Dental medical member and method for producing the same

Abstract

To provide a dental medical member exhibiting superior adhesive strength, and a method for producing the dental medical member.SOLUTION: A dental medical member comprises a zirconia (Zr) material as a substrate, where the substrate includes an ion implantation region with implanted silicon (Si) or phosphorus (P) ions, and where the ion implantation level within 20 nm from the surface is 2×1012 ions / cm2 or more. A method for producing a dental medical member includes a step of implanting silicon (Si) or phosphorus (P) ions into a substrate composed of a zirconia (Zr) material to form an ion implantation region, where the ion implantation level within 20 nm from the surface is 2×1012 ions / cm2 or more.SELECTED DRAWING: Figure 6

Description

[Technical field]

[0001] The present invention relates to a dental medical device and a method for producing the same. [Background technology]

[0002] In dental caries (cavity) treatment, the decayed area is removed (cut) and then artificial materials are used to restore the crown, restoring the bite function. Traditionally, so-called silver fillings, which are alloys mainly made of silver, have been used, but due to the risk of metal allergies and poor aesthetics, efforts are being made to switch to metal-free materials. Composite resin and zirconia are used as metal-free materials. Composite resin has sufficient adhesive strength, but its mechanical strength is inferior to that of zirconia and it is easily discolored. On the other hand, zirconia has excellent mechanical properties, is resistant to discoloration, and has excellent aesthetics, but it has a problem of inferior adhesive strength.

[0003] Zirconia materials used in dentistry are manufactured in dental hospitals or dental laboratories. Dental components made of zirconia materials are roughened by blasting to improve the adhesive strength and anchor effect, but this has the problem of large variations depending on the dentist's instructions and the dental technician's skill. Although not for dental use, several techniques, including ion implantation, have been reported in a report on surface treatment in total hip replacement surgery in research into medical materials (Non-Patent Document 1). In the field of dentistry, there have been several reports on ion implantation into the titanium surface of implant bodies (Non-Patent Documents 2-4, etc.). In Japan, there have been reports on surface modification by fluorine ion implantation into ceramic materials (Non-Patent Document 5). On the other hand, in research on zirconia, there have been reports on the structural characteristics of zirconia polymorphs irradiated with Ar ions, but there are still few reports that are linked to clinical practice (Non-Patent Document 6). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Lappalainen R et al., “Potential of Coatings in Total Hip Replacement.”, Clinical Orthopedics and Related Research, 430:p72-79, 2005. [Non-Patent Document 2] Nayab SN et al., “Effects of calcium ion-implantation of titanium on bone cell function in vitro”, Journal of Biomedical Materials Research Part A., 2007, 83(2):296-302 [Non-Patent Document 3] Jin G et al., “Synergistic effects of dual Zn / Ag ion implantation in osteogenic activity and antibacterial ability of titanium”,Biomaterials.35,27,2014,7699-7713 [Non-Patent Document 4] Lampe I et al., “Investigation of silver nanoparticles on titanium surface created by ion implantation technology”, International Journal of Nanomedicine, 2019;14:4709-4721. [Non-Patent Document 5] Y. Teranishi et al., “Glass carbon surface modified by the fluorine ion irradiation”, Nuclear Instruments and Methods in Physics Research B, No. 272, p. 458-461 (2012) [Non-Patent Document 6] Kurpaska L et al., “Influence of Ar-ion implantation on the structural and mechanical properties of zirconia as studied by Raman spectroscopy and nanoindentation techniques”, Spectrochim Acta Part A:Molecular and Biomolecular Spectrosc,195,15,184-190,2018 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a dental medical component having excellent adhesive strength and a method for producing the same. [Means for solving the problem]

[0006] The means for solving the problems of the present invention are as follows. 1. Zirconia (Zr) material is used as the base material. the substrate has an ion implantation region in which silicon (Si) ions or phosphorus (P) ions are implanted; The amount of ions implanted within a depth of 20 nm from the surface is 2×10 12 pieces / cm 2 A dental medical component characterized by the above. 2. A process for forming an ion implantation region by implanting silicon (Si) ions or phosphorus (P) ions into a substrate made of a zirconia (Zr) material, The amount of ions implanted within a depth of 20 nm from the surface is 2×10 12 pieces / cm 2 The method for producing a dental medical component, characterized by the above. Effect of the Invention

[0007] The dental medical article of the present invention has excellent adhesive strength. Since the dental medical article of the present invention uses an ion implantation method, which is a method with excellent reproducibility, it is less dependent on the skill of the operator and can stably exhibit the desired adhesive strength. [Brief description of the drawings]

[0008] [Figure 1] 1 is an image showing the appearance of a zirconia substrate after silicon ion implantation in Experiment 1, in which the accelerating voltage was 100 keV. [Diagram 2] 1 is a graph showing the dependence of tensile strength of a silicon ion-implanted surface on the amount of ion implantation in Experiment 1. [Diagram 3] 1 is a graph showing the dependence of surface roughness of a silicon ion-implanted surface on the amount of ion implantation in Experiment 1. [Figure 4] 1 is a graph showing the dependence of the contact angle on the amount of ions implanted on a silicon ion-implanted surface in Experiment 1. [Diagram 5] An image showing the abundance ratio of hydroxyl groups measured by TOF-SIMS at the boundary between a region without ion implantation (blank) and a region with a Si ion implantation dose of 1×1015 ions / cm2 (c) of the sample prepared in Experiment 1. [Figure 6] 1 is a graph showing the dependence of the tensile strength of a silicon ion-implanted surface on the amount of ion implantation in Experiment 1 and Experiment 2 in which the acceleration voltage was 50 keV. [Figure 7] 13 is a graph showing a simulation result of the depth profile of Si ions at acceleration voltages of 50 keV and 100 keV. [Figure 8] Graph showing the amount of Si ions (cumulative amount) present from the surface to a depth of 20 nm for Si ion implantation doses of 1×10 13 ions / cm 2 , 1×10 14 ions / cm 2 , and 1×10 15 ions / cm 2 in Experiments 1 and 2. [Figure 9]13 is an image showing the appearance of a zirconia substrate after phosphorus ion implantation in Experiment 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Dental medical materials The dental medical device of the present invention has a base material made of zirconia (Zr), The substrate has an ion implantation region in which silicon (Si) ions or phosphorus (P) ions are implanted, The amount of ions implanted within a depth of 20 nm from the surface is 2×10 12 pieces / cm 2 That's all.

[0010] ·Base The substrate used in the dental medical device of the present invention is made of a zirconia material. The zirconia material may be any material that is mainly made of zirconia, and may be silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), yttrium oxide (Y 2 O 3 ), calcium oxide (CaO), magnesium oxide (MgO), cerium oxide (CeO 2 ), lanthanum oxide (La 2 O 3 ), and dental zirconia materials called Y, 3Y-HA, 4Y, 5Y, and 6Y can also be used. Zirconia materials include zirconia (ZrO 2 ) in an amount of, for example, 80% by mass or more, 85% by mass or more, or 90% by mass or more.

[0011] Ion implantation area The dental medical component of the present invention has an ion implantation region in which silicon (Si) ions or phosphorus (P) ions are implanted. The ion implantation region is formed by irradiating the surface of a substrate with an ion beam of Si ions or P ions. The depth position of the ion implantation region can be controlled by the acceleration voltage of the ion beam, and can be set to, for example, 20 keV or more and 250 keV or less. The amount of ions implanted in the ion implantation region has a Gaussian distribution in the depth direction, and the distribution in the depth direction can be accurately estimated by simulation.

[0012] When the accelerating voltage of the ion beam is high, the ion implantation region is formed at a deeper position, and when it is low, the ion implantation region is formed at a shallower position. Therefore, when the accelerating voltage is high, the ion implantation region is formed at a deeper position, and the ion implantation amount within a depth of 20 nm from the surface is 2 × 10 12 pieces / cm 2 On the other hand, when the acceleration voltage is lowered, the ion implantation region is formed at a shallower position, so that the amount of ions implanted within a depth of 20 nm from the surface is reduced to 2×10 12 pieces / cm 2 It can be more than that.

[0013] In the dental medical device of the present invention, the amount of ions implanted within a depth of 20 nm from the surface is 2×10 12 pieces / cm 2 The dental medical device of the present invention has an ion implantation dose of 2×10 12 pieces / cm 2 In the dental medical device of the present invention, the amount of ions implanted within a depth of 20 nm from the surface is 3×10 12 pieces / cm 2 More than 5×10 is preferable. 12 pieces / cm 2 More preferably, 1×10 13 pieces / cm 2 More preferably, 3×10 13 pieces / cm 2 The above is even more preferred. In addition, the dental medical device of the present invention has an ion implantation amount of 7×10 11 pieces / cm 2 More than 1×10 is preferable. 12 pieces / cm 2 More preferably, 2×10 12 pieces / cm 2 More preferably, 3×10 12 pieces / cm 2 The above is even more preferred. EXAMPLES

[0014] Experiment 1: Silicon (Si) ion implantation 1 (100 keV) Silicon ions were implanted into one zirconia substrate (5 x 5 cm) under different conditions. The ion implantation conditions were as follows: Ion beam acceleration voltage: 100 keV (implantation depth: approximately 82±42 nm) Ion implantation amount: (blank) 0, (a) 1×10 13 pieces / cm 2 , (b) 1×10 14 pieces / cm 2 , (c) 1×10 15 pieces / cm 2 , (d) 1×10 16 pieces / cm 2 The zirconia substrate after ion implantation is shown in FIG.

[0015] It was confirmed that the color of zirconia changes due to ion implantation, and the more the amount of ions implanted, the darker the brown becomes. However, since the dental medical device of the present invention uses the ion-implanted surface as the adhesion surface, there is no problem with aesthetics.

[0016] After the ion implantation, the following measurements were carried out at each site. Tensile Test The cement space was set as a circle with a diameter of 4 mm and a thickness of 100 μm on the zirconia coating surface. 2 O 3The specimen was sandblasted at 0.2 MPa using alumina (alumina oxide), ultrasonically cleaned, and then coated with a dental metal primer (Alloy Primer, manufactured by Kuraray Noritake Dental Co., Ltd.) to serve as the adhesion surface. The jig was attached to the zirconia using dental resin cement (RelyX Ultimate Adhesive Resin Cement, color: translucent, manufactured by 3M). After removing excess cement, the jig was photopolymerized using a dental LED light irradiator and stored at room temperature of 23°C for 30 minutes, and then stored in water at 37°C for 24 hours. The above samples were subjected to tensile tests (n=15, n=9 (E14, E16)) using a universal testing machine (Autograph AGS-J, Shimadzu Corporation) at a crosshead speed of 2 mm / min (Reference paper: Takahashi et al, Dental Materials Journal, 2018, 37(5), 734-739). In addition, the acceleration voltage was 100 keV and the ion implantation dose (c) was 1×10 15 pieces / cm 2 For the specimens, tensile tests were carried out in the same manner after they were left to stand at room temperature for two weeks and two months after ion implantation.

[0017] Surface roughness The surface roughness was measured using a surface roughness measuring device (TALYSURF SERIES2, manufactured by Taylor Hobson) in accordance with JIS B0651:2001 at a reference length of 0.8 mm. Measurements were taken at six randomly selected locations, and the arithmetic mean value was used for evaluation. ·Water contact angle measurement Using an automatic contact angle meter (DM-301, manufactured by Kyowa Interface Science Co., Ltd.), 1 μL of ion-exchanged water was dropped, and the contact angle was measured 1 second after the drop. The measurement was carried out 10 times, and the evaluation was based on the arithmetic mean value.

[0018] Surface hydroxyl groups At the boundary between blank and (c), the amount of hydroxyl groups was measured using a time-of-flight secondary ion mass spectrometer (TRIFT III, manufactured by ULVAC-PHI, Inc.) under the following conditions: primary ion source: gallium ions, primary ion output voltage: 25 kV, measurement mass range: 0.5 to 2000, measurement area: 300 μm × 300 μm.

[0019] ·result The tensile strength measurement results are shown in FIG. It was confirmed that the tensile strength (adhesive strength) increased as the amount of silicon ions implanted increased. 15 pieces / cm 2 The tensile strength reached a maximum of 12.38 MPa, which was 1.5 times that of the blank without ion implantation. Furthermore, when the amount of ion implantation was (c) 1×10 15 pieces / cm 2 The tensile strength of the sample was 12.40 MPa and 12.38 MPa after two weeks and two months, respectively, confirming that the strength did not decrease. In addition, when the appearance was observed after the test, in (blank), (a), and (b), the zirconia and the adhesive had peeled off at the interface, and in (c) and (d), the adhesive had broken down.

[0020] The results of the surface roughness measurements are shown in FIG. No change in surface roughness was observed regardless of whether ion implantation was performed or not. This confirmed that the improvement in adhesion due to ion implantation was not due to the anchor effect.

[0021] ·Contact angle The contact angle measurement results are shown in FIG. Ion implantation amount (a) 1×10 13 pieces / cm 2 When the amount of ions injected was increased, the contact angle became smaller and the surface became hydrophilic. 16 pieces / cm 2 (c) 1 × 10 15 pieces / cm 2 (c) 1×10 15 pieces / cm2 was the most hydrophilic. Although the contact angle is affected by surface dirt and minute irregularities, it has been confirmed that the hydrophilicity is improved by implanting silicon ions into zirconia.

[0022] Surface hydroxyl group amount The measurement results by TOF-SIMS are shown in FIG. In Figure 5, higher brightness (brighter) indicates more hydroxyl groups. It was confirmed that the abundance of hydroxyl groups increased by implanting silicon ions.

[0023] The above results suggest that by forming an ion-implanted layer, the amount of hydroxyl groups on the substrate surface can be increased without damaging the substrate surface, thereby improving the adhesive strength.

[0024] Experiment 2: Silicon (Si) ion implantation 2 (50 keV) Silicon ions were implanted into the zirconia substrate in the same manner as in Experiment 1, except that the ion beam acceleration voltage was set to 50 keV (implantation depth: approximately 41±23 nm). Tensile tests were performed on each part of the obtained substrate. The results are shown in Figure 6 together with the results of 100ke in Experiment 1.

[0025] At an acceleration voltage of 50 keV, the ion implantation dose is (a) 1×10 13 pieces / cm 2 has the same intensity as the blank, and the ion implantation dose is (b) 1×10 14 pieces / cm 2 Above this point the intensity was saturated.

[0026] Experiment 3: Simulation A simulation of implanting 1,000 Si ions into zirconia at acceleration voltages of 100 keV and 50 keV was performed under the following conditions. Simulations used: SRIM-2008(http: / / www.srim.org / SRIM / SRIM-2008.e) Simulation conditions Implanted ion species: Si + Implant acceleration energy: 50keV, 100keV Counterpart material: ZrO 2 Counterpart material (ZrO 2 ) Range (Width): 10000A Counterpart material (ZrO 2 ) Density: 5.68g / cm 3 Plotting Window Depths:Min:0,Max:1000A Total Number of ions:1000 Simulation work method Click and select "TRIM Calculation" DAMAGE:Select Detailed Calculation with Full Damage Cascades Select BasicPlots:ALL FOUR of the above screen

[0027] The depth profile of Si ions is shown in FIG. From the results of the depth profile, the ion implantation dose at accelerating voltages of 50 keV and 100 keV was 1×10 13 pieces / cm 2 , 1×10 14 pieces / cm 2 , 1×10 15 pieces / cm 2 The amount of ions present (cumulative amount) from the surface to a depth of 20 nm was calculated for the specimen. The results of the amount of ions present are shown in Figure 8, and the relationship between the amount of ions present and the tensile strength is shown in Table 1. [Table 1]

[0028] When the accelerating voltage was the same, the amount of ions present at depths of 10 nm and 20 nm from the surface increased as the ion implantation dose increased. When the ion implantation dose was the same, the amount of ions present at depths of 10 nm and 20 nm from the surface increased as the acceleration voltage decreased. This is because the ion implantation depth becomes shallower when the acceleration voltage is lower.

[0029] The tensile strength was equal to or less than that of the control without ion implantation (8 MPa or less), under the conditions (100 keV, 1 × 10 13 pieces / cm 2 ) and conditions (50 keV, 1×10 13 pieces / cm 2 ) is the ion abundance from the surface to a depth of 20 nm, which is approximately 1.2 × 10 12 pieces / cm 2 It was less than that. The tensile strength was 9.42 MPa under the conditions (100 keV, 1×10 14 pieces / cm 2 ) is the ion abundance from the surface to a depth of 20 nm, which is approximately 3.6 × 10 12 pieces / cm 2 It was. The tensile strength was about 12 MPa under the conditions (50 keV, 1×10 14 pieces / cm 2 ), conditions (100 keV, 1×10 15 pieces / cm 2 ), conditions (50keV, 1×10 15 pieces / cm 2 ) in the order of increasing ion abundance from the surface to a depth of 20 nm. These had almost the same tensile strength values, but the fracture occurred in the adhesive. These results suggest that the ion abundance from the surface to a depth of 20 nm is 2×10 12 pieces / cm 2 It was confirmed that above this level, the amount of hydroxyl groups and the amount of Si ions on the substrate surface increased to a level that contributed to the adhesive strength, improving the adhesive strength.

[0030] Experiment 4: Phosphorus (P) ion implantation Phosphorus ions were implanted into one zirconia substrate (5 x 5 cm) under different conditions. The ion implantation conditions were as follows: Ion beam acceleration voltage: 100 keV (implantation depth: approximately 79±40 nm) Ion implantation amount: (blank) 0, (a) 1×10 13 pieces / cm 2 , (b) 1×10 15 pieces / cm 2 In addition, similarly to Experiment 3, phosphorus ions (P + The depth distribution of the Cr was obtained by simulation.

[0031] The zirconia substrate after ion implantation is shown in FIG. It was confirmed that the color of zirconia changes due to ion implantation, and the color becomes darker brown as the amount of ion implantation increases. Since the dental medical device of the present invention uses the ion-implanted surface as the adhesion surface, there is no problem with aesthetics.

[0032] After ion implantation, tensile test measurements (n=9) and surface roughness measurements were performed on each site in the same manner as in Experiment 1. The results are shown in Table 2.

[0033] ·result [Table 2]

[0034] As with silicon ions, there was no change in surface roughness when phosphorus ions were implanted. In addition, the implantation dose of phosphorus ions from the surface to a depth of 20 nm was 2×10 12 pieces / cm 2 The above confirmed a tendency for tensile strength (adhesive strength) to increase.

Claims

1. The substrate is made of zirconia (Zr) material. the substrate has an ion implantation region in which silicon (Si) ions or phosphorus (P) ions are implanted; The amount of ions implanted within a depth of 20 nm from the surface is 2×10 １２ pieces / cm ２ A dental medical component characterized by the above.

2. The method includes a step of implanting silicon (Si) ions or phosphorus (P) ions into a substrate made of a zirconia (Zr) material to form an ion implantation region, The amount of ions implanted within a depth of 20 nm from the surface is 2×10 １２ pieces / cm ２ The method for producing a dental medical component, characterized by the above.

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