JP6090717B2 - Dental adhesive composition, surface treatment agent and dental resin - Google Patents

Description

  The present invention relates to a dental adhesive composition, a surface treatment agent, a dental treatment used for bonding a dental metal (noble metal, non-noble metal, each alloy) and a dental resin, or a dental ceramic and a dental resin. It relates to a resin.

  In order to chemically improve the adhesion between dental precious metals, dental non-precious metals and alloys thereof, dental ceramics, and dental resins, the following dental adhesive compositions are considered.

(1) As a technique for improving the adhesion of dental metals, ceramics, and resins, a technique using an acid catalyst mixed with a compound containing an SH group and a silane coupling agent is disclosed (Patent Document 1). ).
However, in Patent Document 1, the adhesion effect with dental resin is reported by using non-noble metals and ceramics such as stainless steel and cobalt chrome, but the effect on noble metal (gold) is reported. It has not been. In addition, an acid catalyst (acetic acid) is used to enhance the adhesion effect. Generally, when an acid catalyst is added, the silane coupling agents gradually condense with each other, and the adhesive strength decreases when stored for a long period of time. Since it is known, it is necessary to mix the acid catalyst immediately before application in order to actually use it as a primer.

  (2) In addition, it is also disclosed that a composition containing a sulfur compound or a composition comprising a sulfur compound and a silane coupling agent improves the adhesion of dental noble metals and noble metal alloys (Patent Document 2, 3, Non-Patent Document 1). However, the adhesion target of these compositions is only the noble metal and the noble metal alloy, and the non-noble metal, the non-noble metal alloy and ceramics are not the adhesion object.

  (3) In addition, it is disclosed that a dental adhesive composition in which a compound containing a phosphate group and a silane coupling agent are combined improves the adhesion between non-precious metals such as nickel chromium and ceramics and resin. (Patent Document 4). In addition, it has been reported that a silane coupling agent alone as an adhesive component enhances the adhesion between a non-noble metal such as titanium and a dental resin (Patent Document 5). No effect has been reported.

  As described above, conventional primers are generally used for precious metals, non-precious metals and ceramics depending on the object to be bonded, or a method of mixing an acid catalyst immediately before use is generally used, and the technical operation is complicated. There was a problem of becoming.

Japanese Patent Laid-Open No. 2-152915

JP 2000-198966 A

JP 2001-72936 A

JP 7-278499 A

Japanese Patent Application No. 2012-27147

Hironori Koike: Development of hard resin primer using thiol compound, Nippon Dental Technology Journal 24, 79-83, 2003

  The problems to be solved by the present invention include versatility that can be used for all dental precious metals, non-noble metals and their alloys, ceramics, and resins, and without the need for an acid catalyst. An object of the present invention is to provide a dental adhesive composition that exhibits a satisfactory adhesive effect.

前記チオプロピオン酸誘導体またはチオグリコール酸誘導体は、〔化２〕の化学式で表される化合物であること

を特徴とする。
（請求項２記載の発明）
請求項１記載の歯科用接着性組成物を用いた表面処理剤であって、前記表面処理剤は、前記歯科用接着性組成物と揮発性有機溶剤を混合したものであり、前記表面処理剤の総重量１００％に対して、シランカップリング剤の重量を１．０〜３０．０％とし、チオプロピオン酸誘導体またはチオグリコール酸誘導体の重量を０．１〜１．０％とし、揮発性有機溶剤の重量を６９．０〜９８．９％としたことを特徴とする。
（請求項３記載の発明）
請求項１記載の歯科用接着性組成物を用いた歯科用レジンであって、前記歯科用レジンは、前記歯科用接着性組成物と歯科用硬質レジンとを混合したものであり、前記重合性レジンの総重量１００％に対して、シランカップリング剤の重量を１．０〜１０．０％とし、チオプロピオン酸誘導体あるいはチオグリコール酸誘導体の重量を０．５〜４．０％とし、歯科用硬質レジンの重量を８６．０〜９８．５％としたことを特徴とする。 (Invention of Claim 1)
A dental adhesive composition for improving the adhesive strength with a dental resin for all dental precious metals, dental non-precious metals, dental alloys of the metals, and dental ceramics, wherein the dental adhesive composition The product comprises a silane coupling agent having a polymerizable group, a thiopropionic acid derivative or a thioglycolic acid derivative, and a volatile organic solvent, and the silane coupling agent is a compound represented by the chemical formula [Chemical Formula 1] And

The thiopropionic acid derivative or thioglycolic acid derivative is a compound represented by the chemical formula [Chemical Formula 2]

It is characterized by.
(Invention of Claim 2)
A surface treatment agent using the dental adhesive composition according to claim 1, wherein the surface treatment agent is a mixture of the dental adhesive composition and a volatile organic solvent, and the surface treatment agent. The weight of the silane coupling agent is 1.0 to 30.0% and the weight of the thiopropionic acid derivative or thioglycolic acid derivative is 0.1 to 1.0% with respect to the total weight of 100%, and is volatile. The weight of the organic solvent is 69.0 to 98.9%.
(Invention of Claim 3)
A dental resin using the dental adhesive composition according to claim 1, wherein the dental resin is a mixture of the dental adhesive composition and a dental hard resin, and is polymerizable. The total weight of the resin is 100%, the weight of the silane coupling agent is 1.0 to 10.0%, the weight of the thiopropionic acid derivative or thioglycolic acid derivative is 0.5 to 4.0%, The hard resin weight is 86.0 to 98.5%.

(Effect of the Invention of Claim 1)
When a silane coupling agent, a thiopropionic acid derivative and a thioglycolic acid derivative are used at the same time, a dental adhesive composition that improves the adhesion of all dental precious metals, dental non-precious metals, and dental ceramics by a synergistic effect became.
(Effect of invention of Claim 2)
The dental adhesive composition according to claim 1 can be dissolved in a volatile organic solvent and used as a surface treatment agent.
(Effect of invention of Claim 3)
Further, by mixing the dental adhesive composition with the polymerizable resin, it was possible to obtain a dental resin exhibiting excellent adhesive strength even without a normal primer treatment.

FIG. 1 is a perspective view of treatment with a hard resin anterior crown. FIG. 2 is a front view of the frame portion. FIG. 3 is a side view of the frame portion. FIG. 4 is a front view of the treatment tooth. FIG. 5 is a side view of the treated tooth. FIG. 6 is an exploded side view of the adhesion test pieces of Examples 1 and 2. FIG. 7 is an explanatory view showing the procedure of the adhesion test of Example 1. FIG. FIG. 8 is an explanatory diagram showing the procedure of the adhesion test of Example 2.

  As a form for implementing this invention, the content of typical dental treatment is described below.

(1. About typical dental treatment examples)
The treatment tooth 1 is illustrated as an example of a typical dental treatment. The treatment tooth 1 is treated using the front crown 10 and the frame portion 11. As shown in FIG. 1, the treatment tooth 1 is obtained by integrating a front crown 10 and a frame portion 11. A hard resin is used for the front crown 10, and a dental noble metal, a dental non-noble metal, or a dental ceramic is used for the frame portion 11.
2 and 3, a hard resin is built up in a shape as shown in FIGS. 4 and 5 and cured to form a front crown 10, which is then installed in the patient's oral cavity.
Since the front crown 10 that is a hard resin has good aesthetics, it can be placed as the superstructure of the frame 11 that is a dental precious metal, a dental non-precious metal or a dental ceramic, so that dental treatment that maintains a natural appearance is possible. become.
In the frame part 11 using a metal that can be cast and molded, as shown in FIGS. 2 and 3, a retention bead 12 is added to the resin build-up surface, the area is increased, and the adhesion between the metal and the resin can be strengthened. it can.
The present invention can be used in any case for improving the adhesion between dental precious metals, dental non-precious metals and alloys thereof, dental ceramics, and dental resins or hard resins. It is not limited to the content. When the adhesion is made as strong as possible, the use of the present invention is exemplified as follows.

(2. About Embodiment 1)
In order to improve the adhesion between dental precious metals, dental non-precious metals and their alloys and dental ceramics, and dental resins, the dental adhesive composition should be diluted with an organic solvent and used as a surface treatment agent. Can do. That is, a silane coupling agent, a sulfur compound, and a volatile organic solvent are mixed and applied to the surfaces of dental noble metals, dental non-noble metals, alloys thereof, and dental ceramics.

(3. About Embodiment 2)
In order to improve the adhesion between dental precious metals, dental non-precious metals and their alloys and dental ceramics, and dental resins, a silane coupling agent and a sulfur compound (dental adhesive composition) are directly applied to the resin. A mixture can be used. The mixed dental resin can be directly applied and adhered to the surfaces of dental precious metals, dental non-precious metals and their alloys and dental ceramics.

(4. Object of the present invention)
An object of the present invention is a prosthesis that serves as a foundation (for example, the above-described frame portion 11) for building up a dental resin, and a dental adhesive composition that firmly bonds the dental resin, and serves as a foundation. Is a dental precious metal, a dental non-precious metal and alloys thereof, or dental ceramics, and with only one liquid, all surface treatments of various prostheses serving as a foundation for building a dental resin can be performed. Examples of dental precious metals include gold alloys, silver alloys and gold-silver palladium alloys; examples of dental non-precious metal alloys include titanium, titanium alloys, nickel chromium alloys, cobalt chromium alloys; and examples of dental ceramics include porcelain, zirconium oxide and Examples include aluminum oxide.

(5. About silane coupling agent)
Examples of silane coupling agents include 3-methacryloyloxypropyltrimethoxysilane (γ-MPTS), 10-methacryloyloxydecyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, vinyltrimethoxysilane, and 3-methacryloxypropyl. Examples thereof include methyldimethoxysilane, vinyltriethoxysilane, 3-aminopropylethoxysilane, 3-chloropropyltrimethoxysilane, and vinyltrichlorosilane. Particularly preferred is γ-MPTS.

(6. About sulfur compounds)
Examples of the thiopropionic acid derivative or thioglycolic acid derivative that are sulfur compounds include pentaerythritol tetrakis-3-thiopropionate (PETP), pentaerythritol tetrakis-3-thioglycolate, and the like. Particularly preferred is PETP.

(7. About volatile organic solvents)
The volatile organic solvent is volatile, such as ethanol, acetone, methanol, isopropanol, and can be used without limitation as long as the mixture can be dissolved. Particularly preferred is ethanol.

(8. About dental resin)
As the dental resin, generally, a hard resin, a filling composite resin, and a resin cement are used. The dental resin used in the present invention is a composition used as an opaque resin for a dental hard resin, and is composed of a polymerizable monomer, a glass fine powder, an emulsion, a polymerization initiator, a polymerization accelerator, and the like. .
Specifically as said polymerizable monomer, the (meth) acrylic-acid alkylester (C1-C10 of an alkyl group) generally used for dental resin, polyalkylene glycol di (meth) acrylate (carbon) 2-20), monofunctional, polyfunctional (meta) such as ethylene glycol oligomer di (meth) acrylate (2-10 mer), trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate ) Acrylic acid esters and urethane (meth) acrylic acid esters which are the reaction product of 2 moles of (meth) acrylate having a hydroxyl group and 1 mole of diisocyanate, specifically methyl methacrylate, ethylene glycol di Methacrylate, diethylene glycol dimethacrylate, tri There are tylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate, urethane dimethacrylate (UDMA), 2,2-bis (4- (2-hydroxy-3-methacryloxypropoxy) phenyl) propane, especially UDMA and TEGDMA. Is preferably used.
These monomers may be used alone, but two or more kinds of monomers may be mixed and used. Specifically, silica fine particles, zirconia fine particles, Ba glass fine particles, or alumina fine particles that are generally used in dental resins can be used as the inorganic filler.
Specifically, camphorquinone (CQ), benzoyl peroxide, 2,2′-azobisisobutyronitrile or the like generally used for dental resins can be used as the polymerization initiator. Particularly preferred is CQ.
As a polymerization accelerator, 2- (dimethylamino) ethyl methacrylate (DMAEMA), a color pigment, an emulsion, and other various conventionally known additives can be appropriately blended with the resin.

(9. Reaction mechanism)
The reaction mechanism of the present invention will be described using γ-MPTS [Chemical Formula 3] as a silane coupling agent and PETP [Chemical Formula 4] as a thiopropionic acid derivative.
As shown in [Chemical Formula 4], PETP has a structure in which a carbon chain having a thiol group at its end is arranged around one carbon atom.

  When the object to be bonded is a non-noble metal or ceramic, hydroxyl groups exist on the surface. The methoxy group of γ-MPTS is hydrolyzed by moisture in the air and changed to a hydroxyl group. The hydroxyl group of γ-MPTS and the hydroxyl group of the non-noble metal or ceramic surface form a hydrogen bond, and then a strong covalent bond is formed by dehydration condensation. Moreover, the monomer in resin can copolymerize the methacryloyl group of (gamma) -MPTS. For this reason, the composition containing a silane coupling agent as in Patent Document 5 enhances the adhesion effect with a dental resin when used as a primer for non-noble metals and ceramics.

  When the adhesion target is a noble metal (gold), 1 to 3 thiol groups of PETP are adsorbed per molecule on the surface of the noble metal, but at least one thiol group that is not involved in the adsorption always exists. When a resin is applied onto PETP applied to the surface of a noble metal (gold) and then polymerized and cured, the thiol group draws electrons by radicals and becomes a stable sulfur radical. In Non-Patent Document 1, the monomer contained in the resin It is known to make a cross-linked product (urethane dimethacrylate, etc.), and enables strong adhesion between the resin and the noble metal.

  On the other hand, although γ-MPTS does not react with noble metal (gold), it has a methacryl group which is a polymerizable functional group, and thus is radically polymerized and polymerized by being incorporated into the polymer, and therefore does not inhibit the adhesion between the resin and the noble metal. Moreover, since the surface to which the γ-MPTS is applied has water repellency and has an effect of increasing the water resistance of the adhesive interface, it can be expected to increase the adhesive strength by a synergistic effect. Therefore, in the present invention, γ-MPTS that reacts with non-noble metals and ceramics and PETP that reacts with noble metals (gold) are used in combination.

(10. Specific usage of Embodiment 1 and Embodiment 2)
Embodiment 1 is a method of use in which a dental adhesive composition is diluted with an organic solvent and used as a surface treatment agent.
A surface treatment agent containing a silane coupling agent and a sulfur compound is applied to the resin build-up surface of the frame as shown in FIG. This is a mode in which the resin is built up and hardened so as to have a crown shape as shown in FIG. 2 on the resin built-up surface coated with the surface treatment agent.
The surface treatment agent is applied with a brush or the like.
Embodiment 2 is a resin containing a silane coupling agent and a sulfur compound, and is an embodiment in which the resin is directly built on the resin build-up surface and cured.
Examples 1 to 4 used as the above-described Embodiment 1 are described as Example 1, and Examples 5 to 9 used as the Embodiment 2 are described as Example 2 below.

(1. About Example 1)
Example 1 was prepared by using Example 1 as the surface treatment agent of the dental adhesive composition.
The result of the adhesive force measurement test of the said implementation goods 1-4 is described.
(1-1. Outline of Adhesion Test)
In order to perform the adhesion test, an adhesion test piece 4 was prepared. As shown in FIG. 6, the adhesion test piece 4 includes a dental resin cement 40, a stainless bolt 41, a bolt receiver 42, a dental resin 2, an adhesion target 3, and an adhesion surface 30. This test measures the adhesive force between the dental resin 2 (corresponding to the front crown 10 in FIGS. 1 to 5) and the object to be bonded 3 (dental prosthesis to be the frame portion 11 in FIGS. 1 to 5). is there.
Therefore, the dental resin 2 and the bonding object 3 are bonded, the both ends of the bonding 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 adhering the dental resin 2 and the object 3 to be bonded with an adhesive surface 30 having a circular area of 3 mm in diameter.
The dental resin 2 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. In this test, the bolt receiver 42 and the adhesion target 3 are peeled off using a small universal testing machine (Ez-Graph: manufactured by Shimadzu Corporation).
FIG. 7 shows an outline of the test and explains the experimental procedure.

(1-2. About dental metal to be used)
Titanium (JIS standard 4 types, manufactured by Shinko Shoji Co., Ltd.) and a gold alloy (wipe gold type 1-n; manufactured by Yamamoto precious metal bullion) were used as the bonding object 3. The adhesive surface 30 is polished to a smooth surface with water-resistant abrasive paper (# 600: manufactured by Riken Corundum), and then a sand blaster (jet mill 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. 7-1).

(1-3. Surface treatment agent to be used)
The sample used as the implementation products 1-4 was mixed with the following compounding ratios. The addition amount of γ-MPTS was set to 6 wt% of γ-MPTS with reference to the composition of Patent Document 5. Moreover, the sample used as the comparative product 3 was created with reference to the comparative product 1 to which PETP was not added, the comparative product 2 to which γ-MPTS was not added, and the implementation product 1 of Patent Document 1.
The execution product 1 is ethanol 93.75 wt%, γ-MPTS 6 wt%, and PETP 0.25 wt%.
The implementation product 2 is ethanol 93.5 wt%, γ-MPTS 6 wt%, and PETP 0.5 wt%.
The execution product 3 is ethanol 93.25 wt%, γ-MPTS 6 wt%, and PETP 0.75 wt%.
The implementation product 4 is ethanol 93 wt%, γ-MPTS 6 wt%, and PETP 1 wt%.
The above-mentioned Examples 1 to 4 are surface treatment agents using the dental adhesive composition of the present invention.
Comparative product 1 is ethanol 94 wt% and γ-MPTS 6 wt%.
The comparative product 2 is a composition referring to the composition of Non-Patent Document 1, and ethanol 99.25 wt% and PETP 0.75 wt%.
γ-MPTS used was made by Momentive Performance Materials Japan. PETP was manufactured by Sakai Chemical. Ethanol used was made by Nacalai Tesque.

(1-4. Dental Resin 2 Adhering onto Surface Treatment Agent of Adhesive Surface 30)
Invisible opaque (hereinafter referred to as IvO), which is an opaque resin of a hybrid type hard resin “Twiny (manufactured by Yamamoto Precious Metal)” as a dental resin 2 to be bonded onto a surface treatment agent (practical products 1 to 4, comparative products 1 to 2). Ingredients: Polymerizable monomer (UDMA, TEGDMA), inorganic filler (silica filler), polymerization initiator (CQ), polymerization accelerator (DMAEMA) and the like were used.

(1-5. Adhesion process)
The adhesion target 3 subjected to the sandblast treatment described above was ultrasonically washed with water for 10 minutes and sufficiently rinsed with Solmix AP-7 (manufactured by Nippon Alcohol Sales) (FIG. 7-1).
Then, it was made to dry and 1 microliter of surface treatment agents of execution goods 1-4 and comparative goods 1 and 2 were dripped on adhesion surface 30 of each adhesion test piece 4 (Drawing 7-2). Apply a water-resistant tape with a hole of φ3mm and mask (Figure 7-3), apply IvO thinly with a brush (Figure 7-4), and then apply 3 with a dental light irradiator (Alphalite 2: Morita). It was cured by light irradiation for a minute and bonded (FIG. 7-5).

(1-6. Resin provided on IvO)
After applying IvO, apply “Panavia F2.0 (manufactured by Kurarenorita Dental)” as dental resin cement 40 to the IvO-cured surface in order to connect it to the measuring instrument. Sandblasted stainless steel bolt 41 (φ5 mm, length 15 mm) was placed vertically. Light irradiation was performed with a dental light irradiation machine “Pen Cure (Morita)” for 40 seconds, and the stainless steel bolt 41 was adhered to complete the adhesion test piece 4 (FIGS. 7-6).
The adhesion between the IvO, the dental resin cement 40, and the stainless steel bolt 41 is not peeled off before the IvO and the bonding target 3 are peeled off because of the large bonding area.

(1-7. Measurement)
The test piece 4 completed after completion of the adhesion was placed in 37 ° C. water, and the adhesion strength was measured after immersion for 24 hours (FIG. 7-7) (FIG. 7-8).
As measurement conditions, tensile adhesive strength (adhesive force) was measured at a crosshead speed of 0.5 mm / min. The tensile bond strength was measured five times for the test piece 4 and the average value was obtained. The adhesive strength can be expressed as “large, small” or “high, low”. In this case, based on the term “high strength”, “high adhesive strength” is expressed as “high adhesive strength”.

(1-8. Measurement result)
The measurement results are shown in Table 1. About the implementation goods and the comparative product 1, the high adhesive strength with respect to titanium is shown. The implemented product has high adhesive strength not only for titanium but also for the gold alloy, and the adhesive strength for the gold alloy was the highest value, especially when the formulation of the implemented product 2 was used.

  Comparative product 1 containing γ-MPTS has high adhesive strength to titanium, but low adhesive strength to gold alloy. On the contrary, Comparative product 2 containing PETP showed a certain adhesive strength to the gold alloy, but extremely low adhesive strength to titanium. From these results, it was confirmed that a silane coupling agent is essential for titanium (non-noble metal) and a sulfur compound (PETP) is essential for gold alloy (noble metal). Moreover, since the adhesive strength with respect to the gold alloy of Example goods 1-4 is higher than the comparative product 2 which contains only PETP as an adhesive component, it is adhesive strength by using combining a silane coupling agent and a sulfur compound. It was possible to confirm the synergistic effect that increased.

(2. About Example 2)
As an adhesive composition with improved adhesive strength, a mixture of a silane and sulfur compound-containing composition in a resin was used as Example 2, and Examples 5 to 9 were prepared. The result of the adhesive force measurement test of the said implementation goods 5-9 is described.
(2-1. Outline of adhesion test)
The same as in Example 1-1 (1-1. Outline of Adhesion Test).
(2-2. About dental metal to be used)
It is the same as that of Example 1 (1-2. About the dental metal to be used).

(2-3. Surface treatment agent to be used)
In Example 2, a silane coupling agent and a sulfur compound and a dental resin 2 were used without using the adhesive composition as a surface treatment agent as in Example 1 (1-3. Surface treatment agent to be used). And are directly mixed.
In the same manner as in Example 1, the dental resin 2 is an invisible opaque (hereinafter referred to as IvO, component: polymerizable monomer (urethane dimethacrylate), which is an opaque resin of “Twiny” (manufactured by Yamamoto Precious Metal). Triethylene glycol dimethacrylate)) was used.
That is, the process of FIG. 7-2 is omitted, and FIG. 8 is used. In the process of FIG. 8-4, a dental resin that is a mixture of a silane coupling agent, a sulfur compound, and IvO is applied.

(2-4. Dental Resin 2 with Adhesive Surface 30)
Γ-MPTS and PETP were mixed in IvO as an adhesive component at the following blending ratio. The addition amount of γ-MPTS was based on the composition of Patent Document 5.
The product 5 is γ-MPTS 3 wt%, PETP 0.5 wt%, and IvO 96.5 wt%.
The product 6 is γ-MPTS 3 wt%, PETP 1 wt%, and IvO 96 wt%.
The implementation product 7 is γ-MPTS 3 wt%, PETP 2 wt%, and IvO 95 wt%.
The product 8 is γ-MPTS 3 wt%, PETP 3 wt%, and IvO 94 wt%.
The implementation product 9 is γ-MPTS 3 wt%, PETP 5 wt%, and IvO 92 wt%.
Comparative product 3 is a composition referring to the example of Patent Document 5, and is γ-MPTS 3 wt% and IvO 97 wt%.
Comparative product 4 was used as it was without adding an adhesive composition to IvO, which is a twinnie opaque resin. Mixing of γ-MPTS, PETP and IvO was performed by mixing with “Awatori Nertaro” (manufactured by Shinky).

(2-5. Adhesion process)
The adhesion target 3 that has been subjected to the sandblasting treatment described above (1-2. About dental metal to be used) is ultrasonically cleaned with water for 10 minutes, and sufficiently rinsed with Solmix AP-7 (manufactured by Nippon Alcohol Sales). It is.
Then, the surface of the adhesion target 3 is dried, a water-resistant tape with a hole of 3 mmφ is attached and masking is performed, and the dental resin 2 of the above-described products 5 to 9 and comparative products 3 and 4 is thinly applied with a brush, It was cured by light irradiation for 3 minutes with a dental light irradiation machine (Alphalite 2: manufactured by Morita).

(2-6. Resin provided on IvO)
The same as in Example 1 (1-6. Resin provided on IvO).
(2-7. Measurement)
This is the same as (1-7. Measurement) in Example 1.

(2-8. Measurement results)
Table 2 shows the measurement results. As in Example 1, all of the examples had higher values of adhesion strength to the gold alloy than the comparative products, and the effect of improving the adhesion strength to the gold alloy by adding PETP was recognized. Among the implemented products, the implemented product 7 had a high adhesive strength for both titanium and gold alloy.

  Comparative product 3 containing γ-MPTS has high adhesion strength to titanium, but low adhesion strength to gold alloy and does not contain an adhesive component (without primer treatment), comparative product 4 has titanium and The adhesion strength of both gold alloys was low.

(Examination of overall effect of Examples 1 and 2)
Among Example 1 and Example 2, Example 2 and Example 7, which were good results, were further bonded as gold-silver-palladium alloys (parazzets 12-n: Yamamoto Precious Metals), Ni-Cr alloys. [Wiron (registered trademark) 99: manufactured by BEGO], Co-Cr alloy (Wirobon (registered trademark) C: manufactured by BEGO), and zirconia (Aadva (registered trademark): manufactured by GC) were added to measure the adhesive strength. Similarly, Comparative Products 1, 3 and 4 were also measured, and Table 3 was obtained.

(Measurement result)
Table 3 shows the measurement results. The implementation product 2 and the implementation product 7 had high adhesive strength to all the objects to be bonded (titanium, gold alloy, gold-silver palladium alloy, Ni—Cr alloy, Co—Cr alloy, zirconia). Since the comparative product 4 does not contain any precious metal or non-precious metal adhesive component, the adhesive strength is low. In the composition containing a silane coupling agent as in comparative products 1 and 3, high adhesion strength was observed for non-noble metals such as titanium, Ni-Cr alloy and Co-Cr alloy, The adhesive strength is extremely low. Moreover, since the adhesive strength of the implementation products 2 and 7 is higher than that of the comparative products 1 and 3 with respect to the zirconia, the silane coupling agent and the sulfur compound are used not only for the gold alloy but also for ceramics. It was found that the bonding effect is enhanced by combining them at a suitable blending ratio as compared with the case of using them alone.
As described above, the present invention remarkably improves adhesion to a dental resin when used as a primer for all dental precious metals, non-precious metals, alloys thereof, and ceramics, and the same adhesive component is mixed with the dental resin. Thus, a very useful adhesive composition having an excellent adhesive effect can be obtained without primer treatment.

DESCRIPTION OF SYMBOLS 1 Treatment tooth 10 Front crown 11 Frame part 12 Retention bead 2 Dental resin 3 Bonding object 30 Adhesive surface 4 Test piece 40 Dental resin cement 41 Stainless steel bolt 42 Bolt holder

Claims (3)

A dental adhesive composition for improving the adhesive strength with a dental resin for all dental precious metals, dental non-precious metals, dental alloys of the metals, and dental ceramics, wherein the dental adhesive composition Is
A silane coupling agent having a polymerizable group;
A thiopropionic acid derivative or a thioglycolic acid derivative;
Consisting of volatile organic solvents,
The silane coupling agent is
A compound represented by the chemical formula:

The thiopropionic acid derivative or thioglycolic acid derivative is
It is a compound represented by the chemical formula of [Chemical Formula 2]

A dental adhesive composition characterized by the above.
A surface treatment agent using the dental adhesive composition according to claim 1,
The surface treatment agent is
It is a mixture of the dental adhesive composition and a volatile organic solvent,
For a total weight of 100% of the surface treatment agent,
The weight of the silane coupling agent is 1.0 to 30.0%,
A surface treatment agent characterized in that the weight of a thiopropionic acid derivative or a thioglycolic acid derivative is 0.1 to 1.0%, and the weight of a volatile organic solvent is 69.0 to 98.9%.
A dental resin using the dental adhesive composition according to claim 1,
The dental resin is
A mixture of the dental adhesive composition and a dental hard resin,
For a total weight of 100% of the polymerizable resin,
The weight of the silane coupling agent is 1.0 to 10.0%,
A dental resin characterized in that the weight of the thiopropionic acid derivative or thioglycolic acid derivative is 0.5 to 4.0%, and the weight of the dental hard resin is 86.0 to 98.5%.

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