KR101009745B1 - Dental cement composition with antimicrobial activity - Google Patents

Abstract

PURPOSE: A dental cement composition containing monomers, starter and inorganic filler is provided to maintain strength and adhesion and to ensure antibacterial activity. CONSTITUTION: A dental cement composition contains monomers, starter, and inorganic filler. A part of inorganic filler has particle size of 0.005-0.2 um. The content of the monomer is 10-59.9 weight%. The dental cement composition is an antibacterial inorganic filter of which surface is treated by silane compounds containing quarternary ammonium group. The content of the starter and inorganic filler is 0.1-1 weight% and 40.89.9 weight%, respectively. The monomer is a photo-polymerizable monomer. The inorganic filler contains fluorine ion.

Description

Dental cement composition with antimicrobial activity {Dental Cement composition with antimicrobial activity}

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dental cement composition, more particularly comprising a monomer, an initiator and an inorganic filler, and in particular, at least some of the inorganic fillers are surface treated with a silane-based compound comprising a quaternary ammonium group as an antimicrobial component. The present invention relates to a dental cement composition having adhesive strength, compressive strength and antibacterial activity.

Dental adhesives are adhesives that are hardened by a polymerization reaction and chemically bonded, and are conventional cements such as zinc phosphate cement, carboxylate cement, glass ionomer cement, and resin cement, which are known to be hardened by acid-base reaction and mechanically bonded. It is used separately from (plywood).

Dental cements are cements used for bonding or fixing restorations or orthodontics with hemorrhoids, such dental cements are intended to (i) secure the restorations or orthodontics to the teeth, (ii) protect the dimensions and provide the structure of the restoration. It is used for vortex transfer materials and bases, (ⅲ) fillers, etc.

Cement used for bonding or restoring restorations must have low solubility in the oral cavity, have high bonding strength between teeth or restoration and cement by mechanical retention and chemical bonding, and can resist stress at the interface between the restoration and teeth. It must have strength and fracture toughness, be convenient to use and suitable for living body.

However, dental adhesives or restorative materials may cause demineralization of teeth caused by bacteria due to caries or fractures of teeth.If dentin is exposed due to abrasion, the teeth may be sensitive, chemical, bacterial, mechanical or thermal The stimulation causes tissue dentin tubules to be prone to stimulation.

Glass compositions that release fluorinated ions are helpful for preventing caries and for preventing tooth decay and sensitive teeth, but US Pat. Nos. 4,920,082 and WO 88105652 disclose that fluorinated ions are easily ionized (dissolved) by water and oral. It is disclosed as completely unsatisfactory for my use.

Therefore, while fluoride ions are released for a long time, there is a need for materials that are resistant to caries and bacteria of teeth, and thus, various studies and discussions for preventing tooth decay or caries have been conducted.

For example, ceramic restorative materials containing nano silver having bactericidal power have been discussed, and Korean Patent Application Publication No. 2006-111042 discloses blending silver nanomaterials in the tissue of a dental restorative material at 0.01 to 20% by weight. Or it discloses a restoration that can be used to clean and sanitary by preventing the production and reproduction of microorganisms by coating. However, the above technique shows the result after 30 minutes of use of silver nano material in a content of 10% by weight, which is a practical problem in that physical properties in dental adhesives or restoratives usually require an effect of 6 months or more. There is.

Studies on techniques using fluoride glass compositions to treat sensitive teeth have been discussed. For example, Korean Patent Application Publication No. 2006-0097057 discloses a technique for attaching a fluoride releasing glass composition to a patient's teeth to slowly release fluorinated ions over time in order to reduce chronic and / or acute tooth sensitivity. It is starting. However, it is known that this technique does not continuously release fluorinated ions in a constant amount for a long time.

Therefore, there is an urgent need to develop a technology for dental resin cement materials having excellent antibacterial and anti-carious properties without affecting adhesion and strength.

The present invention aims to solve the problems of the prior art as described above and the technical problem that has been requested from the past.

Accordingly, the inventors of the present application, after in-depth study and various experiments, at least a part of the inorganic filler, the dental surface-treated with a silane-based compound containing a quaternary ammonium group and includes an inorganic filler that emits fluorinated ions The cement composition for the present invention was developed, and it was confirmed that such a composition exhibits excellent adhesive strength, compressive strength, and antimicrobial activity, thus completing the present invention.

Accordingly, the dental cement composition according to the present invention comprises a monomer, an initiator and an inorganic filler, wherein at least some of the inorganic fillers have a particle diameter of 0.005 to 20 μm and include quaternary ammonium groups as antibacterial components. Surface-treated with a silane compound, the surface treatment agent including the antimicrobial component is characterized in that less than 5% by weight based on the total weight of the composition.

The silane-based compound is, for example, a silane-based compound in which a quaternary ammonium salt and a trimethoxyl group are bonded to each other, where the trimethoxyl group reacts with a hydroxyl group on the surface of the inorganic filler to form a covalent bond and simultaneously graft organic silicon. Since the thin film is formed by the strong bond to the polymerization, it can add durability and safety of the antibacterial action.

The antimicrobial action is caused by a physical process in which cations of ammonium molecules are electrostatically adsorbed on anion sites on the surface of microbial cells, killing them by stopping the respiratory function by destroying the cell walls of microorganisms by needle bed structure. Thus, the antimicrobial action is widespread on virtually all microorganisms, not on specific microorganisms, and adaptive microorganisms may not occur.

In addition, unlike other antimicrobial agents, the surface treatment agent is strongly bound to the applied surface, does not dissolve or volatilize, and thus does not affect people and the environment, and its effect does not decrease until the surface of the applied surface is peeled off, and It fundamentally prevents the growth of fungi, preventing the smell and contamination caused by bacteria and fungi.

The content of the surface treating agent including the antimicrobial component is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, even more preferably 0.2 to 1% by weight relative to the total composition. If the content of the surface treating agent is too small, it may not exhibit sufficient antimicrobial properties. On the contrary, if the content of the surface treating agent is too high, the antibacterial properties may be improved, but the physical properties of the entire cement composition may be significantly reduced, and foreign substances may be hardened by the surface treating agent alone.

In the present invention, in addition to the surface treatment agent, one or two or more kinds selected from the group consisting of an ordinary epoxy silane treatment agent, a mercetosilane treatment agent, an amine silane treatment agent and a methyl trimethoxy silane treatment agent can be used in combination, It is not limited.

The content of the monomer may vary depending on the field of use and purpose thereof, and is not particularly limited. However, when the content of the monomer is too small, it is difficult to form the desired polymer and the mixing with the inorganic filler is not easy, and thus workability is deteriorated. On the contrary, when the content is too high, the desired physical properties (mechanical strength, polymerization shrinkage, etc.) are exhibited. You won't be able to. In consideration of this, the content of the monomer may be included in 10 to 60% by weight, preferably 20 to 45% by weight based on the total weight of the composition. Preferable examples of the monomers include methacrylic monomers, but are not limited thereto.

In one preferred embodiment, the monomer comprises a photopolymerizable monomer component and a self-polymerizable monomer component, the mixing ratio of the photopolymerizable monomer component and the autopolymerizable monomer component is 10 to 90: 90 to 10 (photopolymerizable) Monomer component: autopolymerizable monomer component).

The photopolymerizable monomer component may be, for example, 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA), ethoxylate bisphenol A dimethacryl Rate (Bis-EMA), urethane dimethacrylate (UDMA), 4-methacryloxyethyltrimeric anhydride (4-META), 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate (HEMA), and at least one selected from the group consisting of methacrylic monomers such as Tri-GMA.

The autopolymerizable monomer component is, for example, 2- (meth) acryloyl group ethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyl Oxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, di [4- (meth) acryloyloxybutyl] hydrogen phosphate, di [8- (meth) acrylooxyoctyl ] Hydrogen phosphate, di [9- (meth) acryloyloxynonyl] hydrogen phosphate, di [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyl Oxypropyl-2-dihydrogen phosphate, (5-methacryloxy) decyl-3-phosphonopropionate, (10-methacryloxy) decyl-3-phosphonoacetate, 2-methacryloyloxyethyl (4-methoxyfail) hydrogenphosphate under 2-methacryloyloxypropyl (4-methoxyphenyl) One member selected from the group consisting of phosphate-based monomers such as draw phosphate may be greater than or equal to.

The composition may further include a diluent for reducing the viscosity of the mixture in an amount of 1 to 20% by weight based on the total weight of the composition.

The diluents are, for example, methyl methacrylate, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), 1,4-butanediol It may be at least one selected from the group consisting of, dimethacrylate, 1,6-hexanediol diketacrylate, and 1-methyl-1,3-propanediol dimethacrylate.

In another preferred embodiment, the composition comprises a first paste containing an inorganic filler containing fluoride ions and capable of chemical reaction with acid, and an inorganic filler containing no fluoride ion and not capable of chemical reaction with acid. It can be made of a combination of the second paste included.

Examples of the first paste include two hydrophobic methacrylate functional groups, low volatility and polymerization shrinkage, fast curing, high molecular weight and high stability monomers (eg Bis-GMA, etc.), viscosity Low and flexible to improve the responsiveness of the resin and to mix more fillers (eg TEGDMA), and fillers that can chemically react with acids by releasing Calcium, Strontium and Aluminum ions (e.g. reactive filler May be used.

As the second paste, for example, a monomer having a methacrylate functional group and a phosphate, which is a chemically bondable functional group, and a filler that does not chemically react with an acid (for example, a quartz, barium glass, barium glass / silica mixture, Mixtures of quartz / barium mixture glasses, silica, zirconia / silica mixtures, aluminosilicates, lithium aluminosilicates, and barium aluminosilicates, and the like can be used.

The content of the polymerization initiator may be 0.1 to 1% by weight, and may be included in the first paste and / or the second paste.

The polymerization initiator may function in various ways, such as a cation formation mechanism, an anion formation mechanism, a radical formation mechanism, and the like, depending on the type of catalyst used in the polymerization reaction, and a double radical formation mechanism is most commonly used. According to these polymerization mechanisms, the polymerization reaction can be carried out by a photopolymerization reaction, a chemical polymerization reaction, or the like.

The photopolymerization reaction is performed by a photopolymerization initiator activated by visible light to initiate a polymerization reaction of monomers, and the photopolymerization initiator is typically an α-diketone-based carbonyl compound photopolymerization initiator such as camphor quinone (CQ), And acyl phosphine oxide photopolymerization initiators. Photopolymerization initiators typically use hydrogen donors as cocatalysts, mainly with tertiary amine based catalysts such as N, N-bis- (2-hydroxyethyl) -p-toluidine (DHEPT).

The chemical polymerization reaction is carried out with a peroxide compound such as benzoyl peroxide (BPO), and is used together with a tertiary amine promoter as described above to form radicals by heat to initiate polymerization.

A polymerization initiator for such a polymerization reaction may be included in the composition within a range that does not affect the physical properties of the product while inducing a polymerization reaction.

In this case, the antimicrobial inorganic fillers are mixed in the composition of the first paste and the second paste, respectively, to improve the mechanical properties of the resin cement and to impart impermeability to X-rays.

The inorganic filler is, for example, a group consisting of quartz, barium glass, barium glass / silica mixture, quartz / barium mixture glass, silica, zirconia / silica mixture, aluminosilicate, lithium alumino silicate, and barium alumino silicate. It may be at least one selected from.

The inorganic filler of the first paste may preferably be an inorganic filler containing fluorine ions. Preferred examples of such inorganic fillers include, but are not limited to, calcium aluminofluorosilicate glass.

The surface treatment agent is mainly used a silane-based coupling agent, for example, gamma-methacryloxy propyltrimethoxy silane (-MPS), vinyl triethoxy silane, dimethyl dichloro silane, hexamethylene disilazane, and One or more selected from the group consisting of dimethyl polysiloxanes can be used.

In one preferred example, the antimicrobial inorganic filler surface-treated with a silane compound containing a quaternary ammonium group may be in a form in which the surface treating agent is bonded to the surface of the inorganic filler in the structure of the following formula (1).

(1)

(One)

Where

R ₁ , R ₂ and R ₃ are each independently hydrogen or methyl;

Y is C _{1 -4} alkyl group and;

X is halogen;

n is an integer from 4 to 30;

m is an integer of 10 to 1,000,000.

Dental compositions comprising fluorine-ion-releasing glass as an inorganic filler can provide the transparency necessary for good esthetics, fluorine-ion-releasing property for preventing tooth decay, and adequate radiopacity to provide an excellent contrast of teeth to X-rays. have.

Other well-known compounds may be added to the composition of the present invention within a range that does not impair the effects of the invention, such materials include polymerization inhibitors, polymerization retardants, light stabilizers, oxidative stabilizers, colorants, oxidizing agents, reducing agents and the like. Can be mentioned.

Notwithstanding the above exemplary description, the cement composition according to the present invention can be combined into various properties, all of which are included within the scope of the present invention.

As described above, the dental cement composition of the present invention is an antimicrobial inorganic filler in which at least a portion of the inorganic filler is surface-treated with a silane-based compound containing a quaternary ammonium group, and thus excellent in antibacterial properties while maintaining strength and adhesive strength. It is useful for use as a resin cement composition.

1 is a photograph of the state before the TSA antimicrobial silane was treated to calcium aluminofluorosilicate glass in Preparation Example 1;
Figure 2 is a photograph of the state after the TSA antimicrobial silane treatment to calcium aluminofluorosilicate glass in Preparation Example 1;
3 is a graph showing the compressive strength of Examples 1 to 3 and Comparative Examples 1 and 2;
4 is a graph showing the adhesive strength of Examples 1 to 3 and Comparative Examples 1 and 2.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

<Manufacture example 1>

0.6 parts by weight of 3-Trimethoxysilylpropyloctadecyl-dimethyl ammonium chloride (TSA) antimicrobial silane, in which 1 to 10 parts by weight of distilled water, 10 to 30 parts by weight of methanol or ethanol and a quaternary ammonium salt and trimethoxyl group are added, acetic acid is added to 0.01 to 5 parts by weight of the mixture was mixed with stirring for 1 to 3 hours, and then silanized by adding 10 to 50 parts by weight of the untreated surface of calcium aluminofluorosilicate glass. The mixture thus prepared is first dried by evaporating the solvent in an oven preheated to 40 to 80 ° C., followed by secondary drying in an oven preheated to 100 to 150 ° C. to have a particle size of 1 to 5 μm, and the antimicrobial agent A surface treated calcium aluminofluorosilicate glass was prepared. Photographs before and after the surface treatment of the TSA antimicrobial silane on the calcium aluminofluorosilicate glass are shown in FIGS. 1 and 2, respectively.

&Lt; Example 1 >

A dental cement composition was prepared by combining a first paste having a composition of Table 1 and a second paste having a composition of Table 2 including the surface-treated calcium aluminofluorosilicate glass prepared in Experimental Example 1 below.

TABLE 1

TABLE 2

<Example 2>

Except for changing the content of Bis-GMA content of the first paste in Example 1, 27% by weight, 8% by weight of TEGDMA, and calcium aluminofluorosilicate glass surface-treated with a TSA antimicrobial agent to 62% by weight. And to prepare a dental cement composition in the same manner as in Example 1.

<Example 3>

Except that in Example 1, the content of Bis-GMA in the first paste was 24% by weight, the content of TEGDMA was 6% by weight, and the content of calcium aluminofluorosilicate glass surface-treated with a TSA antimicrobial agent was changed to 67% by weight. And to prepare a dental cement composition in the same manner as in Example 1.

Comparative Example 1

A dental cement composition was prepared in the same manner as in Example 1, except that 57 wt% of the calcium aluminofluorosilicate glass not treated with the TSA antimicrobial agent was used.

Comparative Example 2

Example 1 except that 57% by weight of calcium aluminofluorosilicate glass surface-treated with 0.6% by weight of gamma-methacryloxypropyltrimethoxy silane (-MPS) instead of the TSA antimicrobial agent was used. In the same manner as in the preparation of the dental cement composition.

Experimental Example 1

The antimicrobial properties of the compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated, and adhesive strength and compressive strength were measured, respectively.

(Antibacterial Evaluation Method)

In order to evaluate the antimicrobial properties, the evaluation specimens were prepared circular specimens of 10.0 mm 1.2 mm. After antimicrobial evaluation, it was stored under UV-lamp after disinfection with alcohol, and E. coli KCTC 2596 was used for evaluation and the antimicrobial activity was measured by contact method. The cells were pre-cultured and suspended in Nutrient broth such that the absorbance (OD600) for the 600 nm wavelength was 0.800-1.000. Inoculate 30 μl into 3 mL of fresh culture and add each test specimen to it. Escherichia coli was cultured at 37 ° C. for 12-14 hours, and then OD600 was measured to confirm the growth of bacteria. Since the bacterial concentration and the OD value of the culture were proportional to each other, it can be seen that the bacterial concentration increased as the value increased. When the OD value is relatively low, the bacterial growth is late or the growth is inhibited. Low concentrations are measured.

(Property evaluation method)

(Adhesive strength)

Adhesion strength was measured by an elongation tester by cutting a tooth specimen into a uniform thickness parallel to the occlusal surface and attaching a tube containing self-adhesive dental resin cement to it.

(Compressive strength)

The device for measuring the compressive strength (hard tester, Korea, Model KST-01M) runs at a crosshead speed of 0.75 0.30 mm / min. After mixing, fill the cement in less than 60 seconds to slightly overflow the cut mold. On the bottom plate, apply some pressure to the molds and clamps used to prepare the sample for testing the compressive strength. Take out the cement shaped into chunks and place the upper metal plate on the mold and press them together. Place frame and plate in screwed clamps and tighten securely. After mixing, the entire composition is transferred to the cabinet within 120 seconds. After 1 hour of mixing, the plate is removed and the end of the specimen is polished perpendicular to its long axis. Wet silicon carbide paper (cubic water # 400) can be used to facilitate polishing, but abrasives should not be rough. When the surface finishes, remove the specimen from the mold and visually inspect it for enlarged air gaps or broken edges. Five samples are prepared, and as soon as each sample is prepared, it is immersed in water corresponding to Level 3 of the International Standard. Measure twice in the range of ± 0.01 mm accuracy so that they are perpendicular to each other and calculate the diameter of the sample as the average. After 24 hours of mixing, place the sample with the edges flattened between the compression plates of the property tester and apply a compressive load to the long axis of the sample. When the sample is broken, record the applied load and calculate the compressive strength according to the following formula.

Where is the maximum load (N) and d is the diameter of the specimen (mm).

The results measured above are shown in Tables 3 and 4, and the adhesion and compressive strength evaluation results are shown in FIGS. 2 and 3, respectively.

[Table 3]

As shown in Table 3, it can be seen that Example 1 treated with TSA, an antimicrobial silane according to the present invention, exhibits superior antimicrobial and adhesive strength and compressive strength compared to Comparative Examples 1 and 2.

In general, the inorganic filler is hydrophilic and incompatible with the hydrophobic monomer, but when the inorganic filler is surface-treated with TSA, the hydrophilic property is close to hydrophobic so that the affinity with the monomer can be increased.

[Table 4]

As shown in Table 4, it can be seen that the antimicrobial properties of Examples 1 to 3 vary depending on the content of the antimicrobial silane treatment agent. In Example 1, in which a relatively small amount of the antimicrobial silane treatment agent was added, the antimicrobial effect was relatively weak. In addition, in the case of Example 3, which is added in a relatively excessive amount, the antimicrobial effect was weaker than that in Example 2, and in this case, there is a problem in that the cost burden for using the antimicrobial agent is increased. However, in Examples 1 to 3, it can be seen that as the antimicrobial silane content increases, the adhesive strength and the compressive strength are excellent.

In summation of the above, Examples 1 to 3 and Comparative Examples 1 and 2 have similar compositions to each other, but there is a difference in the antimicrobial silane content, and thus a difference occurs in the antimicrobial properties, the adhesive strength and the compressive strength, in particular, Examples In case of 3, the adhesive strength and the compressive strength are the most excellent and the antibacterial property is very suitable for use in dental resin cement.

Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (12)

A dental cement composition comprising a monomer, an initiator, and an inorganic filler, wherein at least some of the inorganic filler has a particle diameter of 0.005 to 20 μm and is surface treated with a silane compound including a quaternary ammonium group as an antimicrobial component. It is a filler, the surface treatment agent is bonded to the surface of the inorganic filler in the structure of the following formula 1, the surface treatment agent including the antimicrobial component is characterized in that less than 5% by weight based on the total weight of the composition Cement composition

(One)
Where
R ₁ , R ₂ and R ₃ are each independently hydrogen or a methyl group;
Y is a C _1-4 alkylene group;
X is a halogen atom;
n is an integer from 4 to 30;
m is an integer of 10 to 1,000,000. According to claim 1, wherein the content of the monomer, based on the total weight of the composition is 10 to 59.9% by weight, the content of the initiator is 0.1 to 1% by weight, the inorganic filler is characterized in that the dental filler is 40 to 89.9% by weight Cement composition. The dental cement composition of claim 1, wherein the monomer is a photopolymerizable monomer component. 4. The photopolymerizable monomer component according to claim 3, wherein the photopolymerizable monomer component is 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (Bis-GMA), ethoxylate bisphenol aldehyde Acrylates (Bis-EMA), urethane dimethacrylate (UDMA), 4-methacryloxyethyltrimeric anhydrous (4-META), 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate Dental cement composition, characterized in that at least one selected from the group consisting of late (HEMA), and trifunctional methacrylate prepolymer (Tri-GMA). The dental cement composition of claim 1, wherein the composition further comprises a diluent for reducing the viscosity of the mixture in an amount of 1 to 20 wt% based on the total weight of the composition. 6. The method of claim 5, wherein the diluent is methyl methacrylate, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), 1,4- Dental cement composition, characterized in that at least one member selected from the group consisting of butanediol, dimethacrylate, 1,6-hexanediol diketacrylate, and 1-methyl-1,3-propanediol dimethacrylate. . The composition of claim 1, wherein the composition comprises a first paste containing an inorganic filler containing fluoride ions and capable of chemical reaction with acid, and an inorganic filler containing no fluoride ion and not capable of chemical reaction with acid. Dental cement composition comprising a combination of a second paste containing. According to claim 1, wherein the antimicrobial inorganic filler is a dental cement composition, characterized in that contained in 30 to 100% by weight based on the total amount of the inorganic filler. The inorganic filler of claim 1, wherein the inorganic filler is composed of quartz, barium glass, barium glass / silica mixture, quartz / barium mixture glass, silica, zirconia / silica mixture, aluminosilicate, lithium alumino silicate, and barium alumino silicate. Dental cement composition, characterized in that at least one selected from the group. The dental cement composition of claim 1, wherein the inorganic filler contains fluorine ions. The method of claim 1, wherein the surface treatment agent is selected from the group consisting of gamma-methacryloxy propyltrimethoxy silane (-MPS), vinyl triethoxy silane, dimethyl dichloro silane, hexamethylene disilizane, and dimethyl polysiloxane. Dental cement composition, characterized in that at least one. delete

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