WO2024190888A1 - Dental polymerization kit - Google Patents

Abstract

This dental polymerization kit is used in dentistry in order to polymerize a nonacidic monomer that is free of acidic groups but has ethylenic unsaturated groups. The kit comprises: an agent A that is a combination of an acidic monomer having acidic groups and ethylenic unsaturated groups and an organic peroxide; and an agent B that contains a reducing agent. At least one of agent A and agent B contains a specific benzimidazole compound.

Description

Dental Polymerization Kit

The present invention relates to a dental polymerization kit.

　Conventionally, a dental hardenable composition in a separate package type consisting of a first agent and a second agent has been proposed as a dental hardenable composition. The first agent contains an acidic group-containing polymerizable monomer, a peroxyester, and a copper compound. The second agent contains an aromatic sulfinate salt, and a benzotriazole compound or a benzimidazole compound (see, for example, Patent Document 1).

JP 2012-131717 A

In dental polymerizable compositions such as those described in Patent Document 1, there is a demand for improving the storage stability of each of the first and second agents while ensuring an appropriate hardening time for the mixture of the first and second agents and sufficient adhesive strength of the hardened product to tooth structure.

The present invention provides a dental polymerization kit that can improve the storage stability of each of Agent A and Agent B while ensuring an appropriate hardening time for the mixture of Agent A and Agent B and sufficient adhesive strength of the hardened product to tooth structure.

The present invention [1] includes a dental polymerization kit comprising an acidic monomer having an acidic group and an ethylenically unsaturated group, an agent A containing an organic peroxide, and an agent B containing a reducing agent, and at least one of the agents A and B containing a specific benzimidazole compound represented by the following general formula:

General formula:

(In the above general formula, _R1 represents an aliphatic group, an aromatic group, an amino group, or a hydroxy group. _R2 represents an amino group, a hydroxy group, an aliphatic group, or an aromatic group. _R3 represents an aliphatic group, an aromatic group, an amino group, a hydroxy group, a halogen atom, or a hydrogen atom. n is 0 or an integer of 1 to 4.)
The present invention [2] includes the dental polymerization kit according to the above [1], in which the agent A contains the specific benzimidazole compound.

The present invention [3] includes the dental polymerization kit of [1] or [2] above, in which at least one of the agent A and the agent B contains the non-acidic monomer.

The present invention [4] includes any one of the dental polymerization kits [1] to [3] above, in which both agent A and agent B are in the form of a paste.

The present invention [5] includes any one of the dental polymerization kits [1] to [4] above, in which both the agent A and the agent B contain a filler.

The present invention [6] includes any one of the dental polymerization kits [1] to [5] above, in which the agent B further contains a transition metal compound.

The present invention [7] includes the dental polymerization kit of the above [6], in which the transition metal compound contains a transition metal atom belonging to the fourth period of the periodic table.

The present invention [8] includes the dental polymerization kit of the above [6] or [7], in which the transition metal compound is at least one of a copper compound, an iron compound, a cobalt compound, a chromium compound, a zinc compound, a manganese compound, and a vanadium compound.

The present invention [9] includes any one of the dental polymerization kits [6] to [8] above, in which the transition metal compound is solid in the agent B, and when the agent A and the agent B are mixed, at least a portion of the transition metal compound is soluble in the acidic monomer in the agent A.

The present invention [10] includes the dental polymerization kit of the above [9], in which the transition metal compound is at least one of a copper compound, an iron compound, and a vanadium compound.

The present invention [11] includes any one of the dental polymerization kits [1] to [10] above, in which the agent A contains an inorganic peroxide.

The present invention [12] includes any one of the dental polymerization kits [1] to [11] above, in which the agent A contains a photopolymerization initiator.

The dental polymerization kit of the present invention can improve the storage stability of each of Agent A and Agent B while ensuring an appropriate hardening time for the mixture of Agent A and Agent B and sufficient adhesive strength of the hardened product to tooth structure.

1. Two-component self-adhesive resin cement Two-component self-adhesive resin cement, which is an example of a dental polymerization kit, is used in dental treatment, for example, to bond a prosthesis to a missing tooth site. The two-component self-adhesive resin cement comprises component A and component B. The two-component self-adhesive resin cement is used, for example, by mixing components A and B immediately before use and applying the resulting mixture. The two-component self-adhesive resin cement is also used, for example, by applying component A and then component B.

"Self-adhesive" means that the pretreatment agent has sufficient adhesion to the tooth structure even without being applied to the tooth structure.

(1) Agent A Agent A contains an acidic monomer, an organic peroxide, and a specific benzimidazole compound. Agent A contains a polymerization accelerator, a non-acidic monomer, a filler, an inorganic peroxide, and a photopolymerization initiator as necessary. In addition, when agent B does not contain a non-acidic monomer and a filler, agent A necessarily contains a non-acidic monomer and a filler. Agent A does not contain a tertiary amine and a reducing agent. In this embodiment, agent A is liquid or paste.

(1-1) Acidic Monomer The acidic monomer has an acidic group and an ethylenically unsaturated group.

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

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".

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

Examples of aromatic carboxylic acid derivatives include benzoic acid derivatives, salicylic acid derivatives, phthalic acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, naphthalene tricarboxylic acid derivatives, benzophenone tetracarboxylic acid derivatives, and biphenyl tetracarboxylic acid derivatives.

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.

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

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.

Examples of trimellitic acid derivatives include 4-(meth)acryloyloxyalkyl trimellitic acid, 4-[2-hydroxy-3-(meth)acryloyloxy]butyl trimellitic acid, 2,3-bis(3,4-dicarboxybenzoyloxy)propyl(meth)acrylate, and 2-(3,4-dicarboxybenzoyloxy)-1,3-di(meth)acryloyloxypropane. Examples of 4-(meth)acryloyloxyalkyl trimellitic acid include 4-(meth)acryloyloxymethyl trimellitic acid, 4-(meth)acryloyloxyethyl trimellitic acid, and 4-(meth)acryloyloxybutyl trimellitic acid.

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

An example of a naphthalene tricarboxylic acid derivative is 6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid.

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

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

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.

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 with glycidyl (meth)acrylate, and a reaction product of N-tolylglycine with glycidyl (meth)acrylate.

The acidic monomer having a carboxy group is preferably an aromatic carboxylic acid derivative, more preferably a trimellitic acid derivative, more preferably 4-(meth)acryloyloxyalkyl trimellitic acid, more preferably 4-(meth)acryloyloxyethyl trimellitic acid, more preferably 4-methacryloyloxyethyl trimellitic acid.

Examples of acidic monomers having a phosphate group include aliphatic phosphate esters and aromatic phosphate esters.

Examples of aliphatic phosphate esters include (meth)acryloyloxyalkyl acid phosphate and bis[(meth)acryloyloxyalkyl] acid phosphate.

Examples of (meth)acryloyloxyalkyl acid phosphates 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.

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.

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

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

Examples of acidic monomers having a thiophosphate group include compounds in which the phosphate group of the acidic monomers having a phosphate group described above is replaced with a thiophosphate group.

A preferred example of the acidic monomer is an acidic monomer having a phosphate group.

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

The proportion of acidic monomers in agent A is, for example, 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and for example, 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less.

When at least one of agent A and agent B contains a non-acidic monomer, the ratio of the acidic monomer to the total amount of the non-acidic monomers in agent A and agent B (100 parts by mass) is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less.

(1-2) Organic Peroxides Examples of organic peroxides include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, and hydroperoxides.

Diacyl peroxides include, for example, benzoyl peroxide, diacetyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauroyl peroxide, and m-toluoyl peroxide.

Examples of peroxyesters include t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate.

Examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexane.

Examples of peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, and 4,4-bis(t-butylperoxy)valeric acid-n-butyl ester.

An example of a ketone peroxide is methyl ethyl ketone peroxide.

Examples of hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and p-methane hydroperoxide.

As the organic peroxide, preferably, peroxyester is used, and more preferably, t-butyl peroxybenzoate (BPB) is used.

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

The proportion of organic peroxide in agent A is, for example, 0.05% by mass or more, preferably 0.1% by mass or more, and for example, 1% by mass or less, preferably 0.5% by mass or less.

When at least one of agent A and agent B contains a non-acidic monomer, the ratio of the organic peroxide relative to 100 parts by mass of the total amount of the acidic monomer in agent A and the non-acidic monomer in agent A or agent B is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 3 parts by mass or less, preferably 1 part by mass or less.

(1-3) Specific benzimidazole compound The specific benzimidazole compound is a compound in which the hydrogen atoms at positions 1 and 2 of benzimidazole are substituted with substituents. Specifically, the specific benzimidazole compound is represented by the following general formula:

General formula:

In the above general formula, R ₁ represents an aliphatic group, an aromatic group, an amino group, or a hydroxy group.

Aliphatic groups include, for example, linear alkyl groups having 1 to 12 carbon atoms, or branched alkyl groups having 3 to 12 carbon atoms.

Examples of linear alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups.

Examples of branched alkyl groups having 3 to 12 carbon atoms include isopropyl, isobutyl, sec-butyl, tert-butyl, and 2-ethylhexyl groups.

Examples of aromatic groups include aromatic hydrocarbon groups and aromatic heterocyclic groups.

An example of an aromatic hydrocarbon group is a phenyl group.

Examples of aromatic heterocyclic groups include furyl, thienyl, pyrrolyl, pyridyl, and benzimidazolyl groups.

Hydrogen atoms in the aliphatic and aromatic groups may be substituted with halogen atoms, the aliphatic groups described above, or the aromatic groups described above.

Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine.

An example of a substituted aliphatic group is a perfluoromethyl group.

An example of a substituted aromatic hydrocarbon group is the 4-bromophenyl group.

An example of a substituted aromatic heterocyclic group is the 2-n-propyl-4-methylbenzimidazol-6-yl group.

In the above general formula, _R2 represents an amino group, a hydroxy group, an aliphatic group, or an aromatic group.

The hydrogen atom in the amino group may be substituted with the above-mentioned aliphatic group or the above-mentioned aromatic group. An example of a substituted amino group is a dimethylamino group.

Examples of the aliphatic group include the aliphatic groups described above. Examples of the aromatic group include the aromatic groups described above. _R2 may be the same as _R1 or may be different from _R1 .

In the above general formula, _R3 represents an aliphatic group, an aromatic group, an amino group, a hydroxyl group, a halogen atom, or a hydrogen atom. Examples of the aliphatic group include the aliphatic groups described above. Examples of the aromatic group include the aromatic groups described above. Examples of the halogen atom include the halogen atoms described above.

In the above general formula, n is 0 or an integer from 1 to 4. Preferably, n is 0.

Preferred examples of specific benzimidazole compounds represented by the above general formula include 1,2-dimethylbenzimidazole, 2-amino-1-methylbenzimidazole, 2-(4-bromophenyl)-1-phenylbenzimidazole, and 2-(2-n-propyl-4-methylbenzimidazol-6-yl)-1-methylbenzimidazole.

Certain benzimidazole compounds can be used alone or in combination of two or more types.

The proportion of the specific benzimidazole compound in agent A is, for example, 0.1 mass% or more, preferably 0.2 mass% or more, more preferably 0.3 mass% or more, and for example, 7 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less.

The ratio of the specific benzimidazole compound to 100 parts by mass of the non-acidic monomer in agent A and agent B is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and for example, 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less.

The ratio of the specific benzimidazole compound to 100 parts by mass of the transition metal compound is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, and for example, 20,000 parts by mass or less, preferably 10,000 parts by mass or less.

The ratio of the specific benzimidazole compound to 100 parts by mass of the organic peroxide is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 50 parts by mass or more, and is, for example, 700 parts by mass or less, preferably 500 parts by mass or less, and more preferably 400 parts by mass or less.

(1-4) Polymerization Accelerator The polymerization accelerator is a specific imide compound represented by any one of the following general formulas (1) to (5).

General formula (1):

General formula (1) represents saccharin, saccharin derivatives, and alkali metal salts thereof. In general formula (1), R represents a hydrogen atom, an alkali metal atom, an aliphatic group, or an aromatic group.

Examples of alkali metal atoms include lithium, potassium, and sodium.

Examples of the aliphatic group include the aliphatic groups listed above.

Examples of aromatic groups include the aromatic groups listed above.

Preferred examples of the specific imide compound represented by general formula (1) include saccharin, methylsaccharin (an example of a saccharin derivative), and sodium saccharin hydrate (an example of an alkali metal salt of saccharin).

General formula (2):

General formula (2) shows a cyclic imide and an alkali metal salt thereof. In general formula (2), _R1 shows a hydrogen atom, an alkali metal atom, an aliphatic group, or an aromatic group. Examples of the alkali metal atom include the above-mentioned alkali metal atoms. Examples of the aliphatic group include the above-mentioned aliphatic groups. Examples of the aromatic group include the above-mentioned aromatic groups.

_R2 represents an alkylene group, an alkenylene group, or an arylene group.

Examples of alkylene groups include alkylene groups having 1 to 4 carbon atoms. Specific examples include methylene groups, ethylene groups, and propylene groups.

Examples of alkenylene groups include alkenylene groups having 1 to 4 carbon atoms. Specific examples include ethyleneylene groups.

An example of an arylene group is a phenylene group.

Hydrogen atoms in the alkylene group, alkenylene group, and arylene group may be substituted with the above-mentioned halogen atoms.

Preferred examples of the specific imide compound represented by general formula (2) include succinimide, glutarimide, and maleimide.

General formula (3):

General formula (3) shows acyclic imides and their alkali metal salts. In general formula (3), _R11 shows a hydrogen atom, an alkali metal atom, an aliphatic group, or an aromatic group. Examples of the alkali metal atom include the above-mentioned alkali metal atoms. Examples of the aliphatic group include the above-mentioned aliphatic groups. Examples of the aromatic group include the above-mentioned aromatic groups.

Each of R ₁₂ and R ₁₃ represents an aliphatic group or an aromatic group. Examples of the aliphatic group include the aliphatic groups described above. Examples of the aromatic group include the aromatic groups described above.

A preferred example of the specific imide compound represented by general formula (3) is diacetamide.

General formula (4):

General formula (4) shows a cyclic sulfonimide and an alkali metal salt thereof. In general formula (4), _R21 shows a hydrogen atom, an alkali metal atom, an aliphatic group, or an aromatic group. Examples of the alkali metal atom include the above-mentioned alkali metal atom. Examples of the aliphatic group include the above-mentioned aliphatic group. Examples of the aromatic group include the above-mentioned aromatic group.

_R22 represents an alkylene group, an alkenylene group, or an arylene group. Examples of the alkylene group include the alkylene group described above. Examples of the alkenylene group include the alkenylene group described above. Examples of the arylene group include the arylene group described above.

An example of a specific imide compound represented by general formula (4) is 4,4-difluoro-1,1,3,3-tetraoxide-1,3,2-dithiazetidine.

General formula (5):

General formula (5) shows acyclic sulfonimide and its alkali metal salt. In general formula (5), R ₃₁ shows a hydrogen atom, an alkali metal atom, an aliphatic group, or an aromatic group. Examples of the alkali metal atom include the above-mentioned alkali metal atom. Examples of the aliphatic group include the above-mentioned aliphatic group. Examples of the aromatic group include the above-mentioned aromatic group.

Each of R ₃₂ and R ₃₃ represents an aliphatic group or an aromatic group. Examples of the aliphatic group include the aliphatic groups described above. Examples of the aromatic group include the aromatic groups described above.

Preferred examples of the specific imide compound represented by general formula (5) include dibenzenesulfonimide and N-phenylbis(trifluoromethanesulfonimide).

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

The proportion of the polymerization accelerator in agent A is, for example, 0.05% by mass or more, preferably 0.1% by mass or more, and, for example, 5% by mass or less, preferably 3% by mass or less.

The ratio of the polymerization accelerator to 100 parts by mass of the acidic monomer is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and, for example, 25 parts by mass or less, preferably 20 parts by mass or less.

The ratio of the polymerization accelerator to 100 parts by mass of the tertiary amine in agent B is, for example, 10 parts by mass or more, preferably 15 parts by mass or more, more preferably 30 parts by mass or more, and for example, 400 parts by mass or less, preferably 350 parts by mass or less, more preferably 300 parts by mass or less. Tertiary amines will be explained later.

(1-5) Non-acidic Monomer The non-acidic monomer does not have the above-mentioned acidic group, but has the above-mentioned ethylenically unsaturated group.

Non-acidic monomers are classified into those that have a hydroxyl group, those that have a urethane bond, and those 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. Examples of mono(meth)acrylates having a hydroxyl group include 2-hydroxyethyl(meth)acrylate, and more preferably 2-hydroxyethyl methacrylate (HEMA).

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.

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, polyalkylene glycol di(meth)acrylates, and bisphenol A derivatives.

Examples of the alkanediol di(meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. A preferred example of the alkanediol di(meth)acrylate is neopentyl glycol dimethacrylate (NPGDMA).

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. A preferred example of the polyalkylene glycol di(meth)acrylate is 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 ethoxylated bisphenol A dimethacrylate (EBPADMA).

Non-acidic monomers can be used alone or in combination of two or more types.

Agent A contains at least a non-acidic monomer having a hydroxyl group and a non-acidic monomer having a urethane bond among the non-acidic monomers described above.

The proportion of non-acidic monomers in agent A is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and for example, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less.

(1-6) Filler Examples of the filler include conventionally known fillers that can be used in dental materials. Specifically, examples of the filler include silica, silica alumina, alumina, alumina quartz, glass, titania, zirconia, and ytterbium fluoride. Examples of the silica include fumed silica. Examples of the glass include barium glass. The filler may be surface-treated with a coupling agent or the like to be hydrophobic or hydrophilic.

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

The proportion of the filler in agent A is, for example, 0.5% by mass or more, preferably 5% by mass or more, more preferably 15% by mass or more, and for example, 97% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 85% by mass or less, more preferably 75% by mass or less.

(1-7) Inorganic Peroxides Examples of inorganic peroxides include persulfuric acid compounds, perphosphate compounds, perchloric acid compounds, and hydrogen peroxide derivatives.

Examples of persulfate compounds include sodium persulfate, potassium persulfate, calcium persulfate, magnesium persulfate, and ammonium persulfate.

Examples of perphosphate compounds include sodium perphosphate, potassium perphosphate, calcium perphosphate, magnesium perphosphate, and ammonium perphosphate.

Examples of perchlorate compounds include sodium perchlorate, potassium perchlorate, calcium perchlorate, magnesium perchlorate, and ammonium perchlorate.

Examples of hydrogen peroxide derivatives include hydrogen peroxide and urea peroxide.

Preferably, the inorganic peroxide is a persulfate compound, more preferably, sodium persulfate or potassium persulfate.

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

The proportion of inorganic peroxide in agent A is, for example, 0.01 mass% or more, preferably 0.05 mass% or more, more preferably 0.1 mass% or more, and for example, 10 mass% or less, preferably 7 mass% or less, more preferably 5 mass% or less.

When at least one of agent A and agent B contains a non-acidic monomer, the ratio of inorganic peroxide relative to 100 parts by mass of the total amount of the acidic monomer in agent A and the non-acidic monomer in agent A or agent B is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, and for example, 15 parts by mass or less, preferably 10 parts by mass or less.

(1-8) Photopolymerization Initiator The photopolymerization initiator generates radicals when exposed to light.

Examples of photopolymerization initiators include (bis)acylphosphine oxides, α-diketones, ketals, thioxanthone derivatives, coumarin and its derivatives, and anthraquinone and its derivatives. Examples of (bis)acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, and 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide. 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. Examples of coumarin and its derivatives include coumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-carboxycoumarin, and 3-ethoxycarbonyl-6-methoxycoumarin. Examples of anthraquinone and its derivatives include anthraquinone, 1-bromoanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-hydroxyanthraquinone.

The photopolymerization initiator is preferably an α-diketone, more preferably camphorquinone (CQ).

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

The proportion of the photopolymerization initiator in agent A is, for example, 0.001% by mass or more, preferably 0.01% by mass or more, and for example, 1% by mass or less, preferably 0.1% by mass or less.

When at least one of agent A and agent B contains a non-acidic monomer, the ratio of the photopolymerization initiator relative to 100 parts by mass of the total amount of the acidic monomer in agent A and the non-acidic monomer in agent A or agent B is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and for example, 1 part by mass or less, preferably 0.5 parts by mass or less.

(1-9) Other Additives The agent A may contain a polymerization inhibitor, a thickener, a coupling agent, an ultraviolet absorber, a fluorescent agent, a pigment, and a solvent, as necessary. An example of the polymerization inhibitor is dibutylhydroxytoluene (BHT).

(2) Agent B Agent B contains a reducing agent. Agent B contains a transition metal compound, a non-acidic monomer, and a filler. In addition, when agent A does not contain a non-acidic monomer and a filler, agent B necessarily contains a non-acidic monomer and a filler. Agent B does not contain an acidic monomer, an organic peroxide, an inorganic peroxide, or a polymerization accelerator. Agent B is in a liquid or paste form.

(2-1) Reducing Agent Examples of the reducing agent include tertiary amines, aromatic amino acids, sulfinic acids or salts thereof, thiourea compounds, phosphorous compounds, and sulfurous compounds.

Tertiary amines include, for example, aromatic tertiary amines.

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-dialkyltoluidine include N,N-dimethyl-p-toluidine and N,N-diethyl-p-toluidine.

Examples of N,N-bis(hydroxyalkyl)toluidines include N,N-bis(2-hydroxyethyl)-p-toluidine (BHEPT) 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.

Examples of aromatic amino acids include N-phenylglycinic acid, sodium N-phenylglycinate, and potassium N-phenylglycinate.

Sulfinic acids 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.

　Examples of salts of aromatic sulfinic acid include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, barium benzenesulfinate, butylamine salt of benzenesulfinic acid, aniline salt of benzenesulfinic acid, toluidine salt of benzenesulfinic acid, phenylenediamine salt of benzenesulfinic acid, diethylamine salt of benzenesulfinic acid, diphenylamine salt of benzenesulfinic acid, triethylamine salt of benzenesulfinic acid, tributylamine salt of benzenesulfinic acid, ammonium salt of benzenesulfinic acid, tetramethylbenzenesulfinic acid, etc. ethylammonium, 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, butylammonium p-toluenesulfinate ethylamine 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 salt, p-toluenesulfinic acid tetraethylammonium salt, p-toluenesulfinic acid tetrabutylammonium salt, 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 , sodium p-chlorobenzenesulfinate, potassium p-chlorobenzenesulfinate, calcium p-chlorobenzenesulfinate, barium p-chlorobenzenesulfinate, ethylamine salt of p-chlorobenzenesulfinate, butylamine salt of p-chlorobenzenesulfinate, toluidine salt of p-chlorobenzenesulfinate, N-methylaniline salt of p-chlorobenzenesulfinate, pyridine salt of p-chlorobenzenesulfinate, ammonium salt of p-chlorobenzenesulfinate, tetramethylammonium p-chlorobenzenesulfinate, tetraethylammonium p-chlorobenzenesulfinate, and tetrabutylammonium p-chlorobenzenesulfinate.

As thiourea compounds, for example, thiourea, methylthiourea, ethylthiourea, n-propylthiourea, isopropylthiourea, cyclohexylthiourea, benzylthiourea, phenylthiourea, acetylthiourea, benzoylthiourea, adamantylthiourea, (2-pyridyl)thiourea, 1-(2-tetrahydrofurfuryl)-2-thiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-di-i These include 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 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 sulfurous acid compounds include inorganic sulfurous acid compounds and organic sulfurous acid compounds.

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

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

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

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

The reducing agent is preferably a combination of a tertiary amine, a sulfinic acid or its salt, and a thiourea compound, more preferably a combination of an aromatic tertiary amine, an aromatic sulfinic acid or its salt, and an alkylthiourea, more preferably a combination of N,N-bis(hydroxyalkyl)toluidine, a dialkylaminobenzoic acid ester, p-toluenesulfinic acid or sodium p-toluenesulfinate, and a trialkylthiourea, and more preferably a combination of N,N-bis(2-hydroxyethyl)-p-toluidine, ethyl 4-(dimethylamino)benzoate, sodium p-toluenesulfinate, and trimethylthiourea.

The proportion of the reducing agent in agent B 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 for example, 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less.

The proportion of tertiary amine in agent B is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, and for example, 10% by mass or less, preferably 5% by mass or less.

The ratio of tertiary amine to 100 parts by mass of organic peroxide in agent A is, for example, 100 parts by mass or more, preferably 130 parts by mass or more, and for example, 200 parts by mass or less, preferably 170 parts by mass or less.

The ratio of the reducing agent (excluding tertiary amines) to 100 parts by mass of inorganic peroxide in agent A is, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 100 parts by mass or less, preferably 50 parts by mass or less.

(2-2) Transition Metal Compound The transition metal compound contains a transition metal atom belonging 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 titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn), and more preferred examples of transition metal atoms include vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).

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.

Specific examples of transition metal compounds include 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(I) 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, mercaptobenzothiazole copper, 1,3-propanediamine copper, benzimidazole copper, benzothiazole copper, mercaptobenzimidazole copper (MBI-Cu), and copper thiourea.

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 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) oxide, chromium(VI) oxide, silver(I) chromate, chromium(III) nitrate, potassium dichromate, chromium(III) acetylacetonate, and chromium(III) hexafluoroacetylacetonate.

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.

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.

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 oxide, vanadium(IV) oxide sulfate, ammonium vanadate(V), and sodium orthovanadate(V).

Preferably, the transition metal compound is solid in agent B. In other words, agent B contains the components in agent B and a water-insoluble transition metal compound powder that may be acquired by moisture absorption during storage. 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. There are no limitations on the average particle size of the powder, but if it is too large, it is prone to settling, 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.

If the transition metal compound is a solid in component B, at least a portion of the transition metal compound is soluble in the acidic monomer in component A when components A and B are mixed.

The transition metal compound is preferably at least one of a copper compound, an iron compound, and a vanadium compound.

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

The proportion of the transition metal compound in agent B is, for example, 0.0001 mass% or more, preferably 0.0005 mass% or more, more preferably 0.001 mass% or more, and for example, 1 mass% or less, preferably 0.5 mass% or less, more preferably 0.3 mass% or less.

The ratio of the transition metal compound to 100 parts by mass of the reducing agent is, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The ratio of the transition metal compound to 100 parts by mass of the inorganic peroxide in Agent A is, for example, 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

(2-3) Non-acidic Monomers Examples of the non-acidic monomers in the B component include the same monomers as the non-acidic monomers in the A component.

The proportion of non-acidic monomers in agent B is not limited. The proportion of non-acidic monomers in agent B is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and for example, 99% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less.

(2-4) Filler The explanation for the filler in the agent B is the same as that for the filler in the agent A.

The proportion of the filler in agent B is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass, and for example, 97% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less.

(2-5) Other Additives Agent B may contain a polymerization inhibitor, a neutralizing agent, a thickening agent, a solvent, a coupling agent, an ultraviolet absorbing agent, a fluorescent agent, and a pigment, if necessary. The explanations of the polymerization inhibitor, the thickening agent, the solvent, the coupling agent, the ultraviolet absorbing agent, the fluorescent agent, and the pigment in agent B are the same as those of the polymerization inhibitor, the thickening agent, the solvent, the coupling agent, the ultraviolet absorbing agent, the fluorescent agent, and the pigment in agent A. An example of a neutralizing agent is calcium hydroxide.

2. Reaction mechanism Next, the reaction mechanism of the above-mentioned two-component self-adhesive resin cement will be explained.

To use a two-component self-adhesive resin cement, for example, a mixture of components A and B is applied to at least one of the tooth structure and the prosthesis to bond the two together.

When agent A and agent B are mixed, radicals are generated by an oxidation-reduction reaction between the organic peroxide and inorganic peroxide and the reducing agent. In addition, the transition metal compound reacts with the reducing agent, dissolved oxygen, polymerization accelerator, and oxidizing agent (organic peroxide and inorganic peroxide), generating radicals. At this time, a specific benzimidazole compound coordinates with the transition metal compound, increasing the reaction activity of the transition metal compound and generating more radicals. The generated radicals polymerize acidic and non-acidic monomers. In other words, the dental polymerization kit is used to polymerize non-acidic monomers in dental treatment.

The mixture of components A and B hardens as the acidic and non-acidic monomers polymerize, bonding the prosthesis to the tooth structure.

3. Effects and Effects According to the dental polymerization kit, at least one of the agent A containing an acidic monomer and an organic peroxide and the agent B containing a reducing agent contains a specific benzimidazole compound represented by the above general formula.

As a result, it is possible to ensure an appropriate hardening time for the mixture of agents A and B, and sufficient adhesive strength to tooth structure, while improving the storage stability of each of agents A and B.

4. Other Embodiments Hereinafter, other embodiments of the dental polymerization kit will be described.

(1) Agent A does not have to contain a specific benzimidazole compound. In this case, Agent B contains a specific benzimidazole compound.

(2) The dental polymerization kit may be a two-part dental self-adhesive composite resin. The two-part dental self-adhesive composite resin is used in dental treatment, for example, to fill missing teeth.

(3) The dental polymerization kit may be a two-component dental coating agent. The two-component dental coating agent is used in dental treatment, for example, to coat the surface of tooth tissue.

The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited thereto. 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 values (numerical values defined as "equal to or less than") or lower limit values (numerical values defined as "equal to or more than" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention."

1. Preparation of Agent A and Agent B According to the formulations in Tables 1 to 5, for each of Agent A and Agent B, first, the monomer liquid components were mixed to prepare a monomer liquid, and then a dispersing component (a component that disperses in a solid state in the monomer liquid) was added to the monomer liquid and mixed with a centrifugal mixer. In this way, Agent A and Agent B in a paste form were prepared.

The meanings of the abbreviations in Tables 1 to 5 are listed below.

MDP: 10-methacryloyloxydecyl acid phosphate UDMA: [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate EBPADMA: ethoxylated bisphenol A dimethacrylate NPGDMA: neopentyl glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate TEGDMA: triethylene glycol dimethacrylate BPB: t-butyl peroxybenzoate EDAB: 4-(dimethylamino)ethyl benzoate BHEPT: N,N-bis(2-hydroxyethyl)-p-toluidine TMTU: trimethylthiourea SA: saccharin Benzimidazole A: 1,2-dimethylbenzimidazole Benzimidazole B: 2-amino-1-methylbenzimidazole Benzimidazole C: 2-(4-bromophenyl)-1-phenylbenzimidazole Benzimidazole D: 1-methylbenzimidazole Benzimidazole E: benzimidazole Benzotriazole: mixture of 1-(dimethylamino)benzotriazole and 2-(dimethylamino)benzotriazole Benzimidazole F: 2-methylbenzimidazole CQ: camphorquinone BHT: dibutylhydroxytoluene MBI-Cu: mercaptobenzimidazole copper STS: sodium p-toluenesulfinate PPS: potassium persulfate Ca(OH) ₂ : calcium hydroxide R812: fumed silica, Aerosil _YbF3 : ytterbium(III) fluoride
GM8235: Dental glass, manufactured by Schott G018-117: Dental glass, manufactured by Schott 2. Evaluation (1) Storage stability Agent A and agent B of the dental polymerization kit of each Example and Comparative Example were filled into a syringe. After storing at 65°C for one week, the storage stability of agent A and agent B was evaluated according to the following criteria. The results are shown in Tables 1 to 5.

A: No gelling or hardening is observed.

　B: Some of it gelled or hardened while stored at 65℃ for a week.

C: Almost all of the material gelled or hardened after being stored at 65°C for a week.

D: Agent A or B gelled or hardened during or immediately after preparation.

(2) Curing time Differential scanning calorimetry was carried out at 37°C, and the peak time of heat generation was regarded as the curing time. The curing time was evaluated according to the following criteria. The results are shown in Tables 1 to 5.

A: The curing time is more than 2 minutes but less than 5 minutes.

B: The curing time is less than 2 minutes or more than 5 minutes.

If the curing time is less than 2 minutes, it will harden too quickly. If the curing time is more than 5 minutes, it will harden too slowly. If the curing time is more than 2 minutes but less than 5 minutes, it is suitable for dental treatment.

(3) Tensile Adhesion Strength The tensile adhesion strength was measured according to the method specified in JIS T6611:2019 and evaluated according to the following criteria. The results are shown in Tables 1 to 5.

A: The tensile adhesive strength is 2 MPa or more.

B: The tensile adhesion strength is less than 2 MPa.

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 being limited. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims.

The dental polymerization kit of the present invention is used in dental treatment.

Claims (12)

1. an agent A containing an acidic monomer having an acidic group and an ethylenically unsaturated group, and an organic peroxide;
   and a B agent containing a reducing agent,
   A dental polymerization kit, wherein at least one of the agent A and the agent B contains a specific benzimidazole compound represented by the following general formula:
   General formula:
   
   (In the above general formula, _R1 represents an aliphatic group, an aromatic group, an amino group, or a hydroxy group. _R2 represents an amino group, a hydroxy group, an aliphatic group, or an aromatic group. _R3 represents an aliphatic group, an aromatic group, an amino group, a hydroxy group, a halogen atom, or a hydrogen atom. n is 0 or an integer of 1 to 4.)
2. The dental polymerization kit according to claim 1, wherein the agent A contains the specific benzimidazole compound.
3. The dental polymerization kit according to claim 1, wherein at least one of the agent A and the agent B contains the non-acidic monomer.
4. The dental polymerization kit according to claim 1, wherein both agent A and agent B are in a paste form.
5. The dental polymerization kit according to claim 1, wherein both agent A and agent B contain a filler.
6. The dental polymerization kit according to claim 1, wherein the agent B further contains a transition metal compound.
7. The dental polymerization kit according to claim 6, wherein the transition metal compound contains a transition metal atom belonging to the fourth period of the periodic table.
8. The dental polymerization kit according to claim 6, wherein the transition metal compound is at least one of a copper compound, an iron compound, a cobalt compound, a chromium compound, a zinc compound, a manganese compound, and a vanadium compound.
9. The transition metal compound is a solid in the agent B,
   The dental polymerization kit according to claim 6 , wherein when the A component and the B component are mixed, at least a portion of the transition metal compound is soluble in the acidic monomer in the A component.
10. The dental polymerization kit according to claim 9, wherein the transition metal compound is at least one of a copper compound, an iron compound, and a vanadium compound.
11. The dental polymerization kit according to claim 1, wherein the agent A contains an inorganic peroxide.
12. The dental polymerization kit according to claim 1, wherein the agent A contains a photopolymerization initiator.