WO2020158071A1 - Dental glass ionomer cement liquid and dental glass ionomer cement - Google Patents

Dental glass ionomer cement liquid and dental glass ionomer cement Download PDF

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WO2020158071A1
WO2020158071A1 PCT/JP2019/041656 JP2019041656W WO2020158071A1 WO 2020158071 A1 WO2020158071 A1 WO 2020158071A1 JP 2019041656 W JP2019041656 W JP 2019041656W WO 2020158071 A1 WO2020158071 A1 WO 2020158071A1
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ionomer cement
glass ionomer
dental glass
acid
powder
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PCT/JP2019/041656
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French (fr)
Japanese (ja)
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裕介 島田
大三郎 森
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株式会社ジーシー
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Priority to JP2020569372A priority Critical patent/JPWO2020158071A1/en
Publication of WO2020158071A1 publication Critical patent/WO2020158071A1/en
Priority to JP2022184612A priority patent/JP2023009286A/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/15Compositions characterised by their physical properties
    • A61K6/17Particle size

Definitions

  • the present invention relates to a dental glass ionomer cement liquid used by mixing with a dental glass ionomer cement powder component containing aluminosilicate glass as a main component, and a dental glass ionomer cement.
  • Dental glass ionomer cement is used by reacting a polymer acid mainly composed of an acid such as polycarboxylic acid with glass powder for glass ionomer cement in the presence of water to cure.
  • Glass ionomer cement has an extremely good affinity for living organisms, and the cured product is semitransparent and has excellent aesthetics. Further, the glass ionomer cement has an excellent adhesive force to tooth substances such as enamel and dentin, and further, when the glass powder contains fluorine, the anti-caries action by the fluorine is exerted. It has excellent characteristics such as being present.
  • glass ionomer cement is widely used in the dental field for filling caries cavities, fusion of crown inlay bridges and orthodontic bands, lining of cavities, sealers for root canal filling, abutment construction and preventive filling. It is a material.
  • the form of dental glass ionomer cement is generally composed of a powder component containing fluoroaluminosilicate glass and a liquid component containing a polycarboxylic acid polymer (see, for example, Patent Document 1). This cement is used by mixing and kneading a powder component and a liquid component into a kneaded product, applying it to a treatment site, and then hardening it.
  • the powder component when mixing and kneading the powder component containing the aluminosilicate glass and the liquid component containing the polycarboxylic acid polymer. It is possible to increase the ratio of. However, when the ratio of the powder component is increased, the cement hardens too fast, and there is a problem that there is no time margin for clinical use. That is, it has been difficult to obtain a cement hardened product having high physical strength while ensuring an appropriate operating margin for clinical use.
  • an object of the present invention is to provide a dental glass ionomer cement liquid that can obtain a hardened cement with high physical strength while ensuring an appropriate operating margin for clinical use.
  • One aspect of the present invention is a dental glass ionomer cement liquid containing a polycarboxylic acid polymer, water, and a water reducing agent.
  • the dental glass ionomer cement liquid according to one aspect of the present invention, it is possible to obtain a cement hardened product having high physical strength while ensuring an appropriate operating margin for clinical use.
  • the dental glass ionomer cement liquid of the present embodiment has a polycarboxylic acid-based polymer, water, and a water reducing agent.
  • the polycarboxylic acid polymer is a component necessary for the reaction with the aluminosilicate glass powder contained in the powder component described later.
  • an acid-base reaction occurs in which the aluminum ion eluted from the aluminosilicate glass powder and the conjugate base of the polycarboxylic acid-based polymer undergo ionic cross-linking and are cured. ..
  • the polycarboxylic acid type polymer is a polymer of ⁇ - ⁇ unsaturated monocarboxylic acid or ⁇ - ⁇ unsaturated dicarboxylic acid.
  • ⁇ - ⁇ unsaturated monocarboxylic acid or ⁇ - ⁇ unsaturated dicarboxylic acid For example, one or more selected from acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, and citraconic acid.
  • Examples of the polycarboxylic acid polymer include a copolymer or a homopolymer containing the same. You may use 2 or more types of these.
  • the polycarboxylic acid polymer preferably does not contain a polymerizable ethylenically unsaturated double bond.
  • the blending amount of the polycarboxylic acid polymer is preferably 5 to 60% by mass in the dental glass ionomer cement liquid.
  • the blending amount of the polycarboxylic acid-based polymer is 5% by mass or more, the dentin adhesion, which is a characteristic of a dental glass ionomer cement, is improved.
  • the blending amount of the polycarboxylic acid polymer is 60% by mass or less, the durability of the cured product is improved. More preferably, it is 20 to 50% by mass.
  • Water is a necessary component for acid-base reaction between aluminosilicate glass powder and polycarboxylic acid type polymer.
  • the water content may be the balance of the other components, but it is preferably 30 to 80% by mass in the dental glass ionomer cement liquid. When the amount of water is 30% by mass or more, the miscibility is improved. When the blending amount of water is 80% by mass or less, the physical strength of the cured product becomes high. More preferably, it is 40 to 70% by mass.
  • the water-reducing agent has the effect of preventing the cement from hardening too fast even if the ratio of the powder component is increased in the acid-base reaction by mixing and kneading the dental glass ionomer cement liquid and the powder component.
  • water reducing agent examples include lignin sulfonate-based, oxycarboxylate-based, naphthalene sulfonate-based, melamine sulfonate-based, polystyrene sulfonate-based, and polycarboxylate-based water reducing agents.
  • examples thereof include water reducing agents such as lignin sulfonate, oxycarboxylate, naphthalene sulfonate, melamine sulfonate, polystyrene sulfonate, and polycarboxylate.
  • the refractive index nd of the aluminosilicate glass powder is preferably in the range of 1.42 to 1.47.
  • the difference from the refractive index nd (about 1.42) of the matrix component of the dental glass ionomer cement that is practically useful is small, and the obtained cured dental glass ionomer cement is obtained. Transparency is increased.
  • At least one of the dental glass ionomer cement liquid of the present embodiment and the powder component can be appropriately blended with a contrast agent, an antibacterial agent, a fluorescent agent, a fragrance, a pigment, etc., if necessary.
  • the mass ratio (powder-liquid ratio) of the powder component to the dental glass ionomer cement liquid when preparing a kneaded product of the dental glass ionomer cement is preferably 1 to 5.
  • the powder-liquid ratio is 1 or more, the physical strength of the hardened dental cement is improved.
  • the powder-liquid ratio is 5 or less, the operability of the dental cement is improved.
  • a more preferable powder-liquid ratio is 3 to 4.5, and a further preferable powder-liquid ratio is 3.2 to 4.
  • Dental glass ionomer cement is used by mixing and kneading a powder component and a liquid component into a kneaded product, applying it to the treatment site, and then hardening it.
  • the time from the start of kneading until the shape of the kneading cannot be adjusted is defined as "operation allowance time”.
  • aluminosilicate glass powder ⁇ Preparation of aluminosilicate glass powder> Silica 27.5 g, alumina 12.7 g, aluminum fluoride 16.7 g, strontium fluoride 18.6 g, aluminum phosphate 8.8 g, sodium fluoride 4.2 g, potassium fluoride 5.6 g, lanthanum fluoride 5. 9 g was thoroughly mixed in a mortar. The obtained mixture was put in a magnetic crucible and allowed to stand in an electric furnace. After heating the electric furnace to melt at 1300° C. and homogenizing sufficiently, it was poured into water to obtain a lump of aluminosilicate glass.
  • aluminosilicate glass powder 100 parts by mass of 1% aluminum phosphate aqueous solution was mixed with 100 parts by mass of the aluminosilicate glass powder to prepare a slurry, which was dried at 120°C.
  • Polyacrylic acid powder (average molecular weight: 30,000) was mixed with the obtained powder in an amount of 3% by mass to obtain a powder component.
  • ⁇ Preparation of dental glass ionomer cement liquid The ingredients were mixed in the formulations shown in Table 1 to prepare dental glass ionomer cement solutions of Examples 1 to 13 and Comparative Examples 1 and 2. The unit of the blending amount is mass%.
  • Polyacrylic acid powder Polyacrylic acid powder having an average molecular weight of 25,000 (manufactured by FUJIFILM Wako Pure Chemical Industries) Melflux 5581F: Water-soluble salt of methacrylic acid-acrylic acid copolymer having polyoxyethylene chain having SKW East Asia Melflux 4930F: methacrylic acid having polyoxyethylene chain having acrylic acid and made of SKW East Asia Water-soluble salt of polymer Melment F4000: Water-soluble salt of copolymer of methacrylic acid and acrylic acid having polyoxyethylene chain manufactured by SKW East Asia ⁇ Operation allowance time>
  • a spatula was prepared by mixing the dental glass ionomer cement liquids of Examples 1 to 13 and Comparative Examples 1 and 2 and the powder components with the powder-liquid ratio shown in Table 1. Used and mixed for 30 seconds.
  • the kneaded product was filled in a stainless steel mold having a cavity of 2 mm ⁇ 2 mm ⁇ 25 mm, pressed with a glass plate through a cellophane, and taken out after 1 hour to obtain a prismatic cured product.
  • the obtained cured product was immersed in distilled water at 37° C. for 24 hours and then polished with a #320 water-resistant polishing paper to give a test sample.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dental Preparations (AREA)

Abstract

According to the present invention, a dental glass ionomer cement liquid is configured to contain a polycarboxylic acid polymer, water and a water reducing agent.

Description

歯科用グラスアイオノマーセメント液及び歯科用グラスアイオノマーセメントDental glass ionomer cement liquid and dental glass ionomer cement
 本発明は、アルミノシリケートガラスを主成分とする歯科用グラスアイオノマーセメント粉末成分と混合して用いる歯科用グラスアイオノマーセメント液、及び歯科用グラスアイオノマーセメントに関する。 The present invention relates to a dental glass ionomer cement liquid used by mixing with a dental glass ionomer cement powder component containing aluminosilicate glass as a main component, and a dental glass ionomer cement.
 歯科用グラスアイオノマーセメントはポリカルボン酸等の酸を主成分としたポリマー酸と、グラスアイオノマーセメント用ガラス粉末とを水の存在下で反応させ硬化させることで使用される。グラスアイオノマーセメントは生体に対する親和性が極めて良好であり、硬化体が半透明で審美性に優れている。また、グラスアイオノマーセメントはエナメル質や象牙質等の歯質に対して優れた接着力を有しており、更にはガラス粉末中にフッ素が含まれている場合にはそのフッ素による抗齲蝕作用があること等の優れた特性を有している。よって、グラスアイオノマーセメントは、歯科分野では齲蝕窩洞の充填,クラウン・インレー・ブリッジや矯正用バンドの合着,窩洞の裏層,根管充填用シーラー,支台築造や予防填塞等に広く使用されている材料である。 Dental glass ionomer cement is used by reacting a polymer acid mainly composed of an acid such as polycarboxylic acid with glass powder for glass ionomer cement in the presence of water to cure. Glass ionomer cement has an extremely good affinity for living organisms, and the cured product is semitransparent and has excellent aesthetics. Further, the glass ionomer cement has an excellent adhesive force to tooth substances such as enamel and dentin, and further, when the glass powder contains fluorine, the anti-caries action by the fluorine is exerted. It has excellent characteristics such as being present. Therefore, glass ionomer cement is widely used in the dental field for filling caries cavities, fusion of crown inlay bridges and orthodontic bands, lining of cavities, sealers for root canal filling, abutment construction and preventive filling. It is a material.
 歯科用グラスアイオノマーセメントの形態としては、フルオロアルミノシリケートガラスを含む粉末成分とポリカルボン酸系重合体を含む液体成分とから構成されるものが一般的である(例えば、特許文献1参照。)。このセメントは、粉末成分と液体成分とを混合練和して練和物とし治療部位に適用した後硬化させて使用する。 The form of dental glass ionomer cement is generally composed of a powder component containing fluoroaluminosilicate glass and a liquid component containing a polycarboxylic acid polymer (see, for example, Patent Document 1). This cement is used by mixing and kneading a powder component and a liquid component into a kneaded product, applying it to a treatment site, and then hardening it.
特開2007-91689号公報JP, 2007-91689, A
 ここで、物理的強度の高い歯科用グラスアイオノマーセメントの硬化体を得るためには、アルミノシリケートガラスを含む粉末成分とポリカルボン酸系重合体を含む液体成分とを混合練和する際に粉末成分の比率を高くすることが考えられる。しかしながら、粉末成分の比率を高くするとセメントの硬化が速くなりすぎて、臨床で使用する際の時間的な余裕がなくなるという問題があった。すなわち、臨床使用上適切な操作余裕時間を確保しながら、物理的強度の高いセメント硬化体を得ることは困難であった。 Here, in order to obtain a hardened body of a dental glass ionomer cement having high physical strength, the powder component when mixing and kneading the powder component containing the aluminosilicate glass and the liquid component containing the polycarboxylic acid polymer. It is possible to increase the ratio of. However, when the ratio of the powder component is increased, the cement hardens too fast, and there is a problem that there is no time margin for clinical use. That is, it has been difficult to obtain a cement hardened product having high physical strength while ensuring an appropriate operating margin for clinical use.
 そこで本発明は、臨床使用上適切な操作余裕時間を確保しながら、物理的強度の高いセメント硬化体が得られる歯科用グラスアイオノマーセメント液を提供することを課題とする。 Therefore, an object of the present invention is to provide a dental glass ionomer cement liquid that can obtain a hardened cement with high physical strength while ensuring an appropriate operating margin for clinical use.
 本発明の一態様は、ポリカルボン酸系重合体、水、及び減水剤を含有する歯科用グラスアイオノマーセメント液である。 One aspect of the present invention is a dental glass ionomer cement liquid containing a polycarboxylic acid polymer, water, and a water reducing agent.
 本発明の一態様に係る歯科用グラスアイオノマーセメント液によれば、臨床使用上適切な操作余裕時間を確保しながら、物理的強度の高いセメント硬化体を得ることが可能となる。 According to the dental glass ionomer cement liquid according to one aspect of the present invention, it is possible to obtain a cement hardened product having high physical strength while ensuring an appropriate operating margin for clinical use.
 次に、本発明を実施するための形態を説明する。
<歯科用グラスアイオノマーセメント液>
 本実施形態の歯科用グラスアイオノマーセメント液は、ポリカルボン酸系重合体、水、及び減水剤を有する。
Next, a mode for carrying out the present invention will be described.
<Dental glass ionomer cement liquid>
The dental glass ionomer cement liquid of the present embodiment has a polycarboxylic acid-based polymer, water, and a water reducing agent.
 ポリカルボン酸系重合体は、後述する粉末成分に含まれるアルミノシリケートガラス粉末との反応のために必要な成分である。歯科用グラスアイオノマーセメント液と粉末成分とを混合し練和することにより、アルミノシリケートガラス粉末から溶出したアルミニウムイオンとポリカルボン酸系重合体の共役塩基がイオン架橋する酸塩基反応が起こり、硬化する。 The polycarboxylic acid polymer is a component necessary for the reaction with the aluminosilicate glass powder contained in the powder component described later. By mixing and kneading the dental glass ionomer cement liquid and the powder component, an acid-base reaction occurs in which the aluminum ion eluted from the aluminosilicate glass powder and the conjugate base of the polycarboxylic acid-based polymer undergo ionic cross-linking and are cured. ..
 ポリカルボン酸系重合体は、α-β不飽和モノカルボン酸又はα-β不飽和ジカルボン酸の重合体である。例えば、アクリル酸,メタクリル酸,2-クロロアクリル酸,3-クロロアクリル酸,アコニット酸,メサコン酸,マレイン酸,イタコン酸,フマール酸,グルタコン酸,シトラコン酸の中から選ばれた1種以上を含む共重合体又は単独重合体がポリカルボン酸系重合体の例として挙げられる。これらは2種類以上用いてもよい。 The polycarboxylic acid type polymer is a polymer of α-β unsaturated monocarboxylic acid or α-β unsaturated dicarboxylic acid. For example, one or more selected from acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, and citraconic acid. Examples of the polycarboxylic acid polymer include a copolymer or a homopolymer containing the same. You may use 2 or more types of these.
 ポリカルボン酸系重合体は、重合可能なエチレン性不飽和二重結合を含まないものであることが好ましい。 The polycarboxylic acid polymer preferably does not contain a polymerizable ethylenically unsaturated double bond.
 ポリカルボン酸系重合体は、質量平均分子量が5,000~40,000であるものが好ましい。質量平均分子量が5,000以上であると、硬化体の物理的強度が高くなり、また歯質への接着力も向上する。質量平均分子量が40,000以下であると、歯科用グラスアイオノマーセメント液が適度な粘度となり練和しやすくなる。 The polycarboxylic acid polymer preferably has a mass average molecular weight of 5,000 to 40,000. When the mass average molecular weight is 5,000 or more, the physical strength of the cured product is increased and the adhesive force to the tooth structure is also improved. When the mass average molecular weight is 40,000 or less, the dental glass ionomer cement liquid has an appropriate viscosity and is easily kneaded.
 ポリカルボン酸系重合体の配合量は、歯科用グラスアイオノマーセメント液中に5~60質量%であることが好ましい。ポリカルボン酸系重合体の配合量が5質量%以上であると、歯科用グラスアイオノマーセメントとしての特徴である歯質接着性が向上する。ポリカルボン酸系重合体の配合量が60質量%以下であると硬化体の耐久性が向上する。より好ましくは、20~50質量%である。 The blending amount of the polycarboxylic acid polymer is preferably 5 to 60% by mass in the dental glass ionomer cement liquid. When the blending amount of the polycarboxylic acid-based polymer is 5% by mass or more, the dentin adhesion, which is a characteristic of a dental glass ionomer cement, is improved. When the blending amount of the polycarboxylic acid polymer is 60% by mass or less, the durability of the cured product is improved. More preferably, it is 20 to 50% by mass.
 水は、アルミノシリケートガラス粉末とポリカルボン酸系重合体との酸塩基反応のために必要な成分である。 Water is a necessary component for acid-base reaction between aluminosilicate glass powder and polycarboxylic acid type polymer.
 水の配合量は、他の成分の残部であればよいが、歯科用グラスアイオノマーセメント液中に30~80質量%であることが好ましい。水の配合量が30質量%以上であると、練和性が向上する。水の配合量が80質量%以下であると、硬化体の物理的強度が高くなる。より好ましくは、40~70質量%である。 The water content may be the balance of the other components, but it is preferably 30 to 80% by mass in the dental glass ionomer cement liquid. When the amount of water is 30% by mass or more, the miscibility is improved. When the blending amount of water is 80% by mass or less, the physical strength of the cured product becomes high. More preferably, it is 40 to 70% by mass.
 減水剤は、歯科用グラスアイオノマーセメント液及び粉末成分との混合練和による酸塩基反応において、粉末成分の比率を高くしても、セメントの硬化が速くなりすぎることを抑制する効果をもたらす。 The water-reducing agent has the effect of preventing the cement from hardening too fast even if the ratio of the powder component is increased in the acid-base reaction by mixing and kneading the dental glass ionomer cement liquid and the powder component.
 減水剤としては、例えば、リグニンスルホン酸塩系,オキシカルボン酸塩系,ナフタレンスルホン酸塩系,メラミンスルホン酸塩系,ポリスチレンスルホン酸塩系,ポリカルボン酸塩系等の減水剤が挙げられる。 Examples of the water reducing agent include lignin sulfonate-based, oxycarboxylate-based, naphthalene sulfonate-based, melamine sulfonate-based, polystyrene sulfonate-based, and polycarboxylate-based water reducing agents.
 より具体的には、例えば、リグニンスルホン酸塩,オキシカルボン酸塩,ナフタレンスルホン酸塩,メラミンスルホン酸塩,ポリスチレンスルホン酸塩,ポリカルボン酸塩等の減水剤が挙げられる。 More specifically, examples thereof include water reducing agents such as lignin sulfonate, oxycarboxylate, naphthalene sulfonate, melamine sulfonate, polystyrene sulfonate, and polycarboxylate.
 ポリカルボン酸塩系の減水剤としては、α-β不飽和モノカルボン酸の重合体からなる構造単位、若しくはα-β不飽和ジカルボン酸の重合体からなる構造単位を含む重合体又は共重合体であることが好ましく、これらは水溶性塩であってもよい。 The polycarboxylic acid salt-based water reducing agent is a polymer or copolymer containing a structural unit composed of a polymer of α-β unsaturated monocarboxylic acid or a structural unit composed of a polymer of α-β unsaturated dicarboxylic acid. Are preferable, and these may be water-soluble salts.
 ポリカルボン酸塩系の減水剤としてより具体的には、例えば、炭素数が5~6の鎖状オレフィンとエチレン性不飽和カルボン酸無水物との共重合体の水溶性塩、ポリアルキレングリコールモノ(メタ)アクリル酸エステルと(メタ)アクリル酸との共重合体の水溶性塩、末端にスルホン基を有する(メタ)アクリル酸アミドとアクリル酸エステルと(メタ)アクリル酸との共重合体の水溶性塩、スルホン基を有する単量体と(メタ)アクリル酸とその他の単量体の共重合体の水溶性塩、スルホン基で置換された芳香族環を有する単量体とマレイン酸との共重合体の水溶性塩、末端にスルホン基を有する単量体とポリアルキレングリコールモノ(メタ)アクリル酸エステルとポリアルキレングリコールモノ(メタ)アクリル酸エーテルと(メタ)アクリル酸との共重合体の水溶性塩、及びポリオキシエチレン鎖を有する単量体と(メタ)アクリル酸との共重合体の水溶性塩等が挙げられる。これらは2種以上用いてもよい。 More specifically, the polycarboxylic acid salt-based water reducing agent is, for example, a water-soluble salt of a copolymer of a chain olefin having 5 to 6 carbon atoms and an ethylenically unsaturated carboxylic acid anhydride, polyalkylene glycol mono A water-soluble salt of a copolymer of (meth)acrylic acid ester and (meth)acrylic acid, a copolymer of (meth)acrylic acid amide having a sulfone group at the terminal, an acrylic acid ester and (meth)acrylic acid Water-soluble salts, monomers having a sulfone group, water-soluble salts of copolymers of (meth)acrylic acid and other monomers, monomers having an aromatic ring substituted with a sulfone group, and maleic acid Of water-soluble salts of copolymers, copolymers of monomers having a sulfo group at the end, polyalkylene glycol mono(meth)acrylic acid ester, polyalkylene glycol mono(meth)acrylic acid ether and (meth)acrylic acid Examples thereof include a water-soluble salt of a combination and a water-soluble salt of a copolymer of a monomer having a polyoxyethylene chain and (meth)acrylic acid. You may use 2 or more types of these.
 上記において、ポリオキシエチレン鎖は(-(OC2H4)n-H))と表すことができる。ここでnはポリオキシエチレン単位構造の繰り返し数であり、50~200の範囲であることが好ましく、nが80~190であることがより好ましく、nが120~180であることがさらに好ましい。 In the above, the polyoxyethylene chain can be represented as (-(OC2H4)nH)). Here, n is the number of repeating polyoxyethylene unit structures, preferably in the range of 50 to 200, more preferably in the range of 80 to 190, and further preferably in the range of 120 to 180.
 ポリカルボン酸塩系の減水剤の市販品としては、例えば、Melflux(登録商標。以下同様。) AP 101F、Melflux 2641F、Melflux 2651F、Melflux 5581F、Melflux 4930F、Melflux 6681F、Melflux BF 11F、Melflux BF 11F(FM)(以上、SKWイーストアジア製)等が挙げられる。 Examples of commercially available polycarboxylate-based water reducing agents include, for example, Melflux (registered trademark; the same applies below) AP 101F, Melflux 2641F, Melflux 2651F, Melflux 5581F, Melflux 4930F, Melflux 6681F, MelfluxBflux BF 11 and Melflux BFlu. (FM) (above, manufactured by SKW East Asia) and the like.
 メラミンスルホン酸塩系の減水剤の市販品としては、例えば、MELMENT F10M、MELMENT F4000(以上、SKWイーストアジア製)等が挙げられる。 Examples of commercially available melamine sulfonate-based water reducing agents include MELMENT F10M and MELMENT F4000 (above, manufactured by SKW East Asia).
 ナフタレンスルホン酸塩系の減水剤の市販品としては、例えば、POWERCON-100(SKWイーストアジア製)等が挙げられる。 Examples of commercially available naphthalene sulfonate-based water reducing agents include POWERCON-100 (manufactured by SKW East Asia).
 リグニンスルホン酸塩系の減水剤の市販品としては、例えば、SODIUM LIGNOSULFNATE ARBO N18、NORLIG SA(以上、SKWイーストアジア製)等が挙げられる。 Examples of commercially available lignin sulfonate-based water reducing agents include SODIUM LIGNOSULFNATER ARBO N18, NORLIG SA (above, manufactured by SKW East Asia), and the like.
 減水剤の配合量は、歯科用グラスアイオノマーセメント液中に0.01~10質量%であることが好ましい。減水剤の配合量が0.01質量%以上であるとセメントの硬化が速くなりすぎることが抑制されて操作余裕時間が長くなる。減水剤の配合量が10質量%以下であると臨床使用上の操作性を確保しやすくなる。減水剤の配合量はより好ましくは0.1~5質量%であり、さらに好ましくは0.5~3.5質量%である。 The blending amount of the water reducing agent is preferably 0.01 to 10% by mass in the dental glass ionomer cement liquid. When the blending amount of the water reducing agent is 0.01% by mass or more, it is possible to prevent the cement from being hardened too quickly, and the operation allowance time becomes long. When the blending amount of the water reducing agent is 10% by mass or less, it becomes easy to secure operability in clinical use. The compounding amount of the water reducing agent is more preferably 0.1 to 5% by mass, further preferably 0.5 to 3.5% by mass.
 本実施形態の歯科用グラスアイオノマーセメント液は、さらにpH緩衝成分を含んでもよい。歯科用グラスアイオノマーセメント液がpH緩衝成分を含むことにより、低いpH(酸性条件)を維持しやすくなり、硬化反応が円滑に進行しやすくなる。 The dental glass ionomer cement liquid of the present embodiment may further contain a pH buffer component. When the dental glass ionomer cement liquid contains the pH buffer component, it becomes easy to maintain a low pH (acidic condition), and the curing reaction easily proceeds smoothly.
 pH緩衝成分としては、酒石酸、クエン酸、リンゴ酸、エチレンジアミン四酢酸、乳酸、酪酸、バルビツール酸、リン酸、酢酸、及びシュウ酸、並びにこれらの水溶性塩(例えば、ナトリウム塩、カリウム塩等)等が挙げられる。これらは2種以上併用してもよい。 As the pH buffer component, tartaric acid, citric acid, malic acid, ethylenediaminetetraacetic acid, lactic acid, butyric acid, barbituric acid, phosphoric acid, acetic acid, and oxalic acid, and water-soluble salts thereof (for example, sodium salt, potassium salt, etc.) ) And the like. You may use these 2 or more types together.
 pH緩衝成分を含有する場合の配合量は、歯科用グラスアイオノマーセメント液中に0.1~10質量%であることが好ましい。pH緩衝成分の配合量が0.1質量%以上であると臨床使用上の操作余裕時間を確保しやすいという利点がある。pH緩衝成分の配合量が15質量%以下であるとシャープに硬化するという利点がある。pH緩衝成分の配合量はより好ましくは1~10質量%である。 When the pH buffer component is contained, the blending amount is preferably 0.1 to 10% by mass in the dental glass ionomer cement liquid. When the blending amount of the pH buffer component is 0.1% by mass or more, there is an advantage that it is easy to secure a margin for operation in clinical use. If the blending amount of the pH buffer component is 15% by mass or less, there is an advantage that it is sharply cured. The blending amount of the pH buffer component is more preferably 1 to 10% by mass.
 本実施形態の歯科用グラスアイオノマーセメント液には、さらにシリカ等の充填材、(メタ)アクリレート、増粘剤等を配合することも可能である。これにより性状をペーストにすることが可能であり、操作性を向上させることができる。 The dental glass ionomer cement liquid of this embodiment may further contain a filler such as silica, a (meth)acrylate, a thickener and the like. As a result, the property can be changed to paste and the operability can be improved.
 なお本願明細書及び特許請求の範囲において、(メタ)アクリレートとは、アクリレート又はメタクリレートの各種モノマー、オリゴマーあるいはプレポリマーを意味し、(メタ)アクリロイルオキシ基を1個以上有する。また、(メタ)アクリロイルオキシ基とは、メタクリロイルオキシ基及び/又はアクリロイルオキシ基を意味する。
<粉末成分>
 粉末成分は、本実施形態に係る歯科用グラスアイオノマーセメント液と混合して用いられ、歯科用グラスアイオノマーセメントの硬化体を与える。
In the present specification and claims, (meth)acrylate means various monomers, oligomers or prepolymers of acrylate or methacrylate, and has one or more (meth)acryloyloxy groups. The (meth)acryloyloxy group means a methacryloyloxy group and/or an acryloyloxy group.
<Powder component>
The powder component is used by mixing with the dental glass ionomer cement liquid according to the present embodiment, and gives a hardened body of the dental glass ionomer cement.
 粉末成分は、アルミノシリケートガラス粉末を含む。 Powder components include aluminosilicate glass powder.
 アルミノシリケートガラス粉末は、ガラスを構成する成分としてアルミニウム及びケイ素を含む。このため、歯科用グラスアイオノマーセメント液と粉末成分を混合すると、アルミノシリケートガラス粉末とポリカルボン酸系重合体の酸塩基反応が発生する。この酸塩基反応により、アルミノシリケートガラス粉末から溶出したアルミニウムイオンとポリカルボン酸系重合体の共役塩基がイオン架橋し、硬化する。 The aluminosilicate glass powder contains aluminum and silicon as constituents of glass. Therefore, when the dental glass ionomer cement liquid and the powder component are mixed, an acid-base reaction between the aluminosilicate glass powder and the polycarboxylic acid-based polymer occurs. By this acid-base reaction, aluminum ions eluted from the aluminosilicate glass powder and the conjugate base of the polycarboxylic acid-based polymer are ionically cross-linked and cured.
 アルミノシリケートガラス粉末は、ガラスを構成する成分としてさらにフッ素を含む、フルオロアルミノシリケートガラスであることが好ましい。フッ素を含むことにより歯科用グラスアイオノマーセメントのう蝕防止効果が向上する。 The aluminosilicate glass powder is preferably a fluoroaluminosilicate glass, which further contains fluorine as a constituent of the glass. The inclusion of fluorine improves the dental caries preventive effect of the dental glass ionomer cement.
 アルミノシリケートガラス粉末は、ガラスを構成する成分としてさらにカルシウム、リン、ストロンチウム、ランタン、ナトリウム、カリウム、窒素、マグネシウムバリウム、リン、ホウ素、ジルコニウム、タンタル等を含んでもよい。 The aluminosilicate glass powder may further contain calcium, phosphorus, strontium, lanthanum, sodium, potassium, nitrogen, magnesium barium, phosphorus, boron, zirconium, tantalum, etc. as a constituent of the glass.
 アルミノシリケートガラス粉末の粒径は、平均粒径が0.02~20μmであることが好ましい。平均粒径が20μmを越えると充填用セメントとして使用する際の舌触りが悪くなったり、耐摩耗性が低下したりする傾向がある。一方、平均粒径が0.02μm未満の微粉では練和が極端に困難となり操作性が低下する傾向がある。なお、この平均粒径とは、長径と短径の平均値(長短平均径)である。 The average particle size of the aluminosilicate glass powder is preferably 0.02 to 20 μm. If the average particle size exceeds 20 μm, the texture of the cement when used as a filling cement tends to be poor and the abrasion resistance tends to deteriorate. On the other hand, fine powders having an average particle size of less than 0.02 μm tend to be extremely difficult to knead and the operability tends to deteriorate. In addition, this average particle diameter is an average value of the long diameter and the short diameter (long and short average diameter).
 アルミノシリケートガラス粉末の屈折率ndは、1.42~1.47の範囲にあることが好ましい。屈折率ndがこの範囲内であれば、実使用上有用な歯科用グラスアイオノマーセメントのマトリックス成分の屈折率nd(約1.42)との差が小さくなり、得られる歯科用グラスアイオノマーセメント硬化体の透明性が高くなる。 The refractive index nd of the aluminosilicate glass powder is preferably in the range of 1.42 to 1.47. When the refractive index nd is within this range, the difference from the refractive index nd (about 1.42) of the matrix component of the dental glass ionomer cement that is practically useful is small, and the obtained cured dental glass ionomer cement is obtained. Transparency is increased.
 粉末成分は、歯科用グラスアイオノマーセメント液と同様に、さらにポリカルボン酸粉末を含んでもよい。粉末成分もポリカルボン酸粉末を含むことにより、操作性が向上する。 Like the dental glass ionomer cement liquid, the powder component may further contain polycarboxylic acid powder. By including the polycarboxylic acid powder in the powder component, the operability is improved.
 粉末成分中にポリカルボン酸粉末が含有される場合のポリカルボン酸粉末の配合量は0.1~10質量%であることが好ましい。 When the polycarboxylic acid powder is contained in the powder component, the compounding amount of the polycarboxylic acid powder is preferably 0.1 to 10 mass %.
 本実施形態の粉末成分に、さらに水や(メタ)アクリレート等を配合させてもよい。これにより性状をペーストにすることが可能であり、操作性を向上させることができる。 The water and (meth)acrylate may be further mixed with the powder component of this embodiment. As a result, the property can be changed to paste and the operability can be improved.
 本実施形態の歯科用グラスアイオノマーセメント液、及び粉末成分の少なくとも一方が(メタ)アクリレートを含む場合、さらに歯科用グラスアイオノマーセメント液、及び粉末成分の少なくとも一方に重合開始剤や光重合開始剤を配合させてもよい。これにより、光照射等により(メタ)アクリレートを重合させることが可能なレジン強化型グラスアイオノマーセメントとすることができ、さらに物理的強度の高いセメント硬化体を得ることができる。 Dental glass ionomer cement liquid of the present embodiment, when at least one of the powder component contains (meth) acrylate, further dental glass ionomer cement liquid, and at least one of the powder component a polymerization initiator or a photopolymerization initiator You may mix. As a result, a resin-reinforced glass ionomer cement capable of polymerizing (meth)acrylate by light irradiation or the like can be obtained, and a cement hardened product having higher physical strength can be obtained.
 本実施形態の歯科用グラスアイオノマーセメント液、及び粉末成分の少なくとも一方には、必要に応じて、さらに造影剤、抗菌剤、蛍光剤、香料、顔料等を適宜配合することができる。 At least one of the dental glass ionomer cement liquid of the present embodiment and the powder component can be appropriately blended with a contrast agent, an antibacterial agent, a fluorescent agent, a fragrance, a pigment, etc., if necessary.
 <歯科用グラスアイオノマーセメントの練和物の調製>
 歯科用グラスアイオノマーセメントの練和物を調製する際の、歯科用グラスアイオノマーセメント液に対する粉末成分の質量比(粉液比)は、1~5であることが好ましい。粉液比が1以上であると、歯科用セメントの硬化体の物理的強度が向上する。粉液比が5以下であると、歯科用セメントの操作性が向上する。より好ましい粉液比は3~4.5であり、さらに好ましい粉液比は3.2~4である。
<Preparation of Kneaded Dental Glass Ionomer Cement>
The mass ratio (powder-liquid ratio) of the powder component to the dental glass ionomer cement liquid when preparing a kneaded product of the dental glass ionomer cement is preferably 1 to 5. When the powder-liquid ratio is 1 or more, the physical strength of the hardened dental cement is improved. When the powder-liquid ratio is 5 or less, the operability of the dental cement is improved. A more preferable powder-liquid ratio is 3 to 4.5, and a further preferable powder-liquid ratio is 3.2 to 4.
 歯科用グラスアイオノマーセメントは、粉末成分と液体成分とを混合練和して練和物とし治療部位に適用した後硬化させて使用する。ここで、練和物が硬化体となるまでに、スパチュラ等で練和物を治療部位まで移動させ、さらに形態を整える必要がある。  Dental glass ionomer cement is used by mixing and kneading a powder component and a liquid component into a kneaded product, applying it to the treatment site, and then hardening it. Here, it is necessary to move the kneaded product to a treatment site with a spatula or the like to further shape the kneaded product before it becomes a cured product.
 本発明においては、練和物の形態を整えることができなくなるまでの練和開始からの時間を「操作余裕時間」と定義する。 In the present invention, the time from the start of kneading until the shape of the kneading cannot be adjusted is defined as "operation allowance time".
 臨床使用上適切な操作余裕時間としては、例えば、75秒以上600秒(10分)以下であり、より好ましくは90秒以上360秒(6分)以下である。 The appropriate operation allowance time for clinical use is, for example, 75 seconds or more and 600 seconds (10 minutes) or less, and more preferably 90 seconds or more and 360 seconds (6 minutes) or less.
 以下、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
<アルミノシリケートガラス粉末の作製>
 シリカ27.5g、アルミナ12.7g、フッ化アルミニウム16.7g、フッ化ストロンチウム18.6g、リン酸アルミニウム8.8g、フッ化ナトリウム4.2g、フッ化カリウム5.6g、フッ化ランタン5.9gを乳鉢で十分に混合した。得られた混合物を磁性坩堝に入れて電気炉内に静置した。電気炉を昇温し1300℃で溶解して十分均質化した後、水中に流し出し塊状のアルミノシリケートガラスとした。得られた塊状のガラスをボールミルで20時間粉砕した後、120メッシュの篩を通過させ、アルミノシリケートガラス粉末を得た。
<粉末成分の調製>
 前記アルミノシリケートガラス粉末100質量部に対して、1%リン酸アルミニウム水溶液100質量部を混合しスラリーを作製し120℃で乾燥させた。得られた粉末に対して、ポリアクリル酸粉末(平均分子量:30,000)を3質量%となるように混合し、粉末成分を得た。
<歯科用グラスアイオノマーセメント液の調製>
 表1に示した配合にて各成分を混合し、実施例1~13、比較例1,2の歯科用グラスアイオノマーセメント液を調製した。なお、配合量の単位は質量%である。
<Preparation of aluminosilicate glass powder>
Silica 27.5 g, alumina 12.7 g, aluminum fluoride 16.7 g, strontium fluoride 18.6 g, aluminum phosphate 8.8 g, sodium fluoride 4.2 g, potassium fluoride 5.6 g, lanthanum fluoride 5. 9 g was thoroughly mixed in a mortar. The obtained mixture was put in a magnetic crucible and allowed to stand in an electric furnace. After heating the electric furnace to melt at 1300° C. and homogenizing sufficiently, it was poured into water to obtain a lump of aluminosilicate glass. The obtained lumpy glass was crushed with a ball mill for 20 hours and then passed through a 120-mesh sieve to obtain an aluminosilicate glass powder.
<Preparation of powder component>
100 parts by mass of 1% aluminum phosphate aqueous solution was mixed with 100 parts by mass of the aluminosilicate glass powder to prepare a slurry, which was dried at 120°C. Polyacrylic acid powder (average molecular weight: 30,000) was mixed with the obtained powder in an amount of 3% by mass to obtain a powder component.
<Preparation of dental glass ionomer cement liquid>
The ingredients were mixed in the formulations shown in Table 1 to prepare dental glass ionomer cement solutions of Examples 1 to 13 and Comparative Examples 1 and 2. The unit of the blending amount is mass%.
 なお、表1中の成分の詳細は以下のとおりである。
ポリアクリル酸粉末: 平均分子量25,000のポリアクリル酸粉末(富士フイルム和光純薬製)
Melflux 5581F: SKWイーストアジア製のポリオキシエチレン鎖を有するメタクリル酸とアクリル酸との共重合体の水溶性塩
Melflux 4930F: SKWイーストアジア製のポリオキシエチレン鎖を有するメタクリル酸とアクリル酸との共重合体の水溶性塩
Melment F4000: SKWイーストアジア製のポリオキシエチレン鎖を有するメタクリル酸とアクリル酸との共重合体の水溶性塩
 <操作余裕時間>
 23℃、50%RHに調整した恒温室内にて、実施例1~13、比較例1,2の歯科用グラスアイオノマーセメント液、及び粉末成分を表1に示した粉液比にて、スパチュラを用いて混合し、30秒間練和した。
The details of the components in Table 1 are as follows.
Polyacrylic acid powder: Polyacrylic acid powder having an average molecular weight of 25,000 (manufactured by FUJIFILM Wako Pure Chemical Industries)
Melflux 5581F: Water-soluble salt of methacrylic acid-acrylic acid copolymer having polyoxyethylene chain having SKW East Asia Melflux 4930F: methacrylic acid having polyoxyethylene chain having acrylic acid and made of SKW East Asia Water-soluble salt of polymer Melment F4000: Water-soluble salt of copolymer of methacrylic acid and acrylic acid having polyoxyethylene chain manufactured by SKW East Asia <Operation allowance time>
In a thermostatic chamber adjusted to 23° C. and 50% RH, a spatula was prepared by mixing the dental glass ionomer cement liquids of Examples 1 to 13 and Comparative Examples 1 and 2 and the powder components with the powder-liquid ratio shown in Table 1. Used and mixed for 30 seconds.
 練和物を一塊に集め、練和開始から75秒後にスパチュラを付着させて引っ張り上げた際の付着具合を確認した。以後7.5秒毎にスパチュラへの付着具合を確認し、練和物がスパチュラに付着しなくなるか、付着しても練和物の形態を整えることができなくなった練和開始からの時間を操作余裕時間とした。  The kneaded product was collected in a lump, and after 75 seconds from the start of kneading, a spatula was attached and the adhesion condition when pulled up was confirmed. After that, check the state of adhesion to the spatula every 7.5 seconds, and if the kneaded product does not adhere to the spatula, or if it does not adjust the form of the kneaded product, the time from the start of kneading The operation allowance was set.
 操作余裕時間の判定基準は以下の通りである。 ㆍThe criteria for determining the operation allowance time are as follows.
 優:操作余裕時間が90秒以上360秒(6分)以下である場合
 良:操作余裕時間が75秒以上90秒未満である場合、又は、360秒を超え、600秒(10分)以下である場合
 不可:操作余裕時間が75秒未満である場合、又は、600秒を超える場合
 <三点曲げ強度試験>
 実施例1~13、比較例1,2の歯科用グラスアイオノマーセメント液、及び粉末成分を表1に示した粉液比にて混合し練和した。練和物を2mm×2mm×25mmの空洞が作られたステンレス型内に填入し、セロファンを介してガラス板にて圧接し、1時間後に取り出して角柱型の硬化体を得た。得られた硬化体を37℃の蒸留水に24時間浸漬した後、#320の耐水研磨紙で研磨して試験体とした。
Excellent: When the operation allowance time is 90 seconds or more and 360 seconds (6 minutes) or less Good: When the operation allowance time is 75 seconds or more and less than 90 seconds, or when the operation allowance time is more than 360 seconds and 600 seconds (10 minutes) or less If yes: Operation margin time is less than 75 seconds or more than 600 seconds <Three-point bending strength test>
Dental glass ionomer cement liquids of Examples 1 to 13 and Comparative Examples 1 and 2 and powder components were mixed and kneaded at a powder-liquid ratio shown in Table 1. The kneaded product was filled in a stainless steel mold having a cavity of 2 mm×2 mm×25 mm, pressed with a glass plate through a cellophane, and taken out after 1 hour to obtain a prismatic cured product. The obtained cured product was immersed in distilled water at 37° C. for 24 hours and then polished with a #320 water-resistant polishing paper to give a test sample.
 得られた試験体について、万能試験機(商品名:オートグラフ,島津製作所社製)を使用してクロスヘッドスピード1mm/min.にて三点曲げ強度試験を行った。 About the obtained test piece, crosshead speed of 1 mm/min. was measured using a universal testing machine (trade name: Autograph, manufactured by Shimadzu Corporation). A three-point bending strength test was conducted.
 三点曲げ強度の判定基準は、以下の通りである。 The criteria for three-point bending strength are as follows.
 優:三点曲げ強度が40MPa以上である場合
 良:三点曲げ強度が35MPa以上40MPa未満である場合
 不可:三点曲げ強度が35MPa未満である場合
 表1に、操作余裕時間及び三点曲げ強度試験の評価結果を示す。
Excellent: When the three-point bending strength is 40 MPa or more Good: When the three-point bending strength is 35 MPa or more and less than 40 MPa Not possible: When the three-point bending strength is less than 35 MPa Table 1 shows the operation allowance time and the three-point bending strength. The evaluation results of the test are shown.
Figure JPOXMLDOC01-appb-T000001
 表1より、実施例1~13の歯科用グラスアイオノマーセメント液を用いた場合には、操作余裕時間、三点曲げ強度の何れの評価結果も優又は良となった。この結果より、臨床使用上適切な操作余裕時間を確保しながら、物理的強度の高いセメント硬化体が得られることがわかる。
Figure JPOXMLDOC01-appb-T000001
From Table 1, when the dental glass ionomer cement solutions of Examples 1 to 13 were used, the evaluation results of the operation allowance time and the three-point bending strength were both excellent and good. From these results, it can be seen that a cement hardened product having high physical strength can be obtained while ensuring an adequate operating margin for clinical use.
 一方、比較例の歯科用グラスアイオノマーセメント液を用いた場合について、粉液比が3.4の場合には、三点曲げ強度が低い結果となった(比較例1)。また、粉液比が3.8の場合には、硬化が速すぎて練和すること自体出来ず、操作余裕時間及び三点曲げ強度の測定もできなかった(比較例2)。 On the other hand, in the case of using the dental glass ionomer cement liquid of Comparative Example, when the powder-liquid ratio was 3.4, the three-point bending strength was low (Comparative Example 1). Further, when the powder-liquid ratio was 3.8, the curing was too fast to carry out the kneading itself, and the operation allowance time and the three-point bending strength could not be measured (Comparative Example 2).
 以上、本発明を実施形態に基づいて説明したが、本発明は上記実施形態に限定されるものではなく、特許請求の範囲に記載の範囲内で様々な変形が可能である。 The present invention has been described above based on the embodiment, but the present invention is not limited to the above embodiment, and various modifications can be made within the scope of the claims.
 本願は、日本特許庁に2019年1月30日に出願された基礎出願2019-013735号の優先権を主張するものであり、その全内容を参照によりここに援用する。 This application claims the priority of the basic application 2019-013735 filed on January 30, 2019 to the Japan Patent Office, the entire contents of which are incorporated herein by reference.

Claims (2)

  1.  ポリカルボン酸系重合体、水、及び減水剤を含有する歯科用グラスアイオノマーセメント液。 Dental glass ionomer cement liquid containing a polycarboxylic acid polymer, water, and a water reducing agent.
  2.  ポリカルボン酸系重合体、水、減水剤、及びアルミノシリケートガラスを含有する歯科用グラスアイオノマーセメント。 Dental glass ionomer cement containing polycarboxylic acid polymer, water, water reducing agent, and aluminosilicate glass.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52101893A (en) * 1976-02-24 1977-08-26 Nippon Kayaku Kk Liquid hardener for dental glass ionomer cement
JP2003183112A (en) * 2001-12-17 2003-07-03 Gc Corp Pasty glass ionomer cement composition for dental use
JP2007091607A (en) * 2005-09-27 2007-04-12 Gc Corp Paste-based glass ionomer cement composition for dentistry
JP2011506367A (en) * 2007-12-14 2011-03-03 デンツプライ デトレイ ゲー.エム.ベー.ハー. Curing composition
JP2017061629A (en) * 2015-09-25 2017-03-30 旭化成株式会社 Viscous curing agent composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013053075A (en) * 2011-09-01 2013-03-21 Gc Corp Dental cement composition
JP6734659B2 (en) * 2016-02-15 2020-08-05 株式会社松風 Sealer composition for root canal filling

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52101893A (en) * 1976-02-24 1977-08-26 Nippon Kayaku Kk Liquid hardener for dental glass ionomer cement
JP2003183112A (en) * 2001-12-17 2003-07-03 Gc Corp Pasty glass ionomer cement composition for dental use
JP2007091607A (en) * 2005-09-27 2007-04-12 Gc Corp Paste-based glass ionomer cement composition for dentistry
JP2011506367A (en) * 2007-12-14 2011-03-03 デンツプライ デトレイ ゲー.エム.ベー.ハー. Curing composition
JP2017061629A (en) * 2015-09-25 2017-03-30 旭化成株式会社 Viscous curing agent composition

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