Polymerization initiator-containing composition and dental polymerizable composition

Abstract

The polymerization initiator-containing composition contains a fourth period transition metal compound including a transition metal atom belonging to the fourth period of the periodic table, a tertiary amine compound, and a thiourea compound represented by general formula (1). (In general formula (1), R1-R4 each represent one selected from the group consisting of a hydrogen atom, an alkyl group, an aromatic ring group, and a heterocyclic group.)

Description

[Technical Field]

[0001] The present invention relates to a polymerization initiator-containing composition and a polymerizable composition for dental use. [Background technology]

[0002] In dental treatment for dental caries (tooth decay), after removing the decayed portion, prosthetics such as crowns and inlays are sometimes bonded to the tooth using dental cement. In this case, it is known that the tooth surface is treated with a dental primer before bonding the prosthetic to the tooth to improve the adhesion of the dental cement to the tooth.

[0003] As such a dental primer, for example, a dental primer comprising an acidic (meth)acrylate, a copper compound, a polymerization inhibitor, and water has been proposed (see, for example, Patent Document 1).

[0004] Furthermore, in dental treatment for dental caries (tooth decay), after removing the decayed portion, the cavity of the tooth may be restored by filling it with a dental filling material such as composite resin. In this case, it is known that a dental bonding agent is applied to the cavity before filling it with the dental filling material to improve the adhesion of the dental filling material to the tooth. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-168099 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In recent years, from the perspective of improving the efficiency of dental treatment, there has been a demand for dental materials that can be used as both dental primers and dental bonding agents. However, because the composition of dental cement and dental filling materials differs, it is difficult to achieve both adhesion to dental cement and adhesion to dental filling materials.

[0007] For example, the dental primer described in Patent Document 1 can ensure adhesion to dental cement, but it cannot sufficiently ensure adhesion to dental filling materials.

[0008] Furthermore, dental primers and bonding materials require excellent discoloration resistance from the perspective of maintaining the aesthetic appearance of teeth after treatment.

[0009] The present invention provides a polymerization initiator-containing composition and a dental polymerizable composition that can ensure adhesion to both dental cements and dental filling materials and can be used as either a dental primer or a dental bonding material, and which exhibits excellent discoloration resistance. [Means for solving the problem]

[0010] The present invention [1] includes a polymerization initiator-containing composition comprising a fourth-period transition metal compound containing a transition metal atom belonging to the fourth period of the periodic table, a tertiary amine compound, and a thiourea compound represented by the following general formula (1) in one component.

[0011] [ka]

[0012] (In general formula (1), R 1 ~R 4 Each of these represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aromatic ring group, and a heterocyclic group. The present invention [2] includes the polymerization initiator-containing composition described in [1] above, wherein the fourth periodic transition metal compound includes a copper compound.

[0013] The present invention [3] includes the polymerization initiator-containing composition according to [1] or [2] above, wherein the tertiary amine compound has an aromatic ring.

[0014] The present invention [4] includes the polymerization initiator-containing composition according to [3] above, wherein the tertiary amine compound contains a dialkylaminobenzoic acid ester.

[0015] The present invention [5] includes the polymerization initiator-containing composition according to any one of [1] to [4] above, wherein the thiourea compound contains a trialkylthiourea or a tetraalkylthiourea.

[0016] The present invention [6] includes a dental polymerizable composition including the polymerization initiator-containing composition according to any one of [1] to [5] above and a polymerizable monomer.

[0017] The present invention [7] includes the dental polymerizable composition according to [6] above, wherein the polymerizable monomer contains an acidic group-containing polymerizable monomer.

Advantages of the Invention

[0018] The polymerization initiator-containing composition of the present invention contains the above-mentioned Group 4 transition metal compound and tertiary amine compound in one agent. Therefore, the polymerization initiator-containing composition can impart adhesiveness to both dental cements and dental filling materials in the dental polymerizable composition.

[0019] Further, the polymerization initiator-containing composition further contains the above-mentioned thiourea compound in one agent. Therefore, even when the polymerization initiator-containing composition contains a Group 4 transition metal compound and a tertiary amine compound, it is possible to improve the discoloration resistance of the polymerization initiator-containing composition during storage.

[0020] Furthermore, the polymerizable dental composition of the present invention contains the polymerization initiator-containing composition described above. Therefore, the polymerizable dental composition can ensure adhesion to dental cement, ensure adhesion to dental filling materials, and improve discoloration resistance during storage.

[0021] As a result, the polymerization initiator-containing composition and the dental polymerizable composition can be suitably used as both a dental primer and a dental bonding material. [Modes for carrying out the invention]

[0022] The polymerization initiator-containing composition of the present invention is a dental polymerization initiator-containing composition that can be used as either a dental primer or a dental bonding material. The polymerization initiator-containing composition contains, as essential components, a fourth-period transition metal compound, a tertiary amine compound, and a thiourea compound.

[0023] (1) 4th period transition metal compound Fourth-period transition metal compounds are polymerization initiators. These compounds initiate the polymerization (radical polymerization) of polymerizable monomers, as described later. When a polymerization initiator-containing composition includes a fourth-period transition metal compound, it ensures the adhesion of the dental polymerizable composition (described later) to dental cement.

[0024] Fourth-period transition metal compounds contain transition metal atoms belonging to the fourth period of the periodic table (hereinafter referred to as fourth-period transition metal atoms).

[0025] Fourth-period transition metal atoms are metal atoms belonging to the fourth period of the periodic table and belonging to groups 3 through 13. The periodic table follows the IUPAC Periodic Table of the Elements (version date 22 June 2007) (the same applies hereafter).

[0026] Examples of fourth-period 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).

[0027] Among the fourth-period transition metal atoms, preferred examples include metal atoms belonging to groups 4 through 12 of the periodic table, and more preferably, metal atoms belonging to groups 5 through 12 of the periodic table.

[0028] In other words, preferred fourth-period transition metal compounds include titanium compounds, vanadium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, and zinc compounds, and more preferably vanadium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, and zinc compounds.

[0029] Furthermore, compounds that combine with fourth-period transition metals can be classified into inorganic and organic compounds.

[0030] Examples of inorganic compounds that combine with fourth-period transition metal atoms include inorganic salts of fourth-period transition metal atoms and metal halides of fourth-period transition metal atoms.

[0031] Examples of inorganic salts of fourth-period transition metal atoms include sulfates and nitrates.

[0032] Examples of metal halides of fourth-period transition metal atoms include chlorides and bromides.

[0033] Examples of organic compounds that combine with fourth-period transition metal atoms include organic salts of fourth-period transition metal atoms and organometallic complexes of fourth-period transition metal atoms.

[0034] Examples of organic salts of fourth-period transition metal atoms include carboxylates. Examples of carboxylates include acetates.

[0035] Organometallic complexes of fourth-period transition metal atoms have a fourth-period transition metal atom as the central metal and a ligand that coordinates to the fourth-period transition metal atom. Examples of ligands include diketone ligands, amine ligands, and imine ligands.

[0036] Fourth-period transition metal compounds can be used alone or in combination of two or more types.

[0037] The fourth-period transition metal compound preferably comprises an iron compound and / or a copper compound, more preferably an inorganic copper compound and / or an organic copper compound, even more preferably at least one selected from the group consisting of inorganic copper salts, organic copper salts and copper halides, particularly preferably at least one selected from the group consisting of copper sulfate, copper chloride and copper acetate, and especially preferably copper sulfate and / or copper acetate. Furthermore, the fourth-period transition metal compound preferably comprises an iron compound and / or a copper compound.

[0038] If the fourth-period transition metal compound includes an iron compound and / or a copper compound, the adhesion of the dental polymerizable composition to dental cement, as described later, can be reliably improved. In particular, if the fourth-period transition metal compound includes a copper compound, the adhesion of the dental polymerizable composition to dental cement, as described later, can be improved even more reliably.

[0039] The content of the fourth-period transition metal compound in the dental polymerizable composition described later is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and also, for example, 5.0 parts by mass or less, preferably 3.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.0 part by mass or less, based on 100 parts by mass of the total sum of the polymerizable monomer, the fourth-period transition metal compound, the tertiary amine compound, and the thiourea compound described later.

[0040] (2) Tertiary amine compounds Tertiary amine compounds are reducing agents. When a polymerization initiator-containing composition contains a tertiary amine compound, the adhesion of the dental polymerizable composition described later to composite resin can be ensured.

[0041] Examples of tertiary amine compounds include aromatic ring-containing tertiary amine compounds and aromatic ring-free tertiary amine compounds.

[0042] Aromatic ring-containing tertiary amine compounds have an aromatic ring and a tertiary amino group.

[0043] Examples of aromatic ring-containing tertiary amine compounds include N,N-dialkyltoluidine, N,N-bis(hydroxyalkyl)toluidine, N,N-dialkylaniline, and dialkylaminobenzoic acid esters.

[0044] Examples of N,N-dialkyltoluidines include N,N-dimethyl-p-toluidine and N,N-diethyl-p-toluidine.

[0045] Examples of N,N-bis(hydroxyalkyl)toluidines include N,N-bis(2-hydroxyethyl)-p-toluidine and N,N-bis(2-hydroxypropyl)-p-toluidine.

[0046] Examples of N,N-dialkylanilines include N,N-dimethylaniline and N,N-diethylaniline.

[0047] Examples of dialkylaminobenzoic acid esters include methyl 4-(dimethylamino)benzoate, ethyl 4-(dimethylamino)benzoate, 2-butoxyethyl 4-(dimethylamino)benzoate, and isoamyl 4-(dimethylamino)benzoate.

[0048] Aromatic ring-free tertiary amine compounds lack an aromatic ring and possess a tertiary amino group.

[0049] Examples of aromatic ring-free tertiary amine compounds include N,N-dialkylaminoalkyl(meth)acrylates, trialkylamines, and alkanolamines.

[0050] Examples of N,N-dialkylaminoalkyl(meth)acrylates include N,N-dimethylaminoethyl(meth)acrylate and N,N-diethylaminoethyl(meth)acrylate. (Meth)acrylates include methacrylate and acrylate (the same applies hereinafter).

[0051] Examples of trialkylamines include trimethylamine, triethylamine, and tripropylamine.

[0052] Examples of alkanolamines include N-ethyldiethanolamine and triethanolamine.

[0053] Tertiary amine compounds can be used alone or in combination of two or more types.

[0054] The tertiary amine compound preferably includes an aromatic ring-containing tertiary amine compound. In other words, the tertiary amine compound preferably has an aromatic ring. Furthermore, the tertiary amine compound more preferably consists of an aromatic ring-containing tertiary amine compound.

[0055] Furthermore, the aromatic ring-containing tertiary amine compound preferably comprises N,N-dialkyltoluidine and / or dialkylaminobenzoic acid ester, more preferably comprises dialkylaminobenzoic acid ester, particularly preferably comprises at least one selected from the group consisting of ethyl 4-(dimethylamino)benzoate, 2-butoxyethyl 4-(dimethylamino)benzoate, and isoamyl 4-(dimethylamino)benzoate, and most preferably comprises ethyl 4-(dimethylamino)benzoate.

[0056] When the tertiary amine compound includes an aromatic ring-containing tertiary amine compound, it is possible to impart a good balance of both adhesiveness to dental cement and adhesiveness to composite resin to the dental polymerizable composition described later.

[0057] In particular, if the tertiary amine compound includes a dialkylaminobenzoic acid ester, the adhesion of the dental polymerizable composition to the composite resin, as described later, can be improved even more reliably.

[0058] The content of the tertiary amine compound in the dental polymerizable composition described later is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and also, for example, 10.0 parts by mass or less, preferably 5.0 parts by mass or less, and more preferably 2.0 parts by mass or less, based on 100 parts by mass of the total sum of the polymerizable monomer, the fourth-period transition metal compound, the tertiary amine compound, and the thiourea compound described later.

[0059] (3) Thiourea compounds Thiourea compounds are reducing agents. When a polymerization initiator-containing composition contains a thiourea compound, its resistance to discoloration during storage can be improved.

[0060] Thiourea compounds are represented by the following general formula (1).

[0061] [ka]

[0062] (In general formula (1), R 1 ~R 4 Each of these represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aromatic ring group, and a heterocyclic group. In general formula (1), R 1 ~R 4The alkyl group represented by [alkyl group] preferably represents an alkyl group having 1 to 10 carbon atoms, more preferably represents an alkyl group having 1 to 4 carbon atoms, and still more preferably represents a methyl group.

[0063] In General Formula (1), R 1 ~R 4 Examples of the heterocyclic group represented by [heterocyclic group] include a phenyl group and a benzyl group.

[0064] In General Formula (1), R 1 ~R 4 Examples of the heterocyclic group represented by [heterocyclic group] include a pyridyl group and a pyrazinyl group.

[0065] In General Formula (1), R 1 ~R 4 may be the same as each other or different from each other.

[0066] The thiourea compound can be used alone or in combination of two or more.

[0067] The thiourea compound preferably contains at least one selected from the group consisting of thiourea, alkylthiourea, aromatic ring-containing thiourea, and heterocyclic ring-containing thiourea. The thiourea compound more preferably consists of one selected from the group consisting of thiourea, alkylthiourea, aromatic ring-containing thiourea, and heterocyclic ring-containing thiourea.

[0068] When the thiourea compound is thiourea, in General Formula (1), all of R 1 ~R 4 represent hydrogen atoms.

[0069] Examples of the alkylthiourea include tetraalkylthiourea and trialkylthiourea.

[0070] When the thiourea compound is tetraalkylthiourea, in General Formula (1), R 1 ~R 4All of these exhibit alkyl groups. Examples of tetraalkylthioureas include tetramethylthiourea and tetraethylthiourea.

[0071] When the thiourea compound is a trialkylthiourea, in general formula (1), R 1 ~R 4 One of these represents a hydrogen atom, and the others represent an alkyl group. Examples of trialkylthioureas include trimethylthiourea and triethylthiourea.

[0072] If the thiourea compound is an aromatic ring-containing thiourea, then in general formula (1), R 1 ~R 4 At least one of these represents an aromatic ring group, and the others represent a hydrogen atom or an alkyl group. An example of an aromatic ring-containing thiourea is N,N-diphenylthiourea.

[0073] If the thiourea compound is a heterocyclic thiourea, then in general formula (1), R 1 ~R 4 At least one of these groups represents a heterocyclic group, and the others represent a hydrogen atom or an alkyl group. Examples of heterocyclic thioureas include (2-pyridyl)thiourea and 1-(pyrazine-2-yl)thiourea.

[0074] Among thioureas, alkylthioureas, and heterocyclic thioureas, alkylthioureas are preferred, more preferably trialkylthioureas and tetraalkylthioureas, and even more preferably tetramethylthiourea.

[0075] The content of the thiourea compound in the dental polymerizable composition described later is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and also, for example, 10.0 parts by mass or less, preferably 5.0 parts by mass or less, more preferably 2.0 parts by mass or less, based on 100 parts by mass of the total sum of the polymerizable monomer, fourth-period transition metal compound, tertiary amine compound and thiourea compound described later.

[0076] (4)Optional components (4-1) Solvent The polymerization initiator-containing composition may further contain a solvent as an optional component.

[0077] Examples of solvents include water and organic solvents.

[0078] Examples of organic solvents include alcohols and ketones. Examples of alcohols include ethanol and isopropyl alcohol. Examples of ketones include acetone.

[0079] The solvent can be used alone or in combination of two or more types.

[0080] The solvent preferably comprises water and / or ethanol, and more preferably comprises water and ethanol. Furthermore, the solvent preferably consists of water and / or ethanol.

[0081] The solvent content in the polymerization initiator-containing composition is, for example, 0% by mass or more, preferably 5% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and also, for example, 95% by mass or less, preferably 85% by mass or less, more preferably 75% by mass or less, even more preferably 65% ​​by mass or less, and particularly preferably 45% by mass or less.

[0082] (4-2) Other additives Furthermore, the polymerization initiator-containing composition may contain other additives in appropriate proportions as optional components. Examples of other additives include photopolymerization initiators, polymerization inhibitors, reducing agents, fillers, and silane coupling agents.

[0083] (5) Effects The polymerization initiator-containing composition described above contains the above-mentioned fourth-period transition metal compound and tertiary amine compound in a single component. Therefore, the polymerization initiator-containing composition can impart both adhesion to dental cement and adhesion to dental filling materials to the dental polymerizable composition described later.

[0084] Furthermore, the polymerization initiator-containing composition contains the thiourea compound described above. Therefore, even if the polymerization initiator-containing composition contains a fourth-period transition metal compound and a tertiary amine compound, the discoloration resistance of the polymerization initiator-containing composition during storage can be improved.

[0085] As a result, the polymerization initiator-containing composition can be suitably used as both a dental primer and a dental bonding material.

[0086] (6) Dental polymerizable compositions The polymerization initiator-containing composition described above is suitable for medical polymerizable compositions, particularly dental polymerizable compositions. The dental polymerizable composition contains the polymerization initiator-containing composition described above and a polymerizable monomer.

[0087] (6-1) Polymerizable monomers Examples of polymerizable monomers include polymerizable monomers containing acidic groups and polymerizable monomers that do not contain acidic groups.

[0088] A polymerizable monomer containing an acidic group has both an acidic group and a polymerizable group.

[0089] Examples of acidic groups include free acidic groups and acidic groups that form acid anhydrides.

[0090] The acidic group is located at one end of the molecule, for example, in a polymerizable monomer containing an acidic group.

[0091] Examples of free acidic groups include carboxyl groups, phosphate groups, and sulfo groups.

[0092] Such acidic groups can form acid anhydrides. Acid anhydrides are formed by the dehydration condensation of two acidic groups. In the following, an acidic group that forms an acid anhydride will be referred to as the acid anhydride of the acidic group.

[0093] Examples of acid anhydrides with acidic groups include acid anhydrides with carboxyl groups, acid anhydrides with phosphoric acid groups, and acid anhydrides with sulfo groups.

[0094] The polymerizable monomer containing an acidic group may contain only one acidic group or one acid anhydride of an acidic group, or it may contain two or more acidic groups and / or acid anhydrides of acidic groups.

[0095] The polymerizable group is located, for example, at the opposite end (the other end) from the acidic group in the molecule of an acidic group-containing polymerizable monomer.

[0096] Examples of polymerizable groups include ethylenically unsaturated double bonds, specifically (meth)acryloyloxy groups, (meth)acryloylamide groups, vinyl groups, and vinyl cyanide groups. Among the polymerizable groups, (meth)acryloyloxy groups are preferred. (Methacryloyl and acryloyl are examples of (meth)acryloyl (the same applies hereinafter).

[0097] The molecular weight of the acidic group-containing polymerizable monomer is, for example, 70 or more, preferably 200 or more, and also, for example, 600 or less, preferably 400 or less.

[0098] Examples of polymerizable monomers containing acidic groups include carboxyl polymerizable monomers, phosphate polymerizable monomers, and sulfo polymerizable monomers.

[0099] Carboxylated polymerizable monomers have a carboxyl group and / or an acid anhydride of a carboxyl group.

[0100] Phosphate-type polymerizable monomers have a phosphate group and / or an acid anhydride of a phosphate group.

[0101] Sulfo-type polymerizable monomers have a sulfo group and / or an acid anhydride with a sulfo group.

[0102] Acidic group-containing polymerizable monomers can be used alone or in combination of two or more types.

[0103] The acidic group-containing polymerizable monomer preferably comprises a carboxyl-type polymerizable monomer and / or a phosphate-type polymerizable monomer, and more preferably comprises a phosphate-type polymerizable monomer. The acidic group-containing polymerizable monomer preferably comprises a carboxyl-type polymerizable monomer and / or a phosphate-type polymerizable monomer.

[0104] Specifically, carboxyl polymerizable monomers include carboxyl group-containing polymerizable monomers exemplified in paragraph

[0043] of Japanese Patent Application Publication No. 2006-347943, preferably the anhydride of 4-(meth)acryloyloxyethyl trimellitic acid, and more preferably the anhydride of 4-methacryloyloxyethyl trimellitic acid (hereinafter referred to as 4-META).

[0105] Examples of phosphorylated polymerizable monomers include the phosphorylated group-containing polymerizable monomers exemplified in paragraph

[0045] of Japanese Patent Application Publication No. 2006-347943, preferably 10-(meth)acryloyloxydecylacid phosphate, and more preferably 10-methacryloyloxydecylacid phosphate (hereinafter referred to as MDP).

[0106] MDP consists of a free phosphate group located at one end of the molecule, a methacryloyloxy group (a polymerizable group) located at the other end of the molecule, and a desilene group that connects the phosphate group and the methacryloyloxy group.

[0107] The acid-free polymerizable monomer has the polymerizable group described above, but does not have the acidic group described above.

[0108] The molecular weight of the acid group-free polymerizable monomer is, for example, 70 or more, preferably 100 or more, for example 1000 or less, preferably 700 or less.

[0109] Examples of polymerizable monomers that do not contain acidic groups include polymerizable monomers that contain hydroxyl groups and polymerizable monomers that do not contain hydroxyl groups.

[0110] A hydroxyl group-containing polymerizable monomer does not have the above-mentioned acidic group, but does have a hydroxyl group.

[0111] Examples of acid group-containing polymerizable monomers include hydroxyl group-containing mono(meth)acrylates, hydroxyl group-containing di(meth)acrylates, and hydroxyl group-containing (meth)acrylamides.

[0112] Hydroxyl group-containing polymerizable monomers can be used alone or in combination of two or more types.

[0113] The hydroxyl group-containing polymerizable monomer preferably includes a hydroxyl group-containing mono(meth)acrylate. More preferably, the hydroxyl group-containing polymerizable monomer consists of a hydroxyl group-containing mono(meth)acrylate.

[0114] Examples of hydroxyl group-containing mono(meth)acrylates include 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, and dihydroxypropyl(meth)acrylate.

[0115] Among hydroxyl group-containing mono(meth)acrylates, 2-hydroxyethyl (meth)acrylate is preferred, and 2-hydroxyethyl methacrylate (HEMA) is preferred.

[0116] Hydroxyl group-free polymerizable monomers do not have the above-mentioned acidic groups and hydroxyl groups.

[0117] Examples of hydroxyl group-free polymerizable monomers include monofunctional (meth)acrylates, difunctional (meth)acrylates, and trifunctional (meth)acrylates.

[0118] Hydroxyl group-free polymerizable monomers can be used alone or in combination of two or more types.

[0119] The hydroxyl group-free polymerizable monomer preferably includes a difunctional (meth)acrylate. More preferably, the hydroxyl group-free polymerizable monomer consists of a difunctional (meth)acrylate.

[0120] Preferred difunctional (meth)acrylates include alkylenedi(meth)acrylate, urethane di(meth)acrylate, oxyalkylenedi(meth)acrylate, and aromatic ring-containing di(meth)acrylate, with urethane di(meth)acrylate being more preferred.

[0121] Urethane di(meth)acrylates have urethane bonds. An example of a urethane di(meth)acrylate is [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate.

[0122] Polymerizable monomers can be used alone or in combination of two or more types.

[0123] The polymerizable monomer preferably includes an acidic group-containing polymerizable monomer, more preferably includes an acidic group-containing polymerizable monomer and a hydroxyl group-free polymerizable monomer, and even more preferably includes an acidic group-containing polymerizable monomer, a hydroxyl group-containing polymerizable monomer and a hydroxyl group-free polymerizable monomer.

[0124] When the polymerizable monomer includes an acidic group-containing polymerizable monomer, the content of the acidic group-containing polymerizable monomer in the polymerizable monomer is, for example, 5% by mass or more, preferably 15% by mass or more, and also, for example, 100% by mass or less, preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0125] When the polymerizable monomer includes a hydroxyl-free polymerizable monomer, the content of the hydroxyl-free polymerizable monomer in the polymerizable monomer is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and also, for example, 90% by mass or less, preferably 80% by mass or less.

[0126] When the polymerizable monomer includes a hydroxyl group-containing polymerizable monomer, the content of the hydroxyl group-free polymerizable monomer in the polymerizable monomer is, for example, 1% by mass or more, preferably 5% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less.

[0127] Furthermore, the content of polymerizable monomers in the dental polymerizable composition is, for example, 0% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and also, for example, 99.3% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less.

[0128] Furthermore, the polymerizable monomer is, for example, 0 parts by mass or more, preferably 1,000 parts by mass or more, more preferably 2,000 parts by mass or more, even more preferably 5,000 parts by mass or more, or, for example, 20,000 parts by mass or less, preferably 15,000 parts by mass or less, and more preferably 10,000 parts by mass or less, based on 100 parts by mass of the total sum of the fourth-period transition metal compound, the tertiary amine compound, and the thiourea compound.

[0129] Such a polymerizable dental composition can ensure adhesion to dental cements, ensure adhesion to dental fillings, and improve discoloration resistance during storage. Therefore, it can be suitably used as both a dental primer and a dental bonding agent. In other words, a polymerizable dental composition is a dual-purpose material for both dental primers and bonding agents.

[0130] Specifically, when using a dental polymerizable composition as a dental primer, for example, the dental polymerizable composition is applied to a pre-formed abutment tooth. Then, dental cement is applied to the prosthesis. The dental cement contains, for example, a polymerizable monomer, a filler, a photopolymerization initiator, and a chemical polymerization initiator. The prosthesis is then fitted to the abutment tooth so that the dental cement comes into contact with the dental polymerizable composition applied to the abutment tooth. After that, the dental cement is allowed to harden. This ensures that the prosthesis is securely bonded to the abutment tooth.

[0131] Furthermore, when using a dental polymerizable composition as a dental bonding material, the dental polymerizable composition is applied to the cavity of the tooth. Then, composite resin is filled into the cavity. The composite resin includes, for example, a polymerizable monomer, a tertiary amine compound, a photopolymerization initiator, and a filler. After that, the composite resin is cured. This ensures that the composite resin adheres securely to the tooth. [Examples]

[0132] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. Specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than or equal to") of the blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0133] <Examples 1-26 and Comparative Examples 1-17> Polymerization initiator-containing compositions were prepared by mixing a solvent, a tertiary amine compound, a fourth-period transition metal compound, and a thiourea compound according to the formulations in Tables 1-3. Then, a polymerizable composition for dental use was prepared by mixing the polymerization initiator-containing composition with a polymerizable monomer according to the formulations in Tables 1-3.

[0134] <Rating> 1. Adhesion Test 1.1 Adhesion of dental polymerizable compositions to dental cement A 6mm diameter stainless steel rod was polished with #400 grit durable sandpaper, and then sandblasted. Next, the rod was treated with Superbond® PZ Primer (manufactured by Sun Medical Co., Ltd.) to create a jig for tensile testing.

[0135] Next, the bovine tooth enamel was polished to a flat surface using #180 grit durable abrasive paper. Then, a 150 μm thick seal with a 4.8 mm diameter hole was attached to the bovine tooth enamel to define the adhesion area.

[0136] The dental polymerizable compositions prepared in each example and comparative example were applied as dental primers to the surface of bovine tooth enamel exposed through the seal holes. The coating of the dental polymerizable composition was dried by air blowing to ensure a uniform thickness.

[0137] Next, an appropriate amount of Panavia® V5 (dental cement, manufactured by Kuraray Noritake Dental Co., Ltd.), a primer-type resin cement, was applied to the substrate, which had been primed with a dental polymerizable composition. Then, a tensile testing fixture was pressed against the applied resin cement. After that, it was left to stand for 30 minutes and immersed overnight in 37°C water. This prepared the test specimen.

[0138] Next, using a universal testing machine, Autograph AG-IS (manufactured by Shimadzu Corporation), the tensile adhesive strength of three test specimens was measured at a crosshead speed of 2 mm / min, and the average of the three values ​​was used as the measurement result. Then, the adhesion of the dental polymerizable composition to dental cement when used as a dental primer was evaluated according to the following criteria. The results are shown in Tables 1 and 2. ○: Measurement result is 2 MPa or higher. ×: Measurement result is less than 2 MPa.

[0139] 1.2 Adhesion of dental polymerizable compositions to composite resins A 6mm diameter stainless steel rod was polished with #400 grit durable sandpaper, then sandblasted to create a jig for tensile testing.

[0140] Next, the bovine tooth enamel was polished to a flat surface using #180 grit durable abrasive paper. Then, a 700 μm thick piece of cardboard with a 4.8 mm diameter hole was attached to the bovine tooth enamel using double-sided tape to define the contact area.

[0141] The dental polymerizable compositions prepared in each example and comparative example were applied as dental bonding materials to the surface of bovine tooth enamel exposed through the seal holes. The coating of the dental polymerizable composition was dried by air blowing to ensure a uniform thickness.

[0142] Next, Bulk Base® Hard (manufactured by Sun Medical Co., Ltd.) was filled into the holes in the cardboard as a composite resin. Then, a polyester film was placed on top of the filled composite resin. After that, the composite resin was pressed onto the polyester film using a flat glass plate. Finally, the composite resin was light-cured using PenCure® 2000 (manufactured by Morita Corporation).

[0143] Next, the polyester film was removed, and the tensile testing fixture was embedded in the cured composite resin using Superbond (registered trademark, manufactured by Sun Medical Co., Ltd.). Afterward, it was left to stand for 30 minutes and then immersed overnight in 37°C water. This prepared the test specimen.

[0144] Next, using a universal testing machine, Autograph AG-IS (manufactured by Shimadzu Corporation), the tensile adhesive strength of three test specimens was measured at a crosshead speed of 2 mm / min, and the average of the three values ​​was used as the measurement result. Then, the adhesion of the dental polymerizable composition to composite resin when used as a dental bonding material was evaluated according to the following criteria. The results are shown in Tables 1 and 2. ○: Measurement result is 2 MPa or higher. ×: Measurement result is less than 2 MPa.

[0145] <Colorfastness> The dental polymerizable compositions prepared in each example and comparative example were placed in glass bottles, sealed, and left at 55°C for 24 hours. The discoloration of the dental polymerizable compositions was then visually inspected. The discoloration resistance (storage stability) during storage was evaluated according to the following criteria. The results are shown in Tables 1 and 2. ○: No discoloration compared to before being left in a 55℃ environment. ×: Discoloration has occurred compared to before being left in a 55℃ environment.

[0146] [Table 1]

[0147] [Table 2]

[0148] [Table 3]

[0149] Details of the abbreviations in Tables 1 to 3 are given below.

[0150] MDP:10-Methacryloyloxydecylacidphosphate 4-META:4-Methacryloyloxyethyl trimellitic anhydride UDM: Urethane Dimethacrylate HEMA: 2-hydroxyethyl methacrylate. The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims below. [Industrial applicability]

[0151] The polymerization initiator-containing composition and the dental polymerizable composition of the present invention are used in dental treatment.

Claims

1. A fourth-period transition metal compound containing a transition metal atom belonging to the fourth period of the periodic table, Tertiary amine compounds, The following general formula (1) contains a thiourea compound in one agent, The transition metal atom is an iron atom and / or a copper atom. The polymerization initiator-containing composition comprises at least one selected from the group consisting of an inorganic salt of the transition metal atom and a metal halide of the transition metal atom, wherein the fourth periodic transition metal compound is a polymerization initiator-containing composition. 【Chemistry 1】 (In general formula (1), R １ ~R ４ Each of these represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aromatic ring group, and a heterocyclic group.

2. The polymerization initiator-containing composition according to claim 1, wherein the tertiary amine compound has an aromatic ring.

3. The polymerization initiator-containing composition according to claim 2, wherein the tertiary amine compound comprises a dialkylaminobenzoic acid ester.

4. The polymerization initiator-containing composition according to claim 1, wherein the thiourea compound comprises trialkylthiourea or tetraalkylthiourea.

5. The polymerization initiator-containing composition according to claim 1, A polymerizable composition for dental use, comprising a polymerizable monomer.

6. The polymerizable monomer is a polymerizable monomer containing an acidic group, as described in claim 5, for use in dental polymers.

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