Phosphonic acid compound, and dental adhesive composition containing the compound

Abstract

To provide a phosphonic acid compound that can exhibit superior initial adhesion to enamel and also impart high adhesive durability when applied to a dental adhesive composition, and a dental adhesive composition comprising the same.SOLUTION: The present invention provides a phosphonic acid compound (A) represented by the general formula (1), and a dental adhesive composition containing the phosphonic acid compound (A) (where R1 represents a hydrogen atom or a methyl group, R2 and R3 independently represent a hydrogen atom, a C1-6 hydrocarbon group, or a metal atom, Z represents an oxygen atom or a sulfur atom, Y represents one selected from the group consisting of -O-, -S- and -NH-, n represents an integer of 2-4, and m represents an integer of 3-18).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a phosphonic acid compound and a dental adhesive composition containing said compound, which is useful as a dental material such as a dental bonding material. [Background technology]

[0002] To repair tooth tissue (enamel, dentin, and cementum) damaged by caries or other conditions, dental filling composite resins, filling compomers, and other filling and restorative materials, such as metal alloys, porcelain, and resin materials, are usually used. However, generally, filling and restorative materials and crown restorative materials (both of which may be collectively referred to as "dental restorative materials" in this specification) do not themselves have adhesive properties to tooth structure. For this reason, various adhesive systems using adhesives have been used to bond tooth structure and dental restorative materials. Conventionally widely used adhesive systems include a so-called acid etching type adhesive system in which the surface of tooth structure is etched with an acid etching agent such as an aqueous phosphoric acid solution, and then a bonding agent is applied to bond the tooth structure and dental restorative material.

[0003] On the other hand, there is a so-called self-etching adhesive system that does not use an acid etching agent. The mainstream of this adhesive system is a two-step adhesive system in which a self-etching primer containing an acidic monomer, a hydrophilic monomer, and water is applied to the surface of the tooth, and then, without rinsing with water, a bonding material containing a cross-linking monomer and a polymerization initiator is applied. Recently, a one-step adhesive system using a one-component dental adhesive (one-component bonding material) that combines the functions of a self-etching primer and a bonding material has become widely used.

[0004] 2. Description of the Related Art Dental adhesives containing a compound having a polymerizable group and an acidic group are known, and various compounds have been proposed as such compounds (see, for example, Patent Documents 1 and 2). Patent Document 1 proposes a phosphate ester compound represented by the following formula, which has improved adhesive strength to tooth structure, and reports that it exhibits excellent adhesiveness and high mechanical strength.

[0005] [ka]

[0006] Moreover, Patent Document 2 proposes an adhesive composition containing a polymerizable aminophosphonic acid derivative having a specific structure, such as the compound represented by the following formula. Patent Document 2 explains that adhesives containing (meth)acrylate monomers that contain ester bonds, such as phosphate ester compounds, have problems in that the (initial) adhesive strength is slightly reduced due to hydrolysis of the ester bonds, and that even after use, the adhesiveness decreases due to hydrolysis at the adhesive interface between the adhesive and tooth structure, and it is said that the above adhesive composition solves these problems.

[0007] [ka]

[0008] Furthermore, although not for dental use, Patent Document 3 proposes an adhesive composition containing a phosphonic acid group-containing urethane methacrylate such as the compound represented by the following formula, and discloses that the adhesive composition has excellent aging stability and adhesiveness as measured by a T-peel adhesion test.

[0009] [ka]

[0010] [Patent Document 1] JP 2014-91692 A [Patent Document 2] JP 2009-46397 A [Patent Document 3] International Publication No. 2020 / 046654 Summary of the Invention [Problem to be solved by the invention]

[0011] As a result of the inventors' investigations, it was found that although the composition according to Patent Document 1 has a high initial adhesive strength, there is room for improvement in the adhesive durability, particularly to enamel. In addition, since the adhesive composition according to Patent Document 2 uses a phosphonic acid-containing polymerizable monomer that does not have an ester bond, problems caused by the above-mentioned hydrolysis are unlikely to occur. However, compared with a phosphate ester group-containing polymerizable monomer, the hydrophobicity is too high, which is thought to be due to an imbalance between hydrophilicity and hydrophobicity, and there is a problem that the adhesive durability, especially to enamel, is low. Although the adhesive composition according to Patent Document 3 is described as having excellent T-peel adhesive strength against metals and is intended for use as an industrial adhesive for automotive substrates, there is no suggestion of dental use, and there is no description of tests carried out on tooth tissue or dental prostheses in the presence of a large amount of moisture, which is important for dental use. Furthermore, according to the present inventors' investigations, it was found that when the phosphonic acid group-containing urethane methacrylate described in Patent Document 3 is used in a dental adhesive composition, there is a problem in that the adhesive durability to enamel is low.

[0012] In particular, in Patent Document 3, an evaluation system for evaluating the durability of adhesive performance is performed using an accelerated heating test. However, since enamel constitutes the surface of the teeth and is repeatedly exposed to large amounts of moisture and drastic temperature changes in the oral cavity, the test system for adhesion durability to enamel must include conditions of particularly large amounts of moisture. This point is overlooked, and the durability test in Patent Document 3 is not an evaluation test for properly evaluating adhesion durability to enamel. When evaluated in a test in which a large amount of moisture and rapid temperature changes are both present, in conventional technologies, the ester bonds are hydrolyzed, reducing the adhesive durability to enamel, or the hydrophobicity becomes too high, disrupting the balance between hydrophilicity and hydrophobicity, reducing the adhesive durability to enamel. As a result, in an extremely harsh oral environment, such as exposure to rapid temperature changes and a large amount of moisture, it is difficult to achieve high adhesive durability to enamel, especially in the case of a one-component bonding material without pretreatment such as a self-etching primer, and thus high adhesive durability to enamel has not been achieved in the past.

[0013] Therefore, an object of the present invention is to provide a phosphonic acid compound that can impart excellent initial adhesive strength and adhesion durability to enamel when applied to a dental adhesive composition, and a dental adhesive composition containing the same. [Means for solving the problem]

[0014] As a result of extensive investigations, the present inventors have found that a specific dental adhesive composition can solve the above problems, and after further investigations have completed the present invention.

[0015] That is, the present invention includes the following inventions. [1] A phosphonic acid compound (A) represented by the following general formula (1): [ka] (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a metal atom; Z represents an oxygen atom or a sulfur atom; Y represents one selected from the group consisting of -O-, -S-, and -NH-; n represents an integer of 2 to 4; and m represents an integer of 3 to 18. [2] The phosphonic acid compound (A) according to [1], wherein m is an integer of 5 to 16. [3] R 1The phosphonic acid compound (A) according to [1] or [2], wherein [4]R 2 and R 3 The phosphonic acid compound (A) according to any one of [1] to [3], wherein is a hydrogen atom. [5] A dental adhesive composition containing a phosphonic acid compound (A) represented by the following general formula (1): [ka] (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a metal atom; Z represents an oxygen atom or a sulfur atom; Y represents one selected from the group consisting of -O-, -S-, and -NH-; n represents an integer of 2 to 4; and m represents an integer of 3 to 18. [6] The dental adhesive composition according to [5], wherein m of the phosphonic acid compound (A) is an integer of 5 to 16. [7] R of the phosphonic acid compound (A) 1 The dental adhesive composition according to [5] or [6], wherein is a methyl group. [8]R 2 and R 3 The dental adhesive composition according to any one of [5] to [7], wherein is a hydrogen atom. [9] The dental adhesive composition according to any one of [5] to [8], further comprising a polymerizable monomer (B) copolymerizable with the phosphonic acid compound (A).

[10] The dental adhesive composition according to [9], wherein the polymerizable monomer (B) contains a hydrophilic polymerizable monomer (B-1).

[11] The dental adhesive composition according to any one of [5] to

[10] , further comprising a polymerization initiator (C).

[12] The dental adhesive composition according to any one of [5] to

[11] , further comprising a filler (E).

[13] The dental adhesive composition according to any one of [5] to

[12] , further comprising a solvent (F).

[14] A dental bonding material comprising the dental adhesive composition according to any one of [5] to

[13] . Effect of the Invention

[0016] According to the present invention, there can be provided a phosphonic acid compound which, when applied to a dental adhesive composition, can impart excellent initial adhesive strength and adhesion durability to enamel, and a dental adhesive composition containing the same. In addition, since the dental adhesive composition of the present invention has excellent initial adhesive strength and adhesion durability to enamel, it can be used for various dental treatment applications (e.g., filling and restorative materials, bonding materials, adhesives, etc.), and is particularly useful as a dental material such as a dental bonding material. Furthermore, the dental adhesive composition of the present invention, even when used as a one-component bonding material, has excellent initial adhesive strength and adhesive durability to enamel without the need for primer treatment, and therefore requires simple steps for use and is easy to use. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will be described in detail below. In this specification, "(meth)acrylic" is a general term for methacrylic and acrylic, and the same applies to similar expressions (such as "(meth)acrylic acid" and "(meth)acrylonitrile"). In this specification, the term "monofunctional monomer" means a monomer having one polymerizable group in one molecule. In this specification, the term "bifunctional monomer" refers to a monomer having two polymerizable groups in one molecule. In this specification, the upper and lower limits of numerical ranges (contents of each component, values ​​calculated from each component, and each physical property, etc.) can be combined as appropriate. In addition, in this specification, the embodiments can be modified by combining some or all of them as appropriate, except in cases where the effects of the present invention cannot be obtained.

[0018] The dental adhesive composition of the present invention is a dental adhesive composition containing a phosphonic acid compound (A) represented by the following general formula (1) (hereinafter, also simply referred to as "phosphonic acid compound (A)"). [ka] (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a metal atom; Z represents an oxygen atom or a sulfur atom; Y represents one selected from the group consisting of -O-, -S-, and -NH-; n represents an integer of 2 to 4; and m represents an integer of 3 to 18.

[0019] The dental adhesive composition of the present invention contains the phosphonic acid compound (A), and thus becomes a dental adhesive composition which not only exhibits excellent initial adhesive strength to enamel but also provides high adhesive durability. Therefore, the phosphonic acid compound (A) is highly useful in dental applications. The phosphonic acid compound (A) has excellent initial adhesive strength and adhesive durability to enamel in the oral cavity environment where there are temperature changes and constant exposure to a large amount of moisture, and therefore can be used in various dental treatment applications (e.g., filling and restoring materials, bonding materials, adhesives, etc.), and is particularly useful as a dental bonding material (more preferably a one-liquid bonding material).

[0020] The reason why the phosphonic acid compound (A) exhibits such excellent effects is not entirely clear, but is presumed to be as follows. Compared to polymerizable monomers having a phosphate monoester group or a phosphate diester group, the phosphonic acid group replaces the POC bond with a PC bond, making hydrolysis less likely to occur at the adhesive interface between the adhesive and tooth substance (especially enamel, which is exposed to large amounts of moisture), improving adhesion durability. In addition, a structure in which a carbon atom bonded to a phosphonic acid group and a urethane bond are bonded via an alkyl group having a long chain of a specific length or more also acts to increase hydrophobicity, resulting in improved adhesion durability. On the other hand, for acidic group polymerizable monomers, the balance between hydrophilicity and hydrophobicity within the molecule is important; introducing a phosphonic acid group into the molecule results in higher hydrophobicity compared to the case of a phosphate ester group. Furthermore, if the hydrophobic spacer also acts to increase the hydrophobicity, making the hydrophobicity too high, the balance between hydrophilicity and hydrophobicity within the molecule deteriorates, resulting in reduced adhesion durability to enamel. In contrast, in the case of phosphonic acid compound (A), the spacer between the urethane bond and the (meth)acrylic group in the molecule is bonded via an alkyl group having an ether bond, which gives the compound moderate hydrophilicity, and it is presumed that the balance between hydrophilicity and hydrophobicity is maintained appropriately even in the structure having a phosphonic acid group, thereby improving the adhesion durability.

[0021] <Phosphonic acid compound (A)> First, each symbol used in general formula (1) will be explained.

[0022] In the formula, R 1 represents a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of irritation to the living body when the polymerizable site of the phosphonic acid compound (A) is eliminated by hydrolysis or the like.

[0023] R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a metal atom. The metal atom is preferably a metal atom of Group 1 or 2 of the periodic table, and specific examples include sodium, potassium, calcium, magnesium, and the like.

[0024] Among these, from the viewpoint of the acidity of the phosphonic acid compound (A), R 2 and R 3 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group; R 2 and R 3 It is more preferable that each of the is a hydrogen atom.

[0025] Z represents an oxygen atom or a sulfur atom, and from the viewpoint of ease of production of the phosphonic acid compound (A), an oxygen atom is preferred.

[0026] Y represents one selected from the group consisting of -O-, -S- and -NH-. Among these, from the viewpoint of ease of production of the phosphonic acid compound (A), Y is preferably -O- or -S-, and more preferably -O-.

[0027] n represents an integer of 2 to 4. Among these, n is preferably 2 or 3, and more preferably 2, from the viewpoint of providing the phosphonic acid compound (A) with superior adhesion to tooth structure (particularly enamel) and superior adhesion durability.

[0028] m represents an integer of 3 to 18. Among these, from the viewpoint of providing the phosphonic acid compound (A) with superior adhesiveness and adhesive durability to tooth structure (particularly enamel), m is preferably an integer of 5 to 16, more preferably an integer of 8 to 16, and further preferably an integer of 8 to 12.

[0029] In a preferred embodiment, m / n is preferably more than 1 and 8 or less, more preferably 1.5 or more and 7 or less, and even more preferably 2.5 or more and 6 or less. In the above structure, when m / n is greater than 1, the balance between hydrophilicity and hydrophobicity in the molecule is excellent, and the adhesive has superior adhesiveness and durability to enamel.

[0030] Compositions containing the phosphonic acid compound (A) are expected to be used for a variety of applications in a variety of fields due to the adhesive durability and the balance of hydrophilicity and hydrophobicity derived from the phosphonic acid compound (A). The composition containing the phosphonic acid compound (A) has excellent adhesiveness and adhesive durability to tooth structures (particularly enamel), and is therefore particularly useful in dental applications.

[0031] Therefore, the present invention also provides a dental adhesive composition containing a phosphonic acid compound (A). In the dental adhesive composition, the phosphonic acid compound (A) may be blended alone or in combination of two or more kinds. The dental adhesive composition may contain a polymerizable monomer (B) copolymerizable with the phosphonic acid compound (A) (hereinafter also simply referred to as "polymerizable monomer (B)") as a polymerizable monomer other than the phosphonic acid compound (A). Suitable other components that may be included in the dental adhesive composition include a polymerization initiator (C), a polymerization accelerator (D), a filler (E), a solvent (F), and the like.

[0032] <Polymerizable monomer (B)> The polymerizable monomer (B) is preferably a radically polymerizable monomer having a polymerizable group (preferably a (meth)acryloyl group), which contributes to improving the mechanical strength and adhesiveness of the cured product of the dental adhesive composition.

[0033] Examples of the polymerizable monomer (B) include the following hydrophilic polymerizable monomer (B-1) (hereinafter also simply referred to as "polymerizable monomer (B-1)") and hydrophobic polymerizable monomer (B-2) (hereinafter also simply referred to as "polymerizable monomer (B-2)"). The hydrophilic polymerizable monomer (B-1) and the hydrophobic polymerizable monomer (B-2) do not have an acidic group or an acid anhydride group. The acidic group and the acid anhydride group are exemplified by the acidic group and the acid anhydride group in the polymerizable monomer (B-3) having an acidic group other than the phosphonic acid compound (A) described later.

[0034] The hydrophilic polymerizable monomer (B-1) means a monomer having a solubility in water of 10% by mass or more at 25° C. A monomer having a solubility of 30% by mass or more is preferable, and a monomer that can be dissolved in water at any ratio at 25° C. is more preferable.

[0035] The hydrophilic polymerizable monomer (B-1) can improve the wettability of the dental adhesive composition to tooth structure and the permeability into tooth structure, thereby improving the adhesive strength to tooth structure. The polymerizable groups possessed by the hydrophilic polymerizable monomer (B-1) include a vinyl group, a (meth)acryloyloxy group, and a (meth)acrylamide group. From the viewpoint of ease of radical polymerization, a (meth)acryloyloxy group and / or a (meth)acrylamide group are preferred, and from the viewpoint of adhesion to tooth structure, a (meth)acrylamide group is preferred. The hydrophilic polymerizable monomer (B-1) may be used alone or in combination of two or more kinds.

[0036] The hydrophilic polymerizable monomer (B-1) is preferably one having a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, or an amide group.

[0037] The hydrophilic polymerizable monomer (B-1) may be a monofunctional monomer or a bifunctional monomer.

[0038] Among the hydrophilic polymerizable monomers (B-1), examples of the monofunctional monomer include hydrophilic monofunctional (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 2-((meth)acryloyloxy)ethyltrimethylammonium chloride; N-methylol (meth)acrylamide; and hydrophilic monofunctional (meth)acrylamide monomers such as diacetone (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, 4-(meth)acryloylmorpholine, N-trihydroxymethyl-N-methyl (meth)acrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0039] Examples of the bifunctional monomer include hydrophilic bifunctional (meth)acrylate monomers such as polyethylene glycol di(meth)acrylate (average number of moles of oxyethylene groups added: 9 or more), 1,2-bis(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethane, and 3-(meth)acryloyloxy-2-hydroxypropyl(meth)acrylate.

[0040] Among these hydrophilic polymerizable monomers (B-1), from the viewpoint of adhesion to tooth structure, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and hydrophilic monofunctional (meth)acrylamide monomers are preferred, and 2-hydroxyethyl methacrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide are more preferred.

[0041] The hydrophobic polymerizable monomer (B-2) may be a polymerizable monomer having a solubility in water of less than 10 mass % at 25° C. The hydrophobic polymerizable monomer (B-2) improves the mechanical strength, handleability, etc. of the cured product of the dental adhesive composition. The polymerizable groups possessed by the hydrophobic polymerizable monomer (B-2) include a vinyl group, a (meth)acryloyloxy group, and a (meth)acrylamide group. From the viewpoint of ease of radical polymerization, a (meth)acryloyloxy group and / or a (meth)acrylamide group are preferred, and from the viewpoint of adhesion to tooth structure, a (meth)acrylamide group is preferred.

[0042] Examples of the hydrophobic polymerizable monomer (B-2) include monofunctional monomers, bifunctional monomers, and trifunctional or higher monomers.

[0043] Examples of the monofunctional monomer include aliphatic compound-based monofunctional (meth)acrylate monomers such as n-stearyl methacrylate; aliphatic compound-based monofunctional (meth)acrylate monomers having an ether bond such as butoxydiethylene glycol methacrylate and methoxypolyethylene glycol methacrylate (average molar number of oxyethylene groups added: 9); alicyclic compound-based monofunctional (meth)acrylate monomers such as cyclohexyl methacrylate, isobornyl methacrylate and dicyclopentanyl methacrylate; monofunctional (meth)acrylate monomers having an aromatic ring group such as 2-phenoxyethyl methacrylate and phenoxybenzyl methacrylate; and monofunctional (meth)acrylate monomers having a heterocyclic group (for example, a cyclic ether group) such as tetrahydrofurfuryl methacrylate.

[0044] As the monofunctional (meth)acrylate monomer having an aromatic ring group, one having one or two phenyl groups is preferred.

[0045] As the monofunctional (meth)acrylate monomer having a heterocyclic group, one having one or two heterocyclic groups (for example, a cyclic ether group, etc.) is preferable.

[0046] Among the monofunctional monomers, benzyl methacrylate (commonly known as BEMA), phenoxybenzyl methacrylate (commonly known as POB-MA), and 2-phenoxyethyl methacrylate (commonly known as PEMA) are preferred from the viewpoints of mechanical strength and viscosity.

[0047] Examples of bifunctional monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetra ... bifunctional (meth)acrylate monomers having an aromatic ring group, such as 2-(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane;Erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol Examples of the difunctional (meth)acrylate monomers include aliphatic compounds such as 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane; and N-methacryloyloxyethyl acrylamide. Among these, 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane, glycerol dimethacrylate, triethylene glycol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane, and N-methacryloyloxyethylacrylamide are preferred.

[0048] Examples of trifunctional or higher polymerizable monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane, and the like.

[0049] The phosphonic acid compound (A) has an acid etching effect since it has a phosphonic acid group. In addition to the above-mentioned polymerizable monomer, the phosphonic acid compound (A) may be used in combination with a polymerizable monomer (B-3) having an acidic group other than the phosphonic acid compound (A) (hereinafter, also simply referred to as "polymerizable monomer (B-3)"). Examples of the polymerizable monomer (B-3) having an acidic group other than the phosphonic acid compound (A) include polymerizable monomers having at least one acidic group or acid anhydride group, such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, or a sulfonic acid group, and having at least one polymerizable group, such as a (meth)acryloyl group, a vinyl group, or a styrene group.

[0050] Specific examples of the polymerizable monomer (B-3) having an acidic group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acrylamidoethyl dihydrogen phosphate, bis(6-(meth)acryloyloxyhexyl)hydrogen phosphate, bis(10-(meth)acryloyl phosphate group-containing polymerizable monomers such as bis{2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl}hydrogen phosphate; carboxylic acid group-containing polymerizable monomers such as 11-methacryloyloxy-1,1-undecanedicarboxylic acid, 4-methacryloyloxyethyltrimellitic acid, N-methacryloyl-5-aminosalicylic acid; sulfonic acid group-containing polymerizable monomers such as 2-methyl-2-(meth)acrylamidopropanesulfonic acid; 4-methacryloyloxyethyltrimellitic anhydride; and compounds described in Japanese Patent No. 4611028 and Japanese Patent Laid-Open No. 2010-235465.

[0051] The content of the phosphonic acid compound (A) is preferably from 0.1 to 80 parts by mass, more preferably from 0.2 to 50 parts by mass, and further preferably from 0.5 to 30 parts by mass, in 100 parts by mass of the total amount of the polymerizable monomer components. When the content of the phosphonic acid compound (A) is 1 part by mass or more, the effect of improving sufficient adhesion and adhesion durability to tooth structure (particularly enamel) is further enhanced, and when the content of the phosphonic acid compound (A) is 80 parts by mass or less, sufficient penetration into the tooth structure is achieved, resulting in a good effect of improving adhesion. In the present invention, as described later, the content of the phosphonic acid compound (A) can be adjusted to a suitable range in various embodiments according to the application. For example, the content of the phosphonic acid compound (A) may be 0.1 to 50 parts by mass, 0.25 to 30 parts by mass, 0.5 to 20 parts by mass, 1 to 20 parts by mass, etc., based on 100 parts by mass of the total amount of the polymerizable monomer components, according to the application.

[0052] From the viewpoint of tooth structure penetration, the content of the polymerizable monomer (B-1) is preferably 0 to 60 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of the total amount of the polymerizable monomer components. From the viewpoint of polymerization curing property, the content of the polymerizable monomer (B-2) is preferably 1 to 99.9 parts by mass, more preferably 10 to 90 parts by mass, and even more preferably 20 to 80 parts by mass, in 100 parts by mass of the total amount of the polymerizable monomer components. From the viewpoint of polymerization curing property, the content of the polymerizable monomer (B-3) is preferably 0 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 2 to 20 parts by mass, in 100 parts by mass of the total amount of the polymerizable monomer components. In one embodiment, the content of the polymerizable monomer (B-3) is preferably 1 part by mass or less, and more preferably 0.5 parts by mass or less, per 100 parts by mass of the total amount of the polymerizable monomer components. In the present invention, as described later, in various embodiments according to the application, the content of the polymerizable monomer (B) (the total content of the polymerizable monomer (B-1), the polymerizable monomer (B-2), and the polymerizable monomer (B-3)) can be adjusted to a suitable range. Depending on the application, for example, the content of the polymerizable monomer (B) may be 10 to 99.75 parts by mass, 10 to 99.5 parts by mass, 20 to 99.5 parts by mass, etc., in 100 parts by mass of the total amount of the polymerizable monomer components.

[0053] In addition, the mass ratio [A / B-1] of the phosphonic acid compound (A) to the polymerizable monomer (B-1) is preferably 1 / 10 to 10 / 1, more preferably 3 / 20 to 1 / 1, and even more preferably 1 / 5 to 4 / 5, from the viewpoint of tooth tissue penetration. The mass ratio [A / B-2] of the phosphonic acid compound (A) to the polymerizable monomer (B-2) is preferably from 1 / 25 to 10 / 1, more preferably from 1 / 20 to 1 / 1, and even more preferably from 1 / 10 to 4 / 5, from the viewpoint of polymerization curing properties. The mass ratio [A / B-3] of the phosphonic acid compound (A) to the polymerizable monomer (B-3) having an acidic group is preferably 1 / 10 to 10 / 1, more preferably 1 / 5 to 5 / 1, and even more preferably 1 / 3 to 3 / 1, from the viewpoint of polymerization curing properties.

[0054] The above polymerizable monomers (B) (hydrophilic polymerizable monomer (B-1), hydrophobic polymerizable monomer (B-2), and polymerizable monomer having an acidic group (B-3)) may be used alone or in combination of two or more. In an embodiment, the polymerizable monomer (B) preferably contains a hydrophilic polymerizable monomer (B-1). In the present invention, the total amount of the polymerizable monomer components refers to the combined amount of the phosphonic acid compound (A) and the polymerizable monomer (B).

[0055] <Polymerization initiator (C)> The polymerization initiator (C) used in the present invention can be selected from polymerization initiators used in general industrial fields, and among them, polymerization initiators used for dental purposes are preferably used. In particular, photopolymerization initiators and chemical polymerization initiators are used either alone or in combination of two or more.

[0056] Examples of the photopolymerization initiator include (bis)acylphosphine oxides, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds.

[0057] Among the (bis)acylphosphine oxides used as the photopolymerization initiator, examples of the 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, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl)phosphonate, and salts thereof (alkali metal salts, alkaline earth metal salts, etc.). Examples of bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, and salts thereof (such as alkali metal salts and alkaline earth metal salts).

[0058] Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferred.

[0059] Examples of α-diketones used as the photopolymerization initiator include diacetyl, dibenzyl, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphthenequinone, etc. Among these, dl-camphorquinone is preferred from the viewpoint of having a maximum absorption wavelength in the visible light region.

[0060] Examples of the coumarin compound used as the photopolymerization initiator include 3,3'-carbonylbis(7-diethylamino)coumarin, 3-(4-methoxybenzoyl)coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitrobenzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[f]coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3- Ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-diethylamino)coumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[f]coumarin, 3-(4-ethoxycinnamoyl)-7-methoxycoumarin, 3-(4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-[(3-dimethylbenzothiazole-2 -ylidene)acetyl]coumarin, 3-[(1-methylnaphtho[1,2-d]thiazol-2-ylidene)acetyl]coumarin, 3,3'-carbonylbis(6-methoxycoumarin), 3,3'-carbonylbis(7-acetoxycoumarin), 3,3'-carbonylbis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dibutylamino)coumarin, 3-(2-benzimidazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3'-carbonylbis(7-dibutylamino)coumarin, 3,Examples of the compounds include those described in JP-A-9-3109 and JP-A-10-245525, such as 3'-carbonyl-7-diethylaminocoumarin-7'-bis(butoxyethyl)aminocoumarin, 10-[3-[4-(dimethylamino)phenyl]-1-oxo-2-propenyl]-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one, and 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one.

[0061] Among the above-mentioned coumarin compounds, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are particularly preferred.

[0062] Examples of anthraquinones used as the photopolymerization initiator include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-hydroxyanthraquinone.

[0063] Examples of the benzoin alkyl ethers used as the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0064] Examples of the α-aminoketones used as the photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

[0065] Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides and their salts, α-diketones, and coumarin compounds. This makes it possible to obtain a dental adhesive composition that has excellent photocurability in the visible and near ultraviolet regions and exhibits sufficient photocurability whether a halogen lamp, a light-emitting diode (LED), or a xenon lamp is used as a light source.

[0066] Among the polymerization initiators (C) used in the present invention, organic peroxides are preferably used as chemical polymerization initiators. The organic peroxides used in the above-mentioned chemical polymerization initiators are not particularly limited, and known ones can be used. Representative organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates.

[0067] Examples of the ketone peroxide used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

[0068] Examples of the hydroperoxide used as the chemical polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0069] Examples of the diacyl peroxide used as the chemical polymerization initiator include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0070] Examples of the dialkyl peroxide used as the chemical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne.

[0071] Examples of peroxyketals used as the chemical polymerization initiator 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.

[0072] Examples of peroxyesters used as the chemical polymerization initiator include α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxyisophthalate, di-t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymaleic acid.

[0073] Examples of peroxydicarbonates used as the chemical polymerization initiator include di(3-methoxybutyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, and diallylperoxydicarbonate.

[0074] Among these organic peroxides, diacyl peroxides are preferred from the viewpoint of the overall balance of safety, storage stability, and radical generating ability, and among these, benzoyl peroxide is more preferred.

[0075] The content of the polymerization initiator (C) used in the present invention is not particularly limited, but from the viewpoint of the curability of the obtained composition, it is preferably 0.001 to 30 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer components. If the content of the polymerization initiator (C) is less than 0.001 parts by mass, the polymerization may not proceed sufficiently, which may lead to a decrease in adhesive strength, and is more preferably 0.05 parts by mass or more. On the other hand, if the content of the polymerization initiator (C) exceeds 30 parts by mass, if the polymerization performance of the polymerization initiator itself is low, there is a risk that sufficient adhesive strength cannot be obtained, and furthermore, there is a risk of precipitation from the composition, so it is more preferably 20 parts by mass or less.

[0076] <Polymerization accelerator (D)> The composition of the present invention preferably contains a polymerization accelerator (D). Examples of the polymerization accelerator (D) used in the present invention include amines, sulfinic acid and its salts, triazine compounds, copper compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds, etc. The polymerization accelerator (D) may be used alone or in combination of two or more kinds.

[0077] The amines used as the polymerization accelerator (D) are divided into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, from the viewpoint of the curability and storage stability of the composition, tertiary aliphatic amines are preferred, and among these, N-methyldiethanolamine and triethanolamine are more preferably used.

[0078] Examples of aromatic amines include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-dimethyl-m -toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino)methyl benzoate, 4-(N,N-dimethylamino)n-butoxyethyl benzoate, 4-N,N-dimethylaminobenzoate 2-(methacryloyloxy)ethyl, 4-(N,N-dimethylamino)benzophenone, 4-dimethylaminobenzoate butyl, and the like. Among these, from the viewpoint of imparting excellent curing properties to the composition, at least one selected from the group consisting of N,N-di(2-hydroxyethyl)-p-toluidine, ethyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, and 4-(N,N-dimethylamino)benzophenone is preferably used.

[0079] Examples of sulfinic acid and its salts used as the polymerization accelerator (D) include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, and the like. Examples of the sulfinic acid include 2,4,6-triethylbenzenesulfinate, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, and calcium 2,4,6-triisopropylbenzenesulfinate. Of these, sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are more preferred.

[0080] Examples of the triazine compound used as the polymerization accelerator (D) include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α, α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,Examples of the 6-bis(trichloromethyl)-s-triazine include 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine and 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine.

[0081] Among the above-listed triazine compounds, 2,4,6-tris(trichloromethyl)-s-triazine is more preferable from the viewpoint of polymerization curing property, and 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine are more preferable from the viewpoint of storage stability. The above-listed triazine compounds may be used alone or in combination of two or more kinds.

[0082] Suitable examples of the copper compound used as the polymerization accelerator (D) include copper acetylacetonate, copper (II) acetate, copper oleate, copper (II) chloride, and copper (II) bromide.

[0083] The vanadium compound used as the polymerization accelerator (D) is preferably a tetravalent and / or pentavalent vanadium compound. Examples of trivalent and / or pentavalent vanadium compounds include compounds described in JP-A-2003-96122, such as divanadium(IV) tetroxide, vanadyl acetylacetonate(IV), vanadyl oxalate(IV), vanadyl sulfate(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), bis(maltolato)oxovanadium(IV), vanadium(V) pentoxide, sodium metavanadate(V), and ammonium metavanadate(V).

[0084] Suitable examples of the halogen compound used as the polymerization accelerator (D) include dilauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, and dilauryl dimethyl ammonium bromide.

[0085] Examples of the aldehydes used as the polymerization accelerator (D) include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, pn-octyloxybenzaldehyde, etc. Among these, pn-octyloxybenzaldehyde is preferred from the viewpoint of curability.

[0086] Examples of the thiol compound used as the polymerization accelerator (D) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0087] Examples of the sulfite used as the polymerization accelerator (D) include sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite.

[0088] Examples of the hydrogen sulfite used as the polymerization accelerator (D) include sodium hydrogen sulfite and potassium hydrogen sulfite.

[0089] Examples of the thiourea compound used as the polymerization accelerator (D) include 1-(2-pyridyl)-2-thiourea, thiourea, methylthiourea, ethylthiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, and tetracyclohexylthiourea.

[0090] The content of the polymerization accelerator (D) used in the present invention is not particularly limited, but from the viewpoint of the curability of the obtained composition, it is preferably 0.001 to 30 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer components. If the content of the polymerization accelerator (D) is less than 0.001 parts by mass, the polymerization may not proceed sufficiently, which may lead to a decrease in adhesive strength, and is more preferably 0.05 parts by mass or more. On the other hand, if the content of the polymerization accelerator (D) exceeds 30 parts by mass, if the polymerization performance of the polymerization initiator itself is low, there is a risk that sufficient adhesive strength cannot be obtained, and furthermore, there is a risk of precipitation from the composition, so it is more preferably 20 parts by mass or less.

[0091] <Filler (E)> In some embodiments, the dental adhesive composition of the present invention is preferably further formulated with a filler (E). Such fillers are generally broadly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. The filler (E) may be used alone or in combination of two or more kinds.

[0092] Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, etc., and these may be used alone or in combination of two or more. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoint of the handleability and mechanical strength of the resulting composition, the average particle size of the organic filler is preferably from 0.001 to 50 μm, and more preferably from 0.001 to 10 μm.

[0093] Examples of the inorganic filler material include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. These may also be used alone or in combination of two or more. From the viewpoint of the handleability and mechanical strength of the resulting composition, the average particle size of the inorganic filler is preferably from 0.001 to 50 μm, and more preferably from 0.001 to 10 μm.

[0094] The shape of the inorganic filler may be irregular or spherical. From the viewpoint of improving the mechanical strength of the cured product, it is preferable to use a spherical filler as the inorganic filler. Furthermore, when the spherical filler is used, there is an advantage that when the dental adhesive composition of the present invention is used as a dental composite resin, a dental composite resin having excellent surface smoothness can be obtained. Here, a spherical filler is a filler in which, when a photograph of the filler is taken with a scanning electron microscope (hereinafter abbreviated as SEM), the particles observed within a unit field of view are rounded, and the average uniformity, calculated by dividing the particle diameter in the direction perpendicular to the maximum diameter by the maximum diameter, is 0.6 or more. The average particle size of the spherical filler is preferably 0.1 to 5 μm. If the average particle size is less than 0.1 μm, the filling rate of the spherical filler in the composition may decrease, resulting in a low mechanical strength. On the other hand, if the average particle size exceeds 5 μm, the surface area of ​​the spherical filler may decrease, resulting in a cured product having high mechanical strength.

[0095] The inorganic filler may be surface-treated in advance with a known surface treatment agent such as a silane coupling agent, if necessary, in order to adjust the fluidity of the composition. Examples of surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0096] The organic-inorganic composite filler used in the present invention is obtained by adding a polymerizable monomer to the above-mentioned inorganic filler in advance, forming it into a paste, polymerizing it, and pulverizing it. As the polymerizable monomer, those exemplified as the polymerizable monomer (B) can be used. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler are mixed, polymerized, and then pulverized) can be used. The shape of the organic-inorganic composite filler is not particularly limited, and the particle size of the filler can be appropriately selected. From the viewpoint of the handleability and mechanical strength of the resulting composition, the average particle size of the organic-inorganic composite filler is preferably from 0.001 to 50 μm, and more preferably from 0.001 to 10 μm. In this specification, the average particle size of the filler can be measured by any method known to those skilled in the art, and can be easily measured, for example, by a laser diffraction particle size distribution measuring device. Specifically, the laser diffraction scattering method is convenient for measuring particle sizes of 0.10 μm or more, and electron microscope observation is convenient for measuring the particle sizes of ultrafine particles of 0.10 μm or less. The 0.10 μm refers to a value measured by the laser diffraction scattering method.

[0097] The laser diffraction scattering method can be performed, for example, by a laser diffraction particle size distribution measuring device (SALD-2300: manufactured by Shimadzu Corporation) using a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.

[0098] Observation with an electron microscope can be performed, for example, by taking a photograph of the particles with a scanning electron microscope (Hitachi, S-4000 model) and measuring the particle diameters of the particles (200 or more) observed within a unit field of view of the photograph using image analysis particle size distribution measurement software (Macview (Mountec Co., Ltd.)). At this time, the particle diameter of the particles is determined as the arithmetic mean value of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

[0099] The content of the filler (E) used in the present invention is not particularly limited, and the content of the filler (E) is preferably 1 to 2000 parts by mass per 100 parts by mass of the total amount of the polymerizable monomer components. Since the suitable content of the filler (E) varies greatly depending on the embodiment in which it is used, the suitable content of the filler (E) according to each embodiment is shown below in conjunction with the description of specific embodiments of the dental adhesive composition of the present invention.

[0100] <Solvent (F)> Depending on the specific embodiment, the dental adhesive composition of the present invention preferably contains a solvent (F). Examples of the solvent include water, an organic solvent, and a mixed solvent thereof.

[0101] When the dental adhesive composition of the present invention contains water, it preferably contains 1 to 2000 parts by mass of water per 100 parts by mass of the total amount of the polymerizable monomer components. Moreover, the water preferably does not contain impurities that may have adverse effects, and distilled water or ion-exchanged water is preferred.

[0102] Examples of organic solvents include alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-methyl-2-propanol; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran, diethyl ether, and diisopropyl ether; non-aromatic hydrocarbon solvents such as hexane and cyclohexane; aromatic hydrocarbon solvents such as toluene; chlorine-based solvents such as chloroform; and ester solvents such as ethyl acetate and butyl acetate. Among these, taking into consideration both safety to the living body and ease of removal based on volatility, it is preferable that the organic solvent is a water-soluble organic solvent, and specifically, ethanol, 2-propanol, 2-methyl-2-propanol, acetone, and tetrahydrofuran are preferred.

[0103] The content of the organic solvent is not particularly limited, and in some embodiments, the organic solvent may not be blended. In the embodiment in which the organic solvent is used, the content of the organic solvent is preferably 1 to 2000 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer components.

[0104] In addition, the dental adhesive composition of the present invention may contain pH adjusters, polymerization inhibitors, ultraviolet absorbers, thickeners, colorants, antibacterial agents, fragrances, etc., within the range that does not impair the effects of the present invention.

[0105] The dental adhesive composition of the present invention has high adhesiveness and can be used, for example, as an adhesive for biological hard tissues, metal materials, organic polymeric materials, ceramics, and the like. The dental adhesive composition can be used for dental materials such as dental primer, dental bonding material, self-adhesive dental composite resin, dental cement (dental resin cement, resin-reinforced glass ionomer cement), pit and fissure sealant, denture base resin, etc., and is preferably used as dental primer, dental bonding material (preferably one-liquid type bonding material), self-adhesive dental composite resin, or dental cement. In this case, the dental adhesive composition may be used as a two-part type in which the components are divided into two.

[0106] Dental Primer The adhesive system for dental materials includes a demineralization process in which the tooth structure is etched with an acidic component, a penetration process in which a polymerizable monomer component penetrates into the tooth structure, and a hardening process in which the penetrated polymerizable monomer component hardens to form a hybrid layer (resin-impregnated layer) with the tooth structure. Basically, the product used in the penetration process is a dental primer. In recent years, dental primers include self-etching primers that combine the demineralizing step and the penetration step in a single step. Since the phosphonic acid compound (A) has a demineralizing effect, a self-etching primer can be formed in the dental adhesive composition of the present invention by using a polymerizable monomer (B) having a penetration effect.

[0107] The dental primer of the present invention can be prepared by replacing a part or all of the acidic group-containing polymerizable monomer of a known dental primer containing an acidic group with a phosphonic acid compound (A). An example of a dental primer composition preferably contains 0.1 to 50 parts by mass of a phosphonic acid compound (A) and 1 to 99.9 parts by mass of a polymerizable monomer (B) relative to a total of 100 parts by mass of the polymerizable monomer components, more preferably contains 0.25 to 30 parts by mass of a phosphonic acid compound (A) and 10 to 99.75 parts by mass of a polymerizable monomer (B), and even more preferably contains 0.5 to 20 parts by mass of a phosphonic acid compound (A) and 10 to 99.5 parts by mass of a polymerizable monomer (B). Furthermore, the dental primer composition more preferably contains 0.001 to 30 parts by mass of a polymerization initiator (C) and 0.001 to 30 parts by mass of a polymerization accelerator (D) relative to 100 parts by mass of the total amount of the polymerizable monomer components, and further preferably contains 0.05 to 20 parts by mass of the polymerization initiator (C) and 0.05 to 20 parts by mass of the polymerization accelerator (D). The dental primer composition preferably contains 6 to 3500 parts by mass, and more preferably 7 to 2000 parts by mass, of the solvent (F) relative to 100 parts by mass of the total amount of the polymerizable monomer components. Furthermore, the dental primer composition may contain 0 to 5 parts by mass of a filler (E) for 100 parts by mass of the total amount of the polymerizable monomer components for the purpose of adjusting the viscosity or the like.

[0108] Dental bonding material The product used in the above hardening process is a dental bonding material. The dental bonding material of the present invention can be prepared by replacing a part or all of the acidic group-containing polymerizable monomer of a known dental bonding material containing an acidic group-containing polymerizable monomer with a phosphonic acid compound (A). An example of a dental bonding composition preferably contains 0.1 to 50 parts by mass of a phosphonic acid compound (A) and 5 to 99.9 parts by mass of a polymerizable monomer (B) in a total of 100 parts by mass of the polymerizable monomer components, and more preferably contains 0.5 to 20 parts by mass of the phosphonic acid compound (A) and 20 to 99.5 parts by mass of the polymerizable monomer (B). Furthermore, the dental bonding composition preferably contains 0.001 to 30 parts by mass of a polymerization initiator (C) and 0.001 to 30 parts by mass of a polymerization accelerator (D) relative to 100 parts by mass of the total amount of the polymerizable monomer components, and more preferably contains 0.05 to 20 parts by mass of the polymerization initiator (C) and 0.05 to 20 parts by mass of the polymerization accelerator (D). The filler (E) is preferably contained in an amount of 0 to 30 parts by mass, and more preferably 0 to 15 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer components. In addition, the dental bonding composition used in combination with the dental primer may contain a solvent (F), but preferably does not substantially contain a solvent (F).

[0109] In recent years, one-step bonding materials have been developed that combine the penetration, demineralization, and hardening processes in a single step. Dental bonding materials are divided into two types: two-component types, in which the two components are mixed just before use, and one-component types, in which one component can be used as is, but the one-component types are currently the mainstream. Since the phosphonic acid compound (A) has a demineralizing effect and a hardening effect, the dental adhesive composition of the present invention can constitute a one-step one-liquid bonding material.

[0110] An example of a one-step, one-liquid bonding material composition preferably contains 0.1 to 50 parts by mass of a phosphonic acid compound (A) and 5 to 99.9 parts by mass of a polymerizable monomer (B) in a total of 100 parts by mass of the polymerizable monomer components, and more preferably contains 0.5 to 20 parts by mass of the phosphonic acid compound (A) and 10 to 99.5 parts by mass of the polymerizable monomer (B). Furthermore, the one-liquid bonding material composition preferably contains 0.001 to 30 parts by mass of a polymerization initiator (C) and 0.001 to 30 parts by mass of a polymerization accelerator (D) relative to 100 parts by mass of the total amount of the polymerizable monomer components, and more preferably contains 0.05 to 20 parts by mass of the polymerization initiator (C) and 0.05 to 20 parts by mass of the polymerization accelerator (D). In addition, the one-component bonding material composition preferably contains 0 to 30 parts by mass of the filler (E) relative to 100 parts by mass of the total amount of the polymerizable monomer components, more preferably 0 to 15 parts by mass, and even more preferably 1 to 15 parts by mass. The one-liquid bonding material composition preferably contains 6 to 2000 parts by mass, and more preferably 7 to 1000 parts by mass, of the solvent (F) relative to 100 parts by mass of the total amount of the polymerizable monomer components.

[0111] Self-adhesive dental composite resin A dental composite resin is a dental treatment material that is usually used in the form of filling a cavity after a cavity is formed by cutting a caries-affected site. Since the phosphonic acid compound (A) has a demineralizing effect, a high hardening effect, and a high calcium binding capacity, it is possible to form a self-adhesive dental composite resin from the dental adhesive composition of the present invention.

[0112] The self-adhesive dental composite resin can be prepared by replacing a part or all of the acidic group-containing polymerizable monomer of a known dental composite resin containing an acidic group with a phosphonic acid compound (A). An example of the composition of the self-adhesive dental composite resin is preferably one that contains 0.1 to 50 parts by mass of a phosphonic acid compound (A) and 10 to 99.9 parts by mass of a polymerizable monomer (B) relative to a total of 100 parts by mass of the polymerizable monomer components, and more preferably one that contains 0.5 to 20 parts by mass of a phosphonic acid compound (A) and 20 to 99.5 parts by mass of a polymerizable monomer (B). Furthermore, the self-adhesive dental composite resin preferably contains 0.001 to 30 parts by mass of a polymerization initiator (C) and 0.001 to 30 parts by mass of a polymerization accelerator (D) relative to 100 parts by mass of the total amount of polymerizable monomer components, and more preferably contains 0.05 to 20 parts by mass of the polymerization initiator (C) and 0.05 to 20 parts by mass of the polymerization accelerator (D). The self-adhesive dental composite resin preferably contains 50 to 3000 parts by mass, and more preferably 80 to 2000 parts by mass, of the filler (E) per 100 parts by mass of the total amount of polymerizable monomer components. The self-adhesive dental composite resin may contain a solvent (F), but preferably does not substantially contain a solvent (F).

[0113] Dental cement is a dental treatment material that is usually used as an adhesive when fixing metal or ceramic dental restoration materials called inlays or crowns to teeth. Since the phosphonic acid compound (A) has a demineralizing effect and a hardening effect, it is also possible to form a self-adhesive dental cement from the dental adhesive composition of the present invention. Dental cements include dental resin cements and resin-reinforced glass ionomer cements.

[0114] The dental cement of the present invention can be prepared by replacing a part or all of the acidic group-containing polymerizable monomer of a known cement containing an acidic group with a phosphonic acid compound (A). An example of a dental resin cement composition preferably contains 0.1 to 50 parts by mass of a phosphonic acid compound (A) and 10 to 99.9 parts by mass of a polymerizable monomer (B) relative to a total of 100 parts by mass of the polymerizable monomer components, and more preferably contains 0.5 to 20 parts by mass of the phosphonic acid compound (A) and 20 to 99.5 parts by mass of the polymerizable monomer (B). Furthermore, the dental resin cement composition preferably contains 0.001 to 30 parts by mass of a polymerization initiator (C) and 0.001 to 30 parts by mass of a polymerization accelerator (D) relative to 100 parts by mass of the total amount of polymerizable monomer components, and more preferably contains 0.05 to 20 parts by mass of the polymerization initiator (C) and 0.05 to 20 parts by mass of the polymerization accelerator (D). The dental resin cement composition preferably contains 50 to 2000 parts by mass, and more preferably 80 to 1000 parts by mass, of the filler (E) per 100 parts by mass of the total amount of the polymerizable monomer components. The dental resin cement composition may contain a solvent (F), but preferably does not substantially contain a solvent (F).

[0115] In the dental resin cement composition, it is preferable to use a chemical polymerization initiator as the polymerization initiator (C), and it is preferable to use amines and / or sulfinic acid and its salts as the polymerization accelerator (D). In terms of storage stability, the dental resin cement composition is preferably a two-component type in which the phosphonic acid compound (A) and the polymerization initiator (C) are stored in separate containers, and the polymerization accelerator (D) is stored in separate containers.

[0116] Glass ionomer cement typically reacts and hardens through an acid-base reaction between an inorganic filler such as fluoroaluminosilicate glass and a polyalkenoic acid such as polyacrylic acid. It is believed that the adhesive function is exerted by the interaction between the polyalkenoic acid and calcium in the hydroxyapatite constituting the tooth substance. An example of a glass ionomer cement composition preferably contains 0.1 to 50 parts by mass of a phosphonic acid compound (A) and 10 to 99.9 parts by mass of a polymerizable monomer (B) relative to a total of 100 parts by mass of the polymerizable monomer components, and more preferably contains 0.5 to 20 parts by mass of the phosphonic acid compound (A) and 20 to 99.5 parts by mass of the polymerizable monomer (B). Furthermore, the glass ionomer cement composition preferably contains 0.001 to 30 parts by mass of a polymerization initiator (C) and 0.001 to 30 parts by mass of a polymerization accelerator (D) per 100 parts by mass of the total amount of polymerizable monomer components, and more preferably contains 0.05 to 20 parts by mass of the polymerization initiator (C) and 0.05 to 20 parts by mass of the polymerization accelerator (D). The glass ionomer cement composition preferably contains 10 to 200 parts by mass of polyalkenoic acid and 50 to 500 parts by mass of fluoroaluminosilicate glass, and more preferably contains 10 to 100 parts by mass of polyalkenoic acid and 80 to 400 parts by mass of fluoroaluminosilicate glass, per 100 parts by mass of the total amount of polymerizable monomer components. The glass ionomer cement composition preferably contains 0 to 2000 parts by mass, and more preferably 10 to 1000 parts by mass, of a filler (E) other than fluoroaluminosilicate glass. The glass ionomer cement composition preferably contains 1 to 500 parts by mass, and more preferably 10 to 50 parts by mass, of the solvent (F) per 100 parts by mass of the total amount of the polymerizable monomer components.

[0117] From the viewpoint of storage stability, the glass ionomer cement composition is preferably a two-component type in which the polyalkenoic acid and the fluoroaluminosilicate glass are stored in separate containers. When the two agents are used separately, the phosphonic acid compound (A) is mixed in the polyalkenoic acid side. It is also preferable to store the polymerization initiator (C) and the polymerization accelerator (D) in separate containers. EXAMPLES

[0118] The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples, and many modifications can be made by those having ordinary skill in the art within the scope of the technical concept of the present invention. First, each component of the dental adhesive compositions prepared in the Examples and Comparative Examples will be described.

[0119] [Phosphonic acid compound (A)]

[0120] A-1: A compound represented by the following formula (hereinafter also referred to as "phosphonic acid compound A-1") [ka]

[0121] A-2: A compound represented by the following formula (hereinafter also referred to as "phosphonic acid compound A-2") [ka]

[0122] A-3: A compound represented by the following formula (hereinafter also referred to as "phosphonic acid compound A-3") [ka]

[0123] [Hydrophilic polymerizable monomer (B-1)] HEMA: 2-hydroxyethyl methacrylate DEAA: N,N-diethylacrylamide

[0124] [Hydrophobic polymerizable monomer (B-2)] Bis-GMA: 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane MAEA: N-methacryloyloxyethyl acrylamide

[0125] [Polymerizable monomer (B-3) having an acidic group other than the phosphonic acid compound (A)]

[0126] B-3-1: A compound represented by the following formula (hereinafter also referred to as "polymerizable monomer B-3-1 having an acidic group") [ka]

[0127] B-3-2: A compound represented by the following formula (hereinafter also referred to as "polymerizable monomer B-3-2 having an acidic group") [ka]

[0128] B-3-3: A compound represented by the following formula (hereinafter also referred to as "polymerizable monomer B-3-3 having an acidic group") [ka]

[0129] MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0130] [Polymerization initiator (C)] CQ: dl-camphorquinone BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide

[0131] [Polymerization accelerator (D)] DABE: Ethyl 4-(N,N-dimethylamino)benzoate DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine

[0132] Filler R972: Aerosil (registered trademark) R972, fine silica particles manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm

[0133] [Solvent (F)] purified water ethanol

[0134] [others] BHT: 2,6-di-t-butyl-4-methylphenol (stabilizer (polymerization inhibitor))

[0135] [Synthesis Example 1: Synthesis of phosphonic acid compound A-1] Step 1: Synthesis of 2-(11-bromoundecyloxy)tetrahydro-2H-pyran Under a nitrogen atmosphere, 11-bromo-1-undecanol (150 g, 597 mmol, 1.0 equivalent), dichloromethane (300 mL), and p-toluenesulfonic acid monohydrate (206 mg, 1.20 mmol, 0.002 equivalent) were mixed, and 3,4-dihydro-2H-pyran (65.8 mL, 776 mmol, 1.3 equivalent) was added dropwise and stirred at room temperature for 3 hours. The reaction solution was concentrated. The obtained crude product was purified by column chromatography (eluent: dichloromethane), and the solvent was then distilled off under reduced pressure using a vacuum pump to obtain 2-(11-bromoundecyloxy)tetrahydro-2H-pyran as a colorless liquid (yield: 189.8 g, 94.8%). The desired compound was obtained as follows: 1 This was determined from H-NMR information. 1 H-NMR (400MHz, CDCl3):4.56(t,1H),3.72-3.89(m,2H),3.35-3.52(m,4H),1.61-1.87(m,8H),1.48-1.58(m,4H),1.21-1.38(m,12H)

[0136] Step 2: Synthesis of diethyl 11-(tetrahydro-2H-pyran-2-yloxy)undecylphosphonate Under a nitrogen atmosphere, 2-(11-bromoundecyloxy)tetrahydro-2H-pyran (210 g, 626 mmol, 1.0 equivalent) and triethyl phosphite (312 g, 1.88 mol, 3.0 equivalent) were mixed and refluxed for 16 hours with stirring. The reaction solution was concentrated. The obtained crude product was purified by column chromatography (eluent: hexane / ethyl acetate = 4 / 1 → 2 / 1 → 0 / 100) to obtain diethyl 11-(tetrahydro-2H-pyran-2-yloxy)undecylphosphonate (318.4 g, yield). 1 This was determined from H-NMR information. 1 H-NMR (400MHz, CDCl3):4.57(t,1H),3.81-4.19(m,8H),1.51-1.84(m,12H),1.24-1.43(m,20H)

[0137] Step 3: Synthesis of diethyl 11-hydroxyundecylphosphonate Under a nitrogen atmosphere, diethyl 11-(tetrahydro-2H-pyran-2-yloxy)undecylphosphonate (318 g, 626 mmol, 1.0 equivalent), ethanol (3.0 L), and p-toluenesulfonic acid monohydrate (11.9 g, 62.6 mmol, 0.10 equivalent) were mixed and stirred at room temperature for 3 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with H2O and a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, filtered, and concentrated. The obtained crude product was purified by column chromatography (eluent: hexane / ethyl acetate = 1 / 3 → 0 / 100 → ethyl acetate / ethanol = 9 / 1) to obtain diethyl 11-hydroxyundecylphosphonate (190.1 g, 98.4%). 1 This was determined from H-NMR information. 1 H-NMR (400MHz, CDCl3):4.04-4.11(m,4H),3.59-3.65(m,2H),2.15(s,1H),1.52-1.79(m,4H),1.26-1.38(m,22H)

[0138] Step 4: Synthesis of phosphonic acid compound A-1 precursor Diethyl 11-hydroxyundecylphosphonate (100 g, 324 mmol, 1.0 equivalent), Karenz (registered trademark) MOI-EG (also known as 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 53.8 g, 270 mmol, 0.833 equivalent), dibutyltin dilaurate (100 mg), and BHT (100 mg) were mixed under an air atmosphere and stirred at 80° C. for 3 hours. The reaction solution was allowed to cool to room temperature, and ethyl acetate and H2O were added and separated. The organic layer was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, filtered, and then concentrated. The obtained crude product was purified by column chromatography (eluent: hexane / ethyl acetate = 4 / 1) to obtain a precursor of phosphonic acid compound A-1 (121.2 g, 73.7%). The obtained compound was confirmed by the following: 1 This was determined from H-NMR information. 1H-NMR (400MHz, CDCl3):6.11(s,1H),5.62(s,1H),4.01-4.28(m,8H),3.70-3.7 5(m,2H),3.49-3.58(m,4H),1.93(s,3H),1.58-1.76(m,4H),1.24-1.34(m,22H)

[0139] Step 5: Synthesis of phosphonic acid compound A-1 Under a nitrogen atmosphere, phosphonic acid compound A-1 precursor (94.9 g, 187 mmol, 1.0 equivalent) and N,N-dimethylformamide (865 mL) were mixed, bromotrimethylsilane (143 g, 934 mmol, 5.0 equivalent) was added dropwise, and the mixture was stirred at room temperature overnight. H2O was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with H2O, dried over anhydrous sodium sulfate, filtered, and then concentrated. The obtained crude product was washed by suspending it in hexane and then in hexane / ethyl acetate = 1 / 1 to obtain a colorless solid phosphonic acid compound A-1 (60.5 g, 71.7%). The obtained compound was confirmed by the following: 1 This was determined from H-NMR information. 1 H-NMR (400MHz, CDCl3):6.12(s,1H),5.61(s,1H)4.21-4.24(m,2H),4.03-4.07(m,2H),3 .70-3.74(m,2H),3.45-3.51(m,4H),1.95(s,3H),1.70-1.79(m,4H),1.26-1.59(m,16H)

[0140] [Synthesis Example 2: Synthesis of phosphonic acid compound A-2] Instead of 11-bromo-1-undecanol described in Synthesis Example 1, 8-bromo-1-octanol was used to carry out the same synthesis procedure as in Synthesis Example 1 to obtain phosphonic acid compound A-2. As in Synthesis Example 1, the target compound was obtained. 1 This was determined from H-NMR information.

[0141] [Synthesis Example 3: Synthesis of phosphonic acid compound A-3] A phosphonic acid compound A-3 was obtained by carrying out the same synthesis procedure as in Synthesis Example 1, except that 5-bromo-1-pentanol was used instead of 11-bromo-1-undecanol described in Synthesis Example 1. 1 H-NMR measurement confirmed that the target compound had been obtained.

[0142] [Synthesis Example 4: Synthesis of polymerizable monomer B-3-1 having an acidic group] The same synthesis procedure as in Synthesis Example 1 was carried out using 2-bromoethanol instead of 11-bromo-1-undecanol, to obtain a polymerizable monomer B-3-1 having an acidic group. 1 H-NMR measurement confirmed that the target compound had been obtained.

[0143] [Synthesis Example 5: Synthesis of polymerizable monomer B-3-2 having an acidic group] The polymerizable monomer B-3-2 having an acidic group was synthesized according to the method described in Example 1 of Patent Document 1 (JP 2014-91692 A), 1 H-NMR measurement confirmed that the target compound had been obtained.

[0144] [Synthesis Example 6: Synthesis of polymerizable monomer B-3-3 having an acidic group] The polymerizable monomer B-3-3 having an acidic group was synthesized according to the method described in Example 1 of Patent Document 2 (JP 2009-46397 A), 1 H-NMR measurement confirmed that the target compound had been obtained.

[0145] Examples 1 to 5 and Comparative Examples 1 to 3 (Preparation of one-component bonding material)

[0146] Among the raw materials shown in Table 1, the ingredients other than the filler and the solvent were mixed first, then the filler was added and mixed, and the solvent was further added to obtain a mixture. The mixture was stirred at room temperature (23°C) in a dark place to make it homogenous, and ultrasonically degassed to prepare a liquid dental adhesive composition. The shear adhesive strength of the obtained dental adhesive composition to bovine tooth enamel was measured according to the following method. The results are shown in Table 1.

[0147] [Shear adhesion test to enamel] The test was conducted in accordance with ISO 29022:2013, specifically: The labial surfaces of bovine teeth were polished with #80 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to obtain samples with exposed flat surfaces of enamel. Tape was applied to the bottom surface of a separately prepared mold having 15 holes (15-hole mold, manufactured by Ultradent, φ35 mm×height 25 mm), and the sample bovine tooth was fixed onto the tape. Next, a resin for dental impression trays (trade name "Tray Resin II", manufactured by Matsufu Co., Ltd.) was filled into the mold and left to stand for about 30 minutes to harden the resin for dental impression trays, thereby obtaining a composite of bovine teeth and hardened resin. The composite was taken out of the mold as a sample. The composite was in a state where the bovine tooth was exposed on the upper surface of the hardened resin. The upper surface of the sample was polished under running water with #600 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) until the size of the surface to be adhered (φ2.38 mm or more) was secured, and the surface to be adhered was washed with ultrasonic waves for 5 minutes.

[0148] Next, the one-liquid bonding material prepared in each Example and Comparative Example was applied to the adhesion surface (surface) of the bovine tooth, and after leaving it for 3 seconds, the water and volatile organic solvent were evaporated with a mild air blower.Then, a dental visible light irradiator (Pencure 2000, Morita Corporation) was used to irradiate for 10 seconds in standard mode to photocure the one-liquid bonding material and prepare the adhesion surface of the sample. A separately prepared φ2.38 mm CR filling mold (Bonding Mold Insert, Ultradent) was attached to a dedicated tool (Bonding Clamp, Ultradent). Next, the CR filling mold attached to the dedicated tool was lowered to fix the sample so that the CR filling mold attached to the dedicated tool was in close contact with the adhesion surface of the sample. Next, a dental filling composite resin (trade name "Clearfil (registered trademark) AP-X", manufactured by Kuraray Noritake Dental Co., Ltd.) was thinly filled into the hole of the CR filling mold so that the thickness was within 1 mm. After that, the dental filling composite resin (trade name "Clearfil (registered trademark) AP-X") was filled again into the CR filling mold (up to about 2 / 3 of the mold, about 2 mm thick), and the dental filling composite resin was cured by irradiating light in standard mode for 20 seconds using a dental visible light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.). The sample was removed from the CR filling mold and used as a test sample for the adhesion test. 20 pieces of each test sample for the adhesion test were prepared. Next, the adhesive test samples were immersed in distilled water in a container and left in an incubator set at 37°C for 24 hours, and the shear adhesive strength of 10 samples was measured immediately after removal from the distilled water (hereinafter also referred to as "initial adhesive strength"). The average value of the measurement results is shown as "initial" in each table. For the remaining 10 samples, in order to evaluate the adhesive durability, a thermal cycle was further carried out 20,000 times, in which each cycle consisted of alternating immersion in cold water at 4°C and hot water at 60°C for 1 minute, and then the shear adhesive strength was measured (hereinafter also referred to as "adhesive strength after thermal cycle"). The adhesive strength (shear adhesive strength) was measured by attaching the adhesive test sample to a dedicated holder (Test Base Clamp, Ultradent) and using a dedicated tool (Crosshead Assembly, Ultradent) and a universal testing machine (Shimadzu Corporation) with the crosshead speed set to 1 mm / min. The average values ​​are shown in the table (n=10).

[0149] Using the initial adhesive strength and the adhesive strength after thermal cycling obtained by the above method, the adhesive strength retention was calculated according to the following formula. Adhesive strength retention (%) = (Adhesive strength after thermal cycling (MPa) / Initial adhesive strength (MPa)) x 100

[0150] The retention of adhesive strength of the dental adhesive composition of the present invention to enamel is preferably 75% or more, more preferably 80% or more, and even more preferably 85% or more.

[0151] [Table 1]

[0152] As shown in Table 1, the one-component bonding materials (Examples 1 to 5), which are dental adhesive compositions according to the present invention, exhibit a high initial adhesive strength of 23 MPa or more to enamel, and furthermore, the adhesive strengths to enamel after thermal cycling under the strict conditions of 20,000 thermal cycles are all 18 MPa or more. These results demonstrated high adhesive durability, with adhesive strength to enamel retained at 75% or more after thermal cycling.

[0153] On the other hand, the one-component bonding materials (Comparative Examples 1 to 3) containing a polymerizable monomer having an acidic group other than the phosphonic acid compound (A) had a certain degree of initial adhesive strength to enamel, but the adhesive durability after thermal cycling was all 14 MPa or less, and the adhesive strength retention rate was 64% or less. The polymerizable monomer B-3-1 having an acidic group used in Comparative Example 1 is the compound used in the examples of Patent Document 3 (International Publication No. 2020 / 046654), the polymerizable monomer B-3-2 having an acidic group used in Comparative Example 2 is the compound used in Example 1 of Patent Document 1 (JP Patent Publication No. 2014-91692), and the polymerizable monomer B-3-3 having an acidic group used in Comparative Example 3 is the compound used in Example 1 of Patent Document 2 (JP Patent Publication No. 2009-46397). Therefore, it was confirmed that the conventional techniques did not provide high adhesion durability to enamel under harsh conditions. In contrast, the dental adhesive composition of the present invention, even when used as a one-component bonding material, has been confirmed to provide high adhesive durability to enamel in conditions where the adhesive properties of the components are difficult to exhibit due to the lack of pretreatment such as a self-etching primer and the fact that the composition as a dental product is somewhat limited, and in extremely harsh oral environments such as exposure to severe temperature changes and large amounts of moisture. Therefore, the phosphonic acid compound of the present invention is useful for dental treatment applications (e.g., filling and restoring materials, bonding materials, adhesives, etc.), and is particularly useful as a dental bonding material (more preferably a one-component bonding material). [Industrial Applicability]

[0154] The dental adhesive composition containing the phosphonic acid compound of the present invention can be used for various dental treatment applications requiring adhesiveness and adhesive durability (e.g., filling and restoring materials, bonding materials, adhesives, etc.), and is particularly useful as a dental bonding material.

Claims

1. A phosphonic acid compound (A) represented by the following general formula (1): [Formula 1] (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 are each independently a hydrogen atom , a hydrocarbon group having 1 to 6 carbon atoms, or a metal atom; Z represents an oxygen atom or a sulfur atom; Y represents one selected from the group consisting of -O-, -S-, and -NH-; n represents an integer of 2 to 4; and m represents an integer of 3 to 18.

2. The phosphonic acid compound (A) according to claim 1, wherein m is an integer of 5 to 16.

3. R 1 The phosphonic acid compound (A) according to claim 1 or 2, wherein is a methyl group.

4. R 2 and R 3 The phosphonic acid compound (A) according to claim 1 or 2, wherein is a hydrogen atom.

5. A dental adhesive composition comprising a phosphonic acid compound (A) represented by the following general formula (1): [chemical 2] (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 are each independently a hydrogen atom , a hydrocarbon group having 1 to 6 carbon atoms, or a metal atom; Z represents an oxygen atom or a sulfur atom; Y represents one selected from the group consisting of -O-, -S-, and -NH-; n represents an integer of 2 to 4; and m represents an integer of 3 to 18.

6. 6. The dental adhesive composition according to claim 5, wherein m in the phosphonic acid compound (A) is an integer of 5 to 16.

7. R of the phosphonic acid compound (A) 1 The dental composition according to claim 5 or 6, wherein Adhesive composition.

8. R 2 and R 3 The dental adhesive composition according to claim 5 or 6, wherein is a hydrogen atom.

9. 7. The dental adhesive composition according to claim 5, further comprising a polymerizable monomer (B) copolymerizable with the phosphonic acid compound (A).

10. 10. The dental adhesive composition according to claim 9, wherein the polymerizable monomer (B) contains a hydrophilic polymerizable monomer (B-1).

11. The dental adhesive composition according to claim 5 or 6, further comprising a polymerization initiator (C).

12. The dental adhesive composition according to claim 5 or 6, further comprising a filler (E).

13. The dental adhesive composition according to claim 5 or 6, further comprising a solvent (F).

14. A dental bonding material comprising the dental adhesive composition according to claim 5 or 6.

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