Dental bonding kit

Abstract

To provide a dental adhesive kit with excellent adhesive strength to hardened MTA cement immediately after curing of a self-adhesive dental composite resin by light irradiation.SOLUTION: Provided is a dental adhesive kit, comprising: one material-type self-adhesive dental composite resin (X) containing a monomer (a) having an alkyl or alkylene group having 8 to 16 carbon atoms as a main chain and a divalent phosphoric acid group in a molecule, a monomer (b) having no acidic group, a photoinitiator (c), and a filler (d); and a dental cement composition (Y) containing a portland cement powder (e), and an inorganic filler (f), the content of the portland cement powder (e) being 60 to 90 mass%, the content of the inorganic filler (f) being 10 to 40 mass%, and the flexural modulus of the hardened product obtained by photocuring the self-adhesive dental composite resin (X) being in the range of 1.5 to 6 GPa.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a dental adhesive kit comprising a one-paste type self-adhesive dental composite resin and a dental cement composition. More specifically, the present invention relates to a dental adhesive kit comprising a one-paste type self-adhesive dental composite resin and a dental cement composition, which has excellent adhesive strength to an MTA cement cured product immediately after curing of the self-adhesive dental composite resin by light irradiation.

Background Art

[0002] In recent years, a dental Portland cement called MTA (Mineral Trioxide Aggregate), which is said to have the ability to induce hard tissues, has been commercially available and has begun to be used for diseases of the dental pulp and periapical periodontal tissues.

[0003] Materials such as MTA are produced by micronizing Portland cement used in concrete etc. for dental use and adding inorganic substances having radiopacity such as bismuth oxide so that they can be used in the oral cavity, and are cured by a hydration reaction by kneading with water.

[0004] MTA cement, which cures even in a wet environment where blood oozes out, such as a perforation part of a root canal, has good sealing properties, biocompatibility, calcification promoting action, and antibacterial properties due to strong alkalinity. Therefore, by using MTA cement, it is possible to preserve the nerve even in cases where it was previously necessary to remove the nerve, and it is used in various cases including direct pulp capping (Non-Patent Document 1).

[0005] Since the curing time after kneading of MTA cement is long and it takes several hours to obtain sufficient strength, it is known to fill glass ionomer cement, resin-added glass ionomer cement, dental composite resin, etc. after the MTA cement is completely cured (Non-Patent Documents 2, 3).

[0006] In recent years, self-adhesive dental composite resins have been developed that provide adhesive properties to dental composite resins, and are beginning to be put into practical use as materials that reduce the number of steps in restorative treatment by eliminating the need for dental adhesives. Self-adhesive dental composite resins contain not only the components of conventional dental composite resins, such as polyfunctional polymerizable monomers and fillers to provide mechanical strength and polymerization initiators to improve curability, but also polymerizable monomers with acidic groups that have been conventionally used in dental adhesives to provide adhesion to tooth structure (Patent Documents 1-5, Non-Patent Document 4). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2008-260752 [Patent Document 2] Japanese Patent Publication No. 2017-105716 [Patent Document 3] Japanese Patent Publication No. 2018-065831 [Patent Document 4] U.S. Patent Application Publication No. 2010041786 [Patent Document 5] U.S. Patent Application Publication No. 2011217677 [Non-patent literature]

[0008] [Non-Patent Document 1] Dental World Outlook, 2011, Vol. 118, No. 6, pages 1132-1133 [Non-Patent Document 2] Journal of Endodontics Volume 40, Issue 8, 2014, Pages 1210-1216 [Non-Patent Document 3] Journal of Conservative Dentistry Volume 19, Issue 3, 2016, Pages 254-258 [Non-Patent Document 4] Journal of Conservative Dentistry Volume 19, Issue 2, 2016, Pages 130-133 [Overview of the project] [Problems that the invention aims to solve]

[0009] Non-patent document 2 describes the adhesion of bond / composite resin to MTA cement hardened material. However, our own research has shown that although the adhesion to tooth structure is excellent, there is room for improvement in the adhesion of composite resin to hardened MTA cement immediately after hardening.

[0010] Furthermore, it was found that there is room for improvement in the adhesion of glass ionomer cement and resin-added glass ionomer cement to MTA cement cured products immediately after curing, as described in Non-Patent Literature 3.

[0011] Furthermore, the self-adhesive dental composite resins described in Patent Documents 1-5 and Non-Patent Document 4 could potentially be repurposed as a substitute for dental composite resin after MTA cement filling. However, our investigations have revealed that all of the aforementioned self-adhesive dental composite resins have room for improvement in their adhesion to hardened MTA cement. In particular, the adhesive strength of the self-adhesive dental composite resin to hardened MTA cement immediately after hardening by light irradiation has been found to have room for improvement from a practical standpoint, considering dental treatment using MTA cement in dental clinics.

[0012] The present invention aims to provide a dental adhesive kit that exhibits excellent adhesive strength to MTA cement cured material immediately after the curing of self-adhesive dental composite resin by light irradiation. [Means for solving the problem]

[0013] As a result of diligent research, the inventors discovered that a dental adhesive kit comprising a one-component self-adhesive dental composite resin of a specific composition and an MTA cement of a specific composition could solve the above problems, and further research led to the completion of the present invention.

[0014] In other words, the present invention encompasses the following inventions. [1] A one-component self-adhesive dental composite resin (X) comprising a monomer (a) having an alkyl or alkylene group with 8 to 16 carbon atoms as a main chain and having a divalent phosphate group, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d), A dental cement composition (Y) comprising Portland cement powder (e) and an inorganic filler (f) is provided. The Portland cement powder (e) has a content of 60-90% by mass, and the inorganic filler (f) has a content of 10-40% by mass. A dental adhesive kit in which the self-adhesive dental composite resin (X) is light-cured, and the cured product has a flexural modulus in the range of 1.5 to 6 GPa. [2] The dental adhesive kit according to [1], wherein the content of the filler (d) is 50 parts by mass or more in 100 parts by mass of the total amount of the self-adhesive dental composite resin (X). [3] Filler (d) is a filler (d-ii) with an average particle size of 0.1 μm or more and 1 μm or less. ) and / or fillers (d-iii) with an average particle size greater than 1 μm and less than or equal to 10 μm, [2] The dental adhesive kit described. [4] The filler (d-ii) and / or the filler (d-iii) contains silicon atoms A dental adhesive kit according to [3], comprising an inorganic filler composed of an inorganic filler and / or an oxide of silicon atoms, wherein the inorganic filler has hydroxyl groups on its surface, and the hydroxyl groups are surface-treated with a surface treatment agent. [5] Filler (d) is a filler (di) with an average particle size of 1 nm or more and less than 0.1 μm. (I) A combination of filler (d-ii) with an average particle size of 0.1 μm or more and 1 μm or less, and filler (di) with an average particle size of 1 nm or more and less than 0.1 μm, and filler with an average particle size greater than 1 μm Combination with filler (d-iii) of 0 μm or less (II), average particle size 1 nm or more 0.1 Fillers smaller than μm (di) and fillers with an average particle size of 0.1 μm or more and 1 μm or less (d A dental adhesive kit according to any one of [2] to [4], comprising at least one combination selected from the group consisting of (III) a combination of -ii) and a filler with an average particle size of more than 1 μm and 10 μm or less (d-iii), and (IV) two fillers with an average particle size of 0.1 μm or more and 1 μm or less (d-ii). [6] Portland cement powder (e) has the following composition Calcium oxide (CaO): 55-85% by mass, Silicon dioxide (SiO2): 10-40% by mass, Aluminum oxide (Al2O3): 0-15% by mass, and Iron oxide (Fe2O3): 0-10% by mass, A dental adhesive kit having one of the features described in any of [1] to [5]. [7] A dental adhesive kit according to any one of [1] to [6], wherein the inorganic filler (f) is at least one selected from the group consisting of silica-based fillers, alumina fillers, and zirconia fillers. [Effects of the Invention]

[0015] According to the present invention, a dental adhesive kit can be provided that exhibits excellent adhesive strength to MTA cement cured material immediately after the curing of self-adhesive dental composite resin by light irradiation. [Modes for carrying out the invention]

[0016] The following describes preferred embodiments of the dental adhesive kit according to the present invention. However, the present invention is not limited in any way to the embodiments described below.

[0017] The dental adhesive kit according to this embodiment comprises a one-component self-adhesive dental composite resin (X) containing a monomer (a) having an alkyl or alkylene group with 8 to 16 carbon atoms as a main chain in the molecule and having a divalent phosphate group, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d); and a dental cement composition (Y) containing Portland cement powder (e) and an inorganic filler (f), wherein the content of the Portland cement powder (e) is 60 to 90% by mass, the content of the inorganic filler (f) is 10 to 40% by mass, and the flexural modulus of the cured product obtained by photocuring the self-adhesive dental composite resin (X) is in the range of 1.5 to 6 GPa.

[0018] In this specification, "(meth)acrylic" is a general term for methacrylic and acrylic, and the same applies to similar expressions ("(meth)acrylic acid," "(meth)acrylonitrile," etc.). In this specification, the upper and lower limits of numerical ranges (content of each component, values ​​calculated from each component, and physical properties, etc.) can be combined as appropriate.

[0019] The self-adhesive dental composite resin (X) of the present invention (hereinafter sometimes simply referred to as "self-adhesive dental composite resin (X)") is a dental cement composition ( From the viewpoint of adhesion to the cured product of Y) (hereinafter sometimes referred to as "MTA cement cured product"), the flexural modulus of the light-cured product is in the range of 1.5 to 6 GPa, preferably in the range of 2 to 6 GPa, more preferably in the range of 2.5 to 6 GPa, and even more preferably in the range of 3 to 6 GPa, as it provides superior adhesive strength to the MTA cement cured product immediately after the self-adhesive dental composite resin is cured by light irradiation. The method for measuring the flexural modulus of the cured product is as described in the examples below. If the flexural modulus of the cured product of the self-adhesive dental composite resin (X) is less than 1.5 GPa, the mechanical strength of the cured product is insufficient. Also, if the flexural modulus of the cured product of the self-adhesive dental composite resin (X) exceeds 6 GPa, delamination is likely to occur at the interface with the dental cement (Y) cured product. As a result, the adhesion to the MTA cement cured product immediately after the self-adhesive dental composite resin is cured by light irradiation (hereinafter sometimes referred to as "immediately after light curing") is reduced.

[0020] Although the mechanism by which the dental adhesive kit of the present invention achieves its effects is not clear, it is presumed to be as follows: When a self-adhesive dental composite resin with a high flexural modulus is bonded to a low-strength MTA cement cured material, stress concentrates at the adhesive interface with the MTA cement cured material immediately after light curing, making it impossible to stably obtain the adhesive strength of the self-adhesive dental composite resin immediately after curing. On the other hand, by selecting an appropriate flexural modulus of the self-adhesive dental composite resin and combining it with other components, stress concentration at the MTA cement cured material interface is alleviated, and it is presumed that the self-adhesive dental composite resin exhibits excellent adhesive strength to the MTA cement cured material even immediately after light curing.

[0021] The following describes each component used in the dental adhesive kit of the present invention.

[0022] • One-component self-adhesive dental composite resin (X) The composition of the self-adhesive dental composite resin (X) of the present invention comprises a monomer (a) having an alkyl or alkylene group with 8 to 16 carbon atoms as a main chain and a divalent phosphate group in the molecule, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d).

[0023] <A monomer (a) having an alkyl or alkylene group with 8 to 16 carbon atoms as the main chain within the molecule, and having a divalent phosphate group> The monomer (a) used in the present invention, which has an alkyl or alkylene group with 8 to 16 carbon atoms as a main chain and a divalent phosphate group (hereinafter referred to as "phosphate group-containing monomer (a)"), can be used individually or in appropriate combinations of two or more types. Because the self-adhesive dental composite resin (X) of the present invention contains a phosphate group-containing monomer (a), in addition to having a phosphate group, the structure of the long-chain spacer in the main chain of the phosphate group-containing monomer (a) results in a cured product with superior water resistance when combined with other components. This allows for better adhesion to MTA cement cured products even immediately after light curing of the self-adhesive dental composite resin under the harsh conditions of a humid oral cavity. The number of carbon atoms in the phosphate group-containing monomer (a) is preferably 8 to 12. Specific examples of the phosphate group-containing monomer (a) are given below.

[0024] Examples of monomers (a) having a phosphate group include 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxidedecyl dihydrogen phosphate, 13-(meth)acryloyloxytridecyl dihydrogen phosphate, and 14-(meth)acryloy Examples include oxytetradecyl dihydrogen phosphate, 15-(meth)acryloyloxypentadecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, and their acid chlorides, alkali metal salts, and amine salts.

[0025] Among the monomers (a) having a phosphate group as described above, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and 11-(meth)acryloyloxyundecyl dihydrogen phosphate are selected from the viewpoint of good adhesion strength to tooth structure, adhesion strength to MTA cement cured material immediately after light curing of self-adhesive dental composite resin, and water resistance of the cured material. Hydrogen phosphate and 12-(meth)acryloyl oxide decyl dihydrogen phosphate are preferred, 8-(meth)acryloyl oxyoctyl dihydrogen phosphate, 9-(meth)acryloyl oxynonyl dihydrogen phosphate, and 10-(meth)acryloyl oxydecyl dihydrogen phosphate are more preferred, and 10-(meth)acryloyl oxydecyl dihydrogen phosphate is even more preferred from the viewpoint of balance with curability.

[0026] The content of monomer (a) having a phosphate group is preferably 1 to 40 parts by mass, more preferably 2.5 to 35 parts by mass, and even more preferably 5 to 30 parts by mass, based on 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X), from the viewpoint of good adhesion strength to tooth structure, adhesion strength to MTA cement cured product immediately after light curing of self-adhesive dental composite resin, and water resistance of the cured product.

[0027] The self-adhesive dental composite resin (X) in the present invention may contain monomers having acidic groups other than monomer (a) having a phosphate group. In one embodiment, a dental adhesive kit is provided in which the self-adhesive dental composite resin (X) substantially does not contain monomers having acidic groups other than monomer (a) having a phosphate group. In this specification, examples of acidic groups of monomers having acidic groups other than monomer (a) having a phosphate group include phosphate groups, pyrophosphate groups, thiophosphate groups, phosphonic acid groups, carboxylic acid groups, sulfonic acid groups, and the like.

[0028] <Monomer without acidic groups (b)> Examples of monomers (b) that do not have acidic groups include asymmetric acrylamide-methacrylate ester compounds (b-1); hydrophobic monomers (b-2) that do not have acidic groups and have a solubility in water at 25°C of less than 10% by mass (hereinafter sometimes simply referred to as "hydrophobic monomer (b-2)"); and hydrophilic monomers (b-3) that do not have acidic groups and have a solubility in water at 25°C of 10% by mass or more (hereinafter sometimes simply referred to as "hydrophilic monomer (b-3)"). One type of monomer (b) that does not have acidic groups may be used alone, or two or more types may be used in combination. In the present invention, compounds that do not have an acidic group and contain an acrylamide group and a methacryloyloxy group are defined as asymmetric acrylamide-methacrylate compounds (b-1), and compounds that do not have an acidic group and are not included in asymmetric acrylamide-methacrylate compounds (b-1) are divided into hydrophobic monomers (b-2) and hydrophilic monomers (b-3) according to their degree of hydrophilicity.

[0029] • Asymmetric acrylamide-methacrylate ester compound (b-1) One preferred embodiment is a self-adhesive dental composite resin (X) further comprising an asymmetric acrylamide-methacrylate compound (b-1). The asymmetric acrylamide-methacrylate compound (b-1) improves the adhesion of the self-adhesive dental composite resin (X) to tooth structure, and the adhesion of the self-adhesive dental composite resin to MTA cement curing immediately after light curing, and therefore... It is preferable that the compound is represented by the general formula (1).

[0030] [ka] In the formula, Z is a C1-C8 linear or branched aliphatic or aromatic group which may have substituents, and the aliphatic group is -O-, -S-, -CO-, -CO-O-, -O-CO-, -NR 1 -,-CO-NR 1 -, -NR 1 -CO-, -CO-O-NR 1 -, -O-CO-NR 1 - and -NR 1 -CO-NR 1 - At least one bond selected from the group consisting of It may be interrupted by the base. 1 This represents a linear or branched aliphatic group of C1 to C8, which may have a hydrogen atom or substituents.

[0031] Z is a site for adjusting the hydrophilicity of the asymmetric acrylamide·methacrylic acid ester compound (b-1). The C1-C8 aliphatic group which may have a substituent represented by Z may be either a saturated aliphatic group (alkylene group, cycloalkylene group (for example, 1,4-cyclohexylene group, etc.)) or an unsaturated aliphatic group (alkenylene group, alkynylene group), and from the viewpoints of ease of availability or production and chemical stability, it is preferably a saturated aliphatic group (alkylene group). Z is preferably a linear or branched C1-C4 aliphatic group which may have a substituent, and more preferably a linear or branched C2-C4 aliphatic group which may have a substituent, from the viewpoints of adhesiveness to dentin, adhesiveness to the cured product of MTA cement immediately after photo-curing of the self-adhesive dental composite resin, and polymerization curability. As the aliphatic group, an alkylene group is preferable. Examples of the C1-C8 alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, etc.

[0032] Examples of the aromatic group which may have a substituent represented by Z include an arylene group and an aromatic heterocyclic group. As the aromatic group, an arylene group is more preferable than an aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocyclic ring is preferably a 5-membered ring or a 6-membered ring. As the arylene group, for example, a phenylene group is preferable. Examples of the heterocyclic ring of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a triazole ring, a pyran ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring. Among the above aromatic groups, a phenylene group is particularly preferable.

[0033] R 1 The aliphatic group in It may be either a kenyl group or an alkynyl group, but a saturated aliphatic group (alkyl group) is preferred from the viewpoint of ease of acquisition or manufacture and chemical stability. 1 The straight lines of C1 to C8 in Examples of alkyl groups in the chain or branched chain include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, tert-pentyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 2-ethylbutyl group, with methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group being preferred.

[0034] R 1 More preferably, linear or branched C1-C4 alkyl groups may have hydrogen atoms or substituents, and linear or branched alkyl groups may have hydrogen atoms or substituents. A branched C1-C3 alkyl group is more preferable.

[0035] When the aliphatic group of Z is interrupted by the bonding group, the number of bonding groups is not particularly limited, but may be around 1 to 10, preferably 1, 2, or 3, and more preferably 1 or 2. Furthermore, in formula (1), it is preferable that the aliphatic group of Z is not interrupted by consecutive bonding groups. That is, it is preferable that the bonding groups are not adjacent to each other. As bonding groups, at least one bonding group selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH-, -CO-NH-, -NH-CO-, -CO-O-NH-, -O-CO-NH-, and -NH-CO-NH- is more preferable, and at least one bonding group selected from the group consisting of -O-, -S-, -CO-, -NH-, -CO-NH-, and -NH-CO- is particularly preferable.

[0036] Substituents in Z include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), carboxyl groups, linear or branched acyl groups of C2 to C6, linear or branched alkyl groups of C1 to C6, and linear or branched alkoxy groups of C1 to C6.

[0037] Specific examples of asymmetric acrylamide-methacrylate compounds (b-1) are not limited to the following:

[0038] [ka]

[0039] Among these, asymmetric acrylamide / methacrylate ester compounds in which Z is a linear or branched aliphatic group of C2-C4 which may have substituents are preferred from the viewpoint of adhesion to tooth structure, adhesion to MTA cement cured product immediately after light curing of self-adhesive dental composite resin, and polymerization curing properties. More preferably, N-methacryloyloxyethyl acrylamide (commonly known as "MAEA"), N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl) acrylamide, and N-(2-(2-methacryloyloxyethoxy)ethyl) acrylamide are preferred, and MAEA and N-methacryloyloxypropyl acrylamide are even more preferred from the viewpoint of high hydrophilicity involved in penetration into the collagen layer of dentin.

[0040] The asymmetric acrylamide / methacrylate compound (b-1) may be formulated alone or in combination of two or more types. The content is not particularly limited as long as it achieves the effects of the present invention, but in the self-adhesive dental composite resin (X) of the present invention, the content is preferably 1 to 60 parts by mass, more preferably 2 to 45 parts by mass, even more preferably 3 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass, based on a total amount of monomers of 100 parts by mass.

[0041] • Hydrophobic monomers that do not have acidic groups (b-2) Hydrophobic monomers (b-2) that do not have acidic groups improve the handling properties and mechanical strength of self-adhesive dental composite resins (X). Hydrophobic monomers (b-2) that do not have acidic groups but have polymerizable groups are preferred, and from the viewpoint of easy radical polymerization, the polymerizable groups are preferably (meth)acrylic groups and / or (meth)acrylamide groups. Hydrophilic monomers (b-2) refer to monomers that do not have acidic groups, do not correspond to asymmetric acrylamide / methacrylate ester compounds (b-1), and have a solubility in water at 25°C of less than 10% by mass. Examples of hydrophobic monomers (b-2) include crosslinkable monomers such as difunctional monomers of aromatic compounds, difunctional monomers of aliphatic compounds, and monomers with three or more functions.

[0042] Examples of bifunctional monomers of aromatic compounds include the following general formula (2): [ka] (In the formula, R 12 and R 13 R is a hydrogen atom or a methyl group, 14 and R 15 Each of these is independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; s, t, u, and v are integers from 0 to 6; and p and q are integers from 0 to 8, which may be the same or different from each other. Examples include aromatic di(meth)acrylates represented by .Specific examples of bifunctional monomers of aromatic compounds include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 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)acryloyloxytetraethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxypentaethoxy Examples include phenyl)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. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (with an average number of added ethoxy groups of 2.6, commonly known as "D-2.6E"), 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis (4-(meth)acryloyloxytetraethoxyphenyl)propane and 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane are preferred.

[0043] Examples of aliphatic compound-based difunctional monomers include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and propylene glycol di Examples include (meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)di(meth)acrylate. Among these, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as "3G"), neopentyl glycol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), 1,10-decanediol dimethacrylate (commonly known as "DD"), and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate are preferred.

[0044] Examples of monomers with three or more functionalities include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth)acrylate, and 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane. Among these, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.

[0045] Among the hydrophobic monomers (b-2) described above, aromatic compound-based difunctional monomers and aliphatic compound-based difunctional monomers are preferred in terms of the mechanical strength and handling properties of the cured product. Preferred aromatic compound-based difunctional monomers are Bis-GMA and D-2.6E. Preferred aliphatic compound-based difunctional monomers are glycerol di(meth)acrylate, 3G, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, DD, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, and UDMA.

[0046] Among the hydrophobic monomers (b-2) described above, Bis-GMA, D-2.6E, 3G, UDMA, and DD are more preferred, and D-2.6E, 3G, and Bis-GMA are even more preferred, from the viewpoint of good adhesion to tooth structure when used as a self-adhesive dental composite resin (X) and good adhesion to MTA cement cured material immediately after light curing of the self-adhesive dental composite resin.

[0047] Hydrophobic monomer (b-2) may be included alone or in combination of two or more types. Content of hydrophobic monomer (b-2) in self-adhesive dental composite resin (X) In the self-adhesive dental composite resin (X), the amount of the monomer is preferably 20 to 99 parts by mass, more preferably 40 to 95 parts by mass, and even more preferably 60 to 95 parts by mass, based on the total amount of monomers per 100 parts by mass. When the content of hydrophobic monomer (b-2) is below the upper limit, it is easier to suppress the decrease in wettability of the self-adhesive dental composite resin (X) to the tooth structure and the resulting decrease in adhesion. When the content is above the lower limit, the adhesion to the MTA cement cured product immediately after light curing of the self-adhesive dental composite resin is excellent, and the desired mechanical strength of the cured product is easily obtained.

[0048] • Hydrophilic monomers that do not have acidic groups (b-3) The self-adhesive dental composite resin (X) of the present invention preferably contains a hydrophilic monomer (b-3) that does not have an acidic group. The hydrophilic monomer (b-3) improves the wettability of the self-adhesive dental composite resin (X) to tooth structure. As the hydrophilic monomer (b-3), a radical monomer that does not have an acidic group but has a polymerizable group is preferred, and from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. The hydrophilic monomer (b-3) means that it does not have an acidic group, does not correspond to an asymmetric acrylamide / methacrylic acid ester compound (b1), and has a solubility in water at 25°C of 10% by mass or more, preferably 30% by mass or more, and more preferably soluble in water at 25°C in any proportion. As the hydrophilic monomer, those having hydrophilic groups such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, or an amide group are preferred. Examples of hydrophilic monomers (b-3) 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, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, and polyethylene glycol di(meth)acrylate (those with 9 or more oxyethylene groups); N-Me Examples include hydrophilic monofunctional (meth)acrylamide monomers such as tyrol(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.

[0049] Among these hydrophilic monomers (b-3), 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and hydrophilic monofunctional (meth)acrylamide monomers are preferred from the viewpoint of adhesion to tooth structure and adhesion to MTA cement cured material immediately after light curing of self-adhesive dental composite resins, with 2-hydroxyethyl (meth)acrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide being more preferred. Hydrophilic monomers (b-3) may be formulated individually or in combination of two or more.

[0050] The hydrophilic monomer (b-3) content in the self-adhesive dental composite resin (X) is preferably in the range of 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and even more preferably 0 to 30 parts by mass, based on 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). The hydrophilic monomer (b-3) content may be 0 parts by mass, based on 100 parts by mass of the total amount of monomers. When the hydrophilic monomer (b-3) content in the self-adhesive dental composite resin (X) of the present invention is above the lower limit, a sufficient improvement in adhesion to the MTA cement cured product immediately after light curing of the self-adhesive dental composite resin is easily obtained, and when it is below the upper limit, the desired mechanical strength of the cured product is easily obtained.

[0051] In the self-adhesive dental composite resin (X), the content of monomers (b) that do not have acidic groups is preferably 50 to 99 parts by mass, more preferably 60 to 97 parts by mass, and even more preferably 70 to 95 parts by mass, based on 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). Furthermore, from the viewpoint of adhesion to tooth structure, the mass ratio ((b-2):(b-3)) of hydrophobic monomers (b-2):(b-3) is preferably 10:0 to 1:2, more preferably 10:0 to 1:1, and even more preferably 10:0 to 2:1.

[0052] One preferred embodiment is a self-adhesive dental composite resin (X) that substantially does not contain bifunctional or higher (meth)acrylamide monomers. Another preferred embodiment is a self-adhesive dental composite resin (X) that substantially does not contain trifunctional or higher (meth)acrylamide monomers. In the present invention, "substantially free of a certain polymerizable compound" means that the content of the polymerizable compound is less than 0.5 parts by mass, preferably less than 0.1 parts by mass, more preferably less than 0.01 parts by mass, and may be 0 parts by mass, based on 100 parts by mass of the total amount of polymerizable compounds contained in the composition of the self-adhesive dental composite resin (X). Furthermore, the content of the substantially free polymerizable compound may be less than 0.5% by mass or less than 0.1% by mass in the entire composition. Furthermore, in the present invention, "consisting substantially of only a certain specific component" means that it substantially does not contain any other components other than the specific component. For example, the content of other components besides the specific component is preferably less than 5.0% by mass, more preferably less than 1.0% by mass, even more preferably less than 0.5% by mass, and particularly preferably less than 0.1% by mass.

[0053] Another preferred embodiment is a self-adhesive dental composite resin (X) that is substantially free of (meth)acrylic block copolymers. The molecular weight distribution (weight-average molecular weight / number-average molecular weight) of the (meth)acrylic block copolymer is, for example, 1. The molecular weight may be between 0.2 and 2.00. The molecular weight distribution can be measured by known methods, for example, by gel permeation chromatography (GPC), and calculated as a value on a standard polystyrene basis. The (meth)acrylic block copolymer may be bifunctional or tetrafunctional or tetrafunctional.

[0054] <Photopolymerization initiator (c)> Photopolymerization initiators (c) are classified into water-soluble photopolymerization initiators (c-1) and water-insoluble photopolymerization initiators (c-2). As for the photopolymerization initiator (c), only a water-soluble photopolymerization initiator (c-1) may be used, only a water-insoluble photopolymerization initiator (c-2) may be used, or a combination of a water-soluble photopolymerization initiator (c-1) and a water-insoluble photopolymerization initiator (c-2) may be used, but a combination is preferred.

[0055] • Water-soluble photopolymerization initiator (c-1) The water-soluble photopolymerization initiator (c-1) improves polymerization curing at hydrophilic tooth surface interfaces, enabling high adhesive strength. The water-soluble photopolymerization initiator (c-1) has a solubility in water at 25°C of 10 g / L or more, preferably 15 g / L or more, more preferably 20 g / L or more, and even more preferably 25 g / L or more. A solubility of 10 g / L or more allows the water-soluble photopolymerization initiator (c-1) to dissolve sufficiently in the water in the tooth structure at the adhesive interface, making it easier for the polymerization-promoting effect to manifest.

[0056] Examples of water-soluble photopolymerization initiators (c-1) include water-soluble thioxanthones, water-soluble acylphosphine oxides, and (poly)ethylene glycosides to the hydroxyl group of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one. A polyethylene glycol chain has been introduced to the hydroxyl group and / or phenyl group of 1-hydroxycyclohexyl phenyl ketone, and a polyethylene glycol chain has been introduced to the phenyl group of 1-hydroxycyclohexyl phenyl ketone. - Na + A version that incorporates 2-hydro Xy-2-methyl-1-phenylpropan-1-one with (poly)ethylene glycol chains introduced to the hydroxyl group and / or phenyl group, and 2-hydroxy-2-methyl-1-phenylpropan-1-one with -OCH2COO - Na + Alpha- Examples include hydroxyalkylacetophenones; α-aminoalkylphenones such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-(dimethylamino)-1-[(4-morpholino)phenyl]-1-butanone, which have their amino groups quaternarily ammonium-chlorinated.

[0057] Examples of the water-soluble thioxanthones include 2-hydroxy-3-(9-oxo-9H-thioxanthene-4-yloxy)-N,N,N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3-(1-methyl-9-oxo-9H-thioxanthene-4-yloxy)-N,N,N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3-(9-oxo-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propaneaminium chloride, 2- Hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthene-2-yloxy)-N,N,N-trimethyl-1-propaneaminium chloride, etc., can be used.

[0058] Examples of the aforementioned water-soluble acylphosphine oxides include those represented by the following general formulas (3) or (4).

[0059] [ka]

[0060] [ka]

[0061] In equations (3) and (4), R 2 , R3 , R 4 , R 5 , R 6 , and R 7 They are independent of each other, C1~ A linear or branched alkyl group or halogen atom of C4, where M is a hydrogen ion. Alkali metal ions, alkaline earth metal ions, magnesium ions, pyridinium ions (which may have substituents on the pyridine ring), or HN + R 9 R 10 R 11 (In the formula, R 9 , R 1 0 , and R 11 These are ammonium ions represented by an organic group or a hydrogen atom, independently of each other. Yes, n is 1 or 2, X is a linear or branched alkylene group of C1-C4, R 8 -CH(CH3)COO(C2H4O) p It is represented as CH3, where p represents an integer between 1 and 1000.

[0062] R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 The alkyl group is not particularly limited as long as it is a linear or branched C1-C4 group, and examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group, etc. 2 , R 3 , R 4 , R 5 , R 6 , and R 7The alkyl group is preferably a linear alkyl group of C1 to C3, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. Examples of X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and an n-butylene group. The alkyl group is preferably a linear alkylene group of C1 to C3, more preferably a methylene group or an ethylene group, and even more preferably a methylene group.

[0063] When M is a pyridinium ion, substituents on the pyridine ring include halogen atoms (fluorine, chlorine, bromine, iodine), carboxyl groups, linear or branched acyl groups of C2-C6, linear or branched alkyl groups of C1-C6, and linear or branched alkoxy groups of C1-C6. M can be an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have substituents), or HN + R 9 R 10 R 11 Ammonium ions represented by (wherein the formula, the symbols have the same meaning as above) are preferred. Examples of alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, and cesium ions. Examples of alkaline earth metal ions include calcium ions, strontium ions, barium ions, and radium ions. R 9 , R 10 , and R 11 As for the organic group, the aforementioned P Examples include substituents similar to those on the lysine ring (excluding halogen atoms).

[0064] Among these, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7Compounds in which all groups are methyl groups are particularly preferred in the composition of the self-adhesive dental composite resin (X) from the viewpoint of storage stability and color stability. Examples of ammonium ions include ammonium ions derived from various amines. Examples of amines include ammonia, trimethylamine, diethylamine, dimethylaniline, ethylenediamine, triethanolamine, N,N-dimethylaminomethacrylate, 4-(N,N-dimethylamino)benzoic acid and its alkyl esters, 4-(N,N-diethylamino)benzoic acid and its alkyl esters, and N,N-bis(2-hydroxyethyl)-p-toluidine.

[0065] R 8 From the viewpoint of adhesion, p is preferably 1 or more, more preferably 2 or more, and 3 The above is even more preferable, 4 or more is particularly preferable, 1000 or less is preferable, 100 or less is more preferable, 75 or less is even more preferable, and 50 or less is particularly preferable.

[0066] Among these water-soluble acylphosphine oxides, those represented by general formula (3) are M n+ Compounds represented by general formula (3) in which is a lithium ion, and R 8 A compound represented by general formula (4), synthesized from polyethylene glycol methyl ether methacrylate in which the portion corresponding to the group represented by has a molecular weight of 950, is particularly preferred.

[0067] Water-soluble acylphosphine oxides having such a structure can be synthesized according to known methods, and some are also available commercially. For example, they can be synthesized by methods disclosed in Japanese Patent Publication No. 57-197289 and International Publication No. 2014 / 095724. The water-soluble photopolymerization initiator (c-1) may be used alone or in combination of two or more.

[0068] The water-soluble photopolymerization initiator (c-1) may be dissolved in the self-adhesive dental composite resin (X) or dispersed as a powder in the composition of the self-adhesive dental composite resin (X).

[0069] When dispersing the water-soluble photopolymerization initiator (c-1) in powder form, if the average particle size is too large, it tends to settle, so a size of 500 μm or less is preferred, more preferably 100 μm or less, and even more preferably 50 μm or less. On the other hand, if the average particle size is too small, the specific surface area of ​​the powder becomes too large, reducing the amount that can be dispersed in the composition, so a size of 0.01 μm or more is preferred. In other words, the average particle size of the water-soluble photopolymerization initiator (c-1) is preferably in the range of 0.01 to 500 μm, more preferably in the range of 0.01 to 100 μm, and even more preferably in the range of 0.01 to 50 μm.

[0070] The average particle size of each water-soluble photopolymerization initiator (c-1) powder can be calculated as the volume-average particle size after performing image analysis using image analysis-based particle size distribution measurement software (Mac-View; manufactured by Mountec Co., Ltd.) based on electron microscope images of 100 or more particles.

[0071] When the water-soluble photopolymerization initiator (c-1) is dispersed as a powder, various shapes of the initiator can be used, such as spherical, needle-shaped, plate-shaped, or crushed, but there are no particular limitations. The water-soluble photopolymerization initiator (c-1) can be prepared by conventionally known methods such as grinding, freeze-drying, or reprecipitation. From the viewpoint of the average particle size of the resulting powder, freeze-drying and reprecipitation are preferred, and freeze-drying is more preferred.

[0072] From the viewpoint of the curability of the resulting self-adhesive dental composite resin (X), the content of the water-soluble photopolymerization initiator (c-1) is preferably 0.01 to 20 parts by mass per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X) of the present invention, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, from the viewpoint of adhesion to tooth structure. When the content of the water-soluble photopolymerization initiator (c-1) is above the lower limit, polymerization at the adhesive interface proceeds sufficiently, and sufficient adhesion is easily obtained. On the other hand, when the content of the water-soluble photopolymerization initiator (c-1) is below the upper limit, sufficient adhesion is easily obtained.

[0073] • Non-water-soluble photopolymerization initiator (c-2) From the viewpoint of curing properties, the self-adhesive dental composite resin (X) of the present invention preferably contains, in addition to a water-soluble photopolymerization initiator (c-1), a non-water-soluble photopolymerization initiator (c-2) (hereinafter sometimes referred to as non-water-soluble photopolymerization initiator (c-2)) having a solubility in water at 25°C of less than 10 g / L. The non-water-soluble photopolymerization initiator (c-2) used in the present invention can be any known photopolymerization initiator. The non-water-soluble photopolymerization initiator (c-2) may be formulated alone or in combination of two or more.

[0074] Examples of non-water-soluble photopolymerization initiators (c-2) include (bis)acylphosphine oxides, thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds, in addition to the water-soluble photopolymerization initiators (c-1).

[0075] Among the (bis)acylphosphine oxides, 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, Examples include 3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl)phosphonate, and salts thereof. 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.

[0076] Examples of the thioxanthones include thioxanthone and 2-chlorothioxanthene-9-one.

[0077] Examples of the aforementioned ketals include benzyldimethyl ketal and benzyldiethyl ketal.

[0078] Examples of the α-diketones include diacetyl, benzyl, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, and acenaphthenequinone. Among these, dl-camphorquinone is particularly preferred from the viewpoint of having a maximum absorption wavelength in the visible light range.

[0079] Examples of the aforementioned coumarins include 3,3'-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienoylcoumarin, 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), and 3-benzoyl-6-bromo Coumarin, 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]thiazole-2-ylidene)acetyl]coumarin, 3,3'-carb Nylbis(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-benzoimidazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3'-carbonylbis(7-dibutylaminocoumarin), 3,3'-Carbonyl-7-diethylaminocoumarin-7'-bis(butoxyethyl)aminoc, Examples of compounds described in Japanese Patent Publication No. 9-3109 and Japanese Patent Publication No. 10-245525 include marine, 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]quinoridine-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]quinoridine-11-one.

[0080] Among the coumarins mentioned above, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are particularly preferred.

[0081] Examples of the aforementioned anthraquinones include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-hydroxyanthraquinone.

[0082] Examples of the benzoin alkyl ether compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0083] Examples of the α-aminoketone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

[0084] Among these water-insoluble photopolymerization initiators (c-2), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarins. This results in a self-adhesive dental composite resin (X) that exhibits excellent photocurability in the visible and near-ultraviolet regions and sufficient photocurability regardless of whether a halogen lamp, light-emitting diode (LED), or xenon lamp is used as the light source.

[0085] The content of the water-insoluble photopolymerization initiator (c-2) is not particularly limited, but from the viewpoint of the curability of the resulting self-adhesive dental composite resin (X) composition, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X) of the present invention. Furthermore, by keeping the content of the water-insoluble photopolymerization initiator (c-2) below the above upper limit, sufficient adhesion can be easily obtained if the polymerization performance of the water-insoluble photopolymerization initiator (c-2) itself is low, and the precipitation of the water-insoluble photopolymerization initiator (c-2) itself from the self-adhesive dental composite resin (X) can be suppressed.

[0086] When a water-soluble photopolymerization initiator (c-1) and a water-insoluble photopolymerization initiator (c-2) are used in combination, the mass ratio of the water-soluble photopolymerization initiator (c-1):(c-2) in the present invention is preferably 10:1 to 1:10, more preferably 7:1 to 1:7, even more preferably 5:1 to 1:5, and particularly preferably 3:1 to 1:3. If the water-soluble photopolymerization initiator (c-1) is present in a mass ratio greater than 10:1, the curability of the self-adhesive dental composite resin (X) itself decreases, making it difficult to achieve high adhesion. On the other hand, if the water-insoluble photopolymerization initiator (c-2) is present in a mass ratio greater than 1:10, although the curability of the self-adhesive dental composite resin (X) itself is increased, polymerization promotion at the adhesive interface becomes insufficient, making it difficult to achieve high adhesion.

[0087] <Filler (d)> The self-adhesive dental composite resin (X) of the present invention may contain a filler (d) to adjust handling properties and to increase the mechanical strength of the cured product. Examples of such fillers include inorganic fillers, organic-inorganic composite fillers, and organic fillers. Filler (d) may be used alone or in combination of two or more types.

[0088] Examples of inorganic filler materials include inorganic fillers and oxides containing silicon atoms, such as quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, ytterbium oxide, and silica-coated ytterbium fluoride. These can be used individually or mixed in groups of two or more. Among these, quartz, silica, silica-zirconia, barium glass, ytterbium oxide, and silica-coated ytterbium fluoride are preferred in terms of the excellent mechanical strength and transparency of the resulting self-adhesive dental composite resin (X), and quartz, silica, silica-zirconia, barium glass, and silica-coated ytterbium fluoride are more preferred. From the viewpoint of the handling properties and mechanical strength of the resulting self-adhesive dental composite resin (X), the average particle size of the inorganic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm. In this invention, if the inorganic filler is surface-treated as described later, the average particle size of the inorganic filler refers to the average particle size before surface treatment. One preferred embodiment is a self-adhesive dental composite resin (X) in which filler (d) is an inorganic filler.

[0089] The shape of the inorganic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. Examples include amorphous fillers and spherical fillers. From the viewpoint of improving the mechanical strength of the cured product of the self-adhesive dental composite resin (X), it is preferable to use spherical fillers as the inorganic filler. Here, a spherical filler is a filler in which, when a photograph of the filler is taken with an electron microscope, the particles observed within the unit field of view are rounded, and the average uniformity obtained by dividing the particle size in the direction perpendicular to the maximum diameter by the maximum diameter is 0.6 or more. The average particle diameter of the spherical filler is preferably 0.05 to 5 μm. When the average particle diameter is above the lower limit, it is easier to obtain a sufficient filling rate of spherical fillers in the self-adhesive dental composite resin (X), and the desired mechanical strength is easily obtained. On the other hand, when the average particle diameter is below the upper limit, the surface area of ​​the spherical filler is less likely to decrease, and it is easier to obtain a cured product of the self-adhesive dental composite resin (X) with the desired mechanical strength.

[0090] The inorganic filler may be pre-treated with a known surface treatment agent, such as a silane coupling agent, as needed, to adjust the fluidity of the self-adhesive dental composite resin (X). For example, by surface-treating the hydroxyl groups present on the surface of the inorganic filler with a surface treatment agent, an inorganic filler with surface-treated hydroxyl groups can be obtained. Examples of surface treatment agents include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0091] The surface treatment method can be any known method without particular limitation. For example, it can be a method of spraying the surface treatment agent onto the inorganic filler while vigorously stirring it, a method of dispersing or dissolving the inorganic filler and the surface treatment agent in a suitable solvent and then removing the solvent, or a method of hydrolyzing the alkoxy groups of the surface treatment agent with an acid catalyst in an aqueous solution to convert them to silanol groups, attaching them to the inorganic filler surface in the aqueous solution, and then removing the water. In any of these methods, the reaction between the inorganic filler surface and the surface treatment agent can be completed and the surface treatment performed by heating in the range of 50 to 150°C. The amount of surface treatment is not particularly limited. For example, 1 to 10 parts by mass of the surface treatment agent can be used per 100 parts by mass of the inorganic filler before treatment.

[0092] The organic-inorganic composite filler used in the present invention is obtained by pre-adding monomers to the inorganic filler described above, forming a paste, polymerizing it, and then pulverizing it. The organic-inorganic composite filler refers to a filler containing a polymer of inorganic filler and monomers. As the organic-inorganic composite filler, for example, TMPT filler (a mixture of trimethylolpropane methacrylate and silica filler that has been 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 and used. The organic-inorganic composite filler may also be used alone or in a mixture of two or more types. From the viewpoint of handling properties and mechanical strength of the resulting self-adhesive dental composite resin (X) composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

[0093] Examples of organic filler materials include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-styrene-butadiene copolymer. These can be used individually or as a mixture 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. From the viewpoint of handling properties and mechanical strength of the resulting self-adhesive dental composite resin (X), the average particle size of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

[0094] In this specification, the average particle size of the filler can be determined by laser diffraction scattering or electron microscopy observation of the particles. Specifically, laser diffraction scattering is convenient for measuring the particle size of particles 0.1 μm or larger, while electron microscopy observation is convenient for measuring the particle size of ultrafine particles smaller than 0.1 μm. 0.1 μm is the value measured by laser diffraction scattering.

[0095] Specifically, the laser diffraction scattering method can be used, for example, with a laser diffraction particle size distribution analyzer (SALD-2300: manufactured by Shimadzu Corporation), to measure particle size distribution by volume using a 0.2% sodium hexametaphosphate aqueous solution as the dispersion medium.

[0096] Specifically, electron microscopy observation can be performed by taking an electron microscope (Hitachi, Ltd., S-4000 model) photograph of particles, and then measuring the particle diameter of the particles (200 or more) observed within the unit field of view of that photograph using image analysis particle size distribution measurement software (Mac-View (Mountec Co., Ltd.)). In this case, the particle diameter is determined as the arithmetic mean of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and their respective particle diameters.

[0097] Another preferred embodiment is a dental adhesive kit in which the filler (d) of the self-adhesive dental composite resin (X) includes filler (d-ii) (hereinafter sometimes simply referred to as "filler (d-ii)") with an average particle size of 0.1 μm or more and 1 μm or less (hereinafter sometimes simply referred to as "filler (d-iii)") and / or filler (d-iii) (hereinafter sometimes simply referred to as "filler (d-iii)") with an average particle size of more than 1 μm and 10 μm or less (hereinafter sometimes simply referred to as "filler (d-iii)"). When the filler (d) of the self-adhesive dental composite resin (X) includes filler (d-ii) and / or filler (d-iii), phosphoric acid When the monomer (a) having a group is included in a predetermined amount, and when combined with other components as needed, better adhesion to tooth structure and better adhesion to MTA cement cured material immediately after light curing of the self-adhesive dental composite resin can be obtained. In another preferred embodiment, the filler (d) of the self-adhesive dental composite resin (X) includes filler (d-ii) and / or filler (d-iii), and the filler (d-ii) and / or the filler (d-iii) is an inorganic filler containing silicon atoms Alternatively, a dental adhesive kit may be provided that includes an inorganic filler composed of an oxide, wherein the inorganic filler has hydroxyl groups on its surface, and these hydroxyl groups are surface-treated with a surface treatment agent.

[0098] The self-adhesive dental composite resin (X) of the present invention preferably uses a mixture or combination of two or more fillers having different materials, particle size distributions, and morphologies. By combining two or more fillers, the fillers are densely packed, and the number of interaction points between the fillers and monomers, or between the fillers themselves, increases. Furthermore, the fluidity of the paste can be controlled by the presence or absence of shear force depending on the type of filler. In particular, from the viewpoint of the handling properties and paste properties of the self-adhesive dental composite resin (X) of the present invention, the filler (d) is preferably a filler (di) with an average particle size of 1 nm or more and less than 0.1 μm, and average Combination with filler (d-ii) with particle size between 0.1 μm and 1 μm (I), average particle Fillers (di) with a diameter of 1 nm or more and less than 0.1 μm, and average particle diameters greater than 1 μm and less than or equal to 10 μm. Combination with filler (d-iii) (II), average particle size 1 nm or more and less than 0.1 μm Filler (di), filler (d-ii) with an average particle size of 0.1 μm or more and 1 μm or less, flat A combination with a filler (d-iii) with a uniform particle size greater than 1 μm and less than or equal to 10 μm (III), and a combination of fillers (d-ii) with an average particle size of 0.1 μm or more and less than or equal to 1 μm (IV) are preferred. Among these combinations, (I), (II), and (III) are more preferred from the viewpoint of paste properties and superior adhesion to MTA cement cured material immediately after light curing of self-adhesive dental composite resin when combined with other components such as a predetermined content of monomers (a) having phosphate groups. (I), (II), and (III) are more preferred, with (I) and (II) being even more preferred. Average particle size 0. The combination (IV) of fillers (d-ii) between 1 μm and 1 μm refers to an embodiment that includes two types of fillers (d-ii) with different average particle sizes, ranging from 0.1 μm to 1 μm. In addition, within the above combination, each particle size filler (d) may contain different types of fillers. Furthermore, particles other than fillers may be unintentionally included as impurities, as long as the effects of the present invention are not impaired.

[0099] The content of filler (d) is not particularly limited, but from the viewpoint of the mechanical strength of the cured product and adhesion to tooth structure, it is preferably 50 to 90 parts by mass, more preferably 55 to 85 parts by mass, and even more preferably 60 to 80 parts by mass per 100 parts by mass of self-adhesive dental composite resin (X).

[0100] The method for producing the self-adhesive dental composite resin (X) is not particularly limited, as long as it contains the above components and the content of monomer (a) having a phosphate group is 1 to 30 parts by mass per 100 parts by mass of the total amount of monomers, and preferably the content of filler (d) is 50 to 90 parts by mass per 100 parts by mass of the self-adhesive dental composite resin (X), and can be easily produced by a method known to those skilled in the art.

[0101] The method for producing the self-adhesive dental composite resin (X) of the present invention is not particularly limited as long as it contains a monomer (a) having a divalent phosphate group with an alkyl group or alkylene group having 8 to 12 carbon atoms as the main chain in the molecule, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d), and can be easily produced by methods known to those skilled in the art.

[0102] <Polymerization accelerator (g)> The self-adhesive dental composite resin (X) of the present invention may use a polymerization accelerator (g) together with a water-insoluble photopolymerization initiator (c-2) and / or a chemical polymerization initiator described later. Examples of polymerization accelerators (g) used in the self-adhesive dental composite resin (X) include amines, sulfinic acid and its salts, benzotriazole compounds, benzimidazole compounds, sulfur-containing reducing inorganic compounds, thiourea compounds, aldehydes, thiol compounds, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, and halogen compounds, with amines, sulfinic acid and its salts, sulfur-containing reducing inorganic compounds, thiourea compounds, aldehydes, thiol compounds, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, and halogen compounds being preferred.

[0103] The amines used as polymerization accelerators (g) can be divided into aliphatic amines and aromatic amines. Examples of aliphatic amines 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, tertiary aliphatic amines are preferred from the viewpoint of curability and storage stability of self-adhesive dental composite resins (X), and among them, N-methyldiethanolamine and triethanolamine are more preferably used.

[0104] Furthermore, aromatic amines include, for example, N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(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-diisopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, and N,N-diethyl-p - Examples include 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, ethyl 4-(N,N-dimethylamino)benzoate, methyl 4-(N,N-dimethylamino)benzoate, propyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, 2-(methacryloyloxy)ethyl 4-(N,N-dimethylamino)benzoate, benzophenone, and butyl 4-(N,N-dimethylamino)benzoate. Among these, N,N-bis(2-hydroxyethyl) is selected from the perspective of providing excellent hardening properties to self-adhesive dental composite resin (X). At least one selected from the group consisting of )-p-toluidine, ethyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, and 4-(N,N-dimethylamino)benzophenone is preferably used.

[0105] Examples of sulfinic acid and its salts include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid (sodium salt may be abbreviated as "TPBSS" below), chlorobenzenesulfinic acid, naphthalenesulfinic acid, and their lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts, zinc salts, ammonium salts, tetramethylammonium salts, and tetraethylammonium salts. Among these, lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of 2,4,6-trimethylbenzenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid are preferred in terms of curability and storage stability of the composition, and lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of 2,4,6-triisopropylbenzenesulfinic acid are more preferred.

[0106] Examples of benzotriazole compounds and / or benzimidazole compounds include the compounds represented by the following general formula (5) and the compounds represented by the following general formula (6).

[0107] [ka]

[0108] [ka]

[0109] In the above general formulas (5) and (6), A 1 ~A 8 Each of these independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyl group, an aralkyl group, or a halogen atom.

[0110] A 1 ~A8 The alkyl group represented by may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group. Examples include the methyl group, cyclohexyl group, n-heptyl group, cycloheptanyl group, n-octyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, cyclononyl group, and n-decyl group. Among these, the methyl group and the ethyl group are particularly preferred.

[0111] A 1 ~A 8 The aryl group represented by is preferably one having 6 to 10 carbon atoms, such as a phenyl group, naphthyl group, or anthryl group.

[0112] A 1 ~A 8 The alkoxy group represented by may be linear, branched, or cyclic, and preferably has 1 to 8 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, n-octyloxy, and 2-ethylhexyloxy groups.

[0113] A 1 ~A 8 The alkenyl group represented by may be linear, branched, or cyclic, and preferably has 1 to 6 carbon atoms. Specific examples include vinyl group, allyl group, methyl vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group.

[0114] A 1 ~A 8Examples of aralkyl groups represented by include alkyl groups (especially alkyl groups with 1 to 10 carbon atoms) substituted with aryl groups (especially aryl groups with 6 to 10 carbon atoms), specifically the benzyl group.

[0115] A 1 ~A 8 Examples of halogen atoms represented by include chlorine, bromine, and iodine atoms.

[0116] A 1 ~A 8 A hydrogen atom or a methyl group is preferred.

[0117] Benzotriazole compounds and benzimidazole compounds may be used individually or in combination of two or more. Specific examples of benzotriazole compounds and benzimidazole compounds include 1H-benzotriazole (hereinafter sometimes abbreviated as "BTA"), 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, benzimidazole, 5-methylbenzimidazole, and 5,6-dimethylbenzimidazole. Among these, 1H-benzotriazole and 5-methyl-1H-benzotriazole are preferred in terms of the color tone of the composition and storage stability.

[0118] Examples of sulfur-containing reducing inorganic compounds include sulfites, bisulfites (hydrogen sulfites), pyrosulfites, thiosulfites, thionites, and dithionites. Among these, sulfites and bisulfites are preferred, and specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, and potassium bisulfite. A single sulfur-containing reducing inorganic compound may be used, or two or more may be used in combination.

[0119] Thiourea compounds include thiourea, N-methylthiourea, N-ethylthiourea, ethylenethiourea, dimethylethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, dicyclohexylthiourea, tetracyclohexylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and pyridylthiourea, among which 4,4-dimethylethylenethiourea, pyridylthiourea, and N-benzoylthiourea are mentioned. Urea is preferred.

[0120] Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, and pn-octyloxybenzaldehyde.

[0121] Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, decanethiol, and thiobenzoic acid.

[0122] Specific examples of borate compounds, barbiturate derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, sulfites, and bisulfites are those described in International Publication No. 2008 / 087977.

[0123] The polymerization accelerator (g) may contain one type alone or a combination of two or more types. The content of the polymerization accelerator (g) used in the present invention is not particularly limited, but from the viewpoint of the curability of the resulting dental adhesive kit, it is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). When the content of the polymerization accelerator (g) is above the lower limit, polymerization proceeds sufficiently and sufficient adhesion is easily obtained, and it is more preferably 0.05 parts by mass or more. On the other hand, when the content of the polymerization accelerator (g) is below the upper limit, sufficient adhesion is easily obtained, and furthermore, precipitation of the polymerization accelerator (g) itself from the self-adhesive dental composite resin (X) can be suppressed, so it is more preferably 20 parts by mass or less.

[0124] <Chemical polymerization initiator> The self-adhesive dental composite resin (X) of the present invention may further contain a chemical polymerization initiator. The chemical polymerization initiator is not particularly limited and any known one may be used, including organic peroxides, inorganic peroxides, and transition metal complexes, with organic peroxides being preferred. The chemical polymerization initiator may be used alone or in combination of two or more. The organic peroxide is not particularly limited and any known one may be used. Typical organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates. Specific examples of these organic peroxides are those described in International Publication No. 2008 / 087977. Inorganic peroxides include peroxodisulfate and peroxodiphosphate, among which peroxodisulfate is preferred in terms of curability. Specific examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate.

[0125] Examples of transition metal complexes, though not particularly limited, include copper compounds and vanadium compounds.

[0126] Examples of copper compounds include copper(II) carboxylate, β-copper(II) diketone, β-copper(II) ketoester, copper alkoxide, copper dithiocarbamate, and salts of copper and inorganic acids. Examples of copper(II) carboxylate include copper(II) citrate, copper(II) acetate, copper(II) phthalate, copper(II) tartrate, copper(II) oleate, copper(II) octoate, copper(II) octate, copper(II) naphthenate, copper(II) methacrylate, and copper(II) 4-cyclohexylbutyrate. Examples of β-copper(II) diketone include copper(II) acetylacetone. I) Examples include copper(II) trifluoroacetylacetone, copper(II) hexafluoroacetylacetone, copper(II) 2,2,6,6-tetramethyl-3,5-heptanedionatocopper(II), copper(II) benzoylacetone, etc. Examples of β-ketoester copper(II) include copper(II) acetate. Examples of copper alkoxides include copper(II) methoxide, copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy)ethoxide, copper(II) 2-(2-methoxyethoxy)ethoxide, etc. Examples of copper dithiocarbamate include copper(II) dimethyldithiocarbamate. Examples of copper-inorganic acid salts include copper(II) nitrate, copper(II) bromide, and copper(II) chloride. Among these, copper(II) carboxylate, copper(II) β-diketone, and copper(II) β-ketoester are preferred from the viewpoint of solubility and reactivity with respect to monomers, and copper(II) acetate and copper(II) acetylacetone are more preferred.

[0127] Examples of vanadium compounds include IV-valent and / or V-valent vanadium compounds. Examples of IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadylacetylacetonate (IV), vanadium stearate oxide (IV), oxovanadium oxalate (IV), vanadyl sulfate (IV), vanadium naphthenate, vanadium benzoylacetonate, bis(maltrate)oxovanadium (IV), oxobis(1-phenyl-1,3-butanedione)vanadium (IV), and 5 Examples include vanadium(V) oxide, vanadium(V) oxytriisopropoxide, sodium metavanadate(V), and ammonium metavanadate(V). Among these, vanadium acetylacetonate, vanadylacetylacetonate(IV), and bis(maltrate)oxovanadium(IV) are preferred from the viewpoint of adhesion, with vanadylacetylacetonate(IV) and bis(maltrate)oxovanadium(IV) being preferred.

[0128] <Fluoride ion-releasing substance> The self-adhesive dental composite resin (X) of the present invention may further contain a fluoride ion-releasing substance. By including a fluoride ion-releasing substance, a self-adhesive dental composite resin (X) can be obtained that can impart acid resistance to tooth structure. Examples of fluoride ion-releasing substances include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methacrylate fluoride; metallic fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride; and fluoroaluminosilicate glass. The fluoride ion-releasing substance may be contained alone or in combination of two or more.

[0129] Furthermore, the self-adhesive dental composite resin (X) of the present invention may contain known additives within a range that does not degrade performance. Examples of such additives include polymerization inhibitors, antioxidants, colorants (pigments, dyes), ultraviolet absorbers, solvents such as water and organic solvents, and thickeners. One additive may be used alone, or two or more may be used in combination. In one embodiment, the solvent content (e.g., water, organic solvent) in the self-adhesive dental composite resin (X) is preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass, based on the total amount of the self-adhesive dental composite resin (X).

[0130] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, and 3,5-di-t-butyl-4-hydroxytoluene. The polymerization inhibitor content is preferably 0.001 to 1.0 parts by mass per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X).

[0131] An example of the composition ratio of a self-adhesive dental composite resin (X) is shown. When the total amount of monomers in the self-adhesive dental composite resin (X) is 100 parts by mass, it preferably contains 1 to 40 parts by mass of monomers having a phosphate group (a) and 60 to 99 parts by mass of monomers not having an acidic group (b). In addition, per 100 parts by mass of the total amount of monomers, it preferably contains 0.05 to 10 parts by mass of a photopolymerization initiator (c), 100 to 900 parts by mass of filler (d), and 0.001 to 30 parts by mass of polymerization accelerator (g). In addition, per 100 parts by mass of the total amount of monomers, it preferably contains 2.5 to 35 parts by mass of monomers having a phosphate group (a) and 65 to 97.5 parts by mass of monomers not having an acidic group (b). It is more preferable to include 0.1 to 5 parts by mass of photopolymerization initiator (c), 120 to 560 parts by mass of filler (d), and 0.01 to 10 parts by mass of polymerization accelerator (g) per 100 parts by mass of total monomers, and it is even more preferable to include 5 to 30 parts by mass of monomers having a phosphate group (a) and 70 to 95 parts by mass of monomers not having an acidic group (b) per 100 parts by mass of total monomers, and it is even more preferable to include 0.15 to 2.5 parts by mass of photopolymerization initiator (c), 150 to 400 parts by mass of filler (d), and 0.1 to 5 parts by mass of polymerization accelerator (g) per 100 parts by mass of total monomers.

[0132] The self-adhesive dental composite resin (X) of the present invention is a one-component type (one-paste type) with all components pre-mixed, from the viewpoint of ease of use. The self-adhesive dental composite resin (X) of the present invention is suitably used in resin coating methods. Generally, in resin coating methods, exposed dentin and pulp are protected by applying dental composite resin to the cavity preparation surface. If the dental composite resin used in resin coating methods is a two-component type, it is necessary to mix the two components immediately before use, which may result in the inclusion of air bubbles and may affect the properties of the cured self-adhesive dental composite resin. Therefore, in the present invention, since the self-adhesive dental composite resin (X) is a one-component type, there is no need to mix the two components, and it can be used as is, resulting in excellent operability, no risk of air bubbles being included, and reduced waste of composition paste. The one-component self-adhesive dental composite resin (X) of the present invention is more preferably used filled into a cylindrical syringe container. The cylindrical portion of the syringe container is preferably 10 cm in length and 15 mm or less in inner diameter, and more preferably 7.5 cm in length and 10 mm or less in inner diameter. Alternatively, to improve handling, a nozzle may be attached to the tip of the syringe. The nozzle is preferably 25 mm in length and 1.5 mm or less in inner diameter of the opening, and more preferably 20 mm in length and 0.75 mm or less in inner diameter of the opening.

[0133] • Dental cement composition (Y) The dental cement composition (Y) of the present invention comprises Portland cement powder (e) and an inorganic filler (f). The dental cement composition (Y) of the present invention is an MTA (Mineral Trioxide Aggregate) cement composition.

[0134] In the dental cement composition (Y), the content of Portland cement powder (e) is 60 to 90% by mass, preferably 60 to 80% by mass, and more preferably 65 to 75% by mass. If the content of Portland cement powder (e) is less than 60% by mass, the strength of the hardened cement tends to be lower than that of Portland cement. If the content of Portland cement powder (e) is 90% by mass or more, the fluidity is too low, making mixing and filling operations difficult.

[0135] In the dental cement composition (Y), the inorganic filler (f) content is 10 to 40% by mass, preferably 20 to 40% by mass, and more preferably 25 to 35% by mass. A inorganic filler (f) content of 10 to 40% by mass improves the hardening time after mixing and further increases the strength of the hardened cement. If the inorganic filler (f) content is less than 10% by mass, the fluidity of the paste becomes insufficient, and if it exceeds 40% by mass, the strength of the hardened cement tends to decrease significantly.

[0136] Furthermore, the Portland cement powder (e) and inorganic filler (f) can also be expressed in terms of their mixing ratio (mass ratio). In this case, in the dental cement composition (Y) of the present invention, from the viewpoint of paste fluidity and the strength of the hardened cement, the mass ratio of Portland cement powder (e) to inorganic filler (f) is preferably in the range of 60:40 to 90:10, more preferably in the range of 60:40 to 80:20, and even more preferably in the range of 65:35 to 75:25.

[0137] <Portland cement powder (e)> Examples of Portland cement powder (e) include powders of ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, white Portland cement, sulfate-resistant Portland cement, moderate-heat Portland cement, and low-heat Portland cement as specified in JIS R 5210:2019.

[0138] Of these, the use of white Portland cement is particularly preferable from the standpoint that its white color closely matches that of tooth structure.

[0139] The above Portland cement powder (e) is also known as "clinker" and consists of tricalcium silicate (alite, 3CaO·SiO2) and dicalcium silicate (beelite, 2 CaO·SiO2), calcium aluminate (aluminate, 3CaO·Al2O3), It is a cement whose main component is calcium aluminoferrite (ferrite, 4CaO·Al2O3·Fe2O3). The main compounds of clinker are calcium oxide (CaO), silicon dioxide (SiO2), aluminum oxide (Al2O3), and iron oxide (Fe2O3). Yes, it is possible to adjust the hardening speed of the cement and the mechanical strength of the hardened material by controlling the proportion of each of these components.

[0140] The following are some of the typical compositions of the components contained in the Portland cement powder (e) mentioned above.

[0141] Calcium oxide (CaO): 55-85% by mass Silicon dioxide (SiO2): 10-40% by mass Aluminum oxide (Al2O3): 0-15% by mass Iron oxide (Fe2O3): 0-10% by mass

[0142] Among these, the following components are particularly preferred from the viewpoint of curing properties.

[0143] Calcium oxide (CaO): 60-66% by mass Silicon dioxide (SiO2): 20-26% by mass Aluminum oxide (Al2O3): 3-9% by mass Iron oxide (Fe2O3): 2-5% by mass

[0144] Portland cement powder (e) can be used as a mixture of one or more types.

[0145] The average particle size of the Portland cement powder (e) is preferably 100 μm or less, more preferably in the range of 1 μm to 50 μm, and even more preferably in the range of 5 μm to 25 μm.

[0146] Note that the average particle size of Portland cement powder (e) and inorganic filler (f) is as follows: This refers to the particle diameter at 50% cumulative volume, i.e., D50 (median diameter), in the particle diameter distribution measured on a volume basis by laser diffraction scattering. As for measurement methods using laser diffraction scattering, similar to the average particle diameter of fillers, one example is the measurement method using a laser diffraction particle diameter analyzer (SALD-2300: manufactured by Shimadzu Corporation).

[0147] Portland cement powder can be in powder or granular form.

[0148] <Inorganic filler (f)> The inorganic filler (f) preferably has an average particle size of 0.2 to 50 μm, more preferably 0.3 to 40 μm, and even more preferably 0.3 to 30 μm. In one embodiment, the average particle size of the inorganic filler (f) may be 10 μm.

[0149] When the average particle size of the inorganic filler (f) is less than 0.2 μm, the viscosity of the paste tends to increase.

[0150] When the average particle size of the inorganic filler (f) is 50 μm or larger, the resulting paste composition tends to have a rough or coarse texture on its surface, or its workability tends to decrease.

[0151] There are no particular restrictions on the type of inorganic filler (also called inorganic filler), and known ones can be used. Examples include metal oxides such as silica (silicon dioxide), zirconia (zirconium dioxide), alumina (aluminum oxide), titania (titanium dioxide), and zinc oxide; composite oxides such as silica-zirconia, silica-alumina, and silica-titania; glass types such as quartz glass, barium glass, aluminosilicate glass, lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminoborosilicate glass, and borosilicate glass; and hydroxyapatite, calcium fluoride, yttrium fluoride, and calcium phosphate. In addition to these, silica-based minerals such as diatomaceous earth, clay minerals (such as montmorillonite), activated clay, synthetic zeolite, kaolin, clay, mica, and composites thereof can also be used. Other examples include calcium tungstate, barium sulfate, cerium oxide, tin oxide, zirconium silicate, lanthanum oxide, zinc oxide, ytterbium oxide, ytterbium fluoride, bismuth oxide, bismuth subcarbonate, and bismuth sulfate. Among these, at least one selected from the group consisting of silica-based fillers (silica; silica-zirconia, silica-alumina, silica-titania, and other silica composite oxides), alumina fillers, zirconia fillers, calcium tungstate, and bismuth oxide is preferred, with silica-based fillers and zirconia fillers being particularly preferred. In one embodiment, the inorganic filler (f) is different from the filler (d) of the self-adhesive dental composite resin (X).

[0152] As the inorganic filler (f) mentioned above, for example, one whose surface has been modified with an alkoxysilane or the like may be used.

[0153] Inorganic filler (f) can be used individually or as a mixture of two or more types.

[0154] Furthermore, adding more inorganic filler (f) than necessary may affect the antibacterial and sealing properties that are characteristic of Portland cement.

[0155] Furthermore, from the viewpoint of radiopaqueness, the dental cement composition (Y) of the present invention preferably contains 20% by mass or more of zirconia filler as an inorganic filler (f) in the composition. In particular, the content of zirconia filler in the dental cement composition (Y) is Therefore, 20 to 40% by mass is preferred, and 25 to 35% by mass is more preferred.

[0156] The inorganic filler (f) can be spherical or crushed. Of these, the spherical shape is preferred because it exhibits a bearing effect.

[0157] <Other ingredients> The dental cement composition (Y) of the present invention may contain other additives such as fillers, colorants, and stabilizers, as long as they do not affect the physical properties or handling characteristics. The additives may be used individually or in combination of two or more.

[0158] The content of the additive may be less than 10% by mass in the dental cement composition, preferably 0% to 5% by mass, and more preferably 0% to 3% by mass.

[0159] There are no particular limitations on the method for producing the dental cement composition (Y) of the present invention described above. For example, a method of mixing Portland cement powder (e) (component A) and inorganic filler (f) (component B) all at once; A method of adding component B to component A in several separate additions and mixing them together; A method of adding component A to component B in several stages and mixing them together. These are some examples.

[0160] There are no particular limitations on the method for mixing the dental cement composition (Y) of the present invention, and a method may be used depending on the amount to be used. For example, if a small amount is used, a method of uniform mixing can be used, such as mixing with an agate mortar and pestle and an agate rod. If a large amount is used, a method of mixing can be used, such as using an omni-mixer, Eich mixer, universal mixer, or lei-kai machine, which are commonly used when manufacturing cement compositions.

[0161] There are no particular restrictions on the mixing time; any time required to ensure uniform mixing is acceptable.

[0162] The dental cement composition (Y) obtained by the present invention can be mixed with a predetermined amount of water to obtain a paste.

[0163] The consistency of the paste is usually preferably in the range of 10 to 50 mm, more preferably in the range of 15 to 50 mm, and even more preferably in the range of 20 to 50 mm. In this specification, "concentration" means that a higher value indicates that the paste of the composition is softer and has higher fluidity, and a lower value indicates that the paste of the composition is harder and has lower fluidity.

[0164] The consistency can be measured as follows: 0.4 mL of paste from dental cement composition (Y) was weighed out as a sample. A polyester film (5 cm × 5 cm) was placed on a glass plate (5 cm × 5 cm) in a constant temperature room at 25°C (40% humidity), and the weighed sample was placed in the center, mounded up. Next, another polyester film (5 cm × 5 cm) was placed over it, and a weight was placed on a separately prepared glass plate (5 cm × 5 cm) to make a composite material including the glass plate surface, totaling 1000 g. The glass plate surface of this composite was placed on top of the sample that had been left to stand, and the sample was left to stand, sandwiched between the polyester films. After 30 seconds, the major and minor axes of the sample were measured through the polyester film, and the arithmetic mean of both was calculated as the consistency at 25°C (n=2). The major axis of the sample is the longest diameter passing through the center of the sample, and the minor axis of the sample is the diameter passing through the center of the sample that is perpendicular to the major axis of the sample.

[0165] The dental cement composition (Y) obtained by the present invention can be hardened by mixing it with a predetermined amount of water to obtain a hardened product (hardened body).

[0166] The amount of water mentioned above is not particularly limited as long as it is enough to obtain a paste or hardened product. For example, 20 to 50 parts by mass of water can be added to 100 parts by mass of the dental cement composition (Y) of the present invention, more preferably in the range of 25 to 45 parts by mass, and more preferably in the range of 25 to 40 parts by mass. The curing time for obtaining the hardened product is preferably within 180 minutes. The compressive strength of the hardened product is preferably 30 MPa or more.

[0167] The present invention includes embodiments that combine the above configurations in various ways, within the scope of the technical idea of ​​the present invention, as long as they achieve the effects of the present invention. [Examples]

[0168] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the examples. In the examples, parts refer to parts by mass unless otherwise specified.

[0169] Next, the components of the self-adhesive dental composite resin (X) of type 1 in the examples and comparative examples are listed below, along with their abbreviations.

[0170] • One-component self-adhesive dental composite resin (X) [Monomers containing a phosphate group (a)] MDP:10-Methacryloyloxydecyldihydrogenphosphate [Monomers containing acidic groups] GPDM: Glycerol Phosphate Dimethacrylate 4-META:4-methacryloyloxyethyl trimellitic acid

[0171] [Monomers without acidic groups (b)] Bis-GMA:2-Bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D-2.6E: 2,2-Bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) 3G: Triethylene glycol dimethacrylate MAEA: N-methacryloyloxyethylacrylamide DD:1,10-Decanediol dimethacrylate HEMA-hydroxyethyl methacrylate DEAA: N,N-Diethylacrylamide

[0172] [Photopolymerization initiator (c)] • Water-soluble photopolymerization initiator (c-1) Li-TPO: Lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate • Non-water-soluble photopolymerization initiator (c-2) CQ: Camphorquinone

[0173] [Filler (d)] Filler 1: Ultrafine particle silica "Aerosil®" manufactured by Nippon Aerosil Co., Ltd. 972'', average particle size: 16nm Filler 2: Silane-treated silica powder Silica powder (manufactured by Nichitsu Co., Ltd., product name: High Silica) is crushed in a ball mill, and crushed silica Powder was obtained. The average particle size of the obtained pulverized silica powder was measured by volume using a laser diffraction particle size distribution analyzer (Shimadzu Corporation, model "SALD-2300") and was found to be 2.2 μm. 100 parts by mass of this pulverized silica powder was surface-treated with 4 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain filler 2. Filler 3: Silane-treated barium glass powder 100 g of GM27884 NF180 grade (SCHOTT barium glass, average particle size: 0.18 μm), 13 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3% by mass aqueous acetic acid solution were placed in a three-necked flask and stirred at room temperature for 2 hours. After removing water by freeze-drying, the mixture was heat-treated at 80°C for 5 hours to obtain filler 3 (average particle size: 0.18 μm). Filler 4: Silane-treated barium glass powder 100 g of 8235 UF0.7 grade (SCHOTT barium glass, average particle size: 0.7 μm), 6 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3% by mass aqueous acetic acid solution were placed in a three-necked flask and stirred at room temperature for 2 hours. After removing water by freeze-drying, the mixture was heat-treated at 80°C for 5 hours to obtain filler 4 (average particle size: 0.7 μm).

[0174] [Polymerization accelerator (g)] DABE: 4-(N,N-dimethylamino)ethyl benzoate

[0175] [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0176] Next, the components of the dental cement composition (Y) of the examples and comparative examples are listed below along with their abbreviations.

[0177] • Dental cement composition (Y) [Portland cement powder] White Portland cement powder with an average particle size of approximately 14.2 μm (product name: White Cement) (Manufactured by Taiheiyo Cement Corporation)

[0178] [Silica-based filler] SO-E2: Spherical silica filler with an average particle size of approximately 0.5 μm (manufactured by Admatex Co., Ltd.) SO-E5: Spherical silica filler with an average particle size of approximately 2 μm (manufactured by Admatex Co., Ltd.)

[0179] [Zirconia filler] HT: Rounded, fragmented zirconia filler with an average particle size of approximately 0.5 μm (manufactured by Shin-Nippon Denko Co., Ltd.)

[0180] [Commercially available dental Portland cement powder] Proroot® MTA (manufactured by Dentsply Sirona, Inc., containing Portland cement powder (e) and inorganic filler (f), with the Portland cement powder (e) content ranging from 60% to 90% by mass and the inorganic filler (f) content ranging from 10% to 40% by mass)

[0181] [Examples 1-16 and Comparative Examples 1-3] [Preparation of dental cement composition (Y)] Dental cement compositions with the compositions shown in Table 1 were prepared. Portland sesame seeds were added to an agate mortar. Menthol powder and silica filler were added and mixed with an agate mortar and pestle for 10 minutes to obtain the dental cement composition of the present invention.

[0182] [Preparation of a single-component self-adhesive dental composite resin (X)] The raw materials shown in Tables 2 and 3 were mixed and kneaded at room temperature (23°C) in the dark to prepare a paste-like, one-component self-adhesive dental composite resin, and its properties were examined according to the methods of Test Examples 1 and 2 below. The results are shown in Tables 2 and 3.

[0183] Test Example 1: Flexural Modulus 1-1) Light curing The flexural modulus was evaluated by a bending test in accordance with ISO 4049:2009. Specifically, the following was performed: The prepared paste (a one-component self-adhesive dental composite resin composition) was filled into a stainless steel mold (2 mm long x 25 mm wide x 2 mm thick), and the top and bottom surfaces (2 mm x 25 mm) of the paste were pressed together with a glass slide. Next, the paste was cured by irradiating both sides of the paste at five locations on each side for 10 seconds each using a dental visible light curing unit "PenCure 2000" (manufactured by Morita Corporation) through the glass slide. The resulting cured material was subjected to a three-point bending test using a universal testing machine (Autograph AG-I 100kN, manufactured by Shimadzu Corporation) with a support distance of 12 mm and a crosshead speed of 1 mm / min, and the flexural modulus was measured (n=5), and the average value was calculated.

[0184] Test Example 2: Shear bond strength of dental cement to hardened material immediately after light curing of self-adhesive dental composite resin. The dental cement compositions listed in Table 1 were mixed using a plastic spatula for 30 seconds to a ratio of dental cement composition / purified water of 75 / 25. The mixture was then filled into a metal mold with an inner diameter of 5 mm and a height of 2 mm to obtain a cylindrical hardened product. 120 seconds after the end of mixing, the hardened product was left to stand for 24 hours in a constant temperature and humidity chamber at 37°C and 95% relative humidity. Tape was attached to the bottom of a 15-hole mold (Ultradent Co., Ltd., φ35 mm × height 25 mm) to fix the hardened product. Tray Resin II (Matsukaze Co., Ltd.) was filled into the mold and left to stand for approximately 30 minutes to harden the Tray Resin II, obtaining a composite product of hardened dental cement and hardened resin. The composite product was removed from the mold as a sample. The composite product was defined as having the hardened dental cement exposed on the upper surface of the hardened resin. In a later step, the side of the sample with the hardened dental cement exposed on the upper surface was designated as the adhesion surface, so that it could bond with the self-adhesive dental composite resin.

[0185] Next, a separately prepared φ2.38 mm CR filling mold (Bonding Mold Insert, manufactured by Ultradent) was attached to a dedicated instrument (Bonding Clamp, manufactured by Ultradent). Then, the CR filling mold attached to the dedicated instrument was lowered so that it was in close contact with the bonding surface of the sample, and the sample was fixed in place. Next, the self-adhesive dental composite resin composition prepared in each example and comparative example was thinly filled into the hole in the CR filling mold to a thickness of 1 mm or less. After that, the mold was filled again (to about 2 / 3 of the mold, about 2 mm thick), left for 10 seconds, and then cured by irradiating with a dental LED light curing unit (manufactured by Ultradent, product name "VALO") for 10 seconds. The sample was removed from the mold and used as a test sample for the adhesion test. Next, the adhesive test samples were placed in a constant temperature chamber set to 37°C for 10 minutes, then removed, and the adhesive strength was measured as the adhesive test samples immediately after curing. The adhesive strength (shear adhesive strength) was measured by attaching the adhesive test samples to a dedicated holder (Test Base Clamp, manufactured by Ultradent), using a dedicated jig (Crosshead Assembly, manufactured by Ultradent) and a universal testing machine (manufactured by Shimadzu Corporation), with the crosshead speed set to 1 mm / min. The average values ​​are shown in the table (n=10).

[0186] The shear bonding strength of a self-adhesive dental composite resin to a dental MTA cementite is preferably 5 MPa or higher, more preferably 6.5 MPa or higher, and even more preferably 8 MPa or higher.

[0187] [Table 1]

[0188] [Table 2]

[0189] [Table 3]

[0190] From the results in Tables 2 and 3, it can be seen that the self-adhesive dental composite resin of type 1 in the example has a flexural modulus of 2.6 to 5.7 GPa and excellent adhesive strength to MTA cement hardened material of 6 MPa or more. On the other hand, in Comparative Examples 1, 2, and 3, in which the flexural modulus of the self-adhesive dental composite resin of type 1 was 8.2 GPa or more, MTA cement It was confirmed that the adhesive strength to the hardened product was low, at 4.1 MPa or less. Furthermore, in Comparative Example 4, where the monomer with the acidic group was not a monomer with a phosphate group having 8 to 16 carbon atoms, it was also confirmed that the adhesive strength to the hardened MTA cement was low, at 4.4 MPa. [Industrial applicability]

[0191] The dental adhesive kit comprising dental cement and self-adhesive dental composite resin according to the present invention can be suitably used in dental restorative treatment.

Claims

1. A one-component self-adhesive dental composite resin (X) containing a monomer (a) having an alkyl group or alkylene group having 8 to 16 carbon atoms as a main chain in the molecule and having a divalent phosphate group, a monomer (b) having no acidic group, a photopolymerization initiator (c), and a filler (d); a dental cement composition (Y) containing Portland cement powder (e) and an inorganic filler (f); The content of the Portland cement powder (e) is 60 to 90% by mass, and the content of the inorganic filler (f) is 10 to 40% by mass, A dental adhesive kit, wherein the self-adhesive dental composite resin (X) is photocured to produce a cured product having a flexural modulus in the range of 1.5 to 6 GPa.

2. 2. The dental adhesive kit according to claim 1, wherein the content of the filler (d) is 50 parts by mass or more per 100 parts by mass of the total amount of the self-adhesive dental composite resin (X).

3. 3. The method according to claim 2, wherein the filler (d) comprises a filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less and / or a filler (d-iii) having an average particle size of more than 1 μm and 10 μm or less. Includes dental adhesive kit.

4. The filler (d-ii) and / or the filler (d-iii) contains a silicon atom.

4. The dental adhesive kit according to claim 3, comprising an inorganic filler composed of silicon and / or an inorganic filler composed of an oxide of silicon atoms, the inorganic filler having hydroxyl groups on the surface thereof, and the hydroxyl groups being surface-treated with a surface treatment agent.

5. The filler (d) is a filler (d-i) having an average particle size of 1 nm or more and less than 0.1 μm. (I) a combination of a filler (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less, (d-i) a combination of a filler (d-i) having an average particle size of 1 nm or more and less than 0.1 μm and an average particle size of more than 1 μm and 10 μm or less (II) Combination with filler (d-iii) m or less, average particle size 1 nm or more and 0.1 μm or less Filler (d-i) having an average particle size of 0.1 μm or more and 1 μm or less (d-ii) 5. The dental adhesive kit according to claim 2, comprising at least one combination selected from the group consisting of a combination (III) of a filler (d-iii) having an average particle size of more than 1 μm and 10 μm or less, and a combination (IV) of fillers (d-ii) having an average particle size of 0.1 μm or more and 1 μm or less.

6. Portland cement powder (e) has the following composition: Calcium oxide (CaO): 55 to 85% by mass, Silicon dioxide (SiO 2 ): 10 to 40% by mass, Aluminum oxide (Al 2 O 3 ): 0 to 15% by mass, and Iron oxide (Fe 2 O 3 ): 0 to 10% by mass, The dental adhesive kit according to any one of claims 1 to 5, comprising:

7. 7. The dental adhesive kit according to claim 1, wherein the inorganic filler (f) is at least one selected from the group consisting of silica-based fillers, alumina fillers, and zirconia fillers.