Dental bonding kit

Abstract

The present invention provides a dental adhesive kit which exhibits excellent bonding durability of a multiple-package type dental adhesive composition to a surface that is obtained by coating a tooth formation surface with a one-package type self-adhesive dental composite resin. The present invention relates to a dental adhesive kit which comprises: a one-package type self-adhesive dental composite resin (X) that contains a monomer (a-1) that comprises, as the main chain, a divalent phosphoric acid group that has an alkyl group having 8 to 16 carbon atoms or an alkylene group in each molecule, a monomer (b) having no acidic group, a photopolymerization initiator (c) and a filler (d); and a multiple-package type dental adhesive composition (Y) that comprises a first agent and a second agent, which are packaged separately from each other, wherein the first agent contains a monomer (a) having an acidic group and a chemical polymerization initiator (e), while the second agent contains the monomer (b) having no acidic group. With respect to this dental adhesive kit, the bending modulus of elasticity of a cured product obtained by photocuring the self-adhesive dental composite resin (X) is within the range of 1.5 to 6 GPa; and the bending modulus of elasticity of a cured product obtained by chemically curing the multiple-package type dental adhesive composition (Y) is within the range of 1.5 to 6 GPa.

Description

Technical Field

[0001] The present invention relates to a dental adhesive kit comprising a one-component self-adhesive dental composite resin and a sub-packaged dental adhesive composition. More specifically, the present invention relates to a dental adhesive kit having excellent adhesive durability of the sub-packaged dental adhesive composition to a surface coated with the one-component self-adhesive dental composite resin on a tooth forming surface.

Background Art

[0002] Adhesive materials are used for the repair and treatment of living hard tissues of wet bodies (e.g., dentin, bone, etc.). As an adhesive material used for wet bodies, a resin-based curable composition comprising a radically polymerizable monomer, a polymerization initiator, etc. is widely used.

[0003] Teeth that have lost their function due to caries or accidents, etc. are repaired by fixing a crown repair material made of metal or ceramics, called an inlay or crown, to the tooth. For fixing the crown repair material to the tooth, an adhesive called dental resin cement is used.

[0004] In dental treatment, there are a "direct restoration method" in which a dental restoration material made of composite resin is directly filled into a cavity, and a so-called "indirect restoration method" in which a dental prosthesis such as a crown repair material made of metal or ceramics is adhered to a tooth using dental resin cement for fixing the crown repair material to the tooth. In the indirect restoration method, during the period until the crown restoration is produced, blocking with a temporary filling material or wearing a temporary restoration using a provisional restoration material is generally performed to protect the tooth forming surface.

[0005] In this context, a method has been proposed (hereinafter referred to as the resin coating method) that aims to improve the adhesion of dental resin cement, improve the internal fit of restorations, and protect exposed dentin. This method involves applying dental adhesive and dental composite resin to the cavity preparation surface immediately after cavity preparation and before impression taking to protect the exposed dentin and pulp, and then placing temporary restorations such as temporary fillings and temporary cements, with the aim of improving the adhesion between the dental resin cement and the dentin.

[0006] In recent years, self-adhesive dental composite resins have been developed, adding adhesive properties to conventional dental composite resins. These 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. In addition to the components of conventional dental composite resins, such as polyfunctional polymerizable monomers and fillers to provide mechanical strength and polymerization initiators to improve curability, self-adhesive dental composite resins also contain polymerizable monomers with acidic groups, which have been used in conventional dental adhesives, to provide adhesion to tooth structure (Patent Documents 1-5). Furthermore, Non-Patent Document 1 proposes a method of using self-adhesive dental composite resin as a lining material in "direct restorative methods." [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. 2010 / 041786 [Patent Document 5] U.S. Patent Application Publication No. 2011 / 217677 [Non-patent literature]

[0008] [Non-Patent Document 1] I. Baltacioglu, et al, Journal of Adhesion Science and Technology Vol.31, Issue 24 (2017) Pages 2719-2729 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The self-adhesive dental composite resins described in Patent Documents 1 to 5 could potentially be used as substitutes for dental adhesives and dental composite resins in resin coating methods. However, although all of the aforementioned self-adhesive dental composite resins exhibit excellent adhesion to tooth structure, our research has revealed that there is room for improvement in the adhesive durability of dental resin cement to the coated surface of the cured self-adhesive dental composite resin. Furthermore, while the self-adhesive dental composite resin described in Non-Patent Document 1 is excellent as a lining material for Class II cavities, it has been found to have issues with adhesive durability with dental resin cement when used in resin coating methods in combination with dental resin cement.

[0010] The present invention aims to provide a dental adhesive kit that offers excellent adhesive durability for a pre-packaged dental adhesive composition to a tooth surface coated with a one-component self-adhesive dental composite resin. Another objective of the present invention is to provide a dental adhesive kit in which a one-component self-adhesive dental composite resin exhibits excellent water resistance. [Means for solving the problem]

[0011] 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 a pre-packaged dental adhesive composition of a specific composition could solve the above problems, and further research led to the completion of the present invention.

[0012] In other words, the present invention encompasses the following inventions. [1] A one-component self-adhesive dental composite resin (X) comprising a monomer (a-1) having a divalent phosphate group with an alkyl group or alkylene group having 8 to 16 carbon atoms as the main chain in the molecule, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d), A dental adhesive composition (Y) comprising a first component and a second component, each separately packaged, wherein the first component comprises a monomer (a) having an acidic group and a chemical polymerization initiator (e), and the second component comprises a monomer (b) not having an acidic group, The flexural modulus of the cured product obtained by light-curing the aforementioned self-adhesive dental composite resin (X) is in the range of 1.5 to 6 GPa. A dental adhesive kit comprising a hardened product obtained by chemically curing the aforementioned sachet-type dental adhesive composition (Y), wherein the flexural modulus of the hardened product is in the range of 1.5 to 6 GPa. [2] The dental adhesive kit according to [1], wherein the flexural modulus of the cured product obtained by chemically curing the sachet-type dental adhesive composition (Y) is in the range of 3 to 6 GPa. [3] The dental adhesive kit according to [1] or [2], wherein the ratio ((X) / (Y)) of the flexural modulus of the cured product of the self-adhesive dental composite resin (X) to the flexural modulus of the cured product of the packaged dental adhesive composition (Y) is 0.5 to 3.0. [4] The dental adhesive kit according to any one of [1] to [3], wherein the content of the filler (d) is 50% by mass or more of the total amount of the self-adhesive dental composite resin (X) by 100% by mass. [5] The water absorption capacity of the cured self-adhesive dental composite resin (X) is 50 μg / mm³. 3 A dental adhesive kit as described in any of the following [1] to [4]. [6] The dental adhesive kit according to any one of [1] to [5], wherein the monomer (a) having an acidic group contained in the sachet-type dental adhesive composition (Y) comprises at least one selected from the group consisting of a monomer having a phosphate group, a monomer having a carboxylic acid group, and a monomer having a sulfonic acid group. [7] The dental adhesive kit according to [6], wherein the monomer (a) having an acidic group contained in the sachet-type dental adhesive composition (Y) is the same compound as the monomer (a-1) having a phosphate group contained in the self-adhesive dental composite resin (X). [8] A dental adhesive kit according to any one of [1] to [7], wherein the chemical polymerization initiator (e) comprises an organic peroxide and / or an inorganic peroxide. [9] A dental adhesive kit according to any one of [1] to [8], wherein the first component of the sachet-type dental adhesive composition (Y) further comprises a filler (d).

[10] The dental adhesive kit according to any one of [1] to [9], wherein the first component of the sachet-type dental adhesive composition (Y) further comprises a monomer (b) that does not have an acidic group.

[11] The dental adhesive kit according to any one of [1] to

[10] , wherein the first or second component of the sachet-type dental adhesive composition (Y) further comprises a silane coupling agent (g).

[12] The process includes the steps of curing a self-adhesive dental composite resin (X) of type 1, applying a sachet-type dental adhesive composition (Y) to a predetermined area where the self-adhesive dental composite resin (X) has been cured, and curing the applied sachet-type dental adhesive composition (Y), The self-adhesive dental composite resin (X) comprises a monomer (a-1) having a divalent phosphate group with an alkyl or alkylene group having 8 to 16 carbon atoms as the main chain in the molecule, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d). A method for restoring a tooth, comprising a sachet-type dental adhesive composition (Y) having a first agent and a second agent sachet-separated from each other, wherein the first agent comprises a monomer (a) having an acidic group and a chemical polymerization initiator (e), and the second agent comprises a monomer (b) not having an acidic group. [Effects of the Invention]

[0013] According to the present invention, a dental adhesive kit can be provided that exhibits excellent adhesive durability of a pre-packaged dental adhesive composition to a tooth formation surface coated with a one-component self-adhesive dental composite resin. Furthermore, according to the present invention, a dental adhesive kit can be provided in which a one-component self-adhesive dental composite resin has excellent water resistance. Furthermore, according to the present invention, the adhesive durability of the sachet-type dental adhesive composition to a coated surface coated with a cured self-adhesive dental composite resin is excellent, making it possible to provide a dental adhesive kit that can be suitably used in indirect restorative methods. [Modes for carrying out the invention]

[0014] 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.

[0015] The dental adhesive kit according to this embodiment comprises a one-component self-adhesive dental composite resin (X) (hereinafter sometimes simply referred to as "self-adhesive dental composite resin (X)") and a pre-packaged dental adhesive composition (Y), wherein 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, and the flexural modulus of the cured product obtained by chemically curing the pre-packaged dental adhesive composition (Y) is in the range of 1.5 to 6 GPa.

[0016] 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. Furthermore, the numerical ranges can be changed as appropriate based on the description in this specification. For example, regarding the content of monomer (b) without acidic groups in self-adhesive dental composite resin (X), a preferred range is 50 to 99 parts by mass in 100 parts by mass of the total amount of monomers in self-adhesive dental composite resin (X), but in relation to other components, this range can also be set to, for example, 60 to 99 parts by mass, and such a range is also included in the present invention.

[0017] The self-adhesive dental composite resin (X) of the present invention, from the viewpoint of adhesion to the sachet-type dental adhesive composition (Y), has a flexural modulus of elasticity of the photocured product 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. The method for measuring the flexural modulus of elasticity of the cured product is as described in the examples below. If the flexural modulus of elasticity 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. Furthermore, if the flexural modulus of elasticity of the cured product of the self-adhesive dental composite resin (X) exceeds 6 GPa, delamination is likely to occur at the interface between the self-adhesive dental composite resin (X) and the tooth structure.

[0018] The sachet-type dental adhesive composition (Y) of the present invention, from the viewpoint of adhesion to a self-adhesive dental composite resin (X), has a flexural modulus of 1.5 to 6 GPa in the range of a chemically cured product, 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. 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 sachet-type dental adhesive composition (Y) is less than 1.5 GPa, the mechanical strength of the cured product is insufficient. Furthermore, if the flexural modulus of the cured product of the pre-packaged dental adhesive composition (Y) exceeds 6 GPa, it will be higher than the upper limit of 6 GPa for the flexural modulus of the cured product of the self-adhesive dental composite resin (X). This makes it difficult to more closely approximate the flexural modulus of the cured product of the self-adhesive dental composite resin (X) with that of the pre-packaged dental adhesive composition (Y), and the adhesive durability of the pre-packaged dental adhesive composition (Y) to the surface coated with the self-adhesive dental composite resin (X) tends to decrease.

[0019] Furthermore, the ratio ((X) / (Y)) of the flexural modulus of the cured product of the one-component self-adhesive dental composite resin (X) to the flexural modulus of the cured product of the sachet-type dental adhesive composition (Y) is in the range of 0.25 to 4.0, preferably in the range of 0.5 to 3.0, more preferably in the range of 0.7 to 2.8, and even more preferably in the range of 0.85 to 2.75. The ratio of the flexural moduli of the cured products being within the above range, and the closer the flexural modulus of the cured product of the self-adhesive dental composite resin (X) to the flexural modulus of the cured product of the sachet-type dental adhesive composition (Y), contributes to further reducing the water absorption of the cured product of the self-adhesive dental composite resin (X) and to the superior adhesive durability of the sachet-type dental adhesive composition on the surface coated with the self-adhesive dental composite resin (X).

[0020] The self-adhesive dental composite resin (X) of the present invention suppresses the decrease in flexural modulus due to water absorption of the surface coated on the tooth preparation surface (such as the cavity preparation surface) and the decrease in adhesive durability of the pre-packaged dental adhesive composition, and the water absorption of the cured product of the one-component self-adhesive dental composite resin (X) is 50 μg / mm³. 3 Preferably, it is 45 μg / mm³ 3 More preferably, the following is preferred: 40 μg / mm³ 3 The following is even more preferable. The method for measuring the water absorption of the cured product is as described in the examples below.

[0021] The reason why the dental adhesive kit of the present invention exhibits superior adhesive durability of the sachet-type dental adhesive composition on a tooth formation surface coated with a self-adhesive dental composite resin (X) is not entirely clear, but it is presumed to be as follows. In the bonding of the self-adhesive dental composite resin (X) and the pre-packaged dental adhesive composition (Y) of the present invention, the similarity in flexural moduli of both materials is thought to be one of the reasons why stress concentration at the adhesive interface is reduced, resulting in excellent adhesive durability. Furthermore, the water absorption degradation of the cured self-adhesive dental composite resin (X), which is the adherend, is also a factor that greatly affects adhesive durability. Since the self-adhesive dental composite resin (X) of the present invention contains a monomer (a-1) having a divalent phosphate group with an alkyl or alkylene group having 8 to 16 carbon atoms as the main chain in the molecule, it is presumed that when combined with other components, the cured product has excellent water resistance and exhibits good adhesive durability.

[0022] The following describes each component used in the dental adhesive kit of the present invention.

[0023] • 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-1) having a divalent phosphate group with an alkyl group or alkylene group having 8 to 16 carbon atoms as the main chain in the molecule, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d).

[0024] <Monomer (a-1) having a divalent phosphate group with an alkyl or alkylene group having 8 to 16 carbon atoms as the main chain within the molecule> The monomer (a-1) used in the present invention, which has a divalent phosphate group having an alkyl group or alkylene group with 8 to 16 carbon atoms as its main chain (hereinafter referred to as "phosphate group monomer (a-1)"), can be used alone 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 monomer (a-1), in addition to having a phosphate group, the structure of the long-chain spacer in the main chain of the phosphate group monomer (a-1) allows the cured product to exhibit superior water resistance and better adhesive durability when combined with other components. The carbon number of the phosphate group monomer (a-1) is preferably 8 to 12. Specific examples of the phosphate group monomer (a-1) are given below.

[0025] Examples of monomers (a-1) 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, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, and their acid chlorides, alkali metal salts, and amine salts.

[0026] Among the monomers (a-1) having phosphate groups as described above, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, and 12-(meth)acryloyloxidedecyl dihydrogen phosphate are more preferred from the viewpoint of good adhesion strength to tooth structure and water resistance of the cured product, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, and 10-(meth)acryloyloxydecyl dihydrogen phosphate are even more preferred, and from the viewpoint of balance with curability, 10-(meth)acryloyloxydecyl dihydrogen phosphate is the most preferred.

[0027] From the viewpoint of good adhesion strength to tooth structure and water resistance of the cured product, the content of monomers having phosphate groups (a-1) in the self-adhesive dental composite resin (X) 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, per 100 parts by mass of total monomers.

[0028] <Monomer without acidic groups (b)> Examples of the monomer (b) having no acidic group include an asymmetric acrylamide-methacrylic acid ester compound (b-1); a hydrophobic monomer (b-2) having no acidic group and having a solubility in water at 25° C. of less than 10 g / L (hereinafter sometimes simply referred to as "hydrophobic monomer (b-2)"); and a hydrophilic monomer (b-3) having no acidic group and having a solubility in water at 25° C. of 10 g / L or more (hereinafter sometimes simply referred to as "hydrophilic monomer (b-3)"). The monomer (b) having no acidic group may be used alone or in combination of two or more. In the present specification, a compound having no acidic group and containing an acrylamide group and a methacryloyloxy group is defined as an asymmetric acrylamide-methacrylic acid ester compound (b-1), and a compound having no acidic group and not included in the asymmetric acrylamide-methacrylic acid ester compound (b-1) is classified into a hydrophobic monomer (b-2) and a hydrophilic monomer (b-3) according to the degree of hydrophilicity.

[0029] · Asymmetric acrylamide-methacrylic acid ester compound (b-1) In a preferred embodiment, there is provided a self-adhesive dental composite resin (X) further containing an asymmetric acrylamide-methacrylic acid ester compound (b-1). The asymmetric acrylamide-methacrylic acid ester compound (b-1) is preferably a compound represented by the following general formula (1) because it improves the adhesion of the self-adhesive dental composite resin (X) to dentin and easily adjusts the mechanical strength of the cured product within a desired range.

[0030] [Chemical formula] In the formula, Z is a linear, branched or cyclic aliphatic group or aromatic group which may have a substituent, 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-NR1 - May be interrupted by at least one bonding group selected from the group consisting of -. 1 This represents a linear or branched aliphatic group which may have a hydrogen atom or substituents.

[0031] Z is a site that adjusts the hydrophilicity of the asymmetric acrylamide-methacrylate compound (b-1). The C1-C8 aliphatic group represented by Z, which may have substituents, may be either a saturated aliphatic group (alkylene group, cycloalkylene group (e.g., 1,4-cyclohexylene group, etc.)) or an unsaturated aliphatic group (alkenylene group, alkylylene group), and is preferably a saturated aliphatic group (alkylene group) from the viewpoint of ease of acquisition or manufacture and chemical stability. From the viewpoint of adhesion to tooth structure and polymerization hardening properties, Z is preferably a C1-C8 aliphatic group, more preferably a C1-C4 aliphatic group, and even more preferably a C2-C4 aliphatic group. An alkylene group is preferred as the aliphatic group. Examples of the C1-C8 alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and an n-butylene group.

[0032] Examples of aromatic groups that may have substituents represented by Z include arylene groups and aromatic heterocyclic groups. Of the aromatic groups, arylene groups are preferred over aromatic heterocyclic groups. The heterocyclic ring of an aromatic heterocyclic group is generally unsaturated. The aromatic heterocyclic ring is preferably a 5-membered or 6-membered ring. As an arylene group, phenylene groups are preferred. Examples of heterocyclic rings of an aromatic heterocyclic group include furan rings, thiophene rings, pyrrole rings, oxazole rings, isoxazole rings, thiazole rings, isothiazole rings, imidazole rings, pyrazole rings, furazan rings, triazole rings, pyran rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, and 1,3,5-triazine rings. Of the aromatic groups, phenylene groups are particularly preferred.

[0033] R 1The aliphatic group in this can be either a saturated aliphatic group (alkyl group) or an unsaturated aliphatic group (alkenyl group, alkynyl group), but a saturated aliphatic group (alkyl group) is preferred from the viewpoint of ease of acquisition or manufacture and chemical stability. 1 Examples of linear or branched alkyl groups in this compound 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 Preferably, the group is a linear or branched C1-C8 aliphatic group which may have a hydrogen atom or substituents; more preferably, a linear or branched C1-C4 alkyl group which may have a hydrogen atom or substituents; and even more preferably, a linear or branched C1-C3 alkyl group which may have a hydrogen atom or substituents.

[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 / methacrylic acid 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 and polymerization hardening 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 of the asymmetric acrylamide-methacrylate compound (b-1) in the self-adhesive dental composite resin (X) is not particularly limited as long as the effects of the present invention are achieved, but in the self-adhesive dental composite resin (X) of the present invention, 1 to 60 parts by mass is preferred, 2 to 45 parts by mass is more preferred, 3 to 30 parts by mass is even more preferred, and 5 to 25 parts by mass is particularly preferred, based on 100 parts by mass of the total amount of monomers.

[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 the cured product of self-adhesive dental composite resin (X). As hydrophobic monomers (b-2), radical monomers that do not have acidic groups but have polymerizable groups are preferred, and from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. Hydrophobic 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 g / L. 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-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 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, glycerol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 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"), and 1,10-decanediol dimethacrylate (commonly known as "DD") 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, difunctional monomers based on aromatic compounds and difunctional monomers based on aliphatic compounds are preferred from the viewpoint of mechanical strength and handling properties. From the above viewpoint, Bis-GMA and D-2.6E are preferred as difunctional monomers based on aromatic compounds. From the above viewpoint, 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 are preferred as difunctional monomers based on aliphatic compounds.

[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).

[0047] The hydrophobic monomer (b-2) may be blended alone or in combination of two or more types. The content of hydrophobic monomer (b-2) in the self-adhesive dental composite resin (X) is preferably 20 to 98 parts by mass, more preferably 40 to 95 parts by mass, and even more preferably 60 to 92 parts by mass, based on 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). 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, and when the content is above the lower limit, it is easier to obtain the desired mechanical strength of the cured product.

[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 (b-1), and has a solubility in water at 25°C of 10 g / L or more, preferably 30 g / L 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- Examples include hydrophilic monofunctional (meth)-trihydroxymethyl-N-methyl(meth)acrylamide, N,N-dimethylacrylamide, and acrylamide monomers such as methylol(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, 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 2-hydroxyethyl (meth)acrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide are 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 effect 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 97.5 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 this specification, "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 self-adhesive dental composite resin (X) or the sachet-type dental adhesive composition (Y). 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 this specification, "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 may be, for example, 1.02 to 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 more, or tetrafunctional or more.

[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; 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one with a (poly)ethylene glycol chain introduced to the hydroxyl group; 1-hydroxycyclohexyl phenyl ketone with a (poly)ethylene glycol chain introduced to the hydroxyl group and / or phenyl group; and 1-hydroxycyclohexyl phenyl ketone with an -OCH2COO - Na + A modified version of 2-hydroxy-2-methyl-1-phenylpropan-1-one, in which a (poly)ethylene glycol chain is introduced to the hydroxyl group and / or phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one, with -OCH2COO added to the phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one. - Na +Examples include α-hydroxyalkylacetophenones with the introduction of 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-(dimethylamino)-1-[(4-morpholino)phenyl]-1-butanone, in which the amino group of α-aminoalkylphenones has been 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), R2 , R 3 , R 4 , R 5 , R 6 , and R 7 These are, independently of each other, linear or branched C1-C4 alkyl groups or halogen atoms, where M is a hydrogen ion, alkali metal ion, alkaline earth metal ion, magnesium ion, pyridinium ion (the pyridine ring may have substituents), or HN + R 9 R 10 R 11 (In the formula, R 9 , R 10 , and R 11 R is an ammonium ion represented independently by an organic group or a hydrogen atom, n is 1 or 2, X is a linear or branched alkylene group of C1-C4, and 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 7 The 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 Examples of organic groups include those similar to the substituents on the pyridine ring (excluding halogen atoms).

[0064] Among these, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 Compounds 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] R8 From the viewpoint of adhesion, p is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, particularly preferably 4 or more, preferably 1000 or less, more preferably 100 or less, even more preferably 75 or less, and particularly preferably 50 or less.

[0066] Among these water-soluble acylphosphine oxides, lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate, sodium phenyl(2,4,6-trimethylbenzoyl)phosphinate, 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 in powder form within the composition of the self-adhesive dental composite resin (X).

[0069] When the water-soluble photopolymerization initiator (c-1) is dispersed 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 in powder form, various particle shapes 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 adhesive strength is easily obtained. On the other hand, when the content of the water-soluble photopolymerization initiator (c-1) is below the upper limit, sufficient adhesive strength 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 mentioned above, examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl)phosphonate, and salts thereof. 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,Examples of compounds described in Japanese Patent Publication No. 9-3109 and Japanese Patent Publication No. 10-245525 include 3'-carbonyl-7-diethylaminocoumarin-7'-bis(butoxyethyl)aminocoumarin, 10-[3-[4-(dimethylamino)phenyl]-1-oxo-2-propenyl]-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]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, based on 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 adhesive strength 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 adhesive strength. 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 adhesive strength.

[0087] <Filler (d)> The self-adhesive dental composite resin (X) of the present invention must contain a filler (d) to adjust handling properties and to increase the mechanical strength of the cured product. Examples of filler (d) 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] Inorganic filler materials include quartz, silica; silica-based minerals such as kaolin, clay, mica, and other silica-based minerals; alumina; composite oxides (e.g., silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, silica-alumina-zirconia, and other silica-containing composite oxides); various types of glass (fused silica, lanthanum glass, borosilicate glass, soda glass, zinc glass, strontium glass, aluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium glass) Examples include silica-based glasses such as boroaluminosilicate glass, strontium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, barium glass (barium silicate glass, barium boroaluminosilicate glass, barium fluoroaluminosilicate glass, etc.), ceramics (for example, silica-based ceramics), ytterbium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, and silica-coated ytterbium fluoride. These can also be used individually or in combination of two or more. Among these, quartz, silica, composite oxides, silica-based glasses, silica-based ceramics, 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), more preferably quartz, silica, silica-zirconia, barium glass, ytterbium oxide, and silica-coated ytterbium fluoride, and even more preferably quartz, silica, silica-zirconia, barium glass, and silica-coated ytterbium fluoride. From the viewpoint of 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 specification, 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 dental adhesive kit in which the filler (d) of a self-adhesive dental composite resin (X) comprises an inorganic filler. Commercially available inorganic fillers can be used. Examples of commercially available products include "Aerosil® OX50", "Aerosil® 50", "Aerosil® 200", "Aerosil® 380", "Aerosil® R972", and "Aerosil® 130" (all of which are product names manufactured by Nippon Aerosil Co., Ltd.).

[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 diameter 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. If the average particle diameter is less than 0.05 μm, the filling rate of spherical fillers in the self-adhesive dental composite resin (X) decreases, which may result in lower mechanical strength. On the other hand, if the average particle size exceeds 5 μm, the surface area of ​​the spherical filler decreases, and there is a risk that a cured self-adhesive dental composite resin (X) with high mechanical strength cannot be obtained.

[0090] The inorganic filler may be pre-treated with a known surface treatment agent as needed to adjust the fluidity of the self-adhesive dental composite resin (X). Examples of surface treatment agents include silane coupling agents (g). Examples of silane coupling agents (g) include silane coupling agents represented by the following general formula (5). [ka] (In the formula, R 16This represents an organic group having 1 to 20 carbon atoms having at least one functional group selected from the group consisting of (meth)acryloyl groups, vinyl groups, and epoxy groups; a (meth)acryloyl group; a vinyl group; or an epoxy group. The organic group is not particularly limited and includes saturated or unsaturated aliphatic, cyclic aliphatic, or aromatic hydrocarbon groups. Among these, alkylene groups having 3 to 15 carbon atoms are particularly preferred. The organic group may also have substituents that do not contain carbon atoms, such as halogen atoms, hydroxyl groups, amino groups, mercapto groups, cyano groups, and nitro groups. The organic group may also contain bonds other than carbon-carbon bonds in its structure, such as ether bonds, ester bonds, amide bonds, sulfonyl bonds, urethane bonds, and thioether bonds. 16 Examples include (meth)acryloyloxyalkyl groups, glycidyloxyalkyl groups, aminoalkyl groups, mercaptoalkyl groups, etc. 17 R represents a hydroxyl group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. 17 The alkyl group may be linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, and n-pentyl groups. 18 , R 19 Each of these represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 5 carbon atoms, and R 17 , R 18 , and R 19 The alkoxy group may be linear, branched, or cyclic, and examples include methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, cyclobutoxy, tert-butoxy, n-pentyl, and cyclopentyloxy groups. 17 ~R 19 At least one of them is preferably an alkoxy group having 2 to 5 carbon atoms.

[0091] The silane coupling agent (g) is used in combination of one or more types. Known silane coupling agents (g) can be used without limitation, and silane coupling agents represented by general formula (5) are preferred. Specifically, examples of silane coupling agents (g) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltripoxysilane, vinyltributoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltris(β-methoxyethoxy)silane, 6-(meth)acryloy Examples include oxyhexyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, κ-methacryloyloxydecyltrimethoxysilane, κ-methacryloyloxydecyltriethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltriethoxysilane, γ-aminopropyltriethoxysilane, and (γ-mercaptopropyl)trimethoxysilane.

[0092] As for the surface treatment method, known methods can be used without particular limitation. For example, a method of spraying the surface treatment agent while vigorously stirring the inorganic filler, 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 for 100 parts by mass of inorganic filler before treatment.

[0093] The organic-inorganic composite filler used in the present invention is obtained by pre-adding monomers to the above-mentioned inorganic filler, forming a paste, polymerizing it, and then pulverizing it. 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. From the viewpoint of the handling properties and mechanical strength of the resulting 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.

[0094] 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.

[0095] 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 particle sizes of 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.

[0096] 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.

[0097] 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.

[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 fillers (d) may be a combination of (I) a filler with an average particle size of 1 nm or more and less than 0.1 μm (d-1) and a filler with an average particle size of 0.1 μm or more and less than 1 μm (d-2), a combination of (II) a filler with an average particle size of 1 nm or more and less than 0.1 μm (d-1) and a filler with an average particle size of more than 1 μm and less than 10 μm (d-3), or an average particle size of 1 nm or more and less than 0.1 μm The following combinations are preferred: (III) a filler (d-1) with a filler (d-2) having an average particle size of 0.1 μm or more and 1 μm or less, a filler (d-3) having an average particle size of more than 1 μm and 10 μm or less, and (IV) a combination of fillers (d-2) having an average particle size of 0.1 μm or more and 1 μm or less. Among these combinations, (I), (II), and (III) are more preferred from the viewpoint of the paste properties of the self-adhesive dental composite resin (X), with (I) and (II) being even more preferred. The combination of fillers (d-2) having an average particle size of 0.1 μm or more and 1 μm or less (IV) refers to an embodiment that includes two types of fillers (d-2) with different average particle sizes of 0.1 μm or more and 1 μm or less. In addition, in the above combinations, different types of fillers (d) of each particle size may be included. 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% by mass or more, more preferably 50-90% by mass, even more preferably 55-85% by mass, and particularly preferably 60-80% by mass, based on 100% by mass of the total amount of self-adhesive dental composite resin (X).

[0100] 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-1) having a divalent phosphate group with an alkyl or alkylene group having 8 to 16 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.

[0101] <Polymerization accelerator (f)> The self-adhesive dental composite resin (X) of the present invention may use a polymerization accelerator (f) together with a water-insoluble photopolymerization initiator (c-2) and / or a chemical polymerization initiator described later. Examples of polymerization accelerators (f) 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 compounds, 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 compounds, triazine compounds, copper compounds, tin compounds, vanadium compounds, and halogen compounds being preferred.

[0102] The amines used as polymerization accelerators (f) 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.

[0103] 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, at least one selected from the group consisting of N,N-bis(2-hydroxyethyl)-p-toluidine, 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino)n-butoxyethyl benzoate, and 4-(N,N-dimethylamino)benzophenone is preferably used from the viewpoint of providing excellent curability to the self-adhesive dental composite resin (X).

[0104] 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.

[0105] Examples of benzotriazole compounds and / or benzimidazole compounds include the compounds represented by the following general formula (6) and the compounds represented by the following general formula (7).

[0106] [ka]

[0107] [ka]

[0108] In the above general formulas (6) and (7), R 20 ~R 27 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.

[0109] R 20 ~R27 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, 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.

[0110] R 20 ~R 27 The aryl group represented by preferably has 6 to 14 carbon atoms, and examples include the phenyl group, naphthyl group, and anthyl group.

[0111] R 20 ~R 27 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.

[0112] R 20 ~R 27 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.

[0113] R 20 ~R 27Examples of the aralkyl group represented by include an alkyl group (particularly an alkyl group having 1 to 10 carbon atoms) substituted with an aryl group (particularly an aryl group having 6 to 10 carbon atoms), and specific examples include a benzyl group and the like.

[0114] R 20 ~R 27 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0115] R 20 ~R 27 is preferably a hydrogen atom or a methyl group.

[0116] The benzotriazole compound and the benzimidazole compound may be used alone or in combination of two or more. Specific examples of the benzotriazole compound and the benzimidazole compound include 1H-benzotriazole (hereinafter sometimes abbreviated as "BTA"), 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, benzimidazole, 5-methylbenzimidazole, 5,6-dimethylbenzimidazole, and the like. Among these, 1H-benzotriazole and 5-methyl-1H-benzotriazole are preferable in terms of the color tone and storage stability of the composition.

[0117] Examples of the sulfur-containing reducing inorganic compound include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, and the like. Among these, sulfites and bisulfites are preferable. Specific examples of the sulfur-containing reducing inorganic compound include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and the like. The sulfur-containing reducing inorganic compound may be used alone or in combination of two or more.

[0118] <00Examples of thiourea compounds include 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, tetracyclohexylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and pyridylthiourea. Among these, 4,4-dimethylethylenethiourea, pyridylthiourea, and N-benzoylthiourea are preferred.

[0119] Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, and pn-octyloxybenzaldehyde.

[0120] Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0121] Specific examples of borate compounds, barbiturate compounds, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, and sulfur-containing reducing inorganic compounds (e.g., sulfites and bisulfites) are those described in International Publication No. 2008 / 087977.

[0122] The polymerization accelerator (f) may contain one type alone or a combination of two or more types. The content of the polymerization accelerator (f) 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 (f) is above the lower limit, polymerization proceeds sufficiently and sufficient adhesive strength 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 (f) is below the upper limit, sufficient adhesion is easily obtained, and furthermore, precipitation of the polymerization accelerator (f) itself from the self-adhesive dental composite resin (X) can be suppressed, so it is more preferably 20 parts by mass or less.

[0123] <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 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, inorganic peroxides, and transition metal complexes are exemplified in the chemical polymerization initiator (e) of the sachet-type dental adhesive composition (Y) described later. The chemical polymerization initiator may be used alone or in combination of two or more types.

[0124] <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.

[0125] 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 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 100% by mass of the total amount of the self-adhesive dental composite resin (X).

[0126] 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).

[0127] 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-1) 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 (f). 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-1) and 65 to 97.5 parts by mass of monomers not having an acidic group (b). It is more preferable to include parts by mass of a photopolymerization initiator (c) in the amount of 0.1 to 5 parts by mass of a photopolymerization initiator (c), 120 to 560 parts by mass of a filler (d), and 0.01 to 10 parts by mass of a polymerization accelerator (f) per 100 parts by mass of total monomers, and it is even more preferable to include parts by mass of a photopolymerization initiator (c) in the amount of 0.15 to 2.5 parts by mass of a photopolymerization initiator (c), 150 to 400 parts by mass of a filler (d), and 0.1 to 5 parts by mass of a polymerization accelerator (f) per 100 parts by mass of total monomers.

[0128] 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. Generally, in the resin coating method, exposed dentin and pulp are protected by applying dental composite resin to the cavity preparation surface. If the dental composite resin used in the resin coating method 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 type self-adhesive dental composite resin (X) of the present invention is more preferably used filled in 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, a nozzle can be attached to the tip of the syringe to improve handling. The nozzle is preferably 25 mm in length and 1.5 mm or less in inner diameter at the opening, and more preferably 20 mm in length and 0.75 mm or less in inner diameter at the opening.

[0129] • Individually packaged dental adhesive composition (Y) The sachet-type dental adhesive composition (Y) of the present invention comprises a first agent and a second agent, each sachet separately from the other. The first agent contains a monomer (a) having an acidic group and a chemical polymerization initiator (e), while the second agent contains a monomer (b) that does not have an acidic group. By incorporating the monomer (a) having an acidic group, adhesion to tooth structure and dental prostheses can be imparted.

[0130] <Monomer having an acidic group (a)> Examples of monomers (a) having acidic groups include monomers having at least one acidic group such as a phosphate group, pyrophosphate group, thiophosphate group, phosphonic acid group, sulfonic acid group, or carboxylic acid group, and at least one polymerizable group such as an acryloyl group, methacryloyl group, vinyl group, or styrene group. Monomers (a) having acidic groups have affinity for the adherend and also have a demineralizing effect on tooth structure. Specific examples of monomers (a) having acidic groups are given below.

[0131] Examples of monomers having a phosphate group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, and 8-(meth) ) Acryloyl oxyoctyl dihydrogen phosphate, 9-(meth)acryloyl oxynonyl dihydrogen phosphate, 10-(meth)acryloyl oxydecyl dihydrogen phosphate, 11-(meth)acryloyl oxyundecyl dihydrogen phosphate, 12-(meth)acryloyl oxide decyl dihydrogen phosphate, 16-(meth)acryloyl oxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyl oxyeicosyl dihydrogen phosphate Hydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate Examples include phosphates, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphate, glycerol phosphate di(meth)acrylate, and their acid chlorides, alkali metal salts, ammonium salts, etc.

[0132] Examples of monomers having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and their acid chlorides, alkali metal salts, and ammonium salts.

[0133] Examples of monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, and 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate. Examples include phosphates, 9-(meth)acryloyloxynonyldihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, 11-(meth)acryloyloxyundecyldihydrogenthiophosphate, 12-(meth)acryloyloxidedecyldihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyeicosyldihydrogenthiophosphate, and their acid chlorides, alkali metal salts, ammonium salts, etc.

[0134] Examples of monomers having a phosphonic acid group include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecylphosphonoacetate, and their acid chlorides, alkali metal salts, and ammonium salts.

[0135] Examples of monomers having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.

[0136] Examples of monomers containing a carboxylic acid group include monomers having one carboxyl group in the molecule and monomers having multiple carboxyl groups in the molecule.

[0137] Examples of monomers having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, and 2-(meth)acryloyloxybenzoic acid. Examples include acryloyl acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate, and their acid halides.

[0138] Examples of monomers having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxidedodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, and 4-(meth) Examples include acryloyloxyethyl trimellitate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate, and their acid anhydrides or acid halides.

[0139] The monomer (a) having an acidic group may be used alone or in combination of two or more. Among these monomers (a) having an acidic group, one or more selected from the group consisting of monomers having a phosphate group, monomers having a carboxylic acid group, and monomers having a sulfonic acid group are preferred in terms of having high adhesive strength to dental substrates, and more preferably one or more selected from the group consisting of monomers having a phosphate group having two or more hydroxyl groups bonded to a phosphorus atom, monomers having multiple carboxyl groups in the molecule, and monomers having a sulfonic acid group, and 10-(meth)acryloyloxydecyldihydro One or more selected from the group consisting of dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxyethyl trimellitate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, and 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid are even more preferred. It is preferable that the monomer (a) having an acidic group in the individually packaged dental adhesive composition (Y) contains the same compound as the monomer (a-1) having a phosphate group contained in the self-adhesive dental composite resin (X). One preferred embodiment is a dental adhesive kit in which the monomer (a) having an acidic group in the sachet-type dental adhesive composition (Y) includes a monomer (a-1) having a divalent phosphate group having an alkyl group or alkylene group with 8 to 16 carbon atoms as the main chain in the molecule.

[0140] The content of the monomer (a) having an acidic group in the sachet-type dental adhesive composition (Y) is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 2 to 15 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. When the content of the monomer (a) having an acidic group is 1 part by mass or more, it is easy to obtain high adhesion to the self-adhesive dental composite resin (X), and when the content of the monomer (a) having an acidic group is 50 parts by mass or less, it is easy to maintain a balance between polymerization and adhesion. In this specification, the total amount of monomers in the sachet-type dental adhesive composition (Y) refers to the total mass of the monomer having an acidic group (a), the monomer not having an acidic group (b), and the silane coupling agent (g) described below, which are contained in the first and second components (however, if the sachet-type dental adhesive composition (Y) contains a silane coupling agent having polymerizable groups other than the silane coupling agent (g), then said silane coupling agent is also included in the total amount of monomers).

[0141] <Monomer without acidic groups (b)> Monomer (b) without acidic groups is a monomer that undergoes a radical polymerization reaction by a polymerization initiator to become a polymer. The first component of the sachet-type dental adhesive composition (Y) of the present invention contains monomer (b) without acidic groups. In one preferred embodiment, a dental adhesive kit is provided in which the first and second components of the sachet-type dental adhesive composition (Y) each contain monomer (b) without acidic groups. The monomer (b) without acidic groups of the sachet-type dental adhesive composition (Y) may be used alone or in combination of two or more types. When the first and second components contain monomer (b) without acidic groups, the monomer (b) without acidic groups of the first component and the monomer (b) without acidic groups of the second component may be the same or different. For example, when the first and second components each contain two or more monomers (b) without acidic groups, they may each contain at least one common monomer. The monomer (b) without acidic groups used in the first component of the sachet-type dental adhesive composition (Y) is the same as the monomer (b) without acidic groups used in the self-adhesive dental composite resin (X), and hydrophobic monomers (b-2) and hydrophilic monomers (b-3) are preferred. The monomer (b) without acidic groups contained in the second component is the same as the monomer (b) without acidic groups in the first component.

[0142] The hydrophobic monomer (b-2) improves the mechanical strength and handling properties of the sachet-type dental adhesive composition (Y).

[0143] Among the hydrophobic monomers (b-2) used in the individually packaged dental adhesive composition (Y), aliphatic compound-based bifunctional monomers are preferred, for example, glycerol dimethacrylate, triethylene glycol di(meth)acrylate, neopentyl glycol dimethacrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate, and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.

[0144] The hydrophilic monomer (b-3) used in the sachet-type dental adhesive composition (Y) promotes the penetration of the components of the sachet-type dental adhesive composition (Y) into the tooth structure, and also penetrates the tooth structure itself and adheres to the organic components (collagen) in the tooth structure. As the hydrophilic monomer (b-3) of the sachet-type dental adhesive composition (Y), a hydrophilic polymerizable monofunctional (meth)acrylate monomer is preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.

[0145] The monomers (b) that do not have acidic groups used in the sachet-type dental adhesive composition (Y) may be blended individually or in combination of two or more types. The amount of monomers (b) that do not have acidic groups is preferably 10 to 98 parts by mass, more preferably 50 to 95 parts by mass, and even more preferably 60 to 92 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. The content of hydrophobic monomer (b-2) is preferably 10 to 97 parts by mass, more preferably 50 to 95 parts by mass, and even more preferably 60 to 92 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y). Furthermore, the content of the hydrophilic monomer (b-3) is preferably 1 to 50 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 3 to 10 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention.

[0146] In the case where the monomer (b) of the sachet-type dental adhesive composition (Y) of the present invention, which does not have an acidic group, contains a mixture of two or more aromatic di(meth)acrylates represented by general formula (2), it is preferable that the sachet-type dental adhesive composition (Y) further contains a silane coupling agent (g). For the sachet-type dental adhesive composition (Y), the mixing ratio (mass ratio) of the mixture of two or more aromatic di(meth)acrylates represented by general formula (2) and the silane coupling agent (g) in the total mass of the first and second components is preferably 1:1 to 30:1, more preferably 3:1 to 25:1, and even more preferably 5:1 to 23:1, from the viewpoint of paste properties.

[0147] The first component of the sachet-type dental adhesive composition (Y) of the present invention contains a chemical polymerization initiator (e).

[0148] <Chemical polymerization initiator (e)> Examples of chemical polymerization initiators (e) include organic peroxides, inorganic peroxides, and transition metal complexes. Known initiators are not particularly limited and can be used. Chemical polymerization initiators (e) may be used individually or in combination of two or more.

[0149] Typical organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates. Among these, hydroperoxides and peroxyesters are particularly preferred, and peroxyesters are the most preferred because they show little variation in the usable time even when the sachet-type dental adhesive composition (Y) of the present invention is stored for a long period of time. One type of organic peroxide may be used alone, or two or more types may be used in combination.

[0150] Examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, and acetylacetone peroxide.

[0151] Examples of hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide (hereinafter sometimes abbreviated as "THP").

[0152] Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluylbenzoyl peroxide, and benzoyl peroxide.

[0153] Examples of dialkyl peroxides include α,α-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-bis(t-butylperoxy)3-hexine.

[0154] Examples of peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexanone, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclodecane, 2,2-bis(t-butylperoxy)butane, n-butyl4,4-bis(t-butylperoxy)valerate, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane.

[0155] As peroxyesters, any known peroxyester having an acyl group on one side of the peroxy group (-OO- group) and a hydrocarbon group (or a similar group) on the other side can be used without any limitations. Specific examples include α,α-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t- Examples include butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymalic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-thuloylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-m-thuloylbenzoate, t-butylperoxybenzoate (hereinafter sometimes abbreviated as "BPB"), and bis(t-butylperoxy)isophthalate. These can be used individually or in appropriate combinations of two or more.Among these, t-butylperoxymalic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, and t-butylperoxyacetate are preferred from the viewpoint of storage stability and reactivity, with t-butylperoxybenzoate being more preferred.

[0156] Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(2-methoxybutyl)peroxydicarbonate, and di(3-methyl-3-methoxybutyl)peroxydicarbonate.

[0157] Examples of inorganic peroxides include peroxodisulfates and peroxodiphosphates, and among these, peroxodisulfates are preferred in terms of curability. Specific examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate (hereinafter sometimes abbreviated as "KPS"), aluminum peroxodisulfate, and ammonium peroxodisulfate.

[0158] From the viewpoint of curability, the amount of organic peroxide and inorganic peroxide is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 2 parts by mass, per 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention.

[0159] Examples of transition metal complexes include copper compounds and vanadium compounds.

[0160] As copper compounds, monomer-soluble compounds are preferred. Specific examples include copper(II) carboxylates (e.g., copper(II) acetate, copper(II) isobutyrate, copper(II) gluconate, copper(II) citrate, copper(II) phthalate, copper(II) tartrate, copper(II) oleate, copper(II) octoate, copper(II) octate, copper(II) naphthenate, copper(II) methacrylate, 4-cyclohexylbutyrate (II)); β-diketone copper (e.g., copper(II) acetylacetone, copper(II) trifluoroacetylacetone, copper(II) hexafluoroacetylacetone, 2,2,6,6-tetramethylacetone); Examples include copper(II) carboxylates (e.g., copper(II) benzoylacetone), copper(II) β-ketoesters (e.g., copper(II) acetate), copper alkoxides (e.g., copper(II) methoxide, copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy)ethoxide, copper(II) 2-(2-methoxyethoxy)ethoxide), copper dithiocarbamate (e.g., copper(II) dimethyldithiocarbamate), salts of copper and inorganic acids (e.g., copper(II) nitrate), and copper(II) chloride. These may be used individually or in combination of two or more as appropriate. Among these, copper(II) carboxylates, copper(II) β-diketones, and copper(II) β-ketoesters are preferred from the viewpoint of solubility and reactivity with monomers, and copper(II) acetate and copper(II) acetylacetone are particularly preferred.

[0161] From the viewpoint of curability, the copper compound content is preferably 0.000005 to 1 part by mass per 100 parts by mass of the total amount of monomers (total mass of the first and second components) in the sachet-type dental adhesive composition (Y) of the present invention.

[0162] Examples of vanadium compounds include vanadium acetylacetonate, vanadyl acetylacetonate (hereinafter sometimes abbreviated as "VOAA"), vanadyl stearate, vanadium naphthenate, and vanadium benzoylacetonate, with vanadium acetylacetonate and vanadyl acetylacetonate being particularly preferred.

[0163] From the viewpoint of curability, the vanadium compound content is preferably 0.005 to 1 part by mass per 100 parts by mass of the total amount of monomers (total mass of the first and second components) in the sachet-type dental adhesive composition (Y) of the present invention.

[0164] <Filler (d)> The first and / or second component of the sachet-type dental adhesive composition (Y) of the present invention preferably contains a filler (d).

[0165] Examples of fillers (d) used in the pre-packaged dental adhesive composition (Y) include those similar to those used in the self-adhesive dental composite resin (X). Fillers (d) may be used individually or in combination of two or more types. Furthermore, the fillers (d) of the self-adhesive dental composite resin (X) and the fillers (d) of the pre-packaged dental adhesive composition (Y) may be the same or different. One preferred embodiment is a dental adhesive kit in which the pre-packaged dental adhesive composition (Y) comprises a first agent and a second agent, each packaged separately, wherein the first agent comprises a monomer having an acidic group (a), a monomer without an acidic group (b), a filler (d), and a chemical polymerization initiator (e), and the second agent comprises a monomer without an acidic group (b) and a filler (d).

[0166] As the filler (d) used in the individually packaged dental adhesive composition (Y), an inorganic filler is preferred, and silica, or silica-based ceramics and glass, is more preferred.

[0167] To improve curability, mechanical strength, and handling, the filler (d) used in the sachet-type dental adhesive composition (Y) may be pre-treated with a known surface treatment agent. Examples of surface treatment agents and surface treatment methods are the same as those used for surface treatment of inorganic fillers in self-adhesive dental composite resins (X).

[0168] The content of filler (d) in the sachet-type dental adhesive composition (Y) is preferably 10 to 80% by mass, more preferably 20 to 77% by mass, and even more preferably 30 to 75% by mass, based on 100% by mass of the total amount of the sachet-type dental adhesive composition (Y) of the present invention (total mass of the first and second components).

[0169] <Polymerization accelerator (f-1)> The sachet-type dental adhesive composition (Y) may contain a polymerization accelerator (f-1) in its first and / or second component. In one embodiment, a dental adhesive kit is provided in which the second component of the sachet-type dental adhesive composition (Y) contains a polymerization accelerator (f-1). The polymerization accelerator (f-1) is not particularly limited as long as it is a polymerization accelerator for chemical polymerization. Examples of polymerization accelerators (f-1) include amines, sulfinic acid and its salts, benzotriazole compounds, benzimidazole compounds, sulfur-containing reducing inorganic compounds, and thiourea compounds. Specific examples of amines are the same as those used for polymerization accelerator (f) in self-adhesive dental composite resin (X). The polymerization accelerator (f-1) may be used alone or in combination of two or more types.

[0170] The amines used as polymerization accelerators (f-1) in the individually packaged dental adhesive composition (Y) include aromatic amines and aliphatic amines, similar to those used as polymerization accelerators (f) in the self-adhesive dental composite resin (X). As for aromatic amines, N,N-bis(2-hydroxyethyl)-p-toluidine is preferred in terms of redox reactivity.

[0171] As for aliphatic amines, tertiary aliphatic amines are preferred in terms of redox reactivity, and among them, N-methyldiethanolamine, triethanolamine, and 2-(dimethylamino)ethyl methacrylate are particularly preferred.

[0172] The amine content is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. When the content is above the lower limit, the adhesive strength of the resulting sachet-type dental adhesive composition (Y) to wet bodies such as tooth structure is better. On the other hand, when the content is below the upper limit, the color stability of the resulting sachet-type dental adhesive composition (Y) is better.

[0173] The content of sulfinic acid and its salts is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. In both cases where the content is above the lower limit and below the upper limit, the mechanical strength of the cured product of the resulting sachet-type dental adhesive composition (Y) is superior.

[0174] The benzotriazole compound content is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. In both cases where the content is above the lower limit and below the upper limit, the mechanical strength of the cured product of the resulting sachet-type dental adhesive composition (Y) is superior.

[0175] The benzimidazole compound content is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. In both cases where the content is above the lower limit and below the upper limit, the mechanical strength of the cured product of the resulting sachet-type dental adhesive composition (Y) is superior.

[0176] The content of the sulfur-containing reducing inorganic compound is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. When the content is above the lower limit, the adhesive strength of the resulting sachet-type dental adhesive composition (Y) to wet materials such as tooth structure is superior. On the other hand, when the content is below the upper limit, the mechanical strength of the cured product of the resulting sachet-type dental adhesive composition (Y) is superior.

[0177] The thiourea compound content is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention. In both cases where the content is above the lower limit and below the upper limit, the mechanical strength of the cured product of the resulting sachet-type dental adhesive composition (Y) is superior.

[0178] <Polymerization accelerator for photopolymerization (f-2)> Furthermore, in order to enhance photocurability, a photopolymerization initiator (i), described later, and a polymerization accelerator for photopolymerization (f-2) (hereinafter sometimes simply referred to as "polymerization accelerator (f-2)") may be used in combination. If the sachet-type dental adhesive composition (Y) contains a photopolymerization initiator (i), the polymerization accelerator (f-2) may be included in at least one of the first and second components. For example, if the first component contains a photopolymerization initiator (i), the second component may contain a polymerization accelerator (f-2). The polymerization accelerator (f-2) is not particularly limited as long as it can be used for photopolymerization, and examples include compounds that can be used for photopolymerization among the polymerization accelerators (f) in self-adhesive dental composite resins (X), and a polymerization accelerator that is not included in the polymerization accelerator (f-1) in the sachet-type dental adhesive composition (Y) is preferred. Examples of polymerization accelerators (f-2) include aldehydes, thiol compounds, and triazine compounds (e.g., triazine compounds substituted with trihalomethyl groups). Examples of aldehydes and thiol compounds are the same as those used for polymerization accelerators (f) in self-adhesive dental composite resins (X). Polymerization accelerators (f-2) may be used individually or in combination of two or more. Among the triazine compounds, any known s-triazine compound having at least one trihalomethyl group, such as a trichloromethyl group or a tribromomethyl group, can be used without restriction as a triazine compound substituted with a trihalomethyl group.

[0179] The triazine compound content is preferably 0.005 to 0.3 parts by mass, more preferably 0.008 to 0.2 parts by mass, and even more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention.

[0180] <Silane coupling agent (g)> The silane coupling agent (g) is preferably incorporated into the first or second component of the sachet-type dental adhesive composition (Y) for the purpose of further improving the adhesion of the sachet-type dental adhesive composition (Y) to a surface coated with the self-adhesive dental composite resin (X). Examples of the silane coupling agent (g) include those similar to the silane coupling agent (g) used for surface treatment of the inorganic filler of the self-adhesive dental composite resin (X) (preferably a silane coupling agent represented by general formula (5)). One preferred embodiment is a sachet-type dental adhesive composition (Y) in which the second component of the sachet-type dental adhesive composition (Y) contains a monomer (b) that does not have an acidic group, a filler (d), a polymerization accelerator (f-1), and a silane coupling agent (g).

[0181] Among the silane coupling agents (g) used in the individually packaged dental adhesive composition (Y), particularly in terms of adhesion to surfaces coated with self-adhesive dental composite resin (X), γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 6-(meth)acryloyloxyhexyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, κ-methacryloxydecyltrimethoxysilane, κ-methacryloxydecyltriethoxysilane, 11-(meth)acryloyloxyundecyltrimeth Xysilane and 11-(meth)acryloyloxyundecyltriethoxysilane are preferred, γ-methacryloxypropyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and 11-(meth)acryloyloxyundecyltriethoxysilane are more preferred, and 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and 11-(meth)acryloyloxyundecyltriethoxysilane are even more preferred.

[0182] The content of the silane coupling agent (g) is preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 2 to 30 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention, in order to have excellent adhesive strength. The content of the silane coupling agent (g) is preferably 0.1 to 10.0% by mass of the total amount of the sachet-type dental adhesive composition (Y) of the present invention, in order to have excellent adhesive strength, more preferably 0.5 to 9.0% by mass, even more preferably 1.0 to 8.0% by mass, and particularly preferably 1.2 to 7.0% by mass, from the viewpoint of adhesive durability to the self-adhesive dental composite resin (X). Note that the silane coupling agent (g) incorporated into the sachet-type dental adhesive composition (Y) does not include the silane coupling agent (g) used as a surface treatment agent for surface treatment of the inorganic filler of the sachet-type dental adhesive composition (Y).

[0183] <Photopolymerization initiator (i)> To make the sachet-type dental adhesive composition (Y) of the present invention a dual-cure type in which polymerization is initiated by light irradiation, a photopolymerization initiator (i) may be incorporated into at least one of the first and second components. Examples of the photopolymerization initiator (i) include the water-soluble photopolymerization initiator (c-1) used in self-adhesive dental composite resin (X), a water-insoluble photopolymerization initiator (c-2), α-aminoacetophenones, and water-soluble acylphosphine oxides disclosed in Japanese Patent Publication No. 3-57916. The water-insoluble photopolymerization initiator (c-2) is preferred, and α-diketones and (bis)acylphosphine oxides other than the water-soluble photopolymerization initiator (c-1) are more preferred.

[0184] Examples of α-aminoacetophenones include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-pentanone, and 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-pentanone.

[0185] The photopolymerization initiator (i) may be used alone or in combination of two or more types. The content of the photopolymerization initiator (i) is preferably in the range of 0.005 to 10 parts by mass, and more preferably in the range of 0.01 to 5 parts by mass, based on 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y) of the present invention.

[0186] The sachet-type dental adhesive composition (Y) of the present invention may contain a fluoride ion-releasing substance for the purpose of imparting acid resistance to tooth structure. As the fluoride ion-releasing substance, those exemplified in the self-adhesive dental composite resin (X) can be used.

[0187] The sachet-type dental adhesive composition (Y) of the present invention may contain additives such as stabilizers (polymerization inhibitors), colorants (dyes, pigments), fluorescent agents, ultraviolet absorbers, solvents such as organic solvents, and thickeners. One additive may be used alone, or two or more may be used in combination. The sachet-type dental adhesive composition (Y) may also contain antimicrobial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxide decylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecylammonium chloride, and triclosan. In some embodiments, the solvent content (e.g., water, organic solvent) in the sachet-type dental adhesive composition (Y) 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 100% by mass of the total amount of the sachet-type dental adhesive composition (Y).

[0188] The first agent of the present invention may consist substantially only of a monomer having an acidic group (a), a monomer without an acidic group (b), a chemical polymerization initiator (e), and a filler (d). Similarly, the second agent of the present invention may consist substantially only of a monomer without an acidic group (b), a filler (d), and a polymerization accelerator (f-1).

[0189] The sachet-type dental adhesive composition (Y) of the present invention can be manufactured, for example, by mixing all components except the powdered component (filler (d)), obtaining a solution, and then adding the powdered component.

[0190] The dental adhesive kit of the present invention can be suitably used in dental treatment using indirect restorative methods with dental resin cement. One preferred embodiment is a tooth restoration method comprising the steps of curing a one-component self-adhesive dental composite resin (X), applying a sachet-type dental adhesive composition (Y) to a predetermined area where the self-adhesive dental composite resin (X) has cured, and curing the applied sachet-type dental adhesive composition (Y), wherein the self-adhesive dental composite resin (X) comprises a monomer (a-1) having a divalent phosphate group having an alkyl group or alkylene group with 8 to 16 carbon atoms as a main chain in the molecule, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d), and the sachet-type dental adhesive composition (Y) comprises a first agent and a second agent sachet to each other, wherein the first agent comprises a monomer (a) having an acidic group and a chemical polymerization initiator (e), and the second agent comprises a monomer (b) without an acidic group. The process of applying the sachet-type dental adhesive composition (Y) is not particularly limited, and the sachet-type dental adhesive composition (Y) can be applied, coated, or built up on a predetermined area where the self-adhesive dental composite resin (X) has hardened. The steps of curing the one-component self-adhesive dental composite resin (X) and curing the applied sachet-type dental adhesive composition (Y) are not particularly limited, and known curing methods (photopolymerization, thermal polymerization, etc.) can be used.

[0191] 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]

[0192] 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.

[0193] 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.

[0194] • One-component self-adhesive dental composite resin (X) [Monomers containing a phosphate group (a-1)] MDP:10-Methacryloyloxydecyldihydrogenphosphate [Monomers with acidic groups other than monomers with phosphate groups (a-1)] GPDM: Glycerol Phosphate Dimethacrylate 4-META:4-Methacryloyloxyethyl trimellitic anhydride

[0195] [Monomers without acidic groups (b)] Bis-GMA: 2,2-Bis[4-(2-hydroxy-3-methacryloyloxypropoxy)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 DD:1,10-Decanediol dimethacrylate MAEA: N-methacryloyloxyethylacrylamide DEAA: N,N-Diethylacrylamide HEMA: 2-hydroxyethyl methacrylate

[0196] [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:dl-Camphorquinone BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide

[0197] [Filler (d)] Filler 1: Ultrafine particle silica "Aerosil® R 972" manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm Filler 2: Silane-treated silica powder Silica powder (manufactured by Nichitsu Co., Ltd., product name: High Silica) was crushed in a ball mill to obtain crushed silica powder. The average particle size of the obtained crushed silica powder was measured by volume using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and was found to be 2.2 μm. 100 parts by mass of this crushed silica powder was surface-treated with 4 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain filler 2. Filler 3: 100 g of GM27884 NF180 grade (barium boroaluminosilicate glass manufactured by SCHOTT, 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: 100 g of 8235 UF0.7 grade (barium boroaluminosilicate glass manufactured by SCHOTT, 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).

[0198] [Polymerization accelerator (f)] DABE: 4-(N,N-dimethylamino)ethyl benzoate

[0199] [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0200] Next, the components of the individual-packaged dental adhesive compositions (Y) of the examples and comparative examples are listed below, along with their abbreviations.

[0201] • Individually packaged dental adhesive composition (Y) [Monomers containing acidic groups (a)] MDP:10-Methacryloyloxydecyldihydrogenphosphate GPDM: Glycerol Phosphate Dimethacrylate

[0202] [Monomers without acidic groups (b)] HEMA: 2-hydroxyethyl methacrylate Bis-GMA: 2,2-Bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane D-2.6E: 2,2-Bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) NPG: Neopentyl glycol dimethacrylate

[0203] [Filler (d)] Filler 5: Quartz (manufactured by MARUWA QUARTZ) was ground in a ball mill to obtain quartz powder with an average particle size of approximately 4.5 μm. 100 parts by mass of this quartz powder was surface-treated with 3 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by conventional methods to obtain filler 5. Filler 6: Barium silicate glass (manufactured by ESTEC, product code "Raysorb E-3000") was crushed in a ball mill to obtain barium glass powder with an average particle size of approximately 2.4 μm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by conventional methods to obtain filler 6. Filler 7: Aluminum oxide, manufactured by Nippon Aerosil Co., Ltd., product name "AEROXIDE Alu C", average particle size: 13nm

[0204] [Chemical polymerization initiator (e)] Copper(II) acetate VOAA: Vanadylacetylacetonate BPB: t-butylperoxybenzoate BPO: Benzoylperoxide KPS: Potassium peroxodisulfate THP: 1,1,3,3-tetramethylbutylhydroperoxide

[0205] [Polymerization accelerator (f-1)] TPBSS: Sodium triisopropylbenzenesulfinate (2,4,6-triisopropylbenzenesulfinate) DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine BTA: 1H-benzotriazole DMETU: 4,4-dimethylethylenethiourea

[0206] [Silane coupling agent (g)] γ-MPS: γ-methacryloyloxypropyltrimethoxysilane 8-MOS:8-Methacryloyloxyoctyltrimethoxysilane 11-MUS:11-Methacryloyloxyundecyltrimethoxysilane

[0207] [Photopolymerization initiator (i)] CQ:dl-Camphorquinone

[0208] [others] DABE: 4-(N,N-dimethylamino)ethyl benzoate (polymerization accelerator for photopolymerization) BHT: 3,5-di-t-butyl-4-hydroxytoluene (stabilizer)

[0209] [Examples 1-22 and Comparative Examples 1-7] [Preparation of individually packaged dental adhesive composition (Y)] The first agent and the second agent having the compositions shown in Table 1 were prepared. For the first agent, after mixing the components other than the powdery components (fillers), stirring was performed to obtain a uniform solution, and then the powdery components were kneaded in and defoamed. The powdery components in the first agent were in a dispersed state in the powdery state. Also, for the second agent, after mixing the components other than the powdery components (fillers and TPBSS), stirring was performed to obtain a uniform solution, and then the powdery components were kneaded in and defoamed. The powdery components in the second agent were in a dispersed state in the powdery state. The two agents were each filled into a double syringe (manufactured by SULZER MIXPAC; 5 mL double syringe), and the plunger was set. A mixing tip (manufactured by SULZER MIXPAC) was attached to the tip of the double syringe, and the two agents were automatically mixed at a mass ratio of 1:1, and the mixture was used as a dental adhesive composition, and its properties were examined according to the method of Test Example 1 below. The results are shown in Table 1.

[0210] [Preparation of one-paste type self-adhesive dental composite resin (X)] The raw materials shown in Tables 2 to 4 were mixed and kneaded at room temperature (23°C) in the dark to prepare a paste-like one-paste type 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 to 4.

[0211] Test Example 1 Flexural modulus 1-1) Photo-curing The flexural modulus was evaluated by a flexure test in accordance with ISO 4049:2009. Specifically, it was as follows. The prepared paste (composition for one-paste type self-adhesive dental composite resin) was filled into a SUS mold (vertical 2 mm × horizontal 25 mm × thickness 2 mm), and the top and bottom (2 mm × 25 mm surface) of the paste were pressure-bonded with a slide glass. Then, using a dental visible light irradiator "Pencure 2000" (manufactured by Morita Corporation), the back surface of the paste was irradiated with light at five positions on one side for 10 seconds each through the slide glass to cure the paste. For the obtained cured product, a three-point flexure test was performed using a universal testing machine (Autograph "AG-I 100 kN", manufactured by Shimadzu Corporation) with a span distance of 20 mm and a crosshead speed of 1 mm / min, the flexural modulus was measured (n = 5), and the average value was calculated.

[0212] 1-2) Chemical curing The bending modulus was evaluated by a bending test in accordance with ISO 4049:2009. Specifically, the following was performed: The first and second components of the prepared paste (packaged dental adhesive composition) were automatically mixed in a mass ratio of 1:1 using a mixing tip to obtain the dental adhesive composition, which was then filled into a stainless steel mold (2 mm long x 25 mm wide x 2 mm thick). The top and bottom surfaces (2 mm x 25 mm) of the paste were pressed together with glass slides, and the two glass slides were fixed with a 25 mm wide double clip. The sample fixed with the double clip was left to polymerize and harden in a 37°C incubator for 1 hour. After that, the sample was removed from the incubator, the polymerized and hardened composition was removed from the mold, and it was stored immersed in 37°C distilled water for 24 hours. The hardened 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 20 mm and a crosshead speed of 1 mm / min. The bending modulus was measured (n=5) and the average value was calculated.

[0213] Test Example 2: Water Absorption Strength was evaluated by a water absorption test in accordance with ISO 4049:2009. A single-component self-adhesive dental composite resin was placed in a metal mold (15 mm in diameter, 1 mm thick) which was placed on a glass slide with a polyester film on top. Another polyester film was placed on top, and then pressure was applied using a glass slide to remove excess paste. The sample was then cured by irradiating it with light for 10 seconds at 9 points on both sides using the aforementioned "PenCure 2000" curing lamp. Immediately after irradiation, the mold and test piece were placed in a constant temperature incubator at 37 ± 2°C. Fifteen minutes after the start of irradiation, the test piece was removed from the mold to obtain a cured single-component self-adhesive dental composite resin.

[0214] The cured material was stored in a desiccator at 37°C until its mass stabilized, and its mass was measured (Mass A). The cured material was then immersed in water at 37°C for 7 days. After immersion, the cured material was dried until its mass stabilized, as before immersion, and its mass was measured again (Mass B). The water absorption of the cured material was calculated using the following formula. Water absorption of cured material (μg / mm³) 3 ) = {(mass B - mass A) ÷ volume of hardened material}

[0215] Test Example 3: Tensile bonding strength of dental resin cement to a self-adhesive dental composite resin coated surface. A hydroxyapatite plate (HAp plate, apatite pellet APP-610, φ13×2mm, manufactured by HOYA Technosurgical Corporation) was polished under running water with #1000 silicon carbide paper (manufactured by Nippon Kenji Co., Ltd.). After polishing, the surface was dried by air blowing to obtain a smooth surface. A 0.5mm thick Viton rubber (fluororubber) with a 7mm diameter circular hole was placed on the dried smooth surface, and the self-adhesive dental composite resin prepared in each example or comparative example was filled into the circular hole and covered with a release film (polyester). Next, a glass slide was placed on the release film and pressed down to smooth the surface coated with the self-adhesive dental composite resin. Next, the self-adhesive dental composite resin was irradiated with light for 10 seconds using a dental LED light curing device (Morita Corporation, product name "PenCure 2000") through the release film to cure the self-adhesive dental composite resin and obtain a cured product.

[0216] An adhesive tape with a diameter of 3 mm and a thickness of approximately 150 μm was applied to the surface of the cured self-adhesive dental composite resin (hereinafter also referred to as the resin-coated surface) to define the bonding area. One end face (circular cross-section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) was bonded to the bonding surface using the dental resin cement (packaged dental adhesive composition (Y)) prepared in each example or comparative example. After bonding, the sample was left to stand at room temperature for 30 minutes, and then immersed in distilled water to obtain a test sample for adhesion testing. Ten of these test samples were prepared and left to stand in a constant temperature incubator maintained at 37°C for 24 hours. To evaluate the bonding durability, a thermal cycle was performed 4,000 times, in which the samples were alternately immersed in cold water at 4°C and hot water at 60°C for 1 minute each time, after which the tensile bonding strength was measured.

[0217] The tensile adhesive strength of the aforementioned adhesive test samples was measured using a universal testing machine (Shimadzu Corporation, Autograph "AG-I 100kN") with a crosshead speed set to 2 mm / min, and the average value was determined. In the confirmation of the interface failure rate of the HAp plate-self-adhesive dental composite resin described later, if the interface failure rate was a value other than 0%, it was assumed that the HAp plate-self-adhesive dental composite resin interface fractured first, and the tensile adhesive strength of the dental resin cement to the resin-coated surface could not be measured, and the result was classified as "unmeasurable".

[0218] The tensile adhesive strength of the dental resin cement to the resin-coated surface is preferably 20 MPa or higher, more preferably 25 MPa or higher, and even more preferably 30 MPa or higher.

[0219] Test Example 4: Interfacial failure rate of HAp board-self-adhesive dental composite resin For each of the adhesive test samples in which tensile adhesive strength was measured for the above-mentioned adhesive durability, the state of the interface between the HAp board and the self-adhesive dental composite resin (X) after the test was visually observed, and the percentage of fracture at the interface was calculated using the following formula.

[0220] HAp plate - Self-adhesive dental composite resin (X) interface failure rate (%) = {(Number of samples that failed at the HAp plate - Self-adhesive dental composite resin (X) interface) / 10} × 100 If the interfacial failure rate between the HAp plate and the self-adhesive dental composite resin (X) is 0%, it means that the self-adhesive dental composite resin (X) exhibits good adhesion to HAp.

[0221] [Table 1]

[0222] [Table 2]

[0223] [Table 3]

[0224] [Table 4]

[0225] From the results of Tables 2 and 3, the one-paste type self-adhesive dental composite resin (X) of the examples had a flexural modulus of 2.6 to 5.8 GPa, and its water absorption was 38 μg / mm 3 or less. The flexural modulus of the multi-paste type dental adhesive composition (Y) was 3.8 to 5.7 GPa, and the tensile adhesive strength of the dental resin cement with respect to the coating surface by the self-adhesive dental composite resin was 21 MPa or more, indicating excellent adhesive durability. Also, in the examples, the interfacial fracture rate of the HAp plate - self-adhesive dental composite resin was 0%. From this, it was confirmed that the self-adhesive dental composite resin (X) showed good adhesiveness to dentin. On the other hand, as shown in Table 4, in Comparative Examples 1 and 2 where the flexural modulus of the one-paste type self-adhesive dental composite resin was 7.8 GPa or more, it was confirmed that the tensile adhesive strength of the dental resin cement with respect to the resin coating surface was as low as 16 MPa or less. Also, in Comparative Example 6 where the flexural modulus of the one-paste type self-adhesive dental composite resin was 6.6 GPa, and in Comparative Example 7 where the flexural modulus of the multi-paste type dental adhesive composition (Y) was 6.7 GPa (Composition 9), it was also confirmed that the tensile adhesive strength of the dental resin cement with respect to the resin coating surface was as low as 16 MPa or less. Furthermore, in Comparative Examples 3 to 5 having no monomer (a-1) having a phosphate group, the interfacial fracture rate of the HAp plate - self-adhesive dental composite resin was 100%, and the tensile adhesive strength of the dental resin cement with respect to the resin coating surface could not be measured. [Industrial Applicability]

[0226] The dental adhesive kit of the present invention can be suitably used in indirect restorative methods of dental treatment.

Claims

1. A one-component self-adhesive dental composite resin (X) comprising a monomer (a-1) having a divalent phosphate group with an alkyl group or alkylene group having 8 to 16 carbon atoms as the main chain in the molecule, a monomer (b) without an acidic group, a photopolymerization initiator (c), and a filler (d), A dental adhesive composition (Y) comprising a first agent and a second agent, each packaged separately, wherein the first agent comprises a monomer (a) having an acidic group and a chemical polymerization initiator (e), and the second agent comprises a monomer (b) not having an acidic group, The content of monomer (b) without acidic groups in the self-adhesive dental composite resin (X) is 60 to 99 parts by mass per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). The following conditions (i) and / or (ii) must be met: (i) The monomer (b) in the self-adhesive dental composite resin (X) that does not have an acidic group comprises an asymmetric acrylamide methacrylate compound (b-1), The content of the asymmetric acrylamide / methacrylate compound (b-1) is 1 to 45 parts by mass per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X). (ii) The self-adhesive dental composite resin (X) contains a monomer (b) that does not have an acidic group, and includes a hydrophobic monomer (b-2) that does not have an acidic group. The hydrophobic monomer (b-2) content is 40 to 98 parts by mass per 100 parts by mass of the total monomer amount in the self-adhesive dental composite resin (X). The content of monomer (b) without an acidic group in the sachet-type dental adhesive composition (Y) is 50 to 95 parts by mass per 100 parts by mass of the total amount of monomers in the sachet-type dental adhesive composition (Y), The second agent of the sachet-type dental adhesive composition (Y) contains a monomer (b) that does not have an acidic group, which is at least one selected from the group consisting of hydrophobic monomers (b-2) and hydrophilic monomers (b-3). The flexural modulus of the cured product obtained by light-curing the self-adhesive dental composite resin (X) is in the range of 1.5 to 6 GPa. A dental adhesive kit comprising a hardened product obtained by chemically curing the aforementioned sachet-type dental adhesive composition (Y), wherein the flexural modulus of the hardened product is in the range of 1.5 to 6 GPa.

2. The dental adhesive kit according to claim 1, wherein the flexural modulus of the cured product obtained by chemically curing the sachet-type dental adhesive composition (Y) is in the range of 3 to 6 GPa.

3. The dental adhesive kit according to claim 1 or 2, wherein the ratio ((X) / (Y)) of the flexural modulus of the cured product of the self-adhesive dental composite resin (X) to the flexural modulus of the cured product of the packaged dental adhesive composition (Y) is 0.5 to 3.

0.

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

5. The water absorption capacity of the cured self-adhesive dental composite resin (X) is 50 μg / mm³. 3 The dental adhesive kit according to claim 1 or 2, which is as follows:

6. The dental adhesive kit according to claim 1 or 2, wherein the monomer (a) having an acidic group contained in the sachet-type dental adhesive composition (Y) includes at least one selected from the group consisting of monomers having a phosphate group, monomers having a carboxylic acid group, and monomers having a sulfonic acid group.

7. The dental adhesive kit according to claim 6, wherein the monomer (a) having an acidic group contained in the sachet-type dental adhesive composition (Y) contains the same compound as the monomer (a-1) having a phosphate group contained in the self-adhesive dental composite resin (X).

8. The dental adhesive kit according to claim 1 or 2, wherein the chemical polymerization initiator (e) comprises an organic peroxide and / or an inorganic peroxide.

9. The dental adhesive kit according to claim 1 or 2, wherein the first component of the sachet-type dental adhesive composition (Y) further comprises a filler (d).

10. The dental adhesive kit according to claim 1 or 2, wherein the first component of the sachet-type dental adhesive composition (Y) further comprises a monomer (b) that does not have an acidic group.

11. The dental adhesive kit according to claim 1 or 2, wherein the first or second component of the sachet-type dental adhesive composition (Y) further comprises a silane coupling agent (g).

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