JP6088942B2 - Tooth surface covering material - Google Patents

Description

  The present invention relates to a tooth surface covering material capable of suppressing the adhesion of plaque to the tooth surface by being applied to the tooth surface.

  Dental caries (cavities) in the oral cavity can be said to be a lifestyle-related disease and is caused by the presence of oral bacteria, decreased dental resistance, sugar intake, etc., and oral cavity such as Streptococcus mutans (S. mutans) It is known that bacteria metabolize sugar and the like to release an acid, and the acid dissolves teeth. Bacteria in the mouth form a kind of biofilm called plaque and adhere to the tooth surface (natural tooth or surface of dental prosthesis). In addition, since it is known that the bacteria in the mouth do not release acid unless it adheres to the tooth surface, the occurrence of caries can be prevented or reduced by suppressing the adhesion of plaque to the tooth surface. Generally, the plaque adhering to the tooth surface is removed by brushing the teeth, but it is difficult to remove the plaque between the teeth where the toothbrush tip of the toothbrush is difficult to reach or the deep groove of the occlusal surface. Therefore, there is a problem that it is difficult to suppress the occurrence of caries only by brushing teeth.

  The present applicant has previously aimed to prevent the formation of biofilms by inhibiting the attachment of plaques such as proteins and oral bacteria that cause oral diseases such as bad breath to the dental prosthesis surface. A coating material composition for a dental prosthesis has been disclosed (for example, see Patent Document 1). This composition is a copolymer of 2-methacryloyloxyethyl phosphorylcholine and (meth) acrylic acid ester in a solvent and contains a 2-methacryloyloxyethyl phosphorylcholine component, for dental prosthesis It is a coating material composition. However, since this composition does not contain a polymerizable component, the adhesion to the tooth surface and the durability were insufficient.

  Further, the present applicant includes 1 to 70% by weight of mono-dispersed inorganic fine particles having an average particle diameter of 1 to 100 nm, the surface of which is modified with an alkoxysilane having an unsaturated double bond in the (meth) acrylate monomer. Also disclosed is a photopolymerization type tooth surface treatment material comprising 0.01 to 10 parts by weight of a photopolymerization catalyst with respect to 100 parts by weight of the component, and further having a viscosity of 5000 cP or less at 23 ° C. (For example, refer to Patent Document 2). However, since this tooth surface treatment material has no hydrophilic imparting force to the tooth surface, an effect of suppressing the adhesion of plaque was not observed.

  In addition, a method for suppressing the adhesion of plaque to the tooth surface by utilizing the hydrophilicity of the photocatalytic action of titanium oxide has been considered. For example, a method is disclosed in which dental coating material containing a photocatalytic substance such as titanium dioxide is applied to teeth and irradiated with light to decompose dental plaque (see, for example, Patent Document 3). However, since this dental coating material does not contain a polymerizable component, it has poor adhesion to the tooth surface and durability, and it has been difficult to maintain the effect over a long period of time.

  Furthermore, a composition containing a titanium dioxide powder and a polymerizable component is also disclosed (for example, see Patent Document 4). However, the titanium dioxide in this composition is only added to emphasize the white color of the teeth after bleaching, and is not intended for photocatalysis. Further, titanium dioxide to be blended is a powder, and since it does not contain a water component in the composition, it has almost no hydrophilicity and is not suitable as a material for suppressing the adhesion of plaque to the tooth surface.

  Thus, in the prior art, it is a tooth surface adhesive tooth surface covering material that utilizes the hydrophilicity due to the photocatalytic action of titanium oxide, and is excellent in the ability to suppress the adhesion of plaque to the tooth surface and has durability. The tooth surface covering material having was not disclosed.

JP 2004-194874 A JP 2011-178767 A JP 09-175923 A JP 2002-003327 A

  An object of the present invention is to provide a tooth surface adhesive material with excellent tooth surface adhesiveness that has excellent ability to suppress adhesion of plaque to the tooth surface and has durability.

  As a result of intensive studies, the inventors of the present invention have the ability to suppress adhesion of plaque to the tooth surface by combining specific titanium oxide, surface hydrophilic silicon dioxide, a polymerizable substance, water and an organic solvent. An excellent and durable tooth surface adhesive tooth surface covering material was completed.

  That is, the present invention comprises (a) visible light responsive titanium oxide powder having photoactivity with visible light of 400 nm or more: 0.5 to 10% by weight, (b) surface hydrophilic silicon dioxide: 0.01 to 6% by weight %, (C) (meth) acrylate containing a phosphate group: 1 to 10% by weight, (e) polymerizable (meth) acrylate not containing an acid group: 10 to 50% by weight, (f) water: 10 to 40% It is a tooth surface covering material composed of: wt%, (g) organic solvent: 20 to 70 wt%, and (h) photopolymerization catalyst: 0.01 to 7 wt%. Furthermore, in order to improve adhesive force, (d) (meth) acrylate having a carboxyl group: 1 to 15% by weight may be included.

  The tooth surface covering material according to the present invention is a tooth surface adhesive material having an excellent ability to suppress the adhesion of plaque to the tooth surface and has durability.

  The (a) visible light responsive titanium oxide powder blended in the tooth surface covering material according to the present invention is a titanium oxide powder that exhibits catalytic action in response to visible light of 400 nm or more. By bonding the visible light responsive titanium oxide powder together with the polymerizable component, the tooth surface is covered with a layer of titanium oxide. When visible light is irradiated to this titanium oxide, it becomes super hydrophilic due to photocatalytic action, and therefore, adhesion of plaque to the tooth surface is suppressed. The compounding amount of the visible light responsive titanium oxide powder is 0.5 to 10% by weight in the tooth surface covering material. If the amount is less than 0.5% by weight, the effect cannot be obtained. If the amount exceeds 10% by weight, the amount of transmitted light decreases, so the effect is lowered. In order to maintain sufficient translucency of the tooth surface from the viewpoint of aesthetics, the range of 0.5 to 3% by weight is particularly preferable.

  The (b) surface hydrophilic silicon dioxide blended in the tooth surface covering material according to the present invention is effective in improving the hydrophilicity by coexisting with the visible light responsive titanium oxide as the component (a). Typical examples are hydrophilic silica gel, fused silica, silicic acid, hydrophilic silica fine powder, and the like, and more preferably water-containing substances. The blending amount of these surface hydrophilic silicon dioxides is 0.01 to 6% by weight in the tooth surface covering material. If it is less than 0.01% by weight or exceeds 6% by weight, the effect of improving hydrophilicity becomes small.

  The (c) phosphoric acid group-containing (meth) acrylate blended in the tooth surface covering material according to the present invention has an effect of adhering and retaining the tooth surface covering material to the tooth surface. The compounding quantity of the (meth) acrylate containing a phosphate group is 1 to 10% by weight in the tooth surface covering material. If it is less than 1% by weight, sufficient adhesion performance to the tooth surface cannot be provided, and if it exceeds 10% by weight, the polymerization curability is lowered, which is not practical. The “(meth) acrylate” used in the present invention is an acrylate or methacrylate notation and means an acrylate compound or a methacrylate compound. In consideration of biosafety, the polymerizable (meth) acrylate used for the tooth surface covering material is preferably methacrylate.

  As the (meth) acrylate containing a phosphoric acid group, a phosphoric acid and a (meth) acrylate containing a phosphonic acid group are suitable, and bis (2- (meth) acryloxyethyl) phosphoric acid and 2- (meth) acryloxy Ethyl phosphoric acid, 2- (meth) acryloxyethylphenyl phosphoric acid, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, glycerol di (meth) ) Acrylate dihydrogen phosphate, vinyl phosphonic acid and para-vinyl benzyl phosphonic acid. In addition, (meth) acrylates containing a thiophosphate group are also suitable, and 10- (meth) acryloyloxydecyl dihydrogen phosphate, which has been widely used in dental adhesives, or 10- (meth) Examples include molecules in which acryloyloxydecyl dihydrogen phosphate is di (meth) acrylate bifunctional.

  Furthermore, it is also effective to improve the adhesion performance by adding (d) (meth) acrylate having a carboxyl group to the tooth surface covering material according to the present invention. The amount of the (meth) acrylate having a carboxyl group is 1 to 15% by weight in the tooth surface covering material. If it is less than 1% by weight, the effect cannot be obtained, and if it exceeds 15% by weight, the curability of the composition tends to decrease.

  Examples of the (meth) acrylate having a carboxyl group include (meth) acrylic acid, 1,4-di (meth) acryloxyethyl pyromellitic acid, 6- (meth) acryloxyethylnaphthalene 1,2,6-tricarboxylic acid, N, O-di (meth) acryloxytyrosine, O- (meth) acryloxytyrosine, N- (meth) acryloxytyrosine, N- (meth) acryloxyphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid Acid, N- (meth) acryloyl-o-aminobenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 4- (meth) acryloxyethyl trimellitic acid , 4- (meth) acryloxybutyl trimellitic acid, 4- (meth) acryloxyhexyl trimellitic 4- (meth) acryloxydecyl trimellitic acid, 4- (meth) acryloxybutyl trimellitic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) Acryloyloxybenzoic acid, addition product of 2-hydroxyethyl (meth) acrylate and maleic anhydride, P-vinylbenzoic acid, O- (meth) acryloxytyrosinamide, N-phenylglycine-glycidyl (meth) acrylate, N -(P-methylphenyl) glycine-glycidyl (meth) acrylate, 11- (meth) acryloxy-1,1-undecanedicarboxylic acid, 4-[(2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthal Acid, 5-[(2-hydroxy-3- (meth) acryloyloxypropyl) Amino] isophthalic acid, 3- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid, 4- [N-methyl-N- (2-hydroxy-3- ( Examples include (meth) acryloyloxypropyl) amino] phthalic acid and maleic acid thereof. Moreover, the (meth) acrylate which has a carboxyl group also includes the (meth) acrylate which has acid anhydrides, such as maleic anhydride, as a carboxylic acid precursor.

  The (e) acid group-free (meth) acrylate blended in the tooth surface covering material according to the present invention is a component for curing the composition. The (meth) acrylate which does not contain an acid group can use the substance conventionally used by the composition for dentistry, and the compounding quantity is 10 to 50 weight% in a tooth surface coating | covering material. If it is less than 10% by weight, the curing rate and strength on the tooth surface will decrease, and if it exceeds 50% by weight, the curability of the surface when polymerized after coating will decrease.

  Examples of the (meth) acrylate compound not containing an acid group include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxypropyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane, ethyl Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polybutylene glycol di (meth) acrylate, bisphenol A diglycidyl ( Data) acrylate. These monomers or oligomers or prepolymers can be suitably used. Moreover, as a (meth) acrylate having a urethane bond, di-2- (meth) acryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate, 1,3,5-tris [1,3-bis {( (Meth) acryloyloxy} -2-propoxycarbonylaminohexane] -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione, 2,2-bis-4- (3- (meta ) Acryloyloxy-2-hydroxypropyl) -phenylpropane, etc., and consists of 2,2'-di (4-hydroxycyclohexyl) propane, 2-oxypanone, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate Urethane oligomer (meth) acrylate, 1,3-butanediol and hexamethylene diisocyanate Can be exemplified over preparative and 2-hydroxyethyl (meth) urethane oligomer consisting of acrylates (meth) acrylate. These can be used individually or in mixture of 2 or more types.

  The tooth surface covering material according to the present invention is blended with (f) water. The hydrophilicity is improved by the presence of water, and the tooth surface covering material is easily applied to the tooth surface because it is suppressed from being repelled during application. Furthermore, since the (d) carboxyl group-containing (meth) acrylate is dissociated by the presence of water, the adhesion of the tooth surface covering material to the tooth surface is improved. The blending amount of water is 10 to 40% by weight in the tooth surface covering material. If it is less than 10% by weight, hydrophilicity cannot be appropriately imparted to the tooth surface covering material. On the other hand, if it exceeds 40% by weight, curing of the tooth surface covering material is inhibited. More preferably, it is 15-35 weight%, More preferably, it is 20-30 weight%.

  The tooth surface covering material according to the present invention is one-component and is preferably cured immediately after being applied to the tooth surface, and has a high volatility (g) organic solvent in order to obtain quick-drying in the mouth with high humidity. Is blended. For example, acetone, ethyl alcohol, etc. are common. These compounding quantities are 20 to 70 weight% in a tooth surface covering material. If it is less than 20%, sufficient immediate drying cannot be imparted to the tooth surface covering material. On the other hand, if it exceeds 70% by weight, the amount of the other polymerizable substance is relatively reduced, so that the tooth surface covering material cannot be properly polymerized and cured.

  The tooth surface covering material according to the present invention is one-component. Therefore, (h) a photocuring catalyst is used as the curing catalyst. The blending amount of the photopolymerization catalyst is preferably 0.01 to 7% by weight in the tooth surface covering material. If it is less than 0.01% by weight, a sufficient polymerization reaction cannot be obtained, and if it exceeds 7% by weight, it becomes difficult to control the curing, and the storage stability of the tooth surface coating material before use is also lowered.

  A known photopolymerization catalyst system can be used as the photopolymerization catalyst. As the photopolymerization catalyst, a combination of a sensitizer and a reducing agent is generally used. As the sensitizer, camphorquinone, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl di (2-methoxyethyl) ketal, 4,4′-dimethyl Benzyl-dimethyl ketal, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trif Oromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, 4,4'- Examples include bisdiethylaminobenzophenone, acylphosphine oxides such as (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, and compounds containing an azido group. These can be used individually or in mixture of 2 or more types.

  A tertiary amine or the like is generally used as the reducing agent. As the tertiary amine, N, N-dimethyl-p-toluidine, N, N-dimethylaminoethyl methacrylate, triethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Illustrative is isoamyl acid. Examples of other reducing agents include benzoyl peroxide, sodium sulfinate derivatives, and organometallic compounds.

  The tooth surface covering material according to the present invention will be described below with specific examples, but the present invention is not limited to these examples.

<Example 1>
M10P: 10% by weight, 4-META: 3% by weight, acetone: 36% by weight, TEGDMA: 20% by weight, water: 25% by weight, camphorquinone: 2% by weight, ethyl 4-dimethylaminobenzoate: 1% by weight Prepare a well-mixed liquid. Visible light-responsive titanium oxide powder: 2% by weight and silica gel: 1% by weight were suspended in this solution to complete a tooth surface covering material.
On the other hand, an enamel flake of 5 mm × 5 mm × 1 mm (thickness) was polished with No. 1500 SiC polishing paper, and then a drop of a sufficiently uniform tooth surface covering material was dropped on the surface of the flake using a brush. This was irradiated with light for 30 seconds to polymerize the tooth surface covering material to obtain a test flake.

<Example 2>
M10P: 5 wt%, DM10P: 5 wt%, 4-META: 3 wt%, acetone: 20 wt%, ethyl alcohol: 12 wt%, MMA: 20 wt%, water: 22 wt%, camphorquinone: 2 wt% %, Ethyl 4-dimethylaminobenzoate: A liquid in which 1% by weight is sufficiently mixed is prepared. Visible light-responsive titanium oxide: 10% by weight of powder and silica gel: 0.05% by weight were suspended in this solution to complete a tooth surface coating material coating agent. About the other, the same operation as Example 1 was performed.

<Example 3>
The same operation as in Example 1 was performed, but dental composite (trade name: MI Phil, manufactured by GC Corporation) flakes of the same size were used instead of enamel flakes.

<Example 4>
The same operation as in Example 1 was performed, but instead of enamel flakes, dental glass ionomer cement (trade name: Fuji IX, manufactured by GC Corporation) having the same size was applied to the flakes.

<Example 5>
M10P: 5 wt%, DM10P: 2 wt%, acetone: 20 wt%, ethyl alcohol: 15.5 wt%, MMA: 15 wt%, HEDMA: 10 wt%, water: 24 wt%, camphorquinone: 2 wt% %, Ethyl 4-dimethylaminobenzoate: A liquid in which 1% by weight is sufficiently mixed is prepared. Visible light-responsive titanium oxide powder: 5 wt% and fused silica: 0.5 wt% were suspended in this solution to complete a tooth surface coating material coating agent. About the other, the same operation as Example 1 was performed.

<Example 6>
M10P: 7 wt%, DM10P: 1 wt%, 4-META: 2 wt%, acetone: 30 wt%, ethyl alcohol: 5 wt%, TEGDMA: 8 wt%, MMA: 10 wt%, HEDMA: 4 wt% A liquid in which 26% by weight of water, 2% by weight of camphorquinone, and 1% by weight of methyl 4-dimethylaminobenzoate are sufficiently mixed is prepared. Visible light-responsive titanium oxide powder: 3 wt% and fused silica: 1 wt% were suspended in this solution to complete the tooth surface coating material. About the other, the same operation as Example 1 was performed.

<Comparative Example 1>
The same operation as in Example 1 was performed, except that (a) a visible light responsive titanium oxide powder and (b) a tooth surface covering material not containing surface hydrophilic silicon dioxide were used.

<Comparative Example 2>
The same operation as in Example 2 was performed, except that (a) a visible light responsive titanium oxide powder and (b) a tooth surface covering material not containing surface hydrophilic silicon dioxide were used.

<Comparative Example 3>
The same operation as in Example 1 was performed, but (c) a (meth) acrylate containing a phosphate group, (d) a (meth) acrylate having a carboxyl group, and (e) a polymerizable (meth) containing no acid group. A tooth surface covering material containing no acrylate was used.

<Evaluation of bacterial adhesion>
S. 300 mL of TS liquid medium containing mutans and adjusted to turbidity 1 is prepared, and the test flakes produced in each Example and Comparative Example are immersed in this. After culturing for 48 hours, the TS medium is replaced with an equal volume of PBS solution. Thereafter, the S. cerevisiae that did not adhere to the test flakes by stirring with a vibration mixer. After removing mutans, the S. cerevisiae adhered to the test flakes. Mutans was titrated by the phenol sulfuric acid method.

<Durability evaluation>
(1) The bovine teeth are embedded with dental resin, and the bovine enamel is exposed by mirror polishing with water-resistant abrasive paper.
(2) After applying the tooth surface covering material blended with the composition shown in Table 1 to the entire surface of the mirror-polished bovine enamel, light irradiation was performed for 30 seconds to polymerize the tooth surface covering material.
(3) The remaining condition of the tooth surface coating material was evaluated by visual observation after being left to stand in an environment of an air temperature of 37 ° C. and a humidity of 100% for 1 hour and further subjected to a wear test of 8000 times with a brush wear tester.
○: Tooth surface covering material remained ×: Tooth surface covering material hardly remained

  For each of the examples and comparative examples, the composition of the tooth surface covering material (unit: wt%) and the S.P. The measurement results of the amount of mutans are summarized in Table 1.

Abbreviations in Examples and Table 1 are as follows.
M10P: 10-methacryloyloxydecyl dihydrogen phosphate DM10P: a molecule in which 10- (meth) acryloyloxydecyl dihydrogen phosphate is a bifunctional dimethacrylate 4-META: methacryloxyethyl trimellitic acid TEGDMA: tri Ethylene glycol dimethacrylate MMA: Methyl methacrylate HEDMA: Hydroxyethyl dimethacrylate

  From the results shown in Table 1, it is proved that the tooth surface covering material according to the present invention is a tooth surface covering material that has excellent ability to suppress adhesion of plaque to the tooth surface and has durability.

Claims (2)

(A) Visible light-responsive titanium oxide powder having photoactivity with visible light of 400 nm or more: 0.5 to 10% by weight
(B) Surface hydrophilic silicon dioxide: 0.01 to 6% by weight
(C) (Meth) acrylate containing a phosphate group: 1 to 10% by weight
(E) (Meth) acrylate not containing acid group: 10 to 50% by weight
(F) Water: 10 to 40% by weight
(G) Organic solvent: 20 to 70% by weight
(H) Photopolymerization catalyst: 0.01 to 7% by weight
Tooth surface covering material composed of   Furthermore, (d) (meth) acrylate which has a carboxyl group: The tooth surface coating | covering material of Claim 1 containing 1 to 15 weight%.