JPH08157318A - Antibacterial dental adhesive composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition capable of exterminating bacteria left in fine structures such as dentin tubule on the adhesion interface of tooth and also of exterminating bacteria intruded into the adhesion interface after bonded. CONSTITUTION: This antibacterial dental adhesive composition comprises (A) 0.01-25wt.% of an antibacterial polymerizable monomer, pref. a compound of formula I [R1 is H or CH3 ; R2 is a 2-25C alkylene; X is O, S<1,4-phenylene, CH2 O, etc.; m and n are each 0 or 1; p is 1-3; Y is formula II, III, IV, etc.; R<3> is formula (X)q -R6 -W (q is 0 or 1; R6 is a 3-25C alkylene; W is H, CH3 or phenyl); Z is Cl, Br or I], (B) 5-40wt.% of an acidic group-bearing polymerizable monomer, e.g. 2-(meth)acryloyloxyethyl dihydrogenphosphate, (C) 10-50wt.% of an alcoholic hydroxyl-contg. polymerizable monomer, e.g. 2-hydroxyethyl (meth)acrylate, 20-75wt.% of water, and a polymerization catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dental adhesive adhesive composition having antibacterial properties.

[0002]

2. Description of the Related Art In dental treatment, an acrylic dental adhesive is often used when a tooth defect is restored with a restorative material such as a composite resin, a dental alloy or porcelain. However, when the restorative material is directly adhered to the tooth surface, sufficient adhesive strength cannot be obtained, and the restorative material may fall off or secondary caries or pulpitis due to invasion of bacteria from the adhesive interface between the tooth and the restorative material. It may be caused.

In order to solve such a problem, it has been proposed to pretreat the tooth surface with various tooth surface treating agents in advance. It has been reported that such pretreatment improves the adhesive strength between the tooth and the restorative material. For example, Journal of Dental Research (Journal of Dental Research)
Research) 34, 849-853 (1955).
The so-called acid etching treatment improves the adhesive strength between the restorative material and the tooth enamel. Journal of Dental Research
esearch) 63, 1087-1089 (1984)
1), a primer composition consisting of glutaraldehyde, 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) and water enhances the adhesive strength between the restorative material and dentin. 22328
No. 9 discloses that a primer obtained by adding an acid such as maleic acid, tribromoacetic acid or hydrochloric acid to an HEMA aqueous solution remarkably improves the adhesive force between the restorative material and the enamel or dentin, and the dental material or instrument, Vol. 9, pp. 65-73 (1990), a primer prepared by adding a monomer containing an amino acid residue such as N-methacryloylalanine or N-acryloylalanine to an aqueous HEMA solution is used as a repair material and enamel and dentin. It is described that the adhesive strength is remarkably improved. In addition, Japanese Patent Laid-Open No. 3-24071
No. 2 discloses that (i) water 0.5 to 90% by weight, (ii) alcoholic hydroxyl group-containing polymerizable compound 5 to 90% by weight, and (iii) acidic group-containing polymerizable compound 0.1 to 90%.
%, And (iv) an amino compound having an acidic group 0.
An adhesive composition containing 0.1 to 30% by weight is disclosed, and further, JP-A-4-8368 discloses an adhesive force between a restorative material and dentin by adding an amino compound to the composition. It is described that is dramatically improved.

According to the above pretreatment, although the adhesive strength between the tooth and the restorative material is improved, secondary caries and pulpitis, which are considered to be caused by the invasion of bacteria from the adhesive interface between the two, are said to occur. There's a problem.

On the other hand, attempts have been made to impart antibacterial properties to dental adhesives. For example, Japanese Patent Application Laid-Open No. 1-17107 describes a dental cement containing an antibacterial agent.
Further, JP-A-6-9725 describes a dental composition containing an antibacterial polymerizable monomer and an acidic group-containing polymerizable monomer. However, in the former dental cement containing the above-mentioned antibacterial agent, since the antibacterial agent is eluted into the oral cavity, problems such as destruction of the oral flora and emergence of resistant bacteria are expected, and clinical application. In order to do so, sufficient confirmation of safety is required. Further, in the dental composition containing the latter antibacterial polymerizable monomer,
Its antibacterial property is a non-eluting type antibacterial property in which the antibacterial substance does not elute on the surface of the cured product after polymerization and curing, and it is possible to reduce the bacteria attached to the surface of the cured product, but the adhesion of dentinal tubules, etc. It was not possible to kill the bacteria that remained in the interface microstructure.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and improves the adhesive strength between a tooth and a restorative material in order to prevent bacteria from invading the adhesive interface. And, it is possible to kill bacteria remaining in the fine structure of the adhesive interface such as dentinal tubules, which was impossible with the above-mentioned conventional dental primer,
Furthermore, the present invention provides an antibacterial dental adhesive that can kill bacteria that enter the adhesive interface after bonding.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have proposed a dental composition containing the above-mentioned antibacterial polymerizable monomer and a polymerizable monomer having an acidic group. In addition, by further blending a polymerizable monomer having an alcoholic hydroxyl group and water, it becomes possible to rapidly permeate the antibacterial component into the fine structure of the adhesive interface such as a dentinal tubule and kill the remaining bacteria. It was found that it is possible to kill the invading bacteria even after polymerization and hardening, and the present invention has been completed. That is, 0.01 to 25% by weight of the polymerizable monomer (A) having antibacterial properties, 5 to 40% by weight of the polymerizable monomer (B) having an acidic group, and a polymerizable monomer having an alcoholic hydroxyl group. 10 to 50% by weight of the monomer (C) and 20 to 7 of water
The object of the present invention is achieved by providing an antibacterial dental adhesive composition characterized by containing 5% by weight and a polymerization catalyst.

In the antibacterial dental adhesive composition of the present invention, the antibacterial polymerizable monomer (A), the polymerizable monomer having an acidic group (B) and the polymerizable monomer having an alcoholic hydroxyl group are used. It is necessary to use the monomer (C) and water together. In the dental composition containing only the antibacterial polymerizable monomer (A), the strength of the antibacterial property to be expressed was not sufficient as shown in the data below, and it adhered to the surface of the cured product. Although it only weakens the bacteria, by using the polymerizable monomer having an acidic group (B), the polymerizable monomer having an alcoholic hydroxyl group and water as in the present invention, an adhesive interface such as a dentinal tubule can be formed. The permeation of the antibacterial component into the microstructure is increased, and the bacteria remaining in the microstructure can be killed during the primer treatment. Further, since the non-eluting type antibacterial property is exhibited on the cured surface after polymerization, it is possible to kill bacteria that enter the adhesive interface between the tooth and the restorative material. The composition having such a function can be provided by the present invention for the first time.

In the present invention, the term "adhesive" refers to one used as a primer when directly applied to a tooth and another adhesive applied thereon, and a tooth and a dental restorative material without another adhesive. Means to be used as an adhesive to bond

In order to obtain sufficient antibacterial property during the primer treatment, the antibacterial polymerizable monomer (A), the polymerizable monomer having an alcoholic hydroxyl group (C) and water should be used in combination. It is indispensable, and sufficient antibacterial properties cannot be obtained if any of them is lacking. In order to make the non-eluting antibacterial property after polymerization and curing sufficient, it is essential to use the antibacterial polymerizable monomer (A) and the acidic group-containing polymerizable monomer (B) together. However, when only one of them is added, the antibacterial property becomes weak, and the bacteria that enter the adhesive interface cannot be killed. Further, in order to make the original function of the dental adhesive primer sufficient to improve the adhesive strength of the tooth and the restoration, a polymerizable monomer (B) having an acidic group and a polymerizing compound having an alcoholic hydroxyl group are used. It is necessary to use the polymerizable monomer (C) and water together. From the above, the antibacterial property during primer treatment, the non-eluting antibacterial property after polymerization and curing, and the high adhesive strength between the tooth and the restoration 3
In order to satisfy one requirement, an antibacterial polymerizable monomer (A), an acidic group-containing polymerizable monomer (B), an alcoholic hydroxyl group-containing polymerizable monomer (C) and water are used. It is necessary to use together.

The content of the antibacterial polymerizable monomer (A) used in the present invention is 0.01 to the whole composition.
It is necessary to be within the range of 25% by weight, and
It is preferably in the range of 20% by weight. The content of the antibacterial polymerizable monomer (A) is 0.01 with respect to the entire composition.
When the content is less than wt%, the antibacterial strength to be developed is not sufficient, and the bacteria remaining at the adhesive interface between the tooth and the restorative material and the bacteria entering the adhesive interface cannot be killed. Further, when the content of the antibacterial polymerizable monomer (A) exceeds 25% by weight based on the whole composition, the improvement of the adhesive strength between the tooth and the restorative material cannot be seen.

The polymerizable monomer (B) having an acidic group used in the present invention is a phosphoric acid group, a carboxyl group, a sulfonic acid group, an acidic group such as an acid anhydride residue, and an acryloyl group or a methacryloyl group. , A polymerizable monomer having a polymerizable unsaturated group such as vinyl group, for example, 2-
(Meth) acryloyloxyethyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 2
Compounds containing a phosphoric acid monoester group such as-(meth) acryloyloxyethyl phenyl dihydrogen phosphate, bis (2- (meth) acryloyloxyethyl) hydrogen phosphate, 2- (meth) acryloyloxyethyl hydrogenphenyl Phosphate, 2- (meth) acryloyloxyethyl hydrogenanisyl phosphate and other compounds containing a phosphodiester group, 6- (meth) acryloyloxyhexyl phosphinate, N- (10-phosphonodecyl)
Phosphoric acid derivatives such as (meth) acrylamide, 4-vinylbenzenephosphonic acid, 4-vinylbenzylphosphonic acid,
(Meth) acrylic acid, succinic acid mono (2- (meth) acryloyloxyethyl), isophthalic acid (2- (meth))
Acryloyloxyethyl), 4- (meth) acryloyloxyethyl trimellitic acid, 11,11-dicarboxyundecyl (meth) acrylate, N- (meth) acryloylalanine, N- (meth) acryloyl-5-
Compounds containing a carboxyl group such as aminosalicylic acid and 4-vinylbenzoic acid, and acid anhydrides thereof, 2-
Examples thereof include compounds having a sulfonic acid group such as (meth) acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid.

The content of the polymerizable monomer (B) having an acidic group used in the present invention is 5 to 5 with respect to the entire composition.
It is necessary to be within the range of 40% by weight, and 10 to 3
It is preferably within the range of 0% by weight. The content of the polymerizable monomer (B) having an acidic group is 5 with respect to the entire composition.
When the content is less than wt%, the antibacterial strength to be developed is not sufficient, and the bacteria remaining at the adhesive interface between the tooth and the restorative material and the bacteria entering the adhesive interface cannot be killed. When the content of the polymerizable monomer (B) having an acidic group exceeds 40% by weight based on the whole composition,
The bond strength between the tooth and the restorative material is not improved.
Two or more types of polymerizable monomers having an acidic group may be used in combination.

The polymerizable monomer (C) having an alcoholic hydroxyl group used in the present invention is a polymerizable monomer having an alcoholic hydroxyl group and a polymerizable unsaturated group such as an acryloyl group, a methacryloyl group or a vinyl group. A monomer, for example, 2-hydroxyethyl (meth) acrylate, propylene glycol mono (meth) acrylate,
Glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, N-methylol (meth) acrylamide, N -Hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide and the like can be mentioned.

As the water used in the present invention, it is necessary to use water that does not substantially contain impurities that adversely affect the adhesive strength between the tooth and the restorative material and the development of antibacterial properties. Exchanged water is preferred. Water content is 20-75% by weight with respect to the total composition
It is necessary to be within the range of, and preferably within the range of 25 to 60% by weight. When the water content is less than 20% by weight based on the entire composition, or when the water content exceeds 75% by weight based on the entire composition, the adhesive strength between the tooth and the restorative material is improved. I will not be able to. If desired, a solvent miscible with water, such as ethanol or acetone, may be added and used.

The content of the polymerizable monomer (C) having an alcoholic hydroxyl group used in the present invention must be within the range of 10 to 50% by weight based on the whole composition, and the content of 15 to 15% by weight is preferable. It is preferably in the range of 40% by weight. When the content of the polymerizable monomer (C) having an alcoholic hydroxyl group is less than 10% by weight based on the entire composition, or the content of the polymerizable monomer (C) having an alcoholic hydroxyl group is the composition When it exceeds 50% by weight based on the whole, improvement in the adhesive strength between the tooth and the restorative material is not observed. Two or more kinds of polymerizable monomers having an alcoholic hydroxyl group may be used in combination.

The polymerization catalyst used in the present invention includes organic peroxides such as benzoyl peroxide and cumene hydroperoxide, tributyl borane, benzoyl peroxide / aromatic tertiary amines, aromatic sulfinic acid (or its Examples include room temperature polymerization initiators such as (salt) / aromatic secondary or tertiary amine / acyl peroxide type. Also, camphorquinone, camphorquinone / p-dimethylaminobenzoic acid ester system, camphorquinone / p-dimethylaminobenzophenone,
Examples include photopolymerization initiators such as camphorquinone / aromatic sulfinate, camphorquinone / peroxide, camphorquinone / aldehyde, camphorquinone / mercaptan, and acylphosphine oxide. When performing photopolymerization by ultraviolet irradiation,
Benzoin methyl ether, benzyl dimethyl ketal, benzophenone, 2-ethylthioxanthone, diacetyl, benzyl, azobisisobutyronitrile, tetramethylthiuram disulfide and the like are preferable. Furthermore, both the room temperature polymerization initiator and the photopolymerization initiator can be used at the same time. The polymerization catalyst is usually used within the range of 2 to 15% by weight based on the whole composition.

The antibacterial dental adhesive composition of the present invention comprises:
If desired, an acrylic polymerizable monomer having neither an alcoholic hydroxyl group nor an acidic group can be added. Further, a polymerization inhibitor, a colorant, a fluorescent agent, an ultraviolet absorber, etc. may be added.

Examples of the acrylic polymerizable monomer having no alcoholic hydroxyl group and no acidic group are methyl (meth) acrylate, butyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ-methacryloyloxypropyltrimethoxysilane, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,10-decanediol di (meth) acrylate,
2,2'-bis [((meth) acryloyloxypolyethoxy) phenyl] propane, 2,2'-bis [4-
(3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl] propane, trimethylolpropane tri (meth) acrylate and the like can be mentioned.

The antibacterial dental adhesive composition of the present invention is used for tooth surface treatment according to a conventional method in dental treatment, and thereafter polymerized and hardened at an adhesive interface between a tooth and a restorative material without being washed and removed. It is held at the adhesive interface as it is. In this case, the antibacterial dental adhesive composition may be cured by itself or may be cured in a state of being partially mixed with the dental adhesive.

The above-mentioned dental adhesive is usually an acrylic adhesive, that is, an adhesive composed of an acrylic polymerizable monomer and a polymerization initiator, to which a filler is added if necessary. For example, methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ-methacryloyloxypropyltrimethoxysilane, triethylene glycol di (meth) ) Acrylate, neopentyl glycol di (meth) acrylate, 2,2'-bis [((meth) acryloyloxypolyethoxy) phenyl] propane, 2,2'-bis [4- (3- (meth) acryloyloxy- 2-Hydroxypropoxy) phenyl] propane, 10- (meth) acryloyloxydecyldihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydro Acrylic polymerizable monomers such as gen phosphate, 4- (meth) acryloyloxyethyl trimellitic acid, 4- (meth) acryloyloxyethyl trimellitic anhydride, benzoyl peroxide, benzoyl peroxide / aromatic third Primary amine type, aromatic sulfinic acid (or salt thereof) / aromatic secondary or tertiary amine /
Polymerization initiators such as acyl peroxide, camphor quinone, camphor quinone / tertiary amine, camphor quinone / peroxide, acyl phosphine oxide,
And α-quartz, silica, alumina, hydroxyapatite, fluoroaluminosilicate glass, barium sulfate, titanium oxide, zirconia, silica glass, soda lime silicate glass, barium glass, organic composite filler containing an organic component and an inorganic component, etc. An acrylic adhesive composed of a filler is preferably used.

[0022]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In this Example, the adhesive strength and the antibacterial strength were evaluated by the following methods.

(Test Method for Adhesive Strength) Ten bovine front teeth were used.
No. 00 silicon carbide abrasive paper (Nihon Kenshi Co., Ltd.)
Wet-polishing to expose the enamel surface or the dentin surface, and then the surface water was blown off with a dental air syringe. On the exposed enamel surface or dentin surface, a tape having a hole with a diameter of 5 mm is pasted, the adhesive composition of the present invention is applied to the hole portion with a brush, and left as it is for 30 seconds, then, with an air syringe. Dried. On top of that, a commercially available dental bonding material "Clearfill LB Bond" (manufactured by Kuraray Co., Ltd.) was applied with a brush to a thickness of about 100 microns, and a dental light irradiator "Litel-II" (Gunma Ushio Denki) (Manufactured by Co., Ltd.), light irradiation was performed for 20 seconds to cure. Furthermore, a commercially available photopolymerizable dental composite resin "Photoclear Fill A" (manufactured by Kuraray Co., Ltd.) was placed on the film, and after covering with a film made of EVAL (registered trademark, manufactured by Kuraray Co., Ltd.), The slide glass was pressed from above, and in this state, light irradiation was carried out for 40 seconds with the above light irradiation device to cure it. A commercially available dental resin cement "Panavia 21" (manufactured by Kuraray Co., Ltd.) was used to adhere a stainless steel rod to the hardened surface, which was left for 15 minutes and then immersed in 37 ° C water for 24 hours. Was measured for tensile adhesive strength.

(Antibacterial property test method 1) Evaluation of antibacterial property during primer treatment Bovine front teeth were wet-polished with No. 1000 silicon carbide abrasive paper (manufactured by Nihon Kenshi Co., Ltd.) to remove dentin surface. After the exposure, a 1 mm-thick section was cut using a diamond saw. Apply 40% phosphoric acid aqueous solution on both sides,
After standing for 60 seconds, it was washed under running water and stored in water until use. Streptococcus mutans (Streptococcus mutans) pre-cultured in a Brain Heart Infusion (BHI) liquid medium (manufactured by Nissui Pharmaceutical Co., Ltd.) for 24 hours.
cus mutans., IFO 13955) was diluted with sterile physiological saline to a bacterial concentration of 1 × 10 ⁴ (CFU / ml), and 100 μl was inoculated on the BHI agar medium. Unfolded.

A tape with a hole having a diameter of 5 mm attached to the surface of the above-mentioned dentin slice was placed in the central portion of the above agar medium and lightly pressed for close contact. The adhesive composition of the present invention is applied with a brush to the hole portion of the tape of the section of the section placed on the medium, and the section is left to stand for 60 seconds to allow the primer composition to penetrate into the section tissue. After removing the test piece and culturing the BHI agar medium at 37 ° C. for 48 hours, the growth state of the bacteria was observed and evaluated based on the following criteria. ++) Bacteria are growing in the place where the test piece is placed as in the surrounding area. (It is not recognized that the antibacterial component permeated the section tissue.) +) Bacterial growth was suppressed at the place where the test piece was placed compared to the surrounding area. (It is recognized that some of the antibacterial components have penetrated the tissue of the section.)-) No bacteria grow at the place where the test piece is placed. (It is recognized that the antibacterial component has sufficiently penetrated the section tissue.)

(Antibacterial Test Method 2) Evaluation Method of Antibacterial Property of Surface After Polymerization and Curing A tape made of EVAL (registered trademark, manufactured by Kuraray Co., Ltd.) is pasted with a tape having an inner diameter of 9 mm, and the film surface is Donut-shaped mold (inner diameter 15
mm, outer diameter 40 mm, thickness 0.5 mm). 10 μl of the adhesive composition of the present invention is placed in the hole of the mold.
Was dropped and dried with a dental air syringe. On top of that, a commercially available dental bonding material "Clearfill LB Bond" (manufactured by Kuraray Co., Ltd.) was applied with a brush to a thickness of about 100 microns, and a dental light irradiator "Litel-II" was used to apply 20
It was irradiated with light for a second to cure it. Further, a commercially available photopolymerization type dental composite resin “Photoclear Fill A” (manufactured by Kuraray Co., Ltd.) is placed on it, and a film made of EVAL (registered trademark) is covered, and then a slide glass is pressed from above. , 4 in the above light irradiator in such a state
It was irradiated with light for 0 seconds to be cured. The cured product was removed from the mold and ultrasonically cleaned in water for 1 hour.

[0027] Streptococcus mutans (Streptococcus mutans) pre-cultured in a Brain Heart Infusion (BHI) liquid medium (manufactured by Nissui Pharmaceutical) for 24 hours in advance.
s mutans., IFO 13955) was diluted with sterile physiological saline to a bacterial concentration of 1 × 10 ⁴ (CFU / ml), and 100 μl was inoculated on the surface of the cured product. After standing for 15 minutes, the cured product was turned upside down and placed on a BHI agar medium to collect a bacterial solution. Further, the cured product was pressed against another place on the agar medium, all the residual bacteria adhering to the surface of the cured product were collected, and this was used as a sample. At the same time, the above-mentioned bacterial dilution was directly applied to BHI agar medium at 10
0 μl inoculum was prepared and used as a control. After both were anaerobically cultured at 37 ° C. for 24 hours, they were further cultivated aerobically for 24 hours, the number of formed colonies was counted, and the bacterial killing rate was calculated by the following formula.

[0028]

[Equation 1]

Examples 1 to 4 12-methacryloyl oxide decylpyridinium bromide (hereinafter referred to as MDPB as an antibacterial polymerizable monomer)
Is abbreviated. The structural formula is shown below. ), Β-methacryloyloxyethyl phenyl phosphate as an acidic polymerizable monomer (hereinafter abbreviated as phenyl P. The structural formula is shown below), HEMA, distilled water, N, N-diethanol-p-toluidine (hereinafter This is abbreviated as DEPT), camphorquinone (hereinafter abbreviated as CQ), isoamyl N, N-dimethylaminobenzoate (hereinafter abbreviated as IADMAB), and ethanol in the weights shown in Table 1. Adhesive compositions were prepared by mixing in a ratio, and the adhesive strength was measured and antibacterial tests 1 and 2 were performed by the above-mentioned methods. The results are shown in Table 1.

[0030]

Embedded image

[0031]

[Chemical 6]

Examples 5 to 8 MDPB, 10-methacryloyloxydecyl dihydrogen phosphate (hereinafter referred to as MDP).
The structural formula is shown below. ), HEMA, distilled water, sodium benzenesulfinate (hereinafter abbreviated as BSS) and DEPT at a weight ratio shown in Table 3 to prepare an adhesive composition, and the measurement of the adhesive strength by the method described above. And antibacterial tests 1 and 2 were performed. The results are shown in Table 3.

[0033]

[Chemical 7]

Examples 9 to 12 MDPB, MDP, HEMA, distilled water, DEPT, C
Adhesive compositions were prepared by mixing Q, IADMAB and ethanol in the weight ratios shown in Table 1, and the adhesive strength was measured and antibacterial tests 1 and 2 were performed by the above-mentioned methods. The results are shown in Table 1.

Examples 13 to 16 MDPB, methacrylic acid, HEMA, distilled water, DEP
T, CQ, IADMAB and ethanol were mixed in the weight ratio shown in Table 1 to prepare an adhesive composition, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above.
The results are shown in Table 1.

Examples 17 to 20 MDPB, 4-methacryloyloxyethyl trimellitic acid (hereinafter referred to as 4-MET), HEMA,
Distilled water, DEPT, CQ, IADMAB and ethanol were mixed in the weight ratio shown in Table 2 to prepare an adhesive composition, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the above-mentioned methods. Table 2 shows the results.

Examples 21 to 24 MDPB, 4-methacryloyloxyethyl trimellitic anhydride (hereinafter abbreviated as 4-META), H
EMA, distilled water, DEPT, CQ, IADMAB and ethanol were mixed at the weight ratio shown in Table 1 to prepare an adhesive composition, and the adhesive strength was measured and antibacterial tests 1 and 2 were performed by the above-mentioned methods. Table 2 shows the results.

Examples 25 to 28 MDPB, 4-acryloyloxyethyl trimellitic acid (hereinafter abbreviated as 4-AET), HEMA, distilled water, DEPT, CQ, IADMAB and ethanol in the weight ratios shown in Table 2. Mixing to prepare an adhesive composition,
Measurement of adhesive strength and antibacterial test 1, by the method described above,
Did 2. Table 2 shows the results.

Examples 29 to 32 MDPB, phenyl P, HEMA, distilled water, BSS and DEPT were mixed in a weight ratio shown in Table 3 to prepare an adhesive composition, and the adhesive strength was measured and the antibacterial property was measured by the above-mentioned method. Sex tests 1 and 2 were conducted. The results are shown in Table 3.

Examples 33 to 36 MDPB, methacrylic acid, HEMA, distilled water, BSS and DEPT were mixed in a weight ratio shown in Table 3 to prepare an adhesive composition, and the adhesive strength was measured and the antibacterial property was measured by the aforementioned method. Sex tests 1 and 2 were conducted. The results are shown in Table 3.

Examples 37 to 40 An antibacterial polymerizable monomer having the following structure (hereinafter referred to as D-30
1 monomer), phenyl P, HEMA, distilled water, BSS and DEPT are mixed in the weight ratio shown in Table 4 to prepare an adhesive composition, and the adhesive strength is measured and the antibacterial test 1 2 was done. The results are shown in Table 4.

[0042]

Embedded image

Examples 41 to 44 An antibacterial polymerizable monomer having the following structure (hereinafter referred to as D-30
1 monomer), MDP, HEMA, distilled water,
BSS and DEPT were mixed in the weight ratio shown in Table 4 to prepare an adhesive composition, and the adhesive strength was measured and antibacterial tests 1 and 2 were performed by the above-mentioned methods. The results are shown in Table 4.

[0044]

[Chemical 9]

Examples 45 to 48 An antibacterial polymerizable monomer having the following structure (hereinafter referred to as VB-1
6 monomer), phenyl P, HEMA, distilled water, BSS and DEPT are mixed in a weight ratio shown in Table 4 to prepare an adhesive composition, and the adhesive strength is measured and the antibacterial test 1 is performed by the method described above. 2 was done. The results are shown in Table 4.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

Comparative Examples 1 and 2 MDPB, Phenyl P, HEMA, distilled water, DEPT,
An adhesive composition was prepared in which the contents of CQ, IADMAB and ethanol were changed to the weight ratios shown in Table 5, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above. The results are shown in Table 5.

Comparative Examples 3 and 4 MDPB, MDP, HEMA, distilled water, BSS and D
Adhesive compositions were prepared by mixing EPTs in the weight ratios shown in Table 4, and the adhesive strength and antibacterial tests 1 and 2 were conducted by the above-mentioned methods.
I went. The results are shown in Table 7.

Comparative Examples 5 and 6 MDPB, HEMA, distilled water, DEPT, CQ, IAD
An adhesive composition was prepared in which the contents of MAB and ethanol were changed to the weight ratios shown in Table 5, and the adhesive strength was measured and antibacterial tests 1 and 2 were performed by the above-mentioned methods. The results are shown in Table 5.
Shown in

Comparative Examples 7 and 10 MDPB, Phenyl P, HEMA, DEPT, CQ, I
An adhesive composition was prepared in which the content ratios of ADMAB and ethanol were changed to the weight ratios shown in Table 5, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above. The results are shown in Table 5.

Comparative Examples 11 and 14 MDPB, phenyl P, distilled water, DEPT, CQ, IA
An adhesive composition was prepared in which the contents of DMAB and ethanol were changed to the weight ratios shown in Table 5, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above. The results are shown in Table 5.

Comparative Examples 15 and 16 MDPB, MDP, HEMA, distilled water, DEPT, C
An adhesive composition was prepared in which the contents of Q, IADMAB and ethanol were changed to the weight ratios shown in Table 6, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above.
The results are shown in Table 6.

Comparative Examples 17 and 18 MDPB, HEMA, distilled water, DEPT, CQ, IAD
An adhesive composition was prepared in which the contents of MAB and ethanol were changed to the weight ratios shown in Table 6, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above. The results are shown in Table 6.
Shown in

Comparative Examples 19 and 22 MDPB, MDP, HEMA, DEPT, CQ, IAD
An adhesive composition was prepared in which the contents of MAB and ethanol were changed to the weight ratios shown in Table 6, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above. The results are shown in Table 6.
Shown in

Comparative Examples 23 and 26 MDPB, MDP, distilled water, DEPT, CQ, IADM
An adhesive composition was prepared in which the contents of AB and ethanol were changed to the weight ratios shown in Table 6, and the adhesive strength was measured and antibacterial tests 1 and 2 were carried out by the methods described above. The results are shown in Table 6.

Comparative Examples 27 and 28 MDPB, HEMA, distilled water, BSS and DEPT were mixed in a weight ratio shown in Table 7 to prepare an adhesive composition, and the adhesive strength and antibacterial tests 1 and 2 were conducted by the above-mentioned methods. went. The results are shown in Table 7.

Comparative Examples 29 and 32 MDPB, MDP, HEMA, BSS and DEPT were mixed in a weight ratio shown in Table 7 to prepare an adhesive composition, and adhesive strength and antibacterial tests 1 and 2 were conducted by the above-mentioned methods. It was The results are shown in Table 7.

MDPB, MDP, HEMA, BSS and DEPT were mixed in the weight ratio shown in Table 9 to prepare a primer composition, and the adhesive strength and antibacterial tests 1 and 2 were conducted by the above-mentioned methods. The results are shown in Table 9.

Comparative Examples 33 and 36 MDPB, MDP, distilled water, BSS and DEPT were mixed in a weight ratio shown in Table 7 to prepare an adhesive composition, and the adhesive strength and antibacterial tests 1 and 2 were conducted by the above-mentioned methods. went.
The results are shown in Table 7.

Comparative Examples 37-41 MDPB, Phenyl P, HEMA, DEPT, CQ, I
Adhesive compositions in which the contents of ADMAB and ethanol were changed to the weight ratios shown in Table 8 were prepared, and the adhesive strength was measured and antibacterial tests 1 and 2 were performed by the methods described above. Table 8 shows the results.

Comparative Examples 42 to 46 MDPB, MDP, HEMA, BSS and DEPT were mixed at the weight ratios shown in Table 9 to prepare adhesive compositions, and the adhesive strength and antibacterial tests 1 and 2 were conducted by the above-mentioned methods. It was The results are shown in Table 9.

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

[Table 7]

As is clear from Table 1, when the adhesive compositions of Examples 1 to 4 were used, a very strong adhesive strength of about 20 MPa was obtained for both bovine dentin and enamel. Has been obtained. Further, in the antibacterial property test 1, strong antibacterial property that completely kills the bacteria on the lower surface of the disk was confirmed during the adhesive treatment, and in the antibacterial property test 2, strong antibacterial property that completely kills the bacteria adhered to the surface after curing. The sex was confirmed. On the other hand, as is clear from Table 5, in the case of Comparative Example 1, although good adhesive strength was obtained, neither the antibacterial property during the adhesive treatment nor the antibacterial property of the surface after curing could be observed. . Further, in Comparative Example 2, although the antibacterial property is exhibited, the adhesive strength is obviously lower than in Examples 1 to 4.

Further, in Comparative Examples 5 and 6 in which the polymerizable monomer having an acidic group was not blended, the adhesive strength was obviously lower than that in Examples 1 to 4, and the antibacterial property during the adhesive treatment and The antibacterial property of the surface after curing was also insufficient to kill bacteria. Comparative Example 7 containing no distilled water
-10 and Comparative Examples 11 to 11 not containing HEMA
In No. 14, the antibacterial property after curing was very strong, but the adhesive strength and the antibacterial property during the adhesive treatment were obviously lower than those of Examples 1 to 4. In the case of Comparative Examples 37 to 40 containing 15% by weight of distilled water, which is less than the concentration described in claim 1,
Although the adhesive strength was strong, the antibacterial property during the primer treatment was obviously weaker than that of Examples 1 to 4, and the bacteria on the lower surface of the disc could not be killed. On the contrary, in the case of Comparative Example 41 in which distilled water was blended in an amount of 80% by weight exceeding the concentration described in claim 1, the adhesive strength was obviously lower than in Examples 1 to 4.

Comparative Example 3 containing less than 20% by weight of distilled water
In the case of 7 to 40, the adhesive strength was strong, but the antibacterial property during the primer treatment was clearly weaker than in Examples 1 to 4, and the bacteria on the lower surface of the disc could not be killed. On the contrary, in the case of Comparative Example 41 in which 80% by weight of distilled water was blended, the adhesive strength was obviously lower than in Examples 1 to 4.

As is clear from Table 1, phenyl P, which is the polymerizable monomer having an acidic group used in Examples 1 to 4 was MD.
When P was changed (Examples 9 to 12), a very strong adhesive strength of about 18 MPa was obtained for both bovine dentin and enamel. Furthermore, antibacterial test 1
A strong antibacterial property that completely kills the bacteria on the lower surface of the disc was confirmed in the primer treatment, and a strong antibacterial property that completely kills the bacteria adhered to the surface after curing was confirmed in the antibacterial property test 2. On the other hand, as is clear from Table 6, in the case of Comparative Example 15, although good adhesive strength was obtained, neither the antibacterial property during the primer treatment nor the antibacterial property of the surface after curing could be observed. Further, in Comparative Example 16, although the antibacterial property is exhibited, the adhesive strength is obviously lower than in Examples 9 to 12.

Further, in Comparative Examples 17 and 18 in which the polymerizable monomer having an acidic group was not blended, the adhesive strength was obviously lower than that in Examples 9 to 12, and the antibacterial property and the curing during the primer treatment were observed. The antibacterial properties of the latter surface were also insufficient to kill the bacteria. In Comparative Examples 19 to 22 containing no distilled water and Comparative Examples 23 to 26 containing no HEMA, the antibacterial property after curing was very strong, but the adhesive strength and the antibacterial property during the treatment with the primer were found in Example 9. Significantly lower compared to ~ 12.

As is clear from Table 1, bovine dentin is also obtained when phenyl P, which is the polymerizable monomer having an acidic group used in Examples 1 to 4 is replaced with methacrylic acid (Examples 13 to 16). A very strong adhesive strength of around 18 MPa was obtained for both the quality and the enamel. Further, in the antibacterial property test 1, strong antibacterial property that completely kills the bacteria on the lower surface of the disk was confirmed during the primer treatment, and in the antibacterial property test 2, strong antibacterial property that completely kills the bacteria adhered to the surface after curing. Was confirmed.

As is clear from Table 2, phenyl P which is the polymerizable monomer having an acidic group used in Examples 1 to 4 is
Even when changed to MET (Examples 17 to 20), a strong adhesive strength of about 12 MPa was obtained for bovine dentin and about 15 MPa for bovine enamel. Further, in the antibacterial property test 1, strong antibacterial property that completely kills the bacteria on the lower surface of the disk was confirmed during the primer treatment, and in the antibacterial property test 2, strong antibacterial property that completely kills the bacteria adhered to the surface after curing. Was confirmed.

As is clear from Table 2, phenyl P, which is the polymerizable monomer having an acidic group used in Examples 1 to 4,
Even when changed to META (Examples 21 to 24), a strong adhesive strength of about 12 MPa was obtained for bovine dentin and about 15 MPa for bovine enamel. Further, in the antibacterial property test 1, strong antibacterial property that completely kills the bacteria on the lower surface of the disk was confirmed during the primer treatment, and in the antibacterial property test 2, strong antibacterial property that completely kills the bacteria adhered to the surface after curing. Was confirmed.

As is clear from Table 2, phenyl P which is the polymerizable monomer having an acidic group used in Examples 1 to 4 is
Even when changed to AET (Examples 25 to 28), strong adhesive strength of about 13 MPa was obtained for bovine dentin and about 15 MPa for bovine enamel. Further, in the antibacterial property test 1, strong antibacterial property that completely kills the bacteria on the lower surface of the disk was confirmed during the primer treatment, and in the antibacterial property test 2, strong antibacterial property that completely kills the bacteria adhered to the surface after curing. Was confirmed.

As is clear from Table 3, when the primer compositions of Examples 5 to 8 were used, it was about 6 to 7 MPa for bovine dentin and 11 for bovine enamel.
A strong adhesive strength of about 15 MPa is obtained. Further, in the antibacterial property test 1, strong antibacterial property that completely kills the bacteria on the lower surface of the disk was confirmed during the primer treatment, and in the antibacterial property test 2, strong antibacterial property that completely kills the bacteria adhered to the surface after curing. Was confirmed. On the other hand, as is clear from Table 7, in the case of Comparative Example 3, although good adhesive strength was obtained, neither the antibacterial property during the primer treatment nor the antibacterial property of the surface after curing could be observed. Further, in Comparative Example 4, although the antibacterial property is exhibited, the adhesive strength is obviously lower than in Examples 5 to 8.

Furthermore, in Comparative Examples 27 and 8 in which the polymerizable monomer having an acidic group was not blended, the adhesive strength was obviously lower than those in Examples 5 to 8, and the antibacterial property and curing during the primer treatment were observed. The antibacterial properties of the latter surface were also insufficient to kill the bacteria. Although Comparative Examples 29 to 32 not containing distilled water and Comparative Examples 33 to 36 not containing HEMA have very strong antibacterial properties after curing,
The adhesive strength and the antibacterial property during the primer treatment are shown in Examples 5 to 5.
It was clearly lower than that of 9. Comparative Examples 42 to 45 in which distilled water was blended in an amount of 15% by weight, which is less than the concentration described in claim
In this case, the adhesive strength was high, but the antibacterial property during the primer treatment was clearly weaker than in Examples 5 to 9, and the bacteria on the lower surface of the disc could not be killed. On the contrary, in the case of Comparative Example 46 in which distilled water was blended in an amount of 80% by weight exceeding the concentration described in claim 1, the adhesive strength was found to be in Example 5.
It was clearly lower than that of ~ 9.

Comparative Example 42 containing 15% by weight of distilled water
In the case of No. 45, the adhesive strength was strong, but the antibacterial property during the primer treatment was obviously weaker than in Examples 5 to 9,
The bacteria on the bottom of the disc could not be killed.
On the contrary, when 80% by weight of distilled water was added, the adhesive strength of Comparative Example 46 was obviously lower than that of Examples 5-9.

[0080]

[Table 8]

[0081]

[Table 9]

[0082]

According to the present invention, a dental primer composition having antibacterial properties is provided. According to the antibacterial dental primer composition of the present invention, it becomes possible to prevent the invasion of bacteria to the adhesive interface by improving the adhesive strength between the tooth and the restorative material, and the fine structure of the adhesive interface such as dentinal tubules. It is possible to kill the bacteria remaining in the inside, and it is also possible to kill the bacteria that enter the adhesive interface after bonding, and the effect of preventing secondary caries and dental pulp infection can be realized. It was

Claims (5)

[Claims] 1. The antibacterial polymerizable monomer (A) is added in an amount of 0.01-.
25% by weight, 5 to 5 of the polymerizable monomer (B) having an acidic group
An antibacterial dental adhesive composition containing 40% by weight, 10 to 50% by weight of a polymerizable monomer (C) having an alcoholic hydroxyl group, 20 to 75% by weight of water, and a polymerization catalyst. Stuff. 2. The antibacterial dental adhesive composition according to claim 1, wherein the antibacterial polymerizable monomer (A) is represented by the following general formula (1). Embedded image 3. The antibacterial dental adhesive composition according to claim 1, wherein the antibacterial polymerizable monomer (A) is represented by the following general formula (2). Embedded image 4. The antibacterial dental adhesive composition according to claim 1, wherein the antibacterial polymerizable monomer (A) is represented by the following general formula (3). Embedded image 5. The antibacterial dental adhesive composition according to claim 1, wherein the antibacterial polymerizable monomer (A) is represented by the following general formula (4). [Chemical 4]