JP2690371B2 - Dental composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dental polymerizable composition containing an antibacterial agent. Especially, antibacterial agents used in the state of being exposed in the oral cavity such as dental composite resin, dental adhesive, denture base resin, room temperature polymerization type immediate polymerization resin, pit fissure filling material, and dental cement. The present invention relates to a dental polymerizable composition containing the same.

(Prior Art) Dental caries, which is a typical tooth disease, develops when enamel is dissolved by an acid produced by a microorganism. Among them, the strains of Myutans (Streptococcus muta
ns) is listed as an important causative agent of caries development.
It is also said that periodontitis, which is a disease of periodontal tissues, is caused by oral bacteria. That is, it is important to prevent the formation of plaque formed on the tooth surface by oral bacteria or to quickly remove it for the prevention of any disease. Tooth brushing is recommended for the removal of plaque.

On the other hand, plaque is easily formed on the surface of the organic material when the filling and repair of the carious portion and the prosthesis treatment (eg, denture) of the organic material are performed with the organic material. Are important for preventing secondary caries and periodontitis.

As a method for preventing caries by improving the acid resistance of the enamel, application of an acidic fluorinated phosphoric acid solution or application of a difluorinated diamine silver is performed. However, a method for preventing caries and gingivitis caused by dental plaque formed on the surface of the dental material exposed in the oral cavity is not yet clear. Regarding the dental material containing the antibacterial agent as in the present invention, a composite material containing chlorhexidine [Kanezo Takemura et al., Journal of Japan Dental Conservation Society, Vol. 26, No. 2, pp. 540-547 (1983)
)] And metronidazole-containing calcium phosphate cement [Masaaki Iwahisa et al., Journal of The Japan Society for Dental Conservation, Vol. 30, No. 5, pp. 1444-1448 (1987)]. However, since all the antibacterial agents have high solubility in water, the antibacterial agents are gradually released from the dental material in a short period of time, which is not satisfactory in terms of sustaining the antibacterial effect.

(Problems to be solved by the invention) The elution of the antibacterial agent from the dental composition is concerned not only on the surface of the dental composition but also on the surrounding oral flora. Therefore, the first problem to be solved by the present invention is to provide a composition in which an antibacterial agent is difficult to elute from a dental composition in a short period of time. A second problem is to provide a composition that suppresses the adhesion of plaque formed on the surface of a dental composition and does not cause the growth inhibition of oral bacteria around it (other than the surface of the composition). That is.

(Means for Solving the Problems) The present inventors have little elution of an antibacterial agent and continuously exhibit antibacterial properties, and suppress adhesion of dental plaque due to Streptococcus mutans to the surface of a dental composition. As a result of earnest studies on the dental composition to be carried out, the present invention has been accomplished.

That is, 0.1 to 4% by weight of 5-chloro-2- (2,4-dichlorophenoxy) phenol as a (meth) acrylate-based polymerizable monomer, a polymerization initiator and an antibacterial agent, 2,
A polymerizable dental composition comprising 2'-methylenebis (3,6,4-trichlorophenol) or a mixture thereof.

The dental composition according to the present invention (hereinafter referred to as a dental polymerizable composition unless otherwise specified) contains the above-mentioned phenol compound which is hardly soluble in water as an antibacterial agent, It has the ability to suppress the adhesion of dirt, and the elution of the antibacterial agent is small, and the effect continues.

The poorly soluble in water in the present invention means solute 1 g or
It means that more than 10,000 ml of water is needed to dissolve 1 ml.

The phenolic compound used in the present invention is 5-chloro-
2- (2,4-dichlorophenoxy) phenol, 2,2'-
Methylenebis (3,4,6-trichlorophenol) or a mixture thereof. The concentration in the composition is 0.
1 to 4% by weight is preferred. When the concentration of the antibacterial agent is 0.1% by weight or less, there is no clear antibacterial property against Streptococcus mutans. On the other hand, when the antibacterial agent is contained in an amount of 4% by weight or more, the antibacterial property of the composition is recognized, but the elution amount of the antibacterial agent from the dental composition increases, and there is a concern that it may affect the oral flora. .

Examples of the dental composition of the present invention include dental composites resin, dental adhesive, pit and fissure filling material, denture base resin, temporary restoration resin, and dental cement.

The above-mentioned dental composition is constituted by appropriately combining a polymerizable monomer, an organic polymer, a polymerization initiator, a filler, an inorganic reactive compound and the like according to the purpose. The main constituents will be described below.

As the polymerizable monomer used in the present invention, a monohydric or dihydric alcohol such as (meth) acrylic acid, urethane (meth) acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid or itaconic acid is used. Further, (meth) acrylamides such as N-isobutylacrylamide, vinyl esters of carboxylic acids such as vinyl acetate, vinyl ethers such as butyl vinyl ether, and mono-N such as N-vinylpyrrolidone.
-Vinyl compounds, styrene derivatives and the like can be mentioned, but monofunctional and polyfunctional (meth) acrylic acid esters and urethane (meth) acrylic acid esters as described below are particularly preferable. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid.

(I) Monofunctional methyl (meth) acrylate, n- (meth) acrylate
Alternatively, i-propyl, (meth) acrylic acid n-, i-
Alternatively, t-butyl, 2-hydroxyethyl (meth) acrylate and the like.

(Ii) bifunctional [Here, n represents an integer of 3 to 20, and R represents hydrogen or a methyl group. ] The compound shown by these. For example, di (meth) acrylates such as propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol, eicosanediol, [Here, n represents an integer of 1 to 14 and R represents hydrogen or a methyl group. ] The compound shown by these. For example, di (meth) acrylates such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dodecaethylene glycol, and tetradecaethylene glycol. In addition to these, di (meth) acrylates such as propylene glycol, dipropylene glycol, and tetradecapropylene glycol, glycerin di (meth) acrylate, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) Phenyl] propane (Bi
s-GMA), bisphenol A dimethacrylate, neopentyl glycol di (meth) acrylate, 2,2'-di (4-methacryloxypolyethoxyphenyl) propane (ethoxy group-2 to 10 in one molecule) ), 1,2-bis (3-
Methacryloxy-2-hydroxypropoxy) butane and the like.

(Iii) Trifunctional or higher trimethylolpropane tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate and the like.

(Iv) Urethane (meth) acrylate-based reaction product of 2 mol of (meth) acrylate monomer having hydroxyl group and 1 mol of diisocyanate, both ends
Examples of the reaction product include a reaction product of a urethane prepolymer of NCO and a (meth) acrylate monomer having a hydroxyl group. The structure of the reaction product is represented by the following formula.

[Here, R ¹ is hydrogen or a methyl group, R ² is an alkylene group, and R ³ is an organic residue. As a specific example, a reaction product of 2,2,4-trimethylhexamethylene diisocyanate and oxypropyl methacrylate described in JP-B-51-36960,
The reaction products of urethane prepolymers having isocyanates at both ends and 2-oxyethyl methacrylate described in 55-33687 can be mentioned. In addition, JP-A-56-1524
Tetrafunctional monomers such as those disclosed in 08 are also used.

As the polymerizable monomer, a compound having an acidic group such as a phosphoric acid group or a carboxyl group known to be used in a dental composition can also be used. Examples of these are given below.

(I) those containing a phosphate group [R ¹ and R ² are hydrogen or a methyl group, R ³ and R ⁴ are organic residues] [R ¹ is hydrogen or methyl group, R ² is hydrogen or phenyl group] (ii) Reaction product of (meth) acrylic acid ester having a hydroxyl group as a side chain and phosphoric acid chloride.

 For example, there is one as shown in the following formula.

(Iii) Having a carboxyl group And its anhydride [R ¹ is hydrogen or a methyl group, R ² is an organic residue] For example, there is 4-methacryloyloxyethyl trimellitic anhydride.

[R ¹ is hydrogen or a methyl group, R ² is an organic residue] For example, In the present invention, the filler (filler) contains quartz powder, alumina powder, hydroxyapatite, calcium carbonate, fluoroaluminosilicate glass, barium sulfate, titanium oxide, zirconia powder, glass powder, ultrafine silica particles and organic and inorganic components. An organic composite filler or the like can be used. Further, polymer powder such as polymethylmethacrylate, polystyrene, polyvinyl chloride and the like are added as needed. Examples of such glass include silica glass, soda lime silicate glass, humic silicate glass, barium boroaluminosilicate glass, alumina silicate glass, strontium boroaluminosilicate glass, synthetic silica, titanium silicate glass and the like.

The inorganic filler used in the present invention is preferably surface-treated before use. As the surface treatment agent, organosilicon compounds such as γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane and vinyltri (methoxyethoxy) silane are used, and silanization is performed. Is carried out by a usual method.

Examples of the polymerization initiator include benzoyl peroxide-aromatic tertiary amines, peroxides such as cumene hydroperoxide, tributylborane, aromatic sulfinic acid (or a salt thereof) -aromatic secondary or tertiary. Amine
Examples thereof include acyl peroxide type. Further, photopolymerization initiators such as camphorquinone, camphorquinone-tertiary amine, camphorquinone-peroxide, camphorquinone-aldehyde, camphorquinone-mercaptan, acylphosphine oxide, etc. You can When photopolymerization is carried out by ultraviolet irradiation, benzoyl methyl ether, benzyl dimethyl ketal, benzophenone, 2-methyl thioxanthone, diacetyl, benzyl, azobisisobutyrotolyl, tetramethyl thiuram disulfide and the like are preferable.

If desired, a polymerization inhibitor, a colorant, a fluorescent agent, an ultraviolet absorber, etc. can be added to the composition of the present invention.

 The outline of the composition will be described below with reference to typical examples of applications.

1) Dental composites resin The dental composites resin is composed of a polymerizable monomer, a powdery filler (filler) and a polymerization initiator as main components, and is a powder or liquid package in a two-pack or one-pack paste form. Provided as.

2) Dental adhesive and pit and fissure filling material Generally used as a dental adhesive and pit and fissure filling material, it is composed of a polymerizable monomer and a polymerization initiator, and optionally a filler is added. Sometimes. Also, the polymer or prepolymer may be provided by being dissolved in a solvent.

In the present composition, when the above-mentioned polymerizable monomer having an acidic group is used as a part of the polymerizable monomer, the adhesion between the tooth and the metal or other dental restorative material can be further improved. .

3) Denture Base Resin and Temporary Restoration Resin As components of the denture base resin and temporary restoration resin (room temperature polymerization type immediate polymerization resin), (meth) acrylic polymer powder and (meth) acrylic polymerization are used. A dental composition comprising a polymerizable monomer is common. As the denture base resin, polyether sulfone, polysulfone, polycarbonate, polyester carbonate, polystyrene, polymethylmethacrylate, polymethylpentene-
1 Polymers such as transparent nylon, polyarylate, polyethylene terephthalate and transparent ABS are also used.

In the present invention, in addition to the above-mentioned composition containing an organic compound as a main component, a composition containing an inorganic reactive compound described below as a main component can also be used.

4) Dental cement (1) Glass ionomer cement A composition comprising a powder agent and a liquid agent as components, and comprising fluoroaluminosilicate glass powder, acrylic acid, an itaconic acid copolymer, tartaric acid and the like.

(2) Carboxylate cement A dental composition comprising powder containing zinc oxide, magnesium oxide and polycarboxylic acid and polycarboxylic acid.

(3) Zinc phosphate cement A dental composition comprising powder of zinc oxide, magnesium oxide, silica, alumina, bismuth oxide, rubidium oxide and the like, and orthophosphoric acid, aluminum phosphate and the like.

(4) Calcium phosphate cement A dental composition comprising a powder containing tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] as a main component and a powder of an unsaturated carboxylic acid polymer or two or more copolymers or an aqueous solution. Stuff.

(Examples) Examples 1 to 7 and Comparative Examples 1 to 7 5-chloro-2- as an antibacterial agent was added to commercially available dental materials.
(2,4-dichlorophenoxy) phenol or 2,2 '
-Methylenebis (3,4,6-trichlorophenol) was added in a predetermined amount and uniformly mixed to prepare the compositions of Examples 1 to 7 (Table 1). Moreover, the thing which does not add an antibacterial agent was set to Comparative Examples 1-7.

In order to confirm the antibacterial property, the growth of bacteria on the test piece and the growth inhibition patch of teeth were observed by the following procedure.

1) Method of preparing test piece A composition sterilized with ethylene oxide gas was filled in a Teflon mold and cured to prepare a disc-shaped test piece having a diameter of 10 mm and a thickness of 2 mm.

2) Judgment of antibacterial property Bacteria (Streptococ) cultured overnight on the adjusted BH1 (Brain Heart Injury) agar plate.
cus mutans MT8148 strain) culture solution was applied. After placing the test piece on it and culturing at 37 ° C. for 48 hours, the adhesion state of the bacteria to the test piece and the growth state around the test piece were observed. The judgment was made according to the following criteria, and the judgment results are shown in Table 1.

B) Suppression of bacterial growth on the surface of the composition-: No bacterial growth inhibition is observed on the agar plate directly below the test piece. Bacteria are growing uniformly on the plate.

±: A slight growth inhibitory effect on the agar plate is observed just below the test piece.

+: Almost no growth of bacteria was observed on the agar plate directly below the test piece.

++: No growth of bacteria is observed on the agar plate directly below the test piece.

B) Development of development inhibition spots-: No growth inhibition spots of bacteria are observed around the test piece.

±: A ring-shaped stunted patch with a width of less than about 1 mm is observed around the test piece.

+: A ring-shaped stunting patch having a width of about 1 mm or more and 2 mm or less is observed around the test piece.

++: Growth inhibition spots with a width of more than about 2 mm are observed around the test piece.

3) Antibacterial effect The dental composition according to the present invention suppresses the adhesion of Myotans bacteria, which causes plaque formation, to the surface of the dental composition,
It does not inhibit the growth of bacteria around the dental composition. This means that in the antibacterial test of Examples 1 to 7 shown in Table 1, no growth inhibition spots (antibacterial spots) appear around the dental composition placed on the agar plate, and the dental composition. It is proved by the lack of tooth growth on the contact surface between the object surface and the agar plate. On the other hand, as shown in Table 1, Comparative Examples 1 to 7 of dental compositions containing no antibacterial agent.
Had insufficient growth inhibitory effect.

Examples 8-12 and Comparative Examples 8-10 1) Composition of test piece and test method Bisphenol A diglycidyl methacrylate (Bis)
-GMA) 70 parts by weight and 30 parts by weight of triethylene glycol dimethacrylate to a mixture of dl-camphorquinone.
0.2% by weight, 0.3% by weight of dimethylaminoethyl methacrylate and 0.05% by weight of dibutylhydroxytoluene were added to prepare a polymerizable monomer. Subsequently, 17% by weight of the polymerizable monomer was mixed with 83% by weight of quartz powder surface-treated with γ-methacryloxypropyltrimethoxysilane to prepare a paste. 5-chloro-2- (2,4
-Dichlorophenoxy) phenol or 2,2'-methiene bis (3,4,6-trichlorophenol) was added in a predetermined amount and mixed uniformly to prepare the compositions of Examples 8 to 12 (Table 2). did.

The sample to which no antibacterial agent was added was set as Comparative Example 8, and the sample to which chlorhexidine was added as an antibacterial agent by the same method was set as Comparative Example 9. (Table 2) In the same manner as in Examples 1 to 7, the state of adhesion to the test piece and the state of development of suppression of tooth growth around the test piece were examined. Further, the elution of the antibacterial agent from the test piece was measured by the following method.

A) Method of measuring elution amount The test piece was immersed in 12 ml of distilled water for 5 days, and the distilled water was measured by high performance liquid chromatography to measure the elution amount of the antibacterial agent in water.

2) Antibacterial effect and elution property In Examples 8 to 12, as clearly shown by the fact that the adhesion of Myutans bacteria on the surface of the test piece was suppressed and that the growth inhibition spots did not appear around the test piece. It was found that the composition surface has antibacterial properties and the elution of the antibacterial agent into water is small. It was also found that when the antibacterial agent was added, the amount eluted into water increased when the amount added exceeded 4% by weight.

(Effect of the invention) The composition of the present invention is an excellent dental composition in which the elution of the antibacterial agent into water is small, and the adhesion and growth of Myotanthus bacteria that cause caries on the surface of the composition are suppressed. is there.

Claims (1)

(57) [Claims] 1. A (meth) acrylate-based polymerizable monomer, a polymerization initiator, and 0.1 to 4% by weight of 5-chloro-2- (2,4-dichlorophenoxy) phenol as an antibacterial agent, 2.
A polymerizable dental composition comprising 2'-methylenebis (3,6,4-trichlorophenol) or a mixture thereof.