WO2024075641A1

WO2024075641A1 - Polymer material for use in dentistry

Info

Publication number: WO2024075641A1
Application number: PCT/JP2023/035577
Authority: WO
Inventors: 勇介山田; 宜久紙本
Original assignee: サンメディカル株式会社
Priority date: 2022-10-03
Filing date: 2023-09-29
Publication date: 2024-04-11

Abstract

This polymer material for use in dentistry is used, in dental treatments, to polymerize a nonacidic monomer that does not have acidic groups but does have ethylenic unsaturated groups. The polymer material for use in dentistry contains a photoacid generator, a transition metal compound, and a reducing agent. The transition metal compound is a solid in the polymer material for use in dentistry and can be dissolved by the acid generated when the photoacid generator decomposes.

Description

Dental Polymerization Materials

The present invention relates to a dental polymeric material.

　Conventionally, dental polymerization materials containing a polymerizable monomer and a radical polymerization initiator are known for use in prosthetic treatment of missing teeth, etc. Among such dental polymerization materials, a dental polymerization material using a photopolymerization initiator as the radical polymerization initiator has been proposed (see, for example, Patent Document 1). In detail, the dental polymerization material of Patent Document 1 contains a radical polymerization monomer, an α-diketone compound, an amine compound, and an aryl iodonium salt.

JP 2010-064998 A

On the other hand, dental polymer materials require a high hardening depth to accommodate treatment at deep sites.

However, the dental polymerized material of Patent Document 1 has the disadvantage that it does not cure sufficiently in deep areas where light does not reach, resulting in a low curing depth. Furthermore, because dental polymerized materials are continuously subjected to forces such as occlusal force, there is a demand for improved mechanical strength.

The present invention aims to provide a dental polymeric material that has a high hardening depth and excellent mechanical strength.

The present invention [1] is a dental polymerizable material for polymerizing a non-acidic monomer having no acidic group and an ethylenically unsaturated group in dental treatment, the dental polymerizable material containing a photoacid generator, a transition metal compound, and a reducing agent, the transition metal compound being solid in the dental polymerizable material, and being soluble in the acid generated by decomposition of the photoacid generator.

The present invention [2] includes the dental polymeric material described in [1] above, which contains the non-acidic monomer and does not contain an acidic monomer.

The present invention [3] includes the dental polymeric material described in [1] or [2] above, in which the transition metal compound contains a transition metal atom belonging to the fourth period of the periodic table.

The present invention [4] includes a dental polymeric material according to any one of [1] to [3] above, in which the transition metal compound is at least one selected from the group consisting of copper compounds, iron compounds, cobalt compounds, chromium compounds, zinc compounds, manganese compounds, and vanadium compounds.

The present invention [5] includes a dental polymerizable material according to any one of [1] to [4] above, in which the photoacid generator is soluble in the non-acidic monomer.

The present invention [6] further includes a dental polymeric material according to any one of [1] to [5] above, which contains a filler.

The present invention [7] further includes a dental polymeric material according to any one of [1] to [6] above, which contains a photosensitizer.

The present invention [8] further includes a dental polymerizable material according to any one of [1] to [7] above, which contains a photopolymerization initiator.

The present invention [9] includes a dental polymeric material described in any one of [1] to [8] above, which is a one-component type.

In the dental polymerizable material of the present invention, the photoacid generator decomposes upon irradiation with light, generating radicals and acid. The radicals generated from the photoacid generator photopolymerize the nonacidic monomer. Furthermore, the acid generated from the photoacid generator dissolves the transition metal compound, generating transition metal ions. The generated transition metal ions react chemically with a reducing agent to generate radicals. The radicals generated by the chemical reaction chemically polymerize the nonacidic monomer. Since photopolymerization and chemical polymerization occur simultaneously, the degree of polymerization increases and the mechanical strength improves. In addition, the heat of polymerization generated by photopolymerization and chemical polymerization causes decomposition into the photoacid generator, and polymerization proceeds (frontal polymerization) even in deep areas where light does not directly reach, resulting in a high cure depth.

<One-component dental polymerizable material>
In the present invention, the dental polymerization material may be, for example, a one-component dental polymerization material.

Unlike two-component dental polymerization materials, one-component dental polymerization materials do not require mixing before use. If the one-component dental polymerization material has self-adhesive properties, it can be used by applying it directly to tooth structure. On the other hand, if the one-component dental polymerization material does not have self-adhesive properties, it can be used in combination with a pretreatment material.

"Self-adhesive" means that the material has sufficient adhesion to tooth structure even without applying a pretreatment material to the tooth structure.

In addition, pretreatment materials are used in dental treatment, for example, to improve the adhesion between one-component dental polymerizable materials and at least one of a prosthesis and tooth structure.

Examples of one-component dental polymerizable materials include one-component polymerizable composite resins and one-component polymerizable cements. One-component polymerizable composite resins are used in dental treatment to fill missing teeth. One-component polymerizable cements are used to attach prosthetic devices to missing teeth.

The one-component dental polymerizable material of the present invention contains a photoacid generator, a transition metal compound, and a reducing agent as essential components for polymerizing a non-acidic monomer that does not have an acidic group but has an ethylenically unsaturated group.

In addition, the one-component dental polymeric material preferably contains a non-acidic monomer and does not contain an acidic monomer.

The one-component dental polymerization material may not contain non-acidic monomers and may not contain acidic monomers. In this case, the one-component dental polymerization material is used to polymerize the monomers.

[Non-acidic monomers]
Non-acidic monomers do not have an acidic group and have an ethylenically unsaturated group.

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

In the following explanation, "acryloyl" and "methacryloyl" will be written as "(meth)acryloyl". Also, "acrylate" and "methacrylate" will be written as "(meth)acrylate".

Non-acidic monomers are monomers that do not have an acidic group and are classified into non-acidic monomers that have a hydroxyl group, non-acidic monomers that have a urethane bond, and non-acidic monomers that do not have a hydroxyl group or a urethane bond.

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

Examples of mono(meth)acrylates 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 a mono(meth)acrylate having a hydroxyl group is 2-hydroxyethyl(meth)acrylate.

An example of a di(meth)acrylate having a hydroxyl group is a bisphenol A derivative. An example of a bisphenol A derivative having a hydroxyl group is 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA).

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

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

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

Examples of di(meth)acrylates that do not have hydroxyl groups or urethane bonds include alkanediol di(meth)acrylates, polyoxyalkylene group-containing di(meth)acrylates, and bisphenol A derivatives.

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

An example of a polyoxyalkylene group-containing di(meth)acrylate is a polyoxyethylene group-containing di(meth)acrylate.

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).

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.

Non-acidic monomers can be used alone or in combination of two or more types. It is preferable to use two or more types of non-acidic monomers in combination.

An example of a non-acidic monomer is the combination of UDMA and TEGDMA.

The proportion of non-acidic monomer in the one-component dental polymeric material is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, and, for example, 95% by mass or less, preferably 80% by mass or less, more preferably 65% by mass or less, even more preferably 50% by mass or less, particularly preferably 40% by mass or less.

In one-component dental polymerizable materials, the content of the non-acidic monomer is, for example, 500 parts by mass or more, preferably 1000 parts by mass or more, more preferably 1500 parts by mass or more, and for example, 5000 parts by mass or less, preferably 4000 parts by mass or less, more preferably 3000 parts by mass or less, per 100 parts by mass of the photoacid generator.

[Photoacid generator]
A photoacid generator is a compound that decomposes when exposed to light such as visible light and/or ultraviolet light, generating radicals and acid. As will be described in detail later, the radicals generated from the photoacid generator photopolymerize non-acidic monomers. Furthermore, the acid generated from the photoacid generator dissolves transition metal compounds and generates transition metal ions. The generated transition metal ions react chemically with a reducing agent to generate radicals. The radicals generated by the chemical reaction chemically polymerize the non-acidic monomers.

The photoacid generator is preferably soluble in the non-acidic monomers described above.

Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators.

Ionic photoacid generators include, for example, iodonium salt compounds and sulfonium salt compounds.

Examples of iodonium salt compounds include diaryliodonium compounds.

The diaryliodonium salt compound is a compound represented by the following general formula (1).

(In the formula, R1 to R4 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a nitro group, and X represents an anion.)
In the above general formula (1), R1 to R4 are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a nitro group, and X represents an anion.

Halogen atoms include, for example, fluoro, chloro, bromo, and iodine groups.

Examples of alkyl groups include hydrocarbon groups having 1 to 20 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, pentyl, isopentyl, and hexyl groups.

Aryl groups include, for example, hydrocarbon groups having 6 to 14 carbon atoms. Specific examples include phenyl groups, p-methylphenyl groups, p-chlorophenyl groups, and naphthyl groups.

Examples of alkenyl groups include hydrocarbon groups having 1 to 6 carbon atoms. Specific examples include vinyl groups, allyl groups, isopropenyl groups, butenyl groups, 2-phenylethenyl groups, and 2-(substituted phenyl)ethenyl groups.

Examples of alkoxy groups include alkoxy groups having 1 to 6 carbon atoms. Specific examples include methoxy, ethoxy, propoxy, and butoxy groups.

Aryloxy groups include, for example, aryloxy groups having 6 to 14 carbon atoms. Specific examples include phenoxy, p-methoxyphenyl, and p-octyloxyphenyl.

R1 to R4 are preferably hydrogen atoms or alkyl groups.

Examples of diaryliodonium salt compounds include diaryliodonium salt compounds consisting of cations 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, and anions of chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, trifluorotris(pentafluoroethyl)phosphate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and nonafluorobutanesulfonate. A preferred diaryliodonium salt compound is a diaryliodonium salt compound consisting of a p-isopropylphenyl-p-methylphenyliodonium cation and a trifluorotris(pentafluoroethyl)phosphate anion.

Sulfonium salt compounds include, for example, 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 chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate salts.

Ionic photoacid generators are preferably iodonium salt compounds.

Nonionic photoacid generators include, for example, s-triazine compounds having a trihalomethyl group as a substituent, diazomethane compounds, sulfone compounds, sulfonate compounds, and arylsulfonate compounds.

Examples of s-triazine compounds having a trihalomethyl group as a substituent include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4 ,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl ]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine.

Diazomethane compounds include, for example, bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, and bis(4-methylphenylsulfonyl)diazomethane.

An example of a sulfone compound is 2-methyl-2-([4-methylphenyl]sulfonyl)-1-(4-[methylthio]phenyl)-1-propanone.

Examples of sulfonic acid ester compounds and arylsulfonic acid ester compounds include benzoin tosylate, α-methylolbenzoin tosylate, o-nitrobenzyl p-toluenesulfonate, and p-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate.

Photoacid generators can be used alone or in combination of two or more types.

The proportion of the photoacid generator in the one-component dental polymerizable material is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more, and is, for example, 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less.

In one-component dental polymerizable materials, the content of the photoacid generator is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the non-acidic monomer.

[Transition metal compounds]
At least a part of the transition metal compound is soluble in acid. Preferably, the entire transition metal compound is soluble in acid. The transition metal compound is soluble in acid generated by decomposition of a photoacid generator in a one-component dental polymerizable material. By dissolving in acid, transition metal ions are generated. The transition metal ions react chemically with a reducing agent to generate radicals. The generated radicals polymerize non-acidic monomers.

The transition metal compound contains a transition metal atom that belongs to the fourth period of the periodic table. The periodic table is the IUPAC Periodic Table of the Elements (version date 1 December 2018).

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 preferably copper (Cu).

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.

Transition metal complexes have a transition metal atom as the central metal and ligands that coordinate to the transition metal atom.

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.

Examples of transition metal compounds include copper compounds, iron compounds, cobalt compounds, chromium compounds, zinc compounds, manganese compounds, and vanadium compounds. In other words, the transition metal compound is at least one selected from the group consisting of copper compounds, iron compounds, cobalt compounds, chromium compounds, zinc compounds, manganese compounds, and vanadium compounds.

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

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) oxide, iron(III) oxide, iron(II,III) oxide, metallic iron, iron(II) sulfate, iron(III) sulfate, iron(III) acetylacetonate, iron(III) citrate, and iron(II) gluconate.

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.

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).

As a transition metal compound, a copper compound is preferably used.

The transition metal compound is solid in the one-component dental polymerizable material. That is, the one-component dental polymerizable material contains the components in the one-component dental polymerizable material and a powder of a transition metal compound that is insoluble in water and may be obtained by moisture absorption during storage. At 20°C and 1 atm, the transition metal compound is solid. The amount of the transition metal compound dissolved in 100 g of water at 20°C and 1 atm is, for example, 5 g or less, preferably 4 g or less, and more preferably 3 g or less. That is, in the one-component dental polymerizable material, the transition metal compound being solid means that at least a part of the transition metal compound is solid, and may be partially dissolved. The average particle size of the powder is not limited, but if it is too large, it is likely to settle, and if it is too small, the specific surface area becomes too large and the amount that can be dispersed decreases. Therefore, the average particle size is, for example, 0.01 μm or more, preferably 0.1 μm or more, more preferably 1 μm or more, and, for example, 500 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.

Transition metal compounds can be used alone or in combination of two or more types.

The blending ratio of the transition metal compound in the one-component dental polymeric material is, for example, 0.0001 mass% or more, preferably 0.0005 mass% or more, more preferably 0.001 mass% or more, even more preferably 0.01 mass% or more, and, for example, 1 mass% or less, preferably 0.5 mass% or less, more preferably 0.1 mass% or less, even more preferably 0.05 mass% or less.

In the one-component dental polymeric material, the content of the transition metal compound is, for example, 0.01 parts by mass or more, preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, and for example, 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the non-acidic monomer.

In a one-component dental polymerizable material, the content of the transition metal compound is, for example, 0.5 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, and for example, 8 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, per 100 parts by mass of the photoacid generator.

[Reducing Agent]
The reducing agent reduces the transition metal ions. In other words, the reducing agent is oxidized by the transition metal ions. The reducing agent is oxidized by the transition metal ions to generate radicals.

The reducing agent may be any agent that reduces the above-mentioned transition metal ions, without any particular limitations. Examples of reducing agents include aromatic amine compounds, sulfinic acid compounds or their salts, thiourea compounds, thiosulfate compounds, phosphorous acid compounds, sulfurous acid compounds, (thio)barbituric acid compounds or their salts, ascorbic acid compounds or their salts, and ascorbic acid ester compounds or their salts.

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

Examples of aromatic tertiary amines include N,N-dialkyltoluidine, N,N-bis(hydroxyalkyl)toluidine, N,N-dialkylaniline, and dialkylaminobenzoic acid esters.

Examples of N,N-dialkyl toluidines include N,N-dimethyl-p-toluidine (DMPT) and N,N-diethyl-p-toluidine.

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

Examples of N,N-dialkylanilines include N,N-dimethylaniline and N,N-diethylaniline.

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

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

Sulfinic acid compounds and their salts include, for example, aromatic sulfinic acids and their salts. Aromatic sulfinic acids include, for example, benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, fluorobenzenesulfinic acid, and naphthalenesulfinic acid.

　Salts of aromatic sulfinic acid compounds include, for example, lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, barium benzenesulfinate, butylamine salt of benzenesulfinate, aniline salt of benzenesulfinate, toluidine salt of benzenesulfinate, phenylenediamine salt of benzenesulfinate, diethylamine salt of benzenesulfinate, diphenylamine salt of benzenesulfinate, triethylamine salt of benzenesulfinate, tributylamine salt of benzenesulfinate, ammonium salt of benzenesulfinate, tetraethylamine salt of benzenesulfinate, tetramethyl ... tetramethylammonium, trimethylbenzylammonium benzenesulfinate, lithium o-toluenesulfinate, sodium o-toluenesulfinate, potassium o-toluenesulfinate, calcium o-toluenesulfinate, cyclohexylamine salt of o-toluenesulfinate, aniline salt of o-toluenesulfinate, ammonium salt of o-toluenesulfinate, tetraethylammonium o-toluenesulfinate, lithium p-toluenesulfinate, sodium p-toluenesulfinate (STS), potassium p-toluenesulfinate, calcium p-toluenesulfinate, barium p-toluenesulfinate, ethylamine salt of p-toluenesulfinate, p-toluenesulfinic acid butylamine salt, p-toluenesulfinic acid toluidine salt, p-toluenesulfinic acid N-methylaniline salt, p-toluenesulfinic acid pyridine salt, p-toluenesulfinic acid ammonium salt, p-toluenesulfinic acid tetramethylammonium, p-toluenesulfinic acid tetraethylammonium, p-toluenesulfinic acid tetrabutylammonium, β-naphthalenesulfinic acid sodium salt, β-naphthalenesulfinic acid strontium salt, β-naphthalenesulfinic acid triethylamine salt, β-naphthalenesulfinic acid N-methyltoluidine salt, β-naphthalenesulfinic acid ammonium salt, β-naphthalenesulfinic acid trimethylbenzylammonium salt, p-chlorobenzenesulfinic acid lithium salt p-chlorobenzenesulfinic acid sodium salt, p-chlorobenzenesulfinic acid potassium salt, p-chlorobenzenesulfinic acid calcium salt, p-chlorobenzenesulfinic acid barium salt, p-chlorobenzenesulfinic acid ethylamine salt, p-chlorobenzenesulfinic acid butylamine salt, p-chlorobenzenesulfinic acid toluidine salt, p-chlorobenzenesulfinic acid N-methylaniline salt, p-chlorobenzenesulfinic acid pyridine salt, p-chlorobenzenesulfinic acid ammonium salt, p-chlorobenzenesulfinic acid tetramethylammonium salt, p-chlorobenzenesulfinic acid tetraethylammonium salt, and p-chlorobenzenesulfinic acid tetrabutylammonium salt.

Thiourea compounds include, for example, 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 -isopropylthiourea, 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.

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

Examples of phosphorous compounds include inorganic phosphorous compounds and organic phosphorous compounds.

Examples of inorganic phosphite compounds include calcium hypophosphite and sodium phosphite.

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.

Examples of sulfite compounds include inorganic sulfite compounds and organic sulfite compounds.

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

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

(Thio)barbituric acid compounds and their salts include, for example, 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.

Examples of ascorbic acid compounds and salts thereof include sodium ascorbate, calcium ascorbate, and potassium ascorbate. Ascorbate salts, calcium ascorbate is preferred.

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

Reducing agents can be used alone or in combination of two or more types.

The reducing agent is preferably a salt of an ascorbic acid compound.

The mixing ratio of the reducing agent in the one-component dental polymerizable material is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, and, for example, 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

In one-component dental polymeric materials, the content of the reducing agent is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and for example, 10 parts by mass or less, preferably 7 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the non-acidic monomer.

In one-component dental polymerizable materials, the content of the reducing agent is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and for example, 100 parts by mass or less, preferably 85 parts by mass or less, more preferably 70 parts by mass or less, relative to 100 parts by mass of the photoacid generator.

[Filler]
The one-component dental polymerizable material may contain a filler, if necessary.

The filler may be any of the conventionally known fillers that can be used in dental materials. Specific examples of the filler include silica, silica alumina, alumina, alumina quartz, glass, titania, zirconia, and ytterbium fluoride. Examples of silica include fumed silica. The filler may be surface-treated with a silane coupling agent or the like to be made hydrophobic or hydrophilic.

Fillers can be used alone or in combination of two or more types.

As a filler, a combination of silica and ytterbium fluoride is preferred.

The filler content in the one-component dental polymeric material is, for example, 0.5% by mass or more, preferably 5% by mass or more, more preferably 15% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more, and is, for example, 95% by mass or less, preferably 80% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less.

In one-component dental polymeric materials, the content of the filler is, for example, 30 parts by mass or more, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and for example, 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, per 100 parts by mass of the non-acidic monomer.

In one-component dental polymerizable materials, the content of the filler is, for example, 1,000 parts by mass or more, preferably 2,000 parts by mass or more, more preferably 2,500 parts by mass or more, and for example, 7,000 parts by mass or less, preferably 4,000 parts by mass or less, more preferably 3,500 parts by mass or less, per 100 parts by mass of the photoacid generator.

[Photosensitizer]
The one-component dental polymerizable material may contain a photosensitizer, if necessary.

The photosensitizer transmits the energy it obtains by absorbing light to the photoacid generator, accelerating the decomposition of the photoacid generator.

Examples of photosensitizers include ketone compounds, anthracene compounds, naphthalene compounds, thioxanthone compounds, and coumarin compounds.

Ketone compounds include, for example, α-diketone compounds.

Examples of α-diketone compounds include camphorquinone, benzil, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4'-dimethoxybenzyl, 4,4'-oxybenzyl, 9,10-phenanthrenequinone, and acenaphthenequinone.

Examples of anthracene compounds include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dimethoxyanthracene.

Naphthalene compounds include, for example, 1,4-dimethoxynaphthalene and 1,4-diethoxynaphthalene.

Photosensitizers can be used alone or in combination of two or more types.

Preferably, the photosensitizer is an anthracene compound.

The proportion of the photosensitizer in the one-component dental polymeric material is, for example, 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less.

In one-component dental polymeric materials, the content of the photosensitizer is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and for example, 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the non-acidic monomer.

In one-component dental polymerizable materials, the content of the photosensitizer is, for example, 1 part by mass or more, preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the photoacid generator.

[Other additives]
The one-component dental polymerizable material may contain, as necessary, a polymerization inhibitor, a photopolymerization initiator, an acid amplifier, a thickener, a silane coupling agent, an ultraviolet absorbing agent, a fluorescent agent, a pigment, and a solvent.

A photopolymerization initiator is a compound that is excited and starts polymerization when exposed to light such as visible light and/or ultraviolet light. Photopolymerization initiators do not include photoacid generators.

Examples of photopolymerization initiators include ketone compounds and acylphosphine oxide compounds, with ketone compounds being preferred.

Ketone compounds include, for example, α-diketone compounds.

Examples of α-diketone compounds include camphorquinone, benzil, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4'-dimethoxybenzyl, 4,4'-oxybenzyl, 9,10-phenanthrenequinone, and acenaphthenequinone, and preferably camphorquinone.

Examples of polymerization inhibitors include dibutylhydroxytoluene (BHT) and 4-methoxyphenol (MeHQ), and preferably dibutylhydroxytoluene.

The proportion of the polymerization inhibitor in the one-component dental polymerization material is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less.

In one-component dental polymerization materials, the content of the polymerization inhibitor is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and for example, 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less, per 100 parts by mass of the non-acidic monomer.

In one-component dental polymerization materials, the content of the polymerization inhibitor is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 5 parts by mass or more, and for example, 70 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, per 100 parts by mass of the photoacid generator.

<Reaction mechanism>
Next, the reaction mechanism of the one-component dental polymerizable material will be described.

One-component dental polymeric materials can be applied to tooth structure alone or in combination with a pretreatment material.

When a one-component dental polymerizable material is applied to tooth structure and irradiated with visible light and/or ultraviolet light, the photoacid generator decomposes, generating radicals and acid. The radicals generated from the photoacid generator photopolymerize nonacidic monomers. The acid generated from the photoacid generator dissolves transition metal compounds and generates transition metal ions. The generated transition metal ions react chemically with a reducing agent to generate radicals. The radicals generated by the chemical reaction polymerize the nonacidic monomers. The heat of polymerization generated by photopolymerization and chemical polymerization also causes decomposition of the photoacid generator, and polymerization progresses (frontal polymerization), even in deep areas where light does not directly reach. In other words, dental polymerizable materials polymerize nonacidic monomers during dental treatment.

<Action and effect>
According to the one-component dental polymerization material, photopolymerization and chemical polymerization occur simultaneously, so that the degree of polymerization is increased and the mechanical strength can be improved.

In addition, frontal polymerization occurs, allowing for a high cure depth.

Furthermore, the transition metal compound is a solid in the one-component dental polymerizable material. Therefore, the reaction between the transition metal compound and the reducing agent in the one-component dental polymerizable material can be suppressed.

As a result, thickening or hardening of one-component dental polymerizable materials over time can be suppressed.

<Modification>
In the following modified examples, detailed description of the same materials as those in the above-mentioned embodiment will be omitted. In addition, each modified example can achieve the same effects as those in the first embodiment unless otherwise specified. Furthermore, the first embodiment and its modified examples can be appropriately combined.

In one embodiment described above, the dental polymerizable material is a one-component dental polymerizable material.

However, the dental polymerization material may be a multi-component dental polymerization material. Examples of multi-component dental polymerization materials include two-component dental polymerization materials. Two-component dental polymerization materials have, for example, component A and component B. Two-component dental polymerization materials are used, for example, by mixing components A and B. Two-component dental polymerization materials are also used, for example, by applying component A and then component B. If a two-component dental polymerization material has self-adhesive properties, it can be used by applying it directly to tooth structure. On the other hand, if a two-component dental polymerization material does not have self-adhesive properties, it can be used in combination with a pretreatment material.

When components A and B are mixed together in a two-component dental polymeric material, at least one of components A and B contains a photoacid generator, a transition metal compound, and a reducing agent, and optionally contains a non-acidic monomer, a filler, a photosensitizer, and other additives.

In a two-component dental polymeric material, when component A is applied first, followed by component B, component B located on the surface that is irradiated with light contains a photoacid generator, and at least one of components A and B contains a transition metal compound and a reducing agent, and optionally a non-acidic monomer, a filler, a photosensitizer, and other additives. Furthermore, component A may contain a photoacid generator.

The dental polymerizable material may contain no non-acidic monomers and no acidic monomers. In this case, the dental polymerizable material is used to polymerize the monomers.

The dental polymeric material may not contain a filler. In this case, the dental polymeric material can be used as a dental coating material.

The present invention will be described in more detail below with reference to examples and comparative examples. Note that the present invention is in no way limited to the examples and comparative examples. Furthermore, the specific numerical values of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced 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 ratio (content ratio), physical property value, parameter, etc. described in the above "Form for carrying out the invention."

The components used in the examples and comparative examples are listed below.

UDMA: [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate TEGDMA: triethylene glycol di(meth)acrylate IK-1: Photoacid generator (iodonium salt) manufactured by San-Apro Co., Ltd.
DBA: 9,10-dibutoxyanthracene CQ: camphorquinone Cu(OH) ₂ : copper(II) hydroxide
CaAA: calcium ascorbate dihydrate BHT: dibutylhydroxytoluene R812: fumed silica manufactured by Aerosil YbF ₃ : ytterbium fluoride

<Preparation of one-component dental polymerizable material>
According to the formulation in Table 1, each component was mixed to prepare a one-component dental polymerizable material.

In Example 1 and each of the Comparative Examples, the transition metal compound (Cu(OH) ₂ ) was a solid in the one-part dental polymerizable material.

<Evaluation>
[Mechanical strength]
The one-component dental polymerizable materials of Example 1 and each Comparative Example were filled into a compression test mold made of fluororesin with a hole of 4 mm diameter and 3 mm thickness, and then both sides were irradiated with light for 10 seconds each using a dental irradiator (JETLITE 3000, manufactured by J. Morita Co., Ltd.). Then, the material was left to stand in an oven at 37°C for 24 hours to cure. The mechanical strength (compressive strength) of each cured product was measured using a universal testing machine (AG-10knXPlus, manufactured by Shimadzu Corporation). The mechanical strength was evaluated according to the following criteria. The results are shown in Table 1.
{standard}
◯: 500 MPa or more ×: Less than 500 MPa or insufficient curing, measurement not possible

[Cure depth]
The one-component dental polymerization material of Example 1 and each comparative example was filled into a glass tube with a diameter of 5 mm and a length of 30 mm or more to a depth of 30 mm or more, and the glass tube filled with the one-component dental polymerization material was left with only 10 mm from the tip, and the other part was wrapped with black vinyl tape to block light. The glass tube filled with the one-component dental polymerization material was irradiated with light from the side for 10 seconds. Then, it was left to stand in an oven at 37°C for 24 hours to harden, and the hardening depth was measured.
The cure depth was evaluated according to the following criteria. The results are shown in Table 1.
{standard}
◯: 30 mm or more △: 15 mm or more but less than 30 mm ×: less than 15 mm

The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the claims below.

The dental polymeric material of the present invention is suitable for use in dental treatment to fill missing teeth and to adhere prosthetic devices to missing teeth.

Claims

A dental polymerizable material for polymerizing a non-acidic monomer having no acidic group and an ethylenically unsaturated group in dental treatment, comprising:
A photoacid generator;
A transition metal compound;
A reducing agent,
A dental polymerizable material, wherein the transition metal compound is solid in the dental polymerizable material and is soluble in an acid generated by decomposition of the photoacid generator.
The dental polymeric material according to claim 1, which contains the non-acidic monomer and does not contain an acidic monomer.
The dental polymeric material according to claim 1, wherein the transition metal compound contains a transition metal atom belonging to the fourth period of the periodic table.
The dental polymeric material according to claim 1, wherein the transition metal compound is at least one selected from the group consisting of copper compounds, iron compounds, cobalt compounds, chromium compounds, zinc compounds, manganese compounds, and vanadium compounds.
The dental polymerizable material according to claim 2, wherein the photoacid generator is soluble in the non-acidic monomer.
The dental polymeric material according to claim 1, further comprising a filler.
The dental polymeric material according to claim 1, further comprising a photosensitizer.
The dental polymerizable material according to claim 1, further comprising a photopolymerization initiator.
The dental polymeric material according to claim 1, which is a one-component type.