JP3421072B2 - Dental filling composition - Google Patents

Dental filling composition

Info

Publication number
JP3421072B2
JP3421072B2 JP06272493A JP6272493A JP3421072B2 JP 3421072 B2 JP3421072 B2 JP 3421072B2 JP 06272493 A JP06272493 A JP 06272493A JP 6272493 A JP6272493 A JP 6272493A JP 3421072 B2 JP3421072 B2 JP 3421072B2
Authority
JP
Japan
Prior art keywords
particles
weight
filling composition
inorganic filler
spherical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP06272493A
Other languages
Japanese (ja)
Other versions
JPH06247825A (en
Inventor
哲朗 太田
裕之 佐々木
道弘 池田
英次 服部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to JP06272493A priority Critical patent/JP3421072B2/en
Publication of JPH06247825A publication Critical patent/JPH06247825A/en
Application granted granted Critical
Publication of JP3421072B2 publication Critical patent/JP3421072B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、歯科用充填組成物に係
り、更に詳細には、無機質充填材の充填量が高く、硬化
物の表面平滑性、光沢及び透明性等の審美性、機械的強
度及び耐久性に優れ、加えて優れたX線不透過性を有す
る歯科用充填組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental filling composition, and more specifically, it has a high filling amount of an inorganic filler, and the surface smoothness, gloss and transparency of the cured product, and the aesthetics and mechanical properties. TECHNICAL FIELD The present invention relates to a dental filling composition having excellent mechanical strength and durability, and also having excellent radiopacity.

【0002】[0002]

【従来の技術】近年、重合可能な単量体と無機質充填材
とよりなる歯科用充填組成物が、各種歯牙欠損部の修復
に広く用いられている。かかる歯科用充填組成物は、ア
クリル系単量体とシリカ又は各種ガラス粉末等の無機質
充填材とよりなり、これら充填組成物の性能が、無機質
充填材の組成,形状,粒子径,粒径分布及び充填量によ
り、大きく影響を受けるため、各種の無機質充填材が従
来より提案されている。当初、無機質充填材としては、
粒子径5〜100μmの粉末が使用され、機械的強度に
問題は認められなかったが、大きな粒子の存在により、
滑らかな表面が得られず、審美性の点で不満が残った。
一方、滑らかな表面を得るため粒子径0.01〜0.0
3μmの合成された超微粒子シリカの使用も提案された
が、充填量がたかだか50重量%で、機械的強度及び耐
久性には問題が多く、十分な満足は得られなかった。
2. Description of the Related Art In recent years, a dental filling composition comprising a polymerizable monomer and an inorganic filler has been widely used for repairing various tooth defects. Such a dental filling composition is composed of an acrylic monomer and an inorganic filler such as silica or various glass powders, and the performance of these filling compositions depends on the composition, shape, particle size, and particle size distribution of the inorganic filler. Also, various inorganic fillers have been conventionally proposed because they are greatly affected by the filling amount. Initially, as the inorganic filler,
A powder having a particle size of 5 to 100 μm was used, and no problem was found in mechanical strength, but due to the presence of large particles,
A smooth surface was not obtained and dissatisfaction remained in terms of aesthetics.
On the other hand, in order to obtain a smooth surface, the particle size is 0.01 to 0.0
The use of 3 μm synthesized ultrafine particle silica was also proposed, but the filling amount was at most 50% by weight, and there were many problems in mechanical strength and durability, and sufficient satisfaction was not obtained.

【0003】近年、充填量が高く、機械的強度も優れて
いる無機質充填材として、粒子径10μm以下に調製し
た破砕天然シリカと超微粒子シリカとを併用するハイブ
リッドタイプが提案されている。この場合、確かに機械
的強度及び耐久性は高く、粒子径10μm以下に調製さ
れているため硬化物もある程度の表面平滑性を有してい
るが、なお天然歯に匹敵する審美性とは言い難く、加え
てシリカの使用ではX線不透過性も不十分である。ま
た、粒子径が0.1〜1.0μmの範囲にある球形状の
シリカの使用が、審美性及び機械的強度に優れた歯科用
充填組成物を与えるとの提案も成されている(特開昭5
8−41810)。この場合、比較的小さな粒子の使用
により表面平滑性及び光沢は満足できるが、充填量はた
かだか75重量%であり、機械的強度も低く、かつ吸水
性が高くなり耐久性にも問題が残る。加えて、シリカ
は、X線不透過性はないうえ、重合したアクリル系モノ
マーとの屈折率との屈折率の差が大きく、天然歯なみの
透明性を得るのも困難であった。更に、良好な透明性を
得るために、シリカと周期律表第IV族金属の酸化物を主
な構成成分とする粒子径0.1〜1.0μmの球形状の
無機酸化物の使用が提案されている(特開昭62−89
701)。この場合、屈折率の調整により透明性は良好
で、かつ表面平滑性及び光沢も問題なく、加えて、ジル
コニア等を用いればX線不透過性も満足できる。しか
し、充填量はやはり75重量%に達せず、曲げ強度はた
かだか900kg/cm2 と機械的強度は低い。更に、
粒子径1〜100μmの粒子と前記の粒子径0.1〜
1.0μmの球形状粒子の併用により、流動性を改良
し、かつ、象牙細管等の細管内部への充填材含有量を高
めるとの提案も成されている(特開昭61−14810
9)。しかるに、この提案は流動性及び細管内部への高
充填材含有量が目的であり、曲げ強度はたかだか100
0kg/cm2 と機械的強度は低く、また、平均粒子径
のかなり大きな粒子の使用より推察すると、表面平滑性
も前述したハイブリッドタイプ同様不満足なものであ
る。以上に述べた如く、硬化物の機械的強度と天然歯に
匹敵する審美性を有し、さらに、臨床上必要な優れたX
線不透過性を有する歯科用充填組成物は、未だ得られて
いない。
In recent years, as an inorganic filler having a high filling amount and excellent mechanical strength, a hybrid type using a combination of crushed natural silica having a particle diameter of 10 μm or less and ultrafine silica has been proposed. In this case, the mechanical strength and durability are certainly high, and the cured product has a certain level of surface smoothness because it is prepared with a particle size of 10 μm or less, but it is still said that the aesthetics are comparable to those of natural teeth. Difficulty, and in addition, the use of silica causes insufficient radiopacity. It has also been proposed that the use of spherical silica having a particle size in the range of 0.1 to 1.0 μm provides a dental filling composition having excellent aesthetics and mechanical strength (special feature). Kaisho 5
8-41810). In this case, the surface smoothness and gloss can be satisfied by using relatively small particles, but the filling amount is at most 75% by weight, the mechanical strength is low, the water absorption is high, and durability remains a problem. In addition, silica is not radiopaque and has a large difference in refractive index from the polymerized acrylic monomer, making it difficult to obtain transparency similar to natural teeth. Furthermore, in order to obtain good transparency, it is proposed to use a spherical inorganic oxide having a particle size of 0.1 to 1.0 μm, which mainly contains silica and an oxide of a Group IV metal of the periodic table. (JP-A-62-89)
701). In this case, the transparency is good by adjusting the refractive index, and the surface smoothness and the gloss are not problematic. In addition, the opacity to X-ray can be satisfied by using zirconia or the like. However, the filling amount still does not reach 75% by weight, and the bending strength is 900 kg / cm 2 at most, and the mechanical strength is low. Furthermore,
Particles having a particle size of 1 to 100 μm and the above-mentioned particle size of 0.1 to
Proposals have also been made to improve the fluidity and increase the content of the filler inside the tubules such as dentinal tubules by using spherical particles of 1.0 μm in combination (JP-A-61-14810).
9). However, this proposal is aimed at fluidity and a high content of filler in the thin tube, and the bending strength is at most 100.
The mechanical strength is as low as 0 kg / cm 2, and when it is inferred from the use of particles having a considerably large average particle diameter, the surface smoothness is unsatisfactory as in the hybrid type described above. As described above, the cured product has mechanical strength and aesthetic properties comparable to those of natural teeth.
Dental filling compositions having radiopacity have not yet been obtained.

【0004】[0004]

【本発明が解決しようとする問題点】本発明者等は上述
の問題点を解決すべく鋭意研究した結果、特定の組成及
び粒子径を有する球形状の無機酸化物の組合わせからな
る混合物を充填材として使用すると、かかる問題点の悉
くが解消されることを見いだし本発明を完成したもので
あって、その目的とするところは、無機質充填材の充填
量が高く、硬化物の表面平滑性、光沢及び透明性等の審
美性、機械的強度及び耐久性に優れ、加えて、優れたX
線不透過性を具えた歯科用充填組成物を提供するにあ
る。本発明の他の目的並びに効果は以下の説明から明ら
かにされよう。
DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, have found that a mixture composed of a combination of spherical inorganic oxides having a specific composition and particle size is used. The present invention has been completed by finding that such problems are solved when it is used as a filler, and the purpose thereof is that the filling amount of the inorganic filler is high and the surface smoothness of the cured product is high. Excellent in aesthetics such as gloss and transparency, mechanical strength and durability, as well as excellent X
A dental filling composition having radiopacity is provided. Other objects and effects of the present invention will be apparent from the following description.

【0005】[0005]

【課題を解決するための手段】上述の目的は、重合可能
な単量体と無機質充填材とを含む歯科用充填組成物であ
って、無機質充填材として、 a)平均粒子径1.0〜5.0μmである球形状のジル
コニウム含有ケイ酸塩粒子(A)50〜80重量%と b)粒子径が0.5μm以下であり、かつ粒子径が0.
2μm以下の球形状のシリカ粒子を10〜70重量%含
む球形状のシリカ粒子(B)50〜20重量%との混合
物を用いることを特徴とする歯科用充填組成物により達
成される。
The above object is a dental filling composition containing a polymerizable monomer and an inorganic filler, wherein the inorganic filler comprises a) an average particle diameter of 1.0 to 50 to 80% by weight of spherical zirconium-containing silicate particles (A) having a size of 5.0 μm, and b) a particle size of 0.5 μm or less, and a particle size of 0.
A dental filling composition characterized by using a mixture with 50 to 20% by weight of spherical silica particles (B) containing 10 to 70% by weight of spherical silica particles of 2 μm or less.

【0006】以下、本発明を詳細に説明する。本発明の
重合可能な単量体としては、歯科用充填組成物に使用さ
れるものであれば、特に限定されるものではなく、種々
の単量体が用いられるが、好ましくは重合可能なビニル
モノマーを用いるのがよい。ビニルモノマーとして最も
代表的なものはアクリル基及び/又はメタクリル基を有
する重合可能なビニルモノマーが挙げられる。
The present invention will be described in detail below. The polymerizable monomer of the present invention is not particularly limited as long as it is used in a dental filling composition, and various monomers are used, but preferably polymerizable vinyl. It is advisable to use monomers. The most typical vinyl monomer is a polymerizable vinyl monomer having an acrylic group and / or a methacrylic group.

【0007】例えば、(メタ)アクリル酸メチル、(メ
タ)アクリル酸エチル、(メタ)−アクリル酸n−プロ
ピル、2−ヒドロキシエチルメタクリレート等の一官能
性の(メタ)アクリレート、エチレングリコールジ(メ
タ)アクリレート、トリエチレングリコールジ(メタ)
アクリレート、1,4−ブタンジオールジ(メタ)アク
リレート、1,6−ヘキサンジオールジ(メタ)アクリ
レート、グリセリンジ(メタ)アクリレート、トリメチ
ロールトリ(メタ)アクリレート、ペンタエリスリトー
ルテトラ(メタ)アクリレート、2,2′−ビス〔p−
(γ−メタクリロキシ−β−ヒドロキシプロポキシ)フ
ェニル〕プロパン、ビスフェノールAジメタクリレー
ト、ネオペンチルグリコールジ(メタ)アクリレート、
2,2′−ジ(4−メタクリロキシポリエトキシフェニ
ル)プロパン、1,2−ビス(3−メタクリロキシ−2
−ヒドロキシプロポキシ)エタン等の多官能性(メタ)
アクリレートが挙げられ、また、2,2,4−トリメチ
ルヘキサメチレンジイソシアネートとメタクリル酸オキ
シプロピルとの反応生成物等のウレタン(メタ)アクリ
レート単量体等も好適に使用できる。これらのビニルモ
ノマーは必要に応じて単独で或は混合して使用すればよ
い。また、本発明では、必要に応じて重合開始剤を用い
てもよく、使用する重合開始剤としては、特に限定され
るものではなく公知のものを用いればよい。重合手段と
しては光エネルギーによるもの、過酸化物と促進剤によ
るもの等を用いることができる。
For example, monofunctional (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) -acrylate, and 2-hydroxyethyl methacrylate, ethylene glycol di (meth). ) Acrylate, triethylene glycol di (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2 , 2'-bis [p-
(Γ-methacryloxy-β-hydroxypropoxy) phenyl] propane, bisphenol A dimethacrylate, neopentyl glycol di (meth) acrylate,
2,2'-di (4-methacryloxypolyethoxyphenyl) propane, 1,2-bis (3-methacryloxy-2)
-Polyfunctional (meta) such as hydroxypropoxy) ethane
Acrylate is mentioned, and urethane (meth) acrylate monomers such as a reaction product of 2,2,4-trimethylhexamethylene diisocyanate and oxypropyl methacrylate can also be preferably used. These vinyl monomers may be used alone or as a mixture, if necessary. Further, in the present invention, a polymerization initiator may be used if necessary, and the polymerization initiator to be used is not particularly limited and a known one may be used. As the polymerization means, light energy, a peroxide and an accelerator, or the like can be used.

【0008】本発明の歯科用充填組成物の他の成分は無
機質充填材である。本発明で使用する無機質充填材は a)平均粒子径1.0〜5.0μmである球形状のジル
コニウム含有ケイ酸塩粒子(A)と b)粒子径が0.5μm以下であり、かつ粒子径が0.
2μm以下の球形状のシリカ粒子を10〜70重量%含
む球形状のシリカ粒子(B)の少なくとも2つの群から
なる混合物であることが必要である。このような粒子を
用いることにより、無機質充填材の充填量が高く、硬化
物の機械的強度及び天然歯に匹敵する審美性を有し、さ
らに、優れたX線不透過性を有する歯科用充填組成物を
得ることができる。
Another component of the dental filling composition of the present invention is an inorganic filler. The inorganic filler used in the present invention is a) spherical zirconium-containing silicate particles (A) having an average particle diameter of 1.0 to 5.0 μm and b) having a particle diameter of 0.5 μm or less, and particles. The diameter is 0.
It is necessary that the mixture is composed of at least two groups of spherical silica particles (B) containing 10 to 70% by weight of spherical silica particles of 2 μm or less. By using such particles, the filling amount of the inorganic filler is high, the mechanical strength of the cured product and the aesthetics are comparable to those of natural teeth, and the dental filling has excellent radiopacity. A composition can be obtained.

【0009】本発明の粒子径の大なる平均粒子径1.0
〜5.0μmの球形状の粒子はジルコニウム含有ケイ酸
塩で、一方粒子径の小なる粒子径が0.5μm以下の球
形状の粒子はシリカであることが必要である。粒子径の
大なる粒子としては、天然歯に匹敵する透明性を与える
ために、使用する単量体の重合物との屈折率差の小さい
粒子が好ましく、また、同時にX線不透過性を付与する
ために、ジルコニウム、バリウム及び/又はストロンチ
ウム等の元素を含有するケイ酸塩粒子が用いられるが、
球形状粒子の製造の容易さ及び硬化後の歯科用充填組成
物の耐久性より、ジルコニウム含有ケイ酸塩粒子が最適
である。なお、該ジルコニウム含有ケイ酸塩粒子のジル
コニウム含量はジルコニア換算で5〜50重量%が好ま
しい。ジルコニウム含量がジルコニア換算で5重量%よ
り少ないと、重合した単量体の屈折率に近付けることが
できず透明性が不足し、かつ、臨床上必要なX線不透過
性を得ることもできない。一方、ジルコニア換算で50
重量%を越えると、粒子自体の屈折率が高くなりすぎ、
重合した単量体の屈折率に近付けることができず、返っ
て不透明なものしか得られない。一方、粒子径の小なる
粒子としては、シリカが最適である。まず、かかる小粒
子径の球形状のシリカは、従来より公知であり、その製
造法も確立し、安定した入手が可能である。また、透明
性に関しても、後に述べるように、0.2μm以下の粒
子を含むことにより、適度の透明性を有し自然な審美性
を与える。加えて、シランカップリング剤等の表面処理
材による表面処理効果も顕著で、硬化物の機械的強度及
び耐久性も顕著に向上する。特に、粒子径の小なる粒子
の場合、その比表面積が大きくなることより、表面処理
効果の機械的強度等に及ぼす影響は大きく、この点で
も、シリカの使用が他の粒子、例えば、ジルコニウム含
有ケイ酸塩、チタン含有ケイ酸塩及びバリウムガラス等
の使用より格段に優れている。かかるシリカとしては、
特にアルコキシシランの加水分解重合によって合成され
た球状シリカが好適である。なお、これらのシリカは乾
燥後、500℃以上で焼成したものを用いるのが好まし
い。
The average particle size of the present invention, which has a large particle size, is 1.0
It is necessary that spherical particles of ˜5.0 μm are zirconium-containing silicates, while spherical particles having a smaller particle diameter of 0.5 μm or less are silica. As a particle having a large particle size, a particle having a small difference in refractive index from a polymer of a monomer used is preferable in order to provide transparency comparable to that of a natural tooth, and at the same time, imparts X-ray opacity. For this purpose, silicate particles containing an element such as zirconium, barium and / or strontium are used.
Zirconium-containing silicate particles are optimal because of the ease of manufacture of spherical particles and the durability of the dental filling composition after curing. The zirconium content of the zirconium-containing silicate particles is preferably 5 to 50% by weight in terms of zirconia. When the zirconium content is less than 5% by weight in terms of zirconia, the refractive index of the polymerized monomer cannot be approached, transparency is insufficient, and clinically necessary X-ray opacity cannot be obtained. On the other hand, 50 in terms of zirconia
If it exceeds the weight percentage, the refractive index of the particles themselves becomes too high,
The refractive index of the polymerized monomer cannot be approached, and only an opaque material can be obtained. On the other hand, silica is most suitable for particles having a small particle size. First, such spherical silica having a small particle diameter has been conventionally known, and its manufacturing method has been established, and stable availability is possible. Regarding transparency, as will be described later, by including particles having a particle size of 0.2 μm or less, the particles have appropriate transparency and give natural aesthetics. In addition, the surface treatment effect of a surface treatment material such as a silane coupling agent is remarkable, and the mechanical strength and durability of the cured product are also significantly improved. In particular, in the case of particles having a small particle size, since the specific surface area thereof becomes large, the influence of the surface treatment effect on the mechanical strength and the like is large, and in this respect also, the use of silica causes other particles to contain, for example, zirconium. It is far superior to the use of silicates, titanium-containing silicates and barium glass. As such silica,
In particular, spherical silica synthesized by hydrolysis polymerization of alkoxysilane is suitable. In addition, it is preferable to use those silicas dried and calcined at 500 ° C. or higher.

【0010】本発明で用いるジルコニウム含有ケイ酸塩
粒子(A)は、平均粒子径が1.0〜5.0μmである
ことが必要であり、好ましくは1.0〜3.0μmであ
る。該粒子(A)の平均粒子径が5.0μmを越える
と、硬化物表面の平滑性及び光沢が劣り、また該粒子
(A)の平均粒子径が1.0μmより小さいと、硬化物
表面の平滑性及び光沢は良好であるが、次に述べるシリ
カ粒子(B)との粒子径の差が小さくなるため、無機質
充填材の充填量を高めることができず、機械的強度が低
く、吸水性及び変色等の耐久性に問題のある充填組成物
しか得ることができない。なお、本発明の無機質充填材
が高い充填量を与える理由は、大きい粒子(A)の作る
間隙により小さい粒子(B)が充分に充填されることに
よると考えられるので、該粒子(A)と(B)との粒子
径の差が小さいのは好ましくない。なお、前述のジルコ
ニウム含有ケイ酸塩粒子とは、例えば、テトラエチルシ
リケートとテトラブチルジルコネートの加水分解重合に
より合成されるが、必ずしも本製造法のみに限定される
ものではない。次に、本発明のシリカ粒子(B)は、前
述の如くジルコニウム含有ケイ酸塩粒子(A)の間隙に
充分に充填され、無機質充填材の充填量を高めるため
に、該粒子(B)の粒子径は実質的に0.5μm以下で
あることが必要であり、より好ましくは0.05〜0.
5μmの範囲にあるのが望ましい。該粒子(B)におい
て粒子径が0.05μmより小さい粒子が多くなると、
該粒子(B)の比表面積が増大し、かえって充填量が低
下し、機械的強度が低下する傾向がある。更に、本発明
のシリカ粒子(B)は可視光線の波長(約0.4〜0.
7μm)の半分より小さい0.2μm以下の粒子径を有
するシリカ粒子を該粒子(B)全量に対して10〜70
重量%含むことが必須である。該0.2μm以下の粒子
径を有するシリカ粒子が10重量%より少ないと、歯科
用充填組成物硬化物の可視光線の透過性が低下する傾向
があり、硬化物の透明性が低下し、本発明の目的とする
天然歯に匹敵する審美性が得られない。一方、該0.2
μm以下の粒子径を有するシリカ粒子が70重量%を越
えると、比表面積が増大するため充填量が低下し、本発
明の目的とする優れた機械的強度及び耐久性を得ること
ができない。なおシリカ粒子(B)のうち、0.2μm
以下の粒子径を有するシリカ粒子を(B−1)とし、
0.2μmより大きく0.5μm以下の粒子径を有する
シリカ粒子を(B−2)とするとき、前述のジルコニウ
ム含有ケイ酸塩粒子(A)とシリカ粒子(B)との関係
と同様、粒子(B−2)と粒子(B−1)との粒子径と
の差が大きい場合、粒子(B−2)の間隙に粒子(B−
1)が充分に充填され、より高い充填量を得ることが可
能となるため、粒子(B−2)の平均粒子径が粒子(B
−1)の平均粒子径の2倍以上であることが好ましい。
なお、ジルコニウム含有ケイ酸塩粒子及びシリカ粒子の
粒子径,粒子径分布及び粒子含有量の測定は種々の方法
が採用され、代表的な例としては、走査型あるいは透過
型の電子顕微鏡写真を用いる方法、レーザー回折法、遠
心沈降法等が挙げられるが、これらの方法に限定される
ものではない。
The zirconium-containing silicate particles (A) used in the present invention need to have an average particle diameter of 1.0 to 5.0 μm, preferably 1.0 to 3.0 μm. If the average particle size of the particles (A) exceeds 5.0 μm, the smoothness and gloss of the surface of the cured product will be poor, and if the average particle size of the particles (A) is less than 1.0 μm, the surface of the cured product will be poor. The smoothness and gloss are good, but the difference in particle size from the silica particles (B) described below is small, so that the filling amount of the inorganic filler cannot be increased, the mechanical strength is low, and the water absorption property is low. Also, only a filling composition having a problem of durability such as discoloration can be obtained. The reason why the inorganic filler of the present invention gives a high filling amount is considered to be because the smaller particles (B) are sufficiently filled in the gaps formed by the larger particles (A). It is not preferable that the difference in particle size from (B) is small. The zirconium-containing silicate particles described above are synthesized, for example, by hydrolytic polymerization of tetraethyl silicate and tetrabutyl zirconate, but are not limited to this production method. Next, the silica particles (B) of the present invention are sufficiently filled in the gaps of the zirconium-containing silicate particles (A) as described above, and in order to increase the filling amount of the inorganic filler, The particle size needs to be substantially 0.5 μm or less, and more preferably 0.05 to 0.
It is preferably in the range of 5 μm. When the number of particles having a particle size smaller than 0.05 μm in the particles (B) increases,
The specific surface area of the particles (B) tends to increase, the filling amount tends to decrease, and the mechanical strength tends to decrease. Further, the silica particles (B) of the present invention have a wavelength of visible light (about 0.4-0.
10 to 70 of silica particles having a particle diameter of 0.2 μm or less, which is smaller than half of 7 μm) based on the total amount of the particles (B).
It is essential to include the weight%. When the content of the silica particles having a particle diameter of 0.2 μm or less is less than 10% by weight, the cured product of the dental filling composition tends to have a reduced visible light transmittance, and the cured product has a reduced transparency. The aesthetics comparable to the natural tooth which is the object of the invention cannot be obtained. On the other hand, the 0.2
If the content of silica particles having a particle diameter of μm or less exceeds 70% by weight, the specific surface area increases and the filling amount decreases, so that the excellent mechanical strength and durability aimed at by the present invention cannot be obtained. Of the silica particles (B), 0.2 μm
A silica particle having the following particle diameter is (B-1),
When the silica particles having a particle diameter of more than 0.2 μm and not more than 0.5 μm are referred to as (B-2), the particles are the same as the above-mentioned relationship between the zirconium-containing silicate particles (A) and the silica particles (B). When the difference between the particle diameters of (B-2) and particles (B-1) is large, the particles (B-
Since 1) is sufficiently filled and a higher filling amount can be obtained, the average particle diameter of the particles (B-2) is smaller than that of the particles (B
It is preferably at least twice the average particle diameter of -1).
Various methods are used to measure the particle size, particle size distribution, and particle content of zirconium-containing silicate particles and silica particles. As a typical example, a scanning or transmission electron micrograph is used. Examples include, but are not limited to, methods, laser diffraction methods, centrifugal sedimentation methods, and the like.

【0011】なお、本発明のジルコニウム含有ケイ酸塩
粒子(A)及びシリカ粒子(B)は球形状であること
が、無機質充填材の高充填量及び歯科用充填組成物硬化
物表面の平滑性及び光沢に好適である。更に、本発明の
ジルコニウム含有ケイ酸塩粒子(A)は、無機質充填材
全体に対して50〜80重量%含まれることが必要であ
り、50重量%より少ないと、充填量が低下し、機械的
強度が低下するばかりでなく、臨床上必要なX線不透過
性を得ることもできず、80重量%を越えると、該
(A)粒子の間隙を充填するべきシリカ粒子(B)が不
足し、かえって、充填量が低下する傾向を示し、また、
比較的大きな粒子が増加するため、硬化物表面の平滑性
及び光沢も低下し、審美性に関しても、不満足なものと
なる。一方、本発明のシリカ粒子(B)は、無機質充填
材全体に対して、50〜20重量%であり、50重量%
を越えると、該粒子(B)の比表面積が大きくなり、充
填量が低く機械的強度が低下し、20重量%より少ない
と、(A)粒子の間隙を充分に充填できず、機械的強
度、審美性とも不満足なものとなる。なお、本発明の効
果を阻害しない範囲で、他の非球形状の無機質粒子を加
えてもよく、その配合割合は無機質充填材全体に対して
10重量%以下が望ましい。
The zirconium-containing silicate particles (A) and silica particles (B) of the present invention have a spherical shape so that a high filling amount of the inorganic filler and the smoothness of the surface of the cured product of the dental filling composition. It is also suitable for gloss. Furthermore, the zirconium-containing silicate particles (A) of the present invention need to be contained in an amount of 50 to 80% by weight based on the whole inorganic filler, and if it is less than 50% by weight, the filling amount will decrease, and The X-ray opacity cannot be obtained clinically, and the silica particles (B) to fill the voids of the particles (A) are insufficient if the amount exceeds 80% by weight. On the contrary, the filling amount tends to decrease, and
Since the number of relatively large particles increases, the smoothness and gloss of the surface of the cured product also deteriorate, and the aesthetics becomes unsatisfactory. On the other hand, the silica particles (B) of the present invention are 50 to 20% by weight, and 50% by weight, based on the whole inorganic filler.
If it exceeds, the specific surface area of the particles (B) will be large, the filling amount will be low and the mechanical strength will decrease, and if it is less than 20% by weight, the voids of the particles (A) cannot be sufficiently filled and the mechanical strength , The aesthetics are also unsatisfactory. It should be noted that other non-spherical inorganic particles may be added within a range that does not impair the effects of the present invention, and the mixing ratio thereof is preferably 10% by weight or less based on the whole inorganic filler.

【0012】本発明のジルコニウム含有ケイ酸塩粒子
(A)及びシリカ粒子(B)は、重合可能な単量体にそ
のまま混合練和して、歯科用充填組成物を製造すること
ができるが、重合可能な単量体に混合する前に該粒子
(A)及び(B)をあらかじめ混合して用いるのが、よ
り高い無機質充填材の充填量を得るうえで好ましい。該
粒子の予備的な混合方法としては、湿式混合,乾式混合
等特に限定されないが、湿式混合法としては、アルコー
ル類,グリコール類等の極性溶媒中での混合が有効であ
る。また、乾式混合法としては、通常用いられる各種混
合機を使用することができるが、特に気流中で粒子を混
合する気流型混合機の内、ジェットミル型,エアブレン
ダー型またはジェット・オー・マイザー型等が好適に使
用できる。なお、予備混合した粒子の使用が、無機質充
填材の高充填量を与える理由は必ずしも明らかではない
が、より大きい粒子の間隙に小さい粒子が充填しやすい
粒子分布をしているものと推測される。
The zirconium-containing silicate particles (A) and silica particles (B) of the present invention can be directly mixed and kneaded with a polymerizable monomer to prepare a dental filling composition. It is preferable to previously mix and use the particles (A) and (B) before mixing with the polymerizable monomer in order to obtain a higher filling amount of the inorganic filler. The preliminary mixing method of the particles is not particularly limited such as wet mixing and dry mixing, but mixing in a polar solvent such as alcohols and glycols is effective as the wet mixing method. Further, as the dry mixing method, various kinds of commonly used mixers can be used, and among the air flow type mixers for mixing particles in an air flow, a jet mill type, an air blender type or a jet ohmizer is particularly used. A mold or the like can be preferably used. The reason why the use of the premixed particles gives a high filling amount of the inorganic filler is not always clear, but it is presumed that the particles have a particle distribution in which the smaller particles are easily filled in the spaces between the larger particles. .

【0013】なお、本発明の無機質充填材は、あらかじ
め表面処理して用いることが重合可能な単量体との分散
混合性向上の点で望ましい。かかる表面処理としては、
γ−メタクリロキシプロピルトリメトキシシラン,ビニ
ルトリエトキシシラン,ビニルトリクロロシラン及びビ
ニルアセトキシシラン等の有機珪素化合物系表面処理剤
(シランカップリング剤)が好適に用いられ、表面処理
法は通常の方法で可能である。ついで、無機質充填材と
重合可能な単量体を混合練和し、歯科用充填組成物を調
製すればよい。調製は通常の方法で可能であるが、前記
無機質充填材が充填組成物全体に対して80重量%以上
配合するのが、機械的強度等の点で好ましい。また、本
発明の組成物には、所望により、重合禁止剤,着色剤,
紫外線吸収剤等を添加することができる。
The inorganic filler of the present invention is preferably subjected to surface treatment in advance in order to improve dispersibility and mixing with a polymerizable monomer. As such surface treatment,
Organic silicon compound-based surface treatment agents (silane coupling agents) such as γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and vinylacetoxysilane are preferably used, and the surface treatment method is a usual method. It is possible. Then, the inorganic filler and the polymerizable monomer may be mixed and kneaded to prepare a dental filling composition. The preparation can be carried out by an ordinary method, but it is preferable that the inorganic filler is blended in an amount of 80% by weight or more based on the whole filling composition from the viewpoint of mechanical strength and the like. Further, the composition of the present invention may contain a polymerization inhibitor, a colorant,
An ultraviolet absorber or the like can be added.

【0014】[0014]

【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はその要旨を越えない限り、以下の実施例
に限定されるものではない。なお、以下の実施例及び比
較例においては、テトラエチルシリケートとテトラブチ
ルジルコネートの加水分解重合により合成した球状ジル
コニウム含有ケイ酸塩粒子及びアルコキシシランの加水
分解重合によって合成した球状シリカ粒子を用い、下記
〔1〕の方法で各無機質粒子の表面処理並びに重合可能
な単量体を調製した後、混合練和により充填組成物を作
製し、〔2〕の方法で試験片を作製し、各物性の測定を
行った。
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following Examples and Comparative Examples, spherical zirconium-containing silicate particles synthesized by hydrolytic polymerization of tetraethyl silicate and tetrabutyl zirconate and spherical silica particles synthesized by hydrolytic polymerization of alkoxysilane were used. After the surface treatment of each inorganic particle and the polymerizable monomer were prepared by the method [1], a filling composition was prepared by mixing and kneading, and a test piece was prepared by the method [2]. The measurement was performed.

【0015】〔1〕 各無機質粒子の表面処理 処理は各無機質粒子に対して、4重量%のγ−メタクリ
ロキシプロピルトリメトキシシラン(信越化学製)とと
もに水−エタノール溶媒中で、混合攪拌した後80℃で
2時間、更に105℃で5時間熱風乾燥機内で乾燥、シ
ラン処理無機質粒子を調製した。
[1] Surface treatment of each inorganic particle is carried out by mixing and stirring 4% by weight of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) in a water-ethanol solvent with respect to each inorganic particle. Silane-treated inorganic particles were prepared by drying in a hot air drier at 80 ° C. for 2 hours and at 105 ° C. for 5 hours.

【0016】 重合可能な単量体の調製 ジメタクリロキシエチルトリメチルヘキサメチレンジ−
ウレタン(UDMA:新中村化学製)とトリエチレング
リコールジメタクリレート(TEGDMA:新中村化学
製)を70:30(重量%)の比で配合した単量体混合
物に光重合開始剤としてカンファーキノン(Aldri
ch製)0.5重量%、重合促進剤としてN,N−ジメ
チルアミノエチルメタクリレート(東京化成製)0.5
重量%を添加し、重合可能な単量体混合物を調製した。
Preparation of Polymerizable Monomer Dimethacryloxyethyl trimethylhexamethylene di-
Camphorquinone (Aldri) as a photopolymerization initiator was added to a monomer mixture containing urethane (UDMA: Shin Nakamura Chemical Co., Ltd.) and triethylene glycol dimethacrylate (TEGDMA: Shin Nakamura Chemical Co., Ltd.) in a ratio of 70:30 (% by weight).
ch) 0.5% by weight, N, N-dimethylaminoethyl methacrylate (manufactured by Tokyo Kasei) 0.5 as a polymerization accelerator
Weight% was added to prepare a polymerizable monomer mixture.

【0017】〔2〕 1.試験片の作製 1)圧縮強度 充填組成物を、内径3mm,高さ6mmの穴を有するス
テンレススチール製金型の穴に充填し、上下両面をガラ
ス板で圧接、可視光照射器エコノライト(ヨシダ製)に
て上下両面より各々40秒間光照射を行った。金型より
離型し試験片とした。
[2] 1. Preparation of test piece 1) The compressive strength filling composition was filled into a hole of a stainless steel mold having a hole with an inner diameter of 3 mm and a height of 6 mm, and the upper and lower surfaces were pressure-contacted with a glass plate, and a visible light irradiator Econolite (Yoshida) was used. Light) from both upper and lower surfaces for 40 seconds. The test piece was released from the mold.

【0018】2)曲げ強度 充填組成物を、厚さ2mm,幅2mm,長さ25mmの
ステンレススチール製金型の穴に充填し、上下両面をガ
ラス板で圧接、技工用光重合器ライトエース(ヨシダ
製)にて上下両面より各々120秒間光照射を行った。
金型より離型し試験片とした。
2) Bending strength The filling composition was filled in the holes of a stainless steel mold having a thickness of 2 mm, a width of 2 mm, and a length of 25 mm, and the upper and lower surfaces were pressure-contacted with a glass plate, and a photopolymerizer light ace for industrial use ( Light irradiation was performed for 120 seconds on each of the upper and lower surfaces by Yoshida).
The test piece was released from the mold.

【0019】3)吸水率 充填組成物を、厚さ3mm,幅15mm,長さ20mm
のステンレススチール製金型の穴に充填し、上下両面を
ガラス板で圧接後、2)と同様の重合方法により、試験
片を作製、更に各面を240番のSiC研磨紙にて研磨
した。
3) Water absorption filling composition with a thickness of 3 mm, a width of 15 mm and a length of 20 mm
After filling the holes of the stainless steel mold with the above, and pressing both upper and lower surfaces with glass plates, a test piece was prepared by the same polymerization method as in 2), and each surface was further polished with No. 240 SiC polishing paper.

【0020】4)透明性 充填組成物を、内径20mm,厚さ1mmの穴を有する
ステンレススチール製金型の穴に充填し、上下両面をガ
ラス板で圧接後、2)と同様の重合方法により試験片を
作製した。圧縮強度、曲げ強度及び透明性試験片は、作
製後直ちに37℃水中へ24時間浸漬後、各試験を行っ
た。また、吸水率試験片は、作製後37℃大気中に、重
量が恒量値に達するまで保管し、試験を行った。
4) The transparent filling composition was filled into a hole of a stainless steel mold having a hole having an inner diameter of 20 mm and a thickness of 1 mm, and the upper and lower surfaces were pressed with a glass plate, followed by the same polymerization method as in 2). A test piece was prepared. The compressive strength, flexural strength and transparency test pieces were immersed in 37 ° C. water for 24 hours immediately after production, and then subjected to each test. Further, the water absorption rate test piece was stored in the atmosphere at 37 ° C. after the production until the weight reached a constant value and tested.

【0021】5)表面光沢及び平滑性 充填組成物を、光照射20秒にて平板状に硬化させ、該
光照射平面のホワイトポイント(松風製)による研磨面
を、表面光沢の肉眼観察及び表面粗さ(Rmax)測定
の試験片とした。
5) Surface gloss and smoothness The filling composition is cured into a flat plate shape by light irradiation for 20 seconds, and the polished surface by the white point (made by Matsukaze) of the light irradiation plane is visually observed and surface gloss. The test piece was used for measuring roughness (Rmax).

【0022】6)X線不透過性 充填組成物を、内径10mm,厚さ1mmの穴を有する
ステンレススチール製金型の穴に充填し、上下両面をガ
ラス板で圧接後、2)と同様の重合方法により試験片を
作製した。
6) The X-ray opaque filling composition was filled into the holes of a stainless steel mold having holes with an inner diameter of 10 mm and a thickness of 1 mm, and the upper and lower surfaces were pressed with glass plates and then the same as 2). A test piece was prepared by the polymerization method.

【0023】2.試験方法 1)圧縮強度 インストロン万能試験機(MODEL 4206)を用
い、クロスヘッドスピード2mm/minで行った。 2)曲げ強度 インストロン万能試験機(MODEL 4206)を用
い、クロスヘッドスピード0.5mm/minで行っ
た。
2. Test method 1) Compressive strength An Instron universal tester (MODEL 4206) was used and the test was performed at a crosshead speed of 2 mm / min. 2) Bending strength Using an Instron universal testing machine (MODEL 4206), the crosshead speed was 0.5 mm / min.

【0024】3)吸水率 37℃大気中に保管、重量が恒量値(m1 )に達した時
点より、37℃水中に浸漬、24時間後の重量(m2
を測定、下記式より吸水率を算出した。 (m2 −m1 )/試験片表面積 4)透明性 色差計(東京電色製MODEL TC−1)を用いて、
試験片の背後に標準白板を置いた場合の明度(LW
と、背後に標準黒板を置いた場合の明度(LB )を測
定、下記式より算出した。 (1−LB /LW )×100 なお、この試験方法では、値が大きいほど透明性が高く
なる。値が25以上のものを優、25未満20以上のも
のを良、20未満のものを不良と判定した。 5)表面光沢及び平滑性 試験片のホワイトポイント研磨面の表面光沢を肉眼にて
観察、更に該研磨面を表面粗さ測定機(東京精密製サー
フコム100A)を用い、基準長さ0.25mmにおけ
る表面粗さ(Rmax)を測定した。 6)X線不透過性 X線装置(ソフテックスSCMB12)で試験片を撮影
した。同じ厚さの人歯エナメル質及び象牙質も同時に撮
影し、肉眼観察にて、エナメル質より優れているものを
優、エナメル質〜象牙質程度のものを良、象牙質より劣
るものを不良と判定した。
3) Water absorption rate Stored in the air at 37 ° C, when the weight reached a constant value (m 1 ), immersed in water at 37 ° C and weighed after 24 hours (m 2 ).
Was measured and the water absorption rate was calculated from the following formula. (M 2 −m 1 ) / surface area of test piece 4) Using a transparent color difference meter (MODEL TC-1 manufactured by Tokyo Denshoku),
Lightness (L W ) when a standard white plate is placed behind the test piece
If, measured lightness (L B) in the case of placing the standard blackboard behind, was calculated from the following equation. (1-L B / L W ) × 100 In this test method, the more transparency is a large value is high. A value of 25 or more was judged to be excellent, a value of less than 25 to 20 or more was judged to be good, and a value of less than 20 was judged to be defective. 5) Surface gloss and smoothness The surface gloss of the white point polished surface of the test piece was observed with the naked eye, and the polished surface was measured with a surface roughness measuring device (Surfcom 100A manufactured by Tokyo Seimitsu Co., Ltd.) at a standard length of 0.25 mm. The surface roughness (Rmax) was measured. 6) An X-ray opaque X-ray device (Softex SCMB12) was used to photograph the test piece. Human tooth enamel and dentin of the same thickness were also photographed at the same time, and when visually observed, those superior to enamel were excellent, those from enamel to dentin were good, and those inferior to dentin were bad. It was judged.

【0025】実施例1〜5 表1に記載のジルコニウム含有ガラス粒子と表2に記載
の非晶質シリカ粒子を表4に記載の量比で、前記の重合
性単量体と混合練和することにより、それぞれ充填組成
物を調製し、前記項目に従い、試験を行った。結果を表
4に示す。なお、表1及び表2に記載の最大粒子径及び
平均粒子径は、無機充填材粒子の走査型電子顕微鏡写真
の単位視野内に観察される粒子の粒子径及び粒子数より
求めた。
Examples 1 to 5 The zirconium-containing glass particles shown in Table 1 and the amorphous silica particles shown in Table 2 were mixed and kneaded with the above-mentioned polymerizable monomer in the amount ratio shown in Table 4. Thus, the filling composition was prepared, and the test was performed according to the above items. The results are shown in Table 4. The maximum particle size and average particle size described in Table 1 and Table 2 were determined from the particle size and the number of particles observed in the unit visual field of the scanning electron micrograph of the inorganic filler particles.

【0026】比較例1〜8 表1,表2及び表3に記載の無機質充填材粒子A,B及
びCを表5に記載の量比で、前記の重合性単量体と混合
練和することにより、それぞれ充填組成物を調製し、前
記項目に従い、試験を行った。なお、各粒子は前記各無
機質粒子の表面処理に従い、シラン表面処理をあらかじ
め行った。また、最大粒子径及び平均粒子径は実施例1
〜5と同じ方法で測定した。結果を表5に示す。
Comparative Examples 1 to 8 The inorganic filler particles A, B and C shown in Table 1, Table 2 and Table 3 are mixed and kneaded with the above-mentioned polymerizable monomer in the amount ratio shown in Table 5. Thus, the filling composition was prepared, and the test was performed according to the above items. Each particle was subjected to silane surface treatment in advance according to the surface treatment of each inorganic particle. The maximum particle size and the average particle size are shown in Example 1.
Measured in the same way as ~ 5. The results are shown in Table 5.

【0027】[0027]

【表1】 [Table 1]

【0028】[0028]

【表2】 [Table 2]

【0029】[0029]

【表3】 [Table 3]

【0030】[0030]

【表4】 [Table 4]

【0031】[0031]

【表5】 [Table 5]

【0032】表4及び表5から明らかなように、球状ジ
ルコニウム含有ケイ酸塩粒子(A)を50〜80重量%
かつ、球状シリカ粒子(B)を50〜20重量%の範囲
で配合した混合無機質粒子を用いた実施例の充填組成物
は、比較例に示す充填組成物に比べ、充填材の充填量が
80重量%と高いにもかかわらず、硬化後の強度は高
く、吸水率も非常に低かった。また、表面の光沢、平滑
性及び透明性も高く、優れた審美性を有していたうえ、
更に、臨床上十分なX線不透過性も有し、すべての点で
バランスのとれた歯科用充填組成物が得られた。
As is apparent from Tables 4 and 5, the spherical zirconium-containing silicate particles (A) are contained in an amount of 50 to 80% by weight.
Moreover, the filling composition of the example using the mixed inorganic particles in which the spherical silica particles (B) were blended in the range of 50 to 20% by weight had a filling amount of the filler of 80 as compared with the filling composition shown in the comparative example. Despite the high weight percentage, the strength after curing was high and the water absorption was also very low. In addition, the surface has high gloss, smoothness and transparency, and has excellent aesthetics.
Furthermore, a dental filling composition having clinically sufficient radiopacity and a balance in all respects was obtained.

【0033】実施例6 前述した球状ジルコニウム含有ケイ酸塩粒子A−Iと粒
子径0.4μm以下で、かつ0.2μm以下の球状粒子
を30重量%含み、更に、0.2μm以下の粒子の平均
粒子径が0.11μm、一方、0.2〜0.4μmの粒
子の平均粒子径が0.33μmである球状シリカ粒子B
−IVとを重量比62/38の割合で、ジェットミル型気
流型混合機によりあらかじめ混合した。得られた予備混
合粒子に前記〔1〕の方法で表面処理を行い、得られた
表面処理混合粒子と前記〔1〕の重合可能な単量体を用
い、歯科用充填組成物を調製した。なお、全組成物中の
充填材含有量は88重量%であった。得られた歯科用充
填組成物を用い、前記〔2〕の方法で試験片を作製し、
各物性の測定を行ったところ、圧縮強度3820kg/
cm2 、曲げ強度1550kg/cm2 、吸水率0.5
7mg/cm2 であって、透明性は30.3と優秀で、
表面光沢及び平滑性も優れ、加えて、X線不透過性も優
秀であった。
Example 6 30% by weight of spherical zirconium-containing silicate particles A-I described above and spherical particles having a particle size of 0.4 μm or less and 0.2 μm or less, and further having a particle size of 0.2 μm or less. Spherical silica particles B having an average particle diameter of 0.11 μm and mean particle diameter of 0.2 to 0.4 μm of 0.33 μm
-IV was mixed in advance at a weight ratio of 62/38 by a jet mill type air flow type mixer. The obtained premixed particles were surface-treated by the method [1], and a dental filling composition was prepared using the surface-treated mixed particles thus obtained and the polymerizable monomer [1]. The filler content in the entire composition was 88% by weight. Using the obtained dental filling composition, a test piece is prepared by the above method [2],
When the physical properties were measured, the compressive strength was 3820 kg /
cm 2 , bending strength 1550 kg / cm 2 , water absorption rate 0.5
It is 7 mg / cm 2 , and the transparency is excellent at 30.3,
The surface gloss and smoothness were excellent, and the X-ray opacity was also excellent.

【0034】実施例7 前述した球状ジルコニウム含有ケイ酸塩粒子A−IVと粒
子径0.3μm以下で、かつ0.2μm以下の球状粒子
を60重量%含む、球状シリカ粒子B−Vとを重量比5
5/45の割合で、ジェットミル型気流型混合機により
あらかじめ混合した。得られた予備混合粒子に前記
〔1〕の方法で表面処理を行い、得られた表面処理混合
粒子と前記〔1〕の重合可能な単量体を用い、歯科用充
填組成物を調製した。なお、全組成物中の充填材含有量
は86重量%であった。得られた歯科用充填組成物を用
い、前記〔2〕の方法で試験片を作製し、各物性の測定
を行ったところ、圧縮強度3610kg/cm2 、曲げ
強度1510kg/cm2 、吸水率0.62mg/cm
2 であって、透明性は38.7と優秀で、表面光沢及び
平滑性も優れ、更に、X線不透過性も優れていた。
Example 7 The above-mentioned spherical zirconium-containing silicate particles A-IV and spherical silica particles B-V containing 60% by weight of spherical particles having a particle diameter of 0.3 μm or less and 0.2 μm or less were weighed. Ratio 5
The mixture was preliminarily mixed at a ratio of 5/45 by a jet mill type air flow type mixer. The obtained premixed particles were surface-treated by the method [1], and a dental filling composition was prepared using the surface-treated mixed particles thus obtained and the polymerizable monomer [1]. The filler content in the entire composition was 86% by weight. Using the obtained dental filling composition, a test piece was prepared by the method described in [2] above, and its physical properties were measured. Compressive strength 3610 kg / cm 2 , bending strength 1510 kg / cm 2 , water absorption 0 0.62 mg / cm
2 , the transparency was excellent at 38.7, the surface gloss and the smoothness were excellent, and the X-ray opacity was also excellent.

【0035】[0035]

【発明の効果】本発明によれば、本発明で特定したジル
コニウム含有ケイ酸塩粒子及びシリカ粒子を特定割合で
重合可能な単量体に配合した歯科用充填組成物では、球
形状の大粒子間の間隙に透明性に影響を与えない小粒子
が効率よく充填されるため、無機質充填材の充填量を高
めることができ、機械的強度が高く低吸水性であり、硬
化物表面の光沢及び平滑性に優れ、透明性も高く天然歯
に匹敵する審美性を有しているうえ、臨床上必要なX線
不透過性も有する、あらゆる部位への使用が可能なバラ
ンスのよい歯科用充填組成物が得られる。
EFFECTS OF THE INVENTION According to the present invention, in the dental filling composition in which the zirconium-containing silicate particles and the silica particles specified in the present invention are mixed with the polymerizable monomer in a specific ratio, spherical large particles are used. Since the small particles that do not affect the transparency are efficiently filled in the gaps between them, the filling amount of the inorganic filler can be increased, the mechanical strength is high and the water absorption is low, and the gloss of the surface of the cured product and A well-balanced dental filling composition that has excellent smoothness, high transparency, and aesthetics comparable to natural teeth, and also has X-ray opacity that is clinically necessary, and can be used in all areas. The thing is obtained.

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平4−210609(JP,A) 特開 平3−258707(JP,A) 特開 平2−132102(JP,A) 特開 昭63−88110(JP,A) 特開 昭61−171404(JP,A) 特開 昭61−148109(JP,A) 特開 昭58−41810(JP,A) 特開 昭62−89701(JP,A) 特開 昭60−233007(JP,A) 特表 昭61−501090(JP,A) (58)調査した分野(Int.Cl.7,DB名) A61K 6/00 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-4-210609 (JP, A) JP-A-3-258707 (JP, A) JP-A-2-132102 (JP, A) JP-A-63- 88110 (JP, A) JP 61-171404 (JP, A) JP 61-148109 (JP, A) JP 58-41810 (JP, A) JP 62-89701 (JP, A) JP 60-233007 (JP, A) Special Table 61-501090 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) A61K 6/00

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 重合可能な単量体と無機質充填材とを含
む歯科用充填組成物であって、無機質充填材として、 a)平均粒子径1.0〜5.0μmである球形状のジル
コニウム含有ケイ酸塩粒子(A)50〜80重量%と b)粒子径が0.5μm以下であり、かつ粒子径が0.
2μm以下の球形状のシリカ粒子を10〜70重量%含
む球形状のシリカ粒子(B)50〜20重量%との混合
物を用いることを特徴とする歯科用充填組成物。
1. A dental filling composition comprising a polymerizable monomer and an inorganic filler, wherein the inorganic filler is a) spherical zirconium having an average particle diameter of 1.0 to 5.0 μm. The content of the silicate particles (A) is 50 to 80% by weight, and b) the particle diameter is 0.5 μm or less, and the particle diameter is 0.
A dental filling composition characterized by using a mixture with 50 to 20% by weight of spherical silica particles (B) containing 10 to 70% by weight of spherical silica particles of 2 μm or less.
【請求項2】 無機質充填材が充填組成物全体に対し
て、80重量%以上配合されてなる請求項1記載の歯科
用充填組成物。
2. The dental filling composition according to claim 1, wherein the inorganic filler is blended in an amount of 80% by weight or more based on the whole filling composition.
【請求項3】 ジルコニア換算で5〜50重量%のジル
コニウムを含有する球形状のジルコニウム含有ケイ酸塩
粒子を用いることを特徴とする請求項1及び2記載の歯
科用充填組成物。
3. The dental filling composition according to claim 1, wherein spherical zirconium-containing silicate particles containing 5 to 50% by weight of zirconium in terms of zirconia are used.
JP06272493A 1993-02-25 1993-02-25 Dental filling composition Expired - Fee Related JP3421072B2 (en)

Priority Applications (1)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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Publication Number Publication Date
JPH06247825A JPH06247825A (en) 1994-09-06
JP3421072B2 true JP3421072B2 (en) 2003-06-30

Family

ID=13208604

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
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US8436078B2 (en) 2008-04-28 2013-05-07 Kuraray Noritake Dental Inc. Dental composition and composite resin

Cited By (8)

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Publication number Priority date Publication date Assignee Title
WO2009133912A1 (en) * 2008-04-28 2009-11-05 クラレメディカル株式会社 Dental composition and composite resin
WO2009133911A1 (en) * 2008-04-28 2009-11-05 クラレメディカル株式会社 Dental composition and composite resin
US8436078B2 (en) 2008-04-28 2013-05-07 Kuraray Noritake Dental Inc. Dental composition and composite resin
JP5191534B2 (en) * 2008-04-28 2013-05-08 クラレノリタケデンタル株式会社 Dental composition and composite resin
JP5191535B2 (en) * 2008-04-28 2013-05-08 クラレノリタケデンタル株式会社 Dental composition and composite resin
US8440739B2 (en) 2008-04-28 2013-05-14 Kuraray Noritake Dental Inc. Dental composition and composite resin
US8455564B2 (en) 2008-04-28 2013-06-04 Kuraray Noritake Dental Inc. Dental composition and composite resin
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