JP2015017049A - Pretreatment material composition for dentistry - Google Patents
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本発明は、歯科用前処理材組成物に関する。より詳しくは、シリンジ型のエッチング材等に特に好適な歯科用前処理材組成物に関する。 The present invention relates to a dental pretreatment material composition. More specifically, the present invention relates to a dental pretreatment material composition particularly suitable for a syringe-type etching material or the like.
歯科治療の分野において、生体歯牙組織の修復には、歯牙組織と修復材料との接着が重要となる。現在、一般的な歯科用修復材料としては、コンポジットレジン等に代表される直接修復材料、または金属もしくはセラミックス等に代表される間接修復材料が用いられている。しかし、これらの修復材料自体には接着性がないため、これまでに、歯牙組織と修復材料とを接着するための種々の技術が提案されてきた。 In the field of dental treatment, adhesion between a tooth tissue and a restoration material is important for the restoration of living tooth tissue. At present, as a general dental restoration material, a direct restoration material typified by a composite resin or the like, or an indirect restoration material typified by a metal or ceramics is used. However, since these restoration materials themselves do not have adhesiveness, various techniques for adhering the tooth tissue and the restoration material have been proposed so far.
従来、歯牙組織に修復材料を接着させる際に、当該歯牙組織の修復面をリン酸、カルボン酸化合物等の水溶液（酸水溶液）によりエッチングして脱灰することによって、微細な凹凸を形成する方法が知られている。かかる方法を用いると、歯牙組織と修復材料との接着界面の面積を著しく増大させることができ、歯牙組織に修復材料を強固に接着することができる。また、動揺歯固定法や矯正治療においては、非切削歯面のエッチングによる塑造化のみならず、被着面に付着した唾液や歯垢等の汚れを除去するために酸水溶液が使用されている。しかし、エッチングや清掃に用いる酸水溶液の粘性が低いことに起因し、歯牙組織における治療部分のみに限定して酸水溶液を塗布することが困難であった。すなわち、酸水溶液を歯牙組織の修復面に塗布しても、治療部分の周辺にまで酸水溶液が広がってしまう。このため、健全な歯牙や歯髄または歯肉までも侵襲してしまい、場合によっては患者に対して不要な痛みを与えてしまうという問題がある。特に近年になって、エッチング材や清掃材等の前処理材は、シリンジ型が主流になってきており、細いニードルの先から治療部分へエッチング材を直接塗布する治療方法が一般的になりつつある。そのため、エッチング材を治療部分のみに留め置けることおよびシリンジからの吐出が容易であることの重要性は極めて高いと言える。 Conventionally, when a restoration material is bonded to a tooth tissue, a method for forming fine irregularities by etching and decalcifying the restoration surface of the tooth tissue with an aqueous solution (acid aqueous solution) such as phosphoric acid or a carboxylic acid compound. It has been known. By using this method, the area of the adhesion interface between the tooth tissue and the restoration material can be remarkably increased, and the restoration material can be firmly adhered to the tooth tissue. In addition, in the swing tooth fixing method and orthodontic treatment, an acid aqueous solution is used not only for plasticization by etching of the non-cutting tooth surface but also for removing dirt such as saliva and plaque adhering to the adherend surface. . However, due to the low viscosity of the acid aqueous solution used for etching and cleaning, it was difficult to apply the acid aqueous solution only to the treatment portion in the tooth tissue. That is, even if the acid aqueous solution is applied to the restoration surface of the tooth tissue, the acid aqueous solution spreads to the periphery of the treatment portion. For this reason, even a healthy tooth, pulp, or gingiva is invaded, and in some cases, there is a problem that unnecessary pain is given to the patient. Particularly in recent years, pretreatment materials such as etching materials and cleaning materials have become syringe-type, and a treatment method for directly applying an etching material from the tip of a thin needle to a treatment portion is becoming common. is there. Therefore, it can be said that the importance of being able to keep the etching material only in the treatment portion and being easy to discharge from the syringe is extremely high.
これに応じて、シリンジ型の形態で使用でき、治療部分の周囲に広がりにくい、すなわち難垂れ性を有する歯科用前処理材の開発が行われている。例えば、特許文献１および特許文献２には、酸水溶液に、シリカ、およびポリエチレングリコール等の水溶性高分子増粘剤を添加して粘性を高めた歯科用前処理材が報告されている。特許文献１および特許文献２には、これらの歯科用前処理材は、シリンジから吐出でき、良好な難垂れ性を有することが記載されている。 Accordingly, a dental pretreatment material that can be used in the form of a syringe and is difficult to spread around the treatment portion, that is, has a sag property, has been developed. For example, Patent Document 1 and Patent Document 2 report a dental pretreatment material in which viscosity is increased by adding a water-soluble polymer thickener such as silica and polyethylene glycol to an acid aqueous solution. Patent Document 1 and Patent Document 2 describe that these dental pretreatment materials can be discharged from a syringe and have good sagability.
しかしながら、特許文献１および２に記載された歯科用前処理材は、長時間放置するとシリカが沈降して均一性が低下し、前処理材中の粘度に分布が生じて諸特性に悪影響を及ぼすという欠点を有していた。また、歯科用前処理材は、一般に流水で洗浄除去されるものであり、塗布部の視認性を向上させるために、特許文献１に記載の歯科用前処理材には天然色素類やタール色素類等の着色剤を、特許文献２に記載の歯科用前処理材にはメチレンブルーなどの色素をそれぞれ配合してもよいことが記載されている。これらの有機色素類は前処理材に均一に溶解できる利点があるものの、酸性環境下で変色や退色しやすいという課題を有していた。一方で、歯科用前処理材の粘性を高めた場合には、水洗操作後に塗布部に色残りが見られ、歯科用前処理材が十分に洗浄除去されないという問題も生じる。 However, the dental pretreatment materials described in Patent Documents 1 and 2 have a negative effect on various properties due to the distribution of the viscosity in the pretreatment material because silica settles down when left for a long time. Had the disadvantages. In addition, the dental pretreatment material is generally washed and removed with running water, and the dental pretreatment material described in Patent Document 1 includes natural pigments and tar pigments in order to improve the visibility of the application part. It is described that a coloring agent such as methylene blue and a pigment such as methylene blue may be added to the dental pretreatment material described in Patent Document 2, respectively. Although these organic dyes have the advantage of being able to be dissolved uniformly in the pretreatment material, they have a problem that they are easily discolored and faded in an acidic environment. On the other hand, when the viscosity of the dental pretreatment material is increased, a color residue is observed in the application part after the water washing operation, which causes a problem that the dental pretreatment material is not sufficiently washed and removed.
したがって、シリンジ型の歯科用前処理材には、吐出性と難垂れ性、視認性と色相安定性、水洗による除去性、長期保存後の均一性などの多くの要求特性を同時に満たすことが求められている。 Therefore, syringe-type dental pretreatment materials are required to satisfy many required characteristics at the same time, such as dischargeability and sagability, visibility and hue stability, removability by washing with water, and uniformity after long-term storage. It has been.
そこで、本発明の目的は、吐出性と難垂れ性、視認性と色相安定性、水洗による除去性、および長期保存後の均一性に同時に優れた歯科用前処理材を提供することにある。 Accordingly, an object of the present invention is to provide a dental pretreatment material that is excellent in dischargeability and sagability, visibility and hue stability, removability by washing with water, and uniformity after long-term storage.
上記のようにシリンジ型の歯科用前処理材には多くの要求特性を同時に満たすことが求められているのに対し、歯科用前処理材の一つの成分を変化させると、一つの特性が向上するものの他の特性が低下するなど、バランスよく歯科用前処理材の多くの特性を同時に向上させるのは困難である。しかしながら本発明者は、上記課題を解決すべく鋭意研究を続けた結果、酸水溶液に、フィラー、特定の分子量を有するポリエチレングリコール、および無機顔料をそれぞれ特定の範囲内で配合することで、上記解決課題を解決できることを見出し、本発明を完成するに至った。 As described above, syringe-type dental pretreatment materials are required to satisfy many required characteristics at the same time, but when one component of dental pretreatment material is changed, one characteristic is improved. It is difficult to improve many properties of the dental pretreatment material at the same time in a balanced manner, for example, the other properties of what is to be reduced. However, as a result of continuing intensive research to solve the above problems, the present inventor has formulated the above solution by adding a filler, a polyethylene glycol having a specific molecular weight, and an inorganic pigment to the acid aqueous solution within a specific range. The present inventors have found that the problem can be solved and have completed the present invention.
本発明は、（Ａ）酸、（Ｂ）水、（Ｃ）フィラー、（Ｄ）重量平均分子量１５００〜１５０００のポリエチレングリコール、および（Ｅ）無機顔料を含む歯科用前処理材組成物であって、
前記（Ａ）酸と前記（Ｂ）水の合計１００重量部に対する、前記（Ｃ）フィラーの含有量が５〜１３重量部であり、前記（Ｄ）ポリエチレングリコールの含有量が１３〜２８重量部であり、かつ前記（Ｅ）無機顔料の含有量が０．０１０〜５．０重量部である歯科用前処理材組成物である。
The present invention is a dental pretreatment material composition comprising (A) an acid, (B) water, (C) a filler, (D) polyethylene glycol having a weight average molecular weight of 1500 to 15000, and (E) an inorganic pigment. ,
The content of the (C) filler is 5 to 13 parts by weight, and the content of the (D) polyethylene glycol is 13 to 28 parts by weight with respect to a total of 100 parts by weight of the (A) acid and the (B) water. And (E) a dental pretreatment material composition having an inorganic pigment content of 0.010 to 5.0 parts by weight.
前記（Ａ）酸は、リン酸、クエン酸、および乳酸からなる群より選ばれる少なくとも１種であることが好ましい。 The (A) acid is preferably at least one selected from the group consisting of phosphoric acid, citric acid, and lactic acid.
歯科用前処理材組成物は、歯科用エッチング材に好適である。 The dental pretreatment material composition is suitable for a dental etching material.
本発明の好ましい一実施態様においては、歯科用前処理材組成物が、ニードルを装着可能なシリンジ容器に収容される。 In a preferred embodiment of the present invention, the dental pretreatment material composition is contained in a syringe container to which a needle can be attached.
本発明によれば、吐出性と難垂れ性、視認性と色相安定性、水洗による除去性、および長期保存後の均一性に同時に優れた歯科用前処理材が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the dental pretreatment material which was excellent simultaneously in the discharge property and the sagability, visibility and hue stability, the removability by water washing, and the uniformity after long-term storage is provided.
本発明の歯科用前処理材は（Ａ）酸と、（Ｂ）水と、（Ｃ）フィラーと、（Ｄ）重量平均分子量１５００〜１５０００のポリエチレングリコールと、（Ｅ）無機顔料とを必須成分として含む。まず、これらの必須成分について説明する。 The dental pretreatment material of the present invention comprises (A) an acid, (B) water, (C) a filler, (D) polyethylene glycol having a weight average molecular weight of 1500 to 15000, and (E) an inorganic pigment as essential components. Include as. First, these essential components will be described.
（Ａ）酸および（Ｂ）水
（Ａ）酸および（Ｂ）水は、酸水溶液を形成し、当該酸水溶液は、歯質の脱灰に必要な成分である。（Ａ）酸としては、従来から歯科用酸処理材に用いられているものを使用することができ、例えば、カルボン酸化合物等の有機酸、および、リン酸、硝酸、硫酸、フッ酸等の無機酸を使用することができる。カルボン酸化合物の例としては、クエン酸、乳酸、リンゴ酸、マロン酸、マレイン酸、シュウ酸、酒石酸、酢酸、モノクロロ酢酸、ジクロロ酢酸、トリクロロ酢酸、トリフルオロ酢酸、ギ酸等が挙げられる。これらの酸は、単独でまたは２種以上を組み合わせて使用することができる。（Ａ）酸としては、リン酸、クエン酸、および乳酸からなる群より選ばれる少なくとも１種が好ましく、リン酸および／またはクエン酸がより好ましく、リン酸が最も好ましい。
(A) Acid and (B) Water (A) Acid and (B) water form an acid aqueous solution, and the acid aqueous solution is a component necessary for the decalcification of teeth. (A) As an acid, what is conventionally used for a dental acid treatment material can be used, for example, organic acids, such as a carboxylic acid compound, and phosphoric acid, nitric acid, a sulfuric acid, hydrofluoric acid, etc. Inorganic acids can be used. Examples of the carboxylic acid compound include citric acid, lactic acid, malic acid, malonic acid, maleic acid, oxalic acid, tartaric acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid and the like. These acids can be used alone or in combination of two or more. (A) The acid is preferably at least one selected from the group consisting of phosphoric acid, citric acid, and lactic acid, more preferably phosphoric acid and / or citric acid, and most preferably phosphoric acid.
（Ｂ）水としては、蒸留水、濾過水、イオン交換水等の有害な不純物を含まないものを用いることが好ましい。 (B) It is preferable to use water that does not contain harmful impurities, such as distilled water, filtered water, and ion-exchanged water.
酸水溶液中の酸（Ａ）の濃度は、特に限定されない。高い清掃効果またはエッチング効果が得られることから、（Ａ）酸の好ましい濃度範囲は、（Ａ）酸と（Ｂ）水との合計を１００重量％として、１０重量％以上８０重量％以下の範囲であることが好ましく、１５重量％以上６０重量％以下の範囲であることがより好ましい。 The concentration of the acid (A) in the acid aqueous solution is not particularly limited. Since a high cleaning effect or etching effect can be obtained, the preferable concentration range of (A) acid is in the range of 10% by weight to 80% by weight, with the total of (A) acid and (B) water being 100% by weight. It is preferable that it is in the range of 15 wt% or more and 60 wt% or less.
（Ｃ）フィラー
（Ｃ）フィラーは、組成物の粘度を調整し、諸特性を向上させるための成分である。（Ｃ）フィラーとしては、歯科用組成物に使用される公知のフィラーが何ら制限なく使用される。好ましくは、シリカ、アルミナ、チタニア、ジルコニア等の無機酸化物粒子、またはこれらからなる複合酸化物粒子、燐酸カルシウム、ハイドロキシアパタイト、フッ化イットリウム、フッ化イッテルビウムが用いられる。さらに好ましくは、火炎熱分解法で作製されるシリカ、アルミナ、チタニアの粒子が用いられ、例えば、日本アエロジル（株）製、商品名：アエロジル、アエロキサイドＡｌｕＣ、アエロキサイドＴｉＯ2Ｐ２５、アエロキサイドＴｉＯ2Ｐ２５Ｓ、ＶＰ Ｚｉｒｃｏｎｉｕｍ Ｏｘｉｄｅ ３−ＹＳＺ、ＶＰ Ｚｉｒｃｏｎｉｕｍ Ｏｘｉｄｅ ３−ＹＳＺ ＰＨが用いられる。最も好ましくは、火炎熱分解法で作製されるシリカ粒子が用いられ、例えば、日本アエロジル（株）製、商品名：アエロジルが用いられる。
(C) Filler The (C) filler is a component for adjusting the viscosity of the composition and improving various properties. (C) As a filler, the well-known filler used for a dental composition is used without a restriction | limiting at all. Preferably, inorganic oxide particles such as silica, alumina, titania and zirconia, or composite oxide particles made of these, calcium phosphate, hydroxyapatite, yttrium fluoride, and ytterbium fluoride are used. More preferably, silica is produced by flame pyrolysis, alumina, titania particles are used, for example, Nippon Aerosil Co., Ltd., trade name: Aerosil, Aerokisaido AluC, Aerokisaido TiO 2 P25, Aerokisaido TiO 2 P25S, VP Zirconium Oxide 3-YSZ and VP Zirconium Oxide 3-YSZ PH are used. Most preferably, silica particles produced by a flame pyrolysis method are used. For example, trade name: Aerosil manufactured by Nippon Aerosil Co., Ltd. is used.
（Ｃ）フィラーの平均粒子径としては、組成物中での均一分散性の観点から１〜５０ｎｍが好ましく、５〜４０ｎｍがより好ましい。なお、（Ｃ）フィラーの平均粒子径は、フィラー粒子の電子顕微鏡写真を撮影し、無作為に選択した１００個のフィラー粒子の粒子径の平均値として測定できる。なお、フィラー粒子が非球状である場合には、粒子径は、フィラー粒子の最長と最短の長さの算術平均をもって粒子径とし、凝集粒子である場合には、一次粒子の粒子径とする。 (C) As an average particle diameter of a filler, 1-50 nm is preferable from a uniform dispersible viewpoint in a composition, and 5-40 nm is more preferable. In addition, the average particle diameter of (C) filler can be measured as an average value of particle diameters of 100 filler particles randomly selected by taking an electron micrograph of the filler particles. When the filler particles are non-spherical, the particle diameter is the average particle diameter of the longest and shortest lengths of the filler particles, and when the filler particles are aggregated particles, the particle diameter is the primary particle diameter.
（Ｃ）フィラーの形状としては特に制限されることなく、不定形または球形の粒子の粉末として用いることができる。 (C) The shape of the filler is not particularly limited, and can be used as a powder of irregular or spherical particles.
（Ｃ）フィラーの配合量は、（Ａ）酸と（Ｂ）水の合計１００重量部に対して、５〜１３重量部である。配合量が５重量部未満の場合、増粘効果が小さく易垂れ性となり、組成物が口腔内の塗布部の周囲に広がっていくという不具合を生じる。また、組成物の粘度が不十分となり、長期保存中に（Ｃ）フィラーまたは（Ｅ）無機顔料が沈降して組成物が不均一となる。配合量が１３重量部より多い場合、組成物の粘度が高くなりすぎて、良好な吐出性が得られなくなる。好ましい（Ｃ）フィラーの配合量は、５〜１０重量部である。 The blending amount of (C) filler is 5 to 13 parts by weight with respect to 100 parts by weight of (A) acid and (B) water. If the blending amount is less than 5 parts by weight, the thickening effect is small and the sagability is small, which causes a problem that the composition spreads around the application part in the oral cavity. Moreover, the viscosity of the composition becomes insufficient, and the (C) filler or (E) inorganic pigment settles during long-term storage, resulting in a non-uniform composition. When the blending amount is more than 13 parts by weight, the viscosity of the composition becomes too high and good dischargeability cannot be obtained. A preferable blending amount of the filler (C) is 5 to 10 parts by weight.
（Ｄ）ポリエチレングリコール
（Ｄ）ポリエチレングリコールは、組成物の粘度を調整し、諸特性を向上させるための成分であり、且つ水分の蒸発を抑える役割も果たす。
(D) Polyethylene glycol (D) Polyethylene glycol is a component for adjusting the viscosity of the composition and improving various properties, and also plays a role of suppressing evaporation of moisture.
（Ｄ）ポリエチレングリコールの重量平均分子量は１５００〜１５０００である。重量平均分子量が１５００未満だと増粘効果が小さく組成物の粘度が不十分となり、長期保存中に（Ｃ）フィラーまたは（Ｅ）無機顔料が沈降して組成物が不均一となる。また、難垂れ性が不十分となる場合がある。一方、重量平均分子量が１５０００より大きいと、製造時に酸水溶液中への溶解が不完全になる、あるいは溶解に時間が掛かり、さらに、歯牙部分に塗布した後流水で洗浄する際の除去性が悪くなる。なお、（Ｄ）ポリエチレングリコールの重量平均分子量は、例えば、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により求めることができる。 (D) The weight average molecular weight of polyethylene glycol is 1500-15000. When the weight average molecular weight is less than 1500, the effect of thickening is small and the viscosity of the composition becomes insufficient, and during long-term storage, the (C) filler or (E) inorganic pigment settles and the composition becomes non-uniform. Further, the sagability may be insufficient. On the other hand, if the weight average molecular weight is larger than 15000, the dissolution in the acid aqueous solution becomes incomplete during the production, or it takes a long time to dissolve, and the removability when washed with running water after being applied to the tooth portion is poor. Become. In addition, the weight average molecular weight of (D) polyethyleneglycol can be calculated | required by a gel permeation chromatography (GPC) measurement, for example.
（Ｄ）ポリエチレングリコールの配合量は、（Ａ）酸と（Ｂ）水の合計１００重量部に対して、１３〜２８重量部である。配合量が１３重量部未満の場合、組成物の粘度が不十分となり、長期保存中に（Ｃ）フィラーまたは（Ｅ）無機顔料が沈降して組成物が不均一となる。一方、配合量が２８重量部より多い場合、易垂れ性となり、組成物が口腔内の塗布部の周囲に広がっていくという不具合を生じる。好ましい（Ｄ）ポリエチレングリコールの配合量は、１５〜２５重量部である。 (D) The compounding quantity of polyethyleneglycol is 13-28 weight part with respect to a total of 100 weight part of (A) acid and (B) water. When the blending amount is less than 13 parts by weight, the viscosity of the composition becomes insufficient, and the (C) filler or (E) inorganic pigment settles during long-term storage, resulting in a non-uniform composition. On the other hand, if the blending amount is more than 28 parts by weight, it becomes easy to sag and the composition spreads around the application part in the oral cavity. The blending amount of (D) polyethylene glycol is preferably 15 to 25 parts by weight.
（Ｅ）無機顔料
（Ｅ）無機顔料は歯科用前処理材組成物の視認性を向上させる成分である。有機顔料が酸化−還元状態の変化によってしばしば変色、退色を起こすのに対し、無機顔料は色相安定性が高い点で有利である。
(E) Inorganic pigment (E) An inorganic pigment is a component which improves the visibility of a dental pretreatment material composition. While organic pigments often undergo discoloration and fading due to changes in the oxidation-reduction state, inorganic pigments are advantageous in that they have high hue stability.
（Ｅ）無機顔料としては工業的に用いられる無機顔料が使用でき、視認性の観点から、赤色、青色、または緑色の無機顔料が好ましい。その具体例としては、ウルトラマリン青、コバルト青（例、ピグメントブルー２８，３６，３６：１，７２）、バナジウムジルコニウム青、Ｃｏ−Ｚｎ−Ｓｉ系顔料、Ｃｏ−Ｓｉ系顔料、ピーコック、Ａｌ−Ｃｒ系顔料、Ｃｒ系顔料、Ｃｏ−Ｃｒ系顔料、鉄顔料などが挙げられる。より好ましくは、ウルトラマリン青、コバルト青、バナジウムジルコニウム青、Ｃｏ−Ｚｎ−Ｓｉ系顔料、Ｃｏ−Ｓｉ系顔料が用いられる。 (E) The inorganic pigment used industrially can be used as an inorganic pigment, and a red, blue, or green inorganic pigment is preferable from a viewpoint of visibility. Specific examples thereof include ultramarine blue, cobalt blue (eg, pigment blue 28, 36, 36: 1, 72), vanadium zirconium blue, Co—Zn—Si pigment, Co—Si pigment, peacock, Al— Examples thereof include Cr pigments, Cr pigments, Co-Cr pigments, and iron pigments. More preferably, ultramarine blue, cobalt blue, vanadium zirconium blue, Co—Zn—Si pigment, or Co—Si pigment is used.
（Ｅ）無機顔料の配合量は、（Ａ）酸と（Ｂ）水の合計１００重量部に対して、０．０１０〜５．０重量部である。配合量が０．０１０重量部未満の場合、視認性が不十分となり、５．０重量部より多い場合、組成物中に均一に分散しなくなる。 (E) The compounding quantity of an inorganic pigment is 0.010-5.0 weight part with respect to a total of 100 weight part of (A) acid and (B) water. When the blending amount is less than 0.010 parts by weight, the visibility is insufficient, and when it is more than 5.0 parts by weight, it is not uniformly dispersed in the composition.
この他、本発明の組成物には、本発明の効果を阻害しない範囲で、界面活性剤、ｐＨ調整剤、イオン放出性物質、増粘剤、抗菌剤、香料等を配合してもよい。 In addition, the composition of the present invention may contain a surfactant, a pH adjuster, an ion releasing substance, a thickener, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not inhibited.
本発明の組成物は、歯科用途において酸の作用を利用する前処理操作に制限なく適用でき、例えば、金属やセラミックス製の補綴物の表面清掃材、殺菌材等としても使用可能であるが、好適には、歯科用エッチング材として使用される。歯科用エッチング材は、次のような方法で好適に使用できる。すなわち、研削エナメル質、象牙質または事前に機械的に清掃した未研削エナメル質に歯科用エッチング材を直接塗布し、所定時間後すぐに水洗し、エアーブローで乾燥した後、症例に適した歯牙組織の修復操作を行えばよい。 The composition of the present invention can be applied without limitation to pretreatment operations utilizing the action of acid in dental applications, and can be used as, for example, a surface cleaning material for a prosthesis made of metal or ceramics, a sterilizing material, etc. Preferably, it is used as a dental etching material. The dental etching material can be suitably used by the following method. In other words, apply dental etchant directly to ground enamel, dentin or previously mechanically cleaned unground enamel, rinse with water immediately after a predetermined time, dry with air blow, and then tooth suitable for the case A tissue repair operation may be performed.
本発明の歯科用前処理材組成物の製品形態としては、ニードルを装着可能なシリンジ容器に収容された形態が好適であり、通常、当該容器にはニードルチップが付属される。 As a product form of the dental pretreatment material composition of the present invention, a form accommodated in a syringe container to which a needle can be attached is suitable, and a needle tip is usually attached to the container.
本発明の歯科用前処理材組成物は、吐出性に優れるため、シリンジ型の製品形態において、塗布が容易である。また、難垂れ性にも優れるため、組成物が口腔内の治療部分の周囲に広がりにくい。また、塗布部の視認性と、色相安定性にも優れる。また、水洗による除去性にも優れる。また、長期保存後の組成物の均一性に優れるため、フィラーまたは顔料の沈降によって、易垂れ性の低粘度の液状成分のみがシリンジから吐出されたり、フィラーまたは顔料を多く含む高粘度部分により吐出性が低下して、正確な吐出が困難になるという問題も起こらない。 Since the dental pretreatment material composition of the present invention is excellent in dischargeability, it can be easily applied in a syringe type product form. Moreover, since the sagability is excellent, the composition hardly spreads around the treatment portion in the oral cavity. Moreover, it is excellent also in the visibility of an application part, and hue stability. Moreover, the removability by water washing is also excellent. In addition, since the composition has excellent uniformity after long-term storage, only a liquid component with low viscosity, which is easy to sag, is discharged from the syringe due to sedimentation of the filler or pigment, or discharged from a high-viscosity part that contains a large amount of filler or pigment. Therefore, there is no problem that accurate discharge becomes difficult.
以下、実施例および比較例を挙げて本発明を詳細に説明するが、本発明は、これら実施例に限定されるものではない。なお、以下で用いる略称及び略号については次の通りである。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. The abbreviations and abbreviations used below are as follows.
Ａｒ−１３０：ＡＥＲＯＳＩＬ１３０（日本アエロジル社製親水性フュームドシリカ）
Ａｒ−２００：ＡＥＲＯＳＩＬ２００（日本アエロジル社製親水性フュームドシリカ）
Ａｒ−３８０：ＡＥＲＯＳＩＬ３８０（日本アエロジル社製親水性フュームドシリカ）
ＳＴ−ＰＳＭ：スノーテックスＰＳ−Ｍ（日産化学社製コロイダルシリカ）
ＰＥＧ：ポリエチレングリコール（三洋化成工業社製）
（Ｍ．Ｗ．＝４００）：マクロゴール４００（重量平均分子量４００）
（Ｍ．Ｗ．＝１８００）：マクロゴール２０００（重量平均分子量１，８００）
（Ｍ．Ｗ．＝３２００）：マクロゴール４０００（重量平均分子量３，２００）
（Ｍ．Ｗ．＝８３００）：マクロゴール６０００（重量平均分子量８，３００）
（Ｍ．Ｗ．＝２００００）：マクロゴール２００００（重量平均分子量２０，０００）
Ar-130: AEROSIL130 (hydrophilic fumed silica manufactured by Nippon Aerosil Co., Ltd.)
Ar-200: AEROSIL200 (Nippon Aerosil Co., Ltd. hydrophilic fumed silica)
Ar-380: AEROSIL 380 (hydrophilic fumed silica manufactured by Nippon Aerosil Co., Ltd.)
ST-PSM: Snowtex PS-M (Nissan Chemical Co., Ltd. colloidal silica)
PEG: Polyethylene glycol (manufactured by Sanyo Chemical Industries)
(MW = 400): Macrogol 400 (weight average molecular weight 400)
(MW = 1800): Macrogol 2000 (weight average molecular weight 1,800)
(MW = 3200): Macrogol 4000 (weight average molecular weight 3,200)
(MW = 8300): Macrogol 6000 (weight average molecular weight 8,300)
(MW = 20000): Macrogol 20000 (weight average molecular weight 20,000)
歯科用前処理材組成物の調製
表１および２に記載の各成分（組成の数値の単位：重量部）を常温下で混合して歯科用前処理材組成物を調製した。これらの組成物を用い、後述の方法に従って、吐出力試験、４８時間後吐出力試験、除去性試験、垂れ性試験、沈降性試験、色相安定性試験、および視認性確認試験を行った。組成および評価結果を表１および２に示す。
Preparation of Dental Pretreatment Material Composition Each component (unit of numerical values of composition: parts by weight) shown in Tables 1 and 2 was mixed at room temperature to prepare a dental pretreatment material composition. Using these compositions, a discharge force test, a 48-hour discharge force test, a removability test, a sag test, a sedimentation test, a hue stability test, and a visibility confirmation test were performed according to the methods described later. The compositions and evaluation results are shown in Tables 1 and 2.
吐出力試験
歯科用前処理材組成物をシリンジ容器に収容して２５℃雰囲気下にて１時間放置した後、シリンジ容器の先端に２５Ｇａｕｇｅのニードルチップ（外径φ０．５ｍｍ）を装着し、吐出力を万能試験機（島津製作所社製）にてクロスヘッドスピードを２ｍｍ／分に設定して測定した。
Discharge force test The dental pretreatment material composition was placed in a syringe container and allowed to stand in an atmosphere of 25 ° C for 1 hour. Then, a 25 Gauge needle tip (outside diameter: 0.5 mm) was attached to the tip of the syringe container and discharged. The force was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min.
４８時間後吐出力試験
上記吐出力試験を行った後、２５Ｇａｕｇｅのニードルチップ（外径φ０．５ｍｍ）を装着したまま２５℃雰囲気下にて４８時間さらに放置してから、吐出力を万能試験機（島津製作所社製）にてクロスヘッドスピードを２ｍｍ／分に設定して測定した。
48 hours later discharge force test After carrying out the above discharge force test, it was left to stand in a 25 ° C atmosphere for 48 hours with a 25 Gauge needle tip (outer diameter φ0.5 mm) attached. The crosshead speed was set at 2 mm / min (manufactured by Shimadzu Corporation) and measured.
除去性試験
ウシ下顎前歯の唇面を流水下にて＃８０シリコン・カーバイド紙（日本研紙社製）で研磨して、エナメル質の平坦面を露出させたサンプルを得た。得られたサンプルを流水下にて＃１０００のシリコン・カーバイド紙（日本研紙社製）でさらに研磨した。研磨終了後、表面の水をエアーブローすることで乾燥した。乾燥後の平滑面に歯科用前処理材組成物を塗布し、１分後流水で洗い流した後、色残りの有無を目視にて確認した。色残りがなかった場合は○、色残りがあった場合は×とした。
Removability test The lip surface of bovine mandibular anterior teeth was polished with # 80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain a sample in which the flat surface of enamel was exposed. The obtained sample was further polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi) under running water. After polishing, the surface water was dried by air blowing. The dental pretreatment material composition was applied to the smooth surface after drying, washed with running water after 1 minute, and then visually checked for the presence of color residue. When there was no color residue, it was marked with ◯, and when there was color residue, it was marked with ×.
垂れ性試験
ガラス板上に歯科用前処理材組成物を０．１ｍｌ滴下し、３７℃雰囲気下でガラス板を垂直に立て、１分後の移動距離を測定した。
Dripping test 0.1 ml of the dental pretreatment composition was dropped on a glass plate, and the glass plate was vertically set in a 37 ° C. atmosphere to measure the moving distance after 1 minute.
沈降性試験
２ｍｌポリプロピレン製遠心分離用チューブバイアルに歯科用前処理材組成物を１ｍｌ充填し、遠心分離機（ＭＣＸ−１５０：トミー精工社製）を用いて５０００ｒｐｍで５分間遠心分離した後の組成分離の有無を目視にて確認した。分離が見られなかった場合は○、分離が見られた場合は×とした。
Sedimentability test Composition after filling 1 ml of dental pretreatment composition into a 2 ml polypropylene centrifuge tube vial and centrifuging at 5000 rpm for 5 minutes using a centrifuge (MCX-150: manufactured by Tommy Seiko Co., Ltd.) The presence or absence of separation was confirmed visually. The case where no separation was observed was marked with ◯, and the case where separation was observed was marked with ×.
色相安定性試験（１）
７０℃４週保存した後の歯科用前処理材組成物の変色または退色の有無を目視にて確認した。変色または退色が見られなかった場合は○、見られた場合は×とした。
Hue stability test (1)
The dental pretreatment composition after storage at 70 ° C. for 4 weeks was visually checked for discoloration or fading. When no discoloration or fading was observed, it was marked with ◯.
色相安定性試験（２）
トリエタノールアミンを添加し、ｐＨを２．０まで変化させたときの歯科用前処理材組成物の変色または退色の有無を目視にて確認した。変色または退色が見られなかった場合は○、見られた場合は×とした。
Hue stability test (2)
The presence or absence of discoloration or fading of the dental pretreatment material composition when triethanolamine was added and the pH was changed to 2.0 was visually confirmed. When no discoloration or fading was observed, it was marked with ◯.
視認性確認試験
ヒト抜去歯上に歯科用前処理材組成物を塗布し、処理部／未処理部の視認性を目視にて確認した。処理部／未処理部が明確に確認できた場合は○、明確に確認できなかった場合は×とした。
Visibility Confirmation Test A dental pretreatment material composition was applied on human extracted teeth, and the visibility of the treated / untreated areas was visually confirmed. When the processing part / unprocessed part could be confirmed clearly, it was marked with ◯, and when it was not clearly confirmed, it was marked with ×.
表１および２に示すように、実施例１〜１５の本発明の歯科用前処理材組成物は、吐出性と難垂れ性、視認性と色相安定性、水洗による除去性、および長期保存後の均一性の全てに優れていた。一方、比較例１の歯科用前処理材組成物では、フィラーの沈降性の評価結果が悪く、また実際にシリンジに充填して保存しているとフィラーと液成分の分離が観察された。これは（Ｄ）ポリエチレングリコールの配合量が少な過ぎるため、十分な増粘効果が得られなかったためである。比較例２の歯科用前処理材組成物は易垂れ性を示したが、これは（Ｄ）ポリエチレングリコールの配合量が多過ぎるため、組成全体での液成分が過剰になり、十分な粘度が得られなかったためである。口腔内での使用を想定すると、治療部分以外にまで拡散するおそれがある。比較例３の歯科用前処理材組成物は無機粒子成分の沈降性の評価結果が悪く、また比較例１と同様にシリンジ内に保存中に組成分離が観察された。これは（Ｄ）ポリエチレングリコールの重量平均分子量が小さ過ぎるため、増粘効果が不十分であったためである。比較例４の歯科用前処理材組成物は難除去性を示した。これは（Ｄ）ポリエチレングリコールの重量平均分子量が大き過ぎるため、歯質への沈着効果が高まったためである。比較例５の歯科用前処理材組成物は、無機粒子成分の沈降性の評価結果が悪く、また比較例１および３と同様にシリンジ内に保存中に組成分離が観察された。また、易垂れ性を示した。これは（Ｃ）フィラーの配合量が少なすぎたため、十分な増粘効果が得られなかったためである。比較例６の歯科用前処理材組成物は難吐出性を示した。これは（Ｃ）フィラーの配合量が多過ぎたため、吐出をするには粘度が高まり過ぎたためである。吐出が困難な場合、無理に力がかかるためニードルの先端が震え、限定した場所に塗布することが困難となる。比較例７の歯科用前処理材組成物は、無機粒子成分の沈降性の評価結果が悪く、また比較例１、３および５と同様にシリンジ内に保存中に組成分離が観察された。これは高い均一分散性を有するコロイダルシリカを（Ｃ）フィラーとして用いたものの、（Ｄ）ポリエチレングリコールの配合量が少な過ぎたため、十分な増粘効果を得られなかったためである。比較例８の歯科用前処理材組成物では、ｐＨが１．３前後において緑色から青色への変化が見られた。これは酸化／還元に伴い、青色１号の電子状態が変化してしまったためである。比較例９の歯科用前処理材組成物では、７０℃４週保存後に退色が見られた。これは青色２号アルミニウムレーキが酸性条件下において劣化してしまったためである。色が退色すると処理部／未処理部の判別が困難となってしまう。比較例１０の歯科用前処理材組成物では着色料の配合量が少なすぎるため、ヒト抜去歯上において処理部／未処理部の境界が曖昧となってしまった。比較例１１の歯科用前処理材組成物では、無機顔料が過剰であり、均一な組成物を得ることができなかった。 As shown in Tables 1 and 2, the dental pretreatment material compositions of Examples 1 to 15 of the present invention have ejection properties and sagability, visibility and hue stability, removability by washing with water, and after long-term storage. The uniformity was excellent. On the other hand, in the dental pretreatment material composition of Comparative Example 1, the evaluation result of the sedimentation property of the filler was poor, and when the syringe was actually filled and stored, separation of the filler and the liquid component was observed. This is because (D) the blending amount of polyethylene glycol is too small, so that a sufficient thickening effect could not be obtained. The dental pretreatment material composition of Comparative Example 2 showed easy sag, but because the blending amount of (D) polyethylene glycol was too large, the liquid component in the entire composition was excessive and sufficient viscosity was obtained. It was because it was not obtained. Assuming use in the oral cavity, there is a risk of spreading beyond the treatment area. The dental pretreatment material composition of Comparative Example 3 had a poor evaluation result of the sedimentation property of the inorganic particle component, and composition separation was observed during storage in the syringe as in Comparative Example 1. This is because the thickening effect was insufficient because the weight average molecular weight of (D) polyethylene glycol was too small. The dental pretreatment material composition of Comparative Example 4 exhibited difficult removability. This is because (D) the weight average molecular weight of polyethylene glycol is too large, so that the effect of depositing on the tooth is enhanced. The dental pretreatment material composition of Comparative Example 5 had a poor sedimentation evaluation result of the inorganic particle component, and composition separation was observed during storage in the syringe as in Comparative Examples 1 and 3. In addition, it was easy to sag. This is because the blending amount of the (C) filler was too small, so that a sufficient thickening effect could not be obtained. The dental pretreatment material composition of Comparative Example 6 exhibited difficult ejection properties. This is because the blending amount of the filler (C) was too high, and the viscosity was too high for ejection. When ejection is difficult, force is applied forcefully, and the tip of the needle shakes, making it difficult to apply to a limited place. The dental pretreatment material composition of Comparative Example 7 had poor evaluation results of the sedimentation properties of the inorganic particle components, and composition separation was observed during storage in the syringe as in Comparative Examples 1, 3 and 5. This is because although colloidal silica having a high uniform dispersibility was used as the filler (C), the blending amount of polyethylene glycol (D) was too small, so that a sufficient thickening effect could not be obtained. In the dental pretreatment material composition of Comparative Example 8, a change from green to blue was observed at a pH of around 1.3. This is because the electronic state of Blue No. 1 has changed with oxidation / reduction. In the dental pretreatment material composition of Comparative Example 9, fading was observed after storage at 70 ° C. for 4 weeks. This is because the blue No. 2 aluminum lake has deteriorated under acidic conditions. If the color fades, it becomes difficult to determine the processing unit / unprocessed unit. In the dental pretreatment material composition of Comparative Example 10, since the blending amount of the coloring agent was too small, the boundary between the treated part / untreated part became ambiguous on the human extracted tooth. In the dental pretreatment material composition of Comparative Example 11, the inorganic pigment was excessive, and a uniform composition could not be obtained.
本発明の歯科用前処理材は、歯科用途において酸の作用を利用する前処理操作に制限なく適用でき、特に歯科用エッチング材として好適に使用でき、金属やセラミックス製の補綴物の表面清掃材、殺菌材等としても使用することができる。 The dental pretreatment material of the present invention can be applied without limitation to pretreatment operations that utilize the action of acid in dental applications, and can be particularly suitably used as a dental etching material, and is a surface cleaning material for metal or ceramic prosthesis. It can also be used as a sterilizing material.
Claims (4)
前記（Ａ）酸と前記（Ｂ）水の合計１００重量部に対する、前記（Ｃ）フィラーの含有量が５〜１３重量部であり、前記（Ｄ）ポリエチレングリコールの含有量が１３〜２８重量部であり、かつ前記（Ｅ）無機顔料の含有量が０．０１０〜５．０重量部である歯科用前処理材組成物。 A dental pretreatment material composition comprising (A) acid, (B) water, (C) filler, (D) polyethylene glycol having a weight average molecular weight of 1500 to 15000, and (E) an inorganic pigment,
The content of the (C) filler is 5 to 13 parts by weight, and the content of the (D) polyethylene glycol is 13 to 28 parts by weight with respect to a total of 100 parts by weight of the (A) acid and the (B) water. And a dental pretreatment material composition in which the content of the inorganic pigment (E) is 0.010 to 5.0 parts by weight.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018172354A (en) * | 2017-04-01 | 2018-11-08 | Ｙａｍａｋｉｎ株式会社 | Dental adhesive pretreatment material composition containing phosphate group-containing polymerizable compound |
| CN111467248A (en) * | 2020-05-20 | 2020-07-31 | 四川涑爽医疗用品有限公司 | Phosphoric acid corrosion agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018172354A (en) * | 2017-04-01 | 2018-11-08 | Ｙａｍａｋｉｎ株式会社 | Dental adhesive pretreatment material composition containing phosphate group-containing polymerizable compound |
| CN111467248A (en) * | 2020-05-20 | 2020-07-31 | 四川涑爽医疗用品有限公司 | Phosphoric acid corrosion agent and preparation method thereof |
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| JP6077958B2 (en) | 2017-02-08 |
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