Dental polymerizable composition

Abstract

To provide a dental polymerizable composition that enables enhancement of adhesive strength to dentin.SOLUTION: A dental polymerizable composition comprises a monomer liquid containing a non-acidic monomer having an ethylenically unsaturated group and free from acidic groups, and a photoacid generator, the photoacid generator being solid in the monomer liquid and soluble in water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dental polymerizable composition. [Background technology]

[0002] Conventionally, dental polymerizable materials containing a polymerizable monomer and a radical polymerization initiator have been known for use in prosthetic restorations for missing teeth, etc. Among such dental polymerizable materials, a dental polymerizable material using a photopolymerization initiator as the radical polymerization initiator has been proposed (see, for example, Patent Document 1). More specifically, the dental polymerizable material of Patent Document 1 contains a radical polymerizable monomer, an α-diketone compound, an amine compound, and an aryl iodonium salt (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-064998 Summary of the Invention [Problem to be solved by the invention]

[0004] In the dental polymeric material described in Patent Document 1, further improvement in adhesive strength to tooth structure is required.

[0005] The present invention provides a dental polymerizable composition that can further improve adhesive strength to tooth structure. [Means for solving the problem]

[0006] The present invention [1] includes a dental polymerizable composition comprising a monomer liquid containing a non-acidic monomer having no acidic group but an ethylenically unsaturated group, and a photoacid generator, wherein the photoacid generator is solid in the monomer liquid and is water-soluble.

[0007] The present invention [2] further includes the dental polymerizable composition of the above [1], which contains a photopolymerization initiator.

[0008] The present invention [3] further includes the dental polymerizable composition of the above [1] or [2], which contains an acidic monomer having an acidic group and an ethylenically unsaturated group.

[0009] The present invention [4] includes the dental polymerizable composition according to any one of the above [1] to [3], further comprising a transition metal compound that is solid in the monomer liquid and is soluble in an acid generated by decomposition of the photoacid generator, and a reducing agent.

[0010] The present invention [5] includes a one-component dental polymerizable composition according to any one of the above [1] to [4]. [Effects of the Invention]

[0011] According to the dental polymerizable composition of the present invention, the adhesive strength to tooth structure can be further improved. DETAILED DESCRIPTION OF THE INVENTION

[0012] 1. Dental polymerizable composition Dental polymerizable compositions are used in dental treatment to fill missing tooth sites and to bond teeth to prosthetic appliances. The dental polymerizable composition may be a one-component type or a multi-component type (e.g., a two-component type). The dental polymerizable composition is preferably a one-component type.

[0013] Unlike multi-component dental polymerizable compositions, single-component dental polymerizable compositions do not require mixing before use. Examples of single-component dental polymerizable compositions include single-component self-adhesive composite resins and single-component self-adhesive resin cements.

[0014] The dental polymerizable composition of the present invention has self-adhesive properties. "Self-adhesive properties" means that the composition has sufficient adhesive strength to tooth structure even without applying a pretreatment material to the tooth structure.

[0015] Specifically, the dental polymerizable composition contains a monomer liquid and a dispersing component. The dental polymerizable composition may contain additives, if necessary.

[0016] (1) Monomer liquid The monomer liquid contains a non-acidic monomer. The monomer liquid may contain an acidic monomer, a photopolymerization initiator, a photosensitizer, and a reducing agent, as necessary.

[0017] (1-1) Non-acidic Monomer Non-acidic monomers do not have an acidic group but have an ethylenically unsaturated group.

[0018] Examples of acidic groups include carboxy groups, phosphate groups, thiophosphate groups, and sulfo groups.

[0019] Examples of ethylenically unsaturated groups include acryloyl groups, methacryloyl groups, and vinyl groups.

[0020] In the following description, "acryloyl" and "methacryloyl" will be referred to as "(meth)acryloyl", and "acrylate" and "methacrylate" will be referred to as "(meth)acrylate".

[0021] Examples of non-acidic monomers include non-acidic monomers having a hydroxyl group, non-acidic monomers having a urethane bond, and non-acidic monomers having neither a hydroxyl group nor a urethane bond.

[0022] Examples of non-acidic monomers having a hydroxyl group include mono(meth)acrylates and di(meth)acrylates.

[0023] Examples of the mono(meth)acrylate having a hydroxyl group include 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, and dihydroxypropyl mono(meth)acrylate. A preferred example of the mono(meth)acrylate having a hydroxyl group is 2-hydroxyethyl(meth)acrylate.

[0024] Examples of di(meth)acrylates having a hydroxyl group include bisphenol A derivatives. Examples of bisphenol A derivatives having a hydroxyl group include 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA).

[0025] An example of a non-acidic monomer having a urethane bond is [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]di(meth)acrylate (UDMA).

[0026] Examples of non-acidic monomers that do not have a hydroxyl group or a urethane bond include mono(meth)acrylates and di(meth)acrylates.

[0027] Examples of mono(meth)acrylates that do not have a hydroxyl group or a urethane bond include alkyl(meth)acrylates, such as methyl(meth)acrylate, ethyl(meth)acrylate, and butyl(meth)acrylate.

[0028] Examples of di(meth)acrylates that do not have a hydroxyl group or a urethane bond include alkanediol di(meth)acrylates, polyoxyalkylene group-containing di(meth)acrylates, and bisphenol A derivatives.

[0029] Examples of alkanediol di(meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0030] Examples of polyoxyalkylene group-containing di(meth)acrylates include polyoxyethylene group-containing di(meth)acrylates.

[0031] Examples of polyoxyethylene group-containing di(meth)acrylates include triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and nonaethylene glycol di(meth)acrylate, and preferably triethylene glycol di(meth)acrylate (TEGDMA).

[0032] An example of a bisphenol A derivative that does not have a hydroxyl group or a urethane bond is ethylene oxide-modified bisphenol A di(meth)acrylate.

[0033] The non-acidic monomers preferably include UDMA and TEGDMA.

[0034] The non-acidic monomers can be used alone or in combination of two or more. It is preferable to use two or more non-acidic monomers in combination. Specifically, it is preferable to use UDMA and TEGDMA in combination as non-acidic monomers.

[0035] When the dental polymerizable composition is a one-component type, the blending ratio of the non-acidic monomer in the dental polymerizable composition is, for example, 5% by mass to 95% by mass, preferably 10% by mass to 80% by mass, more preferably 15% by mass to 65% by mass, more preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 40% by mass.

[0036] (1-2) Acidic Monomer The acidic monomer has the above-mentioned acidic group and the above-mentioned ethylenically unsaturated group. The acidic monomer may contain only one type of acidic group, or may contain two or more types of acidic groups.

[0037] Examples of acidic monomers having a carboxy group include aromatic carboxylic acid derivatives, aliphatic carboxylic acid derivatives, and amino acid derivatives.

[0038] Examples of aromatic carboxylic acid derivatives include benzoic acid derivatives, salicylic acid derivatives, phthalic acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, naphthalenetricarboxylic acid derivatives, benzophenonetetracarboxylic acid derivatives, and biphenyltetracarboxylic acid derivatives.

[0039] Examples of benzoic acid derivatives include 4-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-4-aminobenzoic acid, and N-(meth)acryloyl-5-aminobenzoic acid.

[0040] Examples of salicylic acid derivatives include 4-(meth)acryloylaminosalicylic acid and 5-(meth)acryloylaminosalicylic acid.

[0041] Examples of phthalic acid derivatives include 4-[(2-hydroxy-3-(meth)acryloyloxypropyl)amino]phthalic acid, 3-[N-methyl-N-(2-hydroxy-3-(meth)acryloyloxypropyl)amino]phthalic acid, and 4-[N-methyl-N-(2-hydroxy-3-(meth)acryloyloxypropyl)amino]phthalic acid.

[0042] Examples of trimellitic acid derivatives include 4-(meth)acryloyloxyalkyltrimellitic acid, 4-[2-hydroxy-3-(meth)acryloyloxy]butyltrimellitic acid, 2,3-bis(3,4-dicarboxybenzoyloxy)propyl(meth)acrylate, and 2-(3,4-dicarboxybenzoyloxy)-1,3-di(meth)acryloyloxypropane. Examples of 4-(meth)acryloyloxyalkyltrimellitic acid include 4-(meth)acryloyloxymethyltrimellitic acid, 4-(meth)acryloyloxyethyltrimellitic acid, and 4-(meth)acryloyloxybutyltrimellitic acid.

[0043] Examples of pyromellitic acid derivatives include 1,4-di(meth)acryloyloxyethyl pyromellitic acid and a reaction product of 2-hydroxyethyl (meth)acrylate and pyromellitic dianhydride.

[0044] An example of the naphthalene tricarboxylic acid derivative is 6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid.

[0045] An example of a benzophenonetetracarboxylic acid derivative is a reaction product of 2-hydroxyethyl (meth)acrylate and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.

[0046] An example of a biphenyltetracarboxylic acid derivative is a reaction product of 2-hydroxyethyl (meth)acrylate and 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0047] Examples of aliphatic carboxylic acid derivatives include maleic acid, a reaction product of 2-hydroxyethyl (meth)acrylate and maleic anhydride, and 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid.

[0048] Examples of amino acid derivatives include N,O-di(meth)acryloyloxytyrosine, O-(meth)acryloyloxytyrosine, N-(meth)acryloyloxytyrosine, N-(meth)acryloyloxyphenylalanine, a reaction product of N-phenylglycine and glycidyl (meth)acrylate, and a reaction product of N-tolylglycine and glycidyl (meth)acrylate.

[0049] Examples of acidic monomers having a phosphoric acid group include aliphatic phosphoric acid esters and aromatic phosphoric acid esters.

[0050] Examples of the aliphatic phosphate ester include (meth)acryloyloxyalkyl acid phosphate and bis[(meth)acryloyloxyalkyl] acid phosphate.

[0051] Examples of the (meth)acryloyloxyalkyl acid phosphate include 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxypropyl acid phosphate, 3-(meth)acryloyloxypropyl acid phosphate, 4-(meth)acryloyloxybutyl acid phosphate, 6-(meth)acryloyloxyhexyl acid phosphate, 8-(meth)acryloyloxyoctyl acid phosphate, 10-(meth)acryloyloxydecyl acid phosphate, and 12-(meth)acryloyloxydodecyl acid phosphate.

[0052] Examples of bis[(meth)acryloyloxyalkyl] acid phosphates include bis[2-(meth)acryloyloxyethyl] acid phosphate, bis[2-(meth)acryloyloxypropyl] acid phosphate, and bis[3-(meth)acryloyloxypropyl] acid phosphate.

[0053] Examples of aromatic phosphate esters include 2-(meth)acryloyloxyethyl phenyl acid phosphate and 2-(meth)acryloyloxyethyl-p-methoxyphenyl acid phosphate.

[0054] Examples of the acidic monomer having a thiophosphate group include compounds in which the phosphoric acid group of the above-mentioned acidic monomer having a phosphoric acid group is substituted with a thiophosphate group.

[0055] As the acidic monomer, preferably, an acidic monomer having a phosphoric acid group is used, more preferably, (meth)acryloyloxyalkyl acid phosphate is used, and more preferably, 10-methacryloyloxydecyl acid phosphate (MDP) is used.

[0056] The acidic monomers can be used alone or in combination of two or more.

[0057] When the dental polymerizable composition is a one-component type, the blending ratio of the acidic monomer in the dental polymerizable composition is, for example, 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass.

[0058] (1-3) Photopolymerization initiator The photopolymerization initiator is a polymerization initiator that is excited by exposure to light such as visible light and / or ultraviolet light, etc. The photopolymerization initiator does not include a photosensitizer or a photoacid generator, which will be described later.

[0059] Examples of the photopolymerization initiator include α-diketone compounds.

[0060] Examples of the α-diketone compound include camphorquinone, benzil, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, 9,10-phenanthrenequinone, and acenaphthenequinone.

[0061] As the photopolymerization initiator, preferably, an α-diketone compound is used, and more preferably, camphorquinone is used.

[0062] The photopolymerization initiators can be used alone or in combination of two or more.

[0063] When the dental polymerizable composition is a one-component type, the blending ratio of the photopolymerization initiator in the dental polymerizable composition is, for example, 0.01% by mass to 5% by mass, preferably 0.05% by mass to 1% by mass, and more preferably 0.05% by mass to 0.5% by mass.

[0064] The number of parts of the photopolymerization initiator relative to 100 parts by mass of the total of the non-acidic monomer and the acidic monomer is, for example, 0.001 to 5 parts by mass, preferably 0.01 to 2 parts by mass, and more preferably 0.1 to 1 part by mass.

[0065] (1-4) Photosensitizer The photosensitizer accelerates the decomposition of the photoacid generator described below.

[0066] Examples of the photosensitizer include anthracene compounds.

[0067] Examples of anthracene compounds include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene (DBA), and 2-ethyl-9,10-dimethoxyanthracene.

[0068] The photosensitizer preferably includes 9,10-dibutoxyanthracene (DBA).

[0069] The photosensitizers can be used alone or in combination of two or more.

[0070] When the dental polymerizable composition is a one-component type, the proportion of the photosensitizer in the dental polymerizable composition is, for example, 0.001% by mass to 10% by mass, preferably 0.005% by mass to 5% by mass, and more preferably 0.01% by mass to 1% by mass.

[0071] The number of parts of the photosensitizer relative to 100 parts by mass of the total of the non-acidic monomer and the acidic monomer is, for example, 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, and more preferably 0.1 to 1 part by mass.

[0072] The number of parts of the photosensitizer relative to 100 parts by mass of the photoacid generator is, for example, 1 to 20 parts by mass, preferably 1.5 to 10 parts by mass, and more preferably 2 to 5 parts by mass.

[0073] (1-5) Reducing agent The reducing agent reduces the photopolymerization initiator.

[0074] Examples of reducing agents include aromatic amine compounds, sulfinic acid compounds or salts thereof, thiourea compounds, thiosulfuric acid compounds, phosphorous acid compounds, sulfurous acid compounds, (thio)barbituric acid compounds or salts thereof, ascorbic acid compounds or salts thereof, and ascorbic acid ester compounds or salts thereof.

[0075] Examples of aromatic amine compounds include aromatic tertiary amines and aromatic amino acids.

[0076] Examples of aromatic tertiary amines include N,N-dialkyltoluidines, N,N-bis(hydroxyalkyl)toluidines, N,N-dialkylanilines, and dialkylaminobenzoates.

[0077] Examples of N,N-dialkyltoluidines include N,N-dimethyl-p-toluidine (DMPT) and N,N-diethyl-p-toluidine.

[0078] Examples of N,N-bis(hydroxyalkyl)toluidines include N,N-bis(2-hydroxyethyl)-p-toluidine and N,N-bis(2-hydroxypropyl)-p-toluidine.

[0079] Examples of N,N-dialkylanilines include N,N-dimethylaniline and N,N-diethylaniline.

[0080] Examples of dialkylaminobenzoate esters include methyl 4-(dimethylamino)benzoate, ethyl 4-(dimethylamino)benzoate (EDAB), 2-butoxyethyl 4-(dimethylamino)benzoate, and isoamyl 4-(dimethylamino)benzoate.

[0081] Aromatic amino acids include, for example, N-phenylglycine acid, sodium N-phenylglycinate (SPG), and potassium N-phenylglycinate.

[0082] Examples of sulfinic acid compounds and salts thereof include aromatic sulfinic acids and salts thereof.

[0083] Examples of aromatic sulfinic acids include benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, fluorobenzenesulfinic acid, and naphthalenesulfinic acid.

[0084] Examples of salts of aromatic sulfinic acid compounds include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, barium benzenesulfinate, butylamine benzenesulfinate, aniline benzenesulfinate, toluidine benzenesulfinate, phenylenediamine benzenesulfinate, diethylamine benzenesulfinate, diphenylamine benzenesulfinate, triethylamine benzenesulfinate, tributylamine benzenesulfinate, ammonium benzenesulfinate, tetramethylammonium benzenesulfinate, trimethylbenzylammonium benzenesulfinate, lithium o-toluenesulfinate, sodium o-toluenesulfinate, potassium o-toluenesulfinate, calcium o-toluenesulfinate, cyclohexylamine o-toluenesulfinate, aniline o-toluenesulfinate, ammonium o-toluenesulfinate, and o-toluenesulfinic acid. Tetraethylammonium, lithium p-toluenesulfinate, sodium p-toluenesulfinate (STS), potassium p-toluenesulfinate, calcium p-toluenesulfinate, barium p-toluenesulfinate, ethylamine salt of p-toluenesulfinate, butylamine salt of p-toluenesulfinate, toluidine salt of p-toluenesulfinate, N-methylaniline salt of p-toluenesulfinate, pyridine salt of p-toluenesulfinate, ammonium salt of p-toluenesulfinate, tetramethylammonium p-toluenesulfinate, tetraethylammonium p-toluenesulfinate, tetrabutylammonium p-toluenesulfinate, sodium β-naphthalenesulfinate, strontium β-naphthalenesulfinate, triethylamine β-naphthalenesulfinate, N-methyltoluidine β-naphthalenesulfinate, ammonium β-naphthalenesulfinate, trimethylbenzylammonium β-naphthalenesulfinate, lithium p-chlorobenzenesulfinate, sodium p-chlorobenzenesulfinate, potassium p-chlorobenzenesulfinateExamples of suitable chlorobenzenesulfinates include calcium p-chlorobenzenesulfinate, barium p-chlorobenzenesulfinate, ethylamine p-chlorobenzenesulfinate, butylamine p-chlorobenzenesulfinate, toluidine p-chlorobenzenesulfinate, N-methylaniline p-chlorobenzenesulfinate, pyridine p-chlorobenzenesulfinate, ammonium p-chlorobenzenesulfinate, tetramethylammonium p-chlorobenzenesulfinate, tetraethylammonium p-chlorobenzenesulfinate, and tetrabutylammonium p-chlorobenzenesulfinate.

[0085] Examples of the thiourea compounds include thiourea, methylthiourea, ethylthiourea, n-propylthiourea, isopropylthiourea, cyclohexylthiourea, benzylthiourea, phenylthiourea, acetylthiourea, benzoylthiourea, adamantylthiourea, (2-pyridyl)thiourea (PTU), 1-(2-tetrahydrofurfuryl)-2-thiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, and N,N'-di thiourea, N,N'-dicyclohexylthiourea, N,N'-diphenylthiourea, trimethylthiourea (TMTU), triethylthiourea, tri-n-propylthiourea, triisopropylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetraisopropylthiourea, tetracyclohexylthiourea, ethylenethiourea, and 4,4-dimethylethylenethiourea.

[0086] Examples of thiosulfate compounds include sodium thiosulfate, calcium thiosulfate, potassium thiosulfate, and magnesium thiosulfate.

[0087] Examples of the phosphorous acid compound include inorganic phosphorous acid compounds and organic phosphorous acid compounds.

[0088] Inorganic phosphite compounds include, for example, calcium hypophosphite and sodium phosphite.

[0089] Examples of organic phosphite compounds include diethyl phosphite, dibutyl phosphite, diisopropyl phosphite, di-n-propyl phosphite, triphenyl phosphite, triallyl phosphite, diethyl phosphite, dibutyl phosphite, diisopropyl phosphite, di-n-propyl phosphite, triphenyl phosphite, and triallyl phosphite.

[0090] Examples of sulfite compounds include inorganic sulfite compounds and organic sulfite compounds.

[0091] Examples of inorganic sulfite compounds include lithium sulfite, sodium sulfite, potassium sulfite, calcium sulfite, and sodium hydrogen sulfite.

[0092] Examples of organic sulfite compounds include diethyl sulfite, di-n-propyl sulfite, diisopropyl sulfite, glycol sulfite, 1,3-propylene sulfite, and diallyl sulfite.

[0093] Examples of (thio)barbituric acid compounds and salts thereof include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, thiobarbituric acid, and alkali metal or alkaline earth metal salts thereof.

[0094] Examples of ascorbic acid compounds and salts thereof include ascorbic acid, sodium ascorbate, calcium ascorbate, and potassium ascorbate. Preferred ascorbic acid salts include calcium ascorbate.

[0095] Examples of ascorbic acid ester compounds and salts thereof include ascorbic acid palmitate, sodium ascorbic acid palmitate, calcium ascorbic acid palmitate, and potassium ascorbic acid palmitate. A preferred example of the salt of an ascorbic acid ester is potassium ascorbic acid palmitate.

[0096] The reducing agent is preferably a dialkylaminobenzoate, more preferably ethyl 4-(dimethylamino)benzoate (EDAB).

[0097] The reducing agents can be used alone or in combination of two or more.

[0098] When the dental polymerizable composition is a one-component type, the content of the reducing agent in the dental polymerizable composition is, for example, 0.01% by mass to 30% by mass, preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and more preferably 1.0% by mass to 3% by mass.

[0099] The number of parts of the reducing agent relative to 100 parts by mass of the total of the non-acidic monomer and the acidic monomer is, for example, 0.001 to 5 parts by mass, preferably 0.01 to 2 parts by mass, and more preferably 0.1 to 1 part by mass.

[0100] The number of parts of the reducing agent relative to 100 parts by mass of the photopolymerization initiator is, for example, 10 to 1000 parts by mass, preferably 30 to 700 parts by mass, and more preferably 50 to 150 parts by mass.

[0101] (2) Dispersion component The dispersion component is dispersed in a solid state in the monomer liquid. The dispersion component contains a photoacid generator. In other words, the dental polymerizable composition contains a photoacid generator. The dispersion component may contain a transition metal compound and a filler, as needed. In other words, the dental polymerizable composition may contain a transition metal compound and a filler, as needed.

[0102] (2-1) Photoacid generator The photoacid generator decomposes upon exposure to light such as visible light and / or ultraviolet light, generating an acid and radicals.

[0103] The photoacid generator is a solid in the monomer liquid and is water-soluble.

[0104] Specifically, the photoacid generator is a solid at 20°C and 1 atmosphere. The amount of photoacid generator dissolved in 100g of monomer liquid at 20°C and 1 atmosphere is, for example, 20g or less, preferably 10g or less, more preferably 5g or less, and particularly preferably 1g or less. Therefore, the photoacid generator is a solid in the monomer liquid at 20°C and 1 atmosphere.

[0105] The amount of photoacid generator dissolved in 100 g of water at 20° C. and 1 atmosphere is, for example, 0.01 g or more, preferably 0.1 g or more, more preferably 0.5 g or more, and particularly preferably 1 g or more.

[0106] Therefore, when the dental polymerizable composition is applied to a tooth, the photoacid generator dissolves in the water in the tooth and penetrates into the tooth.

[0107] When irradiated with light, the dissolved photoacid generator decomposes, generating acid and radicals. The generated acid promotes demineralization of the tooth, and the generated radicals promote polymerization of monomers (non-acidic monomers and acidic monomers) at the tooth interface. The promotion of demineralization by the generated acid provides self-adhesion to the tooth, and the promotion of polymerization of monomers at the tooth interface improves adhesion to the tooth.

[0108] The water-soluble photoacid generator is a powder or granule. The average particle size of the photoacid generator is not limited as long as it can be dispersed in the monomer liquid. The average particle size of the photoacid generator is, for example, 0.01 μm to 500 μm, preferably 0.1 μm to 100 μm, and more preferably 1 μm to 50 μm. When the average particle size of the photoacid generator is within the above range, a sufficient amount of the photoacid generator can be dispersed in the monomer liquid while suppressing sedimentation of the photoacid generator. The "average particle size" is the volume-based median diameter measured by laser diffraction.

[0109] Examples of water-soluble photoacid generators include ionic photoacid generators.

[0110] Examples of ionic photoacid generators include iodonium salt compounds, triazine compounds, and sulfonium salt compounds.

[0111] Examples of iodonium salt compounds include diaryliodonium compounds represented by the following general formula (1).

[0112] General formula (1):

[0113] [ka]

[0114] In general formula (1), R1 to R4 each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, an aryloxy group, or a nitro group, and R1 to R4 may be the same or different from one another.

[0115] Examples of halogen atoms include fluoro, chloro, bromo, and iodo groups.

[0116] Examples of the aliphatic hydrocarbon group include a linear or branched alkyl group having 1 to 20 carbon atoms and a linear or branched alkenyl group having 1 to 6 carbon atoms.

[0117] Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a 1-methylethyl group (isopropyl group), a butyl group, a sec-butyl group, a pentyl group, an isopentyl group, and a hexyl group.

[0118] Examples of the linear or branched alkenyl group having 1 to 6 carbon atoms include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a 2-phenylethenyl group, and a 2-(substituted phenyl)ethenyl group.

[0119] Examples of aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 14 carbon atoms. Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, and a naphthyl group.

[0120] Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms, specifically methoxy, ethoxy, propoxy, and butoxy groups.

[0121] Examples of the aryloxy group include aryloxy groups having 6 to 14 carbon atoms. Specific examples include phenoxy, p-methoxyphenyl, and p-octyloxyphenyl.

[0122] R1 to R4 are preferably a hydrogen atom or an alkyl group.

[0123] In general formula (1), X - Examples of the cations include chloride ions and bromide ions.

[0124] Specific examples of diaryliodonium salt compounds include chlorides or bromides of diphenyliodonium, bis(p-chlorophenyl)iodonium, ditolyliodonium, bis(p-tert-butylphenyl)iodonium, p-isopropylphenyl-p-methylphenyliodonium, bis(m-nitrophenyl)iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis(p-methoxyphenyl)iodonium, and p-octyloxyphenylphenyliodonium.

[0125] Examples of triazine compounds include 2-[(2-dimethylaminoethyl)amino]-4,6-bis(trichloromethyl)-S-triazine dimethyl sulfate and 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4-trichloromethyl-6-[(2-dimethylaminoethyl)amino]-S-triazine dimethyl sulfate.

[0126] Examples of sulfonium salt compounds include chloride, bromide, p-toluenesulfonate, and tetrafluoroborate salts of dimethylphenacylsulfonium, dimethylbenzylsulfonium, dimethyl-4-hydroxyphenylsulfonium, dimethyl-4-hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8-dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium, and diphenyl-4-phenylthiophenylsulfonium.

[0127] The water-soluble photoacid generator is preferably an iodonium salt compound, more preferably a diaryliodonium salt compound, and more preferably [4-(1-methylethyl)phenyl]-(4-methylphenyl)iodonium chloride. [4-(1-methylethyl)phenyl]-(4-methylphenyl)iodonium chloride is represented by the general formula (1) where R1 is a 1-methylethyl group at the para-position (4-position), R3 is a methyl group at the para-position (4-position), R2 and R4 are hydrogen atoms, and X - is a diaryliodonium salt compound in which

[0128] The photoacid generators can be used alone or in combination of two or more.

[0129] When the dental polymerizable composition is a one-component type, the proportion of the photoacid generator in the dental polymerizable composition is, for example, 0.1% by mass to 10% by mass, preferably 0.5% by mass to 5% by mass, more preferably 1% by mass to 3% by mass, and more preferably 1.5% by mass to 3% by mass.

[0130] The number of parts of the photoacid generator relative to 100 parts by mass of the total of the non-acidic monomer and the acidic monomer is, for example, 1 to 30 parts by mass, preferably 3 to 20 parts by mass, and more preferably 5 to 10 parts by mass.

[0131] (2-2) Transition metal compounds When the dental polymerization composition is a one-component type and does not contain an acidic monomer, the dental polymerization composition may contain a transition metal compound. When the dental polymerization composition is a one-component type and contains an acidic monomer, the dental polymerization composition does not contain a transition metal compound. The transition metal compound is solid in the monomer liquid. In other words, the transition metal compound is solid in the dental polymerizable composition. That is, the transition metal compound is insoluble in the monomer liquid and in moisture that may be acquired by moisture absorption during storage. At 20°C and 1 atmosphere, the transition metal compound is solid. The amount of the transition metal compound dissolved in 100 g of monomer liquid at 20°C and 1 atmosphere is, for example, 5 g or less, preferably 4 g or less, and more preferably 3 g or less.

[0132] The transition metal compound is a powder or granule. The average particle size of the transition metal compound is not limited. The average particle size of the transition metal compound is, for example, 0.01 μm to 500 μm, preferably 0.1 μm to 100 μm, and more preferably 1 μm to 50 μm. When the average particle size of the transition metal compound is within the above range, a sufficient amount of the transition metal compound can be dispersed in the monomer liquid while suppressing sedimentation of the transition metal compound. The "average particle size" refers to the volume-based median diameter measured by laser diffraction.

[0133] At least a portion of the transition metal compound is soluble in the acid generated by decomposition of the photoacid generator. Preferably, the entire transition metal compound is soluble in the acid generated by decomposition of the photoacid generator. The dissolution of the transition metal compound in the acid generates transition metal ions. The reaction of the transition metal ions with a reducing agent generates radicals. The radicals generated by the reaction of the transition metal ions with a reducing agent also polymerize non-acidic monomers and acidic monomers.

[0134] The transition metal compound contains a transition metal atom that belongs to Period 4 of the periodic table, which is the IUPAC Periodic Table of the Elements (version date 1 December 2018).

[0135] Specific examples of transition metal atoms include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and gallium (Ga). Preferred examples of transition metal atoms include vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), and zinc (Zn), and more preferred examples include copper (Cu).

[0136] Examples of transition metal compounds include oxides, hydroxides, halides, carboxylates, sulfates, nitrates, carbonates, and complexes of transition metals. Examples of halides include chlorides and bromides. Examples of carboxylates include formates, acetates, oleates, acrylates, gluconates, phthalates, and citrates.

[0137] A transition metal complex has a transition metal atom as a central metal and a ligand coordinated to the transition metal atom.

[0138] Examples of the ligands include diketone-based ligands, amine-based ligands, thiol-based ligands, urea-based ligands, and thiourea-based ligands. Examples of the diketone-based ligands include acetylacetonate. Examples of the amine-based ligands include alkanediamines, benzimidazole, and benzothiazole. Examples of the thiol-based ligands include mercaptoethanol, mercaptotriazole, mercaptobenzothiazole, and mercaptobenzimidazole. Examples of the urea-based ligands include urea and ethyleneurea. Examples of the thiourea-based ligands include thiourea, acetylthiourea, pyridylthiourea, and ethylenethiourea.

[0139] Examples of transition metal compounds include copper compounds, iron compounds, cobalt compounds, chromium compounds, zinc compounds, manganese compounds, and vanadium compounds.

[0140] Examples of copper compounds include copper(II) hydroxide, copper(I), copper(II) chloride, copper(II), copper(I) bromide, copper(II) bromide, copper(II) formate, copper(I), copper(II) acetate, copper(II) acetate, copper(II) sulfate, copper(II) nitrate, copper(II) iodide, basic copper(II) carbonate, copper(I), copper(II) oxide, copper(II) oxide, metallic copper, copper(II) oleate, copper(II) acrylate, copper(II) gluconate, copper(II) phthalate, copper(II) citrate, copper(II) acetylacetonate, mercaptobenzothiazole copper, 1,3-propanediamine copper, benzimidazole copper, benzothiazole copper, and thiourea copper. A preferred copper compound is basic copper(II) carbonate.

[0141] Examples of iron compounds include iron(II) hydroxide, iron(III) oxide hydroxide, iron(II) chloride, iron(III) chloride, iron(I) bromide, iron(II) bromide, iron(II) acetate, iron(III) acetate, iron(II) carbonate, iron(II), iron(III), iron(III), iron(II, III) oxide, metallic iron, iron(II) sulfate, iron(III) sulfate, iron(III) acetylacetonate, iron(III) citrate, and iron(II) gluconate.

[0142] Examples of cobalt compounds include cobalt(II) hydroxide, cobalt(II) chloride, cobalt(II) acetate, cobalt(II) bromide, basic cobalt carbonate, cobalt(II) sulfate, cobalt(II) oxide, cobalt(III) oxide, cobalt(II, III) oxide, metallic cobalt, cobalt(II) nitrate, and cobalt(III) acetylacetonate.

[0143] Examples of vanadium compounds include vanadium(III) chloride, vanadium(III) bromide, metallic vanadium, vanadium(II) oxide, vanadium(III) oxide, vanadium(V) oxide, vanadium(IV) oxyacetylacetonate, vanadium(III) acetylacetonate, oxovanadium(IV) oxalate, vanadium(IV) stearate, vanadium(IV) oxide sulfate, ammonium vanadate(V), and sodium orthovanadate(V).

[0144] As the transition metal compound, preferably, a copper compound is used.

[0145] The transition metal compounds can be used alone or in combination of two or more.

[0146] When the dental polymerizable composition is a one-component type, the ratio of the transition metal compound in the dental polymerizable composition is, for example, 0.0001% by mass to 1% by mass, preferably 0.0005% by mass to 0.5% by mass, more preferably 0.001% by mass to 0.1% by mass, and more preferably 0.01% by mass to 0.05% by mass.

[0147] The number of parts of the transition metal compound relative to 100 parts by mass of the total of the non-acidic monomer and the acidic monomer is, for example, 0.01 to 3 parts by mass, preferably 0.03 to 1 part by mass, and more preferably 0.05 to 0.5 parts by mass.

[0148] The number of parts of the transition metal compound per 100 parts by mass of the photoacid generator is, for example, 0.5 to 8 parts by mass, preferably 1.0 to 5 parts by mass, and more preferably 1.5 to 3 parts by mass.

[0149] (2-3) Filler Examples of fillers include conventional fillers that can be used in dental materials. Examples of fillers include silica, silica alumina, alumina, alumina quartz, glass, titania, zirconia, and ytterbium fluoride. Examples of silica include fumed silica. The fillers may be surface-treated with a silane coupling agent or the like to be hydrophobic or hydrophilic.

[0150] The fillers can be used alone or in combination of two or more.

[0151] As the filler, a combination of silica and ytterbium fluoride is preferably used.

[0152] When the dental polymerizable composition is a one-component type, the proportion of the filler in the dental polymerizable composition is, for example, 0.5% by mass to 95% by mass, preferably 5% by mass to 90% by mass, more preferably 20% by mass to 85% by mass, more preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.

[0153] The number of parts of the filler relative to 100 parts by mass of the total of the non-acidic monomer and the acidic monomer is, for example, 30 to 500 parts by mass, preferably 50 to 300 parts by mass, and more preferably 100 to 200 parts by mass.

[0154] (3) Additives Examples of the additives include a polymerization inhibitor, an acid multiplier, a thickener, a silane coupling agent, an ultraviolet absorber, a fluorescent agent, a pigment, and a solvent.

[0155] Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT) and 4-methoxyphenol (MeHQ), and preferably dibutylhydroxytoluene.

[0156] When the dental polymerizable composition is a one-component type, the proportion of the polymerization inhibitor in the dental polymerizable composition is, for example, 0.003% by mass to 10% by mass, preferably 0.001% by mass to 5% by mass, and more preferably 0.01% by mass to 1% by mass.

[0157] The number of parts of the polymerization inhibitor relative to 100 parts by mass of the total of the non-acidic monomer and the acidic monomer is, for example, 0.001 to 3 parts by mass, preferably 0.003 to 1.5 parts by mass, and more preferably 0.03 to 1 part by mass.

[0158] 2. Effects According to the dental polymerizable composition, when the dental polymerizable composition is applied to a tooth, the photoacid generator dissolves in the water in the tooth and penetrates into the tooth.

[0159] When irradiated with light, the dissolved photoacid generator decomposes to generate radicals, which promote the polymerization of monomers (non-acidic and acidic monomers) at the tooth interface.

[0160] As a result, the adhesive strength to tooth structure can be improved.

[0161] Furthermore, when the photoacid generator decomposes, an acid is generated along with the radicals.

[0162] Therefore, the generated acid promotes demineralization of the tooth tissue while promoting polymerization of the monomer at the tooth tissue interface.

[0163] As a result, self-adhesion to tooth structure is also achieved.

[0164] 3. Variations Modifications will be described below. Detailed descriptions of the modifications that use the same materials as those in the above-described embodiment will be omitted.

[0165] The dental polymerizable composition may be a two-component type (dental polymerization kit). The dental polymerization kit may include, for example, an A-component and a B-component. The above-mentioned components may be packaged in either the A-component or the B-component, as desired. However, the transition metal compound is separated from the acidic monomer. For example, the A-component contains the above-mentioned monomer liquid and the above-mentioned water-soluble photoacid generator. The water-soluble photoacid generator is solid in the A-component. The B-component contains a transition metal compound. The transition metal compound is solid in the B-component. In this case, the monomer liquid in the A-component may further contain the above-mentioned acidic monomer. On the other hand, the B-component does not contain the acidic monomer. [Example]

[0166] The present invention will be described in more detail below with reference to examples and comparative examples. It should be noted that the present invention is not limited to these examples and comparative examples. The specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be substituted with the upper limit (a numerical value defined as "equal to or less than") or lower limit (a numerical value defined as "equal to or more than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the "Description of the Invention" above.

[0167] 1. Preparation of Dental Polymerizable Composition The monomer liquid components were mixed according to the formulation in Table 1 to prepare a monomer liquid, and then the dispersion components were added to the monomer liquid and mixed using a centrifugal mixer. This resulted in the preparation of a paste-like one-component dental polymerizable composition.

[0168] The meanings of the abbreviations in Table 1 are as follows:

[0169] MDP: 10-methacryloyloxydecyl acid phosphate UDMA: [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate TEGDMA: Triethylene glycol dimethacrylate CQ: Camphorquinone EDAB: Ethyl 4-(dimethylamino)benzoate BHT: Dibutylhydroxytoluene IK-1: [4-(1-methylethyl)phenyl]-(4-methylphenyl)iodonium salt with trifluorotris(pentafluoroethyl)phosphate IK-1Cl: [4-(1-methylethyl)phenyl]-(4-methylphenyl)iodonium chloride CCH: basic copper(II) carbonate R812: Fumed silica, manufactured by Aerosil YbF3: Ytterbium(III) fluoride 2. Evaluation (1) Initial shear bond strength The dental adhesive compositions of each Example and Comparative Example were adhered to bovine dentin using the method specified in ISO29022:2013, and after leaving them at room temperature for 30 minutes, the initial shear bond strength was measured using a precision universal testing machine (Shimadzu Corporation AGS-X) and evaluated according to the following criteria.

[0170] A: The initial shear bond strength is 5 MPa or more.

[0171] B: The initial shear bond strength is 2 MPa or more and less than 5 MPa.

[0172] C: The initial shear bond strength is less than 2 MPa.

[0173] (2) Color stability The dental adhesive composition of each example and comparative example was filled into a mold made of fluororesin with a circular hole (diameter: 15 mm, thickness: 0.08 mm) and cured by irradiating both sides with light from a dental light (product name: αLight V, manufactured by Morita Corporation) for 1 minute each.

[0174] The obtained cured product was immersed in water at 37°C for about 24 hours, then dried, and the color difference ΔE from the cured product before immersion was measured using a spectrophotometer (CM-5, manufactured by Konica Minolta, Inc.) The color stability was evaluated based on the measured color difference ΔE according to the following criteria.

[0175] A: ΔE is 10 or less.

[0176] B: ΔE is greater than 10 and less than or equal to 20.

[0177] C: ΔE is greater than 20.

[0178] [Table 1]

Claims

1. a monomer liquid containing a non-acidic monomer having no acidic group but an ethylenically unsaturated group; Photoacid generator and Contains The dental polymerizable composition, wherein the photoacid generator is a solid in the monomer liquid and is water-soluble.

2. The dental polymerizable composition according to claim 1 , wherein the photoacid generator is a water-soluble iodonium salt compound.

3. The dental polymerizable composition according to claim 1 , further comprising a photopolymerization initiator.

4. The dental polymerizable composition according to claim 1 , wherein the monomer liquid further contains an acidic monomer having an acidic group and an ethylenically unsaturated group.

5. The dental polymerizable composition according to claim 1 , further comprising a reducing agent.

6. The dental polymerizable composition according to claim 1 , further comprising a transition metal compound that is solid in the monomer liquid.

7. The dental polymerizable composition according to any one of claims 1 to 6, which is of a one-component type.

8. 8. The dental polymerizable composition according to claim 7, which is a one-part self-adhesive composite resin or a one-part self-adhesive resin cement.

9. A two-component dental polymerization kit comprising component A and component B, The agent A is a monomer liquid containing a non-acidic monomer having no acidic group but an ethylenically unsaturated group; a photoacid generator that is solid in the agent A and is water-soluble; Contains A dental polymerization kit, wherein the component B contains a transition metal compound that is solid in the component B.

10. the monomer liquid further contains an acidic monomer having an acidic group and an ethylenically unsaturated group, The dental polymerization kit according to claim 9 , wherein the agent B does not contain the acidic monomer.

11. The dental polymerization kit according to claim 9 or 10, wherein the photoacid generator is a water-soluble iodonium salt compound.

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