KR100392609B1 - Dental restorative composite resins with anti-carious activity - Google Patents

Abstract

PURPOSE: Provided is a dental restorative composite resin with anti-carious activity which is composed of inorganic sealing compound, resin composition and antibacterial material of the formula(1). Therefore, it prevent cariousness of tooth, and has no decrease in physical properties. CONSTITUTION: A dental restorative composite resin with anti-carious activity is composed of inorganic sealing compound, resin composition and antibacterial material of the formula(1), wherein R1 is hydrogen atom or methyl group; R2 and R3 are independently C1-4 alkyl group; R4 is C1-4 alkyl group or benzyl group; A is oxygen atom or -NH- group; B is C1-4 alkylene group; and X¬- is halogen anion.

Description

Anticarious Dental Polymeric Restorative Composition

The present invention relates to an anti-carious dental polymer restorative composition, and more specifically, to the composite material consisting of a resin composition and an inorganic filler to prevent the caries of teeth by adding an antimicrobial material represented by the following formula (1), physical properties by elution The present invention relates to an anti-carious dental polymeric restorative composition that does not exhibit deterioration.

[Formula 1]

In the above formula,

R ₁ is a hydrogen atom or a methyl group;

R ₂ and R ₃ are each an alkyl group having 1 to 4 carbon atoms;

R ₄ is an alkyl group or benzyl group having 1 to 4 carbon atoms;

A is an oxygen atom or an -NH- group;

B is an alkylene group having 1 to 4 carbon atoms;

X ⁻ represents a halogen anion.

Dental restorative materials are polymeric materials used over a wide range of conditions, such as restoring the entire crown of a damaged part of a tooth or fixing agitation due to caries or fractures of the tooth. These tooth restorative materials are characterized by physical properties such as mechanical strength to withstand the high occlusal pressure generated when chewing food, thermal expansion similar to teeth, and low pressure shrinkage to prevent peeling of teeth during polymerization curing. In addition, in order to restore the natural feeling, it must meet the same color and luster as natural teeth, and should be able to give the same feeling as natural teeth upon contact with the tongue.

Amalgam is relatively widely used for vortex filling in dental care. These amalgam fillers do not have sufficient adhesion to the teeth, and there is a problem that secondary caries proceeds due to invasion of foreign substances such as saliva or bacteria into the filled vortex due to insufficient sealing between the teeth and amalgam, and amalgam maintains its shape. There is a problem that damages the teeth from caries because the cavity should be formed. And marginal leakage of the vortex restored with amalgam is inevitable. In addition, amalgam cannot be applied to such patients because a large number of patients exhibit hypersensitivity to mercury, a major component of amalgam. Therefore, there is an urgent need for a new tooth restorative material that can replace amalgam, and related researches are being actively conducted.

For example, US Patent Nos. 4,500, 657 and US Patent Nos. 4,814, 362 report dental restorative compositions consisting of polymer resins, and US Pat. Nos. 4,479,782 and 4,657,941 describe improvements in dental adhesives. However, these patents do not consider caries at all, so secondary caries due to marginal leakage is concerned. Therefore, cement liners are used to prevent marginal leakage during repair, thereby improving adhesion to hemorrhoids and dimensional scars. Is less.

Japanese Patent Application Laid-Open No. 93-85915 discloses a main component containing a polymer comprising a vinyl monomer having an acid-fluorine ion group, a metal fluoride, a polymerizable monomer having at least one olefinic double bond, and a polymerization initiator. Dental compositions are described. The composition is intended to slowly release fluorine ions to strengthen hemorrhoids and to improve anti-cariousness (acid resistance), but there is a problem in that it does not persist due to the expression of anti- caries of hemorrhoids in a short time.

In addition, dental glass ionic cement obtained by reaction with an acid component such as polyacrylic acid and fluoroaluminosilicate glass powder is one of the dental restorative materials widely used in the dental field. Glass ionic cement, which shows excellent biocompatibility, has the advantage of strengthening teeth by chemically bonding with teeth and self-containing fluorine ions, thereby releasing fluorine ions slowly. It is used, for example, for restoration fillers, crown adhesives, inlays and briquettes or orthodontic bands, vortex lining root formations, and sutures of chromophores. However, when cement is manufactured only by a combination of aluminosilicate and polyacrylic acid, the flowability and workability are poor, the cementing time is long and the surface of the cement is weak when it comes in contact with saliva. There are disadvantages.

As described above, as a general dental restorative polymer material, a composite restorative material prepared by mixing a cement-based restorative material with an acrylic resin and a silica-based filler is used. Most cement-based restoratives have good biocompatibility and have the advantage of slowly releasing fluorine ions to strengthen hemorrhoids.However, the product strength after the procedure is inherently weak and the strength is weaker after fluorine ion release, and it is not only broken but also the same color selection as teeth. There is a disadvantage that is not easy.

In addition, in the case of the composite restorative material, the strength of the composite restorative material is weak, but the adhesive strength with the tooth is weak and there is no biocompatibility. Accordingly, the present applicant contains the inorganic antibacterial agent and chitosan to give the anti-carious properties of the cement-based restorative material while retaining the advantages of the composite restorative material, thereby maintaining the secondary caries preventing dental caries at the same time without deteriorating other physical properties. There is also a patent application for the composition of the restoration material (Korean Patent Application No. 96-58969).

However, when the organic antimicrobial agent is mixed, since the organic antimicrobial agent is eluted early after the procedure, it is difficult to expect the sustainability of the antimicrobial activity, and the restoring property of the restorative material after the organic antimicrobial elution is expected. Examples of the conventional use of organic antimicrobials in dental materials are as follows.

U.S. Patent No. 5,385,728 discloses a method for producing a caustic having an antimicrobial activity by using benzalkonium chloride as an antimicrobial in a dental caustic. The caustic is a material for pretreatment of the teeth before the dental restorative treatment, and since it is absolutely necessary to maintain the antimicrobial power since it is washed with water after the tooth erosion, the caustic is prepared in the US patent.

In U.S. Patent No. 5,176,901, an antimicrobial toothpaste was prepared using a quaternary ammonium compound. However, the elution of the antimicrobial agent was not considered because the antimicrobial persistence was not required.

In US Pat. No. 5,408,022, a dental composition was prepared using organic antibacterial agents represented by the following formula (2), in which various antimicrobial groups and monomers were combined to improve the elution of organic antimicrobial agents and to maintain antimicrobial properties. However, the side chain of the organic antimicrobial agent used is too long, there is a fear that the physical properties, particularly strength of the final product.

[Formula 2]

In addition, conventional dental polymeric restoratives have been reported to have properties that are susceptible to antibacterial activity.

In the present invention, by containing the organic antimicrobial agent represented by the formula (1) in a composite material consisting of a resin composition and an inorganic filler to maintain anti-carious and at the same time there is no antimicrobial agent elution, antibacterial agent that does not decrease the physical properties of the final product It is an object of the present invention to provide a polymeric dental restorative composition.

The present invention is a dental polymeric restorative composition composed of a resin composition and an inorganic filler, characterized in that the restorative composition contains an organic antibacterial agent represented by the following formula (1).

Formula 1

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , A, B and X ⁻ are each as defined above.

Referring to the present invention in more detail as follows.

The present invention contains the organic antimicrobial agent represented by the general formula (1) in a conventional polymer restorative composition consisting of a resin composition and an inorganic filler, thereby preventing the infection of the teeth by bacteria while maintaining the characteristic properties of the resin composition as it is secondary It relates to a dental polymeric restorative composition for preventing caries.

Specific examples of the organic antibacterial agent represented by Formula 1 used in the present invention include 2-acryloyloxyethyl trimethylammonium chloride, 2-methacryloyloxyethyl trimethylammonium chloride, 3-methacryloylaminopropyl trimethyl Ammonium chloride, 3-methacryloylaminopropyl benzyldimethylammonium chloride and the like.

The dental polymer restorative composition according to the present invention contains 15 to 50% by weight of the resin composition, 50 to 80% by weight of the inorganic filler and 0.1 to 10.0% by weight of the organic antibacterial agent represented by the formula (1).

Hereinafter, the respective composition components used in the present invention will be described in more detail.

The resin composition is, for example, 2,2-bis-4- (3-methacryloxy-2-hydroxypropoxy) phenyl propane, triethylene glycol dimethacrylate, urethane dimethacrylate, ethoxylated bisphenol-A It contains 1 type, or 2 or more types chosen from dimethacrylate and hexamethylene diacrylate. If the resin component is contained in less than 15% by weight of the total restorative composition is not uniformly mixed, if more than 50% by weight there is a problem of lowering the physical properties of the final product.

Inorganic fillers include silica, barium-aluminum silicate, strontium-aluminum silicate, and the like. -Used by surface treatment with a silane coupling agent such as methacryloyloxypropyltrimethoxysilane or 8-methacryloyloxy octyltrimethoxysilane [Korea Patent Application No. 96-33251], and other restorative materials Any inorganic filler used in the case may be used. If the inorganic filler is contained in less than 50% by weight of the total restorative composition, there is a problem that the physical properties of the product is lowered, if it exceeds 80% by weight it is not uniformly mixed.

The organic antimicrobial agent is preferably contained in the total restorative composition in the range of 0.1 to 10.0% by weight. If it is less than 0.1% by weight, it cannot be expected to have a uniform antimicrobial activity. Not only are they unattainable and economically costly, there is also concern about deterioration of physical properties.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, which are not intended to limit the present invention.

Examples 1-4 and Comparative Examples 1-2

Next, the resin composition, the inorganic filler, and the antimicrobial agent were mixed by a method using a kneading mixer in the content ratio as shown in Table 1 to prepare a dental polymeric restorative material.

At this time, the inorganic filler is a silica-based inorganic filler (Aerosil OX-50, Degussa, average particle diameter 0.04 ㎛) The surface treated with methacryloxypropyl methoxysilane was used, which was prepared and used in the same manner as in Example 1 of Korean Patent Application No. 96-33251 filed by the present applicant.

TABLE 1

[Formula 3]

Experimental Example

The dental polymeric restoratives obtained in Examples 1 to 4 and 1 to 2 were measured for antimicrobial activity and physical properties by the following self-assessment experiments, and the results are shown in Table 2 below.

Antibacterial activity (resistance to bacteria)

Test Method: Applied ASTM (American Materials Association Test Method), Shake Flask Method

Test strain: Escherichia Coli (ATCC 25992, American Society of Seedling)

Control: shake culture only test bacteria

Sample: Antibacterial Test

Bacterial count unit: Bacterial count / mℓ

Anti-fog (resistance to mold)

Test Method: AATCC Standard (American Textile Dyeing Society Test Method)

Test strain: Five kinds of molds specified in ATCC

Judgment method: Determined as the degree to which mycelia are recognized at the inoculated portion of the sample after 3 weeks of culture

Good: cannot be observed under a microscope

Medium: can be observed under a microscope

Poor: Can be observed with the naked eye

Indirect tensile strength

Fill a pre-fabricated polymeric restorative material into a hole in a Teflon plate with a diameter of 8 mm and a height of 4 mm, cover the glass plate on both sides, and use a commercially available light irradiator XL-3000 (3M company) for 40 seconds. After irradiating for a while, the specimens were prepared and the specimens were installed in a radial direction using a compression tester (Instron 4469, manufactured by Instron) compressed to 1 mm per minute, and then the strength was measured. Indirect tensile strength was calculated by the following equation 1 by measuring the maximum force (P) required when the specimen rupture.

[Equation 1]

Indirect tensile strength = 2P / (π · d · ℓ)

In the above equation, P is the force applied to the specimen rupture, d is the diameter of the specimen, l is the thickness of the specimen.

TABLE 2

The restorative composition of the present invention contains an organic antimicrobial agent having excellent antimicrobial activity but no elution to prevent tooth infection caused by bacteria in the oral cavity, thereby preventing secondary caries, and also maintaining physical properties while maintaining antibacterial activity. It does not deteriorate.

Claims (2)

A dental polymer restorative composition comprising a resin composition and an inorganic filler, wherein the restorative composition comprises an organic antibacterial agent represented by the following formula (1). Formula 1 In the above formula, R ₁ is a hydrogen atom or a methyl group; R ₂ and R ₃ are each an alkyl group having 1 to 4 carbon atoms; R ₄ is an alkyl group or benzyl group having 1 to 4 carbon atoms; A is an oxygen atom or an -NH- group; B is an alkylene group having 1 to 4 carbon atoms; X ⁻ represents a halogen anion. The method of claim 1, wherein the organic antimicrobial agent represented by Formula 1 is 2-acryloyloxyethyl trimethylammonium chloride, 2-methacryloyloxyethyl trimethylammonium chloride, 3-methacryloylaminopropyl trimethylammonium chloride, And 3-methacryloylaminopropyl benzyldimethylammonium chloride.