JP7428482B2 - dental cleaning materials - Google Patents

Description

The present invention relates to dental restorations such as cured dental composite resins (hereinafter simply referred to as "cured dental composite resins") containing porcelain, ceramics, metal oxides, inorganic fillers, and resins, and This invention relates to dental cleaning materials used for cleaning tooth surfaces and other abutment teeth.

Traditionally, in restorative treatment in the dental field, dental restorations have been made of porcelain, ceramics, metal oxides, cured dental composite resins, etc., and have been used in various ways to fit tooth defects. It's here. This dental restoration is generally trial-inserted before being fixed in order to confirm suitability. In this case, even when a dental rubber dam is used, contamination of the dental restoration and the abutment tooth by protein-containing body fluids (eg, saliva, tooth fluid, blood, etc.) is virtually inevitable. When the dental restoration and the abutment tooth are bonded together afterwards, these protein-containing body fluids are deposited between the dental restoration and the dental adhesive or dental cement, or between the abutment tooth and the dental cement. This results in decreased adhesion with adhesives or dental cement. Dental cleaning materials have been proposed as a means for removing contamination from protein-containing body fluids (Patent Documents 1 and 2).
Patent Document 1 describes a tooth surface cleaning material as a method for removing plaque, coloration, etc. from tooth surfaces. WO 2005/000002 describes a composition containing cleaning particles for cleaning dental restorations, in particular for removing protein contaminants.

JP2016-003213A Patent No. 5607559

However, although Patent Document 1 defines a dental cleaning material containing water, a surfactant, and a basic substance with a pH of 12 to 13, it cannot be used in the oral cavity because it is strongly alkaline, and it is not safe. There was a problem. Further, Patent Document 2 describes a composition containing cleaning particles for removing protein contaminants within the scope of adhesive fixation of dental restorative materials, but this composition contains hydroxylated particles. Since it is a basic substance containing sodium, it cannot be used in the oral cavity, which poses a safety problem.

Further, as a dental cleaning material, it is necessary to suppress the formation of precipitates during storage in a refrigerator. The formation of precipitates can result in non-uniform compositions and variations in performance. Additionally, solids may remain on the surface of the prosthesis during cleaning, resulting in decreased adhesion.

In view of the above circumstances, the problem to be solved by the present invention is to eliminate variations in performance by suppressing the formation of precipitates, and to prevent contamination of dental restorations and abutment teeth with protein-containing body fluids. An object of the present invention is to provide a dental cleaning material that exhibits excellent cleaning properties, has excellent adhesive durability after cleaning, and is safe even when used in the oral cavity.

As a result of extensive studies, the present inventors discovered that the above object could be achieved by containing the acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c). This led to the invention. That is, the present invention includes the following inventions.
[1] A dental cleaning material containing an acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c).
[2] The dental cleaning material according to [1], which has a pH of less than 8.0.
[3] The acidic group-containing radically polymerizable monomer (a) is a phosphoric acid group-containing (meth)acrylic monomer, a pyrophosphoric acid group-containing (meth)acrylic monomer, and a carboxylic acid group-containing ( The dental cleaning material according to [1] or [2], which is at least one selected from the group consisting of meth)acrylic monomers.
[4] The dental cleaning material according to any one of [1] to [3], wherein the organic amine compound (c) contains a tertiary organic amine compound.
[5] The dental cleaning material according to any one of [1] to [4], further containing a basic inorganic compound (d).
[6] The basic inorganic compound (d) is at least one basic substance selected from the group consisting of phosphate, hydrogen phosphate, and dihydrogen phosphate, according to [5]. Dental cleaning materials.
[7] The basic inorganic compound (d) is at least one selected from the group consisting of alkali metal phosphates, alkali metal hydrogen phosphates, and alkali metal dihydrogen phosphates, [5] Or the dental cleaning material according to [6].
[8] Furthermore, at least one gelling agent (e ) The dental cleaning material according to any one of [1] to [7].
[9] The dental cleaning material according to [8], wherein the gelling agent (e) is a hydrophilic filler (e-1) and a hydrophobic filler (e-2).
[10] The dental cleaning according to [9], wherein the hydrophilic filler (e-1) is hydrophilic fumed silica, and the hydrophobic filler (e-2) is hydrophobic fumed silica. Material.
[11] The dental use according to [9] or [10], wherein the mass ratio of the hydrophilic filler (e-1) and the hydrophobic filler (e-2) is in the range of 4:6 to 2:8. Cleaning materials.
[12] A method for producing a dental cleaning material, including the step of mixing an acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c).

The dental cleaning material of the present invention exhibits excellent cleaning properties against contamination of dental restorations and abutment teeth with protein-containing body fluids, has excellent adhesive durability after cleaning, and has excellent adhesive properties when used in the oral cavity. It's also safe. Furthermore, since there is no formation of solid precipitates during storage or use, there is no possibility of variation in performance or inhibition of adhesion. Furthermore, the dental cleaning material of the present invention also has excellent antiseptic properties that prevent the growth of mold and the like.

The dental cleaning material of the present invention is characterized by containing an acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c).

Hereinafter, the acidic group-containing radically polymerizable monomer (a), water (b), and organic amine compound (c), which are the components of the dental cleaning material of the present invention, will be explained.

First, the acidic group-containing radically polymerizable monomer (a) used in the present invention will be explained.

The acidic group-containing radically polymerizable monomer (a) reacts with the organic amine compound (c) to form a salt, and due to its surfactant effect, the acidic group-containing radically polymerizable monomer (a) reacts with the organic amine compound (c) to form a salt, and due to its surfactant effect, it is able to absorb protein-containing body fluids and substances derived from protein-containing body fluids (e.g., plaque, pellicle, etc.). ) to improve cleaning effectiveness against contamination. Further, the acidic group-containing radically polymerizable monomer (a) penetrates into the tooth substance while demineralizing it, bonds to the tooth substance, and improves adhesiveness to the tooth substance. Furthermore, when the acidic group-containing radically polymerizable monomer (a) is combined with the organic amine compound (c), it exhibits excellent adhesion durability to the tooth substance and dental prosthesis after cleaning. Further, the acidic group-containing radically polymerizable monomer (a) exhibits antiseptic properties that prevent the growth of mold and the like when combined with the organic amine compound (c). The acidic group-containing radically polymerizable monomer (a) has at least one acidic group such as a phosphoric acid group, a phosphonic acid group, a pyrophosphoric acid group, a carboxylic acid group, a sulfonic acid group, and an acryloyl group or a methacryloyl group. It is a polymerizable monomer having at least one radically polymerizable group such as , an acrylamide group, or a methacrylamide group. The acidic group-containing radically polymerizable monomer (a) includes a phosphoric acid group-containing (meth)acrylic monomer, a pyrophosphoric acid group-containing (meth)acrylic monomer, and a carboxylic acid group-containing (meth)acrylic monomer. It is preferable that the monomer is at least one selected from the group consisting of monomers. From the viewpoint of adhesion to enamel, the acidic group-containing radically polymerizable monomer (a) is a monofunctional acidic group-containing monomer having any one of an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group. Preferably, it is a meth)acrylic monomer. Specific examples include the following. Note that in this specification, methacrylic and acrylic are collectively referred to as "(meth)acrylic."

Examples of the phosphoric acid group-containing (meth)acrylic monomer include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, and 4-(meth)acryloyloxy. Butyl 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)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl] Hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis [9-(meth)acryloyloxynonyl] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth) Acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl)hydrogen phosphate, 2-(meth)acryloyl Examples include oxypropyl-(4-methoxyphenyl) hydrogen phosphate and amine salts thereof.

Examples of the phosphonic acid group-containing (meth)acrylic monomer include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, and 6-(meth)acryloyloxypentyl-3-phosphonopropionate. Acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-phosphonoacetate, 10-(meth)acryloyloxydecyl -phosphonoacetates, their amine salts.

Examples of the (meth)acrylic monomer containing a pyrophosphate group include bis[2-(meth)acryloyloxyethyl pyrophosphate], bis[4-(meth)acryloyloxybutyl] pyrophosphate, and bis[6-(meth)acryloyloxybutyl pyrophosphate]. -(meth)acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and amine salts thereof.

Examples of carboxylic acid group-containing (meth)acrylic monomers include (meth)acrylic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid; 4-(meth)acryloyloxyethyltrimellitic acid, 4-( meth)acryloyloxybutyloxycarbonylphthalic acid, 4-(meth)acryloyloxyhexyloxycarbonylphthalic acid, 4-(meth)acryloyloxyoctyloxycarbonylphthalic acid, 4-(meth)acryloyloxydecyloxycarbonylphthalic acid, and these Acid anhydride; 5-(meth)acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, 8-(meth)acryloyloxy-1,1-octanedicarboxylic acid, 10- Examples include (meth)acryloyloxy-1,1-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, and amine salts thereof.

Examples of the sulfonic acid group-containing (meth)acrylic monomer include 2-(meth)acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, and amine salts thereof.

Among the acidic group-containing radically polymerizable monomers (a), (meth)acrylic monomers containing phosphoric acid groups, pyrophosphoric acid groups, or carboxylic acid groups are more effective against dental restorations and tooth structure. It is preferable because it exhibits excellent adhesive strength, and phosphoric acid group-containing (meth)acrylic monomers are particularly preferable. Among these, divalent phosphoric acid group-containing (meth)acrylic monomers having an alkyl group or alkylene group having 6 to 20 carbon atoms as a main chain in the molecule are more preferable, and 10-methacryloyloxydecyl dihydrogen A divalent phosphoric acid group-containing (meth)acrylic monomer having an alkylene group having 8 to 12 carbon atoms as a main chain in the molecule, such as phosphate, is most preferred.

The acidic group-containing radically polymerizable monomer (a) may be used alone or in combination of two or more types. If the content of the acidic group-containing radically polymerizable monomer (a) is too small, the effect of blending the acidic group-containing radically polymerizable monomer (a) may not be obtained; if it is too large, the acidic group-containing radically polymerizable monomer (a) A large amount of the group-containing radically polymerizable monomer (a) remains in the dental restoration and the abutment tooth, which may reduce the hardenability of the dental adhesive material applied afterwards, resulting in a decrease in adhesive properties. . The content of the acidic group-containing radically polymerizable monomer (a) is not particularly limited as long as it achieves the effects of the present invention, but it is preferably in the range of 0.1 to 30 parts by mass based on a total of 100 parts by mass of the dental cleaning material. Preferably, the range is from 0.5 to 20 parts by weight, more preferably from 1.0 to 15 parts by weight, and particularly preferably from 2.0 to 8.0 parts by weight.

The dental cleaning material according to the present invention may contain, as a polymerizable monomer, a radically polymerizable monomer that does not contain an acidic group, in addition to the acidic group-containing radically polymerizable monomer (a). Examples of radically polymerizable monomers that do not contain acidic groups include radically hydrophilic polymerizable monomers that do not contain acidic groups, and hydrophobic polymerizable monomers that do not contain acidic groups. A radical hydrophilic polymerizable monomer that does not contain an acidic group means one having a solubility in water of 10% by mass or more at 25°C, preferably one having a solubility of 30% by mass or more, and any It is more preferable to use a substance that can be dissolved in water in a certain proportion. A hydrophobic polymerizable monomer that does not contain an acidic group means one that has a solubility in water at 25°C of less than 10% by mass, and includes, for example, an aromatic compound-based difunctional polymerizable monomer, an aliphatic Examples include crosslinkable polymerizable monomers such as compound-based bifunctional polymerizable monomers and trifunctional or higher functional polymerizable monomers. In a preferred embodiment, the radically polymerizable monomer contains an acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c), and contains substantially no acidic group. Examples include dental cleaning materials that do not contain the body. "Substantially free of radically polymerizable monomers that do not contain acidic groups" means that the content of radically polymerizable monomers that do not contain acidic groups is the total amount of polymerizable monomers contained in the dental cleaning material. It means less than 5.0% by mass, preferably less than 1.0% by mass.

Next, water (b) used in the present invention will be explained.

Water (b) is a solvent that dissolves the organic amine compound (c) and the acidic group-containing radically polymerizable monomer (a). Further, the demineralization effect of the acidic group-containing radically polymerizable monomer (a) on the tooth substance is promoted, and the adhesiveness is improved. The water (b) must be one that does not substantially contain impurities that adversely affect adhesion, and distilled water or ion-exchanged water is preferable. The content of water (b) is preferably in the range of 40 to 99.8 parts by mass, more preferably in the range of 50 to 99 parts by mass, and in the range of 60 to 98 parts by mass, based on a total of 100 parts by mass of the dental cleaning material. is even more preferable.

The dental cleaning material according to the present invention may further contain a solvent other than water. By further blending a solvent other than water, a more efficient cleaning effect may be expected by adjusting the viscosity of the dental cleaning material and concentrating the active ingredients. Examples of solvents other than water include organic solvents such as acetone and ethyl methyl ketone; ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, glycerin, diglycerin, polyglycerin, propylene glycol, di- Examples include alcohols such as propylene glycol, polypropylene glycol, ethylene glycol, diethylene glycol, polyethylene glycol, polyethylene glycol monomethyl ether, 1,2-pentadiol, 1,2-hexanediol, and 1,2-octanediol. The content of the solvent other than water (b) is not particularly limited, but is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 20 parts by mass or less, based on a total of 100 parts by mass of the dental cleaning material. preferable. Further, the content of the solvent other than water (b) is preferably 100 parts by mass or less, more preferably 85 parts by mass or less, and may be 60 parts by mass or less, based on 100 parts by mass of water (b). .

Next, the organic amine compound (c) used in the present invention will be explained.

The organic amine compound (c) has a cleaning effect on contamination caused by protein-containing body fluids and substances derived from protein-containing body fluids, and improves the solubility of the acidic group-containing radically polymerizable monomer (a) in water. The formation of precipitates can be suppressed, and excellent adhesive strength and adhesive durability can be imparted to dental cleaning materials without variations in performance. In addition, a part of the organic amine compound (c) reacts with the acidic group-containing radically polymerizable monomer (a) to form a salt, which further improves the cleaning effect against contamination by protein-containing body fluids due to the surfactant effect. can be done. Furthermore, since the dental cleaning material contains the organic amine compound (c), it provides excellent adhesive strength and adhesive durability to dental restorations and tooth structure after cleaning. The organic amine compound (c) may contain a primary organic amine compound or a secondary organic amine compound, but preferably contains a tertiary organic amine compound from the viewpoint of suppressing side reactions. The organic amine compound (c) may be aliphatic or aromatic. In one embodiment, the organic amine compound (c) is an aliphatic compound having one or more hydroxyl groups because it can impart superior adhesive strength and adhesive durability to the dental cleaning material without variations in performance. It is preferable to include an aromatic tertiary organic amine compound having one or more hydroxyl groups, an aliphatic tertiary organic amine compound having two or more hydroxyl groups, It is more preferable to include an aromatic tertiary organic amine compound having two or more hydroxyl groups.

Examples of aliphatic tertiary organic amine compounds include N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, and N-methyldiethanolamine. Dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine, etc., with no variation in performance and adhesive strength. Triethanolamine and 2-(dimethylamino)ethyl methacrylate are more preferred because they have better adhesive strength and adhesive durability.

Examples of aromatic tertiary organic amine compounds include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4- Isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, N,N-bis(2 -hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p -Toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline , N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, methyl 4-(N,N-dimethylamino)benzoate, 4-(N, Ethyl N-dimethylamino)benzoate, butyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino) Examples include 2-(methacryloyloxy)ethyl benzoate, 4-(N,N-dimethylamino)benzophenone, etc. N,N-bis(2 -hydroxyethyl)-p-toluidine is more preferred.

The organic amine compound (c) may be used alone or in combination of two or more. If the content of the organic amine compound (c) is too low, the effect of blending the organic amine compound (c) may not be obtained, and if it is too high, the basicity will become strong and cause protein denaturation. , safety in the oral cavity may decrease. The content of the organic amine compound (c) is not particularly limited as long as it achieves the effects of the present invention, but from the viewpoint of the pH of the dental cleaning material (solution or suspension), in 100 parts by mass of the dental cleaning material in total. , preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.2 to 10 parts by weight, even more preferably in the range of 0.25 to 5 parts by weight.

The dental cleaning material of the present invention preferably contains a basic inorganic compound (d). The basic inorganic compound (d) is preferably at least one kind of basic substance selected from phosphates, hydrogen phosphates, and dihydrogen phosphates, and even if incorporated in a small amount, protein-containing Provides a cleaning effect against contamination by body fluids and substances derived from protein-containing body fluids. In addition, a part of the basic inorganic compound (d) reacts with the acidic group-containing radically polymerizable monomer (a) to form a salt, and the surfactant effect improves the cleaning effect against contamination by protein-containing body fluids. can be done. Furthermore, since the dental cleaning material contains the basic inorganic compound (d), it has excellent adhesive strength and adhesive durability for dental restorations and tooth tissue after cleaning. Examples of the basic inorganic compound (d) include alkali phosphates such as trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate. Metal salts, alkali metal hydrogen phosphates or alkali metal dihydrogen phosphates; alkaline earth metal phosphates such as tricalcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, alkaline earth metal hydrogen phosphates salts or alkaline earth metal salts of dihydrogen phosphate; examples include trimagnesium phosphate, magnesium hydrogen phosphate, etc.; It is preferable that it is at least one selected from the group consisting of: Among these, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate are more preferred.

The basic inorganic compound (d) may be used alone or in combinations of two or more. If the content of the basic inorganic compound (d) is too small, there is a risk that the effect of the combination of the basic inorganic compound (d) cannot be obtained, and if it is too large, the basicity becomes strong and may cause protein denaturation. This may reduce safety in the oral cavity. In addition, if the amount is too large, the basic inorganic compound (d) itself may precipitate, resulting in decreased operability and a risk that a sufficient cleaning effect on protein-containing body fluids may not be obtained. The content of the basic inorganic compound (d) is not particularly limited as long as it achieves the effects of the present invention, but from the viewpoint of the pH of the dental cleaning material (solution or suspension), the content of the basic inorganic compound (d) is 100 parts by mass in total of the dental cleaning material. The amount is preferably from 0.1 to 20 parts by weight, more preferably from 0.2 to 10 parts by weight, and even more preferably from 0.25 to 5 parts by weight.

The dental cleaning material of the present invention preferably has a pH of less than 8.0. When the pH satisfies the above range, a safer dental cleaning material with excellent adhesive strength and adhesive durability after cleaning can be obtained, preferably 2.0 or more and less than 8.0, and 2.5 or more. It is more preferably 7.5 or less, even more preferably 3.0 or more and 6.5 or less, and particularly preferably 3.5 or more and 5.5 or less. The pH can be measured using a known measuring device. Examples of the measuring device include "LAQUAtwin" manufactured by Horiba, Ltd.

The dental cleaning material of the present invention preferably contains a gelling agent (e). Examples of the gelling agent (e) include a hydrophilic filler (e-1), a hydrophobic filler (e-2), and a polymeric thickener (e-3). The gelling agent (e) may be used alone or in combination of two or more. In one embodiment of the invention, the dental cleaning material contains a hydrophilic filler (e-1) and a hydrophobic filler (e-2) as gelling agent (e). In other embodiments, the dental cleaning material contains only a polymeric thickener (e-3) as the gelling agent (e). In yet another embodiment, the dental cleaning material contains a hydrophilic filler (e-1), a hydrophobic filler (e-2), and a polymeric thickener (e-3). As a dental cleaning material, a gelling agent (e) that is a combination of all three types: a hydrophilic filler (e-1), a hydrophobic filler (e-2), and a polymeric thickener (e-3) is used. It is preferable to contain. The combination of hydrophilic filler (e-1), hydrophobic filler (e-2), and polymeric thickener (e-3) turns the dental cleaning material into a gel, which can be used to clean dental restorations, tooth surfaces, etc. The ease of application to the abutment tooth can be further improved, and the effect of cleaning protein-containing body fluids and substances derived from protein-containing body fluids is brought about without inhibiting the surfactant effect.

The hydrophilic filler (e-1) means a filler whose particle surface has not been subjected to hydrophobization treatment. For example, when the hydrophilic filler (e-1) is a particle having a silanol group on the surface of silica or the like, it means a particle in which the silanol group on the surface is untreated. The hydrophobic filler (e-2) means a filler whose particle surface has been subjected to a hydrophobic treatment. For example, when the hydrophobic filler (e-2) is a particle having a silanol group on the surface of silica or the like, the silanol group on the surface is dimethylsilyl, trimethylsilyl, dimethylpolysiloxane, dimethylsiloxane, aminoalkylsilyl, methacrylsilyl. These are particles made hydrophobic with substituents such as , alkylsilyl, etc. As the hydrophilic filler (e-1), a hydrophilic inorganic filler is preferable, and hydrophilic fumed silica is more preferable. As the hydrophobic filler (e-2), a hydrophobic inorganic filler is preferable, and hydrophobic fumed silica is more preferable. In the present specification, the average particle diameter of the hydrophilic filler (e-1) and the hydrophobic filler (e-2) is not particularly limited, and is preferably 0.0001 to 50 μm, more preferably 0.001 to 10 μm, The thickness is more preferably 0.001 to 1.0 μm from the viewpoint of better applicability of the dental cleaning material. The average particle size of the hydrophilic filler (e-1) and the hydrophobic filler (e-2) is the average primary particle size, and is determined by laser diffraction scattering method or electron microscopic observation of the particles. Specifically, a laser diffraction scattering method is convenient for measuring the particle size of particles of 0.1 μm or more, and electron microscopy is convenient for measuring the particle size of ultrafine particles of less than 0.1 μm. 0.1 μm is a value measured by laser diffraction scattering method. Specifically, the laser diffraction scattering method can be measured using, for example, a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation) using a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium. can. For electron microscopic observation, a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, SU3800, S-4000, etc.) can be used. Specifically, for example, electron microscopy is performed by taking an electron micrograph of particles, and measuring the particle diameters of the particles (200 or more) observed within a unit field of view using image analysis particle size distribution measurement software (Mac-View). (manufactured by Mountec Co., Ltd.)). At this time, the particle diameter is determined as the arithmetic mean value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

Examples of the hydrophilic filler (e-1) include hydrophilic fumed silica: fine particle silica manufactured by Nippon Aerosil Co., Ltd., such as AEROSIL (registered trademark) 90, AEROSIL (registered trademark) 130, AEROSIL (registered trademark) 150, AEROSIL (registered trademark) 200, AEROSIL (registered trademark) 255, AEROSIL (registered trademark) 300, AEROSIL (registered trademark) 380, AEROSIL (registered trademark) OX50, AEROSIL (registered trademark) TT600, AEROSIL (registered trademark) 200 F, Examples include AEROSIL(R) 380 F, AEROSIL(R) 200 Pharma, and AEROSIL(R) 300 Pharma, with AEROSIL(R) 130 being preferred. .

Examples of the hydrophobic filler (e-2) include hydrophobic fumed silica: fine particle silica manufactured by Nippon Aerosil Co., Ltd., such as AEROSIL (registered trademark) R972, AEROSIL (registered trademark) R974, AEROSIL (registered trademark) R104, AEROSIL (registered trademark) R106, AEROSIL (registered trademark) R202, AEROSIL (registered trademark) R208, AEROSIL (registered trademark) R805, AEROSIL (registered trademark) R812, AEROSIL (registered trademark) R812 S, AEROSIL (registered trademark) R816, AEROSIL (registered trademark) R7200, AEROSIL (registered trademark) R8200, AEROSIL (registered trademark) R9200, AEROSIL (registered trademark) R711, AEROSIL (registered trademark) R50, AEROSIL (registered trademark) NY50, AEROSIL (registered trademark) NY50 L, AEROSIL (registered trademark) NY200, AEROSIL (registered trademark) RY200 S, AEROSIL (registered trademark) RX50, AEROSIL (registered trademark) NY50, AEROSIL (registered trademark) RX, AEROSIL (registered trademark) RX00, AEROSIL (registered trademark) R504, AEROSIL (registered trademark) RNX90 S, AEROSIL (registered trademark) NX90 G, AEROSIL (registered trademark) RY300, AEROSIL (registered trademark) REA90, AEROSIL (registered trademark) REA200, AEROSIL (registered trademark) RY51, AEROSIL (registered trademark) NA50 Y, AEROSIL (registered trademark) RA200 HS, AEROSIL (registered trademark) NA50 H, AEROSIL (registered trademark) RA200 HS, AEROSIL (registered trademark) NA130 K, AEROSIL (registered trademark) NA200 Y, AEROSIL (registered trademark) NX130, AEROSIL (registered trademark) RY200 L, AEROSIL (registered trademark) R709, and AEROSIL (registered trademark) R976 S, with AEROSIL (registered trademark) R972 being preferred.

In addition, the polymeric thickener (e-3) refers to a polymer that is added to materials to adjust the viscosity and improves dispersibility and thickening properties, and may be a natural substance or a synthetic It may be a substance. Examples of natural substances include casein, methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, and examples of synthetic substances include polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyethylene glycol, and polyvinylpyrrolidone. Commercially available polymeric thickeners (e-3) can be used, including macrogol 4000 (manufactured by Maruishi Pharmaceutical Co., Ltd.), macrogol 400 (manufactured by Maruishi Pharmaceutical Co., Ltd.), which are polyethylene glycol-based thickeners. Among them, macrogol 4000 (manufactured by Maruishi Pharmaceutical Co., Ltd.) is preferred.

It is preferable that the hydrophilic filler (e-1) is hydrophilic fumed silica, and the hydrophobic filler (e-2) is hydrophobic fumed silica. In addition, from the viewpoint of suppressing separation of the gel component and liquid component contained in the dental cleaning material, the mass ratio of the hydrophilic filler (e-1) and the hydrophobic filler (e-2) is 4:6 to 2: The range is preferably 8, more preferably 4.3:5.7 to 2.2:7.8. Furthermore, regarding the polymeric thickener (e-3), from the viewpoint of suppressing the separation of the gel component and liquid component contained in the dental cleaning material, 1 to The range is preferably 25 parts by weight, more preferably 4 to 20 parts by weight, and even more preferably 8 to 17 parts by weight.

In addition, the dental cleaning material of the present invention may include a fluoride ion-releasing substance, a pH adjuster, a polymerization inhibitor (for example, dibutylhydroxytoluene (BHT), hydroquinone monomethyl ether ( MEHQ)), colorants, fluorescent agents, fragrances, etc. may also be blended. In addition, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecyl ammonium chloride, and triclosan may be added. good.

The method for producing a dental cleaning material of the present invention is characterized by including a step of mixing an acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c). The mixing method and the equipment used for mixing are not particularly limited as long as the effects of the present invention are achieved, but when the solubility of the acidic group-containing radically polymerizable monomer (a) in water (b) is low, an organic amine compound may be used. After mixing (c) with water (b), the radically polymerizable monomer (a) containing an acidic group is mixed, or the organic amine compound (c) is mixed with the radically polymerizable monomer (a) containing an acidic group. A preferred method is to mix water (b) after mixing with water. In addition, when the dental cleaning material contains other components other than the above-mentioned components (a) to (c), the components (a) to (c) and the other components may be mixed at the same time. , (a) to (c) may be combined with a step of mixing the components separately.

The present invention includes embodiments in which the above configurations are combined in various ways within the scope of the technical idea of the present invention as long as the effects of the present invention are achieved.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples. The abbreviations used below are as follows.

[Acidic group-containing radically polymerizable monomer (a)]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate [organic amine compound (c)]
TTA: Triethanolamine DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine DMAEMA: 2-(dimethylamino)ethyl methacrylate [gelling agent (e)]
(e-1): Hydrophilic fumed silica: Fine particle silica "AEROSIL (registered trademark) 130" manufactured by Nippon Aerosil Co., Ltd. (average particle diameter: 16 nm)
(e-2): Hydrophobic fumed silica: Fine particle silica "AEROSIL (registered trademark) R972" manufactured by Nippon Aerosil Co., Ltd. (average particle diameter: 16 nm)
(e-3): Polyvinylpyrrolidone (manufactured by IPS Corporation), Macrogol 4000 (manufactured by Maruishi Pharmaceutical Co., Ltd.)

[Examples 1 to 9 and Comparative Examples 1 to 7]
As examples and comparative examples, dental cleaning materials were prepared as follows.

[Preparation of dental cleaning materials]
A dental cleaning material was prepared by mixing the components listed in Tables 3 and 4 below at room temperature in the mass ratios listed in Tables 3 and 4. The obtained dental cleaning material was filled into a container of "Teeth Mate (registered trademark) Desensitizer Liquid" (manufactured by Kuraray Noritake Dental Co., Ltd.) and used.

[pH measurement]
The pH of the prepared dental cleaning material was measured using a pH meter ("LAQUAtwin" manufactured by Horiba, Ltd.).

[Verification of presence or absence of precipitate formation during refrigerated storage]
Fill a 440mL container with dental cleaning material and store it in a refrigerator at 4°C for one week. Visually check for the presence or absence of precipitates. If no precipitates are formed, mark it as "○," and if there is no precipitate. The generated product was evaluated as "x".

[Verification of presence or absence of antiseptic properties to prevent the growth of mold, etc.]
A preservative efficacy test was conducted according to the reference information "Preservative efficacy test method" of the 17th revised Japanese Pharmacopoeia, and the preservative properties of dental cleaning materials were evaluated. The test bacterial solution was prepared by culturing the test bacterial strains shown in Table 1 below according to the culture conditions of the preservative efficacy test method. The test bacteria solution was added to the dental cleaning material, and the number of viable bacteria was measured two weeks later. The initial number of viable bacteria is 10 ⁵ CPU or more per mL, and after 2 weeks, the number of viable bacteria of all 5 types is less than ¹⁰ CPU. Those in which the number of viable bacteria of at least one species was 10 CPU or more and less than 10 ⁵ CPU were rated "Δ", and those in which the number of viable bacteria of at least one species was 10 ⁵ CPU or more were rated "x".

[Preparation of artificial saliva]
Each component listed in Table 2 below was mixed at room temperature with the composition listed in Table 2 to prepare artificial saliva.

[Adhesion durability test on zirconia after cleaning operation]
A cylindrical (inner diameter 12 mm x height 5 mm) zirconia sintered body (1500°C (fired for 2 hours) was polished with #1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) to obtain a sample with an exposed flat surface. The obtained sample was washed for 5 minutes with an ultrasonic cleaner (manufactured by Yamato Scientific Co., Ltd.), and then dried by air blowing to remove water from the surface. This zirconia sintered body was immersed in artificial saliva for 1 minute, then dried with air blow, applied with the prepared dental cleaning material, rubbed for 10 seconds, and washed with water. Next, after drying by air blowing, an adhesive tape having a thickness of about 150 μm and having a round hole of 5 mm in diameter was attached to define the adhesion area, thereby forming the treated surface of the adherend.

Dental resin cement (manufactured by Kuraray Noritake Dental Co., Ltd., trade name "SA Cement Plus Automix (registered trademark)") was placed on the treated surface of the adherend using a mixing tip. One end surface (circular cross section) of a cylindrical rod (diameter 7 mm, length 2.5 cm) was adhered and left to stand for 60 minutes. After removing excess dental resin cement protruding from the periphery of the stainless steel cylindrical rod, it was immersed in distilled water. The sample immersed in distilled water was left undisturbed in a constant temperature chamber kept at 37° C. for 24 hours, and then left undisturbed in a constant temperature chamber maintained at 70° C. for 7 days to obtain an adhesion test sample. A total of five samples for the adhesion test were prepared.

The tensile adhesive strength of the five adhesive test samples described above was measured using a universal testing machine (manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm/min. The average value of the tensile adhesive strength was taken as the adhesive durability, and the value of the dispersion (SD) of the tensile adhesive strength was calculated. The adhesive durability is preferably 16 MPa or more, more preferably 18 MPa or more, and even more preferably 20 MPa or more. The value of variation (SD) in tensile adhesive strength is preferably 5 or less, more preferably 4 or less, and even more preferably 2.5 or less.

[Cleaning effect test on zirconia]
A cylindrical (inner diameter 12 mm x height 5 mm) zirconia sintered body (inner diameter 12 mm x height 5 mm) made from a zirconia disk (product name: Katana (registered trademark) Zirconia HT, manufactured by Kuraray Noritake Dental Co., Ltd.) for CAD/CAM systems (2 The sample was polished with a wrapping film sheet (manufactured by 3M Co., Ltd., grain size: 1 micron) to obtain a sample with an exposed flat surface. The obtained sample was washed for 5 minutes with an ultrasonic cleaner (manufactured by Yamato Scientific Co., Ltd.), and then dried by air blowing to remove water from the surface. This sample was immersed in artificial saliva for 1 minute and then dried by air blowing. Thereafter, a dental cleaning material was applied, rubbed for 10 seconds, and washed with water. Note that this dental cleaning material was stored in a refrigerator at 4° C. for one week, and if precipitates were formed, they were used for cleaning as they were. Next, after drying by air blowing, the cleaning effect was observed using a scanning electron microscope ("SU3500" manufactured by Hitachi High-Technologies Corporation) at a magnification of 1000 times, and evaluated based on the following criteria.
○: No deposits after cleaning ×: deposits after cleaning

As shown in Table 3, when the dental cleaning material according to the present invention was tested for adhesive durability by applying dental cement to zirconia after cleaning, excellent adhesive durability of 20 MPa or more was obtained. This shows that it has an excellent cleaning effect against contamination by protein-containing body fluids. Further, no formation of precipitates was observed during refrigerated storage. Further, as a result of observing the zirconia surface cleaned using a dental cleaning material stored in a refrigerator at 4° C. for one week using a scanning electron microscope, it was confirmed that it had an excellent cleaning effect. On the other hand, as shown in Table 4, in the comparative example, the cleaning effect against contamination by protein-containing body fluids is low, so the adhesive durability cannot be obtained, and the adhesive durability of dental cement to zirconia after cleaning is 15 MPa or less. In addition, the formation of precipitates was observed during refrigerated storage.

Furthermore, as shown in Table 3, in Examples 5, 7, 8, and 9, antiseptic properties were imparted to suppress the increase in the number of viable bacteria, resulting in an evaluation result of "○". It has been found that the organic amine compound (c) can be used singly or in combination of two or more to exhibit antiseptic properties. It was also found that the basic inorganic compound (d) may be contained and exhibits antiseptic properties.

The dental cleaning material according to the present invention can be used for cleaning dental restorations, abutment teeth, and the like.

Claims (12)

Contains an acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c),
The acidic group-containing radically polymerizable monomer (a) is a phosphoric acid group-containing (meth)acrylic monomer,
The organic amine compound (c) contains a tertiary organic amine compound,
The tertiary organic amine compound is an aliphatic tertiary organic amine compound having one or more hydroxyl groups, an aromatic tertiary organic amine compound having one or more hydroxyl groups, and 2-( At least one member selected from the group consisting of dimethylamino)ethyl methacrylate ,
The aliphatic tertiary organic amine compound having one or more hydroxyl groups is N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine monomethacrylate, triethanol. one or more selected from the group consisting of amine dimethacrylate and triethanolamine,
The aromatic tertiary organic amine compound having one or more hydroxyl groups is N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl) -p-Toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxy ethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, and N , N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline . The dental cleaning material according to claim 1, having a pH of 3.5 or more and less than 8.0. The content of the acidic group-containing radically polymerizable monomer (a) is in the range of 0.1 to 8.0 parts by mass in a total of 100 parts by mass of the dental cleaning material, and the content of the organic amine compound (c) is in the range of 0.1 to 8.0 parts by mass. The dental cleaning material according to claim 1 or 2, wherein the content of is in the range of 0.1 to 20 parts by mass based on a total of 100 parts by mass of the dental cleaning material. Substantially does not contain radically polymerizable monomers that do not contain acidic groups,
Any one of claims 1 to 3, wherein the content of the radically polymerizable monomer that does not contain an acidic group is less than 1.0% by mass based on the total amount of polymerizable monomers contained in the dental cleaning material. Dental cleaning materials described in . The dental cleaning material according to any one of claims 1 to 4, further comprising a basic inorganic compound (d). The dental cleaning according to claim 5, wherein the basic inorganic compound (d) is at least one basic substance selected from the group consisting of phosphate, hydrogen phosphate, and dihydrogen phosphate. Material. 7. The basic inorganic compound (d) is at least one selected from the group consisting of an alkali metal phosphate, an alkali metal hydrogen phosphate, and an alkali metal dihydrogen phosphate. Dental cleaning materials listed. Furthermore, it contains at least one gelling agent (e) selected from the group consisting of a hydrophilic filler (e-1), a hydrophobic filler (e-2), and a polymeric thickener (e-3). The dental cleaning material according to any one of claims 1 to 7. The dental cleaning material according to claim 8, wherein the gelling agent (e) is a hydrophilic filler (e-1) and a hydrophobic filler (e-2). The dental cleaning material according to claim 9, wherein the hydrophilic filler (e-1) is hydrophilic fumed silica, and the hydrophobic filler (e-2) is hydrophobic fumed silica. The dental cleaning material according to claim 9 or 10, wherein the mass ratio of the hydrophilic filler (e-1) to the hydrophobic filler (e-2) is in the range of 4:6 to 2:8. A step of mixing an acidic group-containing radically polymerizable monomer (a), water (b), and an organic amine compound (c),
The acidic group-containing radically polymerizable monomer (a) is a phosphoric acid group-containing (meth)acrylic monomer,
The organic amine compound (c) contains a tertiary organic amine compound,
The tertiary organic amine compound is an aliphatic tertiary organic amine compound having one or more hydroxyl groups, an aromatic tertiary organic amine compound having one or more hydroxyl groups, and 2-( At least one member selected from the group consisting of dimethylamino)ethyl methacrylate ,
The aliphatic tertiary organic amine compound having one or more hydroxyl groups is N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine monomethacrylate, triethanol. one or more selected from the group consisting of amine dimethacrylate and triethanolamine,
The aromatic tertiary organic amine compound having one or more hydroxyl groups is N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl) -p-Toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxy ethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, and N , N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline .