CN101322676B - Dental coating kit - Google Patents

Abstract

The invention provides a dental coating kit with high adhesiveness to teeth that contains a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c) and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h); and a dental coating kit with high adhesiveness to teeth and minimally suffering from chipping and peeling off that contains a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c), a coating composition including a polymeric monomer (d) and a photopolymerization initiator (e), and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). Either dental coating kit is particularly useful as a kit for preventing stain and color return of a bleached tooth.

Description

Dental coating kit

This application is a divisional application of a national PCT application having application No. CN200380101030.1 (international application date: 10/6/2003) entitled "dental coating kit".

Technical Field

The present invention relates to a dental coating kit, and more particularly to a dental coating kit useful for preventing tooth staining and discoloration, and particularly to a dental coating kit useful for preventing staining and color regression (posterolateral り) of a bleached tooth.

Background

Teeth are colored or discolored due to the deposition of colored substances contained in tobacco, coffee, and the like or the propagation of chromogens. In general, it is desirable to prevent staining and discoloration of teeth and to expose white and beautiful teeth, which is especially strong among women than men. For this reason, in recent years, the number of patients who receive the following tooth bleaching treatment has been rapidly increasing among women, particularly young women.

The bleaching treatment of teeth is performed as part of beauty to make teeth white and beautiful, and also as a means to restore stained or discolored teeth to the original natural teeth. Bleaching agents containing hydrogen peroxide, carbamide peroxide, or the like as a main component are generally used in bleaching therapy. Bleaching agents have two functions: the bleaching action of the pigment deposited on the teeth and the action of making the surface of the teeth rough (roughened surface) are decomposed, causing diffuse scattering of light, thereby producing a white turbid feeling. By these two actions, the teeth can be made to appear white. The bleaching treatment is effective for improving the aesthetic appearance, but makes the tooth surface rough, so that plaque, protein, pigment, etc. are easily attached to the teeth after the bleaching treatment. Therefore, there is a need to control the intake of coffee, curry, citrus juices, and smoking, which are prone to staining, for a period of time after the bleaching treatment, especially 2-3 days after bleaching. Even with these dietary restrictions or smoking restrictions, teeth may stain for a short period of time. In addition, dental plaque, protein, pigment, and the like are gradually accumulated on teeth, and the tooth surface roughened by bleaching treatment is gradually and naturally restored by recalcification of saliva in the oral cavity, so that the bleaching color often returns to the color before bleaching treatment after about 6 months to 2 years after bleaching.

Conventionally, in order to suppress staining and color fading of teeth after bleaching, it has been proposed to use a coating composition for surface modification to teeth after bleaching treatment. As such a coating composition for surface modification, for example, a composition containing 10 to 80 wt% of a polyfunctional acrylate monomer, 20 to 80 wt% of a low boiling point solvent and 0.4 to 5 wt% of a visible light polymerization initiator is proposed in Japanese patent laid-open No. 2001-271009; further, Japanese patent application laid-open No. 2002-3327 proposes a composition comprising 10 to 80% by weight of a polyfunctional acrylate monomer, 20 to 80% by weight of a low boiling point solvent, 0.4 to 5% by weight of a visible light polymerization initiator, and 0.5 to 10% by weight of a white inorganic fine powder.

However, the above compositions all have poor adhesion to teeth. In order to eliminate this drawback, the following proposals have been made: each composition further contains 0.1 to 5% by weight of a phosphate-based adhesive monomer (see, for example, items 8, [0030] and [0031] in Japanese patent laid-open No. 2001-271009; and items 10, [0039] and [0040] in Japanese patent laid-open No. 2002-3327).

However, the results verified by the present inventors indicate that: even when a predetermined amount of the phosphate-based adhesive monomer is contained, the adhesion to teeth is hardly improved, and the surface curability is remarkably reduced, so that it is difficult to obtain a coating composition that can be practically used.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a dental coating kit which has excellent adhesion to teeth and is useful in preventing staining and discoloration of teeth.

Disclosure of Invention

In order to achieve the above object, a dental coating kit (hereinafter may be referred to as "kit 1") of the present invention has a primer composition containing an acidic group-containing polymerizable monomer (a), water (b), and a water-soluble solvent (c); the surface lubricating composition contains a polyfunctional polymerizable monomer (f), a volatile solvent (g), and a photopolymerization initiator (h).

The primer composition of the present invention is a substance generally called a self-etching primer, and penetrates into teeth while eroding, and exhibits excellent adhesion. Particularly, the penetration of the roughened tooth after bleaching is deep, and the excellent adhesion is shown. Since the primer composition can ensure adhesiveness to teeth, it is not necessary to add a phosphate-based adhesive monomer to the surface lubricating composition to be reused after the primer composition is used. When the phosphate-based adhesive monomer is not blended in the surface lubricating composition, not only the adhesion to the teeth is excellent by the primer composition, but also a kit having excellent surface curability can be obtained.

The primer composition of the present invention contains an acidic group-containing polymerizable monomer (a), water (b), and a water-soluble solvent (c).

The acidic group-containing polymerizable monomer (a) ensures adhesiveness to teeth. The acid group-containing polymerizable monomer (a) is a polymerizable monomer having an acid group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a carboxylic acid group or a sulfonic acid group, and having a polymerizable unsaturated group such as an acryloyl group, a methacryloyl group, a vinyl group or a vinylbenzyl group. Among them, a polymerizable monomer having an acryloyl group or a methacryloyl group as an unsaturated group is preferable.

The acid group-containing polymerizable monomer (a) is preferably one having a solubility of a calcium salt in water at 25 ℃ of 10% by weight or less, preferably 1% by weight or less, more preferably 0.1% by weight or less, because it is excellent in adhesion and acid resistance. Specific examples of the acidic group-containing polymerizable monomer (a) are given below. In the above description, some of the methacrylic groups and some of the acrylic groups are collectively referred to as (meth) acrylic groups, and some of the methacryloyl groups and the acryloyl groups are collectively referred to as (meth) acryloyl groups.

Examples of the polymerizable monomer containing a phosphoric acid group are: 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyloxydodecyl dihydrogen phosphate, 16- (meth) acryloyloxycetalkyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl phosphate, 4- (meth) acryloyloxybutyl phosphate, 5- (meth) acryloyloxyhexyl phosphate, 6- (meth) acryloyloxydecyl phosphate, 2- (meth) acryloyloxyeicosyl phosphate, 4- [2- (meth) acryloyloxyethyl ] cyclohexyloxyphosphate dihydrogenphosphate, bis [2- (meth) acryloyloxyethyl ] hydrogen phosphate, bis [3- (meth) acryloyloxypropyl ] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl ] hydrogen phosphate, bis [5- (meth) acryloyloxypentyl ] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl ] hydrogen phosphate, bis [7- (meth) acryloyloxyheptyl ] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl ] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl ] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl ] hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl phosphate, hydrogen phosphate, 2- (meth) acryloyloxyethyl hexyl phosphate hydride, 2' -bromooctyl 2- (meth) acryloyloxyethyl phosphate hydride, 2- (meth) acryloyloxyethoctyl phosphate hydride, 2- (meth) acryloyloxyethyl nonyl phosphate hydride, 2- (meth) acryloyloxyethyl decyl phosphate hydride, 2- (meth) acryloyloxybutyl decyl phosphate hydride, and (meth) acryloyloxyethyl phenyl phosphonate; 8-methacryloyloxy octyl 3-phosphonopropionate, 9-methacryloyloxy nonyl 3-phosphonopropionate, 10-methacryloyloxy decyl 3-phosphonopropionate, 6-methacryloyloxy octyl 3-phosphonoacetate, 10-methacryloyloxy decyl 3-phosphonoacetate; 2-methacryloyloxyethyl ester of hydrogenated phosphoric acid (4-methoxyphenyl), 2-methacryloyloxypropyl ester of hydrogenated phosphoric acid (4-methoxyphenyl), hydrophobic polymerizable monomer containing phosphoric acid groups described in Japanese patent application laid-open Nos. 52-113089, 53-67740, 53-69494, 53-144939, 58-128393 and 58-192891, and acid chlorides thereof. In addition, alkali metal salts (sodium salt, potassium salt, lithium salt, etc.) and ammonium salts of the respective phosphoric acid group-containing polymerizable monomers may be mentioned.

Examples of the pyrophosphate-based polymerizable monomer include: bis [2- (meth) acryloyloxyethyl ] pyrophosphate, bis [3- (meth) acryloyloxypropyl ] pyrophosphate, bis [4- (meth) acryloyloxybutyl ] pyrophosphate, bis [5- (meth) acryloyloxypentyl ] pyrophosphate, bis [6- (meth) acryloyloxyhexyl ] pyrophosphate, bis [7- (meth) acryloyloxyheptyl ] pyrophosphate, bis [8- (meth) acryloyloxyoctyl ] pyrophosphate, bis [9- (meth) acryloyloxynonyl ] pyrophosphate, bis [10- (meth) acryloyloxydecyl ] pyrophosphate, bis [12- (meth) acryloyloxydodecyl ] pyrophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

Examples of the thiophosphoric acid group-containing polymerizable monomer are: 2- (meth) acryloyloxyethyl dithiophosphate, 3- (meth) acryloyloxypropyl dithiophosphate, 4- (meth) acryloyloxybutyl dithiophosphate, 5- (meth) acryloyloxypentyl dithiophosphate, 6- (meth) acryloyloxyhexyl dithiophosphate, 7- (meth) acryloyloxyheptyl dithiophosphate, 8- (meth) acryloyloxyoctyl dithiophosphate, 9- (meth) acryloyloxynonyl dithiophosphate, 10- (meth) acryloyloxydecyl thiophosphate, and acid chlorides, alkali metal salts and ammonium salts thereof.

Examples of the carboxylic acid group-containing polymerizable monomer are: 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutoxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonyloxycarbonylphthalic acid and anhydrides thereof, 6- (meth) acryloylaminohexylcarboxylic acid, 8- (meth) acryloyloxyoctylcarboxylic acid, 9- (meth) acryloyloxy-1, 1-nonanedicarboxylic acid, 10- (meth) acryloyloxy-1, 1-decanedicarboxylic acid, 11- (meth) acryloyloxy-1, 1-undecanedicarboxylic acid, (meth) acrylic acid, maleic acid and acid chlorides, alkali metal salts and ammonium salts thereof.

Examples of the sulfonic acid group-containing polymerizable monomer are: sulfonic acid group-containing compounds such as 2- (meth) acrylamidoethylsulfonic acid, 3- (meth) acrylamidopropylsulfonic acid, 4- (meth) acrylamidobutylsulfonic acid, 6- (meth) acrylamidohexylsulfonic acid, 8- (meth) acrylamidooctylsulfonic acid, 10- (meth) acrylamidodecylsulfonic acid, and styrenesulfonic acid, and acid chlorides, alkali metal salts, and ammonium salts thereof.

Among the acidic group-containing polymerizable monomers (a), phosphoric group-containing polymerizable monomers are preferable because of their particularly excellent adhesion. Among these, phosphoric acid group-containing polymerizable monomers having an alkylene group having 6 to 25 carbon atoms and phosphoric acid group-containing polymerizable monomers having an alkyl group and/or a phenyl group are more preferable, and phosphoric acid group-containing polymerizable monomers having an alkylene group having 6 to 12 carbon atoms are most preferable.

The acid group-containing polymerizable monomer (a) may be used alone or in combination of two or more kinds as required. When the amount of the acid group-containing polymerizable monomer (a) is too small or too large, the adhesive strength to the teeth is lowered. The acid group-containing polymerizable monomer (a) is generally incorporated in an amount of 1 to 90% by weight, preferably 5 to 70% by weight, and more preferably 10 to 50% by weight, based on the total weight of the primer composition.

The water (b) enhances the decalcification power of the acid group-containing polymerizable monomer (a) for teeth. It is necessary to use water that does not substantially contain impurities that adversely affect the adhesion. Distilled water or ion-exchanged water is preferred. Too little or too much water (b) may reduce the bonding strength with the teeth. The amount of water (b) is generally from 0.1% to 90% by weight, preferably from 1% to 70% by weight, more preferably from 5% to 50% by weight, relative to the total weight of the primer composition.

The water-soluble solvent (c) can improve permeability to teeth. The acid group-containing polymerizable monomer (a) is soluble in a solvent having a solubility in water at 25 ℃ of 5% by weight or more, preferably 30% by weight, and more preferably soluble in water at any ratio. Examples of the water-soluble solvent (c) are: a water-soluble volatile solvent (c-1) having a boiling point at normal pressure of 150 ℃ or less, preferably 100 ℃ or less, a water-soluble solvent (c-2) having a boiling point at normal pressure of more than 150 ℃, and a water-soluble solvent (c-3) having a polymerizable unsaturated group and having a solubility in water at 25 ℃ of 10% by weight or more (hereinafter may be referred to as "hydrophilic polymerizable monomer (c-3)").

Examples of the water-soluble volatile solvent (c-1) are: ethanol, methanol, 1-propanol, isopropanol, acetone, methyl ethyl ketone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane and tetrahydrofuran.

Examples of the water-soluble solvent (c-2) are: dimethyl sulfoxide, ethylene glycol and polyethylene glycol.

Examples of the hydrophilic polymerizable monomer (c-3) include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acrylate, 2-trimethylaminoethyl (meth) acryloyl chloride, (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate (the number of oxyethylene groups is 9 or more).

Among the water-soluble solvents (c), the water-soluble volatile solvent (c-1) and the hydrophilic polymerizable monomer (c-3) are preferable. The water-soluble volatile solvent (c-1) is preferred because it can be easily volatilized by a dental handpiece. The hydrophilic polymerizable monomer (c-3) is preferable because it can be cured simultaneously with the acidic group-containing polymerizable monomer (a). Among the hydrophilic polymerizable monomers (c-3), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acrylate, 2, 3-dihydroxypropyl (meth) acrylate, and polyethylene glycol di (meth) acrylate (the number of oxyethylene groups is 9) are particularly preferable.

The water-soluble solvent (c) may be used alone or in combination of two or more kinds as required. Too little or too much water-soluble solvent (c) may reduce the permeability into teeth and the adhesive strength. The amount of the water-soluble solvent (c) is usually from 1% by weight to 98% by weight, preferably from 5% by weight to 90% by weight, more preferably from 10% by weight to 60% by weight, based on the total weight of the primer composition.

In order to improve the adhesion, mechanical strength and coatability of the primer composition, the primer composition may further contain a hydrophobic polymerizable monomer having a solubility in water at 25 ℃ of less than 10% by weight, preferably 1% by weight or less, in addition to the acid group-containing polymerizable monomer (a) and the hydrophilic polymerizable monomer (c-3). Examples of the hydrophobic polymerizable monomer are: esters such as α -cyanoacrylate, (meth) acrylate, α -halogenoacrylate, crotonate, cinnamate, sorbate, maleate, itaconate, (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives. Among them, (meth) acrylates are preferred.

Specific examples of (meth) acrylates are given below. Monomers having n (n ═ 1, 2, 3.) -olefinic double bonds are represented as n-functional monomers, and are classified into three types of monofunctional monomers, bifunctional monomers, and trifunctional monomers or more.

Monofunctional monomer:

methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2, 3-dibromopropyl (meth) acrylate, 3-methacryloxypropyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane.

Bifunctional monomer:

ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, 2-bis [4- (meth) acryloyloxyethoxyphenyl ] propane, 2-bis [4- (meth) acryloyloxypolyethoxyphenyl ] propane, 2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy ] phenyl ] propane, 1, 2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy ] ethane, 1, 2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, 2-bis [, [2, 2, 4-trimethylhexamethylene bis (2-carbamoyloxyethyl) ] dimethacrylate.

Trifunctional or higher monomer:

trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, N' - (2, 2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1, 3-diol ] tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

The hydrophobic polymerizable monomers may be used alone or in combination of two or more kinds as required. If the amount of the hydrophobic polymerizable monomer is too large, the permeability to the teeth and the adhesive strength may be reduced. The amount of the hydrophobic polymerizable monomer is usually 70% or less based on the total weight of the primer composition. Preferably 50% by weight or less, more preferably 30% by weight or less.

In order to improve the adhesion, a photopolymerization initiator and/or a chemical polymerization initiator may be blended in the primer composition. Examples of the photopolymerization initiator are: alpha-diketones, ketals, thioxanthones, acylphosphine oxides, alpha-aminoacetophenones.

Examples of α -diketones are: camphorquinone, benzil, 2, 3-pentanedione.

Examples of ketals are: benzyl dimethyl aldehyde acetophenone and benzyl diethyl aldehyde acetophenone.

Examples of thioxanthones are: 2-chlorothioxanthone, 2, 4-diethylthioxanthone.

Examples of acylphosphine oxides are: 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (benzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) phenylphosphine oxide, tris (2, 4-dimethylbenzoyl) phosphine oxide, tris (2-methoxybenzoyl) phosphine oxide, 2, 6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2, 3, 5, 6-tetramethylbenzoyldiphenylphosphine oxide, benzoylbis- (2, 6-dimethylphenyl) phosphonate, 2, 4, 6-trimethylbenzoylethoxyphenylphosphine oxide, and a water-soluble acylphosphine oxide compound disclosed in Japanese examined patent publication No. Hei 3-57916.

Examples of α -aminoacetophenones are: 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -acetone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -acetone-1, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1.

The photopolymerization initiator may be used alone or in combination of two or more kinds as required. The amount of the photopolymerization initiator is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and most preferably 0.1 to 5% by weight, based on the total weight of the polymerizable monomers in the primer composition.

The photopolymerization initiator may be used alone or in combination with a polymerization accelerator such as a tertiary amine, an aldehyde, or a compound having a thiol group to accelerate photocuring.

Examples of tertiary amines are: 2-dimethylaminoethyl (meth) acrylate, N-bis [ (meth) acryloyloxyethyl ] -N-methylamine, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone, N-bis (2-hydroxyethyl) -p-toluidine.

Examples of aldehydes are: dimethylaminobenzaldehyde, terephthalaldehyde.

Examples of compounds having a thiol group are: 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane and thiobenzoic acid.

The polymerization accelerator may be used alone or in combination of two or more kinds as required. The amount of the polymerization accelerator to be blended is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and most preferably 0.1 to 5% by weight, based on the total weight of the polymerizable monomers in the primer composition.

The chemical polymerization initiator is preferably a redox-type polymerization initiator containing an oxidizing agent and a reducing agent. When a redox polymerization initiator is used, it is necessary to separate the packaging form of the primer composition into 2 parts or more in order to isolate the oxidizing agent and the reducing agent.

Examples of oxidizing agents are: organic peroxides such as diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides.

Specific examples of diacyl peroxides are: benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, m-toluoyl peroxide. Specific examples of the peroxyesters include t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate. Specific examples of dialkyl peroxides are: dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide. Specific examples of peroxyketals are: 1, 1-di (tert-butylperoxy) -3, 3, 5-trimethylcyclohexane. Specific examples of ketone peroxides are: methyl ethyl ketone peroxide, cyclohexanone peroxide and methyl acetoacetate peroxide. Specific examples of hydroperoxides are: t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene peroxide.

The reducing agents are preferably tertiary aromatic amines, tertiary aliphatic amines and sulfinic acids and salts thereof.

Examples of aromatic tertiary amines are: n, N-dimethylaniline, N-dimethyl-p-toluidine, N-dimethyl-m-toluidine, N-diethyl-p-toluidine, N-dimethyl-3, 5-dimethylaniline, N-dimethyl-3, 4-dimethylaniline, N-dimethyl-4-ethylaniline, N-dimethyl-4-isopropylaniline, N-dimethyl-4-t-butylaniline, N-dimethyl-3, 5-di-t-butylaniline, N-bis (2-hydroxyethyl) -3, 5-dimethylaniline, N-bis (2-hydroxyethyl) -p-toluidine, N-dimethyl-3, 5-dimethylaniline, N, N-bis (2-hydroxyethyl) -3, 4-dimethylaniline, N-bis (2-hydroxyethyl) -4-ethylaniline, N-bis (2-hydroxyethyl) -4-isopropylaniline, N-bis (2-hydroxyethyl) -4-tert-butylaniline, N-bis (2-hydroxyethyl) -3, 5-diisopropylaniline, N-bis (2-hydroxyethyl) -3, 5-dibutylaniline, ethyl 4-dimethylaminobenzoate, N-butoxyethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (2-methacryloyloxy) ester.

Examples of aliphatic tertiary amines are: trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-N-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2-dimethylamino ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, and triethanolamine trimethacrylate.

Examples of sulfinic acids and salts thereof are: benzene sulfinic acid, sodium benzene sulfinate, potassium benzene sulfinate, calcium benzene sulfinate, lithium benzene sulfinate, toluene sulfinic acid, sodium toluene sulfinate, potassium toluene sulfinate, calcium toluene sulfinate, lithium toluene sulfinate, 2, 4, 6-trimethyl benzene sulfinic acid, sodium 2, 4, 6-trimethyl benzene sulfinate, potassium 2, 4, 6-trimethyl benzene sulfinate, calcium 2, 4, 6-trimethyl benzene sulfinate, lithium 2, 4, 6-trimethyl benzene sulfinate, 2, 4, 6-triethyl benzene sulfinic acid, sodium 2, 4, 6-triethyl benzene sulfinate, potassium 2, 4, 6-triethyl benzene sulfinate, calcium 2, 4, 6-triethyl benzene sulfinate, 2, 4, 6-triisopropylbenzene sulfinic acid, sodium 2, 4, 6-triisopropylbenzene sulfinate, potassium, Calcium 2, 4, 6-triisopropylbenzene sulfinate.

The oxidizing agent and the reducing agent may be used alone or in combination of two or more, as required. The amount of the oxidizing agent and the reducing agent is preferably 0.01 to 10 wt%, more preferably 0.05 to 7 wt%, and most preferably 0.1 to 5 wt%, based on the total weight of the polymerizable monomers in the primer composition.

In order to adjust the coating property, the fluidity, and the like of the primer composition, a filler may be mixed therein. The filler may be an inorganic filler, an organic filler, or an inorganic/organic composite filler.

The inorganic filler is preferably silica, kaolin, clay, mica, or any combination thereofMineral with silicon oxide as base material, and preparation method thereof₂O₃、B₂O₃、TiO₂、ZrO₂、BaO、La₂O₃、SrO₂、CaO、P₂O₅And the like. Specific examples of the glass are lanthanum glass, barium glass, strontium glass, sodium glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, bioglass. In addition, crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconium oxide, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride are also preferable.

Examples of the organic filler include: polymethyl methacrylate, polyfunctional methacrylate polymers, polyamides, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, styrene-butadiene rubber.

Examples of inorganic/organic composite fillers are: a filler obtained by dispersing an inorganic filler in an organic filler, and a filler obtained by coating the surface of an inorganic filler with various polymerizable monomers.

In order to adjust the fluidity of the primer composition or improve the coating property thereof, the filler may be previously surface-treated with a known surface treatment agent such as a silane coupling agent and then mixed into the primer composition. Examples of the surface treatment agent used at this time are: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane.

The filler may be used alone or in combination of two or more kinds as required. The filler is generally incorporated in an amount of 50% by weight or less, preferably 30% by weight or less, relative to the total weight of the primer composition. When the amount exceeds 50% by weight, the permeability or adhesiveness to teeth is lowered.

In addition, in order to increase the decalcifying power of the primer composition to the teeth, an acid having a pKa smaller than that of the acid group-containing polymerizable monomer (a) and having no polymerizable group may be mixed into the primer composition. Examples of the acid include inorganic acids such as phosphoric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid, citric acid, trichloroacetic acid and p-toluenesulfonic acid. However, excessive mixing of these acids having no polymerizable group may cause damage to dentin, elution after use, or decrease the adhesion of the primer composition to teeth. Therefore, the amount of the acid is usually preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the primer composition.

The primer composition may contain a polymerization inhibitor, a coloring agent, a fluorescent agent, an ultraviolet absorber, etc. In order to have antibacterial properties, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxydodecylpyribromide, (meth) acryloyloxycetadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan may be mixed.

The surface lubricating composition of the present invention contains a polyfunctional polymerizable monomer (f), a volatile solvent (g), and a photopolymerization initiator (h).

As the polyfunctional polymerizable monomer (f), a hydrophobic polymerizable monomer having two or more ethylenic double bonds can be used. The hydrophobic polymerizable monomer may be the same as the bifunctional polymerizable monomer or the trifunctional or higher polymerizable monomer of the (meth) acrylate described above, which is mixed as an optional component in the primer composition. From the viewpoint of surface curability, polymerizable monomers having three or more ethylenic double bonds such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable, and polymerizable monomers having five or more ethylenic double bonds such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are particularly preferable. The polyfunctional polymerizable monomer (f) preferably contains 70% by weight or more, more preferably 80% by weight or more, of a polymerizable monomer having three or more ethylenic double bonds based on the total weight of the polyfunctional polymerizable monomer (f).

The amount of the polyfunctional polymerizable monomer (f) is preferably 40 to 98 wt%, and more preferably 80 to 95 wt%, based on the total weight of the surface lubricating composition. If the amount is less than 40 wt%, the coating properties and handling properties of the surface lubricating composition may be reduced.

The volatile solvent (g) dilutes the polyfunctional polymerizable monomer (f) to improve the coatability or workability of the surface lubricating composition. The boiling point of the volatile solvent (g) is preferably 150 ℃ or less, more preferably 100 ℃ or less, at normal pressure. When the volatile solvent (g) having a boiling point at normal pressure exceeding 150 ℃ is used, the surface curability of the surface lubricating composition may be reduced. Examples of volatile solvents (g) are: alcohols such as ethanol, methanol, 1-propanol and isopropanol, ketones such as acetone, methyl ethyl ketone and diethyl ketone, ethers such as 1, 2-dimethoxyethane, 1, 2-diethoxyethane and tetrahydrofuran, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate and butyl acetate, and (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and isopropyl (meth) acrylate. Among them, the (meth) acrylates are preferable from the viewpoint of being curable simultaneously with the polyfunctional polymerizable monomer (f), and methyl methacrylate is particularly preferable from the viewpoint of low toxicity and low boiling point.

The volatile solvent (g) may be used alone or in combination of two or more if necessary. The amount of the volatile solvent (g) is preferably 1 to 59% by weight, more preferably 5 to 50% by weight, and most preferably 10 to 40% by weight, with respect to the total weight of the surface lubricating composition, from the viewpoint of coatability or workability. When the amount exceeds 59% by weight, the surface lubricating composition tends to have too high fluidity, to deteriorate workability and coatability, and to have a strong odor during curing.

The photopolymerization initiator (h) may be the same as the above-mentioned photopolymerization initiator mixed as an optional component in the primer composition. Preference is given to alpha-diketones and acylphosphine oxides. 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide is more preferable in view of light color of the initiator itself and less yellowing after curing.

The photopolymerization initiator (h) may be used alone or in combination of two or more kinds as required. The amount of the photopolymerization initiator (h) is preferably 0.01 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the polymerizable monomers in the surface lubricating composition. The photopolymerization initiator (h) may be used alone, but may be used in combination with a polymerization accelerator in order to accelerate curability. The polymerization accelerator may be the same compound as the polymerization accelerator described above mixed as an optional component in the primer composition. The amount of the polymerization accelerator to be blended is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and most preferably 0.1 to 5% by weight, based on the total weight of the polymerizable monomers in the surface lubricating composition.

Pigments may be mixed in the surface lubricating composition as necessary. By mixing pigments, the hue of the resulting coating can be adjusted. Examples of such pigments are: red iron oxide, phthalocyanine blue, various azo pigments, and titanium oxide. For example, by mixing titanium oxide with the surface lubricating composition to form a composition having a covering property, the beauty of teeth can be enhanced. The pigment may be used alone or in combination of two or more kinds as required. The amount of the pigment blended may be appropriately adjusted in consideration of the color tone and the aesthetic appearance of the coating layer.

A filler may be mixed in the surface lubricating composition as necessary. The filler may be the same as the filler already described as an optional component to be mixed in the primer composition. The filler may be used alone or in combination of two or more kinds as required. The amount of the filler blended is preferably 40 wt% or less, more preferably 20 wt% or less, with respect to the total weight of the surface lubricating composition. If the amount exceeds 40 wt%, the coating property or handling property of the surface lubricating composition may be lowered. The filler is usually an ultrafine particulate filler having an average particle diameter of 0.001 μm to 50 μm, and preferably 0.001 μm to 0.1 μm in order to effectively suppress precipitation of the pigment when the pigment is mixed in the surface lubricating composition. The ultrafine particulate filler is preferably colloidal silica (e.g., japan アエロジル corporation, trade name "アエロジル"). A polymerization inhibitor, a fluorescent agent, an ultraviolet absorber, and the like may be added to the surface lubricating composition as necessary.

In preparing the surface lubricating composition, it is preferable to appropriately select and adjust each component so as to have an appropriate viscosity. From the viewpoint of coatability and workability, the viscosity of the surface lubricating composition at 30 ℃ is preferably 30cP to 3,000cP, more preferably 50cP to 1,000cP, and most preferably 80cP to 500 cP. When the viscosity is less than 30cP, the fluidity is too high, and the adhesive can permeate into gaps between adjacent teeth when being used for teeth; on the other hand, if it exceeds 3,000cP, the coatability may be deteriorated.

The 1 st kit is particularly effective in preventing staining and color reversion of teeth after bleaching. Hereinafter, a method of using the kit 1 will be described by taking a case of coating a bleached tooth as an example.

First, a primer composition is applied to the surface of a bleached tooth, and the primer composition is dried, if necessary, using a dental handpiece (air system) or the like until it does not have fluidity; or when the primer composition contains a polymerization initiator (photopolymerization initiator and/or chemical polymerization initiator), the coating layer is polymerized and cured to form a primer layer (step 1).

Next, a surface lubricating composition is applied to the primer layer, and the applied surface lubricating composition is irradiated with light to be polymerized and cured, thereby forming a surface layer on the bleached tooth surface (step 2). When the primer composition contains a photopolymerization initiator, the primer composition and the surface lubricating composition can be simultaneously polymerized and cured by light irradiation.

The surface lubricating composition is preferably applied at a thickness of 0.005mm to 0.5mm, more preferably 0.01mm to 0.3 mm. Examples of suitable light sources for light irradiation include: xenon lamps, halogen lamps, mercury lamps, light-emitting diodes. The irradiation time of light is related to the wavelength and the amount of light. If a special dental irradiator is used, the curing time can be about 3 seconds to 3 minutes. When a coating is formed on a bleached tooth and a problem occurs due to partial or total peeling of the coating from the surface of the tooth or staining, a dental instrument such as a dental scaler is used to peel off the problematic portion and the like, and then the coating is used again on the surface of the tooth. By repeating such treatments, staining of the bleached teeth and color reversion of the bleached teeth can be effectively prevented.

The 1 st kit is useful for a tooth in which a part of the tooth is restored with a crown restoration material such as a metal, a ceramic material, a ceramic, a cured product of a composite material, or the like. The kit 1 may be used alone or in combination with commercially available dental metal primers, ceramic material-bonding primers, and a tooth surface cleaner such as hypochlorite.

As described above, in the kit 1, since the primer composition can secure adhesiveness to the teeth, a coating layer having good adhesiveness to the teeth can be formed.

However, in the kit 1, since the layer (surface layer) formed of the surface lubricating composition is hard and brittle, peeling (a phenomenon in which a part of the coating is slightly broken and peeled) or cracking of the coating is likely to occur due to stress at the time of occlusion or the like.

Another dental coating kit (hereinafter, may be referred to as "kit 2") of the present invention is invented to solve the above-mentioned problems of the kit 1.

Namely, kit 2 has a primer composition, a coating composition, a surface lubricating composition; wherein the primer composition comprises an acidic group-containing polymerizable monomer (a), water (b), and a water-soluble solvent (c); the coating composition contains a polymerizable monomer (d) and a photopolymerization initiator (e); the surface lubricating composition contains a polyfunctional polymerizable monomer (f), a volatile solvent (g), and a photopolymerization initiator (h).

The primer composition and the surface lubricity composition possessed by kit 2 were the same as those possessed by kit 1 already described.

Therefore, a coating composition unique to only the kit No. 2 will be described below.

The coating composition is a composition for forming an intermediate layer between a layer formed of a primer composition (primer layer) and a layer formed of a surface lubricating composition (surface layer). The intermediate layer functions as a cushion layer for preventing the outermost layer formed of the surface lubricating composition from peeling and cracking.

The coating composition contains a polymerizable monomer (d) and a photopolymerization initiator (e).

The polymerizable monomer (d) is not particularly limited as long as it is a polymerizable monomer capable of forming an intermediate layer on the surface of the primer layer. The polymerizable monomer (d) may be appropriately selected in consideration of the viscosity of the obtained coating composition, the polymerizability, the strength of the obtained coating layer, and the like. Since the coating composition (II) may have reduced coatability, flowability, workability, and the like if the content of the polymerizable monomer (d) is too large, it is preferably 40 to 99.99% by weight, and more preferably 60 to 99.95% by weight, based on the total weight of the coating composition.

The polymerizable monomer (d) may be used alone or in combination of two or more if necessary. Among them, the use of a hydrophilic polymerizable monomer in combination with a hydrophobic polymerizable monomer provides a coating layer which has excellent wettability and permeability to teeth and is effective as a buffer layer having high toughness after polymerization and curing.

The hydrophilic polymerizable monomer not only improves wettability and permeability to teeth, but also improves toughness of the resulting coating. The hydrophilic polymerizable monomer is mixed to improve toughness, because the coating layer containing the hydrophilic polymerizable monomer absorbs water and swells in a wet environment in the oral cavity after polymerization and curing. The hydrophilic polymerizable monomer herein means a polymerizable monomer having a solubility in water at 25 ℃ of 10% by weight or more. The hydrophilic polymerizable monomer is preferably a polymerizable monomer having a solubility of 30% by weight or more.

Specific examples of the hydrophilic polymerizable monomer include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acrylate, 2-hydroxypropyl-1, 3-di (meth) acrylate, 3-hydroxypropyl-1, 2-di (meth) acrylate, pentaerythritol di (meth) acrylate, 2-trimethylammonioethyl (meth) acryloyl chloride, (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate (the number of oxyethylene groups is 9 or more). Among them, 2-hydroxyethyl methacrylate is preferable.

The hydrophilic polymerizable monomer may be used alone or in combination of two or more kinds as necessary. The amount of the hydrophilic polymerizable monomer is preferably 5 to 50 wt% based on the total weight of the coating composition. When the amount is less than 5% by weight, the wettability of the coating composition and the toughness of the resulting cured product tend to be lowered; if the amount exceeds 50% by weight, the strength of the resulting cured product may be lowered. The compounding amount is more preferably 5% by weight to 40% by weight, most preferably 10% by weight to 35% by weight.

Hydrophobic polymer monomers can improve adhesion, mechanical strength, and coatability. The hydrophobic polymerizable monomer herein means a polymerizable monomer having a solubility in water of less than 10% by weight at 25 ℃. The hydrophobic polymerizable monomer is preferably a polymerizable monomer having a solubility of 1 wt% or less.

Specific examples of the hydrophobic polymerizable monomer include: esters such as (meth) acrylate, α -cyanoacrylate, α -halogenoacrylate, crotonate, cinnamate, sorbate, maleate, itaconate, and compounds having a polymerizable unsaturated group such as (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, and styrene derivatives. Among them, (meth) acrylates are preferred. The (meth) acrylate may be the same as the (meth) acrylate already described as an optional component contained in the primer composition.

The kind of the hydrophobic polymerizable monomer may be appropriately selected in consideration of the viscosity, polymerizability, and the like of the coating composition. The hydrophobic polymerizable monomers may be used alone or in combination of two or more kinds as required. From the viewpoint of polymerizability, a bifunctional or higher monomer is preferable. When the amount of the hydrophobic polymerizable monomer is too small, coatability, flowability, workability, and the like of the coating composition may be deteriorated. The amount of the hydrophobic polymerizable monomer is preferably 20 to 90% by weight, more preferably 40 to 80% by weight, based on the total weight of the coating composition.

By mixing a polymerizable monomer (acidic group-containing polymerizable monomer) having one or more acidic groups such as phosphoric acid group, pyrophosphoric acid group, thiophosphoric acid group, carboxylic acid group, or sulfonic acid group and having a polymerizable unsaturated group such as acryloyl group, methacryloyl group, vinyl group, or styryl group as the polymerizable monomer (d), adhesiveness to teeth can be further improved. From the viewpoint of adhesiveness, the acid group-containing polymerizable monomer preferably has a solubility of calcium salt in water at 25 ℃ of 10 wt% or less, more preferably 1 wt% or less, and most preferably 0.1 wt% or less. The acid group-containing polymerizable monomer may be the same as the above-mentioned acid group-containing polymerizable monomer (a) contained as an essential component in the primer composition. The acid group-containing polymerizable monomer is preferably a polymerizable monomer having a phosphoric acid group because of its excellent adhesion. Among these, phosphoric acid group-containing polymerizable monomers having an alkylene group having 6 to 25 carbon atoms, an alkyl group and/or a phenyl group are more preferable, and phosphoric acid group-containing polymerizable monomers having an alkylene group having 6 to 12 carbon atoms are most preferable.

The acid group-containing polymerizable monomer may be used alone or in combination of two or more kinds as required. Since the acidic group-containing polymerizable monomer may decrease the polymerizability (surface curability) of the coating composition if it is too much, the amount of the acidic group-containing polymerizable monomer is preferably 0.1 to 30% by weight, more preferably 0.1 to 20% by weight, based on the total weight of the coating composition.

As the photopolymerization initiator (e) contained in the coating composition, a known photopolymerization initiator can be used. The photopolymerization initiator (e) may be the same compound as the photopolymerization initiator contained as an optional component in the primer composition, for example. The photopolymerization initiator may be used alone or in combination of two or more kinds as required. The amount of the photopolymerization initiator (e) is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, and most preferably 0.1 to 5% by weight, based on the polymerizable monomer (d).

In order to promote photocurability, the photopolymerization initiator (e) may be used in combination with a polymerization accelerator. Examples of the polymerization accelerator include the tertiary amines, aldehydes, and compounds having a thiol group, which are contained as optional components in the primer composition. These compounds may be used alone or in combination of two or more if necessary. The content of the polymerization accelerator is preferably 0.01 wt% to 10 wt%, more preferably 0.05 wt% to 7 wt%, most preferably 0.1 wt% to 5 wt%, relative to the total weight of the coating composition.

If necessary, the photopolymerization initiator (e) may be used in combination with a chemical polymerization initiator. By using a chemical polymerization initiator in combination, the polymerizability inside the coating layer, which is difficult to reach due to light and difficult to photopolymerize, can be improved. The chemical polymerization initiator is preferably a chemical polymerization initiator of a redox system containing an oxidizing agent and a reducing agent. As described above, when the chemical polymerization initiator of redox system is used, it is necessary to separate the packaging form of the coating composition into 2 parts or more and to separate the oxidizing agent and the reducing agent. The oxidizing agent and the reducing agent may be the same as those described above as the oxidizing agent and the reducing agent contained as optional components in the primer composition.

The oxidizing agent and the reducing agent may be used alone or in combination of two or more kinds as required. The amount of the oxidizing agent and the reducing agent is preferably 0.01 to 10 wt%, more preferably 0.05 to 7 wt%, and most preferably 0.1 to 5 wt%, based on the total weight of the polymerizable monomers in the coating composition.

An inorganic filler having a refractive index of 1.9 or more may be added to the coating composition. The refractive index as used herein means a refractive index measured at 20 ℃ with light having a wavelength of 589.3 nm. The inorganic filler having a refractive index of 1.9 or more is extremely useful in improving the appearance, because it not only thins the surface unpolymerized layer after polymerization and curing to improve the surface curability of the coating layer, but also covers the discoloration of teeth to improve the brightness of the coating layer. From the viewpoint of improving the surface curability and the aesthetic appearance, an inorganic filler having a refractive index of 2.1 or more is preferable. When the refractive index is less than 1.9, surface curability may be reduced. Examples of the inorganic filler having a refractive index of 1.9 or more are: titanium oxide (refractive index: 2.49-2.90), zirconium oxide (refractive index: 2.13-2.19), zinc oxide (refractive index: 2.00-2.02). The average particle diameter of the inorganic filler having a refractive index of 1.9 or more is preferably 0.01 μm to 100. mu.m, more preferably 0.1 μm to 80 μm. The reason why the unpolymerized layer becomes thin on the surface after polymerization and curing is not clear, but the present inventors have found the following.

That is, in general, when a polymerizable monomer is polymerized using a photopolymerization initiator, oxygen present in the air acts as a polymerization inhibitor, and as a result, an unpolymerized layer having a thickness of the order of micrometers is formed on the surface portion of the coating layer which is in contact with the air. However, when a small amount of an opaque inorganic filler (corresponding to a pigment) having a refractive index of 1.9 or more is contained in the coating layer, the inorganic filler diffusely reflects light incident on the coating layer (light irradiated at the time of initiation of polymerization), and the polymerizability of the surface portion is improved by the light scattering effect, so that the surface unpolymerized layer after polymerization and curing becomes thin.

One kind of the inorganic filler having a refractive index of 1.9 or more may be used alone, or two or more kinds may be used in combination as required. The amount of the inorganic filler having a refractive index of 1.9 or more is preferably 0.1 to 50% by weight based on the total weight of the coating composition. When the blending amount is less than 0.1% by weight, the surface curability tends to be lowered; when the amount exceeds 50% by weight, the curing depth tends to be shallow and the composition tends not to be cured sufficiently inside only by using the photopolymerizable catalyst. More preferably, the amount is 0.1 to 10% by weight, and most preferably, 0.1 to 5% by weight.

In order to suppress the sedimentation of the inorganic filler having a refractive index of 1.9 or more and improve the mechanical strength, coatability, accessibility from a container, handling properties and the like, other fillers may be used in combination. The fillers used in combination with the inorganic filler having a refractive index of 1.9 or more are: an inorganic filler, an organic filler and an inorganic/organic composite filler having a refractive index of less than 1.9. The inorganic filler, the organic filler, and the inorganic/organic composite filler may be the same as those mentioned above for the inorganic filler, the organic filler, and the inorganic/organic composite filler, which are mixed as optional components in the primer composition.

The filler used in combination with the inorganic filler having a refractive index of 1.9 or more may be used alone, or two or more thereof may be used in combination as required. The amount of the filler used in combination with the inorganic filler having a refractive index of 1.9 or more is preferably 60% by weight or less, and more preferably 40% by weight or less, based on the total weight of the coating composition. The average particle diameter of the filler used in combination with the inorganic filler having a refractive index of 1.9 or more is preferably 0.001 μm to 50 μm. In order to suppress the sedimentation of the filler having a refractive index of 1.9 or more and improve the coatability and workability, colloidal silica having an average particle diameter of 0.001 μm to 0.1 μm may be preferably mixed in an amount of 1 wt% to 40 wt%, more preferably 3 wt% to 35 wt%, most preferably 5 wt% to 30 wt% based on the total weight of the coating composition. Examples of such colloidal silica are: silica having a small particle diameter obtained by a spray pyrolysis method (for example, japanese アエロジル, trade name "アエロジル"), silica sol obtained by a wet method, and monodisperse silica obtained by a sol-gel method.

In order to improve the mechanical strength, coatability, workability, fluidity, etc. of the coating composition, the inorganic filler having a refractive index of 1.9 or more and the filler used in combination therewith may be subjected to surface treatment in advance with a known surface treatment agent such as a silane coupling agent and then used. The surface treatment agent may be the same as the surface treatment agent for filler which has been described above and is mixed as an optional component in the primer composition.

Pigments may be mixed in the coating composition. By mixing pigments, the hue of the resulting coating can be adjusted. Examples of pigments are: iron oxide red, phthalocyanine blue, and various azo pigments. The pigment may be used alone or in combination of two or more kinds as required. The amount of the pigment blended is not particularly limited, and may be appropriately mixed in consideration of the color tone and the aesthetic quality of the coating composition.

The coating composition may contain a fluorine ion releasing substance. By mixing the fluoride ion-releasing substance, the tooth surface can be provided with acid resistance. Examples of the fluoride ion releasing substance are: fluorine glass such as fluoroaluminosilicate glass, metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride and ytterbium fluoride, fluorine ion-releasing polymers such as a copolymer of methyl methacrylate and methacryloyl fluoride disclosed in Japanese patent laid-open No. 5-85912, and hexadecylamine hydrofluoride.

The coating composition may contain a polymerization inhibitor, a fluorescent agent, and an ultraviolet absorber. In order to have antibacterial properties, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth) acryloyloxydodecylpyribromide, (meth) acryloyloxycetadecylpyridinium chloride, (meth) acryloyloxydecylammonium chloride, and triclosan may be mixed.

When preparing the coating composition, it is preferable to appropriately select each component so as to have an appropriate viscosity. The viscosity of the coating composition at 30 ℃ is preferably 300cP to 50,000cP, more preferably 500cP to 30,000cP, and most preferably 1,000cP to 20,000cP, from the viewpoint of coating properties to teeth, handling properties, and the like. When the viscosity is less than 300cP, the fluidity is too high and the workability may be lowered; on the other hand, if the cP exceeds 50,000, the coatability is lowered and the uniformity of color tone of the coating is lowered.

Next, a method of using the 2 nd kit, that is, a method of coating the 2 nd kit will be described.

First, a primer composition is applied to the surface of a tooth, and the primer composition is dried, if necessary, using a dental handpiece or the like until it does not have fluidity; or when the primer composition contains a polymerization initiator (photopolymerization initiator and/or chemical polymerization initiator), the coating layer is polymerized and cured to form a primer layer (step 1).

Next, a coating composition is applied to the surface of the primer layer, and the coating layer is polymerized and cured by light irradiation to form an intermediate layer (step 2). When the primer composition contains a photopolymerization initiator, the primer composition and the coating composition can be simultaneously polymerized and cured by light irradiation.

Finally, the surface of the intermediate layer is coated with a surface lubricating composition, and the coated layer is polymerized and cured by light irradiation to form a surface layer, thereby forming a three-layer structured coating layer on the surface of the tooth (step 3).

After the end of step 2, when there are many unpolymerized layers on the surface of the intermediate layer, the surface curability of the surface layer may be insufficient after the end of step 3. To prevent this problem, it is preferable to wipe off the unpolymerized layer after the end of step 2, for example, using a cotton ball or the like.

The coating thickness of the coating composition in step 2 is preferably 0.005mm to 1mm, more preferably 0.01mm to 0.7mm, most preferably 0.1mm to 0.5 mm.

When the coating layer of the coating composition is irradiated with light to polymerize and cure the coating layer, a light source such as a xenon lamp, a halogen lamp, a mercury lamp, or a light-emitting diode is preferably used. The irradiation time of light is related to the wavelength and the quantity of light, and if a dental-dedicated irradiation device is used, the light can be polymerized and cured usually in about 3 seconds to 3 minutes.

The kit 2 is applicable to not only unbleached tooth surfaces but also bleached tooth surfaces, as in the kit 1. Tooth bleaching has become popular in recent years as a means for whitening teeth, and it is known that the surface of teeth is roughened by bleaching, but the 2 nd kit is preferably used for such roughened teeth as in the 1 st kit, and can achieve the purpose of supplementing the bleaching effect and preventing the tooth color retrogradation phenomenon after bleaching.

The kit 2 can be used not only for teeth but also for surfaces of dental restorative materials such as metals, ceramic materials, ceramics, cured products of composite materials, and the like, as in the kit 1.

The 2 nd kit can be used in combination with commercially available dental metal primers, ceramic material-bonding primers, and a tooth surface cleaning agent such as hypochlorite, as in the 1 st kit.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

First, given an example of the 1 st kit, bleaching of teeth in the following examples 1 to 12 (examples of the 1 st kit) and comparative examples 1 to 4 was all performed in the following manner.

[ method of bleaching teeth ]

3.5ml of 35% hydrogen peroxide water was added to 1 package of bleaching agent (Kerativ, trade name "Powergel"), and mixed thoroughly to prepare a gel-like bleaching agent. The surface of the pulled-out human middle-cut tooth facing the lip, which had been cleaned in advance with a brush (trade name "ブラシコ - ン" by Nippon dental industries Co., Ltd.), was coated with the gel-like bleaching agent to a thickness of about 1 mm. The labial surface of the middle incisor teeth coated with the gel-like bleaching agent was irradiated with light for 30 seconds using a dental visible light irradiator (エア - テクニクス, trade name "ア - クライト"), left for 5 minutes, and then washed with running water. The above-described operations from the application of the gel-like bleaching agent to the washing with running water were repeated 3 times to complete the bleaching.

Abbreviations shown below are as follows.

[ polymerizable monomer (a) having an acidic group ]

MDP: 10- (meth) acryloyloxydecyl dihydrogen phosphate

[ Water-soluble solvent (c) ]

HEMA: 2-Hydroxyethyl methacrylate

[ polyfunctional polymerizable monomer (f) ]

DPHA: dipentaerythritol hexaacrylate

DPPA: penta (penta) acrylic acid dipentaerythritol ester

PTA: pentaerythritol triacrylate

[ volatile solvent (g) ]

MMA: methacrylic acid methyl ester

[ photopolymerization initiator (h) ]

TMDPO: 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide

CQ: camphorquinone

[ polymerization accelerators ]

DMABE: 4-Dimethylaminobenzoic acid ethyl ester

[ adhesive phosphate monomer ]

PMEAP: phenyl (2-methacryloyloxyethyl) acid phosphate

And (3) DPMEP: diphenyl (methacryloyloxyethyl) phosphate

(example 1)

A primer composition was prepared containing MDP (20 wt%), distilled water (25 wt%) and HEMA (55 wt%). A surface lubricating composition containing DPHA (93 wt%), MMA (5 wt%) and TMDPO (2 wt%) was also prepared. The viscosity of the surface lubricating composition in the coating kit containing the primer composition and the surface lubricating composition was determined by the following method (1). The workability, smell and surface curability were examined by the following methods (2) to (4). These results are shown in table 1. The viscosity, handling properties, odor and surface curability obtained in the following examples and comparative examples were obtained by the following methods (1) to (4).

(1) Viscosity of the oil

The viscosity of the surface lubricating composition was measured at 30 ℃ with an E-type viscometer (east China machine industry) at 0.6 cc.

(2) Operability of

The bleached human middle cut teeth were coated with the primer composition prepared in example 1, left as it is for 30 seconds, and then the volatile components were volatilized with a dental handpiece until the primer composition had no fluidity. Next, the flat portion on the labial side of the middle incisor was fixed upward so as to be parallel to the ground, and then the surface lubricating composition prepared in example 1 was applied with a fine hair brush from the incisor edge on the labial side to the tooth neck line, and the liquid flow between the gaps between adjacent teeth or the root surface was visually evaluated, and whether or not there was liquid accumulation in the vicinity of the incisor edge was visually evaluated. No dripping and liquid accumulation were observed, and the evaluation was evaluated as "good", only a few as "delta", and the evaluation was clearly observed as "x".

(3) Smell(s)

The coated surface coated with the surface lubricating composition in (2) above was irradiated with light for 60 seconds with a dental light irradiation lamp (group Ma 12454; \ 12471 オ electric, model No. 'ライテル II') to cure the surface lubricating composition. Upon this curing, the panelists positioned their outer noses 3cm above the coated surface to evaluate the odor of the surface lubricating composition. The evaluation by 7 panelists was 3 points for no odor, 2 points for no unpleasant odor, 1 point for unpleasant odor, 2 points for 2 points or more on the average, and x for less than 2 points.

(4) Surface curing

The surface of the cured surface layer obtained in (3) was rubbed with a wiper (model "JK ワイパ -" available from クレシア) and the surface curability was evaluated by visual observation. The surface was not scratched, and the surface was sufficiently cured and evaluated as O; the surface was scratched, and the surface was insufficiently cured was evaluated as X.

(examples 2 to 7)

DPHA, DPPA, PTA, MMA, ethanol, TMDPO, CQ and DMABE were mixed in the weight ratios shown in table 1 to prepare 6 surface lubricating compositions. The viscosity of the surface lubricating composition was determined for each of the coating kits containing the surface lubricating compositions and the primer composition prepared in example 1, and the workability, odor, and surface curability were examined. The results are shown in Table 1.

TABLE 1

As can be seen from Table 1: the kit 1 of examples 1 to 7 had a small unpleasant odor and was excellent in handling properties. In addition, the surface lubricating compositions in the kit 1 of examples 1 to 7 did not contain a phosphate ester-based adhesive monomer, and thus were also excellent in surface curability.

(example 8)

A primer composition was prepared containing MDP (10 wt%), distilled water (30 wt%) and HEMA (60 wt%). Using a coating kit containing this primer composition and the surface lubricating composition prepared in example 1, a surface layer was formed by the method shown in the following (1), and the surface curability thereof was evaluated. The adhesion strength between the surface layer and the bleached tooth was determined by the method shown in the following (2), and the adhesion strength determined in the following examples 9 to 12 and comparative examples 1 to 4 was also determined by the following method. The results are shown in Table 2.

(1) Formation of a surface layer

A tape having a hole with a diameter of 3mm and a thickness of 150 μm was attached to the center portion of the bleached human central incisor, and the primer composition prepared in example 8 was applied to the hole of the tape. After standing for 30 seconds, the volatile components were volatilized with a dental handpiece until the primer composition did not flow to form a primer layer. Next, the surface of this primer layer was coated with the surface lubricating composition prepared in example 1 to fill the pores. The coated surface was irradiated with light for 60 seconds using a dental light irradiation lamp (group Ma 12454; \12471 オ electric, model No. 'ライテル II') to polymerize and cure the coating, thereby forming a surface layer.

(2) Adhesive strength

A cylindrical rod (diameter: 5mm, length: 1.5cm) made of stainless steel was bonded to the surface layer with a commercially available dental resin cement (クラレ, model No. 'パナビア 21'), and the end face (round face) of the rod was used as a bonding face. After 30 minutes, the test piece was immersed in water at 37 ℃ and the adhesive strength was measured after 1 day. The bond strength was measured as follows: several metal plates with a thickness of 0.5mm were fixed against the teeth, and a stainless steel rod was pulled downward so that the axis of the stainless steel cylindrical rod with respect to the pulling direction was within a range of ± 5 ° or less. The adhesive strength was measured by using a tensile testing apparatus (product name: オ - トグラフ, manufactured by Shimadzu corporation) with a crosshead speed of 2 mm/min. The adhesive strength was determined as an average value of the measured values of 8 test pieces.

(examples 9 to 12)

MDP, distilled water, HEMA, ethanol, CQ and DMABE were mixed in the weight ratio shown in Table 2 to prepare 4 primer compositions. The surface curability of the surface layer of the coating kit containing these various primer compositions and the surface lubricating composition prepared in example 1 was evaluated. The bond strength with the bleached tooth was also determined. The results are shown in Table 2.

Comparative example 1

The center part of the bleached human central incisor teeth was covered with an adhesive tape having a hole of 3mm in diameter and a thickness of 150 μm, and the surface lubricating composition prepared in example 1 was applied to the hole of the adhesive tape. The coated surface was irradiated with light for 60 seconds with a dental light irradiation lamp (a group of maw 12454; \12471 オ electric, model No. 'ライテル II') in a state where the holes of the tape were filled with the surface lubricating composition, to form a coating layer on the surface of the bleached teeth, and the surface curability thereof was evaluated and the adhesion strength to the bleached teeth was also determined. The results are shown in Table 2.

Comparative examples 2 to 4

DPHA, MMA, CQ, DMABE and a phosphate-based adhesive monomer (phenyl (2-methacryloyloxyethyl) acid phosphate or diphenyl (methacryloyloxyethyl) phosphate) were mixed in the weight ratio shown in table 2 to prepare 4 surface lubricating compositions. These surface lubricating compositions were directly applied to the labial side of a bleached human incisor to form a coating layer, and the surface curability thereof was evaluated and the adhesion strength to the bleached teeth was also determined. The results are shown in Table 2.

TABLE 2

As can be seen from Table 2: when the primer layer and the surface layer were formed on the bleached tooth surface in this order using the kit 1 of examples 8 to 12, an extremely high adhesive strength was obtained. In addition, the surface lubricating compositions in the kit 1 of examples 8 to 12 did not contain a phosphate ester-based adhesive monomer, and thus were excellent in surface curability. On the other hand, when the surface lubricating composition was used as it is without forming a primer layer on the bleached teeth (comparative examples 1 and 2), the surface curability was excellent, but the adhesive strength was extremely low. Further, when the composition containing the phosphate-based adhesive monomer was used as it is for bleached teeth without forming a primer layer, the adhesion to the bleached teeth was improved to some extent, but the surface curability was not good (comparative examples 3 and 4).

In the above examples, the case of coating bleached teeth using the kit 1 was described as an example, and the kit 1 can be used for coating unbleached teeth.

An example of the kit of the 2 nd embodiment is described below. Abbreviations shown below are as follows.

MDP: 10- (meth) acryloyloxydecyl dihydrogen phosphate

HEMA: 2-Hydroxyethyl methacrylate

UDMA: 2, 2, 4-Trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate

U-4 TH: n, N' - (2, 2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1, 3-diol ] tetramethylacrylate

Bis-GMA: bisphenol A diglycidyl methacrylate

3G: triethylene glycol dimethacrylate

DPHA: dipentaerythritol hexaacrylate

DPPA: penta (penta) acrylic acid dipentaerythritol ester

MMA: methacrylic acid methyl ester

CQ: camphorquinone

DMABE: 4-Dimethylaminobenzoic acid ethyl ester

TMDPO: 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide

(example 13)

Separately, a primer composition containing MDP (20 wt%), distilled water (40 wt%) and HEMA (40 wt%) was prepared; a coating composition containing UDMA (50 wt%), U-4TH (20 wt%), 3G (29 wt%), CQ (0.5 wt%), DMABE (0.5 wt%); a surface lubricating composition containing DPHA (73 wt%), MMA (25 wt%) and TMDPO (2 wt%). The adhesive strength to the teeth of a coating kit (kit 2) containing the primer composition, the coating composition and the surface lubricating composition was measured by the following adhesive force test method a 1. Chip resistance was evaluated by the following chip resistance test method B1. The results are shown in Table 3.

[ adhesion test method A1]

(1) The enamel surface on the labial side of the incisor teeth of the pulled-out person was cleaned with a brush (trade name "ブラシコ - ン" from Nippon dental industries Co., Ltd.), and then a tape having a hole of 3mm in diameter and a thickness of 150 μm was attached to the central portion of the flat portion of the enamel, and the primer composition prepared in example 13 was applied to the hole of the tape. After leaving as it is for 30 seconds, the volatile components were volatilized with a dental handpiece until the primer composition had no fluidity to form a primer layer. The coating composition prepared in example 13 was applied to the surface of the primer layer to fill the pores. The coated surface was irradiated with light for 30 seconds using a dental light irradiation lamp (manufactured by Maruz54; \12471 オ electric Co., Ltd.; trade name "ライテル II") and cured to form an intermediate layer. The surface lubricating composition prepared in example 13 was applied to the surface of the intermediate layer with a fine brush pen, and the intermediate layer was cured by irradiation with light from the dental light irradiation lamp for 60 seconds to form a surface layer.

(2) A cylindrical bar (5 mm in diameter and 1.5cm in length) made of stainless steel was bonded to the surface of the surface layer with a commercially available dental resin cement (クラレ, model No. 'パナビア 21'), and the end face (round face) of the bar was used as a bonding face. After 30 minutes, the test piece was immersed in water at 37 ℃ and the adhesive strength was measured after 1 day. The bond strength was measured as follows: several metal plates with a thickness of 0.5mm were fixed to teeth, and a stainless steel rod was pulled downward so that the axis of the stainless steel cylindrical rod with respect to the pulling direction was within a range of ± 5 ° or less. The adhesive strength was measured by using a tensile testing apparatus (product name: オ - トグラフ, manufactured by Shimadzu corporation) with a crosshead speed of 2 mm/min. The adhesive strength was determined as an average value of the measured values of 8 test pieces.

[ chip resistance test method B1]

(1) The lingual side of the extracted anterior teeth was cut so as to be parallel to the flat enamel portion on the labial side, and processed into a plate shape having a thickness of 2 mm. The enamel surface on the labial side of the prepared tooth was cleaned with a brush (trade name "ブラシコ - ン" from Nippon dental industries, Ltd.), and then a tape having a thickness of 150 μm and a hole of 5mm in diameter was attached to the central portion of the flat portion of the enamel, and the primer composition prepared in example 13 was applied. After standing for 30 seconds, the volatile components were volatilized with a dental handpiece until the primer composition did not flow to form a primer layer. The coating composition prepared in example 13 was applied to the surface of the primer layer to fill the pores. The coated surface was irradiated with light for 30 seconds using a dental light irradiation lamp (manufactured by Maruz54; \12471 オ electric Co., Ltd.; trade name "ライテル II") and cured to form an intermediate layer. The surface lubricating composition prepared in example 13 was applied to the surface of the intermediate layer with a fine brush, irradiated with the above dental light irradiation lamp for 60 seconds, and then the tape was peeled off to obtain a plate-like tooth having a surface layer with a diameter of 5mm formed on the enamel surface. The plate-like teeth having the surface layer formed thereon were set in the center of a mold having a length of 3cm, a width of 2cm and a thickness of 2mm, the disc-like surface layer was faced upward, the dental composite resin was filled around the disc-like surface layer, the teeth were fixed, and the dental composite resin was polymerized and cured in this state to prepare a test piece. The test piece was fixed to the bottom surface of a water tank filled with water, bristles of a toothbrush (product name: ビトイ - ン, manufactured by ライオン; hardness: general) were vertically brought into contact with the surface of the surface layer, and the toothbrush was slid back and forth at an amplitude of 10cm in a state where a load of 250g was applied.

(2) After the round was repeated 10000 times, 20000 times, and 40000 times, a test piece was taken out, the peripheral edge part of the disk-shaped surface layer was observed with an optical microscope (magnification: 10 times), and whether or not there was any chip having a major axis of 0.1mm or more was examined, and the chip resistance was evaluated according to the following evaluation criteria.

(evaluation criteria)

No peeling scraps were observed

In one to see to peel off bits

(examples 14 to 17)

Each of the primer composition, coating composition and surface lubricative composition having the compositions shown in table 3 was prepared to prepare 4 dental coating kits (kit 2). The adhesive strength of these dental coating kits was determined by the adhesive strength test method a 1. Chip resistance was evaluated by the chip resistance test method B1 described above. The results are shown in Table 3.

Comparative examples 5 and 6

The adhesion strength was determined by the following adhesion test method a2 for the surface lubricating composition prepared in example 13 (comparative example 5) and the surface lubricating composition prepared in comparative example 1 (comparative example 6). Chip resistance was evaluated by the following chip resistance test method B2. The results are shown in Table 3. However, the test piece was taken out after 10000 times of the reciprocal brushing and evaluated for the chip resistance, but the coatings of comparative examples 5 and 6 were not peeled off from the teeth until 10000 times of the reciprocal brushing in the chip resistance test were completed, and thus the chip resistance evaluation could not be performed.

[ adhesion test method A2]

(1) The enamel surface of the incised teeth of the extracted person facing the labial side was cleaned with a brush (trade name "ブラシコ - ン" from japan dental industries, inc.), and then a tape having a hole of 3mm in diameter and a thickness of 150 μm was attached to the central portion of the flat portion of the enamel, and the surface lubricating composition prepared in example 13 or comparative example 1 was applied to the hole of the tape. The coated surface was irradiated with light for 60 seconds using a dental light irradiation lamp (manufactured by Maruz54; \12471 オ electric Co., Ltd.; trade name "ライテル II") and cured to form a coating layer.

(2) The adhesion strength of the coating obtained in (1) above to the teeth was measured by the adhesion test method A1(2) above.

[ chip resistance test method B2]

(1) The tongue side of the extracted anterior tooth was cut so as to be parallel to the flat portion of the labial enamel, and processed into a plate shape having a thickness of 2 mm. The labial enamel surface of the prepared tooth was cleaned with a brush (trade name "ブラシコ - ン" from Nippon dental industries, Ltd.), and then a tape having a hole of 5mm in diameter and a thickness of 150 μm was attached to the central portion of the flat portion of the enamel, and the surface lubricating composition prepared in example 13 or comparative example 1 was applied. The coated surface was irradiated with light for 60 seconds using the dental light irradiation lamp and cured, and then the tape was peeled off to obtain a plate-like tooth having a coating layer of 5mm in diameter formed on the enamel surface.

(2) The coating obtained in (1) was evaluated for chip resistance by the chip resistance test method B1 (2).

TABLE 3

(examples 18 to 22)

A primer composition, a coating composition and a surface lubricating composition having the compositions shown in table 4 were prepared, and 5 dental coating kits (kit No. 2) were prepared. The adhesive strength of these dental coating kits was determined by the adhesive strength test method a 1. Chip resistance was evaluated by the chip resistance test method B1 described above. The results are shown in Table 4.

TABLE 4

Examples 23 to 37

A primer composition, a coating composition and a surface lubricating composition each having a composition shown in Table 5 were prepared, and 7 dental coating kits (examples 23 to 29; kit No. 2) were prepared. Separately, a primer composition and a surface lubricative composition each having a composition shown in Table 6 were prepared, and 8 dental coating kits (examples 30 to 37; kit 1) were prepared. The kit of example 32 and the kit of example 7, the kit of example 33 and the kit of example 2, the kit of example 34 and the kit of example 1, the kit of example 35 and the kit of example 8, the kit of example 36 and the kit of example 9, and the kit of example 37 and the kit of example 10 are respectively mutually identical kits. The adhesive strength of these dental coating kits was determined by the adhesive strength test method a 1. Chip resistance was evaluated by the chip resistance test method B1 described above. The change in tooth brightness due to application was measured by the following brightness change measurement method. The results are shown in tables 5 and 6.

[ method for measuring change in luminance ]

(1) The extracted anterior teeth of the human body were cut to the lingual side so as to be parallel to the flat portion of the labial enamel, and processed into a plate shape having a thickness of 2 mm. The labial enamel surface of the prepared tooth was cleaned with a brush (trade name: ブラシコ - ン, manufactured by Nippon dental industries, Ltd.), and a tape having a hole of 7mm in diameter and a thickness of 150 μm was attached to the center of the flat portion of the enamel, and the brightness index (L) of the hole portion was measured^＊ ₀). Luminance index (L)^＊) The measurement of (2) was carried out using a color difference meter (type Sigma 90, manufactured by Nippon Denshoku Kogyo Co., Ltd., light source D65, viewing angle 2 degrees, color measurement range 5 mm. phi.), with a standard white board placed behind. Here, L is^＊Represents L defined in JIS-Z8729^＊a^＊b^＊Luminance index in a color system.

(2) Next, the primer compositions prepared in examples 23-37 were applied in tape holes. After standing for 30 seconds, the volatile components were volatilized with a dental handpiece until they were free from fluidity to form a primer layer.

(3) Next, the coating compositions prepared in examples 23 to 29 were applied to the surface of the primer layer to fill the pores. The coated surface was irradiated with light for 30 seconds using the dental light irradiation lamp, and polymerized and cured to form an intermediate layer. This step (3) was not performed on the kits of examples 30 to 37 having no coating composition, and the next step (4) was carried out.

(4) The surface lubricating compositions prepared in examples 23 to 37 were applied to the surface of the intermediate layer (the surface of the primer layer in examples 30 to 37) with a fine hair brush, irradiated with light from the above dental light irradiation lamp for 60 seconds, and then the tape was peeled off to obtain plate-like teeth having a coating layer with a diameter of 7mm formed on the enamel surface.

(5) Then, the luminance index (L) of the coated portion of the obtained plate-like tooth was measured in the same manner as in the above (1)^＊ ₁). The change in luminance (Δ L) due to coating was calculated from the following formula^＊)。

Change in luminance (Δ L)^＊)＝L^＊ ₁-L^＊ ₀

TABLE 5

TABLE 6

As shown in tables 3 to 5, when a 3-layer coating was formed on teeth using the kit 2 containing the primer composition, the coating composition and the surface lubricating composition, the resulting coating exhibited excellent adhesion strength to teeth and excellent chipping resistance (examples 13 to 29). In contrast, as shown in table 3, when the surface lubricating composition was directly applied to the surface of the teeth without using the primer composition and the coating composition to form a single-layer coating, the adhesion of the obtained coating to the teeth was low (comparative examples 5 and 6). As shown in table 6, when the primer composition and the surface lubricating composition were applied to the surface of the tooth in this order without using the coating composition to form a 2-layer coating, the adhesion strength was excellent, but the chip resistance was poor.

Examples 30 to 37

As shown in Table 5, when a coating layer having a 3-layer structure was formed on teeth using the kit 2 having a coating composition containing an inorganic filler having a refractive index of 1.9 or more, the brightness of teeth was improved by coating, and the appearance was improved (examples 23 to 29).

Industrial applicability

The dental coating kit of the present invention is particularly useful as a kit for preventing staining and color retraction of teeth after bleaching.

Claims (9)

1. A dental coating kit comprising a primer composition, a coating composition and a surface lubricating composition, wherein,

the primer composition contains an acidic group-containing polymerizable monomer (a) having an acidic group selected from the group consisting of a phosphoric group, a pyrophosphoric group, a thiophosphoric group, a carboxylic acid group and a sulfonic acid group and having a polymerizable unsaturated group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group and a vinylbenzyl group, water (b), and an acidic group-containing polymerizable monomer (a) selected from the group consisting of ethanol, methanol, 1-propanol, isopropanol, acetone, methylethylketone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol, polyethylene glycol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acrylate, 2-trimethylammonioethyl (meth) acryloyl chloride, methacryloyl chloride, At least one water-soluble solvent (c) of (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, and polyethylene glycol di (meth) acrylate in which the number of oxyethylene groups is 9 or more;

the coating composition contains 40 to 99.99 wt% of a polymerizable monomer (d) and at least one photopolymerization initiator (e) selected from the group consisting of α -diketones, ketolides, thioxanthones, acylphosphine oxides and α -aminophenylacetophenones;

the surface lubricating composition contains a polyfunctional polymerizable monomer (f) selected from a bifunctional polymerizable monomer and a trifunctional or higher polymerizable monomer in (meth) acrylate, at least one volatile solvent (g) selected from ethanol, methanol, 1-propanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, tetrahydrofuran, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate, and at least one photopolymerization initiator (h) selected from α -diketones, ketals, thioxanthones, acylphosphine oxides, and α -aminophenylacetones,

wherein,

the polymerizable monomer (d) includes a hydrophobic (meth) acrylate having 2 or more ethylenic double bonds as a hydrophobic polymerizable monomer, the hydrophobic (meth) acrylate is incorporated in an amount of 20 to 90 wt% with respect to the total weight of the coating composition, and the hydrophobic (meth) acrylate has a solubility in water at 25 ℃ of less than 10 wt%,

the coating composition has a viscosity of 300cP to 50,000cP at 30 ℃ and

the primer composition contains 1 to 90% by weight of the acid group-containing polymerizable monomer (a), 0.1 to 90% by weight of the water (b), 1 to 98% by weight of the water-soluble solvent (c); the content of the photopolymerization initiator (e) in the coating composition is 0.01 to 10 wt% with respect to the polymerizable monomer (d); the surface lubricating composition contains 40 to 98 wt% of the polyfunctional polymerizable monomer (f), 1 to 59 wt% of the volatile solvent (g), and 0.01 to 10 wt% of the photopolymerization initiator (h) relative to the total weight of the polymerizable monomers in the surface lubricating composition.

2. The dental coating kit according to claim 1, wherein the polymerizable monomer (d) further comprises at least one hydrophilic polymerizable monomer selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acrylate, 2-trimethylammonioethyl (meth) acryloyl chloride, (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and polyethylene glycol di (meth) acrylate in which the number of oxyethylene groups is 9 or more, in an amount of 5 to 50% by weight of the coating composition.

3. The dental coating kit according to claim 1, wherein the coating composition further contains 0.1 to 50 wt% of an inorganic filler having a refractive index of 1.9 or more based on the total weight of the coating composition.

4. The dental coating kit according to claim 3, wherein the coating composition further comprises 1 to 40% by weight of colloidal silica having an average particle diameter of 0.001 to 0.1 μm.

5. The dental coating kit according to any one of claims 1 to 4, which is a post-bleaching kit for coating teeth.

6. A dental coating method, wherein,

applying an acidic group-containing polymerizable monomer (a) having an acidic group selected from the group consisting of a phosphoric group, a pyrophosphoric group, a thiophosphoric group, a carboxylic acid group and a sulfonic acid group and having a polymerizable unsaturated group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group and a vinylbenzyl group, water (b), an acidic group-containing polymerizable monomer (a), acetone (b), a monomer (a) selected from the group consisting of ethanol, methanol, 1-propanol, isopropanol, acetone, methyl ethyl ketone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol, polyethylene glycol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acrylate, 2-trimethylammonioethyl (meth) acryloyl chloride, methacrylo, A primer composition comprising (c) at least one water-soluble solvent of (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and polyethylene glycol di (meth) acrylate in which the number of oxyethylene groups is 9 or more and, if necessary, a polymerization initiator, and drying or polymerization-curing the primer composition to form a primer layer;

coating a coating composition containing 40 to 99.99 wt% of a polymerizable monomer (d) and at least one photopolymerization initiator (e) selected from the group consisting of α -diketones, ketals, thioxanthones, acylphosphine oxides and α -aminophenylacetophenones on the surface of the primer layer, and polymerizing and curing the coating composition by light irradiation to form an intermediate layer;

applying a surface lubricating composition containing a polyfunctional polymerizable monomer (f) selected from a bifunctional polymerizable monomer in (meth) acrylate and a trifunctional or higher polymerizable monomer, at least one volatile solvent (g) selected from ethanol, methanol, 1-propanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, tetrahydrofuran, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate, and at least one photopolymerization initiator (h) selected from α -diketones, ketals, thioxanthones, acylphosphine oxides, and α -aminoacetophenones on the surface of the intermediate layer, polymerizing and curing the mixture by light irradiation to form a surface layer,

wherein the polymerizable monomer (d) comprises a hydrophobic (meth) acrylate having 2 or more ethylenic double bonds, the amount of the hydrophobic (meth) acrylate is 20 to 90 wt% based on the total weight of the coating composition, and the solubility of the hydrophobic (meth) acrylate in water at 25 ℃ is less than 10 wt%,

the coating composition has a viscosity of 300cP to 50,000cP at 30 ℃ and

the primer composition contains 1 to 90% by weight of the acid group-containing polymerizable monomer (a), 0.1 to 90% by weight of the water (b), 1 to 98% by weight of the water-soluble solvent (c); the content of the photopolymerization initiator (e) in the coating composition is 0.01 to 10 wt% with respect to the polymerizable monomer (d); the surface lubricating composition contains 40 to 98 wt% of the polyfunctional polymerizable monomer (f), 1 to 59 wt% of the volatile solvent (g), and 0.01 to 10 wt% of the photopolymerization initiator (h) relative to the total weight of the polymerizable monomers in the surface lubricating composition.

7. The dental coating method according to claim 6, wherein the polymerizable monomer (d) further comprises at least one hydrophilic polymerizable monomer selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acrylate, 2-trimethylammonioethyl (meth) acryloyl chloride, (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and polyethylene glycol di (meth) acrylate in which the number of oxyethylene groups is 9 or more, in an amount of 5 to 50% by weight of the coating composition.

8. The dental coating method according to claim 6, wherein the coating composition further contains 0.1 to 50 wt% of an inorganic filler having a refractive index of 1.9 or more, based on the total weight of the coating composition.

9. The dental coating method according to claim 8, wherein the coating composition further comprises 1 to 40% by weight of colloidal silica having an average particle size of 0.001 to 0.1 μm.