JP5395362B2 - Dental primer composition and dental kit - Google Patents

Description

  The present invention relates to a dental primer composition and a dental kit that can be used for the treatment of periodontal diseases.

  Numerous proposals have been made of radical initiators such as (meth) acrylic acid esters and polymerization initiators as adhesives used to repair dental teeth damaged by caries or to correct teeth. Yes. That is, a curable composition (Patent Document 1) composed of a (meth) acrylic ester vinyl monomer and a (meth) acryloyl group-containing aromatic carboxylic acid (anhydride), an amine and a sulfinic acid (salt); Has been proposed and implemented as adhesives composed of (meth) acrylic acid ester, amine, sulfinic acid (salt), peroxide, etc., which are liquid at room temperature. However, these adhesives are particularly useful when the adhesive strength varies due to the degree of decalcification at the repair site, the pretreatment method, or the skills of dental care professionals. There is a concern about the occurrence of a gap at the interface between the quality and the adhesive, and the minute leakage. When microleakage occurs at the same time, irritating substances, bacteria, and the like enter through this gap, and the probability of caries reoccurrence at the repaired portion increases. For this reason, an adhesive material that has a particularly excellent adhesive effect and does not cause minute leakage at the same time is desired.

In normal dental practice, hypochlorous acid preparations are frequently used for the sterilization and disinfection of teeth that have been caries-caused. However, after using these preparations, it is clear that this preparation has an adverse effect on the adhesion operation, which is a treatment that is inevitably performed, which is a serious clinical problem.
JP 63-44508 A JP-A-53-39331

  An object of the present invention is to provide a dental adhesive having high adhesiveness that does not cause microleakage or the like. Another object of the present invention is to provide a dental adhesive capable of easily performing a good bonding operation on a sterilized tooth.

As a result of intensive studies by the inventors, it has been found that the above-mentioned problems of the present invention can be solved by a dental primer composition characterized by comprising a metal colloid solution having a particle size in the nano region. It came to complete.
That is, the present invention is such that the colloidal metal particles have an average particle size of 0.6 to 20 nm and 90% or more of the colloidal metal particles have a particle size in the range of 0.3 to 30 nm, It is a dental primer composition characterized by comprising a metal colloid solution using a product as a colloid protective material.
The dental primer composition of the present invention is in the form of a colloidal solution and can be easily applied regardless of the shape of the treatment area. After applying the primer composition of the present invention, if the adherend is adhered with a conventional resin-based dental adhesive, the adhesive strength can be remarkably improved regardless of the type of adhesive.

  With the dental primer composition of the present invention, the adhesive strength can be remarkably improved without modifying or changing a conventionally used resin-based dental adhesive.

  The present invention is described in detail below. Hereinafter, unless otherwise specified, “part” or “%” in this specification indicates a weight basis. Further, in the present specification, “(meth) acryl ...” will be described as a generic term for “acryl ...” and “methacryl ...”.

The dental primer composition of the present invention comprises a metal colloid solution and an additive that is optionally added.
An essential component in the dental primer composition of the present invention is a metal colloid solution. A metal colloid solution refers to a solution in which metal particles are dispersed in a liquid phase. In some cases, even if the metal is in a state of a single atom or close to it, it may be regarded as a metal colloid if it can be stably dispersed in the liquid layer with a protective colloid or the like. The metal is preferably in a reduced state, i.e., not in the form of a cation. There are no particular restrictions on the metal, but transition metals are preferred, and catalytic metals and noble metals are more preferred, gold, nickel, platinum, rhodium, palladium, iridium, ruthenium, and osmium are more preferred, and platinum is particularly preferred. . These metal species may be used alone or in combination of two or more, or may be used as an alloy. As an alloy containing these metals, an alloy containing gold and platinum is preferable, and an alloy containing platinum is particularly preferable. Further, it may be a single metal colloid solution or a mixture of two or more colloid solutions, but a single metal colloid solution, particularly a platinum colloid solution is particularly preferable.

Although distribution in particle size of the metal particles are present, the number average particle diameter thereof, 0.6 to 20 nm, good Mashiku is 0.8～10Nm, more preferably 1 to 6 nm, and most preferably 1.2 ~ 5 nm. The particle size is 0.3 to 30 nm of 90% or more of the metal particles in the particle number, good Mashiku is 0.6～20Nm, more preferably 0.8～10Nm, and most preferably in the range of 1~6nm The one that enters is used. If any of these ranges for the particle size is exceeded, the colloidal state cannot be maintained. The order of dental resin adhesives varies depending on the system used. However, in both cases, the teeth are decalcified to expose the collagen in the teeth, and at the same time, the monomer penetrates into the collagen and the teeth. Harden. When the particle size distribution of the metal colloid is narrow and the average particle size is in the above range, the metal particles penetrate into the exposed collagen chains and / or teeth and improve the adhesive strength of the resin-based dental adhesive. be able to. The particle size of the metal particles can be observed and measured with a scanning probe microscope such as an atomic force microscope, a scanning tunneling microscope, or a scanning near-field optical microscope, or an electron microscope, and dynamic light scattering. Can also be measured. As an example of measurement using a transmission electron microscope, an observation (measurement) sample obtained by immersing a metal colloid solution in a microgrid and drying it at room temperature can be used. Since the metal atom is opaque to the electron beam, it can be measured by observation with a transmission electron microscope without staining, and thus the protective colloid not containing the metal is not included in the particle size. For example, the particle diameter can be calculated by subjecting black particles of a transmission electron microscope image obtained at a magnification of 1,000,000 to 5,000,000 times. In addition, what has a metal particle size less than 0.2 nm largely deviates from the colloidal range, and is excluded from the measurement.

  There are no particular restrictions on the type of dispersion medium that is the liquid phase of the metal colloid solution in the dental primer composition of the present invention, but considering the use of the present invention, water-soluble, such as ethanol, glycerol, acetone, etc. An organic solvent preferably represented by an organic solvent can be used. In particular, it is particularly preferable to use water. You may mix the said organic solvent with water within the range which does not destabilize a colloidal solution. The dispersion medium is contained in the range of preferably 90 to 99.999% by weight, more preferably 92 to 99.99% by weight, still more preferably 94 to 99.9% by weight, based on 100% by weight of the primer composition. . Of the dispersion medium, water is preferably in the range of 30 to 99.999% by weight, more preferably 40 to 99.99% by weight, still more preferably 50 to 99.9% by weight, based on 100% by weight of the primer composition. Included. If the value falls below the lower limit of the numerical range, the colloidal protective material component described later may swell, and the colloidal state may not be maintained.On the other hand, if it exceeds, the improvement in adhesion strength due to platinum cannot be observed. Both are not preferred.

  In the metal colloid solution in the dental primer composition of the present invention, the metal concentration is not particularly limited as long as it does not impair the stability of the colloidal state. Generally, the stability is maintained if it is about 0.01 nmol / L to 10 mmol / L, but the stability of the colloidal state varies depending on each metal, and is not limited to this range. A particularly preferred concentration range is 0.00001 to 0.2% by weight, more preferably 0.0001 to 0.1% by weight, most preferably 0.0002 to 0.05% by weight, based on the total amount of the primer composition. Can be raised. If it is below the above range, the effects of the invention cannot be exhibited. If it exceeds the above range, the stability of the colloidal solution may be impaired.

The colloidal metal solution in the dental primer composition of the present invention contains the colloid protective material. The colloid protective agent coordinates to the metal and improves the affinity of the metal for the dispersion medium. The colloid protective material may be directly blended in the metal colloid solution or may be used in the preparation of the metal colloid solution as described later, but it is preferably used in the preparation of the metal colloid solution.
Colloid protective material, Ru water-soluble polymer der. Examples of the water-soluble polymer include polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid and / or a salt thereof, cyclodextrin, aminopectin, methylcellulose, carboxymethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and the like. These compounds may be used alone or in combination of two or more. The polyvinyl pyrrolidone, for example, poly (1-vinyl-2-pyrrolidone) are preferred, as the salt of polyacrylic acid, sodium polyacrylate, potassium polyacrylate is not preferable.

When the colloid protective material is a polymer, the amount used is the ratio of the number of moles of constituent monomers to the number of moles of metal of the polymer serving as the protective material, that is, the weight of the colloid protective material polymer is the constituent monomer residue When the number of moles of monomer units (M _O ) calculated by dividing by weight per mole is divided by the number of moles of metal (M _I ) (M _O / M _I , hereinafter referred to as R, and the polymer is a copolymer) Can be calculated from the copolymer composition). R in the metal colloid solution is preferably 200 or less, more preferably 80 to 180, and still more preferably 90 to 170. Alternatively, the polymer is preferably contained in the range of 0.0005 to 9% by weight, more preferably 0.005 to 7% by weight, and still more preferably 0.05 to 5% by weight based on 100% by weight of the primer composition. It is. Outside these numerical ranges, the colloid protective agent itself is difficult to disperse in the colloidal solution, which is not preferable.

  Various methods for producing a metal colloid solution are known. JP-B-57-43125, JP-B-59-120249, JP-A-9-225317, JP-A-10-176207, JP-A-2001-79382. No. 1 or JP-A-2001-122723. A person skilled in the art can easily prepare a metal colloid solution by referring to these methods. For example, a chemical method called a precipitation method or a metal salt reduction reaction method or a physical method called a combustion method can be used as the production method. A metal colloid solution prepared by any method may be used, but a metal colloid prepared by a metal salt reduction reaction method is preferably used from the viewpoint of ease of production and quality. As a specific example, a method of preparing a platinum colloid solution by a metal salt reduction reaction method using a platinum salt and a polyacrylate will be described below, but platinum acid is also considered to belong to the platinum salt, Even if polyacrylic acid is regarded as belonging to the polyacrylate, the composition of the present invention will be referred to as polyacrylic acid (salt) or the like without any practical problem.

(1) Preparation of reaction solution A solution containing platinum salt, polyacrylate, alcohol and water is prepared. The platinum salt is preferably soluble in a solvent composed of alcohol and water. The platinum salt is preferably a complex coordinated with an anion such as halogen, and examples thereof include hexachloroplatinic acid and potassium hexachloroplatinate. Of these, hexachloroplatinic acid can be preferably used. The polyacrylic acid salt may be polyacrylic acid that is not a salt of a counter cation, but is preferably a polyacrylic acid salt in which at least a part of the carboxyl group forms a salt. preferable. Examples of such cations include salts with alkali metals such as Li, Na, and K, alkaline earth metals such as Mg and Ca, or mixtures thereof. Na is preferred because of its high solubility in water and easy preparation of a reaction solution. Further, the acrylic acid derivative residue in which the hydrogen atom of the acrylic acid residue of the polyacrylic acid (salt) is substituted with an atom (group) containing a hetero atom such as a hydrocarbon group, halogen, oxygen, nitrogen, phosphorus, sulfur, etc. The group may be a polyacrylic acid derivative, or a copolymer or a mixture thereof. The weight average molecular weight of the polyacrylic acid (salt) is preferably 10,000 to 20,000,000, more preferably 100,000 to 10,000,000, still more preferably 1,000,000 to 6, 000,000. When the value falls below the lower limit of the numerical range, the metal colloid is not stabilized. On the other hand, when the value exceeds the upper limit, the reaction solution becomes highly viscous and difficult to handle. Since the weight molecular weight is usually measured by aqueous GPC, the molecular weight is in an ion dissociated state. Incidentally, the preferred molecular weight of other water-soluble polymers such as cellulose derivatives other than polyacrylic acid (salt) is also approximately the same size as described above, under normal conditions (room temperature, pH neutrality, in an aqueous solvent, etc.) What is ionized may be considered a size in a dissociated state. Further, in the case of an ultrapolymer having a molecular weight exceeding 7 million, it is preferable to measure the molecular weight by a viscosity method or the like, but the molecular weight in this case also uses a value in terms of a dissociated state. As the alcohol, for example, methanol, ethanol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, and ethylene glycol are preferable.
First, the polyacrylate is dissolved in water. The concentration of the polyacrylate in the solution is 0.01 to 0.5 mol / L in terms of constituent monomer residue units (0.94 to 47 g / L in the case of sodium polyacrylate). It is preferable that An aqueous solution containing platinum salt is prepared in another container, and this platinum salt aqueous solution is added to the polyacrylate solution to obtain a platinum salt-polyacrylate solution. The concentration of platinum salt in the platinum salt-polyacrylate solution is preferably 2 mmol / L or less, and more preferably 1 to 2 mmol / l. After adding the platinum salt aqueous solution, the platinum salt-polyacrylate solution is preferably stirred for 30 to 40 minutes. After stirring, alcohol is added to the platinum salt-polyacrylate solution to obtain a reaction solution. The molar ratio of alcohol / platinum salt in the reaction solution is preferably 10-20.

(2) Reaction Subsequently, the reaction solution is refluxed and reacted. The reaction is preferably performed in an inert gas atmosphere. During reflux, an alcohol such as ethanol reduces platinum ions to form a platinum colloid, which is oxidized to an aldehyde. Although depending on the amount of platinum salt in the reaction solution, platinum ions are almost lost when refluxed for 2 to 3 hours, and a platinum colloid having the above particle size range is formed. The disappearance of platinum ions and the formation of platinum nanocolloids can be confirmed by measuring the ultraviolet-visible absorption spectrum of the reaction solution.

(3) Preparation of alcohol solution Alcohol and water are distilled off from the reaction solution after reflux until the volume is about 0.5 to 20% to obtain a concentrated solution. An alcohol such as ethanol is further added to the obtained concentrated liquid and stirred to obtain a platinum alcohol solution. The amount of alcohol added is preferably about 20 to 40 (alcohol / platinum salt molar ratio) with respect to the raw material platinum salt.

(4) Preparation of platinum colloid When the solvent is distilled off from an alcohol solution of platinum, a paste-like platinum colloid is obtained. By adding a desired solvent such as water to the platinum nanocolloid and stirring, a uniform platinum colloid solution can be prepared. If all the solvent is distilled directly from the reaction solution without adding alcohol to the paste-like platinum colloid and preparing the alcohol solution, the resulting residue is very viscous and sticky. Therefore, it is difficult to obtain a uniform platinum colloid solution. On the other hand, according to this manufacturing method, since the alcohol solution is prepared and the step of distilling off the alcohol is performed again, a platinum colloid solution having excellent dispersibility can be produced.

In the dental primer composition of the present invention, as long as the effects of the present invention are not impaired,
Surfactant (excluding those used as colloid protective agents)
Gelling agents such as cellulose, amylose, agar and alginic acid;
Compounds that release soluble effective fluorine ions into the composition, such as disodium fluorophosphate, tin fluoride, sodium fluoride, potassium fluoride, sodium silicon fluoride, fluoroaluminosilicate glass, ammonium fluoride;
Aliphatic alcohols such as ethanol, halogenated aliphatic alcohols such as chlorobutanol, aromatic alcohols such as 2-phenoxyethanol, aldehydes such as glutaraldehyde, and aldehydes under acidic conditions such as hexamethylenetetramine and monomethyloldimethylhydantoin Aldehyde sustained-release agents that can be produced, amides such as chloroacetamide; ureas such as N, N ″ -methylenebis [N ′-(3- (hydroxymethyl) -2,5-dioxo-4-imidazolidinylurea] Inorganic sulfites such as sodium sulfite, bisulfites and pyrosulfites, inorganic acids such as boric acid, organic acid compounds such as formic acid, p-hydroxybenzoic acid ester compounds such as methyl p-hydroxybenzoate, 4-chloro -3-methylphenol, etc. Halogenated phenol compounds, phenol compounds such as 1-methyl-2-hydroxy-4-isopropylbenzene, diphenyl ether compounds such as 2,4,4′-trichloro-2′-hydroxydiphenyl ether, 3,4,4′-trichlorocarba A carbanilide compound such as nilide, a benzamidine compound such as 4,4′-diamidino-α, ω-diphenoxypropane isethionate, a cyclic thiohydroxamic acid such as pyridine-1-oxide-2-thiol sodium salt or a salt thereof, N-acetal compounds such as 5-amino-1,3-bis (2-ethylhexyl) -5-methylhexahydropyrimidine, phthalimide derivatives such as N- (trichloromethylthio) -4-cyclohexane-1,2-dicarboximide 6-acetoxy-2,4- O-acetal compounds such as dimethyl-m-dioxane, oxazolidine compounds such as 4,4-dimethyl-1,3-oxazolidine, quinoline compounds such as 8-hydroxyquinoline, and positive ions such as bis (p-chlorophenyldiguanide) hexane Ionic substances, quaternary salt compounds such as alkyltrimethylammonium bromide, organic mercury compounds such as ethyl mercury thiosalicylate, iodine compounds such as sodium iodate, glyceryl monolaurates, 1-hydroxy-4-methyl-6 -Antibacterial agents represented by pyridone derivatives such as (2,4,4-trimethylpentyl) -2- (1H) pyridone ethanolamine salt;
Bactericides such as chlorhexidine hydrochloride, cetylpyridinium chloride, chlorhexidine gluconate, dipotassium glycyrrhizinate, isopropylmethylphenol, triclosan, benzethonium chloride;
Β-lactams such as ampicillin, aminoglycosides such as kanamycin, tetracyclines such as tetracycline hydrochloride, macrolides such as erythromycin, chloramphenicols, ketolides such as tethromycin, polyene macrolides such as amphotericin B, glycopeptides such as vancomycin , Antibiotics such as nucleic acids such as phosmidine, pyridone carboxylic acids such as levofloxacin, oxazolidinones such as linezolid;
Perfumes such as sorbitol, l-menthol, limonene;
PH adjusters such as sodium hydrogen phosphate;
Blood circulation promoters such as vitamin E, sodium chloride, nicotinic acid-dl-α-tocopherol;
anti-inflammatory agents such as β-glycyrrhetinic acid, glycyrrhizic acid, ε-aminocaproic acid, lysozyme chloride, indomethacin, ibuprofen, epidihydrocholesterin, dihydrocholesterol, hinokitiol, serrapeptase, pronase, buckwheat extract, allantoin;
Vitamins such as retinols, riboflavin, ascorbic acid, cholecalciferols, nicotinic acids;
Chelating agents;
Plaque solubilizers such as amylase, mutanase, dextranase, protease;
Identification of compositions in the oral cavity such as Blue No. 1, Blue No. 404, Red No. 106, Red No. 201, Red No. 220, Red No. 225, Red No. 226, Red No. 227, Yellow No. 4, Gunjo, Conger, etc. Coloring agents to facilitate
Water-soluble metal salts such as magnesium chloride, magnesium acetate, magnesium sulfate, magnesium carbonate, barium sulfate;
Inorganic pigments such as titanium mica, titanium oxide, bismuth oxychloride, synthetic phlogopite, mica, iron oxide;
Dental decalcification materials such as phosphoric acid, ethylenediaminetetraacetic acid, iron (II) chloride, citric acid;
Alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and salts and / or hydroxylated thereof Amino acids such as tranexamic acid and taurine, and analogs thereof;
Poly (meth) acrylates such as poly (methyl (meth) acrylate), polystyrene, polystyrene sulfonic acid, polyvinyl acetate, ethylene-vinyl acetate copolymer, (meth) acrylonitrile-butadiene copolymer, styrene-butadiene copolymer In addition, a viscosity modifier such as an aqueous emulsion of a polymer such as vinyl chloride-vinyl acetate copolymer may be added. The form of these additives is not particularly limited, and can be selected according to the concentration of the solvent or additive.

The dental primer composition of the present invention can remarkably improve the adhesive strength without modifying or changing a conventionally used resin-based dental adhesive. Such an adhesive is not particularly limited, but is preferably effective in a radical polymerization system, particularly a (meth) acrylate system. As a typical example, the dental adhesive composition of the kit according to the present invention described later is used. A thing (B) is mentioned.
Also, priming for materials used in the reaction mechanism similar to that of dental resin-based adhesives, such as materials that coat tooth surfaces to prevent caries and materials that block dentinal tubules to prevent hypersensitivity Naturally, the effect of these materials and the durability in the oral cavity can be improved.

The form of use of the dental primer composition of the present invention is not particularly limited, but after etching the teeth with an etching material attached to the dental resin adhesive, the dental primer composition is used with a brush or the like. An example of applying a prosthesis by applying a resin adhesive after applying to a treatment site and removing excess dispersion medium with air can be given. The application method is not limited to cases such as washing with water after application.
Subsequently, a dental kit including the above-described dental primer composition will be described in detail. The dental kit of the present invention comprises a dental primer (A) and a dental adhesive composition (B). The dental adhesive composition is preferably composed of a radical polymerizable compound (M1) having an acidic group in the molecule, a radical polymerizable compound (M2) having no acidic group in the molecule, and a polymerization initiator (I). The

The dental primer (A) in the dental kit of the present invention is the same as the above-described dental primer composition, and is composed of a metal colloid solution and an additive that is optionally added. The preferred metal particle size and concentration are also as described above.
In the dental adhesive composition (B) in the dental kit of the present invention, the component (M1) is a radical polymerizable compound having an acidic group in the molecule. The component (M1) is not particularly limited as long as it has an acidic group and a radical polymerizable group in the molecule. Examples of the acidic group include a carboxyl group, a phosphoric acid group, a thiophosphoric acid group, a sulfo group, and a sulfino group. In addition, the acidic group is easily decomposed under practical conditions such as an acid anhydride group of a carboxyl group. Those that substantially function as acidic groups, such as, can be regarded as acidic groups. Examples of the radical polymerizable group include a vinyl group, a vinyl cyanide group, a (meth) acryloyl group, and a (meth) acrylamide group.

Specific examples of (M1) include compounds having a carboxyl group in the molecule, such as α-unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid;
Vinyl aromatic ring compounds such as 4-vinylbenzoic acid;
11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and other carboxylic acid compounds in which a linear hydrocarbon group is present between the (meth) acryloyloxy group and the carboxylic acid group;
(Meth) acryloyloxyalkylnaphthalene (poly) carboxylic acids such as 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid;
4- (meth) acryloyloxyalkyl trimellitic acid (4- (meth) acryloyloxymethyl trimellitic acid, 4- (meth) acryloyloxyethyl trimellitic acid, 4- (meth) acryloyloxybutyl trimellitic acid), etc. (Meth) acryloyloxyalkyl trimellitic acid;
A compound further containing a hydroxyl group such as 4- [2-hydroxy-3- (meth) acryloyloxy] butyl trimellitic acid;
Compounds having carboxybenzoyloxy such as 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate;
N- and / or O-mono or di such as N, O-di (meth) acryloyloxytyrosine, O- (meth) acryloyloxytyrosine, N- (meth) acryloyloxytyrosine, N- (meth) acryloyloxyphenylalanine (Meth) acryloyloxyamino acid;
N- (meth) acryloyl-4-aminobenzoic acid, N- (meth) acryloyl-5-aminobenzoic acid, 2- or 3- or 4- (meth) acryloyloxybenzoic acid, 4- or 5- (meth) N- and / or O-mono or di (meth) acryloyl (amino or oxy) benzoic acid compounds such as acryloylaminosalicylic acid;
Addition product of 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride, 2-hydroxyethyl (meth) acrylate and maleic anhydride or 2,3 ', 4,4'-benzophenone tetracarboxylic acid An addition reaction product of a hydroxyalkyl (meth) acrylate and an unsaturated polycarboxylic acid anhydride, such as an addition reaction product of an anhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
Compounds having polycarboxybenzoyloxy and (meth) acryloyloxy such as 2- (3,4-dicarboxybenzoyloxy) -1,3-di (meth) acryloyloxypropane);
An adduct of N-phenylglycine or N-tolylglycine and glycidyl (meth) acrylate;
4- [N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid, 3 or 4- [N-methyl-N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino And N-alkyl-N- (hydroxy (meth) acryloyloxyalkyl) aminophthalic acid compounds such as phthalic acid. Of these, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and 4- (meth) acryloyloxyethyl trimellitic acid are preferably used.

Preferred examples of the group having at least one hydroxyl group bonded to the phosphorus atom and the functional group that can be easily converted to the group in water include, for example, a phosphate ester group having one or two hydroxyl groups. Can do. Examples of the polymerizable monomer having such a group include 2- (meth) acryloyloxyethyl acid phosphate, 2- and 3- (meth) acryloyloxypropyl acid phosphate, 4- (meth) acryloyloxybutyl acid phosphate. (Meth) acryloyl such as 6- (meth) acryloyloxyhexyl acid phosphate, 8- (meth) acryloyloxyoctyl acid phosphate, 10- (meth) acryloyloxydecyl acid phosphate, 12- (meth) acryloyl oxide decyl acid phosphate Oxyalkyl acid phosphate;
An acid phosphate having two or more (meth) acryloyloxyalkyl groups such as bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [2- or 3- (meth) acryloyloxypropyl] acid phosphate;
Aromatic rings such as 2- (meth) acryloyloxyethylphenyl acid phosphate, 2- (meth) acryloyloxyethyl-p-methoxyphenyl acid phosphate, (meth) acryloyloxyalkyl groups and phenylene groups, and oxygen atoms The acid phosphate etc. which have via a hetero atom can be mentioned. The compound which substituted the phosphate group in these compounds by the thiophosphate group can also be illustrated. Of these, 2- (meth) acryloyloxyethyl acid phosphate can be preferably used.

As a polymerizable monomer having a sulfo group or a functional group that can be easily converted into a sulfo group in water, for example, 2-sulfoethyl (meth) acrylate, 2- or 1-sulfo-1- or 2-propyl (meth) acrylate , Sulfoalkyl (meth) acrylates such as 1- or 3-sulfo-2-butyl (meth) acrylate;
An atomic group containing a hetero atom such as halogen or oxygen in the alkyl part such as 3-bromo-2-sulfo-2-propyl (meth) acrylate and 3-methoxy-1-sulfo-2-propyl (meth) acrylate Having a compound;
A compound that is acrylamide instead of the acrylate such as 1,1-dimethyl-2-sulfoethyl (meth) acrylamide, 2-methyl-2- (meth) acrylamidepropanesulfonic acid, and the like;
Furthermore, vinyl aryl sulfonic acid, such as 4-styrene sulfonic acid and 4- (prop-1-en-2-yl) benzene sulfonic acid, etc. can be mentioned. Of these, 4-styrenesulfonic acid can be preferably used. These compounds can be used alone or in combination of two or more.
Among these polymerizable monomers containing at least one acidic group, 4- (meth) acryloxyethyl trimellitic acid and / or its anhydride are most preferable.

  In the dental kit of the present invention, the amount of the component (M1) is preferably 1 to 50% by weight, more preferably 2 to 30% by weight, and still more preferably based on the total amount of the dental adhesive composition (B). It is in the range of 2 to 25% by weight. If it exceeds this range, the stability of the composition during storage may be affected. On the other hand, if it falls below this range, the adhesion to the tooth or prosthesis will be significantly reduced, both being undesirable.

In the dental kit of the present invention, the component (M2) has a radically polymerizable group and is not particularly limited as long as it does not have an acidic group.
Alkyl or cycloalkyl (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate Acrylate;
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
Acetoacetoxyethyl (meth) acrylate;
(Polyhydroxy) alkyl (meth) acrylates such as 1,2- or 2,3-dihydroxypropyl (meth) acrylate, erythritol mono (meth) acrylate;
Polyalkylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate;
Ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, propylene glycol monomethyl ether (meth) acrylate, or polyethylene glycol mono ( Polyalkylene glycol monoalkyl or monoalkenyl ether (meth) acrylate such as a compound in which 10-undecenyl alcohol is ether-added to (meth) acrylate;
(Meth) acrylate having a heterocyclic ring such as (tetrahydrofuran-2-yl) (meth) acrylate, 12- (meth) acryloyloxide decylpyridinium bromide and / or a salt thereof;
Halogenated alkyl (meth) acrylates such as perfluorooctyl (meth) acrylate and hexafluorobutyl (meth) acrylate;
Can be mentioned.
further,
Poly (oxyalkylene) di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate;
Glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, meso-erythritol di (meth) acrylate or tri (meth) acrylate, pentanetriol di (meth) acrylate, tetramethylolmethane di (meth) acrylate or tri ( Di (meth) acrylates or tri (meth) acrylates of alkane polyols such as meth) acrylates, di (meth) acrylates of hexanetriol, di (meth) acrylates of hexanetetraol or tri (meth) acrylates;
A plurality of (meth) acryloyl groups such as N-benzyl-N, N-bis [(meth) acryloyloxyethyl] dodecylammonium chloride and N, N, N-tris [(meth) acryloyloxyethyl] dodecylammonium chloride Having an ammonium salt;
Or following formula (1)

[In the formula, R ¹ is a divalent aromatic residue or cycloalkyl residue which has at least one aromatic ring and may have an oxygen atom or a sulfur atom in the molecule, preferably the following formula (2)

R ² and R ³ each independently represent a hydrogen atom or a methyl group, j and k are each independently 1 to 10, Preferably a positive integer of 1 to 8].
Aliphatic, alicyclic or aromatic epoxy di (meth) acrylate represented by the following formula (3)

[Wherein R ⁴ has a divalent aromatic residue or cycloalkyl residue which has at least one aromatic ring and may have an oxygen atom or a sulfur atom in the molecule, preferably the above formula And any one selected from the group (2), R ⁵ and R ⁶ independently represent a hydrogen atom or a methyl group, and l represents a positive integer of 1 to 10, preferably 1 to 5] ,
Furthermore, a polyfunctional (meth) acrylate having a urethane bond in the molecule represented by the following formula (4)

[Wherein R ⁷ has a divalent aromatic residue or cycloalkyl residue which has at least one aromatic ring and may have an oxygen atom or a sulfur atom in the molecule, preferably the above formula Any one selected from the group of (2), wherein R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group],
Furthermore, a compound having at least one acidic group such as bis (2- (meth) acryloxyethyl) hydrogen phosphate and a plurality of (meth) acryloyl groups can be exemplified.

In addition, a compound that is (meth) acrylamide instead of (meth) acrylic of the above (meth) acrylates, such as methyl (meth) acrylamide and 2,3-dihydroxypropyl (meth) acrylamide, is also preferable. Can be used.
These compounds can be used alone or in combination of two or more.

In the dental kit of the present invention, the blending amount of the component (M2) is preferably 49 to 98% by weight, more preferably 69 to 97% by weight, still more preferably based on the total amount of the dental adhesive composition (B). It is in the range of 74 to 96% by weight. If it exceeds this range, the adhesiveness to the tooth or the prosthesis is remarkably lowered, and if it is below this range, the strength of the polymerizable adhesive composition may be lowered, which is not preferable.
Component (I) of the dental adhesive (B) in the dental adhesive kit of the present invention is a radical polymerization initiator, and is an organic boron compound, an organic peroxide, an inorganic peroxide, an α-diketone compound. , Phosphine oxides, organic amine compounds, organic sulfonic acids, organic sulfinic acids, inorganic sulfur compounds, organic phosphorus compounds, and barbituric acids. These can be used alone or in combination of two or more.

These polymerization initiators can be classified into a room temperature chemical polymerization type and a photopolymerization type for convenience. As a specific example of the component (I), in the room temperature polymerization type,
Triethylboron, tri (n-propyl) boron, triisopropylboron, tri (n-butyl) boron, tri (s-butyl) boron, triisobutylboron, tripentylboron, trihexylboron, trioctylboron, tridecylboron , Trialkyl boron such as tridodecyl boron, tricyclopentyl boron, tricyclohexyl boron;
Alkoxyalkylborons such as butoxydibutylboron;
Dialkylboranes such as butyldicyclohexylborane, diisoamylborane, 9-borabicyclo [3.3.1] nonane;
Aryl borate compounds such as tetraphenyl boron sodium, tetraphenyl boron triethanolamine salt, tetraphenyl boron dimethyl-p-toluidine salt, tetraphenyl boron dimethylaminoethyl benzoate;
Partially oxidized trialkylboron such as partially oxidized tributylboron;
Diacetyl peroxide, dipropyl peroxide, dibutyl peroxide, dicapryl peroxide, dilauryl peroxide, benzoyl peroxide, p, p'-dichlorobenzoyl peroxide, p, p'-dimethoxybenzoyl peroxide, p, p Organic peroxides such as' -dimethylbenzoyl peroxide and p, p'-dinitrodibenzoyl peroxide;
Mention may be made of inorganic peroxides such as ammonium persulfate, potassium chlorate, potassium bromate and potassium perphosphate. Among these, tributyl boron or partially oxidized tributyl boron is preferably used, more preferably partially oxidized tributyl boron, and the polymerization rate is set to an appropriate rate for application to the affected area, for example, in the presence of water or blood. Also has the advantage that the composition can be cured sufficiently.

In addition, as a specific example of the component (I), in the photopolymerization type,
Α-diketones such as 4,4-dichlorobenzyl, diacetyl, dl-camphorquinone;
Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Acetophenones such as propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one;
Benzoin / benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether;
Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone;
Benzophenones such as benzophenone;
Phosphine oxides such as trimethylbenzoyldiphenylphosphine oxide;
And so on.

In the dental composition kit of the present invention, the amount of component (I) is preferably 0.01 to 30% by weight, more preferably 0.5%, based on the total amount of the dental adhesive composition (B). It is in the range of ˜25 wt%, more preferably 1 to 20 wt%, most preferably 1.2 to 15 wt%. If it is below this numerical range, the polymerizability may be lowered, and if it exceeds this range, excessive heat generation during the treatment is a concern, both being undesirable.
In the dental kit of the present invention, the dental adhesive composition (B) can be mixed with a reducing compound (Ir) as desired. Examples of the inorganic compound (Ir) include sulfurous acid, metasulfurous acid, metabisulfurous acid, pyrosulfurous acid, thiosulfuric acid, dithionic acid, dithionic acid, hyposulfite, hydrosulfurous acid, and salts thereof. Among these reducing inorganic compounds, sulfites can be preferably used. As specific compounds of sulfites, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite can be preferably exemplified.

Examples of the organic reducing compound as (Ir) include aromatic compounds such as benzenesulfinic acid, o- or p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, and chlorobenzenesulfinic acid. Sulfinic acid or its salts;
N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-p-toluidine, N, N-dihydroxymethyl-p-toluidine, N, N-dimethyl-pt-butyl In addition to aniline, N, N-dimethylanilysine, N, N-dimethyl-p-chloroaniline, etc., the following formula (6)

(Here, R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an alkyl group which may have a functional group or a substituent, and R ¹² is a hydrogen atom or a metal atom.)
And a compound represented by the following formula (7)

(Here, R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group, and R ¹⁵ is a hydrogen atom, an alkyl group or an alkoxyl group which may have a functional group or a substituent.)
The group represented by these can be mentioned.

Specific examples of the compound included in the above formula (6) include N-phenylglycine, N-tolylglycine, N- (3- (meth) acryloxy-2-hydroxypropyl) -N-phenylglycine and / or these. Can be mentioned. Among these, N-phenylglycine and / or a salt thereof can be preferably used.
Specific examples of the compound included in the above formula (7) include N, N-dimethylaminobenzoic acid and its alkyl ester, N, N-diethylaminobenzoic acid and its alkyl ester, and N, N-di-dioxide. Aliphatic alkylaminobenzoic acid and its alkyl ester represented by propylaminobenzoic acid and its alkyl ester, N-isopropylaminobenzoic acid and its alkyl ester, N-isopropyl-N-methylaminobenzoic acid and its alkyl ester, etc .;
Aliphatic alkylaminobenzaldehydes represented by N, N-dimethylaminobenzaldehyde, N, N-diethylaminobenzaldehyde, N, N-dipropylaminobenzaldehyde, N-isopropyl-N-methylaminobenzaldehyde, and the like;
Fats represented by N, N-dimethylaminoacetylbenzene, N, N-diethylaminoacetylbenzene, N, N-dipropylaminoacetylbenzene, N-isopropylaminoacetylbenzene, N-isopropyl-N-methylaminoacetylbenzene, etc. Examples thereof include aliphatic alkylaminoacetylbenzenes and aliphatic alkylaminoacylbenzenes.
These compounds can be used alone or in combination of two or more.

In the dental kit of the present invention, the blending amount when using the (Ir) component as desired is preferably 0.01 to 30% by weight, more preferably based on the total amount of the dental adhesive composition (B). Is in the range of 0.5 to 25 wt%, more preferably 1 to 20 wt%, most preferably 1.2 to 15 wt%. If it is below this numerical range, the blending effect may not be exhibited, and if it exceeds, not only the storage stability will be affected, but the composition may generate high heat during curing, both being undesirable.
Furthermore, in the dental kit of the present invention, the dental adhesive composition (B) can be blended with a viscosity adjusting material (component (F)) as desired. By using the component (F), operability during application to the oral cavity can be improved. Examples of the component (F) include an organic filler (F1), an inorganic filler (F2), and an organic-inorganic composite filler (F3). (F) By mix | blending component, the fluidity | liquidity of a composition at the time of applying a composition directly to a biological body can be adjusted, and it prevents that a composition flows out to parts other than an affected part carelessly. At the same time, the operability of application can be improved.

Examples of (F1) include polyethylene glycol, polypropylene glycol, polyvinyl alcohol, etc., as well as single monomers listed as the (M) component such as poly (methyl (meth) acrylate) and poly (ethyl (meth) acrylate) Or a copolymer can be mentioned.
Specific examples of (F2) include metal oxide powders such as zirconium oxide, bismuth oxide, titanium oxide, zinc oxide and aluminum oxide particles, silica, bismuth carbonate, zirconium phosphate, barium sulfate, aluminum hydroxide or , CaHPO ₄ , Ca ₃ (PO ₄ ) ₂ , Ca ₅ (PO ₄ ) ₃ OH, Ca ₄ O (PO ₄ ) ₂ , Ca ₈ H ₂ (PO ₄ ) ₆ , Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , CaP ₄ O ₁₁ , Ca (PO ₃ ) ₂ , Ca ₂ P ₂ O ₇ , Ca (H ₂ PO ₄ ) ₂ , CaO, Ca (OH) ₂ , Ca (HCO ₃ ) ₂ , CaCO ₃ , CaCl ₂ Inorganic calcium salts such as 4- (2- (meth) acryloxyethyl) trimellitic acid calcium and 4-styrene calcium calcium , Metal salt powders such as calcium salts of organic acids, silica glass, aluminum-containing glass, barium-containing glass, strontium-containing glass, zirconium silicate glass, and other glass fillers, silver sustained-release fillers, fluorine sustained-release fillers Etc.

  Further, in order to improve the dispersibility in the component (M1) and / or (M2), these inorganic fillers (F2) are subjected to surface treatment such as silane treatment and polymer coating by a conventionally known method. It doesn't matter.

As an example of (F3), trimethylolpropane methacrylate and silica filler can be mixed and polymerized and then pulverized.
Among these components (F), it is preferable to use a homopolymer of the components (M1) and / or (M2), and it is most preferable to use poly (methyl methacrylate).
These (F) components can be used individually or in combination of 2 or more types.
As the particle size of the component (F) is smaller, the viscosity can be adjusted by adding a small amount, but the feeling of application and elongation at the time of application can also be adjusted. Preferably, fillers having an average particle diameter in the range of 1 nm to 50 μm, more preferably 5 nm to 30 μm, and still more preferably 10 nm to 20 μm are used.

The use amount of the component (F) optionally blended in the present invention is preferably 0.5 to 75% by weight, more preferably 1 to 70% by weight, further preferably 2 to 66% by weight based on the total amount of the composition. %, Particularly preferably in the range of 30 to 60% by weight. Below this numerical range, the effect of the blending cannot be confirmed, and when it exceeds, there is a possibility that the fluidity will remarkably increase and the operability may be affected.
In the present invention, `` configured '' is not limited to being all mixed in this composition from the beginning, and if necessary, each component is appropriately sealed and stored, It includes mixing at the time of use.

The use form of the dental kit of the present invention is as follows:
(A) Among the components (I), a photopolymerization initiator is selected, and the dental primer composition (A) and the dental adhesive composition (B) are packed in respective containers. A method of using (B) after polymerization and using a light irradiator for polymerization;
(I) Among the components (I), a component A selected from those other than the photopolymerization initiator and containing the dental primer composition (A), and a container B containing the components (M1) and (M2) (I) A method of using the mixture after storing it separately from the container C containing the components and using (A) after taking out appropriate amounts from the containers B and C;
(U) Container A containing the dental primer composition (A), Container B containing the component (M1), Container C containing the component (M2), and Component (I) A method in which the container D is stored separately, and after using (A), an appropriate amount is taken out from each of the containers B, C, and D and mixed and then used;
Etc. can be illustrated.

  EXAMPLES Hereinafter, although an Example further demonstrates this invention in detail, this invention is not limited at all by an Example.

<Preparation of colloidal platinum solution>
To a GL reactor equipped with a stirrer, a dropping device, a cooling tube and a nitrogen inlet, 0.38 g of sodium polyacrylate (average molecular weight 5 million, manufactured by Nippon Shokubai Co., Ltd.) and 23 ml of purified water are added for 10 minutes. After stirring, 2 ml of an aqueous solution of 1.66 × 10 ⁻² mol / l hexachloroplatinic acid was added and allowed to stir at room temperature for 30 minutes. The system was purged with nitrogen, 25 ml of ethanol was added, and the mixture was refluxed at 100 ° C. for 2 hours to carry out the reaction. After confirming the disappearance of the platinum ion-derived peak from the UV spectrum of the reaction product, about 5 ml of the solvent was distilled off from the reaction product, and 50 ml of ethanol was added and the solvent was distilled off again. Then, 66 ml of purified water was added to the obtained paste-like platinum particles to obtain a metal colloid solution having a polyacrylic acid concentration of 0.58% by weight and a platinum concentration of 0.01% by weight. The R value of the obtained metal colloid solution is 122, and the obtained metal colloid solution is observed with a transmission electron microscope, and the average particle diameter of the metal particles in 2.4 fields randomly extracted is 2.4. It was ± 0.7 nm, and among all the observed particles, the particle size of 90% or more of the metal particles was in the range of 0.1 to 20 nm.

<Preparation of adhesion test specimen>
For convenience, the extracted human crown was cut perpendicularly to the tooth axis with a diamond cutter to expose the dentin, and then polished to water-resistant abrasive paper # 180 to obtain a smooth dentin surface. Moisture was removed from the smooth surface of the ground human teeth once with an air gun.

<Tensile adhesion test>
Human teeth subjected to the below-mentioned adhesion operation were immersed in water at 37 ° C. for 24 hours, and then cut out at about 1 mm intervals in parallel with the tooth axis with a diamond cutter (Ibet made by Buehler) under water injection to obtain an adhesive slice. . The obtained bonded slices were cut with a diamond cutter under water injection and parallel to the tooth axis and perpendicular to the first slice plane at intervals of about 1 mm to obtain a rectangular parallelepiped tensile test evaluation body. After measuring the adhesion area of the obtained evaluation body for tensile adhesion test, the micro tensile strength was measured at a crosshead speed of 1 mm / min with a universal testing machine (EZ Test manufactured by Shimadzu Corporation).

Example 1
The dentin surface of the adhesion test specimen is treated with a dentin surface treatment material green (trade name, dental surface treatment agent for dentin mainly composed of citric acid and ferric chloride, manufactured by Sun Medical Co., Ltd.) for 10 seconds. Treated, washed with water and dried. 30 mg of the above-mentioned metal colloid solution was applied to the dentin surface, and after standing for 10 seconds, excess water was removed with air. Collect 4 drops of superbond C & B (trade name, dental resin-based adhesive) monomer solution from a bottle in a mixing dish, and superbond catalyst (product name, partially oxidized tributyl boron, oxygen addition amount to 1 mol of tributyl boron). 1 drop of 0.5 mol, manufactured by Sun Medical Co., Ltd. from a syringe, and one cup of Super Bond Polymer Powder Clear (trade name, polymethyl methacrylate, manufactured by Sun Medical Co., Ltd.) is taken out with an attached spoon, These were mixed with an adhesive brush, applied to the adhesive tooth surface, and then planted by pressing a rectangular parallelepiped polymethyl methacrylate rod having a side of 1 cm. The adhesive strength described above was 42.2 MPa. Comparison with Comparative Example 1 and Comparative Example 5 confirmed that the adhesion was improved by applying a composition comprising a metal colloid solution.

Example 2
30 μl of a 5% hypochlorous acid aqueous solution was applied to the dentin surface of the adhesion test specimen and sterilized by allowing it to stand for 1 minute. Washed with water and blown with air, then treated with dentin surface treatment material Green (trade name, dental surface treatment agent for dentin mainly composed of citric acid and ferric chloride, manufactured by Sun Medical Co., Ltd.) for 10 seconds. Washed with water and dried. 30 mg of the above-mentioned metal colloid solution was applied to the dentin surface, and after standing for 10 seconds, excess water was removed with air. Collect 4 drops of superbond C & B (trade name, dental resin-based adhesive) monomer solution from a bottle in a mixing dish, and superbond catalyst (product name, partially oxidized tributyl boron, oxygen addition amount to 1 mol of tributyl boron). 1 drop of 0.5 mol, manufactured by Sun Medical Co., Ltd. from a syringe, and one cup of Super Bond Polymer Powder Clear (trade name, polymethyl methacrylate, manufactured by Sun Medical Co., Ltd.) is taken out with an attached spoon, These were mixed with an adhesive brush, applied to the adhesive tooth surface, and then planted by pressing a rectangular parallelepiped polymethyl methacrylate rod having a side of 1 cm. The adhesive strength described above was 23.5 MPa. By comparison with Comparative Example 1, Comparative Example 2, Comparative Example 5, and Comparative Example 6, even in the case of a sterilized tooth, improvement in adhesiveness was confirmed by application of a composition comprising a metal colloid solution.

Example 3
30 mg of the above-mentioned metal colloid solution was applied to the dentin surface of the adhesion test specimen, and after leaving for 10 seconds, excess water was removed with air. Take two drops of AQ Bond SP (trade name, dental resin adhesive, manufactured by Sun Medical Co., Ltd.) solution from the bottle on the dentin surface, soak the attached sponge in the solution, And applied to the dentin surface of the adhesion test specimen. After blowing air for 5 seconds and irradiating the coated surface with a dental halogen light irradiator (Candelux, manufactured by Morita Manufacturing Co., Ltd.) for 3 seconds, a dental composite resin (Metafil C, A3, Sun Medical ( (Made by Co., Ltd.) was built and further irradiated with light for 20 seconds. Next, 4 drops of superbond C & B (trade name, dental resin adhesive) monomer liquid were collected from the bottle, and superbond catalyst (product name, partially oxidized tributyl boron, oxygen addition amount was 0 per 1 mol of tributyl boron). .5 mol, Sun Medical Co., Ltd.) is dropped from a syringe, and a superbond polymer powder clear (trade name, polymethyl methacrylate, Sun Medical Co., Ltd.) is taken out with an attached spoon. Were mixed with an adhesive brush, applied to the adhesive tooth surface, and then planted by press-contacting a rectangular parallelepiped polymethyl methacrylate rod having a side of 1 cm. When the above-described adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 40.5 MPa. Comparison with Comparative Example 3 and Comparative Example 7 confirmed that the adhesion was improved by applying a composition comprising a metal colloid solution.

Example 4
Apply scotch bond etchant (trade name, phosphoric acid-based etching material, manufactured by 3M) to the dentin surface of the adhesion test specimen, leave it for 15 seconds, wash it with water, perform air blow for 1 second, and surplus Water was removed. Subsequently, 30 mg of the above-mentioned metal colloid solution was applied, left standing for 10 seconds and then air blown for 1 second to remove excess water. Immediately a single bond (trade name, dental resin adhesive, manufactured by 3M Company) was applied to the dentin surface using the attached brush. After drying with air, the coated surface was irradiated with light for 5 seconds with a dental halogen light irradiator (Candelux, manufactured by Morita Manufacturing Co., Ltd.), and then a dental composite resin (Z250, A3, manufactured by 3M) And irradiated with light for another 20 seconds. Next, 4 drops of superbond C & B (trade name, dental resin adhesive) monomer liquid were collected from the bottle, and superbond catalyst (product name, partially oxidized tributyl boron, oxygen addition amount was 0 per 1 mol of tributyl boron). .5 mol, Sun Medical Co., Ltd.) is dropped from a syringe, and a superbond polymer powder clear (trade name, polymethyl methacrylate, Sun Medical Co., Ltd.) is taken out with an attached spoon. Were mixed with an adhesive brush, applied to the adhesive tooth surface, and then planted by press-contacting a rectangular parallelepiped polymethyl methacrylate rod having a side of 1 cm. When the above-described adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 75.1 MPa. Comparison with Comparative Example 4 and Comparative Example 8 confirmed that the adhesion was improved by applying a composition comprising a metal colloid solution.

Comparative Example 1
In Example 1, the same operation was performed except that the metal colloid solution was replaced with purified water. The adhesive strength described above was 18.4 MPa.

Comparative Example 2
In Example 2, the same operation was performed except that the metal colloid solution was replaced with purified water. When the above-mentioned adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 15.1 MPa.

Comparative Example 3
In Example 3, the same operation was performed except that the metal colloid solution was replaced with purified water. When the above-described adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 32.1 MPa.

Comparative Example 4
In Example 4, the same operation was performed except that the metal colloid solution was replaced with purified water. When the above-described adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 61.2 MPa.

Comparative Example 5
In Example 1, the same operation was performed except that the metal colloid solution was replaced with an aqueous solution of 1.66 × 10 ⁻⁴ mol / l hexachloroplatinic acid. The adhesive strength described above was 15.3 MPa.

Comparative Example 6
In Example 2, the same operation was performed except that the metal colloid solution was replaced with a 1.66 × 10 ⁻⁴ mol / l hexachloroplatinic acid aqueous solution. When the above-mentioned adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 10.5 MPa.

Comparative Example 7
In Example 3, the same operation was performed except that the metal colloid solution was replaced with a 1.66 × 10 ⁻⁴ mol / l hexachloroplatinic acid aqueous solution. When the above-described adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 29.8 MPa.

Comparative Example 8
In Example 4, the same operation was performed except that the metal colloid solution was replaced with an aqueous solution of 1.66 × 10 ⁻⁴ mol / l hexachloroplatinic acid. When the above-mentioned adhesion test was performed, the fracture occurred at the interface between the adhesive and the tooth, and the adhesion strength was 50.4 MPa.

Claims (5)

The colloidal metal particles have an average particle diameter of 0.6 to 20 nm and 90% or more of the colloidal metal particles have a particle diameter in the range of 0.3 to 30 nm, and a water-soluble polymer compound as a colloid protective material A dental primer composition comprising a colloidal metal solution.   The dental primer composition according to claim 1, wherein the metal of the metal colloid solution is a transition metal.   The dental primer composition according to claim 1 or 2, wherein the metal in the metal colloid solution is platinum.   The dental primer composition according to any one of claims 1 to 3, wherein the metal content is 0.00001 to 0.2% by weight.   A dental kit comprising the dental primer according to any one of claims 1 to 4 and a dental adhesive composition.