JP2013163660A - Silane-containing composition, bonding method using the composition, and prosthesis bonded by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silane-containing composition, a bonding method using the composition, and a prosthesis bonded by the method, and to thereby bond firmly a dental non-noble metal to a dental resin.SOLUTION: A silane-containing composition which is used for surface treatment of a dental non-noble metal for improving bonding force to a resin, includes a silane coupling agent and a volatile organic solvent or a polymerizable resin composition, wherein the silane coupling agent is 3-methacryloxy propyl trimethoxysilane (γ-MPTS), and the weight of the silane coupling agent occupies 0.2-20.0% of the total weight of the silane-containing composition, and the weight of the volatile organic solvent occupies 80.0-99.8% of the total weight of the silane-containing composition, otherwise, the weight of the silane coupling agent occupies 0.5-10.0% of the total weight of the silane-containing composition, and the weight of the polymerizable resin composition occupies 90.0-99.5% of the total weight of the silane-containing composition.

Description

  The present invention relates to a metal adhesive composition used for bonding a dental non-noble metal and a dental resin, a bonding method using the composition, and a prosthesis bonded by the method.

(1. Bonding of dental precious metal and dental resin in the prior art)
A noble metal is used as the dental metal, and examples of the noble metal include gold alloys and gold-silver palladium alloys.
Such a precious metal is to which a dental resin is adhered, and if this adhesion is removed, a patient who has been treated will have a prosthesis in the oral cavity, which is painful and dangerous.
In order to improve the adhesive force between the two, the following mechanical and chemical methods are used.

(2. Mechanical method)
Examples of the mechanical technique include a method of increasing the adhesion area such as creating irregularities on the metal surface using retention beads during casting of noble metal and sand blasting using alumina particles.
(3. Chemical methods)
As a chemical method, there is a method in which a surface treatment is performed on the surface of a noble metal and the surface of a dental resin. An example is a method in which a primer containing a sulfur-based compound having an adhesive effect with gold or the like as a base treatment agent is applied to the surface of a noble metal.

(4. Problems when using non-precious metals for dentistry)
In recent years, implant surgery and the like have become widespread, and dental non-noble metals such as titanium and titanium alloys having biocompatibility are often used instead of the above-mentioned noble metals.
However, with general dental technology equipment (casting machine) and primers containing sulfur-based compounds, it is possible to bond the above-mentioned dental precious metal and dental resin. Have difficulty. Examples of dental non-noble metals include titanium, titanium alloys, nickel chromium alloys, and cobalt chromium alloys.

(5. Problems with mechanical methods)
For example, when the dental non-noble metal is titanium or a titanium alloy, since titanium has a high melting point and is difficult to cast, a mechanical fitting effect due to an increase in contact area using retention beads cannot be obtained. In recent years, with the introduction of CAD / CAM systems, methods for cutting dental non-noble metals by an apparatus rather than casting are increasing.
As a result, dental non-precious metals cannot be expected to improve the adhesive strength by a mechanical method, and a technique for improving the adhesive strength by a chemical method is regarded as important.

(6. Prior art of chemical methods)
As a conventional technique using a chemical method, a surface treatment technique using a strong acid or a strong base is disclosed in order to obtain a chemically active surface for titanium or a titanium alloy (Patent Documents 1 and 2). ).
Also disclosed are acid cleaning and tin electrodeposition after heat treatment. (Patent Document 3).
As a primer for non-noble metals, it is known that an adhesive monomer having a phosphate group at its terminal is effective (Patent Documents 4, 5, and 6). In addition, after pretreatment such as silanopen (Patent Document 7) and Silica Pen (registered trademark) system in which silica particles can be baked on the surface with a gas burner, silane coupling that combines with both silica and resin A technique for improving adhesive force by using a primer containing an agent is disclosed. The LOCATEC (registered trademark) system is a surface of silica that is mechanically struck with a silica component called tribochemical treatment on a non-precious dental surface that is difficult to create irregularities by casting, such as titanium. In this method, a film is coated, and the silica-coated surface is surface-treated with a primer containing a silane coupling agent. This method has a problem that not a general-purpose alumina particle for ordinary sandblasting but a locatec sand dedicated to a locatec system capable of silicate treatment must be used.

JP2005-120022

JP2002-363021A

JP2000-93436

JP 2002-38105 A

JP 2003-238326 A

JP 7-278499 A

JP 2003-238710 A

Echizenya Satoshi: Interface between metal and 4-META / MMA-TBBO resin, Tooth material, 11 (4), 628-641, 1992

  The problem to be solved by the present invention is to provide a silane-containing composition, a bonding method using the composition, and a prosthesis bonded by the method, and firmly bond a dental non-precious metal and a dental resin, It is to enable high-strength and long-term available dental treatment.

(Invention of Claim 1)
The invention described in claim 1 is a silane-containing composition used for the surface treatment of a dental non-noble metal in order to improve adhesion with a dental resin, and the silane-containing composition is volatile with a silane coupling agent. It consists of an organic solvent, the silane coupling agent is 3-methacryloxypropyltrimethoxysilane (γ-MPTS), and 0.2 to 20.0% of the total weight of the silane-containing composition is the weight of the silane coupling agent 80.0 to 99.8% of the total weight of the silane-containing composition is the weight of the volatile organic solvent.
(Invention of Claim 2)
The invention described in claim 2 is a silane-containing composition used as a resin having improved adhesion to a dental non-noble metal surface, the silane-containing composition comprising a silane coupling agent and a polymerizable resin composition. The silane coupling agent is 3-methacryloxypropyltrimethoxysilane (γ-MPTS), the polymerizable resin composition is a dental resin, and the total weight of the silane-containing composition is 0.5. ˜10.0% is the weight of the silane coupling agent, and 90.0 to 99.5% of the total weight of the silane-containing composition is the weight of the polymerizable resin composition.
(Special technical features of claims 1 and 2)
As a whole, the special technical feature of claims 1 and 2 is that 3-methacryloxypropyltrimethoxysilane (γ-MPTS) was used on a dental non-noble metal surface without silicate treatment, Both have the same technical significance of the invention in comparison with the prior art in that the adhesive force is improved.

(Invention of Claim 3)
Invention of Claim 3 is the adhesion method using the silane containing composition of Claim 1, Comprising: The said adhesion method consists of a surface treatment process, a drying process, a resin part formation process, and an integration process, Surface treatment The process is a process of applying a silane-containing composition to the dental non-noble metal surface, the drying process is a process of drying the applied silane-containing composition for 2 to 5 minutes, and the resin part forming process is a dried silane-containing composition. It is a step of applying a dental resin, which is a polymerizable resin composition, on the product, and the integration step is to irradiate at least the applied dental resin and cure it to cure the dental non-noble metal, silane-containing composition, and dental It is the process of integrating the resin for use.
(Invention of Claim 4)
Invention of Claim 4 is the adhesion method using the silane containing composition of Claim 2, Comprising: The said adhesion method consists of a resin part formation process and an integration process, and a resin part formation process is a dental non-precious metal It is a step of applying a silane-containing composition to the surface, and the integration step is a step of integrating the dental non-noble metal and the silane-containing composition by irradiating the applied silane-containing composition with light and curing it. It is characterized by.

(Invention of Claim 5)
Invention of Claim 5 is a prosthesis used for a crown, Comprising: A dental non-noble metal and the resin part are adhere | attached by the method of Claim 3 or Claim 4. It is characterized by.
(Invention of Claim 6)
The invention according to claim 6 is a prosthesis used for a dental crown for dental implant treatment, wherein the dental non-noble metal and the resin part used for the abutment part are the method according to claim 3 or claim 4. It is characterized by being bonded.
(Invention of Claim 7)
The invention according to claim 7 is a prosthesis, wherein the dental non-noble metal according to claim 5 or 6 has at least one of titanium, nickel, chromium, cobalt, or two or more of these. To do.

(Effect of the Invention of Claim 1)
When “3-methacryloxypropyltrimethoxysilane (γ-MPTS)” is used as a silane coupling agent for surface treatment of dental non-noble metals, dental non-noble metals and dental resins can be used without any special surface treatment. The adhesive strength of the conventional technology improved.
(Effect of invention of Claim 2)
Even when 3-methacryloxypropyltrimethoxysilane (γ-MPTS) is mixed with a dental resin that adheres to a dental non-noble metal, the adhesive force is similarly improved. In this case, the application amount is not too much or too little during the primer application operation with a brush or the like. And work time can be shortened. Also, the durability in the thermal cycle test was improved.

(Effect of invention of Claim 3)
Adhesive strength is improved by providing a step of drying the applied silane-containing composition for 2 to 5 minutes.
(Effect of invention of Claim 4)
When the bonding method using the invention of claim 2 is adopted, the resin part forming step of claim 3 can be omitted.
(Effects of inventions of claims 5 and 6)
When the bonding method according to claims 3 and 4 is used, a prosthesis that is firmly bonded can be obtained.
(Effect of the invention of claim 7)
The adhesive force between the dental non-precious metal surface such as titanium, nickel, chromium and cobalt and the dental resin can be improved.

FIG. 1 is a perspective view and a side view relating to the treatment of a tooth with an implant. FIG. 2 is a perspective view relating to the treatment of teeth with a prosthesis. FIG. 3 is an exploded side view of the adhesion test piece. 4A is an overall perspective view of the small universal testing machine, and FIG. 4B is a partially enlarged view. FIG. 5 is a perspective view showing the content of the adhesion test. FIG. 6 is a graph obtained from the numerical values in Table 4. FIG. 7 is a graph obtained from the values in Table 5.

The contents of typical dental treatment as a mode for carrying out the present invention will be described below. As an example of recent dental treatment, treatment with an implant is illustrated in FIG. 1, and treatment with a prosthesis is illustrated in FIG.
In such treatment, at least the esthetic part 1 and the frame part 2 are configured. The esthetic part 1 is mainly made of resin or ceramics to improve the appearance. The frame part 2 is made of a dental noble metal or a dental non-noble metal so as to withstand the biting force.
In such a case, the adhesion between the dental non-precious metal and the dental resin, which is a resin, is important. In order to improve the adhesion, the present invention is exemplified as follows. However, regarding the improvement of the adhesive force between the dental non-precious metal and the dental resin, the present invention can be used in any case and is not limited to the exemplified contents.

In order to improve the adhesion between the dental non-noble metal and the dental resin, a silane-containing composition can be used as a surface treatment agent. When a silane-containing composition is used as a surface treatment agent, a silane coupling agent and a volatile organic solvent are mixed and applied to the surface of a dental non-noble metal (Embodiment 1).
In order to improve the adhesive force between the dental non-noble metal and the dental resin, the silane-containing composition can be used as a dental resin having adhesiveness. This silane-containing composition is prepared by previously mixing a dental resin with a silane coupling agent, and can directly adhere to the surface of a dental non-noble metal (Embodiment 2).

Silane coupling agents include 3-methacryloxypropyltrimethoxysilane (γ-MPTS), 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloyloxypropyltrihexyloxysilane, 3- (Meth) acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, etc. can be illustrated.
Among these, γ-MPTS has the same methacryloyl group in the molecule as the organic functional group contained in the dental polymerizable monomer, and is excellent in reactivity, so it is a silica powder that is combined with the resin. Most preferred for use in surface treatment of inorganic oxides such as As the volatile organic solvent, acetone, ethanol, methanol, isopropanol or the like can be used. It is preferable to use ethanol because of its low toxicity.
The dental resin used in the present invention is a polymerizable resin composition, and is a composition generally used as an opaque resin or body resin of a dental hard resin, a polymerizable monomer, an inorganic filler, a polymerization initiator, and Consists of a small amount of colorant.

Specifically as said polymerizable monomer, (meth) acrylic-acid alkylester (C1-C10 of an alkyl group) generally used for dental hard resin, polyalkylene glycol di (meth) acrylate ( Monofunctional, polyfunctional (2 to 20 carbon atoms), ethylene glycol oligomer di (meth) acrylate (2 to 10-mer), trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. Examples thereof include (meth) acrylic acid esters and urethane (meth) acrylic acid esters which are reaction products of 2 mol of (meth) acrylate having a hydroxyl group and 1 mol of diisocyanate.
Specifically, silica fine particles, zirconia fine particles, barium glass fine particles, alumina fine particles, or composite oxide fine particles containing them, which are generally used for dental hard resins, can be used as the inorganic filler.
Specifically, camphorquinone (CQ), benzoyl peroxide (BPO), 2,2′-azobisisobutyronitrile, and the like generally used for dental hard resins can be used as the polymerization initiator. .
As the polymerization accelerator, 2- (dimethylamino) ethyl methacrylate (DMAEMA), a pigment, and other conventionally known additives can be blended with the resin.

(Embodiment 1: Embodiment used as a surface treatment agent)
A surface treatment agent containing a silane coupling agent is applied to the contact surface 3 between the frame portion 2 and the aesthetic portion 1 with a brush or the like. This is a mode in which a paste-like dental resin that becomes the esthetic part 1 is built up with a spatula or the like on the surface of the frame part 2 to which the surface treatment agent is applied.

(Embodiment 2: Embodiment used as a dental resin)
A dental resin containing a silane coupling agent is applied to the contact surface 3 between the frame part 2 and the aesthetic part 1 with a brush or the like. In this embodiment, a paste-like dental resin that becomes the esthetic part 1 is built up with a spatula or the like on the surface of the frame part 2 to which a dental resin containing a silane coupling agent is applied.

[Embodiment 1]
An embodiment in which a silane-containing composition is used as the surface treatment agent is referred to as Embodiment 1, and an adhesive strength measurement test is performed.
(1) Outline of Adhesion Test This test measures the adhesion between the resin part (dental resin 10) and the dental non-precious metal (titanium 20). Therefore, the adhesion test piece 4 in which the titanium 20 and the dental resin 10 are adhered is prepared, both ends of the adhesion test piece 4 are pulled, and the force required to peel off is measured.
As shown in FIG. 3, the adhesion test piece 4 is obtained by bonding a titanium 20 and a dental resin 10 with a circular contact surface 3 having a diameter of 3 mm.
The dental resin 10 and the stainless steel bolt 41 are firmly bonded by the dental resin cement 40 and did not come off in this test. The other end of the stainless bolt 41 can be screwed to the bolt receiver 42. 4A is an overall perspective view of the small universal testing machine, and FIG. 4B is a partially enlarged view. In this test, as shown in FIG. 4, the bolt receiver 42 and the titanium 20 are peeled off using a small universal testing machine.
FIG. 5 is an experimental procedure showing an outline of the test.

(2) About the dental non-noble metal to be used As the dental non-noble metal to be bonded, titanium (ASTM F67 Grade 4: manufactured by Shinko Corporation) was used. The contact surface 3 is polished to a smooth surface with water-resistant abrasive paper (# 600: manufactured by Riken Corundum), and then a sand blaster (jet blast 3: manufactured by Morita Seisakusho) with a pressure of 0.3 MPa for 2 seconds and a particle size of 50 μm. Sandblasting was performed with alumina particles (FIG. 5-1).

(3) About the surface treating agent to be used The comparative example 1 without a surface treating agent ((gamma) -MPTS) and the samples 1-8 with a surface treating agent were prepared.
Comparative Example 1 is ethanol 100 wt%.
Sample 1 is ethanol 99.75 wt% and γ-MPTS 0.25 wt%.
Sample 2 is ethanol 99.5 wt% and γ-MPTS 0.5 wt%.
Sample 3 is ethanol 99 wt% and γ-MPTS 1 wt%.
Sample 4 is ethanol 97 wt% and γ-MPTS 3 wt%.
Sample 5 is ethanol 94 wt% and γ-MPTS 6 wt%.
Sample 6 is ethanol 91 wt% and γ-MPTS 9 wt%.
Sample 7 is ethanol 82 wt% and γ-MPTS 18 wt%.
Sample 8 is ethanol 70 wt% and γ-MPTS 30 wt%.
γ-MPTS used was made by Momentive Performance Materials Japan. Ethanol used was made by Nacalai Tesque.

(4) Resin part (dental resin 10) that adheres to the surface treatment agent As a resin that adheres to the surface treatment agent, IvO, which is an opaque resin of the dental hard resin “Twiny (manufactured by Yamamoto Precious Metal)” Yamamoto noble metal bullion: polymerizable monomer (urethane dimethacrylate, triethylene glycol dimethacrylate), inorganic filler (silica fine particles), polymerization initiator (CQ) mixture] was used.

(5) Adhesion process Titanium 20 subjected to the above-described sandblast treatment was subjected to ultrasonic cleaning with distilled water for 10 minutes and thoroughly rinsed with ethanol.
Thereafter, it was dried, and 1 μl of the surface treatment agent was dropped on the surface to be bonded. In Comparative Example 1, only ethanol is used (FIG. 5-2).
The drying condition of this surface treatment agent was 120 seconds in air at 25 ° C. After that, a water-resistant tape with a hole of φ3 mm was applied to the titanium surface coated with the surface treatment agent to perform masking (FIG. 5-3), and IvO was applied (FIG. 5-4). Light 2N (Morita Tokyo Seisakusho) "was irradiated for 3 minutes to cure (FIGS. 5-5).

(6) Preparation of test piece After IvO curing, in order to connect with a measuring instrument, dental resin cement 40 (Panavia F2.0: manufactured by Kuraray Medical) was applied to the IvO cured surface, and then stainless steel bolt 41 (φ5 mm, 15 mm long) was placed vertically. While applying a force of 10 N from above, light irradiation was performed for 40 seconds with a dental light irradiation machine (Pencure: manufactured by Morita), and the stainless steel bolt 41 was adhered to complete the adhesion test piece 4 (FIGS. 5-6).
The adhesion between the IvO, the dental resin cement 40, and the stainless steel bolt 41 does not peel off before the IvO and the titanium 20 are peeled off because the bonding area is large.

(7) Measurement The completed adhesion test piece 4, Samples 1 to 8 and Comparative Example 1 were placed in water at 37 ° C., and the adhesion strength was measured after immersion for 24 hours (FIG. 5-7) (FIG. 5-8). .
A small universal testing machine 45 (Ez-Graph: manufactured by Shimadzu Corporation) was used for the measurement, and the tensile adhesive strength (adhesive force) was measured under the condition of a crosshead speed of 0.5 mm / min. The tensile bond strength was shown as an average value of the measured values of five adhesion test pieces 4.
The measured values of the adhesion test are shown in Table 1. As shown in Table 1, when surface treatment is performed with a primer containing γ-MPTS, as shown in Sample 1 to Sample 7, the content of γ-MPTS is drastically under the condition of 0.25 to 18 wt%. Adhesive strength was improved.

(8) Identification of heating and drying conditions The conditions of the above (1), (2), (4), (6) and (7) are the same, and the surface treatment agent used is the sample 5 described in (3). Samples 9 to 16 specified in “Ethanol 94 wt% and γ-MPTS 6 wt%” were prepared. The parameter to be changed was described as (5) “The drying condition of the surface treatment agent was 120 seconds in air at 25 ° C.”, and the thermal drying conditions were specified.

In Sample 5, the surface treatment agent was dried in air at room temperature of 25 ° C. for 120 seconds.
In Sample 9, the surface treating agent was dried in air at room temperature of 25 ° C. for 10 seconds.
In Sample 10, the surface treatment agent was dried in air at room temperature of 25 ° C. for 30 seconds.
In Sample 11, the surface treatment agent was dried in air at room temperature of 25 ° C. for 60 seconds.
In Sample 12, the surface treatment agent was dried in air at room temperature of 25 ° C. for 180 seconds.
In Sample 13, the surface treatment agent was dried in air at room temperature of 25 ° C. for 240 seconds.
In Sample 14, the surface treatment agent was dried in air at room temperature of 25 ° C. for 300 seconds.
In Sample 15, the surface treatment agent was dried in a humidified room temperature 25 ° C. air for 120 seconds.
In Sample 16, the surface treatment agent was dried in heated 37 ° C. air for 300 seconds.
In Sample 17, the surface treatment agent was dried in heated 110 ° C. air for 300 seconds.
In Sample 18, the surface treatment agent was dried with a dryer for 60 seconds.
The measured values are shown in Table 2.

  When the data in Table 1 and Table 2 are integrated, when used as a surface treatment agent, the blending ratio of γ-MPTS: ethanol is preferably 0.2 to 20 wt%: 80 to 99.8 wt%. The surface treatment agent is preferably bonded to the resin after being dried at room temperature for 2 to 5 minutes.

[Embodiment 2]
As a dental resin with improved adhesive strength, a silane coupling agent previously mixed with a dental resin is referred to as Embodiment 2, and an adhesive strength measurement test is described.
(1) and (2) are the same as in the first embodiment. Embodiment 2 is one in which a silane coupling agent and IvO are directly mixed without using the surface treating agent of (3). That is, the process of FIG. 5-2 is omitted, and the mixture of the silane coupling agent and IvO is applied in the process of FIG. 5-4.

(4) About Resin (Dental Resin 10) Adhered to Titanium 20 Surface Comparative Example 2 which is only a dental resin (IvO) not mixed with a surface treatment agent (γ-MPTS) and the dental resin have adhesiveness Samples 19 to 26 prepared by mixing γ-MPTS with IvO were prepared.
Comparative Example 2 is IvO 100 wt%.
Sample 19 is a mixture of γ-MPTS 0.25 wt% and IvO 99.75 wt%.
Sample 20 is a mixture of γ-MPTS 0.5 wt% and IvO 99.5 wt%.
Sample 21 is a mixture of γ-MPTS 1 wt% and IvO 99 wt%.
Sample 22 is a mixture of 3 wt% γ-MPTS and 97 wt% IvO.
Sample 23 is a mixture of 5 wt% γ-MPTS and 95 wt% IvO.
Sample 24 is a mixture of 7 wt% γ-MPTS and 93 wt% IvO.
Sample 25 is a mixture of γ-MPTS 10 wt% and IvO 90 wt%.
Sample 26 is a mixture of 20 wt% γ-MPTS and 80 wt% IvO.
γ-MPTS used was made by Momentive Performance Materials Japan. The mixing of γ-MPTS and IvO was performed by mixing in a mortar.

(5) Adhesion process Titanium 20 subjected to the above-described sandblast treatment was ultrasonically washed with water for 10 minutes and sufficiently rinsed with ethanol.
Thereafter, the surface of the titanium 20 is dried, a water-resistant tape having a hole of φ3 mm is attached, masking is performed, and the samples 17 to 21 and Comparative Example 2 are applied and left for 2 minutes. (2N: manufactured by Morita) and cured by light irradiation for 3 minutes.

(6) (7) is the same as that of Embodiment 1, and measurement was performed on Embodiment 2.
Table 3 shows the measurement results.

  Examining the contents of Table 3, as shown in Sample 20 to Sample 25, the content of γ-MPTS is preferably 0.5 to 10 wt%.

[Comparison test 1: Comparison with the prior art]
The composition of Sample 5 in Embodiment 1 and Sample 20 described in Embodiment 2 is representative of these embodiments. Sample 20 was a mixture of a small amount in a mortar, but it was prepared using a stirrer (Awatori Rentaro: manufactured by Shinky) in order to disperse γ-MPTS more uniformly, assuming mass production. Sample 27 was obtained. And the comparative test with the sample 5 and the sample 27, and the prior art (conventional products 1-4) was done. Comparative Example 2 is the same as Table 3 described above.

[Conventional product 1]
LOCATEC (registered trademark) Sand Plus (manufactured by Sumitomo 3M) was used as the conventional product 1. In this method, the surface is coated with a silane coupling agent-containing primer after the surface is silica-coated by a tribochemical treatment in which a dedicated LOCATEC sand is struck against the contact surface 3.

[Conventional product 2]
Signum metal bond (manufactured by Heraeus Kultzer Japan) was used as the conventional product 2. This is one in which adhesiveness is improved by using an adhesive monomer having a phosphate group at its terminal. Durability is improved by applying an elastic paste after applying the primer.

[Conventional product 3]
Metal link (made by Matsukaze) was used as the conventional product 3. This is one in which adhesion is improved by using a phosphoric acid monomer that is not easily affected by moisture.

[Conventional product 4]
An alloy primer (manufactured by Kuraray Medical) was used as the conventional product 4. This improves the adhesion to various dental metals by blending a sulfur-based monomer having adhesion to a noble metal and a phosphate monomer having adhesion to a non-metal.

[Comparative test]
Samples 5 and 27 and conventional products 1 to 4 were each prepared with 6 types of adhesion methods to produce adhesion test pieces 4. The area of the adhesive surface 3 and the content of the adhesive force measurement test are the same as those in the first and second embodiments.
Two sets of five of the above-mentioned seven types of adhesion test pieces were prepared, one was stored in water for one day, and the other was subjected to thermal cycling 5000 times before measurement to measure 14 types of adhesive strength. .
The adhesion test piece 4 stored for one day in water is immersed in water at 37 ° C. for 24 hours. The adhesion test piece 4 having a thermal cycle of 5000 times is a cycle in which immersion is alternately performed for 1 minute each in cold water at 4 ° C. and hot water at 60 ° C. for 5000 cycles.
Table 4 shows the measurement results. FIG. 6 is a graph of the numerical values in Table 4.

Sample 27 of Table 4 had higher adhesive strength than Sample 20 of Table 3 of the same component. Since the sample 27 was mixed using a machine, the active ingredient was more uniformly dispersed, so that it is considered that the adhesive strength was increased.
As can be seen from Table 4 and FIG. 6, Sample 5 which is Embodiment 1 of the present invention has an adhesive strength of 43.3 MPa after one day storage in water, and an adhesive strength after 5000 thermal cycles is 27.9 MPa. Met. Sample 27, which is Embodiment 2 of the present invention, had an adhesive strength of 45.9 MPa after 1 day storage in water, and an adhesive strength of 34.7 MPa after 5000 thermal cycles.
The adhesion strength to the dental non-noble metal surface after one day storage in water is preferably 35 to 50 MPa (35 to 45 MPa in Embodiment 1, 37 to 47 MPa in Embodiment 2).
The adhesive strength to the dental non-noble metal surface after 5000 thermal cycles is preferably 20 to 40 MPa (20 to 30 MPa in the embodiment 1, 28 to 38 MPa in the embodiment 2).

  In the conventional products 1 to 4, as can be seen from Table 4 and FIG. 6, the adhesive strength after 1 day storage in water does not exceed 32.6 MPa, and the adhesive strength after 5000 thermal cycles exceeds 18.3 MPa. The product of the present invention was superior in adhesive strength.

[Comparison test 2: Target metals]
An adhesion strength test was also conducted on metals to be bonded other than titanium 20 (ASTM F67 Grade 4: manufactured by Shinko Shoji Co., Ltd.). Nickel-chromium alloy (Wiron 99: made by BEGO), cobalt-chromium alloy (willobond C: made by BEGO), gold-silver-palladium alloy (Para Z12-n: made by Yamamoto precious metal bullion), gold alloy (wipe gold type 1-n: Yamamoto Made of noble metal).

The bonding method is the same as described above. After one day of storage in water (24 hours immersion), the adhesive strength was measured using a small universal testing machine 45.
Table 5 shows the contents compared with the adhesive strength of the titanium 20 described above. The graph of Table 5 is FIG.

  As can be seen from Table 5 and FIG. 7, both sample 5 of embodiment 1 and sample 27 of embodiment 2 have better adhesion compatibility with non-noble metals than noble metals. The reason why the adhesive compatibility with nonmetals is good will be discussed below.

[Consideration of action and effect]
Table 6 left shows the oxygen concentration of various pure metal surfaces. This oxygen concentration depends on the amount of oxide film on the surface. The right side of Table 6 shows the components of the dental metal shown in Table 5. Considering Table 5 and Table 6 together, it is considered that the adhesive strength of the product of the present invention depends on the oxygen concentration on the metal surface.

*) Cited document: Satoshi Echizenya: Interface between metal and 4-META / MMA-TBBO resin, dental material, 11 (4), 628-641, 1992

  Both the sample 5 of the embodiment 1 and the sample 27 of the embodiment 2 had low adhesion to a gold alloy containing gold having no oxygen on the surface as a main component. From this, it is considered that the presence of an oxide film on the metal surface is indispensable for γ-MPTS to exert its effect as a primer.

From Table 6, if the oxygen content on the metal surface is high, a reaction with γ-MPTS can be expected, and the higher the oxygen content on the metal surface, the better the adhesion between the metal and the resin by γ-MPTS. Is done. Non-noble metals such as titanium easily oxidize on the surface and easily form a surface oxide layer in the air.
Moreover, since silver, copper, etc. also form a surface oxide film, it is considered that in these gold-silver-palladium alloys having a high ratio, a certain improvement in adhesive strength was observed by γ-MPTS as shown in Table 5 and FIG. .

  The titanium oxide layer reacts with water in the air, and the titanium surface is covered with a hydroxyl group (—OH). γ-MPTS is considered to react with a hydroxyl group on the titanium surface to form a covalent bond (Ti—O—Si). Furthermore, since γ-MPTS has a methacryl group, it is copolymerized with a monomer to form a strong bond between the metal and the resin.

  The present invention uses a commercially available primer or a special adhesive system when used in the surface treatment of Embodiment 1 and Embodiment 2 in which γ-MPTS is an active ingredient for bonding a dental non-precious metal such as titanium to a dental resin. Adhesive strength equal to or better than that of the case.

  The present invention has been conceived for the purpose of improving the adhesive strength between a dental non-precious metal and a dental resin. However, the present invention is not limited to dental use, and can also be used for bonding other non-noble metals and resins.

DESCRIPTION OF SYMBOLS 1 Beauty part 2 Frame part 20 Titanium 3 Contact surface 4 Adhesion test piece

Claims (7)

  A silane-containing composition used for the surface treatment of dental non-noble metals in order to improve adhesion with a dental resin, the silane-containing composition comprising a silane coupling agent and a volatile organic solvent, The coupling agent is 3-methacryloxypropyltrimethoxysilane (γ-MPTS), 0.2 to 20.0% of the total weight of the silane-containing composition is the weight of the silane coupling agent, and the silane-containing composition A silane-containing composition characterized in that 80.0 to 99.8% of the total weight of silane is the weight of a volatile organic solvent.   A silane-containing composition used as a resin having improved adhesion to a dental non-noble metal surface, wherein the silane-containing composition is a mixture of a silane coupling agent and a polymerizable resin composition. The ring agent is 3-methacryloxypropyltrimethoxysilane (γ-MPTS), the polymerizable resin composition is a dental resin, and 0.5 to 10.0% of the total weight of the silane-containing composition is A silane-containing composition, characterized in that the weight of the silane coupling agent is 90.0 to 99.5% of the total weight of the silane-containing composition, which is the weight of the polymerizable resin composition.   It is the adhesion | attachment method using the silane containing composition of Claim 1, Comprising: The said adhesion | attachment method consists of a surface treatment process, a drying process, a resin part formation process, and an integration process, and a surface treatment process is on a dental non-noble metal surface. It is a step of applying a silane-containing composition, a drying step is a step of drying the applied silane-containing composition at room temperature for 2 to 5 minutes, and a resin part forming step is a polymerizable resin on the dried silane-containing composition. It is a process of applying a dental resin, which is a composition. The integration process integrates a dental non-noble metal, a silane-containing composition, and a dental resin by irradiating and curing at least the applied dental resin. A bonding method characterized in that the bonding method is a step of allowing   3. A bonding method using the silane-containing composition according to claim 2, wherein the bonding method includes a resin portion forming step and an integration step, and the resin portion forming step applies the silane-containing composition to a dental non-noble metal surface. The bonding method is characterized in that the integrating step is a step of integrating the dental non-noble metal and the silane-containing composition by irradiating and curing the applied silane-containing composition.   A prosthesis used for a dental crown, wherein the prosthesis is obtained by bonding a dental non-noble metal and a resin part by the method according to claim 3 or 4.   It is a prosthesis used in a dental crown for dental implant treatment, wherein a dental non-noble metal used for an abutment and a resin part are bonded by the method according to claim 3 or 4. Characteristic prosthesis.   The dental non-noble metal according to claim 5 or 6, comprising at least one of titanium, nickel, chromium and cobalt, or two or more kinds thereof.