X-ray radiopaque compound and dental adhesive composition

Abstract

This X-ray radiopaque compound is characterized by including: a structural moiety A that includes a halogen atom and has an acyclic structure; and a structural moiety B that is derived from a (meth)acrylate.

Description

X-ray contrast compound and dental adhesive composition

[0001] The present invention relates to radiopaque compounds and dental adhesive compositions.

[0002]

[0003] In the dental field, dental adhesive compositions are required to have X-ray contrast properties in order to prevent misdiagnosis of secondary caries. Generally, compounds derived from polymerizable monomers or polymerizable polymers contained in dental adhesive compositions do not exhibit X-ray contrast properties. Therefore, dental adhesive compositions containing a filler such as barium are widely used for the purpose of imparting X-ray contrast properties to dental adhesive compositions.

[0003] Since the filler reacts with and inactivates the acidic monomer contained in the dental adhesive composition, there has been a demand in recent years for dental adhesive compositions that do not use fillers and in which X-ray contrast properties are imparted to the compound derived from the polymerizable monomer or polymerizable polymer itself.

[0004] For example, a brominated polymerizable monomer has been proposed that includes a resin matrix containing a specific structure having X-ray contrast properties, a filler matrix in an amount of at least 25% by weight relative to the weight of the dental composition, and an initiator (see, for example, Patent Document 1).

[0005] Special Publication No. 2021-502357

[0006] However, conventional dental adhesive compositions, including the invention described in Patent Document 1, have a halogen having X-ray contrast properties bound to a benzene ring in an aromatic compound contained in the dental adhesive composition, which structurally makes the halogen easily liberated, raising concerns about a problem of reduced X-ray contrast properties. Furthermore, the X-ray contrast compounds have a problem in that their synthetic routes are complicated.

[0007] In view of the problems and concerns of the above-mentioned conventional techniques, the present invention aims to provide an X-ray contrast compound that has excellent X-ray contrast properties, can suppress the liberation of halogen, and can be easily synthesized.

[0008] The X-ray contrast compound of the present invention, which is a means for solving the above-mentioned problems, comprises a structural moiety A which contains a halogen atom and has a non-cyclic structure, and a structural moiety B which is derived from a (meth)acrylate.

[0009] According to the present invention, it is possible to provide an X-ray contrast compound which has excellent X-ray contrast properties, is capable of suppressing the liberation of halogen, and can be easily synthesized.

[0010] The present invention will be described in detail below.

[0011] (X-ray contrast compound) The X-ray contrast compound of the present invention contains a structural moiety A which contains a halogen atom and has a non-cyclic structure, and a structural moiety B derived from a (meth)acrylate, and may contain other structural moieties as necessary.

[0012] The other structural parts can be appropriately selected within a range that does not impair the effects of the present invention.

[0013] In this specification, the "structural moiety A which contains a halogen atom and has a non-cyclic structure" may be simply referred to as the "structural moiety A," and the "structural moiety B derived from (meth)acrylate" may be simply referred to as the "structural moiety B."

[0014] In this specification, the "X-ray contrast compound" may be simply referred to as the "compound."

[0015] As used herein, "(meth)acrylate" refers to either or both of acrylate and methacrylate.

[0016] As described above, the X-ray contrast compound can suppress the release of halogen. In other words, the X-ray contrast compound can suppress the release of halogen and maintain high X-ray contrast properties. In the present invention, the mechanism by which the release of halogen is suppressed has not been clarified, but it is presumed to be due to the structural stability of the X-ray contrast compound.

[0017] Furthermore, the X-ray contrast compound has high X-ray opacity (the property of blocking X-rays when irradiated with X-rays without allowing them to pass through), which can improve X-ray contrast.

[0018] <Structural Moiety A> The structural moiety A is not particularly limited and can be appropriately selected depending on the purpose, as long as it contains a halogen atom and is derived from a non-cyclic structure.

[0019] The non-cyclic structure is not particularly limited as long as it does not have a ring structure and can be appropriately selected depending on the purpose, and examples thereof include saturated or unsaturated non-cyclic hydrocarbon structures.

[0020] The non-cyclic structure is preferably a branched chain, and more preferably has a halogen atom in the side chain. In this specification, "main chain" refers to the longest straight chain in a compound consisting of the structural portion A and the structural portion B, and "side chain" refers to a molecular chain that is not the main chain. Furthermore, the "main chain" in the structural portion A refers to a molecular chain included in the main chain of the compound, and the "side chain" in the structural portion A refers to a molecular chain that is not the main chain. In addition, in the structural portion A, when the branched chains have the same length, the molecular chain having a halogen atom is considered to be the side chain.

[0021] The structural portion A is not particularly limited and can be appropriately selected depending on the purpose as long as it contains a halogen atom and has a non-cyclic structure. From the viewpoint of facilitating the synthesis of the compound, however, those having a hydroxyl group, an isocyanate group, an epoxy group, an amino group, or a carboxyl group are preferred, and those having a hydroxyl group are more preferred.

[0022] <Structural Moiety B> The structural moiety B is not particularly limited as long as it is a structural moiety derived from a (meth)acrylate, and can be appropriately selected depending on the purpose.

[0023] The (meth)acrylate is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of facilitating synthesis of the compound, however, those having a hydroxyl group, an isocyanate group, an epoxy group, an amino group, or a carboxyl group are preferred, and those having a carboxylic acid group are more preferred.

[0024] The (meth)acrylate having a carboxylic acid group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include mono(2-acryloyloxyethyl) succinate and 2-carboxyethyl acrylate.

[0025] The (meth)acrylate may be an appropriately synthesized product or a commercially available product, such as mono(2-acryloyloxyethyl) succinate (manufactured by Tokyo Chemical Industry Co., Ltd.) or 2-carboxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0026] The X-ray contrast compound preferably contains at least one selected from the group consisting of a structure represented by the following general formula (1), a structure represented by the following general formula (2), and a structure represented by the following general formula (3):

[0027] (In the general formula (1), R1 and R2 each independently represent "-H" or "-CH ３ ", X1 and X2 each independently represent "-O-" or "-NH-", and Y1 and Y2 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.

[0028] (In the general formula (2), R3 and R4 each independently represent "-H" or "-CH ３ ", X3 and X4 each independently represent "-O-" or "-NH-", and Y3 and Y4 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.

[0029] (In the general formula (3), R5 and R6 each independently represent "-H" or "-CH ３", X5 and X6 each independently represent "-O-" or "-NH-", and Y5 and Y6 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.

[0030] The method for obtaining the structure represented by the general formula (1) is not particularly limited and can be appropriately selected depending on the purpose. The structure may be synthesized appropriately, or a commercially available product having the structure may be used.

[0031] The commercially available product having the structure represented by the general formula (1) is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include trans-2,3-dibromo-2-butene-1,4-diol (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0032] The method for obtaining the structure represented by the general formula (2) is not particularly limited and can be appropriately selected depending on the purpose. The structure may be synthesized appropriately, or a commercially available product having the structure may be used.

[0033] The commercially available product having the structure represented by the general formula (2) is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include 2,2-bis(bromomethyl)-1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0034] The method for obtaining the structure represented by the general formula (3) is not particularly limited and can be appropriately selected depending on the purpose. The structure may be synthesized appropriately, or a commercially available product having the structure may be used.

[0035] As a method for synthesizing the structure represented by the general formula (3), for example, 2,2,3,3-tetrabromobutane-1,4-diol (TBBD) is reacted with 2-butyne-1,4-diol to form a Br ２ It can be synthesized by adding

[0036] The method for synthesizing the X-ray contrast compound is not particularly limited, and the compound can be synthesized, for example, by the following method. [Example of a Method for Synthesizing an X-ray Contrast Compound] trans-2,3-Dibromo-2-butene-1,4-diol, mono(2-acryloyloxyethyl) succinate, and a solution (e.g., water, ethyl acetate, toluene, etc.) are heated under reflux overnight. At this time, a catalyst (e.g., concentrated sulfuric acid or tosylic acid, etc.) and a condensing agent (e.g., N,N'-dicyclohexylcarbodiimide (DCC), etc.) may be added, if necessary. Furthermore, the synthesis may be performed under a protective gas atmosphere (e.g., nitrogen, etc.) if necessary.

[0037] The reaction product is then cooled to room temperature, extracted from the solution, washed at least once with water, and then added to anhydrous NaCl. ２ SO ４ Dry on a lid and remove the solvent under vacuum.

[0038] The weight average molecular weight of the X-ray contrast compound is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 to 5,000, more preferably 200 to 1,000.

[0039] When the weight-average molecular weight of the X-ray contrast compound is within the above-mentioned range, it becomes possible to mix the X-ray contrast compound well with other components described later when preparing a dental adhesive composition described later, which is therefore preferable because the dental adhesive composition described later can be easily prepared, the operability when using the dental adhesive composition is improved, and appropriate adhesiveness can be ensured.

[0040] (Dental adhesive composition) The dental adhesive composition of the present invention contains an X-ray contrast compound having a structural moiety A which contains a halogen atom and has a non-cyclic structure, and a structural moiety B derived from a (meth)acrylate, and may contain other components as necessary.

[0041] The X-ray contrast compound is the same as that described in the above section (X-ray contrast compound), and therefore a duplicated description will be omitted.

[0042] The content of the X-ray contrast compound is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and even more preferably 15% by mass or more and 50% by mass or less, relative to the total amount of the dental adhesive composition.

[0043] If the content of the X-ray contrast compound is 0.5% by mass or more based on the total amount of the dental adhesive composition, the X-ray contrast property of the cured product of the dental adhesive composition is improved, which is preferable.

[0044] If the content of the X-ray contrast compound is 70 mass% or less relative to the total amount of the dental adhesive composition, the content of the other components described below can be sufficiently ensured, and various performance properties as a dental adhesive composition can be improved, which is preferable.

[0045] <Other Components> The other components are not particularly limited and can be appropriately selected depending on the purpose as long as the effects of the present invention are not impaired. Examples of the other components include a (meth)acrylate having an acid group, a (meth)acrylate not having an acid group, a polymerization initiator, a polymerization inhibitor, a filler, and a solvent.

[0046] <<(Meth)acrylate Having an Acid Group>> Examples of the acid group in the (meth)acrylate having an acid group include a phosphate group, a pyrophosphate group, a thiophosphate group, a sulfonic acid group, a phosphonic acid group, and a carboxylic acid group.

[0047] Among these, (meth)acrylates having a phosphate group, a thiophosphate group, or a carboxylic acid group are preferred from the viewpoints of the solubility of the smear layer on the tooth surface of the dental adhesive composition, the demineralization of tooth tissue, and in particular, the adhesiveness to enamel. Note that the (meth)acrylate having an acid group may have multiple acid groups.

[0048] -(Meth)acrylate with a phosphate group- The (meth)acrylate having a phosphate group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include 2-(meth)acryloyloxyethyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 6-(meth)acryloyloxyhexylphenyl hydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP), 1,3-di(meth)acryloylpropane-2-dihydrogen phosphate, 1,3-di(meth)acryloylpropane-2-phenyl hydrogen phosphate, and bis[5-{2-(meth)acryloyloxyethoxycarbonyl}heptyl]hydrogen phosphate.

[0049] These may be used alone or in combination of two or more.

[0050] —(Meth)acrylate Having a Pyrophosphate Group— The (meth)acrylate having a pyrophosphate group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, and bis[10-(meth)acryloyloxydecyl] pyrophosphate.

[0051] These may be used alone or in combination of two or more.

[0052] —(Meth)acrylate Having a Thiophosphate Group— The (meth)acrylate having a thiophosphate group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate (MDTP), 11-( Examples of suitable alkyl acrylates include 1-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 13-(meth)acryloyloxytridecyl dihydrogen thiophosphate, 14-(meth)acryloyloxytetradecyl dihydrogen thiophosphate, 15-(meth)acryloyloxypentadecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 17-(meth)acryloyloxyheptadecyl dihydrogen thiophosphate, 18-(meth)acryloyloxyoctadecyl dihydrogen thiophosphate, 19-(meth)acryloyloxynonadecyl dihydrogen thiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate.

[0053] These may be used alone or in combination of two or more.

[0054] —(Meth)acrylate Having a Carboxylic Acid Group— The (meth)acrylate having a carboxylic acid group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include 2-methacryloyloxyethyl succinic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 4-(meth)acryloyloxyethyl trimellitic anhydride, 4-(meth)acryloyloxydecyl trimellitic acid, 4-(meth)acryloyloxydecyl trimellitic anhydride, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di(meth)acryloyloxypyromellitic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxyethyl phthalic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid.

[0055] These may be used alone or in combination of two or more.

[0056] -(Meth)acrylate Having a Sulfonic Acid Group- The (meth)acrylate having a sulfonic acid group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include 2-(meth)acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl(meth)acrylate.

[0057] These may be used alone or in combination of two or more.

[0058] —(Meth)acrylate Having a Phosphonic Acid Group— The (meth)acrylate having a phosphonic acid group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include 2-(meth)acryloyloxyethyl phenyl phosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, and 10-(meth)acryloyloxydecyl-3-phosphonoacetate.

[0059] These may be used alone or in combination of two or more.

[0060] These (meth)acrylates having an acid group may be used alone or in combination of two or more.

[0061] Among these, 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP), 10-(meth)acryloyloxydecyl dihydrogen thiophosphate (MDTP), and 4-(meth)acryloyloxyethyl trimellitic anhydride (4-META) are preferred in terms of improving the adhesiveness of the cured dental adhesive composition.

[0062] The content of the (meth)acrylate having an acid group is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and even more preferably 5% by mass or more and 25% by mass or less, relative to the total amount of the dental adhesive composition.

[0063] If the content of the (meth)acrylate having an acid group is 0.1 mass % or more relative to the total amount of the dental adhesive composition, the demineralizing power of the dental adhesive composition on tooth structure is further improved, which is preferable.

[0064] If the content of the (meth)acrylate having an acid group is 40% by mass or less based on the total amount of the dental adhesive composition, the hardening property of the dental adhesive composition is improved, which is preferable.

[0065] <<(Meth)acrylate Having No Acid Group>> The (meth)acrylate having no acid group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ... methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, isopropyl (meth)acrylate, methyl (meth)acrylate, Propyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methylhexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxy-1,3-di(meth)acryloyloxypropane, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polybutylene glycol di(meth)acrylate, bisphenol A diglycidyl ( meth)acrylate, di-2-(meth)acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate, 1,3,5-tris[1,3-bis{(meth)acryloyloxy}-2-propoxycarbonylaminohexane]-1,3,5-(1H,3H,5H)triazine-2,4,6-trione, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropyl)phenyl]propane, N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol] tetramethacrylate, etc.

[0066] These (meth)acrylates having no acid group may be used alone or in combination of two or more.

[0067] Among these, 2-hydroxy-1,3-di(meth)acryloyloxypropane (GDMA) and triethylene glycol di(meth)acrylate (TEGDMA) are preferred in terms of improving the mechanical strength of the cured dental adhesive composition and improving adhesion to ceramics and teeth.

[0068] The content of the (meth)acrylate having no acid group is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less, relative to the total amount of the dental adhesive composition.

[0069] It is preferable that the content of the (meth)acrylate having no acid group is 3 mass % or more relative to the total amount of the dental adhesive composition, since this can improve the operability of the dental adhesive composition.

[0070] When the content of the (meth)acrylate having no acid group is 50 mass % or less based on the total amount of the dental adhesive composition, the mechanical strength of the cured product obtained by curing the dental adhesive composition can be improved, which is preferable.

[0071] <<Polymerization initiator>> The polymerization initiator is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include chemical polymerization initiators, photopolymerization initiators, etc. Among these, photopolymerization initiators are preferred because the dental adhesive composition is often cured by irradiation with visible light or the like.

[0072] Examples of the chemical polymerization initiator include thiourea derivatives, vanadium compounds, tertiary amines, and organic peroxides.

[0073] —Thiourea Derivatives— The thiourea derivatives function as reducing agents among chemical polymerization initiators.

[0074] The thiourea derivative is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ethylene thiourea, N-methyl thiourea, N-ethyl thiourea, N-propyl thiourea, N-butyl thiourea, N-lauryl thiourea, N-phenyl thiourea, N-cyclohexyl thiourea, N,N-dimethyl thiourea, N,N-diethyl thiourea, N,N-dipropyl thiourea, N,N-dibutyl thiourea, N,N-dilauryl thiourea, N,N-diphenyl thiourea, N,N-dicyclohexyl thiourea, trimethyl thiourea, tetramethyl thiourea, N-acetyl thiourea, N-benzoyl thiourea, 1-allyl-3-(2-hydroxyethyl)-2-thiourea, 1-(2-tetrahydrofurfuryl)-2-thiourea, N-tert-butyl-N'-isopropyl thiourea, and 2-pyridyl thiourea.

[0075] Among these, N-benzoylthiourea is preferred from the viewpoint of improving the curability of the dental adhesive composition.

[0076] These thiourea derivatives may be used alone or in combination of two or more.

[0077] The content of the thiourea derivative is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, relative to the total amount of the dental adhesive composition.

[0078] If the content of the thiourea derivative is 0.1% by mass or more based on the total amount of the dental adhesive composition, the hardening property of the dental adhesive composition is improved, which is preferable.

[0079] If the content of the thiourea derivative is 5% by mass or less based on the total amount of the dental adhesive composition, the solubility of the thiourea derivative in the X-ray contrast compound is improved, which is preferable.

[0080] —Vanadium Compound— The vanadium compound functions as a reducing agent among chemical polymerization initiators.

[0081] The vanadium compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include oxovanadium oxalate, vanadyl acetylacetonate, vanadium acetylacetonate, vanadyl stearate, vanadium naphthenate, and vanadium benzoylacetonate.

[0082] Among these, vanadyl acetylacetonate is preferred from the viewpoint of the curability of the dental adhesive composition.

[0083] These vanadium compounds may be used alone or in combination of two or more.

[0084] The content of the vanadium compound is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.0015% by mass or more and 1% by mass or less, and even more preferably 0.002% by mass or more and 0.1% by mass or less, relative to the total amount of the dental adhesive composition.

[0085] If the content of the vanadium compound is 0.001% by mass or more based on the total amount of the dental adhesive composition, the hardening property of the dental adhesive composition is improved, which is preferable.

[0086] If the content of the vanadium compound is 5 mass % or less based on the total amount of the dental adhesive composition, the storage stability of the dental adhesive composition is improved, which is preferable.

[0087] Tertiary Amine The tertiary amine functions as a reducing agent among chemical polymerization initiators. The tertiary amine can also function as a photopolymerization accelerator.

[0088] The tertiary amine is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include tertiary aliphatic amines and tertiary aromatic amines.

[0089] Examples of the tertiary aliphatic amine include N,N-dimethylaminoethyl methacrylate and triethanolamine.

[0090] Examples of the tertiary aromatic amine include alkyl p-dialkylaminobenzoates, 7-dimethylamino-4-methylcoumarin, N,N-dimethylaniline, N,N-dibenzylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N,2,4,6-pentamethylaniline, N,N,2,4-tetramethylaniline, and N,N-diethyl-2,4,6-trimethylaniline.

[0091] Among these, tertiary aromatic amines are preferred, and alkyl p-dialkylaminobenzoates are more preferred.

[0092] Examples of the alkyl p-dialkylaminobenzoate include methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and propyl p-diethylaminobenzoate.

[0093] These tertiary amines may be used alone or in combination of two or more.

[0094] —Organic Peroxide— The organic peroxide functions as an oxidizing agent among chemical polymerization initiators.

[0095] Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane, p-diisopropylbenzene monohydroperoxide, p-methane hydroperoxide, and pinane hydroperoxide.

[0096] Among these, cumene hydroperoxide is preferred from the viewpoint of the curability of the dental adhesive composition.

[0097] These organic peroxides may be used alone or in combination of two or more.

[0098] The content of the organic peroxide is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and even more preferably 0.1% by mass or more and 3% by mass or less, relative to the total amount of the dental adhesive composition.

[0099] If the content of the organic peroxide is 0.01% by mass or more based on the total amount of the dental adhesive composition, the hardening property of the dental adhesive composition is improved, which is preferable.

[0100] If the content of the organic peroxide is 10% by mass or less based on the total amount of the dental adhesive composition, the usable time of the dental adhesive composition is improved, which is preferable.

[0101] The photopolymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples of the photopolymerization initiator include camphorquinone (CQ), ethyl 4-dimethylaminobenzoate (EPA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, benzil ketal, diacetyl ketal, benzil dimethyl ketal, benzil diethyl ketal, benzil bis(2-methoxyethyl)ketal, 4,4′-dimethyl(benzyl dimethyl ketal), anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, and 1-methylanthraquinone. Thioxanthone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropyl thioxanthone, 2-nitrothioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chloro-7-trifluoromethyl thioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, bis(4-dimethylaminophenyl)ketone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0102] Among these, camphorquinone (CQ), ethyl 4-dimethylaminobenzoate (EPA), and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) are preferred from the viewpoint of improving the curability of the dental adhesive composition.

[0103] These photopolymerization initiators may be used alone or in combination of two or more.

[0104] The content of the photopolymerization initiator is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 8% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less, relative to the total amount of the dental adhesive composition.

[0105] If the content of the photopolymerization initiator is 0.01% by mass or more based on the total amount of the dental adhesive composition, the curability of the dental adhesive composition is improved, which is preferable.

[0106] If the content of the photopolymerization initiator is 10% by mass or less based on the total amount of the dental adhesive composition, the usable time of the dental adhesive composition is improved, which is preferable.

[0107] <<Polymerization Inhibitor>> The polymerization inhibitor is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol) (BHT), 6-tert-butyl-2,4-xylenol, 1,4-dihydroxybenzene (HQ), and 4-methoxyphenol (MEHQ).

[0108] Among these, dibutylhydroxytoluene (BHT) is preferred from the viewpoint of improving the curability of the dental adhesive composition.

[0109] These polymerization inhibitors may be used alone or in combination of two or more.

[0110] The content of the polymerization inhibitor is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, relative to the total amount of the dental adhesive composition.

[0111] The content of the polymerization inhibitor is preferably 0.01% by mass or more and 5% by mass or less relative to the total amount of the dental adhesive composition, since this improves the storage stability of the dental adhesive composition.

[0112] <<Filler>> The filler is not particularly limited and can be appropriately selected depending on the purpose. Examples of the filler include colloidal silica, fine particle silica whose surface has been treated to make it hydrophobic (hydrophobic fumed silica), aluminum oxide, fluoroaluminosilicate glass, barium glass, and strontium glass.

[0113] Among these, hydrophobic fumed silica (for example, Aerosil (registered trademark)) is preferred.

[0114] These fillers may be used alone or in combination of two or more.

[0115] The content of the filler is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and even more preferably 1% by mass or more and 10% by mass or less, relative to the total amount of the dental adhesive composition.

[0116] If the content of the filler is 0.1 mass % or more relative to the total amount of the dental adhesive composition, the viscosity of the dental adhesive composition increases, which is preferable as it improves the handleability of the dental adhesive composition.

[0117] When the content of the filler is 30% by mass or less relative to the total amount of the dental adhesive composition, the viscosity of the dental adhesive composition does not become too high, and the operability of the dental adhesive composition can be stabilized.

[0118] <<Solvent>> The solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include water and organic solvents.

[0119] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ethanol, acetone, and propanol.

[0120] These solvents may be used alone or in combination of two or more.

[0121] The X-ray contrast property of the cured product of the X-ray contrast compound is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably 100% or more in terms of the ratio to aluminum.

[0122] The method for evaluating the X-ray contrast property of the cured product of the dental adhesive composition is not particularly limited and can be appropriately selected depending on the purpose. For example, the X-ray contrast property can be measured by the test method for X-ray contrast property of dental materials in accordance with ISO 13116 and JIS T 6006.

[0123] [Physical Properties of Dental Adhesive Composition] The physical properties of the dental adhesive composition are not particularly limited, but the pH and viscosity are preferably as follows.

[0124] The pH of the dental adhesive composition is preferably from 1 to 10, and more preferably from 1.5 to 8. A dental adhesive composition having a pH in the above range has little acidic or basic irritation, is excellent in feel when used, and can stably maintain its properties against environmental changes even when stored for a long period of time.

[0125] The method for measuring the pH is not particularly limited, and examples thereof include a method in which 1 g of the dental adhesive composition is dissolved in 1 mL of an aqueous solvent, and the resulting solution is measured using a pH meter (e.g., HORIBA pH / ION METER F-72).

[0126] The viscosity of the dental adhesive composition is preferably from 10 mPa·s to 1,000 mPa·s, more preferably from 50 mPa·s to 500 mPa·s. A dental adhesive composition having a viscosity within the above range has excellent operability and exhibits high compatibility with an adherend.

[0127] The method for measuring the viscosity is not particularly limited, and can be, for example, measured by the following method. [Example of viscosity measurement method] After a B-type viscometer (Toki Sangyo Co., Ltd.) is kept at a constant temperature of 23°C, 0.6 mL of the dental adhesive composition is measured out and left to stand for 5 minutes to keep the temperature constant. The measurement is carried out at 10 rpm for 5 minutes, and the average value between 2 minutes and 5 minutes is taken as the viscosity.

[0128] The method for producing the dental adhesive composition is not particularly limited, and it can be produced, for example, by mixing and stirring the above-mentioned components.

[0129] The dental adhesive composition may be used for any purpose, but is not particularly limited thereto. For example, the composition may be used for various dental materials.

[0130] Examples of such dental materials include dental cement, dental adhesive, dental temporary sealing material, dental primer, dental coating material, dental filling composite resin, dental hard resin, dental cutting resin material, dental temporary restorative material, dental filling material, and toothpaste.

[0131] Among these, it is preferably used in dental adhesives, dental filling composite resins, and dental cements.

[0132] The present invention will be further described below with reference to examples. In the following, numerical values ​​without units, "parts" or "%" are based on mass unless otherwise specified.

[0133] <Synthesis of Compounds 1 to 5> <<Synthesis of Compound 1>> trans-2,3-Dibromo-2-butene-1,4-diol (manufactured by Tokyo Chemical Industry Co., Ltd.), mono(2-acryloyloxyethyl) succinate (manufactured by Tokyo Chemical Industry Co., Ltd.), and a solution were heated under reflux overnight. At this time, a catalyst and a condensing agent were added together, and synthesis was carried out under a protective gas atmosphere. Next, the reaction product was cooled to room temperature, extracted with a solution, washed at least once with water, and then condensed with anhydrous NaCl. ２ SO ４ Drying on ice and removal of the solvent under vacuum gave compound 1.

[0134] Here, the structure of trans-2,3-dibromo-2-butene-1,4-diol is as follows:

[0135]

[0136] Here, the structure of mono(2-acryloyloxyethyl) succinate is as follows:

[0137]

[0138] <<Synthesis of Compound 2>> Compound 2 was obtained in the same manner as Compound 1, except that 2-carboxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of mono(2-acryloyloxyethyl) succinate. The structure of 2-carboxyethyl acrylate is as follows:

[0139]

[0140] <<Synthesis of Compound 3>> Compound 3 was obtained in the same manner as for Compound 1, except that 2,2-bis(bromomethyl)-1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of trans-2,3-dibromo-2-butene-1,4-diol. The structure of 2,2-bis(bromomethyl)-1,3-propanediol is as follows:

[0141]

[0142] <<Synthesis of Compound 4>> Compound 4 was obtained in the same manner as Compound 1, except that trans-2-butene-1,4-diol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of trans-2,3-dibromo-2-butene-1,4-diol. The structure of trans-2-butene-1,4-diol is as follows.

[0143]

[0144] <<Synthesis of Compound 5>> Compound 5 was obtained in the same manner as for Compound 1, except that 2,5-dibromo-1,4-benzenediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of trans-2,3-dibromo-2-butene-1,4-diol. The structure of 2,5-dibromo-1,4-benzenediol is as follows:

[0145]

[0146] (Examples 1 to 9, Comparative Examples 1 to 3) <Preparation of Dental Adhesive Compositions> Dental adhesive compositions (Examples 1 to 9, Comparative Examples 1 to 3) were prepared with the compositions shown in Tables 1 and 2. For each dental adhesive composition, X-ray contrast properties, halogen release rate, bond strength to ceramics, and bond strength to dentin were evaluated by the following methods. The results are shown in Tables 1 and 2.

[0147] <Evaluation of X-ray contrast properties> When the dental adhesive composition is actually used, the dental adhesive composition is applied to an adherend, dried with air to remove the solvent, and then photocured. Based on this, for the evaluation of contrast properties, dental adhesive compositions from Examples 1 to 9 and Comparative Examples 1 to 3 were used from which the solvent component had been removed.

[0148] An OHP sheet was placed on a glass slide, and a ring with a diameter of 1.5 cm and a thickness of 1.0 mm was placed on it. The ring was filled with each dental adhesive composition from which the solvent had been removed, and then an OHP sheet and a glass slide were placed on top of it in that order to prepare an evaluation sample. Using a light irradiator (G-Light Prima II Plus, manufactured by GC Corporation), nine points were irradiated on each of the front and back of the evaluation sample in 10-second mode. The obtained cured product was subjected to cephalometric photography together with an aluminum step using an X-ray photography device (Aadva GX-100 2D, manufactured by GC Corporation). The obtained image was analyzed using Image J, and the aluminum contrast transmittance (%) was calculated. The evaluation criteria for X-ray contrast transmittance are as follows: - Evaluation criteria - A: Aluminum contrast transmittance is 100% or more B: Aluminum contrast transmittance is 50% or more but less than 100% C: Aluminum contrast transmittance is less than 50%

[0149] <Evaluation of Halogen Release Rate> One drop of each dental adhesive composition was dropped onto a dish, and then the dish was left to stand for 10 minutes under natural light. Thereafter, the color change of the dental adhesive composition was visually observed.

[0150] No visible change in the color of the dental adhesive compositions of Examples 1 to 9 and Comparative Examples 1 and 3 was observed, but discoloration was observed only in the dental adhesive composition of Comparative Example 2. It is presumed that the discoloration of the dental adhesive composition is caused by the liberation of halogen from the dental adhesive composition by natural light.

[0151] <Evaluation of adhesive strength to enamel and adhesive strength to dentin> The tooth structure was polished with #400 waterproof abrasive paper to expose the fresh surface. Each dental adhesive composition was applied and immediately dried with an air blower. A plastic mold with a Φ2.38 mm hole was placed on the test surface, and light irradiation was performed from above the mold for 10 seconds using a light irradiator (G-Light Prima II Plus, manufactured by GC Corporation). Next, a composite resin was filled, and light irradiation was performed for an additional 20 seconds. After immersion in water at 37°C for 24 hours, a shear test was performed on five test specimens using an autograph (EZ-S, Shimadzu) at a crosshead speed of 1 mm / min. The average shear bond strength was calculated to evaluate the adhesiveness of each composite resin to the tooth structure.

[0152] The evaluation criteria for the adhesion (bond strength to enamel and bond strength to dentin) of the composite resin to tooth structures (enamel and dentin) when each dental adhesive composition was used were as follows: - Evaluation criteria - A: The average shear bond strength is 15 MPa or more. B: The average shear bond strength is less than 15 MPa.

[0153]

[0154]

[0155] Examples of aspects of the present invention are as follows: <1> An X-ray contrast compound comprising a structural moiety A which contains a halogen atom and has a non-cyclic structure, and a structural moiety B derived from a (meth)acrylate. <2> The X-ray contrast compound is the X-ray contrast compound according to <1>, which comprises at least one selected from the group consisting of a structure represented by the following general formula (1), a structure represented by the following general formula (2), and a structure represented by the following general formula (3):

[0156] (In the general formula (1), R1 and R2 each independently represent "-H" or "-CH ３", X1 and X2 each independently represent "-O-" or "-NH-", and Y1 and Y2 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.

[0157] (In the general formula (2), R3 and R4 each independently represent "-H" or "-CH ３ ", X3 and X4 each independently represent "-O-" or "-NH-", and Y3 and Y4 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.

[0158] (In the general formula (3), R5 and R6 each independently represent "-H" or "-CH ３ ", X5 and X6 each independently represent "-O-" or "-NH-", and Y5 and Y6 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms, which may have an ether bond, an ester bond, and / or an amide bond.) <3> A dental adhesive composition comprising an X-ray contrast compound having a structural moiety A which contains a halogen atom and is a non-cyclic structure, and a structural moiety B derived from a (meth)acrylate. <4> The dental adhesive composition according to <3>, wherein the X-ray contrast compound comprises at least one selected from the group consisting of a structure represented by the following general formula (1), a structure represented by the following general formula (2), and a structure represented by the following general formula (3):

[0159] (In the general formula (1), R1 and R2 each independently represent "-H" or "-CH ３ ", X1 and X2 each independently represent "-O-" or "-NH-", and Y1 and Y2 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.

[0160] (In the general formula (2), R3 and R4 each independently represent "-H" or "-CH ３ ", X3 and X4 each independently represent "-O-" or "-NH-", and Y3 and Y4 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.

[0161] (In the general formula (3), R5 and R6 each independently represent "-H" or "-CH ３ ", X5 and X6 each independently represent "-O-" or "-NH-", and Y5 and Y6 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms, which may have an ether bond, an ester bond, and / or an amide bond.) <5> The dental adhesive composition according to <3> or <4>, which contains a photopolymerization initiator. <6> The dental adhesive composition according to any one of <3> to <5>, which contains water. <7> The dental adhesive composition according to any one of <3> to <6>, wherein the X-ray contrast property of a cured product of the dental adhesive composition is 100% or more relative to aluminum. <8> The dental adhesive composition according to any one of <3> to <7>, wherein the content of the X-ray contrast compound is 0.5% by mass or more and 70% by mass or less, based on the total amount of the dental adhesive composition.

[0162] The X-ray contrast compound described in <1> or <2> and the dental adhesive composition described in any one of <3> to <8> can solve the conventional problems and achieve the object of the present invention.

[0163] This application claims priority based on Japanese Patent Application No. 2023-144346, filed on September 6, 2023, the entire contents of which are incorporated herein by reference.

Claims

1. An X-ray contrast compound comprising: structural portion A which contains a halogen atom and has a non-cyclic structure; and structural portion B which is derived from a (meth)acrylate.

2. The X-ray contrast compound according to claim 1, which comprises at least one selected from the group consisting of a structure represented by the following general formula (1), a structure represented by the following general formula (2), and a structure represented by the following general formula (3): (In the general formula (1), R1 and R2 are each independently “—H” or “—CH ３ ", X1 and X2 each independently represent "-O-" or "-NH-", and Y1 and Y2 each independently represent a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.) (In the general formula (2), R3 and R4 are each independently “—H” or “—CH ３ ", X3 and X4 each independently represent "-O-" or "-NH-", and Y3 and Y4 each independently represent a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.) (In the general formula (3), R5 and R6 are each independently “—H” or “—CH ３ X5 and X6 each independently represent "-O-" or "-NH-", and Y5 and Y6 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.) 3. A dental adhesive composition comprising an X-ray contrast compound having a structural portion A which contains a halogen atom and is a non-cyclic structure, and a structural portion B which is derived from a (meth)acrylate.

4. The dental adhesive composition according to claim 3, wherein the X-ray contrast compound comprises at least one selected from the group consisting of a structure represented by the following general formula (1), a structure represented by the following general formula (2), and a structure represented by the following general formula (3). (In the general formula (1), R1 and R2 are each independently “—H” or “—CH ３ ", X1 and X2 each independently represent "-O-" or "-NH-", and Y1 and Y2 each independently represent a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.) (In the general formula (2), R3 and R4 are each independently “—H” or “—CH ３ ", X3 and X4 each independently represent "-O-" or "-NH-", and Y3 and Y4 each independently represent a linear or branched hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.) (In the general formula (3), R5 and R6 are each independently “—H” or “—CH ３ X5 and X6 each independently represent "-O-" or "-NH-", and Y5 and Y6 each independently represent a linear or branched hydrocarbon group having from 1 to 20 carbon atoms which may have an ether bond, an ester bond, and / or an amide bond.) 5. A dental adhesive composition according to claim 3 or 4, which contains a photopolymerization initiator.

6. A dental adhesive composition according to any one of claims 3 to 5, which contains water.

7. A dental adhesive composition according to any one of claims 3 to 6, wherein the X-ray contrast property of the cured product of said dental adhesive composition is 100% or more relative to aluminum.

8. A dental adhesive composition according to any one of claims 3 to 7, wherein the content of the X-ray contrast compound is 0.5% by mass or more and 70% by mass or less based on the total amount of the dental adhesive composition.

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