Dental adhesive

Abstract

To provide a one-pack type dental adhesive that exhibits sufficient adhesion to a dentin, as well as, excellent storage stability.SOLUTION: A dental adhesive comprises, in a one-pack formulation: a polymerizable monomer; a transition metal compound containing a transition metal atom belonging to a fourth period of the periodic table; a tertiary amine; a thiourea compound represented by the general formula (1) below; and a first silane compound having a functional group reactive with the polymerizable monomer. In the general formula (1), each of R1 to R4 represents one selected from a group consisting of a hydrogen atom, an alkyl group, an aromatic hydrocarbon group, and a heterocyclic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to dental adhesives. [Background technology]

[0002] Conventionally, a dental polymerizable composition has been proposed that contains a polymerizable monomer, a transition metal compound containing a transition metal atom belonging to the fourth period of the periodic table, a tertiary amine, and a thiourea compound in one agent (see, for example, Patent Document 1 below). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-046656 Summary of the Invention [Problem to be solved by the invention]

[0004] The dental polymerizable composition described in Patent Document 1 is required to have sufficient adhesive strength to tooth structure while also exhibiting further improved storage stability.

[0005] The present invention provides a one-component dental adhesive that has sufficient adhesive strength to tooth structure and excellent storage stability. [Means for solving the problem]

[0006] The present invention [1] includes a dental adhesive comprising, in one component, a polymerizable monomer, a transition metal compound containing a transition metal atom belonging to the fourth period of the periodic table, a tertiary amine, a thiourea compound represented by the following general formula (1), and a first silane compound having a functional group capable of reacting with the polymerizable monomer. General formula (1):

[0007] [ka]

[0008] (In general formula (1), R 1 ~R 4 Each of represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aromatic group, and a heterocyclic group. The present invention [2] further includes the dental adhesive of the above [1], which contains in the first component a second silane compound that does not have a functional group reactive with the polymerizable monomer.

[0009] The present invention [3] includes the dental adhesive of the above [1] or [2], wherein the transition metal compound is a copper compound.

[0010] The present invention [4] includes the dental adhesive of any one of the above [1] to [3], wherein the tertiary amine has an aromatic ring.

[0011] The present invention [5] includes the dental adhesive according to the above [4], wherein the tertiary amine is a dialkylaminobenzoic acid ester.

[0012] The present invention [6] includes the dental adhesive of any one of the above [1] to [5], wherein the thiourea compound is a trialkylthiourea or a tetraalkylthiourea.

[0013] The present invention [7] includes the dental adhesive of the above [1], which contains an acidic monomer as the polymerizable monomer. [Effects of the Invention]

[0014] The dental adhesive of the present invention contains, in one agent, a polymerizable monomer, a transition metal compound, a tertiary amine, a thiourea compound, and a first silane compound having a functional group capable of reacting with the polymerizable monomer.

[0015] Therefore, it has sufficient adhesive strength to tooth structure and excellent storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0016] 1. Dental adhesives The dental adhesive is a one-component dental adhesive. The dental adhesive is used in dental treatment, for example, to adhere a prosthesis to a missing tooth. The dental adhesive contains a polymerizable monomer, a transition metal compound, a tertiary amine, a thiourea compound, and a first silane compound. The dental adhesive may optionally contain a second silane compound, a solvent, a photopolymerization initiator, and a polymerization inhibitor.

[0017] (1) Polymerizable monomer The polymerizable monomer has a polymerizable functional group, such as an ethylenically unsaturated group.

[0018] Examples of the ethylenically unsaturated group include an acryloyloxy group, a methacryloyloxy group, an acryloylamide group, a methacryloylamide group, a vinyl group, and a vinyl cyanide group. Preferred examples of the ethylenically unsaturated group include an acryloyloxy group and a methacryloyloxy group.

[0019] 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".

[0020] Polymerizable monomers include, for example, acidic monomers and non-acidic monomers.

[0021] The acidic monomer has an acidic group and a polymerizable functional group.

[0022] Examples of the acidic group include a carboxy group, a phosphate group, a thiophosphate group, and a sulfo group. The acidic monomer may contain only one type of acidic group, or may contain two or more types of acidic groups.

[0023] Examples of acidic monomers having a carboxy group include aromatic carboxylic acid derivatives, aliphatic carboxylic acid derivatives, and amino acid derivatives.

[0024] 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.

[0025] 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.

[0026] Examples of salicylic acid derivatives include 4-(meth)acryloylaminosalicylic acid and 5-(meth)acryloylaminosalicylic acid.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] An example of the naphthalene tricarboxylic acid derivative is 6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid.

[0031] An example of a benzophenonetetracarboxylic acid derivative is a reaction product of 2-hydroxyethyl (meth)acrylate and 3,3',4,4'-benzophenonetetracarboxylic dianhydride.

[0032] An example of a biphenyltetracarboxylic acid derivative is a reaction product of 2-hydroxyethyl (meth)acrylate and 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0033] 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.

[0034] 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.

[0035] The acidic monomer having a carboxy group is preferably an aromatic carboxylic acid derivative, more preferably a trimellitic acid derivative, more preferably a 4-(meth)acryloyloxyalkyltrimellitic acid, more preferably a 4-(meth)acryloyloxyethyltrimellitic acid, more preferably a 4-methacryloyloxyethyltrimellitic acid.

[0036] Examples of acidic monomers having a phosphoric acid group include aliphatic phosphoric acid esters and aromatic phosphoric acid esters.

[0037] Examples of the aliphatic phosphate ester include (meth)acryloyloxyalkyl acid phosphate and bis[(meth)acryloyloxyalkyl] acid phosphate.

[0038] 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.

[0039] 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.

[0040] Examples of aromatic phosphate esters include 2-(meth)acryloyloxyethyl phenyl acid phosphate and 2-(meth)acryloyloxyethyl-p-methoxyphenyl acid phosphate.

[0041] The acidic monomer having a phosphoric acid group is preferably an aliphatic phosphoric acid ester, more preferably a (meth)acryloyloxyalkyl acid phosphate, more preferably 10-(meth)acryloyloxydecyl acid phosphate, more preferably 10-methacryloyloxydecyl acid phosphate (MDP).

[0042] 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.

[0043] As the acidic monomer, preferably, an acidic monomer having a phosphoric acid group is used.

[0044] The acidic monomers can be used alone or in combination of two or more.

[0045] The non-acidic monomer does not have an acidic group but has a polymerizable functional group.

[0046] Non-acidic monomers are classified into 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.

[0047] Examples of non-acidic monomers having a hydroxyl group include mono(meth)acrylates and di(meth)acrylates.

[0048] 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. Examples of the mono(meth)acrylate having a hydroxyl group include preferably 2-hydroxyethyl(meth)acrylate, and more preferably 2-hydroxyethyl methacrylate (HEMA).

[0049] 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.

[0050] An example of a non-acidic monomer having a urethane bond is [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]di(meth)acrylate (UDMA).

[0051] Examples of non-acidic monomers that do not have a hydroxyl group or a urethane bond include mono(meth)acrylates and di(meth)acrylates.

[0052] 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.

[0053] Examples of di(meth)acrylates that do not have a hydroxyl group or a urethane bond include alkanediol di(meth)acrylates, polyalkylene glycol di(meth)acrylates, and bisphenol A derivatives.

[0054] Examples of the alkanediol di(meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Preferred examples of the alkanediol di(meth)acrylate include neopentyl glycol dimethacrylate (NPGDMA).

[0055] Examples of polyalkylene glycol di(meth)acrylates include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.Preferably, the polyalkylene glycol di(meth)acrylate is triethylene glycol di(meth)acrylate (TEGDMA).

[0056] An example of a bisphenol A derivative that does not have a hydroxyl group or a urethane bond is ethoxylated bisphenol A dimethacrylate (EBPADMA).

[0057] The non-acidic monomers can be used alone or in combination of two or more kinds.

[0058] The dental adhesive preferably contains an acidic monomer as the polymerizable monomer, and more preferably contains an acidic monomer, a non-acidic monomer having a hydroxyl group, and a non-acidic monomer having a urethane bond as the polymerizable monomer.

[0059] The proportion of the polymerizable monomer in the dental adhesive is, for example, 40 mass % or more, preferably 50 mass % or more, and for example, 70 mass % or less, preferably 60 mass % or less.

[0060] When the dental adhesive contains an acidic monomer as a polymerizable monomer, the proportion of the acidic monomer in the polymerizable monomer is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less.

[0061] When the dental adhesive contains a non-acidic monomer having a hydroxyl group as a polymerizable monomer, the proportion of the non-acidic monomer having a hydroxyl group in the polymerizable monomer is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 40% by mass or less, preferably 30% by mass or less.

[0062] When the dental adhesive contains a non-acidic monomer having a urethane bond as a polymerizable monomer, the proportion of the non-acidic monomer having a urethane bond in the polymerizable monomer is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and for example, 80% by mass or less, preferably 70% by mass or less.

[0063] (2) Transition metal compounds The transition metal compound is a polymerization initiator that initiates the polymerization (radical polymerization) of polymerizable monomers.

[0064] 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).

[0065] 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 titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn), and more preferred examples include vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).

[0066] 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.

[0067] A transition metal complex has a transition metal atom as a central metal and a ligand coordinated to the transition metal atom.

[0068] 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.

[0069] Specific examples of the transition metal compound include copper compounds, iron compounds, cobalt compounds, chromium compounds, zinc compounds, manganese compounds, and vanadium compounds.

[0070] Examples of copper compounds include copper(II) hydroxide, copper(I), copper(II) chloride, copper(II), copper(I) bromide, copper(II), copper(II) bromide, copper(II) formate, copper(I), copper(II) acetate, copper(II), copper(II) acetate, copper(II) sulfate, copper(II) nitrate, copper(I) iodide, basic copper(II) carbonate, copper(I), copper(II) oxide, copper(II), 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, mercaptobenzimidazole copper (MBI-Cu), and thiourea copper.

[0071] 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.

[0072] 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.

[0073] Examples of chromium compounds include chromium(III) acetate, chromium(II) chloride, chromium(III) chloride, chromium(IV) chloride, chromium(II) bromide, chromium(III) bromide, chromium(III) fluoride, chromium(V) fluoride, chromium(III) oxide, chromium(III) oxide, chromium(IV), chromium(VI) oxide, silver(I) chromate, chromium(III) nitrate, potassium dichromate, chromium(III) acetylacetonate, and hexafluoroacetylacetonatochromium(III).

[0074] Examples of zinc compounds include zinc acetate, zinc chloride, zinc bromide, zinc iodide, zinc oxide, zinc sulfide, zinc nitrate, zinc sulfate, zinc phosphate, zinc diphosphate, zinc lactate, zinc salicylate, zinc stearate, zinc gluconate, zinc acrylate, and zinc 2-mercaptobenzothiazole.

[0075] Examples of manganese compounds include manganese(II) chloride, manganese(II) bromide, manganese(II) carbonate, manganese(II) fluoride, manganese(II) iodide, manganese(II) nitrate, manganese(IV) oxide, manganese(II) acetate, manganese(III) acetate, manganese(II) phosphate, manganese(II) sulfate, manganese(II) acetylacetonate, and manganese(III) acetylacetonate.

[0076] 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) oxide stearate, vanadium(IV) oxide sulfate, ammonium vanadate(V), and sodium orthovanadate(V).

[0077] The transition metal compounds can be used alone or in combination of two or more.

[0078] The transition metal compound is preferably a copper compound, more preferably copper(II) acetate.

[0079] The proportion of the transition metal compound in the dental adhesive is, for example, 0.01 mass % or more, preferably 0.05 mass % or more, and for example, 1.00 mass % or less, preferably 0.5 mass % or less.

[0080] The ratio of the transition metal compound to 100 parts by mass of the polymerizable monomer is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less.

[0081] (3) Tertiary amines Tertiary amines are polymerization accelerators, and examples of tertiary amines include aromatic tertiary amines and aliphatic tertiary amines.

[0082] Examples of aromatic tertiary amines include N,N-dialkyltoluidines, N,N-bis(hydroxyalkyl)toluidines, N,N-dialkylanilines, and dialkylaminobenzoates.

[0083] Examples of N,N-dialkyltoluidines include N,N-dimethyl-p-toluidine and N,N-diethyl-p-toluidine.

[0084] Examples of N,N-bis(hydroxyalkyl)toluidines include N,N-bis(2-hydroxyethyl)-p-toluidine and N,N-bis(2-hydroxypropyl)-p-toluidine.

[0085] Examples of N,N-dialkylanilines include N,N-dimethylaniline and N,N-diethylaniline.

[0086] Examples of dialkylaminobenzoate esters include methyl 4-(dimethylamino)benzoate, ethyl 4-(dimethylamino)benzoate, 2-butoxyethyl 4-(dimethylamino)benzoate, and isoamyl 4-(dimethylamino)benzoate.

[0087] Aliphatic tertiary amines include, for example, N,N-dialkylaminoalkyl (meth)acrylates, trialkylamines, and alkanolamines.

[0088] Examples of N,N-dialkylaminoalkyl(meth)acrylates include N,N-dimethylaminoethyl(meth)acrylate and N,N-diethylaminoethyl(meth)acrylate.

[0089] Trialkylamines include, for example, trimethylamine, triethylamine, and tripropylamine.

[0090] Alkanolamines include, for example, N-ethyldiethanolamine and triethanolamine.

[0091] The tertiary amines can be used alone or in combination of two or more kinds.

[0092] The tertiary amine is preferably an aromatic tertiary amine, more preferably a dialkylaminobenzoic acid ester, and more preferably ethyl 4-(dimethylamino)benzoate.

[0093] When the dental adhesive contains an aromatic tertiary amine, it is possible to achieve both adhesive strength to dental cement and adhesive strength to compolette resin.

[0094] The proportion of tertiary amine in the dental adhesive is, for example, 0.1 mass % or more, preferably 0.3 mass % or more, and for example, 1.0 mass % or less, preferably 0.7 mass % or less.

[0095] The ratio of the tertiary amine relative to 100 parts by mass of the polymerizable monomer is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and for example, 3.0 parts by mass or less, preferably 1.0 part by mass or less.

[0096] (4) Thiourea compounds The thiourea compound is a stabilizer for transition metal compounds. When the dental adhesive contains a thiourea compound, the storage stability can be improved.

[0097] The thiourea compound is represented by the following general formula (1).

[0098] General formula (1):

[0099] [ka]

[0100] (In general formula (1), R 1 ~R 4 Each of represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aromatic hydrocarbon group, and a heterocyclic group. In general formula (1), R 1 ~R 4 The alkyl group represented by the formula (I) preferably represents an alkyl group having 1 to 10 carbon atoms, more preferably represents an alkyl group having 1 to 4 carbon atoms, and further preferably represents a methyl group.

[0101] In general formula (1), R 1 ~R 4 Examples of the aromatic hydrocarbon group represented by the formula include a phenyl group and a benzyl group.

[0102] In general formula (1), R 1 ~R 4 Examples of the heterocyclic group represented by the formula include a pyridyl group and a pyrazine group.

[0103] In general formula (1), R 1 ~R 4 may be the same as each other or may be different from each other.

[0104] The thiourea compounds can be used alone or in combination of two or more.

[0105] In general formula (1), R 1 ~R 4 When all of are hydrogen atoms, the thiourea compound represented by general formula (1) is thiourea.

[0106] In general formula (1), R 1 ~R 4 When all of the groups are alkyl groups, the thiourea compound represented by general formula (1) is a tetraalkylthiourea. Examples of tetraalkylthioureas include tetramethylthiourea and tetraethylthiourea.

[0107] In general formula (1), R 1 ~R 4 When one of these is a hydrogen atom and the others are alkyl groups, the thiourea compound represented by general formula (1) is a trialkylthiourea. Examples of trialkylthioureas include trimethylthiourea and triethylthiourea.

[0108] In general formula (1), R 1 ~R 4 When at least one of the groups is an aromatic hydrocarbon group and the others are hydrogen atoms or alkyl groups, the thiourea compound represented by general formula (1) is a thiourea having an aromatic hydrocarbon group. An example of a thiourea having an aromatic hydrocarbon group is N,N-diphenylthiourea.

[0109] In general formula (1), R 1 ~R 4 When at least one of the groups is a heterocyclic group and the others are hydrogen atoms or alkyl groups, the thiourea compound represented by general formula (1) is a thiourea having a heterocyclic group. Examples of thioureas having a heterocyclic group include (2-pyridyl)thiourea and 1-(pyrazin-2-yl)thiourea.

[0110] The thiourea compound represented by the general formula (1) preferably includes trialkylthiourea, tetraalkylthiourea, and thiourea having a heterocyclic group, and more preferably includes tetramethylthiourea and (2-pyridyl)thiourea.

[0111] The content of the thiourea compound in the dental adhesive is, for example, 0.1 mass % or more, preferably 0.3 mass % or more, and for example, 1.0 mass % or less, preferably 0.7 mass % or less.

[0112] The ratio of the thiourea compound to 100 parts by mass of the transition metal compound is, for example, 300 parts by mass or more, preferably 400 parts by mass or more, more preferably 500 parts by mass or more, and for example, 1000 parts by mass or less, preferably 700 parts by mass or less.

[0113] (5) First silane compound The first silane compound has at least one hydroxyl group or hydrolyzable group. The first silane compound also has at least one functional group capable of reacting with a polymerizable monomer other than the hydroxyl group or hydrolyzable group. The first silane compound is not included in the polymerizable monomer.

[0114] The hydrolyzable group can form a silanol group together with the silicon atom upon hydrolysis. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a siloxy group, a hydrogen atom, and a halogen atom.

[0115] Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and n-pentyloxy groups.

[0116] Examples of the acyloxy group include a formyloxy group, an acetoxy group, an n-propionyloxy group, an isopropionyloxy group, an n-butanoyloxy group, and an n-pentanoyloxy group.

[0117] An example of the siloxy group is a trimethylsiloxy group.

[0118] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0119] The hydrolyzable group is preferably an alkoxy group, and the first silane compound preferably has three alkoxy groups.

[0120] Examples of functional groups capable of reacting with polymerizable monomers include ethylenically unsaturated groups, amino groups, epoxy groups, thiol groups, and isocyanate groups.

[0121] When the polymerizable monomer has any one of a vinyl group, an allyl group, and a styryl group, the functional group capable of reacting with the polymerizable monomer is preferably at least one selected from ethylenically unsaturated groups.

[0122] When the polymerizable monomer has a (meth)acryloyl group, the functional group capable of reacting with the polymerizable monomer is preferably at least one selected from an ethylenically unsaturated group and an amino group.

[0123] Examples of the first silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldi(2-methoxyethoxy)silane, vinyldimethylmonomethoxysilane, vinyldimethylmonoethoxysilane, vinyldimethylmonochlorosilane, vinyldimethylmonoacetoxysilane, and vinyldimethylmono(2-methoxyethoxy)silane.

[0124] Examples of the first silane compound having an allyl group include allyltriethoxysilane, allylmethyldiethoxysilane, and allyldimethylmonoethoxysilane.

[0125] An example of the first silane compound having a styryl group is p-styrylethyltrimethoxysilane.

[0126] Examples of the first silane compound having a (meth)acryloyl group include 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylmethyldiisopropoxysilane, 3-(meth)acryloyloxypropylmethyldiisopropoxysilane, Acryloyloxypropylmethylditrimethylsiloxysilane, 3-(meth)acryloyloxypropylmethyldihexyloxysilane, (meth)acryloyloxy-2-(2-vinyloxyethoxy)ethylmethyldimethoxysilane, 6-(meth)acryloyloxyhexylmethyldimethoxysilane, (meth)acryloyloxy-p-phenylethylmethyldimethoxysilane, 6-(meth)acryloyloxyhexylmethyldiethoxysilane, 10-(meth)acryloyloxydecylmethyldimethoxysilane, 11-(meth)acryloyloxypropylmethyldihexylmethyldimethoxysilane 11-(meth)acryloyloxyundecylmethyldimethoxysilane, 11-(meth)acryloyloxyundecylmethyldiethoxysilane, 11-(meth)acryloyloxyundecylmethyldihexyloxysilane, 20-(meth)acryloyloxyeicosylmethyldimethoxysilane, 3-(meth)acryloyloxypropylphenyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldichlorosilane, 11-(meth)acryloyloxyundecylmethyldichlorosilane, 11-(meth)acryloyloxyundecylethyldichlorosilane, 3-(meth)acryloyloxypropylmethyldichlorosilane p) acryloyloxypropyldimethylmonomethoxysilane, 3-(meth)acryloyloxypropyldimethylmonoethoxysilane, 3-(meth)acryloyloxypropyldimethylmonoisopropoxysilane, 3-(meth)acryloyloxypropyldimethylmonotrimethylsiloxysilane, 3-(meth)acryloyloxypropyldimethylmonohexyloxysilane, (meth)acryloyloxy-2-(2-vinyloxyethoxy)ethyldimethylmonomethoxysilane, 6-(meth)acryloyloxyhexyldimethylmonomethoxysilane,Examples of suitable silanes include (meth)acryloyloxy-p-phenylethyldimethyl monomethoxysilane, 6-(meth)acryloyloxyhexyldimethyl monoethoxysilane, 10-(meth)acryloyloxydecyldimethyl monomethoxysilane, 11-(meth)acryloyloxyundecyldimethyl monomethoxysilane, 11-(meth)acryloyloxyundecyldimethyl monoethoxysilane, 11-(meth)acryloyloxyundecyldimethyl monohexyloxysilane, 20-(meth)acryloyloxyeicosyldimethyl monomethoxysilane, 3-(meth)acryloyloxypropyldiphenyl monomethoxysilane, 3-(meth)acryloyloxypropyldimethylmonochlorosilane, 11-(meth)acryloyloxyundecyldimethylmonochlorosilane, and 11-(meth)acryloyloxyundecyldiethylmonochlorosilane.

[0127] Examples of the first silane compound having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.

[0128] Examples of the first silane compound having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmonomethoxysilane, and 3-glycidoxypropyldimethylmonoethoxysilane.

[0129] Examples of the first silane compound having a thiol group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0130] An example of the first silane compound having an isocyanate group is 3-isocyanatepropyltriethoxysilane.

[0131] The first silane compound is preferably a first silane compound having a (meth)acryloyl group, and more preferably 3-methacryloyloxypropyltrimethoxysilane (γ-MTPS), 3-(meth)acryloyloxypropyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, and 3-(meth)acryloyloxypropylmethyldiethoxysilane.

[0132] The proportion of the first silane compound in the dental adhesive is, for example, 0.1 mass % or more, preferably 1 mass % or more, and for example, 30 mass % or less, preferably 20 mass % or less.

[0133] When the proportion of the first silane compound in the dental adhesive is equal to or greater than the above lower limit, the storage stability can be improved.

[0134] When the proportion of the first silane compound in the dental adhesive is equal to or less than the above upper limit, sufficient adhesive strength can be achieved to both tooth structure and prosthesis (particularly porcelain).

[0135] The ratio of the first silane compound to 100 parts by mass of the polymerizable monomer is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and for example, 40 parts by mass or less, preferably 30 parts by mass or less.

[0136] (6) Second silane compound The second silane compound has at least one hydroxyl group or the above-described hydrolyzable group. The second silane compound does not have a functional group that can react with the polymerizable monomer. The hydrolyzable group is preferably an alkoxy group.

[0137] Examples of the second silane compound having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

[0138] Examples of the second silane compound having two hydrolyzable groups include dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyldimethoxysilane.

[0139] Examples of the second silane compound having three hydrolyzable groups include methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

[0140] Examples of the second silane compound having four hydrolyzable groups include tetraethoxysilane, 1,2-bis-(methyldiethoxysilyl)ethane, and bis-[(methyldimethoxysilyl)propyl]polypropylene oxide.

[0141] Examples of the second silane compound having six hydrolyzable groups include 1,2-bis-(triethoxysilyl)ethane and 1,6-bis(trimethoxysilyl)hexane.

[0142] Preferably, the molecular weight of the second silane compound is 500 or less, and the second silane compound has five or less hydroxyl groups or hydrolyzable groups per molecule. When the second silane compound is a monomer, the molecular weight of the second silane compound is the sum of the atomic weights of the atoms constituting the second silane compound. When the second silane compound is a polymer, the molecular weight of the second silane compound is the weight-average molecular weight.

[0143] The weight average molecular weight can be calculated using gel permeation chromatography in terms of standard polystyrene.

[0144] If the molecular weight of the second silane compound is 500 or less and the second silane compound has five or less hydroxyl groups or hydrolyzable groups per molecule, the stability of the adhesive strength to dental ceramics can be improved, and the storage stability (adhesion durability after storage) of the dental adhesive can also be improved. The stability of the adhesive strength to dental ceramics can be measured by the method described in the Examples below.

[0145] More preferably, the molecular weight of the second silane compound is 300 or less, and the second silane compound has four or less hydroxyl groups or hydrolyzable groups per molecule.

[0146] The molar ratio of the second silane compound to the first silane compound is, for example, 0.1 or more, preferably 0.3 or more, and for example, 30 or less, preferably 10 or less.

[0147] When the molar ratio of the second silane compound to the first silane compound is equal to or greater than the above lower limit and equal to or less than the above upper limit, storage stability can be improved.

[0148] The proportion of the second silane compound in the dental adhesive is, for example, 0.1 mass % or more, preferably 1 mass % or more, and for example, 30 mass % or less, preferably 20 mass % or less.

[0149] When the proportion of the second silane compound in the dental adhesive is equal to or greater than the above lower limit, the storage stability can be improved.

[0150] When the proportion of the second silane compound in the dental adhesive is equal to or less than the above upper limit, sufficient adhesive strength can be achieved to both tooth structure and prosthesis.

[0151] The ratio of the second silane compound to 100 parts by mass of the polymerizable monomer is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and for example, 40 parts by mass or less, preferably 30 parts by mass or less.

[0152] (7) Solvent Examples of the solvent include water and organic solvents.

[0153] Examples of the organic solvent include organic solvents that are miscible with water. Examples of the organic solvents that are miscible with water include alcohols and ketones. Examples of the alcohols include ethanol and isopropyl alcohol. Examples of the ketones include acetone.

[0154] The solvents can be used alone or in combination of two or more kinds.

[0155] The dental adhesive preferably contains water and ethanol as solvents.

[0156] The ratio of the solvent in the dental adhesive is not limited, and the ratio of the solvent in the dental adhesive is the remainder relative to the components other than the solvent.

[0157] (8) Photopolymerization initiator The photopolymerization initiator generates radicals when exposed to light.

[0158] Examples of photopolymerization initiators include α-diketones, ketals, and thioxanthones. Examples of α-diketones include camphorquinone. Examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

[0159] As the photopolymerization initiator, preferably, an α-diketone is used, and more preferably, camphorquinone (CQ) is used.

[0160] The proportion of the photopolymerization initiator in the dental adhesive is, for example, 0.05 mass % or more, preferably 0.1 mass % or more, and for example, 10 mass % or less, preferably 5 mass % or less.

[0161] (9) Polymerization inhibitor Examples of the polymerization inhibitor include dibutylhydroxytoluene (BHT) and 4-methoxyphenol (MEHQ).

[0162] The proportion of the polymerization inhibitor in the dental adhesive is, for example, 0.01 mass % or more, preferably 0.05 mass % or more, and for example, 3 mass % or less, preferably 1 mass % or less.

[0163] 2. Effects The dental adhesive of the present invention contains, in one component, a polymerizable monomer, a transition metal compound, a tertiary amine, a thiourea compound, and a first silane compound having a functional group capable of reacting with the polymerizable monomer.

[0164] Therefore, it has sufficient adhesive strength to tooth structure and excellent storage stability. [Example]

[0165] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. Specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention."

[0166] 1. Preparation of Dental Adhesive Dental adhesives for each example and comparative example were prepared by mixing the components according to the formulations shown in Tables 1 and 2. In Tables 1 and 2, the unit of the blending amount of each component is "parts by mass."

[0167] The meanings of the abbreviations in Tables 1 and 2 are listed below.

[0168] MDP: 10-methacryloyloxydecyl acid phosphate HEMA: 2-hydroxyethyl methacrylate UDMA: [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate EtOH: ethanol BHT: Dibutylhydroxytoluene MEHQ: 4-methoxyphenol CQ: Camphorquinone DMABAE: ethyl 4-(dimethylamino)benzoate Thiourea Compound A: Tetramethylthiourea Thiourea Compound B: (2-pyridyl)thiourea Transition metal compound: copper(II) acetate monohydrate First silane compound A: 3-methacryloyloxypropyltrimethoxysilane First silane compound B: 8-methacryloyloxyoctyltrimethoxysilane First silane compound C: 3-methacryloyloxypropylmethyldiethoxysilane First silane compound D: 3-methacryloyloxypropyltriethoxysilane Second silane compound A: dimethyldiethoxysilane (molecular weight: 148.28) Second silane compound B: trimethylethoxysilane (molecular weight: 118.25) 2. Evaluation of adhesive strength The dental adhesives of the examples and comparative examples shown in Tables 1 and 2 were evaluated for adhesive strength to bovine dentin (an example of tooth structure) by the following method.

[0169] First, a stainless steel rod with a diameter of 6 mm was polished with durable abrasive paper #600, and then sandblasted to prepare a jig for the tensile test.

[0170] Next, the surface of the bovine dentin was polished flat with durable abrasive paper #180. A 700 μm thick cardboard with a 4.8 mm diameter hole was attached to the polished surface with double-sided tape to define the adhesive surface.

[0171] Next, a dental adhesive was applied to the surface of the bovine dentin. The applied dental adhesive was dried uniformly with an air blower. The dental adhesive was then irradiated with light to harden it.

[0172] Next, the holes in the cardboard were filled with composite resin (product name: Bulk Base Hard II, manufactured by Sun Medical Co., Ltd.).

[0173] Next, with a polyester film placed on top of the filled composite resin, the composite resin was pressed against a flat glass plate, and the composite resin was hardened by irradiating it with light using a Pencure 2000 (Morita Co., Ltd.).

[0174] Next, the polyester film was removed, and a jig was fixed to the cured composite resin. This resulted in obtaining test specimen A for adhesiveness evaluation. Five test specimens A were prepared.

[0175] Separately, specimen B for evaluating storage stability was obtained in the same manner as specimen A for evaluating adhesion, using a dental adhesive that had been left in an environment of 65°C for 12 days. Five specimens B were prepared.

[0176] Each of the five test specimens A and five test specimens B (each test specimen) was left standing for 30 minutes, and then immersed in water at 37° C. overnight (17 hours).

[0177] Next, a tensile test was performed on each specimen using a universal testing machine, Autograph AG-IS (Shimadzu Corporation). The crosshead speed was 2 mm / min. The tensile strength of each of the five specimens A was averaged to evaluate the adhesive strength of specimen A. The tensile strength of each of the five specimens B was averaged to evaluate the adhesive strength of specimen B.

[0178] The tensile strengths of specimen A and specimen B, as well as the difference between the tensile strength of specimen A and that of specimen B (tensile strength of specimen A - tensile strength of specimen B, "reduction" in Tables 1 and 2), are shown in Tables 1 and 2. The larger the reduction, the poorer the storage stability. Furthermore, when the tensile strength of specimen B is greater than that of specimen A (i.e., when the "reduction" value in Tables 1 and 2 is negative), no reduction in adhesive strength was observed, and the storage stability was therefore considered to be excellent.

[0179] If the tensile strength is 1.5 MPa or more, the adhesive strength is sufficient for both bovine dentin and composite resin.

[0180] In Comparative Example 2, the specimen B was left in an environment of 65° C. for 12 days, and as a result, it hardened, so that the tensile strength and the reduction in strength of the specimen B could not be measured.

[0181] [Table 1] [Table 2]

Claims

1. A polymerizable monomer; a transition metal compound containing a transition metal atom belonging to the fourth period of the periodic table; A tertiary amine, A thiourea compound represented by the following general formula (1), a first silane compound having a functional group capable of reacting with the polymerizable monomer; A dental adhesive comprising: General formula (1): 【Chemistry 1】 (In the general formula (1), R １ ~R ４ Each of represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aromatic hydrocarbon group, and a heterocyclic group.

2. The dental adhesive according to claim 1 , further comprising a second silane compound in the first agent that does not have a functional group capable of reacting with the polymerizable monomer.

3. The dental adhesive of claim 1 , wherein the transition metal compound is a copper compound.

4. The dental adhesive of claim 1 , wherein the tertiary amine has an aromatic ring.

5. The dental adhesive of claim 4 wherein the tertiary amine is a dialkylaminobenzoic acid ester.

6. The dental adhesive of claim 1 , wherein the thiourea compound is a trialkylthiourea or a tetraalkylthiourea.

7. The dental adhesive according to claim 1 , comprising an acidic monomer as the polymerizable monomer.

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