JP2010037254A - Photopolymerizable dental surface covering material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface covering material whose covering state can be easily confirmed even after the dental surface covering material is cured to become colorless and transparent. <P>SOLUTION: The photopolymerizable dental surface covering material comprises a (meth)acrylate monomer, 1-30 wt.% inorganic fine particles having an average particle diameter of 1-100 nm, 0.1-3 wt.% fluorescent agent, and 0.01-10 wt.% photopolymerization catalyst. Incorporation of a fluorescent agent into the conventional photopolymerizable dental surface covering material enables simple and clear confirmation of the covering state by exciting the fluorescent agent, for example, by irradiation with ultraviolet rays or a visible ray by a dental photoirradiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is applied to the surface of dental materials such as tooth surfaces, crown restoration materials, dental fillers, dentures, denture base resins, etc., and is polymerized by irradiation with visible light to make the surfaces smooth and durable. The present invention relates to a photopolymerization type dental surface coating material that improves properties and the like.

  Dental treatment uses dental restorations such as inlays, onlays, crowns and bridges, restoration materials for dental defects such as dental cement and dental composite resin, and denture base materials. . Since these dental materials desirably have the surface of the material exposed in the oral cavity as smooth as possible, careful polishing work is required. Since the dental material is used in a harsh environment in the oral cavity, there is a problem in that coloring or contamination due to deterioration of the surface of the dental material occurs if the surface is not smooth. In order to solve these problems, the surface of the dental material is polished smoothly, and then the surface of the dental material is coated with a relatively hard dental surface coating material mainly composed of a polymerizable monomer. Protecting is done.

  Conventional photopolymerization dental surface coating materials include various compositions containing a (meth) acrylate monomer and a photopolymerization initiator (see, for example, Patent Documents 1 to 4). However, since the coating material is worn over time, the effect of the coating decreases. Since the dental surface covering material needs to be colorless and transparent after curing so as not to affect the color of the dental material, the covering state cannot be confirmed when the dental surface covering material is worn. If the covering material is left worn, there is a problem that the dental prosthesis and the tooth surface are colored and contaminated.

JP 63-183904 A JP-A-4-366113 JP-A-4-29910 JP 2005-154212 A

  Then, this invention makes it a subject to provide the surface coating material which can confirm the covering state easily even after the dental surface coating material hardens | cures and becomes colorless and transparent.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors, for example, irradiate ultraviolet light or visible light with a dental light irradiator, for example, by adding a fluorescent agent to a conventional photopolymerization dental surface coating material. Thus, the present invention has been completed by discovering that the coating state can be easily and clearly confirmed by exciting the fluorescent agent.

  That is, in the present invention, the (meth) acrylate monomer contains 1 to 30% by weight of inorganic fine particles having an average particle diameter of 1 to 100 nm, 0.1 to 3% by weight of a fluorescent agent, and 0.01 to 10% of a photopolymerization catalyst. It is a photopolymerization type dental surface covering material characterized by containing% by weight. In particular, the (meth) acrylate monomer is dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,3,5-tris (1,3- One or a combination of two or more selected from bis ((meth) acryloyloxy) -2-propoxycarbonylaminohexane) -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione Preferably it consists of. Further, as a fluorescent agent, diethyl-2,5-dihydroxyterephthalate, o-phthalaldehyde), (2,5-bis (5′-t-butylbenzoxazolyl-2 ′) thiophene, 2,5-bis ( 6,6′-bis (tert-butyl) -benzoxazol-2-yl) thiophene), (3-phenyl-7- (4-methyl-5-phenyl-1,2,3-triazol-2-yl) Coumarin, 3-phenyl-7- (2H-naphtho [1,2-d] -triazol-2-yl) coumarin), (N-methyl-5-methoxynaphthalimide), (4,4′-bis ( It is preferably composed of one or a combination of two or more selected from diphenyltriazinyl) stilbene, 4,4-bis (benzoxazol-2-yl) stilbene) and benzothiazole. A There photopolymerizable dental surface coating material.

  The photopolymerization type dental surface covering material according to the present invention is an excellent surface covering material capable of easily confirming the covering state even after the dental surface covering material is cured and becomes colorless and transparent.

  The inorganic fine particles having an average particle diameter of 1 to 100 nm used in the present invention are known composite oxides such as silica, silica-alumina, and silica-zirconia, and those whose surface is modified with alkoxysilane are particularly preferable.

  Alkoxysilanes can be silane compounds conventionally used in dental materials, and in particular 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacrylic. Loxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 2-methacryloxyethoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2methoxyethoxy ) Preferably, one or more selected from silanes.

  The inorganic fine particles having an average particle diameter of 1 to 100 nm used in the present invention must be blended in an amount of 1 to 30% by weight in the (meth) acrylate monomer. If it is less than 1% by weight, sufficient strength cannot be secured on the surface of the photopolymerization type dental surface coating material after curing, and if it exceeds 30% by weight, the viscosity of the photopolymerization type dental surface coating material becomes too high. Not. A more preferable blending amount is 5 to 15% by weight.

  In the photopolymerizable dental surface coating material according to the present invention, the (meth) acrylate monomer, which is a base material containing inorganic fine particles having an average particle diameter of 1 to 100 nm, has been conventionally used in dental materials. Any (meth) acrylate monomer that has been used can be used, but the volatile (meth) acrylate monomer in the entire photopolymerizable dental surface coating material is 15 to 70 in the (meth) acrylate monomer. When used in the range of% by weight, the volatile (meth) acrylate monomer on the surface of the coating film rapidly evaporates when the photopolymerizable dental surface coating material is applied to the surface of the dental resin material. It is preferable because the concentration of the photopolymerization initiator in the surface portion is increased, and the surface curability of the photopolymerizable dental surface coating material can be improved. If it is less than 15% by weight, the drying property and strength on the surface tend to be lowered, and if it exceeds 70% by weight, the curability of the surface tends to be lowered. (Meth) acrylate means acrylate and methacrylate.

  Examples of volatile (meth) acrylate monomers include dentistry such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2,2,2-trifluoroethyl acrylate, and 2,2,2-trifluoroethyl methacrylate. Conventionally used (meth) acrylates can be used. Among them, methyl methacrylate is most preferable in consideration of safety and volatility.

  In the photopolymerizable dental surface coating material according to the present invention, a polyfunctional (meth) acrylate monomer having 4 or more (meth) acryloyl groups in one molecule is used as the (meth) acrylate monomer. It is preferable to do. A polyfunctional (meth) acrylate monomer having 4 or more (meth) acryloyl groups in one molecule is a monomer having a plurality of (meth) acryloyl groups acting as a crosslinking agent, and a plurality of (meth) acryloyl groups It is preferable to select a monomer having as many polymerization reactive groups as possible from among monomers having at least four hydroxyl groups in one molecule such as pentaerythritol (meth) acrylate or dipentaerythritol (meth) acrylate. A polyfunctional (meth) acrylate monomer modified with an acrylate ester is preferred. Specifically, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,3,5-tris (1 1,3-bis ((meth) acryloyloxy) -2-propoxycarbonylaminohexane) -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione It is preferable that it is a seed or more, and in consideration of operability and safety, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,3,5- Tris (1,3-bis ((meth) acrylo Yloxy) -2-propoxycarbonylamino hexane) -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione is most preferred.

  The photopolymerizable dental surface coating material according to the present invention may contain a (meth) acrylate monomer having an adhesive functional group in the entire (meth) acrylate monomer. In this case, the directness to dental cement, dentine, dental metal, etc. having low adhesion to the light-curing dental surface coating material is improved. Examples of the (meth) acrylate monomer having an adhesive functional group include the alkoxysilane having the unsaturated double bond and the (meth) acrylate monomer having an acid group. As the (meth) acrylate monomer having an acid group, for example, a polymerization having an unsaturated group polymerizable with a carboxyl group, a phosphoric acid group, an acid anhydride residue, an acid amide group, etc., for example, an acryloyl group, a methacryloyl group, etc. Monomer, oligomer or polymer is preferred.

  Examples of the (meth) acrylate monomer 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-methacryloxytyrosine, N- (meth) acryloxyphenylalanine, N- (meth) acryloyl-p- Aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 4- (meth) acryloxyethyltri Merit acid, 4- (meth) acryloxybutyl trimellitic acid, 4- (meth) acryloxyhexyltri Lit acid, 4- (meth) acryloxydecyl trimellitic acid, 4-acryloxybutyl trimellitic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyl Oxybenzoic 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] phthalic acid , 5-[(2-hydroxy-3- (meth) acryloyloxyp Pyr) amino] isophthalic acid, 3- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid, 4- [N-methyl-N- (2-hydroxy-3) -(Meth) acryloyloxypropyl) amino] phthalic acid, maleic acid and the like are exemplified, and 4-acryloxyethyl trimellitic acid and 4-methacryloxyethyl trimellitic acid are particularly preferable.

  As the (meth) acrylate monomer containing a phosphoric acid group, for example, a phosphoric acid and a (meth) acrylate monomer containing a phosphonic acid group are suitable, for example, female (2- (meth) acryloxyethyl) phosphoric acid. (2- (meth) acryloxyethylphenyl) phosphoric acid, 10- (meth) acryloyloxydecyl dihydrodienphosphate, vinylphosphonic acid and para-vinylbenzylphosphonic acid. In addition, a (meth) acrylate monomer containing a thiophosphate group can also be used.

  Examples of the (meth) acrylate monomer containing an acid anhydride residue include 4- (meth) acryloxyethyl trimellitic anhydride, 6- (meth) acryloxyethyl naphthalene 1,2,6-tricarboxylic acid anhydride , 6- (meth) acryloxyethylnaphthalene 2,3,6-tricarboxylic anhydride, 4- (meth) acryloxyethylcarbonylpropionoyl 1,8-naphthalic anhydride, 4- (meth) acryloxy Ethyl naphthalene 1,8-tricarboxylic acid anhydride and the like. Two or more of these polymerizable compounds having an acid group may be used in combination as desired.

  The amount of the (meth) acrylate monomer having an adhesive functional group is preferably 0.1 to 10.0% by weight, more preferably 0.5 to 5%, based on the entire (meth) acrylate monomer. 0.0% by weight. If it is less than 0.1% by weight, the adhesiveness of the light-curing dental surface coating material is lowered, and if it exceeds 10.0% by weight, the curability of the surface of the light-curing dental surface coating material tends to be lowered. .

  As the fluorescent agent used in the present invention, those showing a fluorescent reaction with a dental light irradiator can be used. Specific examples include inorganic fluorescent pigments such as calcium tungstate, magnesium arsenate, barium silicate, Sulfides, silicates, phosphates, tungstates of alkaline earth metals such as calcium phosphate and zinc zinc phosphate; organic fluorescent pigments; organic fluorescent dyes such as phthalic acid derivatives (diethyl-2,5-dihydroxyterephthalate, o -Phthalaldehyde), thiophene derivatives (2,5-bis (5'-t-butylbenzoxazolyl-2 ') thiophene, 2,5-bis (6,6'-bis (tert-butyl) -benzoxazole -2-yl) thiophene), coumarin derivatives (3-phenyl-7- (4-methyl-5-phenyl-1,2, -Triazol-2-yl) coumarin, 3-phenyl-7- (2H-naphtho [1,2-d] -triazol-2-yl) coumarin), naphthalimide derivatives (N-methyl-5-methoxynaphthalimide) , Stilbene derivatives (4,4′-bis (diphenyltriazinyl) stilbene, 4,4′-bis (benzoxazol-2-yl) stilbene), benzothiazole derivatives, etc., among which phthalic derivatives and Thiophene derivatives are preferred.

  Since the blending amount is very small, there is almost no influence, but the fluorescent agent itself is preferably as colorless and transparent as possible. In this respect, the wavelength peak of the fluorescent agent is preferably 420 nm or less, and more preferably 320 to 400 nm. The content of the fluorescent agent is preferably 0.1 to 3% by weight, more preferably 0.5 to 2% by weight, in the (meth) acrylate monomer.

  The photopolymerizable dental surface coating material according to the present invention is a photopolymerization type and uses a known photopolymerization catalyst system. As the photopolymerization catalyst, a combination of a sensitizer and a reducing agent is generally used. The sensitizer includes camphorquinone, benzyl, diacetyl, benzyldimethyl ketal, benzyldiethyl ketal, benzyldi (2-methoxyethyl) ketal, 4, 4′-dimethylbenzyl-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- Rolo-7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, There are 4,4′-bisdiethylaminobenzophenone, acylphosphine oxides such as (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, compounds containing an azide group, etc., which can be used alone or in combination.

  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 Isoamyl acid is preferred. Other reducing agents include benzoyl peroxide, sodium sulfinate derivatives, organometallic compounds, and the like.

  The photopolymerization catalyst used by this invention is mix | blended 0.01 to 10weight% with respect to the whole composition. When the amount is less than 0.01% by weight, the polymerization curability is inferior. When the amount exceeds 10% by weight, the storage stability of the photopolymerizable dental surface coating material before use is lowered.

  The viscosity of the photopolymerizable dental surface coating material according to the present invention is desirably 5000 cP or less at 23 ° C. When the viscosity exceeds 5000 cP, not only the application operation to the surface of the dental material becomes difficult, but also the coating becomes thicker, or the strength of the surface after curing decreases. The viscosity is preferably low, and more preferably 100 cP or less.

  In addition, a colorant, a polymerization inhibitor, an ultraviolet absorber, an antibacterial agent, a fragrance and the like can be conveniently added to the photopolymerizable dental surface coating material according to the present invention.

Examples 1 to 5 and Comparative Examples Table 1 shows the formulations of Examples 1 to 5 and Comparative Examples. 0.5 parts by weight of camphorquinone, 0.25 parts by weight of methyl 4-dimethylaminobenzoate, with respect to 100 parts by weight of the total of (meth) acrylate monomer, inorganic fine particles, and fluorescent agent blended as shown in Table 1. After adding 0.5 parts by weight of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide and mixing, each photopolymerization type dental surface coating material was worn to confirm the remaining degree of coating.

<Confirmation of coating>
Photopolymerization type of each example and comparative example on a disk-like cured body (diameter: 15 mm, height: 1.5 mm) made with glass ionomer cement for filling and repairing (trade name: Fuji IILC, manufactured by GC Corporation) A dental surface coating material is applied uniformly and cured by light irradiation for 20 seconds with a dental light irradiator (trade name: Labolite LV-II, manufactured by GC Corporation), and then subjected to the following wear test and dental light irradiation. The state of the coating material on the surface of the specimen was visually observed. The results are summarized in Table 1.

The condition of the surface coating material was confirmed.
The condition of the surface coating material could not be confirmed ×

<Measurement of viscosity>
The viscosity was measured at room temperature (23 ° C.) using a B-type rotational viscometer. The results are summarized in Table 1.

<Table 1>

MMA: Methyl methacrylate AA: Acrylic acid DPE-6A: Dipentaerythritol hexaacrylate U6HA: 1,3,5-tris (1,3-bis ((meth) acryloyloxy) -2-propoxycarbonylaminohexane) -1, 3,5- (1H, 3H, 5H) triazine-2,4,6-trione DPE-4A: dipentaerythritol tetraacrylate 4-AETA: 4-acryloxyethyl trimellitic acid 10P: 10- (meth) acryloyloxy Decyl dihydrodiene phosphate

Claims (3)

  The (meth) acrylate monomer contains 1 to 30% by weight of inorganic fine particles having an average particle diameter of 1 to 100 nm, 0.1 to 3% by weight of a fluorescent agent, and 0.01 to 10% by weight of a photopolymerization catalyst. A photopolymerization type dental surface covering material.   The (meth) acrylate monomer is dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,3,5-tris (1,3-bis ( (Meth) acryloyloxy) -2-propoxycarbonylaminohexane) -1,3,5- (1H, 3H, 5H) consisting of one or a combination of two or more selected from triazine-2,4,6-trione The photopolymerizable dental surface coating material according to claim 1.   The fluorescent agent is diethyl-2,5-dihydroxyterephthalate, o-phthalaldehyde), (2,5-bis (5′-t-butylbenzoxazolyl-2 ′) thiophene, 2,5-bis (6, 6'-bis (tert-butyl) -benzoxazol-2-yl) thiophene), (3-phenyl-7- (4-methyl-5-phenyl-1,2,3-triazol-2-yl) coumarin, 3-phenyl-7- (2H-naphtho [1,2-d] -triazol-2-yl) coumarin), (N-methyl-5-methoxynaphthalimide), (4,4′-bis (diphenyltri) The compound according to claim 1 or 2, comprising one or a combination of two or more selected from azinyl) stilbene, 4,4-bis (benzoxazol-2-yl) stilbene), and benzothiazole. Photopolymerization type dental surface coating material of.