CN102423270A - Method for sputtering protective film on surface of denture stent - Google Patents
Method for sputtering protective film on surface of denture stent Download PDFInfo
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- CN102423270A CN102423270A CN2011103029775A CN201110302977A CN102423270A CN 102423270 A CN102423270 A CN 102423270A CN 2011103029775 A CN2011103029775 A CN 2011103029775A CN 201110302977 A CN201110302977 A CN 201110302977A CN 102423270 A CN102423270 A CN 102423270A
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Abstract
The invention discloses a method for sputtering a protective film on the surface of a denture stent and relates to the denture stent. The method comprises the following steps of: pretreating a test piece of the denture stent; performing gas plasma treatment on the surface layer of the test piece of the denture stent, namely exposing the test piece of the denture stent in the plasma atmosphere of mixed gas consisting of nitrogen and helium, treating, importing a carbon-containing organic compound so as to form a layer of nitridized diamond-like carbon film on the surface of the test piece of the denture stent, and ensuring that gas ingredients and the surface of the test piece of the denture stent form a firm structure by using plasmas; and performing heat treatment on the test piece of the denture stent which is subjected to plasma treatment to obtain the denture stent of which the surface is sputtered with the protective film. The pulsed vacuum arc ion plating is adopted, and hydrogen does not participate in the process of preparing the diamond-like film, so the film has stable performance; and a substrate does not have negative bias, so the phenomenon that the film is damaged due to the discharging of the negative bias can be avoided.
Description
Technical field
The present invention relates to a kind of denture stent, especially relate to a kind of method at denture stent surface sputtering protecting film.
Background technology
Artificial tooth (artificial tooth) support is prone to abrasive particle in daily use; These abrasive particles can cause the local inflammation reaction and cause oral cavity partial to infect; PH value alters a great deal in the oral environment; And alloy as repair materials in oral environment functionating as with hard food repeated friction, or the daily cleaning artificial tooth all can damage artificial tooth.For this reason, use surface modified technology to overcome these defectives of dental alloy and give alloy new performance, to satisfy the specific (special) requirements in different application field.In recent years, DLC film (DLC) has attracted many material supplier authors' very big concern with its unique advantage and good performance.DLC film has many performances similar with diamond thin; But the DLC thin film does not have the progress of making a breakthrough property in medical domain especially Oral Repair is used in recent years; One very important reasons be exactly that the internal stress of thin film is excessive, be prone to cause rete to come off.
Chinese patent CN1030870 discloses the orthopedic clinical denture stent surface to metal structure of a kind of medical tooth section and carries out the brush coating technology, is to solve artificial dental crown through acid bronze alloy, cochrome, 18～8 chromium nickel stainless steel material, bridge, snap ring, support, base etc. and has intensity difference, not wear-resisting, perishable, dezincify pore-forming and color technical problem attractive in appearance inadequately.
Chinese patent CN1889898 has disclosed a kind of method of definite artificial tooth shape; Comprise: the coupling part (14) of scanning tooth base (10) at least; The coupling part (14) that wherein said tooth base (10) comprises first fixed body (12) and is attached thereto is gone up the formation physical model in said coupling part (14) and is scanned said pontic (22) at least to make pontic (22), to reach; Thereby in scanning step, also scan the surface of first fixed body (12), and can carry out said scanning step with arbitrary order.Can scan to provide about the data of first fixed body (12) with coupling part (14) relative position tooth base (10), it can be used to be aligned in the data that obtain in the said scanning step.Also disclosed a kind of method and a kind of method of producing artificial tooth of making denture model.
Summary of the invention
The object of the present invention is to provide a kind of method at denture stent surface sputtering protecting film.
The present invention includes following steps:
1) the denture stent test specimen is carried out pretreatment;
2) gas plasma process is carried out on denture stent test specimen top layer; Its concrete grammar is the denture stent test specimen to be exposed in the plasma atmosphere of the mist of being made up of nitrogen and helium handle; Import carbonaceous organic compound then; Form one deck nitriding diamond-like carbon film on artificial tooth test specimen surface, and make the surface of gas componant and artificial tooth test specimen form strong construction by plasma;
3) will be through step 2) denture stent test specimen after the Cement Composite Treated by Plasma heat-treats, surface sputtering has the denture stent of protecting film.
In step 1), said pretreated method can be: with the denture stent test specimen with abrasive paper for metallograph two-sidedly polish step by step, polish, clean, drying; Said cleaning can be adopted the acetone ultrasonic cleaning.
In step 2) in, saidly the denture stent test specimen is exposed to the vacuum of handling in the argon plasma can be 0.01～10mPa, be preferably 0.1～5mPa; Saidly the denture stent test specimen is exposed to the time of handling in the mist of forming by nitrogen and helium and can be 10～200s, be preferably 20～60s; The power density on said denture stent test specimen surface can be 2～5000mW/cm
2, be preferably 1000～3000mW/cm
2Carbon content in the said carbonaceous organic compound can be the molecule percent of 0.01～70g of mist, preferably the molecule percent of 0.1～30g; The organic compound of said carbon can be selected from methane etc.; The frequency that said plasma passes through can be the alternating current discharge of 15～75kHz, the preferably alternating current of 20～40kHz discharge; Said denture stent test specimen is the artificial tooth test specimen that tooth section common metal is adopted on denture stent test specimen surface, and said tooth section common metal can adopt a kind of in titanium, nichrome, the cochrome etc.
In step 3), said heat treated condition can be pressure 0.01～1mPa, 60～1000 ℃ of temperature, time 15～200s.
Using plasma pulsed arc ion plating technique of the present invention and non-balance magnetically controlled sputter technology deposit high rigidity at the bottom of the pure titanio, high tenacity with strong wearability TiN/TiC/DLC nano composite membrane is.Through scanning electron microscope, energy spectrum analysis, the influence that parameters such as the film structure of means research laminated films such as AFM, thicknesses of layers change membrane stress is in the hope of obtaining the laminated film of low stress high film substrate bond strength.Nano combined DLC film preparing technology parameter at the bottom of the acquisition oral medical titanio.Through film is optical design, and adjustment laminated film surface color is in the hope of reaching ideal surface of denture aesthetic effect.To the microstructure of DLC laminated film sample, mechanical property and biocompatibility characterize, and optimizing film is the design and processes parameter, and through medical clinical test, set up effective medical assessment system.
The present invention adopts pulse vacuum arc ion deposition, in the process of preparation DLC film, does not have hydrogen to participate in, thereby film performance is stable, and substrate does not have back bias voltage, so do not have the phenomenon that the back bias voltage discharge destroys rete.
Description of drawings
Fig. 1 is a microscopic examination Vickers impression.In Fig. 1, the unit of abscissa and vertical coordinate is microns (micron); A:9.6% is nitrogenous, and b:9.8% is nitrogenous, and c:3.4% is nitrogenous, and d:0% is nitrogenous; The microhardness testers impression: 9.6% nitrogenous group of resistance to pressure and hardness with 9.8% nitrogenous group DLC film is higher than 3.4% nitrogenous group and 0% nitrogenous group; Appear around 0% nitrogenous group of impression obvious crack and to around diffusion, 3.4% nitrogenous group also has the crack to form, diffusion is not seen obvious crack less than 0% nitrogenous group around 9.6% nitrogenous group of impression.
Fig. 2 is 0% o'clock DLC film surface and cross-section morphology (* 50000) for SEM observation nitrogen content.
Fig. 3 is 3.4% o'clock DLC film surface and cross-section morphology (* 50000) for SEM observation nitrogen content.
Fig. 4 is 9.8% o'clock DLC film surface and cross-section morphology (* 50000) for SEM observation nitrogen content.
Fig. 5 is 9.6% o'clock DLC film surface and cross-section morphology (* 50000) for SEM observation nitrogen content.
Fig. 6 is the surface topography SEM photo (* 1000) before and after the abrasion of DLC group.A1 is for before wearing and tearing, and A2 is for after wearing and tearing.
Fig. 7 is the surface topography SEM photo (* 1000) before and after the abrasion of TiN group.A1 is for before wearing and tearing, and A2 is for after wearing and tearing.
Fig. 8 is the surface topography SEM photo (* 1000) before and after the abrasion of anodic oxidation group.A1 is for before wearing and tearing, and A2 is for after wearing and tearing.
Fig. 9 is the surface topography SEM photo (* 1000) before and after the blank control group abrasion.A1 is for before wearing and tearing, and A2 is for after wearing and tearing.
Figure 10 is the critical load of 5 groups of test specimen cuts.In Figure 10, vertical coordinate is acoustic emission value (Acoustic emission), and curve a is anodic oxidation, and curve b is a blank, and curve c is simple plating DLC, and curve d is Ti, and curve e is N-DLC.
Figure 11 is the electrokinetic potential polarization curve.In Figure 11, abscissa is nominal current density (Log current density) (A/cm
2), vertical coordinate be oxidizing potential vs. reference electrode (Potential vs.SCE) (V); Curve a is N-DLC, and curve b is Ti-N, and curve c is Anodizing, and curve d is Ti.
Figure 12 is at the denture stent of denture stent surface sputtering protecting film and the structural representation of artificial tooth.
The specific embodiment
Following examples will combine accompanying drawing that the present invention is further described.
Concrete grammar at denture stent surface sputtering protecting film is following:
1) the casting volume is 15mm * 15mm * 2.2mm titanium denture stent test specimen (being the titanium base plate) 1, polishes step by step, polishes with abrasive paper for metallograph is two-sided.The acetone ultrasonic cleaning, dry back is subsequent use.
2) adopt Y в H и IIA-1-001 type plasma coating machine to strengthen chemical vapour deposition (CVD) and prepare nitriding DLC (N-DLC) thin film 3; This equipment is furnished with a gas phase and cleans ion source and a high purity graphite target; Methane is as carbon source, and argon is as ionized gas, when vacuum reaches 5 * 10
-3During Pa, charge into argon and clean, heating 30min (360 ℃ of temperature) connects direct-current arc titanium ion source, and inflated with nitrogen is coated with TiN transition zone 2 (electric current 75A, voltage 150V is coated with 30min, cooling 20min).Charge into methane through the gaseous ion source then and reach 150Pa, open carbon ion source deposition nitriding DLC film 3.Running voltage is 200V, and operating frequency is 20 * 10
3Hz, apart from 270mm, angle of incidence is controlled in 30 °, and the time is 20min; The reaction pressure that assorted system is oozed in the realization of control nitrogen flow is 1.3Pa.Fixedly the flow of methane (10ml/min) is constant in experiment, and nitrogen flow is controlled in 0～100ml/min scope.
Fixedly the flow of methane (10ml/min) is constant in experiment, and nitrogen flow is controlled in 0～100ml/min scope.
Table 1 is listed among the nitriding DLC film preparation technology, when changing the flow-rate ratio of methane/nitrogen, and the measurement and the observed result of nitrogen-atoms percentage composition, film thickness, microhardness and the adhesive force of thin film.Wherein nitrogen content is calculated and is got by XPS measuring.The result shows that nitrogen content increases with the methane/nitrogen flow-rate ratio, and is tending towards saturated.Film thickness is 12～1.5 μ m, and microhardness is that 3 electric data of measurement get average, and load is 5g in the measurement, and the impression shape is rule comparatively.Adhesive force is observed and is selected load 25g for use.Figure 12 is given in the denture stent of denture stent surface sputtering protecting film and the structural representation of artificial tooth, and in Figure 12, labelling A is an artificial tooth.
The mechanical property that table 1 thin film is relevant with adhesive force
Fig. 1 provides microscopic examination Vickers impression, and wherein a:9.6% is nitrogenous, and b:9.8% is nitrogenous, and c:3.4% is nitrogenous, and d:0% is nitrogenous.The microhardness testers impression: 9.6% nitrogenous group of resistance to pressure and hardness with 9.8% nitrogenous group DLC film is higher than 3.4% nitrogenous group and 0% nitrogenous group; Appear around 0% nitrogenous group of impression obvious crack and to around diffusion, 3.4% nitrogenous group also has the crack to form, diffusion is not seen obvious crack less than 0% nitrogenous group around 9.6% nitrogenous group of impression.
Fig. 2 provides SEM, and to observe nitrogen content be 0% o'clock DLC film surface (a) and cross-section morphology (b) (* 50000).
Fig. 3 provides SEM, and to observe nitrogen content be 3.4% o'clock DLC film surface (a) and cross-section morphology (b) (* 50000).
Fig. 4 provides SEM, and to observe nitrogen content be 9.8% o'clock DLC film surface (a) and cross-section morphology (b) (* 50000).
Fig. 5 provides SEM, and to observe nitrogen content be 9.6% o'clock DLC film surface (a) and cross-section morphology (b) (* 50000).
Fig. 2～5 provide different nitrogen contents DLC thin film, and to get SEM surface topography map: Fig. 2 be 0 o'clock for nitrogen element content, and thin film internal junction crystallization is not obvious, and the surface presents the fish scale shape, and crystal disperses, and distance is bigger between the section crystal column; Along with nitrogen content increases, the DLC film surface is to pile up the crystalline solid that transfers tiny densification gradually to by the comparatively thick amorphous particle of yardstick, gos deep into after the nitrogen element; Originally some granules to upper process have appearred in film surface uniformly, and along with the increase of nitriding amount, the density between the outstanding granule increases thereupon; And yardstick is reduced to tens nanometers from the hundreds of nanometer gradually; Crystal presents the burr shape when reaching capacity like Fig. 5 nitrogen content on the surface, and the section crystal pitch almost disappears, and crystal column is arranged closely; Along with nitrogen content increases, DLC thin-membrane section thickness increases gradually, visible DLC lens cylinder from the growth of TiN transition zone by loose to densification, the crystal diameter refinement.
Comprehensive Experiment and analysis result can draw following results:
1. with the increase of methane/nitrogen ratio in the technology, nitrogen content increases thereupon in the thin film.
2. after nitrogen mixes the DLC thin film, change the microstructure of thin film, produced the granule of tens nanometer scale.
3. the fine and close nano composite structure of DLC/CNx has reduced the internal stress of thin film, has improved the adhesive force of thin film to substrate.
1. the wearability of nanometer nitriding diamond-film-like is analyzed
1.1 test specimen divides into groups and handles
Test specimen is divided into 4 groups at random: i.e. N-DLC film group, TiN magnetron sputtering group, anodic oxidation group, blank group.Every group of 5 test specimens.Chinese toothpaste with fluoride 150g and distilled water 350ml are mixed with mixed liquor, with method white jade are not had fluorine toothpaste and also be mixed with mixed liquor.Test specimen is scrubbed tow sides 25h with two kinds of toothpaste mixed liquors on toothbrush abrasion test machine, load on the toothbrush head 2.45N vertically to power, the speed of scrubbing is 50 times/min totally 75000 times, normally brushes teeth 3 years to simulate.Before and after handling, every group of experiment measure its configuration of surface of surface roughness, reflectance and color-values (CIE L*a*b*) scanning electron microscopic observation of every test specimen respectively.Experimental result is carried out comparing between front and back contrast and group.
1.2 roughness concentration
Use the TR240 surface roughometer, measure the roughness that every group of test specimen handled front and back, CUT-OFF is 0.8mm, and evaluation length is 4.0mm, and resolution is 0.22 μ m.Each test specimen is measured 2 times, gets its meansigma methods as final measurement.
1.3 film-Ji adhesion
Select two nitriding diamond-like carbon film-coating samples at random and plate DLC thin film, anodic oxidation, Ti-N plated film test specimen and blank group test specimen merely with the automatic scratching instrument of WS-2000 coating adhesion (diamond circular cone pressure head; 120 ° of cone angles; Tip diameter 0.2mm, cut loading speed 100N/min) measures the thin film of five groups of surface treatment methods of contrast and the adhesion of substrate.
2. result
2.1 roughness concentration result: table 2 provides and respectively organizes all differences of test specimen roughness Ra value added: the DLC minimum; The blank group is maximum; TiN, anodic oxidation, blank group and DLC difference be (P＜0.01) obviously, and each is organized test specimen and between fluorine-containing and no fluorine toothpaste processing factor, relatively has only the blank group that significant difference (P＜0.05) is arranged.
Four groups of different test specimen surface finish measurement value Ra (um) of table 2,
are (n=5)
This group of " * " note has significant difference (P＜0.01) with each group
2.2 scanning electron microscopic observation result: Fig. 9 is the surface topography SEM photo (* 1000) before and after the blank control group abrasion (before the D1 abrasion, D2 wears and tears the back), blank control group is scrubbed the back pattern; Before contrast is scrubbed; There is sparse point corrosion pit on the surface, and surperficial brush mark is clear continuously, disruption do not occur; Fig. 8 after the anodic oxidation group is scrubbed, also has sparse point corrosion pit on the surface for the surface topography SEM photo (* 1000) before and after the abrasion of anodic oxidation group (before the C1 abrasion, C2 wears and tears the back), and surperficial brush mark is clear; Fig. 7 is the surface topography SEM photo (* 1000) before and after the abrasion of TiN group (before the B1 abrasion, B2 wears and tears the back), and TiN scrubs the back and do not see obvious brush mark on the surface, but the residual tiny vestige of processed is arranged; Fig. 6 is the surface topography SEM photo (* 1000) (before the A1 abrasion, A2 wear and tear the back) before and after the abrasion of DLC group, and obvious brush mark was not seen on the surface after DLC scrubbed, and rarely seen have a residual tiny vestige of processed.
2.3 film-Ji contrast test result
Figure 10 shows that the critical load of nitriding DLC plated film is 52N, and the sofar signal that computer shows sharply increases, and the load of this moment is that thin film begins to peel off, and the film-substrate cohesion average of this test sample has notable difference with the critical load 38N that is coated with the DLC thin film merely.Also be higher than simultaneously TiN, anode oxide film and blank group.
Conclusion
External scrub test can simulate well daily brush teeth and factor such as toothpaste to the stress wearing and tearing of dummy; Thereby the various surface modification modes of Indirect evaluation prolonged application effect in mouth; With regard to wearability; Nanometer nitriding DLC film is best, and the TiN thin film takes second place, and anodic oxidation film and blank control group are the poorest.Wear-resisting, corrosion resistant N-DLC film not only can improve the service property (quality) that also can improve dummy service life of dummy, in the clinical practice in future, has vast potential for future development.
Below provide the corrosion resistance analysis of nanometer nitriding DLC film:
1. experiment is divided into groups
Test specimen is divided into four groups at random, 8 every group, i.e. N-DLC composite membrane group, TiN magnetron sputtering group, anodic oxidation group, blank group.
2. experimental situation
Press ISO/TR10271
[123]The standard fabrication artificial saliva is put into 37 ℃ of thermostatic water tanks with the electrolyzer that fills the 500ml artificial saliva, with NaOH adjustment pH value to 5, adds 0.25g fluoride gel (with reference to fluoride treatment, onset concentration 0.1%) in artificial saliva, and electrolyte is without degasification.
3. experimental technique
In three electrolyzers, sample is used clamp clamps, the test area that makes exposure is 10mm
2, be immersed in the artificial saliva.Each electrode is put into electrolyzer on request.Input electrokinetic potential scanning ordering parameter, wherein initial potential is-250mV (with respect to corrosion potential), final current potential is+3V (with respect to reference electrode) that scanning speed is that 1m V/s and software foundation are got in touch.Initial delay finishes laggard action potential polarization scanning, and the record result draws the anodic polarization curves of electrokinetic potential scanning, and Figure 11 provides the electrokinetic potential polarization curve.
The result:
Table 3 provides 4 kinds of corrosion sample corrosion potential (Ecorr)/transpassivation current potential (Etp) numerical value.
Experimentation shows; Nitriding DLC film process for treating surface can effectively improve the apparent condition of pure titanium framework; Carry the decay resistance on high purity titanium surface, thereby improve the pure titanium false tooth quality, for the important clinical meaning is arranged the service life of improving the dental metal dummy.
4 kinds of corrosion of table 3 sample corrosion potential (Ecorr)/transpassivation current potential (Etp) numerical value
Claims (10)
1. method at denture stent surface sputtering protecting film is characterized in that may further comprise the steps:
1) the denture stent test specimen is carried out pretreatment;
2) gas plasma process is carried out on denture stent test specimen top layer; Its concrete grammar is the denture stent test specimen to be exposed in the plasma atmosphere of the mist of being made up of nitrogen and helium handle; Import carbonaceous organic compound then; Form one deck nitriding diamond-like carbon film on artificial tooth test specimen surface, and make the surface of gas componant and artificial tooth test specimen form strong construction by plasma;
3) will be through step 2) denture stent test specimen after the Cement Composite Treated by Plasma heat-treats, surface sputtering has the denture stent of protecting film.
2. a kind of method at denture stent surface sputtering protecting film as claimed in claim 1 is characterized in that in step 1), and said pretreated method is: with the denture stent test specimen with abrasive paper for metallograph two-sidedly polish step by step, polish, clean, drying; Said cleaning can be adopted the acetone ultrasonic cleaning.
3. a kind of method as claimed in claim 1 at denture stent surface sputtering protecting film; It is characterized in that in step 2) in; Said the denture stent test specimen is exposed to the vacuum of handling in the argon plasma is 0.01～10mPa, is preferably 0.1～5mPa.
4. a kind of method as claimed in claim 1 at denture stent surface sputtering protecting film; It is characterized in that in step 2) in; Said the denture stent test specimen to be exposed to the time of handling in the mist of being made up of nitrogen and helium be 10～200s, is preferably 20～60s.
5. a kind of method at denture stent surface sputtering protecting film as claimed in claim 1 is characterized in that in step 2) in, the power density on said denture stent test specimen surface is 2～5000mW/cm
2, be preferably 1000～3000mW/cm
2
6. a kind of method as claimed in claim 1 at denture stent surface sputtering protecting film; It is characterized in that in step 2) in; Carbon content in the said carbonaceous organic compound is the molecule percent of 0.01～70g of mist, preferably the molecule percent of 0.1～30g.
7. a kind of method at denture stent surface sputtering protecting film as claimed in claim 1 is characterized in that in step 2) in, the organic compound of said carbon is selected from methane.
8. a kind of method at denture stent surface sputtering protecting film as claimed in claim 1 is characterized in that in step 2) in, the frequency that said plasma passes through is the alternating current discharge of 15～75kHz, the preferably alternating current of 20～40kHz discharge.
9. a kind of method as claimed in claim 1 at denture stent surface sputtering protecting film; It is characterized in that in step 2) in; Said denture stent test specimen is the artificial tooth test specimen that tooth section common metal is adopted on denture stent test specimen surface, and said tooth section common metal preferably adopts a kind of in titanium, nichrome, the cochrome.
10. a kind of method at denture stent surface sputtering protecting film as claimed in claim 1 is characterized in that in step 3) said heat treated condition is pressure 0.01～1mPa, 60～1000 ℃ of temperature, time 15～200s.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106510876A (en) * | 2016-11-01 | 2017-03-22 | 东莞市爱嘉义齿有限公司 | Metal ceramic repairing body inner crown and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197629A (en) * | 1997-03-11 | 1998-11-04 | 赫罗伊斯库尔泽有限公司 | Surface treating method |
| JP2005013719A (en) * | 2003-06-03 | 2005-01-20 | Kokusai Apatite Kenkyusho:Kk | Intra-orally worn body |
| CN101871086A (en) * | 2010-05-24 | 2010-10-27 | 广州有色金属研究院 | Preparation method for catalytic plasma nitrocarburized and diamond-like carbon composite film |
| CN201850306U (en) * | 2010-08-17 | 2011-06-01 | 中国人民解放军第四军医大学 | Mini type plasma film coating device for stomatological department |
-
2011
- 2011-09-28 CN CN 201110302977 patent/CN102423270B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197629A (en) * | 1997-03-11 | 1998-11-04 | 赫罗伊斯库尔泽有限公司 | Surface treating method |
| JP2005013719A (en) * | 2003-06-03 | 2005-01-20 | Kokusai Apatite Kenkyusho:Kk | Intra-orally worn body |
| CN101871086A (en) * | 2010-05-24 | 2010-10-27 | 广州有色金属研究院 | Preparation method for catalytic plasma nitrocarburized and diamond-like carbon composite film |
| CN201850306U (en) * | 2010-08-17 | 2011-06-01 | 中国人民解放军第四军医大学 | Mini type plasma film coating device for stomatological department |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106510876A (en) * | 2016-11-01 | 2017-03-22 | 东莞市爱嘉义齿有限公司 | Metal ceramic repairing body inner crown and preparation method thereof |
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Owner name: XIAMEN XINDAXING FALSE TOOTH MANUFACTURING CO., LT Free format text: FORMER OWNER: YIN LU Effective date: 20140109 |
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| C41 | Transfer of patent application or patent right or utility model | ||
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Effective date of registration: 20140109 Address after: The abundance of Industrial Park No. 215 Yuehua road Huli District of Xiamen city in Fujian province 361000 No. 3 building two floor Patentee after: Xiamen Xinda Xingyi tooth Manufacture Co., Ltd. Address before: The Lake District of Xiamen City, Fujian province 361000 three in Wuyuan No. 4 East Building Room 1502 Patentee before: Yin Lu |
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| CP01 | Change in the name or title of a patent holder |
Address after: The abundance of Industrial Park No. 215 Yuehua road Huli District of Xiamen city in Fujian province 361000 No. 3 building two floor Patentee after: Xiamen Xin Xing Xing Medical Technology Co., Ltd. Address before: The abundance of Industrial Park No. 215 Yuehua road Huli District of Xiamen city in Fujian province 361000 No. 3 building two floor Patentee before: Xiamen Xinda Xingyi tooth Manufacture Co., Ltd. |
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| CP01 | Change in the name or title of a patent holder |