JP2014084301A - Tooth coloring method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tooth coloring method capable of forming a film having durability higher than before in a cosmetic tooth coloring method using manicure without scraping the tooth.SOLUTION: A tooth coloring method is characterized in that 0.01 to 10 pts.wt. of a photopolymerization catalyst and a photopolymerization type composition comprising a coloring material based on 100 pts.wt. of a substrate where 1 to 70 wt.% of an inorganic fine particle with an average particle diameter of 1 to 100 nm are comprised, in monodispersion state, in 15 to 70 wt.% of methyl (meth)acrylate and 15 to 70 wt.% of at least one kind selected from dipentaerythritolhexa(meth)acrylate, dipentaerythritolpenta (meth)acrylate, and 1,3,5-tris(1,3-bis((meth)acryloiloxy)-2-propoxycarbonylaminohexane)-1,3,5-(1H,3H,5H)triazine-2,4,6-trione is coated on a white spot of the tooth surface for photopolymerization.

Description

  The present invention relates to a cosmetic tooth coloring method for adjusting the color tone of a tooth having white spots and having deteriorated aesthetics.

  On the tooth surface in the oral cavity, decalcification in which calcium ions and phosphate ions are eluted from the tooth by acid produced by plaque bacteria, and re-incorporation of calcium ions and phosphate ions into the tooth. Calcification is repeated for a long period of time, and when the balance between the two is lost and the decalcification state continues for a long time, subsurface demineralization that is a non-axillary caries without substantial defect occurs. As this symptom progresses, it is clinically confirmed as a white spot on the enamel. This vitiligo can be repaired by applying a substance that promotes remineralization to the tooth surface because it is an initial caries (see, for example, Patent Documents 1 and 2).

  On the other hand, there are also vitiligo caused by excessive intake of fluorine for a long period of time or intake of a high concentration of fluorine during childhood. This vitiligo is a vitiligo caused by causes other than demineralization due to enamel hypoplasia, so it is difficult to repair by the above-described method. For this reason, repairs have been performed in which white spots are removed by cutting and filled with resin, or the entire tooth surface is cut and veneers are applied. However, it is not preferable to scrape a healthy tooth even though vitiligo is present.

  Then, the composition for whitening a tooth by applying a nail polish to the surface of a tooth, without shaving a tooth | gear, or adjusting the color tone of a tooth is developed (for example, refer patent documents 3-5). However, these compositions can easily change the color of the teeth, but since the durability of the composition after application to the tooth surface is low, it was necessary to frequently apply the nail polish.

JP 2005-145952 A JP 2008-195636 A Special table 2008-546844 JP 2010-083833 A International Publication No. 04/032884

  SUMMARY OF THE INVENTION An object of the present invention is to provide a tooth coloring method capable of forming a highly durable film in a cosmetic tooth coloring method using nail polish without shaving teeth. .

  As a result of intensive studies to solve the above problems, the present inventors have found that methyl (meth) acrylate is 15 to 70% by weight, 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) triazine-2,4,6-trione 1 to 70% by weight of inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified by an alkoxysilane having an unsaturated double bond is contained in at least one kind of 15 to 70% by weight. A photopolymerization type composition containing 0.01 to 10 parts by weight of a photopolymerization catalyst and a colorant is applied to 100 parts by weight of the base material on the white spots of the tooth surface and photopolymerized. When coloring method of a tooth, characterized in that, to complete the present invention have found that it is possible to solve the above problems.

  The tooth coloring method according to the present invention is an excellent tooth coloring method capable of forming a highly durable film.

  The method for coloring teeth according to the present invention is characterized in that a specific photopolymerization type composition shown below is applied onto the white spots on the tooth surface and photopolymerized. Although the application method is not limited, application with a brush is preferred because it is the simplest.

  In the composition used for the tooth coloring method according to the present invention, inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified with an alkoxysilane having an unsaturated double bond are used. This material can be used without particular limitation as the surface of a complex oxide such as silica, silica-alumina, silica-zirconia, etc., modified with alkoxysilane. Inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified by an alkoxysilane having an unsaturated double bond used in the composition used for the tooth coloring method according to the present invention are in a monodispersed state in the composition. Since it is necessary to be blended, for example, a raw material supplied in a monodispersed state in the production process of (meth) acrylate as disclosed in JP-A-7-291817 is used.

  Moreover, as the alkoxysilane having an unsaturated double bond used in the composition used in the method for coloring a tooth according to the present invention, a silane compound conventionally used in dental materials can be used, particularly 3-methacryloxy. Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane , 2-methacryloxyethoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane are preferable.

  The 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, must be blended in an amount of 1 to 70% by weight in (meth) acrylate. If it is less than 1% by weight, sufficient strength on the surface of the composition after curing cannot be secured, and if it exceeds 70% by weight, the viscosity of the composition becomes too high, which is not appropriate. A more preferable blending amount is 5 to 30% by weight.

  As a base material containing inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified with an alkoxysilane having an unsaturated double bond, when methyl (meth) acrylate is used, the composition is applied to the tooth surface, Volatile (meth) acrylate on the coating surface rapidly evaporates, resulting in an increase in the concentration of the photopolymerization initiator on the surface portion, and the surface curability of the composition can be improved.

  Methyl (meth) acrylate refers to methyl acrylate and / or methyl methacrylate. In view of safety, methyl methacrylate is most preferable. The amount of methyl (meth) acrylate used in the present invention is required to be 15 to 70% by weight in the composition in consideration of the drying property of the coated surface and the strength after curing. The drying property and strength on the surface are reduced, and if it exceeds 70% by weight, the surface curability is reduced.

  In the composition used for the tooth coloring method according to the present invention, methyl (meta) is used as a base material containing inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified with the above-mentioned alkoxysilane having an unsaturated double bond. In addition to acrylate), 15 to 70% by weight of polyfunctional (meth) acrylate having 4 or more (meth) acryloyl groups in one molecule is used in the composition. A polyfunctional (meth) acrylate 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 monomer having a plurality of (meth) acryloyl groups. Among them, it is preferable to select a monomer having as many polymerization reactive groups as possible. For example, polyfunctionality in which four or more hydroxyl groups are modified with (meth) acrylic acid ester in one molecule such as dipentaerythritol (meth) acrylate. (Meth) acrylate is preferred. Specifically, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,3,5-tris (1,3-bis ((meth) acryloyloxy) -2-propoxycarbonylaminohexane ) -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione.

  As a base material containing inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified by the above-mentioned alkoxysilane having an unsaturated double bond used in the tooth coloring method according to the present invention, further alkoxysilane or acid It is also possible to use 0.1 to 15% by weight of (meth) acrylate having a group. In this case, the adhesion to the tooth is improved. Examples of these (meth) acrylates include alkoxysilanes having the unsaturated double bond and (meth) acrylates having the following acid groups. The (meth) acrylate having an acid group is preferably a polymerizable monomer or oligomer having, for example, an acryloyl group or a methacryloyl group together with a carboxyl group, a phosphoric acid group, an acid amide group, or the like.

  Examples of the (meth) acrylate having a carboxyl group include (meth) acrylic acid, 1,4-di (meth) acryloxyethylpyromellitic 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-amino Benzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 4- (meth) acryloxyethyl trimellit Acid, 4- (meth) acryloxybutyl trimellitic acid, 4- (meth) acryloxyhexyl trimellitic acid, 4- (meth) acryloxydecylto Merit acid, 4- (meth) acryloxybutyl trimellitic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, 2-hydroxyethyl ( Addition product of (meth) acrylate and maleic anhydride, P-vinylbenzoic acid, O- (meth) acryloxytyrosine amide, 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) acryloyloxypropyl) amino] isophthalic acid, 3- [N-methyl-N- (2-hydroxy-3- (meth) acrylic Yl oxy propyl) amino] phthalic acid, 4-[N-methyl--N-(2-hydroxy-3- (meth) acryloyloxy propyl) amino] phthalic acid, and the like of these maleic acid. The (meth) acrylate having a carboxyl group also includes (meth) acrylate having an acid anhydride such as maleic anhydride as a carboxylic acid precursor.

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

  Examples of the (meth) acrylate 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) acryloxyethylnaphthalene 1 , 8-tricarboxylic acid anhydride and the like, and two or more polymerizable compounds having these acid groups may be used in combination as appropriate.

  The compounding quantity of alkoxysilane and the (meth) acrylate which has an acid group is 0.1 to 15 weight% in a composition, More preferably, it is 0.5 to 5 weight%. If it is less than 0.1% by weight, the adhesiveness of the composition is lowered, and if it exceeds 15% by weight, the curability of the surface of the composition tends to be lowered.

  The composition used for the tooth coloring method according to the present invention is a photopolymerization type, and a known photopolymerization catalyst system can be used. As a photopolymerization catalyst, a combination of a sensitizer and a reducing agent is generally used. Examples of the sensitizer include 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-trifluoro Tilthioxanthone, 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'-bis Examples include diethylaminobenzophenone, acylphosphine oxides such as (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, and compounds containing an azide group, 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 in the composition used in the method for coloring teeth according to the present invention is 0.01 to 10 parts by weight based on 100 parts by weight of the base material, which is the sum of the (meth) acrylates and the filler. Part by weight is blended. When the amount is less than 0.01 part by weight, sufficient curability cannot be obtained, and when the amount exceeds 10 parts by weight, the storage stability of the composition is lowered.

  The composition used for the tooth coloring method according to the present invention preferably has a viscosity of 5000 cP or less at 23 ° C. When the viscosity exceeds 5000 cP, not only the application operation to the tooth surface becomes difficult, but also the film becomes thick, or the strength of the surface after curing decreases. The viscosity is preferably low, and more preferably 100 cP or less.

<Raw material 1>
A silica-alumina methyl methacrylate monodispersed sol whose surface was modified with 3-methacryloxypropyltrimethoxysilane (average particle diameter 12 nm, silica-alumina concentration 20 wt%) was used.

<Raw material 2>
A silica methyl methacrylate monodispersed sol whose surface was modified with 3-methacryloxypropyltrimethoxysilane (average particle size of 80 nm, silica concentration of 20% by weight) was used.

<Raw material 3>
A silica / zirconia methyl methacrylate monodispersed sol whose surface was modified with 3-methacryloxypropyltrimethoxysilane (average particle size 30 nm, silica / zirconia concentration 20 wt%) was used.

Example 1
0.5 parts by weight of camphorquinone, 0.25 parts by weight of methyl 4-dimethylaminobenzoate, (2,4) with respect to 100 parts by weight of the mixture obtained by adding (meth) acrylate and inorganic fine particles described in Table 1 to the raw material , 6-Trimethylbenzoyl) diphenylphosphine oxide 0.5 parts by weight and a colorant were added and mixed, and then evaluated by the following method. Regarding the coloring material, referring to the method described in Japanese Patent Application Laid-Open No. 2010-083833, the color tone of the applied tooth was reproduced by appropriately mixing with one composition of each Example and Comparative Example.

The meanings of the symbols used in the table are as follows. * Indicates an acid group.
MMA: Methyl methacrylate MA: Methyl acrylate 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 3APT *: 3-acryloxypropyl Trimethoxysilane AA *: acrylic acid 3FE: 2,2,2-trifluoroethyl methacrylate

<Table 1>

<Evaluation of aesthetics>
A dental light irradiator (trade name: Labolite LV-II, manufactured by uniformly applying the composition of each example and each comparative example on the surface of a tooth having white spots of about 1 mm in length and about 0.7 mm in width. The surface was colored by irradiation with light for 20 seconds. The tooth surface after curing was visually observed to evaluate the conspicuousness of vitiligo.
Vitiligo is inconspicuous ○
Vitiligo stands out ×

<Curability of surface>
The teeth were colored using the compositions of Examples and Comparative Examples as in the evaluation of aesthetics. The cured tooth surface was visually observed to evaluate the curability of the composition.
There is no stickiness on the surface of the cured product ○
The surface of the cured product is not polymerized and is sticky ×

<Durability evaluation>
With respect to the teeth for which the aesthetic evaluation was performed, the surface properties of the teeth were visually observed after half a year, and the conditions were evaluated according to the following criteria. The results are summarized in Table 1.
The surface of the cured body is the same as during application and polymerization, and the white spots are not noticeable.
The composition on the surface of the cured product is peeled off and white spots are conspicuous ×

  All the examples gave good results. Comparative Examples 1 to 3 had low durability because inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface was modified with an alkoxysilane having an unsaturated double bond were not included in a monodispersed state. Since the specific polyfunctional (meth) acrylate was not contained in the comparative example 3, surface curability was bad and the curability of the sticky surface was low.

Claims (2)

  15% to 70% by weight of methyl (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) triazine-2,4,6-trione and at least one kind selected from 15 to 70% by weight and an unsaturated double bond The photopolymerization catalyst is added in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of a base material containing 1 to 70% by weight of inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified by alkoxysilane having A method for coloring a tooth, comprising applying a photopolymerization composition containing 10 parts by weight and a coloring material onto vitiligo on a tooth surface and performing photopolymerization.   15% to 70% by weight of methyl (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) triazine-2,4,6-trione and at least one kind selected from 15 to 70% by weight and an unsaturated double bond 1 to 70% by weight of inorganic fine particles having an average particle diameter of 1 to 100 nm whose surface is modified with an alkoxysilane having a monodispersed state, and at least selected from a carboxyl group, a phosphate group, and an acid amide group 0.01 to 10 parts by weight of a photopolymerization catalyst with respect to 100 parts by weight of a base material containing 0.1 to 15% by weight of (meth) acrylate having one, and A method for coloring a tooth, characterized in that a photopolymerization type composition containing a coloring material is applied onto a white spot on a tooth surface and photopolymerized.