KR20200000138A - An orthodontic cement composition having the improved adhesion strength - Google Patents

Abstract

The present invention relates to an orthodontic cement composition having improved adhesion strength. The orthodontic cement composition according to the present invention comprises the mixture in an amount of 0.1 to 10 wt% based on the total weight of the orthodontic cement composition by mixing bisphenol A-glycidyl methacrylate (Bis-GMA) as an oligomer with urethane dimethacrylate (UDMA) to a weight ratio of 6:4 to 8:2. The orthodontic cement composition is useful in various dental and orthodontic applications including a dental flotation, a dental adhesive, a dental cement, a cavity liner, an orthodontic adhesive, a dental sealant, and a dental coating agent since the composition is very excellent in adhesion strength compared to an existing cement composition. The composition can be used in manufacturing of dental articles by hardening the composition so as to form, for example, a dental mill blank, a dental crown, a dental filling, a dental prosthesis and an orthodontic device.

Description

An orthodontic cement composition having the improved adhesion strength}

The present invention relates to a dental orthodontic cement composition with improved adhesive strength, more specifically, bisphenol A-glycidyl methacrylate (Bis-GMA) and urethane dimethacrylate ( Urethane Dimethacrylate (UDMA) relates to an improved orthodontic cement composition characterized in that it comprises a specific content.

Repair of caries teeth, including tooth decay, caries dentin or carved enamel, is often performed using a dental adhesive followed by a dental material (e.g., restorative material) sequentially to the tooth. Similar compositions are used to join orthodontic devices to the teeth. Often, various pretreatment methods are used to promote the bonding of the adhesive to dentin or enamel. Typically, this pretreatment step involves, for example, etching with an inorganic or organic acid and then priming to improve the bond between the tooth and the adhesive placed thereon.

Various dental and orthodontic adhesives, cements and restorations are currently available. Compositions comprising fluoroaluminosilicate glass fillers are the most widely used dental material type. These compositions include filling and repairing caries lesions; Bonding of crowns, inlays, dentures or orthodontic bands; Caries lining; Core reconfiguration; And widespread uses such as hole and gap closure.

Tooth caries is a phenomenon in which the components such as calcium and phosphorus on the surface of the tooth are dissolved by acid and the components such as protein are broken down to create holes in the teeth. Dental caries is generally called tooth decay.

In case of widespread dental caries, conventional root canal treatment and direct or indirect pulp can be applied. Root canal treatment is usually performed, but this has the disadvantage of requiring a long procedure time, a complicated procedure, and a large treatment cost.

In general, the adhesion of hemorrhoids is largely divided into enamel and dentin adhesion. First, in enamel adhesion, Bunocore in 1955 changed the smooth surface of the enamel into a rough surface by acid corrosion, facilitating the capillary phenomenon, enabling the microcavity penetration of dental restorative materials, resulting in an excellent retention. After that, the excellent properties obtained through enamel adhesion can be found in US Pat. Nos. 4,102,856 and 4,131,729.

In terms of dentin adhesion, enamel is a tissue that lacks vitality, but dentin is predominantly anatomical and histological in view of the extension of the dimension. Therefore, the material applied to the dentin should be free of biologically harmful effects and the biological stability of teeth. It should not be a threat.

Kanca has demonstrated that adhesive strength is increased by using a hydrophilic primer and an adhesive monomer having both hydrophilicity and hydrophobicity (Japanese Patent Publication Nos. 53-33687, 54-10986, and Japanese Patent Application No. 56). Since then, various compounds have been proposed, and with the development of the method of treatment, current adhesives, primers, adhesives, or preservatives are first applied with a two-stage procedure, followed by primers and adhesives. Products that express the mainstream.

In addition, one step of the acid preservatives, primers, adhesives are also performed with respect to dentin adhesion, but the adhesive strength obtained by the first step is inferior to the adhesive strength obtained by the above mentioned two step.

Therefore, the technical problem to be solved in the present invention is to provide a dental orthodontic cement composition with improved adhesive strength.

In order to solve the above technical problem, in the present invention, bisphenol A-glycidyl methacrylate (Bis-GMA) and urethane dimethacrylate (UDMA) 6: 4 as an oligomer. It is mixed to a weight ratio of 8: 2 to provide an orthodontic cement composition with improved adhesive strength, characterized in that it comprises an amount of 0.1 to 10% by weight based on the total weight of the orthodontic cement composition.

The present invention is characterized by using a mixture of Bis-GMA and UDMA raw materials that can maintain the strength in the oligomer. The Bis-GMA is a compound having a reactive end as shown in the following formula (1) has a double bond at both ends of the polymer and has a high Tg value of itself, which may affect flexural strength and adhesive strength when combined with cement inorganic materials. have.

The UDMA is a compound having a reactive end as shown in the following formula (2).

In the present invention, the strength of the cement composition can be maintained by mixing Bis-GMA and UDMA in a weight ratio of 6: 4 to 8: 2, preferably in a weight ratio of 7: 3. At this time, when Bis-GMA and UDMA are mixed in a weight ratio of Bis-GMA lower than 6 for UDMA 4, the viscosity is too strong to be used as a cement composition, and Bis-GMA is higher than 8 for UDMA 2 When mixed at a large weight ratio, the viscosity becomes so weak that it is difficult to obtain an effect of improving the adhesive strength of the cement composition.

In the present invention, it is characterized by using the BTS-GMA mixed with Bis-GMA and UDMA, wherein BTS-GMA is contained in an amount of 0.1 to 10% by weight based on the total weight of the orthodontic cement composition When the BTS-GMA is used in an amount of less than 0.1% by weight, it is not possible to improve the adhesive strength of the cement composition, even when the BTS-GMA is used in an amount of more than 10% by weight Strength cannot be improved.

According to one embodiment of the present invention, conventional oligomers may be added and mixed with the BTS-GMA. For example, it may further include UDMA, triethyleneglycol dimethacrylate (TEGDMA), trimethylopropane trimethacrylate (TMPTMA), and the like.

In addition, according to one embodiment of the present invention, the oligomer having a phosphate group that can improve the bond strength by pre-treatment of the anti-carious effect and the tooth surface of the dimethyl acrylate-based oligomer having a part function with the oligomer for the living body Use additionally.

Dimethacrylates having such phosphate groups include 10-MDP (10-Methacryloyloxydecyl dihydrogen phosphate), MPC (2-methacryloyloxyethyl phosphoryl choline) having anti-carious functionality, acrylic ether phosphonic acid, and phosphoric acid 2-hydroxyethyl methacrylate. ester), MPS (3- (Trimethoxysilyl) propy methacrylate).

The calibration cement composition of the present invention may be prepared according to a conventional method, and may be prepared according to a basic material mixing process, an oligomer mixing process, an oligomer and basic material mixing process, an inorganic material mixing process, and an oligomer and inorganic filler mixing process. have.

The basic material mixing process is carried out by mixing a predetermined amount after dilution and photoinitiator, catalyst, preservative, inhibitor, etc., for example, the mixing conditions are conditions of speed: 60rpm, mixing time: 1 hour, temperature 30 ~ 35 ℃.

The oligomer mixing process is mixed with Bis-GMA and UDMA after a certain amount of metering, wherein the mixing conditions are carried out at a speed / operating time (minutes): 20rpm / 5M-> 80rpm / 60M, temperature: 32 ℃.

The oligomer and base material mixing process mixes the oligomer mixed product and the initiator material, where the mixing conditions are carried out under the conditions of speed / operating time (minutes): 20 rpm / 5M-> 80 rpm / 60M, temperature: 32 ℃. .

The inorganic material mixing process is carried out by powder mixing after weighing the inorganic material, wherein the mixing conditions are carried out under the conditions of speed / operating time (minutes): 40rpm / 90M, temperature: 32 ℃.

The oligomer and inorganic filler mixing process is carried out by mixing a predetermined amount of the prepared oligomer in the inorganic material mixture, wherein the mixing conditions are speed / operating time (minutes): 20rpm / 10M-> 75rpm / 25M, and the final step The vacuum (-76 cmHg) holding condition is a condition of holding speed / operation time (minutes): 20 rpm / 5M and temperature: 32 ° C.

According to one embodiment of the present invention, the inorganic filler mixed with the oligomer may be at least two inorganic fillers selected from the group consisting of Ba, silica, Ca (OH) ₂ and quartz.

The compositions according to the invention are useful for a variety of dental and orthodontic applications, including dental restorations, dental adhesives, dental cements, tooth decay liners, orthodontic adhesives, dental sealants and dental coatings. The composition can be used to prepare dental articles, for example, by hardening them to form dental mill blanks, dental crowns, dental fillers, dental prostheses and orthodontic devices.

Dental orthodontic cement composition comprising the oligomer according to the present invention in a certain ratio is very excellent in adhesive strength compared to the conventional cement composition.

1 illustrates a coating test process of the orthodontic cement.
Figure 2 is a photograph of the adhesive area and cement adhesive strength specimens used to measure the adhesive strength of orthodontic cement.
FIG. 3 is a photograph of a decayed specimen used to measure adhesion strength of orthodontic cement. FIG.
FIG. 4 is a photograph of a decayed specimen used for measuring adhesive strength by applying a dental orthodontic cement and a primer. FIG.

Hereinafter, examples and the like will be described in detail to help understand the present invention. However, embodiments according to the present invention can be modified in many different forms, the scope of the invention should not be construed as limited to the following examples. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Example 1 Preparation of Calibration Cement Composition

To prepare a cement composition for calibration having the composition (g) shown in Table 1 below.

Specifically, Bis-GMA and UDMA are mixed at a weight ratio of 7: 3, and then BTS-GMA is prepared, and the base material mixing process, oligomer mixing process, oligomer and base material mixing process according to the composition shown in Table 1 below. According to the inorganic material mixing process and oligomer and inorganic filler mixing process was prepared a cement composition for calibration.

Substance Orthodontic Cement Composition S1 S2 S3 S4 BTS-GMA 1.1 9.4 9.4 9.4 UDMA 44.2 11.8 11.8 11.8 TEGDMA 4.4 2.4 2.4 2.4 TMPTMA 4.4 4.7 4.7 4.7 PHM 4.4 3.3 3.3 3.3 MPS 8.8 4.7 4.7 4.7 HEMA 11.5 5.6 5.6 5.6 CQ 0.5 0.3 0.3 0.3 EDB 1.1 0.6 0.6 0.6 Preservative 0.1 0.1 0.1 0.1 Acetone 4.4 1.4 1.4 1.4 Ethanol 4.4 2.8 2.8 2.8 Ba particles 0.5 11.1 11.1 16.6 Silica 34.5 11.1 0 0 Thickener 0.4 0.8 11.1 16.6 NaF 3.5 5.5 5.5 5.5 Ca (OH) ₂ 0.5 11.1 11.1 5.5 Quartz particles 68.4 72.2 72.2 66.6

< Test Example  1> of orthodontic cement Film performance test

The coating performance test for the calibration cement prepared in Example 1 was performed as follows by the method illustrated for the coating degree test procedure shown in FIG. 1. 1 illustrates a coating test process of the orthodontic cement.

(1) area (200 ± 25) mm ^2, hayeoteum measure the thickness by attaching the two pieces of glass plate thickness of 5 mm with a micrometer to 1 μm units: A

(2) Place 0.1 mL of the sample mixed with the sample in the center of the lower glass plate, place it on the load device and cover with another glass plate.

(3) A load of (150 ± 2) N was applied vertically to the center of the sample for (180 ± 10) seconds through the upper glass plate immediately after mixing.

(4) Removed the load and irradiated the sample for twice the light irradiation time suggested by the manufacturer and measured the combined thickness of the two glass plates and the sample: B

(5) The film thickness was measured and recorded three times to the micrometer unit as shown in Equation 1 below.

The results are as shown in Table 2 below.

Psalter Glass plate (mm)
A Glass plate + sample (mm)
B Result (mm)
BA Average film thickness
(Μm) S1 9.688 9.727 0.039 28 9.674 9.693 0.019 9.663 9.690 0.027 S2 9.685 9.774 0.089 92 9.595 9.683 0.088 9.66 9.759 0.099 S3 9.585 9.667 0.082 71 9.615 9.685 0.070 9.636 9.697 0.061 S4 9.652 9.745 0.093 99 9.650 9.753 0.103 9.669 9.770 0.101

In addition, the comparative test results using the 3M ESPE self-adhesive resin cement as a control is shown in Table 3 below.

Psalter Glass plate (mm)
A Glass plate + sample (mm)
B Result (mm)
BA Average film thickness
(Μm) 3M 9.620 9.639 0.019 23 9.647 9.676 0.029 9.582 9.602 0.020

As shown in Table 2 and Table 3, the coating degree test results, based on the ISO 4049: 2009 standard, the first cement was evaluated as a sample closer to the development product of the present research relative to the cement of 2-4.

<Test Example 2> Adhesion strength test of the calibration cement

Adhesion strength test (artificial bone) for the calibration cement prepared in Example 1 was performed as follows.

(1) A rectangular specimen of 10 mm in width, 50 mm in length, and 8 mm in thickness of artificial bone was produced.

(2) Polish the attachment surface of the specimen with P600.

(3) Store the ground specimen in a constant temperature water bath at (37 ± 1) ° C.

(4) Before attaching the bracket, remove moisture from the bonding surface of artificial bone with air.

(5) Apply cement to the bracket with brush.

(6) Place the cemented bracket on the adhesive side of the artificial bone.

(7) Using a static load, apply a load of 1 kg at the top of the specimen for 5 seconds.

(8) After removing the load, perform light polymerization for 10 seconds on the upper, left and right sides of the bracketed specimen.

(9) Measure the adhesion force (N) by applying shear load to the cross-head speed of the tension and compression tester at 1.0 mm / min.

(10) Calculate and record the adhesive strength (B) according to the following equation (2).

F: Maximum load for sample separation (N)

A: adhesive area (mm ² )

The results are as shown in Table 4 below. Figure 2 is a photograph of the adhesive area and cement adhesive strength specimens used to measure the adhesive strength of orthodontic cement.

Psalter Surface area (mm ² ) Load (N) Adhesive force (MPa) medium Standard Deviation S1 8.28 35.42 4.28 4.34 0.37 8.28 39.23 4.74 8.28 33.25 4.02 S2 8.28 21.32 2.57 2.36 0.40 8.28 15.79 1.91 8.28 21.60 2.61 S3 8.28 19.48 2.35 2.63 0.52 8.28 19.06 2.30 8.28 26.77 3.23 S4 8.28 22.07 2.67 2.12 0.48 8.28 15.25 1.84 8.28 15.26 1.84

In addition, the comparative test results using the 3M ESPE self-adhesive resin cement as a control is shown in Table 5 below.

Psalter Surface area (mm ² ) Load (N) Adhesive force (MPa) medium Standard Deviation 3M 8.28 30.34 3.66 3.79 0.82 8.28 25.17 3.04 8.28 38.60 4.66

As shown in Tables 4 and 5, in the adhesive strength test applying only cement to artificial bones, cement No. 1 had a relatively high adhesive strength compared with cements of 2 ~ 4, and compared to the control group, which is closer to the development product of the present study. The sample was evaluated.

<Test Example 3> Adhesion strength test of the calibration cement

Adhesion strength test (ouch) for the calibration cement prepared in Example 1 was performed as follows.

(1) Cut and wash the bovine intact and store it in distilled water until the test.

(2) Using acrylic resin, fix the tooth surface facing upward.

(3) Polished and cleaned with # 600 Silicon carbide paper to reveal the enamel layer of the Loach.

(4) Air is removed from the surface of the decay.

(5) Apply cement to the bracket with brush.

(6) Place the cemented bracket on the adhesive surface of the uchi.

(7) Using a static load, apply a load of 1 kg at the top of the specimen for 5 seconds.

(8) After removing the load, perform light polymerization for 10 seconds on the upper, left and right sides of the bracketed specimen.

(9) Measure the adhesion force (N) by applying shear load to the cross-head speed of the tension and compression tester at 1.0 mm / min.

(10) Calculate and record the adhesive strength (B) according to the following equation (3).

F: Maximum load for sample separation (N)

A: adhesive area (mm ² )

The results are as shown in Table 6 below. FIG. 3 is a photograph of a decayed specimen used to measure adhesion strength of orthodontic cement. FIG.

Psalter Surface area (mm ² ) Load (N) Adhesive force (MPa) medium Standard Deviation S1 8.28 32.37 3.91 4.13 2.50 8.28 52.12 6.29 8.28 36.53 4.41 8.28 0.32 0.04 8.28 49.59 5.99

In addition, the comparative test results using the 3M ESPE self-adhesive resin cement as a control is shown in Table 7 below.

Psalter Surface area (mm ² ) Load (N) Adhesive force (MPa) medium Standard Deviation 3M 8.28 45.50 5.50 4.94 2.20 8.28 30.06 3.63 8.28 30.35 3.67 8.28 70.95 8.57 8.28 27.61 3.33

    As shown in Table 6 and 7, in the adhesive strength test applied only cement to the raindrops showed a similar level compared to the control.

<Test Example 4> Adhesive strength test after applying the calibration cement and primer

After applying the calibration cement and primer prepared in Example 1, the adhesion strength test (ouch) was performed as follows.

(1) Cut and wash the bovine intact and store it in distilled water until the test.

(2) Using acrylic resin, fix the tooth surface facing upward.

(3) Polished and cleaned with # 600 Silicon carbide paper to reveal the enamel layer of the Loach.

(4) Air is removed from the surface of the decay.

(5) Etched for 15 seconds using 3M Scotchbond Etchant and washed with distilled water.

(6) Apply primer to the etching site and dry for 5 seconds.

(7) Apply cement to the bracket with brush.

(8) Place the cemented bracket on the adhesive surface of the uchi.

(9) Using static load, apply a load of 1 kg at the top of the specimen for 5 seconds.

(10) After removing the load, perform light polymerization for 10 seconds on the upper, left and right sides of the bracketed specimen.

(11) Store the specimens in water at 37 ° C for 24 hours.

(12) Measure the adhesive force (N) by applying shear load to the cross-head speed of the tensile and compression tester at 1.0 mm / min.

(13) Calculate and record the adhesive strength (B) according to the following equation (4).

F: Maximum load for sample separation (N)

A: adhesive area (mm ² )

The results are as shown in Table 8 below. FIG. 4 is a photograph of a decayed specimen used for measuring adhesive strength applying a dental orthodontic cement and a primer.

Psalter Surface area (mm ² ) Load (N) Adhesive force (MPa) medium Standard Deviation S1 8.28 44.18 5.34 7.31 1.29 8.28 73.68 8.90 8.28 63.87 7.71 8.28 59.32 7.16 8.28 61.40 7.42

In addition, the comparative test results using the 3M ESPE self-adhesive resin cement as a control is shown in Table 9 below.

Psalter Surface area (mm ² ) Load (N) Adhesive force (MPa) medium Standard Deviation 3M 8.28 33.51 4.05 6.41 2.02 8.28 43.98 5.31 8.28 62.74 7.58 8.28 76.36 9.22 8.28 48.89 5.90

As shown in Tables 8 and 9, a primer containing a UDMA isomer (photopolymerized monomer) and a 10-MDP (adhesive monomer) was developed and compared with the control primer, and the adhesive strength was slightly higher than that of the control. Indicated.

Claims (4)

Dental correction by mixing bisphenol A-glycidyl methacrylate (Bis-GMA) and urethane dimethacrylate (UDMA) as an oligomer in a weight ratio of 6: 4 to 8: 2 Orthodontic cement composition with improved adhesive strength, characterized in that it comprises an amount of 0.1 to 10% by weight based on the total weight of the cement composition for. The method of claim 1,
10-MDP (10-Methacryloyloxydecyl dihydrogen phosphate), MPC (2-methacryloyloxyethyl phosphoryl choline), acrylic ether phosphonic acid (Phosphoric acid 2-hydroxyethyl methacrylate ester), MPS (3- (Trimethoxysilyl) propy methacrylate) Orthodontic cement composition improved adhesion strength, characterized in that the addition of at least one oligomer selected from the group consisting of. Claim 1 or 2 according to the orthodontic cement composition according to claim 1, 1) basic material mixing process, 2) oligomer mixing process, 3) oligomer and base material mixing process, 4) inorganic material mixing process and 4) oligomer and inorganic filler As a method according to the process consisting of a mixing step,
1) The basic material mixing process is carried out by weighing and mixing the diluent and photoinitiator, catalyst, preservative, inhibitor, the mixing conditions are speed: 60rpm, mixing time: 1 hour, temperature 30 ~ 35 ℃ maintenance conditions,
2) The oligomer mixing process is carried out by measuring and mixing UDMA and Bis-GMA, wherein the mixing conditions are speed / operating time (minutes): 20rpm / 5M-> 80rpm / 60M, temperature: 32 ℃ holding conditions,
3) The oligomer and base material mixing process mixes the oligomer mixed product and the initiator material, wherein the mixing conditions are the speed / operating time (minutes): 20rpm / 5M-> 80rpm / 60M, temperature: 32 ℃ maintenance conditions ,
4) The inorganic material mixing process is carried out by mixing the powder after weighing the inorganic material, wherein the mixing conditions are conditions of speed / operating time (minutes): 40rpm / 90M, temperature: 32 ℃,
5) The oligomer and inorganic filler mixing process is carried out by mixing the prepared oligomer in the inorganic material mixture, wherein the mixing conditions are speed / operating time (minutes): 20rpm / 10M-> 75rpm / 25M, in the final step The vacuum (-76 cmHg) holding condition is a speed / operation time (minutes): 20 rpm / 5M, temperature: 32 ° C. The method of claim 3, wherein
The inorganic filler mixed with the oligomer in step 5) is at least two inorganic fillers selected from the group consisting of Ba, silica, Ca (OH) ₂ and quartz.

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