JP2012153640A - Complex restorative material for dental use - Google Patents
Complex restorative material for dental use Download PDFInfo
- Publication number
- JP2012153640A JP2012153640A JP2011013790A JP2011013790A JP2012153640A JP 2012153640 A JP2012153640 A JP 2012153640A JP 2011013790 A JP2011013790 A JP 2011013790A JP 2011013790 A JP2011013790 A JP 2011013790A JP 2012153640 A JP2012153640 A JP 2012153640A
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- Prior art keywords
- composite
- silica
- mass
- particles
- oxide
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 claims abstract description 217
- 239000002245 particle Substances 0.000 claims abstract description 144
- 239000000945 filler Substances 0.000 claims abstract description 83
- 229910000309 titanium group oxide Inorganic materials 0.000 claims abstract description 81
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 239000011022 opal Substances 0.000 claims abstract description 54
- 239000010419 fine particle Substances 0.000 claims abstract description 50
- 239000011164 primary particle Substances 0.000 claims abstract description 46
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 160
- 239000000377 silicon dioxide Substances 0.000 claims description 80
- 239000011350 dental composite resin Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 28
- 238000009826 distribution Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 49
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- 239000000203 mixture Substances 0.000 description 28
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- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 22
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- 230000000704 physical effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 238000011049 filling Methods 0.000 description 12
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- 229910003475 inorganic filler Inorganic materials 0.000 description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
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- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 9
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- -1 diisocyanate compound Chemical class 0.000 description 8
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- 238000003860 storage Methods 0.000 description 8
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
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- 238000003786 synthesis reaction Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
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- 238000000149 argon plasma sintering Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-N 0.000 description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical group CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 210000004268 dentin Anatomy 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
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- RYWGNBFHIFRNEP-UHFFFAOYSA-N (4-benzoylphenyl) 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 RYWGNBFHIFRNEP-UHFFFAOYSA-N 0.000 description 1
- BSPJSKYURNZWFE-UHFFFAOYSA-N (4-methyl-3-oxopent-4-enyl) N-(2,2,3-trimethyloxan-3-yl)carbamate Chemical compound C(=O)(C(=C)C)CCOC(=O)NC1(C(OCCC1)(C)C)C BSPJSKYURNZWFE-UHFFFAOYSA-N 0.000 description 1
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Dental Preparations (AREA)
Abstract
Description
本発明は、歯科用複合修復材料に関する。詳しくは、良好な透明性とオパール効果を有し、審美性に優れる歯科用複合修復材料に関する。 The present invention relates to a dental composite restorative material. More specifically, the present invention relates to a dental composite restorative material having good transparency and an opal effect and excellent in aesthetics.
歯科用複合修復材料は、天然歯牙色と同等の色調を付与できることや操作が容易なことから、治療した歯牙を修復するための材料として急速に普及し、近年においては、前歯の治療の大部分が複合修復材料によって行われているばかりでなく、高い咬合圧のかかる臼歯部等の修復にも使用されるようになってきている。 Dental composite restorative materials have rapidly spread as a material for restoring treated teeth because they can provide the same color tone as natural tooth colors and are easy to operate.In recent years, most of the treatment of front teeth Is being used not only with composite restorative materials, but also for the restoration of molars and the like that are subject to high occlusal pressure.
近年、咬合の回復だけではなく、自然な歯に見えるような審美的な修復への要求が高まりつつあり、単なる同等の色調だけではなく、歯牙の各所の透明性や色調をも再現できる修復材料が求められている。 In recent years, not only restoration of occlusion but also demand for aesthetic restoration that looks like natural teeth is increasing, and restoration materials that can reproduce not only the equivalent color tone but also the transparency and color tone of each part of the tooth Is required.
天然歯は、象牙質とエナメル質とからなり、その色又は色合いは、ほとんどが象牙質から生じ、ほぼ透明で無色であるエナメル質を通って歯の表面に伝達される。特に、前歯の切端部は、エナメル質を多く含む箇所であるため、他の箇所に比べ透明性が高く、エナメル質特有の乳白光を放つことが知られている。 Natural teeth consist of dentin and enamel, and their color or shade is mostly from dentin and is transmitted through the enamel, which is almost transparent and colorless, to the tooth surface. In particular, since the incisal portion of the front tooth is a portion containing a large amount of enamel, it is known that it has higher transparency than other portions and emits milky light peculiar to enamel.
乳白光とは、鉱物のオパールに代表される「オパール効果」として説明され、短波長光の散乱によって反射された光が青く、透過光がオレンジ色を生じる、透明物質中の光散乱現象である。審美的な修復を行うためには、このような繊細な色調も再現する必要があり、複合修復材料としても、高い透明性で且つオパール効果を有する材料が求められてきている。 Milky white light is a light scattering phenomenon in a transparent material that is described as an “opal effect” typified by the mineral opal, in which the light reflected by the scattering of short wavelength light is blue and the transmitted light is orange. . In order to perform aesthetic restoration, it is necessary to reproduce such a delicate color tone. As a composite restoration material, a material having high transparency and an opal effect has been demanded.
歯科用複合修復材料は、一般に重合性単量体（モノマー）、フィラー、及び重合触媒から主に構成されるが、硬化前ペーストの操作性、並びに硬化体の審美性及び機械的強度等は、使用するフィラーの種類、形状、粒子径、及び充填量等によって大きく左右される。例えば、複合修復材料を操作性の良いペースト性状にし、硬化体の機械的強度を十分にするためには、液状を呈する重合性単量体に対してフィラーは好適には等量程度は配合することが必要になる。また、硬化体の機械的強度を高めるためには、粉砕して得られる不定形フィラーが効果的とされている。しかし、不定形フィラーの配合は研磨性や耐摩耗性が悪くなり、臨床的に天然歯と同様な艶のある仕上がり面を得られないといった問題が生じる。また、粒子径分布が広いものとなり、上記オパール効果も得られにくい。 The dental composite restorative material is generally composed mainly of a polymerizable monomer (monomer), a filler, and a polymerization catalyst, but the operability of the paste before curing, the aesthetics and mechanical strength of the cured body, This greatly depends on the type, shape, particle diameter, filling amount, etc. of the filler used. For example, in order to make the composite restorative material into a paste property with good operability and sufficient mechanical strength of the cured body, the filler is preferably blended in an equivalent amount with respect to the polymerizable monomer exhibiting a liquid state. It will be necessary. In order to increase the mechanical strength of the cured body, an amorphous filler obtained by pulverization is effective. However, the blending of the amorphous filler deteriorates the polishing properties and wear resistance, and causes a problem that a glossy finished surface similar to natural teeth cannot be obtained clinically. Further, the particle size distribution is wide, and the above opal effect is hardly obtained.
この問題点を解決するために、比較的小さめの粒径の無機フィラー、特に、球状の無機粒子及び／又はその凝集体からなる無機フィラーを用いることが種々提案されている。このうち、上記オパール効果を有するものとして、０．２〜０．６μｍの粒径範囲の無機フィラーを用いる例（特許文献１、特許請求の範囲）や、平均粒子径０．１８〜０．２８μｍの無機フィラーを用いる例（特許文献２、 In order to solve this problem, various proposals have been made to use an inorganic filler having a relatively small particle diameter, particularly an inorganic filler composed of spherical inorganic particles and / or aggregates thereof. Among these, as examples having an opal effect, examples using an inorganic filler having a particle size range of 0.2 to 0.6 μm (Patent Document 1, Claims), and an average particle size of 0.18 to 0.28 μm Examples using inorganic fillers (Patent Document 2,
欄）等が知られている（以下、これらの無機フィラーを「オパール性付与フィラー」と称する）。これらのオパール性付与フィラーは、形状が上記球形である他、さらに粒子径分布がよりシャープであるほど、オパール効果がより鮮明に発現するため有利である。また、これらのオパール性付与フィラーの配合例では、フィラー充填量を増加し、操作性の良いペースト性状や高い機械的強度を獲得するため、該オパール性付与フィラー以外に、さらに、平均一次粒子径が０．１μｍ以下の微小無機フィラーも配合されている。 Column) and the like (hereinafter, these inorganic fillers are referred to as “opal imparting fillers”). These opal imparting fillers are more advantageous because the opal effect becomes clearer as the particle size distribution becomes sharper in addition to the spherical shape. In addition, in these blending examples of the opal property-imparting filler, in addition to the opal property-imparting filler, the average primary particle size is further increased in order to increase the filler filling amount and to obtain a paste property and high mechanical strength with good operability. Is also blended with a fine inorganic filler of 0.1 μm or less.
これらの歯科用複合充填材料において、無機フィラーは、重合性単量体との屈折率差が小さく、硬化体が透明でオパール効果が発現し易いことから、シリカ系粒子が好適とされている。その中でも、複合比を変えて屈折率が微調整可能であることから、シリカと他の金属酸化物とからなるシリカ系複合酸化物粒子を用いるのが有利であり、特に、上記屈折率差が特に小さく、Ｘ線不透過性も付与できることから、シリカ・ジルコニア粒子やシリカ・チタニア粒子等のシリカとチタン族酸化物との複合酸化物粒子（シリカ・チタン族酸化物系複合酸化物粒子）が最適である。 In these dental composite filler materials, silica-based particles are suitable because the inorganic filler has a small difference in refractive index from the polymerizable monomer, the cured product is transparent, and the opal effect is easily exhibited. Among these, since the refractive index can be finely adjusted by changing the composite ratio, it is advantageous to use silica-based composite oxide particles composed of silica and other metal oxides. Since it is particularly small and can impart radiopacity, composite oxide particles of silica and titanium group oxide (silica / titanium group oxide composite oxide particles) such as silica / zirconia particles and silica / titania particles Is optimal.
なお、特許文献２では、上記オパール性付与フィラーや微小無機フィラーの他に、任意添加材の一つとして、有機無機複合フィラーが記載されている（ In addition, in patent document 2, the organic inorganic composite filler is described as one of arbitrary additives other than the said opal provision filler and a fine inorganic filler (
欄参照）。しかし、フィラー中に分散される無機フィラーについては、粉砕ガラスやシリカ等の多様なものが示されており、その粒径についても何ら具体的な説明はない。 Column). However, as for the inorganic filler dispersed in the filler, various types such as pulverized glass and silica are shown, and there is no specific explanation for the particle size.
本発明者らは、上記オパール性付与フィラーと微小無機フィラーとを組合せた歯科用複合充填材料について、これら各フィラーとして前記シリカ・チタン族酸化物系複合酸化物粒子を用いた場合で種々追試した。そうすると、微小無機フィラーの平均一次粒子径が０．１０μｍ以下であると、前記のとおりフィラー充填量が増加できペーストの操作性や機械的強度が良好である他、粒径が可視光波長より十分に小さいため硬化体の透明性も高く保持され、オパール効果が極めて良好に発現する結果が得られた。 The present inventors have made various additional trials for the dental composite filling material in which the above-mentioned opalizing filler and the fine inorganic filler are combined, when the silica / titanium group oxide composite oxide particles are used as these fillers. . Then, if the average primary particle size of the fine inorganic filler is 0.10 μm or less, the filler filling amount can be increased as described above, and the operability and mechanical strength of the paste are good, and the particle size is sufficiently larger than the visible light wavelength. Therefore, the transparency of the cured product was kept high, and the opal effect was obtained very well.
しかしながら、この複合充填材料は、色調の保存安定性が十分ではなく、ペーストを長期に保存すると変色し、上記折角付与したオパール効果が大きく低減するものであった。これは、シリカ・チタン族酸化物系複合酸化物粒子の表面酸点は格別に強酸点であり、加えて上記微小無機フィラーは比表面積が大きいため、重合性単量体成分や重合開始剤成分の安定性が損なわれることが原因と考えられる。しかして、オパール効果は前記微妙な光散乱現象により生じるものであるため、僅かな変色でも、その発生を大きく低減させる。 However, this composite filling material has insufficient storage stability of the color tone, and when the paste is stored for a long period of time, the color changes and the above-mentioned opal effect imparted with a corner is greatly reduced. This is because the surface acid point of the silica-titanium group oxide-based composite oxide particles is a particularly strong acid point, and the minute inorganic filler has a large specific surface area, so that the polymerizable monomer component and the polymerization initiator component This is thought to be due to the loss of stability. Since the opal effect is caused by the delicate light scattering phenomenon, the occurrence of slight discoloration is greatly reduced.
以上から、ペーストの操作性や機械的強度が良好で、透明性に優れ、オパール効果も有する歯科用複合修復材料において、ペーストを長期間保存しても該オパール効果が高度に維持されるものを開発することが大きな課題であった。 From the above, in the dental composite restorative material having good operability and mechanical strength of the paste, excellent transparency, and also having an opal effect, the opal effect is highly maintained even if the paste is stored for a long period of time. Developing was a major challenge.
上記の課題に鑑み、本発明者らは鋭意研究を続けてきた。その結果、平均一次粒子径が０．０１〜０．１０μｍのシリカ・チタン族酸化物系複合酸化物微粒子の少なくとも一部を、有機無機複合フィラーに含有させて用いることにより、上記の課題が解決できることを見出し、本発明を完成するに至った。 In view of the above problems, the present inventors have continued intensive research. As a result, by using at least a part of silica-titanium group oxide composite oxide fine particles having an average primary particle diameter of 0.01 to 0.10 μm in an organic-inorganic composite filler, the above-mentioned problems are solved. The present inventors have found that this can be done and have completed the present invention.
即ち、本発明は、（Ａ）重合性単量体１００質量部、
（Ｂ）平均一次粒子径が０．１５〜０．５０μｍの範囲であり、該粒子径分布の標準偏差が１．３０以内にある球形のシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕を４０〜２００質量部、
（Ｃ）平均一次粒子径が０．０１〜０．１０μｍの範囲のシリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕を有機樹脂マトリックス中に４０〜７５質量％分散させてなる、（Ａ）重合性単量体の硬化体との屈折率差が０．１以下である有機無機複合フィラーを、９０質量部以上で、且つ（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕との合計量が５５０質量部を越えない配合量、および
（Ｄ）有効量の重合開始剤
を含んでなる歯科用複合修復材料である。
That is, the present invention includes (A) 100 parts by mass of a polymerizable monomer,
(B) Spherical silica / titanium group oxide-based composite oxide particles [I−] having an average primary particle size in the range of 0.15 to 0.50 μm and a standard deviation of the particle size distribution within 1.30. 1] 40-200 parts by weight,
(C) Silica / titanium group oxide composite oxide fine particles [II-1] having an average primary particle diameter in the range of 0.01 to 0.10 μm are dispersed in an organic resin matrix by 40 to 75 mass%. (A) 90 mass parts or more of the organic-inorganic composite filler having a refractive index difference of 0.1 or less with respect to the cured product of the polymerizable monomer, and (B) silica / titanium group oxide composite oxide particles A dental composite restorative material comprising a blending amount of [I-1] not exceeding 550 parts by mass and (D) an effective amount of a polymerization initiator.
本発明の歯科用複合修復材料は、ペーストの操作性や機械的強度が良好なだけでなく、高い透明性とオパール効果を有し、歯牙の自然な修復が可能である。また、これらの優れた審美的性状の保存安定性にも優れ、特に、複合修復材料を長期間保存しても上記オパール効果の消失が高度に抑制できる。 The dental composite restorative material of the present invention not only has good operability and mechanical strength of the paste, but also has high transparency and an opal effect, and allows natural restoration of teeth. Further, these excellent aesthetic properties are also excellent in storage stability, and in particular, the disappearance of the opal effect can be highly suppressed even when the composite restoration material is stored for a long period of time.
本発明の歯科用複合修復材料は、（Ａ）重合性単量体、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕、（Ｃ）有機無機複合フィラー、（Ｄ）重合開始剤を含有してなる。ここで有機無機複合フィラーとは、ポリマーと複合酸化物微粒子との複合フィラーを意味する。 The dental composite restorative material of the present invention comprises (A) a polymerizable monomer, (B) silica / titanium group oxide composite oxide particles [I-1], (C) an organic-inorganic composite filler, (D) It contains a polymerization initiator. Here, the organic-inorganic composite filler means a composite filler of a polymer and composite oxide fine particles.
本発明の最大の特徴は、ペーストの操作性や機械的強度を良好にするために配合する、前記平均一次粒子径が０．０１〜０．１０μｍのシリカ・チタン族酸化物系複合酸化物微粒子〔II〕について、その少なくとも一部（〔II−１〕）を、（Ｃ）有機無機複合フィラー中に含有させた点にある。これにより、その粒子表面に多数存在する強酸点は、有機樹脂マトリックス中に包含されることになり、（Ａ）重合性単量体成分や（Ｄ）重合開始剤成分と直接的に接触しなくなる。この結果、（Ａ）重合性単量体成分や（Ｄ）重合開始剤成分の変質が抑制され、複合修復材料を長期間保存しても色調が高度に維持され、延いてはオパール効果も低下しないものになる。また、斯様に（Ｃ）有機無機複合フィラーを配合することは、複合修復材料の硬化時における重合収縮の低下にも効果的である。 The greatest feature of the present invention is that the silica-titanium group oxide composite oxide fine particles having an average primary particle size of 0.01 to 0.10 μm are blended to improve the operability and mechanical strength of the paste. About [II], it exists in the point which included at least one part ([II-1]) in the (C) organic inorganic composite filler. As a result, a large number of strong acid points existing on the particle surface are included in the organic resin matrix and do not come into direct contact with the (A) polymerizable monomer component or (D) polymerization initiator component. . As a result, alteration of (A) the polymerizable monomer component and (D) the polymerization initiator component is suppressed, and the color tone is maintained at a high level even when the composite restoration material is stored for a long period of time. It will not do. In addition, blending the (C) organic-inorganic composite filler in this manner is also effective in reducing polymerization shrinkage when the composite restorative material is cured.
以下、本発明の歯科用硬化性材料の各成分について説明する。
＜（Ａ）重合性単量体＞
本発明の歯科用複合修復材料において重合性単量体は、公知のものが特に制限なく、ラジカル重合性単量体やカチオン重合性単量体等が使用できる。歯科用途として見た場合、重合速度の観点から、ラジカル重合性単量体を用いるのが好ましく、多官能のものがより好ましい。特に好ましいラジカル重合性単量体は、多官能（メタ）アクリレート系重合性単量体である。多官能の（メタ）アクリレート系重合性単量体を例示すれば、下記（イ）〜（ハ）に示すものが挙げられる。
Hereinafter, each component of the dental curable material of the present invention will be described.
<(A) Polymerizable monomer>
In the dental composite restorative material of the present invention, known polymerizable monomers are not particularly limited, and radical polymerizable monomers and cationic polymerizable monomers can be used. When viewed as a dental use, from the viewpoint of polymerization rate, it is preferable to use a radical polymerizable monomer, and more preferably a polyfunctional one. Particularly preferred radical polymerizable monomers are polyfunctional (meth) acrylate polymerizable monomers. Examples of polyfunctional (meth) acrylate polymerizable monomers include those shown in the following (a) to (c).
（イ）二官能重合性単量体
（ｉ）芳香族化合物系のもの
２，２−ビス（メタクリロイルオキシフェニル）プロパン、
２，２−ビス［４−（３−メタクリロイルオキシ）−２−ヒドロキシプロポキシフェニル］プロパン、
２，２−ビス（４−メタクリロイルオキシフェニル）プロパン、
２，２−ビス（４−メタクリロイルオキシポリエトキシフェニル）プロパン、
２，２−ビス（４−メタクリロイルオキシジエトキシフェニル）プロパン、
２，２−ビス（４−メタクリロイルオキシテトラエトキシフェニル）プロパン、
２，２−ビス（４−メタクリロイルオキシペンタエトキシフェニル）プロパン、
２，２−ビス（４−メタクリロイルオキシジプロポキシフェニル）プロパン、
２（４−メタクリロイルオキシジエトキシフェニル）−２（４−メタクリロイルオキシトリエトキシフェニル）プロパン、
２（４−メタクリロイルオキシジプロポキシフェニル）−２−（４−メタクリロイルオキシトリエトキシフェニル）プロパン、
２，２−ビス（４−メタクリロイルオキシプロポキシフェニル）プロパン、
２，２−ビス（４−メタクリロイルオキシイソプロポキシフェニル）プロパン
及びこれらのメタクリレートに対応するアクリレート；
２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート等の−ＯＨ基を有するメタクリレートあるいはこれらメタクリレートに対応する−ＯＨ基を有するアクリレートと、ジイソシアネートメチルベンゼン、４，４‘−ジフェニルメタンジイソシアネートのような芳香族基を有するジイソシアネート化合物との付加から得られるジアダクト等。
(I) Bifunctional polymerizable monomer (i) Aromatic compound-based 2,2-bis (methacryloyloxyphenyl) propane,
2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane,
2,2-bis (4-methacryloyloxyphenyl) propane,
2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane,
2,2-bis (4-methacryloyloxydiethoxyphenyl) propane,
2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane,
2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane,
2,2-bis (4-methacryloyloxydipropoxyphenyl) propane,
2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane,
2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane,
2,2-bis (4-methacryloyloxypropoxyphenyl) propane,
2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates;
Methacrylates having —OH groups such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, etc., or acrylates having —OH groups corresponding to these methacrylates, diisocyanate methylbenzene, 4, 4 Diadduct obtained by addition with a diisocyanate compound having an aromatic group such as' -diphenylmethane diisocyanate.
（ii）脂肪族化合物系のもの
エチレングリコールジメタクリレート、
ジエチレングリコールジメタクリレート、
トリエチレングリコールジメタクリレート、
テトラエチレングリコールジメタクリレート、
ネオペンチルグリコールジメタクリレート、
１，３−ブタンジオールジメタクリレート、
１，４−ブタンジオールジメタクリレート、
１，６−ヘキサンジオールジメタクリレート、
１，２−ビス（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）エチル
およびこれらのメタクリレートに対応するアクリレート；
２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート等の−ＯＨ基を有するメタクリレートあるいはこれらメタクリレートに対応する−ＯＨ基を有するアクリレートと、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジイソシアネートメチルシクロヘキサン、イソフォロンジイソシアネート、メチレンビス（４−シクロヘキシルイソシアネート）のようなジイソシアネート化合物との付加体から得られるジアダクト等。
(Ii) aliphatic compound-based ethylene glycol dimethacrylate,
Diethylene glycol dimethacrylate,
Triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate,
Neopentyl glycol dimethacrylate,
1,3-butanediol dimethacrylate,
1,4-butanediol dimethacrylate,
1,6-hexanediol dimethacrylate,
1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl and acrylates corresponding to these methacrylates;
Methacrylates having —OH groups such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, etc., or acrylates having —OH groups corresponding to these methacrylates, hexamethylene diisocyanate, trimethylhexamethylene Diaducts obtained from adducts with diisocyanate compounds such as diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, and methylenebis (4-cyclohexylisocyanate).
（ロ）三官能重合性単量体
トリメチロールプロパントリメタクリレート、
トリメチロールエタントリメタクリレート、
ペンタエリスリトールトリメタクリレート、
トリメチロールメタントリメタクリレート
およびこれらのメタクリレートに対応するアクリレート等。
(B) Trifunctional polymerizable monomer trimethylolpropane trimethacrylate,
Trimethylolethane trimethacrylate,
Pentaerythritol trimethacrylate,
Trimethylol methane trimethacrylate and acrylates corresponding to these methacrylates.
（ハ）四官能重合性単量体
ペンタエリスリトールテトラメタクリレート、
ペンタエリスリトールテトラアクリレート；
ジイソシアネートメチルベンゼン、ジイソシアネートメチルシクロヘキサン、イソフォロンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、メチレンビス（４−シクロヘキシルイソシアネート）、４，４−ジフェニルメタンジイソシアネート、トリレン−２，４−ジイソシアネートのようなジイソシアネート化合物とグリシドールジメタクリレートまたはグリシドールジアクリレートとの付加体から得られるジアダクト等。
(C) tetrafunctional polymerizable monomer pentaerythritol tetramethacrylate,
Pentaerythritol tetraacrylate;
Diisocyanate compounds and glycidol such as diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, tolylene-2,4-diisocyanate Diaducts obtained from adducts with dimethacrylate or glycidol diacrylate.
これらの多官能の（メタ）アクリレート系重合性単量体は、硬化体の屈折率（２５℃）が通常、１．４５〜１．６０、より好適には１．５２〜１．５６の範囲である。これらの中から、使用する（Ｃ）有機無機複合フィラーの屈折率（２５℃）に応じて、その差が小さくなるよう選定して使用するのが好ましい（屈折率の差の具体値については後述する）。重合性単量体の２種以上を組合せて、全体で所望の屈折率に調整して用いても良い。一般に、芳香族系重合性単量体は高屈折率を示すものが多く、脂肪族系重合性単量体は低屈折率を示すものが多い。通常は、芳香族系重合性単量体を、重合性単量体の全量に対して２０質量％以上配合させて調整するのが好ましい。 These polyfunctional (meth) acrylate-based polymerizable monomers usually have a cured product having a refractive index (25 ° C.) of 1.45 to 1.60, more preferably 1.52 to 1.56. It is. Among these, it is preferable to select and use such that the difference becomes small according to the refractive index (25 ° C.) of the (C) organic-inorganic composite filler to be used (specific values of the refractive index difference will be described later). To do). Two or more kinds of polymerizable monomers may be combined and adjusted to a desired refractive index as a whole. In general, many aromatic polymerizable monomers exhibit a high refractive index, and many aliphatic polymerizable monomers exhibit a low refractive index. Usually, it is preferable to adjust by adding 20% by mass or more of the aromatic polymerizable monomer with respect to the total amount of the polymerizable monomer.
さらに、必要に応じて、重合性単量体には、
メチルメタクリレート、
エチルメタクリレート、
イソプロピルメタクリレート、
ヒドロキシエチルメタクリレート、
テトラヒドロフルフリルメタクリレート、
グリシジルメタクリレート等のメタクリレート、
及びこれらのメタクリレートに対応するアクリレート等
の単官能の（メタ）アクリレート系単量体や、上記（メタ）アクリレート系単量体以外のラジカル重合性単量体を用いても良い。
Furthermore, if necessary, the polymerizable monomer includes
Methyl methacrylate,
Ethyl methacrylate,
Isopropyl methacrylate,
Hydroxyethyl methacrylate,
Tetrahydrofurfuryl methacrylate,
Methacrylates such as glycidyl methacrylate,
In addition, monofunctional (meth) acrylate monomers such as acrylates corresponding to these methacrylates, or radical polymerizable monomers other than the (meth) acrylate monomers may be used.
＜（Ｂ）平均一次粒子径が０．１５〜０．５０μｍの範囲であり、該粒子径分布の標準偏差が１．３０以内にある球形のシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕＞
本発明の歯科用複合修復材料には、オパール効果を与える目的で、平均一次粒子径が０．１５〜０．５０μｍであるシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕が配合される。ここで、オパール効果の発現には、該複合酸化物粒子〔Ｉ−１〕の平均一次粒子径が０．１５〜０．５０μｍであることが重要である。即ち、オパール効果の発現は、ブラッグ条件に則って回折干渉が起こり、特定波長の光が強調されることによるものであるところ、上記粒子径の粒子を配合すると、その複合修復材料の硬化体には、同審美性状が発現するようになる。オパール効果を一層に高める観点から、シリカ・チタン族酸化物系複合酸化物の平均一次粒子径は０．１５〜０．３０μｍがより好適であり、０．１８〜０．２８μｍが特に好適である。
<(B) Spherical silica / titanium group oxide-based composite oxide particles having an average primary particle size in the range of 0.15 to 0.50 μm and a standard deviation of the particle size distribution within 1.30 [I -1]>
The dental composite restorative material of the present invention contains silica / titanium group oxide composite oxide particles [I-1] having an average primary particle size of 0.15 to 0.50 μm for the purpose of giving an opal effect. Is done. Here, for the expression of the opal effect, it is important that the average primary particle diameter of the composite oxide particles [I-1] is 0.15 to 0.50 μm. In other words, the expression of the opal effect is due to diffraction interference occurring in accordance with the Bragg condition and the enhancement of light of a specific wavelength. Will develop the aesthetic properties. From the viewpoint of further enhancing the opal effect, the average primary particle diameter of the silica / titanium group oxide-based composite oxide is more preferably 0.15 to 0.30 μm, and particularly preferably 0.18 to 0.28 μm. .
なお、シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕は一次粒子径が上記平均値範囲にあることが重要であり、この要件を満足する粒子であれば該一次粒子の個々は多少の凝集粒子として存在していても良い。しかしながら、できるだけ独立粒子として存在しているのが好ましく、具体的には、１０μｍ以上の凝集粒子が１０体積％未満であることが好ましい。 In addition, it is important that the silica-titanium group oxide-based composite oxide particles [I-1] have a primary particle diameter in the above average value range. If the particles satisfy this requirement, each of the primary particles is It may exist as some aggregated particles. However, it is preferable to exist as independent particles as much as possible. Specifically, it is preferable that aggregated particles of 10 μm or more are less than 10% by volume.
本発明において、粒子の平均一次粒子径は、走査型電子顕微鏡により粉体の写真を撮影し、その写真の単位視野内に観察される粒子の３０個以上を選択し、それぞれの粒子径（最大径）を求めた平均値をいう。 In the present invention, the average primary particle size of the particles is obtained by taking a photograph of the powder with a scanning electron microscope, selecting 30 or more of the particles observed within the unit field of view of the photograph, (Mean diameter) is the average value.
また、シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕の形状は、散乱する光が均一になり、鮮やかな発色が現れるようになることから球形であることが必要である。さらに、粒度が揃っている方が散乱する光の均一性が高まるため、一次粒子径分布の標準偏差が１．３０以内、好適には１．２０以内のものを用いる。 Further, the shape of the silica / titanium group oxide composite oxide particles [I-1] needs to be spherical because scattered light becomes uniform and vivid color appears. Furthermore, since the uniformity of the scattered light increases when the particle size is uniform, the standard deviation of the primary particle size distribution is within 1.30, preferably within 1.20.
ここで、粒子が球状とは、略球状であればよく、必ずしも完全な真球である必要はない。一般には、走査型電子顕微鏡で粒子の写真を撮り、その単位視野内にあるそれぞれの粒子（３０個以上）について、その最大径に直交する方向の粒子径をその最大径で徐した平均均斉度が０．６以上、より好ましくは０．８以上のものであればよい。 Here, the particles are spherical as long as they are substantially spherical, and are not necessarily perfect spheres. In general, a photograph of particles is taken with a scanning electron microscope, and for each particle (30 or more) in the unit field of view, the average uniformity in which the particle diameter in the direction perpendicular to the maximum diameter is gradually reduced by the maximum diameter. Is 0.6 or more, more preferably 0.8 or more.
他方、粒子の粒子径分布は、走査型電子顕微鏡により粉体の写真を撮影し、その写真の単位視野内に観察される粒子の３０個以上を選択し、下記算出式より求めた値をいう。 On the other hand, the particle size distribution of the particles is a value obtained from the following calculation formula by taking a photograph of the powder with a scanning electron microscope, selecting 30 or more particles observed in the unit field of view of the photograph. .
本発明においてシリカ・チタン族酸化物系複合酸化物とは、シリカとチタン族（周期律表第ＩＶ族元素）酸化物との複合酸化物であり、シリカ・チタニア、シリカ・ジルコニア、シリカ・チタニア・ジルコニア等が挙げられる。このうち表面酸点の酸強度が強くオパール効果の消失の低減効果が顕著に発揮される他、高いＸ線不透過性も付与できることから、シリカ・ジルコニアが好ましい。その複合比は特に制限されないが、十分なＸ線不透過性を付与することと、屈折率を後述する好適な範囲にする観点から、シリカの含有量が７０〜９５モル％であり、チタン族酸化物の含有量が５〜３０モル％であるものが好ましい。シリカ・ジルコニアの場合、このように各複合比を変化させることにより、その屈折率を１．４８〜１．５６の範囲で自在に変化させることができる。 In the present invention, the silica-titanium group oxide-based composite oxide is a composite oxide of silica and a titanium group (group IV element of the periodic table), such as silica-titania, silica-zirconia, silica-titania. -Zirconia etc. are mentioned. Among these, silica / zirconia is preferred because it has a strong acid strength at the surface acid point and a remarkable effect of reducing the disappearance of the opal effect, and can also impart high radiopacity. The composite ratio is not particularly limited, but the content of silica is 70 to 95 mol% from the viewpoint of imparting sufficient radiopacity and making the refractive index in a suitable range described later, and the titanium group The thing whose content of an oxide is 5-30 mol% is preferable. In the case of silica zirconia, the refractive index can be freely changed in the range of 1.48 to 1.56 by changing the composite ratios in this way.
なお、これらシリカ・チタン族酸化物系複合酸化物には、少量であれば、シリカ及びチタン族酸化物以外の金属酸化物の複合も許容される。具体的には、酸化ナトリウム、酸化リチウム等のアルカリ金属酸化物を１０モル％以内で含有させても良い。 These silica / titanium group oxide-based composite oxides are allowed to be combined with metal oxides other than silica and titanium group oxides, as long as the amount is small. Specifically, an alkali metal oxide such as sodium oxide or lithium oxide may be contained within 10 mol%.
こうしたシリカ・チタン族酸化物系複合酸化物粒子の製造方法は特に限定されないが、例えば、加水分解可能な有機ケイ素化合物と加水分解可能な有機チタン族金属化合物とを含んだ混合溶液を、アルカリ性溶媒中に添加し、加水分解を行って反応生成物を析出させる、いわゆるゾルゲル法が好適に採用される。 The method for producing such silica / titanium group oxide composite oxide particles is not particularly limited. For example, a mixed solution containing a hydrolyzable organosilicon compound and a hydrolyzable organotitanium group metal compound is used as an alkaline solvent. A so-called sol-gel method is preferably employed in which the reaction product is precipitated by addition into the product and hydrolysis.
これらのシリカ・チタン族酸化物系複合酸化物粒子は、シランカップリング剤により表面処理されても良い。シランカップリング剤による表面処理により、（Ａ）重合性単量体の硬化体部分との界面強度に優れたものになる。代表的なシランカップリング剤としては、例えばγ−メタクリロイルオキシアルキルトリメトキシシラン、ヘキサメチルジシラザン等の有機ケイ素化合物が挙げられる。これらシランカップリング剤の表面処理量に特に制限はなく、得られる複合修復材料の機械的物性等を予め実験で確認したうえで最適値を決定すればよいが、好適な範囲を例示すれば、粒子１００重量部に対して１〜１０重量部の範囲である。 These silica / titanium group oxide composite oxide particles may be surface-treated with a silane coupling agent. By the surface treatment with the silane coupling agent, the (A) polymerizable monomer is excellent in interfacial strength with the cured body portion. Examples of typical silane coupling agents include organosilicon compounds such as γ-methacryloyloxyalkyltrimethoxysilane and hexamethyldisilazane. There is no particular limitation on the surface treatment amount of these silane coupling agents, and it is sufficient to determine the optimum value after confirming in advance the mechanical properties and the like of the resulting composite restoration material, but if a suitable range is exemplified, The range is 1 to 10 parts by weight with respect to 100 parts by weight of the particles.
前記したようにオパール効果は、硬化体の透明性が高い場合により鮮明に発現する。そのためシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕は、（Ａ）重合性単量体の硬化体との屈折率差が０．１０以下、より好ましくは０．０５以下であって、透明性をできるだけ損なわないものを選定して用いるのが好ましい。 As described above, the opal effect appears more clearly when the cured product is highly transparent. Therefore, the silica / titanium group oxide composite oxide particles [I-1] have a refractive index difference of 0.10 or less, more preferably 0.05 or less, from the cured product of the polymerizable monomer (A). Therefore, it is preferable to select and use one that does not impair the transparency as much as possible.
本発明における（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕の配合量は、（Ａ）重合性単量体１００質量部に対して、４０〜２００質量部である。シリカ・チタン族酸化物系複合酸化物〔Ｉ−１〕を４０質量部以上配合することにより、オパール効果が良好に発現するようになる。他方、平均一次粒子径が０．１５〜０．５μｍの粒子を２００質量部を越えて多量に配合するのは一般的には困難である。また、複合酸化物粒子〔Ｉ−１〕として、（Ａ）重合性単量体の硬化体との屈折率差が前記０．１０を上回るものを用いる場合において、硬化体の透明性が低下して、オパール効果も十分に発現しなくなる虞がある。これらを勘案すると、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕の配合量は、（Ａ）重合性単量体１００質量部に対して６０〜１８０質量部が好適であり、７０〜１６０質量部が特に好適である。 The blending amount of (B) silica-titanium group oxide composite oxide particles [I-1] in the present invention is 40 to 200 parts by mass with respect to 100 parts by mass of (A) polymerizable monomer. By blending 40 parts by mass or more of silica / titanium group oxide-based composite oxide [I-1], the opal effect is favorably expressed. On the other hand, it is generally difficult to blend a large amount of particles having an average primary particle size of 0.15 to 0.5 μm exceeding 200 parts by mass. In addition, as the composite oxide particles [I-1], when the difference in refractive index from the cured product of the polymerizable monomer (A) exceeds 0.10, the transparency of the cured product is reduced. As a result, the opal effect may not be sufficiently exhibited. Considering these, the blending amount of (B) silica / titanium group oxide composite oxide particles [I-1] is preferably 60 to 180 parts by mass with respect to 100 parts by mass of (A) polymerizable monomer. 70 to 160 parts by mass is particularly preferable.
＜（Ｃ）平均一次粒子径が０．０１〜０．１０μｍの範囲のシリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕を有機樹脂マトリックス中に４０〜７５質量％分散させてなる、（Ａ）重合性単量体の硬化体との屈折率差が０．１０以下である有機無機複合フィラー＞
本発明の最大の特徴は、平均一次粒子径が０．０１〜０．１０μｍの範囲であるシリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕の少なくとも一部を、有機無機複合フィラーに含有させた点にある。これにより、この粒子表面に存在する強酸点は、（Ａ）重合性単量体成分や（Ｄ）重合開始剤成分と直接的に接触しなくなり、長期間保存しても硬化体の透明性は低下せず、オパール効果の低下の問題が大きく改善される。
<(C) Silica / titanium group oxide composite fine particles [II-1] having an average primary particle size in the range of 0.01 to 0.10 μm are dispersed in an organic resin matrix in an amount of 40 to 75% by mass. (A) Organic-inorganic composite filler having a refractive index difference of 0.10 or less from the cured product of the polymerizable monomer>
The greatest feature of the present invention is that at least part of the silica / titanium group oxide-based composite oxide fine particles [II-1] having an average primary particle diameter in the range of 0.01 to 0.10 μm is used as the organic / inorganic composite filler. It is in the point made to contain. As a result, the strong acid point present on the particle surface does not come into direct contact with the (A) polymerizable monomer component or (D) polymerization initiator component, and the transparency of the cured product is maintained even after long-term storage. The problem of a decrease in the opal effect is greatly improved.
ここで、シリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕の平均一次粒子径は０．０１〜０．１０μｍの範囲であることが必要である。即ち、この粒子径であれば可視光波長よりも十分に小さいため、光の散乱は起き難く、硬化体の透明性を高く保持しつつ、フィラー充填量を増加でき、複合修復材料の硬化体の機械的強度を高めることが可能になる。なお、平均一次粒子径が０．０１μｍ未満の粒子は、粘度が高くなり、取扱が困難である。シリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕の平均一次粒子径は、０．０１〜０．０８μｍであるのがより好適であり、０．０５〜０．０８μｍであるのが特に好適である。 Here, the average primary particle diameter of the silica / titanium group oxide composite fine particles [II-1] needs to be in the range of 0.01 to 0.10 μm. That is, since this particle size is sufficiently smaller than the visible light wavelength, light scattering is unlikely to occur, and the filler filling amount can be increased while maintaining the transparency of the cured body high, and the cured body of the composite repair material can be increased. It becomes possible to increase the mechanical strength. Note that particles having an average primary particle diameter of less than 0.01 μm have a high viscosity and are difficult to handle. The average primary particle diameter of the silica / titanium group oxide composite oxide fine particles [II-1] is more preferably 0.01 to 0.08 μm, and 0.05 to 0.08 μm. Particularly preferred.
シリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕も前記複合酸化物粒子〔Ｉ−１〕と同じく多少の凝集粒子が存在していても良い。また、その形状は、十分に小さい粒径であるため、球状でも不定形でも用いることができる。さらに、一次粒子径分布は、特に制限されるものではないが、光散乱効果を阻害しないように、標準偏差が１．３０以内のものが好ましく、１．２０以内のものが特に好ましい。 The silica / titanium group oxide composite oxide fine particles [II-1] may have some aggregated particles as in the composite oxide particles [I-1]. Moreover, since the shape is a sufficiently small particle diameter, it can be used in a spherical shape or an indefinite shape. Further, the primary particle size distribution is not particularly limited, but the standard deviation is preferably within 1.30, particularly preferably within 1.20 so as not to inhibit the light scattering effect.
この複合酸化物微粒子〔II−１〕を構成するシリカ・チタン族酸化物系複合酸化物も、前記複合酸化物粒子〔Ｉ−１〕で説明したものと同じものが使用される。もちろん、シランカップリング剤により表面処理したものであっても良い。 As the silica-titanium group oxide composite oxide constituting the composite oxide fine particles [II-1], the same one as described in the composite oxide particles [I-1] is used. Of course, it may be surface-treated with a silane coupling agent.
シリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕の有機無機複合フィラーへの含有量（有機無機複合フィラーに対する充填率）は、４０〜７５質量％である。有機無機複合フィラーへの含有量が４０質量％未満では、複合修復材料の硬化体の機械的強度を十分に高め難くなる。また、複合酸化物微粒子〔II−１〕を７５質量％を越えて有機無機複合フィラー中に含有させることは操作上困難であったり、均質なものが得難くなる。複合酸化物微粒子〔II−１〕の有機無機複合フィラーへのより好適な含有量は、４５〜７５質量％である。 The content of silica / titanium group oxide composite fine particles [II-1] in the organic-inorganic composite filler (filling ratio with respect to the organic-inorganic composite filler) is 40 to 75% by mass. When the content in the organic-inorganic composite filler is less than 40% by mass, it is difficult to sufficiently increase the mechanical strength of the cured body of the composite restorative material. In addition, it is difficult in terms of operation to make the composite oxide fine particles [II-1] more than 75 mass% contained in the organic-inorganic composite filler, or it becomes difficult to obtain a homogeneous product. A more preferable content of the composite oxide fine particles [II-1] in the organic-inorganic composite filler is 45 to 75% by mass.
（Ｃ）有機無機複合フィラーにおいて、有機樹脂マトリックスは、前述の（Ａ）重合性単量体として記載したものと同じ重合性単量体の単独重合体又は複数種の共重合体が、なんら制限なく採択可能である。 (C) In the organic-inorganic composite filler, the organic resin matrix is not limited to a homopolymer or a plurality of copolymers of the same polymerizable monomer as that described as the (A) polymerizable monomer. Can be adopted.
上記（Ｃ）有機無機複合フィラーは、その配合により、複合修復材料の透明性を低下させないために、（Ａ）重合性単量体の硬化体との屈折率差が０．１０以下、より好ましくは同屈折率差が０．０５以下に調整されたものを用いる必要がある。これにより、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕によるオパール効果を良好に発現させることが可能になる。このような（Ｃ）有機無機複合フィラーの屈折率の調整は、使用する複合酸化物微粒子〔II−１〕や有機樹脂マトリックスの種類や配合比等を適宜に選定して実施すれば良い。 The (C) organic-inorganic composite filler does not lower the transparency of the composite restorative material due to its blending, so that the refractive index difference from the cured product of the (A) polymerizable monomer is 0.10 or less, more preferably It is necessary to use those having the same refractive index difference adjusted to 0.05 or less. As a result, the opal effect of (B) silica / titanium group oxide-based composite oxide particles [I-1] can be favorably expressed. Such adjustment of the refractive index of the (C) organic-inorganic composite filler may be carried out by appropriately selecting the type and blending ratio of the composite oxide fine particles [II-1] to be used and the organic resin matrix.
本発明において、（Ｃ）有機無機複合フィラーは、複合酸化物微粒子〔II−１〕、重合性単量体、及び重合開始剤の各成分の所定量を混合し、加熱あるいは光照射等の方法で重合させた後、粉砕する、有機無機複合フィラーの一般的製造方法に従って製造すれば良い。重合開始剤は、公知の重合開始剤が特に制限なく用いられるが、より黄色度の低い硬化体を得ることができることから、熱重合開始剤を用いるのが好適であり、さらにその構造中に芳香族環を有していない化合物からなるものを用いるのがより好ましい。 In the present invention, (C) the organic-inorganic composite filler is a method of mixing predetermined amounts of each component of the composite oxide fine particles [II-1], the polymerizable monomer, and the polymerization initiator, and heating or light irradiation. The polymer may be produced according to a general production method of an organic-inorganic composite filler that is polymerized and then pulverized. As the polymerization initiator, a known polymerization initiator is used without particular limitation. However, since a cured product having a lower yellowness can be obtained, it is preferable to use a thermal polymerization initiator, and further, an aromatic substance is included in the structure. It is more preferable to use a compound made of a compound having no group ring.
本発明において（Ｃ）有機無機複合フィラーの平均粒子径は、特に制限されるものではないが、硬化体の機械的強度や硬化性ペーストの操作性を良好にする観点から、２〜１００μｍが好ましく、さらには５〜５０μｍがより好ましく、１５〜３０μｍであるのが特に好ましい。 In the present invention, the average particle diameter of the organic-inorganic composite filler (C) is not particularly limited, but is preferably 2 to 100 μm from the viewpoint of improving the mechanical strength of the cured body and the operability of the curable paste. Furthermore, 5-50 micrometers is more preferable, and it is especially preferable that it is 15-30 micrometers.
（Ｃ）有機無機複合フィラーには、シリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕の他に、シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕と同じ範疇の粒子（〔Ｉ−２〕）も含有させるのが有効である。オパール効果は、複合修復材料中において、オパール性付与フィラーがより均一に分散しているほど良好に発揮されるため、該複合酸化物粒子〔Ｉ−２〕は有機無機複合フィラー中にも含有させることにより、同審美性状を一層に高めることができ好ましい。 (C) In addition to silica / titanium group oxide composite oxide particles [II-1], the organic / inorganic composite filler has the same category as silica / titanium group oxide composite oxide particles [I-1]. It is effective to contain particles ([I-2]). The opal effect is better exhibited in the composite restorative material as the opal imparting filler is more uniformly dispersed. Therefore, the composite oxide particle [I-2] is also contained in the organic-inorganic composite filler. Therefore, it is possible to further enhance the aesthetic properties.
（Ｃ）有機無機複合フィラーにシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−２〕を含有させる場合、その含有量は、有機樹脂マトリックス中に５質量％以上で、且つ（Ａ）重合性単量体の硬化体との屈折率差が前述の０．１０以下に維持される量が好ましい。また、該シリカ・チタン族酸化物系複合酸化物粒子の〔Ｉ−２〕と〔II−１〕とを併用して含有させる場合には、互いの粒子径の相違による充填性向上効果により、前記〔II−１〕を単独で含有させる場合よりも、その含有総量を増加させることができる。このため、複合酸化物粒子〔Ｉ−２〕の有機無機複合フィラーへの配合量は、シリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕との合計が８５質量％を越えない量であるのが好ましくなる。 (C) When the organic-inorganic composite filler contains silica / titanium group oxide composite oxide particles [I-2], the content is 5% by mass or more in the organic resin matrix, and (A) polymerization The amount by which the difference in refractive index from the cured monomer is maintained at 0.10 or less is preferred. In addition, when [I-2] and [II-1] of the silica-titanium group oxide-based composite oxide particles are used in combination, due to the effect of improving the filling property due to the difference in the particle diameter of each other, The total content can be increased as compared with the case where [II-1] is contained alone. For this reason, the compounding amount of the composite oxide particles [I-2] to the organic-inorganic composite filler is such that the total amount with the silica / titanium group oxide composite oxide fine particles [II-1] does not exceed 85% by mass. Is preferred.
さらに、より均一なオパール効果の発現を勘案すれば、有機無機複合フィラー中における、複合酸化物粒子〔Ｉ−２〕の含有量は、（Ａ）重合性単量体に対する（Ｂ）複合酸化物粒子〔Ｉ−１〕の配合量とあまり差がなく（０．５〜２．０質量倍の範囲内）するのが好ましい。 Furthermore, in consideration of the expression of a more uniform opal effect, the content of the composite oxide particles [I-2] in the organic-inorganic composite filler is (B) the composite oxide with respect to (A) the polymerizable monomer. It is preferable that the blending amount of the particles [I-1] is not so different (within a range of 0.5 to 2.0 mass times).
なお、有機無機複合フィラーに含有させる上記複合酸化物粒子〔Ｉ−２〕は、複合酸化物微粒子〔II−１〕と同種のシリカ・チタン族酸化物系複合酸化物であるのが好ましいが、異種のものであっても構わない。 The composite oxide particles [I-2] to be contained in the organic-inorganic composite filler are preferably the same type of silica / titanium group oxide composite oxide as the composite oxide fine particles [II-1] Different types may be used.
（Ｃ）有機無機複合フィラーには、その効果を阻害しない範囲で、公知の添加剤を配合することができる。具体的には、顔料、重合禁止剤、蛍光増白剤等が挙げられる。また、有機無機複合フィラーは、歯科用複合修復材料として使用するに先だって、更に洗浄やシランカップリング剤等による表面処理を行ってもよい。 (C) A well-known additive can be mix | blended with the organic inorganic composite filler in the range which does not inhibit the effect. Specific examples include pigments, polymerization inhibitors, and fluorescent brighteners. In addition, the organic-inorganic composite filler may be further subjected to a surface treatment with a cleaning agent, a silane coupling agent or the like before being used as a dental composite restorative material.
本発明における（Ｃ）有機無機複合フィラーの配合量は、（Ａ）重合性単量体１００質量部に対して９０質量部以上で、且つ（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕との合計量が５５０質量部を越えない配合量である。即ち、有機無機複合フィラーの配合により複合修復材料のペーストの操作性や硬化体の機械的強度を良好にするためには、該有機無機複合フィラーは１２０質量部以上、より好適には１４０質量部以上は配合することが必要になる。 The blending amount of the (C) organic-inorganic composite filler in the present invention is 90 parts by mass or more with respect to (A) 100 parts by mass of the polymerizable monomer, and (B) silica / titanium group oxide composite oxide particles. The total amount with [I-1] does not exceed 550 parts by mass. That is, in order to improve the operability of the composite restoration material paste and the mechanical strength of the cured body by blending the organic-inorganic composite filler, the organic-inorganic composite filler is 120 parts by mass or more, more preferably 140 parts by mass. The above needs to be blended.
また、（Ｃ）有機無機複合フィラーを（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕との合計量で５５０質量部を越えて多量に配合させることは操作上困難であり、均質な複合修復材料が得難くなる。さらに、複合修復材料の硬化体の透明性が低下して、オパール効果も十分に発現しなくなる虞がある。これらを勘案すると、（Ｃ）有機無機複合フィラーの配合量は、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕との合計量が４７０質量部を越えない配合量であるのがより好ましい。 In addition, it is difficult in terms of operation to add a large amount of (C) organic-inorganic composite filler in excess of 550 parts by mass in total with (B) silica / titanium group oxide-based composite oxide particles [I-1]. It is difficult to obtain a homogeneous composite repair material. Furthermore, the transparency of the cured body of the composite restorative material is lowered, and the opal effect may not be sufficiently exhibited. Considering these, the blending amount of (C) the organic-inorganic composite filler is such that the total amount with (B) silica / titanium group oxide composite oxide particles [I-1] does not exceed 470 parts by mass. More preferably.
＜（Ｄ）重合開始剤＞
本発明で用いる重合開始剤は、本組成を重合硬化させる目的で配合させるが、公知の如何なる重合開始剤が特に制限されることなく用いられる。
<(D) Polymerization initiator>
The polymerization initiator used in the present invention is blended for the purpose of polymerizing and curing the present composition, and any known polymerization initiator is used without particular limitation.
中でも、口腔内で硬化させる場合が多い歯科の直接充填修復用途では光重合開始剤（組成）、又は化学重合開始剤組成が好ましく、混合操作の必要が無く簡便な点から、光重合開始剤（組成）が好ましい。 Among them, a photopolymerization initiator (composition) or a chemical polymerization initiator composition is preferable for dental direct filling and restoration use, which is often cured in the oral cavity, and there is no need for a mixing operation. Composition) is preferred.
光重合に用いる重合開始剤としては、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルなどのベンゾインアルキルエーテル類、ベンジルジメチルケタール、ベンジルジエチルケタールなどのベンジルケタール類、ベンゾフェノン、４，４'−ジメチルベンゾフェノン、４−メタクリロキシベンゾフェノンなどのベンゾフェノン類、ジアセチル、２，３−ペンタジオンベンジル、カンファーキノン、９，１０−フェナントラキノン、９，１０−アントラキノンなどのα−ジケトン類、２，４−ジエトキシチオキサンソン、２−クロロチオキサンソン、メチルチオキサンソン等のチオキサンソン化合物、ビス−（２，６−ジクロロベンゾイル）フェニルホスフィンオキサイド、ビス−（２，６−ジクロロベンゾイル）−２，５−ジメチルフェニルホスフィンオキサイド、ビス−（２，６−ジクロロベンゾイル）−４−プロピルフェニルホスフィンオキサイド、ビス−（２，６−ジクロロベンゾイル）−１−ナフチルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）―フェニルホスフィンオキサイドなどのビスアシルホスフィンオキサイド類等が使用できる。 Polymerization initiators used for photopolymerization include benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, benzophenone, and 4,4′-dimethylbenzophenone. Benzophenones such as 4-methacryloxybenzophenone, diacetyl, 2,3-pentadionebenzyl, camphorquinone, 9,10-phenanthraquinone, α-diketones such as 9,10-anthraquinone, 2,4-dike Thioxanthone compounds such as ethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzene) Zoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) -phenylphosphine oxide, etc. can be used.
なお、光重合開始剤には、しばしば還元剤が添加されるが、その例としては、２−（ジメチルアミノ）エチルメタクリレート、４−ジメチルアミノ安息香酸エチル、Ｎ−メチルジエタノールアミンなどの第３級アミン類、ラウリルアルデヒド、ジメチルアミノベンズアルデヒド、テレフタルアルデヒドなどのアルデヒド類、２−メルカプトベンゾオキサゾール、１−デカンチオール、チオサルチル酸、チオ安息香酸などの含イオウ化合物などを挙げることができる。 Incidentally, a reducing agent is often added to the photopolymerization initiator. Examples thereof include tertiary amines such as 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate, and N-methyldiethanolamine. Aldehydes such as lauryl aldehyde, dimethylaminobenzaldehyde and terephthalaldehyde, and sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid and thiobenzoic acid.
更に、上記光重合開始剤、還元性化合物に加えて光酸発生剤を加えて用いる例がしばしば見られる。このような光酸発生剤としては、ジアリールヨードニウム塩系化合物、スルホニウム塩系化合物、スルホン酸エステル化合物、およびハロメチル置換−S−トリアジン有導体、ピリジニウム塩系化合物等が挙げられる。 Furthermore, there are many cases where a photoacid generator is used in addition to the photopolymerization initiator and the reducing compound. Examples of such a photoacid generator include diaryl iodonium salt compounds, sulfonium salt compounds, sulfonate ester compounds, halomethyl-substituted S-triazine conductors, pyridinium salt compounds, and the like.
本発明において、シリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕による複合修復材料の色調の変化は、重合開始剤に還元剤としてアミン類が含有されていた場合に顕著に生じるため、本発明では斯様にアミン類を成分に含む重合開始剤に適用するのが特に効果的である。 In the present invention, the change in color tone of the composite restorative material due to the silica / titanium group oxide composite oxide fine particles [II-1] occurs remarkably when amines are contained as a reducing agent in the polymerization initiator. In the present invention, it is particularly effective to apply to a polymerization initiator containing an amine as a component.
これら重合開始剤は単独で用いることもあるが、２種以上を混合して使用してもよい。重合開始剤の配合量は目的に応じて有効量を選択すればよいが、重合性単量体１００重量部に対して通常０．０１〜１０重量部の割合であり、より好ましくは０．１〜５重量部の割合で使用される。 These polymerization initiators may be used alone or in combination of two or more. The blending amount of the polymerization initiator may be an effective amount depending on the purpose, but is usually 0.01 to 10 parts by weight, more preferably 0.1 to 100 parts by weight of the polymerizable monomer. Used in a proportion of ˜5 parts by weight.
＜（Ｅ）平均一次粒子径が０．０１〜０．１０μｍの範囲であり、該粒子径分布の標準偏差が１．３０以内にあるシリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕＞
本発明の歯科用複合修復材料には、平均一次粒子径が０．０１〜０．１０μｍの範囲のシリカ・チタン族酸化物系複合酸化物微粒子〔II〕を、前記（Ｃ）有機無機複合フィラーに配合させるもの（〔II−１〕）の他に、別成分〔II−２〕として配合させても良い。即ち、複合修復材料の硬化体に十分な機械的強度を付与しようとすると、（B）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕と（C）有機無機複合フィラーを配合させるだけでは不足する場合があり、また、この機械的強度は複合修復材料のフィラー充填量が多いほど高くなるため、斯様に別成分としても（A）重合性単量体に対してシリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕を配合するのが好適になる。
<(E) Silica-titanium group oxide composite oxide fine particles having an average primary particle size in the range of 0.01 to 0.10 μm and a standard deviation of the particle size distribution within 1.30 [II-2 ]>
In the dental composite restorative material of the present invention, silica / titanium group oxide composite oxide fine particles [II] having an average primary particle diameter in the range of 0.01 to 0.10 μm are used. In addition to what is added to (II-1), it may be added as a separate component [II-2]. That is, in order to impart sufficient mechanical strength to the cured body of the composite restorative material, (B) silica / titanium group oxide composite oxide particles [I-1] and (C) an organic-inorganic composite filler are blended. As the mechanical strength increases as the filler filling amount of the composite restorative material increases, as a separate component, (A) silica / titanium with respect to the polymerizable monomer It is preferable to add group oxide composite oxide fine particles [II-2].
前記したようにシリカ・チタン族酸化物系複合酸化物微粒子〔II〕を、有機無機複合フィラーに含有させることなく、そのまま複合修復材料中に配合すると、ペーストを長期間保存した場合にオパール効果が低下して行く。しかし、本発明では、シリカ・チタン族酸化物系複合酸化物微粒子〔II〕のあくまで一部として配合（〔II−２〕）するだけなので、上記有機無機複合フィラーに配合（〔II−１〕）した量分だけは、このオパール性の低減を防止する効果は発揮される。 As described above, silica-titanium group oxide composite oxide fine particles [II] are blended in the composite restorative material as they are without being included in the organic-inorganic composite filler, and the opal effect is obtained when the paste is stored for a long period of time. Go down. However, in the present invention, since it is only blended ([II-2]) as a part of the silica / titanium group oxide composite oxide fine particles [II], it is blended with the organic-inorganic composite filler ([II-1] ) The effect of preventing the reduction of the opal property is exhibited only by the amount obtained.
（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕は、光散乱効果を阻害せず、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕の一次粒子における粒径範囲との区別を明確にするため、その一次粒子径分布の標準偏差が１．３０以内であり、さらには１．２０以内のものを用いる。なお、この他の（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕の詳細な粒子性状は、（Ｃ）有機無機複合フィラーに配合させるシリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕と同様である。 (E) The silica / titanium group oxide composite oxide fine particles [II-2] do not inhibit the light scattering effect, and (B) the primary particles of the silica / titanium group oxide composite oxide particles [I-1]. In order to clearly distinguish the particle size from the particle size range, the standard deviation of the primary particle size distribution is within 1.30, and further within 1.20. The detailed particle properties of the other (E) silica / titanium group oxide composite fine particles [II-2] are as follows: (C) silica / titanium group oxide composite oxide mixed with the organic / inorganic composite filler This is the same as the fine particle [II-1].
本発明における（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕の配合量は、前記した（Ｃ）有機無機複合フィラーの配合理由と同様の理由から、（Ａ）重合性単量体１００重量部に対して、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕及び（Ｃ）有機無機複合フィラーとの合計量が５５０質量部を越えない範囲である。また、前記オパール効果の低下を防止する観点からは、シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕の配合量は、（Ａ）重合性単量体１００重量部に対して１２０質量部以下、より好適には１００質量部以下に留めるのが好ましい。 In the present invention, the blending amount of the (E) silica / titanium group oxide composite oxide fine particles [II-2] is the same as the reason for blending the (C) organic-inorganic composite filler. The total amount of (B) silica / titanium group oxide composite oxide particles [I-1] and (C) organic-inorganic composite filler does not exceed 550 parts by mass with respect to 100 parts by weight of the monomer. is there. Further, from the viewpoint of preventing a decrease in the opal effect, the amount of the silica / titanium group oxide composite oxide fine particles [II-2] is 120 with respect to 100 parts by weight of the polymerizable monomer (A). It is preferable to keep it below mass parts, more preferably below 100 mass parts.
さらに、この（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕の配合効果を十分に発揮させる観点からは、（Ａ）重合性単量体１００質量部に対して５０質量部以上、より好ましくは７０質量部以上を配合するのが望まれる。 Furthermore, from the viewpoint of sufficiently exerting the blending effect of the (E) silica / titanium group oxide composite fine particles [II-2], 50 masses per 100 mass parts of the polymerizable monomer (A). It is desirable to blend at least 70 parts by weight, more preferably at least 70 parts by weight.
＜その他の添加剤＞
本発明の歯科用複合修復材料には、その効果を阻害しない範囲で、上記（Ａ）〜（Ｅ）成分の他、公知の他の添加剤を配合することができる。具体的には、重合禁止剤、顔料、紫外線吸収剤等が挙げられる。
<Other additives>
In the dental composite restorative material of the present invention, other known additives can be blended in addition to the components (A) to (E) as long as the effect is not impaired. Specific examples include a polymerization inhibitor, a pigment, and an ultraviolet absorber.
＜歯科用複合修復材料の硬化体のオパール性＞
本発明の歯科用複合修復材料の硬化体は、優れた透明性を有し、良好なオパール性状を有する。すなわち、複合修復材料製造時における硬化体において、透明性を示す指標である、１ｍｍ厚の試験片のコントラスト比が通常、０．３０以下の優れた値であり、より好ましくは０．２５以下のものも得られる。ここで、コントラスト比は、色差計を用いて、三刺激値のＹ値を背景色黒及び白で測定し、下記式に基づいて求めた値である。
<Opal properties of cured composite restoration materials>
The cured product of the dental composite restorative material of the present invention has excellent transparency and good opal properties. That is, the contrast ratio of a 1 mm-thick test piece, which is an index indicating transparency, in the cured body at the time of manufacturing the composite restoration material is usually an excellent value of 0.30 or less, more preferably 0.25 or less. Things are also obtained. Here, the contrast ratio is a value obtained by measuring the Y values of the tristimulus values with the background colors black and white using a color difference meter, and based on the following equation.
コントラスト比＝背景色黒の場合のＹ値／背景色白の場合のＹ値
そして、同１ｍｍ厚の試験片は、オパール効果を示す指標である、ΔＣ*が通常、１８以上の優れた値であり、より好ましくは２０以上のものも得られる。ここで、ΔＣ*は、下記式で求められる。なお、透過光のオレンジ色は、赤−緑を表すａ＊、反射光の青色は青−黄を表すｂ＊で表されるものである。
Contrast ratio = Y value in the case of black background color / Y value in the case of white background The test piece with the thickness of 1 mm is an index showing the opal effect, and ΔC * is usually an excellent value of 18 or more. More preferably, 20 or more are also obtained. Here, ΔC * is obtained by the following equation. The orange color of transmitted light is represented by a * representing red-green, and the blue color of reflected light is represented by b * representing blue-yellow.
ΔＣ*＝√（ａ＊ ｂ−ａ＊ ｗ）２＋（ｂ＊ ｂ−ｂ＊ ｗ）２
（ａ＊ ｂ、ｂ＊ ｂ：背景色黒での色質指数、ａ＊ ｗ、ｂ＊ ｗ： 背景色白での色質指数）
さらに、同１ｍｍ厚の試験片の黒背景色の時の分光反射率は、４２０〜４７０ｎｍの波長において極大となるものが得られる。黒背景色という条件は、試験片を反射した光の測定を意味し、本発明の歯科用複合修復材料の硬化体は、優れた透明性とオパール性状のため、青色の光を示す４２０〜４７０ｎｍの波長で極大を示す。
ΔC * = √ (a * b− a * w ) 2 + (b * b− b * w ) 2
(A * b , b * b : Color quality index with black background, a * w , b * w : Color quality index with white background)
Furthermore, the spectral reflectance when the test piece having the same thickness of 1 mm is a black background color is maximized at a wavelength of 420 to 470 nm. The condition of the black background color means measurement of light reflected from the test piece, and the hardened body of the dental composite restorative material of the present invention shows blue light due to excellent transparency and opal properties, 420 to 470 nm. The maximum is shown at the wavelength of.
本発明の歯科用複合修復材料における、硬化体が斯様に優れた透明性やオパール性を示す性状は、該複合修復材料を長期間保存しても良好に維持される。 In the dental composite restorative material of the present invention, the properties of the cured body exhibiting such excellent transparency and opal properties are well maintained even when the composite restorative material is stored for a long period of time.
本発明の歯科用複合修復材料は、一般に、前記各必須成分及び必要に応じて各任意成分を所定量とって十分に混練し、さらに必要に応じてこのペーストを減圧下脱泡して気泡を除去することによって得ることができる。 In general, the dental composite restorative material of the present invention is sufficiently kneaded by taking a predetermined amount of each of the essential components and, if necessary, each optional component, and if necessary, defoaming the paste under reduced pressure to remove bubbles. It can be obtained by removing.
本発明の歯科用複合修復材料は、充填用コンポジットレジンの一般的使用方法に従って使用すれば良い。具体的には、（Ｄ）重合開始剤が光重合開始剤のものであれば、修復すべき歯の窩洞を適切な前処理材や接着材で処理した後に、これを直接充填し、歯牙の形に形成した後に専用の光照射器にて強力な光を照射して重合硬化させる方法等が挙げられる。
The dental composite restorative material of the present invention may be used in accordance with a general method for using a filling composite resin. Specifically, if (D) the polymerization initiator is a photopolymerization initiator, the cavity of the tooth to be restored is treated with an appropriate pretreatment material or adhesive, and then directly filled with the tooth cavity. Examples thereof include a method of irradiating with strong light with a dedicated light irradiator and then curing by polymerization after forming into a shape.
以下、実施例によって本発明をさらに具体的に説明するが、本発明はこれらの実施例に制限されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
本発明における各種物性測定方法は、それぞれ以下のとおりである。
（１）複合酸化物微粒子の平均一次粒子径および粒子径分布の標準偏差
走査型電子顕微鏡（日本電子社製、「Ｔ−３３０Ａ」）で粉体の写真を撮り、その写真の単位視野内に観察される粒子の数（３０個以上）および粒子径を測定し、測定値に基づき下記式により平均粒子径および標準偏差を算出した。
Various physical property measuring methods in the present invention are as follows.
(1) Average primary particle size and standard deviation of particle size distribution of composite oxide fine particles Take a picture of the powder with a scanning electron microscope (manufactured by JEOL Ltd., “T-330A”), and within the unit field of view of the photograph The number of particles to be observed (30 or more) and the particle diameter were measured, and the average particle diameter and standard deviation were calculated from the following formula based on the measured values.
（２）複合酸化物微粒子の平均斉度
走査型電子顕微鏡で粉体の写真を撮り、その写真の単位視野内に観察される粒子について、その数（ｎ：３０以上）、粒子の最大径を長径（Ｌｉ）、該長径に直交する方向の径を短径（Ｂｉ）を求め、下記式により算出した。
(2) Average asymmetry of composite oxide fine particles Take a picture of the powder with a scanning electron microscope, and the number of particles observed in the unit field of view (n: 30 or more), the maximum diameter of the particles The major axis (Li) and the minor axis (Bi) were calculated from the diameter in the direction perpendicular to the major axis, and calculated according to the following formula.
（３）複合酸化物微粒子の比表面積測定
比表面積測定装置「フローソーブII２３００」（島津製作所製）を用い、ＢＥＴ法にて測定した。なお、窒素３０％ヘリウム７０％混合気を用い、冷媒として液体窒素を用いた。
(3) Specific Surface Area Measurement of Composite Oxide Fine Particles A specific surface area measurement apparatus “Flowsorb II2300” (manufactured by Shimadzu Corporation) was used for measurement by the BET method. Note that a mixture of 30% nitrogen and 70% helium was used, and liquid nitrogen was used as the refrigerant.
（４）屈折率の測定
２３℃の恒温室において、１００ｍｌサンプルビン中、複合酸化物微粒子１ｇを無水トルエン５０ｍｌ中に分散させる。この分散液をスターラーで攪拌しながら１−ブロモトルエンを少しずつ滴下し、分散液が最も透明になった時点の分散液の屈折率をアッベ屈折率計にて測定し、得られた値を複合酸化物微粒子の屈折率とした。
(4) Measurement of refractive index In a thermostatic chamber at 23 ° C., 1 g of composite oxide fine particles are dispersed in 50 ml of anhydrous toluene in a 100 ml sample bottle. While stirring this dispersion with a stirrer, 1-bromotoluene was dropped little by little, and the refractive index of the dispersion when the dispersion became the most transparent was measured with an Abbe refractometer, and the obtained value was combined. The refractive index of the oxide fine particles was used.
（５）オパール効果の評価
歯科用複合修復材料のペーストを７ｍｍφ×１ｍｍの孔を有する型にいれ、両面はポリエステルフィルムで圧接した。可視光線照射器（トクヤマ製、パワーライト）で両面を３０秒ずつ光照射し硬化させた後、型から取り出して、色差計（東京電色製、「ＴＣ−１８００ＭＫＩＩ」)を用いて、背景色黒および白で測定を行い、下記式に基づいてΔＣ＊を求め、オパール効果の指標とした。ここで、オパール効果の特徴である透過光のオレンジ色は、赤−緑を表すａ＊、反射光の青色は青−黄を表すｂ＊で表される。
(5) Evaluation of opal effect The paste of the dental composite restorative material was put into a mold having a hole of 7 mmφ × 1 mm, and both sides were pressed with a polyester film. After irradiating and curing both sides with a visible light irradiator (Tokuyama, Powerlight) for 30 seconds each, remove it from the mold, and use a color difference meter (“TC-1800MKII”, manufactured by Tokyo Denshoku) Measurement was performed in black and white, and ΔC * was calculated based on the following formula, which was used as an index of the opal effect. Here, the orange color of transmitted light, which is a feature of the opal effect, is represented by a * representing red-green, and the blue color of reflected light is represented by b * representing blue-yellow.
ΔＣ＊＝√（ａ＊ ｂ−ａ＊ ｗ）２＋（ｂ＊ ｂ−ｂ＊ ｗ）２
（ａ＊ ｂ、ｂ＊ ｂ：背景色黒での色質指数、ａ＊ ｗ、ｂ＊ ｗ： 背景色白での色質指数）
また、下記指標に基づいて、目視評価を行った。
ΔC * = √ (a * b− a * w ) 2 + (b * b− b * w ) 2
(A * b , b * b : Color quality index with black background, a * w , b * w : Color quality index with white background)
Moreover, visual evaluation was performed based on the following parameter | index.
４：背景色黒において非常に鮮やかな青白い発色が見られる。 4: A very vivid pale white color is seen in the background color black.
３：背景色黒において鮮やかな青い発色が見られる。 3: A bright blue color is seen in the background color black.
２：背景色黒において青い発色が見られる。 2: A blue color is seen in the black background.
１：背景色黒において青い発色が見られない、あるいは、黄色い。 1: Blue color is not seen in the background color black or yellow.
（６）硬化体のオパール効果の保存安定性評価
歯科用複合修復材料のペーストを５０℃で保存した。保存開始から４週間後、６週間後、８週間後のペーストを（５）と同様に硬化体を作成し、同様な指標に基づいて、目視評価を行った。
(6) Storage stability evaluation of opal effect of cured body A paste of a dental composite restorative material was stored at 50 ° C. After 4 weeks, 6 weeks, and 8 weeks from the start of storage, a cured product was prepared in the same manner as in (5), and visual evaluation was performed based on the same index.
（７）透明性の評価
（５）と同様に色差計を用いて、三刺激値のＹ値を背景色黒及び白で測定した。下記式に基づいてコントラスト比を計算し、透明性の指標とした。
(7) Evaluation of transparency Using the color difference meter in the same manner as in (5), the Y values of the tristimulus values were measured with the background color black and white. The contrast ratio was calculated based on the following formula and used as an index of transparency.
コントラスト比＝背景色黒の場合のＹ値／背景色白の場合のＹ値 Contrast ratio = Y value when the background color is black / Y value when the background color is white
実施例及び比較例で用いた重合性単量体、重合開始剤等は以下のとおりである。
［重合性単量体］
・２，２−ビス［（３−メタクリロイルオキシ−２−ヒドロキシプロピルオキシ）フェニル］プロパン（以下、「ｂｉｓ−ＧＭＡ」と略す。）
・トリエチレングリコールジメタクリレート（以下、「３Ｇ」と略す。）
・２，２−ビス（４−メタクリロイルオキシポリエトキシフェニル）プロパン（以下、「Ｄ−２．６Ｅ」と略す。）
・１，６−ビス（メタクリルエチルオキシカルボニルアミノ）トリメチルオキサン（以下、「ＵＤＭＡ」と略す。）
［重合開始剤］
・アゾビスイソブチロニトリル（以下、「ＡＩＢＮ」と略す。）
・カンファーキノン（以下、「ＣＱ」と略す）。
・Ｎ，Ｎ−ジメチルｐ−安息香酸エチル（以下、「ＤＭＢＥ」と略す）。
［重合禁止剤］
・ヒドロキノンモノメチルエーテル（以下、「ＨＱＭＥ」と略す。）
・ジブチルヒドロキシトルエン（以下、「ＢＨＴ」と略す。）
［紫外線吸収剤］
・２−ヒドロキシ−４−メトキシベンゾフェノン（以下、「ＢＳ１１０」と略す。）
The polymerizable monomers, polymerization initiators, etc. used in the examples and comparative examples are as follows.
[Polymerizable monomer]
2,2-bis [(3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane (hereinafter abbreviated as “bis-GMA”)
Triethylene glycol dimethacrylate (hereinafter abbreviated as “3G”)
2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (hereinafter abbreviated as “D-2.6E”)
1,6-bis (methacrylethyloxycarbonylamino) trimethyloxane (hereinafter abbreviated as “UDMA”)
[Polymerization initiator]
Azobisisobutyronitrile (hereinafter abbreviated as “AIBN”)
Camphorquinone (hereinafter abbreviated as “CQ”).
N, N-dimethyl p-ethyl benzoate (hereinafter abbreviated as “DMBE”).
[Polymerization inhibitor]
Hydroquinone monomethyl ether (hereinafter abbreviated as “HQME”)
Dibutylhydroxytoluene (hereinafter abbreviated as “BHT”)
[Ultraviolet absorber]
2-hydroxy-4-methoxybenzophenone (hereinafter abbreviated as “BS110”)
製造例１〔有機樹脂マトリックスの調整〕
表１に示すような重合性単量体を各混合し、マトリックスＭ−１〜Ｍ−４を調製した。
Production Example 1 [Adjustment of organic resin matrix]
Polymerizable monomers as shown in Table 1 were mixed to prepare matrices M-1 to M-4.
本発明で用いた粒子の製造方法を以下に示す。
製造例２〔シリカ・チタン族酸化物系複合酸化物粒子〔I〕及び微粒子〔II〕の製造〕
以下の方法により、実施例および比較例で使用した、シリカ・チタン族酸化物系複合酸化物粒子を各製造した。
２−１）〔平均一次粒子径０．２５μｍの球状シリカ−チタニア粒子の合成〕
テトラエチルシリケート（コルコート社製，製品名：エチルシリケート２８）１７０ｇをメタノール４００ｇと混合し、０．０４質量％塩酸水溶液を５ｇ加えて温度３０℃約１時間攪拌しながら加水分解した。その後、この溶液にテトラブチルチタネート２７ｇとナトリウムメチラートメタノール溶液（濃度３０質量％）１０ｇをイソプロピルアルコール２００ｇに溶かした溶液を攪拌しながら混合して、テトラエチルシリケートとテトラブチルチタネートの混合溶液を調整した。次に攪拌装置付きの内容積３ｌのガラス製容器にメタノール１０００ｇを導入し、これに２５質量％アンモニア水溶液２５０ｇを加えてアンモニア性アルコール溶液を調整した。これにシリカ種粒子をつくるためのテトラエチルシリケート２ｇを添加し、３０分間撹拌した後に上記テトラエチルシリケートとテトラブチルチタネートの混合溶液を約５時間かけて滴下した。
The method for producing the particles used in the present invention is shown below.
Production Example 2 [Production of Silica / Titanium Group Oxide Composite Oxide Particles [I] and Fine Particles [II]]
The silica / titanium group oxide-based composite oxide particles used in Examples and Comparative Examples were produced by the following methods.
2-1) [Synthesis of spherical silica-titania particles having an average primary particle diameter of 0.25 μm]
170 g of tetraethyl silicate (manufactured by Colcoat, product name: ethyl silicate 28) was mixed with 400 g of methanol, 5 g of a 0.04 mass% hydrochloric acid aqueous solution was added, and the mixture was hydrolyzed while stirring at a temperature of 30 ° C. for about 1 hour. Thereafter, a solution prepared by dissolving 27 g of tetrabutyl titanate and 10 g of a sodium methylate methanol solution (concentration 30% by mass) in 200 g of isopropyl alcohol was mixed with this solution while stirring to prepare a mixed solution of tetraethyl silicate and tetrabutyl titanate. . Next, 1000 g of methanol was introduced into a glass container having an internal volume of 3 liters equipped with a stirrer, and 250 g of a 25% by mass aqueous ammonia solution was added thereto to prepare an ammoniacal alcohol solution. To this was added 2 g of tetraethyl silicate for producing silica seed particles, and after stirring for 30 minutes, the mixed solution of tetraethyl silicate and tetrabutyl titanate was added dropwise over about 5 hours.
なお、反応中は反応槽の温度を４０℃に保った。反応終了後、白濁した反応槽液から溶媒を留去し乾燥し９５０℃、１時間焼成しシリカ−チタニア粒子（ＰＦ−１）を得た。このシリカ−チタニア粒子は、粒子径分布０．２３〜０．２７μｍ、平均一次粒子径０．２５μｍであり、その形状はＳＥＭ観察から球状であった。得られた粒子は、更にγ−メタクリロイルオキシプロピルメトキシシランで表面処理した。得られた粒子の各種物性を表２に示した。 During the reaction, the temperature of the reaction vessel was kept at 40 ° C. After completion of the reaction, the solvent was distilled off from the clouded reaction vessel liquid, dried and baked at 950 ° C. for 1 hour to obtain silica-titania particles (PF-1). The silica-titania particles had a particle size distribution of 0.23 to 0.27 μm and an average primary particle size of 0.25 μm, and the shape thereof was spherical from SEM observation. The obtained particles were further surface-treated with γ-methacryloyloxypropylmethoxysilane. Various physical properties of the obtained particles are shown in Table 2.
２−２）〔平均一次粒子径０．１９μｍの球状シリカ−ジルコニア粒子の合成〕
テトラエチルシリケート（コルコート社製，製品名：エチルシリケート２８）１２０ｇをイソブチルアルコール（東然石油化学社製）４００ｇと混合し、０．０５％希硫酸水溶液５ｇを加えて４０℃で約１時間攪拌しながら加水分解した。その後、この溶液にテトラブチルジルコネート（日本曹達社製）２５ｇとナトリウムメチラートメタノール溶液（濃度２８質量％）１０ｇをイソブチルアルコール２００ｇに溶かした溶液を攪拌しながら混合して、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混合溶液を調整した。次に攪拌装置付き内容積３ｌガラス製容器にメタノール１０００ｇ，２５％アンモニア水２５０ｇを導入したアンモニア性アルコール溶液中に攪拌しながらテトラエチルシリケートを４ｇ添加し３０分間攪拌した後に上記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混合溶液を約６時間かけて滴下した。
2-2) [Synthesis of spherical silica-zirconia particles having an average primary particle diameter of 0.19 μm]
120 g of tetraethyl silicate (manufactured by Colcoat, product name: ethyl silicate 28) is mixed with 400 g of isobutyl alcohol (manufactured by Tosho Petrochemical), 5 g of 0.05% dilute sulfuric acid aqueous solution is added, and the mixture is stirred at 40 ° C. for about 1 hour. While hydrolyzing. Thereafter, a solution prepared by dissolving 25 g of tetrabutyl zirconate (manufactured by Nippon Soda Co., Ltd.) and 10 g of sodium methylate methanol solution (concentration: 28% by mass) in 200 g of isobutyl alcohol was mixed with stirring, and tetraethyl silicate and tetrabutyl were mixed. A mixed solution of zirconate was prepared. Next, 4 g of tetraethyl silicate was added while stirring in an ammoniacal alcohol solution into which 1000 g of methanol and 250 g of 25% aqueous ammonia were introduced into a 3 l glass container with a stirrer and stirred for 30 minutes, and then the tetraethyl silicate and tetrabutyl zirco were added. The mixed solution of nate was added dropwise over about 6 hours.
なお、反応中は反応槽の温度を４０℃に保った。反応終了後、白濁した反応槽液から溶媒を留去し乾燥し９５０℃、１時間焼成しシリカ−ジルコニア粒子（ＰＦ−２）を得た。このシリカ−ジルコニア粒子は、粒子径分布０．１６〜０．２０μｍ、平均一次粒子径は０．１９μｍで、形状は球状であった。得られた粒子は、更にγ−メタクリロイルオキシプロピルメトキシシランで表面処理した。得られた粒子の各種物性を表２に示した。 During the reaction, the temperature of the reaction vessel was kept at 40 ° C. After completion of the reaction, the solvent was distilled off from the cloudy reaction vessel liquid, dried, and calcined at 950 ° C. for 1 hour to obtain silica-zirconia particles (PF-2). The silica-zirconia particles had a particle size distribution of 0.16 to 0.20 μm, an average primary particle size of 0.19 μm, and a spherical shape. The obtained particles were further surface-treated with γ-methacryloyloxypropylmethoxysilane. Various physical properties of the obtained particles are shown in Table 2.
２−３）〔平均一次粒子径０．０８μｍの球状シリカ−チタニア微粒子の合成〕
テトラエチルシリケート（コルコート社製，製品名：エチルシリケート２８）１７０ｇをメタノール４００ｇと混合し、０．０４質量％塩酸水溶液を５ｇ加えて温度３０℃約１時間攪拌しながら加水分解した。その後、この溶液にテトラブチルチタネート（日本曹達社製）２６ｇとナトリウムメチラートメタノール溶液（濃度２８質量％）１０ｇをイソプロピルアルコール２００ｇに溶かした溶液を攪拌しながら混合して、テトラエチルシリケートとテトラブチルチタネートの混合溶液を調整した。次に攪拌装置付き内容積３ｌのガラス製容器にメタノール１０００ｇ導入し、これに２５％アンモニア水溶液２５０ｇを加えてアンモニア性アルコール溶液を調整した。これにシリカ種粒子をつくるためのテトラエチルシリケート２ｇを添加し、３０分間撹拌した後に上記テトラエチルシリケートとテトラブチルチタネートの混合溶液を約５時間かけて滴下した。
2-3) [Synthesis of spherical silica-titania fine particles having an average primary particle diameter of 0.08 μm]
170 g of tetraethyl silicate (manufactured by Colcoat, product name: ethyl silicate 28) was mixed with 400 g of methanol, 5 g of a 0.04 mass% hydrochloric acid aqueous solution was added, and the mixture was hydrolyzed while stirring at a temperature of 30 ° C. for about 1 hour. Thereafter, a solution prepared by dissolving 26 g of tetrabutyl titanate (manufactured by Nippon Soda Co., Ltd.) and 10 g of sodium methylate methanol solution (concentration 28% by mass) in 200 g of isopropyl alcohol was mixed with stirring, and tetraethyl silicate and tetrabutyl titanate were mixed. The mixed solution was prepared. Next, 1000 g of methanol was introduced into a glass container with an internal volume of 3 liters equipped with a stirrer, and 250 g of 25% aqueous ammonia solution was added thereto to prepare an ammoniacal alcohol solution. To this was added 2 g of tetraethyl silicate for producing silica seed particles, and after stirring for 30 minutes, the mixed solution of tetraethyl silicate and tetrabutyl titanate was added dropwise over about 5 hours.
なお、反応中は反応槽の温度を４０℃に保った。反応終了後、白濁した反応槽液から溶媒を留居し乾燥し１０００℃、１時間焼成しシリカ−チタニア粒子（ＰＦ−３）を得た。このシリカ−チタニア粒子は、粒子径分布０．０７２〜０．０９５μｍ、平均一次粒子径は０．０７９μｍであり、形状はＳＥＭ観察から球状であった。得られた微粒子は、更にγ−メタクリロイルオキシプロピルメトキシシランで表面処理した。得られた粒子の各種物性を表２に示した。 During the reaction, the temperature of the reaction vessel was kept at 40 ° C. After completion of the reaction, the solvent was retained from the cloudy reaction vessel liquid, dried and fired at 1000 ° C. for 1 hour to obtain silica-titania particles (PF-3). The silica-titania particles had a particle size distribution of 0.072 to 0.095 μm, an average primary particle size of 0.079 μm, and a spherical shape from SEM observation. The obtained fine particles were further surface-treated with γ-methacryloyloxypropylmethoxysilane. Various physical properties of the obtained particles are shown in Table 2.
２−４）〔平均一次粒子径０．０６μｍの球状シリカ−ジルコニア微粒子の合成〕
テトラエチルシリケート（コルコート社製，製品名：エチルシリケート２８）８０ｇをイソブチルアルコール（東然石油化学社製）４００ｇと混合し、０．０５％希硫酸水溶液５ｇを加えて４０℃で約１時間攪拌しながら加水分解した。その後、この溶液にテトラブチルジルコネート（日本曹達社製）２１ｇとナトリウムメチラートメタノール溶液（濃度２８質量％）１３ｇをイソブチルアルコール２００ｇに溶かした溶液を攪拌しながら混合して、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混合溶液を調整した。次に攪拌装置付き内容積３ｌガラス製容器にメタノール１０００ｇ，２５％アンモニア水２００ｇを導入したアンモニア性アルコール溶液中に攪拌しながら上記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混合溶液を約３時間かけて滴下した。
2-4) [Synthesis of spherical silica-zirconia fine particles having an average primary particle diameter of 0.06 μm]
80 g of tetraethyl silicate (manufactured by Colcoat, product name: ethyl silicate 28) is mixed with 400 g of isobutyl alcohol (manufactured by Tosho Petrochemical), 5 g of 0.05% dilute sulfuric acid aqueous solution is added, and the mixture is stirred at 40 ° C. for about 1 hour. While hydrolyzing. Thereafter, a solution obtained by dissolving 21 g of tetrabutyl zirconate (manufactured by Nippon Soda Co., Ltd.) and 13 g of sodium methylate methanol solution (concentration 28% by mass) in 200 g of isobutyl alcohol was mixed with stirring, and tetraethyl silicate and tetrabutyl were mixed. A mixed solution of zirconate was prepared. Next, the mixed solution of tetraethyl silicate and tetrabutyl zirconate was dropped over about 3 hours while stirring in an ammoniacal alcohol solution into which 1000 g of methanol and 200 g of 25% ammonia water were introduced into a 3 l glass container with a stirrer. did.
なお、反応中は反応槽の温度を４０℃に保った。反応終了後、白濁した反応槽液から溶媒を留去し乾燥し９５０℃、１時間焼成しシリカ−ジルコニア粒子（ＰＦ−４）を得た。このシリカ−ジルコニア粒子は、粒子径分布０．０４〜０．０８μｍ、平均一次粒子径は０．０６４μｍで、形状は球状であった。得られた微粒子は、更にγ−メタクリロイルオキシプロピルメトキシシランで表面処理した。得られた粒子の各種物性を表２に示した。 During the reaction, the temperature of the reaction vessel was kept at 40 ° C. After completion of the reaction, the solvent was distilled off from the cloudy reaction vessel liquid, dried, and calcined at 950 ° C. for 1 hour to obtain silica-zirconia particles (PF-4). The silica-zirconia particles had a particle size distribution of 0.04 to 0.08 μm, an average primary particle size of 0.064 μm, and a spherical shape. The obtained fine particles were further surface-treated with γ-methacryloyloxypropylmethoxysilane. Various physical properties of the obtained particles are shown in Table 2.
２−５）〔平均一次粒子径０．４０μｍ球状シリカ−ジルコニア粒子の合成〕
テトラエチルシリケート（コルコート社製，製品名：エチルシリケート２８）１２０ｇをイソブチルアルコール（東然石油化学社製）４００ｇと混合し、０．０５質量％希硫酸水溶液５ｇを加えて４０℃で約１時間攪拌しながら加水分解した。その後、この溶液にテトラブチルジルコネート（日本曹達社製）２４ｇとナトリウムメチラートメタノール溶液（濃度２８質量％）１０ｇをイソブチルアルコール２００ｇに溶かした溶液を攪拌しながら混合して、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混合溶液を調整した。次に攪拌装置付き内容積３ｌガラス製容器にメタノール１０００ｇ，２５％アンモニア水２５０ｇを導入したアンモニア性アルコール溶液中に攪拌しながらテトラエチルシリケートを４ｇ添加し３０分間攪拌した後に上記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混合溶液を約６時間かけて滴下した。
2-5) [Synthesis of spherical silica-zirconia particles having an average primary particle size of 0.40 μm]
120 g of tetraethyl silicate (manufactured by Colcoat, product name: ethyl silicate 28) is mixed with 400 g of isobutyl alcohol (manufactured by Tosho Petrochemical Co., Ltd.), 5 g of 0.05% by weight dilute sulfuric acid aqueous solution is added, and the mixture is stirred at 40 ° C. for about 1 hour. Hydrolysis. Thereafter, a solution prepared by dissolving 24 g of tetrabutyl zirconate (manufactured by Nippon Soda Co., Ltd.) and 10 g of sodium methylate methanol solution (concentration 28% by mass) in 200 g of isobutyl alcohol was mixed with stirring, and tetraethyl silicate and tetrabutyl were mixed. A mixed solution of zirconate was prepared. Next, 4 g of tetraethyl silicate was added while stirring in an ammoniacal alcohol solution into which 1000 g of methanol and 250 g of 25% aqueous ammonia were introduced into a 3 l glass container with a stirrer and stirred for 30 minutes, and then the tetraethyl silicate and tetrabutyl zirco were added. The mixed solution of nate was added dropwise over about 6 hours.
なお反応中は反応槽の温度を４０℃に保った。反応終了後、白濁した反応槽液から溶媒を留去し乾燥し９５０℃、１時間焼成しシリカ−ジルコニア粒子（ＰＦ−５）を得た。このシリカ−ジルコニア粒子は、粒子径分布０．３６〜０．４３μｍ、平均一次粒子径は０．４０μｍで、形状は球状であった。得られた粒子は、更にγ−メタクリロイルオキシプロピルメトキシシランで表面処理した。得られた粒子の各種物性を表２に示した。 During the reaction, the temperature of the reaction vessel was kept at 40 ° C. After completion of the reaction, the solvent was distilled off from the cloudy reaction vessel liquid, dried, and calcined at 950 ° C. for 1 hour to obtain silica-zirconia particles (PF-5). The silica-zirconia particles had a particle size distribution of 0.36 to 0.43 μm, an average primary particle size of 0.40 μm, and a spherical shape. The obtained particles were further surface-treated with γ-methacryloyloxypropylmethoxysilane. Various physical properties of the obtained particles are shown in Table 2.
２−６）〔平均一次粒子径０．６１μｍの球状シリカ−チタニア粒子の合成〕
テトラエチルシリケート（コルコート社製，製品名：エチルシリケート２８）１２０ｇをメタノール４００ｇと混合し、０．０４質量％塩酸水溶液を５ｇ加えて温度３０℃約１時間攪拌しながら加水分解した。その後、この溶液にテトラブチルチタネート２０ｇとナトリウムメチラートメタノール溶液（濃度３０質量％）１０ｇをイソプロピルアルコール１００ｇに溶かした溶液を攪拌しながら混合して、テトラエチルシリケートとテトラブチルチタネートの混合溶液を調整した。次に攪拌装置付きの内容積３ｌのガラス製容器にメタノール１０００ｇを導入し、これに２５質量％アンモニア水溶液２５０ｇを加えてアンモニア性アルコール溶液を調整した。これにシリカ種粒子をつくるためのテトラエチルシリケート２ｇを添加し、３０分間撹拌した後に上記テトラエチルシリケートとテトラブチルチタネートの混合溶液を約５時間かけて滴下した。
2-6) [Synthesis of spherical silica-titania particles having an average primary particle diameter of 0.61 μm]
120 g of tetraethyl silicate (manufactured by Colcoat, product name: ethyl silicate 28) was mixed with 400 g of methanol, 5 g of 0.04 mass% hydrochloric acid aqueous solution was added, and the mixture was hydrolyzed while stirring at 30 ° C. for about 1 hour. Thereafter, a solution prepared by dissolving 20 g of tetrabutyl titanate and 10 g of sodium methylate methanol solution (concentration 30% by mass) in 100 g of isopropyl alcohol was mixed with this solution while stirring to prepare a mixed solution of tetraethyl silicate and tetrabutyl titanate. . Next, 1000 g of methanol was introduced into a glass container having an internal volume of 3 liters equipped with a stirrer, and 250 g of a 25% by mass aqueous ammonia solution was added thereto to prepare an ammoniacal alcohol solution. To this was added 2 g of tetraethyl silicate for producing silica seed particles, and after stirring for 30 minutes, the mixed solution of tetraethyl silicate and tetrabutyl titanate was added dropwise over about 5 hours.
なお反応中は反応槽の温度を４０℃に保った。反応終了後、白濁した反応槽液から溶媒を留去し乾燥し９５０℃、１時間焼成しシリカ−チタニア粒子（ＰＦ−６）を得た。このシリカ−チタニア粒子は、粒子径分布０．５６〜０．６４μｍ、平均一次粒子径０．６１μｍであり、その形状はＳＥＭ観察から球状であった。得られた粒子は、更にγ−メタクリロイルオキシプロピルメトキシシランで表面処理した。得られた粒子の各種物性を表２に示した。 During the reaction, the temperature of the reaction vessel was kept at 40 ° C. After completion of the reaction, the solvent was distilled off from the cloudy reaction vessel liquid, dried, and calcined at 950 ° C. for 1 hour to obtain silica-titania particles (PF-6). The silica-titania particles had a particle size distribution of 0.56 to 0.64 μm and an average primary particle size of 0.61 μm, and the shape was spherical from SEM observation. The obtained particles were further surface-treated with γ-methacryloyloxypropylmethoxysilane. Various physical properties of the obtained particles are shown in Table 2.
製造例３〔有機無機複合フィラーの製造〕
乳鉢に、表３に示した各複合酸化物粒子を、製造しようとしている有機無機複合フィラー中に表３に示した充填率になる量で夫々計りとった。この複合酸化物粒子に対し、予め、重合開始剤ＡＩＢＮを０．５質量％溶解してある表３に示したマトリックスを徐々に添加して混合し、各ペースト化した。該ペーストは、９５℃、窒素雰囲気中で１時間重合した。得られた重合物をロールクラッシャーで粉砕後、振動ボールミル（中央化工機株式会社製、ニューライトミル）において、φ２５ｍｍのジルコニアボールを１０個とともに４００ｍｌのポットに入れた条件で３０分間粉砕し、有機無機複合フィラー原体を得た。
Production Example 3 [Production of organic-inorganic composite filler]
In the mortar, each composite oxide particle shown in Table 3 was weighed in an amount corresponding to the filling rate shown in Table 3 in the organic-inorganic composite filler to be produced. To this composite oxide particle, a matrix shown in Table 3 in which 0.5% by mass of a polymerization initiator AIBN was previously dissolved was gradually added and mixed to form pastes. The paste was polymerized at 95 ° C. in a nitrogen atmosphere for 1 hour. The polymer obtained was pulverized with a roll crusher, and then pulverized for 30 minutes in a vibration ball mill (New Light Mill, manufactured by Chuo Kako Co., Ltd.) under the condition that 10 φ25 mm zirconia balls were put in a 400 ml pot. An inorganic composite filler raw material was obtained.
この有機無機複合フィラー原体５０ｇの夫々をエタノール７５ｍｌ、３０％過酸化水素水６．６ｍｌの混合液に加え、８０℃でリフラックスし、その後、濾過・洗浄し乾燥することにより脱色した有機無機複合フィラーを得た。得られた各有機無機複合フィラーは更にγ−メタクリロイルオキシプロピルメトキシシランで表面処理した。
得られた有機無機複合フィラーの各種物性を表３に夫々示した。
50 g of each organic / inorganic composite filler material was added to a mixed solution of 75 ml of ethanol and 6.6 ml of 30% hydrogen peroxide solution, refluxed at 80 ° C., and then decolorized by filtration, washing and drying. A composite filler was obtained. Each obtained organic-inorganic composite filler was further surface-treated with γ-methacryloyloxypropylmethoxysilane.
Various physical properties of the obtained organic-inorganic composite filler are shown in Table 3, respectively.
実施例１
（Ａ）マトリックスＭ−１に対して、ＣＱを０．２質量％、ＤＭＢＥを０．３質量％、ＨＱＭＥを０．１５質量％、ＢＨＴを０．０２質量％、ＢＳ１１０を０．５質量％加えて混合し、均一な重合性単量体組成物を調製した。次に、乳鉢に、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕、および（Ｃ）有機無機複合フィラーＣＦ−１を計りとり、上記マトリックスＭ−１から調製した重合性単量体組成物１００質量部を赤色光下にて徐々に加えていき、暗所にて十分に混練し均一な硬化性ペーストとした。さらにこのペーストを減圧下脱泡して気泡を除去し歯科用複合修復材料を製造した。得られた複合修復材料について、上記の方法に基づいて各物性を評価した。組成及び結果を表４に示した。
Example 1
(A) 0.2% by mass of CQ, 0.3% by mass of DMBE, 0.15% by mass of HQME, 0.02% by mass of BHT, and 0.5% by mass of BS110 with respect to matrix M-1. In addition, mixing was performed to prepare a uniform polymerizable monomer composition. Next, (B) silica / titanium group oxide composite oxide particles [I-1] and (C) organic-inorganic composite filler CF-1 were weighed in a mortar and prepared from the matrix M-1. 100 parts by mass of the curable monomer composition was gradually added under red light and sufficiently kneaded in a dark place to obtain a uniform curable paste. Further, this paste was degassed under reduced pressure to remove bubbles to produce a dental composite restorative material. About the obtained composite restoration material, each physical property was evaluated based on said method. The composition and results are shown in Table 4.
実施例２〜８
実施例１と同じ複合修復材料組成において、（Ｃ）有機無機複合フィラーＣＦ−１を表４に示した種類（ＣＦ−１またはＣＦ−２）および配合量に変更し、さらに (Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕のＰＦ−３も表４に示した配合量で用いる（実施例５では未配合）以外は該実施例１と同様に実施してペーストを調製し、歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表４に示した。
Examples 2-8
In the same composite restorative material composition as in Example 1, (C) the organic-inorganic composite filler CF-1 was changed to the type (CF-1 or CF-2) and blending amount shown in Table 4, and (E) Silica The paste was prepared in the same manner as in Example 1 except that PF-3 of the titanium group oxide composite oxide fine particles [II-2] was also used in the blending amounts shown in Table 4 (unblended in Example 5). Prepared and manufactured dental composite restorative material. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 4.
実施例９〜１０
実施例３と同じ複合修復材料組成において、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕のＰＦ−１に代えて、ＰＦ−２またはＰＦ−５を表４に示した配合量で用いる以外は該実施例３と同様に実施してペーストを調製し歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表４に示した。
Examples 9-10
Table 4 shows PF-2 or PF-5 instead of PF-1 in (B) silica / titanium group oxide-based composite oxide particles [I-1] in the same composite restorative material composition as in Example 3. A paste was prepared in the same manner as in Example 3 except that it was used in a different blending amount to produce a dental composite restorative material. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 4.
実施例１１
実施例３と同じ複合修復材料組成において、（Ａ）マトリックスＭ−１に代えて、マトリックスＭ−３を用いてペーストを調整し歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表４に示した。
Example 11
In the same composite restorative material composition as in Example 3, (A) Instead of the matrix M-1, a paste was prepared using a matrix M-3 to produce a dental composite restorative material. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 4.
実施例１２
実施例１１と同じ複合修復材料組成において、（Ｃ）有機無機複合フィラーＣＦ−１に代えて、有機無機複合フィラーＣＦ−２を用いてペーストを調製し歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表４に示した。
Example 12
In the same composite restorative material composition as in Example 11, instead of (C) the organic / inorganic composite filler CF-1, a paste was prepared using an organic / inorganic composite filler CF-2 to produce a dental composite restorative material. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 4.
実施例１３
実施例３と同じ複合修復材料組成において、（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕のＰＦ−３に代えて、ＰＦ−４を用いてペーストを調製し歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表４に示した。
Example 13
In the same composite restorative material composition as in Example 3, instead of PF-3 of (E) silica-titanium group oxide composite oxide fine particles [II-2], a paste was prepared using PF-4, and dental A composite restorative material was produced. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 4.
実施例１４
実施例９と同じ複合修復材料組成において、（Ａ）マトリックスＭ−１、（Ｃ）有機無機複合フィラーＣＦ−１、（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕のＰＦ−３に代えて、Ｍ−４、ＣＦ−３、ＰＦ−４を表４に示した配合量で各用いる以外は該実施例９と同様に実施してペーストを調製し歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表４に示した。
Example 14
In the same composite restorative material composition as in Example 9, (A) Matrix M-1, (C) Organic-inorganic composite filler CF-1, (E) Silica-titanium group oxide composite oxide fine particles [II-2] A dental composite restorative material was prepared in the same manner as in Example 9 except that M-4, CF-3, and PF-4 were used in the blending amounts shown in Table 4 instead of PF-3. Manufactured. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 4.
実施例１〜１４の全てにおいて、ペーストの操作性が良好で、コントラスト比が小さく、オパール効果の強く、背景色黒の時の分光反射率が４４０ｎｍ付近で極大となる歯科用複合修復材料が得られた。さらに、色調の保存安定性も長期間安定であり、特に、（Ｅ）成分のシリカ・チタン族酸化物系複合酸化物微粒子の配合量が多め〔（Ａ）重合性単量体１００重量部に対して１００質量部を越える量〕である実施例４，８，１４以外は、非常に良好な保存安定性を示した。 In all of Examples 1 to 14, a dental composite restorative material is obtained in which the operability of the paste is good, the contrast ratio is small, the opal effect is strong, and the spectral reflectance when the background color is black is maximum near 440 nm. It was. Furthermore, the storage stability of the color tone is also stable for a long period of time. In particular, the amount of the (E) component silica / titanium group oxide composite oxide fine particles is large [(A) 100 parts by weight of the polymerizable monomer. Except for Examples 4, 8, and 14 in which the amount exceeds 100 parts by mass, very good storage stability was exhibited.
比較例１
（Ａ）マトリックスＭ−３に対して、ＣＱを０．２質量％、ＤＭＢＥを０．３質量％、ＨＱＭＥを０．１５質量％、ＢＨＴを０．０２質量％、ＢＳ１１０を０．５質量％加えて混合し、均一な重合性単量体組成物を調製した。次に、乳鉢に表５に示した（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕および（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕を計りとり、上記マトリックスＭ−３から調製した重合性単量体組成物１００質量部を赤色光下にて徐々に加えていき、暗所にて十分に混練し均一な硬化性ペーストとした。さらにこのペーストを減圧下脱泡して気泡を除去し歯科用複合修復材料を製造した。得られた複合修復材料について、上記の方法に基づいて各物性を評価した。組成及び結果を表５に示した。
Comparative Example 1
(A) 0.2% by mass of CQ, 0.3% by mass of DMBE, 0.15% by mass of HQME, 0.02% by mass of BHT, and 0.5% by mass of BS110 with respect to matrix M-3 In addition, mixing was performed to prepare a uniform polymerizable monomer composition. Next, (B) silica / titanium group oxide composite oxide particles [I-1] and (E) silica / titanium group oxide composite oxide particles [II-2] shown in Table 5 in a mortar. Weighed and 100 parts by weight of the polymerizable monomer composition prepared from the matrix M-3 was gradually added under red light, and was sufficiently kneaded in a dark place to obtain a uniform curable paste. Further, this paste was degassed under reduced pressure to remove bubbles to produce a dental composite restorative material. About the obtained composite restoration material, each physical property was evaluated based on said method. The composition and results are shown in Table 5.
比較例１は、本発明の必須成分である（Ｃ）有機無機複合フィラーが配合されておらず、ペーストの操作性がべたつきの非常に大きいものとなり、また、（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕の配合量が多いため、オパール効果の保存安定性が非常に低いものとなった。 In Comparative Example 1, (C) the organic-inorganic composite filler, which is an essential component of the present invention, is not blended, and the operability of the paste is very sticky. (E) Silica / titanium group oxide Since the compounding amount of the system composite oxide fine particles [II-2] is large, the storage stability of the opal effect is very low.
比較例２
実施例１１と同じ複合修復材料組成において、（Ｃ）有機無機複合フィラーと（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕を表５に示した配合量で用いる以外は該実施例１１と同様に実施してペーストを調製し歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表５に示した。
Comparative Example 2
In the same composite restorative material composition as in Example 11, except that (C) organic-inorganic composite filler and (E) silica / titanium group oxide composite fine particles [II-2] were used in the blending amounts shown in Table 5. A paste was prepared in the same manner as in Example 11 to produce a dental composite restorative material. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 5.
比較例２は、（Ｃ）有機無機複合フィラーの配合量が少なく、また、（Ｅ）シリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕の配合量が多いため、オパール効果の保存安定性が低いものとなった。 In Comparative Example 2, the amount of (C) the organic / inorganic composite filler is small, and the amount of (E) silica / titanium group oxide composite oxide fine particles [II-2] is large, so that the opal effect is preserved. The stability was low.
比較例３
実施例１と同じ複合修復材料組成において、（Ａ）マトリックスＭ−１と（Ｃ）有機無機複合フィラーＣＦ−１を代えて、マトリックスＭ−３、有機無機複合フィラーＣＦ−４を用いてペーストを調製し、歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表５に示した。
Comparative Example 3
In the same composite restorative material composition as in Example 1, instead of (A) the matrix M-1 and (C) the organic-inorganic composite filler CF-1, the paste was prepared using the matrix M-3 and the organic-inorganic composite filler CF-4. Prepared and manufactured dental composite restorative material. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 5.
比較例３は、本発明の必須成分である（Ｃ）有機無機複合フィラーとして有機フィラーを配合したもので、オパール効果がほとんど発現しないものとなった。 The comparative example 3 mix | blended the organic filler as (C) organic inorganic composite filler which is an essential component of this invention, and the opal effect hardly expressed.
比較例４
実施例１１と同じ複合修復材料組成において、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕であるＰＦ−１に代えて、ＰＦ−６を用いてペーストを調製し歯科用複合修復材料を製造した。得られた複合修復材料について、各物性を評価した。結果を表５に示した。
Comparative Example 4
In the same composite restorative material composition as in Example 11, instead of PF-1, which is (B) silica-titanium group oxide composite oxide particles [I-1], a paste was prepared using PF-6 and dental A composite restorative material was manufactured. Each physical property of the obtained composite restorative material was evaluated. The results are shown in Table 5.
比較例４は、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕の粒径が本発明の範囲外であり、良好なペーストの操作性が得られるが、コントラスト比が高く、またΔＣ*が小さくなり、オパール効果がほとんど発現しないものとなった。 In Comparative Example 4, the particle size of (B) silica / titanium group oxide composite oxide particles [I-1] is outside the range of the present invention, and good operability of the paste can be obtained. Further, ΔC * was small and the opal effect was hardly exhibited.
Claims (6)
（Ｂ）平均一次粒子径が０．１５〜０．５０μｍの範囲であり、該粒子径分布の標準偏差が１．３０以内にある球形のシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕を４０〜２００質量部、
（Ｃ）平均一次粒子径が０．０１〜０．１０μｍの範囲のシリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕を有機樹脂マトリックス中に４０〜７５質量％分散させてなる、（Ａ）重合性単量体の硬化体との屈折率差が０．１０以下である有機無機複合フィラーを、９０質量部以上で、且つ（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕との合計量が５５０質量部を越えない配合量、および
（Ｄ）有効量の重合開始剤
を含んでなる歯科用複合修復材料。 (A) 100 parts by mass of a polymerizable monomer,
(B) Spherical silica / titanium group oxide-based composite oxide particles [I−] having an average primary particle size in the range of 0.15 to 0.50 μm and a standard deviation of the particle size distribution within 1.30. 1] 40-200 parts by weight,
(C) Silica / titanium group oxide composite oxide fine particles [II-1] having an average primary particle diameter in the range of 0.01 to 0.10 μm are dispersed in an organic resin matrix by 40 to 75 mass%. (A) 90 mass parts or more of the organic-inorganic composite filler having a refractive index difference of 0.10 or less with respect to the cured product of the polymerizable monomer, and (B) silica / titanium group oxide composite oxide particles A dental composite restorative material comprising a blending amount of [I-1] not exceeding 550 parts by mass and (D) an effective amount of a polymerization initiator.
（Ｅ）平均一次粒子径が０．０１〜０．１０μｍの範囲であり、該粒子径分布の標準偏差が１．３０以内にあるシリカ・チタン族酸化物系複合酸化物微粒子〔II−２〕を、（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕及び（Ｃ）有機無機複合フィラーとの合計量が５５０質量部を越えない配合量
で含んでなる、請求項１に記載の歯科用複合修復材料。 further,
(E) Silica / titanium group oxide composite oxide fine particles [II-2] having an average primary particle size in the range of 0.01 to 0.10 μm and a standard deviation of the particle size distribution within 1.30. The total amount of (B) silica / titanium group oxide composite oxide particles [I-1] and (C) the organic-inorganic composite filler does not exceed 550 parts by mass. The dental composite restorative material described in 1.
平均一次粒子径が０．１５〜０．５０μｍの範囲であり、該粒子径分布の標準偏差が１．３０以内にある球形のシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−２〕を、有機樹脂マトリックス中に５質量％以上で、且つ（Ａ）重合性単量体の硬化体との屈折率差が０．１０以下に維持される配合量で分散されたものである、請求項１または請求項２に記載の歯科用複合修復材料。 (C) The organic-inorganic composite filler is further
Spherical silica / titanium group oxide composite oxide particles [I-2] having an average primary particle diameter in the range of 0.15 to 0.50 μm and a standard deviation of the particle diameter distribution within 1.30. The organic resin matrix is dispersed in an amount of 5% by mass or more and (A) a polymerizable monomer is maintained in a blending amount so that the difference in refractive index from the cured product is maintained at 0.10 or less. The dental composite restorative material according to claim 1 or 2.
（Ａ）重合性単量体１００質量部、
（Ｂ）平均一次粒子径が０．１５〜０．５０μｍの範囲であり、該粒子径分布の標準偏差が１．３０以内にある球形のシリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕を４０〜２００質量部、
（Ｃ）平均一次粒子径が０．０１〜０．１０μｍの範囲のシリカ・チタン族酸化物系複合酸化物微粒子〔II−１〕を有機樹脂マトリックス中に４０〜７５質量％分散させてなる、（Ａ）重合性単量体の硬化体との屈折率差が０．１０以下である有機無機複合フィラーを、９０質量部以上で、且つ（Ｂ）シリカ・チタン族酸化物系複合酸化物粒子〔Ｉ−１〕との合計量が５５０質量部を越えない配合量、および
（Ｄ）有効量の重合開始剤
の各成分を混合してなる歯科用複合修復材料の製造方法。 At least (A) 100 parts by mass of a polymerizable monomer,
(B) Spherical silica / titanium group oxide-based composite oxide particles [I−] having an average primary particle size in the range of 0.15 to 0.50 μm and a standard deviation of the particle size distribution within 1.30. 1] 40-200 parts by weight,
(C) Silica / titanium group oxide composite oxide fine particles [II-1] having an average primary particle diameter in the range of 0.01 to 0.10 μm are dispersed in an organic resin matrix by 40 to 75 mass%. (A) 90 mass parts or more of the organic-inorganic composite filler having a refractive index difference of 0.10 or less with respect to the cured product of the polymerizable monomer, and (B) silica / titanium group oxide composite oxide particles The manufacturing method of the dental composite restorative material which mixes the compounding quantity whose total amount with [I-1] does not exceed 550 mass parts, and each component of the polymerization initiator of (D) effective amount.
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| JP7422994B2 (en) | 2019-11-26 | 2024-01-29 | 株式会社トクヤマデンタル | Dental curable composition |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002255721A (en) * | 2000-12-25 | 2002-09-11 | Tokuyama Corp | Curable composition for dental use |
| JP2003511400A (en) * | 1999-10-07 | 2003-03-25 | カー コーポレイション | Opalescent filler for dental restorative composites |
| JP2007532518A (en) * | 2004-04-07 | 2007-11-15 | イボクラー ビバデント アクチエンゲゼルシャフト | Hardenable dental material with adjustable translucency |
-
2011
- 2011-01-26 JP JP2011013790A patent/JP5769429B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003511400A (en) * | 1999-10-07 | 2003-03-25 | カー コーポレイション | Opalescent filler for dental restorative composites |
| JP2002255721A (en) * | 2000-12-25 | 2002-09-11 | Tokuyama Corp | Curable composition for dental use |
| JP2007532518A (en) * | 2004-04-07 | 2007-11-15 | イボクラー ビバデント アクチエンゲゼルシャフト | Hardenable dental material with adjustable translucency |
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| JP7321456B2 (en) | 2019-12-04 | 2023-08-07 | 株式会社トクヤマデンタル | dental restorative kit |
| WO2021131490A1 (en) * | 2019-12-23 | 2021-07-01 | 株式会社トクヤマデンタル | Dental filling and repairing material kit |
| RU2821271C1 (en) * | 2019-12-23 | 2024-06-19 | Токуяма Дентал Корпорейшн | Set of filling restoration materials |
| WO2024070260A1 (en) * | 2022-09-27 | 2024-04-04 | 株式会社トクヤマデンタル | Dental curable composition, blank for dental-cutting work, production method for silica-based composite oxide powder body, and dental filler |
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