substance using n-butyl ether or butyl butyrate (Patent Document 1, Patent Document 2), or covering a tooth using a ceramic veneer or the like. There are ways to improve color tone. As chemical methods, a method for promoting remineralization with an oral composition containing hydroxyapatite (Patent Document 3, Patent Document 4), an oxidative bleaching method using a peroxide (Patent Document 5), A method of using a tooth whitening composition in which a self-curing calcium phosphate compound and a fluorine compound are mixed with an oxide (Patent Document 6), and an oral composition containing a liquefied calcium phosphate compound promotes remineralization of enamel. A method (Patent Document 7) and the like are known.

しかしセラミックベニヤ等を用いる方法は、歯質を削除する必要があり、この方法の使用には歯科医による指導や処置が必要である。そして専門家による施術は高価なものにならざるを得ない。過酸化物を用いて酸化漂白する方法は、歯の酸化漂白が可能な濃度の過酸化物を用いる必要があるため、専門家の指導に従って慎重に行なう必要がある。   However, the method using ceramic veneer or the like needs to delete the tooth quality, and the use and treatment of a dentist is necessary for the use of this method. And the treatment by specialists must be expensive. The method of oxidative bleaching using a peroxide requires the use of a peroxide at a concentration that enables oxidative bleaching of teeth, and therefore must be performed carefully in accordance with expert guidance.

ヒドロキシアパタイト等のリン酸カルシウム系化合物を用いて歯の再石灰化を促進する方法は、主に、エナメル質表面をアパタイトにより補修することにより歯を健常化するものであるが、美白効果は充分とはいえない。   The method of promoting tooth remineralization using calcium phosphate compounds such as hydroxyapatite is mainly to make the teeth healthy by repairing the enamel surface with apatite, but the whitening effect is sufficient I can't say that.

また最近では、特許文献8に、(A)フッ素イオン供給成分0.02〜0.7質量%(フッ素原子換算)、(B)pKa(25℃)が2.5〜6.0である酸性化合物及びその塩0.1〜5mol/kg及び(C)水5〜90質量%を含有し、組成物そのもの又は当該組成物の30質量%水溶液のpHが3〜5.5である口腔用組成物を用いて歯の表面に白さとつやを与える方法が記載されている。   Recently, Patent Document 8 discloses that (A) a fluorine ion supply component of 0.02 to 0.7 mass% (in terms of fluorine atom) and (B) an acid having a pKa (25 ° C.) of 2.5 to 6.0. A composition for oral cavity containing 0.1 to 5 mol / kg of a compound and a salt thereof and (C) 5 to 90% by mass of water, and the composition itself or a 30% by mass aqueous solution of the composition having a pH of 3 to 5.5. It describes a method for giving whiteness and gloss to the tooth surface using an object.

上記特許文献8に記載された口腔用組成物は、フッ化カルシウム層を歯表面に形成して、歯の表面に白さとつやを与えるものである。   The composition for oral cavity described in the said patent document 8 forms a calcium fluoride layer in a tooth surface, and gives white and gloss to the tooth surface.

特開平1−203316号公報JP-A-1-203316 特開平1−104004号公報JP-A-1-104004 特開平1−305020号公報JP-A-1-305020 特開平9−202718号公報JP-A-9-202718 特公平6−8248号公報Japanese Patent Publication No. 6-8248 特開平11−116421号公報JP-A-11-116421 特開平8−319224号公報JP-A-8-319224 特開平2002−37721号公報JP-A-2002-37721

本発明の目的は、従来知られている方法とは全く異なる原理に基づいて歯に優れた美白効果を与える組成物を提供することを目的とする。   An object of the present invention is to provide a composition that gives an excellent whitening effect to teeth based on a completely different principle from a conventionally known method.

歯のエナメル質層の深部に内因性着色物質が沈積すると、エナメル質層自身が通常透明であるため、その色が外部に透き通って歯が黄色く見える。ここで、歯のエナメル質層の内部に光散乱層が形成されると、この光散乱層は遮蔽層として機能し、これらの内因性着色物質を除く必要もなく、かつ、歯が白く見えるようになる。そのためには、この遮蔽層が単にエナメル質層の深部に沈積された内因性着色物質が外部から見えないようにするだけでは足りず、遮蔽層自身が白く見えるものでなければならない。   When the endogenous coloring substance is deposited deep in the enamel layer of the tooth, the enamel layer itself is usually transparent, so that the color is transparent to the outside and the tooth looks yellow. Here, when a light scattering layer is formed inside the tooth enamel layer, this light scattering layer functions as a shielding layer, it is not necessary to remove these intrinsic coloring substances, and the teeth appear white. become. For this purpose, it is not necessary for the shielding layer to simply prevent the endogenous coloring substance deposited in the deep part of the enamel layer from being visible from the outside, and the shielding layer itself must appear white.

本発明は上記のような発想を実現したものであり、次の成分(A)、(B)、(C)及び(D)を含有する練り歯磨き組成物であって、
(A)フッ素イオン供給成分 0.02〜0.2質量%(フッ素原子換算)、
(B)リンゴ酸及び/又は酒石酸及びその塩 0.03〜0.3mol/kg、
(C)カリウムイオン 0.03〜0.5mol/kg、
(D)水、
前記練り歯磨き組成物を水で30質量%に稀釈したときのpHが3〜5.5であり、カルシウムイオンを含有しない練り歯磨き組成物であって、前記練り歯磨き組成物が歯に適用されるときに、歯のエナメル質層内において内因性着色物質を遮蔽する光散乱層が形成される歯美白用組成物、更に、当該歯美白用組成物を用いた歯を美白する方法を提供する。
The present invention realizes the above idea, and is a toothpaste composition containing the following components (A), (B), (C) and (D),
(A) Fluorine ion supply component 0.02-0.2 mass% (fluorine atom conversion),
(B) Malic acid and / or tartaric acid and its salt 0.03-0.3 mol / kg,
(C) potassium ion 0.03-0.5 mol / kg,
(D) water,
When the toothpaste composition is diluted to 30% by mass with water, the pH is 3 to 5.5 and does not contain calcium ions, and the toothpaste composition is applied to teeth. Sometimes, a tooth whitening composition in which a light scattering layer that shields endogenous coloring substances in the enamel layer of a tooth is formed, and a method for whitening teeth using the tooth whitening composition are provided.

つまり、本発明に係る口腔用組成物を歯に適用するか又はチューインガムを噛むと、歯のエナメル質層を構成するエナメル小柱間のわずかな隙間(以下において「小柱間隙」という)に存在するリン酸カルシウムが、フッ素を含有する微粒子(以下において「フッ素含有微粒子」という)に変化し、外部からの光に対して乱反射を生じる光散乱層を形成する。その結果、いままで透き通って見えていたエナメル質層の内部に沈積された内因性着色物質が、白く見えて不透明な光散乱層によって遮蔽され、歯を白く見せることを可能にした。   That is, when the composition for oral cavity according to the present invention is applied to a tooth or chewing gum is chewed, it exists in a slight gap between enamel trabeculae constituting the enamel layer of the tooth (hereinafter referred to as “trabecular gap”). The calcium phosphate that is converted into fine particles containing fluorine (hereinafter referred to as “fluorine-containing fine particles”) forms a light scattering layer that causes irregular reflection with respect to light from the outside. As a result, endogenous coloring matter deposited inside the enamel layer, which had been seen through until now, appeared white and was shielded by an opaque light scattering layer, making it possible to make teeth appear white.

本発明の歯美白用組成物を口腔内に適用することによって、歯の内因性着色に対して高い美白効果が認められることから、日常の口腔の手入れ又はチューインガムの愛用を通じて、手軽に歯の美白を実行することが可能となり、極めて有用である。   By applying the composition for tooth whitening of the present invention to the oral cavity, a high whitening effect on the intrinsic coloring of the teeth is recognized. Therefore, it is easy to whiten the teeth through daily oral care or regular use of chewing gum. Is extremely useful.

特に、本発明の歯美白用組成物にカリウムイオンを添加することにより、さらには、リンゴ酸及び/又は酒石酸とその塩からなる緩衝液系を用いることにより、組成物自身の酸味が弱く、酸味以外の味覚要素も穏和なため、使用感がよくなる。また、必要に応じて甘味成分や香料等を添加することで味や香りの調節も可能である。従って、使用者にとってより使用感のよい口腔用組成物を提供することができる。   In particular, by adding potassium ions to the tooth whitening composition of the present invention, and further using a buffer system consisting of malic acid and / or tartaric acid and its salt, the composition itself has a weak acidity, sourness. Other taste elements are also mild, so the feeling of use is improved. Moreover, the taste and fragrance can be adjusted by adding a sweetening ingredient, a fragrance or the like as required. Therefore, it is possible to provide a composition for oral cavity that has a better feeling for the user.

有機酸又は無機酸は、本発明の歯美白用組成物を口に含んだ時に、口腔内を酸性pH環境に維持するために用いる。歯美白用組成物に用いる有機酸又は無機酸としては、口腔内で使用可能な物質であれば特に限定されない。   The organic acid or inorganic acid is used to maintain the oral cavity in an acidic pH environment when the tooth whitening composition of the present invention is included in the mouth. The organic acid or inorganic acid used for the tooth whitening composition is not particularly limited as long as it can be used in the oral cavity.

無機酸としては、例えば、塩酸、硫酸、炭酸、リン酸等が挙げられる。有機酸としては、例えば、ギ酸、酢酸、プロピオン酸等の一塩基酸;シュウ酸、コハク酸、フマル酸、アジピン酸、マレイン酸等の二塩基酸;乳酸、グリコール酸、酒石酸、リンゴ酸、クエン酸、アスコルビン酸、グルコン酸、グリセリン酸等のヒドロキシカルボン酸;グルタミン酸、アスパラギン酸等の酸性アミノ酸;ピルビン酸、アセト酢酸、レブリン酸等のケト酸;安息香酸、サリチル酸等の芳香族カルボン酸;エチレンジアミンテトラ酢酸等のポリカルボン酸類等が挙げられる。   Examples of the inorganic acid include hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid and the like. Examples of organic acids include monobasic acids such as formic acid, acetic acid and propionic acid; dibasic acids such as oxalic acid, succinic acid, fumaric acid, adipic acid and maleic acid; lactic acid, glycolic acid, tartaric acid, malic acid, citric acid Hydroxycarboxylic acids such as acids, ascorbic acid, gluconic acid and glyceric acid; acidic amino acids such as glutamic acid and aspartic acid; keto acids such as pyruvic acid, acetoacetic acid and levulinic acid; aromatic carboxylic acids such as benzoic acid and salicylic acid; ethylenediamine And polycarboxylic acids such as tetraacetic acid.

有機酸又は無機酸は、二種以上を組み合わせて用いても良い。さらに、口腔内のpHをより安定に保つために、有機酸及び/又は無機酸と共に、それらの塩を組み合わせて緩衝系を調製してもよい。   Two or more organic acids or inorganic acids may be used in combination. Further, in order to keep the pH in the oral cavity more stable, a buffer system may be prepared by combining salts thereof with an organic acid and / or an inorganic acid.

有機酸及び無機酸の中でも、酢酸、乳酸、リンゴ酸、酒石酸、クエン酸、グリコール酸、コハク酸、リン酸から選ばれる1種又は2種以上を用いることが効果発現の点から好ましく、更に口腔用組成物の味・風味の改善、原料の入手しやすさ、コストの低減の点から乳酸、リンゴ酸、酒石酸がより好ましい。   Among organic acids and inorganic acids, it is preferable to use one or more selected from acetic acid, lactic acid, malic acid, tartaric acid, citric acid, glycolic acid, succinic acid and phosphoric acid from the viewpoint of effect, and further to the oral cavity. Lactic acid, malic acid, and tartaric acid are more preferable from the viewpoints of improving the taste and flavor of the composition, ease of availability of raw materials, and cost reduction.

白く且つ遮蔽性が高い光散乱層を形成するためには、フッ素含有微粒子が歯のエナメル質層の適度な深さまで形成されることが好ましい。かかる観点から、歯美白用組成物に含有される有機酸及び/又は無機酸としては、歯美白用組成物を適用した口腔内においてpHを3〜6に保つ緩衝系を形成できるものを用いることが好ましく、特に、pH4〜5が好ましい。   In order to form a light scattering layer that is white and has a high shielding property, it is preferable that the fluorine-containing fine particles are formed to an appropriate depth of the tooth enamel layer. From this point of view, as the organic acid and / or inorganic acid contained in the tooth whitening composition, one that can form a buffer system that maintains a pH of 3 to 6 in the oral cavity to which the tooth whitening composition is applied is used. In particular, pH 4-5 is preferred.

フッ素イオン供給成分としては、口腔内で使用可能な物質であれば特に限定されず、例えばフッ化ナトリウム、フッ化カリウム、フッ化アンモニウム、フッ化リチウム、モノフルオロホスフェイト(例えばモノフルオロリン酸ナトリウム、モノフルオロリン酸カリウム、モノフルオロリン酸アンモニウム等)等の無機性フッ化物、アミンフッ化物等の有機性フッ化物が挙げられ、中でも安全性、溶解性及び風味等の点からフッ化ナトリウム、モノフルオロリン酸ナトリウム、フッ化スズ、フッ化リチウム、フッ化アンモニウムが好ましい。このうち、モノフルオロホスフェイトは、フッ素イオンではなく先ずモノフルオロホスフェイトイオンを供給し、口腔中で徐々にフッ素イオンを供給する。   The fluorine ion supply component is not particularly limited as long as it can be used in the oral cavity. For example, sodium fluoride, potassium fluoride, ammonium fluoride, lithium fluoride, monofluorophosphate (for example, sodium monofluorophosphate) Inorganic fluorides such as potassium monofluorophosphate and ammonium monofluorophosphate) and organic fluorides such as amine fluorides. Among them, sodium fluoride, mono Sodium fluorophosphate, tin fluoride, lithium fluoride, and ammonium fluoride are preferred. Of these, monofluorophosphate supplies monofluorophosphate ions first, not fluorine ions, and gradually supplies fluorine ions in the oral cavity.

本発明の歯美白用組成物には、光散乱層を形成させることを可能にするため、一定量の有機酸及び/又は無機酸を配合する必要がある。しかし、これらの有機酸及び/又は無機酸が多量に存在すると、口腔用組成物を口に含んだ時又はチューインガムを噛んだ時に酸味が強く感じられるので、使用者によっては味覚的に抵抗を感じる場合が生じ得る。   In order to make it possible to form a light-scattering layer, it is necessary to mix | blend a fixed amount of organic acid and / or an inorganic acid with the composition for tooth whitening of this invention. However, when these organic acids and / or inorganic acids are present in a large amount, when the oral composition is included in the mouth or when chewing gum is chewed, the acidity is felt strongly, so that some users feel resistance taste. Cases can arise.

これに対し、本発明の歯美白用組成物中にカリウムイオンを添加すると、カリウムイオンは当該組成物に配合すべき酸(無機酸及び/又は有機酸)の効果を強めることができ、酸の量が少なくても光散乱層を形成することができる。また、組成物に配合する酸の含有量を低減することにより歯美白用組成物の味覚が良好となり、使用感が改善される。   On the other hand, when potassium ions are added to the composition for whitening the teeth of the present invention, the potassium ions can strengthen the effect of the acid (inorganic acid and / or organic acid) to be blended in the composition. Even if the amount is small, the light scattering layer can be formed. Further, by reducing the content of the acid blended in the composition, the taste of the tooth whitening composition is improved and the feeling of use is improved.

カリウムイオンの供給成分としては、口腔内で使用可能な物質であれば特に限定されず、様々なカリウム塩を用いることができる。例えば、水酸化カリウム、フッ化カリウム、塩化カリウム、臭化カリウム、リン酸カリウム、炭酸カリウム、リンゴ酸カリウム、クエン酸カリウム、酒石酸カリウム、メタリン酸カリウム、ピロリン酸カリウム、ソルビン酸カリウム、硝酸カリウム、アスパラギン酸カリウム、アルギン酸カリウム等が挙げられるが、風味や保存安定性の点から、水酸化カリウム、フッ化カリウム、塩化カリウム、リンゴ酸カリウム、クエン酸カリウム、リン酸カリウムが好ましい。   The supply component of potassium ions is not particularly limited as long as it can be used in the oral cavity, and various potassium salts can be used. For example, potassium hydroxide, potassium fluoride, potassium chloride, potassium bromide, potassium phosphate, potassium carbonate, potassium malate, potassium citrate, potassium tartrate, potassium metaphosphate, potassium pyrophosphate, potassium sorbate, potassium nitrate, asparagine Potassium acid, potassium alginate and the like can be mentioned, and potassium hydroxide, potassium fluoride, potassium chloride, potassium malate, potassium citrate and potassium phosphate are preferred from the viewpoint of flavor and storage stability.

また、カリウムイオンは、本発明における必須成分又は任意成分の対イオンとして歯美白用組成物に添加することが好ましい。例えば、フッ素イオン供給成分としてフッ化カリウムを用いたり、有機酸及び/又は無機酸と共にそれらのカリウム塩又は水酸化カリウムを用いて緩衝液系を調製することで、カリウムイオンを添加することができる。   Moreover, it is preferable to add a potassium ion to the composition for a tooth whitening as a counter ion of the essential component or arbitrary components in this invention. For example, potassium ions can be added by using potassium fluoride as a fluorine ion supply component, or preparing a buffer system using a potassium salt or potassium hydroxide together with an organic acid and / or an inorganic acid. .

カリウムイオンの含有量は、口腔用組成物中の酸濃度を充分に低くしながらも優れた歯の美白効果を得る点から、口腔用組成物中に0.1〜5質量%、0.5〜3質量%の割合で含有することが好ましい。   The potassium ion content is 0.1 to 5% by mass, 0.5% in the oral composition from the viewpoint of obtaining an excellent tooth whitening effect while sufficiently reducing the acid concentration in the oral composition. It is preferable to contain in the ratio of -3 mass%.

本発明の歯美白用組成物には、前記成分の他、例えば発泡剤、発泡助剤、研磨剤、湿潤剤、粘結剤、増量剤、甘味剤、保存料、殺菌剤、薬効成分、粘着剤、顔料、色素、香料等を適宜含有させることができる。また、従来用いられた美白成分であるポリエチレングリコールなどの併用も制限されない。   In addition to the above components, the composition for whitening teeth of the present invention includes, for example, foaming agents, foaming aids, abrasives, wetting agents, binders, bulking agents, sweeteners, preservatives, bactericides, medicinal ingredients, and adhesives. Agents, pigments, dyes, fragrances and the like can be appropriately contained. Moreover, combined use, such as polyethyleneglycol which is a whitening component used conventionally, is not restrict | limited.

本発明の歯美白用組成物は、例えば溶液状、ゲル状、ペースト状といった剤形に調製され、粉歯磨剤、潤性歯磨剤、練り歯磨剤、液状歯磨剤、洗口剤等の口腔用組成物、或いは、チューインガムとして用いることが出来る。それらどの剤形においてもポリエチレングリコール、プロピレングリコール、グリセリン、ソルビトール、マルチトール、キシリトール、ラクチトール、エリスリトール等を湿潤剤あるいは粘稠剤等の目的で含有させることができる。また、溶液状組成物の粘稠剤あるいはゲル状組成物のゲル化剤として更にはペースト状組成物とする場合の粘結剤としてカルボキシメチルセルロースナトリウム、ヒドロキシエチルセルロース、カルボキシビニルポリマー、キサンタンガム、カラギーナン、アルギン酸ナトリウム、ヒドロキシプロピルセルロース、グアガム、コンドロイチン硫酸ナトリウム等を含有させることができる。特に緩衝液系の為に高塩濃度となる場合は、非イオン性のポリマー即ちヒドロキシエチルセルロース、グアガム、ヒドロキシプロピルセルロース等を含有させることも出来る。   The tooth whitening composition of the present invention is prepared into a dosage form such as a solution, a gel, or a paste, and is used for oral cavity such as powder dentifrice, moisturizing dentifrice, toothpaste, liquid dentifrice, mouthwash, etc. It can be used as a composition or a chewing gum. In any of these dosage forms, polyethylene glycol, propylene glycol, glycerin, sorbitol, maltitol, xylitol, lactitol, erythritol and the like can be contained for the purpose of a wetting agent or a thickening agent. Further, as a thickening agent for a solution-like composition or as a gelling agent for a gel-like composition, as a binder for a paste-like composition, carboxymethylcellulose sodium, hydroxyethylcellulose, carboxyvinyl polymer, xanthan gum, carrageenan, alginic acid Sodium, hydroxypropyl cellulose, guar gum, sodium chondroitin sulfate and the like can be contained. In particular, in the case of a high salt concentration due to the buffer solution system, a nonionic polymer, that is, hydroxyethyl cellulose, guar gum, hydroxypropyl cellulose, or the like can be contained.

特に味覚が良好な歯美白用組成物としては、次の成分(A)と、(B)と、(C)と、(D)とを含有する組成物であって、該組成物を水で30質量%に稀釈したときのpHが3〜5.5である処方の口腔用組成物を例示することができる。
(A)フッ素イオン供給化合物 0.02〜0.2質量%(フッ素原子換算)、
(B)リンゴ酸及び/又は酒石酸及びその塩 0.03〜0.5mol/kg、
(C)カリウムイオン 0.03〜0.5mol/kg、
(D)水、
(E)必要に応じて、その他の任意成分
Particularly, the tooth whitening composition having a good taste is a composition containing the following components (A), (B), (C), and (D), and the composition is water: An example of the composition for the oral cavity having a pH of 3 to 5.5 when diluted to 30% by mass can be given.
(A) Fluorine ion supply compound 0.02 to 0.2% by mass (in terms of fluorine atom),
(B) Malic acid and / or tartaric acid and its salt 0.03-0.5 mol / kg,
(C) potassium ion 0.03-0.5 mol / kg,
(D) water,
(E) Other optional components as required

この処方は、味が良く且つ高い緩衝能を有するリンゴ酸及び/又は酒石酸とその塩を組み合わせること、及び、カリウムイオンを添加して酸の含有量を低減することによって、歯のエナメル質層内に光散乱層を形成する効果が高く、しかも酸味が抑えられ使用感に優れている。   This formulation is a combination of malic acid and / or tartaric acid and its salts with good taste and high buffer capacity, and the addition of potassium ions to reduce the acid content, thereby reducing the content of the enamel in the teeth. In addition, the effect of forming a light scattering layer is high, and the acidity is suppressed and the feeling of use is excellent.

リンゴ酸及び/又は酒石酸とその塩からなる緩衝液系と同等な範囲のpH環境は、他の酸性化合物を用いた緩衝液系でも得られるが、リンゴ酸及び/又は酒石酸とその塩からなる緩衝液系においては、酸濃度を低くした状態でも充分にフッ素含有微粒子を形成させることができ、しかも、酸味が抑えられているため味の点で特に優れている。   A pH environment in the same range as a buffer system composed of malic acid and / or tartaric acid and its salt can be obtained by a buffer system using other acidic compounds, but a buffer composed of malic acid and / or tartaric acid and its salt. In the liquid system, fluorine-containing fine particles can be sufficiently formed even in a state where the acid concentration is low, and the acidity is suppressed, so that the taste is particularly excellent.

すなわち、成分(B)であるリンゴ酸及び/又は酒石酸とその塩からなる緩衝液系は緩衝能が強いことから、口腔内においてフッ素含有微粒子を形成するpH環境を維持する能力が特に優れており、同濃度の他の緩衝液系と比べた場合には格段に歯の美白効果が高く、その使用量を少なくして酸濃度を低くした場合でも歯の優れた美白効果が得られる。   That is, since the buffer solution system consisting of malic acid and / or tartaric acid and its salt as component (B) has a strong buffering capacity, the ability to maintain a pH environment for forming fluorine-containing fine particles in the oral cavity is particularly excellent. When compared with other buffer systems of the same concentration, the tooth whitening effect is remarkably high, and even when the amount of use is reduced to reduce the acid concentration, an excellent whitening effect on the teeth can be obtained.

またリンゴ酸と酒石酸は、共に果物やワインなどの食品に含まれているものであり、酸味を抑えられるだけでなく、風味が良く、かつ、安全であることから、味の良い口腔用組成物を調製することが可能である。   In addition, malic acid and tartaric acid are both contained in foods such as fruits and wines, and not only can suppress acidity, but also have a good taste and safety, so that the composition for oral use has a good taste. Can be prepared.

リンゴ酸又は酒石酸の塩としては、ナトリウム塩、カリウム塩、アルギニン塩、アンモニウム塩等が挙げられるが、ナトリウム塩、カリウム塩のアルカリ金属塩等が好ましい。本発明組成物を調製するにあたり、リンゴ酸又は酒石酸の塩を直接添加してもよいが、リンゴ酸及び酒石酸のような有機酸、及び、水酸化ナトリウム、水酸化カリウム等のアルカリを別個に配合し、組成物中で酸性化合物とその塩の緩衝液系を形成させてもよい。   Examples of the salt of malic acid or tartaric acid include sodium salt, potassium salt, arginine salt, ammonium salt, and the like, and alkali metal salts of sodium salt and potassium salt are preferable. In preparing the composition of the present invention, malic acid or tartaric acid salt may be added directly, but organic acids such as malic acid and tartaric acid and alkalis such as sodium hydroxide and potassium hydroxide are separately added. Then, a buffer system of an acidic compound and its salt may be formed in the composition.

上記処方においては、特にカリウムイオンの供給源として成分(B)を利用することが好ましく、その場合には、リンゴ酸及び/又は酒石酸とそのカリウム塩を混合するか、或いは、リンゴ酸及び/又は酒石酸を水酸化カリウムで中和することによって緩衝液系を形成する。   In the above formulation, it is particularly preferable to use the component (B) as a source of potassium ions, in which case malic acid and / or tartaric acid and its potassium salt are mixed, or malic acid and / or A buffer system is formed by neutralizing tartaric acid with potassium hydroxide.

成分(B)におけるリンゴ酸及び/又は酒石酸及びその塩は、酸味を充分に抑えながらも高い美白効果を得る点から、本発明の口腔用組成物中にリンゴ酸及び/又は酒石酸及びその塩の総量として0.03〜0.5mol/kg、特に0.05〜0.3mol/kg含有するのが好ましい。また、充分な緩衝能をもたせるためには、酸と塩の比をモル比で10対1〜1対10とするのが好ましい。   Malic acid and / or tartaric acid and its salt in component (B) are malic acid and / or tartaric acid and their salts in the oral composition of the present invention from the viewpoint of obtaining a high whitening effect while sufficiently suppressing acidity. The total amount is preferably 0.03 to 0.5 mol / kg, more preferably 0.05 to 0.3 mol / kg. In order to provide sufficient buffering capacity, it is preferable that the ratio of acid to salt is 10 to 1 to 1 to 10 in terms of molar ratio.

成分(C)であるカリウムイオンは、成分(B)のリンゴ酸及び/又は酒石酸の酸濃度を充分に低くしながらも優れた歯の美白効果を得る点から、本発明の口腔用組成物中に0.03〜0.5mol/kg、特に0.05〜0.3mol/kg含有するのが好ましい。   In the composition for oral cavity of the present invention, the potassium ion as the component (C) has an excellent tooth whitening effect while sufficiently reducing the acid concentration of the malic acid and / or tartaric acid of the component (B). 0.03 to 0.5 mol / kg, particularly 0.05 to 0.3 mol / kg.

また、成分(D)である水の含有量は、本発明の組成物中に5〜90%であるのが好ましい。緩衝能を発揮するためには水溶液状態であることが本質的に必要である。また、エナメル質に対して直ちにフッ素イオンを供給するためにも水が必要である。   Moreover, it is preferable that content of the water which is a component (D) is 5-90% in the composition of this invention. In order to exhibit the buffering capacity, it is essentially necessary to be in an aqueous solution state. Also, water is necessary to supply fluorine ions immediately to the enamel.

更に上記処方の口腔用組成物は、当該組成物を水で30質量%に稀釈したときのpHが3〜5.5であることが、フッ素含有微粒子を効果的に形成させるという点で重要である。なお歯の強度を保つためにpH3以上とすることが好ましい。より好ましいpHはpH4〜5である。   Furthermore, the oral composition of the above formulation is important in that the pH when the composition is diluted to 30% by mass with water is 3 to 5.5 in order to effectively form fluorine-containing fine particles. is there. In order to maintain the strength of the teeth, the pH is preferably 3 or more. A more preferred pH is pH 4-5.

上記処方においては、任意成分(E)として陰イオン界面活性剤を含有させることが、歯の美白効果を更に高めるうえで好ましい。当該陰イオン界面活性剤としては、高級アルキル硫酸エステル塩、N−アルキルザルコシン塩、高級脂肪酸モノグリセリドモノ硫酸塩が好ましい。これらの界面活性剤のアルキル基又は脂肪酸残基の炭素数は8〜24、特に8〜18が好ましい。また、これら界面活性剤の塩としてはアルカリ金属塩、アンモニウム塩、有機アミン塩が好ましい。当該界面活性剤は、歯の美白効果の点から、本発明の組成物中に0.1〜5質量%、特に0.2〜2質量%含有させるのが好ましい。   In the said prescription, it is preferable to contain an anionic surfactant as an arbitrary component (E) in order to further enhance the whitening effect of the teeth. As the anionic surfactant, higher alkyl sulfate ester salts, N-alkyl sarcosine salts, and higher fatty acid monoglyceride monosulfate are preferable. The number of carbon atoms of the alkyl group or fatty acid residue of these surfactants is preferably 8 to 24, particularly 8 to 18. Further, as the salt of these surfactants, alkali metal salts, ammonium salts, and organic amine salts are preferable. The surfactant is preferably contained in the composition of the present invention in an amount of 0.1 to 5% by mass, particularly 0.2 to 2% by mass, from the viewpoint of tooth whitening effect.

本発明の歯美白用組成物は、その剤型に応じて、歯美白用組成物の一般的な製法に準じて製造することができる。例えば練歯磨剤の場合には、精製水、研磨剤、湿潤剤、粘結剤、香味剤、保存料、甘味剤、緩衝液成分及びフッ素イオン供給成分、更に必要に応じてその他の薬効成分等の各成分を処方量計測した後、一定の製造条件に従って混合、粘結剤を膨潤させ、更に研磨剤及び発泡剤を加えて脱泡混合することにより製造できる。必要に応じpHの調整は組成物調製後に行っても良い。   The composition for tooth whitening of this invention can be manufactured according to the general manufacturing method of the composition for tooth whitening according to the dosage form. For example, in the case of a toothpaste, purified water, abrasive, wetting agent, binder, flavoring agent, preservative, sweetener, buffer solution component and fluoride ion supply component, and other medicinal components as necessary After measuring the prescribed amount of each of the above components, they can be produced by mixing according to certain production conditions, swelling the binder, and further adding an abrasive and a foaming agent and defoaming and mixing. If necessary, the pH may be adjusted after preparing the composition.

本発明に係る口腔用組成物を歯に適用するか又はチューインガムを噛むことによって、歯美白用組成物又はその含有成分を歯に接触させると、前記歯美白用組成物の成分が口腔中の唾液等と混合することにより、一定のpHをより安定に保つことができる緩衝系が形成される。口腔中の前記混合された緩衝系のpHが酸性に保たれた状態で、歯のエナメル質層が酸の作用によって、エナメル質層を構成するエナメル小柱の間隙部分に存在するリン酸カルシウムに変化が生じる。   When the composition for oral whitening according to the present invention is applied to teeth or chewing gum is chewed to bring the composition for whitening of teeth or its component into contact with the teeth, the components of the composition for whitening of teeth become saliva in the oral cavity. Etc., a buffer system capable of keeping a constant pH more stable is formed. In the state where the pH of the mixed buffer system in the oral cavity is kept acidic, the tooth enamel layer changes due to the action of acid in the calcium phosphate existing in the gaps of the enamel trabeculae that make up the enamel layer. Arise.

この場合に、前記歯美白用組成物の成分によって歯の表面のみならず小柱間隙にもフッ素含有微粒子が形成される。   In this case, fluorine-containing fine particles are formed not only on the tooth surface but also in the space between the trabeculae by the components of the tooth whitening composition.

すなわち小柱間隙に存在するリン酸カルシウムが、フッ素含有微粒子に変化することで屈折率の低い部分構造を生じ、外部からの光に対して乱反射を生じる光散乱層を形成する。その結果、光散乱層によって反射された色が白く見えるため、歯がより白く見える。さらに、本来透明であったエナメル質層を透き通って外部から見えていた内因性による歯のエナメル質層の深部にある着色層は、前記の白く見えて不透明な光散乱層により遮断され、これらの着色が外部から見えなくなる。そして、エナメル層内での上記光散乱層の乱反射作用と遮蔽作用によって、歯が白く美しく見えるようになる。   That is, the calcium phosphate present in the space between the small columns is changed to fluorine-containing fine particles to form a partial structure having a low refractive index, thereby forming a light scattering layer that causes irregular reflection with respect to light from the outside. As a result, the teeth reflected appear white because the color reflected by the light scattering layer appears white. In addition, the colored layer in the deep part of the intrinsic tooth enamel layer that was visible from the outside through the enamel layer, which was originally transparent, was blocked by the above-mentioned white and opaque light scattering layer. Coloring disappears from the outside. Then, the teeth appear white and beautiful by the irregular reflection action and shielding action of the light scattering layer in the enamel layer.

通常、光散乱層は、歯のエナメル質層の表面から500μmの間に形成される。充分な白さと遮蔽性を得る点から、光散乱層の厚さは50μm以上であることが好ましい。   Usually, the light scattering layer is formed between 500 μm from the surface of the tooth enamel layer. From the viewpoint of obtaining sufficient whiteness and shielding properties, the thickness of the light scattering layer is preferably 50 μm or more.

フッ素含有微粒子は、一定範囲の酸性pHに保たれた口腔内において、フッ素イオン供給化合物のフッ素イオンが、歯の成分や唾液中の成分と反応して形成され、主にフッ化カルシウムから構成されるが、通常は、リン酸カルシウム・フッ化物複合体等の他の成分も含まれる。   Fluorine-containing fine particles are formed mainly by calcium fluoride in the oral cavity maintained at a certain range of acidic pH, by reacting the fluorine ions of the fluorine ion supply compound with the tooth components and saliva components. Usually, however, other components such as calcium phosphate / fluoride complex are also included.

前記歯美白用組成物中にカリウムイオンを配合すると、カリウムイオンは、ナトリウムイオンやリチウムイオンに比べイオン半径が大きいため、酸との結合が弱くなる。また、ヒドロキシアパタイトの2価カルシウムイオンと、1価のカリウムイオンが置換する場合、荷電の不釣り合いが生じるため、対イオンとしてリン酸ではなく炭酸イオンあるいはリン酸水素イオンが入り、ヒドロキシアパタイト結晶が壊れやすくなると一般的に考えられている。このことは、カリウムイオンを添加することにより、歯美白用組成物中の酸のヒドロキシアパタイトへの溶解力が高くなることを意味する。   When potassium ions are added to the tooth whitening composition, potassium ions have a larger ionic radius than sodium ions and lithium ions, so that the bond with the acid is weakened. In addition, when divalent calcium ions of hydroxyapatite and monovalent potassium ions are substituted, a charge imbalance occurs, so that carbonate ions or hydrogen phosphate ions enter instead of phosphoric acid as a counter ion, and hydroxyapatite crystals are formed. It is generally considered to be fragile. This means that the addition of potassium ions increases the dissolving power of the acid in the tooth whitening composition in hydroxyapatite.

つまり、カリウムイオンの存在により、酸のヒドロキシアパタイトへの溶解力が高くなり、歯美白用組成物中の無機酸及び/又は有機酸の量を減らしても、エナメル質の小柱間隙に存在するリン酸カルシウム分の反応性が増し、フッ素含有微粒子が前記隙間に形成される作用を維持することができる。その結果、カリウムイオンを添加することにより、光散乱層を形成する能力を低下させることなく、歯美白用組成物中の無機酸及び/又は有機酸の酸の含有量を低減することが可能となる。   In other words, the presence of potassium ions increases the solubility of the acid in hydroxyapatite, and even if the amount of inorganic acid and / or organic acid in the tooth whitening composition is reduced, it exists in the interlamellar space between enamels. The reactivity of the calcium phosphate content is increased, and the action of forming fluorine-containing fine particles in the gap can be maintained. As a result, by adding potassium ions, it is possible to reduce the content of inorganic acids and / or organic acids in the tooth whitening composition without reducing the ability to form a light scattering layer. Become.

実施例Aシリーズ
<口腔用組成物の調製>
表A1に示す組成に従って、実施例A1−1〜A1−3及び比較例A1−1〜A1−3の練り歯磨きを調製した。また、表A2に示す組成に従って実施例A2−1〜A2−3及び比較例A2−1〜A2−3の液状歯磨きを調製した。また、表A3に示す組成に従って、実施例A3−1〜A3−3及び比較例A3−1〜A3−3の洗口液を調製した。また、表A4に示す組成に従って、実施例A4−1〜A4−3及び比較例A4−1〜A4−3の口中清涼剤を調製した。また、表A5に示す組成に従って実施例A5−1〜A5−3及び比較例A5−1〜A5−3のチューインガムを調製した。
Example A Series <Preparation of Oral Composition>
According to the composition shown in Table A1, toothpastes of Examples A1-1 to A1-3 and Comparative Examples A1-1 to A1-3 were prepared. Moreover, according to the composition shown in Table A2, liquid toothpastes of Examples A2-1 to A2-3 and Comparative Examples A2-1 to A2-3 were prepared. Moreover, according to the composition shown in Table A3, mouthwashes of Examples A3-1 to A3-3 and Comparative Examples A3-1 to A3-3 were prepared. Moreover, according to the composition shown in Table A4, the mouth fresheners of Examples A4-1 to A4-3 and Comparative Examples A4-1 to A4-3 were prepared. Moreover, according to the composition shown in Table A5, chewing gums of Examples A5-1 to A5-3 and Comparative Examples A5-1 to A5-3 were prepared.

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

<評価方法>
(1)光散乱層の有無
表A1及び表A2に示す組成物をイオン交換水で30質量%に希釈し、この希釈液の中に牛の歯(表面は鏡面研磨)を40時間浸漬した。また、表A3及び表A4に示す組成物中に牛の歯(表面は鏡面研磨)を40時間浸漬した。さらに、表A5の場合は、チューインガムを細かくした後、濃度が30質量%になるようにイオン交換水を加え、十分撹拌した液の中に牛の歯(表面は鏡面研磨)を40時間浸漬した。
<Evaluation method>
(1) Presence / absence of light scattering layer The compositions shown in Tables A1 and A2 were diluted to 30% by mass with ion-exchanged water, and bovine teeth (the surface was mirror-polished) were immersed in this diluted solution for 40 hours. Moreover, cow's teeth (the surface was mirror-polished) were immersed in the compositions shown in Table A3 and Table A4 for 40 hours. Further, in the case of Table A5, after making the chewing gum fine, ion-exchanged water was added so that the concentration became 30% by mass, and the cow's teeth (the surface was mirror-polished) were immersed in the well-stirred solution for 40 hours. .

色差計で浸漬した牛の歯の白さの変化を測定し、CIE-1976 L***表色系(JIS Z8729-(1980))を用いて色差を示した。L***を用いた三次元座標系によって色の相互関係を色感覚に近いスケールによって表すことができる(図1)。図1において、縦軸L*で視感明度を示し、a*、b*により色度を示す。L***表色系において、b*の値が0に近いほど、黄色味が少なく、白さが増すことを意味する。 The change in whiteness of cattle teeth immersed in a color difference meter was measured, and the color difference was shown using the CIE-1976 L * a * b * color system (JIS Z8729- (1980)). The three-dimensional coordinate system using L * a * b * can represent the interrelationship of colors with a scale close to color sense (FIG. 1). In FIG. 1, the vertical axis L * indicates the luminous brightness, and a * and b * indicate the chromaticity. In the L * a * b * color system, the closer the b * value is to 0, the less yellowish the whiteness is.

表A6に示したように、本発明に係る口腔用組成物の処理によりb*は大きく低下し、値が0に近づいている。これは歯片の黄色みがなくなり白色になっていることを意味する。 As shown in Table A6, b * is greatly reduced by the treatment of the oral composition according to the present invention, and the value approaches 0. This means that the tooth pieces are no longer yellow and white.

Figure 0003820402
Figure 0003820402

各実施例の口腔用組成物で処理した歯を色差計で測定し白くなることを確認した(表A6)。白くなったと確認された牛の歯を割って、その割断面をマイクロスコープで写真撮影した。エナメル質の表層下に光散乱層が形成されているか否かを確認した(図2)。光散乱層が認められたもの(図2(a))を○、光散乱層が認められなかったもの(図2(b))を×とした。   The teeth treated with the oral composition of each Example were measured with a color difference meter and confirmed to be white (Table A6). The teeth of the cow that were confirmed to be white were broken, and the cut surface was photographed with a microscope. It was confirmed whether or not a light scattering layer was formed under the enamel surface (FIG. 2). A sample in which a light scattering layer was observed (FIG. 2A) was marked with ◯, and a sample in which a light scattering layer was not recognized (FIG. 2B) was marked with ×.

(2)美白効果の有無
表A1及び表A2に示す組成物をイオン交換水で30質量%に希釈し、この希釈液の中にあらかじめ写真撮影した牛の歯(表面は鏡面研磨)を40時間浸漬した。また、表A3及び表A4に示す組成物中にあらかじめ写真撮影した牛の歯(表面は鏡面研磨)を40時間浸漬した。さらに、表A5の場合は、チューインガムを細かくした後、濃度が30質量%になるようにイオン交換水を加え、十分撹拌した液の中にあらかじめ写真撮影した牛の歯(表面は鏡面研磨)を40時間浸漬した。
(2) Existence of whitening effect The composition shown in Tables A1 and A2 is diluted to 30% by mass with ion-exchanged water, and the bovine teeth (surface is mirror-polished) photographed beforehand in this diluted solution for 40 hours Soaked. Further, bovine teeth (the surface was mirror-polished) photographed in advance in the compositions shown in Tables A3 and A4 were immersed for 40 hours. Furthermore, in the case of Table A5, after making the chewing gum fine, ion-exchanged water was added so that the concentration was 30% by mass, and the bovine teeth photographed beforehand (the surface was mirror-polished) in the well-stirred solution Soaked for 40 hours.

牛の歯を引き上げた後に当該歯の写真撮影を行った。処理前後の歯を撮影した写真を15名のパネルに見てもらい、全員が白くなったと判断したものは◎、半数以上が白くなったと判断したものを○、それ以外は×と評価した。評価の結果は、それぞれ、表A1〜A5に示した。   After raising the cow's teeth, the teeth were photographed. A panel of 15 people who took photographs of the teeth before and after treatment was evaluated as ◎ if all were judged to be white, ◯ if more than half were judged white, and x otherwise. The results of evaluation are shown in Tables A1 to A5, respectively.

<総合結果>
実施例A1−1〜A1−3の練り歯磨きでは、歯のエナメル質層内部に光散乱層の形成が認められ、美白効果も認められたのに対して、比較例A1−1の練り歯磨きでは、有機酸は含むがフッ素イオン供給化合物を含まず、また、比較例A1−2の練り歯磨きでは、フッ素イオン供給化合物は含むが有機酸及び/又は無機酸を含まないため、さらに、比較例A1−3の練り歯磨きでは、有機酸の配合量が多いため、歯のエナメル質層内部に光散乱層の形成は認めらなかった。
<Overall results>
In the toothpaste of Examples A1-1 to A1-3, the formation of a light scattering layer was recognized inside the enamel layer of the tooth, and the whitening effect was also observed, whereas in the toothpaste of Comparative Example A1-1 In addition, the toothpaste of Comparative Example A1-2 contains a fluorine ion supply compound but does not contain an organic acid and / or an inorganic acid. In the toothpaste No. -3, since the amount of the organic acid was large, no light scattering layer was found inside the enamel layer of the tooth.

実施例A2−1〜A2−3の液状歯磨きでは、歯のエナメル質層内部に光散乱層の形成が認められ、美白効果も認められたのに対して、比較例A2−1の液状歯磨きでは、有機酸は含むがフッ素イオン供給化合物を含まず、また、比較例A2−2の液状歯磨きでは、フッ素イオン供給化合物は含むが有機酸及び/又は無機酸を含まないため、さらに、比較例A2−3の液状歯磨きでは、有機酸の配合量が多いため、歯のエナメル質層内部に光散乱層の形成は認められなかった。   In the liquid toothpaste of Examples A2-1 to A2-3, the formation of a light scattering layer was recognized inside the enamel layer of the tooth and the whitening effect was also observed, whereas in the liquid toothpaste of Comparative Example A2-1 In addition, the liquid toothpaste of Comparative Example A2-2 contains an organic acid but does not contain a fluorine ion supply compound. In addition, the liquid toothpaste of Comparative Example A2-2 contains a fluorine ion supply compound but does not contain an organic acid and / or an inorganic acid. In the liquid toothpaste No. -3, since the amount of the organic acid was large, the formation of a light scattering layer was not observed inside the tooth enamel layer.

実施例A3−1〜A3−3の洗口液では、歯のエナメル質層内部に光散乱層の形成が認められ、美白効果も認められたのに対して、比較例A3−1の洗口液では、有機酸は含むがフッ素イオン供給化合物を含まず、また、比較例A3−2の洗口液では、フッ素イオン供給化合物は含むが有機酸及び/又は無機酸を含まないため、さらに、比較例A3−3の洗口液では、有機酸の配合量が多いため、歯のエナメル質層内部に光散乱層の形成は認められなかった。   In the mouthwashes of Examples A3-1 to A3-3, the formation of a light scattering layer was recognized inside the tooth enamel layer, and the whitening effect was also observed, whereas the mouthwash of Comparative Example A3-1 In the liquid, the organic acid is included but the fluorine ion supply compound is not included. In the mouthwash of Comparative Example A3-2, the fluorine ion supply compound is included but the organic acid and / or the inorganic acid is not included. In the mouthwash of Comparative Example A3-3, since the amount of the organic acid was large, formation of a light scattering layer was not observed inside the enamel layer of the teeth.

実施例A4−1〜A4−3の口中清涼剤では、歯のエナメル質層内部に光散乱層の形成が認められ、美白効果も認められたのに対して、比較例A4−1の口中清涼剤では、有機酸は含むがフッ素イオン供給化合物を含まず、また、比較例A4−2の口中清涼剤では、フッ素イオン供給化合物は含むが有機酸及び/又は無機酸を含まないため、さらに、比較例A4−3の口中清涼剤では、有機酸の配合量が多いため、歯のエナメル質層内部に光散乱層の形成は認められなかった。   In the mouth fresheners of Examples A4-1 to A4-3, the formation of a light scattering layer was observed inside the enamel layer of the teeth and the whitening effect was also observed, whereas the mouth refresher of Comparative Example A4-1 The agent contains an organic acid but does not contain a fluorine ion supply compound, and the mouth freshener of Comparative Example A4-2 contains a fluorine ion supply compound but does not contain an organic acid and / or an inorganic acid. In the mouth freshener of Comparative Example A4-3, since the amount of the organic acid was large, the formation of a light scattering layer was not observed inside the enamel layer of the teeth.

実施例A5−1〜A5−3のチューインガムでは、歯のエナメル質層内部に光散乱層の形成が認められ、美白効果も認められたのに対して、比較例A5−1のチューインガムでは、有機酸は含むがフッ素イオン供給化合物を含まず、また、比較例A5−2のチューインガムでは、フッ素イオン供給化合物は含むが有機酸及び/又は無機酸を含まないため、さらに、比較例A5−3のチューインガムでは、有機酸の配合量が多いため、歯のエナメル質層内部に光散乱層の形成は認められなかった。   In the chewing gums of Examples A5-1 to A5-3, the formation of a light scattering layer was recognized inside the tooth enamel layer, and the whitening effect was also observed, whereas in the chewing gum of Comparative Example A5-1, The chewing gum of Comparative Example A5-2 contains an acid but does not contain a fluoride ion supply compound, and also contains a fluoride ion supply compound but does not contain an organic acid and / or an inorganic acid. In the chewing gum, since a large amount of organic acid was added, no light scattering layer was formed inside the enamel layer of the teeth.

実施例Bシリーズ
<口腔用組成物の調製>
表B1に示す組成に従って、実施例B1〜3及び比較例B1〜3の練り歯磨きを調製した。また、表B2に示す組成に従って、実施例B4〜6及び比較例B4〜6の液状歯磨きを調製した。さらに、表B3に示す組成に従って、実施例B7〜9及び比較例B7〜9の洗口液を調製した。
Example B Series <Preparation of Oral Composition>
According to the composition shown in Table B1, toothpastes of Examples B1 to B3 and Comparative Examples B1 to B3 were prepared. Moreover, according to the composition shown in Table B2, liquid toothpastes of Examples B4 to 6 and Comparative Examples B4 to 6 were prepared. Furthermore, according to the composition shown in Table B3, mouth washes of Examples B7 to 9 and Comparative Examples B7 to 9 were prepared.

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

<評価方法>
(1)味の評価
被験者10名(男性5名、女性5名)が、日常使用している歯ブラシに練り歯磨、あるいは液状歯磨きを1gとり、約2分間自由にブラッシングして以下の基準で評価した。また、洗口液については、洗口液5mlを口に含み約15秒間含嗽後、同様に以下の基準で評価した。
許容できる場合を○、許容できない場合を×とした。半数以上が○であったものを合格、それ以外は不合格とした。
<Evaluation method>
(1) Taste Evaluation Ten subjects (5 men and 5 women) took 1g of toothpaste or liquid toothpaste on a toothbrush used everyday, brushed freely for about 2 minutes, and evaluated according to the following criteria did. Further, the mouthwash was evaluated according to the following criteria in the same manner after containing 5 ml of mouthwash in the mouth and rinsing for about 15 seconds.
The case where it was acceptable was marked with ◯, and the case where it was not acceptable was marked with X. Those in which more than half were ○ were accepted and others were rejected.

(2)光散乱層の有無
表B1及び表B2に示す組成物をイオン交換水で30質量%に希釈し、この希釈液の中に牛の歯(表面は鏡面研磨)を40時間浸漬した。また、表B3に示す組成物中に牛の歯(表面は鏡面研磨)を40時間浸漬した。
その後、実施例Aシリーズの評価方法(1)と同じ手順で、光散乱層の有無を評価した。その結果を表B4に示す。本発明に係る口腔用組成物の処理によりb*の値は大幅に低下し、値が0に近づいたことから、歯片の黄色みがなくなり白色になっていることを確認できた。
(2) Presence / absence of light scattering layer The compositions shown in Tables B1 and B2 were diluted to 30% by mass with ion-exchanged water, and bovine teeth (the surface was mirror-polished) were immersed in this diluted solution for 40 hours. Moreover, cow's teeth (the surface was mirror-polished) were immersed in the composition shown in Table B3 for 40 hours.
Then, the presence or absence of the light scattering layer was evaluated by the same procedure as the evaluation method (1) of Example A series. The results are shown in Table B4. The b * value was significantly reduced by the treatment of the oral composition according to the present invention, and the value approached 0, so that it was confirmed that the tooth pieces were no longer yellow and white.

Figure 0003820402
Figure 0003820402

また、本発明の各実施例の口腔用組成物による処理で白くなったと確認された牛の歯の割断面を、実施例Aシリーズと同様の手順及び評価基準で確認し、光散乱層が認められたもの(図1(a))を○、光散乱層が認められなかったもの(図1(b))を×と評価した。   In addition, the cut section of the cow's teeth that were confirmed to be whitened by the treatment with the oral composition of each example of the present invention was confirmed by the same procedure and evaluation criteria as in Example A series, and a light scattering layer was recognized. What was obtained (FIG. 1A) was evaluated as ◯, and what the light scattering layer was not observed (FIG. 1B) was evaluated as ×.

(3)美白効果の有無
表B1及び表B2に示す組成物をイオン交換水で30質量%に希釈し、この希釈液の中にあらかじめ写真撮影した牛の歯(表面は鏡面研磨)を40時間浸漬した。また、表B3に示す組成物中にあらかじめ写真撮影した牛の歯(表面は鏡面研磨)を40時間浸漬した。
牛の歯を引き上げた後に当該歯の写真撮影を行い、以下の基準で評価した。処理前後の歯を撮影した写真を15名のパネルに見てもらい、白くなったか又は変わらなかったかを判断した。また、処理によりつやが無くなったと感じたものは、たとえ白くなっていたとしても変わらなかったと判断した。そして、全員が白くなったと判断したものは◎、半数以上が白くなったと判断したものを○、それ以外は×と評価した。評価の結果は、それぞれ、表B1〜B3に示した。
(3) Existence of whitening effect The composition shown in Tables B1 and B2 is diluted to 30% by mass with ion-exchanged water, and the bovine teeth (surface is mirror-polished) photographed beforehand in this diluted solution for 40 hours Soaked. In addition, bovine teeth (the surface was mirror-polished) photographed beforehand were immersed in the composition shown in Table B3 for 40 hours.
After raising the cow's teeth, the teeth were photographed and evaluated according to the following criteria. Fifteen people took pictures of the teeth before and after the treatment, and judged whether they were white or not changed. In addition, it was judged that what was felt to have lost the gloss was not changed even if it turned white. And it was evaluated as ◎ if all were judged to be white, ○ if judged more than half were white, and x otherwise. The results of evaluation are shown in Tables B1 to B3, respectively.

<総合結果>
実施例B1〜B3の練り歯磨きでは、カリウムイオンを配合することで、必要とする有機酸及び/又は無機酸の量が低くて足り、歯のエナメル質層内部に光散乱層が形成され、それによる美白効果に優れ、かつ、味が良好である。これに対して、比較例B1の練り歯磨きでは、使用される有機酸及び/又は無機酸の量が低いため、味は良いが、光散乱層を形成することができず、美白効果も認められなかった。また、比較例B2及び比較例B3は、使用される有機酸及び/又は無機酸の量が多いため、光散乱層を形成することができず、美白効果の点においてやや低く、味は悪いという結果であった。
<Overall results>
In the toothpaste of Examples B1 to B3, the amount of organic acid and / or inorganic acid required is sufficient by adding potassium ions, and a light scattering layer is formed inside the enamel layer of the tooth. The whitening effect is excellent and the taste is good. On the other hand, in the toothpaste of Comparative Example B1, since the amount of organic acid and / or inorganic acid used is low, the taste is good, but a light scattering layer cannot be formed, and a whitening effect is also observed. There wasn't. In addition, Comparative Example B2 and Comparative Example B3 have a large amount of organic acid and / or inorganic acid used, and therefore cannot form a light scattering layer, are slightly lower in terms of whitening effect, and have a bad taste. It was a result.

実施例B4〜B6の液状歯磨きでは、カリウムイオンを配合することで、必要とする有機酸及び/又は無機酸の量が低くて足り、光散乱層を形成することができ、美白効果に優れ、かつ、味が良い。これに対して、比較例B4の液状歯磨きでは、使用する有機酸及び/又は無機酸の量が低いので味が良い反面、光散乱層を形成することができず、美白効果も認められなかった。また、比較例B5及び比較例B6は、使用される有機酸及び/又は無機酸の量が多いため、味が悪く、さらに、光散乱層も形成されず、美白の点もやや低いという結果であった。   In the liquid toothpaste of Examples B4 to B6, by adding potassium ions, the amount of the required organic acid and / or inorganic acid is sufficient, a light scattering layer can be formed, and the whitening effect is excellent. And the taste is good. In contrast, in the liquid toothpaste of Comparative Example B4, the amount of organic acid and / or inorganic acid used was low, so the taste was good, but a light scattering layer could not be formed, and no whitening effect was observed. . Further, Comparative Example B5 and Comparative Example B6 have a bad taste due to the large amount of organic acid and / or inorganic acid used, and further, no light scattering layer is formed, and the whitening point is slightly low. there were.

実施例B7〜B9の洗口液では、カリウムイオンを配合することで、必要とされる有機酸及び/又は無機酸の量が低くて足り、さらに、光散乱層が形成されることによって、美白効果に優れ、かつ、味が良かった。これに対して、比較例B7の洗口液では、使用される有機酸及び/又は無機酸の量が低いので味が良い反面、光散乱層を形成することができず、美白効果は認められなかった。また、比較例B8及び比較例B9は使用する有機酸及び/又は無機酸の量が多いため、味が悪く、さらに、光散乱層の形成も認められず、美白効果の点においてもやや低いという結果であった。   In the mouthwashes of Examples B7 to B9, by adding potassium ions, the amount of organic acid and / or inorganic acid required is low, and further, a light scattering layer is formed, thereby whitening. Excellent effect and good taste. On the other hand, in the mouthwash of Comparative Example B7, the amount of organic acid and / or inorganic acid used is low, so the taste is good, but a light scattering layer cannot be formed, and a whitening effect is recognized. There wasn't. Further, Comparative Example B8 and Comparative Example B9 have a bad taste due to the large amount of organic acid and / or inorganic acid used, and further, the formation of a light scattering layer is not recognized, and the whitening effect is slightly low. It was a result.

実施例Cシリーズ
<口腔用組成物の調製>
表C1に示す組成に従って、実施例C1〜C3及び比較例C1の練り歯磨きを調製した。また、表C2に示す組成に従って、実施例C4〜C6及び比較例C2の液状歯磨きを調製した。さらに、表C3に示す組成に従って、実施例C7〜C9及び比較例C3の洗口液を調製した。
Example C Series <Preparation of Oral Composition>
According to the composition shown in Table C1, toothpastes of Examples C1 to C3 and Comparative Example C1 were prepared. Moreover, according to the composition shown in Table C2, liquid toothpastes of Examples C4 to C6 and Comparative Example C2 were prepared. Furthermore, according to the composition shown in Table C3, mouth washes of Examples C7 to C9 and Comparative Example C3 were prepared.

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

Figure 0003820402
Figure 0003820402

<評価方法>
(1) 味の評価
被験者15名が参加し、実施例Bシリーズの評価方法(1)と同じ手順及び評価基準で味を評価した。
<Evaluation method>
(1) Taste Evaluation Fifteen subjects participated and evaluated the taste by the same procedure and evaluation criteria as the evaluation method (1) of Example B series.

(2) 美白効果
各組成物をイオン交換水で30質量%に希釈し、この希釈液の中にあらかじめ写真撮影した牛の歯(表面は鏡面研磨)を40時間浸漬した。引き上げた後に写真撮影を行い、処理前の歯と色を比較し、実施例Bシリーズの評価方法(3)と同じ手順及び評価基準で美白効果を評価した。
(2) Whitening effect Each composition was diluted to 30% by mass with ion-exchanged water, and cow's teeth (the surface was mirror-polished) photographed beforehand were immersed in this diluted solution for 40 hours. After raising, the photograph was taken, the teeth before treatment were compared with the color, and the whitening effect was evaluated by the same procedure and evaluation criteria as the evaluation method (3) of Example B series.

<総合結果>
実施例C1〜C3の練り歯磨きでは、カリウムイオンを配合することで、必要とする有機酸の量が低くて足り、美白効果に優れ、かつ、味が良いのに対して、比較例C1の練り歯磨きでは、必要とする有機酸の量が多いため味が悪く、カルシウムイオンを含有するために、美白効果の点においても不十分であった。
<Overall results>
In the toothpaste of Examples C1 to C3, the amount of organic acid required is sufficient by blending potassium ions, the whitening effect is excellent, and the taste is good, whereas the paste of Comparative Example C1 is used. Toothbrushing has a bad taste due to the large amount of organic acid required, and it contains calcium ions, so it is insufficient in terms of whitening effect.

実施例C4〜C6の液状歯磨きでは、カリウムイオンを配合することで、必要とする有機酸の量が低くて足り、美白効果に優れ、かつ、味が良いのに対して、比較例C2の液状歯磨きでは、必要とする有機酸の量が多いため味が悪く、カルシウムイオンを含有するために、美白効果の点においても不十分であった。   In the liquid toothpastes of Examples C4 to C6, the amount of the organic acid required is sufficient by adding potassium ions, the whitening effect is excellent, and the taste is good, whereas the liquid of Comparative Example C2 is liquid. Toothbrushing has a bad taste due to the large amount of organic acid required, and it contains calcium ions, so it is insufficient in terms of whitening effect.

実施例C7〜C9の洗口液では、カリウムイオンを配合することで、必要とする有機酸の量が低くて足り、美白効果に優れ、かつ、味が良いのに対して、比較例C3の洗口液では、必要とする有機酸の量が多いため味が悪く、カルシウムイオンを含有するために、美白効果の点においても不十分であった。   In the mouthwashes of Examples C7 to C9, by adding potassium ions, the amount of organic acid required is sufficient, the whitening effect is excellent, and the taste is good. The mouthwash has a poor taste due to the large amount of organic acid required, and it contains calcium ions, so it is insufficient in terms of the whitening effect.

CIE-1976 L***表色系(JIS Z8729-(1980))を用いた三次元座標系によって色の相互関係を示す図である。It is a figure which shows the correlation of a color by the three-dimensional coordinate system using CIE-1976 L * a * b * color system (JISZ8729- (1980)). 牛の歯の割断面をマイクロスコープで観察した写真である。(a)は本発明の組成物によって処理された牛の歯の割断面である。(b)は処理されていない牛の歯の割断面である。It is the photograph which observed the cleavage surface of the cow's tooth with the microscope. (A) is a split section of cattle teeth treated with the composition of the present invention. (B) is a fractured section of an untreated cow tooth.

Claims (2)

次の成分(A)、(B)、(C)及び(D)を含有する練り歯磨き組成物であって、
(A)フッ素イオン供給成分 0.02〜0.2質量%(フッ素原子換算)、
(B)リンゴ酸及び/又は酒石酸及びその塩 0.03〜0.3mol/kg、
(C)カリウムイオン 0.03〜0.5mol/kg、
(D)水、
前記練り歯磨き組成物を水で30質量%に稀釈したときのpHが3〜5.5であり、カルシウムイオンを含有しない練り歯磨き組成物
A toothpaste composition containing the following components (A), (B), (C) and (D):
(A) Fluorine ion supply component 0.02-0.2 mass% (fluorine atom conversion),
(B) Malic acid and / or tartaric acid and its salt 0.03-0.3 mol / kg,
(C) potassium ion 0.03-0.5 mol / kg,
(D) water,
A toothpaste composition having a pH of 3 to 5.5 when the toothpaste composition is diluted to 30% by mass with water and containing no calcium ions .
次の成分(A)、(B)、(C)及び(D)を含有する練り歯磨き組成物であって、
(A)フッ素イオン供給成分 0.02〜0.2質量%(フッ素原子換算)、
(B)リンゴ酸及び/又は酒石酸及びその塩 0.03〜0.3mol/kg、
(C)カリウムイオン 0.03〜0.5mol/kg、
(D)水、
前記練り歯磨き組成物を水で30質量%に稀釈したときのpHが3〜5.5であり、カルシウムイオンを含有せず、前記練り歯磨き組成物が歯に適用されるときに、歯のエナメル質層において光散乱層が形成される練り歯磨き組成物
A toothpaste composition containing the following components (A), (B), (C) and (D):
(A) Fluorine ion supply component 0.02-0.2 mass% (fluorine atom conversion),
(B) Malic acid and / or tartaric acid and its salt 0.03-0.3 mol / kg,
(C) potassium ion 0.03-0.5 mol / kg,
(D) water,
When the toothpaste composition is diluted to 30% by weight with water and has a pH of 3 to 5.5, does not contain calcium ions, and the toothpaste composition is applied to teeth, tooth enamel A toothpaste composition in which a light scattering layer is formed in the quality layer .
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